Materials Science in Semiconductor Processing 29 (2015) 201205

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Electrochromic properties of amorphous and crystalline WO3

thin films prepared by thermal evaporation technique
M.M. El-Nahass a, M.M. Saadeldin b, H.A. M. Ali a, M. Zaghllol b,n
a
Physics Department, Faculty of Education, Ain-Shams University, Cairo 11757, Egypt
b
Physics Department, Faculty of Science, Cairo University, Giza 12613, Egypt

a r t i c l e i n f o abstract

Available online 19 March 2014 The tungsten trioxides thin films were deposited by thermal evaporation method onto
Keywords: indium tin oxides coated onto glass substrates. The structural properties of the films were
Tungsten trioxides investigated by X-ray diffractometer and atomic force microscopy techniques. The as-
Electrochromic deposited film shows a polycrystalline nature related to indium tin oxides planes and the
Coloration efficiency WO3 planes appears by annealing film to 773 K for 2 h. The 2D and 3D images were
Thermal evaporation carried out using atomic force microscopy techniques. The film color is converted from
transparent to deep blue color after applying electric field, and bleaching occurs by
applying reverse electric field. The F-like color centers model was used to investigate the
coloration in amorphous films. On the other hand, the crystalline films were characterized
by the free carrier absorption mechanism. Both coloration response and coloration
efficiency for the amorphous films are greater than crystalline. The coloration efficiency
is found to be 31.25 cm2/C for the as-deposited films and decreases to 18.3 cm2/C by
annealing films at 723 K.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction There are many theoretical investigations to explain how

the coloration occurs inside WO3 thin films. Amorphous
Transition metal oxides represent a large family of films are investigated by the small polarons transition, an
materials which have various interesting application in field intervalance transition [4] or F-like color centers [5,6]. On the
of electrochromic display and smart windows such as other hand, the crystalline films are explained by Drude-like
(WO3V2O5MoO3). These materials are effective in blocking free electron absorption [7]. Generally the electrochromic
solar heat gain inside the building and are provided with the behavior of WO3 process associated with reversible process
satisfied heat inside it [1]. There is a new actively-optical changes the films coloring from blue to bleach. The blue
layer that occurs by electroactive glass species where the tungsten bronze (Mx WO3
y) is obtained by injecting films
surface coloration occurs by electrochemical process. This by electrons and positively charged ions (MH , Na , Li ,
phenomenon is called electrochromism which appears in etc.). During the charge injunction, electrons are localized at
coloration and bleaching processes. These processes are tungsten sites which changes the valancy of tungsten ions
reversible by changing applied voltage. Due to reversibility, from W6 to W5 . These localized electrons are accompa-
it is very promising on applications such as smart windows, nied with a lattice distortion which formed blue color in film
solar cell and solar energy control [2,3]. [8]. It is well known that the film properties are dependent
on the method of deposition and preparation conditions.
WO3 thin films were prepared by different methods such as
n
Corresponding author. Tel.: 20 01095107709.
solgel, electro deposition, pulsed laser, sputtering and spray
E-mail address: [email protected] (M. Zaghllol). pyrolysis [913]. There are also conventional techniques like

http://dx.doi.org/10.1016/j.mssp.2014.02.051
1369-8001 & 2014 Elsevier Ltd. All rights reserved.
202 M.M. El-Nahass et al. / Materials Science in Semiconductor Processing 29 (2015) 201205

chemical deposition, thermal evaporation and electron beam ITO

(002)

(122)
(200)

(202)

(222)
evaporation [1416]. In this work, the deposition was carried

(420)
WO3
out using conventional thermal evaporation method.
(e)

2. Experimental technique

Tungsten trioxides (WO3) in powder form was obtained (d)

from BDH chemical Ltd. Co. from England with purity of

Intensity (a.u)
(99.986%). Thin films of WO3 were deposited by conven-
tional thermal evaporation technique model (Edwards, (c)
E306A) onto indium tin oxide (ITO), with sheet resistance
about 40 /cm2. The deposition of WO3 thin films was
carried out from molybdenum boat in vacuum reaches to
104 Pa. The deposition rate and film thickness were calcu-
(b)
lated using a quartz crystal thickness monitor (FTM4,
Edwards). The deposition rate was controlled at 2.5 nm s
1.
The film thickness was ranged from 400 to 700 nm. The

(200)
(020)
(002)
annealing was carried to films at 673 K and 773 K.

(022)
(202)
(120)
The structural properties of both powder and thin film

(122)

(420 )
(204)
(040 )
(400)
(123)
(004)

(224)
(222)
(122)
were investigated using X-ray diffraction technique model (a)
(X'pert Philips), with monochromatic CuK, at 40 kV and
25 mA. The 2D and 3D images of the films were examined 10 20 30 40 50 60 70
using atomic force microscopy, model (Wet-SPM Shi- 2
madzu). The crystal size and roughness of WO3 films were
Fig. 1. XRD patterns: (a) WO3 powder, (b) as-deposited WO3 thin film,
calculated by using computer programming.
(c) ITO coated glass substrate, (d) annealed WO3 thin film at 673 K and
Electrochromic measurements of WO3 thin film were (e) annealed film at 773 K.
investigated for the as-deposited annealed films. There are
three electrodes used in measurements working electrode 2 2 2
the value becomes (f
b)1/2 where f belongs to film and
(glass/ITO/WO3) thin film, platinum sheet as counter 2
b belongs to bulk. Crystallite size is found to be 73.9 nm.
electrode and Ag (AgCl) as a reference electrode which
were immersed in 0.1 M H2SO4. 3.1.2. Atomic force microscopy (AFM) microanalysis
The optical properties were measured using spectro- Figs. 2 and 3(a) and (b) present the typical views of 2D
photometer techinque model (JASCO V-570) in wavelength and 3D atomic force microscopy for both as-deposited and
range 2002500 nm at different coloration time and differ- annealed WO3 thin film at 773 K. The as-deposited film
ent annealing temperature. shows that nanocrystalline grains around 73 nm which are
calculated from the 2D image. The roughness of the as-
deposited film was found to be 1.36 nm which is calculated
3. Results and discussion from 3D image. Annealing effect on the film to 773 K, leads
to a decrease in the mean radius which reaches 68 nm and
3.1. Structural properties roughness also decreases to 1.26 nm.

3.1.1. X-ray diffraction investigation 3.2. Electrochromic characterization

Fig. 1 shows that the XRD patterns for WO3 in powder
form (a), as-deposited WO3 film (b), ITO film coated glass Electrochromic measurements for as-deposited and
substrate (c), annealed WO3 film at 673 K and (d) annealed at annealed WO3 thin films were investigated using the
773 K for 1 h. The XRD pattern of WO3 in powder form electrochemical cell. The color of films converts from
shows a polycrystalline nature. By indexing the peaks, WO3 bleaching to deep blue in electrochemical cell under
is exhibited a monoclinic crystal system with lattice para- applied voltage.
meter, [a7.3170.05 , b7.60370.05 , c7.71370.05
and 89.930] (ICCD Card no.83-0951) [17,18]. The as- 3.2.1. Optical transmission (T) and reflection (R)
deposited film shows a polycrystalline nature which belongs Fig. 4 shows the spectral distribution of transmission
to (ITO) planes. After annealing reaches to 673 K, there are no for as-deposited WO3 thin films at different times of
new detected peaks related to WO3. Once, the annealing coloration. From this figure, the color changes due to
reaches to 723 K, the planes that belong to WO3 are increasing the proton concentration inside the film. The
observed. The average crystallite size was measured for transmittance decreases by increasing insertion time from
(200) plane using DebyeScherer's formula [19]. 20 s to 60 s. The value of transmittance for as-deposited
film approaches 90% and until proton insertion, the trans-
D 0:95= cos 1
mittance decreases sharply to 40% which is measured at
where D is the crystallite size, is the wavelength of incident 550 nm. Several models have been put in order to explain
radiation CuK line, is the Bragg's angle and for correction the electrochromism in WO3. For amorphous film, there
 M.M. El-Nahass et al. / Materials Science in Semiconductor Processing 29 (2015) 201205 203

Fig. 2. AFM images of as-deposited WO3 thin film [(a (2D and )b) 3D].

Fig. 3. AFM images of annealed WO3 thin film at 773 K [(a (2D and )b) 3D].

was initially a suggestion by Deb that F-like color centers Fig. 5 shows the typical spectral distribution of trans-
could be responsible for the coloration inside the film mission for annealed WO3 thin films at 773 K at different
[5,6]. The density of the color center was computed coloration time. It shows that the transmittance decreases
through approximate Smakula's equation [5]: in similar tendency as it had been observed for the as-
deposited film shown in Fig. 4. The transmittance
Ns f s 0:89  107 n=n2 22 m 2
decreases from 70% at the bleach state to reach to 32%
where Ns is the density of color centers, fs is the oscillation after 60 s of coloration.
strength equal unity which was suggested by Deb [5], n is On the other hand, the basic coloration mechanism that
the refractive index of the film and equal to 2.014 for as- occurs in the crystalline film is attributed to the Drude-like
deposited WO3 thin film [17], is the absorption coeffi- free electron absorption with the same behavior of the
cient in cm
1, is the width at half maximum of the heavily doped semiconductors [2122]. When ions and
absorption peak. The calculation from the previous equa- electrons are inserted into the crystalline tungsten oxide
tion showed that the color center density approximately films, the electrons enter extended states in the WO3 band
equal to 5  1018 cm
3 for as-deposited WO3 which is in structure and undergo scattering by impurities resulting
good agreement with pervious work [20]. in high reflectance in the infrared region. Therefore the
204 M.M. El-Nahass et al. / Materials Science in Semiconductor Processing 29 (2015) 201205

100 100
as-deposited as-deposited
20 second 20 second
40 second
40 second
80 60 second 80
bleached 60 second
bleached

60 60
T%

T%
40 40

20 20

0
0
500 1000 1500 2000 2500 500 1000 1500 2000 2500
[nm] [nm]
Fig. 4. Spectral distribution of transmittance at different time of colora- Fig. 5. Spectral distribution of transmittance at different time of colora-
tion for as-deposited WO3 thin film. tion for annealed WO3 thin film at 773 K.

Drude theory based on free electron theory can be applic- 100

as-deposited
able to crystalline WO3 thin film. According to Drude 90 20 second
40 second
model the concentration of the free carrier model that 80 60 second
caused the coloration given by equation [23]: bleached
70
N f =mn p 2 o 1 =e2 3 R % 60
*
where Nf is the concentration of free carrier, m is the free 50

mass of the electron, o is the permittivity of the free 40

space, 1 n2, n is the refractive index given by Hutchins 30
et al. [17]; p is the plasma frequency and e is the charge of 20
the electron. Fig. 6 shows the reflectance as a function of
10
wavelength at different time of coloration for film
annealed at 723 K. The reflectance characterized by plasma 0
500 1000 1500 2000 2500
frequency edge around 1460 nm shifted to higher fre-
[nm]
quency with increasing the time of proton insertion. The
concentration of the free carrier was found to be approxi- Fig. 6. Spectral distribution of reflectance at different time of coloration
for annealed WO3 thin film at 773 K.
mately equal 2.9  1021 cm
3, which is in good agreement
by Svensson et al. [7].
100
Fig. 7 shows the reflectance behavior of as-deposited as-deposited
90 20 second
WO3 thin film. There is an observable plasma frequency 40 second
80 60 second
edge for the as-deposited film but by insertion the proton bleached
inside the film, the edge of plasma frequency shift dis- 70
appears and there is no any sequence in the reflectance 60
such that occurred in as-deposited film behavior.
R%

50

40
3.2.2. Coloration potential
30
Figs. 8 and 9 show transmittance behavior for as-
deposited and annealed WO3 thin film at different applied 20

voltage. The as-deposited WO3 film shows high transmit- 10

tance value approaches to 75% at 550 nm. By applying 0
external voltage, the transmittance decrease approaches 500 1000 1500 2000 2500
20% at 2.5 V, and then returns to bleaching by applying [nm]
voltage in reverse direction. The difference between trans- Fig. 7. Spectral distribution reflectance at different time of coloration for
mittance from coloring to bleaching shows high optical as-deposited WO3 thin film.
modulation between coloring and bleaching. On the other
hand, Fig. 9 shows transmittance behavior for WO3 thin 3.2.3. Electrochromic efficiency
film annealed at 773 K. It shows that the transmittance of The coloration efficiency, is an important factor in
film without any applying voltage reaches 50% and by electrochromic devices, which depends on the method of
applying external voltage of 2.5 V the transmittance preparation, the quality of the films and the microstruc-
decreases to 20%. This means that optical modulation in ture of films. The coloration efficiency is defined by the
annealed thin film is less than that occurred in the as- formula [24]
deposited. In general, to prevent the film damage, voltage
needs for coloration is2 V and for bleaching is
1 V. OD=Q 4
 M.M. El-Nahass et al. / Materials Science in Semiconductor Processing 29 (2015) 201205 205

100 4. Conclusions
Volt
90
-1
The deposition of WO3 thin films was carried out by
-0.5
80 thermal evaporation technique onto ITO-coated glass sub-
0

70
0.5 strates. The structural properties of as-deposited and
1
1.5
annealed film were investigated by using XRD and AFM.
60
2 The as-deposited film exhibits a polycrystalline nature and
the crystallinity increases by annealing. Analysis of AFM
T%

2.3
50
2.5
results shows that the mean roughness of the films
40
decreases by annealing process. The electrochromic char-
30 acteristics were observed for the as-deposited and
annealed WO3 thin films. The as-deposited film exhibited
20
a good optical modulation rather than annealed films at
10 773 K.
0
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