Full Paper

Single-Source CVD of Zinc Sulfide-Based Thin Films from Zinc

bis(O-Ethylxanthate)**
By Davide Barreca,* Eugenio Tondello, Donocadh Lydon, Trevor R. Spalding, and Monica Fabrizio

A novel single-source precursor, zinc bis(O-ethylxanthate), was employed for the CVD of ZnS-based thin films. The coatings
were deposited on SiO2 and SiO2/Si(100) substrates in a N2 atmosphere in a cold-wall reactor in the temperature range 250
400 C. The optical properties of the films were investigated by ultra violet-visible (UV-vis) absorption and Fourier transform
infrared (FTIR) spectroscopies. The surface and in-depth chemical composition were studied by X-ray photoelectron spec-
troscopy (XPS), X-ray excited Auger electron spectroscopy (XE-AES), and secondary ion mass spectrometry (SIMS). Final-
ly, atomic force microscopy (AFM) was employed to analyze the surface morphology of the coatings. Very thin films, with
thickness less than 30 nm and no evidence of crystalline phases, were grown at temperatures of at least 300 C. Optical mea-
surement showed that the coatings were highly transparent ( > 80 %) throughout the visible and IR spectral ranges.

Keywords: Single-source precursor, Surface techniques, ZnS

1. Introduction Zinc sulfide thin films have been produced by several

Pure and doped ZnS-based thin films have attracted con-
siderable interest for the production of blue lasers, light-
emitting diodes, and anti-reflection coatings.[1] In recent
years, alternating current thin-film electroluminescent
(ACTFEL) devices, with a ZnS layer as the active element,
have received increasing attention in the field of optoelec-
tronics for possible use in flat-panel displays.[2] The light-
emitting properties of ZnS-based materials have been tai-
lored, either by the preparation of composite sulfides like
ZnxCd1xS, where 0 < x < 1,[3] or by metal ion doping (AgI,
CuII, MnII, ).[4]
synthetic routes, such as electron beam evaporation,[5]
radio frequency (RF) sputtering,[6] pulsed laser ablation,[7]
molecular beam epitaxy (MBE),[8] solgel,[9] and spray-py-
rolysis.[10] Within this widespread scenario, the growth of
ZnS thin films by CVD has attracted much attention,
thanks to the possibility of tailoring the film properties by a
judicious choice of precursor compound and reaction con-
ditions.
Conventional CVD processes for ZnS rely on the use of
two separate sources for zinc and sulfur: Me2Zn and
H2S,[1,11,12] Et2S,[13] or propylene sulfide.[14,15] The occur-
rence of gas-phase side reactions has been partially inhib-

ited by using Me2Zn/NEt3 in conjunction with Et2S2,[16] or

[*] Dr. D. Barreca, Prof. E. Tondello
Istituto di Scienze e Tecnologie Molecolari del CNR
Sezione di Padova and INSTM
Via Marzolo 1, I-35131 Padova (Italy)
E-mail: barreca@chin.unipd.it
Dr. D. Lydon, Prof. T. R. Spalding
Department of Chemistry
University College Cork
National University of Ireland
Cork, College Road, Cork (Ireland)
Dr. M. Fabrizio
Istituto per l'Energetica e le Interfasi CNR
Corso Stati Uniti 4, I-35127 Padova (Italy)
[**] The authors are grateful to Prof. L. Operti (Dipartimento di Chimica
Generale ed Organica Applicata, Universit, Torino) for the EI-MS
spectra of the precursor, to Dr. P. Traldi and Dr. R. Seraglia for the
ESI measurements on the same compound. Thanks are due also to
Dr. O. Sasso, F. Carli, and A. Venzo (Dipartimento CIMA-Universit
di Padova) for help in the experimental work and for the NMR analy-
sis of the precursor, and to Prof. L. E. Depero and Dr. E. Bontempi
(INFM and Dipartimento di Chimica e Fisica per l'Ingegneria e per i
Materiali-Universit di Brescia) for the XRD measurements. Mr. Ste-
fano Girardi is gratefully acknowledged for skilful technical assistance.
Progetto Finalizzato Materiali Speciali per Tecnologie Avanzate II
and Programma Materiali Innovativi Legge 95/95 provided financial
assistance.
tert-BuSH.[14,15,17] Recently, electrostatic spray-assisted va-
por deposition has been used to deposit highly oriented
ZnS films from ZnCl2 and thiourea.[18]
An attractive alternative to using multiple reagents is the
use of a single-source molecule (SSM) precursor, compris-
ing all the elements to be deposited.[19,20] The advantages
offered by such compounds include easier control of stoi-
chiometry and limitation of unwanted side reactions. In this
framework, CVD of ZnS films has been performed, start-
ing from dialkylmonothiocarbamates like Zn(SOCCH3)-
TMEDA, from Zn(S2COCHMe2)2 by both thermal and la-
ser-driven CVD, and from Zn dialkyldithiocarbamates.[19,21]
Nevertheless, the choice of a single-source precursor
remains problematic because many different types of zinc
sulfur complexes are polymeric in the solid state, resulting
in reduced volatility.
In this paper, a CVD method using a new single-source
precursor for the growth of ZnS-based thin films under
relatively mild conditions, is developed. To this end,
zinc bis(O-ethylxanthate) (Zn(O-EtXan)2, with O-EtXan =

Chem. Vap. Deposition 2003, 9, No. 2 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0948-1907/03/0203-0093 $ 17.50+.50/0 93

S2COCH2CH3) was used as the precursor.[22] This com-
pound contains ZnS bonds with average distances of
2.35 ,[23] very similar to those in the various ZnS poly-
morphs,[24] and it can be decomposed to ZnS under rela-
tively mild conditions. Moreover, it has an appreciable vol-
atility and ambient stability.
The focii of the present study are the interrelationships
between the composition, microstructure, and morphology
of very thin ( 30 nm) ZnS films. Even if such materials
might allow the peculiar features offered by nanosystems
to be exploited, characterization may be complicated (even
with advanced surface techniques) either by the small
amount of material present, or by the difficulty of identify-
ing the composition of different layers along the thickness.
In order to investigate the influence of the substrate on
film characteristics, ZnS-based coatings were grown on two
different substrates, SiO2 and SiO2/Si(100). While the for-
mer is amorphous, thermally stable, and optically transpar-
ent in the visible range, the latter (a single-crystal wafer
with a SiO2 overlayer 5 nm thick) is almost transparent in
the IR-range.
2. Results and Discussion
Preliminary information on zinc bis(O-ethylxanthate) as
a possible CVD precursor was obtained by studying the
decomposition pattern of the compound with thermal anal-
yses and mass spectrometry (MS). Thermogravimetric
analysis (TGA) (Fig. 1), performed in flowing N2 (heating
rate = 10 C min1), clearly showed that zinc bis(O-ethyl-
xanthate) was stable up to 100 C. At higher temperatures,
a significant loss of mass took place, corresponding to an
100
90
142.2C
80
% weight
70
60
50
40
31.40%
30
100 200 300 400
Temperature (C)
Fig. 1. TGA and DTA analyses performed on a sample of zinc(II) O-ethyl-
xanthate (N2, heating rate = 10 C min1).
endothermic process. In the following region (200300 C),
a second weight loss occurred, finally leading to a plateau
at 31.4 % of the original mass. This value corresponds to
the quantitative formation of ZnS (theoretical value:
31.7 %).[25]
The electron impact mass spectrometry (EI-MS) image
of the precursor revealed the parent molecular ion species
94 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Full Paper
.
(Zn(O-EtXan)+2 , m/z = 306) as the base peak, indicating
that zinc bis(O-ethylxanthate) is a relatively stable molecu-
lar compound in the gas phase, and not a polynuclear zinc
species. Nevertheless, since zinc bis(O-ethylxanthate) has a
polymeric structure in the solid state,[23] oligomeric gas-
phase species might have been destroyed by the EI ioniza-
tion conditions. Therefore, a softer ionization technique
such as electrospray ionization (ESI)[26,27] would clearly
be a useful analytical tool for assessing the presence of
oligomers in the vapor phase. The ESI spectra, in negative
ion mode, showed the presence of the base peak (100 %) at
m/z = 427, which was assigned to the species [Zn(O-Et-
Xan)3]. No peaks attributable to species containing more
than one zinc atom were detected, indicating that zinc
bis(O-ethylxanthate) is monomeric in the vapor phase at
low pressures. Even if these observations constitute an in-
teresting starting point for the use of zinc bis(O-ethyl-
xanthate) as a single-source CVD precursor, it is worth-
while noting that the obtained results are not necessarily
completely transferable to decomposition of the precursor
in the evaporator during CVD.
Several deposition experiments were carried out varying
the substrate temperature in the range 250400 C. Crack-
free and colorless coatings were obtained in all cases. Typi-
cal film thicknesses were 25 2 nm and 15 2 nm for SiO2
and SiO2/Si(100) supported coatings, respectively. These
values corresponded to growth rates of 0.4 nm s1 and
0.25 nm s1, a result almost independent of the substrate
temperature, under the conditions used. This feature might
indicate that the CVD processes involved are diffusion-lim-
ited.[29]
A detailed analysis of the chemical composition of the
coatings was initially carried out by XPS and XE-AES. In
order to discriminate the ZnLMM Auger signal contribution
6 from the O1s peak (overlap in Al Ka source) or the C1s
peak (overlap in Mg Ka source),[29] all the spectra were
5
acquired using both excitation lines. X-ray photoelectron
Deriv. weight (%/C)
4 spectroscopy (XPS) surface scans of the films (Fig. 2) re-
vealed the presence of zinc, sulfur, oxygen, and carbon.
3
The latter were related to atmospheric exposure of the
2 films.[30] At deposition temperatures lower than 300 C, the
presence of substrate signals due to silicon was detected.
1
0
Zn2p
500
ZnLMM
Intensity (a.u.)
CKVV
O1s
OKLL
Zn3p
Zn3s
S2p
C1s
S2s
Zn3d
1200 1000 800 600 400 200 0
Binding Energy (eV)
Fig. 2. XPS wide-scan spectrum (01300 eV) for a ZnS-based film deposited
on SiO2/Si(100) at 400 C (excitation source: Al Ka).
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Full Paper

This result possibly reflects the fact that complete xanthate
decomposition occurs only when T 300 C (see thermal
analysis, Fig. 1).
The surface Zn2p3/2 component for all the obtained films
had a binding energy (BE) of approximately 1022.0 eV
(full width at half maximum (FWHM) 2.1 eV). Since lit-
erature values for the Zn2p3/2 BEs are quite similar for ZnS
(1021.6 eV) and ZnO (1022.1 eV),[31,32] the Auger a param-
eter, a = BE(Zn2p3/2) + KE(ZnLMM),[33] was evaluated and
used in order to obtain an unambiguous identification of
the presence of ZnS. Irrespective of the substrate and the
preparation conditions, the calculated values (Fig. 3 for
films deposited on SiO2/Si(100)) were always intermediate
2012.0
2011.5 (ZnS)
2011.0
(eV)
CVD processes. Ionic species related to the film compo-
nents (ZnxO+/ +/
y , 1 x 2, 0 y 2,4; ZnxS , 1 x 2;
+/
ZnSOx, 1 x 3; ZnOxH , 1 x 2) and Si-containing
clusters (ZnSixO+y, 1 x 2, 0 y 1) were detected. In all
cases, the isotopic pattern of S and S-related species was
unambiguously identified in the spectra. The presence of
overlapping signals originating from the contributions of
S- and O-containing ionic clusters was always revealed in
the spectra for all the samples, confirming the co-presence
of sulfide and oxide in the films, in agreement with XPS
and XE-AES results. The composition throughout the
thickness of the film was investigated by analyzing the con-
tribution of signals of interest as a function of depth. As an
example, Figure 4 shows the behavior of the main ionic
species for a representative coating, the composition of
a)
1.0E+07

2010.5
1.0E+06 +
2010.0 (ZnO) intensity (cps) SiO
+
2009.5 1.0E+05 Zn
2009.0
260 280 300 320 340 360 380 400 1.0E+04 +
ZnO
T (C)

Fig. 3. Dependence of the surface Auger parameters on the deposition tem- 1.0E+03 ZnS+
perature for the coatings deposited on SiO2/Si(100). The literature values 34 +
S
for ZnO and ZnS are shown for comparison. 1.0E+02
0 10 20 30 4

between literature values for ZnO (2010.2 eV)[34] and ZnS b)

(2011.3 eV),[35,36] indicating that both species were present 1.0E+07

on the film surface. This was further confirmed by the S/Zn 1.0E+06 -
surface atomic ratio, which was lower than the stoichio- O
intensity (cps)

metric value (0.5). Nevertheless, the S2p3/2 peak was cen- 1.0E+05
tered at BEs typical of sulfide (S2) species (161.8 eV; 34
S
-
1.0E+04
FWHM 2.0 eV) and unambiguously ruled out the pres-
ence of sulfates, since their signals would be located at BEs 1.0E+03 ZnO-
7.0 eV higher.[29] ZnS
-

The O1s surface signal consisted of two components: the 1.0E+02

first, at BE 530.0 eV (FWHM 2.2 eV), could be as-
cribed to ZnO species, and the second, at BE 531.9 eV
(FWHM 2.2 eV), related to OH groups[30] arising from
atmospheric exposure.[31]
Secondary ion mass spectrometry (SIMS) analyses were
performed in an attempt to describe the distribution of
chemical species throughout the film thickness and to in-
vestigate eventual filmsubstrate interaction effects. Pre-
liminary measurements were carried out comparing the
spectra obtained with either a Ar+ or O+2 primary ion beam,
in order to distinguish the film component responses from
the eventual artifacts induced by the reaction with the pri-
mary ion beam. Taking this precaution, the spectra were
collected using an O+2 beam, since higher ionic yields were
obtained. Except for signals due to adventitious contami-
nants (Li+, B+, CH+/ + + + +/
x , 0 x 3, Na , Mg , Al , Cl , K ,
+
+
Ca ), SIMS spectra revealed the film to be very pure, indi-
cating a clean conversion of the precursor to ZnS in the
0 10 20 30 40 50
thickness (nm)
Fig. 4. a) Positive and b) negative ion SIMS depth profiles of selected spe-
cies recorded for a ZnS-based film deposited on SiO2 at 400 C.
which was qualitatively similar to the other analyzed sam-
ples. Zn+ and ZnO+ signals (Fig. 4a) exhibited similar be-
haviors up to the filmsubstrate interface. Notably, the Zn+
and ZnO+ ionic yield displayed a maximum in this region,
as already verified for metal and metal oxide ions when an
oxidized environment is encountered along the thick-
ness.[37] ZnS+ signal exhibited a constant value for more
than 15 nm but, corresponding to the maximum of Zn+ and
ZnO+ signals, its intensity decreased more sharply than that
of 34S+. Substrate-related signals (for instance, SiO+ in
Fig. 4) were detectable throughout the film thickness, an
observation attributed to film/substrate intermixing, since
coating discontinuity was excluded by atomic force micros-

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 Full Paper

copy (AFM) morphological analysis (see below). The nega-
tive ion profiles (Fig. 4b) confirmed the behaviors observed
in positive mode, suggesting the co-presence of O-contain-
ing species, together with zinc sulfide. As a matter of fact,
analogous to ZnS+, the ZnS signal decreased more rapidly
than 34S and ZnO that exhibited the same O behavior in
the film.
The optical absorption spectrum in the UV-vis range for
the ZnS film deposited on the SiO2 substrate at 350 C is
shown in Figure 5a. All spectra obtained were in agree-
ment with those reported in the literature for zinc sul-
a)
0.35
T=350C
0.30 thickness 23 nm
0.25
Absorbance
EG is the band gap and n is an exponent the value of which
depends on the nature of the electronic transitions. As
regards ZnS, the best fit to the experimental data of Equa-
tion 2 was obtained with n = 1/2, corresponding to direct
allowed transitions.[38] On this basis, the plot of (ahm)2 vs
hm (Fig. 5b for one of the samples) yielded the bandgap by
extrapolating the linear relationship to zero. The estimated
optical bandgaps for the films were all very close to 3.3 eV.
This value was lower than that for the bulk material (EG
3.8 eV)[3840] and could be ascribed to sulfur deficiency, in
agreement with previous literature reports.[12] This defi-
ciency could be associated with a disordered microstructure
or a partial oxidation, taking into account that both SIMS
and XPS analyses revealed the presence of zinc oxide, ener-
gy gap of which is reported to be very close to that of ZnS
(EG 3.5 eV).[43] As a result, the detected red shift of the
optical absorption edge, attributable to the presence of

localized defect energy levels in the gap,[44] might be

0.20
related to the formation of a ZnSO network.
0.15 Nevertheless, more detailed analyses (for instance, spec-
troscopic ellipsometry) are needed in order to further
0.10
investigate the relations between microstructure and opti-
0.05 cal properties.
The FTIR transmittance spectra of the films showed
300 400 500 600 transmittance values higher than 80 % throughout the IR
(nm) spectral region (4000400 cm1).[45] The characteristic
absorptions of the xanthate ligands were not detected, sug-
b)
gesting an essentially complete precursor decomposition at
experimental the temperatures used.[38]
9
200x10 fit AFM analyses revealed that the surface morphology was
influenced more by the substrate than by the growth tem-
2
(h) (cm eV)

150 perature. Figure 6 shows a representative AFM micrograph

-1

for a film deposited on SiO2/Si(100) at T = 400 C. The tex-

2

100

50

2.8 3.0 3.2 3.4 3.6 3.8 4.0

h (eV)
Fig. 5. a) Optical absorption spectrum for a sample supported on SiO2.
b) Plot of (ahm)2 vs. hm for the same film.

fide.[3840] No absorption occurred in the visible range at

k > 550 nm. The absorbance increase below k 420 nm
could be associated with electronic interband transitions of
ZnS. The absorption coefficient, a, was estimated from the
approximate relation[41] given in Equation 1.
at ln(T1)
t is the film thickness and T is the transmittance. Using the
calculated value for a, the optical bandgap for the films
could be obtained from Equation 2.[42]
a(hm) (hm EG)n
Fig. 6. AFM surface micrograph (4 lm 4 lm) for a ZnS-based film on
SiO2/Si(100) (T = 400 C).
ture appeared smooth and regular, without cracks or pin-
holes. The average surface roughness depended on the
(1) nature of the substrate, and was 1 nm and 5 nm for the
SiO2/Si(100)- and SiO2-supported coatings, respectively.
This observation possibly reflects the influence of the sub-
strate structure on nucleation from the vapor phase. The
SiO2/Si(100) substrate is likely to induce a more ordered
growth of the zinc sulfide films, while the amorphous SiO2
(2) surface is expected to give rise to a less regular particle

96 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0948-1907/03/0203-0096 $ 17.50+.50/0 Chem. Vap. Deposition 2003, 9, No. 2
Full Paper
nucleation process, resulting in a higher surface roughness.
This effect is particularly evident in the present work be-
cause of the low coating thickness, and the conformal sub-
strate coverage typical of CVD experiments.[28]
Finally, the microstructure of the films was investigated
by grazing incidence X-ray diffraction, in order to enhance
the film contribution with respect to that of the substrate.
Irrespective of the deposition temperature, none of the
recorded diffractograms showed any reflections attribut-
able to crystalline forms of ZnS and/or ZnO. This observa-
tion could be explained by hypothesizing that, either the
obtained films were amorphous, or a ZnSO network
might have formed. Nevertheless, film thinness could be
responsible for the absence of XRD peaks. On this basis, it
was reasonable to suppose an average crystallite size not
greater than a few nanometers, resulting in no clearly de-
tectable diffraction peaks. According to this hypothesis, the
film being investigated would be best described as between
nanocrystalline and amorphous materials.
3. Conclusions
Zinc bis(O-ethylxanthate) was proposed as a new single-
source precursor for the CVD of thin zinc sulfide-based
films. The formation of the ZnS-based films from zinc
bis(O-ethylxanthate) at temperatures between 250 C and
400 C has been studied, and information about the first
stages of ZnS formation from the vapor phase has been
obtained. Thin (1030 nm) ZnS-based films have been de-
posited on SiO2/Si(100) and SiO2 substrates. The coatings
obtained were carbon-free and displayed no evidence of
crystalline phases. This was possibly due to their thinness
and/or small crystallite size. Irrespective of the synthesis
conditions, compositional analyses of the films after expo-
sure to atmosphere revealed the coexistence of ZnO and
ZnS, and the presence of sulfur deficiencies, confirmed by
optical absorption spectroscopy. The coatings were trans-
parent in the visible and IR-spectral ranges.
Nevertheless, the feasibility of faster growth rates must
be considered for the development of this work since the
obtained films are probably much thinner than required for
most applications. To this end, attempts to obtain thicker
ZnS films at higher precursor evaporation temperatures,
together with more detailed analyses aimed at obtaining a
deeper insight into their microstructure, will be the subject
of future investigation.
4. Experimental
Synthesis and Characterization of Zn(O-EtXan)2: The precursor was
synthesized (yield = 86 %) starting from zinc(II) nitrate hexahydrate
(Zn(NO3)26 H2O) and potassium O-ethylxanthate (K(S2COCH2CH3) (Al-
drich Chemical Co. Ltd.) [23]. The cream-colored powders could be manipu-
lated in air and were characterized by elemental analysis, NMR, FTIR, vis-
NIR (near infrared) spectroscopies, thermal analyses, EI-MS, and ESI-MS.
Chem. Vap. Deposition 2003, 9, No. 2 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Elemental Analysis: Found, C 23.2 %; H 3.2 %; calculated for
C6H10O2S4Zn: C 23.4 %; H 3.3 %.
FTIR: 1034 cm1(s), C=S group [46]; 1126 cm1(s) and 1211 cm1(s), C
OC symmetric and asymmetric stretching, respectively [47].
1
H NMR: (400.13 MHz, CDCl3, 298 K, tetramethylsilane (TMS) refer-
ence). 1.51 ppm(t), CH3; 4.59 ppm(q), CH2.
13
C NMR: (100.61 MHz, CDCl3, 298 K, TMS). 14.28 ppm, CH3;
44.90 ppm, CH2; 231 ppm, CS2=.
Optical Absorption: (EtOH, 104 M). 295 nm(s), n p*; 223 nm(s), n
r*. These bands were ascribed to electronic transitions typical of the ligand,
since they are very similar to other reported metal O-ethylxanthates [48].
Thermal Analysis: Thermal analysis of the precursor was performed using
an SDT 2960 apparatus (TA Instruments, New Castle, USA) which allows
the simultaneous performance of differential scanning calorimetry and ther-
mogravimetric analysis measurements. The spectra were recorded in a N2
flow with a heating rate of 10 C min1.
Mass Spectrometry Analysis: Precursor mass spectra were obtained using
a single-focus magnetic instrument VG-MS16 (mass resolution = 5000) un-
der standard electron ionization conditions (EI = 70 eV). The parent molec-
ular ion was observed at m/z = 306. Other peaks were attributable to the
.
following species: [Zn(O-EtXan)S2CO+], m/z = 277 (3 %); [Zn(O-Et-
Xan)S2C+], m/z = 261 (3 %); [Zn(O-EtXan)SC+ ], m/z = 229 (23 %); [Zn-
(O-EtXan)S+], m/z = 217 (42 %); [Zn(O-EtXan)+], m/z = 185 (66 %);
.
[ZnS2COH+], m/z = 157 (45 %); [SC(OEt)2+], m/z = 134 (100 %); [O-Et-
XanH+ ], m/z = 122 (41 %); [CH3CO+], m/z = 43 (100 %).
The ESI mass spectra were obtained using a LCQ instrument (Finnigan,
Palo Alto, CA, USA). The entrance capillary temperature was 200 C and
the capillary voltage was kept at 3.5 kV. Solutions of the precursor com-
pound (5 105 M in MeOH) were introduced by direct infusion at a flow
rate of 10 lL min1.
Film Deposition: The films were deposited in a cold-wall low-pressure
horizontal CVD reactor with a quartz tubular chamber (tube length = 20 cm;
inner diameter = 3 cm) and a resistively heated susceptor. The precursor
pyrolysis was performed in a N2 atmosphere (flow rate = 300 sccm; total
pressure = 10 mbar). ZnII O-ethylxanthate was placed in a vaporization ves-
sel connected to the reactor tube and maintained at 100 C throughout each
film deposition. The pressure was measured by a capacitance manometer
(BOC Edwards, Crawley, UK) and the gas flow was controlled by a mass
flow controller (MKS Instruments, Andover, USA). Herasil SiO2 slides
(Heraeus, Hanau, Germany) and SiO2-coated n-type Si(100) (r = 1 X cm)
(SGS, Catania, Italy) substrates were cleaned prior to each deposition
according to a previously reported procedure [49].
The deposition time was always 1 h. The substrate temperature was var-
ied between 250 C and 400 C. The repeatability of the experiments was
ascertained by performing different film depositions under the same condi-
tions.
Film Characterization: XPS and XE-AES Analyses: Spectra were re-
corded by a Perkin Elmer U 5600ci spectrometer with non-monochroma-
tized Al Ka (1486.6 eV) and Mg Ka (1253.6 eV) sources at a pressure lower
than 5108 Pa. The spectrometer was calibrated by assuming the BE of the
Au4f7/2 line at 84.0 eV with respect to the Fermi level. The standard deviation
for the BE values was 0.2 eV. The reported BEs were corrected for charg-
ing effects, assigning to the C1s line of adventitious carbon the BE value of
284.8 eV [33]. Survey scans were collected in the 01350 eV and 01100 eV
ranges (Al Ka and Mg Ka sources, respectively) and detailed spectra were
recorded for the following regions: Zn2p, Zn3p, S2p, O1s, C1s, and ZnLMM.
After a Shirley-type background subtraction [50], the raw spectra were
fitted using a non-linear least-square fitting program, adopting Gaussian
Lorentzian peak shapes for all the peaks. The atomic compositions were
evaluated using sensitivity factors as provided by U V5.4A software.
SIMS and Profiler Analyses: A quasi-static SIMS [51] was used to carry
out SIMS analysis. A monochromatic (6 keV, ionic current ^ 400 nA) O+2
ion beam collimated to 50 lm was generated in a mass-filtered duoplasma-
tron ion gun (DP50B, VG Fisons, UK). A mass-energy analyzer (EQS1000,
Hiden, UK) with a 45 sector field energy analyzer and a quadrupole mass-
filter were used for negative- and positive-ion detection in counting mode.
Lens and energy analyzer potentials, quadrupole electronic control units,
and the detection system were controlled via a Hiden HAL IV interface.
The ion species were identified by resolving the overlapped m/z signals
with an isotope pattern simulation program. In-depth distributions were
analyzed following selected signals as a function of sputtering time. Due to
film thinness, the raster area (500 lm 500 lm) was set larger than usual in
order to slow down the erosion and increase the acquisition time window.
Border effects were avoided using electronic gating: only the 20 % of the
raster area limited to the central part of the crater contributed to the ionic
signals. That this area was flat was verified by analyzing the images obtained
by a profiler (Tencor P-10 profiler, Tencor, USA). By means of this equip-
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ment, film thickness was measured and SIMS erosion rate (1015 nm min1)
could also be estimated, the ion current being constant during the experi-
ments. Charging phenomena were compensated using a flood gun.
Optical Absorption: Optical absorption spectra of the films were
recorded in the range 300800 nm on a Cary 5E (Varian) UV-vis NIR dual-
beam spectrophotometer, with a spectral bandwidth of 1 nm. In each spec-
trum, the substrate contribution was subtracted.
FTIR Analyses: FTIR spectra of the coatings supported on SiO2/Si(100)
were recorded on a Nicolet Nexus 870 instrument operating in transmit-
tance mode at normal incidence.
AFM Analysis: Images were taken using a Park Autoprobe CP instru-
ment operating in contact mode in air. The background was subtracted from
the images using the ProScan 1.3 software from Park Scientific. Images of
different areas of each sample were recorded in order to assess the film sur-
face homogeneity.
XRD: The grazing incidence XRD patterns were collected using a Philips
PW 1820 diffractometer (Cu Ka radiation, 40 kV, 50 mA) equipped with a
thin film attachment (glancing angle = 0.5).
Received: May 05, 2002
Final version: June 5, 2002
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