Thermal Energy Transport in Oxide Nuclear Fuel

David H. Hurley1*, Anter El-Azab2, Matthew S. Bryan3, Michael W. D. Cooper4, Cody A. Dennett1, Krzysztof Gofryk1,
Lingfeng He1, Marat Khafizov5, Gerard H. Lander6, Michael E. Manley3, J. Matthew Mann7, Chris A. Marianetti8, Karl Rick-
ert9, Farida A. Selim10, Michael R. Tonks11, Janelle P. Wharry2
1
Idaho National Laboratory, 1955 N Fremont Ave, Idaho Falls, ID 83415, USA
2
School of Materials Engineering, Purdue University, 701 W Stadium Ave, West Lafayette, IN 47907, USA
3
Materials Science and Technology Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37831, USA
4
Materials Science and Technology Division, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545, USA
5
Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Ave, Columbus, OH 43210, USA
6
European Commission, Joint Research Center, Postfach 2340, D-76125 Karlsruhe, Germany
7
US Air Force Research Laboratory, Sensors Directorate, 2241 Avionics Circle, Wright Patterson AFB, OH 45433, USA
8
Department of Applied Physics and Applied Mathematics, Columbia University, 500 West 120th Street, New York, New York 10027, USA
9
KBR, 2601 Mission Point Boulevard, Suite 300, Dayton, OH 45431, USA
10
Department of Physics and Astronomy, Bowling Green State University, 705 Ridge Street, Bowling Green, OH 43403, USA
11
Department of Materials Science and Engineering, University of Florida, 158 Rhines Hall, Gainesville, FL 32611, USA

Abstract

To efficiently capture the energy of the nuclear bond, advanced nuclear reactor concepts seek solid fuels that must withstand unprecedented
temperature and radiation extremes. In these advanced fuels, thermal energy transport under irradiation is directly related to reactor perfor-
mance as well as reactor safety. The science of thermal transport in nuclear fuel is a grand challenge due to both computational and experi-
mental complexities. Here, we provide a comprehensive review of thermal transport research on two actinide oxides: one currently in use in
commercial nuclear reactors, uranium dioxide (UO2), and one advanced fuel candidate material, thorium dioxide (ThO2). In both materials,
heat is carried by lattice waves or phonons. Crystalline defects caused by fission events effectively scatter phonons and lead to a degradation
in fuel performance over time. Bolstered by new computational and experimental tools, researchers are now developing the foundational
work necessary to accurately model and ultimately control thermal transport in advanced nuclear fuel. We begin by reviewing research aimed
at understanding thermal transport in perfect single crystals. The absence of defects enables studies that focus on the fundamental aspects of
phonon transport. Next, we review research that targets defect generation and evolution. Here, the focus is on ion irradiation studies used as
surrogates for damage caused by fission products. We end this review with a discussion of modeling and experimental efforts directed at
predicting and validating mesoscale thermal transport in the presence of irradiation defects. While efforts into these research areas have been
robust, challenging work remains in developing holistic tools to capture and predict thermal energy transport across widely varying environ-
mental conditions.

Table of Contents

1 Introduction ............................................................................................................................................................................................. 2
1.1 Origins of Phonon Thermal Conductivity ................................................................................................................................. 4
2 Thermal transport in perfect single crystals........................................................................................................................................... 5
2.1 Inelastic neutron and X-ray scattering ...................................................................................................................................... 5
2.1.1 Phonon dispersion and thermal conductivity ........................................................................................................................... 5
2.1.2 Techniques for measuring phonons.......................................................................................................................................... 5
2.1.3 Triple-axis neutron measurements of the phonon lifetimes in UO2 ......................................................................................... 6
2.1.4 Inelastic X-ray measurements of phonons in irradiated epitaxial thin films of UO2 ............................................................... 6
2.1.5 Time-of-flight neutron measurements reveal nonlinear modes in ThO2 and UO2 ................................................................... 7
2.2 First-principles thermal transport in perfect crystals.............................................................................................................. 7
2.2.1 General considerations ............................................................................................................................................................. 7
2.2.2 First-principles approaches for crystals beyond DFT .............................................................................................................. 7
2.2.3 Computing phonons and their interactions from first principles.............................................................................................. 8
2.2.4 Computing thermal transport from phonons and their interactions ......................................................................................... 8
2.2.5 First-principles calculations of UO2 and ThO2 ........................................................................................................................ 9
1
 2.3 Thermophysical properties ......................................................................................................................................................... 9
2.3.1 Introduction .............................................................................................................................................................................. 9
2.3.2 Heat capacity .......................................................................................................................................................................... 10
2.3.3 Thermal conductivity ............................................................................................................................................................. 10
2.3.4 Elastic constants and thermal expansion ................................................................................................................................ 11
2.4 Crystal growth ........................................................................................................................................................................... 11
2.4.1 Challenges in growing single crystals .................................................................................................................................... 11
2.4.2 Bulk crystal growth techniques .............................................................................................................................................. 11
2.4.3 Epitaxial thin films ................................................................................................................................................................. 12
2.5 Outlook ....................................................................................................................................................................................... 13
3 Crystalline defect generation, evolution, and characterization ........................................................................................................... 13
3.1 Intrinsic point defects ................................................................................................................................................................ 13
3.1.1 Characterization techniques ................................................................................................................................................... 14
3.1.2 Intrinsic point defects: characterization and modeling .......................................................................................................... 16
3.2 Irradiation induced defects ....................................................................................................................................................... 17
3.2.1 Characterization techniques ................................................................................................................................................... 17
3.2.2 Irradiation-induced point defects ........................................................................................................................................... 19
3.2.3 Dislocation loops .................................................................................................................................................................... 19
3.2.4 Cavities and Precipitates ........................................................................................................................................................ 20
3.3 Modeling of defect clustering.................................................................................................................................................... 21
3.3.1 Simple rate theory model of defect evolution ........................................................................................................................ 21
3.3.2 Cluster dynamics approach to defect evolution ..................................................................................................................... 22
3.4 Grain Boundaries ...................................................................................................................................................................... 23
3.4.1 Intrinsic Grain Boundaries ..................................................................................................................................................... 23
3.4.2 Restructured grain boundaries ................................................................................................................................................ 23
3.5 Outlook ....................................................................................................................................................................................... 24
4 Thermal conductivity under irradiation ............................................................................................................................................... 24
4.1 Fuel performance codes and thermal conductivity ................................................................................................................ 25
4.2 Experimental measurement of thermal conductivity ............................................................................................................. 26
4.3 Boltzmann transport framework ............................................................................................................................................. 27
4.3.1 Phonon scattering ................................................................................................................................................................... 28
4.3.2 Klemens-Callaway-Debye approximation ............................................................................................................................. 29
4.3.3 Single Mode relaxation time approximation .......................................................................................................................... 29
4.4 Molecular dynamics simulations of thermal conductivity ..................................................................................................... 30
4.4.1 Bulk thermal conductivity ...................................................................................................................................................... 30
4.4.2 Point defect scattering using molecular dynamics ................................................................................................................. 32
4.4.3 Extended defects .................................................................................................................................................................... 32
4.5 Impact of grain boundaries and porosity ................................................................................................................................ 32
4.6 Comparison between experiment and modeling..................................................................................................................... 33
4.6.1 Impact of point defects in low temperature, low dose irradiated UO2 ................................................................................... 33
4.6.2 Impact of dislocation loops in high temperature proton irradiated CeO2 .............................................................................. 33
4.6.3 Mixed impact of point defects and loops in ThO2 ................................................................................................................. 33
4.6.4 Impact of grain boundaries..................................................................................................................................................... 34
4.7 Future Outlook .......................................................................................................................................................................... 34
5 Concluding Remarks ............................................................................................................................................................................. 35

1 Introduction is then converted to electricity using a steam turbine. For a fossil

Currently, about 73 percent of the electricity in the world is gener- fuel-powered plant, the heat source (i.e. exhaust gas) moves, allow-
ated using heat engines [1]. This includes heat generated by burn- ing additional heat to be extracted by increasing the length of the
ing fossil fuels (coal, gas, oil), by concentrated solar energy, and by heat exchanger. A nuclear plant is fundamentally different in this
nuclear fission. On the surface, the anatomy of a heat engine power regard; heat is generated by nuclear fission in a crystalline solid and
plant looks similar regardless of the heat source. Heat extracted by must be conducted through the fuel and transferred to the coolant,
passing a coolant over the heat source is used to create steam, which
2
as shown in Figure 1. This perspective illustrates the close connec-
tion between conduction of thermal energy (heat) and electricity
generation in nuclear power plants.

Figure 1. Schematic of a nuclear energy plant. The heat extracted from the solid fuel is used to drive a steam turbine and generate electricity.

Nuclear reactors operating in the world today primarily use actinide grain boundary surface area [6], and decreases the lattice defect con-
oxides (uranium dioxide, UO2, and mixed oxides containing UO2 centration due to segregation to grain boundaries [7], the thermal
and plutonium dioxide, PuO2) as the fuel material. These oxide fuels conductivity is larger than in similar fuel that has not formed HBS
have a large energy density (a single commercial reactor fuel pellet [8, 9]. The myriad of defect types and interactions in nuclear fuel
weighing about 10 g stores the same amount of energy as a 1.4 tons under irradiation has motivated researchers to consider improving
of coal (~1300 kg), 285 gallons of oil (~1 m3), or 38,800 cubic feet function by controlling defect evolution and structure. Examples in-
of natural gas (~150 m3) [2]) and electricity generation does not in- clude using dopants to control defect concentrations by modifying
volve the release of greenhouse gases. In nuclear fuel, a fissile nu- grain size [10, 11, 12, 13], simulating HBS using nanocrystalline
clide absorbs a neutron, becomes unstable, and splits, creating at UO2 to improve fission gas retention and improve mechanical prop-
least two new atoms (referred to as fission fragments), producing erties [14, 15], and directly adding other materials to UO2 to raise
gamma rays and neutrons, and imparting about 200 MeV of kinetic the thermal conductivity [16, 17, 18, 19, 20, 21, 22, 23, 24]. Expe-
energy into those fission fragments (as illustrated in Figure 2) [3]. diting progress towards tailoring defects and microstructure to bring
The transfer of this kinetic energy to the crystalline lattice of the fuel about desired thermal properties will require further development of
generates thermal energy that must be conducted through the fuel fundamental, predictive models of phonon transport in actinide ox-
and transferred to the coolant for eventual conversion to electricity. ide fuels containing irradiation-induced defects [25, 26, 27, 28, 29].
The thermal energy is conducted through the fuel almost entirely by
lattice waves or phonons, due to the scarcity of free electrons in ox- This desire to understand and tailor the thermal properties of fuels
ide fuels [4]. The rapid transfer of the kinetic energy from the fis- to improve the efficiency, safety, and reliability of electricity gener-
sion event to the lattice also produces defects (vacancies, interstitials ation has driven a great deal of fundamental research over the past
and extended defects) with fission fragments depositing as impurity 60 years. Our current understanding of thermal transport in actinide
atoms. These defects effectively scatter phonons, reducing the ca- oxides can be traced back to early work involving phonon transport
pacity of the fuel to conduct heat. Over the lifetime of the fuel in a in semiconductors and insulators. This work, using analytical ex-
reactor, the thermal conductivity decreases by as much as 70 percent pressions to represent conductivity, provided a mechanistic under-
[5]. standing of phonon thermal transport in the presence of defects [30,
31, 32, 33]. More recently, a first-principles theoretical approach has
produced accurate results for simple semiconductors with no adjust-
able parameters [34, 35, 36]. Similar work using the Green’s func-
Fission event Phonon transport tion T-matrix approach has been used to calculate phonon scattering
_ rates for simple lattice defects from first principles [37, 38, 39]. On
Heat generation +
the experimental side, this effort has included phonon structure
measurements using bright neutron and X-ray sources and spatially
resolved thermal conductivity measurements [40, 41, 42]. Extend-
ing these approaches to actinide oxides containing irradiation-in-
Actinide atom duced defects remains a grand challenge due to several factors.
These include challenges associated with fabricating high-quality
Figure 2. Nuclear fission is used to generate heat. Fission fragments create single crystal samples for phonon structure measurements, complex-
damage and deposit as chemical impurities. Heat is carried by phonons in ities encountered in accurately treating electron correlation in 5f
oxide nuclear fuels. electron systems, seeding samples with specific defect populations
found in reactor fuel, accurately characterizing the spectrum of de-
However, in some cases, a cooperative influence between multiple fects, and measuring thermal transport on length scales commensu-
defect types has a positive effect by increasing the lattice thermal rate with defect accumulation.
conductivity over that expected if the defects acted in isolation. For
example, in the high burnup structure (HBS) of nuclear fuels, where Here, we review the current understanding of phonon thermal
considerable irradiation-driven restructuring greatly increases the transport in oxide nuclear fuel, highlighting the above-mentioned

3
challenges. Specifically, we provide a comprehensive review of pre- The time-space evolution of N(w) is governed by the Boltzmann
vious work on two actinide oxides: one currently in use in commer- transport equation (BTE) for phonons. This equation is in general
cial nuclear reactors, UO2, and one advanced fuel candidate mate- difficult to solve. The two solution methods that will be discussed
rial, thorium dioxide (ThO2). ThO2 additionally acts as a surrogate in this review are the exact iterative solution [43, 44] and the relax-
material for UO2 as it lacks the complexity of electron correlation ation time approximation (RTA) [45]. The iterative solution to the
effects. We also provide a narrower review of other oxide materials BTE is well suited to calculate thermal conductivity of perfect single
relevant to UO2 and ThO2 research. Our focus is primarily on defects crystals but remains too computationally expensive to model crys-
produced by ion irradiation as ions provide a convenient and expe- tals with nontrivial defects. For the RTA, lattice dynamics is not re-
dient approach to inject defects that are found in real fuel specimens. quired to compute relaxation times as they can also be calculated
Emphasis is placed on identifying remaining knowledge gaps and using molecular dynamics. It is this aspect that makes the RTA well
revealing new opportunities to improve thermal transport in reactor suited for treating thermal transport in crystals containing a range of
fuel. defects from point defects to extended defect clusters.
1.1 Origins of Phonon Thermal Conductivity Under the RTA, the conductivity can be represented as:
In nuclear fuel, thermal transport can be viewed from both a macro- ! /
κ = , ∑-. 𝐶-. 𝜈-. 𝜏-. , (2)
scopic and an atomistic viewpoint. On the macroscopic scale, ther-
mal transport is treated within a continuum framework to obtain the
temperature distribution in a fuel pellet. On an atomistic scale, ther- where s enumerates the number of possible phonon modes for a
mal transport is treated within a quantum mechanical framework to given phonon wave vector q. The right-hand side of this equation
obtain an expression for the thermal conductivity, which controls contains the branch-specific phonon lifetime (tqs), phonon velocity
the temperature distribution. Phonon thermal conductivity is most (nqs), and specific heat (Cqs), with the latter two being a function of
often calculated using one of two methods: (1) Molecular dynamics only phonon dispersion (the relation between frequency and
simulation using empirical interatomic potentials (EIP) or potentials wavevector, w(q)). The lifetime is determined by phonon scattering,
derived from first principles (FPIP); (2) Seeking solutions to the lin- which ultimately limits thermal conductivity. Above cryogenic tem-
earized Boltzmann transport equation for phonons (see Figure 3). peratures, in nearly perfect single crystal materials, phonon scatter-
ing is dominated by scattering with other phonons, mediated by lat-
Boltzmann tice anharmonicity (3rd and higher order terms in the interatomic po-
Molecular Transport tential).
Dynamics Equation
a b
FPIP EIP Relaxation time Iterative q1
Time Constants approximation approach

q2
Callaway-Holland q3¢
Thermal conductivity
Debye model
Fit constants to DV
q2
k(T) experimental data q1

Figure 3. Different ways to calculate thermal conductivity. Figure 4. Phonon scattering: (a) anharmonic 3-phonon Umklapp scattering,
does not conserve total momentum and plays an outsized role in limiting
While this review will cover studies using both methods, this section conductivity and (b) phonon defect scattering.
provides an overview of the Boltzmann framework as this best illus- Structural defects caused by irradiation also influence the lifetime
trates the motivation for the organization of this review. In crystals, by introducing phonon scattering sites. Both scattering processes are
vibrational energy is exchanged between phonon modes. In thermal illustrated in Figure 4. Using Matthiessen’s rule, the total phonon
equilibrium, the average number of modes with energy ℏw is given lifetime can be written as:
by the Bose-Einstein relation:
! +! (𝜔) +! +! +!
N(w) =
"#$(ℏw/(! ))+!
. (1) 𝜏-. = 𝜏0120345167 + 𝜏89:97; ! + 𝜏89:97; / + ⋯, (3)

The number of modes of a particular energy increases with increas- to account for scattering from multiple mechanisms, both intrinsic
ing temperature. Another way of stating this is that phonons are cre- (anharmonic) and extrinsic (defects). This Boltzmann transport
ated by increasing the temperature, and destroyed by decreasing the framework provides a template that is used to organize the material
temperature (i.e. the number of phonons is not conserved). The presented in this review:
strong temperature dependence of thermal conductivity in insulators
and semi-conductors results partially from this lack of conservation. Section 2: Thermal transport in perfect single crystals
A thermal gradient imposed by an external heat source will force the
This section addresses the input to Equation 2 in terms of phonon
system away from equilibrium. The thermal conductivity depends
dispersion and lifetime, discussing previous work aimed at under-
on the extent to which the phonon distribution can deviate from
standing thermal transport in perfect single crystals.
equilibrium for a specific thermal gradient.
Section 3: Defect generation evolution and characterization

4
This section discusses the body of work involving the generation a b c d
and evolution of defects in actinide oxides using energetic ion irra-
diation.
Section 4: Thermal conductivity under irradiation
This section reports on the output of Equation 2, reviewing model-
ing and experimental efforts directed at predicting and validating
thermal conductivity in the presence of defects.

2 Thermal transport in perfect single crystals Figure 5. Relationship between phonon dispersion and thermal conductivity.
The absence of defects enables studies that focus on the fundamental (a) Phonon dispersion curve for a typical acoustic mode. The slope provides
aspects of phonon transport including the impact of strong electron the phonon group velocity, 𝑣! ; the linewidth, Γ, is inversely related to the
correlation. Experimentally, prior efforts ranging from synthesis of phonon lifetime, 𝜏, as indicated. (b) The mode partial phonon density of
single crystals to inelastic neutron and X-ray scattering are dis- states scales as 𝑔(𝜔) ∝ 𝑞 " (𝜔)(𝑑𝑞 ⁄𝑑𝜔 ). (c) Phonon group velocity squared,
cussed. Computationally, previous work aimed at the application of 𝑣!" = (𝑑𝜔 ⁄𝑑𝑞 )". (d) Product of the density of states, group velocity squared,
advanced electronic structure calculations to systems that exhibit and lifetimes give a distribution for the contributions to the thermal conduc-
strong electron correlation is reviewed. In keeping with the scope tivity tensor assuming full thermal occupation (kBT >> ℏ𝜔#$% ), where each
mode contributes equally to the heat capacity. At low temperatures the higher
delineated in the Introduction, the empahsis of this section and the frequency phonons thermally depopulate and no longer contribute as much
sections to follow is focused on providing a review of key discover- heat.
ies, highlighting fundamental mechanisms, and identifying remain-
ing knowledge gaps.
2.1.2 Techniques for measuring phonons
2.1 Inelastic neutron and X-ray scattering The earliest measurements of the phonon dispersion curves of acti-
nide oxides UO2 [49] and ThO2 [50] were performed using the reac-
tor-based triple-axis neutron scattering technique (Figure 6a) that
2.1.1 Phonon dispersion and thermal conductivity was first established for measuring phonon dispersion curves by
Brockhouse [51, 52]. However, the early work on actinide oxides
Measurements of the phonon dispersion curves in a material offer a primarily focused on determining the phonon dispersion curves or
unique window into the microscopic mechanisms controlling pho- density of states and left out the phonon lifetimes, which are more
non thermal transport (see Figure 5). These dispersion curves relate difficult to measure but crucial to understanding the thermal con-
phonon wave vector, q, to frequency, ω, through the interatomic ductivity. Additionally, because of large neutron absorption cross-
force constants. In principle, thermal conductivity can be repre- sections and crystal size requirements (>0.2 cm3), certain actinide
sented using the measured dynamical structure factor [46]. The oxides (e.g. plutonium dioxide) remained impractical to measure
mode partial phonon density of states, g(ω) is evaluated by differ- with neutrons.
entiating the phonon branches [47] and can be used to evaluate the
heat capacity and vibrational entropy per mode [48]. The slope of a The situation changed with the advent of high-energy resolution
measured dispersion curve determines the phonon group veloci- synchrotron-based inelastic X-ray scattering (IXS) spectrometers
ties, 𝑣= , and the linewidth of the curve is inversely related to the [53, 54, 55, 56] (Figure 6b), which have no isotope requirements and
phonon lifetime. As illustrated in Figure 5b, for a typical acoustic crystal sizes can be as small as a few micrometers [57]. This allows
phonon, the partial density of states available to carry heat becomes the measurements of individual crystal grains within a polycrystal
very small for states near the zone center (q=0). Consequently, even sample. The first measured phonon dispersion curves for plutonium
though the velocities (see Figure 5c) and lifetimes are large in this metal [58] and the first phonon density of states of PuO2 [59] were
region, the contributions to the thermal conductivity can still be both obtained using IXS rather than neutron scattering. IXS also
small. At high temperatures, with full thermal occupation (kBT >> opened up measurements of phonons at high pressures and in thin
ℏ𝜔>?# ), the heat capacity term in Equation 2 follows the density of films using grazing incidence. Actinides are particularly well suited
states, and the contributions to thermal conductivity are more to IXS measurements in small geometries since the X-ray scattering
broadly distributed over the curve (Figure 5d), peaking in im- per atom increases as the square of the atomic number. However,
portance near the middle of the curve. Similar arguments can be there are a limited number of facilities available for these measure-
made for dispersive optical phonons. For this reason, understanding ments and, like triple-axis neutron scattering, it takes considerable
the thermal conductivity at high temperatures requires measure- beamtime to map a full set of phonon dispersion curves. A full set
ments of the full set of dispersion curves, including linewidths, and of phonon dispersion curves takes about two weeks to map, which
this requires neutron or X-ray scattering techniques at large user fa- may require multiple experimental cycles. An example is the recent
cilities. phonon dispersion curves for NpO2 taken from a very small crystal
with X-rays at the European Synchrotron Radiation Facility (ESRF)
[60].
Another important advance in measuring phonons in actinide oxides
came with the wide-angle range time-of-flight spectrometers at
next-generation spallation neutron sources such as the Spallation
Neutron Source (SNS) at Oak Ridge National Laboratory [61],

5
which came online in the mid to late 2000s (Figure 6c). These in- 2.1.3 Triple-axis neutron measurements of the phonon
struments and sources enable measurements of higher energy modes lifetimes in UO2
than are normally accessible with reactor-based triple-axis measure-
Building on the pioneering work of Dolling et al. [49], Pang et al.
ments and provide a sampling of a large volume of energy-momen-
[27, 63] have shown using triple-axis inelastic neutron scattering
tum space in a single measurement – allowing the full mapping of
(Figure 7) that the principal contribution to the thermal conductivity
the dispersion curves. These two advantages have proven useful in
the discovery of new high energy dynamical features [62]. These of UO2 comes from the acoustic phonons together with a steep and
relatively low energy longitudinal optic phonon, LO1 (see Figure
measurements, however, also require large samples.
7a).
In most crystalline insulators the majority of thermal heat transport
is carried by the acoustic phonons, since they typically have the larg-
est group velocities and the longest lifetimes. However, the triple-
axis measurements [27] indicate that the steep longitudinal optic
mode carries the largest amount of heat by branch at 295 K in UO2
(see Figure 7b), which was not expected. It was also not predicted
in previous simulations [64] because they underestimated the group
velocities and lifetimes of the LO1 phonon compared to experiment
[27], rendering it less important in the simulated thermal conductiv-
ity. The steeply dispersing LO1 phonon is a general feature of the
a fluorite crystal structure and is thus likely important in the thermal
conductivity of all of the actinide oxides considered herein.
a(a) b(b)

b
Figure 7. Phonon dispersion curves and branch thermal conductivity of UO2,
after Pang et al. [27]. (a) Phonon dispersion curves measured using triple-
axis neutron scattering at 295 K (blue) and 1200 K (red). (b) Phonon branch
thermal conductivity derived from the measured phonon dispersion and life-
times (‘Experiment’) and from calculations (‘Simulation’). Adapted with
permission from [27]. Copyright 2013 American Physical Society.

2.1.4 Inelastic X-ray measurements of phonons in ir-

radiated epitaxial thin films of UO2
The focus of this section thus far has been on neutron scattering
measurements on perfect or nearly perfect single crystals. However,
c as mentioned previously, IXS can provide phonon structure infor-
mation on thin films using grazing incidence methods. Here we ex-
Figure 6. Important scattering techniques for measuring phonon dispersion tend our focus momentarily to consider IXS on ion irradiated UO2
curves in actinides. (a) Triple-axis neutron scattering spectrometer at a reac-
thin films, as this gives a phonon-level description on the impact of
tor source. A monochromator fixes the incident neutron wavevector, 𝒌& , and
an analyzer crystal selects the final wavevector, 𝒌' , from which momentum irradiation. An experiment by Rennie et al. [65] involved epitaxial
transfer, 𝑸 = 𝒌& − 𝒌' , and energy transfer, ℏ𝜔 = ℏ"1𝑘&" − 𝑘'"3/2𝑚, can be films (thickness 300 nm) of UO2 that were irradiated with 2.1 MeV
selected to measure phonon dispersion curves. (b) Inelastic X-ray scattering He2+ ions to 0.15 dpa, resulting in homogeneous damage and a lat-
at a synchrotron. Similar to a triple-axis instrument in operation but with a tice swelling of Da/a ~ 0.6%. The film was then examined by graz-
more selective monochromator to extract ~1 meV resolution from a ~20 keV ing-incidence X-ray inelastic scattering using synchrotron radiation
beam. (c) Time-of-flight direct geometry inelastic neutron scattering spec- (Figure 6b) to measure whether the acoustic phonons showed any
trometer. Incident energy is selected using a chopper and final energies and change under these conditions.
wavevectors are determined by the time of flight of the scattered neutrons
arriving at a wide-angle detector bank and allows for a broad sampling of The results showed that the frequency of the phonons was not
energy-momentum space. changed, but their widths G (Figure 5a) were substantially increased.
Although it is difficult to measure optical phonons with this tech-
nique, the results with acoustic phonons are consistent with the drop
in the thermal conductivity for this level of radiation damage [66].
These experiments confirm that the effects of irradiation in UO2 are

6
intrinsic to the microscopic structural changes caused by the dam- 2.2.1 General considerations
age, and result in shorter lifetimes of the acoustic phonons. The neg- The foundation of any first-principles prediction of thermal
ligible impact of irradiation damage on phonon velocity will provide transport in crystals begins with the computation of the various qua-
important information for studies, discussed in subsequent sections, siparticles which will be carriers of heat (e.g. electrons, phonons,
aimed at the forward problem of predicting the thermal conductivity etc.), requiring the approximate solution to the many-body Schrö-
in defective oxides using the BTE formalism. dinger equation for electrons interacting with some symmetric ar-
2.1.5 Time-of-flight neutron measurements reveal non- rangement of nuclei. Fortunately, we have elegant mathematical for-
linear modes in ThO2 and UO2 malisms, such as density functional theory (DFT) [69, 70, 71, 72,
73], which have allowed us to make substantial progress in obtain-
The vibrational motions in crystalline solids are typically phonons, ing approximate solutions to this many-body problem that repre-
equivalent to the normal modes of classical mechanics. The total sents the forefront of mathematical and computational physics. Fur-
number of phonon modes in a system with N atoms in the primitive ther, first-principles computations of various sorts will then be
cell is 3N. In the case of the fluorite structured ThO2 and UO2, N=3 needed to calculate the intrinsic scattering mechanisms of the re-
and there is a total of 9 phonon branches. Recent inelastic neutron spective quasiparticles, and we will focus on phonon-phonon inter-
scattering measurements observe all 9 branches [67]. However, in actions in the subsequent sections.
addition to the 9 phonon modes expected, a dispersing mode has
been observed in this system at energies above the highest energy
phonon mode, which is referred to as the Nonlinear Propagating
Mode (NPM). This mode is observed in UO2 and ThO2, as well as 2.2.2 First-principles approaches for crystals beyond
in natural fluorite, CaF2. It is observable at temperatures ranging DFT
from 5 K to 1200 K. The observed dispersion and linewidth are com- 2.2.2.1 Hybrid Functionals and DFT+U
parable to a typical phonon dispersion and linewidth in this system. Hybrid functionals mix standard DFT exchange-correlation func-
It also repeats with the same symmetry as the phonon modes, evi- tionals with some fraction of Hartree-Fock exchange [74]. Generi-
dence that the NPM propagates with the same periodicity as the pho- cally speaking, this approach has been very successful for correcting
nons. ground and excited state properties in atoms and molecules [75, 76],
weakly correlated band insulators [74], defect energetics [77], and
Additional degrees of freedom can lead to additional modes but
strongly magnetic insulators [78, 79, 80, 81]. However, hybrid func-
given the wide range of observations and no evidence of a phase
tionals can be unreliable for metals [82] and can fail completely for
transition leading to the absence or appearance of the NPM, this is
strongly-correlated electron materials. For example, the Heyd-
unlikely. Nonlinear terms in the equations of motion, as a result of
Scuseria-Ernzerhof hybrid functional [83] is qualitatively wrong for
the interatomic potential not being perfectly harmonic, can also pro-
the classical material VO2 [84], where the undistorted rhombohedral
duce additional modes as observed previously [68]. It has been ar-
phase is predicted to be insulating [85], while it is known to be me-
gued that this is the source of the mode in these materials with sup-
tallic [84]; the dimerized monoclinic phase is predicted to be higher
port from first-principles calculations [68].
in energy than the rhombohedral phase in addition to being a mag-
The high group velocity of the NPM suggests that it may make a netic insulator [85], while it is experimentally known to be the
positive contribution to thermal conductivity. However, the high en- ground-state structure [84] and nonmagnetic (i.e. no local moments
ergy of the mode indicates that this could only be the case at high observed) [86]; and the predicted band gap of 2.23 eV is in poor
temperatures (80 meV corresponds to about 930 K). The mode may comparison with the experimental value of 0.6-0.8 eV [87]. A fur-
also act as an additional scattering channel for normal phonons, de- ther limitation of hybrid functionals is the rather large computational
creasing thermal conductivity, so the impact of NPMs on thermal cost when using a plane wave basis, scaling approximately as the
conductivity remains an open question. A full accounting of the pho- cube of the number of atoms in the unit cell [88].
nons and NPMs from first principles is needed to resolve this ques-
tion. DFT+U [89] bears many similarities to hybrid functionals, in that
DFT+U can be viewed as a sort of local hybrid functional. The con-
2.2 First-principles thermal transport in perfect crystals nection between DFT+U and hybrid functionals has indeed received
ThO2, a band insulator, does not have ground state f-shell electrons, attention from a methodological perspective [90, 91]. While DFT+U
while UO2 has a partially filled f shell and is a Mott insulator. Thus, does not contain the non-local aspects of a hybrid functional, it does
in addition to being of interest to the nuclear fuels community, these account for the important local aspects present in many strongly cor-
materials are model systems for understanding the role of electron related materials. More importantly, the computational cost of
correlation. We begin by generically considering the state of first- DFT+U is considerably smaller than hybrid functionals. Addition-
principles computations of electronic and lattice properties of crys- ally, while DFT+U has more empirical parameters than hybrid func-
tals as compared to experimental measurement on high purity single tionals (i.e. U, J, and double counting in DFT+U vs. the alpha mix-
crystals. After the general discussion, we critically review the liter- ing parameter in hybrids), this is not entirely a disadvantage because
ature concerning application of first-principles computation to ther- it facilitates an empirical exploration of the various components of
mal transport in ThO2 and UO2, highlighting main findings and the functional. Altogether, DFT+U is a very efficient theory, which
identifying open issues. can operate in the same spirit as DFT, performing full structural re-
laxations and exploring a wide phase space of possibilities.

7
2.2.2.2 DFT + Dynamic mean-field theory 2.2.3 Computing phonons and their interactions from
All known implementations of DFT break down in certain strongly- first principles
correlated electron materials, illustrating the difficulty of develop- Computing phonons and their interactions from first principles
ing sufficiently robust approximations for the exchange-correlation amounts to computing the Taylor series expansion of the Born-Op-
functional. Instead of creating functionals of the density, one can penheimer potential of a given first-principles approach with respect
choose to create functionals of other observables, which might be to the nuclear displacements of the crystal. A crystal is infinite in
more sensitive to capturing the physics of strong correlations, such extent, and therefore the computed Taylor series at each order must
as the single particle Green's functions [92, 93, 94]. In such ap- be truncated at some maximum range in real space, or density in
proaches, there is an analogy to the exchange-correlation functional, reciprocal space. A sufficient resolution needs to be obtained at each
which embodies the unknown portion of the energy as a functional order such that the observable at hand is converged to within a suf-
of the Green's function, and the functional derivative of this quantity ficient tolerance, and therefore the necessary resolution will vary
with respect to the Green's function is the well-known self-energy. depending on which observable is being considered. For a compre-
The dynamical mean-field theory (DMFT) can be viewed as a tool hensive review of computing phonons and their interactions from
which allows for the approximate computation of the self-energy first-principles we refer the reader to [113].
[95].
There are two basic approaches for computing derivatives of a Born-
DMFT was created in the context of the Hubbard model [96, 97, 98], Oppenheimer potential [114, 115]: perturbative approaches and fi-
which is one of the simplest models of interacting electrons on a nite displacements. We use the latter term broadly to include any
lattice; consisting of an on-site Coulomb repulsion and a nearest approach which explicitly displaces the nuclear coordinates and
neighbor hopping parameter to embody both the kinetic energy and solves the Schrödinger equation of the displaced structure, including
some external potential. The Hubbard model cannot be solved in usual finite difference approaches or more complicated fitting pro-
general, but it can be solved in one dimension using the Bethe ansatz cedures based on finite displacements. The nature of the perturbative
[99, 100] and in infinite dimensions in conjunction with DMFT approach and the order to which it can be carried out will depend on
[101]. DMFT maps the Hubbard model to an effective Anderson the particular first-principles approach that is being used. Finally,
impurity model (AIM), where the bath is determined via the DMFT these two approaches are naturally combined, using a perturbative
self-consistency condition. Some other approach is then needed to approach to obtain some low order derivatives (e.g., Hellman-Feyn-
solve the AIM, and most prevalent approaches to the many-body man forces) and finite displacements for higher order derivatives,
problem have been applied [101, 102]. Given that the AIM is still a allowing many derivatives to be simultaneously measured in a given
tractable many-body problem, DMFT allows for the infinite dimen- finite displacement calculation [113, 116, 117].
sional Hubbard model to be solved numerically exactly, using tech-
niques such as quantum Monte Carlo [103, 104]. These numerically
exact techniques, however, are computationally expensive, limited
to finite temperatures, and may face minus sign problems [105]. 2.2.4 Computing thermal transport from phonons and
their interactions
While DMFT can clearly capture the physics of the Mott transition
The anharmonic vibrational Hamiltonian poses a nontrivial many-
in the infinite dimensional Hubbard model, it is not tractable for
body problem of interacting bosons, and exactly evaluating the ther-
treating all the electrons in a strongly correlated electron material.
mal conductivity is highly nontrivial. The most common approach
Fortunately, it is only a subset of electrons in real materials that give
is the linearized BTE [118]. The inputs to the BTE are the phonon
rise to strongly correlated electron behavior – typically d and f elec-
eigenvalues and eigenvectors, the phonon velocities, and typically
trons. It is then natural to combine the best aspects of both DFT and
the cubic phonon interactions. The BTE may be numerically solved
DMFT by constructing an energy functional of two variables: the
without approximation using iterative techniques [44] and varia-
density and the local Green's function of the correlated orbitals
tional approaches [119], where the latter guarantees numerical con-
[102]. This functional is then approximated using some exchange-
vergence. Solutions to the BTE based on phonons and phonon inter-
correlation functional for DFT, along with DMFT, yielding the so-
actions have been executed over a large number of material systems
called DFT+DMFT approach. DFT+DMFT has been placed on the
[120, 121], often resulting in impressive agreement with experi-
same footing as DFT, allowing for detailed total energy calculations
ment, though most systems that have been studied are band insula-
of complex materials where DFT sometimes qualitatively breaks
tors.
down [106, 107, 108, 109, 110, 111].
Typical approaches to the Boltzmann equation have numerous lim-
Upon executing a DFT+DMFT calculation, one needs some ap-
itations. For example, most studies only account for scattering via
proach to solve the effective AIM of the DMFT portion of the cal-
cubic phonon interactions and do not account for thermal expansion
culation, and there is always a balance between accuracy and com-
of the crystal, and both of these assumptions are only valid at suffi-
putational cost. The impurity solver with the smallest computational
ciently low temperatures. Several recent studies have attempted to
expense is Hartree-Fock, and this leads to the well-known DFT+U
go beyond these limitations, by including quartic phonon interac-
approach. It is worth noting that DFT+U [112] was developed
tions [122, 123, 124, 125] and thermal expansion [125] when solv-
around the same time as DMFT, and therefore DFT+U greatly pre-
ing the Boltzmann equation. If one only needs results in the classical
ceded DFT+DMFT. Therefore, it is often not appreciated that
regime, another approach is to use Kubo-Green linear response in
DFT+U is a special case of DFT+DMFT [102].
conjunction with classical molecular dynamics [126, 127]. A poten-
tial advantage of this route in conjunction with first-principles mo-
lecular dynamics is to retain phonon interactions to all orders and
include all possible allowed scattering process.

8
2.2.5 First-principles calculations of UO2 and ThO2 -I approximation [146], and continuous time quantum Monte Carlo
The ground state and thermodynamic properties of ThO2, including (CTQMC) [146]. It is straightforward for DFT+DMFT to capture
the phonons, are reasonably well described by DFT [128, 129, 130, the paramagnetic insulating state in all cases. Studying small energy
131], as expected for a band insulator. A recent study [132] com- details with DFT+DMFT is still challenging due to the severe
pared the accuracy of three different exchange-correlation function- tradeoff between precision and computational expense when solving
als to experimental results (see Figure 8). Overall, the Strongly the DMFT impurity problem. Precise techniques such as CTQMC
Constrained and Appropriately Normed (SCAN) functional and the will inherently hit a computational wall at sufficiently low tempera-
Local Density Approximation (LDA) show better agreement with tures, while inexpensive techniques such as Hubbard-I are not terri-
experiment than the Generalized Gradient Approximation (GGA). bly reliable. A technique that is well suited to the paramagnetic state
UO2 nominally contains two electrons in the uranium f shell, given at zero temperature for UO2 is the rotationally invariant slave boson
that the remaining four uranium valence electrons will be transferred theory [147], which finds UO2 to be an orbitally-selective Mott in-
to the oxygen atom. However, in reality, hybridization substantially sulator. However, the shortcoming of this approach is that it only
alters this nominal charge counting. The partially filled f shell gives has a semi-quantitative characterization of Mott physics, and more
rise to a low energy Hamiltonian, which will exhibit a competition precise methods are needed to further investigate these findings.
between the strong on-site Coulomb repulsion and delocalization, With these approaches for the lattice properties of UO2 and ThO2,
resulting in the "actinide Hamiltonian" [133], which is a combina- thermal conductivity has been computed for both materials in vari-
tion of the well-known Hubbard and periodic Anderson model. ous levels of approximations. The lowest level approximation only
Therefore, one is faced with a challenging many-body problem, with includes the anharmonicity at the level of the mode averaged Grü-
potential for strongly correlated electron behavior. Moreover, the neisen parameter in conjunction with the Slack equation [148], and
physics of UO2 are further complicated by the relatively strong spin- this has been executed using various DFT functionals in ThO2 [129,
orbit coupling in uranium. 130, 131, 149]; and it has been executed for UO2 using
DFT(GGA)+U [150] in addition to DFT+DMFT where the DMFT
impurity problem is solved via exact diagonalization using a trun-
cated bath [64]. The next level of approximation is directly compu-
ting the cubic phonon interactions from first principles, computing
the phonon lifetimes from perturbation theory, and then using the
RTA. This has been executed for ThO2 using DFT [151, 152] and
UO2 using DFT+U [27], where the latter demonstrated rather sub-
stantial deviation from experiment. The next level of approximation
goes beyond the RTA and fully solves the BTE, which has been ex-
ecuted for ThO2 [153, 154]. It should be noted that quantitative dif-
ferences were found in the two aforementioned studies, despite the
fact that the calculations were nominally very similar, highlighting
some sort of methodological shortcomings.
2.3 Thermophysical properties
2.3.1 Introduction
In addition to thermal conductivity, the heat capacity, thermal ex-
pansion, and the elastic constants are all directly determined by the
phonon structure. The thermophysical properties of actinide oxides
Figure 8. Phonon dispersion for ThO2 computed using DFT with three dif- have been a subject of many studies during the last 70 years. This
ferent exchange-correlation functionals (LDA, GGA, SCAN) and measured fundamental research, initiated by the Manhattan Project, started
using inelastic neutron scattering. Right panel: The phonon density of states. various systematic studies of actinide oxides that led, among others,
Reproduced with permission from [132]. Copyright 2021 Dennett et al. (Pub- to the discovery of phase transitions in both UO2 [155] and NpO2
lished by Elsevier Ltd.). [156] at temperatures below 50 K. Neutron diffraction experiments
A large number of DFT, DFT+U, hybrid functional, DFT+DMFT, established the antiferromagnetism in UO2 below 30 K, [157, 158],
and other first-principles calculations have been performed on UO2 but the situation in NpO2 remained a mystery for many years. The
[134]. The LDA and GGA qualitatively fail, producing a metallic antiferromagnetsim (AF) of UO2 was originally thought to be a sim-
state [135]. The PBE0 and HSE hybrid functionals both produce an ple type I AF single-k (1k), but work by Burlet, et al. [159] strongly
antiferromagnetic insulator [136, 137]. DFT+U also produces an an- suggested that the ordering was of a 3k nature, and this was con-
tiferromagnetic insulator and can even capture the proper 3k struc- firmed unambiguously by Blackburn and coworkers [160]. In such
ture [138, 139, 140, 141]; reasonable agreement with the spin-wave a magnetic structure, the moment directions are non-collinear but
spectra is also obtained [142]. DFT+U calculations can provide point along alternate <111> directions. At the same time, resonant
moderate agreement with the experimental phonon spectrum [143, X-ray experiments [161] had established that the ordering at 25 K in
144]. Of course, DFT+U is confined to ordered states, and NpO2 was of the electric quadrupoles, and they were also found soon
DFT+DMFT will be needed to extend to the paramagnetic state. after in UO2 [162]. Much of these complications and the associated
theory is reviewed in [163], and the latest excitation spectra of UO2,
DFT+DMFT calculations for UO2 have been executed using a vari- as measured with polarized neutrons, was published in 2011 [164].
ety of different approximations to solve the DMFT impurity prob- Hints of the elusive quadrupolar excitations [165] were found in this
lem, including exact diagonalization for a small bath [145], Hubbard
9
study, but an unambiguous proof of their existence remains a chal- there are much fewer studies on the specific heat of NpO2 and PuO2.
lenge. A more recent (shorter) review on these challenges in UO2 NpO2 has electric quadrupole ordering at 25.5 K [161] and a com-
appeared in 2020 [166]. plex ordering of a higher order magnetic multipoles [163, 174, 175,
176]. Similar to ThO2, the temperature dependence of PuO2 (poly-
Our focus here is on studies that target low temperature (room tem-
crystalline samples) shows no anomaly in agreement with a temper-
perature and below) thermophysical properties. This is in keeping
ature-independent Pauli paramagnetic state [170, 171, 177], which
with our later discussion of thermal transport in the presence of de-
arises from the singlet-ground state established for this Pu4+ (5f4)
fects. When investigating the influence of irradiation defects, it is
material [178]. The similarity in the behavior of heat capacity in
often advantageous to freeze out phonon-phonon interaction by con-
these oxides agrees with the similarities in phonon dispersions ob-
ducting experiments at low temperatures.
served in these materials. Also, the low-temperature electronic con-
2.3.2 Heat capacity tribution to the specific heat can be extrapolated to zero at T = 0, in
perfect agreement with their Mott insulating ground state.
The low-temperature heat capacity of ThO2 has been measured on
both polycrystalline samples and single crystals [29]. As expected 2.3.3 Thermal conductivity
for a diamagnetic insulator, the heat capacity does not show any sign
Despite its importance as a nuclear fuel material, the thermal con-
of phase transitions, and its temperature dependence is governed by
ductivity of ThO2 single crystals has been measured only recently
the acoustic and optical contributions which can be described using
[179]. Overall, the temperature dependence of the thermal conduc-
the DFT harmonic approximation (see Figure 9). UO2 orders anti-
tivity of ThO2 is typical for diamagnetic insulators with a character-
ferromagnetically (non-collinear 3k magnetic structure) below the
istic maximum below 40 K. Its behavior can be described by phonon
Neel temperature, TN = 30.5 K, as discussed above. In UO2 the tran-
thermal transport by taking into account boundary, defects, and
sition is accompanied by a Jahn-Teller distortion of the oxygen at-
Umklapp phonon-phonon scattering mechanisms [180]. Uranium
oms, discovered in 1976 [167], and the electric quadrupolar ordering
dioxide, in contrarst, shows an anomalous behavior with a double-
(3k type) [142, 163]. Because of that, the heat capacity shows a large
peak structure (see Figure 10) and low magnitude of k(T).
first-order-type anomaly at the transition (see Figure 9).
a b

Figure 10. (a) The thermal conductivity of ThO2 (green circles) and UO2
Figure 9. The heat capacity of ThO2 (green triangles) [29], UO2 (blue circles)
(blue circles) single crystals measured along the <100> crystallographic di-
[168], NpO2 (purple squares) [169] single crystals, and polycrystal PuO2 (red
line) [170, 171]. In the case of UO2, a large first-order type anomaly is ob- rection. Note the significant differences in k(T) and its magnitude between
served at 30.5 K resulted from structural Jahn-Teller distortion and antifer- ThO2 and UO2. (b) The temperature dependence of the thermal conductivity
of UO2 single crystal measured in the <100> <110> and <111> crystallo-
romagnetic ordering. For NpO2 the transition at 25.5 K is caused by the or-
dering of high-order magnetic multipoles. The increase of heat capacity be- graphic directions. ThO2 data adapted with permission from [179]. Copy-
low 3 K in various neptunium systems is usually associated with a nuclear right 2010 American Chemical Society. UO2 data adapted with permission
from [180]. Copyright 2014 Gofryk et al. (Published by Springer Nature).
Schottky term due to the splitting of the I = 5/2 nuclear ground level of the
237
Np nuclei by the hyperfine field. In NpO2, however, the origin of the That behavior cannot simply be explained by different strength of
anomaly is unclear since the nuclear contribution seems to be too small to
defect or grain boundary scattering processes present in different
explain the difference [172]. UO2 data adapted with permission from [168].
Copyright 2019 American Physical Society. NpO2 data adapted with permis- materials as the thermal conductivity of UO2 is similar for stoichio-
sion from [169]. Copyright 2016 American Physical Society. PuO2 data metric pellets, polycrystals, and single crystals [181]. To explain
adapted with permission from [170]. Copyright 1976 American Institute of that discrepancy, it has been suggested that the reduction of the ther-
Physics. ThO2 data adapted with permission from [29]. Copyright 2020 Den- mal conductivity in UO2 is due to the strong resonant scattering pro-
nett et al. (Published by AIP Publishing). cess of phonons and electronic degrees of freedom, such as spins,
with the characteristic energy of the order of 10 meV [180]. Similar
The anharmonic effects, first observed in diffraction experiments by
Willis and colleagues [173], are important in describing the heat ca- behavior has also been suggested to describe the k(T) behavior in
other magnetic materials [182, 183, 184]. Furthermore, the thermal
pacity in this oxide family. In UO2, the observation of a small an-
harmonic specific heat contribution is the result of relatively large conductivity of UO2 appears to exhibit anisotropic behavior (Figure
energy-dependent anharmonic effects which have opposite signs, 10b) with slightly smaller (~10%) heat conduction along the <100>
leading to a total contribution near zero [168]. As might be expected, direction [180]. If confirmed, this unusual behavior for the second-

10
rank thermal conductivity tensor indicates that there is some "hid- ments [194, 195]. This is more completely discussed in a recent neu-
den" anisotropic behavior (in certain phonon interactions or cou- tron inelastic scattering study [164], the review article [163], and the
plings) that break the cubic symmetry in this material and lead to 2020 review [166].
anisotropic thermal transport. Some microscopic evidence to sup-
port these macroscopic measurements has come from measuring the Recently, the thermal expansion of UO2 has been studied under high
low-temperature phonon linewidths with IXS [185]. A strong ani- magnetic field. It was found that UO2 becomes a piezomagnet when
sotropy is found in that the linewidths are strongly broadened over the magnetic field is applied along the <111> direction in the anti-
the energy range 5–15 meV in the <100> direction, but no effects ferromagnetic state and exhibits a peculiar memory effect due to a
are observed in the <011> direction. Further study is needed to de- partial domain reorientation [196]. These effects are due to the
finitively connect these phonon features and macroscopic thermo- strong magnetoelastic interactions and symmetry of the non-collin-
physical properties. ear 3k antiferromagnetic order in this material that allows the ap-
pearance of the piezomagnetism in UO2 [197].
2.3.4 Elastic constants and thermal expansion
2.4 Crystal growth
Elastic constants have been studied experimentally using a pulse
echo technique on single crystals of ThO2 and UO2 at room temper- 2.4.1 Challenges in growing single crystals
ature [186, 187]. The thermal expansion of UO2 single crystals has Many of the experimental efforts discussed herein either require sin-
been measured by Brandt and Walker in 1967 [188, 189]. That was gle crystals or perform best when analyzing single crystals. The AO2
the first direct demonstration that the phase transition is first-order (A= Ce, Th, U, or Pu) family, however, is extremely challenging to
in the lattice properties. The volume collapse at TN was first ob- grow as single crystals because the high melting points (2470-
served in 1974 [190] and, more recently, by X-ray diffraction [191]. 3377°C) [198, 199, 200, 201] exceed those of the containers used in
Furthermore, the measurements of elastic constants versus temper- melt growth syntheses and the solubilities are low in most industri-
ature have not only exhibited changes at the magnetic transition but ally feasible solvent systems [202, 203, 204, 205]. Overviews of the
also confirmed that the elastic properties at high temperature (up to successful growth techniques have been published elsewhere [206,
room 207, 208, 209, 210]), but herein the discussion is focused on how
each successful growth technique maximizes some of the desired
attributes while having shortcomings in other aspects. As a result,
when approaching a study of the AO2 family, or even any individual
member, compromises must typically be made with what single
crystal properties are of highest importance. The main areas where
this tradeoff occurs is in the crystal purity, growth speed, structural
quality, and size. The various oxidation states that are available for
U and Pu further complicate crystal production [211].
2.4.2 Bulk crystal growth techniques
The cornerstone of large (>1 m), high purity (>>99.9%), high qual-
ity crystal growth in the semiconductor industry is the pulled melt
crystal growth methodology, such as that employed in the Czochral-
ski method. Maintaining a feedstock of molten AO2, however, is in-
feasible because their melting points exceed that of widely used con-
tainment vessels. This has resulted in the AO2 family being the sub-
ject of more exotic crucible methods, such as the cold crucible tech-
nique (ThO2 and UO2 [212]), closed capsule zone melting (UO2
[213]), and using a floating zone furnace (UO2 [214, 215]). An al-
ternative route to avoiding crucible destruction is to have a much
Figure 11. Change in elastic constants with temperature for UO2. Data more rapid melt growth, such as in arc melting (UO2 [214, 216, 217,
adapted with permission from [188]. Copyright 1967 American Physical So- 218] and ThO2 [219, 220, 221, 222, 223]), a solar furnace (UO2
ciety. [224] and ThO2) [225]), or the Verneuil method (UO2 [226]). Alt-
temperature) are much more complicated than anticipated. Similar hough many of these techniques yield large (>1 cm3) products, they
indications have come from susceptibility measurements [192] and are never single crystal for the AO2 family. Rather, agglomerates of
of polarized neutron studies [193] that showed the short-range order multiple single crystals that are sintered together are produced [227].
up to at least 200 K. Elastic constants are directly related to low fre- Samples used for analysis are often cut from these large domains
quency dispersion of the three acoustic phonon modes. In cubic sys- such that a single crystal is acquired. This means that all single crys-
tems, there are three independent elastic constants, C11, C12, and C44. tals thus obtained have been mechanically altered which, in the case
In UO2, the temperature dependence of C44 (shear along the <111> of A = U or Pu, could mean that the surface adopts a new cation-to-
crystallographic direction – the cube diagonal) is highly anomalous anion ratio. Furthermore, the production of large crystal domains
[188, 189] and indicative of a considerable interaction between lat- signifies that orientation control is difficult for melt growth of these
tice and spins even well above the Neel temperature (see Figure 11). refractive oxides. The presence of these large domains indicates
The strong spin-phonon coupling and magnetoelastic interactions growth conditions are quite heterogeneous, suggesting that crystal
have also been confirmed by inelastic neutron scattering experi- quality might vary within a single given domain, but experimental
investigations have rarely been performed to assess this.

11
If the melt growth is eschewed because of these assorted shortcom- High temperature sintering is essentially limited by growth time, as
ings, the next most common growth techniques dissolve the feed- grains will slowly enlarge, but the atomic mobility is extremely low
stock under conditions well below the melting point and then crys- compared to fluid or gas growth mechanisms. Despite these chal-
tallize out the feedstock from the solution. Chemical vapor deposi- lenges, high quality crystals have been produced by these tech-
tion (CVD) or chemical transport (UO2 [228, 229, 230, 231], UxTh1- niques, but they are often small, contain impurities, or both.
xO2 [232], and U1-xPuxO2 [233]), flux (CeO2 [234, 235, 236, 237,
238, 239, 240, 241], ThO2 [220, 223, 234, 235, 236, 237, 238, 242, In the techniques discussed here, some type of tradeoff is necessi-
tated in the crystal purity, growth speed, structural quality, or size.
243, 244, 245, 246, 247], UO2 [217, 248, 249], UxTh1-xO2 [249], and
Even with these compromises, however, at the present there is not a
PuO2 [242, 250, 251, 252, 253]), and hydrothermal or solvothermal
direct route to making large (> 1 cm3) single crystals of any member
synthesis (CeO2 [254], ThO2 [29, 67, 179, 255, 256, 257, 258, 259,
of the AO2 family. Growth procedures are discussed that report
260, 261, 262], U1-xThxO2 [262, 263, 264], UO2 [256, 257, 258, 264,
larger crystals, but these often have grain boundaries or large do-
265, 266, 267], and PuO2 [268]) fall into this category and have been mains such that the term “single crystal” cannot readily be applied.
employed for the entire AO2 family. High-quality, well-faceted sin- As of now, however, there are some leaders in the crystal growth of
gle crystals of ThO2 and UO2 produced using the hydrothermal
each AO2 member. Dark brown CeO2 crystals with edges up to 8
method are shown in Figure 12. Whereas melt crystal growth is
mm, for example have been grown with a (100) cubic morphology
largely a physical growth method (although oxidation, reduction,
using a flux mixture of Pb3P2O8, PbF2, Al2O3, NaF, MgF2, and V2O5
and crucible contamination can become major chemical factors), so-
[235]. The crystal purity might be low, however, as similar flux so-
lution-based growth techniques are truly chemical growth methods.
lutions have displayed > 1 wt. % Pb inclusions in CeO2 [240]. Ad-
This complicates matters in that the solvent-reactant, -product, and
justing the flux to Li2WO4 has resulted in lower impurity concentra-
–container interactions all become variables in addition to chemical
tions (200 ppm W and <50 ppm Li), but the size decreases to maxi-
species and oxidation/reduction. The added complexity means that
mum edge sizes of 2 mm [239]. For ThO2, a 18.92 x 9.69 x 0.85 mm
large, high-quality single crystals can be grown, but the develop-
single crystal with (100) cubic morphology has been grown by the
ment of a reliable, large-scale technique is often a cumbersome un-
hydrothermal technique [67] and the bulk purity (> 99 at. % for cat-
dertaking. Furthermore, solvent contamination is an inherent chal-
lenge, frequently resulting in measurable impurities in single crys- ion content) is higher than the starting ThO2 feedstock material [29].
tals produced via these pathways. In some cases, however, ideal sol- The first 50 nm of the surface, however, have a high concentration
vents can be found, such as how the highest purity CeO2 single crys- of impurities, demonstrating that the impurities from the starting
tals have been fabricated by the hydrothermal technique in a KF so- ThO2 feedstock were purified out of the bulk material and then de-
lution with impurities of only 100 ppm of K and 10 ppm of F [254]. posited on the sample during the final cooling cycle. UO2 crystals
Despite the purity, the 100-micrometer size somewhat limits their with side lengths approaching 10 mm and a variety of crystal mor-
phologies have been synthesized with electrolytic decomposition in
utility. Seeded growth can be performed easily in most of these tech-
niques (provided a suitable seed can be procured), enabling orienta- a molten flux [274]. Altering conditions decreases the size to 3 mm
tion control and iteratively improving crystal quality. per side but obtains crystals with highly defined cubo-octahedral
morphology and a decrease of ~33% of the impurities present in the
a b starting material [273]. The radiological concerns of PuO2 make its
crystal growth a rare endeavor, but 2 ´ 2 ´ 3 mm single crystals with
a (111) octahedral morphology have been grown from a Li2Mo4O7
flux with relatively low concentration of impurities (highest was Fe
at 200 ppm) [251].
2.4.3 Epitaxial thin films
Size bar Epitaxial thin films of AO2 (CeO2 [277], ThO2 [278], UO2
[211,279,280], PuO2 [211]) produced via reactive magnetron sput-
0.5 mm tering, polymer assisted deposition, and sol-gel techniques represent
an alternative route to the synthesis of bulk single crystals. While
Figure 12. A high quality, well faceted single crystal of a) ThO2 and b) UO2 much remains to be done before samples of the quality used in the
produced using the hydrothermal method. semiconducting industry are available, this field has started to pay
There are a few techniques that fall outside of the purview of both dividends. For example, antiferromagnetism of UO2 thin films on
melt techniques and transport assisted growths, including sublima- different substrates has been studied [281] and shows the effect of
tion in vacuum or from a plasma (ThO2 [269] and UO2 [217, 269, induced strain by the substrate-film interaction.
270]), thermal decomposition (UO2 [271] and PuO2 [272]), electro- Currently, films are commonly produced using commercially avail-
deposition (UO2 [273, 274, 275, 276]), and high temperature sinter- able substrates such as LaAlO3, SrTiO3, or YSZ, which impart strain
ing (UO2 [217]). Sublimation has thus far only yielded crystals (4 to into the grown oxide layer. This explains, in part, why thin films
12 mm) of AO2 with purities that are often worse than the starting have been shown to have broad X-ray diffraction (XRD) rocking
material. Thermal decomposition, where something other than AO2 curves [282], large deviations from bulk lattice parameters [282],
(such as AOCl2) is the feedstock for a flux growth, maintains the and columnar grains [283]. Nonetheless, tremendous potential exists
same drawbacks of flux growth with the added complication of the in this field as suitable single crystal AO2 substrates become availa-
starting material itself being a source for impurities. Electrodeposi- ble. A start along this line is reported on U/UO2 interfaces [284] and
tion suspends two electrodes in a molten flux containing the feed- UO2/ThO2 interfaces [258].
stock material, repeating the same shortcomings of flux growth and
enhancing them with the possibility of electrode contamination.
12
 2.5 Outlook boundaries [5,8] (see Figure 13). Until recently, the impact of many
Foundational work on phonon transport in nearly perfect single of these defects on thermal transport has only been treated empiri-
crystals is the first step in developing a comprehensive understand- cally as the concentration, size, and distribution of these defects is
ing of thermal transport in oxide nuclear fuel under irradiation. On controlled by complex mechanisms and are highly dependent upon
the experimental side, this portion of the review focused on inelastic local irradiation conditions. Accordingly, here we primarily focus
particle scattering to obtain detailed information about the phonon on smaller-scale defects that can be introduced in a controlled ion
structure and measurement of low temperature thermophysical beam environment and where recombination, saturation and cluster-
properties. These studies revealed gaps in understanding that are the ing play an outsized role.
source of continued research. Examples include the origin of non- In the last several decades, a number of studies have focused on ra-
linear propagating modes found in several fluorite crystal structures, diation damage in UO2, including dislocation loop formation [285],
including UO2 and ThO2, and the possibility for anisotropic thermal radiation induced lattice expansion [286, 287, 288], HBS develop-
conductivity in UO2 due to phonon interactions that locally break ment [6, 289] and fission gas release [290, 291, 292, 293, 294]. The
cubic symmetry. On the modeling side, electronic structure calcula- irradiation microstructure of CeO2, an important surrogate material
tions were reviewed with focus on strongly correlated materials. for oxide nuclear fuels, has started to receive significant attention
The shortcomings of DFT to accurately predict the branch specific over the last decade [28, 295, 296, 297, 298]. ThO2 has received
contribution to conductivity in UO2 point to new opportunities for sporadic attention since the 1960s but is now receiving more con-
DFT-DMFT modeling approaches. Lastly, central to all fundamen- sideration as it has emerged as a promising advanced nuclear fuel
tal studies, a short review was presented on growth of single crystals [299, 300, 301, 302, 303].
of actinide oxides. As new high-quality single crystal substrates of
actinide oxides become available, opportunities exist for synthesis In this section, we discuss the nature of irradiation induced defects
of epitaxial thin films with quality rivaling that found in the semi- as revealed in experiments, select methods for characterization of
conductor industry. Having access to interfaces with chemical pre- defects and their evolution, off-stoichiometry and equilibrium point
cision would open new frontiers for understanding thermal transport defect disorder in oxides, the mechanisms of defect clustering and
under irradiation in nuclear fuel. long-term evolution in irradiated oxides, and give an outlook on re-
quired future developments in understanding defects from the per-
spective of thermal transport. The primary focus here will be key
findings tied to ion beam irradiation studies. Ion beam irradiation
3 Crystalline defect generation, evolution, and charac- has proven a flexible tool for the generation of defects found in real
terization fuel [29, 304, 305, 306, 307, 308, 309, 310, 311, 312, 313, 314, 315,
In line with the main goal of this review, here we present an over- 316, 317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328].
view of defects in UO2, ThO2 and CeO2 that is closely tied to thermal While beyond the scope of this review, it is noted here that comple-
transport. Defects play a critical role in thermal transport because of mentary studies involving neutron [329], 𝛼-particle [286, 287, 288,
their ability to scatter phonons. Experiments have shown that the 330], or electron [331] irradiation can be used to judge the efficacy
thermal conductivity in UO2 under reactor conditions is influenced of using a particular ion irradiation conditions (e.g. ion mass, energy
by: (1) irradiation defects, (2) intragranular clustering of fission and fluence).
products, and (3) clustering at existing and newly formed grain

Point defect (0D) ® 1/t ~ w4 Soluble fission

Vacancies, Interstitials, soluble Vacancy
Vacancy products
Soluble fission product

fission products

Planar defect (2D) ® 1/t ~ w2

Dislocation loops
Disk-shaped precipitates

Volumetric (3D) ® 1/t ¹ f(w)

Fission gas bubbles, Self-interstitial
Self-interstitial Frenkel pair Dislocation loop
Dislocation Void
Void
Fission bubble or precipitate
Fission bubble Grain Boundry
Grain
precipitates loop or precipitate boundary
Frenkel pair

Figure 13. Illustration of irradiation defects found in oxide nuclear fuel. The phonon scattering rate is sensitive to the dimensionality of the defect.

As shown in the left pane of Figure 13, the frequency dependence 3.1 Intrinsic point defects
of the phonon scattering rate, t-1, is sensitive to the dimensionality Intrinsic point defects are present in single crystal oxides under
of the defect with respect to the wavelength of the heat carrying thermodynamic equilibrium in the form of vacancies, interstitials,
phonons. Thus, to provide a distinct phonon transport perspective, and native dispersed impurities. The presence of these point defects
this section is organized according to the size and dimensionality makes oxides off-stoichiometric. Off-stoichiometry is important in
of the defect. In particular, we introduce intrinsic point defects first, understanding structural properties, thermo-kinetic properties, and
followed by point defects and defect clusters that form under irra- performance of oxide nuclear fuels. Moreover, carefully account-
diation, then other extended defects such as defect decorated grain ing for the impact of intrinsic defects on thermal transport is the
boundaries and grain boundaries formed due to restructuring. first step in providing a comprehensive description of thermal
transport under irradiation.
13
3.1.1 Characterization techniques current (DC) slow e+ beam is then accelerated to variable energies,
Accurate characterization of the size and distribution of intrinsic, typically up to 30 keV, where variable energy DBS (VEDBS) can
sub-nanometer defects remains a challenge. Here we provide a be performed. VEDBS can provide qualitative information about
brief review of two experimental techniques used to gleam infor- the defect structures and measure the overall defect level in ion ir-
mation about sub-nanometer defects. Point defects in oxides such radiated materials. Such measurements were applied in the last few
as UO2, CeO2, and ThO2 have been extensively characterized using decades to ion irradiated actinide oxides and the knowledge learned
light source techniques [322, 332, 333, 334, 335, 336, 337, 338, from them will be briefly discussed in the next section. However,
339, 340, 341, 342, 343, 344]. This field of study has recently been the full characterization of radiation induced defects in terms of
review by Lang, et al. [345]. However, our focus here will be on size, density, and depth distributions can only be extracted from
positron annihilation spectroscopy and optical spectroscopy, which PALS measurements which require pulsed positron beams with
short pulses on the order of 100-200 ps. In the last several years,
have so far seen limited use in oxide fuels, but show particular
reactor- and accelerator-based pulsed positron beams have been de-
promise for characterizing the spectrum of point defects and small
veloped with sufficient temporal resolution for characterization of
clusters that reside in ion-irradiated oxide fuels and fuel surrogates.
While each technique exhibits demonstrated potential, particular small defects induced by ion irradiation in some metals as a func-
care must be paid to the characterization of point defects in ion ir- tion of depth [349]. While these user facility adaptations of posi-
radiated oxides. tron characterization provide the irradiation materials science com-
munity with tremendous new capability, multiple measurement
3.1.1.1 Positron annihilation spectroscopy methodologies cannot be easily accommodated. Current efforts di-
Positron annihilation spectroscopy (PAS) can accurately probe in- rected at developing pulsed positron beams derived from radioac-
dividual atomic vacancies as well as small and large vacancy clus- tive isotopes (see Figure 14) will usher in a new era in positron
ters with remarkable sensitivity of less than 1 ppm providing quan- characterization, by enabling in-situ measurements of materials
titative information about their size and density [346]. When intro- during ion irradiation [350]. Figure 14 shows the incorporation of
duced into a solid, a positron quickly loses its kinetic energy and a bunching system to a magnetically transported beam to convert
eventually annihilates with an electron, producing two photons that the DC slow e+ to pulses with hundred picoseconds width relevant
are emitted in nearly opposite directions. The emitted photons are for PALS measurements in a wide range of ion irradiated materials.
Doppler shifted by the longitudinal momentum of the electron. Then both DBS and PALS can be simultaneously done as illus-
Measurement of this shift has been developed as an effective trated in Figure 14.
method known as Doppler broadening spectroscopy (DBS) to pro- Acceleration Target
vide information about the concentration and characteristics of de- Magnetic
fects in solids, as the electron momenta sampled by the positron is Energy lenses
filter Helmholtz
strongly affected by trapping at defects. Magnetic coils Drift
bending tube
The positron annihilation rate is governed by the overlap between Bunching
system
the positron wave function and the electron density at the annihila-
tion site, providing information about the local electron density
which is directly related to the defect nature and size. Thus, posi-
DC slow Pulsed
tron annihilation lifetime spectroscopy (PALS) provides a direct e+ position e+ beam
Magnetic
method for measuring the size and density distributions of atomic lenses Chopper
scale defects. It can discriminate between vacancy clusters from HPGe
Prebuncher Main
single vacancies to ~50-100 vacancies until they become large buncher detector
(CDBS)
enough to be resolvable by transmission electron microscopy. Fast
13% annihilation scintillator
While standard PAS techniques are extremely useful, the typical (PALS)
penetration depth is several hundreds of micrometers and as a con- 87% Fast e+ Target
sequence they cannot be applied to ion irradiated materials as the chamber
Shield
10-4 3ev moderated e+
damage layer is only a few micrometers thick. In the 1980s, the Source Fast e+
development of slow positron beams and variable energy positron capsule 1-3µmW Positron moderation
techniques made depth-resolved measurements and characteriza- Moderator
tion of ion irradiated materials possible. The first studies of depth
resolved PAS were performed on He ion irradiated Cu and Ni Figure 14. A simplified schematic of a magnetically transported slow
pulsed positron beam with positron annihilation lifetime spectrometer and
[347].
coincidence Doppler broadening spectrometer. Vacuum components,
Laboratory-based slow positrons or variable energy positron beams HV/current sources, and beam diagnostic tools are not shown.
begin with a positron source having a continuous energy distribu-
tion. The most commonly used source is the radioactive isotope 3.1.1.2 Optical spectroscopy
22
Na. The fast positrons emanated from the source are moderated Optical absorption and luminescence spectroscopy are convenient
down to ~75 meV as they pass through a thin foil (e.g. W and Ni) methods for characterizing point defects in irradiated oxides as ox-
[347, 348]. The positrons extracted from the moderator are then ygen vacancies have prominent signatures. While these spectrosco-
guided through a vacuum system to the target using magnetic or pies have been applied to characterize a large range of irradiated
electrostatic lenses. The extracted positrons are unmoderated and oxides [351, 352, 353], application to irradiated actinide oxides is
of high energy, so need to be filtered through crossed electric and limited. The optical response of oxides depends strongly on the pre-
magnetic fields (E´B filter) or a magnetic velocity selector. The ferred charge state of the cation. We thus start our discussion with
left side of the schematic of a magnetically transported positron ThO2 as Th has only one preferred charge state. We then discuss
beam in Figure 14 illustrates the extraction of slow positrons CeO2 and UO2, both of which have multiple charge states.
through a magnetic velocity selector. The figure also shows the
moderation process. After extracting the slow positrons, the direct
14
 In ThO2, Th only exhibits a +4 charge state. Therefore, when one adapted with permission from [132]. Copyright 2021 Dennett et al. (Pub-
considers an oxygen vacancy, two electrons (in a neutral defect) lished by Elsevier Ltd.). Data in (b) adapted with permission from [360].
and one electron (in a positively charged defect) are localized on Copyright 1994 Elsevier Sciences B.V.
the vacant site and create a virtual atom having specific electronic Electronic band-structure for pristine UO2 have been thoroughly
states. Optical induced transitions of an electron within this virtual investigated experimentally [361]; however, investigation of the
atom contribute to the emergence of absorption and luminescence electronic structure of defects has been limited to computational
bands within the bandgap. Owing to their impact on optical permit- efforts involving DFT+U treatments of electron correlation [362,
tivity, these defects are referred to as color centers. Figure 15(a) 363]. While in ThO2 and CeO2 the highest populated level corre-
shows representative spectra for proton irradiated ThO2 exhibiting sponds to 2p-bands of oxygen, in UO2 it corresponds to 5f-bands.
absorption peaks at 1.8 and 2.0 eV [132]. The location of these In ThO2, the lowest unoccupied state is 5d, whereas in CeO2 it is 4f.
peaks matches previous reports on irradiated ThO2 [219, 354]. In In UO2 an additional effect is present, where the f-band is split due
contrast to Al2O3 and MgO [351, 352, 353], the number of studies to strong electron correlation effects making it a Mott insulator
of electronic structure of defects in ThO2 has been limited [149, [364]. The challenge here involves properly treating electron cor-
355]. Accordingly, assignment of these absorption/luminescence relation to accurately assign absorption/luminescence peaks to de-
peaks to defect type requires more systematic studies. fect type.
In CeO2, the oxygen vacancy induced peaks have a different origin Raman Spectroscopy
[356, 357]. Unlike ThO2, CeO2 does not have color centers as extra Raman spectroscopy allows probing of vibrational properties of

tion 2: Optical spectroscopy

electrons are localized on cerium ions, causing them to change
charge state from Ce4+ to Ce3+. The extra electron on the Ce3+ ion
occupies the 4f electron state, which is empty in Ce4+. Additionally,
fluorite crystals [365, 366, 367] and can be used to characterize
point defects and small defect clusters. Raman spectra of UO2 has
been presented in a number of studies [258, 368], while reports on
it has been reported that 5d-band electrons in Ce3+ exhibit addi- ThO2 are more limited [29, 321]. An extensive body of literature
tional crystal field splitting. In perfect CeO2, Ce4+ has an octahedral exists for CeO2 and ZrO2 [369, 370]. A perfect crystal structure of
coordination leading to a splitting of 5d-bands into two groups of these fluorites exhibit a mode at ~ 450 cm-1, characterized as a tri-
bands, each with T2g and Eg symmetry (Figure 15e) [358]. When ply degenerate mode with T2g symmetry at the Γ-point [371]. The
defects are present, the symmetry of the crystal structure is reduced other 3 optical modes at the Γ-point (see Figures 7 and 8) have sym-
which results in further splitting of d-bands (Figure 15e). Overall, metry T1u and are not Raman active, but infrared active. Point de-
this leads to an emergence of additional absorption bands corre- fects contribute to the emergence of new vibration modes, some of
sponding to electron transitions from 4f bands into crystal field split which are Raman active [372, 373, 374]. The vibrational structure
5d bands as shown in the spectra of irradiated CeO2 (Figure 15b), of anion vacancies, interstitial and cation substitution have been an-
which exhibits an additional absorption peak at 2.8 eV [359]. Com- alyzed in fluorites using the Green’s function approach for lattice
putationally, there is strong evidence supporting localization of dynamics [370, 372, 373, 374]. Group theory considerations are
electrons on Ce ions [355]. used to determine the symmetry of the defect structure and its vi-
a
(a) b
(b) bration modes [370].
F
(au)

pristine
Coun ts (au)

irradiated
a (a)
(a) b
(b)
(b)
Absorbance

+
F UO2
445
ThO2
465

Counts (au)
Counts (au)

irradiated
539
pristine
514
527 572 590 622
630

1.6 1.8
2.0 2. 4 2.0
2 .82.2 3 .2
2.4 32.6
.6 2.8
4.0 3.04. 4
3.2
EEnergy (eV))
nergy (eV 350 400 450 500 550 600 650 700 350 400 450 500 550 600 650 700
-1 -1
Wavenumber (cm ) Wavenumber (cm )
c
(c) d
(d)
c
(c) T2g d(d) A1g e(e) A1g

-M - Ioct

- - V
-O - Vo

Figure 16. Raman spectra in pristine and irradiated (a) UO2 and (b) ThO2.
Th4+ - VTh Ce4+ O2- Ce3+
O2- - (c-e) Cartoon representation of the vibrational modes in perfect and de-
fected fluorite systems. Data in (a) and (b) adapted with permission from
e
(e) f
(f)
[368]. Copyright 2015 Elsevier B.V.
T2g
Th-6d Th-6d Ce-5d
Ce-5d
Eg
excited
Eg ground
7 eV 4f0 1.9 eV Figure 16a depicts the Raman spectra in proton irradiated UO2 and
4 eV 4f1 Figure 16b depicts the same for ThO2 [29]. Observed defect peaks
O-2p O-2p O-2p O-2p share features similar to ones in CeO2. In CeO2, the peak at 560 cm-
1
is attributed to oxygen vacancies and the peak 590 cm-1 is associ-
ated with substitutions on the cation sublattice [371, 375]. In UO2,
Figure 15. Optical characterization of defects in irradiated fluorite oxides.
peaks at 630 cm-1 have been attributed to cube-octahedral clusters
Optical absorption in (a) proton irradiated ThO2 and (b) electron irradiated
CeO2. Atomic configuration of oxygen vacancies in (c) ThO2 and (d) CeO2, [376], while the peak at 570 cm-1 corresponds to a mode having T1u
corresponding electronic band diagrams are shown in (e-f). Data in (a) symmetry that is Raman activated in the presence of disorder [377].
Another feature observed in irradiated fluorites is a broadening and
15
 peak shift of T2g owing to disorder-induced phonon confinement Figure 17. Positron lifetime spectra measured for doped and undoped UO2
effect [277, 371]. Assignment of the defect peaks in irradiated fuel samples, compared with the spectrometer resolution (Co-60 spectrum)
ThO2 is pending further studies [29]. and defect free Fe metal. The doped sample is referred to as the ADOPT
sample (Advanced Doped Pellet Technology), the undoped sample is re-
3.1.1.3 Correlative Characterization ferred to as the Standard Optima 2 sample (Std Opt2). Reproduced with
permission from [383]. Copyright 2017 Chollet et al. (Published by EDP
It is important to note that the positron and optical characterization
Sciences).
methods described above have unique advantages and limitations.
While PALS can size-discriminate from single vacancy-type de- X-ray diffraction (XRD) has proven to be a useful tool to shed light
fects through di-vacancy to larger scale clusters, it is not sensitive on the nature of point defects in fluorite oxides. Using Vegard’s
to interstitial-type defects. In contrast, optical spectroscopy can law, which relates the lattice constant to radius of each ion, the im-
provide information about both vacancy- and interstitial-type de- pact of oxygen vacancies in hypostoichiomteric CeO2-x and triva-
fects, but its ability to size-discriminate is somewhat limited. There lent lanthanide (Ln) doped Ce1-xLnxO2-y on lattice constant have
are thus advantages in combining these techniques. Optical, photo- been well documented [384]. Similar analysis has been applied to
luminescence, and Raman spectroscopies can successfully detect Ln-doped and nonstoichiometric UO2 [385]. Ionic radii for differ-
oxygen vacancies while PAS directly measures cation vacancies ent charge states of Ce, U, and Ln agree well with those tabulated
and the defect complexes of vacancies and impurities. Combining [386]. However, because X-ray diffraction provides an average lat-
more than one technique such as PAS and Raman spectroscopy can tice constant, it is often difficult to tell if off-stoichiometric defects
thus be effective in revealing the variety of different types of de- are isolated point defect or if they combine into larger clusters or
fects present in actinide oxides [378]. For example, applying PAS even precipitate into different phases. To address these shortcom-
and optical spectroscopies can solve the challenge in assigning ab- ings, researchers have started to combine XRD with first principles
sorption/luminescence peaks to a specific type of defect. For in- models to delineate between different scenarios. Recently ab-initio
stance, certain emission (luminescence) peaks in oxides may be due methods have been implemented to further investigate impact of
to donor-acceptor recombination. Detecting cation vacancies by the charge state of defects on the relaxation volume of the defected
PAS can often reveal the origin of such luminescence peaks. cell, which is expected to be related to the radii of associated ionic
representation of defects [387]. Furthermore, more careful analysis
3.1.2 Intrinsic point defects: characterization and of the lattice constant in non-stoichiometric UO2 considering a pos-
modeling sibility of different defects’ charge states using thermodynamics
For homogenously distributed intrinsic defects, standard positron has suggested that uranium vacancies are absent in UO2+x [388].
techniques can also be used to characterize vacancy-type point de-
The impacts of defects in nonstoichiometric and doped UO2 on Ra-
fects and small clusters. PAS measurements have been applied to
man spectra has been investigated in several studies [377, 389,
characterize defects in oxidized uranium metal [379], UO2 and
390]. Raman spectra of the pristine samples exhibit two primary
ThO2 powders [380, 381, 382], and doped UO2 [383]. Changing U
peaks. The first peak at 445 cm-1 is attributed to T2g symmetry pho-
concentrations strongly modifies the density and size of U vacan-
cies as revealed from PALS and DBS measurements. There is nons also visible in neutron scattering measurements. The second
strong evidence that UO2 doped with metal oxides can increase the peak at 1150 cm-1 is the 2nd order Raman peak corresponding to
grain size in fresh fuel, leading to enhanced fission gas retention second harmonic of LO mode located at 575 cm-1 and thus denoted
as 2LO peak. Upon introduction of trivalent lanthanides into UO2,
[10, 11, 12, 13]. However, it is not clear what influence doping
a broad feature centered around 560 cm-1 has been reported [377].
has on intergranular intrinsic point defects. From a phonon
Detailed analysis of the broad feature suggests a presence of two
transport perspective, the presence of intrinsic point defects is im-
portant as they effectively scatter phonons. Arborelius et al. used closely located peaks at 540 cm-1 and 575 cm-1. The first has been
PALS to characterize point defects in Cr and Al doped UO2 [383]. attributed to oxygen vacancies emerging due to the trivalent nature
of the dopants and the latter is attributed to Raman activation of LO
The PALS measurements presented in Figure 17 reveal that doping
mode caused by symmetry breaking. Oxygen rich UO2 as well as
with Cr and Al using the advanced doped pellet technology
oxidized U1-xLnxO2-y exhibit defect peaks, the most prominent of
(ADOPT) leads to a large number of vacancies and complete posi-
which is located at 630 cm-1 and is attributed to oxygen interstitials
tron trapping. M. Chollet et al.: EPJ Nuclear Sci. Technol. 3, 3 (2017) 3
forming cuboctahedral clusters such as in U4O9 [389, 390]. All
these studies suggest that presence of the peaks can be used as an
indication for a particular defect type and peak intensity can be re-
lated to defect concentration.
The above examples illustrate that the state of defects in oxides can
be more complex than just dispersed vacancies, self- or impurity-
interstitials, and substitutional impurities. The presence of point de-
fects is also often associated with other electronic carriers such as
electrons and holes. Thermodynamic modeling of equilibrium de-
fect disorder can capture these carriers simultaneously with the
atomic defects themselves. However, under irradiation, this goal is
far from complete. Here we review the equilibrium point defect dis-
order calculations focusing on UO2 and ThO2.
UO2 can exist in the form UO2±x, where x denotes the deviation
from the reference stoichiometric state UO2. The finding that UO2
can be off-stoichiometric agrees with experimental data of oxygen
partial pressure against O/U ratio published by Gúeneau et al. [391]
where O/U ratios are calculated up to 2.2 for temperatures ranging
60
Fig. 2. Positron lifetime spectrum of the two investigated UO2 materials, defect-free Fe sample and calibration
from 800 K to 2500 K. As for ThO2, the phase diagram reported in
Co source.

16
seen in Figure 2. A minor uncertainty could be introduced be higher in the ADOPT material than in Std Opt2,
by not considering the effect of backscattered positrons in indicating a higher number of point defects in the doped
the calibration Fe sample. This uncertainty was considered material. This is very likely due to the incorporation of
negligible due to using of “fast” unmoderated positrons trivalent cations (Cr3+) in the structure.
from radioisotope source. As mentioned above, the spectra have been decomposed
into two lifetimes t1 and t 2. Two lifetime components are
generally reported for UO2 [5,9,10]. Such decomposition
3 Results enables to calculate the lattice lifetime t bulk. For the Std
Opt2 sample, tbulk = 180 ps was obtained. The first
Analytical data processing was performed using the LT 9.0 measured component t 1 of the Std Opt2 sample is by
Agarwal and Parida [392] based on published data [393, 394, 395] and its dependence on temperature can be used to properly compute
shows the oxide system to exist as a hypo-stoichiometric oxide the same for internal energy of formation of defects.
above 1300 K. Past work by Murphy et al. [396] and Bergeron et
al. [397] investigated the off-stoichiometric properties of ThO2 by 3.2 Irradiation induced defects
density functional theory (DFT) simulations using the CASTEP The complexity of the radiation environment associated with nu-
code and through thermodynamic modeling, respectively, showing clear fuels brings about a rich spectrum of defects. This includes
ThO2 to exhibit hypo-stoichiometry. defects created directly by fast neutron damage [404], by high-en-
ergy fission products [329], defects created by alpha decay of radi-
Point defect disorder models for oxides predict the concentrations oactive uranium isotopes [329, 405], and defects created by beta
of point defects, electrons, and holes under prescribed temperature
and gamma decay. However, damage caused by high energy fission
and oxygen pressure conditions. A typical model is based on mini-
fragments is the most significant damage source by orders of mag-
mizing the Gibbs free energy of the defective oxide, subjected to
nitude. After the damage event, the lattice contains isolated fission
the constraint of electroneutrality and prescribed temperature and
product atoms, point defects, and to a lesser degree small defect
oxygen pressure. The results of this approach, adapted from
clusters [302]. Over time and at temperature, these defect popula-
Schmalzried [398], are discussed below [149, 399].
tions evolve to form a rich spectrum of defect from point defects to
Common Brouwer diagram depiction of oxides show that O va- large clusters. As a surrogate to damage caused by neutrons, ion
cancy defects dominate the hypo-stoichiometric regime and are beam irradiation has proven to be a convenient approach to separate
charge compensated by free electrons. Meanwhile, O interstitial de- the effects of specific defects on thermal transport. Proton (and He)
fects dominate the hyper-stoichiometric regime and are charge beam irradiations provide a relatively flat damage profile over tens
compensated by free holes in the system [400]. Findings by Hassan of micrometers (and close to 10 µm), respectively, using ion ener-
et al. [401] for defects in UO2 show domination of U vacancy in gies of a few MeV, which is sufficiently thick for modern thermal
the hyper-stoichiometric regime of UO2 instead of O interstitial de- transport measurements [29, 42, 315, 406, 407]. Moreover, proton
fects. Subsequent work by other authors then showed further inves- irradiation has been shown to be an effective means for producing
tigation of the specific conditions in which this case occurs. For irradiated microstructures comparable to those produced by neu-
instance, Cooper et al. [402] found that if vibrational entropy is tron irradiation [408]. This is a very rich field of research and
omitted, O interstitials are predicted to be the dominant mechanism providing a comprehensive, historical review is well beyond the
of excess oxygen accommodation over only a small temperature scope of this article. Instead, in this section we present a review of
range (1265 K-1350 K). Conversely, if vibrational entropy is in- main finidings and open issues, with the intent of identifying new
cluded, O interstitials dominate from 1165 K to 1680 K (Busker opportuinites for impactful research.
potential) or from 1275 K to 1630 K (CRG potential). Below these
temperature ranges, excess oxygen is predicted to be accommo-
3.2.1 Characterization techniques
dated by U vacancies, while above them the system is hypo-stoi- In section 3.1.1, we discussed two under-utilized techniques for
chiometric with oxygen deficiency accommodated by O vacancies characterization of point defects. Here we focus on two techniques,
[402]. A similar deduction was made by Soulié et al. [403] who analytical TEM and atom probe tomography (APT), that show
found that at high temperature O interstitials are dominant, either promise for characterizing of larger scale defects that form due to
in isolated form or in clusters depending on the deviation from stoi- clustering. For irradiated metals, these two characterization tech-
chiometry. At temperatures lower than 1300 K, they predict U va- niques are starting to be used in a correlative fashion. Extending
cancies to be dominant in the near-stoichiometric material. As correlative studies to oxides is an area of research with tremendous
shown in the hyper-stoichiometric regime, there is ongoing debate opportunities.
with respect to the defect – U vacancy or O interstitial – ultimately
responsible for this stoichiometry.
3.2.1.1 Analytical transmission electron microscopy
Conventional TEM has been widely used to study extended defects,
For ThO2, it is found that the oxide exists mostly as a hypo-stoichi- dislocation loops and cavities in irradiated actinide oxides and their
ometric oxide. Murphy et al. [396] predict the hypo-stoichiometric non-radioactive surrogates. A variation of conventional TEM,
regime to be characterized by O vacancy defects, charge compen- scanning transmission electron microscopy (STEM), involves ras-
sated by conduction band electrons. The simulations also highlight ter scanning a tightly focused (~0.1 nm) electron beam over a sam-
the importance of the poroxo-oxygen interstitial defect, which is ple to form an image. This configuration makes STEM suitable for
predicted to form with a significantly higher concentration than oc- analyzing local chemistry using spectroscopy methods. Electron-
tahedral O interstitial defects under hyper-stoichiometric condi- energy loss spectroscopy (EELS) and energy dispersive X-ray
tions. ThO2 is hypo-stoichiometric when subjected to high temper- spectroscopy (EDS), are powerful tools for imaging radiation in-
atures (2400 – 2655 K) [399]. It is found that the extent of hyper- duced defects, phase changes, and small-scale changes in compo-
stoichiometry in the (Th,U)O2 system depends strongly on temper- sition. EDS, a relatively simple technique to apply, is well suited
ature and oxygen partial pressure [399]. to measure elemental composition and has been used extensively
to characterize phases and fission products in nuclear fuel [328,409,
In summary, extensive work has been done to study the thermody- 410]. However, EDS is not capable of measuring changes in stoi-
namics of oxides. However, there is still much work ahead in this chiometry which is required for understanding how interfaces, such
field. For instance, the study of the effect of vibrational entropy is as grain boundaries, influence local stoichiometry. It is thought
relatively incomplete and is yet to be extended to study the thermo- that interfaces that are decorated with defects can have an important
dynamics of mixed oxides. Proper calculation of entropy of for- role in determining thermal conductivity of fuels.
mation of defects take into consideration its temperature depend-
ence. This, however, does not seem to be the practice followed in EELS has been successfully used in identifying oxidation state of
computing the internal energy of formation, where the defect for- U and Ce in their oxides. Phonon scattering at interfaces such as
mation energies are often computed at 0 K. Interestingly, the lattice grain boundaries may significantly affect the thermal transport of
vibrational information used to compute the entropy of formation materials. The grain boundary chemistry in CeO2 has been revealed
using STEM/EELS mapping of the Ce M4,5 edge, which reflects the
17
transitions from the Ce 3d → 4f states [407, 411, 412, 413, 414]. STEM/EDS has been routinely used to quantify local chemical
The relative intensities of M4 and M5 are characteristic of the 4f- compositions at the nanoscale. The elemental sensitivity of EDS
shell occupancy and have been used to determine oxidation state of depends on the atomic number of the elements. The quantification
Ce and O vacancy concentration. The O vacancy concentration at of light elements, such as O and N is based on low-energy X-rays,
grain boundaries depends on the boundary character, and the more K peaks and their k-factors depend on X-ray absorption. Because
distorted boundary, the more oxygen vacancies it forms. Similarly of inaccuracy of the absorption correction due to self-absorption of
the U M4,5 edge, which results from the transitions from the U 3d low energy X-rays, their poor detection efficiency, and the low flu-
→ 5f states has been used to characterize the oxidation state of U orescence yield, the quantification of light elements is very chal-
[415, 416]. Compared to the Ce M4,5 edge, the U M4,5 edge at higher lenging. Compared to EDS, EELS tends to work better for rela-
energy loss has a lower signal, thus requiring long collection times tively low atomic numbers. However, quantification of EELS spec-
to obtain an appropriate signal-to-noise ratio and subsequently pre- tra relies on obtaining single scattering profiles, which can only be
senting experimental difficulties due to beam drifting. This leads to realized when very thin samples are used. In thicker samples, mul-
a reduced spatial resolution, and the overall ability to measure tiple inelastic scattering changes edge shapes and intensities and
chemical changes at the nanometer and atomic scale is affected. therefore quantification errors can be introduced [434]. When the
Recently, atomic-scale EELS for U using the U M4,5 edge has been size of the target defect is smaller than the sample thickness, the
achieved thanks to large probe convergence angles, high currents measured composition is an effective composition that is an aver-
and small probe sizes in modern aberration corrected microscopes age over the sample thickness and may not be representative of the
[417]. target defects.
The quantitative element analysis at the near-atomic scale using
3.2.1.2 Atom probe tomography APT is rather robust because ionic species, in most cases, can be
APT relies on field evaporation of the specimen to produce a three- simply identified according to their mass-to-charge ratio, while
dimensional (3D) reconstruction containing atom-by-atom posi-
there are intrinsic challenges associated with quantification of O
tion-sensitive composition information. The use of a laser (as op- especially from nano-sized features. It is well known that the con-
posed to the conventional voltage APT mode) is necessary to in-
centration of O in materials is strongly dependent on the analysis
duce field evaporation in semiconducting and insulating materials parameters of APT, such as laser wavelength, laser pulse energy,
[418]. Effective field evaporation in oxides requires uniform laser
and field condition of the specimen [435, 436]. For example, at
absorption and efficient dissipation of thermal energy, which are
high laser energies, metal atoms are preferentially evaporated
highly dependent upon the optical properties, thermal properties, where O atoms diffuse and desorb, due to inhomogeneous thermal
and surface chemistry of the oxide [419]. Field evaporation param- absorption of the laser, leading to inaccuracies in the measured
eters must therefore be tailored or optimized in each oxide for ac-
composition. In addition, APT only measures chemical composi-
curate chemical quantification [420, 421, 422, 423, 424, 425, 426]. tion in a very localized volume ~106 nm3, in comparison to the vol-
Poorly optimized field evaporation parameters can produce thermal
ume ~1010 nm3 used for STEM/EDS/EELS measurement in TEM
artifacts, surface diffusion, and preferential evaporation that ulti- [430].
mately degrade the accuracy of APT quantitative compositional
analysis [427]. Spatially correlated TEM and APT studies are of significance to
understand the radiation effects in nuclear materials. Recently re-
There is no clear trend in optimal APT field evaporation parameters
searchers have investigated combining APT and STEM, with the
for nuclear fuel oxides and their surrogates. For example, CeO2
advantages of one offsetting the limitations of the other technique.
can yield sufficient field evaporation with low energy laser pulses
Wang et al. [432] quantify chemical compositions around nano-
[422], while UO2 requires moderate laser energies [420], and ThO2
voids in NiCoCr solid solution alloys. Figure 18 shows an example
requires high laser energies with a low specimen temperature [255].
of correlative imaging using STEM and APT. Lach et al. [431]
In CeO2, higher laser energy and low base temperature results in
characterized the radiation-induced segregation around grain
degradation of mass spectrum resolution [422]. Recent work has
boundaries and dislocation loops, together with precipitation in a
used Bayesian expectation-maximization statistical methods to as-
304 stainless steel. These correlative studies thus far have been
sign ion identities to data convoluted in thermal tails, enabling ac- applied to metals, thus while there is great potential for extending
curate quantification of the chemical composition of thermally-af-
correlative studies to oxides, there exist considerable challenges.
fected mass spectra in ThO2 [255]. While challenges remain for
APT characterization of oxides, there exists considerable oppor-
tunity for using APT in a correlative fashion with analytical trans-
mission electron microscopy.
3.2.1.3 Correlative TEM-APT characterization
While TEM and APT have several advantages for characterizing
composition at the nanoscale, each characterization technique has
well known limitations [428, 429, 430, 431, 432]. TEM/STEM is
excellent in crystallographic/structural analysis. Grain orientations,
phase structure, and defects can be identified or visualized using
electron diffraction and high-resolution imaging techniques. The
grain orientations may also be measured by APT, but the spatial
resolution of APT datasets is determined by the regularity of the
field-evaporation sequence. The dependence of field-evaporation
on grain orientations and on the local bonding state may reduce the
spatial resolution in the reconstructed 3D atom maps, especially at
locations of defects or interfaces [428, 433].

18
Figure 18. STEM and APT images acquired for a NiCoCr needle-shaped
specimen at different rotation angles. The scale bar for both sets of images
is 40 nm. Adapted with permission from [432]. Copyright 2020 Wang et al.
(Published by Springer Nature).

3.2.2 Irradiation-induced point defects

At near room temperature and low damage ranges (<0.1 dpa), the
formation of extended defects is limited due to limited diffusion.
Several reports have applied Raman spectroscopy to characterize
point defects in irradiated fluorite oxides [437, 438, 439]. One no-
table study performed depth resolved radiation damage upon irra-
diation of UO2 by 25 MeV He2+ ions [438]. The ion impacted re-
gion of the cross-sectional scan exhibited a reduction in intensity
of the T2g peak at 445 cm-1 and emergence of new defect peaks at
527, 574, and 634 cm-1. The peaks at 527 and 634 cm-1 peaks were Figure 19. Defect parameter S as a function of depth in UO2: Reference
attribute to oxygen vacancies and interstitials, respectively. The sample, Xe implanted sample, and post Xe-implantation annealing samples.
peak at 574 cm-1 has been attributed to activation of the Raman- (Inset) Schematic illustrating how S-parameter is extracted from the 511
forbidden LO peak caused by symmetry breaking. A cross-sec- keV peak in DBS. Adapted with permission from [444]. Copyright 2013
tional line scan along the incident direction of the implanted He Elsevier B.V.
ions was performed, and it was shown that the intensity of T2g peak In the early 1990s, researchers first demonstrated the applicability
decreases and the intensity of the defect peak increases proportional of using slow positrons to perform depth resolved studies of ion
to the amount of depth-dependent displacement damage predicted implanted UO2 [445]. More recent studies applied variable energy
using SRIM [438]. In a more recent report, it was postulated that DBS (VEDBS) to characterize vacancy type defects in electron and
the LO peak is due to defects on the uranium sublattice and associ- light ion irradiated UO2 [446, 447, 448]. In one study involving
ated with changes of the charge state of uranium from U4+ to either electron irradiation of UO2, results reveal that of U-related vacan-
U3+ or U5+ [439]. cies are formed when stepping from 1 MeV irradiation to 2.5 MeV
Similar measurements have been performed in light ion irradiated irradiation [446]. In another study involving 1 MeV He implanta-
ThO2 [29, 368]. In 2 MeV proton irradiated ThO2, 4 prominent tion, it was found that the nature of the irradiation induced vacancy
peaks at 515, 535, 585 and 630 cm-1 were identified [29]. The latter type defects does not change with fluence [447]. VEDBS was also
3 are similar to the defect peaks in UO2, whereas the peak at 515 applied to investigate the depth distributions of defects in Xe im-
cm-1 has not been reported in other fluorite oxides. Similar peaks planted UO2. As an example, Figure 19 [449] depicts the defect
were observed in 21 MeV He2+ irradiated ThO2 at 514, 539, 590 parameter S extracted from DBS measurements as a function of
and 622 cm-1, but were not identified as Raman peaks by the au- depth for unirradiated UO2 (reference sample), a Xe implanted
thors and instead were attributed to luminescence [368]. sample, and a post-Xe irradiated annealing sample. The large non-
linear increase in S indicates the formation of Xe-bubbles after an-
XRD diffraction has been applied to monitor microstructure evolu- nealing.
tion in irradiated UO2 [287, 440]. During isochronal annealing of
neutron and alpha particle irradiated UO2 different stages of defect 3.2.3 Dislocation loops
recovery were identified. These stages were attributed to mobility At intermediate temperatures and low damage levels, ion irradia-
of different defect types. These results enabled the determination tion may create both point defects and dislocation loops [28, 29,
of migration barriers and relaxation volume of Frenkel pairs, with- 315]. Detailed TEM and atomic resolution STEM imaging shows
out clear differentiation between uranium and oxygen sublattices. the dislocation loop characteristics of single crystal ThO2 (Figure
Similar measurements have been applied to alpha irradiated CeO2 20) [303]. They are interstitial faulted loops or Frank loops with
and PuO2 [286]. Burgers vector, 𝑏4⃗ of 1/3〈111〉 and a habit plane of {111}. The large,
extended strain field around faulted loops scatter phonons signifi-
For self-irradiation studies involving doping with a radioactive iso- cantly, leading to a larger reduction of thermal conductivity com-
tope, traditional PAS can be used to measure vacancy type defect pared to perfect loops [315]. In neutron and ion-irradiated UO2,
distribution throughout the bulk. One such example used PALS to
characterize the damage generated by alpha self-irradiation in UO2 ThO2 and CeO2, both faulted loops with 𝑏4⃗ of 1/3<111> and perfect
[441]. This study suggested that the point defects observed using loops with 𝑏4⃗ of 1/2 <110> are found. MD simulations
PALS correspond to uranium vacancies. From a phonon transport [298,303,326] showed that mainly 1/3<111> Frank loops are ener-
perspective, defects on the uranium and oxygen sublattices can in- getically favorable when the loop size is small (several nm), and
fluence phonon scattering in significantly different ways. In the that 1/2<110> perfect loops are preferred when the loops grow.
case of high energy electron and ion irradiation, defects are gener- Thus, there must be an unfaulting process of loops under irradiation
ated in the bulk of the samples and traditional PALS was success- and the formation of perfect loops can be ascribed to a reaction be-
fully applied to study defects in CeO2 and UO2 using this approach tween a Frank partial and a Shockley partial [298, 303, 326].
[442]. Additionally, coupling experimental results to a density However, this unfaulting process during loop growth has not been
functional theory description revealed detailed information about directly observed in actinide oxides and their surrogate, CeO2.
the structure of vacancy type defects in UO2. Wiktor et al. [443]
used this approach to reveal that the dominant irradiation induced
defect in 45 MeV alpha-irradiated UO2 is a neutral bound Schottky
defect of neutral VU+2VO tri-vacancies.

19
 3.2.4 Cavities and Precipitates
Defects that are large in comparison to the wavelength of the pho-
nons responsible for thermal transport can have a significant impact
on thermal conductivity. While voids and bubbles can be formed
under heavy ion irradiation, precipitates can form due the coalesc-
ing of impurities, doping atoms and fission products. Formation of
these large-scale defects typically requires long range diffusion.
While heavy ion irradiation has been used to study fission gas dif-
fusion in UO2 [310, 311, 314, 317], ThO2 [299] and Th1-xUxO2
[300], fission gas bubble nucleation, growth, migration, and self-
organization in ThO2 and Th1-xUxO2 is has yet to be studied in de-
tail.
3.2.4.1 Cavities
Cavities, including voids and fission gas bubbles, have been char-
acterized extensively in UO2 and CeO2. Generally TEM has been
used to characterize bubble sizes and distributions [308, 450, 451,
452, 453], while techniques such as secondary ion mass spectros-
copy (SIMS) [454] and XAS [455, 456, 457] have been used to
quantify gas pressures.
Michel et al. [452] performed one of the earliest in situ TEM studies
of bubble evolution UO2 irradiated using 390 keV Xe ions. Their
results confirm the rapid formation of a small (less than 1 nm) bub-
ble population. The novel result lies in the fact that the bubble con-
centration reaches a near asymptotic value. While providing inval-
uable data against which cluster dynamics models may be assessed,
no clear physical explanation was found for saturation of the bubble
concentration. Theoretical and experimental work is currently on-
going to elucidate this longstanding conundrum.
Figure 20. Weak beam dark field TEM image (top left), atomic resolution
STEM image (top right) dislocation loops in ThO2 and schematic represen- Using Kr irradiation, He at al. [311] showed the bubble size to be
tation (bottom) of 1⁄3〈111〉 Frank partial dislocation loop showing extra half a weak function of ion dose but strongly dependent on the temper-
plane and Burgers vector 𝑏:⃗ when seen along [011] zone axis. Adapted with ature. Kr bubble formation at room temperature was observed for
permission from [303]. Copyright 2021 Elsevier B.V. the first time, indicating that either U vacancies are mobile at room
temperature, or that Kr bubbles may directly nucleate at the va-
cancy clusters produced during cascades with such a process not
In the past decade, the formation and evolution of extended defects, requiring Kr and U vacancies to be diffusive. In a similar study
dislocation loops and bubbles under heavy ion irradiation have also involving Xe irradiation of UO2 single crystals, it was shown that
been well studied using in situ ion irradiation facilities such as the small bubbles (1-2 nm) were formed at room temperature indicat-
Intermediate Voltage Electron Microscope (IVEM) at Argonne Na- ing the bubble formation does not require long-range diffusion of
tional Laboratory [295, 296, 312, 314] or JANNuS-Orsay in France Xe atoms nor U vacancies [314]. These studies involving Kr irra-
[309, 317, 318, 324, 325, 326]. The size and density of dislocation diation indicating bubble formation at room temperature are to be
loops increase with the irradiation dose, before the density saturates contrasted with another study involving gas atom precipitation in
and then dislocation loops start to transform to dislocation seg- CeO2 at room temperature and 600°C [295]. In this study, no gas
ments and tangled networks at higher doses through coalescence bubbles were observed at room temperature.
and coarsening mechanisms [295, 296, 312, 313]. Both dislocation
loops and cavities can nucleate under heavy ion irradiation at room In a study by Ye et al. [296] that looked at the effect of Xe irradia-
temperature [311, 314, 318], which is different with light ion (e.g. tion on cavity formation in UO2 and CeO2, it was suggested that
proton) irradiation. At a low irradiation temperature, some disloca- implanted Xe ions were trapped in vacancy clusters and aggregated
tion loops can nucleate directly at the clusters produced in cascades into bubbles at elevated temperature. The size and density of those
and such a process does not require U interstitials and U vacancies features are comparable to the fission gas bubbles in low burnup
to be diffusive. Electrons or light ions such as protons will produce UO2 fuel in a similar temperature range. Kinetic Monte Carlo anal-
damage as isolated Frenkel pairs or in small clusters while heavy ysis revealed that O mobility in UO2/CeO2 is substantially higher
ions and neutrons produce damage in large clusters. The direct nu- in hypo-stoichiometric conditions (MO2−x) than hyper-stoichio-
cleation of extended defects at small clusters is more difficult com- metric conditions (MO2+x).
pared to large clusters, which may explain why loops do not form Void formation has been studied using Au irradiation of thin UO2
under proton irradiation at room temperature. For in situ irradiation, foils. Because most of the Au passes through the foil, this irradia-
it is noted that the TEM samples are very thin (~100 nm) and the tion regime only creates ballistic damage. In one study, Onofri et
surface is a strong sink for irradiation induced defects. For those al. [327] found that void nucleation is a heterogeneous process
samples prepared by focused ion beam (FIB) milling, FIB damage since new voids do not involve long-range diffusion of point de-
may contribute to the defect evolution. fects and gas atoms. In a related study by Sabathier et al. [458] it
was suggested that heterogeneous nucleation of voids was induced
by energetic cascade overlap. Such nanovoids are likely to act as
sinks for mobile fission products during reactor operation.
20
Researchers are now looking beyond TEM methods to characterize doped CeO2. The fact that these precipitates only form at very high
fission gas bubbles. One of the early studies in this area involved doses, indicated a dose threshold in their formation.
using APT to map the Kr profile in ion irradiated UO2 as a function
of depth [311]. The Kr concentration measured by APT was con- Oxide fuels are also known to exhibit steep radial gradients in
burnup, which can have significant implications on chemical clus-
siderably smaller than predicted by SRIM. This was attributed to
tering and segregation. Bachhav and coworkers [467] have recently
the gas being lost to the vacuum within the analysis chamber and
demonstrated a novel APT-based approach to determine local
not registered by the detector. However, using APT to directly
burnup in irradiated fuels. This method, which relies upon isotopic
characterize bubbles can be problematic. For instance, aberrations
ratios of 235U, 236U, 238U, 239Pu, and 237Np, provides localized un-
are associated with tomographic reconstructions near surfaces (in-
ternal and external) and may change the evaporative characteristics derstanding of U enrichment and local burnup. In a follow-on study
of atoms. As mentioned in a previous section, correlative studies [468], the team linked burnup to local fission product chemistry.
By conducting APT at the center and on the edge of an irradiated
that utilize STEM and APT are beginning to demonstrate promis-
UO2 pellet, they observed burnup-related differences in the irradi-
ing results tied to characterization of bubbles in metallic samples.
ation-induced nucleation of metallic fission product Mo-Tc-Ru-
A recent study by Perrin-Pellegrino [459], extended this approach
Rh-Pd precipitates. Precipitates were larger at the pellet edge than
to oxides. Using APT in concert with TEM revealed the existence
in the center.
of nanoclusters enriched in Xe with a size and density comparable
to bubble populations observed with TEM. 3.3 Modeling of defect clustering
Coincidence Doppler broadening spectroscopy (CDBS) is another There are several methods used to model defect evolution. Molec-
powerful tool to characterize the chemistry of gas bubbles, identify ular dynamics (MD) can be used to investigate defect evolution at
the chemical environments around vacancies and probe atomic very short time scales and provide useful information on initial con-
scale precipitates [460]. Nagi et al., [461] employed it to detect the ditions used for modeling approaches that target long time evolu-
ultrafine precipitation of Cu impurities in nuclear reactor pressure tion. For scales of interest to the materials discussed in this review,
vessel (RPV) steel. The work revealed that positrons can be trapped there are two main modeling methods, kinetic Monte Carlo and rate
by embedded ultrafine particles forming a quantum dot-like posi- theory models. While kinetic Monte Carlo retains spatial correla-
tron states, thus enabling the detection of atomic scale precipitates. tion, all possible events and their rates must be known in advance.
In general, correlative studies using PAS and TEM will prove usful Conversely, rate theory does not retain spatial correlation but \ ex-
to characterize the size, size distribution and local chemistry of de- hibit predictive capability. Rate theory models have been used ex-
fects ranging from single vacancies to clusters and large voids [462, tensively for metallic systems; however, more development is re-
463]. This will be crucial to understanding defect formation at the quired for application to oxide nuclear fuel. Accordingly, our focus
early stages and the mechanisms of defect accumulation and re- in this section is on reviewing recent work and identifying future
combination. opportunity associated with rate theory models.

Two types of rate theory models exist in the literature to model

3.2.4.2 Precipitates point defect and cluster evolution in irradiated oxides. The first is a
Precipitation in irradiated oxide fuel can have significant impact on simplified model designed to yield the time evolution of point de-
physical properties including swelling, melting point, and thermal fects interacting with a mean density of features such as loops and
conductivity. Moreover, the irradiation-induced aggregation of so- voids at an average evolving size. The second, termed cluster dy-
lute species into precipitates can bring about a cooperative effect namics, is one in which the density of clusters of all sizes evolve
wherein the integrated impact on thermal conductivity of impurity simultaneously with point defects. These models are briefly re-
atoms in solution differs from that of precipitates composed of the viewed below.
same elemental species. Characterization of precipitates in oxide
fuels and surrogates is commonly performed using TEM, APT, and 3.3.1 Simple rate theory model of defect evolution
light source techniques. Simple rate theory models consider three processes: point defect
generation by irradiating particles, mutual recombination of inter-
In a recent study involving emulated spent fuel, Jiang et al. [464]
stitial-vacancy pairs, and defect clustering into dislocation loops
used TEM and APT to study thin films of CeO2 doped with metallic
and voids [297, 328, 469]. However, for low dose proton irradiation
fission products. They found a uniform distribution of doped met-
at intermediate temperatures, void nucleation may be suppressed
als within the as-grown film. Pd particles of ~3 nm appeared near
for kinetic reasons in some oxides, e.g., ThO2, and loop nucleation
dislocations after He irradiation. Annealing at 1073 K in air leads
dominates due to the relatively higher mobility of interstitials. A
to precipitates of Mo and Pd at grain boundaries and further anneal-
rate theory for such a situation consists of a set of ordinary differ-
ing results in precipitate coarsening.
ential equations [328]:
The structure of the precipitate (e.g. crystalline versus amorphous) !"!
can have a significant impact of phonon scattering and transmission !#
= 𝐺 − 𝑆$% 𝐶$ 𝐶% , (5)
through the precipitate. In addition to studies that investigate the
composition of precipitates, there have been several studies that describing the time rate of change for defect type (i,j), including
have addressed the structure of precipitates. In one study, the local monomers Oi, VO, Thi, VTh and loops (L). G is the generation rate
atomic structure of chromium bearing precipitates in chromia for monomers and di-interstitial formation for loop nucleation. Mu-
doped uranium dioxide was investigated by combining micro-beam tual interactions between defects (𝑆@A ) represent recombination for
X-ray diffraction and absorption spectroscopy [465]. The XRD each (Oi, VO) and (Mi, VM) cation pair and di-interstitial formation
data indicated that the chromia precipitates contain structural dis- for two cation interstitials. These di-interstituals act as the only
order and µ-XAS results provide insight into the oxidation state of source of dislocation loop nucleation. Terms 𝑆@B capture absorption
the chromium. In a study targeting fission gas bubble formation, of monomers by loops and contribute to loop size evolution [328],
Yun et al. [466] found solid Xe precipitates in irradiated 5% La which is given by:

21
 & '( Irradiation of oxides generates charged point defects of different
& 𝑅+, 𝐶+ ( = 𝑆$+ 𝐶$ 𝐶+ , (6)
&# )*" species in the displacement cascade; for instance, in irradiated UO2
the point defects obtained are O-self interstitial atoms (SIAs), U-
with 𝑅B being the loop radius, b the Burgers vector, and ΩC the SIAs, O-vacancies and U-vacancies denoted with their nominal
volume per atom. The 𝑆@A rate constants depend on monomer dif- charge states as 𝑂@+/ , 𝑈@DE , 𝑉FD/ , and 𝑉G+E , respectively. The point
fusion coefficients and geometrical factors capturing atomic struc- defects can also have non-nominal charges; for instance, 𝑈@D, , 𝑉G+, ,
ture of defects. Expressions of these coefficients can be found in etc. depending on the stability of individual ionic species in the ir-
[328]. Figure 21 compares the predicted evolution of loop diameter radiated oxide [401]. To make a CD approach tractable, some limits
and loop density in proton irradiated CeO2, ThO2 and UO2 [29, 315, must be placed on the charges and spectrum of cluster sizes consid-
328] to experimental measurement. It can be seen that the loop ered. Skorek et al. [487] studied the evolution of fission gas bubbles
growth rate and loop concentration are inversely correlated and are in UO2, assuming Schottky defects, i.e, 𝑈@ − 2𝑂@ and 𝑉G − 2𝑉F de-
proportional to the mobility of cation interstitials in this system. fect complexes are generated in the cascade rather than isolated
Faster cation mobility promotes faster loop growth, however, leads SIA and vacancies. They further assumed that Schottky defect
to lower supersaturated concentration of monomers [470, 471]. complexes are mobile and hence migrate and agglomerate into
These results indicate that cation interstitial migration is fastest in clusters having stoichiometric compositions, preserving the charge
CeO2 and slowest in ThO2. neutrality of the matrix. The clusters trap fission gas atoms, which
are otherwise highly mobile, and impede their rate of escape to
a b grain boundaries. Though the simplified CD model was able to pre-
dict the experimentally observed release rate of the fission gas, it
did not allow for the matrix to become hyper-stoichiometric under
irradiation. A more detailed mean-field approach was later taken
by Khalil et al. by allowing for the asymmetric (non-stoichio-
metric) generation of point defects of different species in the dis-
placement cascade due to their varying displacement energies, and
also allowing for the possibility of point defect agglomeration into
clusters having non-stoichiometric compositions [488]. They de-
Figure 21. Comparison of dislocation loop evolution in proton irradiated fined the cluster composition space (CCS) for loops, as shown in
CeO2, ThO2, and UO2 using rate theory modeling (solid lines) to experi- Figure 22a, by counting the respective point defects i.e, 𝑂@+/ , 𝑈@DE
mental measurement (symbols). UO2 data adapted with permission from for SIA loops and 𝑉FD/ , 𝑉G+E for vacancy loops, in the fluorite crystal
[28]. Copyright 2020 Elsevier Ltd. ThO2 data adapted with permission from structure of UO2. The mesh points in Figure 22a represent all pos-
[132]. Copyright 2021 Dennett et al. (Published by Elsevier Ltd.). CeO2 sible defect compositions, where each point (𝑚, 𝑛) indicates va-
data adapted with permission from [315]. Copyright 2019 The American
Ceramic Society.
cancy clusters with 𝑚 𝑉G and 𝑛 𝑉F and can either move horizon-
tally or vertically by interaction (absorption or emission) with U
3.3.2 Cluster dynamics approach to defect evolution and O defects, respectively. Figure 22b gives the time evolution of
The formation of extended defects such as dislocation loops and SIA clusters at 800˚C and a dose rate of 9.2×10-4 dpa/s, showing
voids under irradiation results from the diffusion and interaction of off-stoichiometric loop growth at higher doses. Vacancy loops
vacancies and interstitials produced by atomic displacements. This evolve similarly, favoring off-stoichiometric compositions with
dynamic generation and interaction process may be studied using larger loop sizes. This modified CD model gives detailed insight
cluster dynamics (CD), an approach based on chemical reaction into the wide range of stoichiometry of defect clusters and their
rate theory [472,473]. In this approach, the temporal evolution of evolution with time. However, a significant source of error in this
the density of defect clusters in size space is controlled by the emis- model may lie in the assignment of binding energies for each defect
sion and absorption of mobile point defects generated in the colli- species. These energies are routinely assigned for defect clusters in
sion cascade. The CD approach assumes a uniform distribution of pure materials using molecular dynamics, although in reality these
defect clusters of varying sizes and considers that the above-men- too may change as a function of stoichiometry.
tioned interactions take place continuously in space and time. CD
approaches have been used extensively in the study of radiation- a b
induced defect generation and evolution, including spatially-de-
pendent approaches which take into account the local configuration
of defects of different sizes [474, 475, 476, 477]. However, these
spatially-correlated approaches have, so far, found wide use in me-
tallic systems, while mean-field approaches lacking spatial correla-
tion have been applied more readily to oxide fuel materials [478,
479, 480]. In either case, the rate at which clusters of a specific size
accumulate in the material is obtained as a sum of their generation
and depletion rates due to the absorption and emission of point de-
fects by similar or different-sized clusters. This approach has been
used extensively to study defect evolution in materials like Fe
[481], stainless steel [482, 483], and Zr [484], as a robust multiscale Figure 22. (a) CCS for vacancy loops. The blue and brown lines represent
method that takes input from atomistic simulations and success- the minimum and maximum number of 𝑉( that can exist in a cluster with a
fully predicts the evolution of defect densities over extended length given number of 𝑉) . The middle green line represents the 2:1 ratio of 𝑉( to
and time scales. In multicomponent systems, the CD framework 𝑉) . (b) Time evolution of SIA cluster density. Adapted with permission
from [488]. Copyright 2017 Elsevier B.V.
has been used to study precipitation kinetics in binary [485, 486]
and ternary alloys [485]. While the approach described above relies on the input of defect
monomers only, MD simulation of primary radiation damage in the
22
mixed Th1-xUxO2 oxide system shows that small vacancy and SIA tion due to the cooperative behavior of pre-existing grain bounda-
clusters may be produced directly in the damage cascade [302]. ries and mass transport can have a profound impact on thermal
Thus, in modified next-generation CD models for oxides, the pro- transport properties [501].
duction rate of small clusters should be provided as input parame-
ters similar to monomers. Also, the strict assumption of monomers Computational studies have confirmed that the grain boundary
being the only mobile species in the general CD model [478, 488] character has a large impact on both intergranular bubble nuclea-
needs to be discarded. Instead, the spatial and temporal evolution tion and growth. In a study involving the segregation of Xe to a
of loops and voids, driven by the diffusion of small clusters should select group of grain boundaries in UO2 [496], it was suggested that
be targeted directly. Such a modified CD model can be extended to segregation properties of grain boundaries may result in different
introduce new terms in the cluster evolution equations that govern nucleation rates for fission gas bubbles. This was investigated in
the migration of vacancy and SIA clusters. As reviewed by Kohnert more detail using random-walk Monte Carlo simulations [502],
and coworkers [489], spatially resolved cluster dynamics has showing that the segregation energy of a grain boundary has a large
proven useful in modeling the evolution of complex metallic mi- impact on its intergranular bubble nucleation rate. It was also
crostructures resulting from defect diffusion. Such spatially-corre- shown that the interconnection rate of intergranular bubbles is de-
lated methods are, indeed, the next logical progression for the CD pendent on the grain boundary character, since the grain boundary
approach applied to oxide fuel materials. energy dictates the contact angle of the bubble with the grain
boundary [503].

3.4 Grain Boundaries Similarly, grain boundary segregation of dopants in CeO2, as a

model material or fuel cell component, is dependent upon grain
Here we first look at microstructure evolution in the presence of boundary character [504]. Li et al. [505] used APT to investigate Y
isolated grain boundaries. Characterization of isolated boundaries segregation in doped CeO2. They found that Y segregates at grain
is a notably easier task than characterizing boundaries in nanocrys- boundaries but is uniformly distributed within the grains. In a sim-
talline materials. Moreover, new experimental tools have enabled ilar study involving Gd-doped CeO2 [506], it was found that Gd
studies that target the impact of isolated boundaries on thermal strongly segregates at the grain boundary and within nano-sized do-
transport. These studies of thermal transport can then be compared mains within the grains. CeO2 accommodates aliovalent dopants
with prediction in a one-to-one fashion. The ultimate goal for ma- such as Gd and Mn through a dopant-defect complex. First princi-
terials scientists will be to translate understanding of isolated ples studies from Dholabhai et al. [504] suggest that the arrange-
boundaries to nanocrystalline restructured oxide fuel. ment of these complexes at grain boundaries strongly influences
the stability of oxygen vacancies. However, Sun et al. [507] used
3.4.1 Intrinsic Grain Boundaries atomistic simulations to show that dopant arrangements at disloca-
Grain boundaries can significantly influence microstructure evolu- tions in CeO2, in concert with the strain fields around the disloca-
tion in the environments in which nuclear fuels operate. In addition tion, can slow oxygen ion transport along the dislocation. The re-
to providing sinks and sources for defects, grain boundaries can ac- duced ionic conductivity in Gd-doped CeO2 is supported by exper-
celerate mass diffusion. Numerous studies have identified acceler- imental evidence of grain boundary segregation of Gd and the for-
ated mass transport pathways along grain boundaries in UO2 for mation of nanosized Gd-rich domains within CeO2 grains, as ob-
self-diffusion (i.e. U and O species) [490, 491, 492, 493, 494] and served by laser-assisted APT [506].
He [495]. In general, grain boundaries in UO2 have a higher con-
centration of mobile charge carriers than the bulk, leading to en- 3.4.2 Restructured grain boundaries
hanced oxygen transport along grain boundaries [493]. The result The formation of HBS in commercial reactor fuel was first ob-
is highly anisotropic ionic diffusion localized along grain bounda- served in the late 1950s and early 1960s [508, 509]. This area of
ries, dependent upon temperature, local structure, and grain bound- research remained relatively untouched until the mid-1980s when
ary character [493, 496]. researchers readdressed the subject in a response to the industrial
trend towards increasing fuel burn-up. This structure, characterized
The impact of grain boundary structure in UO2 on segregation has by the formation of submicrometer-sized grains and micrometer-
also been studied with MD simulations [497, 498]. It was found sized intergranular fission gas bubbles, forms near the rim of the
that high-angle grain boundaries are energetically favored to ac- fuel pellet where the temperature is relatively low, and the damage
commodate Xe versus low angle boundaries. Motivated by this accumulation is relatively high. The high damage rate is due to
computational study, Valderrama et al. [499] investigated segrega- creation of fissile 239Pu caused by resonant absorption of epithermal
tion of Kr at grain boundaries in ion irradiated UO2. It was found neutrons by 238U. In this region, the fission product concentration
that high angle grain boundaries contain substantially more Kr than and damage levels are significantly higher than average values.
low angle grain boundaries. They also found that excess Kr grain Originally, it was thought that the formation of the rim structure
boundary segregation leads to bubble formation. In another study would negatively impact thermal transport, leading to high center-
targeting bubble evolution in Kr-irradiated UO2 during annealing line temperatures and enhanced fission gas transport [510]. In the
[310], it was found that the size of intergranular bubbles increased early 2000s, Spino and Papaioannou [511] speculated that for-
more rapidly than intragranular ones, and bubble denuded zones mation of the rim structure would have a net positive impact on
near grain boundaries formed in all the annealed samples at 1000 thermal conductivity by removing intragranular, uniformly distrib-
to 1600˚C. The area density of strong segregation sites in the high- uted defects (point defects, dislocation loops, and fission products).
angle grain boundaries is much higher than that in the low angle In 2004, Ronchi et al.[5] provided a systematic study of the impact
grain boundaries. The geometric constraints for intergranular bub- of the HBS on thermal conductivity using a combination of stand-
bles, restricted to planar surfaces, results in the spacing between ard commercial reactor fuel and fuel samples irradiated in a test
these large bubbles being much smaller than spacing between in- reactor. They found that the formation of the HBS has a net bene-
tragranular bubbles [500]. This deviation from a random distribu- ficial impact on thermal conductivity, with an intrinsic conductivity
gain of 6-7% over fuel irradiated at intermediate temperatures

23
where the HBS did not form. Bai et al. used simulations to show Most post-irradiation measurements are not able to capture this su-
that the likely cause of this thermal conductivity gain is the reduc- persaturated state, as by the time the ex-situ characterization is done
tion in fission gas within the matrix due to grain boundary segrega- a different distribution of point defects is probed. Evidence for this
tion [512]. There have been several research efforts aimed at un- effect has been demonstrated in several recent in-situ measure-
derstanding the formation mechanisms and the impact on physical ments of various properties including thermal conductivity [520,
properties using samples exposed to neutron irradiation. Compre- 521], elastic properties [522, 523, 524], vibrational spectra ob-
hensive reviews of these studies are provided by Ronndinella and served using Raman spectroscopy [525] and optical properties
Wiss [6] as well as by Wiss et al. [513]. [526, 527]. Similar approaches can be applied to the material sys-
tems considered in this review.
Here we focus on ion irradiation studies aimed at investigating the
formation mechanisms responsible for the formation of the HBS The ongoing efforts in developing in-situ PAS techniques during
[510, 514, 515, 516, 517]. There are two broad groups of theories ion irradiation would offer great opportunities to detect the for-
for the formation of the HBS [6]. The first involves nucleation and mation of defects at the very early of stages of irradiation and mon-
growth either at highly defective sites (e.g. dislocation tangles) or itor their evolution to larger clusters and voids in actinide oxides.
at amorphous regions near fission tracks. The second involves PAS can detect atomic size vacancies with sensitivity better than 1
polygonization, where grains subdivide along dislocation networks part per million, thus providing new capabilities not attained by in-
produced by radiation damage. It is generally thought that nuclea- situ TEM. Capabilities for the indirect measurement of defect con-
tion and growth will lead to high angle grain boundaries and centrations through their impact on thermophysical properties un-
polygonization will lead to low angle grain boundaries. In an effort der ion irradiation are also rapidly being developed through the use
to isolate the formation mechanism, researchers in the 1990s started of in-situ transient grating spectroscopy and other laser-based tech-
to investigate dislocation produced by heavy ion irradiation. One niques [522, 528]. As thermal transport in oxides is impacted by
of the earlier studies involved Xe irradiation of single crystal UO2 the in-situ defect content which cannot be predicted from ex-situ
samples to a dose of 1´1017 ions/cm2 [510]. Using Rutherford chan- measurements, gaining insight into defect concentrations while ac-
neling and X-ray diffraction measurements, it was found that a fine tive generation is ongoing is of highest priority.
grained polycrystal was formed having a misalignment between
grains of a few degrees. Another study in support of the polygoni- Computational modeling of defects is important to conduct simul-
zation mechanism involved investigation of ion tracks in UO2 irra- taneously with experiments. Thermodynamics modeling requires
diated with 100 MeV Zr and Xe ions [516]. In this study it was ab initio underpinning, especially in fuels containing U and Pu.
argued that overlapping fission tracks led to the formation of sub- This type of modeling is not just useful in understanding the dom-
grains at relatively low temperatures. A more recent study used 84 inant defects in the oxide in both the hypo- and hyper-stoichio-
MeV Xe ion irradiation and found that grain polygonization due to metric regimes, but it is also important in understanding and inter-
accumulation of radiation-induced dislocations caused the fine preting self-diffusion data for both cations and anions near thermal
grains to form [518]. There are many opportunities for new re- equilibrium conditions. Cluster dynamics modeling, on the other
search involving ion studies aimed at unraveling the formation hand, is important in yielding the cluster size and composition dis-
mechanisms of the HBS. For instance, the role that fission products tributions, which represents a critical input to thermal transport
play in the formation of the HBS could be addressed by using doped models. While the recent trends in cluster dynamics of oxides paid
samples. Another area that may provide rich physics involves stud- attention to the cluster composition issues, more research in this
ies that target the role of existing grain boundaries. This is espe- area is still required to account for the variability of cluster shapes
cially interesting in light of a recent study [519] using modern elec- and the charge effects in both the energetics and kinetics of cluster-
tron microscopy techniques that suggest that the formation of low- ing in oxides.
angle boundaries initiate at existing high angle boundaries.
4 Thermal conductivity under irradiation
3.5 Outlook In this section, we review key studies aimed at modeling and meas-
Irradiation produces a wide range of defects in oxide fuels. A clear uring thermal conductivity in the presence of irradiation defects.
understanding of the role of these defects requires isolating the in- From the modeling side, we focus on studies that use both the
dividual defects and studying them individually. While proton irra- Boltzmann transport framework as well as molecular dynamics to
diation at low temperature can generate point defects and very predict thermal conductivity in UO2, ThO2, and oxide fuel surro-
small clusters, intermediate temperature irradiation can generate gates, each containing crystalline defects found in reactor fuels.
loops and point defects. Higher temperature annealing, however, From the experimental side, we focus on work that uses ion beams
can be used to eliminate point defects and control the size distribu- to either directly emulate the multi-feature microstructures found
tion of loops via coarsening. In the presence of gaseous species in real fuels or to perform single-effects studies to isolate individual
such as He, bubbles may also evolve in specimens that have loops. populations of microstructural features [304, 529]. The use of ion
As such, a hierarchy of irradiation experiments can be used to in- beam studies has been necessitated by the extreme difficulty asso-
vestigate the different defects one by one, for comparison with ciated with measuring conductivity of reactor-irradiated fuel, as
computational modeling. At high temperature, the unfaulting of well as the challenge of connecting measurements of conductivity
Frank loops could happen in proton irradiated samples. Since the to specific microstructural features in multi-feature systems (e.g.
effects of faulted and unfaulted loops on thermal transport are quite point defects and defect clusters) [530]. Moreover, when paired
different due to strain fields, it is of significance to distinguish loop with new experimental methods for measuring thermal conductiv-
types and quantify their size and density and also measure the strain ity of thin damaged layers, ion irradiation experiments can be con-
fields around them. In situ TEM visualization under irradiation ducted rapidly, enabling researchers to probe a large parameter
could be used to capture the unfaulting process. space of exposure and test conditions. The diagram shown in Figure
23 exemplifies a diverse set of methods that are needed to conduct
There is a common understanding that a nonequilibrium point de- a comprehensive study of phonon transport in defective crystals.
fect concentration is established under an irradiating particle flux.

24
 and CeO2 are summarized in Table 1 and representative conductiv-
ity profiles as a function of temperature are shown in Figure 24.
The simplified formulation, and minor variations thereof, has been
used to describe the thermal conductivity of fresh and irradiated
UO2 fuel [538, 539], mixed uranium-plutonium dioxide (MOX)
fuel [540, 541, 542], and rare-earth doped UO2 [543].

Table 1. Parameters for high temperature conductivity of pristine fluorite

oxides.

Material References B [m/W] A0 [m·K/W]

UO2 [544] 2.165×10-4 0.0375

Figure 23. Illustration of the methods discussed in this section. Modulated
thermal reflectance is used to extract the thermal conductivity of the thin
damage layer caused by ion irradiation. Various levels of solutions to the
ThO2 [545] 2.25×10-4 4.2×10-4
Boltzmann transport equation for phonons are then compared to measured
values of conductivity.
CeO2 [407] 1.89×10-4 7.84×10-4
We begin by discussing the limitations of current fuel performance
codes and highlighting the promise of advanced codes currently un-
der development, with an emphasis on thermal conductivity. We In these fuel performance codes, the temperature distribution is
then discuss recent experimental efforts that have enabled measure- used to predict important physical properties that impact fuel per-
ments of thermal conductivity on length scales commensurate with formance, including the behavior of fission products, swelling,
damage accumulation associated with ion irradiation. This is fol- creep, and the release of fission gases [533]. However, the approx-
lowed by a discussion of atomistic and atomistically-informed imate treatment of thermal conductivity leads to increased uncer-
models of thermal transport in the presence of irradiation-induced tainty [546] and, correspondingly, to larger safety margins. Thus,
microstructure. We end this section by reviewing recent work di- microstructure-based fuel performance codes will be required to
rected at comparing model prediction to experimental measurement expand the application of these codes to higher burnups and/or al-
of thermal conductivity in defective single crystals of ThO2, UO2, ternative fuel utilization schemes proposed by new reactor concepts
and surrogate oxides. [547].
In the 1990s, researchers started to develop more advanced mech-
4.1 Fuel performance codes and thermal conductivity anistic descriptions of thermal conductivity of UO2. One of the
The safe and efficient operation of commercial nuclear reactors re- more notable studies [530] used measurements on simulated fuel
lies on analysis provided by fuel performance codes [531, 532, (SIMFUEL) to extract the impact of dissolved fission products and
533]. The temperature distribution within the fuel, governed by the large fission gas bubbles on thermal conductivity. Recently, several
fuel thermal conductivity, plays a central role in fuel performance. effective medium models have been developed to capture the im-
Fuel performance codes must consider thermal conductivity as a pact of large, intergranular fission gas bubbles on the fuel thermal
time- and space-dependent property that changes dynamically dur- conductivity [26, 501, 548]. General models that predict the impact
ing operation due to fission damage, the buildup of fission gases, of randomly distributed bubbles on the thermal conductivity, such
and a myriad of other parameters [5]. as the Maxwell-Eucken equation [549], do not accurately describe
the impact of the intergranular gas bubbles because they are not
Current light water reactor fuel performance codes based on UO2,
randomly distributed; they are aligned on grain boundaries that also
such as FRAPCON [531], TRANSURANUS [532], and, more re-
provide some thermal resistance [501]. Initial models were devel-
cently, BISON [534, 535] rely on empirical correlations between
oped by fitting to mesoscale finite element method predictions of
conductivity, burnup, and temperature [5,9]. Within these codes,
the thermal conductivity [501, 548]. Later, a model was developed
the fuel thermal conductivity, 𝜅, is modeled using a simple expres-
that represented the impact of the grain boundary and intergranular
sion derived from the kinetic theory of gasses that approximates a
bubbles on the fuel thermal conductivity using a network of thermal
broad phonon spectrum by a narrow phonon band [536, 537]:
resistors that predicted an effective thermal resistance of the grain
boundary as a function of the fraction of the grain boundary area
! (4)
𝜅= . that was covered by gas bubbles [26]. A later sensitivity analysis
HDI)
showed that the thermal resistor model did not demonstrate the
In Equation 4, A captures any conductivity reduction due to defects same sensitivities to the average bubble radius as a mesoscale finite
and B parametrizes intrinsic conductivity. Fuel performance codes element model [550], indicating that it may be an over-simplifica-
use the functional form of Equation 4 to define the thermal conduc- tion of the heat transport through fuel with intergranular fission gas
tivity of the fuel by defining A and B as a function of fuel burnup bubbles.
and irradiation temperature [5]. In particular, A can be represented
as 𝐴 = 𝐴C + ∑ 𝑥@ 𝐴J@ , where i is a summation over defects, 𝑥@ is their
concentration, 𝐴J@ is the scattering parameter for individual defects,
and 𝐴C is the residual value for a pristine material [25, 530]. Rec-
ommended values of A0 and B for pristine samples of UO2, ThO2,

25
 femtosecond and continuous wave (CW) laser-based approaches
[320,564]. In the following, we review several efforts used to un-
derstand thermal conductivity specifically in ion irradiated fuel and
surrogate materials with a special emphasis on recent efforts target-
ing single effects studies employing ion beam irradiations.

In the last decade, to overcome challenges associated with the small

damage volumes created by ion beam irradiation, several pump-
probe optical techniques relying on photothermal material excita-
tion have been developed. A brief description of the three which
have been utilized most frequently - transient grating spectroscopy
(TGS), time domain thermoreflectance (TDTR), and modulated
thermoreflectance (MTR) – will be provided. For each of these
methods, the key parameter which must be matched to the ion irra-
diation conditions is the thermal wave penetration depth, Lth. Im-
portantly, the range of Lth values available through these methods
spans from ~0.5 to ~30 µm. This length scale is commensurate with
the damage profile associated with ion irradiation. Schematics of
Figure 24. High temperature thermal conductivity of selected fluorite ox- each of these methods at the sample surface are shown in Figure
ides. Solid lines are predicted values using Equation 4 and the open symbols 25. These methods are non-destructive, allowing for thermal
are data taken from the literature. CeO2 data (model and experiment)
transport characteristics to be captured while leaving as-irradiated
adapted with permission from [407]. Copyright 2014 The American Ceram-
ics Society. UO2 experimental data adapted with permission from [551]. material available for detailed microstructure characterization
Copyright 2013 Elsevier B.V. ThO2 model data adapted with permission when necessary.
from [545]. Copyright 1997 Elsevier Science B.V. UO2 model data adapted
with permission from [544]. Copyright 2000 Elsevier Science B.V. ThO2 TGS utilizes periodic laser excitation generated by crossing two la-
experimental data adapted with permission from [154]. Copyright 2019 ser pulses from the same source, with the fringe pattern spacing
Elsevier B.V. determined by the optical geometry. The resulting periodic thermal
Most of the effective medium modeling approaches have focused and elastic excitation is monitored by the diffraction of a CW probe
on fission gas bubbles, which are typically large in comparison to from the sample [565]. The resulting thermal wave penetration is
the wavelength of the phonons responsible for transporting thermal commonly given as Lth=L/π, where L is the fringe spacing pro-
energy. However, it has been recognized for some time that smaller jected onto the sample surface [566]. The most detailed work to
radiation-induced defects such as dislocation loops, and sub-TEM- date using TGS to study thermal transport in ion irradiated materi-
resolution defect clusters, contribute significantly to a reduction in als has focused on metals irradiated with both light and heavy ions
thermal conductivity. Until recently, the impact of smaller defects [566, 567]. In situ ion irradiation capabilities with concurrent TGS
has been neglected as they are more difficult to characterize and property monitoring have also recently been developed [522, 564].
require a more detailed accounting of phonon structure [29, 66,
315, 552, 553, 554, 555]. The TDTR methodology most often relies on a train of ultrafast
laser pulses which are split into pump and probe beam paths
[406,568]. The pump injects high frequency thermal waves into the
4.2 Experimental measurement of thermal conductivity sample and the probe measure the temperature field evolution by
monitoring small changes in temperature induced optical reflectiv-
While our focus here is on measuring the thermal conductivity of ity (thermoreflectance). The simplest form for the thermal wave
fuel surrogates, it is important, contextually, to mention the large penetration for the TDTR geometry is given as 𝐿KL = H𝐷/(𝜋𝑓) ,
amount of work that has been devoted to measuring thermal con- where D is the diffusivity of the substrate and f is the pump modu-
ductivity of reactor fuel. Since the early 2000s, researchers primar- lation frequency [406, 569]. TDTR has been used to study a variety
ily in Europe and Japan have sought to investigate thermal conduc- of ion irradiated materials including nuclear fuel [570], nuclear
tivity in real fuel specimens that have been reinstrumented with fuel cladding [571], silicon carbide [572] metallic multi-layers
thermocouples and tested in research reactors. These studies illus- [571], silicon [571, 573], sapphire [574], and diamond [575] across
trate the challenge of truly understanding thermal transport in nu- orders of magnitude in thermal conductivity.
clear fuel under irradiation. Most studies performed used two
measurements of temperature (fuel centerline and cladding temper-
ature) along with estimates of the magnitude and distribution of the
heat source to extract information on the average thermal conduc-
tivity of the fuel across the pellet radius.

Using these tools, irradiation effects have been measured directly

on neutron exposed samples [8, 543] and simulation fuel - where
the irradiation induced microstructure was emulated through addi-
tion of fission products [556, 557] and porosity controlled via con-
ventional ceramic processing methods [558, 559, 560, 561]. Out-
side of reactor environments, the thermal conductivity of fresh
fuels and their surrogates has been measured extensively using la-
ser flash methods [407, 551, 558, 559, 560, 562, 563], direct heat-
flow conductivity measurements [179, 180], and recently with

26
 Figure 26. Summary of thermal conductivity measurement in ion irradiated
fluorites. For Tirr/Tm< 0.2 microstructure is point defect dominated, whereas
for Tirr/Tm > 0.3 it is loop dominated (Tir/Tm is the ratio of irradiation tem-
Figure 25. Schematics of the TGS, TDTR, and MTR optical geometries at perature to melting temperature). 200˚C UO2 data adapted with permission
the sample surface. For each case, irradiated layer thicknesses, and corre- from [320]. Copyright 2014 Elsevier B.V. 300˚C UO2 data adapted with
sponding thermal wave depths, are given as examples of those used in the permission from [586]. Copyright 2018 Elsevier B.V. 700˚C CeO2 data
literature and do not describe an exhaustive range. adapted with permission from [315]. Copyright 2019 The American Ce-
ramic Society. ThO2 data adapted with permission from [29]. Copyright
2020 Dennett et al. (Published by AIP Publishing). 600˚C CeO2 data
MTR, also referred to as spatial domain or beam-offset thermore- adapted from [297]. Copyright 2021 Acta Materialia Inc.
flectance [576, 577, 578, 579, 580, 581], has been used in the ma-
jority of studies of ion irradiated actinide oxides and their surro- Example MTR-measured values of thermal conductivity reduction
gates. MTR utilizes modulated continuous wave (CW) lasers to in- in ion irradiated UO2, CeO2, and ThO2 are shown in Figure 26 [29,
ject thermal waves into a sample under investigation. Pump and 297, 315, 320, 586]. A major trend evident in Figure 26 is the in-
probe beams generated through either free-space or fiber-coupled verse correlation between irradiation temperature and thermal con-
CW lasers are focused onto a sample of interest coated with a trans- ductivity reduction; as irradiation temperature increases, more con-
ducer film [529]. The spatial extent of the thermal wave is meas- ductivity is retained in these fluorite materials. Irradiations per-
ured by scanning either the pump or the probe along the surface of formed at lower temperatures cause degradation of thermal conduc-
the sample [578, 582]. In this geometry, Lth is again controlled by tivity primarily due to point defects (vacancies, interstitials, and
the applied modulation frequency of the pump and given by the charged defects) [29]. By increasing irradiation temperature, point
same expression shown above for TDTR. MTR has also been ap- defects become more mobile and mutually recombine at higher
plied on a variety of materials following ion irradiation including rates. This recombination results in a lower density of point defects
silicon [583], sapphire [584], fuel cladding alloys [585], and a va- even at higher irradiation doses. In parallel, however, at higher tem-
riety of oxide nuclear fuels and surrogates including UO2 [586], peratures the increased point defect mobility also allows disloca-
CeO2 [315], and ThO2 [29]. Recent work has focused on measure- tion loops to nucleate and grow; these loops tend to dominate the
ments of defect-bearing oxides at cryogenic temperatures in order microstructure of fluorite oxides irradiated at elevated temperatures
to discriminate between phonon scattering resulting from multiple [29, 297, 315]. A qualitative investigation of data in Figure 26 sug-
types of defects [132]. gests that dislocation loops contribute to the observed conductivity
reduction for irradiations at 600˚C and higher.
Experimental studies focusing on thermal transport in ion irradiated
oxide nuclear fuel and surrogates have found the most success to 4.3 Boltzmann transport framework
date using MTR. Of these methods, MTR has the combination of
highest spatial resolution – using spot sizes on the order 1-2 µm – In this section, we review efforts to model thermal transport in ac-
and highest sensitivity to low-conductivity materials. Both of these tinide fuels and surrogate oxides using the Boltzmann transport
features are key when interrogating the actinide oxide fuels as de- equation. Our discussion of Boltzmann transport applied to oxide
tailed surface preparation is often challenging due to material han- fuels and surrogates only considers the RTA as it is best suited for
dling constraints, leaving surfaces to be measured which are not treating thermal transport in crystals containing a range of defects
optically smooth over hundreds of micrometerss. MTR also retains from point defects to extended defect clusters. We first discuss
theoretical sensitivity to both in-plane and cross-plane thermal phonon scattering by both intrinsic 3-phonon processes and defects
transport relative to the free surface [584], useful for systems such as the cross-sections defined for these processes can be used for any
as UO2 where intrinsic or imposed thermal anisotropy has been level of approximation. Within the RTA formalism, individual pho-
identified [180]. In contrast, the other methods described retain pri- non scattering mechanisms are independently treated and added to-
mary sensitivity to only a single direction of transport (TGS, in- gether using Matthiesen’s rule defined previously in Equation 3.
plane; TDTR, cross-plane). MTR has a final advantage of requiring We pay close attention to the form of the cross section for point
simple, compact, CW laser sources. This has allowed MTR to be defects as this model has been used frequently to gauge the impact
deployed in complex physical environments such as a highly radi- of irradiation on thermal conductivity in oxide fuels. This is fol-
oactive glove box for the direct study of spent nuclear fuel [587]. lowed by a short discussion of early work aimed at simple analyti-
cal solutions to the RTA. We end this section by discussing the
single mode relaxation time approximation (SMRT) that more ac-
curately captures phonon structure.

27
4.3.1 Phonon scattering by the density of available states that a phonon can scatter into sub-
Three-phonon scattering processes shown in Figure 4 provide an ject to applicable conservation laws, including energy and the tan-
intrinsic limitation to phonons’ ability to conduct heat in anhar- gential component of the momentum assuming a specular reflec-
monic crystals. They are considered as perturbations to a harmonic tion occurs [30]. Larger scale defects, including grain boundaries,
oscillation resulting in finite phonon lifetimes. As a result the 3- large voids and bubbles, precipitates, and macroscale porosity are
phonon interactions shown in Figure 4a can be represented by most frequently accounted for using effective medium approaches
[588]: [26, 530]. Phonon interactions with point defects require a defect-
type-dependent scattering cross-section to be defined.
+! (012) (5)
𝜏-.,012 = 𝑃-. 𝑁, (𝑞𝑠, 𝜔)

(012)
where 𝑃-. is average anharmonicity parameter and 𝑁, (𝑞𝑠, 𝜔) is
the occupation weighted density of states that captures the 3-pho-
non scattering phase space, satisfying energy and momentum con-
servation laws.

Defects act as phonon scattering centers, reducing phonon lifetimes

and mean free paths. Scattering by the core of the defect is due to
atomic mass mismatch and changes to interatomic force constants.
Additionally, defects introduce a strain field which scatters phonon
through anharmonic interactions. The general form for scattering
rate due to phonon interactions with the defect depicted in Figure
4b can be written in a form similar to Equation 5:
34 (012)
𝜏-.,012 = 𝑉-. 𝐷, (𝒒, 𝜔), (6)
(89:)
where 𝑉-. is the defect induced perturbation to the interatomic
potential energy and 𝐷/ (𝒒, 𝜔) is the density of states that captures
phonon-defect scattering phase space [536]. In the Debye approx-
imation, this perturbation may be carried out to define simple func- Figure 27. Schematic illustrating a change in mass, force constants, and
tional forms for defect scattering rates for various types of defects. atomic radius resulting from a point defect present in a crystal lattice. Each
A list of these are provided in Table 2. change is modeled by Klemens’ expression (Equation 7) for the scattering
strength or scattering cross-section for phonon-point defect scattering [30].
Table 2. Phonon scattering rates with various defects. For point defects specifically, the perturbation to the local potential
has several components, including changes in atomic mass, force
Type Core Strain field constants, and strain field surrounding the defect. Using a second-
Point defect 0D 𝑉+ 𝑉+ order perturbation theory, Klemens derived a general expression
𝑛% 𝑆*" 𝜔. 𝑛% 𝑆/" 𝜔.
[30] 4𝜋𝑁𝑣,- 4𝜋𝑁𝑣,- for a “scattering parameter” or “scattering strength” for phonon-
point defect interactions, Γ, in terms of the mass difference of lat-
tice points, harmonic force constant difference, and the elastic
Line defect 1D .⁄-
𝑉+ 0.06𝛾 " 𝑏 " 𝑁0 𝜔
𝑁0 𝜔- strain scattering due to atomic radius change [30] (Figure 27). This
(screw dislocations) 𝑣,. parameter Γ is given by:
[30,589]
Δ𝑀/
Planar defect 2D ∝ 𝜔"
𝑁'
0.7𝑎 " 𝛾 " "
𝜔 𝛤 = S 𝑛@ 𝑆@/ = S 𝑛@ T /@
(stacking faults) 𝑣, 𝑀
@ @ (7)
[590]
/
Δ𝐾@ Δ𝑅@
Platelets -disk 24𝜋ℎ" 𝑅2" " N/A +2W − 2𝑄𝛾 [ \
shaped precipitates 𝑁2 𝜔 𝐾 𝑅
𝑣,
[591,592]

Voids 3D [593,594] 𝜋𝑣, 𝑅3" 𝑁3 N/A where ni is the fractional concentration of the ith defect type, γ is
Grüneisen anharmonicity parameter, and Q approximates the num-
56!" ber of distorted nearest-neighbor bonds surrounding the point de-
𝑛% are the point defect concentrations of a given species, 𝑆4" = and
6" fect (3.2 for substitutional defects and 4.2 for vacancies in the
57! 58! "
𝑆," = 2J − 2𝑄𝛾 L are point defect scattering cross-sections for fluorite oxide lattice). However, for significant densities of point
7 8
that species, 𝑁0 is dislocation line density, 𝑁' is stacking fault den- defects, the permutations of defect configurations within a unit cell
sity, 𝑁2 and 𝑅2 are platelet density and radius, 𝑁3 and 𝑅3 are spherical must be accounted for [407, 558, 595]. Furthermore, Klemens’
void density and radius. Note that technically 1st term in 𝑆," can be original formula assumes a single atom per unit cell, and the treat-
treated as a part of core scattering. ment of compound materials requires further consideration.
Gurunathan et al. provided a detailed description of this and
showed that refined Klemens’ general formulation may still be used
It should be noted that the power exponent for frequency in core by careful accounting of the average unit cell mass around defects
scattering scales with defect dimensionality, which is determined of different types [596, 597].

28
 Here, the correction due to defects is:
4.3.2 Klemens-Callaway-Debye approximation 𝜔8 , 4𝑁𝛾 , 𝑘; 𝑇 1
One convenient approximation to BTE approach is a method gen- 7 8 =< B ,
𝜔: 𝑀𝑣., 𝛤 (11)
erally referred to as the Klemens-Callaway method (KCM) [536,
598], which approximates phonon branches by a simple Debye
model. This allows the summation over q-space to be replaced by where G is computed via the expression given in Equation 7. These
an integral over frequency, ω, where scattering rates are also ex- analytical forms are useful comparison tools for estimating contri-
pressed in terms of frequencies. In the KCM, thermal conductivity butions from individual microstructural features, however more
is defined as: care in accounting for all contributions to phonon-defect scattering
7# must normally be taken when comparing the results of a computa-
(8) tion to measured values of conductivity.
𝜅 = 2 𝐶(𝜔, 𝑇)𝑣., 𝜏 34 (𝜔)𝐷(𝜔)𝑑𝜔
8 4.3.3 Single Mode relaxation time approximation
The simple nature of Equation 4 as used in performance codes
where 𝐷(𝜔) = 3𝑁𝜔/ ⁄𝑉C 𝜔N, is the Debye density of states, makes it practical for engineering application, however, its validity
𝜔N, = 6𝜋 / 𝑣., 𝑁⁄𝑉C defines the Debye frequency, 𝐶(𝜔, 𝑇) is spe- is limited to high temperatures where phonon-phonon scattering
cific heat defined in terms of Bose-Einstein distribution 𝐶(𝜔, 𝑇) = dominates. The KCM approach described above is a first step in
OP"(Q,))
ℏ𝜔 O) , and for fluorite oxides N = 3 (the number of atoms making more accurate calculations of low temperature conductiv-
per primitive cell). Other parameters are defined and are listed for ity. However, the Debye approximation is known to underrepresent
UO2, ThO2 and CeO2 in Table 3. Phonon scattering rates are calcu- the role of long mean free path phonons, requiring a more accurate
lated using perturbation theory assuming all phonons are repre- representation of phonons across the Brillouin zone [42, 599]. As
sented by a single band. In this approximation the 3-phonon scat- discussed in Section 1, numerous phonon modes exist in the crys-
+!
tering rate is given by 𝜏,$L (𝑇, 𝜔) = 𝐵𝑇𝜔/ exp(− 𝑇N ⁄3𝑇) where talline structure of solids, each having its own vibration frequency,
velocity, and lifetime. All these details influence the thermal con-
B is fit from experimental data [32]. ductivity of a given material [536, 600, 601]. Different approaches
for calculating thermal conductivity using first principles in defect-
If only point defects are considered in the high temperature limit, free systems have been reviewed in Section 2. Since it is computa-
such that they and intrinsic 3-phonon scattering are the sole scat-
tionally expensive to follow similar methods for systems having
tering mechanisms present, Equation 8 can be analytically inte-
/R# (!
non-trivial defects, we consider here several levels of simplifica-
grated when τ+!
,$L (𝑇, ω) = 𝑇ω/ is defined in terms of re- tion, which bring both intrinsic anharmonic and defect perturba-
ST$# U%
/ VW# T$# tions to similar levels of complexity.
duced Debye frequency ω> = to obtain:
X "

𝜔8 𝜔: A simplification in the calculation of the 3-phonon scattering phase

𝜅9 = 𝜅$ 7 8 atan 7 8, may be made based on the single mode relaxation time (SMRT)
𝜔: 𝜔8 ((9)
approximation [600]. In the SMRT, the scattering phase-space term
in Equation 6 retains exact phonon dispersion, but the anharmonic
where ki is intrinsic conductivity in the absence of defects: interaction term is represented by a single Grüneisen parameter.
,
𝑀𝑣. 𝜔: 1 This method is especially useful for systems like UO2, where the
𝜅$ = < , , B . accuracy of current DFT methods is questionable [27, 602]. While
4𝜋 𝛾 𝑁 𝑇 (10) dispersion curves can be easily validated by neutron scattering ex-
periments, the data on 3-phonon scattering is limited. This ap-
Table 3. Parameters for calculation of thermal conductivity following KCM proach has been applied recently to ThO2 [555] to predict bulk, sin-
approach. gle-crystal thermal conductivity in comparison to measured values
[179]. Figure 28 compares some of the notable results from previ-
Property UO2 ThO2 CeO2 ous studies that considered thermal conductivity of ThO2.
[320] [179] [407]

Velocity, 𝑣. (m/s) 2644 3145 3270

Unit cell volume, 𝑉C (A3) 163.6 175.2 159.2

Debye Frequency, (THz) 43 50.2 53.8

Debye temperature, 𝑇N (K) 328 381 409

B, (s/K) ×10-18 1.6 1.2 1.2

Grüneisen parameter 1.8 — 2.5

29
 standard implementation of BTE at higher temperature may arise
from the fact that materials undergo thermal expansion resulting in
phonon softening. A detailed accounting for this effect would re-
quire recalculation of phonon dispersion and relevant anharmonic
terms as a function of temperature. Nevertheless, while these higher

Figure 28. Comparison of different methods for calculation of thermal con-

ductivity in ThO2. SMRT by Deskins et al. [555] (red curve) and bulk ThO2,
NEMD results by Cooper et al. [603] (dotted line), and BTE-DFT results
by Malakkal et al. [154] (green dashed line) and Jin et al. [152] (blue dashed
line). The black circles are experimental results by Mann et. al. [179] for
96.7 TD ThO2 single crystal and cyan diamonds for polycrystalline ThO2 Figure 29. Reduction of thermal conductivity presented by Deskins et al.
[154]. Data by Deskins et al. adapted with permission from [555]. Copy- (solid lines) compared to experimental and MD results containing 20% ura-
right 2021 AIP Publishing. Data by Cooper et al. adapted with permission nium substitutional defects. Each value is normalized by the respective pure
from [603]. Copyright 2015 Elsevier B.V. Data by Malakkal adapted with ThO2 value at 300 K from each study. Adapted with permission from [555].
permission from [154]. Copyright 2019 Elsevier B.V. Data by Jin et al. Copyright 2021 AIP Publishing.
adapted with permission from [152]. Copyright 2021 IOP Publishing Ltd.
Data by Mann et al. adapted with permission from [179]. Copyright 2010
American Chemical Society.

The associated phonon-point defect scattering rate of a phonon with order effects are important to the broader community, they do not
wave number q and polarization s, accounting for the actual disper- come into play for work reviewed in this section for two reasons.
sion curves, can be written in terms of the scattering parameter as First, in an effort to isolate the role of defects, experiments are typ-
[596]: ically carried out at room temperature and below to reduce the ob-
scuring influence of phonon-phonon interactions. Second, meas-
+! 𝛤𝑉C E (12) urements at elevated temperature of ion irradiated material intro-
𝜏YZ,[\ = / 𝜔 ,
4𝜋𝑣],[\ 𝑣^,[\ duce significant complications due to kinetic defect processes such
as recombination and agglomeration.
where vp,qs is the phonon phase velocity. In the Debye limit, this
form reduces to that listed in Table 2 for point defects. Equation 12 4.4 Molecular dynamics simulations of thermal con-
takes into account the dispersive nature of the phonon and distin- ductivity
guishes between phonon group and phase velocities. The expansion Molecular dynamic simulations offer an alternative way of calcu-
of phonon scattering rates in Table 2 to SMRT requires recasting lating thermal conductivity in lattices where defects and other fea-
them into a form that accounts for differences between 𝑣< and 𝑣= . tures can be directly specified. It can be applied to defective struc-
Using dispersion curves fit to inelastic neutron scattering data [50], tures and captures higher order anharmonic effects, which are too
Deskins et al. [555] have implemented the SMRT approximation computationally expensive to be implemented within the BTE. The
in the case of uranium substitutional defects in ThO2 and compared application of additional post-processing can reveal detailed mech-
the resulting temperature dependence of thermal conductivity to anisms of phonon scattering.
measured values [604] and those from MD simulation [603] (Fig- 4.4.1 Bulk thermal conductivity
ure 29). This comparison shows that in these fluorite oxide systems, Classical molecular dynamics (MD) involves solving Newton’s
making the SMRT approximation still produce a reasonable de- equations of motion to determine the trajectories of atoms within a
scription of thermal conductivity in defect-bearing systems across crystal lattice [606]. To approximate an infinite lattice, a structure
a wide temperature range through the BTE. As more accurate first of many thousands of atoms can be replicated periodically in all
principles treatments of thermal transport in UO2 become available, dimensions, creating a supercell. The behavior of the system is dic-
researchers will be able to revisit assumptions regarding lattice an- tated by the description of interatomic forces using an interatomic
harmonicity and phonon-defect scattering that are tied to the potential, derived empirically by fitting to experimental material
SMRT. properties or to forces calculated from DFT. During MD simula-
tions, thermal transport within such an ensemble can be evaluated
However, the Boltzmann framework, at any level of approximation using either the non-equilibrium MD (NEMD) method or the
discussed here, typically only considers 3 phonon processes (cubic Green-Kubo equilibrium method [607].
phonon interactions) and may be inadequate to describe phonon
thermal transport at high temperature where four-phonon scattering
can become significant [123, 605]. An additional limitation of the

30
During NEMD, the system is driven out of its equilibrated state by can be used as a fitting parameter. However, the majority of fit pa-
application of a heat flux (Figure 30), which creates a thermal gra- rameters are still contained within the short-range interactions.
dient [608], or by application of a thermal gradient, which creates Most UO2 potentials use a Buckingham form [612] to describe the
a heat flux [609]. In either case, following a certain amount of time repulsive force due to the Pauli-exclusion principle and intermedi-
the system will reach steady state, whereby the heat flux, 𝑞⃗, and ate-range dispersive forces due to Van der Waals interactions. Ad-
thermal gradient, 𝑑𝑇⁄𝑑𝑥, become constant, and the thermal con- ditionally, a Morse potential [613] can be included to capture a de-
ductivity is defined by Fourier’s Law: gree of covalency in UO2; for example, in the Basak [614] and Ya-
kub [615] potentials. Several UO2 potentials, such as the Morelon
𝑞⃗ (13) [616] and Jackson [617] potentials, utilize the 4-range formulation
𝜅= ,
𝑑𝑇⁄𝑑𝑥 of the Buckingham potential, which retains the exponential descrip-
tion of forces at short ranges and the dispersive term at longer dis-
Finite size effects arise due to the separation of the hot and cold tances, with splines used near the potential minima. This approach
regions being shorter than the phonon mean free path [609, 610, avoids the unphysical energies at short ranges due to the asymptotic
611]. In NEMD, the true bulk thermal conductivity, 𝑘_ , must be nature of the r-6 dispersion term. A number of potentials account
extrapolated from the following relationship 𝜅+! = 𝐴𝐿+! +! for ionic polarizability using the shell model, representing a devia-
# + 𝑘_ ,
where 𝜅 is the thermal conductivity of the system with supercell tion from a strictly pairwise description that enables the dielectric
length 𝐿# . constant and the Cauchy violation in the elastic constants to be re-
produced [618]. More recently, Cooper, Rusthon and Grimes
The Green-Kubo method is carried out on a system in its equilib- (CRG) extended a Coulombic-Buckingham-Morse pair potential
rium state, whereby the system is held at constant temperature. The form to include many-body interactions through the embedded
thermal conductivity is determined from the ensemble average of atom method (EAM), allowing the temperature dependence of bulk
the heat-current autocorrelation function, 〈𝑱(0) ∙ 𝑱(𝑡)〉, such that: modulus to be captured, which was also later demonstrated by
Soulie et al. [619] for the Sattonay potential [620]. The Sattonnay
>
𝑉 (14) and Li [621] potentials moved beyond a rigid-ion model to include
𝜅= 2 〈𝑱(0) ∙ 𝑱(𝑡)〉 𝑑𝑡, charge transfer between atoms. A number of detailed studies [602,
3𝑘; 𝑇 , 8
618, 622, 623, 624, 625] have compared the properties of contem-
porary potentials to expertimental or DFT data, such as thermal ex-
where V is the volume of the system, T is the temperature, and kB is
pansion, mechanical properties, and defect energies. The ability of
the Boltzmann constant. For long simulation times, 𝑱(𝑡) becomes
a potential to capture such properties is the primary metric used to
uncorrelated with respect to 𝑱(0), such that 〈𝑱(0) ∙ 𝑱(𝑡)〉 tends to
evaluate the quality of the potential.
zero, enabling convergence of κ. A benefit of the Green-Kubo
method is that finite size effects appear to be less severe than for
However, frequently, empirical potentials are not fit to the phonon
the NEMD method; however, long simulation times are required properties of a material and the ability of a potential to accurately
and the force on an atom due to each of its neighbors must be pre-
describe thermal transport must be rigorously validated. Notably,
cisely defined, which for many-body empirical potentials is not
classical MD struggles to reproduce the low thermal conductivity
trivial [607, 611].
of UO2, particulary at low temperatures [602, 626, 627, 628, 629],
whereas MD potentials tend to perform better for ThO2 [154, 630,
631]. It has been suggested that this is due to spin-phonon reso-
nance associated with low lying f-electron states in UO2 that cannot
be included directly in classical MD but when accounted for in the
Klemens-Callaway model, greatly improve the comparison be-
tween MD and experiment [25, 26, 180]. Chernatynskiy et al. ap-
plied a non-MD lattice dynamic approach, finding that several po-
tentials performed reasonably well for UO2 and suggested an an-
harmonic correction to improve results [632].

Recently, the CRG [923] potential was rigorously accessed for ac-
curate predictions of phonon dispersion, lifetime, and branch spe-
cific conductivity for UO2 and ThO2 [152]. It was found that the
CRG potential captures the dispersion of the acoustic branches
well, but exhibits significant discrepancies for the optical branches,
Figure 30. A schematic of the NEMD method, whereby a UO2 supercell leading to an overestimate of phonon lifetime and conductivity for
with a large aspect ratio is used. A heat flux is applied, which causes a ther-
mal gradient. This, in turn, causes a resultant heat flux. Under steady-state,
both materials. Similary, it has been found that several UO2 poten-
the applied heat flux and the resultant heat flux are equal and opposite. tials accurately capture the dispersion of the acoustic branches,
while inaccuracies in the optical branches result in a poor descrip-
Inherent to both methods are uncertainties regarding the choice of tion of thermal properties [602]. These findings suggest that the
empirical potential and its ability to describe thermal transport in empirical potential needs to be further optimized for robust predic-
the system being studied. Commonly, pairwise empirical potential tion of thermal conductivity both in perfect crystals and in the pres-
forms have been employed for oxides, whereby the interaction en- ence of complex defects. Moreover, the methods discussed here are
ergy of pairs of U-U, U-O, and O-O atoms are independent of the only suitable for modeling classical thermal transport due to pho-
positions of other atoms in the system. The total system energy is nons and do not address polaron contributions, which can be sig-
given by a sum over all pair interactions. Typically, a pair potential nificant at high temperatures in semi-conductors like UO2 [633], or
consists of long-range Coulomb and short-range interactions. Often spin-phonon resonance processes.
partial ionic charges are used, meaning that the degree of ionicity

31
4.4.2 Point defect scattering using molecular dynamics 4.4.3 Extended defects
The thermal transport of defective crystals can be addressed using MD simulations can be employed to simulate the impact that ex-
the same methods outlined above. First, the defect-free lattice ther- tended defects (such as dislocations, grain boundaries, voids, and
mal conductivity should be determined as a baseline. Subsequently, bubbles) have on phonon-mediated thermal conductivity. For ex-
defects can be introduced to the system by adding new atoms at ample, the reduction in thermal conductivity of UO2 for several
interstitial sites, removing atoms to create vacancies, or substituting concentrations of edge dislocations has been predicted to develop
one atom for another to create impurity defects [25, 627, 634, 635, an analytical form suitable for use in a fuel performance code [637].
636]. The now-defective system should then be allowed to equili- The impact of grain boundaries on UO2 thermal conductivity has
brate before repeating the thermal conductivity assessment of the also been estimated and extrapolated from MD simulations, reveal-
system, taking care to treat finite size effects. This process can be ing only a small impact for micrometer-sized grains (as are typi-
repeated with varying defect concentrations. The phonon thermal cally present in fresh fuel) [638, 639, 640, 641]. However, because
conductivity calculated as a function of concentration can be fitted grain boundaries serve as sinks for point defects, it is expected that
with either the simple model represented by Equation 4 or the the impediment to thermal transport caused by grain boundaries
Klemens-Callaway model to determine the effective phonon scat- will increase under irradiation [407, 552]. MD simulations have
tering cross-section for each defect or defect grouping [25, 28]. been used to investigate the degradation of thermal conductivity
due to porosity [553] and the accumulation of fission gas (Xe) [642]
Broadly speaking, impurity defects have a lesser impact on thermal or decay gas (He) [643] into bubbles. As expected, an increased
conductivity than interstitials and vacancies, and of the fission porosity reduces the thermal conductivity; however, Chen et al.
products, Xe has the most significant impact on the thermal con- [642] and Lee et al. [643] both showed a decrease in thermal con-
ductivity of UO2 [25, 26, 555]. An additional complexity for ionic ductivity as the voids were filled with Xe and He, respectively. For
materials is the fact that scattering due to charge compensating de- He this was attributed to the resolution of He into the lattice,
fects must also be considered. For example, Figure 31 shows the whereas for Xe resolution did not occur and it was attributed to UO2
significant impact that a particular charge compensating mecha- atom distortion at the bubble-UO2 interface. Nonetheless, Tonks et
nism has on the thermal conductivity of UO2 doped with 5 wt% Gd al. demonstrated that the thermal conductivity degradation due to
[635]. If Gd impurities are compensated by U5+ substituted at a U4+ dispersed gas in the lattice greatly outweighs that of gas in the bub-
site the thermal conductivity is significantly higher than if oxygen bles [26].
vacancies (VO) are used. This is despite the lower concentration of 4.5 Impact of grain boundaries and porosity
VO needed to charge compensate 5 wt% Gd. By reducing the num-
ber of phonon-scattering centers, binding increases the thermal While the impact of atomistic-level defects is best captured using
conductivity with respect to a random distribution of defects. This RTA, the effect of multiple grain boundaries on phonon thermal
demonstrates the complexity that must be considered for all defects conductivity is better captured using effective medium approxima-
in oxide nuclear fuel, be they formed by fission product accommo- tions. The impact of grain boundaries on thermal conductivity may
dation, irradiation damage, or by varying off-stoichiometry. Under- be represented using a series resistance model:
standing the scattering due to individual point defects allows the 4 4 @%&
coupling of phenomena, such as fission gas behavior or radiation ?$
=? + &
, (15)
"
damage, to thermal conductivity models [26, 28]. Lastly, phonon
thermal conductivity calculated using either the NEMD or the
Green-Kubo method can be fitted with either the simple model rep- where the effective thermal conductivity, 𝜅A , is a function of the
resented by Equation 4 or the Klemens-Callaway model to deter- single crystal conductivity, 𝜅8 , the average grain size, d, and the
mine the effective phonon scattering cross-section for each case grain boundary interfacial thermal, or Kapitza, resistance RGB. At
[25, 28]. low temperatures, where the Debye model serves as a good approx-
imation for the density of states, the acoustic mismatch model and
a b the diffusive mismatch model have been developed to explain the
temperature drop across boundaries [644]. Unfortunately, neither
model provides good predictive capability across a wide range of
grain boundary types. These failures result from interface scatter-
ing processes which depend sensitively on atomic structure and are
difficult to treat in analytical models. Recent studies have used
molecular dynamics [552, 645] to understand the impact of atomic
structure on thermal transport across grain boundaries. One of the
first efforts involving UO2 was performed by Watanabe and
coworkers [552]. Their results demonstrated that the calculated
value of the grain boundary resistance depends strongly on the
choice of interatomic potential. A more recent molecular dynamic
study [645] that considered larger grain sizes reported Kaptiza re-
sistances that were 50% smaller than reported by Watanabe. It was
Figure 31. (a) The thermal conductivity of UO2 containing 5 wt% Gd cal- suggested that this difference is due to the polycrystalline averaging
culated using NEMD by Qin et al. Each data set corresponds to a different scheme employed by Watanabe.
charge compensating mechanism, as shown by (b) the schematic of atomic
configurations. Adapted with permission from [635]. Copyright 2020 Else-
vier B.V. Corrections to thermal conductivity resulting from volumetric po-
rosity have also been accounted for by including a correction fac-
tor:

32
 sample thermal conductivity and lattice constant were measured us-
𝜅9 = 𝜅A 𝑓(𝑝, 𝑇), (16)
ing MTR and XRD respectively (Figure 32). The reduction in con-
ductivity and lattice expansion did not follow a similar trend with
using the Loeb expression or Maxwell-Eucken formula, which ac- dose for these two different irradiation conditions. The results were
count for fractional volume of porosity, shape factor, and tempera- analyzed using simple models for lattice expansion and thermal
ture [530]. This expression does not account for pore size and conductivity reduction, informed by atomistic simulations rom the
breaks down for nanometer-sized pores that have dimensions on literature. It was concluded that microstructure evolution under H
the scale of the phonon mean free path. Clearly, more accurately and He ion irradiation produced different types of defects owing to
accounting for nanovoids requires models that consider the atomic differences in defect clustering and electronic-ionization-induced
structure of the defects. In parallel with grain boundaries, recent mobility of the defects.
molecular dynamics modeling work has aimed to understand the
role of atomic structure at pore/bubble boundaries [642, 646]. Zhu 4.6.2 Impact of dislocation loops in high temperature
et al. [646] used non-equilibrium molecular dynamics to study the proton irradiated CeO2
impact of Xe bubbles on thermal transport in UO2. They found that
many defects are produced at the bubble interface, leading to a sub-
stantial increase in the interfacial thermal resistance and an overall A study targeting the impact of dislocation loops on conductivity
decrease in the thermal conductivity. by Kafizov et al. [315] involved measuring the conductivity reduc-
tion caused by proton irradiation of CeO2 at 700°C. As revealed by
TEM analysis, the microstructure was dominated by dislocation
4.6 Comparison between experiment and modeling loops. A rate theory model parametrized by analyzing two sets of
In this section, we review efforts to correlate microstructural de- samples irradiated at 600 and 700°C revealed that the conductivity
fects produced by ion irradiation to thermal conductivity using the reduction in 700˚C irradiated sample is due to dislocation loops,
Boltzmann transport framework and MD. Very little work had been whereas at 600°C the reduction is primarily attributed to point de-
done in this area until recently due the difficulty in accurately char- fects (Figure 33) [297]. One interesting observation that follows
acterizing the range of defects produced by ion irradiation and ac- from these studies is that thermal conductivity reduction due to
curately measuring thermal conductivity of thin damage layers. As loops is unusually high and is attributed to long range strain fields
mentioned above, the most recent work in this area has been the [315].
experimental measurement of low-temperature conductivity in de-
fect-bearing crystals. At reduced temperatures, the relative contri-
bution of defects to the total scattering time is the largest, allowing
the most information to be collected on fundamental mechanisms
of phonon-defect interactions.

4.6.1 Impact of point defects in low temperature, low

dose irradiated UO2
One of the first efforts along these lines was the work of Weisensee
et al. [570]. They investigated the effect of room temperature Ar
ion irradiation on thermal conductivity of thin film of UO2 using
TDTR. While the lattice strain associated with the lattice mismatch
between substrate and film prevented a detailed study of baseline
microstructure, it was suggested that the UO2 was slightly hyper-
stoichiometric. XRD data revealed a broadening of the diffraction Figure 33. Analysis of thermal conductivity degradation due to dislocation
peaks and a shift to lower angles, an indication that the U4O9 phase loops in proton irradiated CeO2. Adapted with permission from [297]. Cop-
was not formed under irradiation. A simple model of phonon ther- yright 2021 Acta Materialia Inc.
mal conductivity was used to extract an effective non-dimensional
scattering strength for point defects in UO2.
4.6.3 Mixed impact of point defects and loops in ThO2
a b More recently, efforts have been directed at drawing a closer con-
nection between microstructure and thermal conductivity using
more comprehensive defect characterization techniques, discussed
in section 3 of this review, and a more complete accounting of the
physical mechanisms of phonon transport.

Dennett and coworkers experimentally studied the impact of 2

MeV proton irradiation on thermal transport in single crystal tho-
rium dioxide grown using the hydrothermal synthesis method using
MTR [29]. ThO2 was irradiated at 25˚C from 0.016 to 0.16 dpa and
Figure 32. Analysis of thermal conductivity degradation in H+ and He++ ion at 600˚C from 0.47 to 0.79 dpa. At 25˚C, the thermal conductivity
irradiated UO2. Adapted with permission from [28]. Copyright 2020 Acta in the irradiated layer dropped to 20% of the pristine value for all
Materialia Inc. doses investigated, while at 600˚C, 40% of the pristine conductivity
was retained at both doses. For both temperatures investigated, the
In another study targeting the impact of point defects, polycrystal- thermal conductivity was found to be consistent between all doses,
line UO2 was irradiated using 2.6 MeV protons and 3.9 MeV he- suggesting a saturation in the defect population imparted via irra-
lium ions at 300 and 200°C, respectively [28]. After irradiation, the

33
 diation at these levels. Top-down Raman spectra collected follow- normal. In another study involving UO2, experimental measure-
ing irradiation suggested the presence of defect clusters in both ments of thermal conductivity were performed on a series of poly-
cases, with a higher density or larger clusters expected at 600˚C due crystalline samples having grain sizes ranging from ~100 nm to
to the higher mobility of defects. The retention of higher thermal several micrometerss [650]. Using equation 15, it was found that
conductivity at 600˚C is attributed to the concentration of defects the extracted Kapitza resistance was considerably larger than cal-
into larger clusters and loops, reducing the total number of phonon culated using molecular dynamics [552, 645]. It was suggested that
scattering sites retained in the lattice [520, 554, 583]. the difference between measurement and model may be due to local
changes in oxygen stoichiometry near the boundary.
Further measurements of the thermal conductivity in defected sin-
gle crystal ThO2 were conducted on a subset of the crystals irradi- Another study by Khafizov et al. [407], of more direct connection
ated at 600˚C over a temperature range of 77 to 300 K using MTR to thermal transport behavior in the HBS, involved measuring con-
(see Figure 34) [132]. These data provide a low-temperature com- ductivity in highly non-stoichiometric nanocrystalline ceria [407].
parison for BTE calculations of defect-affected thermal transport In this study, it was found that the measured conductivity was much
(similar to the 300K and higher BTE calculation of transport in U- larger than that predicted assuming that the oxygen defects were
doped ThO2 shown in Figure 29). To compute the thermal conduc- uniformly distributed. Electron energy loss spectroscopy revealed
tivity of defect-bearing ThO2, dislocation loop characteristics were that oxygen defects were segregating at grain boundaries leaving
measured directly using transmission electron microscopy (TEM) the grain interior relatively defect free (Figure 35). The authors
in order to compute scattering rates from stacking fault type defects speculated that the increase in the grain boundary resistance due to
as shown Table 2 (as these loops are observed to be faulted Frank segregation was more than offset by a reduction in phonon scatter-
loops). In addition, point defect contributions to scattering were es- ing by intragranular oxygen defects. This supposition has since
timated through the use of a rate theory model for defect generation been supported by MD and multiscale modeling studies of UO2
and evolution [297] and used to seed the calculation of the scatter- [512, 552]. Watanabe et al. found that the grain boundary thermal
ing rates based on Equation 12. Using fitting parameters only to resistance that was two orders of magnitude larger than that ex-
account for native impurities in the as-synthesized crystals, good pected from pristine interfaces calculated using molecular dynam-
agreement was found between MTR-measured conductivity and ics simulation [552], while Bai et al. found that grain boundary seg-
that computed using the BTE in the SMRT approximation as shown regation leads to higher intragranular thermal conductivity [512].
in Figure 34 for ThO2 irradiated to 0.16 and 0.47 dpa.

a
(a)
(a) b (b)
(b)
a b

Figure 35. Impact of defect segregation on interface thermal resistance of

grain boundaries. Adapted with permission from [407]. Copyright 2019 The
Figure 34. Comparison of MTR-measured thermal conductivity and BTE
American Ceramic Society.
computed thermal conductivity for single crystal ThO2 irradiated with 2
MeV protons at (a) 0.16 dpa at 600˚C and (b) 0.47 dpa at 600˚C. Computed
conductivities considering only one type of extrinsic defect (dislocation 4.7 Future Outlook
loops or point defects) are shown in the dotted lines, while the total conduc-
tivity considering both defect populations is shown in the solid red line in While the works described above have shown some success in con-
each. Adapted with permission from [132]. Copyright 2021 Dennett et al. necting models of varying complexity to experimental measure-
(Published by Elsevier Ltd.). ments of thermal transport in defected actinide oxides, gaps still
exist in the ability to capture the unique influence of the entire spec-
4.6.4 Impact of grain boundaries trum of radiation-induced defects on phonon scattering. Models be-
The segregation of defects at grain boundaries is thought to have a yond the RTA are needed to accurately treat conductivity at suffi-
significant impact on thermal conductivity in the HBS. Generally, ciently low temperatures where normal processes dominate over
the HBS corresponds to a rim in the nuclear fuel where the fuel Umklapp processes. Furthermore, the RTA can be problematic in
remains coldest and has largest damage owing to a higher fission certain classes of materials, such as epitaxial films, that introduce
rate. In this region, extensive damage is accommodated by grain symmetries not found in the bulk. MD models may help address
subdivision and subsequent defect segregation. The net beneficial the shortcomings of the RTA but require interatomic potentials that
effect on intrinsic conductivity suggested by Rondinella and Wiss accurately capture phonon transport properties. First principles de-
[6] has motivated recent work that has looked at understanding the scriptions of the details of the phonon band structure can provide
role that interfaces have on phonon transport in fuel surrogates. important benchmarks for developing new, more accurate intera-
tomic potentials. While the computational tools needed to perform
Hua et al. [647] reported the Kapitza resistance for grain boundaries this task are available, this will no doubt be a challenge for strongly
in large-grained CeO2 using an investigative approach first devel- electron correlated materials.
oped for Si bicrystals [648, 649]. This study provided a correlation
between the measured Kapitza resistance and misorientation angle Currently, the Green’s function T-matrix method is the most fun-
between grain boundaries. To form this correlation, it was assumed damental approach to capture the impact of defects on phonon scat-
that the plane of the grain boundaries coincided with the surface tering rates [651, 652]. Work using this method has demonstrated
34
the shortcomings of using perturbation theory to treat the impact of Dr. Anter El-Azab is a Professor of Materials Science and Engi-
vacancies in diamond, silicon carbide, and boron arsenide. These neering at Purdue University. He is Science Question Lead for the
methods are currently finding applications in predicting scattering Center for Thermal Energy Transport under Irradiation, funded by
rates of phonons with extended defects such as clusters and dislo- the U.S. DOE’s Energy Frontier Research Centers program. Prior
cation loops [653, 654]. However, extending these approaches to to coming to Purdue, he was a Professor of Computational Science
materials that exhibit strong electron correlation remains a difficult and Materials Science at Florida State University and a research
task for first principles calculations. scientist at Pacific Northwest National Laboratory. He obtained his
doctorate degree at the University of California, Los Angeles. His
5 Concluding Remarks research and teaching focus on microstructure complexity in mate-
This review focused primarily on phonon thermal transport in two rials.
actinide oxides: one currently in use in commercial nuclear reac-
tors, UO2, and one advanced fuel candidate material, ThO2. A com- Matthew S. Bryan
prehensive understanding of phonon transport in these actinide ox- Dr. Matthew S. Bryan is a postdoctoral researcher in the Materials
ides under irradiation remains a grand science challenge. This area Science and Technology Division at Oak Ridge National Labora-
of research contains rich physics including the 5f electron chal- tory. He obtained his PhD from Indiana University in physics in
lenge, defect generation and evolution, and the development of ex- 2019. His work focuses on using inelastic neutron and X-ray scat-
perimentally validated mesoscale models of thermal conductivity tering to study phonon dispersion, line widths, and density of states
in the presence of defects. New computational tools such a DMFT- and how these measurements relate to thermal transport in actinide
DFT and new experimental tools enabled by new synthesis capa- bearing materials.
bility are ushering in a new era, enabling scientists to study, in ex-
quisite detail, the fundamental mechanisms that control phonon Michael W.D. Cooper
transport. Dr. Michael Cooper is currently a Scientist in the Materials Sci-
ence and Technology Division of Los Alamos National Labora-
Meeting this challenge will provide new opportunities for the nu- tory, where he was also a postdoc from 2015 to 2018. He obtained
clear fuels community. For example, accurate calculations of elec- a PhD in Materials Science from Imperial College London in
tronic structure in 5f systems will provide the scientific community 2015. His research interests focus on the application of classical
with key information for constructing accurate interatomic poten- molecular dynamics and density functional theory to understand-
tials required for high-throughput compositional screening of ad- ing the atomic scale processes that govern nuclear fuel behavior.
vanced fuels. The development of a comprehensive understanding In particular, he derives parameters for defects, fission products,
of thermal energy transport, while intimately connected to ad- and thermophysical properties relevant to ceramic fuels of various
vanced nuclear fuels, can provide opportunities for energy-related forms, such as oxides, nitrides, and silicides.
technologies beyond nuclear energy. Examples include tailoring
electron scattering in textured nanocrystals to enhance thermal con-
ductivity of metal interconnects, simultaneously controlling elec- Cody A. Dennett
tron and phonon transport across interfaces in thermoelectric de- Dr. Cody A. Dennett is currently an Applied Physicist in the Mate-
vices, specifying the interaction of electrons with dislocations in rials Science and Engineering Department at the Idaho National
topological insulators, and harnessing strong electron correlation to Laboratory. He obtained his PhD from the Massachusetts Institute
realize new paradigms for quantum materials. of Technology in 2019. He was the recipient of the INL Russell L.
Heath Distinguished Postdoctoral Fellowship and prior to INL was
AUTHOR INFORMATION a US Department of Energy National Nuclear Security Administra-
tion Stewardship Science Doctoral Fellow. His work focuses on la-
Corresponding Author - [email protected]
ser-based measurements of thermophysical properties in dynamic
Author Contributions or extreme environments to understand defect kinetics and
transport phenomena in metals and ceramics.
The manuscript was written through contributions of all au-
thors. All authors have given approval to the final version of Krzysztof Gofryk
the manuscript. Dr. Krzysztof Gofryk is a distinguished staff scientist and a group
lead for actinide science in the Irradiated Fuels and Materials De-
Biographies partment at the Idaho National Laboratory (INL). He obtained his
David H. Hurley Ph.D. from the Institute of Low Temperature and Structure Re-
Dr. David H. Hurley is a Laboratory Fellow and a group lead in the search (Polish Academy of Sciences) in 2006. Before joining INL,
Materials Science and Engineering Department at Idaho National he worked at Los Alamos and Oak Ridge National Laboratories.
Laboratory. He received his Ph.D. in Materials Science and Engi- He is a recipient of the DOE Early Career Award, the Presidential
neering from Johns Hopkins University in 1999. He was a Japa- Early Career Award for Scientists and Engineers, and INL's excep-
nese Society for the Promotion of Science Postdoctoral Fellow in tional achievement award. Dr. Gofryk’s work focuses on strongly
the Applied Solid State Physics Laboratory at Hokkaido Univer- correlated electron systems at low temperatures and strong mag-
sity. He is the recipient of the INL Outstanding Innovation Award netic fields including transport and magnetism in 5f-electron mate-
for development of a hot-cell compatible instrument for nanoscale rials, quantum criticality, heavy fermion physics, and spin-orbit
thermal transport measurements. Currently, he is the founding di- coupled systems.
rector of the Center for Thermal Transport under Irradiation, an En-
ergy Frontier Research Center funded by the US Department of En- Lingfeng He
ergy, Office of Basic Energy Sciences. Dr. Lingfeng He a distinguished staff scientist and High-Resolution
Materials Characterization Group leader in Advanced Characteri-
Anter El-Azab zation Department at Idaho National Laboratory (INL). He is the

35
deputy director of the Center for Thermal Energy Transport under crystalline materials from the first-principles of quantum mechan-
Irradiation, an Energy Frontier Research Center funded by the US ics. Applications span the periodic table, with particular emphasis
Department of Energy, Office of Basic Energy Sciences. He re- on materials with strong electronic correlations. Dr. Marianetti re-
ceived his Ph.D. in Materials Science at the Chinese Academy of ceived a Ph.D. in Materials Science and Engineering from MIT in
Sciences in 2009. He worked as a post-doctoral research associate 2004, and B.S./M.S. from The Ohio State University. He held post-
and assistant scientist at Nagaoka University of Technology in Ja- doctoral positions in the Department of Physics at Rutgers Univer-
pan and the University of Wisconsin-Madison before joining INL sity and at Lawrence Livermore National Laboratory. Dr. Marian-
in 2014. He is the recipient of INL Laboratory Director’s 2020 Ex- etti was the recipient of the NSF CAREER and DARPA Young
ceptional Scientific Achievement Award. Faculty awards.

Marat Khafizov Karl Rickert

Dr. Marat Khafizov is an associate professor in Mechanical and Dr. Karl Rickert is currently a Senior Chemist at KBR, contracted
Aerospace Engineering at The Ohio State University. He received to the Sensors Directorate at the Air Force Research Laboratory.
his Ph.D. degree in Physics from University of Rochester in 2008. Prior to this, he was an Oak Ridge Institute for Science and Educa-
He was a postdoctoral research associate and R&D scientist at tion Postdoctoral Fellow at the Air Force Institute of Technology
Idaho National Laboratory (2010-2014), before joining OSU in after receiving his PhD from Northwestern University in 2016. His
2014. His research focus is on understanding the impact of defects work focuses on the growth and characterization of actinide oxides
and radiation damage on physical properties of materials. He is a and their implementation in detection devices.
Phonon Transport Thrust Lead for the Center for Thermal Energy
Transport under Irradiation. Farida A. Selim
Dr. Farida Selim is an associate Professor of Physics and a member
Gerard H. Lander of the Center for Photochemical Science at Bowling Green State
Dr. Gerry Lander obtained his Ph.D. at Cambridge (UK) in 1967. University. She obtained her PhD in a joint program between Har-
He worked for 19 years at Argonne. For the last 5 years, he was the vard and Alexandria University in Egypt. She is the lead of Thrust
Director of Argonne’s Pulsed Neutron Source. In 1986 he returned 1 “Point Defects” for the Center for Fundamental Understanding of
to Europe to work at the EU Transuranium Institute in Karlsruhe, Transport under Reactor Extreme, an Energy Frontier Research
where he was Director from 2002-2006, when he retired. He is a Center funded by the US Department of Energy, Office of Basic
Fellow of the APS, was a John Wheatley Fellow at LANL, a con- Energy Sciences. She is known for inventing a new positron anni-
sultant to the Japanese Atomic Energy Commission, was awarded hilation spectroscopy technique (Gamma Induced Positron Spec-
an Honorary Professorship by the Polish Academy of Science, and troscopy). Her research spans a wide range of areas in defect stud-
received the Walter Halg Prize from the European Neutron Scatter- ies, exploring novel electronic phenomena in wide band gap oxides
ing Association in 2011. He is now a Visiting Professor at Bristol and developing new instrumentation for defect and photoemission
University, UK. s studies.

Michael E. Manley Michael R. Tonks

Dr. Michael E. Manley is a Senior Researcher at Oak Ridge Na- Dr. Michael R. Tonks is a Professor and Alumni Professor of Ma-
tional Laboratory in the Materials Science and Technology Divi- terials Science and Engineering and Nuclear Engineering at the
sion. He received his PhD in Materials Science from the California University of Florida. He received his Ph.D. in Mechanical Engi-
Institute of Technology in 2001 and was awarded the 18th Louis neering from the University of Illinois at Urbana-Champaign in
Rosen Prize for his thesis. He was a Director’s Postdoctoral Fellow 2008. Before coming to UF he was a staff scientist at Idaho Na-
at Los Alamos National Laboratory before being promoted to Tech- tional Laboratory for six years and an Assistant Professor at Penn
nical Staff Member. He then moved to Lawrence Livermore Na- State for two years. He is a recipient of the Presidential Early Ca-
tional Laboratory in 2006 and then to his current position at Oak reer Award for Scientists and Engineers and the INL Early Career
Ridge in 2012. He won the 2021 TMS FMD Distinguished Scien- Exceptional Achievement Award. His work uses multiscale mod-
tist Award for his research on the thermophysical properties of ma- eling and simulation to investigate the co-evolution of microstruc-
terials and the discovery of intrinsic localized modes in anharmonic ture and properties in materials in harsh environments.
materials. He is Science Question Lead for the Center for Thermal
Energy Transport under Irradiation, funded by the U.S. DOE’s En- Janelle P. Wharry
ergy Frontier Research Centers program. Dr. Janelle P. Wharry is an Associate Professor in the School of
Materials Engineering at Purdue University. Her research aims to
J. Matthew Mann understand structure-property-functionality relationships in irradi-
Dr. Matthew Mann is a Senior Research Chemist for the Sensors ated materials, with an emphasis on deformation mechanisms and
Directorate with the Air Force Research Laboratory. He received mechanical behavior at the nano/microscale. She is a recipient of
his Ph.D. in Inorganic Chemistry from Clemson University in the US Department of Energy Early Career Award and National
2009. He is the recipient of the 2019 Dr. Brian Kent Award for his Science Foundation CAREER Award. She is an Editor of Materials
innovative research in the area of neutron detection. His current re- Today Communications. She received her Ph.D. from the Univer-
search interests include crystal growth and characterization of radi- sity of Michigan in 2012.
oactive materials, neutron detectors, novel laser hosts, and next
generation high powered electronics.
ACKNOWLEDGMENT
Chris A. Marianetti
Dr. Chris Marianetti is an Associate Professor of Materials Science D.H.H., A.E., M.S.B., C.A.D., K.G., L.H., M.K., M.E.M., C.A.M.,
and Applied Physics and Applied Mathematics at Columbia Uni- J. M. M., K. R. and J.P.W. acknowledge support from TETI (Ther-
versity. Marianetti's research focuses on computing the behavior of mal Energy Transport under Irradiation), an Energy Frontier Re-
search Center funded by the US Department of Energy, Office of
36
Science, Office of Basic Energy Sciences. F.A.S. acknowledges support from the Nuclear Energy Advanced Modeling and Simula-
support from FUTURE (Fundamental Understanding of Transport tion (NEAMS) program funded by the US Department of Energy,
under Reactor Extremes), an Energy Frontier Research Center Office of Nuclear Energy.
funded by the U.S. Department of Energy, Office of Science, Of-
fice of Basic Energy Sciences. M.R.T. and M.W.D.C. acknowledge

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