Adma 202007355
Adma 202007355
Adma 202007355
www.advmat.de
Adv. Mater. 2021, 33, 2007355 2007355 (1 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advmat.de
Figure 1. a) A schematic depiction of a flat substrate with micrometer-sized resistive pattern. When the current flows through the pattern, the tem-
perature can be probed in the lifetime imaging experiment with high thermal and spatial resolution. b) A Boltzmann sigmoid function used to describe
typical temperature dependence of the emission decay lifetime τ of the thermal phosphors. The working range of the phosphor is defined as the linear
region around the 50% quenched point Tq. c) Molecular geometry of the structurally isolated SbX52− center and typical organic cations that can be used
to form organic–inorganic hybrid compounds.
Recent years have seen revived interest in luminescent retention and successful detection of the thermal gradients
metal halides, in particular, 0D halides of ns2-ions (e.g., Ge2+, present within the sample requires a homogeneous and con-
Sn2+, Pb2+, Sb3+, Bi3+, Te4+, Cu+).[26–44] These typically exhibit formal coating with minute amounts of luminophore. The
color-tunable, broadband emission from self-trapped excitons use of encapsulating coating layers atop the luminophores is
(STE)[45–47] often with high photoluminescence quantum yield then required, which is orthogonal to the purpose of faithful
(PLQY) at RT. While these halides are typically discussed in retention of the thermal gradients and can be prohibitively
the context of utility-scale applications such as solid-state laborious. Therefore, air-durable alternatives, such as the
lighting,[48] we have recently demonstrated their use as ther- Sb(III)-halides,[47,52] are required. Such materials usually com-
moluminophores in remote thermometry and millimeter-scale prise isolated SbX52− anions separated by bulky organic cations
thermography owing to the steep temperature dependence (Figure 1c). The vast library of 0D Sb(III)-halides allows the
of their luminescence decay rates.[49] The temperature distri- Tq to be adjusted from below 200 K (iodides), to around RT
bution of a surface can therefore be mapped by conducting (bromides), and above 400 K (chlorides).[45,52–70]
fluorescence-lifetime imaging (FLIM, Figure 1a). The emission Targeting a sensitivity range around RT, we focus on tetra-
lifetime–temperature (τ–T) dependence (Figure 1b), to be reli- phenylphosphonium (TPP) Sb(III) pentabromide (TPP2SbBr5).
ably applied in thermography, has to be intrinsic to the mate- Two synthetic routes were pursued: i) by dissolving stoichio-
rial of a given structure and composition and without batch- metric amounts of TPPBr and SbBr3 salts in a polar organic
to-batch variability. The steep τ–T dependence in STE emitters solvent (dichloromethane, DCM) and using diethyl ether (Et2O)
arises from thermal activation of phonon-assisted nonradiative as an antisolvent, or ii) melting the TPPBr and SbBr3 in a stoi-
channels for the detrapping of STEs that become competitive chiometric ratio at 230 °C (Figure 2a; see the Experimental Sec-
with radiative STE recombination within a specific tempera- tion for details). TPP2SbBr5 is obtained in either a disordered
ture range. This temperature range, in which both PLQY and (route i) or ordered (route ii) phase (Figure 2b and Figure S1,
τ decrease until the emission vanishes, is referred to as the Supporting Information), both without organic solvent or water
sensitivity range of the thermoluminophore, and it typically molecules in their crystal structures. The disordered phase is
spans a range of 100 K, which can be engineered for a specific characterized by the static disorder of the alignment of SbBr52−
application by adjusting the crystal structure and composition. square pyramids, resulting in 50% occupancy of axial positions
Regardless of the physics of STE quenching, τ–T dependence by Br atoms, whereas in the ordered phase, the static disorder
can be fitted with a sigmoid law (Figure 1b) that shows that the is eliminated, and Br atoms occupy 100% of axial position. The
optimal operating region is around Tq (temperature at which ordering of the disordered phase can be observed at 186 °C and
emission is quenched to 50% of its maximum value). Practi- is an irreversible process (Figure S2, Supporting Information).
cally speaking, compounds with moderate RT-PLQYs (Tq close Such an interplay between kinetic and thermodynamic pro-
to RT) may be considered for a broad range of thermal sensing cesses has been previously observed in Bi(III)-based organic–
applications, such as bio-imaging (physiological temperatures, inorganic halides,[71] and, to the best of our knowledge, this is
i.e., 20–50 °C), heat distribution in electronics (RT-120 °C), etc. the first example for Sb(III) halides. The softness of ns2-metal
An important characteristic of STE-emissive ns2-metal halide halides culminates in their hybrid organic–inorganic variants,
luminophores is their moderate-to-slow radiative rates in a as seen not only from low melting points (<300 °C) but also
nonquenched state, which are then drastically increased by up from the increasingly evident impact of the structural disorder
to two orders of magnitude with increasing temperature, thus on the optical characteristics; for Sb(III) halides, see examples
yielding high specific detection sensitivities (up to 0.06 °C−1).[49] in refs. [69,72,73]. In the following, we establish and rationalize
The respective τ-values are typically in the microsecond-to- such effects for TPP2SbBr5 and showcase their importance for
nanosecond range, making for a good match to various inex- applications in high-spatial-resolution thermography.
pensive PL lifetime measurement schemes.[50,51] While we have Both ordered and disordered TPP2SbBr5 are characterized
observed these characteristics and attained tunable sensitivity by PL excitation (PLE) extending from below 250 nm to about
ranges with several hybrid organic–inorganic Sn(II) halides 500 nm and largely Stokes-shifted red emission (Figure 2c,d
and the fully inorganic Cs4SnBr6,[49] these compounds inher- and Figure S3, Supporting Information). On the contrary,
ently suffer from oxidation in air, making their use in high- Sn(II)-bromide luminophores can be excited only at wave-
spatial-resolution thermography unfeasible. In particular, the lengths below 400 nm,[29,74] posing a challenge for both the
Adv. Mater. 2021, 33, 2007355 2007355 (2 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advmat.de
Figure 2. a) A scheme depicting chemical and phase transformations occurring in the TPPBr-SbBr3 system. A wet synthetic route from the solvent–
antisolvent method (DCM-Et2O) results in the TPP2SbBr5 product which is a disordered phase (half-filled Br atoms indicate 50% occupancy). The
ordered phase can be obtained either by melting TPPBr and SbBr3 in stoichiometric ratio above 230 °C or by heating the disordered phase above 186 °C.
After heat treatment, the cooled ordered phase does not transform back to the disordered phase, indicating that the ordered phase is thermodynami-
cally stable at room temperature. b) Crystallographic unit cells of the ordered and disordered phases of TPP2SbBr5. c) Photos of the corresponding
disordered and ordered TPP2SbBr5 powders under daylight and UV excitation (365 nm). d) PLE and PL spectra of the ordered and disordered phases,
demonstrating characteristic broad and largely Stokes shifted emission from isolated center. e) Lifetime–temperature dependence for disordered (black
squares) and ordered (red circles) TPP2SbBr5 powders and corresponding Boltzmann–Sigmoid fits with fitting parameters. f) Depiction of the local
geometry distortion occurring upon excitation in SbBr52−. The axial SbBr bond is elongated, and equatorial SbBr bonds are shortened; the Sb atom
experiences out-of-plane distortion. g) Seitz–Mott single configurational coordinate model depicting processes involved in radiative and nonradiative
exciton recombination pathways in organic–inorganic Sb(III) halide hybrids. The radiative process involves excitation (vertical transition E–B) with
subsequent relaxation to the excited state geometry (horizontal transition B–A involving phonons) and emission (vertical transition A–D) with relaxa-
tion to the ground state geometry (horizontal transition D–E). A nonradiative process occurs when the system can reach the crossing point of two
parabolas (horizontal transition B–C) and relax back to ground state E without emission of a photon (horizontal transition C–E). Depending on the
excited state parabola offset from the ground state (ΔQ, shaded region), the crossing point C can occur energetically close to point B or much above.
The latter case results in higher-temperature quenching point Tq as the phonon modes involved in transition B–C need to be activated.
excitation-detection instrumentation and some applications molecular geometry. For 0D emissive centers, the electronic
(increased autofluorescence background in bio-imaging). The states are highly localized.[29,39,45] Excitation leads to a large
disordered TPP2SbBr5 phase is characterized by PLE shifted structural distortion, as depicted in Figure 2f. An atomistic pic-
to higher energies, whereas the PL band is shifted to lower ture of the involved processes can be depicted using a single-
energies as compared to the ordered phase (Figure 2d). This coordinate configurational diagram model, where ground and
results in a significant increase of the Stokes shift from 1.08 eV excited states are represented by parabolic potential functions
(253 nm) in the ordered phase to 1.42 eV (339 nm) in the disor- (harmonic for the simplicity, Figure 2g).[75] The abscissa depicts
dered phase. At RT, the disordered phase exhibits lower PLQY the change in the bond length or atomic coordinates; energy
(3.3%) and Tq (248 K) than the ordered phase (PLQY = 33%; see is placed on the ordinate. The minimum of the parabola rep-
Table S3, Supporting Information; Tq = 290 K; see τ–T depend- resents the equilibrium bond distance, which is different for
ence in Figure 2e). These properties together with the Stokes the ground and excited states. A Seitz–Mott model is adopted
shift are intricately related to the ground and excited state to rationalize the optical properties.[76] Thermal activation is
Adv. Mater. 2021, 33, 2007355 2007355 (3 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advmat.de
required to enable the nonradiative pathway and hence Tq 24 h. However, after thermal annealing or aging, the ordered
scales with the energy difference between points C and B film exhibits far more grain boundaries, which is incompatible
(Figure 2g). When this difference is small (case II), the emis- with the high spatial resolution that we aim to demonstrate
sion will be nearly quenched already at RT. Likewise, the Stokes (Figure S6d, Supporting Information). This is summarized
shift (Figure 2g, BE-AD) increases with the molecular geometry in Figure 3a. Eventually, for the FLIM experiment we have
change upon excitation (Figure 2g, shaded area related to ΔQ) used a freshly deposited homogenous film on a flat glass
and is thus larger for case II. We now connect the Seitz–Mott substrate patterned with a small, micrometer-scaled, indium
model to our experimental data. First, regarding the ordinate in tin oxide (ITO) pattern that mimics a structure similar to a
Figure 2g, our optical spectroscopy data suggest that the ordered microelectronic component. This pattern was made by photo
phase of TPP2SbBr5 classifies as case I, while the disordered lithography with the smallest feature having a size of about
phase as case II: both thermal quenching and Stokes shift are 3 µm. The quality of the film before the FLIM experiment can
more pronounced in the latter. Second, regarding the abscissa be concluded from the homogenous PL detected from the film
in Figure 2g, we then use X-ray-based structure determination over the region of interest (Figure 3b). The τ–T dependence of
and density functional theory (DFT) calculations to confirm that such a film is plotted in Figure 3c. Although Tq is similar to the
the disordered phase (case II) indeed also exhibits a larger pho- disordered bulk phase, τ0 is more than two times smaller. This
toinduced structural distortion than the ordered phase (case I). could be an evidence that the film, due to its thickness, is even
The computed SbBr52− excited-state geometries are comparable more disordered and hence more quenched. The differences
in both phases (with elongated axial SbBr bonds of about 3 Å in exciton dynamics between bulk and thin film morphology
and pronounced out-of-plane distortion of Sb; see the Experi- of low-dimensional metal halides are relatively unknown, with
mental Section for details on the DFT calculations). The geom- the exception of a recent study by Thomaz et al. that points
etries of the ground state are, however, markedly different: the out the difference in excitation decay time in bulk and thin
X-ray-based structure determination finds axial SbBr bond film forms of a corrugated lead(II) bromide compound.[79] To
lengths of 2.38 and 2.53 Å in the disordered and ordered phase, further confirm the identity of the ordered and disordered
respectively, and minor changes in the equatorial SbBr bonds films and to probe the local disorder, we have analyzed the
(Tables S4–S7, Supporting Information). Thus, we conclude lower frequencies of the Raman spectra (at RT) for the fresh
that photoexcitation causes a larger structural distortion in the and annealed films and compared them to those recorded for
disordered phase, which, in line with the Mott–Seitz model, ordered and disordered bulk powders (Figure 3d). To analyze
results in the larger Stokes shift and lower temperature for these spectra, we have simulated the phonon density of states
thermal PL quenching. We note that the Seitz–Mott diagram plot at 300 K and identified the region where Sb and Br con-
also helps rationalizing other temperature-dependent proper- tribute the most, around 120–160 cm−1 (Figure S7, Supporting
ties in 0D metal halides, such as the homogeneous broadening Information). The experimental spectra of the ordered bulk
of PL and PLE bands (Figure S4, Supporting Information). and ordered film are quite similar and feature sharp peaks. On
An important difference exists between Sn-based thermal the contrary, fresh thin film spectra match best with the dis-
luminophores studied in the ref. [49] and the herein pre- ordered bulk phase, which along with the broadened Raman
sented Sb-based compounds, due to the more complex peaks and τ–T profile confirms the disordered state of the
excited state structure in the latter, which arises from the fresh film. As to the thermal performance, specific sensitivi-
nondegeneracy of the lowest unoccupied molecular orbital ties of the ordered film and disordered bulk are rather compa-
(LUMO) states in square pyramidal molecular geometry rable, spanning from 0.03 to 0.045 °C−1 in the ranges around
and exciton–phonon interactions.[47,68,77] TPP2SbBr5 exhibits RT (Figure S8, Supporting Information), which is at the higher
spectral variation in emission relaxation times (shorter end among those reported.[80]
relaxation times for shorter wavelengths and longer relaxa- Figure 4 demonstrates the ability of remote-optical thermog-
tion times for longer wavelengths, Figure S5a,c, Supporting raphy to achieve high spatial resolution. With confocal micros-
Information) and non-monoexponential behavior in the copy equipped with FLIM and having diffraction-limited reso-
traces detected in narrow spectral windows (Figure S5b, Sup- lution, the obtained thermographic resolution is determined
porting Information), as previously demonstrated for other by factors such as patterned feature size, heat distribution in
pnictogen halides.[78] the film, and the luminophore film thickness. A FLIM micro-
To test the TPP2SbBr5 as a thermal phosphor for high-spatial- scope acquires point-by-point lifetimes of the luminophore
resolution thermography, thin films were prepared by spin- film that, with high sensitivity, reproduces the sample surface
coating from the precursor solution containing TPPBr and temperature. Without a current passing through the ITO pat-
SbBr3 in an organic solvent (CH3CN or DCM). The best homo- tern, the sample temperature is homogenous, and a careful
geneity and uniformity can be achieved in the 150 nm thin film measurement allows for an estimate of the lifetime value
(Figure S6a,b, Supporting Information). Although very thin, distribution. The FWHM of this distribution (Figure S9, Sup-
such a film has sufficient absorbance (Figure S6c, Supporting porting Information) shows the pixel-to-pixel lifetime τ meas-
Information). The film can be coated on a wide range of sub- urement variation for the instrument and for our recording
strates including, but not limited to, glass, quartz, and silicon conditions (including spatial resolution and exposition time).
(see the Experimental Section for details). The as-prepared The resulting Δτ is about 2 ns, which is equivalent to about 1 K
film is close to the disordered phase from its optical proper- in ΔT as thermographic accuracy of our luminophores. When
ties, and the ordered phase can be achieved by annealing the a current passes through the pattern, it generates local heat
film at higher temperatures or by slow aging over more than (recorded in low spatial resolution by microbolometer camera
Adv. Mater. 2021, 33, 2007355 2007355 (4 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advmat.de
Figure 3. a) A schematic description of the TPP2SbBr5 phosphor disordered thin film (spin-coated from polar organic solvent) and its subsequent trans-
formation. The morphology of the film influences the outcome of the FLIM experiment: ordering of the thin film from annealing or aging is accompanied
by formation of grain boundaries which lower the spatial resolution. b) Optical microscopy image (in PL detection mode) of a homogenous 150 nm
thin film of TPP2SbBr5 (disordered phase) on a glass substrate and ITO resistive pattern. c) Lifetime–temperature dependence for the disordered thin
film of TPP2SbBr5. d) Raman spectra for ordered and disordered bulk and thin film samples. Highlighted are the peaks which mostly originate from Sb
and Br contribution in calculated phonon density of states.
on Figure 4a). Figure 4b–e compares the performance of both avoided through the use of a simple 1/e evaluation (Figure S12
disordered and ordered (obtained by thermal annealing) films and Note S1, Supporting Information).
in the FLIM experiment. The ordered film displays low spatial In conclusion, we demonstrate the untapped potential of Sb(III)
resolution due to large grains, which can also be seen in fluo- 0D hybrid ns2-metal halide organic–inorganic emitters as thermal
rescence images (Figure S10, Supporting Information). The phosphors for high-spatial-resolution thermography around RT
temperature-induced changes in the disordered film are much ranges. Thin-film Sb(III)-based phosphors do not suffer from
sharper (Figure 4e), as is also emphasized in Figure S11a instability in air (Figure S13, Supporting Information), as opposed
(Supporting Information), where the corresponding lifetime to Sn(II)-based ones, for which prevention of oxidation is para-
measurement distributions (red curve from Figure S11b, Sup- mount at all steps (preparation, deposition, and use). Thin films
porting Information) demonstrate the decrease of the emis- of such halides harness their high specific thermal sensitivity
sion relaxation times (more on the heating pattern, less in the (0.03–0.045 °C−1 for TPP2SbBr5) and allow for micrometer resolu-
surroundings of the patterned sample area). This is also dem- tion of thermography. On the example of TPP2SbBr5, this work
onstrated by the reversibility that is shown from the lifetime emphasizes the existence and necessitates the study of the differ-
distributions (blue and green curves from Figure S11b, Sup- ences in the structure and hence in the respective optical charac-
porting Information) recorded from a cold sample before and teristics that occur when transitioning from the bulk to thin-film
after heating. The spatial resolution of the imaged features forms of these soft halides. An unchartered research avenue is to
from Figure 4e, estimated with a Gaussian fit (Figure 4c), is attain higher spatial resolution using colloidal nanoparticles of
about 1 µm, far better than what can be achieved with remote STE-emissive materials. Eventually, a vast library of STE-emissive
detection of blackbody radiation at RT. metal halide phosphors, accessible through facile solution syn-
The non-monoexponential decay characteristics of thesis and processing, will provide an a la carte selection of a
TPP2SbBr5 add a degree of complexity to the analysis of PL suite of optical characteristics (PL and PLE bands, temperature
lifetimes in FLIM experiments, which can drastically increase sensitivity range, etc.) required for a specific thermometric and
the time required to process thermal images. This issue can be thermographic application and/or detection scheme.
Adv. Mater. 2021, 33, 2007355 2007355 (5 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advmat.de
Figure 4. a) Image of the TPP2SbBr5 disordered thin film on the glass substrate with resistive pattern with a conventional micrometer bolometer
camera. The inset image shows the bright-field light microscopy image of the small features to demonstrate the scale. b,c) Optical (PL mode) of the
disordered and ordered films of TPP2SbBr5 on the nonpatterned glass substrates, comparing the uniformity of the film. d,e) Confocal FLIM micros-
copy images of the disordered and ordered films of TPP2SbBr5 on the patterned ITO substrate with current running through the resistive pattern. The
ordered (disordered) film results in low (high) spatial resolution. f) The pixel intensity for a line scan across one of the heated features in (e); a spatial
resolution as high as about 1 µm can be estimated from a Gaussian fit.
Adv. Mater. 2021, 33, 2007355 2007355 (6 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advmat.de
Temperature dependences of PL and PLE spectra were acquired mode occupation of AIMD (each mode of energy ℏω features a thermal
with FluoTime 300 spectrometer from PicoQuant GmbH coupled with occupation according to kBT/ℏω) into a Bose–Einstein occupation. For
CS204, closed cycle helium cryostat, from Advanced Research Systems. the calculation of all phonon densities of states, care was taken to reach
Excitation was provided from Xe lamp (power of 300W) passed through sufficient thermal equilibration (typically within the first 3 ps) before
a monochromator and cut at emission monochromator with 400 nm analyzing the AIMD trajectory.
longpass filter. The temperature of the sample was ramped with a speed FLIM Thermography Imaging Experiment: As a heating element,
of 2 K min−1. Spectra were corrected on the spectral sensitivity of the a patterned ITO thin film on a 1 mm thick glass substrate was used.
detector and spectral power density of the lamp. The patterning was performed by a standard photolithography process.
Absolute values of PLQY were measured using a Quantaurus-QY Briefly, AZ5214E photoresist was spin-coated on the ITO-on-glass
spectrometer from Hamamatsu in powder mode. substrates, baked for 120 s at 90 °C, the structure was exposed (DWL66+
UV–vis absorbance spectra were obtained using the Kubelka–Munk by Heidelberg), baked for 120 s at 115 °C, the entire substrate was
transformation of diffuse reflectance of the microcrystalline powders exposed (MJB3 by Karl Süss), and the structure was developed with
that were collected using a Jasco V670 spectrophotometer equipped MF319 developer for 45 s and rinsed with water. The ITO was etched
with a deuterium (D2) lamp (190–350 nm) for UV, a halogen lamp with 10% hydrochloric acid solution for 30 s, rinsed with water, and the
(330–2700 nm) for UV–NIR, and an integrating sphere (ILN-725) with a remaining resist was stripped with acetone and rinsed with 2-propanol.
working wavelength range of 220–2200 nm. The heat distribution in the obtained ITO pattern was checked
Optical absorption of thin films was measured with Jasco V770 by a LWIR camera: Seek Thermal Compact Pro customized with a
equipped with integrating sphere ISN-923. The sample was placed in homemade ZnSe lensed macro-objective made according to the project
front of integrating sphere to reduce influence of scattering. Absorption https://www.thingiverse.com/thing:525605.
coefficient was recalculated from thickness of the film, which was Thin films in a range 150–650 nm were spin-coated from acetonitrile
measured using stylus profilometer (D-120 by KLA Tencor). 100 mg mL−1 precursor according to the procedure described above. The
Raman spectra were measured using a Horiba LabRAM HR Evolution current through the ITO pattern was provided by Keithley 236 Source-
confocal microscope. An objective (100× magnification, NA = 0.9) was Measure Unit in the voltage stabilization mode. Picosecond laser with
used to induce and collect Raman scattered light from micrometer-scale wavelength of 440 nm and repetition rate of 2.5 MHz was applied for the
regions of the samples, using laser excitation at 785 nm (cw, 30 mW). No excitation of thermography images. The FLIM imaging was performed
sample degradation was observed during or after the typical acquisition with a Leica TCS SP8 confocal microscope coupled to PicoHarp
time of ≈100 s. 300 TCSPC and Leica SP8 FALCON FLIM modules. Both modules after
Scanning electron microscopy was carried out at FEI Quanta 200F optimization of scanning speed and exposure time parameters provided
FEG-SEM (Thermo Fischer Scientific) at an acceleration voltage of 20 kV similar results in the thermographic accuracy.
in secondary electron detection mode.
Simulation Details: The excited state geometry calculations were
carried out at the density functional theory level as implemented in the Supporting Information
open-source CP2K[83] quantum chemistry code. A single crystallographic
unit cell was used. For the disordered phase, the occupancy of one of Supporting Information is available from the Wiley Online Library or
the axial Bromine atoms (irrespective of which one as both positions from the author.
are related by the inversion center) was set to 100% and the other to
0%. A mixed plane-wave and Gaussian basis set approach was used
to describe the wave function and electronic density, respectively. The Acknowledgements
kinetic energy cutoff of the plane-wave basis was set to 400 Rydberg,
while a double-ζ basis set with polarization functions was used to The authors are indebted to Dr. Michael Wörle for assistance with
describe the molecular orbitals. Scalar relativistic effects were accounted crystal structure solution, Dr. Frank Krumeich for electron microscopy,
for by using effective core potential functions in the basis set. Spin–orbit Dr. Markus Suta for valuable discussions and Debora Thöny for assisting
coupling effects were not included. Calculations with lattice relaxation with thermogravimetric analysis. The authors acknowledge the support of
for the ground state geometry optimization were performed to account the Scientific Center for Optical and Electron Microscopy (ScopeM) of the
for statistical disorder in the experimental crystal structures. Unit cell Swiss Federal Institute of Technology (ETHZ) for the Raman spectroscopy
parameters were taken from experimental data and not relaxed, whereas measurements. Numerical simulations were performed on the ETH
atomic coordinates were optimized until the force reached 0.023 eV Å−1. Zürich Euler cluster. This work was financially supported by the European
For the excited state geometry, the unrestricted Kohn-Sham approach Union through Horizon 2020 research and innovation programme (ERC
with a triplet multiplicity was used, unit cell was not optimized, while Consolidator Grant SCALE-HALO, Grant Agreement No. 819740), Swiss
atomic coordinates were optimized until the force reached 0.023 eV Å−1. National Science Foundation (Project “Novel inorganic light emitters:
The phonon density of states g(ω) at 300 K was analyzed via the synthesis, spectroscopy and applications,” Grant Agreement No. 188404),
CP2K computational package and the TRAVIS analyzer.[84,85] Briefly, g(ω) and by The Netherlands Organization of Scientific Research (NWO) via
and the several partial phonon densities of states gi(ω) for selected the Innovational Research Incentives (Veni) Scheme (Project “Heating
subgroups i (i = Sb, Br, organic moiety) were obtained from the mass- and cooling at the nanoscale,” Grant Agreement No. 722.017.011).
weighted Fourier transformation of an ab initio molecular dynamics
(AIMD) trajectory at 300 K (within the NPT ensemble, a velocity
rescaling thermostat with time constant of 50 fs was used) according to Conflict of Interest
The authors declare no conflict of interest.
g i (ω ) = miω 2 F {ri ( t )} b (ω ,T )(1)
2
b (ω ,T ) =
ω
(
kBT ) −1
1+ e ω /(kBT ) − 1 (2)
Keywords
metal halide luminescence, remote thermography, thermographic
phosphors
g (ω ) = ∑g i (ω ) (3)
i
Received: October 27, 2020
where F {ri(t )} denotes a Fourier transformation of the position Revised: December 13, 2020
correlation function ri(t) and the term b(ω, T) converts the semiclassical Published online: January 22, 2021
Adv. Mater. 2021, 33, 2007355 2007355 (7 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advmat.de
[1] C. F. Chapman, Y. Liu, G. J. Sonek, B. J. Tromberg, Photochem. [34] Z. F. Tan, J. H. Li, C. Zhang, Z. Li, Q. S. Hu, Z. W. Xiao, T. Kamiya,
Photobiol. 1995, 62, 416. H. Hosono, G. D. Niu, E. Lifshitz, Y. B. Cheng, J. Tang, Adv. Funct.
[2] C. L. Wang, R. Z. Xu, W. J. Tian, X. L. Jiang, Z. Y. Cui, M. Wang, Mater. 2018, 28, 1801131.
H. M. Sun, K. Fang, N. Gu, Cell Res. 2011, 21, 1517. [35] C. K. Zhou, H. R. Lin, H. L. Shi, Y. Tian, C. Pak, M. Shatruk, Y. Zhou,
[3] C. Gosse, C. Bergaud, P. Low, in Thermal Nanosystems and P. Djurovich, M. H. Du, B. W. Ma, Angew. Chem., Int. Ed. 2018, 57,
Nanomaterials, Vol. 118 (Ed: S. Volz), Springer, Heidelberg, Germany 1021.
2009, Ch. 10. [36] Y. Y. Jing, Y. Liu, J. Zhao, Z. G. Xia, J. Phys. Chem. Lett. 2019, 10, 7439.
[4] E. M. Graham, K. Iwai, S. Uchiyama, A. Prasanna de Silva, [37] A. S. Kshirsagar, A. Nag, J. Chem. Phys. 2019, 151, 161101.
S. W. Magennis, A. C. Jones, Lab Chip 2010, 10, 1267. [38] M. Z. Li, J. Zhou, G. J. Zhou, M. S. Molokeev, J. Zhao, V. Morad,
[5] W. J. Liu, B. Z. Yang, Sens. Rev. 2007, 27, 298. M. V. Kovalenko, Z. G. Xia, Angew. Chem., Int. Ed. 2019, 58, 18670.
[6] S. W. Allison, G. T. Gillies, 2011 Future of Instrumentation Int. Work- [39] S. R. Li, J. J. Luo, J. Liu, J. Tang, J. Phys. Chem. Lett. 2019, 10, 1999.
shop (FIIW) Proc., IEEE, Piscataway, NJ, USA 2011, pp. 48–51, https:// [40] V. Morad, Y. Shynkarenko, S. Yakunin, A. Brumberg, R. D. Schaller,
doi.org/10.1109/FIIW.2011.6476833. M. V. Kovalenko, J. Am. Chem. Soc. 2019, 141, 9764.
[7] M. D. Dramicanin, Methods Appl. Fluoresc. 2016, 4, 042001. [41] R. Roccanova, A. Yangui, H. Nhalil, H. Shi, M.-H. Du, B. Saparov,
[8] G. Kucsko, P. C. Maurer, N. Y. Yao, M. Kubo, H. J. Noh, P. K. Lo, ACS Appl. Electron. Mater. 2019, 1, 269.
H. Park, M. D. Lukin, Nature 2013, 500, 54. [42] R. Roccanova, A. Yangui, G. Seo, T. D. Creason, Y. T. Wu, D. Y. Kim,
[9] T. E. Beechem, R. A. Shaffer, J. Nogan, T. Ohta, A. B. Hamilton, M. H. Du, B. Saparov, ACS Mater. Lett. 2019, 1, 459.
A. E. McDonald, S. W. Howell, Sci. Rep. 2016, 6, 26457. [43] C. K. Zhou, H. R. Lin, J. Neu, Y. Zhou, M. Chaaban, S. Lee,
[10] M. Mecklenburg, W. A. Hubbard, E. R. White, R. Dhall, S. B. Cronin, M. Worku, B. H. Chen, R. Clark, W. H. Cheng, J. J. Guan,
S. Aloni, B. C. Regan, Science 2015, 347. P. Djurovich, D. Z. Zhang, X. J. Lu, J. Bullock, C. Pak, M. Shatruk,
[11] J. H. Xiong, M. S. Zhao, X. T. Han, Z. M. Cao, X. T. Wei, Y. H. Chen, M. H. Du, T. Siegrist, B. W. Ma, ACS Energy Lett. 2019, 4, 1579.
C. K. Duan, M. Yin, Sci. Rep. 2017, 7, 41311. [44] S. J. Lee, C. K. Zhou, J. Neu, D. Beery, A. Arcidiacono, M. Chaaban,
[12] J. Christofferson, K. Maize, Y. Ezzahri, J. Shabani, X. Wang, H. R. Lin, A. Gaiser, B. H. Chen, T. E. Albrecht-Schmitt, T. Siegrist,
A. Shakouri, J. Electron. Packag. 2008, 130, 1101. B. W. Ma, Chem. Mater. 2020, 32, 374.
[13] C. D. S. Brites, P. P. Lima, N. J. O. Silva, A. Millan, V. S. Amaral, [45] D. Han, H. L. Shi, W. M. Ming, C. K. Zhou, B. W. Ma, B. Saparov,
F. Palacio, L. D. Carlos, Nanoscale 2012, 4, 4799. Y. Z. Ma, S. Y. Chen, M. H. Du, J. Mater. Chem. C 2018, 6, 6398.
[14] M. Dramićanin, in Luminescence Thermometry (Eds: M. Dramićanin), [46] X. M. Wang, W. W. Meng, W. Q. Liao, J. B. Wang, R. G. Xiong,
Woodhead Publishing, Sawston, UK 2018, Ch. 4. Y. F. Yan, J. Phys. Chem. Lett. 2019, 10, 501.
[15] S. W. Allison, G. T. Gillies, Rev. Sci. Instrum. 1997, 68, 2615. [47] K. M. McCall, V. Morad, B. M. Benin, M. V. Kovalenko, ACS Mater.
[16] P. Kolodner, J. A. Tyson, Appl. Phys. Lett. 1983, 42, 117. Lett. 2020, 2, 1218.
[17] J. Brübach, T. Kissel, M. Frotscher, M. Euler, B. Albert, A. Dreizler, [48] M. Worku, Y. Tian, C. K. Zhou, S. Lee, Q. Meisner, Y. Zhou,
J. Lumin. 2011, 131, 559. B. W. Ma, ACS Appl. Mater. Interfaces 2018, 10, 30051.
[18] A. P. Herrera, M. Rodríguez, M. Torres-Lugo, C. Rinaldi, J. Mater. [49] S. Yakunin, B. M. Benin, Y. Shynkarenko, O. Nazarenko,
Chem. 2008, 18, 855. M. I. Bodnarchuk, D. N. Dirin, C. Hofer, S. Cattaneo,
[19] C. E. Estrada-Perez, Y. A. Hassan, S. C. Tan, Rev. Sci. Instrum. 2011, M. V. Kovalenko, Nat. Mater. 2019, 18, 846.
82, 4901. [50] A. Esposito, T. Oggier, H. C. Gerritsen, F. Lustenberger,
[20] G. W. Walker, V. C. Sundar, C. M. Rudzinski, A. W. Wun, F. S. Wouters, Opt. Express 2005, 13, 9812.
M. G. Bawendi, D. G. Nocera, Appl. Phys. Lett. 2003, 83, 3555. [51] M. Raspe, K. M. Kedziora, B. van den Broek, Q. Zhao, S. de Jong,
[21] X. D. Wang, O. S. Wolfbeis, R. J. Meier, Chem. Soc. Rev. 2013, 42, J. Herz, M. Mastop, J. Goedhart, T. W. J. Gadella, I. T. Young,
7834. K. Jalink, Nat. Methods 2016, 13, 501.
[22] J. Brubach, C. Pflitsch, A. Dreizler, B. Atakan, Prog. Energy Combust. [52] V. Morad, S. Yakunin, M. V. Kovalenko, ACS Mater. Lett. 2020, 2, 845.
Sci. 2013, 39, 37. [53] B. V. Bukvetskii, T. V. Sedakova, A. G. Mirochnik, J. Struct. Chem.
[23] P. Low, B. Kim, N. Takama, C. Bergaud, Small 2008, 4, 908. 2009, 50, 322.
[24] K. M. Schreiter, T. Glawdel, J. A. Forrest, C. L. Ren, RSC Adv. 2013, [54] D. Chen, F. Dai, S. Hao, G. Zhou, Q. Liu, C. M. Wolverton, J. Zhao,
3, 17236. Z. Xia, J. Mater. Chem. C 2020, 8, 7322.
[25] A. Nakano, J. H. Luo, A. Ros, Anal. Chem. 2014, 86, 6516. [55] P. W. M. Jacobs, J. Phys. Chem. Solids 1991, 52, 35.
[26] R. Reisfeld, L. Boehm, B. Barnett, J. Solid State Chem. 1975, 15, 140. [56] K. M. McCall, C. C. Stoumpos, S. S. Kostina, M. G. Kanatzidis,
[27] E. R. Dohner, A. Jaffe, L. R. Bradshaw, H. I. Karunadasa, J. Am. B. W. Wessels, Chem. Mater. 2017, 29, 4129.
Chem. Soc. 2014, 136, 13154. [57] A. G. Mirochnik, T. V. Sedakova, Y. M. Nikolenko, V. E. Karasev,
[28] Z. Yuan, C. K. Zhou, Y. Tian, Y. Shu, J. Messier, J. C. Wang, J. Struct. Chem. 2006, 47, 247.
L. J. van de Burgt, K. Kountouriotis, Y. Xin, E. Holt, K. Schanze, [58] E. W. J. L. Oomen, W. M. A. Smit, G. Blasse, Chem. Phys. Lett. 1984,
R. Clark, T. Siegrist, B. W. Ma, Nat. Commun. 2017, 8, 14051. 112, 547.
[29] B. M. Benin, D. N. Dirin, V. Morad, M. Worle, S. Yakunin, G. Raino, [59] E. W. J. L. Oomen, W. M. A. Smit, G. Blasse, Chem. Phys. Lett. 1987,
O. Nazarenko, M. Fischer, I. Infante, M. V. Kovalenko, Angew. 138, 23.
Chem., Int. Ed. 2018, 57, 11329. [60] N. V. Petrochenkova, T. V. Storozhuk, A. G. Mirochnik, V. E. Karasev,
[30] P. F. Fu, M. L. Huang, Y. Q. Shang, N. Yu, H. L. Zhou, Y. B. Zhang, Russ. J. Coord. Chem. 2002, 28, 468.
S. Y. Chen, J. K. Gong, Z. J. Ning, ACS Appl. Mater. Interfaces 2018, [61] T. V. Sedakova, A. G. Mirochnik, Russ. J. Phys. Chem. A 2017, 91, 791.
10, 34363. [62] T. V. Sedakova, A. G. Mirochnik, V. E. Karasev, Opt. Spectrosc. 2008,
[31] H. R. Lin, C. K. Zhou, Y. Tian, T. Siegrist, B. W. Ma, ACS Energy Lett. 105, 517.
2018, 3, 54. [63] F. Seitz, J. Chem. Phys. 1938, 6, 454.
[32] L. L. Mao, P. J. Guo, M. Kepenekian, I. Hadar, C. Katan, J. Even, [64] Z. P. Wang, Z. Z. Zhang, L. Q. Tao, N. N. Shen, B. Hu, L. K. Gong,
R. D. Schaller, C. C. Stoumpos, M. G. Kanatzidis, J. Am. Chem. Soc. J. R. Li, X. P. Chen, X. Y. Huang, Angew. Chem., Int. Ed. 2019, 131, 9974.
2018, 140, 78. [65] C. Zhou, S. Lee, H. Lin, J. Neu, M. Chaaban, L.-J. Xu, A. Arcidiacono,
[33] N. N. Shen, M. L. Cai, Y. Song, Z. P. Wang, F. Q. Huang, J. R. Li, Q. He, M. Worku, L. Ledbetter, X. Lin, J. A. Schlueter, T. Siegrist,
X. Y. Huang, Inorg. Chem. 2018, 57, 5282. B. Ma, ACS Mater. Lett. 2020, 2, 376.
Adv. Mater. 2021, 33, 2007355 2007355 (8 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advmat.de
[66] C. K. Zhou, H. R. Lin, Y. Tian, Z. Yuan, R. Clark, B. H. Chen, L. J. van [77] A. Noculak, V. Morad, K. M. McCall, S. Yakunin, Y. Shynkarenko,
de Burgt, J. C. Wang, Y. Zhou, K. Hanson, Q. J. Meisner, J. Neu, M. Wörle, M. V. Kovalenko, Chem. Mater. 2020, 32, 5118.
T. Besara, T. Siegrist, E. Lambers, P. Djurovich, B. W. Ma, Chem. Sci. [78] B. M. Benin, K. M. McCall, M. Worle, V. Morad, M. Aebli,
2018, 9, 586. S. Yakunin, Y. Shynkarenko, M. V. Kovalenko, Angew. Chem., Int. Ed.
[67] J. Zhou, M. Li, M. S. Molokeev, J. Sun, D. Xu, Z. Xia, J. Mater. Chem. 2020, 59, 14490.
C 2020, 8, 5058. [79] J. E. Thomaz, K. P. Lindquist, H. I. Karunadasa, M. D. Fayer, J. Am.
[68] A. Vogler, H. Nikol, Comments Inorg. Chem. 1993, 14, 245. Chem. Soc. 2020, 39, 16622.
[69] C. K. Zhou, M. Worku, J. Neu, H. R. Lin, Y. Tian, S. J. Lee, Y. Zhou, [80] O. A. Savchuk, P. Haro-Gonzalez, J. J. Carvajal, D. Jaque,
D. Han, S. Y. Chen, A. Hao, P. I. Djurovich, T. Siegrist, M. H. Du, J. Massons, M. Aguilo, F. Diaz, Nanoscale 2014, 6, 9727.
B. W. Ma, Chem. Mater. 2018, 30, 2374. [81] G. M. Sheldrick, Acta Crystallogr., Sect. C 2015, 71, 3.
[70] Z. Y. Li, Y. Li, P. Liang, T. L. Zhou, L. Wang, R. J. Xie, Chem. Mater. [82] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard,
2019, 31, 9363. H. Puschmann, J. Appl. Crystallogr. 2009, 42, 339.
[71] N. N. Shen, J. Li, G. Li, B. Hu, J. R. Li, T. Q. Liu, L. K. Gong, [83] T. D. Kuhne, M. Iannuzzi, M. Del Ben, V. V. Rybkin, P. Seewald,
F. Q. Huang, Z. P. Wang, X. Y. Huang, Inorg. Chem. 2019, 58, F. Stein, T. Laino, R. Z. Khaliullin, O. Schutt, F. Schiffmann, D. Golze,
8079. J. Wilhelm, S. Chulkov, M. H. Bani-Hashemian, V. Weber, U. Borstnik,
[72] G. M. Song, M. Z. Li, S. Z. Zhang, N. Z. Wang, P. F. Gong, Z. G. Xia, M. Taillefumier, A. S. Jakobovits, A. Lazzaro, H. Pabst, T. Muller,
Z. S. Lin, Adv. Funct. Mater. 2020, 30, 2002468. R. Schade, M. Guidon, S. Andermatt, N. Holmberg, G. K. Schenter,
[73] N. N. Shen, Z. P. Wang, J. Jin, L. K. Gong, Z. Z. Zhang, X. Y. Huang, A. Hehn, A. Bussy, F. Belleflamme, G. Tabacchi, A. Gloss, M. Lass,
CrystEngComm 2020, 22, 3395. I. Bethune, C. J. Mundy, C. Plessl, M. Watkins, J. VandeVondele,
[74] B. Su, G. Song, M. S. Molokeev, Z. Lin, Z. Xia, Inorg. Chem. 2020, M. Krack, J. Hutter, J. Chem. Phys. 2020, 152, 194103.
59, 9962. [84] M. Brehm, B. Kirchner, J. Chem. Inf. Model 2011, 51, 2007.
[75] A. G. Paulusz, J. Lumin. 1978, 17, 375. [85] M. Brehm, M. Thomas, S. Gehrke, B. Kirchner, J. Chem. Phys. 2020,
[76] G. Blasse, J. Solid State Chem. 1974, 9, 147. 152, 164105.
Adv. Mater. 2021, 33, 2007355 2007355 (9 of 9) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH