Optical properties of ZrTiO4 films grown by radiofrequency magnetron

sputtering
DeAn Chang, Pang Lin, and TseungYuen Tseng

Citation: J. Appl. Phys. 77, 4445 (1995); doi: 10.1063/1.359472

View online: http://dx.doi.org/10.1063/1.359472
View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v77/i9
Published by the American Institute of Physics.

Additional information on J. Appl. Phys.

Journal Homepage: http://jap.aip.org/
Journal Information: http://jap.aip.org/about/about_the_journal
Top downloads: http://jap.aip.org/features/most_downloaded
Information for Authors: http://jap.aip.org/authors

Downloaded 22 Apr 2013 to 131.247.112.3. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions
 Optical properties of ZrTi04 films grown by radio-frequency magnetron
sputtering
De-An Chang,) Pang Lin,b)lc)and Tseung-Yuen Tsenga)
National Chiao-Tung University, Hsinchu, Taiwan, Republic of China
(Received 11 October 1994; accepted for publication 24 January 1995)
Thin films of zirconium titanate on quartz glass were prepared using radio-frequency magnetron
sputter deposition at various substrate temperature (Td from 25 to 450 C). Crystallinity of the films
sets in either at T,=400 C or after annealing in air up to 650 C. The refractive index showed
monotonic increase with Td from 2.22 to 2.37 at 550 nm while the extinction coefficient ranging
from 1.OX1O-3 to 4.7X10w3 increased with decreasing Ti/Zr stoichiometric ratio (from 1.08 to
1.03) of the films. The influence of the Ti/Zr ratio on the oxygen deficiency and absorption
properties of the films was attributed to the stronger attraction of the Ti+ ions compared with Zr4+
ions to the condensing oxygen atoms or ions on the surface of growing film. The optical band gap
was found to be 3.4 eV of indirect-transition type. A single-oscillator model was used to fit the
dispersion of the refractive index with the wavelength, indicating that the amorphous and crystalline
ZrTi04 films are similar in short-range-order structure. The inhomogeneity and packing density of
the films were analyzed using well-known relations. 0 1995 American Institute of Physics.

I. INTRODUCTION II. EXPERIMENT

The deposition of films was carried out in a home built
Several oxide films are extensively used in optical thin
magnetron sputtering system, which was arranged in a
film device applications because of their desirable optical
sputter-up configuration with a horizontal rotatable substrate
properties. Among them, titania and zirconia films have been
holder 8 cm away from a ZrTi04- powder target. The zirco-
studied intensively due to their high refractive indices, hard-
nium titanate powder was synthesized via solid-state reaction
ness, durability, and low absorption, etc. Each, however, has
of TiOz (anatase) and ZrQ (baddelyite) powders, with 0.5/
a number of polymorphic phases which usually are concur-
0.5 mole fractions, at 1400 C for 4 h. An operating pressure
rent in the deposited film and may change their relative per-
of 10 mTorr was maintained by a mixture of high-purity
centage with the deposition or annealing conditions.-3 The
argon (N 60) and oxygen (N 45) at a flow rate ratio of 80/20.
variable heterogeneous composition of the films makes the
All films were deposited at a fixed radio-frequency (rf)
control of film properties difficult and is considered one of
power level of 250 W which enables a deposition rate of
the factors degrading film qualities such as refractive index
around 1 nm/min. The substrates used are Heraeus Suprasil-2
and homogeneity.g-5 It is noted that the compound of these
fused silica plates for optical measurements. The crystal
two oxides, ZrTi04, in contrast to them, exhibits only one
structures of the films were examined using a Siemens
phase with a minor allowable variation in a stoichiometric
D5000 XRD with Cu Kcu radiation. Stoichiometric analysis
ratio of Ti/Zr. The compound is known as a high dielectric
of the fdm composition was performed by an EPMA of
material and has been tested to be very corrosion resistant.7
JOEL, JXA-8800M, on three areas (10 PmX 10 pm per area)
The synthesis of ZrTiO, thin film was reported recently and
for each sample. The morphology of film surfaces was
the structure of the film grown on Corning glass at 400 C
mapped by an atomic force microsco-pe of Digital Instru-
indeed showed only the orthorhombic structure.* Thus, the ments, NanoScope III. Transmittance and reflectance in the
study of optical properties of ZrTiO, film should be of inter- wavelength range 250-800 nm was measured at near-normal
est for its potential technological applications.
incidence by a Hitachi model U-3410 double-beam spectro-
In this work, thin films of zirconium titanate were pre- photometer. The optical constants and film thicknesses were
pared using radio frequency magnetron sputter deposition. calculated using the spectral transmittance based on the en-
The fihn structure and properties such as refractive index, velope technique.
extinction coefficient, band gap, packing density, and inho-
mogeneity were also characterized. The substrate tempera-
ture was varied from 25 to 450 C during deposition. The Ill. RESULTS AND DISCUSSION
effect of the substrate temperature as well as the post-
A. Crystal structure and composition
deposition annealing on the properties and structure of the
films were also studied. The parameters related to the short- X-ray diffraction studies of ZrTiO, films prepared at
range-order structure of ZrTiO, films were analyzed using substrate temperatures, 25-450 C, showed that the films de-
the refractive index data based on single-oscillator model. posited at a temperature below 300 C were amorphous to x
ray and the crystallinity was observed at 400 C with a dis-
tinct peak of zirconium titanate (111) [Figs. l(a) and l(b)],
*)Dqutment of Electronics Engineering and Institute of Electronics.
bJInstitute of Materials Science and Engineering. which exhibited 100% relative intensity in the x-ray diffrac-
jAuthor to whom correspondence should be addressed. tion (XRD) spectra of the ZrTi04 powder used for the target

J. Appl. Phys. 77 (9), 1 tvlay 1995 0021-6979/95/77(9)/444.5/7/$6.00 Q 1995 American Institute of Physics 4445

Downloaded 22 Apr 2013 to 131.247.112.3. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions
 80
8
8 60
2
3 --substrate
(d) Ta = 650C g 40
A. E
20
(c) Target
-2 3; t= ZG 0
%%F!
cy- YV yJ E3 250 350 450 550 650 750 850
AAAAAJJ Wavelength (nm)

FIG. 2. Transmittance spectra as a function of wavelength for zirconium

titanate films at different substrate temperatures.

(b) Td = 45Oc
uted in octahedral cation sites of the crystal lattice of sput-
tered ZrTiO, films, thus the observed minor deviation from
n ideal stoichiometry would not give rise to an equivalent con-
centration of Zr vacancies in the crystalline films.

B. Optical properties
(a) Td = 400C
The spectral transmittance of the as-deposited films are
I 8 I I I I I I

25 30 35 40 45 50 55 60 I shown in Fig. 2. It is noted that the transmittance maxima of

28 (degree)
FIG. 1. X-ray diffraction of zirconium titanate films and powder, (a) and (b)
tilms deposited at T,=400 and 450 C, (c) target powder, (d) film annealed
at Ta=6500C.
[Fig. l(c)]. To evaluate the thermal stability of the films, the
sample deposited at 25 C was annealed in air at tempera-
tures ranging from 300 to 650 C in sequence, each for 2 h.
The annealed film. remained amorphous in structure up to
650 C at which (111) 28 peak was observed in the corre-
sponding diffraction pattern [Fig. l(d)]. Detailed results on
the film structure had been reported in the previous study* in
which various crystalline materials and Corning 7059 glass
were used as substrates.
The measured stoichiometric ratio of Ti/Zr of the as-
deposited films, as summarized in Table 1, showed that the
I concentration of Ti was slightly higher than that of Zr in the
I whole range of deposition temperature (Td) and the ratio
closest to 1:l occurred at T,--300 C. The tolerable TiKr
ratio limit is from 45755 to 58/42 for a stable ZrTi04 phase.
It was shown that the Zr and Ti ions were randomly disttib-
TABLE I. Composition and thickness for zirconium titanate films at differ-
ent substrate temperatures.
Substrate temperature (Td)
25 C 300C 400C
TiiZr ratio 1.08 1.03 1.05
i Thickness (nm) 502 383 366
films grown at 25 and 450 C are higher compared with
those films of intermediate T,. Apparently, the absorption
properties of the films have no obvious relation to the depo-
sition temperature.
The corresponding refractive index (n) and extinction
coefficient (k) of the tilms were derived from the spectra
transmittance by the envelope technique, and plotted as a
function of wavelength (A) in Fig. 3. The behavior of n ver-
sus A can be fitted into the Cauchy formula, n=A +Bh-
+CX-4, as shown by solid lines in the figure.
It was seen that the refractive index increased monotoni-
cally from 2.22 to 2.37 (at 550 nm) as Td varied from 25 to
450 C. While the dependence of n on Td for the films was
consistent with those normally observed in many oxides such
as TiO, 4 and ZrO, films,5 the variation of k with Td ap-
peared not a simultaneous-increase relation as held in the
former two cases. Instead, k increased with decreasing Ti/Zr
stoichiometric ratio. Several studies4V-3 on the absorption
in oxide films attributed this effect to oxygen deficiency
which might arise from preferential resputtering of oxygen
from the growing films or less condensation rate of oxygen
at elevated substrate temperatures. However, the concurrence
of two different cations in ZrTi04 film may affect the defi-
ciency implicitly.
Because of the random distribution of Zr and Ti ions in
the octahedral sites as mentioned in Sec. III A, both cations
would experience identical average nearest-neighbor envi-
ronments (to zero order approximation) inside the body of
film as well as on the uppermost surface of growing film. On
450 C the average the Ti4+ ions on the surface would have a stron-
1.06 ger bonding to the newly condensed neighboring oxygen at-
349 oms or ions compared with the Zr+ ions in a similar situa-
tion. This results from the smaller ionic radius of Ti4 (0.61

4446 J. Appl. Phys., Vol. 77, No. 9, 1 May 1995 Chang, Lin, and Tseng

Downloaded 22 Apr 2013 to 131.247.112.3. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions
 Td A 8x10-4 CxlO-
@ 2SC! 2.056 4.832 4.831 80
L-
0 300C 2.096 4.696 1.608
A 400 C 2.132 5.774 4.046
Q
V 45OT 2.177 6.068 2.265
; 60
---substmlc
h .!I -- asdeposited
d 2.5
V j 40 ---Am3cKfe
. ..-.&)&@
G
c 20 ----Am.5oooc
1 -----Am. 6oOk
P
r(
24.
0
1,,I,, , , , , , , , , , , , , , , , , , , , ,
----AM. 650%
L-
250 350 450 550 650 750 850
Wavelength (nm)
4P4 23.
FIG. 4. Transmittance spectra as a function of wavelength for the as-
deposited (Td=2S C) and annealed zirconium titanate films.

tion range investigated) for a film may enhance the conden-

300 400 500 600 700 800 900 sation rate of oxygen, leading to less oxygen deficiency and,
Wavelength ( nm ) consequently, a lower extinction coefficient.
The annealed film showed no significant change in trans-
mittance in the early annealing stages (Fig. 4) up to 650 C at

0
0
Td=25OC
Td = 300 C
which the transmittance maxima decreased and the interfer-
ence pattern shifted toward a longer wavelength region. The
lowering of transmission was mainly due to strong scattering
- A Td = 400 OC
? V Td=450OC of light in the film caused by some discernible microcracks
z IO- arising from mismatched thermal expansion of the film and
LJ substrate. Suhail et aL4 deposited TiO? by using dc reactive
&i
magnetron sputtering at room temperature and found that the
5 8- film, after annealing at 700 C, showed an increase in refrac-
tive index, Anln =+7.3% at 550 nm, a thickness reduction,
4 AdId= -2O%, and a shift of spectra pattern to a lower wave-
0, 6
length region (A&/A,<O) resulting from the effect of inter-
%
.,-s ference fringe, 2nd=mX,. The current result on the an-
tj 4- nealed ZrTiO, film with AX&,>0 indicated a lesser
-g thickness reduction, which was confirmed by profile mea-
ti
2-
surements with stylus on the film showing a minor change,

I-- L\
AdId=-4%, after annealing at 650 C.
The film thickness (d) involved in the calculation of ex-
0 .I ~-r -7-T-1----r ---I tinction coefficient was obtained from the slope of plots for
300 350 400 450 500 550 600 650 700 750 the interference-fringe equation,
Wavelength ( nm ) 1/2=2d(nlh)-j, 1=0,1,2,3 .... (1)

FIG. 3. Variation of (a) refractive index and (b) extinction coefficient as a

function of wavelength for zirconium titanate films at different substrate
temperatures.
A> than Zr4+ (0.72 8) which would allow O- ions to relax
to a position closer to the Ti+ ions temporarily before the
cation-O, octahedron was formed completely and subse-
quently covered by the next condensing layer. The lower
static Coulomb energy with the Ti4 ions occurring in the
transition period would permit fewer oxygen atoms to escape
from the surface. (The above argument may apply to the
amorphous film, since, as will be discussed in the latter, its
short-range-order structure is similar to that of crystalline
film.) Therefore, a higher Ti/Zr ratio (within the solid solu-
in which the order number of the observable first extreme
(Z=O) of the spectrum is j. The resulting plots for films of
different Td , as shown in Fig. 5, were fitted well into straight
lines with a common cut off around -3(=-j) on the y axis.
To check the validity of the technique used in the previous
calculations, the derived n, k, and d were substituted back
into the original transmission equation to regenerate the
spectral transmittance. The typical regeneration, as shown by
the discrete points in Fig. 6, was in good agreement with the
originally observed curve.
The absorption data for these films was analyzed based
on the well known relations
Ct!hV=C,(hV-E,p, ia
and

J. Appl. Phys., Vol. 77, No. 9, 1 May 1995 Chang, Lin, and Tseng 4447

Downloaded 22 Apr 2013 to 131.247.112.3. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions
 Td Thickness (nm)
25 C 502t 2.5 8 80 - /*
300 C 383 + 1.9
400% 366k1.8
450 C 349 + 1.8 3 co :
z
.A
B 40 - Td = 300 C
ii
c 0 regenerated
20 - ---experimental

LLL-LLI1
250 350 450 550 650 750 850

Wavelength(MI)
100

2 3 4 5 6 7
n / h (10-3 run-l)
FIG. 5. Plot of Z/2 vs n/A for zirconium titanate films at different substrate
temperatures to determine the order number and thickness.
ahv=C2(hv-Eg2)2,
for direct and indirect transitions respectively, where C, and
C2 are constants, a=4?rklX is the absorption coefficient, h v
is the photon energy, E,, and Eg2 are the direct and indirect
baud gaps. The absorption behavior of amorphous materials
also obeys Eq. (3) if they have parabolic band edges.14
The (c&v)~ versus hv plots for films of different Td
(Fig. 7) were well represented by Eq. (3) in the high-
absorption region beyond CY-2.5X104/cm. The plots of
(ah vj2 versus h ZJwere found not to be straight lines over any
part of the absorption spectra, thus supporting the model of
indirect band gap for the deposited films. As shown in Table
II, the band gaps found are around 3.4 eV, indicating a rela-
tively weak effect of crystallinity on the band gap for ZrTi04
films. The theoretical band model or detailed optical data on
the corresponding bulk materials is not available in the lit-
erature, preventing an appropriate comparison with our re-
sults at present time.
The variation of refractive index with the wavelength for
the single-oscillator model in the region of low absorption is
given by the expressionI
EnEd
n-2.-1=
E,2-(h#
where E. is the single-oscillator energy and Ed is the disper-
sion energy. The values of E, and Ed can be obtained from
the intercept and slope of plot for ll(n2 - 1) versus 1/X2. The
plots shown in Fig. 8 for the films of various Td exhibited a
sufficiently extended region of linearity until the wavelength
was lower than 400 nm where strong absorption was present.
80
8
8 60
3
8
.r
g 40 Td = 450 =C
B regenerated
&
l
-experimental
450
_.- -l-- ..__ 1-- .___L-.
550 650 750
J
850
Wavelength(nm)
(3)
PIG. 6- Observed and regenerated transmittance spectra for films as a func-
tion of wavelength. (a) T,=300 C and (b) 450 C.
The corresponding Eo, as summarized in Table II,
showed a decrease with increasing Td while the Ed values
appeared to be close to a constant. Since Ed is related to the
coordination number, valency, and ionicity of the cation-
oxygen complex structure for the material considered,15 the
similarity in Ed for the amorphous and crystalline ZrTiO,
films strongly suggests similarity in their structures of short
range order. The table also includes the values of
P=E,IN,Z,N, eV, where N, (=6) is the coordination num-
ber of the cation nearest neighbor to the anion, 2, (=2) is the
formal chemical valency of the anion, N, (- 8) is the effec-
tive number of valence electrons per anion. It is seen that the
observed p values are in conformity with the empirical rela-
tion given by /3=0.26+0.04 eV, which were obeyed by most
bulk oxides.15
The optical inhomogeneity in the as-deposited films was
analyzed by using the near normal reflectance of the films
and the reflectance from the bare substrate surface (Fig. 9).
The variation of refractive index (An) along the film thick-
ness was determined using the empirical relationI
An=no-ni=n,,(Rf-R,)l(4.4R,), (5)
where p1,,is the refractive index at the air-film interface and
ni at the film-substrate interface. The average index (n,,)
was calculated by the Valeev method.17*8R, and Rf are the
reflectance at the front surfaces of the substrate and films.

4448 J. Appl. Phys., Vol. 77, No. 9, 1 May 19% Chang, Lin, and Tseng

Downloaded 22 Apr 2013 to 131.247.112.3. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions
 0.28
e Td=25C
. Td=25OC 0 Td = 300 *C
0 Td=300C 0.26 A Td = 400 C
V Td = 450 oC!

0.24

h
;
5 0.22
.
v 0

0.20 0
e

. 3.0 3.3 3.6 3.9 4.2 4.5

Photonenergy(ev) 0.18

1200 V
0.16 -
I- I I I t I I
1000 * Td = 400 OC 1 2 3 4 5 6 7 8 9
v Td = 450 C
Ill.2 (pm-Z>
4 800 (b)
g FIG. 8. Plotsof refractive-indexfactor(n2- 1)-l vs A - for zirconiumti-
& 600 tanatefilms at differentsubstrate
temperatures.
v!
3
3 400 The inhomogeneity of the films, h/n,, , calculated at
x
the points of reflectance minima around 550 nm, as shown in
200 Table III, was found to vary from -5.0% to +8.4% as the
substrate temperature was increased from 25 to 450 C. The
0 r films prepared at intermediate temperatures -300-400 C
3.0 3.3 3.6 3.9 4.2 4.5 appeared to be more homogeneous in optical properties.
Photonenergy(ev) The packing density (P) of the films has been deter-
mined by the Bragg and Pippard mode12using the refractive
FIG. 7. Plots of (&zJ)~ vs hv for zirconiumtitanatefilms at different indices of the films (at A=550 nm) and of bulk ZrTiO,
substrate
temperatures.(a) Td=25 and300C (b) 400ami450C. materia121(n =2.37). Water-filled voids in films with rz= 1.33
was also assumed.The calculated packing density (Table III)
showed to increa$e with the substrate temperature as fre-
Both can be computed from the observed reflectance of the quently observed in the deposition of most optical thin films.
bare and coated substrates, R,, , and Rfo using the following Full densification was achieved for the film deposited at
expressions,g respectively,

-- 2RS (6) 70
-uncoated substrate
R-(l+R,)
60 -3coY
-4wc
R,(1-Rf)2
Rf=Rff (1 -RfRR,) g?
v 50 E
-450%!

g 40

3 30
TABLE II. Energygapsand the fitting parameters from single-oscillator I2
modelfor zirconiumtitanatefilms at differentsubstrate
temperatures. 20
10
Substrate Single Dispersion Empirical
temperature Ew7y gap oscillatorenergy energy ratio I I I
Td (C) E, W) EOW) Ed (ev) P W
250 350 450 5.50 650 750 8.50
25 3.54 6.60 22.10 0.24 Wavelength
(nm)
300 3.44 6.42 22.85 0.24
400 3.45 6.04 22.83 0.26 FIG19. Observed refiectance
spectraas a functionof wavelength for bare
450 3.46 5.86 24.48 0.24 substrate
(R,,) andzirconiumtitanatefilms (RfO)at differentsubstrate
tem-
peratures.

J. Appl. Phys., Vol. 77, No. 9, 1 May 1995 Chang, Lin, and Tseng 4449
Downloaded 22 Apr 2013 to 131.247.112.3. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions
 TABLE III. Optical inhomogeneity analysis and packing density for xirco-
nium titanate films at different substrate temperatures.
Substrate Refractive Optical
temperature index inhomogeneity
Td (cl sue Ahme
25 2.304 (X=553 nm) -0.5%
300 2.315 (A=572 nm) 1.7%
400 2409 (X-560 nm) -2.4%
450 2.474 (X=549 nm) 8.4%
T,=450 C and moderate dense film with P-O.9 could be
obtained at room temperature, which was consistent with the
above mentioned results on the thickness shrinkage of the
annealed film. A drastic increase in packing density was ob-
served in the films as Td increased from 400 to 450 C. Simi-
lar variation for the computed values of P with Td was also
obtained by the model of Kinosita and Nishiboriz2 and
Chopra et al.=
According to the modified structure zone model pro-
posed by Thornton,4Y25 the sputtered films may exhibit a
specific characteristic structure in each zone of deposition
conditions (namely the operating pressure of argon and sub-
strate temperature) at which they are prepared. Within the
range of low deposition temperature for a given pressure
(zone 1) the formed columnar microstructure with voided
boundaries in the film was ascribed to the low adatom diffu-
sion and shadowing effect on the growing surface of the film.
As Td increased to reach into zone T, the enhanced adatom
diffusion would result in a microstructure characterized by a
dense array of fibrous grains without open boundaries.4 By
this model, the deposition conditions in our study,
T,=400 C. (0.32T,, melting point of ZrTi04 T,,,=2093 K)
and 450 C! (0.35TJ at a pressure of 10 mTorr, belong to
zone 1 and zone T, respectively.26
This model on the zone dependence of film structure
may offer an expIanation for the jump in packing density
between Td=400 and 450 C, considering the elimination of
open column boundaries. The microstructures revealed by
atomic force micrographs of the film surfaces, as shown iu
Fig. 10, confirmed the transition from zone 1 to zone T. It is
seen that the column diameter for the film of 450 C is about
six times as large as that of 400 C and the boundary gaps
were seaIed accompanied with columns of rounded top shape
due to a higher atomic mobility, in contrast to the rugged
surface morphology for the film of 400 C with tapered col-
umns and unfilled space in between.
IV. CONCLUSION
ZrTi04 films were prepared on quartz glass by rf mag-
netron sputtering method at various deposition temperatures
(Tdj. Crystallinity of the films sets in either at T,=400 C or
after annealing in air up to 650 C. The refractive index
showed an increase with increasing Td , while the extinction
coefficient increased with decreasing TiiZr stoichiometsic ra-
tio of the films. The influence of the TiiZr ratio on oxygen
deficiency and, consequently, on the absorption properties of
the films was attributed to the stronger attraction of the .Tii+
4450 J. Appl. Phys., Vol. 77, No. 9, 1 May 1995
Downloaded 22 Apr 2013 to 131.247.112.3. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions
Packing
density
0.90
0.92
0.93
1.0
FIG. 10. Surface morphology mapped by atomic force microscope for zir-
conium titanate films at substrate temperature (a) 400 and (b) 450 C.
ions compared with Zr4 ions to the condensing oxygen at-
oms or ions on the surface of growing films. The energygap
of the as-deposited films was found to be around 3.4 eV of
indirect-transition type. The variation in refractive index with
the wavelength was shown to follow a single-oscillator
model, from which the parameters, Ee, Ed, and /3 were de-
termined and appeared to conform with the empirical rela-
tion for most oxides. This also indicates the similarity in
structure of short range order for the amorphous and crystal-
line ZrTiO, films. The inhomogeneity of deposited films in-
creased, approximately, with Td in a range - -5%-+8%
with a better homogeneous quality occurring at intermediate
Td . High packing density without open boundaries could be
achieved for ZrTiO, films sputtered at deposition conditions
in zone T.
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support
from the National Science Council of the Republic of China
under Contract No. NSC 82-0404-E009-394. Dr. Tsung-
Eong Hsieh is thanked for many useful discussions.
C. K. Kwok and C. R. Aita, J. Vat. Sci. Technol. A 7, 1235 (1989).
2D. Wicaksana, A. Kobayashi, and A. Kinbara, J. Vat. Sci. Technol. A 10,
1479 (1992).
R. E. Klinger and L. K. Carniglia, Appl. Opt. 24, 3184 (1985).
M. H. Suhail, G. M. Rao, and S. Mohan, J. Appl. Phys. 71, 1421 (1992).
M. H. Suhail, G. Mohan Rao, and S. Mohan, Mater. Sci. Eng. B 12, 247
(1992).
Chang, Lin, and Tseng
 E H. Brown, Jr. and P. Duwez, J. Am. Ceram. Sot. 37, 129 (1954).
R A. Lessing, Z. Z. Yang, G. R. Miller, and H. Yamada, J. Electrochem.
Sot. 135, 1049 (1988).
sD. A. Chang, P Lin, and T. Y. Tseng, Appl. Phys. Lett. 64, 3252 (1994).
R. Sawnepoel, J. Phys. E. Sci. Instrum. 16, 1214 (1983).
A. E. Mchale and R. S. Roth, J. Am. Ceram. Sot. 69, 827 (1986).
E. Ritter, J. Vat. Sci. Bxhnol. 6, 225 (1966).
H. Kuster and J. Ebert. Thin Solid Films 70, 43 (1980).
t3K. N. Rao and S. Mohan, J. Vat. Sci. Technol. A 8, 3260 (1990).
14S. R. Elliott, in Ph,ysicsof Amorphous Materials (John Wiley & Sons,
New York, 1990), p. 328.
S. H. Wemple and M. Didomenico, Phys. Rev. B 3, 1338 (1971).
16D. R Arndt, R. M. Azzam, J. M. Bennett, J. P, Borgono, C. K. Camiglia,
W. E. Case, J. A. Dobrowolski, U. J. Gibson, T. Tuttel-Hart, E C. Ho, V.
A. Hodgkin, W. R. Klapp, H. A. Macleod, E. Pelletier, M. K. Pwis, D.
J. Appl. Phys., Vol. 77, No. 9, 1 May 1995
Downloaded 22 Apr 2013 to 131.247.112.3. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions
M. Quinn, D. H. Stome, R. Swenson, P. A. Temple, and T. E Thoun, Appl.
Opt. 23, 3571 (1984).
17A. S. Valeev, Opt. Spectrosc. USSR 15, 269 (1963).
A. S. Valeev, Opt. Spcctrosc. USSR 18, 498 (1965).
19R. Jacobsson, Arkiv Fys. 24, 17 (1963).
W. L. Bragg and A. B. Pippard. Acta Crystollgr. 6. 865 (1953).
IL. W. Coughanour, R. S. Roth, and V. A. DeProsse, J. Res. Natl. Bur.
Stand. 52, 2470 (1954).
K. Kinosita and M. Nishibori, J. Vat. Sci. Technol. 6, 730 (1969).
=K. L. Chopra, S. K. Sharma, and V. N. Yadava, Thin SoIid Films 20, 209
(1974).
s4J. A. Thornton, Ann. Rev. Mater. Sci. 7, 239 (1977).
25J. A. Thornton, J. Vat. Sci. Technol. 11, 666 (1974).
26J . A . Thornton, in Deposition TechnologiesjbfbpFilms and Coatings,edited
by R. F. Bunshab (Noyes, Park Ridge, 1982), p. 214.
Chang, Lin, and Tseng 4451