TECHNICAL ARTICLE

Characterization of nanograined powder samples using the Rietveld method

applied to electron diffraction ring patterns
A. Serafini,1,a) L. Lutterotti,2 S. Gross,3 and S. Gialanella2
1
Dipartimento di Chimica, Materiali e Ingegneria Chimica “Giulio Natta”, Politecnico di Milano, Italy
2
Dipartimento di Ingegneria Industriale, Università degli Studi di Trento, Italy
3
Dipartimento di Scienze Chimiche, Istituto di Chimica della Materia Condensata e di Tecnologie per l’Energia – ICMATE-CNR,
Università degli Studi di Padova, Italy
(Received 15 September 2016; accepted 6 March 2017)
A full-pattern fitting procedure based on the Rietveld method was applied to electron diffraction ring
patterns of a two-phase system, exhibiting the co-presence of zinc sulfide (sphalerite) and zinc oxide
(Wurtzite). Bright and dark field (DF) images reveal the presence of micrometric aggregates, com-
posed of quasi-spherical nanosized crystallites. These conventional transmission electron microscopy
imaging methods provide a general morphological characterization of the specimens although, in the
present case, they are not suitable for a detailed characterization of the microstructural features of the
analyzed samples. Owing to the overlap and broadening of the diffraction rings of the two phases, DF
images cannot provide a satisfactory picture of the individual crystallites of each single phase. To
overcome this limit, the mentioned Rietveld approach was applied to model the electron diffraction
data. The crystalline domain size and relevant shapes for both phases were successfully evaluated
using the proposed methodological approach. The excellent results obtained in the microstructural
characterization of the nanostructured multiphase samples demonstrate the capability of this tech-
nique, that may represents a fully quantitative method for the routine characterization of crystalline
nanomaterials. © 2017 International Centre for Diffraction Data.
[doi:10.1017/S0885715617000343]

Key words: electron diffraction, Rietveld method, TEM, nanograins, quantitative analysis, size-strains

I. INTRODUCTION some occasions, diffraction contrast imaging, based on bright

Nowadays nanomaterials are widely diffused and they are field (BF) and dark field (DF) micrographs, does not allow to
increasingly studied for being applied in many different fields, determine unambiguously the microstructure, e.g., particle
such as health and medicine (Jain et al., 2008), food products dimension and shape, defect structures, etc. of nanosized mate-
(Silvestre et al., 2011), textiles (Yetisen et al., 2016), electron- rials. In particular, these methods may fail in the presence of
ics (Simon and Gogotsi, 2008), energy, and environment agglomerated aggregates of nanoparticles (Dieckmann et al.,
(Klaine et al., 2008). For regulatory purposes, the European 2009; Bell et al., 2012), and multiphase nanocrystalline sys-
Commission has recently issued a common definition of the tems. An alternative approach is proposed herewith, and relies
term “nanomaterial” (Linsinger et al., 2012): “nanomaterial on the attainment of microstructural information directly from
means a natural, incidental or manufactured material contain- the electron diffraction patterns, following a procedure adopted
ing particles, in an unbound state or as an aggregate or as an with other diffraction methods, like XRD and neutron diffrac-
agglomerate and where, for 50% or more of the particles in tion, using a full-pattern fitting approach (Gemmi et al., 2011;
the number size distribution, one or more external dimensions Boullay et al., 2014), based on the Rietveld method (Rietveld,
is in the size range 1–100 nm”. In the proposed legislation, the 1969). In the present study, a mixture of two phases, namely
particle size distribution is present as a fundamental parameter zinc sulfide (ZnS) and zinc oxide (ZnO) was firstly investi-
for deciding whether a certain material can be classified as a gated by means of XRD and conventional TEM diffraction
nanomaterial or not. Electron microscopy, scanning probe contrast mode: BF/DF TEM and selected area electron diffrac-
microscopy, X-ray diffraction (XRD), and dynamic light scat- tion (SAED). Subsequently, a microstructural characterization
tering are some of the measurement methods available for the of the powders was carried out by applying the Rietveld
determination of the characteristic dimensions of nanomateri- method to the selected area electron diffraction patterns.
als (Hassellöv et al., 2008; Baer et al., 2010; Linkov et al., Finally, the results obtained with the two methodologies
2013). Certainly, transmission electron microscopy (TEM) is have been comparatively discussed, even as concerns the
one of the best tools for the characterization of nanostructured phase quantification on different length scales.
systems. It is routinely used for the investigations on grain size
and other microstructural aspects down to sub-nanometric
scale (Lascialfari et al., 2014; Giorgetti et al., 2015). On II. MATERIALS AND METHODS
A. TEM characterization
a)
Author to whom correspondence should be addressed. Electronic mail: TEM analysis was carried out using a Philips CM12 trans-
andrea.serafi[email protected] mission electron microscope operating at 120 kV and

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 equipped with an energy-dispersive X-ray spectroscopy microstructural characterization of crystalline domain size
(EDXS) system, occasionally used for localized chemical and shape, the instrumental broadening function was deter-
analyses. The powder samples were ultrasonically suspended mined following the method proposed by Boullay et al.
in ethanol and a drop of this suspension was deposited onto a (2014). For this purpose, our reference material was a nano-
200 mesh holey carbon-coated copper grid. SAED patterns crystalline TiO2 single-phase powder. The first step of the cal-
and TEM micrographs, both DF and BF images, were ibration procedure is to determine the average size and shape
acquired. For the identification of the phases and indexing of the crystallites using an X-ray powder diffractometer with a
of the relevant peaks, Process Diffraction software was used known instrumental function. The obtained parameters were
(Lábár, 2008, 2009; Lábár et al., 2012). Image analysis of used as an input in the analysis of the electron diffraction pat-
TEM DF micrographs were performed using the ImageJ soft- terns of the reference material to extract the instrumental peak
ware (Schneider et al., 2012), quite useful to estimate dimen- shape function.
sion and shape of coherent scattering domains and relevant
statistical distributions. In particular, the mean values and
widths of the statistical asymmetric distribution (σ−, σ+) of C. Powder XRD measurements
crystallites were evaluated by fitting the experimental values The XRD data were collected with a Bruker D8 Advance
with a log-normal function. diffractometer equipped with a Göbel mirror and CuKα
radiation.
For all details on the sample preparation procedure and
B. Rietveld method applied to electron diffraction ring additional characterization results, the reader is referred to
patterns the paper of Dolcet et al. (2015).
The Rietveld analysis of SAED patterns was carried out
using the MAUD program (Lutterotti, 2010) using electron
atomic scattering factors from Peng et al. (1996). Intensity III. RESULTS AND DISCUSSION
integration along the Debye rings of the nanopowder SAED Firstly, the selected nanograined powders, synthesized
pattern was performed using ImageJ plug-in implemented following the procedure described by Dolcet et al. (2015)
directly in MAUD, which allows us to import two- were fully characterized by XRD and TEM methods. The
dimensional (2D) diffraction data coming from the TEM cam- analyses were conducted to characterize the microstructure
era or imaging-plate detectors directly, preserving the original (crystalline domain shape and dimension) of the powders.
image coordinate position for each data point (Ischia et al., The indexing of the SAED pattern (Figure 1) reveals the pres-
2005; Lutterotti et al., 2007, 2014). Using an adequate number ence of a two phase crystalline system, composed of ZnS,
of diffraction rings it was possible to correct for possible tilt- cubic, sphalerite and ZnO, hexagonal, Wurtzite. The SAED
ing errors and center displacement directly in the Rietveld pattern exhibits a substantially continuous distribution of the
refinement (Lutterotti et al., 2014). Two kinds of data-set plot- diffracted intensity along the rings. This indicates a reduced
ting were used. (1) The 2D plot depicts the azimuthal variation crystallite dimension of both phases and the lack of any pref-
of the diffraction intensity plotted vs. the momentum transfer. erential orientation. Indeed, the DF micrograph shows the
(2) Intensity profile obtained summing up all the azimuthal presence of nanosized coherently scattering crystalline
plots (corresponding to a full integration along Debye– domains. The displayed crystallites are organized in pseudos-
Scherrer rings). SAED patterns were acquired with the beam pherical aggregates, clearly visible in TEM BF micrograph
stopper inserted to reduce the intensity of the transmitted (Figure 1), with dimensions from 50 to 100 nm. On the
beam. This masked portion of the image was removed and other hand, the XRD analysis (Figure 2) reveals the presence
not considered in data modeling. The background of the dif- of one phase only: ZnS (cubic, sphalerite). The discrepancy
fraction pattern was fitted with a polynomial function and an between SAED and XRD data can be explained by admitting
additional Gaussian peak at 0 Q, in order to model the strong the formation of a thin ZnO surface layer on the ZnS grains
low angle signal rise, mainly because of the transmitted beam. with an overall volume fraction below the XRD detection
In general, no important contribution was detected from the limit. However, ZnO would significantly contribute to
supporting holey carbon film, so that no further background electron diffraction, since this is coming from thinner
correction was needed (Kim et al., 2009). For the electron-transparent regions where the oxide layer is a

Figure 1. BF TEM micrograph of nanopowder aggregates (left); DF TEM micrograph of the nanopowder aggregates (center); SAED ring pattern (right) of the
nanopowder aggregates indexed by Process Diffraction software, showing the presence of two phases: ZnS and ZnO.

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 Figure 2. Rietveld method applied to the powder
XRD pattern of the nanostructured powders: ZnS is
the only detected phase present. Experimental data
points in dotted line; continuous black line:
calculated profile.

comparatively more important component. The scheme in provide quantitative information on nanostructured systems.
Figure 3 is depicting this situation concerning the different Recently, Boullay et al. (2014) have shown the potential of
region sampled in XRD and electron diffraction. In SAED, the Rietveld method applied to the characterization of nano-
the size of the analyzed region is determined by the selected structured crystalline samples using SAED data. In this
area aperture employed for the acquisition. In our case, the work, we apply for the first time this method to a two-phase
electron diffraction pattern of the ZnS/ZnO sample was sample to achieve significant information on the crystalline
acquired centering the selected area aperture in corre- domain size and shape of both phases, particularly when
spondence of the region visualized in the BF image in phase contrast, i.e., BF and DF imaging, cannot be profitably
Figure 1, corresponding to a sampled area of about 0.5 µm2. employed. For a reliable microstructural characterization
Moreover, not all of the displayed area would contribute to using Rietveld analysis of SAED patterns, it is recommended
coherent scattering event but only the thinner, electron trans- to use diffraction patterns with a homogeneous intensity distri-
parent regions, with a thickness below 50 nm approximately. bution all along the Debye–Scherrer rings, in order to avoid
These data indicate that the volume under investigation is the graininess problem. A homogeneous intensity is obtained
well below the fraction of μm3 in SAED. On the other hand, when the number of randomly oriented crystallites is large
common values for the analyzed volume region in XRD are enough. Owing to the reduced analyzable region in SAED
of several mm3. This difference in sampled volumes and the this requirement is fulfilled with materials with nanometric
localization of the ZnO phase on the surface regions explain crystal grains. The ZnS/ZnO system considered herewith rep-
the discrepancy between the results obtained with the two resents an appropriate test sample for the proposed approach,
techniques. From these considerations it turns out how impor- since both phases in SAED analysis exhibits homogenous dif-
tant it is to combine different diffraction methods, such as fraction rings without any graininess (Figure 1). Actually, in
XRD and SAED, to perform a complete characterization at this system ZnO is the undesired passivation layer formed
different length scales of nanostructured materials. Indeed, on the surface of the wanted ZnS. Nevertheless, the knowl-
XRD supplies information on bulk phase content, while edge of the exact chemical nature and composition of the
SAED is able to provide localized phase identification also surface is essential for the development of effective function-
at the nanoscale level. Actually, electron diffraction may alization strategies and for understanding the functional
behavior (i.e., catalytic or sensors properties) of this material.
The first step of Rietveld analysis was importing SAED
images in MAUD and unrolling each one in several intensity
profile patterns. Then the crystal structures of the ZnO and
ZnS phases, previously identified by indexing the relevant
SAED (Figure 1), were loaded into the software from COD
(Crystallography Open Database) using the Crystallographic
Information File (CIF) format (Gražulis et al., 2009). The
first refinement cycle was used to adjust the background, the
overall scale factor, the instrumental parameters (tilting error
and center displacement) and the crystal structure, respec-
tively. In the final step, the microstructure of both phases
was refined using the Popa model (Popa, 1998), to take into
account the possible shape anisotropy of the analyzed
crystalline-scattering domains.
The Rietveld analysis converged quickly to the results
reported in Table I. All patterns were treated using kinematical
approximation with Blackman two-wave dynamic correction
Figure 3. (Color online) Graphical representation of the comparison between
XRD and SAED results. (Blackman, 1939) implemented in MAUD (Boullay et al.,

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 TABLE I. Results of electron and XRD Rietveld analysis (Figures 2 and 4). The numbers in parentheses denotes the estimated standard deviation in the last digit.

Electron diffraction

Phase Microstructure Structure

Identification Quantification (%) Shape Size (nm) Space group a (Å) c (Å)

ZnS Sphalerite 45.4 ± 0.6 h = 4.5 ± 0.2 F-43m 5.384(3)

w = 4.8 ± 0.2

ZnO 54.5 ± 0.9 h = 3.1 ± 0.1 P63mc 3.283(2) 5.194(5)

Wurtzite w = 3.7 ± 0.2
Reliability factor: Rw = 2.49%

XRD

Identification Quantification (%) Shape Size (nm) Space group a (Å)

ZnS 100 h = 4.3 ± 0.1 F-43m 5.381(1)

Sphalerite w = 4.5 ± 0.2

Reliability factor: Rw = 7.41%

2014). Calculated and experimental diffraction profiles plotted pseudodisc-shaped crystallite with the following dimension:
in one and two dimensions are shown in Figure 4 together 3.7 nm along the [011] and 3.1 nm along the [001] directions.
with the residual curve obtained after the final refinement. It These data were compared with the morphology and dimen-
is worth noting that the intensity profile fitting was made by sion of the coherent scattering domains as obtained from the
a model that does not take account texture features, since DF TEM image, Image J processed, in Figure 5. The analysis
the ZnS/ZnO system does not exhibit any preferential orienta- of DF image, consisting in counting more than 200 crystalline
tion. For this reason the intensities and the line broadening in scattering domain, provides a mean value for the crystallite
experimental 2D pattern display slight changes at different azi- size of 4 nm with associated standard deviations for the
muthal angles, which is not the case in 2D calculated pattern asymmetric statistical distribution of: σ− = 1 and σ+ = 3 nm
(inset of Figure 4). (Figure 5). These values are of course in good agreement
The microstructural analysis exhibits a roughly cubic with the results obtained from the Rietveld method, with the
crystallite shape for the ZnS phase with an average round strong limitation not to provide any information on the actual
dimension of 5 nm. On the other hand, ZnO exhibits size and shape for the crystallites of each one of the identified

Figure 4. (Color online) Rietveld method applied to

electron diffraction pattern of ZnS/ZnO
nanopowders. Dot line: Experimental intensity
profile; red line: calculated profile; green line: ZnO
intensity contribution (54.5%); blue line: ZnS
intensity contribution (45.4%). In the inset the two-
dimensional multiplot of the calculated (upper part)
and experimental (bottom part) profile are displayed.

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 Figure 5. Dark Field Image Analysis on ZnS/ZnO nanopowders aggregates: threshold of Dark Field TEM micrograph of the ZnS/ZnO nanopowder aggregates
(left); each ellipse in the image represent the analyzed particle (top left corner); histogram of size distribution of crystallites (right).

phases. The microstructural analysis was performed also using evidence suggests that, as expected, ZnO is prevalently pre-
the XRD data (Figure 1). Crystallite size and shape for ZnS, sent on the surface of the investigated areas in agreement
the only detected phase, are in excellent agreement with the with the proposed hypothesis of the formation of an ultrathin
results obtained with the electron diffraction data (see layer of oxide on the ZnS aggregates. Finally, as the results
Table I). One limitation of the diffraction analysis is that the obtained through the electron diffraction have shown that
shape information obtained can be different from the real the phase quantitative analysis data are highly dependent on
one, as the refined shape is symmetrized by the Laue point the selection of the electron transparent region and, conse-
group of the crystal structure as we cannot distinguish between quently, to the interaction volume.
equivalent crystallographic directions.
The Rietveld analysis of electron diffraction pattern is
able to provide information on the content of crystalline IV. FINAL COMMENTS AND FURTHER DEVELOPMENTS
phases inside the investigated volume. The ZnS/ZnO system Crystalline domain sizes and relevant shapes for both ZnS
in the analyzed region shows that the volume fraction of the and ZnO phases were successfully evaluated using the
oxide (55%) and the sulfide (45%) are almost comparable Rietveld method applied to electron diffraction ring patterns.
(see Table I). Of course, these values do not correspond to The results obtained from the microstructural characterization
the bulk phase content but to the local composition of the elec- of nanostructured ZnS/ZnO two-phase sample demonstrate
tron transparent regions displayed in the BF image in Figure 1. the capabilities of this technique that may represent a fully
Phase quantification is highly dependent on the state of aggre- quantitative method for the routine characterization of crystal-
gation and actual local thickness of the agglomerates. From line nanomaterials and of their outer layers. The proposed
the analysis of different areas we confirm that the ZnO volume approach combines BF/DF-TEM and SAED analyses to
fractions are comparatively lower than ZnS in case of larger improve the determination of size and shape of nanocrystalline
aggregates with higher thickness. An example of this situation domain ensembles. By applying the Rietveld method to the
is displayed in Figure 6 and relevant Table II, where the phase electron diffraction pattern a proper microstructural character-
composition (ZnS 69, ZnO 31%) is significantly different ization is achieved even in case of agglomerated aggregates
from the previously analyzed zone. This experimental and multiphase samples. These samples, owing to the strong

Figure 6. (Color online) TEM measurements on a larger area of ZnS/ZnO system and higher average thickness as compared with the clusters in Figure 1: BF
micrograph (left); SAED ring pattern (inset); Rietveld method applied to electron diffraction pattern (right). Dot line, experimental intensity profile; red line,
calculated profile; green line, ZnO intensity contribution (39.2%); blue line, ZnS intensity contribution (60.8%).

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