804 Applied Surface Science 33/34 (1988) 804 811

North-Holland, Amsterdam

CHARACTERIZATION OF EVAPORATED AMORPHOUS WO 3 FILMS

BY R A M A N A N D YTIR S P E C T R O S C O P I E S

Y. S H I G E S A T O , A. M U R A Y A M A , T. K A M I M O R I a n d K. M A T S U H I R O
R&D Division, Asahi Glass Co. Ltd., Hazawa-cho, Kanagawa-ku, Yokohama 221, Japan

Received 23 August 1987; accepted for publication 23 October 1987

The crystallinity of the frame work structure of evaporated amorphous tungsten oxide films
was investigated using Raman spectroscopy. It was found from the deconvolution analysis of two
W-O stretching modes that the full width at half maximum (FWHM) of the peak at 807 cm-1
was sensitive to the degree of crystallinity of a - W O 3. The FWHM of the 807 cm- ~ peak decreased
by 35% as the substrate temperature was raised from 40 to 145 o C. This change seems to be
caused by the growth of clusters constituting the FWS. A characteristic splitting of the absorption
peak of the O-H stretching mode was observed using FTIR spectroscopy for films deposited at
substrate temperatures higher than 145 C and annealed subsequently at 150 C for 1 h. This was
interpreted to be caused by the formation of structurally involved water molecules such as seen in
c r y s t a l l i n e M o O 3. 2H20.

1. Introduction

E v a p o r a t e d a m o r p h o u s t u n g s t e n oxide (a-WO3) films have been k n o w n to

exhibit electrochromic (EC) properties [1]. It is well recognized that the EC
properties of a-WO3 films d e p e n d o n the following three closely related
factors: (1) crystallinity of frame work structure (FWS), (2) water c o n t e n t a n d
its b o n d i n g state to the FWS, a n d (3) stoichiometry.
F r o m a diffuse X-ray scattering study, the F W S of a - W O 3 films was
clarified to consist of a n e t w o r k of corner-shared W O 6 o c t a h e d r o n units [2].
These o c t a h e d r o n units are c a p a b l e of f o r m i n g clusters having different types
of structures, such as: (1) closed, spatial dense-packed structure (crystalline
WO3-1ike structure) [3], (2) closed, p l a n a r dense-packed structure [4] (crystal-
line M o O 3 2 H 2 0 - l i k e structure [5]), a n d (3) open chain-like structure com-
posed of the r i n g - m e m b e r e d 3,4,5,6 o c t a h e d r o n s [2]. These clusters are sup-
posed to be c o n n e c t e d to each other by W - O - W b o n d s or by h y d r o g e n b o n d s
t h r o u g h water bridges [6]. Of prime i m p o r t a n c e with respect to the EC
properties is to k n o w how the structure can be affected by the p r e p a r a t i o n
c o n d i t i o n s of a - W O 3 films.
I n this study we report o n the crystallinity of the F W S as it relates to the
substrate t e m p e r a t u r e d u r i n g the deposition a n d s u b s e q u e n t heat t r e a t m e n t in

0 1 6 9 - 4 3 3 2 / 8 8 / $ 0 3 . 5 0 Elsevier Science Publishers B.V.

( N o r t h - H o l l a n d Physics P u b l i s h i n g Division)
 Y. Shigesato et at / Characterization of evaporated amorphous WO3 films 805

air. Moreover we measured the density of the film which reflects porosity and
observed how the clusters were dense-packed to form the film. The bonding
state of water in the film was also investigated by applying F T I R spec-
troscopy; the results will be discussed as they relate to the structure.

2. Experimental

The a - W O 3 films were deposited on soda lime glass substrates by electron

b e a m evaporation of WO 3 powder of purity 99.9%. This powder was treated at
700 C for 8 h prior to the evaporation, which eliminates ambiguities about
the water content and stoichiometry of the starting material. The thickness
was about 6000 ,~. The vacuum chamber was evacuated down to 4 10 - 6
Torr, then back-filled to 4 10 -4 Torr by introducing oxygen. The substrate
temperature (T~) was varied from 40 to 350 C. Post-annealing was carried out
for films deposited at 40 C for 1 h at different temperatures ( Ta).
R a m a n spectra were measured at a scattering angle of 90 o. The wavelength
and power of the Ar ion laser used for excitation were 5145 A and 5 mW,
respectively. For R a m a n measurements, samples of the powder were scraped-
off from an ITO substrate. After the sampling, exposure to moist air was
avoided as much as possible until the end of all measurements. I R spectra
were taken from films deposited on Si wafers.

3. Results and discussion

3.1. Crystallinity o f the a- W O 3 F W S

Fig. 1 shows the R a m a n spectra (RS) for the W O 3 films deposited at

various TS. The R a m a n spectra of a-WO 3 films is considerably different from
that of c-WO3: an additional peak is present at 960 cm -1 which has been
assigned to the W = O stretching mode of terminal oxygen possibly on the
surface of the cluster [7]. Also, a broad peak is observed in the range 600-900
c m - 1 attributed to the W - O stretching vibration. This peak must correspond
to the two sharp peaks of the crystalline phase at 719 and 807 cm -1. The RS
of the film deposited at 370 C shows these two sharp peaks, indicating that a
considerable amount of crystalline phase exists. The two stretching modes
cannot be distinguished for the films deposited at T~ less than 340 C. It must
be noted here that the shape of the broad stretching mode changes depending
on Ts. Corresponding structural changes cannot be detected by X-ray diffrac-
tion analysis. The change is largest for T~ in the range from RT to 145 C.
To analyze the changes of the shape, a deconvolution was performed in
which the broad peak was assumed to be composed of two gaussian compo-
806 Y. Shigesato et al. /Characterization of eoaporated amorphous WO3 films

Ts = 3 . 7 0 " c _ / ~

%-
c
= Ts=3

Z
Ts=3
LIJ
}--
_z
Z
,< Ts = 290"c./

re Ts=I '

Ts = 40"c / ~ " ~ /
14'''" I I
1200 800 400
RAMAN SHIFT (cm-~)
Fig. 1. Raman spectra of a-WO3 films deposited at different substrate temperatures.

nents. Fig. 2 shows the result. Observed curves were satisfactorily fitted by
assuming appropriate Raman intensities and full widths at half maximum
( F W H M ) values. The effect of the presence of the 960 cm 1 peak from the
W=O stretching mode was also taken into account. Comparing the position of
the two gaussian components constituting the broad W - O stretching peak in
amorphous material with the two W - O stretching peaks of the crystalline
phase, it was found that in amorphous WO 3 only the lower energy peak shifted
towards lower wavenumbers by about 20 cm -1. On the other hand, the
F W H M of the 807 cm 1 component showed a steady decrease by 35% without
changing its position over the ~ range of 40 to 145 C. The F W H M of the 700
cm-1 component did not change up to below the crystallization temperature.
This result is in good agreement with the study of Salije et al. [8,9]. They
reported the change in the RS of c-WO 3 to be caused by a phase transition.
The location of the peak at 807 c m - I was hardly changed by the phase
transition, while the peak at 719 cm -1 splitted into more than two peaks
whose position shifted to lower energies. Therefore, it is reasonable to assume
that in c-WO 3 the 719 cm -a mode is highly sensitive to the changes in crystal
symmetry as well as to lattice distortion. However, this peak may not be
suitable for the evaluation of the FWS of a-WO 3 because this peak is sensitive
only to the structural change from crystalline to amorphous. On the other
 Y. Shigesato et aL / Characterization of evaporated amorphous WO3 films 807

I I I

: EXPERIMENTAL
CALCULATED .A.,'~ ~.

Ts=4o.c
-'- ---.-. 2"'"-, "~
:'5.J, i,
,- ,
~ II /
Z
ud

Z
_ Ts=145"c ~'~

< [", / \A
" y
/\
/\
s I
~s s \

1000 800 600

R A M A N SHIFT (cm "1)

Fig. 2. Deconvohition analysis of the R a m a n spectra of a-WO 3 films. Solid lines show calculated
curves which were obtained by the synthesis of three gaussian components. Triangles show the
observed spectra.

hand, the 807 c m - 1 peak was found to be sensitive in the sense that the shape
becomes narrower when some improvement in crystallinity occurs.
The 35% decrease of the F W H M of the 807 cm -1 peak reflects a consider-
able improvement in the structural order in terms of bond length and angle of
the W - O - W bonding. This change can be attributed to the growth of clusters.
It is necessary to find some reference value which is independent of changes
inside the bulk in order for this to be conclusive. Gabrusenoks et al. have
pointed out that the W = O mode at 960 cm-1 arises from W = O bonds at the
surface of clusters [7]. Actually, the F W H M of the 960 c m - 1 peak did not
show any dependence on T, or on annealing. This seems to confirm their
consideration. A higher crystallinity of the film corresponds to a smaller
integrated intensity ratio of the two stretching modes W = O / W - O .
The changes in the F W H M with T~ and Ta, are shown in fig. 3 for the three
deconvoluted gaussian components. As for the dependence on T,, the F W H M
showed no change up to 1 5 0 C and a decrease of roughly 10% at 300C.
Thus, subsequent annealing up to 150 C gave no appreciable change in the
F W H M , irrespective of T,. The change is small even upon annealing at
300 C. The RS of a sample annealed at 350 o C, the crystallization tempera-
ture of a-WO3, is shown in fig. 4. This spectrum can be understood as a
808 Y. Shigesato et al. / Characterization of evaporated amorphous I4/03 films

I I I I
1
- A'%, 700cm- ,IL--A
200
E w-o ~ .... , ',

v .m--ram I ,,
100 W=O 960cm-1 ~
G_
L9 as,flq., \0
Z

tO 0
0 1 00 200 300 400
Ts;SUBSTRATE TEMPERATURE(c)
~0
0
200 ._,VV-0 , , A ~ ~ .~--" -A (AMORPHOUS
7
/ H*SE
O
100 W=0 960cm" ~,,
Ts 40'(: x~-- CRYSTALLINE
PHASE
0 I ] I I
n-
0 100 200 300 400
Ta ;ANNEALING TEMPERATURE (C)

Fig. 3. Change ot full width at half m a x i m u m (FWHM) of the gaussian components having peaks
at 700, 807 and 960 cm i as a function of T~ and Ta.

mixture of crystalline and amorphous phases. X-ray diffraction of this sample

revealed no peak. One possibility is that microcrystallites are embedded in an
amorphous matrix, as reported for phosphorus-doped Si : F" H alloys [10].

I I I I I

~" Ta=350. c
D ]~ L I N E PHASE

Z
ILl

_z
7
<

<
r~ AMORPHOUSPHASE
I I I I I
1000 800 600 400 200
RAMAN SHIFT (cm "1)
Fig. 4. Raman spectrum of the a-WO 3 films post-annealed at 350 C . Both crystalline and
amorphous phase can be observed.
 Y. Shigesato et al. / Characterization of evaporated amorphous WO3 films 809

The density measurement of the films indicated that dense packing of

clusters took place mainly for the T~ range 1 4 5 - 2 9 0 C and the Ta range
3 0 0 - 3 5 0 o C. The density is a direct measure of porosity and reflects macro-
scopic crystallinity rather than the structural order discussed in the previous
section. W e can speculate about the change in the structure as follows. With
increasing T~ from 40 to 145 o C, the growth of clusters occurs without an
obvious increase in the density. Further increases from 145 to 290 C make
clusters dense-packed, resulting in a decrease in the porosity. As to the
post-annealing the density increase was less than 10% even at Ta = 3 0 0 C ,
indicating that the dense-packing of clusters was not remarkable. At Ta =
350 C the clusters turn into microcrystallites and simultaneously their dense-
packing occurred.

3.2. The bonding state o f water in the f r a m e work structure

T h e F T I R spectra of O - H stretching modes before and after post-anneal-

ing at 1 5 0 C for 1 h are shown in fig. 5 for a - W O 3 films deposited at various
Ts. The stretching modes are located at 2800-3600 cm -1, which is at lower
energies c o m p a r e d to those in the vapor phase; 1,1 = 3657 cm -1 and v3 = 3756
cm -1 [11]. This is p r o b a b l y due to the presence of hydrogen bonding. These
modes were observed as a single b r o a d absorption peak for the as-deposited
films. This absorption splits into three narrow peaks u p o n post-annealing, but
only when films were deposited at temperatures higher than 145 o C. The three
peaks are located at 3050, 3200 and 3530 cm -1. Most of the water lost during
annealing could be assigned to the b o n d i n g state having an absorption a r o u n d
3400 c m - 1.

I i I I I I I I
Ts = 1415'c as depo Ts=290"c as depo

J
I I I
annealed at 150C annealed at 150"C annealed at 150"C

r i i
4000 3500 3000 2500 4000 3500 3000 2500 4000 3 5I0 0 3 0I0 0 25'00

WAVENUMBER (cm"~)
Fig. 5. FTIR spectra, before and after annealing at 150 C for 1 h, of a-WOa films deposited at
different Ts.
810 1I. Shigesato et al. / Characterization of evaporated amorphous WO3 films

Water in a-WO 3 films has been thought to be present in various forms of

physical absorption; chemisorption known as BriSnsted acid site W O - H , and
structurally involved water (structural water hereafter). Using DSC and ther-
mogravimetry, Zeller et al. have found two desorption peaks, at 1 5 0 - 1 7 0 C
and 300 respectively, which were confirmed to be due to the loss of water.
Yoshiike et al. have assigned the O - H stretching mode at 3400 c m - 1 in F T I R
spectra to chemisorbed water [12], so the water lost during annealing at 150 C
was in a chemisorbed state. According to the analysis of the crystal structure
of M o O 3 2 H 2 0 [5], crystal water molecules are present between the layers
consisting of corner-shaped MoO 6 octahedrons or coordinated to Mo atoms at
the center of the octahedrons. These interlayer water molecules are also
connected loosely to each other through hydrogen bonding. Hence, there are
three kinds of hydrogen bondings due to differences in bond length, whose
stretching energies are at 3215, 3415 and 3500 cm -1 [13].
Therefore, the results of a - W O 3 suggest that water which had survived the
1 5 0 C annealing and desorbs at 3 0 0 C must be structural water. Slight
differences in the O - H stretching energies might be attributed to the dif-
ference in metal atom. Furthermore, the reason for the splitting taken place
only for films deposited at higher temperatures, is the improvement in the
average crystallinity of the FWS. Post-annealing at 150 C makes the bonding
energy of structural water well-defined.

4. Conclusion

F r o m the deconvolution analysis of the R a m a n spectra of evaporated

a-WO 3 films, it is found that the crystallinity of FWS is improved as the
substrate temperature is raised from 40 to 145C. Post-annealing in air at
150 C did not alter the crystallinity.
Characteristic splitting of O - H stretching absorption peaks is found in
F T I R spectra for the post-annealed films deposited at temperatures higher
than 145C. These peaks are assigned to structurally involved w~:.~r mole-
cules.

Acknowledgments

The authors are grateful to Dr. M. Mizuhashi for making valuable sugges-
tions and for a critical reading of the manuscript. They also thank Professor J.
Nakahara, Professor Y. Oka and Professor K. Tanaka for their helpful
discussions and encouragement, and Mr. A. Masui for the measurement of
F T I R spectra.
 Y. Shigesato et al. / Characterization of evaporated amorphous WO3 films 811

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