Characterization of Nanomaterials

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Surface characterization of nanomaterials and nanoparticles: Important

needs and challenging opportunities
Article in Journal of Vacuum Science & Technology A Vacuum Surfaces and Films · September 2013
DOI: 10.1116/1.4818423 · Source: PubMed
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Surface characterization of nanomaterials and nanoparticles: Important needs and
challenging opportunities
Donald R. Baer, Mark H. Engelhard, Grant E. Johnson, Julia Laskin, Jinfeng Lai, Karl Mueller, Prabhakaran
Munusamy, Suntharampillai Thevuthasan, Hongfei Wang, Nancy Washton, Alison Elder, Brittany L. Baisch, Ajay
Karakoti, Satyanarayana V. N. T. Kuchibhatla, and DaeWon Moon
Citation: Journal of Vacuum Science & Technology A 31, 050820 (2013); doi: 10.1116/1.4818423
View online: http://dx.doi.org/10.1116/1.4818423
View Table of Contents: http://scitation.aip.org/content/avs/journal/jvsta/31/5?ver=pdfcov
Published by the AVS: Science & Technology of Materials, Interfaces, and Processing
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REVIEW ARTICLE
Surface characterization of nanomaterials and nanoparticles: Important

needs and challenging opportunities
Donald R. Baer,a) Mark H. Engelhard, Grant E. Johnson, Julia Laskin, Jinfeng Lai,
Karl Mueller, Prabhakaran Munusamy, Suntharampillai Thevuthasan, Hongfei Wang,
and Nancy Washton
Pacific Northwest National Laboratory, EMSL, P.O. Box 999, Richland, Washington 99352
Alison Elder and Brittany L. Baisch
Department of Environmental Medicine, University of Rochester, Rochester, New York
Ajay Karakoti and Satyanarayana V. N. T. Kuchibhatla
Battelle Science and Technology India, Pune, Maharashtra, India
DaeWon Moon
Daegu Gyeongbuk Institute of Science and Technology, Daeju, Korea
(Received 20 April 2013; accepted 25 July 2013; published 27 August 2013)
This review examines characterization challenges inherently associated with understanding
nanomaterials and the roles surface and interface characterization methods can play in meeting
some of the challenges. In parts of the research community, there is growing recognition that
studies and published reports on the properties and behaviors of nanomaterials often have reported
inadequate or incomplete characterization. As a consequence, the true value of the data in these
reports is, at best, uncertain. With the increasing importance of nanomaterials in fundamental
research and technological applications, it is desirable that researchers from the wide variety of
disciplines involved recognize the nature of these often unexpected challenges associated with
reproducible synthesis and characterization of nanomaterials, including the difficulties of
maintaining desired materials properties during handling and processing due to their dynamic
nature. It is equally valuable for researchers to understand how characterization approaches
(surface and otherwise) can help to minimize synthesis surprises and to determine how (and how
quickly) materials and properties change in different environments. Appropriate application of
traditional surface sensitive analysis methods (including x-ray photoelectron and Auger electron
spectroscopies, scanning probe microscopy, and secondary ion mass spectroscopy) can provide
information that helps address several of the analysis needs. In many circumstances, extensions of
traditional data analysis can provide considerably more information than normally obtained from
the data collected. Less common or evolving methods with surface selectivity (e.g., some
variations of nuclear magnetic resonance, sum frequency generation, and low and medium energy
ion scattering) can provide information about surfaces or interfaces in working environments
(operando or in situ) or information not provided by more traditional methods. Although these
methods may require instrumentation or expertise not generally available, they can be particularly
useful in addressing specific questions, and examples of their use in nanomaterial research are
presented. VC 2013 American Vacuum Society. [http://dx.doi.org/10.1116/1.4818423]
I. INTRODUCTION address important issues, such as product lifetimes and ques-

tions that are relevant to occupational and public health.
It is increasingly recognized that nanomaterials present a
range of characterization challenges that have the potential Concerns related to adequate characterization of nanomateri-
to inhibit or delay the scientific and technological impact of als are not new, and a variety of issues have been highlighted
by many research groups, multiorganizational teams of
nanoscience and nanotechnology. The incomplete character-
ization and under-reporting of data needed for reproducing researchers, and the scientific press.2,3,7–12 Challenges to
and validating experimental findings1–6 involving nanomate- appropriate characterization of many types of nanomaterials
create frustration for researchers and engineers who would
rials limits scientific understanding, slows the development
of new technologies, and makes it difficult to reliably like to either use them for biomedical, energy, or other appli-
cations, as well as for regulatory bodies that need to under-
stand their impact on human health and the environment.1
a)
Electronic mail: [email protected] The incomplete characterization reports on many materials
050820-1 J. Vac. Sci. Technol. A 31(5), Sep/Oct 2013 0734-2101/2013/31(5)/050820/34/$30.00 C 2013 American Vacuum Society
V 050820-1
050820-2 Baer et al.: Surface characterization of nanomaterials and nanoparticles 050820-2
are viewed by some as a significant failure on the part of the Kingdom. In 2000, then U.S. President Bill Clinton
scientific community.2 announced the U.S. National Nanotechnology Initiative
There are several reasons why complete nanomaterial (NNI), and Congress subsequently enacted the 21st Century
characterization is not achieved, despite the inherent desire Nanotechnology Research and Development Act in 2003,
of most research groups to do high-quality research. First, which significantly expanded the research focus and financial
nanomaterials present some unique preparation and analysis support in the area. A 2010 World Technology Evaluation
difficulties (described in following sections) that are new to Center (WTEC.org) and National Science Foundation (NSF)
some of the disciplines and researchers now involved in report, “Nanotechnology Research Directions for Societal
nanomaterials-related research. Second, because of the mul- Needs in 2020,”17 assessed the impacts of nanotechnology
tidisciplinary nature of the field, not every research team has from 2000 to 2010 and looked toward the future. Quite appro-
access to the range of characterization tools needed to obtain priately, the report highlighted both the numbers of nanotech-
potentially important information. Third, the range of infor- nology patent applications (growing from 224 in 1991 to
mation needed to understand nanomaterials may require the nearly 13,000 in 2008) and the market size of products
application of tools and data analysis beyond the expertise involving nanotechnology (approximately $91 billion in
of the research teams, sometimes leading to less-than- 2009). The report also notes that nanotechnology has pene-
optimum application of important methods and/or incom- trated “most production sectors of the economy” and is used
plete understanding of the data produced. Nanoscience and in a wide range of commercial products, “including coatings,
nanotechnology are relatively immature fields, and the industrial chemicals, cosmetics, textiles, and magnetic storage
research community is just beginning to understand some of devices, among many others.”17 The report concludes that
the limitations of analytical approaches that have been suc- future impacts will be both greater and more revolutionary
cessfully applied in other areas.13 As understanding evolves, than what has been observed to date.
improvements to established methodologies, new technolo- As expected, the number of publications related to nano-
gies, and approaches are being developed. Thus, most of the technology mirrors the historical time line. Results from a
sample preparation and characterization challenges can be Web of Science search combining the terms “nanomaterial,”
addressed to differing degrees, especially when they are rec- “nanoparticle,” and “nanostructure” show dramatic growth in
ognized at the outset. After exploring the nature and causes published papers (Fig. 1), from less than 100 in 1990 to
of some of the analytical challenges, we consider the ability almost 45,000 in 2011. Similarly, nanotechnology plays a sig-
of current- and next-generation surface analysis tools and nificant role in many technical societies and has spawned new
developing capabilities to address some of the seemingly ones, as well as several journals focused on all things “nano.”
daunting materials characterization issues. Nanotechnology within the American Vacuum Society (AVS)
Although we focus much attention on engineered nano- follows a similar time line. The AVS Nanoscience and
particles, many of the characterization challenges apply Nanotechnology Division was established in 1993. Since
equally to other natural and engineered nanomaterials, as 1995, program activities specifically identified as “nano” have
well as to areas such as atmospheric aerosols.14 In the first had a continuous presence in the annual AVS Symposium. By
section, we highlight the need for the characterization of 1995, 5% of the papers in the Journal of Vacuum Science and
nanomaterials by showing the large and increasing impact of Technology (JVST) A and JVST B were topically related to
nanoscience and nanotechnology on science and technology “nano” in some way with about 2% of the papers related to
around the world. The section after examines the challenges nanomaterials. Nano-related work in JVST grew at a nearly
associated with nanomaterial characterization. In later sec- linear rate until 2003 when new NNI funding began appearing
tions, we explore the roles that traditional surface analysis in significant amounts, and growth accelerated. By the end of
methods can play in addressing analysis problems and show,
by example, a few other methods that address questions
related to characterizing nanomaterial interfaces in working
environments (in situ) and determining the uniformity of
coatings (intentional or accidental) on nanoparticles. The
discussion and conclusion sections make recommendations,
indicating approaches for overcoming synthesis and charac-
terization challenges.
II. IMPACT OF NANOSCIENCE

AND NANOTECHNOLOGY
The origin of nanotechnology usually is associated with a
1959 lecture by Richard Feyman.15 Possibly, the first use of
the term “nanotechnology” in the scientific literature was in a
1974 paper involving “ion-sputter machining” by Taniguchi.16
FIG. 1. (Color online) All “nanomaterials” publications identified by a Web
The first nanotechnology journal, Nanotechnology, was of Science topic search (including: nanomaterials AND nanoparticles AND
launched in 1990 by the Institute of Physics in the United nanostructure) by year.
J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013
diminish the ability to assess the impact of these materials

on the environment or their health and safety implications.
These characterization challenges are readily noted in
papers, such as “Common pitfalls in nanotechnology…,”23
“The characterization bottleneck,”1 and “Discriminating the
states of matter in metallic nanoparticle transformations:
What are we missing?,”24 and in scientific news articles,
such as “Tiny traits cause big headaches….”2 The nature of
some of these “headaches” is described in the next section.
III. NANOMATERIAL CHARACTERIZATION

SURPRISES
Research on the synthesis and properties of a range of
nanomaterials takes place in the Environmental Molecular
FIG. 2. (Color online) Percentage of publications in JVST A and B that Sciences Laboratory (EMSL), a national scientific user facil-
include “nano” as a topic, 䉬 as identified in the Web of Science and those
focused on nanomaterials 䉱. ity sponsored by the U.S. Department of Energy’s Office of
Biological and Environmental Research (DOE-BER) and
located at Pacific Northwest National Laboratory (PNNL),
and the authors of this review paper have been associated
2011, nearly 40% of all JVST publications were linked to the
with EMSL as staff members, research partners, or users.
key word “nano” in some way with about 15% identified as
We have found that appropriate characterization of nanoma-
nanomaterial related using the three search terms described
terials can be more difficult and, in many circumstances,
earlier (Fig. 2).
more interesting than expected. Because of our long-term in-
The focus on things “nano” in the AVS and other soci-
terest in the interactions of iron-25–28 and cerium-based29–32
eties occurs not only because we now have the label “nano”
nanoparticles in a variety of environments, many of the
and due to significant funding in areas labeled nanotechnol-
examples shown herein are directly derived from our work
ogy, but the work we now call “nanotechnology” is part of a
on these materials. The issues that have impacted our
natural progression in many different areas of science
research are similar to those identified in a variety of studies
coupled with development of new tools that enable research-
on other materials systems.
ers to see, model, and control structures at the nanometer
Nanomaterials can take a variety of forms, including free-
scale.18–20 Although, in many ways, nanotechnology is not
standing nano-objects (such as nanoparticles and carbon
new, experimental and computational tool development ena-
nanotubes), materials with nano-sized holes (including po-
bles research to be done that was not previously possible.
rous films), and other types of materials with a variety of dif-
New approaches can be taken to address previously intracta-
ferent nanoscale structures (such as nanometer-thick layered
ble problems. Therefore, nanoscience and nanotechnology
structures). Many of the examples in this paper focus on
do not represent a new discipline, but rather advancements
behaviors and properties of nanoparticles. However, the
within several disciples and a convergence of concepts and
detailed characterization of other types of nanomaterials of-
ideas across disciplines.19 As such, nanotechnology introdu-
ten has produced results that have surprised the researchers
ces important new ideas and cross-fertilization that enables
involved in this study (described in the next section). These
scientific breakthroughs and development of various new
and other examples from the literature are used to identify
technologies.
some of the common issues and challenges that should be
The productive cross-fertilization of multiple disciplines
considered whenever analyzing nanomaterials.
also places new demands on research teams by requiring an
expanded range of scientific, analytical, and other skills that
are not always readily available. In addition, the fundamen- A. Inconsistent behaviors and disappearing
tal nature of nanomaterials introduces characterization particles—cerium oxide nanoparticles
issues that are not routinely addressed by many analytical Ceria (CeO2) is used in a variety of applications, includ-
tools.7,11,13 The same characteristics of nanomaterials that ing functioning as a catalyst and catalyst support,33 serving
make them scientifically interesting actually cause some of as an antioxidant in medical treatment,34,35 and having good
the analysis challenges. Nanoparticles have a physical size ion conductivity that might prove useful for solid oxide fuel
characteristic of biological molecules,21 and, in some ways, cells.36 For some applications, one of ceria’s important prop-
they can be described as having protein-like properties.7,22 erties is the ease at which Ce can switch oxidation states
Similar to biological molecules, nanoparticles also may between þ3 and þ4. Several studies suggest that as ceria
change their structure and properties, depending upon the particles decrease in size, the dominant chemical state of Ce
physical environment.7 Particles may undergo structural in the particles changes from þ4 to þ3.37
transformation, dissolve, agglomerate, or pick up coatings in Unfortunately, published reports regarding ceria nanopar-
different environments. These behaviors complicate the abil- ticles report properties that often contradict one another.32
ity to identify and predict properties of these materials and We were interested in the sources of variability in measured
JVST A - Vacuum, Surfaces, and Films
band gaps for particles of similar size32 and the range of con- oxidation state of ceria particles responds to the environ-
flicting reports on the toxicity of ceria in biological sys- ment, changing from þ3 to þ4 [Fig. 3(b)] when an oxidizing
tems.30 As summarized herein, our studies have shown that agent is added and slowly reverting back to þ3 as the solu-
particle properties can be changed by variations in environ- tion ages and the oxidizing condition of the solution
mental conditions, the synthesis routes used to create the changes. Furthermore, it was shown that the rate of change
particles, and even seemingly inconsequential changes in depended on the composition of the media in which the par-
well-established synthesis or sample handling processes. ticles were synthesized or suspended. For example, in a
study of the effects of polyhydroxyls added to an aqueous
1. Environmental and time-dependent properties solution, the kinetics of switching of oxidation states in solu-
tion was observed to be slower in basic medium compared to
Until recently, many reports regarding nanoparticle prop- acidic medium.29 Taken together, these results suggest that
erties in the early literature assumed that their physicochemi-
some of the inconsistencies in particle properties reported in
cal properties remained relatively constant after they the literature may be related to the differing synthesis, proc-
formed. In contrast, we found that the chemical properties of essing, and environmental conditions experienced by par-
3- to 10-nm ceria particles suspended in aqueous solution
ticles in the different studies.
changed depending on the nature of the solution and aging
time32 [shown in Fig. 3(a)]. This work demonstrated that the
2. Contradictory biological impacts
Different research reports in the literature indicate ceria
nanoparticles to be oxidative or antioxidative in biological
systems and to be toxic or benign depending on the particle
or the biological test conducted. We examined the literature
to explore the hypothesis that some of these apparently con-
tradictory results might be due to particles differences.
Although some of the published reports were too incomplete
for an adequate evaluation, it was possible to determine that
fundamentally different synthesis and processing routes were
taken to produce the ceria particles used in different studies.
Many of the ceria nanoparticles fit into one of three catego-
ries: (1) particles produced in solution at room tempera-
ture,34,38,39 (2) those produced by thermal hydrolysis (in the
presence of various solvents/oxidizing conditions) involving
heating of particles in solution,40–42 and (3) others synthe-
sized by a variety of elevated temperature processes43–45 that
involve either no solution or heating particles to elevated
temperatures after synthesis (Fig. 4).
When these synthesis routes were linked to the biological
endpoints, it was found that in solution-based synthesis proc-
esses not involving heating produced particles that often
were either nontoxic or antioxidative. Meanwhile, particles
that had been heated to elevated temperatures were more
likely to have undesirable effects (Fig. 5).30 Heating is likely
to influence a variety of particle properties, including grain,
particle size, and crystallinity. Although other factors, such
as specific biological endpoint and particle coatings (deliber-
ate or accidental), also will have impact, the literature survey
suggests that synthesis route and particle history can signifi-
cantly impact the biological properties of nanoparticles.
Detailed observations made by a University of California,
FIG. 3. (Color online) (a) Schematic representation of the regenerative capa- Los Angeles-led research team for a set of well-characterized
bility and oxidation state switching of ceria nanoparticles in an aqueous silica nanoparticles also highlight differences produced by a
environment. The pictures of the bottles containing the nanoparticle suspen-
high-temperature process route, showing toxicity, while silica
sion in DI water indicate color and oxidation state changes after different
aging periods. (b) XPS Ce 3d spectra from particles removed from solution nanoparticles produced by low-temperature colloidal synthe-
after one day and three weeks. Consistent with the optical measurements sis were nontoxic in a variety of tests.46 Taken together, both
and solution color, the particles were mostly Ceþ4 after one day and mostly studies strongly indicate that synthesis and processing history
Ceþ3 after three weeks. When H2O2 was added to the aged nanoparticles in
can have a major impact on nanoparticle behaviors and
solution, they switched from Ceþ3 back to Ceþ4. Adapted with permission
from Kuchibhatla et al., J. Phys. Chem. C 116, 14108 (2012). Copyright properties. Unfortunately, because processing history, storage
2012, American Chemical Society. time, and conditions, and other information sometimes are
FIG. 4. Three categories of synthesis and processing approaches used to produce ceria particles: high-temperature processing (a)–(c) (Refs. 43–45), indirect
heating of precursors or nanoparticles in solution (d)–(f) (Refs. 40–42), and room-temperature synthesis of nanoparticles (g)–(i) (Refs. 34, 38, and 39).
Adapted from Ref. 30.
missing in reports in the literature, it is not always possible to the same process did not have the same long-term stability,
resolve the sources of apparently conflicting results. and the particles disappeared from solution in less than 60
days.30 Follow-up studies showed that switching the storage
vial from glass to plastic altered some properties of the solu-
3. Disappearing particles tions, the particle lifetime, and effective diameter. We also
In some cases, low-temperature colloidal synthesis proc- found that variations in the precursor chemicals [from the
esses, as noted, tend to produce particles with nontoxic same vendor but with different x-ray diffraction (XRD) pat-
behaviors. In the case of ceria, antioxidative behaviors often terns] and using different sources of deionized (DI) water for
have been observed.31,34 A significant body of work has the synthesis impacted the long-term stability of the par-
been established by Sudipta Seal’s group at the University of ticles.30 Regardless of the specific cause of the particles’
Central Florida for particles synthesized by a room- behavior changes, we note that subtle, seemingly insignifi-
temperature solution process.32 Particles synthesized by this cant, or unintentional changes in precursor chemicals or
process have been observed to remain relatively stable in so- processes can have a significant impact on the lifetime and
lution for periods of more than a year. Oddly, in-house work properties of nanoparticles.
with particles produced by some of the same people using
B. Surprise on the surface—copper oxide
nanoparticles
Copper and copper oxide nanomaterials are useful in a
range of commercial applications and products, including
being used as catalysts, superconductors, and lithium–ion
electrodes.47 Although several studies of Cu-based nanopar-
ticles suggest they can be toxic,48 it is recognized that as
these nanoparticles age in different environments, their prop-
erties will change as a function of time.47 To assess the
impacts of different chemical states of Cu nanoparticles,
studies have been undertaken that include measurements of
the biological response to Cu-based nanoparticles, where the
particles are delivered with a known surface chemistry.
In one such study, copper oxide nanoparticles (42 nm
primary particle size) were generated using spark discharge
FIG. 5. (Color online) Summary of the relationships among synthesis catego-
ries and biological impacts, showing that synthesis routes have a significant (Palas Karlsr€uhe) between opposing high-purity (99.95%)
impact of biological outcomes. Adapted from Ref. 30. Cu rods. The aim was to generate fresh Cu (II) oxide
nanoparticles for inhalation exposures. Preliminary XRD products are known to induce acute and severe lung inflam-
measurements revealed that the particles were a mix of me- mation.52 In vivo assessment of the toxicological response to
tallic Cu, Cu2O, and CuO. To further characterize the nature these particles as CuO nanoparticles could have been mis-
of the particle surfaces, the material was shipped to EMSL leading because the particles also were coated with PTFE
in an argon atmosphere for x-ray photoelectron spectroscopy and damaged PTFE.
(XPS) analysis. At EMSL, the container was opened, and the Before XPS analysis was done on these particles, they had
particles were mounted on a sample holder in a glove box been examined by XRD and transmission electron micros-
that was connected directly to an XPS spectrometer. copy (TEM), including energy-dispersive x-ray spectroscopy
Although high-energy resolution spectra focused on the Cu (EDS). Due to the likely thin surface coating and a noncrystal-
2p region could answer questions about the chemical nature line nature of the F either in the particle or on the particle
of the Cu, consistent with recommended practice (but not surfaces, the presence of F was not detected by these methods.
universally applied by all),49 we routinely collect large Without the surface sensitive analysis (XPS, in this case), the
energy regions (survey spectra) to verify the nature and qual- presence of the contamination at the particle surface may
ity of samples provided. The high-energy resolution analysis have remained unrecognized. A careful evaluation of the syn-
of the Cu 2p region indicated that the particle surfaces were thesis process helped determine the source of the F and steps
mostly Cu(II) (apparently, including CuO and Cu(OH)2). were made to successfully reduce the F contamination by
However, the presence of fluorine in the wide-energy survey replacing PTFE components in the generator with machinable
spectra [Fig. 6(a)] was not expected. A higher energy resolu- glass. Tools with high surface sensitivity provide information
tion spectrum of the F 1s photoelectron region [Fig. 6(b)] regarding surface contamination that may not be detected by
found peaks that were consistent with polytetrafluoroethyl- other methods. The XPS data provided important information
ene (PTFE) and CuF2. Analysis of the C 1s region [Fig. critical to the development of the planned toxicology study by
6(d)] showed several carbon peaks consistent with the pres- confirming and reinforcing the need for characterizing the sur-
ence of PTFE and PTFE breakdown products.50,51 For com- face of nanoparticles upon generation and also during expo-
parison, a spectrum from undamaged PTFE also is shown sure to properly interpret the in vivo responses.
[Fig. 6(c)]. Not only did the particles contain an element on It is easy for unexpected contamination to occur during
the surface that was unplanned, but PTFE breakdown the nanoparticle synthesis (as reinforced by another example
FIG. 6. (Color online) XPS spectra from Cu oxide nanoparticles and clean PTFE reference: (a) XPS survey spectra with unexpected F lines; (b) High-energy re-
solution F 1s region, showing photoelectron peaks consistent with the presence of PTFE and CuF2; (c) High-energy resolution spectrum C 1s region from clean
PTFE, showing a photoelectron peak consistent with CF2 bonds in PTFE; and d) High-energy resolution C 1s, showing the presence of breakdown products
from PTFE (e.g., CF3, CF2, CF2-CHF, CHF-CHF, along with CH from advantageous surface contamination; a small amount of C-O and C ¼ O is possible but
not included in this peak fit). XPS identified the presence of F that was not expected or desired on these particles.
later in this paper). Although researchers know to avoid or rate and caused the apparently thickening. To explain the ob-
minimize contamination, the tools needed may not be readily servation, several different hypotheses regarding changes in
available and/or are not always applied. If not detected and the film structure or chemistry and/or deposition of material
properly considered, the presence of contaminants in and on within the porous structures were considered and tested
nanoparticles used for toxicology tests can introduce an before we concluded that some IPA was retained in the
uncontrolled variable. The toxicity of some carbon nano- nanostructured films even after drying for several hours in
tubes, for example, was found to be associated with contami- air and vacuum. Thus, the apparent differences in thickness
nants that remained from the synthesis process.53 Catalysts were due to additional mass being included in the film.
used in the growth of carbon nanotubes can remain as resi- Eventually, we learned that leaving the samples in vacuum
dues that make up as much as 40% of the final product for more than 48 h would remove the retained liquid, and the
weight. time to sputter through the films for unexposed and IPA-
exposed films became consistent.54 Capillary forces were
C. Clean and dry?—surprises associated with sample sufficiently strong to retain significant amounts of a highly
processing and preparation for analysis volatile solvent after hours in air and vacuum.
Many types of nanostructured materials and nanoparticles
are synthesized, shipped, processed, cleaned, tested, or used 2. Removing nanoparticles from solution without
in combination with solutions of various types. The interac- destroying important information
tions of nanoparticles with these solutions can have a variety
For many types of detailed analyses, it is necessary to
of both intended and unintended consequences. Two exam-
remove particles from synthesis, process, or testing solution
ples from our work demonstrate related causes but differing
prior to analysis. As outlined by Nurmi et al.,26 there are sev-
effects.
eral factors that need to be taken into consideration including:
(1) removing residual solutes to minimize deposition of salts
1. Apparent changes in thickness of nanoporous or other solution species, (2) removing solvent and cosolvents
films due to solvent treatment
in a manner that minimizes aggregation and interference with
In earlier work, nanoporous silica films were examined as the measurement process, (3) eliminating nonstructural water
a method to create low-k dielectric materials for advanced or other solvent without significantly altering particle phases,
high-density integrated circuits. These films were synthe- (iv) minimizing erosion of original surface coatings by disso-
sized, processed, and cleaned in a variety of ways. Ion sput- lution or abrasion, and (v) avoiding reactions with the me-
ter profiling and XPS analysis were applied to obtain an dium or its contaminants that may occur upon exposure to
estimate of relative layer thickness. As part of these studies, oxygen and other potentially reactive species that will alter
we found that films exposed to isopropyl alcohol (IPA) the samples either immediately or as a function of time. Two
appeared to be thicker than those not exposed to IPA. The different particles extraction processes are described herein
samples exposed to IPA had been removed from solution, that highlight the need to tailor the extraction process to the
dried, and placed in vacuum for several hours before being particle type and analysis objectives.
subjected to Ar ion sputtering.54 Figure 7 shows the apparent A variety of extraction or immersion processes are used as
changes in film thickness. Based upon the sputter time to ex- reported in the literature. Techane et al.55 described the pro-
pose the interface, the exposure to IPA appeared to thicken cess they used to remove Au nanoparticles coated with a self-
the films. Our initial assumption was that the IPA exposure assembled monolayer (SAM) from the solution. In this case,
altered the film in some way that likely altered the sputter the objective was to remove the particles from the solution
where the SAM was grown on the particles, minimizing any
organic residue from excess 16-mercaptohexadecanoic acid
(C16-COOH) thiol remaining in the solution. The process for
removing the particles from the AuNP C16 COOH-SAM so-
lution and depositing the particles on a substrate for XPS
analysis involved several steps, including dialyzing the solu-
tion three times, concentrating the particles by centrifugation,
and multiple deposits of solution on a clean silicon substrate.
The samples were stored under N2 gas until surface analysis
measurements were conducted, usually within about 2 h.55
This procedure produced SAM-coated Au nanoparticles con-
sistent with good-quality coatings found on Au flat surfaces.
Our research conducted on metal-core oxide-shell Fe
nanoparticles (nano-Fe0), which focused on understanding
FIG. 7. (Color online) Sputter depth profiles of plasma processed p-OSG film the impact of variations in nanoparticle synthesis, composi-
before and after exposure to IPA. Based on comparison to the sputter rate
tion, and structure on the reduction of contaminants in
for SiO2 the apparent thickness was approximately 157 nm with no IPA ex-
posure and 205 nm after IPA exposure. From Gaspar et al., Surf. Interface groundwater,27 had somewhat different analysis objectives
Anal. 37, 417 (2005), Copyright 2005, John Wiley & Sons, Ltd. and required a different sample preparation method. Because
the particles were reacting with both the water and contami-
nants in the water, we needed to stop the reaction to obtain
the desired analysis. In the work’s early stages, a “flash” dry-
ing process was developed to extract particles from solution
as part of a method to “quench” particles into a stable state
at different times during the reaction process. The aim was
to stop the reaction or aging process and minimize solution
contaminants remaining on the particles. The drying pro-
cess26 involved removing the particles from solution in a
glove box using a standard vacuum filtration apparatus
assembled with a 0.02-lm PTFE filter and a vacuum pump
capable of producing 20 mm Hg. After pouring the nano-
particle suspension onto the filter, approximately 30 s were
needed to remove the original solvent. Then, the filtrate was
washed three times with acetone (or other hygroscopic sol-
vent), each time using just enough to completely cover the
filtered nanoparticles. After washing, the vacuum was main-
tained until the particle layer appeared dry (typically
5–10 min). At this stage, most types of nano-Fe0 were a
loose powder that was readily transferred to a container for
storage or testing.
Although the samples appeared dry using this procedure,
electrochemical measurements made on particles showed
that they continued to change as a function of time. A range
of thermal analysis, mass spectrometry, and other measure-
ments demonstrated that a variable amount of water was
retained in the sample (even though the powder appeared
dry). Slightly different types of particles retained variable
amounts of moisture, in some cases up to nearly 20 wt. %
of the sample. The thermal analysis helped the development
of a revised drying procedure that involved simple but im-
portant changes. After the third and final wash with solvent,
the top of the B€ uchner funnel was sealed with a silicone
stopper [Fig. 8(a)], and a vacuum gauge was used to adjust
the pressure inside the funnel to 20 mm Hg. This condi-
FIG. 8. (Color online) (a) Image of filter and pump arrangement used to
tion was maintained for 30 min as it was determined this “flash dry” nanoparticles removed from aqueous solution for detailed. (b)
was sufficient time for removal of most of the residual sol- Graph showing percent weight (moisture) loss as a function of drying time
vent [shown in Fig. 8(b)]. The vacuum was relieved without under 20 mm Hg vacuum (open circles). Without the vacuum assist, vari-
disrupting the layer of nanoparticles on the filter by slowly able amounts of moisture often were retained in the collection of particles.
As shown by the horizontal line, an additional 2 to 3% of moisture could be
opening a needle valve on a stainless-steel tube that pierced removed by storing the particles for 24 h in a desiccator filled with 50:50 an-
the silicone stopper. The flash-dried powder usually was hydrous calcium sulfate and activated charcoal. Reprinted with the permis-
transferred to an amber vial and stored (loosely capped) in sion from Nurmi et al., J. Nanopart. Res. 13, 1937 (2010). Copyright 2010,
a vacuum desiccator containing a 50/50 mix of DrieriteV R Springer Science and Business Media.
and activated charcoal.26 This process removed most of the
moisture from the samples (some additional moisture was IV. NANOMATERIAL PROPERTIES AND
removed by storage in the desiccator), effectively stopped CHARACTERIZATION CHALLENGES
the changes observed in the electrochemical studies due to The following summary highlights general areas or analy-
storage time, and also increased the reproducibility of other sis challenges important for many types of nanomaterial
experiments. characterization, including the importance of surfaces and
Both the nanoporous film and nanoparticle immersion interfaces; enhanced significance of synthesis, handling,
results highlight the fact that capillary forces can be quite processing, and storage conditions; and the dynamic nature
effective at retaining a range of solvents within various types of nanosized objects. A variety of effects have been grouped
of nanostructures. For the nano-Fe0 studies, it was particu- into topics as shown in Fig. 9 and Table I.
larly important to effectively stop the changes taking place
when the particles were in the solution to relate the physical A. Nanomaterial surfaces and interfaces control many
behaviors of the particles to the particle reactivity and sur- material properties
face chemistry when ex situ measurements were It is widely recognized that as particle size decreases,
conducted.28 surfaces and interfaces begin to dominate and control the
control properties of nanoparticles and other nanomaterials.

Such “nanosurface” analysis10 has been extensively used to
characterize supported nanoparticle catalysts but generally
unused to characterize unsupported nanoparticles in biomedi-
cal and other applications. Because of the significant fraction
of atoms or molecules associated with surfaces and interfaces
of nanomaterials, surface impurities, surface enrichment or
depletion, and surface contamination10 on nanomaterial prop-
erties can dominate material properties. For example, the
electrical characteristics of Si nanowires are highly depend-
ent on the nature of the environment and wire surface.56 The
nature and impact of surfaces may depend upon the applica-
tion and properties of interest. However, Karakoti and co-
workers12 note that the importance of nanoparticle surface
chemistry, especially as applied to toxicology, has been sig-
nificantly underemphasized.
Others have noted57 that adsorption is a spontaneous pro-
cess on high surface energy materials that reduces the free
energy of nanoparticles. Consequently, thermodynamics
drives the formation of many types of adlayers on particles
during synthesis, processing, and storage. In relation to bio-
logical systems, Jones et al.57 observed that adsorbate layers
on nanomaterials, not the virgin nanomaterial chemistry, are
increasingly thought to be the primary surface that interacts
with biological components. The segregation of components
FIG. 9. (Color online) Properties of nanoparticles that often introduce char- during synthesis or in different environments also can create
acterization challenges; also see Table I. materials for which the surface is significantly different from
the bulk material. An excellent example where such segrega-
properties of nanostructured materials. However, the chemi- tion was unexpected has been observed during the formation
cal and physical nature of these surfaces and interfaces often of organic aerosols.58
are not measured or reported. Grainger and Castner10 point As shown by the Cu oxide nanoparticle study, where F was
out that over the past 40 years, surface scientists have identified by XPS, efforts must be made to characterize nano-
obtained detailed knowledge about the behavior of surfaces, particle surfaces because the presence of unexpected contami-
including the important role of deliberate and accidental sur- nants or the unanticipated surface enrichment of a component
face layers. They note that the rigor needed to understand the species would make the nature of the particles significantly
chemistry of other surfaces also is required to understand and different than expected. In many circumstances, nanomaterials
TABLE I. Challenges associated with characterization of nanoparticles.
Nanomaterial surfaces and interfaces control properties
• Most atoms on small nanoparticles are surface atoms or next to a surface atom
• If the nature of the surface is not known, particles are not well defined or characterized
• Surface coatings are not identified by many of the analysis techniques commonly used to characterize nanomaterials
“Equivalent” nanoparticles usually are not
• Different synthesis routes often produce totally different types of nanoparticles

• Minor changes in synthesis, handling, and processing often alter particle properties
• Purchased particles often have properties very different from those initially determined by a vendor
Nano-sized objects are dynamic: they change with time and respond to their environment
• Particles grow or dissolve, agglomerate

• Shape and size can change
• Adsorb molecules from the environment: most single-phase nanoparticles really are core–shell particles with the shell com-
ing from the environment
• Particles are easily damaged and can change as a function of temperature and exposure to light
• Environmental can change chemical state of surfaces and whole particles
• Time for changes can vary between fractions of a second and years
synthesis involves using surfactants to control particle shape59 catalytic reactions to occur.” Similar observations were
during growth, and different types of chemicals are used dur- made regarding the activity of catalysts associated with the
ing synthesis or processing. Residue from these processes23 growth of nanofibers.64,65 It is possible to observe shape
may remain on particle surfaces or in the solutions in which changes for nanoparticles during electron microscopy.66 It
many particles are stored and shipped. Often, the routinely may be important to think of nanoparticles as dynamic,
applied analytical methods cannot identify such adlayers on rather than static, objects. Many studies have shown the
particle surfaces. Consequently, lack of surface characteriza- dynamic nature of natural and engineered nanoparticles,
tion contributes to the uncertainly and variability of results in especially for particles smaller than 10 nm,67,68 which has
the literature. Detailed reporting of synthesis, processing, and many different types of manifestations and implications. In
storage processes also can assist efforts to track down possible particular, they can change with time, may be altered by
differences in particle behaviors. proximity to other particles or surfaces, can be easily dam-
aged during analysis, and frequently change in response to
B. “Equivalent” nanoparticles usually are not— their environment.
nanoparticles are not created equal
1. Particle shapes can change
When we compared the ability of two types of Fe metal-
core oxide-shell nanoparticles (nano zero-valent iron) created In reviewing structure and shape changes for nanosized
by different synthesis processes to reduce CCl4, we found the particles, Yacaman et al.66 noted that different configura-
reaction rates and reaction pathways to vary significantly.27,60 tions for a nanoparticle have very similar energy, thereby
In further work, we identified residue from different salts that making shape transformation easy and common. The types
could be used to synthesize particles61 by the “same” process of energies we commonly apply during analysis will provide
significantly altered the properties of particles. As described energy adequate to stimulate such changes.7 It may be appro-
previously, we found that ceria particles can behave differ- priate to consider the dynamic nature of particles an essential
ently, even when we have attempted to produce them using characteristic that gives rise to important chemical properties
an identical process,30 and differences in the toxicity of par- as previously noted.63,65
ticles that are the same material but have been processed in
different ways now are well established.30,46 Subtle differen- 2. Particles dissolve, grow, and adsorb material from
ces, as well as not-so-subtle differences, in materials synthe- the environment
sis, processing, and storage (time, temperature, and light) The high surface energy of many types of particles is low-
may effectively make “similar” nanomaterials have different ered by growing57 or dissolving.69 Particles also may assem-
characteristics (some of which are not readily identified by ble into larger units57,70 that may be easy (soft agglomerates)
most characterization methods). or difficult (aggregates) to break apart. As noted, to reduce
Two observations from the Nanotechnology Characterization surface energy, most particles naturally adsorb material from
Laboratory (NCL) of the National Cancer Institute further their environment.57 When nanoparticles are placed into bio-
emphasize some important issues.23,62 Similar to our chal- logical media, a protein coating (corona) forms around the
lenges to reproduce the formulation of ceria particles, they particles that may be tens of nm thick.71 The protein corona
frequently observe batch-to-batch variation in particle proper- forms quickly, and the composition is influenced by the size
ties. They report measurements on chemically attached poly- of the nanoparticles.72 In many environments, even single-
ethylene glycol, or PEGylated, gold nanoparticles, where a material nanoparticles quickly become core-shell particles,
series of important measurements produced identical results, either by adsorbing material from the environment or react-
but only one batch produced highly inflammatory lung ing with that environment (e.g., oxidation/corrosion).28
lesions. A highly detailed analysis eventually showed a dif-
ference in the degree of PEG coating between the batches, 3. Environmentally induced changes in structure and
which impacted the degree of plasma protein binding.23,62 chemistry (including sample preparation and
Another important observation made by NCL staff over the processing)
years is that many researchers use commercial materials and
In addition to forming surface coatings, the environment
the manufacturer specifications at face value without further
can alter either physical structure or chemistry of a nanopar-
testing.23 Because of history, shipping, storage, and other
ticle. Changes in the chemical state of ceria nanoparticles
effects, this is a highly questionable practice. Particles made
have been found to vary due to the presence of peroxide in
and characterized at one time and location are often not iden-
the solution in which they are suspended.32 The crystalline na-
tical for the same material at a different time or location.
ture of ZnS nanoparticles was observed to change when the
particles’ environment varied from wet to dry.73 As expected,
C. Properties of nanosized objects are dynamic—they oxide-shell metal-core iron nanoparticles oxidize in water,
often change with time and environment impacting their ability to reduce contaminants such as CCl4.28
In an article on metal nanoparticle catalysts, Somorjai The impact of environmentally induced particle changes
and Park63 comment: “The restructuring of the surface coin- has implications in at least two different ways: impacts on
cides with the mobility of the adsorbate; thus the surface, sample preparation and analysis and how they may trans-
both the metal and the adsorbate, has to be dynamic for form in their “native” or working environments. Many
surface analysis methods require placing samples in environ- nanoparticles.7,22 This behavior can be used to create materi-
ments (often vacuum) that differ from those in which the als with tuned properties76 or as the physical basis of a nano-
samples are normally found. This can alter the particles and scale ruler.77 Implications of proximity effects related to
needs to be considered as part of the analysis and sample sample mounting78,79 include substrate interactions, particle
preparation process. Issues associated with sample handling charging, coupling of quantum states, and spacing impacts on
and removal of samples from the natural environment to the electronic and magnetic properties of the effective composite.
analysis environment also apply here. The deliberate need to We have found, for example, that the chemical state observed
stop a process in the environment of interest was the focus by XPS may depend upon the concentration of particles
on the flash-drying study noted earlier.26 The need to remove loaded onto a substrate as shown in Fig. 10. The ceria par-
components from the solution environment that were not ticles examined were deposited on a silicon wafer by placing
associated with the particles was a focus of both the flash- a drop of solution on the substrate in a glove box and letting
drying process and the extraction process of the SAM-coated the solution evaporate. After the solvent evaporated, a non-
Au nanoparticles.55 uniform distribution of particles formed on the surface. XPS
There also are broader implications of environmental- analysis of portions of the deposit with a low density indi-
induced transformation, both for application and aspects of cated Ceþ3 [Fig. 10(b)], while the portion of the deposit with
analysis. Wiesner et al.67 commented on the “Ubiquity and a higher density contained at least some Ceþ4 [Fig. 10(a)].
Mutability of Nano-Sized Materials in the Environment.” It
is important to realize that nanomaterials (especially nano-
particles) may change in some ways if their local environ-
ment changes during incorporation into a product, they are
introduced into a biological system, or they are released into
the natural environment. Cohen et al.74 noted the importance
of comprehending particle–media interaction to understand
the particle dose delivered to cells for either toxicological
impacts or pharmaceutical purposes. The need to understand
particles and their transformations in the native environment
underscores the demand for various types of in situ real-time
measurements.
The nature of sample preparation must be linked directly
to analysis and the testing to be conducted. To examine the
reaction intermediates during a catalysis reaction, Krier
et al.75 conducted a study that combined both of the two pre-
ceding issues. They noted that organic ligands typically are
used to stabilize nanoparticles during synthesis, and these
remain on the particles after synthesis. However, the pres-
ence of an organic capping agent may block a significant
fraction of active sites when the particles are intended for ca-
talysis studies. Their specific study focused on the applica-
tion of sum frequency generation-vibrational spectroscopy
(SFG-VS). They observed that the capping layer produced a
strong signal that inhibited measurement of the reaction
intermediates of interest. They tested both solvent cleaning
and ultraviolet (UV) cleaning for removing the capping
layers and found that both cleaning processes enabled the
collection of the needed SFG signals. They further noted that
the solvent cleaning process did not remove the entire cap-
ping layer, while the UV cleaning enabled complete re-
moval. However, the solvent cleaning produced particles
that were stable under reaction conditions, while the UV-
cleaned particles had significant aggregation and were effec-
tively unstable, actually complicating the study objectives.
In this case, the “partial” cleaning produced the most useful
material and stable material.
FIG. 10. (Color online) Ce 3d XPS spectra from ceria nanoparticles depos-
ited on a Si substrate. Based on optical data, we would expect the ceria to be
4. Proximity effects mostly Ceþ3. The deposition process produced regions of high (a) and low
(b) particle density. The XPS photoelectron spectrum from the higher den-
The properties of individual or isolated nanoparticles may sity of particles differed (some Ceþ4) from the lower density region (only
change as they are in contact or near surfaces or other Ceþ3).
When we first observed this behavior, we asked a few others depending on the synthesis process used to create the par-
if they had ever observed similar behaviors. One group ticles. For the higher particle density, multiple spectra are
agreed that they had observed something very similar on a shown in Fig. 10(a). This set of spectra is presented again in
different substrate, but they thought something had gone Fig. 11(a), showing that although the Ceþ4 signal never
wrong with the measurement. We think this behavior is a totally went away, it decreased upon x-ray exposure.81 In
proximity or environmental effect. In the region of higher contrast, a set of spectra in Fig. 11(b) shows an example of
particle density, the particles were interacting with each other the Ceþ4 increasing with time. We believe that the different
(ceria nanoparticles with other ceria nanoparticles). damage processes are due to differences in the synthesis of
Meanwhile, for the region of lower particle density, ceria the particles. In the first example showing damage-related
nanoparticles had greater interaction with the substrate. reduction, the sample synthesis included the use of toluene,
where a residue on the particle surface produced a locally
reducing environment upon x-ray exposure. The second set
5. Ease of sample damage
of particles was synthesized in an aqueous solution contain-
The energies associated with chemical binding, particle ing no added organics, and an oxidizing environment was
bending or fracture, and charge buildup become roughly produced upon radiation.
equal and less than those associated with analysis methods These and many other observations7 highlight that nano-
for nanoparticles.7,21 One consequence of the similar ener- materials in various forms are easily damaged during analy-
gies is that particles are easily damaged during analysis or sis, and the nature of the damage may be altered by the
upon exposure to the environmental conditions of the analy- specific nature of the particles and the environment where
sis method. Samples have been observed to melt upon expo- the damage takes place.
sure to an electron beam,80 change oxidation upon x-ray81 or
electron beam exposure,82 and sputter at enhanced rates.83
During XPS analysis of ceria nanoparticles, we discov- 6. Time-dependent behaviors
ered that the type of damage observed could change For all of the preceding reasons, the properties and char-
acteristics of nanoparticles frequently alter with time, a pro-
cess sometimes called “aging.”28,32,47 This time dependence
can be influenced by the synthesis process, exposure to light,
storage conditions, temperature, and other aspects of the
sample environment. Consequently, true characterization of
nanoparticles might be considered a four-dimensional chal-
lenge60 with the axes being space, composition or structure,
time, and environment. Although this might seem to present
an overwhelming challenge for nanoparticle analysis and
application, the rate of change is sufficiently slow in many
cases as to be of no concern, and, in other circumstances,
aging of nanoparticles presents an opportunity to tune par-
ticles for desired properties and lifetime or life cycle.
Because the time scales of change can range from fractions
of seconds to many years, the impact of any changes
depends on the particle, environment, and nature of the study
or application being considered.
Understanding these and other characteristics of nanopar-
ticles and other nanomaterials enables researchers to design
the types of analyses and characterization needed for specific
research activities. It is clear, for example, that characteriza-
tion of objects months or years before application or use
may not provide useful information,4 unless the reliability of
that information is confirmed. Understanding the changes a
particle will undergo in particular environmental conditions
is useful for determining the time frame and handling needed
for a specific experiment. Keeping and reporting detailed
records of the date of synthesis, storage times, and condi-
FIG. 11. (Color online) Changes in the Ce 3d XPS spectra collected as a tions, and times of analyses will facilitate the understanding
function of time for (a) particles formed in an aqueous solution, containing of similarities and differences between studies. Because of
some amount of organic (toluene) (after Ref. 81), or (b) particles synthesized environmental impact on particle properties and behaviors, it
in a solution with no added organic. The 3–5 nm diameter particles produced
is important to monitor particles in the actual environment of
in the solution with toluene (a) tended to become reduced upon x-ray expo-
sure, while 10–14 nm particles formed in aqueous solution without added interest, to the extent possible.11 Because the information
organics (b) tended to become oxidized upon x-ray exposure. available from such in situ measurements is often incomplete
and less detailed than desired, it usually is important to com- tools, as well as expanding types of information that can be
bine real-time in situ measurements with a range of ex situ obtained from these tools.
measurements, where sample handling has been carefully
planned and appropriate integration of results is undertaken A. Information available from common surface
(we have attempted such integration in our Fe metal-core ox- analysis methods
ide-shell work26–28).
The range of useful information about nanomaterials that
can be obtained from data collected using traditional surface
V. ROLE OF SURFACE ANALYSIS IN SUITE OF analysis methods exceeds what generally is expected by
INFORMATION NEEDS many analysts. The information available from several sur-
Incomplete characterization impacts several aspects of face analysis methods is summarized in Table II. These sur-
nanomaterials research, including the reproducibility of face sensitive analysis methods can be applied in two
somewhat different modes. For example, in many circum-
research results, the process of scaling production to meet
manufacturing needs, and human health and environmental stances, it is highly useful to simply recognize the presence
risk assessment.4,10,57,84 Several different research, regula- or absence of contaminants or to confirm the chemical state
of elements present in the nanomaterial. Such uses dominate
tory, economic development, and standards-related commun-
ities have worked to identify the minimum measurements the literature, and their importance cannot be understated.
needed to adequately characterize nanomaterials. Stefaniak However, with additional thoughtful analysis, an expanded
range of information can be extracted—even from what was
et al.4 have examined 28 of these lists to understand the most
critical needs related to metrological challenges and the de- initially collected as qualitative data. In earlier reviews and
velopment of nanoscale reference materials. As might be summaries focused on XPS,78 nanoparticles, carbon nano-
tubes,60,79 and nanomaterials,7,86,87 we provided many
expected, particle size, surface area, particle composition
(bulk), surface chemistry, agglomeration/aggregation, surface examples of how the most available surface analysis meth-
charge, and surface reactivity are prominent on many lists. ods can be applied for nanomaterial characterization. Here,
we highlight important underlying concepts, discuss some
Additional features, such as particle stability, solubility in bi-
ological media, and surface structure, are critical but less recent applications.
commonly discussed.
In a perspective article, Grainger and Castner10 observed 1. X-ray photoelectron spectroscopy
that the information and experience obtained from surface Because evidence suggests that XPS is the most common
science often is not integrated into studies of nanomaterials. surface analysis method applied to nanomaterials,88 we will
In an impressive review of stabilization and functionaliza- highlight several examples of its application. It is important
tion of iron oxide nanoparticles for biomedical applications, to recognize that although XPS is highly used and can pro-
Amstad et al.85 summarized the information needs and wide vide valuable information, as normally applied in the labora-
range of tools that have been applied to gather relevant data. tory, it requires placing a sample in ultrahigh vacuum and
Although they note the value of XPS for certain types of ad- involves the analysis of many particles supported on a sub-
sorbate measurements, surface sensitive methods generally strate. Strengths and limitations of XPS and other methods
play a minor role in these studies. It is our view that surface are noted in Table III.
analysis methods of various types are underused as important The nanostructure of a material impacts the peak inten-
components in the suite of tools needed for appropriate sities, peak energies, and structure (including background
nanomaterial characterization. Although we have applied a signals) of x-ray-excited photoelectron peaks.78 It is possible
range of methods to characterize the Fe metal-core oxide- to invert the process and use details of the XPS peak shape
shell nanoparticles,27 XPS became one of the few core meth- and intensity to learn about the nanostructure of the materials
ods applied in almost every circumstance to assure consis- being examined. The surface and structural sensitivity in
tency and verify that contamination or other changes in the XPS comes from the short distances that the excited photo-
particles surface had not taken place. electrons can travel before losing the energy that identifies
The underuse of surface analysis methods for characteri- them as photoelectrons. The contribution to the detected sig-
zation of nanomaterials may have multiple sources. First, nal from a depth z into the material is attenuated by material
because the most common surface analysis tools have sur- covering the layer closer to the surface. Although the equa-
face sensitivity in only one dimension and usually do not tion is only approximately valid, the relationship between
have the resolution to examine individual particles, some depth into a sample and signal strength can be usefully
researchers do not consider applying the tools. A second pos- expressed as
sible reason is that these tools can require instrument access,
as well as appropriate care in sample preparation and analy- dIz I1 exp ½z=ðL cos hÞdz; (1)
sis, that may exceed the expertise available to prepare sam-
ples, collect data, and understand results. If applied or where dIz is the intensity of the detected signal at depth z, I1
interpreted inappropriately, incorrect, inconsistent, or mis- is the intensity that would have been produced if the layer
leading results may be produced. A variety of research were at z ¼ 0 (the outer surface), L is the photoelectron
groups are demonstrating the application and value of these attenuation lengths, h is the angle of the detected electron
TABLE II. Characteristics of common surface analysis methods and types of information available for nanomaterials.
050820-14 Baer et al.: Surface characterization of nanomaterials and nanoparticles

Surface analysis methods Information available Probe Detected Lateral resolution Information depth Depth resolution
Electron Spectroscopies
X-ray photoelectron spectroscopy • Analysis of a collection of particles deposited X-rays Photoelectrons 2 mm 10 nm 2 nm
on a substrate or other support System
dependent
• Surface composition and/or chemical state
• Enrichment or depletion of elements at surface
• Presence and/or thickness of coatings or contaminants
• Nanoparticle Size (when smaller than 10 nm,
can sometimes determine average particle size when
too small to be detected by other methods or in complex matrix)
• Surface functionalization and presence of defects
• Electrical properties of nanoparticles and coatings
Auger electron spectroscopy • Surface composition of individual large nanoparticles Electrons Auger 10 nm 10 nm 2 nm
or distribution of smaller nanoparticles (3 to 20 kV) electrons
(depending on spatial resolution of specific instrument)
• Enrichment or depletion of elements at surface
• Presence and/or thickness of coatings and/or contaminants
Incident Ion Methods
Secondary ion mass spectrometry • Usually analysis of a collection of particles or larger individual Ions Sputtered 50 nm (inorganic) 1 nm 1 nm (inorganic)
particles deposited on a supporting substrate (3 – 20 kV) ions > 200 nm (organic) 10 nm (organic)
• Presence of surface coatings or contaminants on collections
of nanoparticles
• Functional groups on surface
Low-energy ion scattering • Presence of ultrathin coating or contamination Ions Elastically 100 mm 10 nm 0.1 nm
• Continuity or defects in surface layers (2 to 10 kV) scattered ions
• Effects of size
Medium-energy ion scattering • Depth Distribution in particles and coatings Ions Elastically 10 mm (TOF) 10 s nm 0.1 nm
• Buried layers and particles (50–200 kV) scattered ions 1 mm (ESA)
Scanning Probe Microscopies

Scanning tunneling microscopy • Electrical characteristics of individual nanoparticles Stylus Tunneling 1 nm 10 nm
• Nanoparticle formation and/or size distribution of particles current
deposited or grown on a surface
Atomic force microscopy • Shape, texture and roughness of individual particles and their Stylus Force or 1 nm 10 nm
distribution for an assembly of particles displacement
050820-14
• When particle structure is known, can provide information
about crystallographic orientation
TABLE III. Strengths and limitations of primary methods discussed in this review.
Technique Strengths Limitations or issues
XPS • Generally available and easy to obtain useful qual- • Needs appropriate sample preparation and handling to
itative information about the near surface region of minimize information loss.
films or particles • Requires vacuum
• Identifies unexpected elements and oxidation state • Laboratory configurations cannot analyze individual
• Useful to estimating average coating thickness less particles, requires collection of particles
than 10 nm • New developments could speed quantitative analysis
• Significant range of other quantitative information of nanomaterials
possibleusing detailed analysis and modeling
AES • Identifies unexpected elements present • Requires vacuum
• Useful for estimating coating thickness if less than • Needs appropriate sample preparation and handling to
10 nm minimize information loss
• With limitations can characterize individual • Beam damage a concern, particularly with regard to
nanoparticles insulators and organic particles and coatings
SIMS • Can provide molecular information about film and • Most instruments cannot characterize individual par-
particles surfaces ticles, therefore requires a collection of particles
• Determine presence of trace elements • Needs appropriate sample preparation and handling to
minimize information loss
• Sputter rates accelerated for nanoparticles
• Nanoparticles can melt or transform, sputtering can
destroy the size, shape, and composition of the particles
• Requires vacuum
LEIS • Sometimes describes as the most surface sensitive • Contamination easily masks signal, needs careful
analysis method sample preparation and handling to minimize infor-
• Easily determines the presence of elements at the mation loss
outer atomic layer of a sample, therefore great at • Requires vacuum and a collection of particles for
looking at coating uniformity and presence of some analysis—high sensitivity
defects on nanoparticle and flat surface coatings
MEIS • With sample structure modeling provides high • Cannot analyze individual particles and most infor-
resolution depth distribution in films and particles mation if single layer of particles on a substrate that
does not interfere with desired analysis
• Requires vacuum
AFM • Easily identifies presence of particles and particle • Tip shape can become convoluted with measurements
shape on a flat surface • Cannot provide direct chemical information
• Measurements can be made in vacuum, gas or liq-
uid environments
STM • Easily visualize presence of particles • No direct structural or chemical information
• Can be conducted in vacuum, gaseous and in some • Requires some degree of electrical conduction
cases liquid environments
SFG-VS • Selectively probe chemical identity, molecular • Requires modeling and spectral data interpretation
structure and interactions from vibrational spectra
of particle surfaces or interfaces in vacuum, liquid
or gaseous environment with submonolayer
sensitivity
• No need for total internal reflections
NMR • Molecular information available from a variety of • Not inherently surface sensitive
environments • “Tricks” may need to be employed to obtain sensitiv-
ity and extract desired information
average nanoparticle size (if less than 10 nm).92,93 It is also

possible to use XPS to determine the electrical characteris-
tics of particles or coatings and the distribution of Lewis and
Brønsted acid sites on zeolite surfaces.79
A variety of methods can be used to extract the thickness
of coatings on particles or flat films from XPS data—all effec-
tively based on Eq. (1).89–91,94–96 Computer algorithms using
different approaches are available for layer thickness and
structure determination, including MultiQuantTM,95–98 which
looks at the impact of different particle shape and surface
layer models on photoelectron peak signal strength, and
94,99–102
QUASES, which considers the impacts of the surface
nanostructure on signal strength and the related background
signals around photoelectron peaks. Using simulation of elec-
tron spectra for surface analysis (SESSA)103 and Topofactor90
approaches to determine the thickness of coating on nanopar-
FIG. 12. (Color online) Schematic model for the carboxylic-terminated SAM
on a flat gold surface that was used in the SESSA calculations. Reprinted ticles is discussed in more detail in an example to follow. The
with permission from Techane et al., Anal. Chem. 83, 6704 (2011). impact of particle shape depends somewhat on size. For those
Copyright 2011, American Chemical Society. larger than 30 or 40 nm in diameter, the particles are effec-
tively objects with curved surfaces, and the analytical
relative to the surface normal, and dz is the thickness of the approach to determining coating thickness will vary with par-
layer. The information depths from which detectable signal ticle shape but is independent of particle size. For smaller par-
intensities can be extracted are typically in the range of ticles, for which photoelectrons can traverse the whole
1–20 nm. Because L depends on energy, Eq. (1) demon- particle, it is necessary to know the particle size and shape to
strates both the energy and angle dependence of the signal accurately relate signal strength to a layer or coating
intensity from depth z. Applying the surface sensitivity of structure.78,90
XPS, including the energy dependences of L and the impact One of the recent tools for assisting the application of
of angle, a range of information can be extracted from XPS Auger electron spectroscopy (AES) and XPS is SESSA.103 In
spectra,78 including surface composition and chemical state, the initial form, the program provides important physical
presence and nature of functional groups, enrichment or information to allow simulation of AES and XPS spectra
depletion of elements at the surface, presence and thickness from flat surfaces and (nano)-layered structures. Although a
of coatings55,89,90 or contaminants (and reaction rates),91 and new version explicitly incorporating three-dimensional
FIG. 13. (Color online) For application of SESSA to predict the signal strengths from SAM-coated Au nanoparticles, the particles were modeled as multiconcentric
cylinders, where each cylinder surface has an average photoelectron take-off angle of ai. The XPS detector is positioned at 0 from the central axis of the AuNP.
(a) The sphere is divided into nine concentric cylinders. (b) The end of each cylinder is modeled as a flat surface tiled relative to the axis of the spectrometer with
infinite thickness of gold, and (c) the surface composition of each flat Au sample is weighted by its geometric factor then summed together to find the AuNP sur-
face composition. Reprinted with permission from Techane et al., Anal. Chem. 83, 6704 (2011). Copyright 2011, American Chemical Society.
nanostructures, such as particles and wires, is being devel-

oped, Techane et al.55 modeled a C16 COOH-SAM adsorbed
onto Au nanoparticles (AuNPs) using the flat surface version.
This was done by constructing a “model” spherical nanopar-
ticle made up of concentric cylinders with “flat” surfaces with
a SAM coating (Fig. 12) at varying angles with respect to the
axis of the analyzer as shown in Fig. 13.
The study involved experimental measurements and
SESSA modeling of XPS photoelectron signal strengths
from two systems: (1) the SAM layer on a flat Au surface as
a function of electron takeoff angle and (2) SAM-coated
nanoparticles. SESSA was used to simulate both the angle
FIG. 14. (Color online) Schematic diagram showing the relationships of peak
variation of signals from the flat surface and the signals from intensity ratios (a) and shell thickness’ of nanoparticles based upon knowledge
spherical nanoparticles. In the initial form, SESSA can cal- of the radius of the nanoparticles. Reprinted with permission from Shard, J.
culate signal strengths from a layered surface and the layer Phys. Chem. C 116, 16806 (2012). Copyright 2012, American Chemical
structure for the SAM on a flat Au surface. Figure 12 shows Society.
the SAM structure used in SESSA. The SESSA calculations
as a function of angle then were compared to those observed not include the contributions of the O- and S-containing
experimentally. Appropriate agreement between the model layers at the top and bottom of the SAM, it can be concluded
and experiment was obtained when a small amount of sur- that the 1.74-nm thickness compares quite well with the
face contamination was included in addition to the SAM 1.85-nm total shell thickness determined by detailed calcula-
layer and Au substrate. As indicated in Fig. 13, a nanopar- tions of Techane et al.55 using SESSA. The advantage of the
ticle was approximated as a series of cylinders where the simple method is that it is fast and simple to use. However,
detected photoelectron signals will have different takeoff for cases when more detail is required, such as core–shell
angles. For both the flat surface and nanoparticle, the SAM particles with multilayers or an outer contaminant layer, nu-
thickness and relative surface roughness (RSA) in SESSA merical simulations still are preferred.
were optimized to determine the best agreement between We have used the procedure described by Shard105 to
simulated and experimental surface composition. As sum- examine Ag nanoparticles that were produced for a National
marized by Techane et al.,55 a SAM thickness of 0.11 nm/ Institute of Environmental Health Sciences (NIEHS)
CH2 group, an RSA of 1.05, and a 0.15-nm CH2-contamina- Consortium that is examining the toxicology of nanopar-
tion overlayer (total film thickness ¼ 2.15 nm) provided the ticles. During the course of the initial research with the par-
best agreement with the experimental XPS data. After apply- ticles, we learned the Ag particles had been formed around
ing the appropriate area weighting factors and summing the 7- to 8-nm Au cores. The presence of Au also had been iden-
SESSA flat surface compositions, the most applicable results tified in the XPS survey spectra. Au was observed by XPS in
for the C16 COOH-SAM thickness and surface roughness on particles nominally 20 nm in diameter but was not observed
the AuNPs were determined to be 0.09 nm/CH2 group and in particles exceeding 100 nm in diameter. Before we could
1.06 RSA with a 0.15-nm CH2-contamination overlayer obtain any microscopy evidence of the Au cores, we used
(total film thickness ¼ 1.85 nm). The 0.3 nm difference in Shard’s simple method to check the consistency of the XPS
SAM thickness between the flat Au and AuNP surfaces sug- results with the assumption of the presence of a 7- to 8-nm
gests that the SAM’s alkyl chains may be slightly more tilted Au core within 20-nm Ag particles.
or disordered on the AuNP surfaces. SESSA and other Based on a standard atomic percent calculation, the appa-
detailed analysis approaches can provide a remarkable rent atom ratio of Ag to Au for the 20-nm particles was
amount of information about the details of nanopar- approximately 64. This value becomes parameter A in
ticles89,104 and are especially useful when this type of infor- Shard’s approach.105 The second important factor in determin-
mation is required. However, these analysis methods are not ing the coating thickness is the ratio of electron attenuation
yet easy to apply to “routine” samples. Sometimes, less rig- lengths for Au and Ag photoelectrons in the particle shell. For
orous methods can provide useful information as well. the Ag-shell Au-core particles, B ¼ L(Ag in Ag)/L(Au in Ag),
Shard has developed a simple approach for analyzing where L(Ag in Ag) is the attenuation length of Ag photoelec-
XPS data to obtain the thickness of coatings on nanopar- trons in the Ag shell (overlayer) and L(Au in Ag) is the attenua-
ticles.90,105 The method involves measuring peak intensity tion length for Au (from the substrate) in the Ag shell.
ratios (Fig. 14), knowing the general structure and approxi- It is possible to calculate an approximate value using B
mate particle diameters. It can be applied using either analyt- (Eo/Es)0.75 as noted in earlier work,90,106 but attenuation
ical formulas or a simple graphical method. Shard has lengths and electron mean free path lengths can be calculated
applied the method105 to the data from Techane et al.55 (as using several methods and sources, including National
analyzed using SESSA) using the ratio for the C 1s and Au Institute of Standards and Technology databases107 and the
4f photoelectron peak ratios and relevant photoelectron formulas contained in computer codes, such as QUASES.100
attenuation lengths. The coating thickness calculated by the Using the experimental value of A and the calculated value of
simple approach is 1.74 nm. As the simple calculation does B, Eq. (6) of Ref. 105 was applied to calculate the thickness
TABLE IV. Parameters used to calculate the shell thickness for Ag-shell Au-
core nanoparticles using XPS signal strengths.
Parameter Description or unit Value
A Ag/Au atom ratio 64

B Attenuation length ratio 0.82
T Normalized flat surface thickness 5.1
Topo Topofactor 0.67
L Attenuation length (nm) 1.6
Shell thickness nm 5.5
Particle diameter
(assuming 8 nm core) nm 19
of the overlayer normalized by the attenuation length (L(Ag in

Ag)),assuming the data was from a flat sample (see Table IV).
The conversion from the flat film calculation to the spherical
nanoparticle geometry was done using the average Topofactor FIG. 15. STEM dark field images of Ag-shell Au-core nanoparticles clearly
show the presence of Au cores in most particles.
of 0.67 that applies to particles significantly larger than L(Ag in
Ag). Multiplying the corrected (but normalized) thickness by
L(Ag in Ag) produces the estimate of the particle shell’s thick- tendency to look at a scanning electron image available in an
ness. The shell thickness determined by this calculation was AES instrument and assume, when collecting AES data from
5.5 nm. Assuming an 8-nm Au core surrounded by a 5.5-nm- a feature identified in the image, that the entire signal is
thick shell produces a particle size of 19 nm—quite consist- derived only from the area where the electron beam strikes.
ent with a nominal size of 20. A later set of scanning TEM When the electron beam penetrates through a nanoparticle or
(STEM) measurements (Fig. 15) confirmed the presence of other nanosized feature below or into the surrounding mate-
the Au core in most particles. rial, the Auger signals produced and detected usually come
The analysis depth of XPS included in Table II is based from both the nanofeature and surrounding region.
upon the most common x-ray sources for laboratory-based When the potential issues are understood, AES can be
instruments. By using alternative energies, particularly those quite effective in providing information about nanostruc-
associated with synchrotrons, it is possible to extend the tured material, and it has been particularly useful in combi-
depth of analysis and to use x-ray energy as a method of tun- nation with other methods. Liang et al.111 were interested in
ing the analysis depth. Haverkamp et al.108 used this the formation of what they called “Cu2O nanodots” for pos-
approach to understand the complex core-shell structure of sible chemical or photochemical applications. AES was used
IrO2, RuO2, Sb2O5, and SnO2 electrocatalyst nanoparticles. to examine the nature of the nanodots formed on a SrTiO3
It is useful to note that accurate knowledge of attenuation substrate after deposition using oxygen plasma assisted mo-
lengths is likely the most important limitation on the ability to lecular beam epitaxy. In the AES instrument, it was possible
accurately determine layer thicknesses of both films and on to obtain secondary electron images of the nanodots, along
nanoparticles. The accuracy of these lengths is likely no better with AES maps for Cu, Ti, and O (shown in Fig. 5 from Ref.
than 10% at one standard deviation.107,109 Furthermore, the 79). One objective of the AES analysis was to determine if a
attenuation length information is normally applied to thin Cu2O wetting layer was observed between the Cu2O nano-
films (“nano” in one dimension), not for objects of “nano” dots. This wetting layer was not observed. The secondary
size in three dimensions. The uncertainty in attenuation electron images and AES maps showed that nanodots could
lengths limits overall accuracy of the analysis but still allows be formed with differing shapes. This process was also
a great deal of information to be extracted. examined as a function of the amount of material deposited
combining AES with atomic force microscopy (AFM) (Fig.
2. Auger electron spectroscopy 6 of Ref. 79).
As another example, AES was teamed with scanning
Because both XPS and electron-induced AES involve
electron microscopy (SEM) and TEM to examine the
detection of electrons of similar energies, many of the con-
location of a composite organic–inorganic nanoparticle on
siderations described for XPS apply to AES. However, as
leukemia cells. The combined technique provided reliable,
generally defined, AES involves an incident electron beam
high-resolution information about the nanoparticles and how
with a spatial resolution that can sometimes be used to col-
they bind to cell surface antigens.79,112
lect information about individual nanoparticles. It can be of
importance to recognize that because AES involves electron
excitation, issues of electron backscattering and transmission 3. Secondary ion mass spectrometry
through a particle mean some additional parts of the sample During secondary ion mass spectrometry (SIMS), meas-
may be stimulated to produce Auger electrons, which will urements, primary ion beams with energies between 3 and
limit the actual spatial resolution.110 Analysts have a 20 keV are incident on the surface, and the ions removed
(sputtered) from the surface are detected. Surface selectivity efforts are being made to increase the range of applicability.
arises from the depth of the region where the sputtered ions Klapetek et al.124 have developed an approach to do AFM
arise. Using cluster ion beams has enhanced the surface sen- analysis of nanoparticles on rough surfaces and with overlap-
sitivity and, for some materials, minimized the region of ping particles. Because a variety of tip artifacts can influence
damage, allowing sputter depth profiles of organic the accuracy of the measurements, international standards
layers.113,114 To extract surface molecular information, committees (ASTM E42 and ISO TC201) have subcommit-
SIMS is used in a “static” mode that involves a low density tees working on relevant standards and guides to address
and low total dose of ions, so the surface damage and altera- these effects.125 Braga and Ricci devoted a book chapter to
tion are minimized. Both atomic and molecular secondary recognizing and avoiding artifacts in AFM imaging.126 The
ions are used to extract the surface information.115 Like the fact that AFM can be conducted in vacuum, under ambient
electron spectroscopies, SIMS is useful for obtaining infor- conditions, within liquids, or other environments127 makes it
mation about surface layers, functional groups added to the a valuable tool for in situ studies.
surface, and contamination. Two differences between the The relatively low cost of AFM systems has allowed many
electron spectroscopies and SIMS are: (1) the high sensitiv- research groups to extend the applicability in a variety of cre-
ity (HS) of time-of-flight SIMS (TOF-SIMS) to many trace ative ways. Using nanoparticles (or molecules) attached to
elements and functional groups and (2) the changes (dam- scanning probe tips, it is possible to measure interactions of
age) induced to the surface due to ion sputtering. The func- individual nanoparticles (or molecules) with either a flat sur-
tional group sensitivity has been usefully applied in many face or to other nanoparticles.128 These measurements provide
ways. For example, TOF-SIMS has been used to examine information about interaction forces and enable these forces
peptides conjugated to Au nanoparticles as part of a protein to be examined in various environments. AFM also has been
kinase assay116 and to examine a multilayer, plasma- used to determine the roughness of nanoparticle surfaces.
produced organic coating deposited on alumina nanopar- This is highly valuable as most methods for measuring surface
ticles.117 For relatively large nanoparticles produced during roughness cannot be used on such small, curved surfaces.
welding, SIMS with sputter profiling has been used to exam- AFM also has been combined with TEM to investigate the
ine the complex layers that form on the particles.118 Unlike impact of synthesis processes and particle size on the surface
XPS, which often infers chemistry indirectly from binding roughness of ceria nanoparticles.129
energy shifts, SIMS has the advantage of measuring molecu-
lar fragments directly.
Because SIMS depends on the sputtering process, it inher- VI. APPLICATIONS OF LESS COMMON METHODS,
ently damages a nanostructured material under study, and NEW DEVELOPMENTS, AND A SYNTHESIS
this must be taken into consideration. Although many nano- PROBLEM-SOLVING EXAMPLE
materials and nanoparticles have been successfully examined Although important information can be obtained by using
using SIMS, it is now established that nanoparticles sputter the most common surface analysis tools and each of these
at different rates than flat surfaces or films.119–121 Recent methods has strengths and limitations, some critical questions
work shows that in several circumstances, nanoparticles melt cannot be fully answered using these methods. Two of several
or evaporate after direct or grazing impact from many types important topics that challenge many tools are: (1) testing the
of primary ions.122 Thus, it has been demonstrated that uniformity of particle coatings at the atomic level and (2)
SIMS can be a useful and important tool for characterization measurements in the particles’ native or working environ-
of nanomaterials, but appropriate consideration should be ments (in situ tools).11 Even before “nanotechnology” was a
given to potential implications of enhanced sputter rates or commonly used term, Dick Brundle frequently observed that
sample melting. as feature size gets smaller, the distinction between bulk and
surface analysis disappears.130 Certainly, the distinctions
between bulk (core) and surface analysis tend to get blurred
4. Scanning probe microscopy for nanoparticles and other nanomaterials. Methods that are
Unlike other surface analysis tools, the nanocharacteriza- not part of the traditional set of surface analysis tools are pro-
tion credentials of scanning probe microscopy (SPM) are viding highly valuable information about surfaces and thin
widely recognized, and there are many variations of SPM- layers. For example, it is possible to observe individual atoms
based methods: scanning tunneling microscopy (STM) and move across particle surfaces using STEM, and it can be
AFM are the most common examples. AFM can provide highly useful in examining the atomic distribution in nanopar-
three-dimensional imaging/visualization of nanoparticles ticles, including core-shell structure.
distributed on a flat surface. It also can provide qualitative In this section, we examine four methods that provide in-
and, in some cases, quantitative information on physical formation not as easily available from the more common
properties of nanoparticles, including size, morphology, sur- surface analysis techniques. In addition to the surface compo-
face texture, and roughness. With appropriate care in dealing sition that can be obtained with the aforementioned methods,
with possible tip artifacts, AFM-generated images can be two focus more on characterization of the surface molecular
used to extract particle-size distributions and even particle structure and binding interactions. SFG is inherently sensitive
volumes.123 Although most high-value measurements of to interfaces, and improved technology and the application of
nanoparticles are made for isolated particles on flat surfaces, theoretical modeling now enable SFG to provide information
about the binding of molecules on nanoparticle surfaces in liq- SFG-VS experiments on nanoparticles have been conducted
uid environments. Although not a traditional surface method, in the presence of liquid, usually probing the C–H stretching
nuclear magnetic resonance (NMR) can be used to obtain in- vibrations (2800–3000 cm1).141,142
formation about interactions on particles in liquid and gaseous In a recent study, Lu et al.143 used in situ SFG-VS to
environments. Low energy and medium energy ion scattering study the binding of deuterated acetic acid on ceria nanopar-
(MEIS) can provide information about the outer layers and ticles with different oxidation states in aqueous solution.143
layer structure of particles, and recent technology develop- The objectives were to directly measure ligand binding
ments increase their sensitivity and potential applicability to vibrational spectra signatures on ceria nanoparticle surfaces
nanomaterials. in solution and understand how the oxidation state of ceria
These methods are not among those commonly applied to can influence the type of molecular bonding at the nanopar-
nanomaterials. They may involve unique or uncommon ticle surface. In the experiment, ceria nanoparticles were de-
instrumentation or require an expertise well beyond that gen- posited on the flat surface of a CaF2 hemisphere
erally available to many members of the research commu- incorporated into an experimental cell that allowed contact
nity. Nonetheless, it is useful to know that they can provide with acetic acid solutions (shown in Fig. 16). Ceria nanopar-
information not available through the most commonly avail- ticles deposited on the bottom (flat surface) of the CaF2
able methods. Through the use of user facilities and collabo- hemisphere were exposed to solutions containing acetic acid.
ration, the research community may gain access to such Analysis of peaks in the spectra shown in Fig. 17 illustrates
instrumentation to address specific questions. that neutral acetic acid at relatively low pH was deproto-
We (and others) often discuss nanomaterial characteriza- nated before being adsorbed on oxidized (Ceþ4) and mixed
tion as if the only objective were adequate characterization oxidation state ceria (þ3 and þ4) nanoparticles. From the
of the material. In many cases, characterization is part of a polarization dependence in the SFG spectra, the two peaks
feedback loop related to obtaining material of the desired can only be attributed to the symmetric stretch modes of
composition, structure, size, or property (function). Some bidentate binding structures. The two major peaks then are
level of characterization may be needed to initiate the pro- identified as bidentate bridging and chelating species of
cess, but the whole effort usually involves identification of roughly equal intensity for the partially reduced particles.
characteristics or problems and a cycle of synthesis, charac- The measurements also suggest that the chelated species is
terization, process checks, and other steps. Often, multiple decreased for the fully oxidized particles. The direct obser-
passes are required to produce the product or property of in- vation on the coexistence of the bidentate chelating and
terest. This section will conclude with one such example. bridging ligand binding, as well as their dependence on the
surface oxidation states, is encouraging for characterization
and understanding of the surface structure and reactivities of
A. Use of sum frequency generation to determine nanoparticles. These types of measurements, in combination
molecular binding states on nanoparticle surfaces with modeling of adsorbates on model ceria clusters, suggest
Developed in the 1980s, SFG spectroscopy is a nonlinear that SFG-VS can be a powerful spectroscopic tool for in situ
laser spectroscopy method that involves mixing two laser characterization of binding on nanoparticles surfaces.
beams at a surface or interface that generate an output beam
with a frequency equal to the sum of the two input frequen-
cies. SFG is a more generalized version of second harmonic
generation (SHG), where the initial frequency of one laser is
doubled at an interface. The interface selectivity of SHG and
SFG comes from the symmetry requirement for the second-
order nonlinear processes that only molecules at the surface
or interface of an amorphous or isotropic material or liquid
can contribute to the SHG or SFG signal. Because it is an op-
tical method, it can be used in a variety of environments (in
situ) to deduce the composition, orientation, and some struc-
tural information of molecules at gas–solid, gas–liquid, and
liquid–solid interfaces. With a well-designed instrument and
setup, SFG can have sub-monolayer sensitivity. Due to the
ability to tune one of the incoming laser beams, vibrational
spectra can be obtained (SFG-VS), providing a highly interfa-
cially sensitive version of infrared spectroscopy.131,132
FIG. 16. (Color online) Illustration of the SFG liquid cell and experimental
Work in the 1990s demonstrated that SHG could be readily geometry. The cell body was made of Teflon. The nanoparticles were depos-
applied to sub-micron and nanoparticles.133,134 Although there ited on the flat bottom of a CaF2 1 in. diameter hemisphere, which served as
now are many publications involving SFG characterization of the optical window. The liquid flowed through ports sealed by Teflon plugs
for studies not requiring the following liquid. The visible and infrared beams
nanoparticles, SFG-VS studies on nanoparticles mostly have
were propagated through the CaF2 hemisphere and overlap at the center of
been conducted in the dry environment, focusing on either the the flat surface of the CaF2 hemisphere. The SFG signals were collected in a
hydrocarbon chains135–138 or carbon monoxide.139,140 A few reflective geometry.
to samples in various physical and chemical states, with

wide-ranging reports from samples in gaseous, liquid, and
solid phases.
Although not a common method for characterizing nano-
particle surfaces, in many cases, the nanoparticle surfaces
can be probed directly or indirectly through chemical func-
tionalization,148,149 and there are a number of reports
describing NMR’s utility for nanoparticle studies (see Ref.
150 and references therein). Given ideal conditions, the high
surface area of a collection of nanoparticles makes the study
of their surfaces more straightforward than for larger particu-
lates. However, when the surface atoms contain so-called
“quadrupolar nuclei” (those with nuclear spin quantum num-
bers greater than 1=2), additional couplings between the elec-
tric quadrupole moment of the nonspherical nuclei and local
gradients in the electric field can cause additional line broad-
ening,151,152 resulting in decreased spectral sensitivity and
resolution. However, reports of direct, surface-sensitive
NMR spectroscopy or the use of probe molecules to indi-
rectly survey local surface structure describe the use of iso-
tropic chemical shift as the predominant interaction for
structural elucidation.148
In work at EMSL, we have been interested in the evalua-
tion of reactive sites on the surfaces of materials, including
nanoparticles. Such studies are important for understanding
FIG. 17. (Color online) SFG-VS spectra (2-cm1-step scan) of (a) partially
reduced ceria nanoparticles and (b) oxidized ceria nanoparticles in contact
bonding within composite materials, where nanoparticles or
with CD3CO2H solutions. The vertical dashed lines reveal the shift of peak other materials are added to, for example, polymer systems to
positions. The two major peaks are identified as bidentate bridging and che- change physical or chemical behavior. In our fundamental
lating species of deprotonated acetic acid adsorbed on the particle surfaces. studies, small organic molecules, such as alcohols and organic
The relative ratio of the type of bonding varies for reduced and oxidized
surfaces. There are two lines for each set of data related to the polarization
acids, are particularly well-suited for evaluating various bond-
combinations of the incident and SFG signals. The series ssp identifies s- ing environments on the surfaces of nanoparticles. Because
polarizations for the SFG and visible beams and p-polarization for the IR the chemical reactivities of these molecules typically are asso-
beam, and ppp indicates p-polarizations for the SFG, visible, and IR beams. ciated with the –CR2OH and –COOH functionalities, 13C-
containing versions of small organic molecules labeled at
these terminal functional sites often are used.
B. Reactivity of anatase nanoparticles with ethanol Measurements of ethanol’s reactivity with TiO2 nanopar-
measured by nuclear magnetic resonance ticles provide an example of NMR measurements to deter-
NMR is well-known as a nondestructive characterization mine the nature of small molecule binding on nanoparticle
method based on the excitation, evolution, and detection of surfaces. Anatase TiO2 nanoparticles initially were heated to
spin coherences between nuclear magnetic substates. In the 400 C under vacuum for 4 h to remove surface waters.
proper circumstances, it can be used directly or indirectly to Then, the particles were exposed to 1–13C-ethanol vapor for
probe the surfaces of nanoparticles. 3 h in a dosing apparatus kept at 100 C. After evacuating
Typically, NMR is performed by placing a sample con- the remaining gas phase ethanol, the dosing apparatus was
taining nuclei with nuclear spin quantum numbers greater sealed and moved to a dry glove box, where the sample was
than zero within a static magnetic field followed by irradia- transferred to an NMR sample holder. Magic angle spinning
tion of these nuclei with radiofrequency magnetic fields at or (MAS) 13C NMR was performed on these systems using a
near to their Larmor frequencies.144–146 The evolution fre- cross-polarization pulse sequence with high-field 1H decou-
quencies of spin coherences detected in an NMR experiment pling.153 This MAS-NMR method provides high resolution
are typically reported in values of parts-per-millions (ppm) for the 13C on the solid surfaces and also benefits from the
of a shift from the evolution frequencies detected from a transfer of polarization from highly polarized 1H spins that
known standard, and these shifts depend on the local electro- are nearby to the 13C being detected. These experiments
magnetic environment of the nuclei.147 Hence, NMR shifts were conducted using a spectrometer with a 17.6 Tesla mag-
report on local structure (bond lengths, number of bonds, netic field strength (corresponding to resonance frequencies
identity of nearby atoms, bonding electron polarization, of 750 MHz for 1H and 188 MHz for 13C) to take advantage
nearby unpaired electrons, etc.) and dynamics (through aver- of the gains in both sensitivity and resolution obtained when
aging of these local features), so it has become an indispen- moving to such high-field strengths.
sable tool for scientists and engineers seeking to understand, As shown in Fig. 18, two major resonance lines are
monitor, and control local structure. NMR is also applicable observed for labeled ethanol reacted with the anatase
physisorbed to the titania surface. The chemical shift of this

peak is close to that of neat ethanol (57.0 ppm), and this res-
onance presumably represents ethanol that is hydrogen-
bonded to surface hydroxyls or other species present on the
titania nanoparticle surfaces. The second broader resonance
peak at 70 ppm represents the ethanol molecules that have
formed C–O–Ti ether linkages with the surface of the
nanoparticles.
C. Low and medium energy ion scattering

1 13
measurements of nanoparticle surfaces
FIG. 18. (Color online) H/ C cross-polarization MAS NMR spectrum of
1-13C-ethanol dosed onto a sample of titania (anatase) nanoparticles, exhib- For more than 40 years, low, medium, and high energy
iting two bonding environments for the ethanol molecules reacted with the ion scattering have been important tools for the characteriza-
anatase surface. Data were obtained at a 13C resonance frequency of
tion and modification of materials surfaces.154 Recent advan-
188.657 MHz, and a 1H resonance frequency of 750.198 MHz with TPPM
1
H decoupling after a 2 ms cross-polarization contact time, using a 1H 90 ces in both low energy ion scattering (LEIS) and MEIS
pulse of 6.5 ls and a 5 s recycle delay. A total of 8192 transients were col- enhance their ability to provide more routine and useful in-
lected, and the data processing included 50 Hz of Lorentzian broadening. formation about the outer layers of nanoparticles. In these
featured examples, both LEIS and MEIS are used to under-
nanoparticle surfaces, indicating ethanol molecules attached stand the nature of bi- and trimetal catalysts and are being
in two distinct bonding environments. The two resonance developed to maintain high catalytic activity while lowering
lines at 60 and 70 ppm [shift from a tetramethylsilane (TMS) the cost by decreasing the amount of precious metals
reference sample] arise from 13C nuclei originally attached required.
to the –OH group on the 1-13C-ethanol. An additional,
smaller resonance from the naturally abundant 13C in the 1. LEIS and nanoparticle surface characterization
methyl groups was detected at lower frequency (approxi-
mately 17 ppm). Under these treatment and loading condi- LEIS involves the elastic scattering for 1 to 10 kV ions
tions, the more highly populated environment, detected as a (often helium) from surfaces. Also known as ion scattering
resonance at 60 ppm, arises from ethanol molecules that are spectrometry (ISS), LEIS is a well-established but not
widely used method. The amount of energy lost by the ion
during this scattering process is used to determine the iden-
tity of the elements present in the outermost atomic layer of
the material under analysis. Only species heavier than the
primary (incident) ion are detected, and the mass resolution
(ability to distinguish different elements) depends on the pri-
mary ion and the mass of the species being analyzed. Recent
developments and the availability of a fully integrated com-
mercial instrument have made it particularly useful because
of the high sensitivity to the outermost atomic layers of a
sample.
This high surface specificity has been demonstrated for
Pt3Fe alloys by showing that the outer atomic layer of these
alloys contains no Fe after annealing.155 The LEIS for the
annealed alloy (Fig. 19) shows an elastically scattered peak
for only Pt, while the same surface after some sputtering
shows the presence of both Fe and Pt. This high surface se-
lectivity provides important information about the true outer
nature of surfaces. This useful surface sensitivity applies
equally to nanoparticles, and, with some assumptions and
calculations, LEIS can readily be used to determine the size
of single metal nanoparticles and the surface enrichment of a
species in a bimetal catalyst.156
Although most of the LEIS signal comes from the very
FIG. 19. (Color online) Surface characterization of a Pt3Fe alloy using 1 keV outer surface layer, it also is possible to extract information
Neþ LEIS to collect data from mildly sputtered and annealed surfaces. As about the thickness and atom profile of layers a few mono-
indicated by the schematic model, no Fe is observed for the annealed sur- layers thick. Rafati et al.157 used high sensitivity LEIS (HS-
face, indicating the formation of a thin Pt skin, which is destroyed upon
LEIS) to determine the thickness of the SAM layer on Au
even very mild sputtering. Reprinted with permission from Stamenkovic
et al., Nat. Mater. 6, 241 (2007). Copyright 2007, Macmillan Publishers nanoparticles discussed earlier. The LEIS determined thick-
Nature Publishing Group. ness was 1.8 nm, which lies between the SESSA-determined
value of 1.85 nm and 1.74 nm obtained by Shard’s simplified then may be investigated to determine which properties need
approach.90 to be adjusted to maximize their catalytic activity.
Soft landing of mass-selected ions is a novel method that
2. MEIS and nanoparticle characterization enables precise control over the size, composition, and surface
density of complex molecules, clusters, and nanoparticles
MEIS involves elastic scattering of ions with energies delivered to substrates.170–175 Ion soft landing combined with
between 50 and 200 kV. Because of the higher energy, it is magnetron sputtering of a metal in a high-pressure inert gas
sensitive to a thicker layer of material than LEIS, but, with has been demonstrated as an effective technique for generat-
high energy resolution, it also can sense a single atom layer. ing and depositing well-defined nanoparticles across a range
MEIS using electrostatic analyzers (ESA) typically involves of sizes and compositions.164,165,168,176–178 Direct current
mm-sized beams and considerable time for data collection. A (DC) magnetron sputtering of up to three independent targets
new-generation of TOF analyzers has increased sensitivity with Ar in the same vacuum region has been used to generate
and affords analysis of smaller areas. A web presentation by Pt-alloy nanoparticles containing one and two additional met-
Grande158 highlights some of the recent advances in MEIS, als.179 Using this multitarget sputtering approach, we have
including several examples of application to nanoparticles. generated ternary Pt-alloy, core–shell, and cluster-in-cluster
Because MEIS signals are themselves influenced by nanopar- nanoparticles. The anionic nanoparticles were size-selected,
ticle shapes and sizes, the resultant data can be used to deter- employing a quadrupole mass filter,180 and soft landed onto
mine nanoparticle shapes and sizes, as well as the profile of the surface of highly oriented pyrolytic graphite (HOPG) and
elements within particles. To minimize confusion, profiles Si(100) substrates at low kinetic energy. Following soft land-
of nanoparticle-layered structures require a nearly single layer ing, the substrates were analyzed using a combination of
of nanoparticles on a support. By comparing data to a model TOF-MEIS, AFM, and XPS to determine the size, composi-
for CdSe-core ZnS-shell nanoparticles, MEIS determined the tion, and coverage of the supported nanoparticles.
core (Cd0.65 Se0.35) and shell (Zn0.41S0.59) stoichiometries, Precise control of the process parameters during magne-
core diameter (5 nm), and shell thickness (0.6 nm).158 tron sputtering coupled with mass-selection of the anionic
nanoparticles prior to soft landing enables substrates to be
3. Using MEIS and XPS to identify the source of coated with accurate amounts of monodispersed nanopar-
contamination on soft-landed nanoparticles generated ticles. The well-defined nature and precise surface coverage
by magnetron sputtering of the soft-landed nanoparticles makes them particularly
In an effort to learn more about the distribution of ele- amenable to analysis by TOF-MEIS. When 8 1012 particles
ments in multi-component particles supported on a substrate, are deposited on Si(100), AFM images show the nanopar-
MEIS has been applied to Pt/V/Cu nanoparticles. The data ticles are predominately isolated and distributed evenly
obtained highlight the value of applying a surface sensitive across the surface. Figure 20(a) shows the 90-keV Heþ ion
analysis method (MEIS) and demonstrate the challenges scattering spectrum of 8 1012 6 nm diameter Pt/V/Cu nano-
associated with preparing and characterizing nanoparticles. particles soft landed onto a Si(100) substrate. The peak for
In addition, it is shown that even nanoparticles prepared Pt, the primary component of the particles, is clearly
using extremely well-controlled physical synthesis methods resolved, while the peaks for Cu and V are weaker and super-
may suffer from unexpected and undesirable contamination, imposed. Unfortunately, the large background peak for Si
and multiple analytical techniques may be needed to confi- makes it difficult to detect other low energy peaks, such as
dently identify the presence and confirm the removal of oxygen.
unwanted additional materials. To eliminate the large background signal at low energy
The Pt-catalyzed oxygen reduction reaction (ORR) that associated with Si in the TOF-MEIS measurement, HOPG
occurs at the cathode in proton exchange membrane fuel surfaces were used as the soft-landing substrate. Topography
cells (PEMFCs) has been widely examined.159 For PEMFCs measurements obtained using AFM reveal that at low cover-
to compete commercially with conventional engines, the Pt age, the soft-landed nanoparticles stick preferentially along
mass activity at the cathode needs to be improved by a factor the step edges of the HOPG surface, creating linear chains.
of four.160 Alloying of Pt with one or two other metals has Unfortunately, at the higher coverages needed to obtain an
been demonstrated to produce more active and less costly adequate signal-to-noise ratio for the TOF-MEIS measure-
catalysts for the ORR.161 Studies of bulk surfaces have ments, the nanoparticles begin to pile on top of each other,
shown that bimetallic Pt3M (M ¼ Fe, Co, Ni) alloys exhibit forming a dense aggregated layer. Therefore, an intermediate
improved catalytic activity toward the ORR compared to coverage, where the majority of nanoparticles remained iso-
pure Pt.162 Consequently, supported bi- and trimetallic alloy lated yet with sufficient material to provide a good signal-to-
nanoparticles are promising candidates for use as ORR cata- noise ratio, was needed.
lysts in PEMFCs. Because it is difficult to use solution chem- To create defect sites that could pin or stabilize the par-
istry to form well-defined binary and ternary alloy particles, ticles deposited on the surface, plasma sputtering of the
a variety of physical synthesis techniques163–169 are being HOPG surfaces was attempted. The HOPG surfaces were
developed to generate bare alloy nanoparticles of exact size subjected to low power (30 W) radio frequency (RF) plasma
and composition and deposit them onto surfaces at con- sputtering in Ar for 10 min prior to soft landing of nanopar-
trolled coverage. Such well-defined supported nanoparticles ticles. The TOF-MEIS spectrum from 5 1012 4 nm
procedure described, and allowed to reside in vacuum for

90 min. Both surfaces then were examined using XPS.
Figure 21(a) depicts the XPS spectrum of the bare HOPG
surface allowed to reside in the deposition instrument for
90 min. The C 1s peak is dominant, and there are no other
significant features in the spectrum. In contrast, the results
for the HOPG surface that was RF plasma sputtered reveal
the presence of intense peaks assigned as Mo, C, and O [Fig.
21(b)]. The O peak could be explained as a result of the oxi-
dation of the defects created on the sputtered HOPG surface
following its removal from vacuum. However, the Mo peak
source was more subtle. The sample holder used to mount
the substrates in the instrument for RF plasma cleaning and
soft landing of nanoparticles is made of Mo. Therefore, dur-
ing the effort to create more defects and functional groups
on the surface of HOPG to pin isolated nanoparticles, the
surface was inadvertently covered with the sample holder
element, Mo. These findings are particularly relevant as RF
plasma sputtering is often recommended by instrumentation
manufacturers as a way to clean surfaces prior to further
modification by deposition or chemical synthesis.
FIG. 20. (a) TOF-MEIS spectrum of 6 nm Pt/V/Cu nanoparticles soft landed

onto Si(100). The spectrum shows the composition of the particles, but the
large peak associated with Si makes it difficult to detect low energy peaks
from the particles, such as oxygen. (b) TOF-MEIS spectrum of 4 nm Pt/V/
Cu nanoparticles soft landed onto RF plasma cleaned HOPG. The new peak
appearing after deposition on the HOPG substrate was from Mo that was
unintentionally deposited on the substrate during the cleaning process.
diameter Pt/V/Cu nanoparticles deposited onto RF plasma,

pretreated HOPG is shown in Fig. 20(b). Because the peaks
for Pt, Cu, and V were more intense on HOPG compared to
Si(100) and as the large Si background peak is not present
on HOPG, it was possible to measure the oxygen peak at
55 keV. However, the most striking difference between the
two TOF-MEIS spectra was the appearance of an additional
intense peak between Pt and Cu on the plasma-treated
HOPG surface that is not present on Si(100).
Because there was no obvious explanation for the addi-
tional peak in the TOF-MEIS spectrum of the nanoparticles
deposited on the plasma-treated HOPG, a series of experi-
ments were conducted to determine the contaminant source.
Two freshly cleaved HOPG surfaces were mounted in the
sample holder used for the previous uncontaminated samples
then introduced into the soft landing instrument. The first
FIG. 21. (a) XPS spectrum of HOPG placed in vacuum for 90 min. (b) XPS
surface was allowed to reside in vacuum for the duration of
spectrum of HOPG RF plasma cleaned in Ar for 10 min. XPS data demon-
a typical soft landing experiment (90 min) and removed. The strates that Mo was introduced into the soft landing process during the sput-
second surface was RF plasma cleaned, following the same ter cleaning of the HOPG substrate.
Soft landing is a unique and powerful approach for creat- Based on experiences among our research teams, some
ing highly controlled, well-defined nanoparticle (and large guidelines for nanoparticles synthesis are listed (as follows).
biological molecule) layers on substrates. However, as is all These may be especially useful to enhance repeatable syn-
too common, when one part of the sample preparation pro- thesis of nanoparticles and maintain stable properties for
cess was altered, a surprise element was introduced. Only nanoparticles produced by wet chemical and other particle
via the application of multiple methods sensitive to thin sur- generating methods.
face layers was it possible to determine how this minor vari-
ation in the soft landing procedure resulted in nanoparticle (1) Plan and organize the experiment to minimize (or hold
contamination. MEIS and XPS now are being used to deter- constant) the number of parameters that can vary in the
mine the elemental profile of metals in the alloy nanopar- process. Without adequate planning and records, the pro-
ticles without the unwanted contamination. cess and particle properties usually will change (however
slightly) with each different person and over time.
VII. DISCUSSION (2) Emphasis should be given to the cleaning of glassware or
This review is written in the context of what some other synthesis components (from instruments or auto-
researchers consider a crisis regarding the adequate charac- clave, etc.). Several oxidizing and/or reducing agents are
terization and underreporting of nanomaterial information. available commercially for cleaning glassware. If the syn-
We have highlighted a range of issues, challenges, and thesis is carried out on routine basis, it is advisable to pur-
opportunities associated with nanomaterials synthesis and chase dedicated glassware and instruments for a particular
characterization. In many ways, nanoscience and nanotech- type of nanomaterial to avoid cross contamination.
nology are immature, developing fields that have made re- (3) In common practice, a master batch of nanoparticles is
markable progress. Although there are important analysis stored separately, and small aliquots are taken out from
and characterization challenges, there also are major advan- the batch when required for characterization. However,
ces and exciting new scientific and significant technological the repeated opening of the master batch of nanoparticles
developments. The community is increasingly recognizing suspension/powder to atmospheric condition is undesired
the need to pay additional attention to characterization of and can be a source of contamination. Repeated use of a
nanomaterials, and the tools described or mentioned in this spatula or pipette tips in the master batch also should be
paper and others allow most of the analysis issues to be avoided to minimize contamination. It is suggested that
addressed. Somewhat less recognized is the importance of instead of preparing and storing the nanoparticles sample
recording and reporting details of the processes and history in one master batch, the material should be stored in sev-
of nanomaterials used in a variety of studies. Such informa- eral small, pre-cleaned vials. This will minimize repeated
tion cannot be ignored or cited as trivial in the case of exposure of the entire sample to the external environment.
nanomaterials. If surface oxidation or chemical state information is im-
There is a close relationship between systematically portant, once exposed to the environment, a vial should
developing a reliable nanoparticle synthesis process and not be used for surface characterization studies, although
characterization methodology. Herein, we make some gen- bulk characterization and property measurements might
eral recommendations related to particles synthesis, prepara- still be done on the same sample.
tion of particles for analysis, and convey an approach for (4) Seemingly harmless instruments, such as pH/conductiv-
selecting the tools to be applied for “routine” characteriza- ity probes, temperature measurement probes, etc., should
tion of nanoparticles. be cleaned thoroughly before placing in contact with the
batch of nanoparticles. The exposure to a master batch
A. Synthesis, processing, and documentation of nanoparticles should be avoided (if possible), and
smaller aliquots taken out of the master batches should
The core of nanomaterials research, with many implica- be used for measurement.
tions for applications, starts with controlled synthesis of (5) The storage conditions for nanoparticles should also be
materials that exhibit the desired and, often, tunable proper- considered. Our experience suggests that storage condi-
ties. We have shown examples of how surface sensitive anal- tions, such as light, dark, temperature (room tempera-
ysis methods can be important tools for developing reliable ture, refrigerated, or frozen), humidity, and duration of
synthesis methods and examining the consistency and repro- storage, can affect the stability and reactivity of nanoma-
ducibility of these processes. However, we also have discov- terials. For example, on several occasions, we have
ered that minor changes in synthesis steps and inadvertent observed that solutions of well-dispersed nanoparticles
introduction of minor contaminants, sometimes below the cannot be resuspended after they have been frozen once.
level that can readily be detected, can alter material behav- (6) Researchers synthesizing nanomaterials for biological
iors. In other words, we cannot always characterize our way applications should treat the nanoparticles as a biological
out of difficulties introduced during synthesis. Therefore, it sample. It is advised that the materials and biological sci-
can be important to take extreme care in handling and keep entists work together to understand the nuances of pro-
thorough records that can identify procedural or other steps cess parameters and how it can influence the biological
in a synthesis process that may introduce unintended end points. All nanomaterials used in biological studies
changes in nanomaterial properties. should be handled analogous to live biological samples,
and the contamination from various sources, such as steps. Both ASTM E42 and ISO TC201 have guides for sam-
bare hands, glassware, hoods, working benches, etc., ple preparation and handling181,182 with many of the prac-
should be minimized. All glassware and work benches tices appropriate for nanomaterials. In addition, TC201 has a
should be sterilized, and the researchers should use good working group developing a guide specifically for prepara-
laboratory practices, sterilized tips and glassware, and tion and mounting of nanomaterials for surface analysis.
personal protective equipment for materials synthesis.
(7) Select an appropriate core set of characterization tools C. Characterization—what type and how much?
(including a surface sensitive method) to verify the A range of characterization issues or challenges have been
repeatability and consistency of the synthesis approach. identified and discussed in other parts of this review, and the
(8) Records related to chemicals used in synthesis, dates of value of surface sensitive analysis methods has been noted.
synthesis, and means of storage should be kept and Although the challenges of adequate characterization may
linked to samples, as well as to batches of samples, so seem daunting, by focusing on a few important issues and
the parentage and history of materials can be maintained gaining an understanding of the nature of the material
and possible similarities and sources of differences can involved, many of the challenges can be effectively addressed.
be tracked if they are identified. Times between synthe-
sis and use or characterization should be recorded and 1. Surfaces, coatings, and time
reported.
Although important aspects of the characterization for a
nanomaterial must be dictated by the function and purpose
B. Sample preparation of the material, the nature of the surface of a nanomaterial
Several of the examples described in this paper have impacts how the material will interact with other materials
noted the importance and sometimes difficulties of preparing and its surrounding environment.
samples for analysis. There are two major components to Because interactions of a material with its environment
sample preparation. The first is to collect the sample (e.g., usually alter the material, information about the rate of any
removing particles from the master batch of solution or pow- changes (including the formation and alteration of surface
der or extracting the sample from a test environment). Two coatings) in relevant environments is important for funda-
methods of removing nanoparticles from solution for mental understanding, as well as for assessing material reli-
detailed analysis were discussed earlier. Another challenge ability and predicting environmental (or biological) impacts.
is preparing material for analysis without either destroying Consequently, there is a need for increased attention to sur-
the desired information26 or having that information masked face and coating characterization and for advancing the
by components from the solution.55 The specific information understanding of the kinetics of particle change (surface and
requirements for the analysis will determine the require- “bulk”).
ments related to sample handling and minimizing the loss of
information. Obtaining the desired information may require 2. Selecting “core” characterization tools
mounting samples in anaerobic environments, using techni- The essential characterization needs for a specific nano-
ques that can obtain information in the working environ- material are not always clear, and unnecessary characteriza-
ment, or even freezing a specimen. tion can be costly while providing little added value. In our
In addition, each analysis method will have a set of sam- experience with iron metal-core oxide-shell nanoparticles,
ple requirements. For example, XPS requires enough sample we found that we needed to obtain a general understanding
material within the analysis area (tens to hundreds of square of the nanoparticles we were studying, and this initial under-
micrometers) such that it is usually desirable to have enough standing required the application of a variety of tools.27
material deposited on the supporting substrate to totally However, once the nature of the particles (and how they
block the substrate signal. These piles of particles need to be change) was understood, a routine core set of tools was
appropriately considered in quantitative analysis of coatings adequate, in most circumstances, to provide the information
on particles.90 In contrast, for MEIS, it is desirable to have a we needed to assess the nature of a particular set of particles
single layer of nanoparticles distributed/supported on a sub- and how they changed with time.28 In many types of studies,
strate that will produce only a small background signal. For a routine set of measurements can help assure that the mate-
MEIS, a “pile” of particles would complicate the data analy- rials being examined have properties consistent with those
sis. Because the information needs and method requirements tested or applied at earlier times. For example, particle size
will vary, there will be no universally “correct” method of and surface potential measured by a dynamic light scattering
sample preparation and mounting. instrument may be an important check on material consis-
Consideration of analysis needs, including the nature of tency just prior to in vitro biological studies.
the question, required speed of analysis, number or speci- It seems unlikely that there will be a unique set of essen-
mens to be analyzed, and amount of material available, will tial characterization tools that apply to all or most nanomate-
impact choices and options for sample preparation. As rials. The critical measurements will be material and
described for sample synthesis and processing, understand- application dependent. However, we have discovered that
ing discrepancies and differences among results can be mini- we almost always need to collect some of the data that
mized by documenting and reporting sample preparation appear on many of the characterization lists,8 including
The tools we have discussed in relation to surface analysis

each have strengths and limitations as summarized in Table
IV. The strength column does not include all of the types of
information that can be obtained by the techniques, but it
highlights information that might be most easily obtained.
Because of the importance of surface properties, some type
of surface sensitive characterization method should be used
to characterize most nanomaterials. However, the selection
of the method to be used can be based on the accessibility,
ease of use, and type of information needed.79,86,87 We have
found that XPS can be quick and easily applied, particularly
for screening various types of compositional or chemical
state surprises.78
The relative amount of application of a variety of analysis
methods for characterization of nanomaterials is shown in
Fig. 22. This use frequency was obtained by combining the
search terms used for Fig. 1 (nanomaterial AND nanoparticle
AND nanostructure) with terms related to the specific tech-
nique (full technique name OR the common identifier). The
most commonly applied methods are XRD, TEM, and SEM.
Although both AFM and XPS are the most commonly used
surface analysis tools, we have argued that their importance
warrants increased application. The data also suggests that
the application of MEIS, LEIS, and SFG to nanomaterials is
currently very uncommon.
FIG. 22. (Color online) Comparison of the relative rates of application of a
wide range of analysis tools to nanomaterials based on a Web of Science
search as described in the text. The most widely used surface analysis tools
are XPS and AFM. Techniques not previously discussed in this paper
include: Fourier transform infrared (FTIR) spectroscopy, dynamic light scat- 3. Combining in situ real-time and ex situ
tering (DLS), ultraviolet–visible spectroscopy (UV-VIS), x-ray adsorption measurements
spectroscopy (XAS), extended x-ray adsorption fine structure (EXAFS), and
x-ray absorption near edge structure (XANES). Because particles may change as the environment around
them is altered, it is useful to obtain information in the envi-
particle size, shape, structure (TEM and XRD), and surface ronment of interest and have the ability to make measure-
composition (XPS). The need for multimethod analysis is ments as a function of time in that environment, or conduct
particularly valuable in addressing issues related to the reli- in situ and in situ real-time measurements.11 In many cir-
able synthesis of materials and obtaining an initial under- cumstances, a combination of in situ real-time and ex situ
standing about how the materials may change with time or in measurements may be needed to obtain the appropriate
an altered environment. understanding of a system, as we discovered in our iron
Jensen et al.183 observed that need for multitechnique metal-core oxide-shell nanoparticle work.28 Depending on
analysis for adequate characterization of new materials is the nature of the system, there are many different types of
well recognized but not always put into practice. In their methods that could be used to provide in situ and real-time
study of a set of papers reporting on new carbon nanotube- data. Although they are not discussed in detail, Table V pro-
templated thin layer chromatography plates,183 they found vides an indication of methods that might be used and some
that half of the papers analyzed used three or fewer techni- of the types of information that can be obtained. When used
ques to characterize new materials, whereas for the specific in combination with other surface and “bulk” analysis meth-
materials they were examining, the application of five or ods, they can provide a “picture” of how nanomaterials are
more methods was used to provide the needed information behaving in realistic environments and how they alter with
in more complete studies. As discussed, there is no specific time. In some cases, a simple measurement, such as zeta
number of methods required to characterize a material, the potential, corrosion current, or gas evolution, can provide
needed testing will depend on the material and application, time-relevant information easily and at low cost. When sim-
as well as how well the material is understood. Nonetheless, ple in situ tools are appropriately combined with ex situ
it appears that many research papers would benefit from con- methods, mechanistic information can be obtained.
sidering of a wider range of characterization tools, at least There are several environments where important informa-
during early stages of research. The knowledge gained by tion cannot yet be readily obtained. For example there is a
forming a self-consistent picture of a nanomaterial’s bulk, need to obtain additional information from “buried” interfa-
surface, and interface structure, and composition can be used ces, such as the solid–liquid and solid–solid interfaces
to identify the core set of analysis methods needed for rou- involving nanomaterials such as those occurring in nano-
tine characterization during a research project. composites. Such specific needs provide opportunities for
TABLE V. Examples of measurements that can be used to collect in situ or in situ real-time information about nanomaterials. The importance depends on the
property of interest. Techniques not otherwise discussed in this paper include: attenuated total reflectance FTIR (ATR-FTIR), optical fluorescence, scanning x-
ray transmission microscopy (STXM), and infrared-scattering scanning near-field optical microscopy (IR-sSNOM).
Method Type of information Comments
AFM Surface topography and particle shape with nm resolution Gas and liquid environment, including high pressure
Electrochemical Electrochemical currents and corrosion potentials Can sometimes see product formation
Optical Requires appropriate environmental transparency
FTIR Molecular vibrations in analysis region ATR-FTIR has enhanced interface sensitivity
SHG Selectively probe non-resonant or electronic Excellent in observing changes but data usually
responses from molecular or atomic interfaces cannot tell chemical identity
SFG Chemical identity, molecular structure and interactions Data modeling useful to understand environmental
at surfaces and interfaces effects on molecular vibrations
Fluorescence Tagged particle fluorescence can provide particle or
reaction locations in a complex environment including living cells
VU-VIS Size of metal nanoparticles and chemical state of Commonly used for particles in solution
some oxide particles
Tip-enhanced IR-sSNOM Vibrational information with high spatial resolution Can be done in various gaseous environments
DLS Common method for sizing particles in solution Often done in combination with zeta
potential measurements
X-ray
XRD Structures present and grain size Microbeams and synchrotrons allow liquid and
gas environment analysis
XAS Localized structure and chemical state Environment around specific atoms
STXM XAS information with 10 s nm resolution Gas or liquid environments now possible
XPS Surface composition chemical state Differentially pumped systems allow measurements
to be made in some gaseous environment
NMR Molecular structure and phase information Gas or liquid environments, needs careful planning
Transmission Electron Microscopy Morphology and structure with high resolution Can now be done in gas and liquid environment
and conducted on designed systems such as
model batteries
creative development and application of new methods and incompletely characterized. This can be a major handicap to
analysis approaches. both advancing science and development of reliable technol-
ogies. However, because of traits inherent in their nature, the
4. Qualitative versus quantitative characterization of nanomaterials often is significantly more
complex than recognized by parts of the research commu-
Although the most common application of surface analy-
nity, as well as by those charged with regulating their health
sis of nanoparticles is qualitative in the sense that the pres-
and safety. Nonetheless, tools are currently available to an-
ence of contamination, nature of surface coatings, or
swer many of the important questions. In many cases, appli-
chemical state of the surface can be readily determined, a
cation of an expanded set of tools will provided the needed
good deal of additional information also can be obtained by
information.
combining the surface information with knowledge about
The time-dependent and environmentally responsive na-
particle size or what is known about layered structures. To
ture of nanomaterials complicates determination of their
determine the nature of nanostructured materials, several
essential properties. In fact, understanding the response of
models and computer codes have been developed for inter-
nanomaterials to changes in their native or working environ-
preting data from XPS and AES.90,94–97,101,103,105 These
ments is central to understanding and predicting their behav-
codes can provide quantitative information about the enrich-
iors and long-term impacts (in vitro and in vivo for
ment or depletion of elements at a surface, the thickness of
biological studies) and on their physicochemical properties
surface layers on particles of various shapes, and island for-
for almost any application. The need to follow these materi-
mation. Evolving surface analysis tools will rely heavily on
als and their interactive surfaces as a function of time in
links between computation modeling and experiment. There
native environments places a premium on the development
is more valuable information in surface analysis data than
of real-time in situ analysis methods.
commonly used, and the value of surface analysis methods
Because surfaces and interfaces play predominant roles in
increases when quantitative information is extracted.
determining properties of nanomaterials, appropriate analy-
sis of these surfaces is critical to both science and technology
VIII. SUMMARY AND CONCLUSIONS of nanomaterials. Both qualitative and quantitative applica-
There is growing recognition in the research community tion of common surface analysis methods (as described in
that in too many circumstances, nanomaterials are this paper) can help address some of these analysis needs. In
the view of the current authors, these tools are underused. training grant (T32 ES07026). G.E.J. acknowledges support
Although simple qualitative use of surface tools can provide from the Linus Pauling Fellowship and PNNL’s Laboratory
critical information, such as the presence of contaminants or Directed Research and Development Program.
confirmation of some aspect of chemistry, needs and oppor-
tunities exist for more advanced modeling and interpretation
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1961). ing what is now PNNL in 1976. He is a fellow
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T. P. Das and E. L. Hahn, Nuclear Quadrupole Resonance Spectroscopy of the American Vacuum Society (AVS) and the
(Academic Press, New York, 1964). American Association for the Advancement of Science and holds affiliate
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154
D. R. Baer et al., in Handbook of Deposition Technologies for Films and try at the University of Washington. Dr. Baer has served as an Associate
Coatings, edited by P. M. Martin (William Andrew Press, Oxford, UK, Editor of JVST, is an Associate Editor of Surface Science Spectra, and is the
2009). Reviews Editor of Surface and Interface Analysis. Most of his research has
155
V. R. Stamenkovic, B. S. Mun, M. Arenz, K. J. J. Mayrhofer, C. A. Lucas, explored the impact of surfaces and interfaces on material properties and
G. Wang, P. N. Ross, and N. M. Markovic, Nat. Mater. 6, 241 (2007). has required the use a variety of surface sensitive analysis tools. Research
156
W. P. A. Jansen, J. M. A. Harmsen, A. W. Denier v.d. Gon, J. H. B. J. topics have included understanding the behaviors of nanoparticles in aque-
Hoebink, J. C. Schouten, and H. H. Brongersma, J. Catal. 204, 420 ous and biological systems, determining the role of interface chemistry on
(2001). stress corrosion cracking, and examining various surface properties of
157
A. Rafati, R. ter Veen, and D. G. Castner, Surf. Interface Anal. oxides and minerals. He has more than 250 publications and has served as
158
P. L. Grande, “Recent advances of MEIS for near surface analysis,” Chair of the ASTM Committee E42 on Surface Analysis, Chair of the
http://www.slideshare.net/Engenharia.de.Superficies/recent-advances-of- Applied Surface Science Division of the AVS, and leads a working group
meis-for-near-surface-analysis (2011). on surface characterization nanomaterials for ISO Committee TC201 on
Surface Chemical Analysis. He has received the Albert Nerken Award from she is interested in understanding the effect of organic oligomers in OA on
the AVS, the John Rivière Award of the UK Surface Analysis Forum, and physical properties of aerosols relevant to climate change. Finally, she is
has been a member of teams receiving a Federal Laboratory Consortium involved in the development of imaging and analysis capabilities of the
Technology Transfer award, a Microscopy Today Innovation award, and a nanospray desorption electrospray ionization (nano-DESI) mass spectrome-
DOE Division of Materials Sciences Outstanding Scientific try for imaging of fully hydrated biological samples in their native environ-
Accomplishment award. ment and for analysis of complex mixtures directly from solid substrates.
Dr. Laskin has been honored with several prestigious awards including
Mark Engelhard is a Senior Research Scientist Presidential Early Career Award (PECASE) in 2007, ASMS Biemann
in the Interface Spectroscopy and Diffraction Medal in 2008, Honor issue of JASMS in 2009, and other. She served as a
Facility in EMSL, a Department of Energy treasurer of the ASMS in 2006–2008. She is a member of the Editorial
national scientific user facility located at PNNL. Board of JASMS, Frontiers in Microbiology, and Russian Journal of Mass
Since 1978, he has specialized in the use of sur- Spectrometry and a member of the Advisory Board of Analyst. She is an
face sensitive techniques to study surface and editor of a book "Principles of Mass Spectrometry Applied to
interphase chemistry. His considerable experi- Biomolecules" published by John Wiley & Sons in 2006. She is an author
ence in surface analysis methods has facilitated and co-author of more than 140 peer-reviewed publications.
collaborative research in both fundamental and
applied studies. He has served as principal in- Jinfeng Lai is an Associate Scientist in the
vestigator, and project manager on various Research Center of the Phillips 66 company. He
research projects funded by governmental and industrial clients and as a fa- received his B.S. degree in Chemistry in 1999
cility cognizant space manager in EMSL. Engelhard has managed and coor- and M.S. degree in Inorganic Chemistry in
dinated scientific collaborations involving the application of XPS, 2002, both from the Xiamen University. He
ultraviolet photoelectron spectroscopy (UPS), AES, and TOF-SIMS techni- received a Ph.D. degree in Chemistry from the
ques. These techniques have been applied in numerous studies encompass- University of California, Riverside in 2009.
ing physical, chemical, geological, and biological sciences. Mark’s work, From 2011 to 2012, he was a Postdoctoral
much of it performed using XPS as a primary technique, is reported in over Research Associate at the EMSL at Pacific
290 peer-reviewed scientific publications and three book chapters. His pub- Northwest National Laboratory. His research
lications have been cited over 6000 times in the literature and his H-index is interests include Nuclear Magnetic Resonance
currently 42. He serves on the AVS Publications Committee, Vice Chair of spectroscopy as a probe of chemical structure and dynamics. He has pub-
the Pacific Northwest Chapter of the AVS, Associate Editor of the AVS lished over 20 journal and proceeding papers. He is a reviewer for over 20
journal Surface Science Spectra, Secretary of ISO TC-201 Surface journals, including the Journal of the American Chemical Society.
Chemical Analysis SC-2 General Procedures, Executive Committee
Member of ASTM International E42 Surface Science, and subcommittee Karl Mueller is a Laboratory Fellow within the
Chair of ASTM E42-08 Ion Beam Sputtering. Engelhard received the EMSL at the PNNL. He received a B.S. in
George T. Hanyo Award from the American Vacuum Society in 1997; the chemistry in 1985 from the University of
DOE Outstanding Scientific Accomplishment in Materials Chemistry Rochester and a Ph.D. in chemistry in 1991
Award; the Pacific Northwest National Laboratory Director’s Award for from the University of California at Berkeley.
Excellence; and the EMSL Director’s Award in 2007 and 2008. He was a postdoc at the University of British
Columbia, where he was awarded a Killam
Dr. Grant E. Johnson received his B.S. degree Memorial Postdoctoral Fellowship and an
in chemistry from the University of Delaware NSERC International Postdoctoral Fellowship.
Honors Program in 2002. He was employed as a Prior to his arrival at PNNL, Dr. Mueller spent
chemist with the United States Army at the 18 years on the faculty of Penn State University,
Edgewood Chemical Biological Center in where he advanced to the position of Professor of Chemistry and mentored
Edgewood, Maryland, from 2002 to 2004. He over twenty graduate students through completion of their doctoral degrees.
received his Ph.D. in chemistry from the He currently holds a dual appointment between PNNL and Penn State. He
Pennsylvania State University under Professor has published over ninety research papers, focusing on the development and
A.W. Castleman, Jr., in 2009. He was awarded a implementation of novel methods of solid-state nuclear magnetic resonance
National Science Foundation Central Europe spectroscopy. In his current role as the Lead Scientist for Magnetic
Summer Research Institute fellowship in 2006 Resonance at EMSL, he and his staff work at the forefront of applications
to study with Professor Vlasta Bonacic-Koutecky at the Humboldt and development of magnetic resonance techniques, both in sponsored
University in Berlin, Germany. He received a Department of Energy fellow- research projects and as collaborators with many visiting users of the mag-
ship to attend the 2006 meeting of Nobel Laureates in chemistry in Lindau, netic resonance facilities at EMSL. Dr. Mueller is the recipient of an Arnold
Germany. He was awarded a Linus Pauling Distinguished Postdoctoral fel- and Mabel Beckman Foundation Young Investigator Award and an Alfred
lowship at the Pacific Northwest National Laboratory from 2010 to 2012. P. Sloan Research Fellowship, and the Research Corporation for Science
He is currently a scientist in the Separations, Detection, and Analysis pro- Advancement has named him as a Cottrell Scholar. In 2012, he was
gram working with Laboratory Fellow Dr. Julia Laskin. inducted as a Fellow of the American Association for the Advancement of
Science.
Julia Laskin is a Laboratory Fellow at PNNL.
She received her M.Sc. in Physics from the Prabhakaran Munusamy is a materials scien-
Leningrad Polytechnical Institute (1990) and her tist/polymer specializing in nanotechnology. He
Ph.D. in Physical Chemistry from the Hebrew received his bachelors in chemical engineering
University of Jerusalem (1998). She was a post- First Class from University of Madras, India. He
doctoral fellow at the University of Delaware received his master’s degree in Applied Polymer
(1998–1999) and at PNNL (2000–2002). She Science from Martin Luther University in
became a research scientist at PNNL in 2002. Germany, where he also had the opportunity to
Dr. Laskin’s research is focused on obtaining a work in several reputed labs such as the Max
fundamental understanding of the interactions of Planck Institute and Fraunhofer Institute and
complex ions and molecules with surfaces for where he specialized in porous nanomaterials
improved identification of large molecules using mass spectrometry and for fabrication. After coming to the United States,
selective modification of substrates using beams of mass-selected ions (ion Munusamy received his Ph.D. from Virginia Polytechnic Institute and State
soft-landing). Another area of Dr. Laskin’s research is related to characteri- University while working with Professor Gary Pickrell’ s group in the
zation of the chemical composition of organic aerosols (OA). In particular, Materials Science and Engineering Department. His Ph.D. focused on
nanomaterials for biomedical applications. He developed a novel Nancy Washton is a Research Scientist within
nanoparticle-based drug delivery system using inorganic nanoparticles. the EMSL at the PNNL, where she is also the
Munusamy’s Ph.D. research was supported by Institute for Critical Capability Lead for Magnetic Resonance. She
Technology and Applied Sciences predoctoral funding. He also received received a B.S. degree in chemistry in 2001 from
Tau Beta Pi engineering honor during his Ph.D. program. He then joined the University of Nevada, Las Vegas and a Ph.D.
Pacific Northwest National Laboratory as a postdoctoral research associate in chemistry in 2007 from Penn State University.
in EMSL, a Department of Energy national scientific user facility. At Prior to her arrival at PNNL, Dr. Washton spent
PNNL, Munusamy’s research has primarily focused on synthesis and char- two years as a Senior Research Chemist in
acterization of engineered nanoparticles for nanotoxicological studies. Since Fiberglass Science and Technology at PPG. She
2003, he has published over 15 journal and proceeding papers with a total of was also an Assistant Professor of Chemistry at
200 citations. His area of expertise and interest are template synthesis of po- the Community College of Baltimore County
rous nanomaterials fabrication, semiconductor and luminescent nanostruc- from 2007 to 2008. Her main research has focused on the interactions of
tures, and engineered nanoparticle formulation for targeted drug delivery water and other small molecules at oxide surfaces, including the characteriza-
applications. tion of reactive surface area in the environment. In her current role at EMSL,
she manages a suite of 13 NMR spectrometers, ranging in magnetic field
Dr. Suntharampillai Thevuthasan is a Staff strength from low (for paramagnetic-containing samples) to ultrahigh (for
Scientist and manager of the Interfacial inorganic solids, biomolecular samples, and energy systems).
Spectroscopy and Diffraction group at
Environmental Molecular Sciences Molecular Alison Elder, Associate Professor of
Sciences Laboratory (EMSL), a Department of Environmental Medicine at the University of
Energy national scientific user facility located at Rochester, is an inhalation toxicologist with
PNNL. He received a B.Sc. (Honors) in Physics research interests that include the pulmonary, car-
from the University of Peredeniya, Sri Lanka, diovascular, and central nervous system inflam-
and M.Sc. in Energy Technology from the Asian matory and oxidative stress-related effects of
Institute of Technology, Thailand. He received engineered nanomaterials and ambient air particu-
his Ph.D. in Physics (Surface Science) from the late matter and the physicochemical properties of
University of Maine in 1989 and started his postdoctoral research at the the particles that are linked to response outcomes.
University of Florida. Before joining PNNL in 1993, he was a postgraduate Particle biokinetics and the impacts of age and
researcher at University of California-Davis and a guest scientist at other underlying vulnerabilities on response are
Lawrence Berkeley National Laboratory for three years. At PNNL, he has also of interest. Dr. Elder has authored numerous research papers in the field,
been developing experimental capabilities associated with research in sur- as well as review articles and book chapters. She is an editorial board member
face science, material synthesis and characterization including nanomateri- of four journals and is deputy Editor-in-Chief of Nanotoxicology. She also
als, and buried interface analysis in thin films, and nanomaterials. He made serves on the Threshold Limit Value-Chemical Substances committee of the
significant contributions to the study of surface structures of pure and American Conference of Governmental Industrial Hygienists.
adsorbate-covered single crystal surfaces, thin film and interfacial character-
izations using XPS/diffraction, photoelectron holography and high energy Brittany Baisch is a Ph.D. student in the
ion beam techniques. Thevuthasan further contributed to the understanding Toxicology program at the University of
of synthesis and characterization of nanomaterials, ionic transport processes Rochester in the laboratory of Dr. Alison Elder,
in single- and multilayer oxide thin film electrolytes, growth and characteri- where she studies the role of deposited dose rate
zation of oxide thin films, and understanding radiation effects in ceramics in nanoparticle-induced inflammatory responses
and oxides. He has authored more than 225 peer reviewed research papers in in respiratory tract target cells. She graduated
these areas. He has organized several symposia and workshops as a part of summa cum laude with a triple B.A. in
international conferences. Thevuthasan is a Fellow of AVS. He has received Chemistry, Biochemistry and Spanish from
PNNL’s awards and honors include multiple Outstanding Team Western Connecticut State University in 2008.
Performance awards, the Chester L. Cooper Mentor of the Year Award and Prior to graduate school, Brittany was a formu-
the Fitzner-Eberhardt Award for mentoring junior scientists. lations chemist at Advanced Technology
Materials, Inc., where she coauthored 2 patents for green formulas that clean
Dr. Hongfei Wang is a Chief Scientist at the logic and microelectronic devices. In 2011, she earned her M.S. in
EMSL of the U.S. Department of Energy’s Toxicology from the University of Rochester, and is expected to complete
PNNL at Richland, Washington. He received his her Ph.D. in 2013. Brittany has earned several awards for her research,
B.S. degrees in chemical physics and conducted including an internship at Bristol-Myers Squibb (2009), Colt Foundation
M.S. studies in laser chemistry, both at the Travel Award for the Nanotoxicology Conference in Edinburgh, Scotland
University of Science and Technology of China (2010), 1st Place Outstanding Graduate Student Award for the
(USTC) at Hefei, China in 1988 and 1991. He Nanotoxicology Specialty Section (2011), the Young Scholar Award for an
then received his Ph.D. degree in Chemistry in Outstanding Student Presentation at the Nanotoxicology Conference in
1996 from Columbia University in the City of Beijing, China (2012), and 2nd place in Multi-Cellular/Organismal Studies
New York. He was a postdoc at the DuPont by the University of Rochester’s Graduate Student Society (2013). She has
Marshall Laboratory at Philadelphia, Laboratory been a member of the Society of Toxicology (SOT) since 2009 and is a
for Research of Structure of Matter (LRSM) and the Department of member of SOT’s Nanotoxicology and Inhalation & Respiratory Specialty
Chemistry at the University of Pennsylvania until 1999 when he became a Sections. She is the current student representative for SOT’s Committee on
full research professor at the Molecular reaction Dynamics Laboratory Diversity Initiatives and the Women in Toxicology Special Interest Group.
(MRDLab) at the Institute of Chemistry, Chinese Academy of Sciences
(ICCAS) in Beijing. Before he joined PNNL in 2009, he served as the direc- Dr. Ajay S. Karakoti is a Research Scientist at
tor of the MRDLab at ICCAS (2000–2004), and also served as the the Battelle Science and Technology Pvt. Ltd.
Executive Associated Editor of the Chinese Journal of Chemical Physics India. He completed B.S (1999) and M.S.
(CJCP) of the Chinese Physical Society (2006–2009). He was the recipient (2001) in Chemistry from Delhi University in
of the Chinese Academy of Sciences’s Hundred Talent Program India and another M.S. in Corrosion Science and
(1999–2002), and also a Distinguished Young Scholar of the National Engineering from Indian Institute of
Natural Science Foundation of China (NSFC) (2005–2008). He has pub- Technology Bombay, India in 2003. Thereafter
lished over 50 peer-reviewed articles on surface nonlinear spectroscopy, and he worked as a trainee in for one year in India
on spectroscopy and structure of molecular interfaces. In recognition of his increasing his knowledge in particulate materi-
research, he was elected as fellow of the American Physical Society in als. He received his Ph. D in Materials Science
2012. and Engineering from University of Central
Florida in the year 2010 where he worked with Prof. Sudipta Seal on nano- polycrystalline ceria thin films, influence of aging and environment on the
particulate materials. He received UCF. Presidential Doctoral Fellowship to size, shape, self-assembly and chemistry of ceria nanoparticles were studied
pursue his Ph.D and was also a winner of the Dorothy M and Earl Hoffman with the help of experiments and atomistic calculations over last several
Fellowship as a “top level graduate student” from the AVS in the year 2008. years. Satya contributed to 30 peer reviewed publications, delivered five
He joined Pacific Northwest National Lab in 2010 for his postdoctoral stud- invited talks and contributed to 100þ presentations at various international
ies where he looked at the characterization challenges in nanomaterials at conferences.
the Environmental and Molecular Sciences Laboratory. He was awarded the
M. T. Thomas award for “Outstanding Postdoctoral Achievement” in the DaeWon Moon is a DGIST fellow and a profes-
year 2012. Ajay joined Battelle Science and Technology Pvt. Ltd, India in sor of Department of New Biology at DGIST.
September 2012. He has published over 45 research articles, two book chap- He is a member of Korean Academy of Science
ters and filed for 4 patent applications (one granted). He has presented his and Technology. He received a B.S degree in
research in several national and international conferences on the topics chemistry from Seoul National University in
related to nanomaterials. 1975, a M.S. degree in chemistry from KAIST
in 1977 and a Ph.D. degree in chemistry from
Satyanarayana V. N. T. Kuchibhatla In his Pennsylvania State University in 1984. After his
current role, as a Research Scientist and group postdoctoral training in Princeton University, he
leader, Satya works with an interdisciplinary moved to KRISS in 1985 as a principal
team of scientists to provide innovative solu- researcher. His main research areas are nano and
tions to client specific, energy, environment, and surface analysis of thin films. In his early career, his primary research inter-
materials related problems. His interests include est was to understand the composition and structure of the interfaces of
nanoscale particulate materials, thin films and semiconductor films at the nano-scale mainly using ion beams such as SIMS
coatings, materials characterization, ceramics and medium-energy ion scattering (MEIS). Recently, he developed a TOF
and powder metallurgy. Before joining Battelle MEIS system with 10 lm spatial resolution, which facilitates the atomic
India, in October 2011, Satya Kuchibhatla was a scale analysis of nanobio materials. Since 2003, he became interested in
senior research scientist in EMSL, PNNL, applying nanosurface analysis tools for bioimaging to understand the bioin-
Richland, WA, USA. He received his doctoral degree in 2008 from terfaces of cells and tissues at the nanoscale using his previous experience in
University of Central Florida, Orlando, Florida, USA. His research is semiconductor nanosurface science. His contribution to this research field
broadly focused on surfaces and interfaces, understanding/controlling/tuning was the development of three label-free nanobioimaging techniques: multi-
the characteristics of materials having impact on nuclear energy, electrolytes plex coherent anti-Stokes Raman scattering, surface plasmon resonance
for SOFC, gas sensors, self-healing, radiation protection materials, and imaging ellipsometry, and bio-SIMS. He has published over 170 articles and
nanoparticles for biomedical applications. This task is primarily achieved holds 19 patents. He has moved to DGIST as of September 1, 2012. DGIST
through an intelligent combination of various spectroscopy, diffraction and is a brand-new university supported by the Korean government as one of the
high-resolution microscopy tools. Specifically, influence of dopant and va- strategic convergence science and technology-oriented universities. In
cancy interactions in ceria/zirconia electrolytes, crystalline quality of the DGIST, he takes more challenges to develop noble nanobio imaging tools
electrolyte on the oxygen ion conduction, radiation tolerance of single and for innovative biomedical science.
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Surface characterization of nanomaterials and nanoparticles: Important

Donald R Baer Mark H Engelhard

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Grant E Johnson Julia Laskin

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Surface characterization of nanomaterials and nanoparticles: Important

I. INTRODUCTION address important issues, such as product lifetimes and ques-

II. IMPACT OF NANOSCIENCE

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

diminish the ability to assess the impact of these materials

III. NANOMATERIAL CHARACTERIZATION

JVST A - Vacuum, Surfaces, and Films

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JVST A - Vacuum, Surfaces, and Films

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

JVST A - Vacuum, Surfaces, and Films

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

control properties of nanoparticles and other nanomaterials.

TABLE I. Challenges associated with characterization of nanoparticles.

Nanomaterial surfaces and interfaces control properties

• Different synthesis routes often produce totally different types of nanoparticles

• Particles grow or dissolve, agglomerate

JVST A - Vacuum, Surfaces, and Films

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

JVST A - Vacuum, Surfaces, and Films

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

JVST A - Vacuum, Surfaces, and Films

050820-14 Baer et al.: Surface characterization of nanomaterials and nanoparticles

Scanning Probe Microscopies

Technique Strengths Limitations or issues

JVST A - Vacuum, Surfaces, and Films

average nanoparticle size (if less than 10 nm).92,93 It is also

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

nanostructures, such as particles and wires, is being devel-

JVST A - Vacuum, Surfaces, and Films

Parameter Description or unit Value

A Ag/Au atom ratio 64

of the overlayer normalized by the attenuation length (L(Ag in

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

JVST A - Vacuum, Surfaces, and Films

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

to samples in various physical and chemical states, with

JVST A - Vacuum, Surfaces, and Films

physisorbed to the titania surface. The chemical shift of this

C. Low and medium energy ion scattering

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013

JVST A - Vacuum, Surfaces, and Films

procedure described, and allowed to reside in vacuum for

FIG. 20. (a) TOF-MEIS spectrum of 6 nm Pt/V/Cu nanoparticles soft landed

diameter Pt/V/Cu nanoparticles deposited onto RF plasma,

J. Vac. Sci. Technol. A, Vol. 31, No. 5, Sep/Oct 2013