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Effect of oxygen flow ratio on the performance of RF magnetron sputtered Sn-

doped Ga2O3 films and ultraviolet photodetector

Article in Ceramics International · November 2022

DOI: 10.1016/j.ceramint.2022.11.251

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 Ceramics International 49 (2023) 10634–10644

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effect of oxygen flow ratio on the performance of RF magnetron sputtered

Sn-doped Ga2O3 films and ultraviolet photodetector
Chen Wang a, b, Wei-Hang Fan a, Yu-Chao Zhang a, Pin-Chun Kang c, Wan-Yu Wu d,
Dong-Sing Wuu e, Shui-Yang Lien a, b, f, *, Wen-Zhang Zhu a, c
a
School of Opto-electronic and Communication Engineering, Xiamen University of Technology, Xiamen, 361024, China
b
Fujian Key Laboratory of Optoelectronic Technology and Devices, Xiamen University of Technology, Xiamen, 361024, China
c
National Measurement and Testing Center for Flat Panel Display Industry, Xiamen Institute of Measurement and Testing, Xiamen, 361004, China
d
Department of Materials Science and Engineering, National United University, Miaoli, 36063, Taiwan
e
Department of Applied Materials and Optoelectronic Engineering, National Chi Nan University, Nantou, 54561, Taiwan
f
Department of Materials Science and Engineering, Da-Yeh University, Dacun, Changhua, 51591, Taiwan

A R T I C L E I N F O A B S T R A C T

Keywords: This work explored the properties of RF magnetron sputtered Sn-doped Ga2O3 films grown on sapphire substrates
Sn-doped Ga2O3 films at different oxygen flow ratios from 0.0 to 2.5%. The in situ optical emission spectroscopy was conducted to
RF magnetron Sputtering monitor the plasma radicals generated during the films’ deposition. All the films deposited at room temperature
Oxygen flow ratio
show amorphous structures with some nanoparticles. The deposition rate decreased monotonically with
Conductive mechanism
Ultraviolet photodetector
increasing oxygen flow ratio. The proposed conductive mechanism of the films can be mainly attributed to the
changes in the ratio of substitutional Sn (Sn4+ valance state) atoms replacing lattice Ga sites (Ga3+ valance state)
and the SnO2 phase in the films. Metal–semiconductor–metal solar-blind photodetectors were developed and
analyzed to illustrate the effect of oxygen flow ratio. A high performance photodetector with a low dark current
of 1.14 pA, high on/off ratio of 812 and short rise/decay time of 0.05 s/0.12 s was realized at an optimization
growth condition. The elaboration of the conductive mechanism and effect of oxygen flow ratio on the perfor­
mance of Sn-doped Ga2O3 films and their photodetectors is crucial for the preparation of high-quality Sn-doped
Ga2O3 films and its application in optoelectronic devices.

1. Introduction
Gallium oxide (Ga2O3) films as wide-bandgap oxide semiconductors
have garnered increasing research interest owing to their remarkable
physical, chemical, and photoelectrical properties, such as high thermal
stability and breakdown electric field [1,2]. Hence, Ga2O3 films have
been applied in many research fields, such as solar cells [3], solar blind
photodetectors (PDs) [4], high-power electronic devices [5],
light-emitting diodes [6] and gas sensors [7] and photocatalysis [8].
However, the poor conductivity of unintentional-doped Ga2O3 limits its
application in high-performance optoelectronic semiconductor devices.
The Ga2O3 bandgap and electrical properties can be modulated by
introducing shallow impurity levels [9]. Thus far, many dopants have
been adopted to be doped into Ga2O3 film, such as Al [8], Si [10], In
Ref. [11], and tin (Sn) [12]. Among these impurities, the Sn4+ ion has
been proven to be an excellent impurity to substitute Ga3+ for Ga2O3,
which introduces extra free electrons and improves conductivity [13,
14]. Further, the Sn4+ ion has a comparable ionic radius of 0.69 Å with
the Ga3+ ionic radius of 0.62 Å [15,16], which causes an insignificant
lattice expansion and improves the carrier mobility [17]. These advan­
tages will promote the performance of devices, such as photodetector
[17]. Many techniques have been used to prepare and explore the
properties of the Sn-doped β-Ga2O3, such as metal organic vapor-phase
epitaxy (MOVPE) [18], molecular beam epitaxy (MBE) [19], sol–gel
[20], metal organic chemical vapor deposition (MOCVD) [21], mist
chemical vapor deposition (mist-CVD) [22], pulsed laser deposition
(PLD) [23], and radio frequency magnetron sputtering (RFMS) [24]. The
methods, such as MBE, ALD, and MOCVD, can be good at achieving
high-quality Ga2O3 films; however, the used equipment is usually highly
expensive and displays a relatively slow film deposition rate; further,
their deposition area may be limited to relatively small value or they
involves dangerous chemical reactions [25,26]. Compared with other

* Corresponding author. School of Opto-electronic and Communication Engineering, Xiamen University of Technology, Xiamen, 361024, China.
E-mail address: sylien@xmut.edu.cn (S.-Y. Lien).

https://doi.org/10.1016/j.ceramint.2022.11.251
Received 18 August 2022; Received in revised form 12 October 2022; Accepted 20 November 2022
Available online 24 November 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
C. Wang et al.
Fig. 1. The photograph and structure description of the RF magnetron sputtering instrument and OES measurement.
methods, many studies [27,28] have reported that RF magnetron sput­
tering has the advantages of large-area uniformity, strong adhesion,
good repeatability, simple operation, precise controllability, no poi­
sonousness, non-polluting products, and cost effectiveness. Thus, it is a
good choice for Ga2O3 thin film preparation in the industry. The
acquirement of pure [29,30] and doped [31] Ga2O3 films using the
RFMS method under different deposition conditions has been exten­
sively researched. However, few studies [24,25] have investigated the
RFMS deposition process of Sn-doped Ga2O3 film. Kudou et al. [24]
prepared the Sn-doped Ga2O3 films using RFMS at room temperature
(RT) with a fixed working pressure of 2 Pa by introducing a 10%
O2/(O2+Ar) ratio. Subsequently, the films were annealed at 600 ◦ C and
900 ◦ C for 15 and 60 min, respectively. Two type of Sn content films of
0.6% and 1.5% were obtained. X-ray diffraction, scanning electron mi­
croscopy, and transmission spectrum were adopted to investigate
properties of the films. Vega et al. [25] studied the properties of Ga2O3
films using RFMS under various conditions, namely working gases,
deposition temperature and annealing temperature. The Sn-doped
Ga2O3 films with different Sn concentrations were fabricated by
co-sputtering Ga2O3 and Sn, which were analyzed using X-ray diffrac­
tion, and transmission spectrum. Ref. [24] and Ref. [25] did not argue
the influence of RFMS depositional conditions on the characteristics of
Sn-doped Ga2O3 films. Furthermore, to the best of our knowledge, no
report has used Sn-doped Ga2O3 films by RFMS to develop and inves­
tigate solar-blind photodetectors.
Herein, Sn-doped Ga2O3 films were developed using RFMS at RT
under various oxygen flow ratios. In situ optical emission spectroscopy
was performed to investigate the plasma radicals generated during the
deposition process. The impact of oxygen flow ratio on the character­
istics of the films was demonstrated and the conductive mechanism was
explored. The Sn-doped Ga2O3 films by RFMS were employed to
fabricate solar-blind ultraviolet photodetectors, which were analyzed
comprehensively.
2. Experiments
Sn-doped Ga2O3 films were developed on Al2O3(0001) substrates
using an in-line RF magnetron sputtering instrument modeled SP-122I
Ljuhv from Jhubei City in Taiwan. A mixed ceramic target of
Sn0.2Ga1.8O3 with 99.99% purity and 12.5 × 30.7 cm2 size was adopted
for the good performance of the conductive characteristics of the pre­
pared films [17,21]. Fig. 1 displays a photograph and structure
description of the RF magnetron sputtering instrument and optical
emission spectroscopy (OES) measurement. The RF magnetron sputter­
ing instruments mainly comprise a loading chamber, process chamber,
and unloading chamber, showing a linear arrangement. The process
chamber contains a heater and a deposition chamber. After a series of
cleaning processes [32], the sapphire substrates were loaded into the
deposition chamber immediately. The deposition chamber was pumped
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Ceramics International 49 (2023) 10634–10644
Table 1
Fabrication parameters of RFMS Sn-doped Ga2O3 films.
Parameter Value
Substrate Al2O3(0001)
Target Material Sn0.2Ga1.8O3
Back Pressure (Torr) 5.0 × 10− 7
Working Pressure (Torr) 9.0 × 10− 3
Sputtering Power (W) 500
Total Flow Rate (sccm) 40
Thickness (nm) ~110
Substrate Temperature (◦ C) RT
Oxygen flow ratio O2/(Ar + O2) (%) 0.0、0.5、1.0、1.5、2.0、2.5
to 5.0 × 10− 7 torr before films’ growth to avoid adventitious contami­
nation. The vertical distance between the target and the substrate was
maintained at 52 mm. The 9.0 × 10− 3 torr working pressure during the
growth and the substrate temperature at RT was controlled. The sput­
tering power was fixed at 500 W. Argon (Ar) gas and oxygen (O2) gases
with a high purity of 99.999% and total flow rate of 40 sccm were
introduced into the deposition chamber as working gases. The flow ratio
of O2/(O2+Ar) in the sputtering ambient was varied from 0.0% to 2.5%.
The deposition rate of the film was obtained by fixing the deposition
time to 30 min. Moreover, previous studies have reported that the
thickness of Ga2O3 films influences their properties [33,34]. Hence, to
eliminate the effect of thickness, the film thickness was controlled at
~110 nm by modulating the deposition time under various O2 gas ratios.
The detailed fabrication parameters of Sn-doped Ga2O3 film are tabu­
lated in Table 1.
The average thickness of Sn-doped Ga2O3 films were measured and
calibrated using a spectroscopic ellipsometer (SE) based on several
different test points. An in situ OES with a model of SD2048DL from USA
Verity instrument was used to monitor the real-time intensity of plasma
radicals during film deposition at a certain position, as shown in Fig. 1.
To collect the signal from the thin film accurately, the crystalline texture
of Sn-doped Ga2O3 films was presented by X-ray diffraction (XRD) using
a grazing incident mode. XRD patterns were obtained by selecting an
extremely low incident angle of 0.5◦ within a 2θ range of 10◦ –80◦ . The
surface morphology of the samples was presented by a combination of
high resolution field emission scanning electron microscopy (FESEM)
and atomic force microscopy (AFM). The equipment of X-ray photo­
electron spectroscopy (XPS) with a model ESCALAB 250Xi from USA
was used to investigate the chemical composition of the as-grown
samples. XPS measurements were performed without high-energy Ar+
pre-etching because some literatures [35–37] manifest it have a signif­
icant impact on the change in oxidation valence states in Ga2O3 film. For
XPS analyses, the size of the analyzed area was kept as 700 × 300 μm2 to
obtain the synthesis information of the sample accurately. The optical
bandgap was obtained by plotting a Tauc graph based on the ultra­
violet–visible transmission spectra of the films using a
C. Wang et al.
Fig. 2. The deposition rate of Sn-doped Ga2O3 film as a function of O2/(Ar +
O2) ratio.
spectrophotometer with a model of Lambda850 from USA PerkinElmer.
The resistivity, carrier concentration, and mobility of the films were
evaluated using the Hall Effect measurement (Ecopia HMS-5000, Korea)
with a four-probe method. The element profiles and Sn concentrations of
the film were obtained via time-of-flight secondary ion mass spectrom­
etry (TOF-SIMS) with a model ION-TOF TOF-SIMS V from Germany and
an analyzed area of 100 × 100 μm2. The metal–semiconductor–metal
(MSM) solar-blind PDs were developed using Sn-doped Ga2O3 films
deposited under various oxygen flow ratios. The current–voltage (I–V)
and transient response characteristics of the MSM PDs were obtained at
RT using a Keithley 4200 and an UV light source of 254 nm wavelength
with an incident optical power (Pin) of 3.34 × 10− 5 W.
Fig. 3. (a) In situ OES spectra during the deposition of Sn-doped Ga2O3 film at various O2/(Ar + O2) ratios. The detail of (b) Ga peaks and (c) O peak. (d), (e) and (f)
are the intensity of Ga, O and Ar plasma species as a function of O2/(Ar + O2) ratio, respectively.
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Ceramics International 49 (2023) 10634–10644
3. Results and discussions
The relationship between the deposition rate of Sn-doped Ga2O3
films and O2/(Ar + O2) ratio is shown in Fig. 2. The O2/(Ar + O2) ratio
had a strong effect on the deposition rate of the Sn-doped Ga2O3 film.
The deposition rate decreased with increasing O2/(Ar + O2) ratio from
32.7 nm/min to 14.4 nm/min monotonically. With the increasing ratio
of O2 gas in the working gases, a surface layer will be formed and
thickened owing to the enhanced chemisorption of oxygen on the
ceramic target [38]. The surface layer will hinder the sputtering process
yielding a decrease of deposition rate. Moreover, with increasing oxygen
content, the relative percentage of Ar gas was reduced corresponding to
the reduced excited Ar plasma species in the sputtering atmosphere. The
sputtering yield of oxygen is lower than that of Ar, affording a reduced
net sputtering rate [39,40]. Furthermore, the scattering effect [40] on
the Ar plasma species was enhanced by the increased oxygen molecules.
A similar phenomenon was observed in other reports [40,41].
To further study the deposition phenomenon, an in situ OES was used
to detect the intensity of the plasma radicals during the deposition of Sn-
doped Ga2O3 film under different O2/(Ar + O2) ratio from 0.0 to 2.5%,
as shown in Fig. 3 (a). From Fig. 3 (b), two Ga* emission lines located at
403.2 and 417.2 nm, which can be identified Ga plasma signals based on
other reports [42,43]. Further, a relative weak emission line at 777.1 nm
can be observed corresponding to the emission of O* [44], shown in
Fig. 3 (c). The rest of the emission lines can be defined from the Ar* and
Ar+ plasma species [45]. The symbols * and + represent excited neutral
radicals and cations, respectively. Moreover, no any Sn emission lines
are observed possibly owing to the extremely weak intensity of Sn
emission lines beyond the detection limits of the OES equipment. Ac­
cording to Fig. 3 (d)–(f), Ga and Ar peak intensities decrease with
increasing O2/(Ar + O2) ratio while the O peak intensity increases. This
can be due to the increase in the oxygen content, which reduces the
excited Ar plasma species in the sputtering ambient. These results are
consistent with the variation in the deposition rate shown in Fig. 2.
The crystal characteristics of the films deposited under different O2/
(Ar + O2) flow ratios were evaluated using XRD measurement, as shown
in Fig. 4. Almost no obvious diffraction signals are observed from it,
indicating that all the films are amorphous or may contain some
C. Wang et al. Ceramics International 49 (2023) 10634–10644

Fig. 4. XRD diffraction characteristics of the films grown at various oxygen
flow ratios.
nanocrystals but could hardly be detected using XRD. This can be due to
the low deposition temperature at RT, leading to insufficient energy
supplied during the growth process for the migration of surface ad-
atoms to form good crystalline phases [46].
The surface topography of the Sn-doped Ga2O3 films deposited under
different O2/(Ar + O2) ratios from 0.0% to 2.5% was investigated using
FESEM and AFM, as shown in Fig. 5 (a)-(f). A large number of clusters
and nanoparticles were found on the surface of all the prepared films
possibly owing to the large deposition power (500 W) adopted during
the film’s growth using RFMS. This causes the production of argon
plasma species with high energy to bombard the target and causes the
sputtering atoms to migrate to a suitable lattice position [47]. Similar
surface texture has also been reported in other literatures [39,47] that
were explained as the microcrystalline states of the film. Compared to
the Sn-doped Ga2O3 films deposited with the mixed introduction of
oxygen and Ar gases, the film deposited under a working gas of pure Ar
gas shows a smaller size of nanoparticles. This can be due to the fact that
the production of excited oxygen plasma may be more difficult than that
of Ga and Ar plasma [48]. The intensity of Ga and Ar plasma is stronger
than that of O, as demonstrated in Fig. 3 (d)–(f). Hence, the introduction
of oxygen into the chamber during deposition can supply some oxygen
to the film. Furthermore, in Fig. 5 (g), the cluster number along the
diagonal direction (the yellow dashed line) of the samples grown under
different oxygen flow ratios is counted, which increases from 33 to 46 pc
as the oxygen flow ratio increases from 0% to 1.0%. This may be because
of the incremental supply of oxygen to film nucleation during the

Fig. 5. FESEM and AFM graphs of the Sn-doped Ga2O3 film deposited under different O2/(Ar + O2) ratio: (a) 0.0%, (b) 0.5%, (c) 1.0%, (d) 1.5%, (e) 2.0%, (f) 2.5%.
(g) Variation in cluster number and (h) the surface roughness root mean square (RMS) with O2/(Ar + O2) ratio.

10637
C. Wang et al.
Fig. 6. (a) XPS full spectra scan, (b) atomic ratio of Ga, O, C, and Sn, and (c) the
Sn/Ga ratio of the Sn-doped Ga2O3 film prepared at different O2/(Ar +
O2) ratio.
deposition process. As the oxygen flow ratio increases continuously, the
cluster number reduces, which can be due to the reduced deposition
rate, affording a decremental number of nucleation sites. The root mean
square (RMS) of the surface roughness was obtained from AFM mea­
surements and is shown in Fig. 5 (h). The RMS of the film deposited
under 0.0% oxygen content shows the lowest value of 0.54 nm, which
increases sharply to 0.75 nm at 0.5%. Afterward, the RMS values slightly
increase with increasing oxygen content. The films became rougher after
introducing oxygen during deposition, which could be due to excess Ga
[48] compensated by oxygen, yielding more and larger size clusters.
XPS measurements were conducted to explore the integral chemical
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Ceramics International 49 (2023) 10634–10644
composition of the Sn-doped Ga2O3 films grown at different oxygen flow
ratios. The XPS full spectra scan are shown in Fig. 6 (a). The C 1s peak
with a binding energy of 284.8 eV was commonly adopted to be a
calibration peak to correct the XPS data. Ga, O, C, and Sn were observed
and their atomic ratios were extracted using the XPS fine spectra, as
displayed in Fig. 6 (b). The high percentage of C elements in the samples
can be due to the inevitable introduction from the external environment
because XPS tests were conducted without Ar+ pre-etching [36,37]. The
value of Sn atomic ratio varying in the range of 3.1%–3.7% is close to the
Sn content of ~4.4% in the Sn0.2Ga1.8O3 target. The impact of the ox­
ygen flow ratio on the percentage of Sn/Ga of the films was studied, as
shown in Fig. 6 (c). When only pure Ar gases are used to sputter the
target and deposit the film, the Sn/Ga ratio has a relatively high value of
~10.8% owing to the high energy and density Ar+ plasma. Thus, the Sn
and Ga atoms are easier to be sputtered from the ceramic target. The
excess Ga and deficient O atoms shown in the film yield a low ratio O/Ga
of ~1.15. Thus, extra oxygen is needed to compensate the excess Ga or
oxygen vacancies [12,48]. Afterward, once the oxygen was introduced,
the Sn/Ga ratio reduced to ~9.9% abruptly. This may be attributed to
the decrease of Sn and Ga sputter yield shown in OES. Although the yield
of Ga decreases, the intensity and number density of Ga plasma radicals
is excessive. With the continuous increase in oxygen content, the Sn/Ga
ratio progressively increases (~11.1% at 2.5% oxygen ratio). That may
be attributed to the following explanations. (1) Excess Ga and oxygen
vacancies are compensated by introduced oxygen, affording a relatively
reduced Ga atomic ratio; (2) the Sn bonding with oxygen (Sn–O) has a
larger bonding energy than Ga–O, yielding a higher Sn atomic ratio
[49]. Moreover, similar results were reported in previous literature [50].
The XPS spectra of the O 1s and Sn 3d core levels of the films pre­
pared under different oxygen contents were investigated in detail, as
displayed in Fig. 7 (a) and (b), respectively. From Fig. 7 (a), the O 1s
spectra of all the films can be resolved into three overlapping compo­
nents. The one component representing lattice oxygen (OL) bonding to
Ga atoms is varied in the binding energy range of 530.46–530.66 eV,
which is consistent with that in other reports [39,51,52]. The second
peak focusing in the scope of 531.06–531.5 eV denotes oxygen vacancy
(OV) [52–54], indicating lattice oxygen deficiency. The last one peak
located in the binding energy range of 531.93–532.48 eV demonstrates
the existence of surface chemisorptive oxygen groups (OS) on the film,
such as hydroxyl (H–O) and carbonate (C–O) species [51–55]. The
OL/(OL + OV + OS) and OV/(OL + OV + OS) ratios varying with oxygen
content were calculated, as exhibited in Fig. 7 (c). The lattice oxygen OL
ratio is ~64% of the film deposited in a pure Ar sputtering atmosphere,
which indicates the presence of non-lattice oxygen in the film and ox­
ygen deficiency in sputtering ambient. Correspondingly, OV and OS ra­
tios are 31% and 5%, respectively. Afterward, as the oxygen gas ratio
increases, the center position of O 1s gradually shifts to the lower
binding energy direction, which implies that the OL ratio rises contin­
uously. It is up to 73.6% for the film grown at 2.5% O2/(Ar + O2) ratio,
which may indicate the reduction percentage of OV with 10% as well as
improved Sn-doped Ga2O3 film quality. The main reasons for this may be
the enhanced compensation and oxidation of excess Ga [48,49].
The Sn dopant presenting in Ga2O3 film can display divalent Sn2+
and tetravalent Sn4+. The Sn 3d spectra were slightly broader, indicating
that the multiple oxidation valence states of Sn exist in the films. Hence,
from Fig. 7 (b), the Sn 3d spectra of all the films can be resolved into four
overlapping peaks, namely, Sn2+ 3d3/2, Sn2+ 3d5/2, Sn4+ 3d3/2, and Sn4+
3d5/2 oxidation valence states. The Sn4+ 3d3/2 and Sn4+ 3d5/2 valence
states are located in the binding energy range of 486.6–486.79 eV and
494.83–495.07 eV, respectively, which is related to the substitutional Sn
atom replacing the lattice Ga site [16,56]. The other two lower binding
energy components of Sn2+ 3d3/2 and Sn2+ 3d5/2 at 486 eV and
491.49–491.96 eV, respectively, can correspond to the incomplete
oxidation state of SnO [57,58]. The area ratio of Sn4+/(Sn2++Sn4+) was
calculated and plotted as a function of oxygen content, as shown in Fig. 7
(d). The Sn4+/(Sn2++Sn4+) ratio shows a low value ~44.7% of the
C. Wang et al.
Fig. 7. XPS spectral core level (a) O 1s, (b) Sn 3d, and the ratio of (c) OL and OV (d) Sn4+/(Sn4++Sn2+) of the films at various oxygen flow ratios.
Sn-doped film prepared in a pure Ar sputtering atmosphere, which
manifests the oxygen deficiency during the deposition. Hence, extra
oxygen should be introduced into the film. As the oxygen gas flow ratio
increases in the sputtering ambient, extra oxygen atoms can be incor­
porated into the films. Consequently, the Sn4+ percentages are promoted
because some Sn atoms of the SnO phase are transformed into the sub­
stitutional Sn atoms, replacing the lattice Ga site in the film. As the
oxygen content increases to 1%, the Sn4+/(Sn2++Sn4+) ratio rises to
~66%. Subsequently, it deceases monotonously to 57.5% as the oxygen
content increases to 2.5%, which may be contributed to the increase in
the Sn content and the limitation of Sn doping concentration in Ga2O3
film [16,55]. When the Sn content exceeds the limit, the proportion of
SnO phase will increase corresponding to the reduction of Sn4+ per­
centages and the deterioration of film quality.
The UV–Vis transmittance spectra of the Sn-doped Ga2O3 film grown
on a sapphire substrate under various oxygen flow ratios were measured
and are shown in Fig. 8 (a). The transmittance spectrum of the substrate
is used as a background baseline, which presents about 85% trans­
mittivity at the wavelengths from 300 to 800 nm. The band-to-band
transition of the absorption predicts a sharp decrease in the trans­
mittance in the UV wavelength. With increasing oxygen flow ratio, the
absorption cutoff edge shows blue shift to a shorter wavelength corre­
sponding to the increment of the band gap (Eg). The film deposited under
pure Ar sputtering ambient shows a lower transmittance than that ob­
tained by introducing extra oxygen, which may be attributed to the
reduced oxygen deficiency. Based on Fig. 8 (a), the Tauc graph of (αhν)2
vs hν has been plotted and displayed in Fig. 8 (b), α is the absorption
coefficient and hν is the incident photon energy. The Eg values were
worked out by extrapolating the linear part of the Tauc plot using the
formula [59] of (αhν)2 = κ(hν–Eg), where κ is a proportional factor. The
variation of the bandgap as a function of the oxygen flow ratio is
demonstrated in Fig. 8 (c). Further, the Eg values of the samples increase
continuously from 4.78 eV at 0.0% oxygen content to 4.86 eV at 2.5%.
The ratio of OV is coherent to the optical bandgap of the Ga2O3 films. The
oxygen deficiency can afford a reduced bandgap which will introduce a
series of defect energies below the minimum level of conduction band
[12,60]. Hence, with increasing oxygen flow ratio, the OL ratio rises to
improve the film quality and the oxygen deficiency is mitigated,
affording an increased bandgap.
All the films were investigated using SIMS measurement. The overall
distribution of O, Ga, Sn, H, C and Al elements in the Sn-doped Ga2O3
film grown on a sapphire substrate at 1.0% oxygen flow ratio is shown in
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Ceramics International 49 (2023) 10634–10644
Fig. 9. The thickness of the film is estimated to be ~112 nm, which is
consistent with the test result of SE. The high intensity of the C element
present in the film surface can be due to the inevitable introduction of
the polluted components from the external environment. Sn, O, and Ga
elements show a uniform distribution in Sn-doped Ga2O3 film. More­
over, some percentage of H element distributed uniformly in the film
that may act as a donor impurity in Ga2O3 film [62].
The carrier concentration, activation rate, resistivity and mobility of
the Sn-doped Ga2O3 films as a function of O2 flow ratio have been
depicted in Fig. 10. All the prepared films display an n-type conductive
characteristic. With increasing oxygen flow ratio, the carrier concen­
tration increases first and then declines (Fig. 10 (a)). When the oxygen
flow ratio is 1%, the carrier concentration reaches its maximum value.
Based on the SIMS and Hall-effect measurements, the activation ratios of
Sn in Ga2O3 have been calculated and are equal to the ratio of the Hall
carrier concentration with Sn concentration, which shows a variation
trend similar to that of the carrier concentration, as shown in Fig. 10 (a).
The Sn concentrations extracted by SIMS of the films under various O2
flow ratios are 7.04 × 1018, 6.21 × 1018, 6.23 × 1018, 6.28 × 1018, 6.27
× 1018, and 6.84 × 1018 cm− 3. Correspondingly, the Sn activation ratio
is 1.56%, 2.31%, 4.45%, 4%, 2.5%, and 2.01%, respectively, which is
limited to a low level. It is close to the Sn doping ratio of 0.2%–3.8% in
the Ga2O3 films grown via the MOVPE and Mist-CVD [18,22] process
with an Sn concentration over 1020 cm− 3. However, it is much less than
the doping ratio obtained using the PLD and MBE [23] processes of
41.1%–68.5%. This indicates a considerable compensation and/or
electrically inactive incorporation of Sn. The low activation ratio can be
contributed to the Sn-doped Ga2O3 films deposited at RT with an
amorphous nature. Hence, to achieve a high activation ratio, the
deposition temperature should be increased or a post-activation
annealing is needed to crystallize the film and activate the Sn dopants.
Form Fig. 10 (b), by contrast, the change law of resistivity with ox­
ygen flow ratio shows a completely inverse trend, which may be
attributed to its close and dominant relation with the carrier concen­
tration. However, the mobility shows a similar trend with the carrier
concentration, as displayed in Fig. 10 (b). To clarify the change rule in
Fig. 10, a diagram of the conductive mechanism of Sn-doped Ga2O3 film
has been plotted and analyzed in Fig. 11. Firstly, several studies [61–64]
have investigated the role of OV in Ga2O3 film and found that the OV are
a deep donor and not an ideal donor dopant. For example, Varley et al.
[62] demonstrated that OV could not explain the n-type conductivity
property shown in Ga2O3 films because they are a deep-level donors
C. Wang et al. Ceramics International 49 (2023) 10634–10644

Fig. 9. SIMS data of the Sn-doped Ga2O3 films grown at 1% oxygen flow ratio.

Fig. 8. (a) The transmittance spectra, (b) the Tauc plot of (αhν)2 vs hν, and (c)
the bandgap of the films deposited under various oxygen flow ratios.

with extremely large ionization energies of 1 eV. The weak n-type

conductivity of the film may be attributed to the background and un­
intentional introduction of impurities such as hydrogen (H) and Si in the
film, confirmed by the SIMS measurement. Fig. 11 (a) denotes the ox­
Fig. 10. (a) Carrier concentration, activation ratios and (b) resistivity, mobility
ygen deficiency state of the film when the oxygen flow ratio is less than
of the Sn-doped Ga2O3 films as a function of O2 flow ratio.
1.0%. In this region, the films had a large number of OV with a relatively
low ratio of OL and Sn4+ valence state. Moreover, most of the Sn atoms
exist in SnO phase that cannot provide free electrons to contribute the
conduct electricity of Sn-doped Ga2O3 film. Besides, the substitutional

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Fig. 11. Schematic of the conductive mechanism of Sn-doped Ga2O3 film under (a) oxygen deficiency; (b) moderate oxygen content; (c) excess oxygen content.

Fig. 12. (a) Schematic of the fabricated MSM PD. The I–V characteristics without (b) and with (c) illumination of PDs as a function of O2 flow ratio. (d) The
multiperiod of the transient responses of the PDs with various O2 flow ratios.

Sn (Sn4+ valance state) atom replacing the lattice Ga sites (Ga3+ valance
state) will provide one extra electron, acting as mobile conduction
electrons to promote the electric property for the film. The SnO2 phase
will also improve the electricity conduction. When extra oxygen gases
were introduced into the film deposition, the oxygen vacancy defects
were suppressed and many SnO phases were transformed into Sn-doped
Ga2O3 or SnO2 phases of the film. Consequently, the carrier concentra­
tion increases and resistivity decreases with the increment of oxygen
flow ratio from 0.0% to 1.0% because of the improved film quality and
the increased ratio of the Sn4+ state, as shown in Fig. 11 (b). However, as
the oxygen flow ratio increases continuously beyond 1.0%, the ratio of
Sn4+ valence state reduces corresponding to the decreased number of
substitutional Sn atoms or SnO2 phase. This may be due to the reactions
of Sn-doped Ga2O3 with oxygen gases transformed into SnO2 and Ga2O3
[65]. Further, SnO2 reacts with Sn to generate SnO [66], as shown in
Fig. 11 (c). Both of them lead to the reduction ratio of Sn-doped Ga2O3
and SnO2 phases, which will degrade the conductive property of the
film. Matsuzaki et al. [67] also reported that the Sn-doped Ga2O3 films
were insulating at high oxygen pressure because the Sn dopant was
deactivated by excess oxygen. The variation of mobility in the Sn-doped
Ga2O3 films with O2 ratio is shown in Fig. 10 (c). The mobility increases
with the oxygen flow ratio from 0.0% to 1.0% primarily due to the
improvement in film quality. Subsequently, it reduces with the oxygen
flow ratio from 1.0% to 2.5%.
To study the effect of the oxygen flow ratio on film properties, the
MSM PDs were developed and a diagram is depicted in Fig. 12 (a). The
PDs own 10 pairs of interdigitated electrodes with a 200-nm-thick
aluminum (Al) layer in contact with the film surface. The size of the
PD was 2000 μm wide and 2200 μm long. The length, width, and spacing
of the electrode fingers are 900, 100, and 100 μm, respectively. Fig. 12
(b) and (c) describe the dark current and photocurrent of the Sn-doped
β-Ga2O3 PD at a bias voltage from − 5 to 5 V. The dark current (Id) at − 5
V bias of the PD prepared using the Sn-doped β-Ga2O3 film deposited
with 0.0% oxygen flow ratio is 4.89 pA, which decreases continuously
with increasing oxygen flow ratio and reduces to an extreme value of
~1.14 pA at 1.0% oxygen flow ratio. This may be due to the reduced
density of oxygen vacancy defects in thin films confirmed using XPS and
the improved film quality [20,55,68,69] with increasing oxygen flow
ratio despite more Sn atoms turning into effective donors. Further, the
dark current increases with the oxygen flow ratio (1.5%–2.5%), which
may be due to the formation of increasing SnO phases [65,66]. A similar
change law was observed in photocurrent (Iopt). During the illumination
process, many electron–hole pairs will be generated and collected by the
electrodes, which affords a decrease of the Schottky barrier height. The

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Table 2 Declaration of competing interest

Characteristic parameters of the PDs with various O2 flow ratios.
O2 flow ratio Id (pA) Iopt (nA) Iopt/Id R (μA/W) tr (s) td (s) The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
0.0% 4.89 2.93 598 87.6 0.1 0.25
0.5% 1.74 1.06 606 31.6 0.07 0.2 the work reported in this paper.
1.0% 1.14 0.93 812 27.8 0.05 0.12
1.5% 28.5 1.36 47.8 40 33.07 0.89 Acknowledgments
2.0% 59.4 19.3 325 576 36.65 3.93
2.5% 66.2 27.7 419 829 38.68 3.98
This work is sponsored by the National Natural Science Foundation
of China (No.61904155), the Science and Technology Project of Xiamen
ratio of Iopt/Id of PDs was computed at the same bias at − 5 V. The PD (No. 3502ZCQ20191002), the Natural Science Foundation of Fujian
with an oxygen flow ratio of 1.0% presented the largest Iopt/Id ratio of Province (Nos. 2018J05115, 2020H0025, 2020J01298 and
812. All the Id, Iopt, and Iopt/Id ratios of the PDs with various oxygen flow 2020J05239), the scientific research projects of Xiamen University of
ratios from 0% to 2.5% are tabulated and shown in Table 2 at a bias Technology (Nos. YKJ19001R, 30319003, and YKJCX2020078), the
voltage of − 5 V. The improved quality of the film yields a superior Science and technology project of Fujian Provincial Department of Ed­
photoelectric characteristic because of its low density of oxygen defects. ucation (No. JAT200484), and the Xiamen Scientific Research Start-up
Moreover, the responsibility (R) of PDs was calculated by deducing the Foundation for the Returned Oversea Chinese Scholars (No.
ratio of (Iopt− Id)/Pin at − 5 V bias and shown in Table 2. The change of R 5010320004). This study is also sponsored by Fujian Association for
is the same as Iopt and Id with the variation of oxygen flow ratios. Science and Technology.
The multi-period of the transient responses was investigated to
explore the stability of the photodetectors with various O2 ratios. Fig. 12 References
(d) depicts the time-dependent photoresponse of all the photodetectors
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