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Electronic and optical properties of nanocrystalline WO
3
thin films studied by optical
spectroscopy and density functional calculations
View the table of contents for this issue, or go to the journal homepage for more
2013 J. Phys.: Condens. Matter 25 205502
(http://iopscience.iop.org/0953-8984/25/20/205502)
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IOP PUBLISHING JOURNAL OF PHYSICS: CONDENSED MATTER
J. Phys.: Condens. Matter 25 (2013) 205502 (11pp) doi:10.1088/0953-8984/25/20/205502
Electronic and optical properties of
nanocrystalline WO
3
thin lms studied by
optical spectroscopy and density
functional calculations
Malin B Johansson
1
, Gustavo Baldissera
2
, Iryna Valyukh
3
,
Clas Persson
2,4
, Hans Arwin
3
, Gunnar A Niklasson
1
and Lars

Osterlund
1
1
Division of Solid State Physics, Department of Engineering Sciences, The

Angstr om Laboratory,
Uppsala University, PO Box 534, SE-75121 Uppsala, Sweden
2
Division of Applied Materials Physics, Department of Materials Science and Engineering, Royal
Institute of TechnologyKTH, SE-100 44 Stockholm, Sweden
3
Laboratory of Applied Optics, Department of Physics, Chemistry and Biology, Link oping University,
SE-58183 Link oping, Sweden
4
Department of Physics, University of Oslo, PO Box 1048 Blindern, NO-0316 Oslo, Norway
E-mail: Malin.Johansson@angstrom.uu.se
Received 12 February 2013, in nal form 22 March 2013
Published 25 April 2013
Online at stacks.iop.org/JPhysCM/25/205502
Abstract
The optical and electronic properties of nanocrystalline WO
3
thin lms prepared by reactive
dc magnetron sputtering at different total pressures (P
tot
) were studied by optical spectroscopy
and density functional theory (DFT) calculations. Monoclinic lms prepared at low P
tot
show
absorption in the near infrared due to polarons, which is attributed to a strained lm structure.
Analysis of the optical data yields band-gap energies E
g
3.1 eV, which increase with
increasing P
tot
by 0.1 eV, and correlate with the structural modications of the lms. The
electronic structures of triclinic -WO
3
, and monoclinic - and -WO
3
were calculated using
the Green function with screened Coulomb interaction (GW approach), and the local density
approximation. The -WO
3
and -WO
3
phases are found to have very similar electronic
properties, with weak dispersion of the valence and conduction bands, consistent with a direct
band-gap. Analysis of the joint density of states shows that the optical absorption around the
band edge is composed of contributions from forbidden transitions (>3 eV) and allowed
transitions (>3.8 eV). The calculations show that E
g
in -WO
3
is higher than in the -WO
3
and -WO
3
phases, which provides an explanation for the P
tot
dependence of the optical data.
(Some gures may appear in colour only in the online journal)
1. Introduction
Tungsten trioxide (WO
3
) is one of the most studied
electrochromic materials [1]. Recently, its applications
in renewable energy technology have been highlighted,
including solar hydrogen production, solar cells, and
photocatalysis [26]. However, WO
3
exists in several phases,
with similar crystal structures near room temperature,
and is readily reduced to form sub-stoichiometric WO
3x
structures. The WO
3
structure is based on a common WO
6
octahedral structure arranged in at least ve crystallographic
modications. The thermodynamic stability of these (at 1 bar)
is reported to be monoclinic P2
1
/c (-WO
3
) up to 230 K,
triclinic P

1 (-WO
3
) between 230 and 300 K, monoclinic
P2
1
/n ( -WO
3
) between 300 and 623 K, orthorhombic
Pnma (-WO
3
) between 623 and 1020 K, tetragonal P
4
/ncc
(-WO
3
) between 1020 and 1171 K, and nally tetragonal
P
4
/nmm (-WO
3
) up to the melting point at 1700 K [711].
1 0953-8984/13/205502+11$33.00
c
2013 IOP Publishing Ltd Printed in the UK & the USA
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al
Moreover, the structure of nano- and microcrystalline WO
3
depends sensitively on the preparation conditions, which
modies the WO
3
phase diagram [1215] and further
complicates the analysis of these materials.
The electronic structure of WO
3
and sub-stoichiometric
WO
3x
is intimately linked to the structural properties,
and has been the subject of several studies [1, 4, 1622].
The valence band (VB) consists mainly of O 2p orbitals,
and the conduction band (CB) consists mainly of W 5d
orbitals [1621]. Phase transitions result in changes of the
band-gap, E
g
, due to modications of the W 5d states.
Bullet [20] and Stashans and Lunell [18] studied the inuence
of alkali intercalation on cubic, room-temperature monoclinic
and Perovskite structures by semi-empirical calculations.
They showed that distortion of the ideal cubic structure to a
monoclinic structure increased E
g
from 1.5 to 2.4 eV with
an up-shift of the W 5d states. Sub-stoichiometric WO
3x
gives rise to broad absorption in the near infrared (NIR)
region due to the electron transfer from W
5+
to neighboring
W
6+
sites [23]. Excess electrons can be localized (small
polarons), or delocalized over several neighboring ions (large
polarons) [1, 17].
Reported experimental values of E
g
in WO
3
vary
considerably, in the range from 2.6 to about 3.2 eV [1, 4,
15, 16, 22, 24]. This is partly due to variations of the WO
3
structure, but also due to the model which has been used
to extract E
g
. In particular, values of E
g
< 3 eV are often
obtained assuming an indirect band-gap [4, 15, 24]. The
importance of surface area and interphase boundaries on the
W charge state is well documented (see [1] and references
therein). Oxygen decient WO
3x
and associated extended
defects has an impact on color and electrical properties,
and give e.g. rise to observed color changes from slight
yellow to greenish for WO
3
and WO
3x
, respectively. In
nanostructured WO
3
lms prepared by reactive sputtering,
E
g
has been reported to correlate with the O
2
sputtering
pressure and the O vacancy concentration [15]. Changes
in E
g
, d-band occupancy, and the positions of the VB
maximum and the CB minimum have been observed for
different phases of WO
3
[17, 25]. Calculations of cubic WO
3
using density functional theory (DFT) calculations have been
reported to underestimate E
g
with about 0.6 eV compared
with experimental values of E
g
2.6 eV, inferred for an
indirect band-gap [19]. The band dispersion near the band-gap
region for the -WO
3
, -WO
3
, -WO
3
and -WO
3
phases
are found to be small using ab initio calculations [26], which
is a consequence of the small differences in bond angles and
lattice constants among the different phases.
In this paper we report on the electronic and optical
properties of well characterized, nanocrystalline WO
3
lms
prepared by reactive dc magnetron sputtering. We examine
the experimentally determined absorption coefcient and
dielectric constants obtained from optical spectrophotometry
and ellipsometry, and relate this to specic WO
3
phase
compositions, without making any assumptions on the
character of the optical band-gap transition. The results are
compared with calculations performed with the self-consistent
GW approximation. Using this quasi-particle approach, which
goes beyond DFT, E
g
is much better described compared with
regular DFT band structures.
2. Materials and methods
2.1. Sample preparation
The tungsten oxide (WO
3
) thin lms were prepared on
13 mm diameter CaF
2
substrates (Crystran Ltd) by reactive
dc magnetron sputtering using a versatile deposition system
based on a Balzers UTT 400 unit. The sputter target was
a 5 cm diameter plate of tungsten with 99.95% purity
(Plasmaterials). Sputtering was conducted in an Ar and
O
2
plasma. The purity of the gases was 99.998% and the
sputtering power was 200 W for all the lms. The O
2
/Ar ratio
was kept at 0.43, and the samples were sputtered at a substrate
temperature of T
s
= 553 K and subsequently post-annealed
at T
a
= 673 K for 1 h ex situ. The CaF
2
substrates were
cleaned with de-ionized water and ethanol before sputtering.
Samples were sputtered at working pressures, P
tot
= 10,
15, 20, 25 and 30 mTorr, respectively, and the deposition
rate varied as a function of the working pressure from
36 nm min
1
at P
tot
= 10 mTorr to 11 nm min
1
at
P
tot
= 30 mTorr. The sputtering conditions employed for the
different WO
3
lms are summarized in table 1. WO
3
thin
lms sputtered on CaF
2
substrates were highly transparent.
Films prepared at low P
tot
exhibited a slightly bluish color,
indicating sub-stoichiometry [23, 27]. The samples sputtered
at P
tot
= 20, 25 and 30 mTorr were slightly yellowish and red,
characteristic of stoichiometric WO
3
.
2.2. Materials characterization
The structure of the lms were determined by grazing
incidence x-ray diffraction (GIXRD), using a Siemens D5000
Th2Th instrument, employing parallel-plate sollers which
had a resolution of 0.14

and 0.3

(2), respectively. The

grain size determined from the XRD data was in the
range 1555 nm for all lms, and suggests that their
physical properties should be similar to the corresponding
bulk materials. Composition and density were determined
using Rutherford backscattering spectroscopy (RBS) on lms
deposited on carbon substrates. The RBS measurements were
carried out at the Uppsala Tandem Accelerator Laboratory
using
4
He ions with an energy of 2 MeV. An azimuth of
7

was applied to the sample holder to avoid the risk of

channeling into the crystals. The ions were backscattered at
an angle of = 172

. Data analysis was performed with the

program SIMNRA [28]. The physical properties of the WO
3
lms are compiled in table 1. A thorough characterization
of the WO
3
lms has been presented elsewhere, where the
dependence of the physical properties of the lms on the
deposition conditions is explained in more detail [27].
2.3. UV/vis/NIR spectrophotometry
Optical measurements in the 3002500 nm wavelength
region were performed using a Perkin-Elmer Lambda 900
2
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al
Table 1. Sputter deposition parameters and physical properties of WO
3
lms prepared by reactive dc magnetron sputtering in this study.
Sample Thickness Refractive index Grain size
Crystal phase
Density
P
tot
(mTorr) d
S
a
(nm) d
C
b
(nm) n
a
D
c
(nm)
d
(g cm
3
)
10 1016 1016 2.14 15 6.58
15 996 1050 2.07 28
20 877 772 2.03 35 ,
25 789 774 2.10 49 ,
30 857 819 2.01 55 , () 6.38
a
From Swanepoel analysis of UVvis transmittance data [29] in the range 500600 nm.
b
From the Cauchy model applied to ellipsometry data [30].
c
From the WilliamsonHall method [31].
d
From RBS measurements [28].
double-beam UV/vis/NIR spectrophotometer, which was
equipped with an integrating sphere attachment, using a
Spectralon reectance standard. The refractive index, n, and
thickness, d, of WO
3
lms on CaF
2
were calculated from
the interference fringe method of Swanepoel using data from
transmittance measurements [29]. The absorption coefcient,
, can be determined from the spectral transmittance, T(),
and reectance, R(), namely [32].
() =
1
d
ln

1 R()
T()

. (1)
The band-gap energy, E
g
, can be obtained from the equation:
E = A(E E
g
)
p
(2)
where E is the photon energy, A is a constant, and the exponent
p depends on the type of optical transition [33]. Depending on
the type of electronic transition in bulk semiconductors, the
exponent is p = 2, 1/2, 3 and 3/2 for indirect allowed, direct
allowed, indirect forbidden and direct forbidden transitions,
respectively, using the parabolic band approximation around
the absorption threshold. Equation (2) can be recast in the
form
d(ln(E))
d(E)
=
p
(E E
g
)
. (3)
A plot of d ln(E)/d(E) as a function of E yields a divergence
at E
g
, which can thus be determined without assumptions
about the nature of the optical transition, as previously
demonstrated for nanostructured CdSZnO thin lms [34]. It
should be noted that equations (2) and (3) are strictly valid
only for E > E
g
. However, the absorption tail commonly
present in optical spectra at E < E
g
will result in a lowpositive
value of the derivative in equation (3). Therefore the band-gap
is determined by the maximum in the plot of d(ln(E))/d(E)
versus E. With E
g
determined in this manner for all WO
3
lms, corresponding p values may be determined from the
slope of ln(E) versus ln(E E
g
).
2.4. Ellipsometry
To extend the optical characterization further out into the
ultraviolet region we have used spectroscopic ellipsometry
(SE). The ellipsometry parameters and have been
measured between 0.62 and 5.5 eV with a variable angle
rotating analyzer ellipsometer (VASE from J.A. Woollam Co.,
Inc.). First, transmittance at normal incidence was measured
for the CaF
2
substrate and for WO
3
lms deposited on CaF
2
.
Then, the back side of the samples was covered with Scotch
tape in order to avoid incoherent backside reections. SE
measurements in reection mode were performed at several
different angles of incidence between 50

and 75

and
approximately at the same point of the sample where
transmittance measurements were made. All measurements
were performed at room temperature.
Ellipsometry is an indirect method, and an appropriate
model, based on the physical properties of the samples, must
be constructed to interpret the data. Optical constants ( =

1
+ i
2
and N =

= n + ik) were obtained through
the complex reection coefcients, R
p
and R
s
, from the
fundamental ellipsometry equation [35]:
R
p
R
s
= tan exp(i), (4)
where the subscripts p and s correspond to polarization of
the electric eld of the light parallel and perpendicular to the
plane of incidence, respectively. The experimental data were
then tted to the models to reproduce measured and
using the LevenbergMarquardt regression algorithm [36].
The optical properties of the CaF
2
substrate were
determined by using the Cauchy model for the refractive index
n and assuming k = 0, namely [30]
n = A +
B

2
+
C

4
(5)
where is the wavelength and A, B and C are t parameters.
The optical constants for the CaF
2
substrate were kept
constant in the further analysis.
The electronic structure of WO
3
exhibits a complicated
behavior in the region close to the band-gap, as discussed
below in section 3. As a consequence, we could not obtain
sufciently good ts of the dielectric function to standard
models over the whole energy range. Instead we analyzed
the ellipsometric data in two steps. First, the thickness and
refractive index of WO
3
, as well as parameters representing
the roughness at the lm/air interface were determined from
experimental data in the region between 2.2 and 2.8 eV, where
3
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al
the lms are transparent and the extinction coefcient k is
negligible. The dielectric function of the WO
3
thin lms were
represented by the Cauchy model, equation (5). The lm
roughness was estimated by SE employing the Bruggeman
effective medium approximation (EMA) method [37]. This
is appropriate for amorphous and polycrystalline lms
exhibiting microscopically rough surfaces in the analysis of
SE data [3840]. The SE roughness was determined within
a multilayer model, which included the following layers:
air/roughness layer/WO
3
lm/CaF
2
substrate. The roughness
layer was represented by a thickness d
rough
, and an effective
dielectric function,
eff
modeled as a two-composite EMA
layer, consisting of 50% WO
3
and 50% voids.
Secondly, we used a model-independent point-by-point
t method to obtain the dielectric function of the WO
3
lms in the UV range. This approach is facilitated because
nanocrystalline WO
3
lms deposited on CaF
2
substrates
are opaque in the photon energy range 3.55.5 eV. In the
point-by-point tting method,
1
and
2
are determined for
a xed lm roughness for each wavelength separately. For
opaque lms in the UV region, the measured dielectric
properties of materials are independent on the lm thickness,
whereas the surface roughness can inuence signicantly.
The value for d
rough
was xed at the value obtained from the
analysis in the transparency region.
2.5. Computational details
Density functional theory (DFT) calculations with the GW
correction were performed within the VASP package [41].
Potentials and basis set were described by the projector
augmented wave (PAW) method [42, 43], where the
W-5p
6
6s
2
5d
4
states and the O-2s
2
2p
4
states were treated as
valence states. WO
3
was modeled using three different types
of crystalline structures: the triclinic structure (-phase; space
group P

1; space group number 2), and both of the monoclinic

structures (-phase; space group P2
1
/c; space group number
14; -phase; space group P2
1
/n; space group number 14).
Both monoclinic structures have the same space group and
the difference is due to their different cell choices. The
structures were relaxed using the local density approximation
(LDA) using a 4 4 4 k-mesh, until forces on the atoms
were less than 10 meV

A
1
. The energy cut-off was taken
to be 400 eV. The density of states (DOS), as well as the
dielectric function, (E) =
1
(E) + i
2
(E), were obtained
from a partially self-consistent GW approach using LDA
wavefunctions, where the Greens function G is updated
iteratively, whereas the screened Coulomb potential, W, is
kept xed. The imaginary part
2
(E) of the dielectric function
is calculated from the equation [44]:

2
(E) =
4
2
e
2

lim
q0
1
q
2

c,v,k
2w
k
(E
ck
E
k
E)
u
ck+e

q
|u
k
u
ck+e

q
|u
k

(6)
where E
ck
and E
vk
are the energies for the CB and VB
states, respectively, and u
ck
and u
vk
are the corresponding
Bloch-periodic part of the eigenfunctions. is the volume


Figure 1. XRD spectra of WO
3
thin lms prepared at P
tot
= 10 and
30 mTorr, respectively. Diffraction peaks are labeled according to
1 = 23.15

, 2 = 23.65

, 3 = 24.2

, 4 = 33.35

and 5 = 34.1

.
of the primitive cell, w
k
is the k-point weights, e

and
e

are the unit vectors of the Cartesian coordinates, and

q is the Bloch vector of the incident wave. The Brillouin
zone summation was performed by the modied tetrahedron
integration method with a -centered 4 4 4 k-mesh.
The real part of the dielectric function
1
(E) was obtained
from the KramersKronig relations. The GW approach
models quasi-particles by taking into account single-particle
excitations. Thereby it generates a better value of the
energy gap that directly improves the accuracy of absorption
spectra [45, 46]. The absorption coefcient was calculated
according to
(E) =

2E
2
c
2
0
h
2

2
1
(E) +
2
2
(E)
1
(E)

(7)
where c
o
is the speed of light and h is Plancks constant.
3. Result and discussion
3.1. Crystal structure
The XRD pattern for nano-WO
3
lms sputtered at 10 and
30 mTorr are shown in gure 1. The diffraction angles labeled
1 = 23.15

, 2 = 23.65

, and 3 = 24.25

in gure 1 agree
with the (002), (020), and (200) planes, respectively, in both
-WO
3
and monoclinic -WO
3
[9]. Both phases have been
reported to co-exist at room temperature, and have similar
atomic distances and bond angles [9, 47, 48]. The peak labeled
4 in gure 1 is dominant at low P
tot
, and shifts from 33.3

to
33.5

at P
tot
= 15 mTorr, after which it gradually decreases,
and the peak labeled 5 at 34.2

becomes dominant, see

gure 2. The diffraction angle of this latter peak is common to
all three of the possible monoclinic -, -WO
3
, and triclinic
-WO
3
structures [9, 49]. However, -WO
3
is also expected
to have a diffraction peak at 34.46

, which is not observed.

We therefore conclude that the triclinic phase is not present,
or is a minority phase in the lms. This is in agreement
4
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al




Figure 2. Close up on the XRD spectra for different P
tot
in the characteristic 2 regions for WO
3
: (a) 21.5

25.5

and (b) 31

36

.
to previous studies, which show that the monoclinic - and
-WO
3
structures are stabilized in microcrystalline WO
3
[12].
While peak 4, for the lm prepared at 10 mTorr, appears
to coincide with the 33.34

reection corresponding to the

(

112) plane in -WO

3
, the large broadening of peaks 1, 2
and 3, rather suggests that the structure of this lm is mainly
composed of a slightly sub-stoichiometric (WO
3x
, x < 0.1),
strained monoclinic phase, which is supported by a strain
analysis [27]. As we shall see in section 3.3 below, this
interpretation of the phase composition at P
tot
= 10 mTorr,
which is slightly different from our previous analysis [27],
is qualitatively supported by the ab initio calculations. In
addition, the position of peak 3 is shifted towards lower
diffraction angle, compared with the database value of the
monoclinic -WO
3
(200) planes at 24.37

(gures 1 and 2), at

higher P
tot
[9]. This can be attributed to an increased fraction
of the inter-mixed monoclinic -WO
3
phase with increasing
P
tot
, since -WO
3
is the only phase which exhibits such a
small shift in diffraction angle due to the (110) planes located
at 24.11

[50]. We note, however, that the position of peak 3

for the lm prepared at P
tot
= 30 mTorr deviates somewhat
from the lms prepared at P
tot
= 20 and 25 mTorr. This is
also reected in the optical properties of this particular lm
(see below), which suggests that the -WO
3
composition in
the P
tot
= 30 mTorr lm is slightly lower. In contrast, the
peak 3 position for the lm sputtered at P
tot
= 15 mTorr
shows very good agreement with a monoclinic -WO
3
phase,
and indicates that the transition from pure monoclinic -WO
3
to an inter-mixed monoclinic -WO
3
phase occurs at P
tot
=
20 mTorr. Detailed analysis of XRD data reveal that the thin
lms have a preferred growth direction that changes with
increasing P
tot
from [

202] to [200] [27]. In summary, the

XRD results show that phase composition of the nano-WO
3
lms changes as a function of sputtering conditions, and
result in several co-existing phases with the main components
being a strained monoclinic phase at P
tot
15 mTorr, and
a (unstrained) monoclinic -WO
3
phase inter-mixed with a
minor monoclinic -WO
3
phase at P
tot
20 mTorr (table 1).
3.2. Optical properties
Transmittance and reectance of the WO
3
lms were
measured in the wavelength range 3002500 nm. Figure 3


Figure 3. Transmittance and reectance of WO
3
lms on CaF
2
substrates deposited at working pressures P
tot
of 10 and 30 mTorr.
shows T and R for WO
3
thin lms prepared at P
tot
10 and
30 mTorr. The diffuse transmittance and reectance were
found to be <0.5% in all cases and can be neglected. The
transmittance of the CaF
2
substrate is 94% throughout the
whole wavelength range. All WO
3
lms are highly transparent
in the visible region as evident from visual inspection,
whereas strong polaron absorption in the NIR region occurs
due to the electronphonon interactions [50]. From the
interference fringes the lm thicknesses were determined to
be between 850 and 1020 nm (see table 1).
Figure 4 shows the absorptance of the WO
3
thin lms
dened by A = 1 T R, together with the absorption
coefcient calculated by means of equation (1), for energies
up to 3.65 eV and from ellipsometry data at higher energies,
employing lm thicknesses determined from ellipsometry. It
is clear that there are only small differences between the
samples near the absorption edge, and that decreases with
increasing P
tot
by approximately 30% in the photon energy
range 2.75.5 eV. In gure 4(a) polaron absorption is evident
in the photon energy range 0.51.5 eV, and is seen to increase
with decreasing P
tot
. This has previously been attributed to the
presence of a strained monoclinic structure at low P
tot
, which
5
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al
1 2 3 4
0
20
40
60
80
100
Energy (eV)
A
b
s
o
r
p
t
a
n
c
e

(
%
)


10
30
25
20
15
a)
mTorr
1 2 3 4 5
0
1
2
3
4
5
6
x 10
7
Energy (eV)

(
m

1
)


30
25
20
15
10
b)
mTorr
Figure 4. (a) Absorptance, and (b) absorption coefcient , calculated from spectrophotometry (0.53.65 eV) and ellipsometry
measurements (3.55.5 eV) of WO
3
thin lms prepared at different working pressure P
tot
.
1 2 3 4
2
1
0
1
2
3
4
5
6
Energy (eV)
d
(
l
n
(

E
)
)
/
d
(
E
)


10 mTorr, E
g
= 3.10 eV
15 mTorr, E
g
= 3.12 eV
20 mTorr, E
g
= 3.13 eV
25 mTorr, E
g
= 3.15 eV
30 mTorr, E
g
= 3.18 eV
Figure 5. Derivative of optical absorption coefcient times energy
d(ln(E))/d(E) as a function of E (3) for WO
3
thin lms prepared
at different P
tot
between 10 and 30 mTorr.
has been associated with the order of 1 at.% O vacancies in
the lms [27].
The band-gap E
g
for the different nano-WO
3
thin lms
prepared at different P
tot
were estimated from the UVvis
data using equation (3) [34]. Figure 5 shows a plot of
d(ln(E))/d(E) versus E, where the peak position gives E
g
.
The band-gap obtained in this manner is in the range of
E
g
3.103.18 eV and increases with increasing P
tot
.
The E
g
values obtained from the analysis in gure 5
can be used to nd the exponent p in equation (3) by a
plot of ln(E) versus ln(E E
g
) as shown in gure 6. It
is evident from gure 6 that this linearization procedure, as
proposed by Panda et al [34] is ambiguous and is not valid
in an extended region away from E
g
. Different p values in
different energy ranges are obtained, which prevents denitive
determination of p near E
g
from the simple analysis given by
equation (3). Thus the simple parabolic band model is shown
to be inadequate to describe the optical properties of the WO
3
lms near E
g
and this will be discussed further below.
15.5
16
16.5
17
ln(EE
g
) [eV]
l
n
(

E
)



10 mTorr
15 mTorr
20 mTorr
25 mTorr
30 mTorr
2.5 2 1.5 1
Figure 6. A plot of ln(E) versus ln(E E
g
) for the WO
3
thin
lms with P
tot
= 10, 15, 20, 25, and 30 mTorr.
Table 2. The maxima of the two Gaussian functions G
1
and G
2
that
were tted to ellipsometry data for WO
3
lms deposited at different
working pressures, P
tot
.
P
tot
(mTorr) 10 15 20 25 30
G
1
(eV) 4.57 4.60 4.67 4.67 4.5
G
2
(eV) 6.07 6.03 6.48 6.15 5.85
Figure 7 shows
1
and
2
, respectively, for the WO
3
lms on CaF
2
substrates between 3.5 and 5.5 eV, as obtained
from ellipsometry data, using the point-by-point method.
A KramersKronig consistent model dielectric function
based on two Gaussian absorption bands were tted to the
experimental data with a good agreement as seen in gure 8.
In table 2 the Gaussian peak positions obtained in this manner
are displayed for all lms.
It is evident from gure 8 that
2
in the WO
3
thin
lms consists of two peaks in the UV region, one in the
range 4.54.7 eV and the other at 6.06.5 eV (table 2). With
6
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al
3.5 4 4.5 5 5.5
2
3
4
5
6
7
8

1
Photon energy (eV)
25
30
20
15
10
a)
mTorr
3.5 4 4.5 5 5.5
0
1
2
3
4
5
6

2
Photon energy (eV)
b)
mTorr
10
15
30
20
25
Figure 7. The real (a) and imaginary part (b) of the dielectric function obtained from ellipsometry for WO
3
lms deposited at different
working pressures P
tot
.
Figure 8. The optical constants of a WO
3
lm sputtered at a
working pressure of P
tot
= 20 mTorr tted to a model dielectric
function with two KramersKronig consistent Gaussian functions.
A decomposition into the Gaussians is also shown.
increasing P
tot
the absorption in the UV region decreases,
and the positions of the absorption peaks in the UV region
are shifted to higher energies. The
2
peak positions for the
lm prepared at P
tot
= 30 mTorr was obtained by employing
an additional Gaussian peak in the 12 eV region to be
able to accurately model the
2
data. Despite this it is seen
that Gaussian peaks in the UV region are red-shifted for
this lm, which appears to falter the P
tot
trend in table 2.
This is, however, in qualitative agreement with the XRD data
presented above, which suggested that the lm prepared at
P
tot
= 30 mTorr has a structure similar to those prepared at
lower P
tot
and thus contains less of the -phase. In gure 7
it is also seen that
2
decreases with increasing P
tot
, in good
agreement with the data in gure 4(b). This may be explained
by increasing lm porosity with increasing P
tot
. Although this
is qualitatively also corroborated by the RBS data (table 1),
the small density change cannot fully explain the large
decrease of the optical constants. Further investigations of the
lm porosity should be performed to explore the morphology
dependence. The blue-shift of
2
as a function of P
tot
close
to the band edge relates to a change of electronic structure,
which is elaborated in section 3.3.
3.3. Electronic structure
Figure 9 shows the calculated band structure of triclinic
phase and both monoclinic and phases in WO
3
thin lms
obtained with the GW approach (circles in gure 9). For
comparison, we present also the LDA results (solid lines),
where the absolute energies of the CBs have been shifted by a
constant in order to force the LDA band-gap energy to agree
with that of GW. Overall, LDA and GW show very similar
band curvatures. The triclinic and the monoclinic -phase
crystalline structures have both at energy bands along the
(001) direction, and the CB at the Z point has a comparable
energy level to the CB at the point; this is in agreement with
earlier studies [17, 26, 51]. The calculated band-gap energies
are very comparable for these two structures: E
g
= 3.04 eV
(-point) for the triclinic -WO
3
and E
g
= 2.93 eV (-point)
for the monoclinic -WO
3
obtained from the single-particle
transitions across the point (table 3). Monoclinic -WO
3
has a very at band in the (110) direction and the phase
shows an indirect gap of E
g
= 3.27 eV with the VB maximum
at the A point (1/2 1/2 0). The energy difference between
the indirect gap at the A point and the direct -point gap
is however only 0.06 eV, and the direct transitions at the
point will completely dominate the optical absorption.
These calculated GW band-gap energies are larger than those
found in the literature [17, 26], since the GW quasi-particle
correction increases the band-gap. Our values are comparable
with results obtained from hybrid functional calculations
that also generate rather accurate band-gap energies [51].
Moreover, variations in having direct/indirect transitions for
the different tungsten phases are also found in the literature,
but these deviations are normally small, and most likely this
is a consequence of the at curvatures of the bands [25, 26,
51].
It is evident from the band structure of the three
phases (gure 9) that even for relatively low photon energies
around E
g
3.5 eV both direct and indirect transitions may
contribute to the optical absorption. However, it is expected
7
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al
V Z
2
1
0
1
2
3
4
5
6
(110) (001)
Triclinic
Eg= 3.04 eV
E
n
e
r
g
y

(
e
V
)
A Z
(110) (001)
Monoclinic
Eg= 2.93 eV
A Z
(110) (001)
Monoclinic
Eg= 3.27 eV
Figure 9. Electronic band structure of the triclinic (left), monoclinic (center) and monoclinic (right) phases. Zero energy represents
the top of the VB (dotted line). The solid lines in the gure show the LDA results, whereas the circles are results from the GW method. The
LDA CB energies were shifted by a constant to match the CB minima from the GW results at the point.
Table 3. Band-gap energies E
g
determined from the GW calculation using three different methods: (1) directly from the single-particle
energies at the point from gure 9, (2) from the DOS in gure 10, and (3) from the absorption coefcient in gure 12.
Method for band-gap determination
WO
3
structure
E
g
triclinic E
g
monoclinic E
g
monoclinic
(P

1) (eV) (P2
1
/n) (eV) (P2
1
/c) (eV)
1. From point states 3.0 2.9 3.3
2. From DOS 3.0 2.9 3.3
3. From (equation (7)) 3.8 3.8 4.3
that the direct transitions will dominate in the energy region
where they are present, since they represent a more probable
electronic transition process.
The similarities in the band structures are a direct
consequence of the fact that the phases have similar crystalline
structures. This is also reected in the total energy of the
structures. The total energy is E
t
= 40.127, 40.124,
and 40.106 eV per formula WO
3
unit for the triclinic
, monoclinic and monoclinic phases, respectively.
Interestingly, the cubic phase of WO
3
(Pm

3m) also has a

similar crystalline structure [52]. However, that phase reveals
a more pronounced dispersion of its topmost VB yielding a
strong indirect band-gap of 1.55 eV.
Figure 10 shows the DOS as a function of energy in the
VB and CB regions for the , and structures. Clearly,
the three phases have overall very comparable DOS, which
is a direct consequence of their very similar crystal structures.
The E
g
values determined from the DOS analysis yield the
same values as those determined from the band structure at
the point (table 3). This is due to the strong DOS around
the -point, as discussed above. Moreover, based on the
GW results it is expected that the optical properties (i.e., the
dielectric functions and the absorption coefcients) near E
g
for the three phases should be very similar, and be dominated
by the direct transitions at the point.
The calculated GW dielectric functions (gure 11) are
in good agreement with the ellipsometry data presented in
gure 7 and table 2, and further support that the majority WO
3
phase in the nano-WO
3
lms are -WO
3
at low P
tot
.
It is, however, clear that dielectric functions of triclinic
- and monoclinic -phases appear very similar, and cannot
4 2 0 2 4 6
0
1
2
3
4
5
D
e
n
s
i
t
y

o
f

s
t
a
t
e
s

(
1
/
e
V

f
o
r
m
u
l
a

u
n
i
t
)
Energy (eV)


Triclinic

Monoclinic
Monoclinic
Figure 10. DOS of the triclinic phase (black line), the monoclinic
phase (red thick line) and the monoclinic (green dasheddotted
thick line) phase of WO
3
. Energies are referred to the VB maximum
(dotted vertical line), and the DOS is in units of 1/eV formula units,
where the DOS was divided by the number of WO
3
units in each
unit cell. The spectra are presented with a Lorentzian broadening of
0.1 eV.
be distinguished merely based on their dispersion relations. In
contrast, the monoclinic -phase has a slightly higher energy
threshold for absorption. The shift of
1
and
2
towards higher
energies at high P
tot
seen in gure 7, further supports the
presence of the -phase in lms prepared at high sputtering
pressure. In particular, the peak in
2
in the 56 eV region
is well-described corresponding to the interband transition
8
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al
0 1 2 3 4 5 6
0
2
4
6
8
10
12
D
i
e
l
e
c
t
r
i
c

f
u
n
c
t
i
o
n
Energy (eV)
phase
2
(E)
phase
2
(E)
phase
2
(E)
phase
1
(E)
phase
1
(E)
phase
1
(E)
Figure 11. Dielectric function of the triclinic (thin black),
monoclinic (red thicker) and monoclinic (green thicker) phases
obtained from GW calculations. The dash-dotted curves represent
the real part,
1
(E), of the dielectric function,
(E) =
1
(E) +i
2
(E), whereas the solid curves are the imaginary
part,
2
(E).
from deeper lying VB states evidenced in gures 10 and 11,
whereas the shoulder in the 45 eV region correspond to
transitions just below the VB maximum, in good agreement
with the ellipsometry results (gure 7 and table 2).
The trends in the dielectric functions are further
emphasized in the absorption coefcients (E), shown in
gure 12 for the three WO
3
structures. Here, the joint density
of states (JDOS) is also presented. JDOS can represent
direct VB to CB transitions when the transition rules are
neglected, and thus by comparing the JDOS with (E) one
can understand the strength of the optical transitions. The
JDOS spectra demonstrate that all three WO
3
structures have a
threshold at a lower energy than the true threshold for optical
absorption. This indicates that the structures exhibit a band
edge region, where the absorption is dominated by forbidden
optical transitions. It is noticeable that the threshold energy
estimated from the JDOS extrapolation (gure 12) as well
as from the band structure (gure 9) indicates that E
g

3 eV for the -WO
3
phase (table 3), which is the dominant
phase for the lms prepared at low P
tot
. The monoclinic
-phase has a 0.30.4 eV larger band-gap compared with
the other two phases, but overall all three structures have
similar absorption coefcients. This agrees well with the
analysis of the spectrophotometry data presented above, and
give further support that the -phase, which develops at
high P
tot
, yields lms with different electronic properties and
higher band-gap than those prepared at low P
tot
. Finally, we
comment on the inuence of O vacancies. Defects, such as O
vacancies may also affect the electronic structure and modify
the band edge positions [22]. In our case, this may affect
the WO
3
lms prepared at low P
tot
= 10 mTorr, where a
slight sub-stoichiometry (of the order of 1 at.%) was inferred,
but not as much for the lms prepared at high P
tot
. Thus
the E
g
values determined experimentally at low P
tot
may be
expected to be more uncertain than those at high P
tot
, and
this may also explain the smaller shifts of E
g
versus P
tot
3 3.5 4 4.5 5
0
10
20
30
40
50
A
b
s
o
r
p
t
i
o
n

c
o
e
f
f
i
c
i
e
n
t

(
1
0
J
D
O
S

(
a
r
b
.

u
n
i
t
s
)
4
/
c
m
)
Energy (eV)


phase

phase
phase
JDOS

Eg
Eg
Eg
Figure 12. Absorption coefcient (E) (solid curves) near the
band-gap energy for the triclinic (black), monoclinic (red) and
monoclinic (green) structures. In order to analyze transition
probabilities, the corresponding joint density of states, JDOS
(dash-dotted curves) is shown in the same graph in arbitrary units.
observed experimentally compared to the predicted calculated
E
g
for the associated WO
3
phases (table 3). Regardless, this
will not change the conclusions about the different band-gaps
(in the range 0.30.4 eV) in the monoclinic epsilon phase
compared to the triclinic and monoclinic gamma phases, nor
the comparisons of the dielectric function between DFT and
the optical measurements.
4. Conclusion
We have shown that the optical and electronic properties
of nanocrystalline WO
3
thin lms prepared by reactive
dc magnetron sputtering depend sensitively on the total
pressure, P
tot
, in the preparation process. While the
morphology and phase composition of the lms depend
strongly on the sputtering conditions, the electronic structure
resembles their bulk phase counterparts, with close to
stoichiometric composition. We have shown that a low-
temperature monoclinic phase (-phase) co-exists with
the monoclinic ( -phase) WO
3
at high P
tot
. At low
P
tot
the main constituent is a strained phase, which
exhibits pronounced near infrared absorption. The electronic
properties of monoclinic and triclinic WO
3
were calculated
within the GW approximation. By comparison with optical
spectrophotometry and ellipsometry data it is shown that the
optical band-gap increases for lms prepared at high P
tot
due
to the presence of -WO
3
, which inter-mixes with -WO
3
.
Analysis of the calculated density of states shows that the
optical absorption aroundthe band edge, which is apparent
between 3 and 4 eV in optical spectroscopy, is composed of
contributions from forbidden transitions (with a threshold at
around 3 eV), and allowed, direct optical transitions (with a
threshold at 3.8 eV). These results may reconcile previous
discrepancies of reported band-gap values for micro- and
nanocrystalline WO
3
, and facilitate rational fabrication of
WO
3
lms with controlled electronic properties.
9
J. Phys.: Condens. Matter 25 (2013) 205502 M B Johansson et al
Acknowledgments
This work is supported by the Swedish Energy Agency, the
Swedish Research Council, the European EM ECW program
EUBRANEX, and the computers centers HPC2N and NSC
through SNIC/SNAC and MATTER.
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