Flexible vanadium oxide film for broadband transparent photodetector

Hong-Sik Kim, Khushbu R. Chauhan, Joondong Kim, and Eun Ha Choi

Citation: Appl. Phys. Lett. 110, 101907 (2017); doi: 10.1063/1.4977426

View online: http://dx.doi.org/10.1063/1.4977426
View Table of Contents: http://aip.scitation.org/toc/apl/110/10
Published by the American Institute of Physics

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 APPLIED PHYSICS LETTERS 110, 101907 (2017)

Flexible vanadium oxide film for broadband transparent photodetector

Hong-Sik Kim,1 Khushbu R. Chauhan,1 Joondong Kim,1,a) and Eun Ha Choi2,b)
1
Photoelectric and Energy Device Application Lab (PEDAL) and Department of Electrical Engineering,
Incheon National University, 119 Academy Rd. Yeonsu, Incheon 406772, South Korea
2
Plasma Bioscience Research Center, Kwangwoon University, Seoul, 01897, South Korea
(Received 23 October 2016; accepted 12 February 2017; published online 9 March 2017)
A High-performing transparent and flexible photodetector was achieved by reactive sputtering method.
Vanadium pentoxide (V2O5) thin films were deposited on flexible polyethylene terephthalate (PET)
substrates at room temperature. The transparent and flexible photodetectors with the configurations
V2O5/ZnO/ITO/PET showed high-performing photoresponse with a quick response time (4.9 ms) and
high detectivity of 1.45  1012 Jones, under a light intensity of 1 mW/m2. We demonstrated high-
performing V2O5 film-based transparent and flexible broadband photodetectors which may provide a
promising approach for transparent electronic applications. Published by AIP Publishing.
[http://dx.doi.org/10.1063/1.4977426]

Transparent and flexible thin films are the basis of modern to realize fast switching photoelectric devices. In this regard,
technologies and next generation photoelectric devices. Many a little work has been carried out to demonstrate the viability
wide band gap materials have been tried to fabricate transparent of V2O5 in efficient photodetector devices.26–28
and efficient optoelectronic devices. In the search of emerging In this research, we investigate for functional light-
materials, transition metal oxides have gained a great interest absorbing layer of V2O5 thin films for a broadband photodetec-
due to their extraordinary electrical and optical properties.1–3 tor. A highly transparent V2O5 thin film was deposited by using
In this group of materials, recently, vanadium oxide fam- room temperature reactive sputtering method, which enables to
ily is attaining a lot of attention because of their reversible apply flexible substrates. The transparent and flexible V2O5
phase transitions between metals and semiconductors.4,5 VO2 film-based photodetectors provided high-performing photores-
has been utilized in a variety of applications like IR bolome- ponse of quick response time (4.9 ms) with high detectivity
ters,6 switching devices,7 smart windows,8 optical storage (1.45  1012 Jones). The photodetection properties of V2O5/
devices,9 photo-conversion10 and IR photodetectors.11 ZnO/ITO/PET photodetector will also be discussed.
Amongst the vanadium oxide family, vanadium pentoxide Transparent and flexible polyethylene terephthalate
(V2O5) is the most stable crystal structure. It is also possible to (PET) films were used as substrates for the fabrication of
fabricate nanowires, nanotubes, and nanobelts of V2O5 which V2O5 thin films as well as photodetectors. The deposition of
have been useful in photodetection, transistors, sensors, charge V2O5 thin films was achieved by reactive sputtering at room
storage, and organic solar cells.12–18 However, till date, such temperature. Different from the conventional sputtering
devices use V2O5 or VO2 materials deposited at elevated tem- method, the reactive sputtering would engineer the oxide stoi-
peratures. The detection ability of such nanostructured sensors chiometry. Moreover, the reactive sputtering approach is
is strongly dependent on the process temperature and hence effective to form the compound oxide material with a high
usually the temperatures above 400  C are required. On the yield and low energy use. To form the V2O5 film, the reactive
other hand, room temperature deposition allows the deposition sputtering method was applied by modulating the flow ratio
of amorphous thin films which may be a low cost alternative to of plasma (Ar) gas and oxygen reactive gas. The photodetec-
design efficient devices out of vanadium oxide family. tors with the configuration V2O5/ZnO/ITO/PET were fabri-
V2O5 possesses a direct band gap of 2.2 to 2.7 eV which cated by using DC or RF reactive sputtering. The sputtering
makes it suitable for optoelectronic and photoelectric devi- parameters for the deposition of V2O5 thin films and each
ces. Researchers use a variety of techniques like physical layer of the photodetector are listed in Table I. X-ray diffrac-
vapor deposition, electro spinning, hydrothermal, and poly- tion (XRD) patterns of the films were recorded using Rigaku,
condensation to fabricate V2O5 thin films.19–22 On the other
hand, the phase transition in VO2 films can be achieved by TABLE I. Sputtering parameters for the fabrication of V2O5/ZnO/ITO/PET
photodetector.
electrical or optical excitations23 or by interfacial strain.24
Deposition of controllable and highly reproducible thin films Working
of VO family is a challenging task because of their affinity Sputter Power pressure Ar:O2 Time Thickness
to exist in different oxidation states.25 A great control over target (W) (mT) (sccm) (min) (nm)
the deposition parameters is required for the fabrication of
ITO ITO DC-300 5 30:0.3 10 200
high quality V2O5 or VO2 thin films. The appropriate (99.9%, TASCO)
bandgap and absorption properties of V2O5 may be suitable ZnO ZnO RF-300 5 50:0 15 100
(99.9%, TASCO)
a)
H. Kim and K. R. Chauhan contributed equally to this work. V2O5 Vanadium RF-300 5 30:2 30 50
b)
Authors to whom correspondence should be addressed. Electronic (99.9%, TASCO)
addresses: joonkim@inu.ac.kr and ehchoi@kw.ac.kr

0003-6951/2017/110(10)/101907/5/$30.00 110, 101907-1 Published by AIP Publishing.

101907-2 Kim et al. Appl. Phys. Lett. 110, 101907 (2017)

FIG. 1. (a) XRD spectrum, inset:

actual photograph of V2O5 thin film
(b) Raman spectrum (c) Transmittance
of V2O5 thin film on various substrates
and (d) Tauc plot for V2O5 thin films.

SmartLab which utilizes the CuKa radiation with a character- in amorphous films. According to Raman analysis, it can be
istic wavelength k ¼ 1.5406 Å. Micro-domain analysis of confirmed that the deposited V2O5 thin films are amorphous
V2O5 thin film was done by using Raman spectroscopy (lab in nature comprising of distorted structures. The optical data
made laser confocal microscope and spectrometer) with a of V2O5 thin film are presented in Fig. 1 in the form of (c)
514 nm Ar laser as an excitation source. The optical character- transmittance and (d) Tauc plot. It can be seen that V2O5
ization of V2O5 thin films was carried out using UV-Vis spec- film on a glass substrate exhibits a very high transmittance of
trophotometer (Shimadzu, UV-2600) in the wavelength range
of 200 to 1400 nm. The dark and illuminated I-V spectra of
the photodetectors were recorded by using the source measure
unit (Keithley-2400). Photoresponse spectra of the photode-
tectors were recorded for three different LEDs (LEDENGIN,
455 6 10, 515 6 10 and 620 6 10 nm) operated at a chopping
frequency of 2 Hz.
Fig. 1(a) shows the XRD spectrum of V2O5 thin film
deposited by room temperature reactive sputtering. Inset
shows the actual photograph of the V2O5 film. It was found
that the amorphous V2O5 films do not show any sharp XRD
peaks. Such properties of V2O5 amorphous phase were also
noticed by other research groups.29
The Raman spectroscopy was used to investigate the
local structure changes in V2O5 films, as shown in Fig. 1(b).
The Raman bands of the V2O5 structure are classified for
either x and y displacements of O1 atoms or z displacement
of O21 and O22 atoms30 in the frequency region from 200 to
400 cm1. The broad band at 306 cm1 corresponds to the
modes with y oscillations of O1 atoms together with the z
oscillations of O2 atoms. The small peak available at
489 cm1 is due to the bending vibrations of V-O3-V bridge
angle in V2O5 structure. The other two bands at 616 and
776 cm1 correspond to the stretching vibrations of V3-O
and V2-O bonds in a disordered V-O-V, respectively.31 The
bond stretching modes were also detected at 1000 and
1029 cm1. The peak at 1000 cm1 corresponds to the V ¼ O FIG. 2. V2O5/ZnO/ITO/PET photodetector (a) FE-SEM image (b) V2O5/
stretching mode due to unshared oxygen. On the other hand, ZnO/ITO/PET device schematics and an actual device photograph (c) Energy
band diagram for V2O5/ZnO/ITO (d) Dark I-V characteristics of V2O5/ZnO/
a relatively sharp peak at 1029 cm1 can be assigned to the ITO/PET device (e) V2O5/ITO/PET device schematics (f) Dark I-V character-
V5þ ¼ O stretching mode of terminal surface oxygen atoms istics of V2O5/ITO/PET.
101907-3 Kim et al.
(>95%) in the wavelength range 550–1400 nm. For the flexi-
ble PET substrate, V2O5/PET shows the relatively high trans-
mittance. Moreover, the configuration of V2O5/ZnO/PET
device has an average transmittance of 77.73% in the wave-
length range 550–800 nm to ensure the visible transparency.
However, a drastic decrease in the transmittance was
observed for the wavelengths below 500 nm. The band gap of
the film was confirmed to be 2.6 eV from Tauc plot. A very
high absorption coefficient of the order of 105 cm1 was
obtained for amorphous V2O5 films, which confirm that only
a 100 nm thin film will be enough to absorb the available solar
spectrum. The surface morphology of V2O5 film is presented
in Fig. 2(a). As discussed in the previous paragraph, 100 nm
thick films were enough to absorb the whole solar spectrum
and hence only 50 nm V2O5 thin films were deposited for their
further use in photodetection. The transparent V2O5/ZnO/ITO
device schematics are shown in Fig. 2(b) with a photograph of
the actual device. Fig. 2(c) is a band diagram of the corre-
sponding device. As clearly presented, the existing ZnO layer
is effective to tune the conduction band (Ec) and the valence
band (Ev), as a configuration of V2O5/ZnO/ITO. For the dark
I-V characteristics, V2O5/ZnO/ITO device clearly provides
the rectifying current flows, as shown in Fig. 2(d). In case of
the absence of ZnO layer, as shown in Fig. 2(e), the Ev loca-
tion of V2O5 and Ec of ITO are too close, which readily
nullify the photogenerated carriers by recombination. The I-V
characteristics of the V2O5/ITO device show the ohmic con-
tact, without the current rectifying profiles (Fig. 2(f)). The
insertion of the ZnO layer is obvious to provide the electron
transport from V2O5 to ITO. Similarly, the hole transport
route is tuned from ITO to V2O5.
The dark and illuminated curves of the photodetector for
three different wavelengths (ks), blue light (k ¼ 455 6 10 nm,
13.7 mW/cm2), green light (k ¼ 515 6 10 nm, 12.29 mW/cm2),
and red light (k ¼ 620 6 10 nm, 20.94 mW/cm2) are presented
TABLE II. Photodetection properties of V2O5/ZnO/ITO/PET photodetector for different lights at 1.5 V and an illumination intensity of 1 mW/m2.
Wavelength (nm) ID (A) Rise time (ms) Fall time (ms)
10
455 6 10 9.45  10 4.90 9.79
515 6 10 9.42  1010 12.73 9.79
620 6 10 9.43  1010 16.14 4.38
Appl. Phys. Lett. 110, 101907 (2017)
FIG. 3. (a)–(c) Dark and light illumi-
nated I-V characteristics (d)–(f)
Photocurrent spectra under chopped
light illumination conditions for V2O5/
ZnO/ITO/PET photodetector.
in Figs. 3(a)–3(c). It can be seen from Fig. 3 that the dark char-
acteristic of the photodetector follows near to ideal diode char-
acteristics with a very low dark current density of the value
9.4  1010 A. It can be noticed that the reverse bias character-
istic of the photodetector changed drastically when the junction
between V2O5/ZnO was continuously illuminated by visible
lights. The maximum photocurrent of the value 2.3  107 A
was recorded at 1.5 V by illuminating the junction with the
blue light. This is due to the exact matching of the V2O5 band
gap with the incident wavelength of the light. Such an exact
matching is of much value in designing the selective wave-
length photodetectors. The ratios of dark to light current (pho-
tocurrent gain) extracted at 1.5 V for all three wavelengths
are presented in Table II. It can be seen from the table that max-
imum photocurrent gain of the value 247 can be achieved by
blue light illumination. In addition, V2O5–thin film photodetec-
tor was also able to detect green and red light with the photo-
current gains of the values 240 and 102, respectively. The
broadband photodetection is a unique feature of our design
which utilizes only a 50 nm thick V2O5 film. ZnO is a wide
band gap (3.4 eV)32 material and hence active only in the ultra-
violet region of the solar spectrum. Hence all the photodetec-
tion properties are the characteristics of amorphous V2O5 thin
film.
The photocurrent spectra of the device under chopping
light conditions are presented in Figs. 3(d)–3(f). The
dynamic performance of V2O5 based photodetector was
found to be composed of the generation and recombination
processes from depletion as well as quasi-neutral regions.
The calculated values of rise and fall time for different
wavelengths are presented in Table II. The V2O5 thin film
transparent photodetector exhibited an excellent perfor-
mance with quick response time of 4.9 ms, which is quite
faster compared to those utilizing V2O5 nanosheets
(65 s).27 However, fastest photodetectors (sr ¼ 258.8 ls)
Photocurrent gain R (mA/W) D* (Jones) LDR (dB)
12
247 20 1.45  10 58
240 55 4.13  1012 63
102 20 1.48  1012 59
101907-4 Kim et al. Appl. Phys. Lett. 110, 101907 (2017)

Responsivity (R), detectivity (D*), and linear dynamic

range (LDR) are the key important parameters of the photo-
detectors. The responsivity of any photodetector can be
defined as
Jph
R¼ ; (1)
Pin

where Jph is the photocurrent density, and Pin is the intensity

of incident illumination.
Whereas the detectivity is defined as
R
D ¼ pffiffiffiffiffiffiffiffiffiffiffi : (2)
2 q Jd

Here q is the charge of electron, and Jd is the dark current

density of the photodetector.
The values of LDR can be derived from the equation
 
Jph
LDR ¼ 20 log : (3)
Jd

FIG. 4. Responsivity and detectivity of V2O5/ZnO/ITO/PET photodetector
for (a) Blue light (b) Green light, and (c) Red light with a variation of an
illumination intensity.
based on V2O5 material utilizes a single crystalline
nanobelt structure developed by the CVD method.28 A sig-
nificantly high temperature of 1000  C was applied to
embed the V2O5 nanobelts on an opaque Si substrate.
Different from this, reactive sputtered V2O5 thin film
can be used to directly fabricate the photodetector on flexi-
ble and transparent substrate of PET. The further improve-
ment may be possible by controlling the properties of
V2O5 thin film.
The calculated values of R, D*, and LDR for all the inci-
dence wavelengths are presented in Table II. The variations
in R and D* with an illumination intensity are presented in
Fig. 4 for three different wavelengths. It can be noticed that
the responsivity reaches its maximum value of 55 mA/W
under a green light illumination (intensity of 1 mW/m2). At
the same time, a maximum detectivity of the value 4  1012
Jones was achieved under a corresponding light illumination
condition. The values of D* for all wavelengths are compa-
rable with the other efficient photodetectors utilizing vana-
dium oxide family materials (D* is 9.23  1012 Jones for
VO2/V2O5 core/shell photodetectors).33 However, responsiv-
ity of the amorphous V2O5 photodetector was found to be
only 20 mA/W for blue and red light. In contrast, V2O5 nano-
wires possess extremely high values of responsivity (7900 A/
W) at a low incident power.37 The lower responsivity may
be due to the low crystallinity of the film which enhances the
recombination in the device and suppresses the photocurrent
values. The values of LDR were found to be 58 dB, 63 dB,
and 59 dB for blue, green, and red light, respectively. LDR is
the measure of linearity for photosensitivity of any detector.
In other words, it is the ratio of minimum to maximum
detectable power from any photodetector. The values of
LDR for V2O5 thin film photodetector were found to be bet-
ter than the VO2 microwire photodetectors (45 dB) which
exhibited extremely high responsivity.34 The better values of

TABLE III. Performances of V2O5 photodetectors.

Condition, illumination Rise time Fall time Responsivity Detectivity References

No. Structure wavelength (s) (s) (A/W) (Jones) (shape)

1 V2O5/ZnO 0 V, 455 nm 0.049 0.098 0.02 1.45  1012 This work (film)
2 Ag/V2O5/Ag 1 V, 540 nm 0.914 0.573 0.948 … 35 (Nanorods)
3 ITO/V2O5/ITO 1 V, 365 nm 65 75 0.062 … 27 (Nanosheet)
4 Ag/V2O5/Ag 0.5 V, 530 nm 0.753 0.134 0.042 … 36 (Nanorods)
5 Au/Ti/V2O5/Ti/Au 1 V, 450 nm … … 482 … 26 (Nanowires)
6 Au/V2O5/Cr 2 V, 671 nm 258.8 ls 153.2 ls … … 28 (Nanobelt)
7 VO2/V2O5 coreshell 3 V, 990 nm 0.05 0.23 2873.7 9.23  1012 33 (Nanobeam)
8 Au/Ti/V2O5/Ti/Au 0.1 V, 325 nm >1000 >2000 7900 … 37 (Nanowire)
101907-5 Kim et al. Appl. Phys. Lett. 110, 101907 (2017)

LDR can be attributed to the low dark current of the photo-
detector. The photodetectors based on amorphous V2O5 thin
films may be of unique use due to its simple configuration,
fast and stable operation with wider LDR values. Different
from other reports (Table III), the V2O5/ZnO/ITO/PET pho-
todetector can be operated at zero-bias condition, which is
an important advantage for self-bias operating photoelectric
devices. This is due to the functional ZnO layer between
ITO and V2O5 to provide the effective routes for photogener-
ated carriers.
In conclusion, the transparent and flexible photodetec-
tors utilizing amorphous V2O5 thin films have been deve-
loped. The room temperature reactive sputtering was used to
fabricate ultrathin films of V2O5. The developed photodetec-
tor of the configuration V2O5/ZnO/ITO/PET showed a broad-
band (455 nm to 620 nm) photodetection with very high
detectivity (4  1012 Jones) values. The amorphous structure
of V2O5 material has been proposed for the fabrication of
fast reactive photodetectors. The photodetectors exhibited a
fast response time of 4.9, 12.7, and 16.1 ms for blue, green,
and red light, respectively. The linear dynamic range of the
photodetector was found to be 58 dB, 63 dB, and 59 dB for
blue, green, and red light, respectively. We have demon-
strated the broadband photodetection capabilities of V2O5
material with a wide linear dynamic range and fast operation.
We may suggest a low cost alternative to fabricate the
flexible and transparent photodetectors and energy devices
with distinctive characteristics.
The authors acknowledge the financial support of the
Incheon National University, Republic of Korea (2016-2074)
and Basic Science Research Program through the National
Research Foundation of Korea funded by the Korean
government (MSIP) (2010-0027963).
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