materials
Article
Fabrication and Optical Characterization of VO2-Based Thin
Films Deposited on Practical Float Glass by Magnetron
Sputtering and Professional Annealing
Xinhong Chu 1, *, Qiusheng Xie 1 , Xiaoming Zhang 1 , Bingfeng Guo 1 , Jianqing Liao 1 and Xiujian Zhao 2, *
Citation: Chu, X.; Xie, Q.; Zhang, X.;
Guo, B.; Liao, J.; Zhao, X. Fabrication
and Optical Characterization of
VO2 -Based Thin Films Deposited on
Practical Float Glass by Magnetron
Sputtering and Professional
Annealing. Materials 2022, 15, 2990.
https://doi.org/10.3390/ma15092990
Academic Editor: Bogdana Mitu
Received: 15 March 2022
Accepted: 18 April 2022
Published: 20 April 2022
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Copyright: © 2022 by the authors.
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Attribution (CC BY) license (https://
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4.0/).
Materials 2022, 15, 2990. https://doi.org/10.3390/ma15092990
1 College of Physics Science and Engineering Technology, Yichun University, Yichun 336000, China;
lr@jxycu.edu.cn (Q.X.); zhangxm@jxycu.edu.cn (X.Z.); guobingfeng@jxycu.edu.cn (B.G.);
jq-liao@jxycu.edu.cn (J.L.)
2 State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology,
Wuhan 430070, China
* Correspondence: cxh@jxycu.edu.cn (X.C.); opluse@whut.edu.cn (X.Z.)
Abstract: In this paper, VO2 thin films with good optical properties are fabricated on practical float
glass by magnetron sputtering and a professional annealing method. The near-infrared switching effi-
ciency (NIRSE) of the prepared film reaches 39% (@2000 nm), and its near-infrared energy modulation
ability (∆Tir ) reaches 10.9% (780–2500 nm). Further, the highest integral visible transmittance Tlum is
63%. The proposed method exhibits good reproducibility and does not cause any heat damage to the
magnetron sputtering machine. The crystalline structure of the VO2 film is characterized by X-ray
diffraction (XRD). The lattice planes (011) and (−211) grow preferentially (JCPDS 65-2358), and a
large number of NaV2 O5 crystals are detected simultaneously. The microstructures are characterized
by scanning electron microscopy (SEM), and a large number of long sheet crystals are identified.
The phase transition temperature is significantly reduced by an appropriate W doping concentration
(Tc = 29 ◦ C), whereas excessive W doping causes distortion of the thermal hysteresis loop and a
reduction in the NIRSE. Oxygen vacancies are created by low pressure annealing, due to which the
phase transition temperature of VO2 film decreases by 8 ◦ C. The addition of an intermediate SiO2
layer can prevent the diffusion of Na+ ions and affect the preparation process of the VO2 thin film.
Keywords: VO2 ; sputtering; annealing; float glass; W doping; oxygen vacancy; Na+ ions
1. Introduction
Vanadium dioxide is a typical thermochromic smart material, which was discovered
by Morin in 1959 [1]. Below 68 ◦ C, it is a monoclinic semiconductor, while above 68 ◦ C, it
becomes a tetragonal conductor. Near the critical point, the electrical and optical properties
of VO2 change by 2–5 orders of magnitude, and the infrared transmittance can change by
40–60% [1–4]. Therefore, VO2 has garnered considerable research attention for preparing
smart windows [5,6], optical switches [7], biomedical sensors [8], relaxation oscillator [9],
and so on.
Magnetron sputtering [10,11], chemical vapor deposition (CVD) [12], sol-gel process-
ing [4,13], pulsed laser deposition [14], and molecular beam epitaxy [15] are often used to
prepare VO2 films. Among these methods, magnetron sputtering is the most widely used
method owing to its advantages of controllable film thickness, high speed, low temperature,
good adhesion, high production efficiency, environmental friendliness, and great industrial
potential, and it can be used to prepare compact, homogeneous, and stable films. However,
it faces the problems of complex process, difficult operation, and poor reproducibility in
preparing VO2 thin films. Therefore, Gurvitch et al. [16] and Luo et al. [17] firstly used mag-
netron sputtering to prepare metal V film and then utilized in situ oxidative annealing to
prepare VO2 thin films, which exhibited good repeatability. However, the in-situ annealing
https://www.mdpi.com/journal/materials
Materials 2022, 15, 2990 2 of 16

operation at high temperature (above 300–500 ◦ C) can damage the magnetron sputtering
equipment and shorten its working life. Liu et al. [18], Xu et al. [19], and Ba et al. [20]
deposited V metal films on glass and sapphire by magnetron sputtering or ion-assisted
sputtering technology and then obtained VO2 films by oxidative annealing in pure oxygen
atmosphere or air atmosphere in a furnace. This two-step technique was beneficial to
improve the reproducibility and protect the sputtering equipment, but they did no fur-
ther works in studies of substrates, visible transmittance improvement, doping, oxygen
vacancies, and so on. Silicon [21], quartz [10,22], sapphire [10,23], and other materials
are often used as substrates for depositing VO2 film to achieve better phase transition
performance. However, these substrates are expensive, difficult to obtain, and inconsistent
with the actual glass used in windows and doors. Float glass (Na-Ca-Si ternary glass,
Na~13.8%, Ca~8.6%, Si~72.8%, others~4.8%) is the most widely used practical glass in
modern buildings, so it must be explored as a substrate for VO2 to be applied in smart
windows. Presently, the most vital problem of float glass is that small Na+ ions can easily
diffuse into the VO2 film, which results in poor thermochromic properties [24]. VO2 thin
films have been prepared on Si3 N4 [25], TiO2 [26], ZnO [27], SnO2 [28], and other buffer
layers, but the preparation methods and properties were quite different. For application
in smart windows, the VO2 film’s visible transmittance should be above 60%, and the key
performance of the transition temperature must be reduced to a practical range of 25–30 ◦ C.
Tungsten doping and oxygen vacancy production have been considered to be effective
methods [29–31], but the mechanisms of tungsten doping for reducing the phase transition
temperature and the equivalent effect of oxygen vacancy are still not clear.
In this study, a two-step method of magnetron sputtering and professional annealing
with good reproducibility and no heat damage to the sputtering machine was successfully
utilized to deposit VO2 -based thermochromic thin films on a practical float glass, including
intrinsic VO2 thin films, VO2 thin films with intermediate SiO2 layers, and W-doped VO2
thin films. Further, the annealing control, visible transmittance adjustment, the effect of
100-nm-thick intermediate SiO2 layer on preventing the diffusion of Na+ ions, and the
equivalent action of W dopant and O vacancy were investigated.

2. Materials and Methods

2.1. Preparation of V-Based Metal Films by Magnetron Sputtering
The practical float glass used in this study was SAIL BRAND 7101 with a thickness
of 1 mm. The magnetron sputtering machine used was ADV-ZKS-0350 (Aitmet Vacuum
Machinery Co., Ltd., Foshan, Guangdong, China). The float glass (hereafter referred to as
glass) was cut into a size of 25.4 mm × 38.1 mm, then ultrasonically cleaned in acetone
and anhydrous ethanol for 30 min, and subsequently dried off for later use. The sputtering
vacuum chamber was thoroughly cleaned, and then the V metal target (ϕ: 56 mm, 99.9%
purity) and glass substrate were installed. The chamber was vacuumized to 3.0 × 10−3 Pa,
and then Ar gas (99.99% purity) was passed through it to achieve a pressure of 1 Pa. DC
magnetron sputtering was utilized to deposit the V-based metal films at room temperature
(20 ◦ C). The impurity atoms on the target surface were removed by pre-sputtering for
10 min, and then the baffle was opened to deposit films at a power of 77 W. The sputtering
time was controlled to 5, 7.5, and 10 min to obtain V metal films with thicknesses of 30,
45, and 60 nm (calculated by statistical average deposition rate), respectively. The main
process parameters are shown in Table 1, and the quartz glass is a contrast substrate.
 Materials 2022, 15, x FOR PEER REVIEW 3 of 17

Materials 2022, 15, 2990 3 of 16

Table 1. Preparation parameters of V-based metal films by magnetron sputtering.

Background PreparationWorking
parameters ofSubstrate
V-based metalSputtering
films by magnetron V Film
Table 1.Working Powersputtering.
Sputtering
Substrate Target Pressure Pressure Temperature Thickness
Gas Method (W) Time (min)
(Pa)
Background Working
(Pa)
Working
(°C)
Substrate
Sputtering Power Sputtering
(nm)
V Film
Substrate Target Temperature Thickness
Pressure (Pa) Gas Pressure (Pa)
(◦ C)
Method (W) 5,
Time (min) 30,
(nm)
Glass V 3.0 × 10−3 Ar 1 20 DC 77 7.5,
5,
45,
30,
Glass V 3.0 × 10 − 3 Ar 1 20 DC 77 10
7.5, 45,60
Quartz 10 60
Quartz
V
V 3.0
3.0 × 10
×−10
3
−3
Ar
Ar 1
1 20
20
DC
DC 77
77 5
5 30
30
glass
glass
SiO
SiO
2 2
V V × 10×−10
3.0 3.0 3
−3 Ar Ar 11 20
20 DC
DC 7777 55 3030
(/glass)
(/glass)
Glass W/V 3.0 × 10 − 3 Ar 1 20 DC 77 7.5 45
Glass W/V 3.0 × 10−3 Ar 1 20 DC 77 7.5 45

W/V
W/V inlaid
inlaid target
target (ϕ:
(φ: 56
56 mm,
mm, W W purity:
purity: 99.95%,
99.95%, V V purity:
purity: 99.9%,
99.9%, Figure
Figure 1)1)and
andDCDC
magnetron sputtering technology were applied to execute W doping
magnetron sputtering technology were applied to execute W doping in an appropriate in an appropriate
ratio
ratio(0–1.0%,
(0–1.0%,the
theratio
ratioofof
the area
the areaof of
WW bars to the
bars total
to the areaarea
total of the
of target). According
the target). to the
According to
sputtering
the sputtering yield, sputtering area, and atomic concentration, the W dopant ratio by can
yield, sputtering area, and atomic concentration, the W dopant ratio by mol mol
be calculated
can according
be calculated to thetoarea
according ratio ratio
the area of Wof bars. The W
W bars. Thedopant’s ratiosratios
W dopant’s by area of 0%,
by area of
0.5%, and 1%
0%, 0.5%, andcorrespond
1% correspond to thetoratios by mol
the ratios by of 0%,
mol of2.83%, and 5.53%,
0%, 2.83%, respectively.
and 5.53%, For
respectively.
convenience, the W dopant ratio in this paper represents the area ratio unless otherwise
For convenience, the W dopant ratio in this paper represents the area ratio unless other-
specified. The sputtering time for the W:V metal film was 7.5 min, and the thickness was
wise specified. The sputtering time for the W:V metal film was 7.5 min, and the thickness
approximately 45 nm. The main process parameters are shown in Table 1.
was approximately 45 nm. The main process parameters are shown in Table 1.

3.6°
1.8° 3.6°
V W V
W W
V V
3.6° W W 3.6°
V V
W W V
V
3.6° V W 1.8°
3.6°

Figure1.1. Schematic
Figure Schematicofofthe
thetungsten-vanadium
tungsten-vanadium inlaid target
inlaid (when
target W bars
(when are fully
W bars embedded,
are fully dop-
embedded,
ing ratio-max: 7%). (The blue bar is W. One 1.8° ◦W bar represents 0.5% doping ratio by area,
doping ratio-max: 7%). (The blue bar is W. One 1.8 W bar represents 0.5% doping ratio by area, and and
one 3.6°
◦ W bar represents 1.0% doping ratio by area; Increase the number of W bars can get different
one 3.6 W bar represents 1.0% doping ratio by area; Increase the number of W bars can get different
W doping concentrations, and the maximum can reach 7%.).
W doping concentrations, and the maximum can reach 7%).
RFmagnetron
RF magnetronsputtering
sputteringtechnology
technologywas
wasused
usedtotodeposit
depositthe
theSiO
SiO2layer
layerononthe
theglass
glass
2
for blocking the sodium ion diffusion. The main process parameters are shown
for blocking the sodium ion diffusion. The main process parameters are shown in Table 2. in Table
2. Then,
Then, 30 nm
30 nm V metal
V metal filmfilm
waswas spread
spread on the
on the intermediate
intermediate SiOSiO 2 layer (Table 1).
layer (Table 1).
2

Table 2. Preparation parameters of the intermediate SiO2 layer by RF magnetron sputtering.

Background Working Substrate SiO2 Film

Sputtering Sputtering
Substrate Target Pressure Pressure Temperature Power (W) Thickness
Method Time (min)
(Pa) (Pa, Ar) (◦ C) (nm)
Glass SiO2 3.0 × 10−3 1 200 RF 100 50 100
Materials 2022, 15, 2990 4 of 16

2.2. Preparation of VO2 -Based Films by Professional Annealing

The deposited V-based metal films (V, W:V, V/SiO2 ) were placed in a vacuum tube
furnace (ECFK-6-14), vacuumized to a needed low pressure, heated to 400 ◦ C at 5 ◦ C/min,
annealed in low pressure air atmosphere for 1 h, and then naturally cooled to room
temperature to obtain VO2 -based films. The main process parameters are shown in Table 3,
and the quartz glass is a contrast substrate.

Table 3. Preparation parameters of VO2 -based films by professional annealing.

Annealing Background Annealing Heating Rate Annealing

Metal Film/Substrate
Atmosphere Pressure (Pa) Temperature (◦ C) (◦ C/min) Time (h)
50, 100, 200, 450,
30 nm V/glass air 400 5 1
1500
45 nm V/glass air 200, 450, 700 400 5 1
60 nm V/glass air 450 400 5 1
30 nm V/quartz glass air 1500 400 5 1
30 nm V/SiO2 /glass air 200, 450, 600 400 5 1
45 nm W:V/glass air 300, 450 400 5 1

2.3. Testing and Characterization

The transmittance of the film was examined using ultraviolet-visible-infrared spec-
trophotometry (UV-3600 MPC 3100, Shimadsu, Kyoto, Japan), where the testing wavelength
range was 250–2500 nm, the step length was 1 nm, and the testing temperature was 20 and
90 ◦ C. The heating attachment was a small numerical control furnace with a temperature
error of ±1 ◦ C. The near-infrared switching efficiency (NIRSE) is defined as the difference
between the transmittance at low temperature and the transmittance at high temperature
at 2000 nm. The thermal hysteresis loop was drawn using the transmittance curves at
different temperatures in the range of 20–90 ◦ C with an interval of 5 ◦ C both in the heating
and cooling process. Further, each temperature point was held for at least 5 min before
obtaining the transmittance curve. Moreover, a standard VO2 film sample (quartz glass
substrate, NIRSE 50%, i.e., the VO2 film by “30 nm V/quartz glass” in Table 3) was used to
complete the transmittance measurement in whole wavelength 250–2500 nm at any two
temperature points, e.g., 20 ◦ C and 40 ◦ C, to check the sameness and uniformity of the
transmittance curve before every loop test. To obtain the thermal hysteresis loop of the
VO2 film, the transmittance values at 2000 nm in each curve were considered as the Y-axis,
and temperature points were taken for the X-axis.
The phase composition of the as-prepared VO2 -based films were analyzed by X-ray
diffraction (XRD; PANalytical Empyrean, PANalytical B.V., Almelo, Netherlands; Cu target,
λ = 1.540598 Å, acceleration voltage = 40 kV, and current = 10 mA). The micro morphologies
of these films were investigated by field emission scanning electron microscopy (FESEM;
Hitachi S-4800, Hitachi, Tokyo, Japan). The oxygen vacancies of related films were investi-
gated by X-ray photoelectron spectroscopy (XPS; VG Mutilab 2000, Thermo Electron Co.,
Bedford, MA, USA; Al Kα, hν = 1486.6 eV, resolution 0.47 eV).

2.4. Data Treatment

According to the transmittance curve and Equation (1), the visible spectral trans-
mittance can be obtained [32], which is also known as the integrated visual photopic
transmission (IVPT, denoted by Tlum ). This kind of transmittance takes the people’s vi-
sual perception into account and is more suitable for the daylighting evaluation of green
buildings. It is calculated as follows:
R 780
380 Dλ V (λ) T (λ)dλ
Tlum = R 780 (1)
380 Dλ V ( λ ) dλ
Materials 2022, 15, 2990 5 of 16

where Dλ is the relative spectral distribution of illuminant D65, V(λ) is the spectral lu-
minous efficiency for photopic vision, and T(λ) is the visible transmittance. Further, the
values of Dλ ·V(λ)·∆λ were obtained from the international standard ISO 9095-2003.
According to the transmission curve and Equation (2), the near-infrared spectral
transmittance (Tir ) can be calculated [32]. The regulation ability to near-infrared light (∆Tir )
is expressed as the difference between Tir at high temperature and Tir at low temperature.
Tir is calculated as follows:
R 2500
Sλ T (λ)dλ
Tir = 780R 2500 (2)
780 Sλ dλ
where Sλ is the relative spectral distribution of solar radiation, T(λ) is the near-infrared
transmittance, and the values of Sλ ·∆λ were obtained from the international standard
ISO 9095-2003.

3. Results
3.1. Transmittance and Microstructure of VO2 Film Based on the Optimization of Thickness
and Pressure
Figure 2a shows that at the annealing pressure of 450 Pa, the NIRSE (39%) of the VO2
film prepared by the 45 nm V metal film is higher than that prepared by the 30 nm, 60 nm
V metal films (20%, 26%). This indicates that the optimal thickness of the V film under this
condition is nearly 45 nm. Furthermore, Figure 2b shows that for the 45 nm V metal film,
the NIRSE (39%) of VO2 film prepared at the annealing pressure of 450 Pa is higher than
that at 200 and 700 Pa (16%, 30%). This suggests that the optimal annealing pressure of the
V film under this condition is approximately 450 Pa. When the thickness and annealing
pressure of the VO2 film are optimized, the NIRSE is enhanced, and the values of 4Tir and
Materials 2022, 15, x FOR PEER REVIEW 6 of 17
Tlum change accordingly. Generally, as NIRSE increases, ∆Tir increases. When the thickness
of the V metal film decreases or the annealing pressure increases, Tlum increases, and vice
versa, as illustrated in Table 4.
100 100
30nm @450 Pa 700 Pa @45nm V
45nm 450 Pa
80 60nm 80 200 Pa
Transmittance %

M-VO2 20℃
Transmittance %

60 60 M-VO2 20℃

40 40

T-VO2 T-VO2 90℃

20 90℃
20
a b
0 0
500 1000 1500 2000 2500 500 1000 1500 2000 2500
Wavelength nm Wavelength nm

Figure
Figure 2. 2.
(a)(a)Transmittance
Transmittanceofof VO
VO22 films
filmsprepared
preparedby byprofessional
professionalannealing of Vofmetal
annealing filmsfilms
V metal withwith
different thicknesses at 450 Pa. (b) Transmittance of VO 2 films prepared by professional annealing
different thicknesses at 450 Pa. (b) Transmittance of VO2 films prepared by professional annealing
of 45 nm V films at different pressures; all at 400 °C for 1 h; solid line: 20 °C (monoclinic M-VO2),
of 45 nm V films at different pressures; all at 400 ◦ C for 1 h; solid line: 20 ◦ C (monoclinic M-VO2 ),
dashed line: 90 °C (tetragonal T-VO2).
dashed line: 90 ◦ C (tetragonal T-VO2 ).
Table 4. Optical properties of VO2 thin films prepared by professional annealing under optimized
thickness
Table and pressure.
4. Optical properties of VO2 thin films prepared by professional annealing under optimized
thickness and pressure.
V Film Thickness (nm)- NIRSE ΔTir Tlum Tlum Tlum
Annealing
V Film Pressure
Thickness (Pa)
(nm)-Annealing (@2000 NIRSE
nm) ∆Tir nm)
(780–2500 Tlum
(20 °C) (90T°C)
lum Tlum
(Average)
Pressure (Pa) (@2000 nm) (780–2500 nm) (20 ◦ C) (90 ◦ C) (Average)
30–450
30–450
20% 20% 7.0%
7.0%
63%
63%
63%
63%
63%63%
45–450
45–450 39% 39% 10.9%
10.9% 44%
44% 45%
45% 44.5%
44.5%
60–450 26% 10.1% 41% 38% 39.5%
45–200
60–450 26% 16% 7.4%
10.1% 43%
41% 44%
38% 43.5%
39.5%
45–700 30% 4.2% 61% 61% 61%
45–200 16% 7.4% 43% 44% 43.5%

45–700 30% 4.2% 61% 61% 61%

The XRD pattern in Figure 3a shows that the phase composition of VO2 films pre-
Materials 2022, 15, 2990 6 of 16

The XRD pattern in Figure 3a shows that the phase composition of VO2 films prepared
by annealing of 30, 45, and 60 nm V film at 450 Pa. With the thickness increasing of V film,
the concentration ratio of NaV2 O5 : VO2 decreases. Because of the low concentration and
micro size of the VO2 particles, the VO2 film from 30 nm V presents nearly no correspond-
ing diffraction peaks. The VO2 film prepared by annealing of 45 and 60 nm V film at 450 Pa
includes not only a VO2 , but also a NaV2 O5 diffraction peak. The (011) and (−211) lattice
planes of VO2 grow preferentially, and their diffraction peaks are stronger. The crystalline
phase (M, monoclinic) of the VO2 film corresponds to the standard card JCPDS 65-2358.
Moreover, the particle sizes of the VO2 films by 45 and 60 nm V are both about 15 nm, as
calculated by Scherrer formula. The SEM image in Figure 3b suggests that the microstruc-
ture of VO2 films prepared by annealing of 30, 45, and 60 nm V film at 450 Pa is more or
less the same. Take the VO2 film from 45 nm V for instance, where the microstructure is
composed of long sheet crystals (length: 210 nm, width: 50 nm, thickness: 20 nm). It can be
Materials 2022, 15, x FOR PEER inferred
REVIEW that the long sheets are NaV2 O5 crystals, which present obvious oriented growth.7 of 17
The same morphology of NaV2 O5 crystals was reported by Mjejri et al. [33]. Smaller VO2
crystalline particles are scattered in the interspace of NaV2 O5 crystals, which are difficult
to observe due to the influence of the depth of field of the long sheet NaV2 O5 crystals.

* VO2 □ NaV2O5
□
011
*
60nm V □ 211
220
* 210
* □ *
□
Intensity (a.u.)

011
□□*
45nm V □ 211
* 210 220
* □ *
JCPDS 65-2358

30nm V □
□ □

a □

10 20 30 40 50 60
2θ (deg.)
Figure 3. XRD patterns (a) and SEM images (b) of the VO2 thin films prepared by professional
Figure 3. XRD patterns (a) and SEM images (b) of the VO2 thin films prepared by professional an-
annealing of the 30,30,
45,45,
60 nm V metal films at 450 Pa,Pa, ◦ C for 1 h.
400400
nealing of the 60 nm V metal films at 450 °C for 1 h.

The XRD pattern in Figure 4a shows the phase composition of VO2 films prepared
The XRD pattern in Figure 4a shows the phase composition of VO2 films prepared by
by the annealing of 45 nm V film at pressures 200, 450, 700 Pa. Compared to 200 Pa, the
the annealing of 45nm V film at pressures 200, 450, 700 Pa. Compared to 200 Pa, the 450
450 and 700 Pa result in an obvious higher concentration of NaV2 O5 , and the 450 Pa leads
and 700 Pa result in an obvious higher concentration of NaV2O5, and the 450 Pa leads to a
to a higher ratio of VO2 : NaV2 O5 than the 700 Pa. Moreover, the VO2 film by 450 Pa
higher ratio of VO2: NaV2O5 than the 700 Pa. Moreover, the VO2 film by 450 Pa performs
performs crystalline phase (M) corresponding to the standard card JCPDS 65-2358. And the
crystalline phase (M) corresponding to the standard card JCPDS 65-2358. And the particle
particle sizes of the VO2 films by 45 nm V at pressures 200, 450, and 700 Pa are about 12, 15,
sizes of the VO2 films by 45 nm V at pressures 200, 450, and 700 Pa are about 12, 15, and
and 11 nm respectively, calculated by the Scherrer formula. The SEM image in Figure 4b
11 nm respectively, calculated by the Scherrer formula. The SEM image in Figure 4b sug-
suggests that the microstructures of VO2 films prepared by the annealing of 45 nm V film
gests that the microstructures of VO2 films prepared by the annealing of 45 nm V film at
at pressures 200, 450, and 700 Pa are quite different. With the pressure increasing, the film
pressures 200, 450, and 700 Pa are quite different. With the pressure increasing, the film
microstructure presents bigger and bigger single crystals with an obvious oriented growth
and amicrostructure presents bigger
long sheet morphology, whichand
arebigger single
inferred crystals
to be NaV2 O with an obvious oriented growth
5 likewise. VO2 crystalline
and a long sheet morphology, which are inferred to be NaV 2O5 likewise. VO2 crystalline
particles are scattered in the single crystals with depth of field and are difficult to observe.
particles are scattered in the single crystals with depth of field and are difficult to observe.
 □ * VO2 □ NaV2O5
011
* □ 211
700 Pa
Materials 2022, 15, x FOR PEER REVIEW
210
8 of 17
Materials 2022, 15, 2990 * * □ 7 of 16

□
Intensity (a.u.)

011
□* * VO2 □ NaV2O5
□□
450 Pa □ 011211
* □* 210 211*
220
700 Pa 210□ *
JCPDS 65-2358 * * □

□
Intensity (a.u.)

□ 011
□□*
450 Pa 011 □ 211
200 Pa *
211 * *
210 220
□ □ 220*
JCPDS 65-2358 * 210
* □ *
a
□
10 20 30 011 40 50 60
200 Pa 2θ (deg.)
*
□ 211
* 210
*
220
□ *
a (a) (b)
10 20 30 40 50 60
2θ (deg.)
Figure 4. XRD patterns (a) and SEM images (b) of the VO2 thin films prepared by profess
nealing of 45 nm V films at 200, 450, 700 Pa respectively, 400 °C for 1 h.
Figure 4. XRD
Figure patterns
4. XRD (a) and
patterns SEMSEM
(a) and images (b) (b)
images of the VOVO
of the 2 thin films prepared by professional
2 thin films prepared by professional an-
annealing of 45 nm V films at 200, 450, 700 Pa respectively, 400 ◦ C for 1 h.
nealing of 45 nm V films at 200, 450, 700 Pa respectively, 400 °C for 1 h.
When the thickness of V film is reduced from 45 nm to 30 nm, the optimal an
WhenWhen
pressure thereduced
is thickness of V
to
the thickness 100film
of V is
Pa, reduced
filmasisshownfromin
reduced 45Figure
fromnm 45tonm
30 nm,
5.toIn the
nm,optimal
30general, annealing
thicker
the optimal V metal f
annealing
pressure
quire is reduced
higherisoptimal
pressure to 100
reduced to Pa,
annealingas shown in
100 Pa, as pressure Figure 5. In
to obtain
shown in Figure general,
5. In large thicker
NIRSE,
general, V metal
thickerand films
thinner
V metal films V
re-met
require higher
quirelower optimal
higheroptimal annealing
optimal annealing pressure to
pressure obtain large
to obtain NIRSE,
large NIRSE,and thinner V metal
and thinner films
V optical
metal films
require annealing pressure to obtain large NIRSE.
require lower optimal annealing pressure to obtain large NIRSE. The optical properties of
The prop
require lower optimal annealing pressure to obtain large NIRSE. The optical properties of
thereduced
the reduced VOVO 2 thin
thin filmsfilms are shown
are shown in Tablein5. Table 5.
the reduced2 VO2 thin films are shown in Table 5.

100 100
450450PaPa
200200PaPa
80 80 100100PaPa 20℃
20℃
50 Pa
50 Pa
Transmittance %
Transmittance %

60
60
40
90℃
40
20 90℃

20
0
500 1000 1500 2000 2500
Wavelength nm
0
500
Figure 5. 1000of thinner
Transmittance 1500
VO2 films 2000
prepared by 2500
professional annealing of 30 nm V metal
Wavelength
films at different pressures, nm1 h; solid line: 20 °C, dashed line: 90 °C.
400 °C for

Figure5.5.Transmittance
Figure Transmittanceof thinner VO2 films
of thinner VOprepared by professional
2 films prepared annealing of 30
by professional nm V metalof
annealing 30 nm
films at different pressures, 400 ◦ C for 1 h; solid line: 20 ◦ C, dashed line: 90 ◦ C.
films at different pressures, 400 °C for 1 h; solid line: 20 °C, dashed line: 90 °C.
 Table 5. Optical properties of thin VO2 films prepared by 30 nm V metal films at different annealing
pressures.

Annealing Pressure NIRSE ΔTir Tlum Tlum Tlum

(Pa)2022, 15, 2990
Materials (@2000 nm) (780–2500 nm) (20 °C) (90 °C) (Average)
8 of 16

450 20% 7.0% 63% 63% 63%

Table 5. Optical properties of thin VO2 films prepared by 30 nm V metal films at different anneal-
200 30%
ing pressures. 7.2% 57% 57% 57%

100 35%Annealing NIRSE8.0% ∆Tir 56%Tlum T58%

lum Tlum57%
Pressure (Pa) (@2000 nm) (780–2500 nm) (20 ◦ C) (90 ◦ C) (Average)
50 30% 450 20%
7.3% 7.0%
55%63% 57%
63% 63%
56%
200 30% 7.2% 57% 57% 57%
100 35% 8.0% 56% 58% 57%
3.2. Transmittance,
50 Loops
30%and Microstructure
7.3% of W-Doped
55% VO2 Thin57%
Films 56%
According to the transmittance curves in Figure 6a and the thermal hysteresis loops
3.2. Transmittance,
in Figure Loops and Microstructure
6b of the W-doped VO2 films byof45W-Doped
nm W:V VO ThinPa,
at2 450 Films
the phase transition tem-
peratureAccording to the transmittance
(Tc) of 0.5%W-doped VO2 curves
thin filmin Figure 6a and the thermal
is significantly decreasedhysteresis
(Tc = 29 loops
°C).inHow-
Figure 6b of the W-doped VO films by 45 nm W:V at 450 Pa, the phase
ever, the NIRSE remains high (27%), and the shape of the thermal hysteresis loop is not
2 transition tempera-
ture (Tcseriously.
) of 0.5%W-doped VO ◦ C). However,
distorted With the 2 thin film
increase in is
thesignificantly
concentration decreased (Tc = 29 to
of W dopant 1% (i.e., 1.0%W-
the NIRSE remains high (27%), and the shape of the thermal hysteresis loop is not distorted
doped VO2 film), the phase transition temperature does not decline continuously but rises,
seriously. With the increase in the concentration of W dopant to 1% (i.e., 1.0%W-doped VO2
especially above the temperature Td or Td’ (33 °C or 28 °C), due to which the average Tc
film), the phase transition temperature does not decline continuously but rises, especially
decreases
above the to temperature
39 °C. In addition,
Td or Td0the(33 NIRSE
◦ C or 28is◦ C),
negatively affected
due to which and reduces
the average to 13%. At
Tc decreases
thetosame
39 C. In addition, the NIRSE is negatively affected and reduces to 13%. At the the
◦ time, the shape of the thermal hysteresis loop is seriously distorted: sameheight
decreases
time, the(13%,
shapewhile
of thefor 0.5%W:
thermal 27%), the
hysteresis loopgradient becomes
is seriously more
distorted: thegentle,
height and the width
decreases
(13%, while
increases for 0.5%W:(16
considerably 27%),
°C, the
whilegradient becomes
for 0.5%W: more gentle, and the width increases
7 °C).
considerably (16 ◦ C, while for 0.5%W: 7 ◦ C).

0% W 0% W
heating
60 0.5% W 38% 60 0.5% W
1.0% W 1.0% W
cooling
Transmittance %

Transmittance %

27% 13
40 40 d
20℃ 7
13% 16
d'
90℃ 20
20
50℃
39℃
a b 29℃
0 0
500 1000 1500 2000 2500 0 20 40 60 80
Wavelength nm Temperature ℃

Figure 6. Transmittance curves (a) and thermal hysteresis loops (b) of VO2 films with different W
Figure 6. Transmittance curves (a) and thermal hysteresis loops (b) of VO2 films with different W
doping concentrations prepared by professional annealing of 45 nm W:V films at 450 Pa, 400 ◦ C for
doping concentrations prepared by professional annealing of 45 nm W:V films at 450 Pa, 400 °C for
1 h; solid line: 20 ◦ C, dashed line: 90 ◦ C in (a).
1 h; solid line: 20 °C, dashed line: 90 °C in (a).
The XRD pattern in Figure 7a shows that the peak intensities of the crystal NaV2 O5
andThetheXRD pattern
crystalline VO in2 Figure 7a shows
both decrease withthat
the the peakofintensities
increase W dopant.ofThe theSEMcrystal NaV2O5
image
and the crystalline VO2 both decrease with the increase 2of5W dopant. The SEM image in
in Figure 7b suggests that the size of the long sheet NaV O crystal declines gradually
with 7b
Figure thesuggests
increase that
of Wthedopant,
size ofwhich corresponds
the long to the
sheet NaV 2O5result of declines
crystal XRD. Thegradually
W-doped with
VO crystallites cannot be seen in the SEM image for the depth
the increase of W dopant, which corresponds to the result of XRD. The W-doped
2 of field of the long sheet VO2
NaV2 O5 crystals, but the particle size calculated from XRD pattern by the Scherrer formula
crystallites cannot be seen in the SEM image for the depth of field of the long sheet NaV2O5
presents a decline trend too, with 15, 13, and 11 nm, corresponding to 0%, 0.5%, and 1.0%W
crystals, but the particle size calculated from XRD pattern by the Scherrer formula pre-
respectively. W doping makes local T-VO2 phase increase and M-VO2 phase decrease,
sents a decline
which results intrend too,lattice
tighter withstructure
15, 13, andand 11 nm, difficulty
greater corresponding to 0%, 0.5%,
for Na diffusion and
into the 1.0%W
film.
respectively.
In addition,W W doping
atom hasmakes local
more free T-VO2 which
electrons, phase leads
increase and M-VO
to a greater 2 phaseofdecrease,
reducibility the
which
doped results
V filminand
tighter
higher lattice structure
consumption of and greater
oxygen. difficulty the
In conclusion, forabove
Na diffusion
two reasonsinto the
result in the decrement of the crystal NaV2 O5 and the crystalline VO2 .
 film. In addition, W atom has more free electrons, which leads to a greater reducibility
the doped V film and higher consumption of oxygen. In conclusion, the above two reaso
Materials 2022, 15, 2990 9 of 16
result in the decrement of the crystal NaV2O5 and the crystalline VO2.

* VO2 □ NaV2O5
□
011
1.0%W *□ 211
* 210 220
* *
Intensity (a.u.)

□
011
0.5%W *□ 211
* 210 220
* *
□

011
0%W □□*
□ 211
* 210 220
a JCPDS 65-2358 * □ *
10 20 30 40 50 60
2θ (deg.)
Figure 7. XRD patterns (a) and SEM images (b) of the W-doped VO2 thin films prepared by profes-
Figure 7. XRD patterns (a) and SEM images (b) of the W-doped VO2 thin films prepared by prof
sional annealing of 45 nm W:V films at 450 Pa, 400 ◦ C for 1 h.
sional annealing of 45 nm W:V films at 450 Pa, 400 °C for 1 h.
3.3. Performance and Micro Morphology of VO2 Film on Intermediate SiO2 Layer
3.3.
ThePerformance
thickness ofand
theMicro Morphology
intermediate of VO
SiO2 layer 2 Film on Intermediate SiO2 Layer
prepared by RF magnetron sputtering is
approximately 100 nm (Figure
The thickness of the 8a). Then, 30 nm
intermediate SiOV 2film
layer is deposited
preparedon byitRF
by magnetron
DC magnetron sputtering
sputtering (Table 1). Further,
approximately 100 nm (Figure VO 2 8a). Then, 30 nm V film is deposited on it of
films are prepared by professional annealing bythe
DCVmagnetr
metal films at 200,
sputtering (Table450,1).
andFurther,
600 Pa (Table 3). According
VO2 films are preparedto the SEM image of the annealing
by professional VO2 film of the
prepared at the optimized pressure 450 Pa (Figure 8c), although the SiO2 layer is partly
metal films at 200, 450, and 600 Pa (Table 3). According to the SEM image of the VO2 fi
punctured, the number of long sheet crystals is significantly reduced. Moreover, it becomes
prepared
easier at the
to observe theoptimized pressure
VO2 crystallites (size 450
aboutPa14(Figure 8c), although
nm by Scherrer the scattering
Formula) SiO2 layer is par
punctured, the number of long sheet crystals is significantly
in the film (size about 14 nm too by SEM and software Nano Measurer 1.2.5). Compared reduced. Moreover, it
comes
with the VO easier
2 filmto observe
without SiOthe VO2incrystallites
2 layer Figure 3b-30 (size
nm V,about 14 nmthat
it indicates by Scherrer Formula) sc
the SiO2 layer
+ ions, which leads to an increase of
tering
plays in therole
a crucial filmin(size about
blocking the14diffusion
nm too by SEM
of Na and software Nano Measurer 1.2.5). Co
thepared
ratio of VOthe
with 2 : Na-V-O
VO2 filmaccording
withouttoSiO the2 layer
XRD patterns
in Figure in3b-30
Figures
nm3aV,and 8d, 30 nmV.
it indicates that the Si
Consequently,
layer plays the NIRSErole
a crucial risesin(22% at 450the
blocking Pa, diffusion
Figure 8b; of original: 20%,
Na+ ions, Figureleads
which 2a), and
to an increa
the near-infrared energy modulation ability 4Tir is also enhanced (8.8%; original: 7.0%).
of the ratio of VO2: Na-V-O according to the XRD patterns in Figures 3a and 8d, 30 nm
Meanwhile, the XRD pattern (Figure 8d) demonstrates that the 100 nm intermediate SiO2
Consequently, the NIRSE rises (22% at 450 +Pa, Figure 8b; original: 20%, Figure 2a), a
layer cannot completely prevent the diffusion of Na ions, and a large number of NaV2 O5
the near-infrared
crystals are still generatedenergy
due modulation the SiO△T
to pinholes inability ir is also enhanced (8.8%; original: 7.0%
2 and diffusion of Na through it.
Meanwhile, the XRD pattern (Figure 8d) demonstrates that the 100 nm intermediate Si
layer cannot completely prevent the diffusion of Na+ ions, and a large number of NaV2
crystals are still generated due to pinholes in the SiO2 and diffusion of Na through it.
Materials 2022, 15, x FOR PEER REVIEW 11 of 17
Materials 2022, 15, 2990 10 of 16

Figure
Figure8.8.Cross-sectional
Cross-sectional SEM SEMimage
imageofofthe
the intermediate
intermediate SiO2SiO 2 layer
layer (a); transmittance
(a); transmittance curvescurves
of VO2 of VO2
thin films
thin filmson onSiO
SiO22prepared
prepared by professionalannealing
by professional annealing of nm
of 30 30 nm
V atVdifferent
at different pressures
pressures (b);(c)
(b); SEM SEM (c)
and
and XRD (d) patterns of the VO2 thin film on SiO2 prepared by professional annealing of 30 nm V at V at
XRD (d) patterns of the VO 2 thin film on SiO 2 prepared by professional annealing of 30 nm
450 Pa;
450 Pa;allallatat400
400°C
◦ C for
for 1 h.
1 h.

4. 4. Discussion
Discussion
4.1. Necessity of Two Equipments and Two Steps
4.1. Necessity of Two Equipments and Two Steps
The two-step method of magnetron sputtering-professional annealing used in this
The
study nottwo-step method
only has good of magnetron
repeatability, but alsosputtering-professional annealing
causes no heat damage to the magnetron used
sput-in this
study
teringnot only haswhich
equipment, goodcanrepeatability, but also
prolong the service lifecauses no heat damage
of the equipment. to the using
Crystallization magnetron
sputtering equipment, which
special high-temperature can prolong
equipment the service
can promote lifephase
a better of thetransition
equipment. Crystallization
performance.
The method
using special can be easily optimized
high-temperature to adjust the
equipment candoping
promoteconcentration, oxygen
a better phase vacancies,
transition perfor-
content of high-valence NaV O , film thickness, etc., which are very useful
mance. The method can be easily optimized to adjust the doping concentration, oxygen
2 5 to regulate the
phase transition temperature, visible transmittance, and other thermochromic properties.
vacancies, content of high-valence NaV2O5, film thickness, etc., which are very useful to
regulate theofphase
4.2. Effect transition
Substrate temperature,
on the Preparation visibleoftransmittance,
and Property VO2 Thin Film and other thermochromic
properties.
Generally, the NIRSE of VO film on the glass substrate is lower than that on the
2
quartz glass substrate (Figure 9a). This is because a part of the V atoms react with Na
4.2. Effectfrom
atoms of Substrate
glass, O on the Preparation
atoms from glass, and
andProperty of VO
air to form 2 Thin
NaV Film
2 O5 , which results in low
production
Generally, of crystalline
the NIRSE VOof2 , VO
as shown
2 film in
onthe XRD
the pattern
glass (Figure
substrate is 9b). In terms
lower than of theon the
that
preparation technique, the VO film prepared on the quartz glass by
quartz glass substrate (Figure 9a). This is because a part of the V atoms react with
2 annealing 30 nm V Na
film at 1500 Pa exhibits a NIRSE value of 50% (Figure 9a). However, the film prepared on
atoms from glass, O atoms from glass, and air to form NaV2O5, which results in low pro-
the glass by annealing 30 nm V film at 1500 Pa shows a NIRSE value of 0%. Nevertheless,
duction of crystalline VO2, as shown in the XRD pattern (Figure 9b). In terms of the prep-
aration technique, the VO2 film prepared on the quartz glass by annealing 30 nm V film
at 1500 Pa exhibits a NIRSE value of 50% (Figure 9a). However, the film prepared on the
glass by annealing 30 nm V film at 1500 Pa shows a NIRSE value of 0%. Nevertheless,
15, x FOR PEER REVIEW 12 of 17

Materials 2022, 15, 2990 11 of 16

achieved. The surface of VO2 film on quartz glass is flat and compact (Figure 9c), and like
a passivation coating, can stand up to the high oxidation pressure 1500 Pa. Meanwhile,
when the annealing pressure is reduced to 100 Pa, a high NIRSE value (35%, Figure 9a) is
the surface of VOachieved.
2 film on glass is a loose structure consisted of disordered long sheet
The surface of VO2 film on quartz glass is flat and compact (Figure 9c), and like a
NaV2O5 crystals and pinholes,
passivation whichcan
coating, results
standinupgreater
to the easiness of oxygen
high oxidation indiffusion
pressure 1500 Pa. from
Meanwhile, the
the atmosphere and easiness
surface of VO2of oxidization
film on glass is aofloose
V tostructure
high valence
consistedNaV 2O5 underlong
of disordered a high
sheet NaV2 O5
pressure. In addition, there
crystals andarepinholes,
more free non-bridged
which results in oxygen atoms inofthe
greater easiness glass substrate.
oxygen indiffusion from the
Despite the muchatmosphere and easiness
greater difficulty of O2−ofion
oxidization
outdiffusionof V tothan
highNavalence NaV
+ for its 2 O5 under
strong a high pressure.
Coulomb
force, there still isInthe
addition, thereof
possibility are
Omore free non-bridged
emigrating oxygen
to the surface atoms
and in the glass
oxidizing the Vsubstrate.
metal Despite
the much greater difficulty of O 2− ion outdiffusion than Na+ for its strong Coulomb force,
film during the annealing. However, in quartz glass, O atoms are firmly bonded with Si
there still is the possibility of O emigrating to the surface and oxidizing the V metal film
atoms by the covalent bonds and are very difficult to move. So, in conclusion, when on
during the annealing. However, in quartz glass, O atoms are firmly bonded with Si atoms
glass substrate, the byoxidation
the covalentpressure is much
bonds and lower,
are very because
difficult of theSo,
to move. loose surface ofwhen
in conclusion, the on glass
film majorly, as well as the O outdiffusion from the substrate minorly; and when on quartz
substrate, the oxidation pressure is much lower, because of the loose surface of the film
glass, the oxidation pressure
majorly, could
as well beOmuch
as the higher,from
outdiffusion because of the compact
the substrate surface
minorly; and whenofon the
quartz glass,
film. the oxidation pressure could be much higher, because of the compact surface of the film.

100
quartz glass 30nm V-1500Pa quartz glass 30nm V-1500Pa
glass 30nm V-1500Pa □ glass 30nm V-100Pa

*
80 glass 30nm V-100Pa
VO2□ NaV2O5
Intensity (a.u.)
Transmittance %

60
□ 211
35% *
40
211
50% *
20 210
a b * 220
*
0
500 1000 1500 2000 2500 10 20 30 40 50 60 70 80
Wavelength nm 2θ (deg.)

Figure 9. Transmittance
Figurecurves (solid line:curves
9. Transmittance 20 °C,(solid
dashline:
line:2090◦ C,
°C) (a),line:
dash XRD 90patterns (b) of
◦ C) (a), XRD VO2 films
patterns (b) of VO2 films
prepared by professional
preparedannealing of 30 nm
by professional V metal
annealing offilms
30 nmon two contrastive
V metal films on twosubstrates
contrastiveofsubstrates
quartz of quartz
glass and float glassglass
at set pressures,
and float glass400 °Cpressures,
at set for 1 h; and
400SEM
◦ C forimage (c)SEM
1 h; and of the VO2(c)
image film from
of the VO“quartz
2 film from “quartz
glass 30 nm V-1500 glass
Pa”. 30 nm V-1500 Pa”.

4.3. Choice between4.3. Choiceand

NIRSE between
Tlum NIRSE and Tlum
The primary goal of VO film preparation is to maximize the value of NIRSE, which
2
The primary goal of VO2 film preparation is to maximize the value of NIRSE, which
means that the content and purity of VO2 in the film should reach the highest level. How-
means that the content and
ever, for purity
smart of VOboth
windows, 2 in the film should reach the highest level. How-
NIRSE and visible transmittance Tlum should be considered.
ever, for smart windows,
The minimum daylightingvisible
both NIRSE and rate of transmittance
green building T lum should
glass be considered.
is generally required to be above
The minimum daylighting rate it
60%. Therefore, ofisgreen
usefulbuilding
to sacrificeglass
a partisofgenerally
NIRSE to required
improve theto Tbe
lumabove
, while ensuring
60%. Therefore, itan
is useful to sacrifice
appropriate a part
high value of of NIRSE
NIRSE. tocommon
The improvemethod
the Tlumto
, while
improveensuring
the visible trans-
mittance
an appropriate high valueisof
to NIRSE.
deposit anti-reflection
The commonfilms. method However, two other
to improve the simple
visible approaches
trans- were
used in
mittance is to deposit this study: thinning
anti-reflection the V metaltwo
films. However, film other
and increasing the annealing
simple approaches pressure. For
were
used in this study: thinning the V metal film and increasing the annealing pressure. For decreases
instance, when the V metal film is thinned from 45 nm to 30 nm, the NIRSE
from 39% to 20%, but the Tlum increases from 44.5% to 63%, as shown in Figure 2a and
instance, when the V metal film is thinned from 45 nm to 30 nm, the NIRSE decreases from
39% to 20%, but the Tlum increases from 44.5% to 63%, as shown in Figure 2a and Table 4.
When the annealing pressure of 45 nm V film increases from 450 Pa to 700 Pa, the NIRSE
decreases from 39% to 30%, but the Tlum increases from 44.5% to 61%, as shown in Figure
Materials 2022, 15, 2990 12 of 16

Table 4. When the annealing pressure of 45 nm V film increases from 450 Pa to 700 Pa, the
NIRSE decreases from 39% to 30%, but the Tlum increases from 44.5% to 61%, as shown in
Figure 2b and Table 4. The two methods’ mechanism is: at the same high enough oxidation
pressure, thinner V metal films will be more easily oxidized into high-valence vanadium;
and for the V metal films with same thickness, higher oxidation pressure will result in
more high-valence vanadium likewise. The content of low-valence vanadium (mainly
crystalline VO2 ) in the film decreases, and the content of high-valence vanadium (mainly
crystal NaV2 O5 ) increases, which leads to an increase in the optical band gap, and results
in the increase of the visible transmittance of the film. Moreover, there is another for the
thinner film reason, namely lower light absorption.

4.4. Mechanism of W Doping and Equivalent Effect of O Vacancy

There are two mechanisms through which W doping reduces the phase transition
temperature (Tc ) of VO2 : Peierls mechanism and Mott mechanism. Among them, the
Peierls mechanism is described by the energy band theory [34–36], where structural change
is considered as the driving force. After larger W atoms replace the smaller V atoms, the
lattice expands and the V-V dimerization pairs are destroyed, which results in the change
of energy band position. The band gap between V3d// and π* becomes narrower, the
electronic migration becomes easier, and the phase transition barrier is reduced, so the Tc
decreases. In addition, according to the energy band theory, Tc continues to decline with the
increase in the concentration of W dopant, which disagrees with our experimental results
(decreases first and then rises). Therefore, this paper supports the second theory of the
Mott mechanism. The Mott mechanism is described by the charge-doping theory [37–39],
where electron correlation is the driving force. After V4+ ions are replaced by W6+ ions,
the excess electrons enter the empty π* band, and then local conduction bands and local
metallic phases are formed. Therefore, the transformation into tetragonal phase becomes
easier, and thus the transition temperature Tc declines. However, excessive W doping can
cause superabundant electrons to enter the empty π* band, and the interaction of electrons
is enhanced, which results in the splitting of π* band and the formation of a new band gap.
The phase transition barrier becomes larger, and thus the Tc rises again. The mechanism
of W doping to reduce the phase transition temperature of VO2 is still under debate, just
like the debate between Peierls mechanism and Mott mechanism for the intrinsic phase
transition of pure VO2 [40,41]. Presently, there is no unified theory that can fully describe
the effect of W doping.
Although the phase transition temperature is reduced by W doping, the thermochromic
properties are adversely affected, and the most significant change is that the NIRSE declines
significantly. The local conduction bands are formed after W doping, and the electronic
transition becomes easier. At low temperature, the ability of reflecting infrared radiation is
enhanced, and the infrared transmittance is reduced, and thus the NIRSE is clearly reduced.
With the increase of W dopant, the thermal hysteresis loop becomes gentle (Figure 6b) and
is no longer steep. This is directly related to the reduction of phase transition temperature
at low temperature (below Td or Td’ ), the rise of phase transition temperature at high
temperature (above Td or Td’ ), and the decline of NIRSE. At low temperature (below Td
or Td’ ), due to the increase of W dopant, local conduction bands in empty π* band are
increased, and the monoclinic-tetragonal phase transition can be easily realized, which
results in the reduction of the phase transition temperature. At high temperature (above Td
or Td’ ), due to the gradual increase of tetragonal metallic phase, more and more electrons
enter the empty π* band, and the interaction becomes increasingly stronger, which results
in worse fragmentation of the π* band, a wider band gap, larger phase transition barrier,
and thus the increase of the phase transition temperature.
Similar to W doping, the oxygen vacancies can lower the phase transition temperature
of VO2 , which were created by lowering the annealing pressure. For example, the Tc of
VO2 film fabricated by annealing 45 nm V film at 200 Pa is 8 ◦ C lower than that of VO2
film fabricated by annealing 45 nm V film at 450 Pa, as shown in Figure 10a. The oxygen
 Materials 2022, 15, x FOR PEER REVIEW 14 of 17
Materials 2022, 15, 2990 13 of 16

vacancies
whichlead to the
enter thetransformation
empty π* band V4+ form
of and into Va3+local
and conduction
generation of excess
band. Theelectrons,
growth of the
which charge
enter the empty π* band and form a local conduction band. The growth
carrier concentration and the enhancement of the metal phase results of the in
charge
the decline
carrierof
concentration
phase transition temperature, which is similar to the effect of W doping at phase
and the enhancement of the metal phase results in the decline of low concen-
transition temperature,
tration. However, which is similar
it should be notedto that
the effect
when of WW doping
dopant at low
is used forconcentration.
lowering the phase
However, it should be noted that when W dopant is used for lowering
transition temperature of VO2, and the concentration has reached an the phase transition
optimal value, i.e., a
temperature of VO2 , and the concentration has reached an optimal value, i.e., a level (such
level (such as 0.5%W) that can cause Tc to rise rather than continually decline, the prepa-
as 0.5%W) that can cause Tc to rise rather than continually decline, the preparation of
ration of oxygen vacancies has an opposite effect. For instance, the Tc of the VO2 film pre-
oxygen vacancies has an opposite effect. For instance, the Tc of the VO2 film prepared by
pared by annealing 45 nm 0.5%W/V film at 300 Pa is 10 °C higher than that of the VO2 film
annealing 45 nm 0.5%W/V film at 300 Pa is 10 ◦ C higher than that of the VO2 film prepared
prepared by annealing 45 nm 0.5%W/V film at 450 Pa, as shown in Figure 10a. The for-
by annealing 45 nm 0.5%W/V film at 450 Pa, as shown in Figure 10a. The formation of
mation of oxygen vacancies is indicated by the increase of the ratio of V3+: V4+ in the V2p3/2
oxygen vacancies is indicated by the increase of the ratio of V3+ : V4+ in3+the V2p3/2 XPS
XPS spectra (Figure 10b). The three fitting peaks correspond to V (515.2 eV), V4+ (516.0
spectra (Figure 10b). The three fitting peaks correspond to V3+ (515.2 3+ eV), 4+V4+ (516.0 eV),
eV), and V (517.2 eV), respectively [42]. It is found that the V : V ratio increases from
5+
and V5+ (517.2 eV), respectively [42]. It is found that the V3+ : V4+ ratio increases from
0.86 to 0.98 when the annealing pressure decreases from 450 Pa to 200 Pa for 45 nm V, and
0.86 to 0.98 when the annealing pressure decreases from 450 Pa to 200 Pa for 45 nm V, and
increases from 0.59 to 0.75 when the annealing pressure decreases from 450 Pa to 300 Pa
increases from 0.59 to 0.75 when the annealing pressure decreases from 450 Pa to 300 Pa for
for 45 nm 0.5%W/V.
45 nm 0.5%W/V.

45nm 0.5%W/V @ V2P3/2 45nm 0.5%W/V

@300Pa
heating 450Pa 3+
V :V
4+
60
300Pa =0.75
cooling
45nm V @ 45nm 0.5%W/V
450Pa @450Pa
Transmittance %

3+ 4+
V :V

Intensity (a. u.)

40 200Pa =0.59

45nm V
@200Pa
3+ 4+
V :V
20 =0.98 5+
V
4+
50℃ 3+
V
42℃ V 45nm V
@450Pa
a 39℃
3+
V :V
4+

29℃ =0.86 b
0
0 20 40 60 80 513 514 515 516 517 518 519 520
Temperature ℃ Binding energy (eV)

Figure Figure 10. (a)ofEffect

10. (a) Effect of lowering
lowering the annealing
the annealing pressure
pressure on on the
the thermal thermal loop
hysteresis hysteresis loop of the pre-
of the prepared
pared VO films and W/VO films (from 450 Pa to 200 Pa for 45 nm V;
VO2 films and W/VO2 films (from 450 Pa to 200 Pa for 45 nm V; from 450 Pa to 300 Pa for
2 2 from 450 Pa to 45
300nm
Pa for 45
nm 0.5%W/V; all
◦ at 400 °C for 1 h); (b) XPS spectra
3+ of
4+ V 3+, V4+ of the corresponding VO2 films and
0.5%W/V; all at 400 C for 1 h); (b) XPS spectra of V , V of the corresponding VO2 films and
films.2 films.
W/VO2W/VO

In addition,
In addition, the causes
the causes of the decrement
of the decrement of Tc should
of Tc should probably
probably include include the in
the strain strain in
the film, as studied by Elia [43], Paez [44], and so on [45]. The substrate
the film, as studied by Elia [43], Paez [44], and so on [45]. The substrate used her is glass, used her is glass,
so thereso would
there would
not benot be induction
induction for strain
for strain generation
generation by certain
by certain lattice lattice
planesplanes
such assuch as
TiO[43–45].
TiO2 (001) 2(001) [43–45].
However,However,
in spiteinofspite
this,ofthere
this,would
there would bestrain
be some some inevitably
strain inevitably existing
existing
in the interface
in the interface between between glass
glass and and W/VO
W/VO film, boundaries,
2 film, 2grain grain boundaries,
lattice lattice deformation,
deformation, and and
so on. soSo,on.
theSo,
strain in the in
the strain film
theafter
filmWafter
doping wouldwould
W doping be another cause for
be another Tc reduction,
cause for Tc reduction,
thoughthough
not thenot
mainthecause.
main cause.

4.5. Effect
4.5.ofEffect
100 nm Intermediate
of 100 SiO2 Layer
nm Intermediate SiO2 Layer
As described in Section 3.3, a 100-nm-thick
As described in Section 3.3, a 100-nm-thick intermediate SiO2 layer
intermediate SiO2pre-deposited on
layer pre-deposited on
the glass plays an obvious role in blocking the diffusion of Na + ions. However, it does not
the glass plays an obvious role in blocking the diffusion of Na ions. However, it does not
+
stop the diffusion
stop completely,
the diffusion and many
completely, andNaV 2 O5 crystals
many NaV2O5are still generated.
crystals As a next step,
are still generated. As a next
increasing the thickness of the intermediate SiO
step, increasing the thickness of the intermediate 2 layer or replacing it with
SiO2 layer or replacing a better layer
it with a better
(compact,
layerhard, narrow
(compact, lattice
hard, plane,lattice
narrow etc.) can completely
plane, etc.) can block the diffusion
completely block the Na+ ions.of Na+
of diffusion
Meanwhile, the additionthe
ions. Meanwhile, of addition
the intermediate SiO2 layer changes
of the intermediate SiO2 layer thechanges
technical
theparameters
technical param-
for theeters
preparation of VO2 thin of
for the preparation film,
VOand the optimal oxidation pressure increases from
2 thin film, and the optimal oxidation pressure increases
100 Pa to 450 Pa (Figures 5 and 8b). Similar to the mechanism described in Section 4.2,
Materials 2022, 15, 2990 14 of 16

the intermediate SiO2 layer causes fewer long sheet NaV2 O5 crystals and a flatter, more
compact surface than that on glass substrate (Figure 3b-30 nm V, Figure 8c), which results
in the difficulty of oxygen indiffusion from the atmosphere. Besides, the intermediate
SiO2 blocks the migration of non-bridged oxygen atoms from the glass into the film. In
conclusion, the demand of oxidation annealing pressure rises, mainly because of the
compacter surface of the film, and minorly because of the block of O immigration into film
from glass.

5. Conclusions
Magnetron sputtering and the professional annealing method have the advantages
of simple operation, convenient optimization, good repeatability, and no heat damage to
the sputtering machine. Therefore, the represent an appropriate method for the fabrication
and systematical examination of VO2 thin films. To obtain the largest NIRSE value is
the primary objective. The thickness must match with the optimal pressure. Otherwise,
the value of NIRSE will decline. Under the fixed annealing condition of 400 ◦ C (1 h), a
thicker V-based metal film requires a higher optimal annealing pressure, and the thinner
film requires a lower optimal annealing pressure. When a glass substrate is used, mainly
because of the loose surface structure of disordered long sheet NaV2 O5 and pinholes, the
oxidation annealing pressure reduces sharply. In this study, it was verified that compared
with the quartz glass substrate, the annealing pressure of the 30 nm V metal film on the glass
substrate decreased by more than 90%. Increasing the annealing pressure or decreasing
the thickness of V metal film was demonstrated as a new effective method to improve the
visible transmittance Tlum . The 100 nm intermediate SiO2 layer played an obvious role in
preventing the diffusion of Na+ ions, though not completely. Thicker or new intermediate
layers need to be further studied. This study supports the charge-doping theory. A proper
concentration of W dopant can lead to the formation of local conduction bands in the π*
band, which can reduce the Tc of VO2 thin film. However, excessive W doping can lead to
the splitting of π* band, which results in the formation of a new band gap and an increase
in the phase transition barrier, and thus the Tc increases. In terms of lowering the Tc of
VO2 film, oxygen vacancy and W dopant have an equivalent effect. Further, when the W
doping concentration is optimal, no more oxygen vacancies should be added. Otherwise,
an opposite effect can occur.

Author Contributions: Conceptualization, X.C. and X.Z. (Xiujian Zhao); methodology, X.C. and
Q.X.; software, X.C.; validation, X.C., B.G., X.Z. (Xiaoming Zhang) and J.L.; formal analysis, X.C.,
Q.X. and X.Z. (Xiujian Zhao); investigation, X.C. and Q.X.; resources, X.C., X.Z. (Xiujian Zhao) and
X.Z. (Xiaoming Zhang); data curation, X.C., Q.X. and X.Z. (Xiujian Zhao); writing—original draft
preparation, X.C.; writing—review and editing, X.C., X.Z. (Xiaoming Zhang) and X.Z. (Xiujian Zhao);
visualization, X.C. and B.G.; supervision, X.Z. (Xiaoming Zhang) and X.Z. (Xiujian Zhao); project
administration, X.C. and X.Z. (Xiujian Zhao); funding acquisition, X.C. All authors have read and
agreed to the published version of the manuscript.
Funding: This work was supported by the Natural Science Foundation of Jiangxi Province (20202BABL
211011, 20202BABL202012), and Science and Technology Project of Jiangxi Provincial Department of
Education (GJJ180860, GJJ190864, GJJ201631).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: The authors would like to thank all the reviewers for their useful comments and
suggestions on the manuscript.
Conflicts of Interest: The authors declare no potential conflict of interest with respect to the research,
authorship, and/or publication of this article.
Materials 2022, 15, 2990 15 of 16

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