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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.
3234 J. Mater. Res., Vol. 21, No. 12, Dec 2006 © 2006 Materials Research Society
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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 nominally about 60–100 nm thick and had a sheet resis-
since 1998.29–33 Powder mixtures of ZnO and Bi2O3 tance of 15–25 ⍀/ⵧ. Substrate strips (0.70 × 2 cm) were
were subsequently prepared by this technique,34 and Li+- cut and cleaned in three 5-min steps of cleansing by
doping of ZnO nanocrystals was also achieved by the ultrasonication in acetone, ethanol, and ultrapure water.
combustion method for luminescence applications.35 On Doped and undoped ZnO films were then made by dip-
the other hand, polytypes of (ZnO)mIn2O3 comprised of coating the transparent conducting oxide substrates in the
alternate blocks of wurtzite ZnO with cubic bixbyite powder suspensions (2-propanol containing 10 g/L oxide
In2O3 layers were prepared by combustion synthesis, as dose) after carefully masking one side with cellophane
mentioned earlier in the introduction.17,18 The present tape. After the dip, the films were baked in the oven for
study was prompted by the possibility of using combus- 10 min at 300 °C. The dip-bake sequence was repeated
tion synthesis to dope ZnO with In rather than to form eight times, after which the final coated films were baked
polytypes, as in the earlier studies.17,18 for 17 h at 300 °C. The oxide film thus built up on the
Finally, the photoelectrochemical response of Cd- and ITO surface had a thickness in the 0.5–1.0 m range. A
In-doped ZnO samples is shown to be superior to the standard single-compartment, three-electrode cell was
undoped material. 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
II. EXPERIMENTAL DETAILS and reference electrodes, respectively. All potentials be-
Zinc nitrate (99%; Alfa Aesar, Ward Hill, MA), urea low are quoted with respect to the Ag/AgCl reference.
(99.995%; J.T. Baker, Phillipsburg, NJ), indium chloride Photoaction spectroscopy was performed on a voltam-
(99%; Alfa Aesar), and cadmium chloride (99%; Merck, mograph (model CV-27 BAS; Soltec, San Fernando,
West Point, PA) were used without further purification. CA) equipped with a recorder (model VP-6414S Soltec
All other chemicals were from commercial sources and X-Y; Soltec). The monochromator used was a model
were of the highest purity available and were used with- 82-415 (Thermo Jarrel Ash Corp., Franklin, MA) with a
out further purification. grating blazed at 300 nm. The light source was a 150 W
Urea was used as the fuel (reducing agent) in this xenon arc lamp (Oriel, Stratford, CT) with an output of
study. Stoichiometric compositions of the combustion ∼4.1 mW/cm2, as measured with a meter (model 70260
mixtures were calculated based on the total oxidizing and Radiant Power/Energy; Oriel). X-ray photoelectron spec-
reducing valencies of the oxidizer (O) and fuel (F; in this troscopy (XPS) used a model 5000C system (Perkin
case, urea) so that the equivalence ratio (⌽c ⳱ O/F) was Elmer/Physical Electronics, Norwalk, CT) with other de-
unity (i.e., the energy released was maximum).36 For this tails given elsewhere.37 Diffuse reflectance spectroscopy
purpose, the elements C, H, and Zn are considered36 as was performed on a spectrophotometer (Lambda 6; Per-
reducing elements with corresponding valencies +4, +1, kin Elmer) with BaSO4 as the standard. Films were cast
and +2, respectively. The valency of N is considered to on glass slides (25 × 25 mm) for this purpose. X-ray
be 0. Oxygen is taken to be an oxidizing element with a powder diffraction (XRD) patterns of the samples were
valency of −2. The combustion mixtures thus formulated obtained on a powder diffractometer (D-500; Siemens,
contained zinc nitrate and urea in the mole ratio 1:1.667. New York, NY) using CuK␣ radiation. The step size and
CdCl2 (for Cd-doped ZnO) and InCl3 (for In-doped ZnO) the dwell time were set to 0.01 degree and 1 s, respec-
were added such that the atom ratios (Cd)/[(Cd)+(Zn)] tively, to obtain high-resolution diffractograms. Scan-
and (In)/[(In)+(Zn)] in the combustion mixtures were ning electron microscopy (SEM) images and energy dis-
equal to 0.06. persive x-ray (EDX) analyses were obtained using a Su-
Aqueous solutions of the combustion mixtures were pra 55 instrument (Zeiss, Jena, Germany) with nominal
poured into a platinum crucible and placed on a hot plate electron beam voltages of 5 and 10 kV, respectively.
that was preheated to a nominal temperature of 250 °C.
The solutions initially melted and underwent dehydration
followed by decomposition, which was accompanied by III. RESULTS
the release of a large amount of gases (oxides of nitrogen,
NH3, and HCNO). The mixtures then took on a viscous A. Preliminary observations
appearance and rapidly generated a mild explosion, pro- The use of cadmium nitrate as a dopant precursor in
ducing a dry foamy oxide as the product. the combustion mixture did not result in Cd uptake by the
For photoaction spectroscopy measurements, the pow- ZnO matrix. This is because the nitrate salt generates the
ders were thoroughly washed with double-distilled water corresponding oxide during the combustion process. In-
(Corning Megapure; Corning, NY) and coated onto terestingly, in the aforementioned study on the prepara-
transparent conducting oxide substrates. These substrates tion of (ZnO)mIn2O3, precursor salts for Zn and In were
consisted of ITO coated on soda-lime glass. They were nitrate. On the other hand, for Li+ doping of ZnO via the
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
冑
d共hkl兲 = , (1)
4 2 l2a2
共h + k2 + hk兲 + 2
3 c
FIG. 4. Survey XPS profiles for (a) Cd-doped and (b) In-doped ZnO FIG. 5. (a) UV-visible transmittance spectra and (b) Tauc plots for
samples. 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).
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. in the 250–850 nm wavelength region. The transmittance
A comparative discussion of the XPS and EDX dopant is found to decrease with doping. This decrease may stem
assays is deferred to a subsequent section below. 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-
F. Optical behavior tons may also contribute to the reduction in optical trans-
Figure 5(a) contains the UV-visible transmittance data mittance.40
for the undoped, Cd-doped, and In-doped ZnO samples The Tauc plots shown in Fig. 5(b) were constructed
using the diffuse reflectance data in Fig. 5(a). The inter- IV. DISCUSSION
cepts of these plots afford an estimate of the optical band
gap energy of the corresponding sample.41 A value of Perhaps the most significant result emerging from this
3.14 eV is obtained for combustion-synthesized ZnO, study is that the use of chloride precursors in combustion
whereas the corresponding values for the doped samples synthesis for introducing dopants into the host oxide lat-
are 3.07 eV (Cd) and 3.02 eV (In), respectively. Inter- tice avoids problems associated with phase separation as
estingly enough, the Eg value of our undoped ZnO in the nitrate precursor case. Thus, Cd- and In-doped
samples is lower than that typical of ZnO obtained by ZnO samples were successfully prepared by combustion
other synthesis methods (3.2–3.3 eV). This is presumably synthesis using CdCl2 and InCl3 precursors.
because of the effect exerted by the carrier concentration The choice of these particular dopants was dictated by
in the host material, as elaborated below. On the other previous studies, as outlined in the introductory para-
hand, our Eg value is in accord with that previously re- graphs. Cadmium is isovalent with zinc but has a differ-
ported for combustion-synthesized ZnO.35 ent ionic size. Thus, Cd-doped ZnO is expected to ex-
Once again, a comparison of these Eg values for Cd- pand the wavelength tunability (for a variety of applica-
and In-doped ZnO with values reported by other authors tions) by virtue of its smaller optical band gap.4 On the
is deferred to Sec. IV. other hand, n-type doping of ZnO results from In incor-
poration as with the corresponding Al and Ga (Group III)
G. Photoelectrochemical behavior dopant counterparts. The data from the present study on
Cd- and In-doped ZnO samples from combustion syn-
Figure 6 contains photoaction spectra for the undoped, thesis are now discussed in the light of corresponding
Cd-doped, and In-doped ZnO samples in 0.5 M Na2SO4 data trends in the literature.
supporting electrolyte. These spectra were acquired at a The decrease in particle size on doping (as assessed by
bias potential of 0.34 V. Clearly, the doped samples show XRD data analyses) is consistent with the findings from
a superior photoresponse to undoped ZnO over the entire a recent study on In-doped ZnO thin films using spray
wavelength range from ∼300 to ∼450 nm. The shift of the pyrolysis.16 These authors also observed an increase in
band edge cut-off to longer wavelengths (lower energies) the FWHM of the XRD peaks for (002) and (101) re-
for the two doped samples, relative to undoped ZnO, is flections, consistent with our own observations on the
also entirely consistent with the trends seen earlier in Fig. (100; and the other XRD) peaks in this study. Indium
5. Doping of ZnO with Cd or In clearly results in visible doping levels ranging from 0.005–0.05 were reported in
light sensitization of the parent oxide. 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
FIG. 6. Photoaction spectra of undoped, Cd-doped, and In-doped ZnO by our own group in a companion study using electro-
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 deposition.12 On the other hand, in a previous study using
In-doped ZnO, respectively. IPCE, incident photon-to-electron con- spray pyrolysis, only a “slight” increase in Eg (3.3–3.33
version efficiency. eV) was reported16 on In doping. Much more sizeable
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