Cadmium- and indium-doped zinc oxide by combustion

synthesis using dopant chloride precursors

G. Yogeeswaran
Materials Science and Engineering Program, The University of Texas, Arlington, Texas 76019-0065
C.R. Chenthamarakshan, N.R. de Tacconi, and K. Rajeshwara)
Center for Renewable Energy Science and Technology, Department of Chemistry and Biochemistry,
The University of Texas, Arlington, Texas 76019-0065

(Received 21 January 2006; accepted 19 September 2006)

Cadmium-doped ZnO was prepared for the first time by combustion synthesis using
CdCl2 as a dopant precursor, with zinc nitrate and urea as the combustion mixture.
Unlike previous studies of combustion synthesis of ZnO in the presence of an indium
nitrate precursor, which resulted in (ZnO)mIn2O3 (m ⳱ 3 or 4) compound formation,
In-doped ZnO was prepared by combustion synthesis in this study using an InCl3
precursor. The doped samples were compared and contrasted with undoped ZnO using
scanning electron microscopy, x-ray powder diffraction, energy-dispersive x-ray
analyses, and x-ray photoelectron spectroscopy. Diffuse reflectance spectroscopy
showed the optical band gap of ZnO to shrink from 3.14 to 3.07 eV and 3.02 eV on
Cd and In doping, respectively. Finally, the doped samples showed an improved
photoelectrochemical response relative to undoped ZnO over the wavelength range
from ∼300 to ∼450 nm.

I. INTRODUCTION A pioneering study of the Zn–In–O material system

Zinc oxide (ZnO) is an important material for many
applications, including varistors, transistors, piezoelec-
tric devices, solar cell windows, UV and blue light-
emitting devices, and the like. For many of these appli-
cations, it is important to control the physical, electronic,
and optical properties of ZnO by doping. In this article,
the preparation and characterization of Cd- and In-doped
ZnO by combustion synthesis are described. The primary
motivation for doping of ZnO is wavelength tunability
for optoelectronic applications, although doping also re-
sults in marked improvement in the photoelectrochemi-
cal properties of ZnO as demonstrated in this work.
Since the first report in 1996,1 a raft of studies have
begun to appear on the Zn–Cd–O material system.2–12
These interesting materials have been prepared by the
sol-gel process,1 spray pyrolysis,2,3,5 pulsed laser depo-
sition,4 molecular beam epitaxy,6 DC reactive magnetron
sputtering,8 coevaporation,9–11 plasma-enhanced metal
organic chemical vapor deposition,10 and electrodeposi-
tion.12 Conspicuously absent from this array of prepara-
tion techniques is combustion synthesis.
a)
Address all correspondence to this author.
e-mail: rajeshwar@uta.edu
DOI: 10.1557/JMR.2006.0399
appeared in 1995.13 This study, using pulsed laser depo-
sition, showed that Zn–In–O films had similar electrical
conductivity but better transparency in the visible and
infrared spectral regions compared with Sn-doped In2O3
(ITO). Subsequent studies on this system have used si-
multaneous RF and DC magnetron sputtering,14 electro-
deposition,15 and spray pyrolysis16 as the preparation
techniques. Very recent studies by another group have
described the preparation of (ZnO)mIn2O3 (m ⳱ 3 or 4)
powder by gel-combustion from nitrate/glycine or ni-
trate/citric acid mixtures.17,18
Combustion synthesis begins with a mixture of reac-
tants comprised of an oxidizer (e.g., a nitrate salt) and an
organic fuel (e.g., urea, glycine, citric acid, etc.).19 The
mixture is brought to ignition, culminating in a fast exo-
thermic combustion reaction, with temperatures exceed-
ing 1000 °C. The product is a dry powder that is usually
crystalline and is not agglomerated, resulting in a high
degree of dispersion and a large specific surface area.
Other than these attributes of the reaction product, com-
bustion synthesis offers an energy-efficient route to ma-
terials preparation because the high reaction temperature
is attained by the inherent exothermicity of the combus-
tion process. A wide range of materials have been pre-
pared via this route, including catalysts,19,20 ceram-
ics,21–23 perovskites,21,24–26 and binary oxides such as
SnO2,27 TiO2,28 etc.

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 G. Yogeeswaran et al.: Cadmium- and indium-doped zinc oxide by combustion synthesis using dopant chloride precursors
ZnO itself has been prepared by combustion synthesis
since 1998.29–33 Powder mixtures of ZnO and Bi2O3
were subsequently prepared by this technique,34 and Li+-
doping of ZnO nanocrystals was also achieved by the
combustion method for luminescence applications.35 On
the other hand, polytypes of (ZnO)mIn2O3 comprised of
alternate blocks of wurtzite ZnO with cubic bixbyite
In2O3 layers were prepared by combustion synthesis, as
mentioned earlier in the introduction.17,18 The present
study was prompted by the possibility of using combus-
tion synthesis to dope ZnO with In rather than to form
polytypes, as in the earlier studies.17,18
Finally, the photoelectrochemical response of Cd- and
In-doped ZnO samples is shown to be superior to the
undoped material.
II. EXPERIMENTAL DETAILS
Zinc nitrate (99%; Alfa Aesar, Ward Hill, MA), urea
(99.995%; J.T. Baker, Phillipsburg, NJ), indium chloride
(99%; Alfa Aesar), and cadmium chloride (99%; Merck,
West Point, PA) were used without further purification.
All other chemicals were from commercial sources and
were of the highest purity available and were used with-
out further purification.
Urea was used as the fuel (reducing agent) in this
study. Stoichiometric compositions of the combustion
mixtures were calculated based on the total oxidizing and
reducing valencies of the oxidizer (O) and fuel (F; in this
case, urea) so that the equivalence ratio (⌽c ⳱ O/F) was
unity (i.e., the energy released was maximum).36 For this
purpose, the elements C, H, and Zn are considered36 as
reducing elements with corresponding valencies +4, +1,
and +2, respectively. The valency of N is considered to
be 0. Oxygen is taken to be an oxidizing element with a
valency of −2. The combustion mixtures thus formulated
contained zinc nitrate and urea in the mole ratio 1:1.667.
CdCl2 (for Cd-doped ZnO) and InCl3 (for In-doped ZnO)
were added such that the atom ratios (Cd)/[(Cd)+(Zn)]
and (In)/[(In)+(Zn)] in the combustion mixtures were
equal to 0.06.
Aqueous solutions of the combustion mixtures were
poured into a platinum crucible and placed on a hot plate
that was preheated to a nominal temperature of 250 °C.
The solutions initially melted and underwent dehydration
followed by decomposition, which was accompanied by
the release of a large amount of gases (oxides of nitrogen,
NH3, and HCNO). The mixtures then took on a viscous
appearance and rapidly generated a mild explosion, pro-
ducing a dry foamy oxide as the product.
For photoaction spectroscopy measurements, the pow-
ders were thoroughly washed with double-distilled water
(Corning Megapure; Corning, NY) and coated onto
transparent conducting oxide substrates. These substrates
consisted of ITO coated on soda-lime glass. They were
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nominally about 60–100 nm thick and had a sheet resis-
tance of 15–25 ⍀/ⵧ. Substrate strips (0.70 × 2 cm) were
cut and cleaned in three 5-min steps of cleansing by
ultrasonication in acetone, ethanol, and ultrapure water.
Doped and undoped ZnO films were then made by dip-
coating the transparent conducting oxide substrates in the
powder suspensions (2-propanol containing 10 g/L oxide
dose) after carefully masking one side with cellophane
tape. After the dip, the films were baked in the oven for
10 min at 300 °C. The dip-bake sequence was repeated
eight times, after which the final coated films were baked
for 17 h at 300 °C. The oxide film thus built up on the
ITO surface had a thickness in the 0.5–1.0 ␮m range. A
standard single-compartment, three-electrode cell was
used in all the electrochemical experiments considered in
this article. A Pt coil and a Ag|AgCl|satd. KCl probe
(Microelectrode Inc., Bedford, NH) served as the counter
and reference electrodes, respectively. All potentials be-
low are quoted with respect to the Ag/AgCl reference.
Photoaction spectroscopy was performed on a voltam-
mograph (model CV-27 BAS; Soltec, San Fernando,
CA) equipped with a recorder (model VP-6414S Soltec
X-Y; Soltec). The monochromator used was a model
82-415 (Thermo Jarrel Ash Corp., Franklin, MA) with a
grating blazed at 300 nm. The light source was a 150 W
xenon arc lamp (Oriel, Stratford, CT) with an output of
∼4.1 mW/cm2, as measured with a meter (model 70260
Radiant Power/Energy; Oriel). X-ray photoelectron spec-
troscopy (XPS) used a model 5000C system (Perkin
Elmer/Physical Electronics, Norwalk, CT) with other de-
tails given elsewhere.37 Diffuse reflectance spectroscopy
was performed on a spectrophotometer (Lambda 6; Per-
kin Elmer) with BaSO4 as the standard. Films were cast
on glass slides (25 × 25 mm) for this purpose. X-ray
powder diffraction (XRD) patterns of the samples were
obtained on a powder diffractometer (D-500; Siemens,
New York, NY) using CuK␣ radiation. The step size and
the dwell time were set to 0.01 degree and 1 s, respec-
tively, to obtain high-resolution diffractograms. Scan-
ning electron microscopy (SEM) images and energy dis-
persive x-ray (EDX) analyses were obtained using a Su-
pra 55 instrument (Zeiss, Jena, Germany) with nominal
electron beam voltages of 5 and 10 kV, respectively.
III. RESULTS
A. Preliminary observations
The use of cadmium nitrate as a dopant precursor in
the combustion mixture did not result in Cd uptake by the
ZnO matrix. This is because the nitrate salt generates the
corresponding oxide during the combustion process. In-
terestingly, in the aforementioned study on the prepara-
tion of (ZnO)mIn2O3, precursor salts for Zn and In were
nitrate. On the other hand, for Li+ doping of ZnO via the
3235
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 G. Yogeeswaran et al.: Cadmium- and indium-doped zinc oxide by combustion synthesis using dopant chloride precursors

combustion method, the corresponding chloride salt was

deployed. Therefore, in all subsequent experiments on
the Cd- and In-doped ZnO in the present study, CdCl2
and InCl3 were used as the dopant precursor, respec-
tively. On the other hand, zinc nitrate was used as usual
for generating ZnO during the combustion reaction. Ap-
parently, the use of a thermally labile precursor com-
pound, and one that does not form the corresponding
oxide, is a prerequisite for effective doping of the target
matrix.

B. SEM
Figure 1 compares and contrasts the morphology of
ZnO [Fig. 1(a)], Cd-doped ZnO [Fig. 1(b)], and In-doped
ZnO [Fig. 1(c)] powders as obtained by combustion syn-
thesis in this study. The doped samples are clearly finer-
grained relative to the morphology of the undoped speci-
men. Interestingly, the Cd- and In-doped samples also
present rather different morphologies for the ZnO grains
[see, Figs. 1(b) and 1(c)].

C. XRD
Figure 2 compares and contrasts survey x-ray diffrac-
tograms for undoped ZnO, Cd-doped ZnO, and In-doped
ZnO. No other reflections other than those corresponding
to the host ZnO matrix are seen in these powder XRD
patterns. It is worth noting that the as-prepared samples
are highly crystalline in all the three cases (also see Fig.
1), attesting to the effectiveness of the combustion syn-
thesis to induce in situ crystallization during oxide for-
mation. By way of contrast, other preparation techniques
(e.g., sol-gel chemistry and electrodeposition) usually re-
quire a postdeposition thermal anneal for inducing crys-
tallinity in the prepared samples. The increased noise
associated with the diffractograms of the doped samples
is because of rescaling of the three sets of diffractograms
(Fig. 2, inset), but is also consistent with the smaller
cluster size as seen by SEM. The elevated baseline
counts for the diffractograms of the two doped samples
(Fig. 2, inset) may arise from luminescence (as pointed
out by a reviewer). In this regard, it is worth noting that
the three diffraction patterns were not zero-shifted (i.e.,
offset) relative to one another.
The close correspondence of all the three XRD pat-
terns in Fig. 2 (and assignable to ZnO) stands in stark
contrast to the situation when (ZnO) m In 2 O 3 is FIG. 1. Representative SEM images of (a) undoped, (b) Cd-doped,
and (c) In-doped ZnO samples.
formed.17,18 For example, distinct reflections assignable
to (ZnO)3In2O3 were observed when a gelled mixture of effect on the XRD behavior, as illustrated in Fig. 2 (inset)
zinc and indium nitrates, along with glycine, was sub- for the Cd- and In-doped cases. The (100) reflection scan
jected to combustion.17 This polytype grows epitaxially is amplified in this figure to show the influence of Cd and
in a rhombohedral or hexagonal lattice along the c-axis In incorporation into the ZnO lattice. Thus, this peak is
sharing the c-plane of wurtzite ZnO and the (111) plane shifted from 2␪ ⳱ 31.84° for the undoped ZnO case to
of cubic In2O3.38,39 31.52° and 31.49° for the Cd- and In-doped cases, re-
Doping of the host ZnO matrix exerts a more subtle spectively [Fig. 2, (inset)]. These shifts of the diffraction

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 G. Yogeeswaran et al.: Cadmium- and indium-doped zinc oxide by combustion synthesis using dopant chloride precursors

The width (FWHM) of the XRD peaks can be ex-

FIG. 2. Comparison of survey XRD patterns for (a) undoped,
(b) Cd-doped, and (c) In-doped ZnO samples. Inset shows the high-
resolution diffractograms of the (100) peak for undoped, Cd-doped,
and In-doped ZnO samples.
pressed as a linear combination of the contribution from
lattice strain and crystal size using the equation
␤ cos ␪ 1 ␩ sin ␪
= + , (2)
␭ ⑀ ␭
where ␤ is the measured peak width (FWHM), ␪ is the
Bragg angle of the peak, ␭ is the XRD wavelength, ⑀ is
the effective particle size, and ␩ is the effective strain.31
␤ cos ␪/␭ was plotted versus sin ␪/␭ for the samples (not
shown), and the effective particle sizes for the undoped,
Cd-doped, and In-doped samples (taking strain into ac-
count) were found to be equal to 99.0 nm, 43.3 nm, and
73.4 nm, respectively. The slopes of the fitted lines in-
dicated the presence of strain in the ZnO lattice as would
be expected from dopant incorporation.
D. EDX analyses
Figure 3 contains the EDX spectra for undoped [Fig.
3(a)], Cd-doped [Fig. 3(b)], and In-doped ZnO [Fig. 3(c)]
samples. Quantitative analyses of these data afford Cd
and In atom ratios of 0.106 and 0.0992, respectively, in
the ZnO host matrix. The Cl signals in the EDX spectra
of the doped samples [Figs. 3(b) and 3(c)] originate from
the corresponding chloride precursors used (see below).
E. XPS
Figures 4(a) and 4(b) contain survey XPS data for Cd-
and In-doped ZnO samples, respectively. In the high-
resolution spectra (not shown), the dopant signals are

peaks in the doped ZnO cases (relative to undoped ZnO),

as well as the broadening induced from the ZnO lattice
[the full width at half maximum (FWHM) of the (100)
peaks in the undoped, Cd-doped, and In-doped ZnO
samples, for example, are 0.16°, 0.22°, and 0.25° respec-
tively], are consistent with the strain induced by dopant
incorporation as demonstrated next.
The lattice unit cell constants a and c for the undoped,
Cd-doped, and In-doped ZnO samples were estimated
based on the positions of the (100) and (002) peaks using
the equation

冑
d共hkl兲 = , (1)
4 2 l2a2
共h + k2 + hk兲 + 2
3 c

and were found to be a ⳱ 3.240 Å, c ⳱ 5.195 Å, a ⳱

3.274 Å, c ⳱ 5.237 Å, a ⳱ 3.277 Å, and c ⳱ 5.243 Å,
respectively. The increase in the unit cell dimensions
for the doped samples (relative to the starting material)
is consistent with the notion of induced strain by the FIG. 3. EDX spectra for (a) undoped, (b) Cd-doped, and (c) In-doped
dopant. ZnO samples.

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 G. Yogeeswaran et al.: Cadmium- and indium-doped zinc oxide by combustion synthesis using dopant chloride precursors

FIG. 4. Survey XPS profiles for (a) Cd-doped and (b) In-doped ZnO
samples.
split because of spin-orbit coupling into two peaks.
Quantitative analyses of these data afford Cd and In atom
ratios (relative to Zn) of 0.144 and 0.355, respectively.
A comparative discussion of the XPS and EDX dopant
assays is deferred to a subsequent section below.
F. Optical behavior
Figure 5(a) contains the UV-visible transmittance data
for the undoped, Cd-doped, and In-doped ZnO samples
FIG. 5. (a) UV-visible transmittance spectra and (b) Tauc plots for
undoped, Cd-doped, and In-doped ZnO samples. ␣ is the absorption
coefficient computed as a function of the energy (h␯) from the UV-
visible diffuse reflectance data in (a).
in the 250–850 nm wavelength region. The transmittance
is found to decrease with doping. This decrease may stem
from the increased scattering of photons by doping-
induced crystal defects or from the formation of grainy
surfaces. The (increased) free carrier absorption of pho-
tons may also contribute to the reduction in optical trans-
mittance.40
The Tauc plots shown in Fig. 5(b) were constructed

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 G. Yogeeswaran et al.: Cadmium- and indium-doped zinc oxide by combustion synthesis using dopant chloride precursors
using the diffuse reflectance data in Fig. 5(a). The inter-
cepts of these plots afford an estimate of the optical band
gap energy of the corresponding sample.41 A value of
3.14 eV is obtained for combustion-synthesized ZnO,
whereas the corresponding values for the doped samples
are 3.07 eV (Cd) and 3.02 eV (In), respectively. Inter-
estingly enough, the Eg value of our undoped ZnO
samples is lower than that typical of ZnO obtained by
other synthesis methods (3.2–3.3 eV). This is presumably
because of the effect exerted by the carrier concentration
in the host material, as elaborated below. On the other
hand, our Eg value is in accord with that previously re-
ported for combustion-synthesized ZnO.35
Once again, a comparison of these Eg values for Cd-
and In-doped ZnO with values reported by other authors
is deferred to Sec. IV.
G. Photoelectrochemical behavior
Figure 6 contains photoaction spectra for the undoped,
Cd-doped, and In-doped ZnO samples in 0.5 M Na2SO4
supporting electrolyte. These spectra were acquired at a
bias potential of 0.34 V. Clearly, the doped samples show
a superior photoresponse to undoped ZnO over the entire
wavelength range from ∼300 to ∼450 nm. The shift of the
band edge cut-off to longer wavelengths (lower energies)
for the two doped samples, relative to undoped ZnO, is
also entirely consistent with the trends seen earlier in Fig.
5. Doping of ZnO with Cd or In clearly results in visible
light sensitization of the parent oxide.
FIG. 6. Photoaction spectra of undoped, Cd-doped, and In-doped ZnO
in 0.5 M Na2SO4. The spectra were acquired at 0.34 V. The arrows
indicate the position of the band gaps for ZnO, Cd-doped ZnO, and
In-doped ZnO, respectively. IPCE, incident photon-to-electron con-
version efficiency.
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IV. DISCUSSION
Perhaps the most significant result emerging from this
study is that the use of chloride precursors in combustion
synthesis for introducing dopants into the host oxide lat-
tice avoids problems associated with phase separation as
in the nitrate precursor case. Thus, Cd- and In-doped
ZnO samples were successfully prepared by combustion
synthesis using CdCl2 and InCl3 precursors.
The choice of these particular dopants was dictated by
previous studies, as outlined in the introductory para-
graphs. Cadmium is isovalent with zinc but has a differ-
ent ionic size. Thus, Cd-doped ZnO is expected to ex-
pand the wavelength tunability (for a variety of applica-
tions) by virtue of its smaller optical band gap.4 On the
other hand, n-type doping of ZnO results from In incor-
poration as with the corresponding Al and Ga (Group III)
dopant counterparts. The data from the present study on
Cd- and In-doped ZnO samples from combustion syn-
thesis are now discussed in the light of corresponding
data trends in the literature.
The decrease in particle size on doping (as assessed by
XRD data analyses) is consistent with the findings from
a recent study on In-doped ZnO thin films using spray
pyrolysis.16 These authors also observed an increase in
the FWHM of the XRD peaks for (002) and (101) re-
flections, consistent with our own observations on the
(100; and the other XRD) peaks in this study. Indium
doping levels ranging from 0.005–0.05 were reported in
the aforementioned study.16 On the other hand, our as-
says of the Cd and In dopant levels via EDX far exceed
the estimates obtained from the XRD peak shifts. Taking
into consideration the fact that Cd and In solution doses
in the initial combustion mixture were 0.06 (atom ratio)
in each case and that the thermodynamic solid solubility
limit for impurities in the ZnO lattice is ∼2%, we can
conclude that the dopant levels in the ZnO lattice are
significantly lower. The higher Cd and In levels seen by
the XPS and EDX probe possibly translate to a prefer-
ential migration of the dopants to the ZnO surface, thus
forming an amorphous grain boundary phase. This is
consistent with the observations made by other authors.15
The discrepancy in the Cd and In assays between the
EDX and XPS is easily rationalized when one recalls the
very different sampling depths inherent in the two tech-
niques, i.e., the XPS probe samples the surface rather
than the bulk unlike EDX. Note that the photoelectron
escape depth is only ∼2 nm, whereas the x-ray escape
depth is ∼2 ␮m.
The shrinking of the band gap on Cd doping is con-
sistent with the trend seen by other authors4 and also that
by our own group in a companion study using electro-
deposition.12 On the other hand, in a previous study using
spray pyrolysis, only a “slight” increase in Eg (3.3–3.33
eV) was reported16 on In doping. Much more sizeable
3239
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 G. Yogeeswaran et al.: Cadmium- and indium-doped zinc oxide by combustion synthesis using dopant chloride precursors
increases in Eg (3.27–3.42 eV) were noted on In-doped
ZnO samples prepared by electrodeposition.15 On the
other hand, Li+ ion doping of ZnO decreased the Eg value
from 3.2 to 3.1 eV,35 whereas Ga-doping of ZnO thin
films (as prepared by plasma-enhanced metal organic
chemical vapor deposition) increased the Eg value from
∼3.25 to ∼3.55 eV.42
The Eg variation with In doping of ZnO can be ex-
plained in terms of the resultant perturbation in the car-
rier concentration in the conduction band. When ZnO is
doped with a Group III element such as In, the dopant
presumably acts as a singly charged donor by substitut-
ing for Zn. The excess carriers furnished by the dopant
impurity in the conduction band (after ionization) con-
tribute to a blue-shift of the optical band-to-band transi-
tion (the so-called Burstein-Moss effect).43 However,
when the carrier concentration in the conduction band of
the host exceeds a critical threshold (in this case, 5 × 1019
cm−3) band gap narrowing becomes significant because
of merging of donor and conduction band energy levels,
band-tailing by impurity-induced potential fluctuations,
and electron-electron and screened electron-ion many-
body contributions to the electron and hole self ener-
gies.44 This “anomalous” effect was seen for n-type In-
doped ZnO films by other authors,44 and the shrinking of
Eg observed in our study for doping of ZnO with In or Cd
is attributed to a similar effect.
Finally, it would be tempting to ascribe some of the
aforementioned trends in Eg to chloride incorporation
into the ZnO lattice as seen by EDX and XPS probes
(Figs. 3 and 4). However, this is highly unlikely; previ-
ous authors45 have found no influence of chloride incor-
poration on the optical properties of ZnO films prepared
by electrodeposition from chloride baths.
V. CONCLUSIONS
This study demonstrates that combustion synthesis is
useful for preparing doped ZnO powders with vastly im-
proved photoresponses relative to the undoped samples.
The use of metal chlorides (instead of the commonly
used metal nitrate salts in combustion synthesis) as the
dopant precursor facilitates dopant incorporation into the
ZnO lattice.
ACKNOWLEDGMENTS
We thank Professor W.L. Balsam (Department of
Earth and Environmental Sciences, The University of
Texas at Arlington) for access to the diffuse reflectance
spectroscopy instrument, and Dr. N. Basit (NanoFab
Center, The University of Texas at Arlington) for the
SEM data. We also thank the three anonymous reviewers
for constructive criticisms of an earlier manuscript ver-
sion.
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