Thin Solid Films 345 (1999) 229±235

W- and F-doped VO2 ®lms studied by photoelectron spectrometry

W. Burkhardt, T. Christmann, B.K. Meyer, W. Niessner, D. Schalch, A. Scharmann*
I. Physikalisches Institut, Justus-Liebig-UniversitaÈt Giessen, Heinrich-Buff-Ring 16, D 35392Giessen, Germany
Received 27 April 1998; accepted 4 September 1998

Abstract
Thermochromic tungsten- and ¯uorine-doped vanadium dioxide ®lms, which are in discussion as intelligent window coatings, were
deposited by reactive sputtering. Results of optical measurements and photoelectron spectrometry (XPS, UPS) at low doping levels (#2.6%)
are presented, and together with structural properties they can be well correlated. By applying antire¯ective coatings the transmittance of
®lms in the visible spectral range may be enhanced to more than 60% with fairly good switching characteristics at room temperature in the
case of tungsten doping. q 1999 Published by Elsevier Science Ltd. All rights reserved.
Keywords: Optical coatings; Photoelectron spectrometry; Vanadium dioxide

1. Introduction dk band is split into an empty and a ®lled one. Goodenough's

Over the last decade thermochromic vanadium dioxide
has been discussed as an intelligent window coating by
which the solar energy transmission may be controlled
passively. Vanadium dioxide is a thermochromic compound
showing a reversible metal±semiconductor phase transition
at a temperature Tt ˆ 341 K in single crystals. Above Tt it
has a tetragonal rutile (TiO2) structure and exhibits metallic
properties, below Tt it is a narrow gap (0.7 eV) semiconduc-
tor with a monoclinic structure. Thin VO2 ®lms are poly-
crystalline and the phase transition is smeared out over a
more or less broad temperature interval, the broadness of
which depends on the size of the crystallites.
The ®rst theoretical description of the switching charac-
teristics of VO2 was given by Goodenough [1] in terms of
the so-called metal±insulator transition (MIT), applying
crystal ®eld and molecular orbital theory. In the rutile-
type high-temperature phase the V 41 ion with one 3d elec-
tron is in the centre of an oxygen octahedron. The lattice
structure is characterized by chains of equidistant vanadium
ions. The p * and dk bands resulting from the t2g levels of the
VO2 octahedra overlap at the Fermi level, thus being respon-
sible for the metallic properties above Tt. In the semicon-
ducting state V±V pairing and off-axis displacement occurs
along the vanadium chains resulting in a monoclinic struc-
ture. The V±O hybridization is changed, the V±V bonding is
stronger, and the p * band rises above the Fermi level. The
* Corresponding author. Tel.: 1 49-641-993-3110; fax: 1 49-641-993-
3139.
description of the MIT in VO2 agrees qualitatively well with
experiments. Though further theoretical work has been
undertaken considering electron±electron correlation, elec-
tron±phonon interaction or a combination of both effects,
the metal±insulator transition in vanadium dioxide is not
understood in detail up to now.
Since Granqvist [2] proposed thermochromic VO2 ®lms
as `intelligent' window coatings, many experimental efforts
have been undertaken to deposit suitable ®lms, e.g. by reac-
tive r.f., DC, and magnetron sputtering, reactive thermal and
electron beam evaporation, CVD techniques, oxidation of
deposited metal ®lms, and sol-gel techniques. So far, all
these investigations did not result in coatings which suf®-
ciently accomplish the demands for economical application,
e.g. high transmittance in the visible spectral range both
below and above the phase transition, good switching char-
acteristics in the near infrared, and a Tt near room tempera-
ture.
In former experiments [3,4] we had applied photoelectron
spectrometry and electron energy loss spectrometry on
undoped VO2 ®lms, in addition to optical, structural, and
electrical measurements so far reported in literature, in order
to get a deeper understanding of the material. Concerning
transmittance and switching characteristics the results were
promising. If antire¯ection coatings (SiOxNy, refractive
index n < 1:65) are used, the transmittance in the visible
is increased to $60%. But it is not possible to deposit
undoped ®lms with a transition temperature range lower
than about 320 K.
It is well-known from literature [2,5±7] that doping of

0040-6090/99/$ - see front matter q 1999 Published by Elsevier Science Ltd. All rights reserved.
PII: S 0040-609 0(98)01406-0
230 W. Burkhardt et al. / Thin Solid Films 345 (1999) 229±235

VO2 ®lms with e.g. W, Mo, Nb, and also F results in transi-
tion temperature lowering, but simultaneously there is a
decrease of transmittance in the visible range especially at
the band edge. It was the aim of this work to investigate
tungsten- and ¯uorine-doped ®lms not only by optical and
electrical measurements as done by the authors above, but
also by photoelectron spectrometry, in order to correlate
density of states (DOS) changes especially in the VO2
valence band regime with results of the classical methods
(DOS in quotation marks means that we will neglect possi-
ble contributions of ®nal states to the low-energy photoelec-
tron intensities in the following).

2. Experimental

The ®lms were deposited by reactive r.f. sputtering from a

vanadium target in an argon/oxygen atmosphere. Previous
to ®lm deposition the sputter chamber was evacuated to
about 10 25 Pa using a turbomolecular pump together with
a liquid nitrogen trap. (110) silicon disks and quartz glasses
were used as substrates. Argon and oxygen had typical puri-
ties of 99.999%, the vanadium target had a purity of 99.98%
containing about 250 ppm, mainly Al, Nb, Si, and Ta as
impurities. For tungsten doping a varying number of
small, 99.95% pure tungsten rods were screwed asymmetri-
cally into the vanadium target in order to deposit ®lms with
different W concentrations within one run. Fluorine doping
Fig. 1. Optical transmittance of undoped and tungsten-doped VO2 ®lms.
was performed by adding ¯uoromethane at different partial
Deposition temperature of ®lms <800 K, thicknesses 120 nm (undoped,
pressures to the argon/oxygen sputter ambient. The ®lms 0.7% and 2.6% W) and 80 nm (1.8% W), respectively.
were deposited at substrate temperatures between <400
and <800 K. Typical sputter parameters were as follows:
the infrared become poorer with increased tungsten content
total sputter gas pressure 10 21 Pa, oxygen to argon ratio
(Fig. 1, 2.6% W). But in contrast to literature data (e.g. Ref.
0.16, r.f. power 300 W, deposition rate 2.5±4 nm/min.
[7]) the transmittance in the visible range does not change
Film thicknesses were typically 80 to 120 nm.
signi®cantly. This may be due to different deposition proce-
Photoelectron spectrometry was performed using VG
dures. The ¯uorine-doped ®lms exhibit a similar behaviour
Instruments equipment applying the Mg Ka line at 1253.6
to the tungsten-doped ones, as far as the ¯uorine doping
eV and the He I line at 21.21 eV for XPS and UPS, respec-
level is below about 1% (see below). One feature is worth
tively. The electron energy analyser was a CLAM- type
mentioning: ¯uorine-doped samples switch only above
hemispherical one. The mu metal analysis chamber was
wavelengths of about 1000 nm, whereas the tungsten-
equipped with an ion pump and a liquid nitrogen-cooled
doped samples switch already at lower wavelength, i.e.
sublimation pump, thus enabling a residual gas pressure of
they are more effective. This may be due to the fact that
less than 10 28 Pa.
¯uorine built into the ®lms was not possible at temperatures
above <600 K. It is well-known from doped and undoped
3. Results and discussion ®lms that low-temperature deposition results in smaller
sizes of VO2 crystallites and also in poorer switching char-
3.1. Optical properties acteristics (e.g. Ref. [3]).
Also presented in Fig. 1 are results of preliminary tests
We provide here a short summary of our studies on opti- with an antire¯ective coating of 60 nm silicon oxinitride
cal transmittance of deposited ®lms. In Fig. 1 some repre- (n < 1:65) sputtered onto a 80 nm tungsten-doped (1.8%)
sentative examples of transmittance measurements on ®lm. In the visible there is an enhancement of transmit-
undoped and tungsten-doped ®lms in the metallic and in tance to about 65%, one third due to the reduction of ®lm
the semiconducting phase are presented. The undoped and thickness and two thirds due to the antire¯ective coating.
the three tungsten-doped ®lms were deposited under the The maximum of transmittance is close to the maximum of
same conditions (deposition temperature <800 K, thickness the solar spectrum. Obviously the switching property of the
80±120 nm). It is observed that switching characteristics in coated ®lm has suffered from sputtering the second ®lm. It
 W. Burkhardt et al. / Thin Solid Films 345 (1999) 229±235
Fig. 2. Hysteresis loops of optical switching recorded from undoped and
tungsten- and ¯uorine-doped ®lms. Undoped and tungsten-doped ®lms:
deposition temperature <800 K, thickness 120 nm; ¯uorine-doped ®lms:
deposition temperature <600 K, thickness 80 nm.
is proposed that a softer technique should be applied for
antire¯ective coating, e.g. a sol-gel technique, by which
ion bombardment-induced damage and/or diffusion into
the VO2 ®lm is avoided. The assumption of bombard-
ment-induced damage in the ®lms is supported by the
observation, that switching disappears upon Ar sputtering
of ®lms for surface cleaning previous to photoelectron
spectrometry.
We are sure that further improvement of the ®lm char-
acteristics are possible if the VO2 ®lm thickness and in
particular the AR coating to ®lm thickness ratio is opti-
mized.
In Fig. 2, transmittance hysteresis loops recorded at a
®xed wavelength of 2000 nm are shown for some represen-
tative ®lms. The hysteresis loop of the undoped ®lm is rela-
tively steep but not as steep as experienced from VO2 single
crystals. This is believed to be due to the polycrystalline
structure of ®lms. Note that if the notion `transition tempera-
ture' is used in the following, the centre of the hysteresis
loop is denoted for convenience. As the concentration of
tungsten in the ®lms is enhanced (Fig. 2, 2.6%), the hyster-
esis loops become more narrow, the hysteresis loop widths
are markedly decreased, and also the switching ef®ciency is
decreased. But the temperature interval of switching does
231
not change signi®cantly. Therefore it may be assumed that
the effect of tungsten built-in on vanadium sites in the lattice
is another than the reduction of switching ef®ciency in
undoped ®lms due to smaller crystallite sizes (e.g. Ref. [3]).
Concerning ¯uorine doping, similar hysteresis loops are
observed at lower concentrations. At higher concentrations
the temperature interval of switching is broadened appreci-
ably, possibly due to the growth of smaller crystallites at the
reduced deposition temperatures (<600 K). From a practi-
cal point of view this means that the ¯uorine- doped ®lms
are not well-suited for window coating.
3.2. Photoelectron spectrometry
3.2.1. Tungsten-doped ®lms
Fig. 3a shows representative XPS spectra recorded from
undoped and doped VO2 ®lms in the V3p band range. The
tungsten concentrations in the ®lms were determined by
deconvolution of e.g. the spectra 2 to 4, and measuring
the W4f7/2 peak areas. Other tungsten-related peaks in the
spectra are too small and not well-suited for quantitative
evaluation. For calibration purposes some Rutherford back-
scattering (RBS) measurements were performed, especially
at 2.6% tungsten content in the ®lms where the W4f5/2 and
the W4f7/2 peaks can be well resolved by deconvolution.
There is considerable agreement with XPS sensitivity
factors for tungsten and vanadium [8].
The dependence of the phase transition temperature on
the tungsten concentration is linear (Fig. 3b), in agreement
with literature data (e.g. Refs. [5,7]). The transition
temperature in the ®gure is taken from optical measure-
ments on the same samples. The transition temperature
lowering is <20 K/1% W. From Fig. 3b it can be concluded
that with tungsten doping at a level of about 2%, the transi-
tion temperature range (about 290 K) is suitable for window
coating.
Films which were deposited at temperatures lower than
<800 K show a very similar concentration-dependent tran-
sition temperature shift. The tungsten built into the ®lms is
enhanced if the deposition temperature is lowered (Fig. 4).
At a deposition temperature of <400 K the tungsten concen-
tration in the ®lms is about 20% higher than in ®lms sput-
tered at <800 K, presumably due to a temperature-
dependent nucleation process in VO2:W ®lms. But the 400
K ®lms, both doped and undoped, have minor transmittance
and switching properties because of smaller crystallite sizes
[3].
Fig. 5 shows XPS valence band spectra of representative
VO2 ®lms containing different amounts of tungsten,
recorded below and above the transition temperature
range. Energy shifts due to different tungsten concentrations
are very small or even zero, and a de®nite tendency cannot
be stated, although each spectrum presented in the ®gure is
the result of 100 single scans. Note that the energy resolu-
tion of our analyser is about 0.1 eV. This is in the same order
of magnitude as the observed small shifts upon successively
232 W. Burkhardt et al. / Thin Solid Films 345 (1999) 229±235

Fig. 4. XPS peak area of the W4f7/2 band versus deposition temperature of
®lms, measured at temperatures below (250 K) and above (370 K) the phase
transition; ®lm thicknesses 120 nm.

of homopolar V 41±V 41 bonding destabilizes the semicon-

ducting phase and lowers the metal±semiconductor transi-
tion temperature [9,10]. Both groups of authors have
described the doping effect of tungsten [9] and niobium
[10] in VO2 in terms of a local model in which coupled
pairs of ions have de®nite valences and form local paramag-
netic moments. Nevertheless, the phase transition is a
collective phenomenon, the doped VO2 is believed to
consist of weakly interacting magnetic regions in the case
Fig. 3. (a) XPS spectra in the V3p and W4f bands range at different
of tungsten doping [9].
tungsten concentrations recorded in the metallic phase; deposition tempera-
ture of ®lms <800 K, ®lm thicknesses 120 nm. (b) Phase transition It is of course uncertain whether this model is appropriate
temperature versus tungsten concentration in the ®lms. for the low doping levels in our polycrystalline ®lms
(#2.6%), where only very small or even zero energy shifts
in the `DOS'are observed (Fig. 5). In the investigations
enhanced concentrations in this energy range. Therefore we
do not like to overinterpret small energy shifts and peak
heights differences in terms of tungsten concentrations. At
least it can be stated from the photoelectron spectra that
tungsten doping at levels #2.6% does not result in addi-
tional lattice distortion as large as in the case of ¯uorine
doping (see below).
On the other hand, a marked energy shift of the V3d band
is evident in comparing the semiconducting and the metallic
phase. The enhanced `DOS' at the Fermi level is responsible
for the metallic properties of the ®lms above the transition
temperature. But there is nearly zero in¯uence of doping in
the vicinity of the Fermi level. Our corresponding UPS
results are very similar to the XPS results presented above.
From studies of the temperature-dependent magnetiza-
tion in tungsten-doped ®lms, Tang et al. [9] have concluded
that each tungsten ion in the VO2 lattice breaks up a V 41±
V 41 homopolar bond. For charge compensation, two W 3d Fig. 5. XPS spectra in the V3d and O2p bands range at different tungsten
electrons are transferred to a nearest neighbour vanadium concentrations below (250 K) and above (370 K) the phase transition;
ion, thus forming a V 31±W 61and a V 31±V 41pair. The loss deposition temperature of ®lms <800 K, ®lm thicknesses 120 nm.
 W. Burkhardt et al. / Thin Solid Films 345 (1999) 229±235
Fig. 6. (a) XPS spectra from ¯uorine-doped VO2 ®lms in the F1s band
range at different F concentrations recorded in the semiconducting phase.
Deposition temperature of ®lms <600 K, ®lm thicknesses 80 nm. (b) Phase
transition temperature versus ¯uorine concentration in the ®lms.
mentioned above [9,10], the doping levels considered are 5±
33% (W) and 2±5% (Nb). If the model holds even for poly-
crystalline ®lms, the magnetic interaction should be limited
to the single grains. It is not believed that the interaction can
surmount grain boundaries because of its weakness. Then, a
broadening of the phase transition temperature interval may
be expected due to varying crystallite size in a ®lm, which
should not mixed-up with severe lattice distortions as
observed, e.g., in ¯uorine-doped ®lms.
Energy shifts in photoelectron spectra may be larger at
enhanced dopant concentrations, but we have not studied
®lms with larger doping levels, since the decrease of the
phase transition temperature at about 2% tungsten is suf®-
cient for window coating.
XRD records from our undoped polycrystalline ®lms
which exhibit only one sharp re¯ex at 2Q ù 288,
FWHM ù 0.28 (for ®lms deposited at <800 K), were
reported in Ref. [3]. As the tungsten content of ®lms is
increased, this re¯ex becomes successively narrower and
shifts to about 27.58 (at 2.6% W), and a second well sepa-
rated peak appears at 2Q ˆ 298. Since XRD was performed
at room temperature, the ®lms containing 1.8% and 2.6%
tungsten are measured in the phase transition regime and in
233
the tetragonal metallic phase above Tt (see Fig. 2), respec-
tively. This may also be responsible for the narrow widths of
the hysteresis loops at larger tungsten concentrations (Fig.
2). We believe that the second XRD peak at 2Q ˆ 298
originates from the tetragonal metallic phase and the shifted
peak at 2Q ˆ 288¼27:58 is due to remaining monoclinic
regions in the ®lms, which are slightly distorted by tungsten
built-in. In fact it has been assumed from UPS data of
undoped ®lms that the phase transition and the lattice trans-
formation, respectively, in VO2 is incomplete in polycrys-
talline and even in single crystalline material [3,11].
Presumably, these remaining monoclinic regions are micro-
crystalline grains which exhibit a different or even no
switching behaviour. We do not believe that both phases
coexist in single grains. The model of weakly interacting
paramagnetic domains as discussed above would not allow
such a coexistence of phases in small well switching grains
in polycrystalline ®lms.
3.2.2. Fluorine-doped ®lms
In Fig. 6a, representative XPS spectra recorded from
doped VO2 ®lms in the F1s band range at different doping
levels are shown. The ¯uorine concentrations were again
determined by measuring the peak areas, which were
normalized with respect to the well measurable oxygen
concentrations in order to have consistent values. The
results presented in Fig. 6b are poorer than those achieved
with tungsten (Fig. 3b). It is evident from Fig. 3 that the XPS
intensities are small at low concentrations, and the back-
ground noise is relatively large, though each spectrum
represents the sum of 100 single scans. The F1s UPS
peaks are more or less asymmetric and consist of two
components if deconvoluted. It is unknown whether both
correspondent ¯uorine sites in the lattice are active with
regard to the switching mechanism. RBS calibrations were
not possible because of zero signal intensities at ¯uorine
backscattering energies.
Furthermore, after a series of measurements we learned
that there was a memory effect due to absorbed ¯uorine at
the preparation chamber walls. Obviously, there were
uncontrolled temperature-induced desorptions of ¯uorine
during some deposition runs. Nevertheless, there is an
approximate linear relation between ¯uorine concentration
and optically determined phase transition temperature (Fig.
6b). The straight line is calculated from measured values by
linear regression. Extrapolation to zero ¯uorine content
results in a corresponding temperature of about 340 K,
which is in good agreement with the transition temperature
of undoped VO2 ®lms. It is evident from Fig. 6b that switch-
ing in the room temperature range is achieved at about 1%
¯uorine in the ®lms. A ®gure like Fig. 4 for tungsten cannot
be given since ¯uorine is hardly built-in in the ®lms at
deposition temperatures above <600 K. So all ¯uorine-
doped ®lms were sputtered at <600 K.
In Fig. 7, UPS spectra of ¯uorine-doped ®lms recorded at
temperatures below and above the correspondent transition
234 W. Burkhardt et al. / Thin Solid Films 345 (1999) 229±235
Fig. 7. UPS spectra recorded from ¯uorine-doped VO2 ®lms in the valence
bands range at different F concentrations; deposition temperature of ®lms
< 600 K, ®lm thicknesses 80 nm. (a) Metallic phase; (b) semiconducting
phase.
temperature are presented. The variation of slopes with
¯uorine content is more signi®cant than those observed at
tungsten-doped ®lms (Fig. 5). Considering the vanadium
oxide O2p valence band, there is decrease of intensity at
the lower-energy ¯ank and an increase at the higher energy
¯ank accompanied by a broadening, as the ¯uorine concen-
tration is enhanced (arrows). The lower energy part of the
O2p peak of VO2 is assigned to p molecular orbitals [1].
The shoulder at energies of about 6 to 7 eV (attributed to s
orbitals) is not in¯uenced as much. If we take the UPS
intensities as an approximation of the `DOS' distribution,
we may interpret the development of slopes with enhanced
¯uorine doping as a reduction of the density of p states, a
more or less constant density of s states, and the appearance
of additional tail states at the high-energy ¯ank.
The V3d valence band is also broadened upon successive
¯uorine doping, the `DOS' seems to be enhanced in this
region, and the overlap of V3d and O2p states increases
with higher doping levels. An interesting feature can be
observed in the semiconducting phase (Fig. 7b): as the ¯uor-
ine concentration rises to 1.5% and above, the V3d states
tail versus the Fermi level. This correlates well with results
of our optical transmittance measurements. These ®lms
exhibit no optical switching in the studied temperature
range, they have metallic properties independent of
temperature.
In XRD records of our ¯uorine-doped ®lms, no typical
peaks are observed as in pure or in tungsten-doped ®lms if
the ¯uorine concentration is larger than 0.7%. This is again
consistent with the results of optical and photoelectron spec-
trometry. The microcrystalline structure of those ®lms is
poor, and therefore the optical switching characteristics
are poor, too, and the `DOS' distribution is smeared out.
Presumably, the difference of oxygen and ¯uorine ionic
radii prevents the built-in of ¯uorine on oxygen sites in
the VO2 lattice to a larger amount without severe deteriora-
tion of VO2 structure.
We have also deposited a number of tungsten- and ¯uor-
ine-codoped ®lms. With ¯uorine contents in excess of 0.7%,
the ®lms exhibit the same poor properties independent of
their tungsten contents.
4. Summary and conclusions
(1) From a practical point of view, tungsten-doped VO2
®lms exhibit promising characteristics with regard to optical
transmittance and switching properties. At a tungsten
doping level of about 2% the reversible phase transition
occurs in the room temperature regime, well-suited for
window coating. Application of antire¯ective coating
enhances the transmittance in the visible spectral range to
more than 60%. Fluorine-doped ®lms are not suited for
window coating because of their poor switching behaviour
at room temperature due to the strong distortion of the VO2
host lattice. Concerning economical application, we are sure
that further improvements of the ®lm properties are possi-
ble, e.g. by improved primary nucleation on the substrates in
order to grow larger crystallites, by optimization of ®lm to
antire¯ective coating thickness ratio, and by a more suitable
deposition technique for the antire¯ective layer.
(2) Correlations between structural and optical properties
and the results of photoelectron spectrometry are evident:
structural order and disorder, respectively, are re¯ected by
transmittance spectra, phase transition temperature range,
and also by `DOS' variation. Concerning tungsten doping,
the model of Tang et al. [9] seems appropriate. In polycrys-
talline ®lms their concept of weakly interacting magnetic
regions is limited to single microcrystals, and the size of
microcrystals has strong in¯uence on the interaction.
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