Materials Science in Semiconductor Processing 98 (2019) 19–28

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Materials Science in Semiconductor Processing

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Effects of Sn doping on the optoelectronic properties of reactively T

evaporated In4Se3 thin films
R. Anuroop∗, B. Pradeep
Solid State Physics Laboratory, Department of Physics, Cochin University of Science and Technology, Kochi, 22, Kerala, India

ARTICLE INFO ABSTRACT

Keywords: Polycrystalline In4Se3: Sn thin films are prepared on glass substrate by reactive evaporation under a vacuum of
Sn doped In4Se3 thin films 10−5 mbar. The characterizations of the samples are done using XRD, FESEM, XPS and UV-Vis-NIR spectro-
Reactive evaporation photometer. The optical band gap shift of the sample, above the carrier concentration of 1.833 × 1017 cm−3, is
Burstein-moss effect well described by Burstein-Moss model. The resistivity of the samples is found to decrease as a result of Sn
incorporation. Our results show that in all samples, impurity scattering and lattice vibration scattering are the
main factors affecting the electrical properties. Photoconductivity studies at room temperature show that visible
photoresponsivity of the films increases with increase in Sn concentration. These improvements in optoelec-
tronic properties facilitate the usefulness of such films in device applications.

1. Introduction evaporation of In1-ySey (with 0.49 ≤ y ≤ 0.62) polycrystalline material

The growth and characterization of group III-VI compound semi-
conductors have been attracting much interest due to their potential
applications in photovoltaic, optoelectronic and thermoelectric devices.
Among them indium selenide (InxSey) attracts considerable attention.
InxSey exists in wide range of stoichiometric compositions such as InSe,
In2Se3, In4Se3, In5Se7, In6Se7 and In9Se11 [1]. Among them InSe and
In2Se3 are studied extensively due to their favorable optoelectronic
properties that are useful for the fabrication of photovoltaic devices
[2,3], solid-state batteries [4], switching devices [5,6], memory devices
[7], catalysts for hydrogen evolution reaction [8], photodetector ap-
plications [9,10], gas sensing [11] and Schottky diodes [12,13]. Duman
et al. studied schottky contact behavior in n-InSe(:Sn) and reported an
abnormal decrease in barrier height with decrease in temperature [14].
InSe is an interesting material for nanoelectronics due to its direct band
gap [15] and high mobility of charge carriers [16]. Even though ultra-
thin flakes of InSe are ambient stable [17], the exfoliated InSe nano
sheets are susceptible to rapid degradation in ambient conditions. This
will limit the use of InSe for device applications. Recently this problem
is rectified using seeded ALD alumina encapsulation [18]. In4Se3 is a
stable phase of indium selenide [1], but few reports are available on the
preparation and characterization. One of the difficulties encountered
during the preparation is the coexistence of different phases in a single
film. Several authors have reported the presence of In4Se3 phase with
InSe [19,20]. Julien et al. prepared In4Se3 thin films using flash
and studied the structural and electrical properties by varying Se/In
ratio [21]. Benramdane et al. studied the optical properties of flash
evaporated In4Se3 thin films in the far infrared spectrum [22]. Khu-
sayfan et al. reported the fabrication of Au/In4Se3/Ga2S3/C field effect
transistor [23]. Thermoelectric properties of In4Se3 compound have
also been reported by many research groups [24–27].
Literature survey shows that the effects of Sn doping on the op-
toelectronic properties of In4Se3 thin films are not investigated yet.
Here we report the preparation and characterization of In4Se3 and Sn
doped In4Se3 thin films by reactive evaporation technique, a variant of
Günther's three temperature method. With proper experimental con-
ditions, In4Se3: Sn thin films having extreme purity are obtained in this
way. Optoelectronic properties and room temperature photo-
conductivity in the films are investigated and the results are reported.
2. Materials and methods
Thin films of In4Se3 and Sn doped In4Se3 are prepared by reactive
evaporation, a variant of Günther's three temperature method [28].
Using reactive evaporation technique, polycrystalline thin films with
excellent reproducibility can be obtained, which is useful for fabricating
high efficiency solar cells. The detailed experimental procedure of thin
film deposition by reactive evaporation has been described elsewhere
[29]. Briefly, high purity indium (99.999%) and selenium (99.99%) are
evaporated simultaneously from two resistively heated sources at an

∗
Corresponding author.
E-mail address: anuroop@cusat.ac.in (R. Anuroop).

https://doi.org/10.1016/j.mssp.2019.03.020
Received 31 December 2018; Received in revised form 22 February 2019; Accepted 17 March 2019
1369-8001/ © 2019 Elsevier Ltd. All rights reserved.
R. Anuroop and B. Pradeep
Table 1
Impingement rate of In, Se and Sn in the prepared samples.
Name Impingement rate (atoms cm−2 s−1)
In Se Sn
15 15
Sample A 2.7 × 10 2.0 × 10 –
Sample B 1.18 × 1014
Sample C 2.23 × 1014
optimized deposition rate. The deposition is performed at a pressure of
10−5 mbar on to the glass substrate kept at 548 ± 5 K. To prepare Sn
doped In4Se3 thin films, high purity Sn (99.999%) is evaporated si-
multaneously from another resistively heated source during the de-
position of indium and selenium. By controlled evaporation, Sn dopants
can be uniformly dispersed in the crystal lattice of In4Se3 [30]. The
optimized deposition conditions used in the present work are given in
Table 1. For convenience the prepared samples are named as Sample A,
Sample B and Sample C respectively. Sample A is undoped In4Se3.
Samples B and C are Sn doped In4Se3. To prepare Sample B, mass of Sn
taken is 5 wt% of In and to prepare sample C, mass of Sn taken is 10 wt
% of In.
X-ray diffraction patterns are recorded in the range 2θ = 5°–60° by
Bruker AXS D8 advance X-ray diffractometer with Cu Kα
(λ = 1.5406 Å) radiation as source. The composition and the oxidation
states of individual element in the samples are analyzed by Kratos
Analytical AMICUS X-ray photoelectron spectrometer fitted with Mg
Kα/Al Kα dual anode X-ray source. Using Carl Zeiss Sigma Field
Emission Scanning Electron Microscope, the surface morphology of the
samples is analyzed. The optical transmission spectra of the prepared
samples are recorded using JASCO V 570 UV-Vis-NIR spectro-
photometer in the wavelength range 2500 nm to cutoff. Using APLAB
1015 digital multimeter, the photocurrent in the samples are measured.
A quartz halogen tungsten filament lamp (12 V, 100 W) is used as the
source of illumination. The variations of dc conductivity with tem-
perature of the samples are studied in a conductivity cell at a pressure
of 10−2 mbar. The measurements are done at the interval of 5 K for
three continuous heating cooling cycles using dc two probe method.
The thickness of the film ∼ 300 nm is measured by Veeco Dektak 6 M
Stylus Profiler. Hall measurements in the prepared samples are done
using Ecopia HMS-3000 system.
3. Results and discussion
3.1. Structural studies
X-ray diffraction patterns of In4Se3: Sn thin films with different Sn
concentrations are shown in Fig. 1.
A comparison of the d-values calculated from XRD pattern with
standard powder diffraction data (JCPDS card No: 00-051-0808) is
shown in Table 2.
Matching of the diffraction lines with the standard pattern of In4Se3
confirms that all prepared samples are polycrystalline with orthor-
hombic crystal structure. XRD pattern of undoped In4Se3 thin film
shows peak corresponding to (330), (040), (431), (820) and (930)
planes. The lattice parameters for undoped sample a = 15.31 Å,
b = 12.43 Å and c = 4.16 Å calculated from X-ray diffraction data are
in agreement with the reported values [31]. Peaks of Sn or Sn com-
pounds are not detected even in log-scale intensity, which indicates that
Sn dopants are incorporated in the In4Se3 lattice. A decrease in the
intensity of the peak corresponding to (040) plane and absence of re-
flections from (431) and (820) planes in Sample C is probably due to the
strain and lattice disorder induced in the In4Se3 lattice due to the en-
hanced incorporation of Sn at the In sites, which indicates that Sn
doping slightly disturbed the crystal structure of In4Se3.
To check whether doping resulted in textured growth, the texture
20
Materials Science in Semiconductor Processing 98 (2019) 19–28
Fig. 1. X-ray diffraction patterns of In4Se3: Sn thin films along with JCPDS data.
behavior of the films is investigated by calculating Harris texture
coefficient (Tc) [32]. Tc is given by
Im (hkl)/I0 (hkl)
Tc (hkl) = n
n
I (hkl)/ I0 (hkl) (1)
1 m
where Im (hkl) is the observed relative intensity of the peak corre-
sponding to (hkl) plane, I0 (hkl) is the relative intensity of the same peak
in the standard powder diffraction file and n is the total number of
diffraction peak selected for calculation. When Tc (hkl) 1, the sample
possess random orientation and a value > 1 means preferential or-
ientation of the (hkl) plane [33]. Using equation (1), Tc (hkl) is calcu-
lated in all prepared samples. Five diffraction peaks {(330), (040),
(431), (820) and (930)} are chosen in Sample A, Sample B and three
diffraction peaks {(330), (040) and (930)} are chosen in Sample C.
I0 (hkl) in all samples are obtained from the standard pattern (JCPDS
Card No: 00-051-0808). The obtained values of Tc (hkl) are given in
Table 3.
The results indicates that Sample A and Sample B composed of (330)
and (040) texture components. It is seen that at higher doping con-
centration (sample C) Tc (040) significantly decreased. Thus it can be
concluded that higher doping concentration of Sn caused preferential
orientation of In4Se3 along (330) direction.
To study the influence of Sn doping on the structural properties, we
determined the average crystallite size and microstrain in the sample
using Williamson-Hall plot, which is a simple method to separate the
contribution of crystallite size and microstrain to the line broadening in
the XRD pattern [34]. Williamson Hall equation is given by
K
cos = + 4 sin
D (2)
where K is the shape factor (K =0.9), is the wavelength of X-ray, is
the full width at half maximum in radians, is the Bragg angle, D is the
crystallite size and is the microstrain [35]. Plots are drawn by taking
sin along x-axis and cos along y-axis, as shown in Fig. 2. Crystallite
size and strain present in the sample are determined from the intercept
and slope of the linear fit made to the experimental data points. Dis-
location density ρ in the prepared samples are determined using = 2
1
D
. The results are shown in Table 4.
An increase in the density of dislocations with increase in the do-
pant concentration indicates the formation of shallow donor levels as a
result of Sn doping. The decrease in crystallite size value with increase
in Sn concentration may be caused by the enhanced incorporation of Sn
ions into the In4Se3 lattice.
R. Anuroop and B. Pradeep Materials Science in Semiconductor Processing 98 (2019) 19–28

Table 2
Comparison of the observed ‘d’ values from XRD data with standard ‘d’ values.
Name d330 (Å) d040 (Å) d431 (Å) d820 (Å) d930 (Å)

Observed Std. Observed Std. Observed Std. Observed Std. Observed Std.

Sample A 3.19 3.20 3.11 3.08 2.33 2.31 1.82 1.83 1.58 1.57
Sample B 3.19 3.20 3.11 3.08 2.33 2.31 1.82 1.83 1.58 1.57
Sample C 3.19 3.20 3.12 3.08 – – – – 1.58 1.57

Table 3
Texture coefficients of the prepared samples from XRD data.
Name Tc (330) Tc (040) Tc (431) Tc (820) Tc (930)

Sample A 2.21 2.26 0.17 0.08 0.28

Sample B 2.21 2.23 0.18 0.09 0.29
Sample C 2.12 0.64 – – 0.24

3.2. Morphological analysis

Fig. 3 shows field emission scanning electron microscope (FESEM)

image of In4Se3: Sn thin films at 25 KX magnification. It is seen that the
films consist of irregularly shaped grains with well-defined grain
boundaries. Sample C shows more densely packed grains over the film
surface.
From the FESEM images, the average value of particle size obtained
is 295 nm, 175 nm and 168 nm for Sample A, Sample B and Sample C Fig. 2. Williamson-Hall plot of the prepared samples.
respectively.

Table 4
3.3. Electrical studies
Structural parameters of In4Se3: Sn samples from X-ray diffraction analysis.

Electrical properties of the prepared samples are investigated at Name D (nm) ε ρ (lines m−2)

room temperature using Hall measurement technique carried out under
van der Pauw geometry. The results are shown in Table 5.
The data indicates that both undoped and Sn doped sample contains
n-type carriers. As the dopant concentration is increased, the mobility
increases slightly and the resistivity decreases. In addition, Hall mea-
surements show that Sn doped In4Se3 has a carrier concentration almost
one order higher than that of the undoped sample. These results con-
firm that the incorporated Sn atoms replaced some In atoms and acted
as electron donors in In4Se3 lattice. The temperature dependence of dc
conductivity of In4Se3: Sn samples in continuous heating cooling cycles
are shown in Fig. 4.
Shape of the curves indicates that in the measured temperature
range all samples show semiconducting nature and follows thermally
activated Arrhenius conduction mechanism. From the slope of the
heating cooling curves, the activation energy of the charge carriers
responsible for the electronic transport is obtained (Table 6).
Decrease in activation energy with increase in dopant concentration
clearly indicates the formation of new donor levels nearer to the con-
duction band. To find the effect of grain boundary scattering on the
transport properties, the mean free path of electrons l in In4Se3: Sn films
are determined using [36].
h 3N 1/3
l= µ Deconvoluted XPS spectrum of In 3d5/2 in the samples contain main
2e
Here h is the Planck's constant, N is the free carrier concentration, μ is
the mobility and e is the charge of electron. The l values corresponding
to different dopant concentrations are given in Table 7.
In all prepared samples, the mean free path is much lower compared
to the crystallite size obtained from structural studies. This means that
grain boundary scattering is not dominant in these samples [36].
Sample A 42 1.25 × 10−3 5.67 × 1014
Sample B 37 1.34 × 10−3 7.31 × 1014
Sample C 27 2.49 × 10−3 1.37 × 1015
Therefore main factors affecting the electrical properties in the present
case are lattice vibration scattering and impurity scattering [37].
3.4. XPS analysis
XPS analysis is performed to study the mechanism responsible for
the change in electrical properties of Sn doped In4Se3 thin films.
Figs. 5–7 shows full scan XPS survey spectra and high resolution XPS
spectra of In 3d, Se 3d, Sn 3d and O 1s in the prepared samples.
To find out the atomic composition, elemental analysis is performed
using the XPS data. The results are shown in Table 8.
Elemental analysis shows that undoped In4Se3 sample is Se-rich. To
determine the oxidation states of individual elements present in the
samples, the spectral data are further analyzed (See Figs. 5–7 and Fig.
S1 of the supplementary material). The obtained binding energies from
In 3d5/2, Sn 3d5/2, Se 3d and O 1s core-level photoelectron spectra in
the samples are shown in Table 9.
(3)
peaks at 444.11–444.24 eV (corresponds to In0 [38]) and
444.92–445 eV (assigned to In+ in InBr [39]. The binding energy of Se
3d at 53.71–53.78 eV confirms the existence of Se2− in the prepared
samples [40]. This suggests that In4Se3 crystal structure contains
bonding of atoms with mixed valency [41]. The deconvoluted XPS
spectrum of Sn 3d5/2 in the doped samples are at 484.27–484.46 eV
(Sn0 [42]), 485.61–485.69 eV (Sn2+ [43]) and 486.27–486.43 eV (Sn4+

21
R. Anuroop and B. Pradeep Materials Science in Semiconductor Processing 98 (2019) 19–28

Fig. 3. FESEM image of (a) Sample A, (b) Sample B and (c) Sample C.

Table 5
Hall measurement results in In4Se3: Sn thin films.
Name Resistivity ρ (Ω cm) Mobility μ (cm2 V−1s−1) Carrier concentration N (cm−3) Carrier type n or p

16
Sample A 59.56 2.08 5.025 × 10 n
Sample B 16.26 2.34 1.640 × 1017 n
Sample C 3.11 2.84 7.077 × 1017 n

Substances on the contamination layer like H2O, CO2, O2 etc. can be

Fig. 4. Variation of ln(I) versus 1000/T of the prepared samples.
[44]). These results indicate the presence of mixed valence states of Sn
in the crystal lattice of In4Se3.
It is commonly observed that there exists a contamination layer on
the surface of the film prepared by physical vapor deposition [45].
adsorbed on the film surface. It is proved that the adsorption of water
molecule on the surface of indium selenide is dissociative. The energy
for dissociation of water molecule is greatly reduced by the presence of
defects [16]. Usually indium selenide has Se-vacancies. But since the
current sample is Se-rich, the dominant defect is SeIn [46]. The high
resolution O 1s analysis can be used to identify the water related sur-
face states (hydroxyl groups) and oxide (O2−) species in the prepared
samples [47]. High resolution O 1s spectra of undoped sample (Sample
A) contains peak at 531.5 eV. This is assigned to hydroxide species
(OH−) [48–50]. The deconvoluted XPS spectrum of O 1s in Sn doped
samples B and C contains two peaks. A lower peak with binding energy
ranging from 529.50 eV to 529.81 eV (Assigned to oxide (O2−) species
[48–50]) and a higher peak with binding energy ranging from
531.23 eV to 531.54 eV (Assigned to hydroxide species (OH−)
[48–50]). A small fraction of O2− in Sn doped samples indicates that
some Sn4+ dopants in the lattice formed SnO2 during film growth
process. Here the lattice oxygen comes from the residual gases in the
vacuum chamber during film preparation. The lower concentration of
O2− in the lattice is due to the fact that the deposition is done at
10−5 mbar pressure. Also the absence of In3+ peak in all samples
suggests that In2O3 is not formed during film growth. Sn4+ or Sn2+
occupying at In+ sites in In4Se3 (SnIn3+ or SnIn+) can act as active
donors. As the dopant concentration is increased, the concentration of
Sn ions in In4Se3 lattice is increased, which leads to an increase in n-
type carrier concentration. These are in good agreement with the

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R. Anuroop and B. Pradeep Materials Science in Semiconductor Processing 98 (2019) 19–28

Table 6 concentration in the film with doping [53]. So the refractive index of
Variation of dc activation energy with the sample can be controlled by Sn doping concentration. It can be seen
doping. that the extinction coefficient k of all samples decreases gradually with
Name Ea (eV) increase in wavelength. This indicates that the transparency of the film
increases as the wavelength increases, which are evident from the
Sample A 0.22 transmission spectrum. The optical band gap of In4Se3: Sn samples are
Sample B 0.20
determined using Tauc's relation [54] given by
Sample C 0.14
( h ) = A (h Eg )r (4)

Table 7 where α is the optical absorption coefficient, hν is the photon energy, Eg

Variation of mean free path of the prepared
samples with doping.
Name l (nm)
Sample A 0.016
Sample B 0.026
Sample C 0.052
previous results from Hall measurements.
3.5. Optical studies
Fig. 8 shows the optical transmission spectrum of In4Se3: Sn thin
films.
The formation fringes in the transmission spectrum indicate that the
deposited films are uniform with good surface homogeneity [51]. The
variation of absorption coefficient α of the prepared samples with wa-
velength is shown in the inset of Fig. 8. All prepared samples show high
optical absorption coefficient (α > 0.5 × 105 cm−1) in the visible re-
gion. Using Swanepoel's method [52], the refractive index n and ex-
tinction coefficient k of In4Se3: Sn films at different doping levels are
determined. This is illustrated in the inset of Fig. 9.
It is observed that the refractive index of In4Se3 thin film decreases
with increasing doping level. This is due to the increase of free carrier
is the optical band gap energy and r is the number which determines the
type of transition. A good fit to the data points obtained for r = 1/2
suggests direct allowed transition in the prepared samples. The optical
band gap of the samples are determined by extrapolating the linear
section of (αhν)2 versus hν curve to the energy-axis where α = 0
(Fig. 9). The determined band gap of In4Se3 film is found to be equal to
1.68 eV, which agrees with the direct band energy of single crystal
In4Se3 [31]. The effective mass of the charge carriers in the prepared
samples are evaluated from the values of n and k using the relation
[55].
Ne 2
1 =
m0 2 (5)
where 1 = n2 k2 , is the relative dielectric constant of the medium
at very high frequencies, N is the free carrier concentration, 0 is the
permittivity of free space, m is the effective mass of free carriers and
is the angular frequency of the infrared radiation. Fig. 10 shows the
variation of 1 vs 2 of the prepared In4Se3: Sn samples.
From the slope of the curves shown in Fig. 10 and using the value of
N from Hall measurements, the effective mass of electron m in the
prepared samples is determined. It is found to be 0.032m0, 0.036m0,
0.045m0 for Sample A, Sample B and Sample C respectively. Here m0 is
the rest mass of electron. Since the effective mass is almost independent
of carrier concentration, it can be assumed that the shape of the con-
duction band of In4Se3 is parabolic [56]. Using m = 0.0377m0 (average

Fig. 5. (a) Full scan XPS survey spectrum of Sample A. High resolution XPS spectra of (b) In 3d (c) Se 3d and (d) O 1s in sample A.

23
R. Anuroop and B. Pradeep
Fig. 6. (a) Full scan XPS survey spectrum of Sample B. High resolution XPS spectra of (b) In 3d (c) Se 3d (d) Sn 3d and (e) O 1s in sample B.
value of effective mass determined), the conduction band critical den-
sity Nc in In4Se3 thin film is determined using the relation [37].
3/2
2 mkT
Nc = 2
h2
The obtained value of Nc is 1.833 × 1017 cm−3. When the carrier
concentration increases above Nc, the lowest states in the conduction
band will commence to fill with electrons [57]. This give rise to an
increment in the energy gap (Burstein-Moss shift) given by Ref. [58].
h2N 2/3
E=
8 2/3m
Hall measurement results shows that the carrier concentration N of
Sample C is greater than conduction band critical density Nc. The value
of ΔE calculated for this sample using equation (7) is 0.037 eV. Optical
studies show that the band gap energy in Sample C is blue shifted by
0.04 eV, which is consistent with Burstein-Moss theory of band filling.
Materials Science in Semiconductor Processing 98 (2019) 19–28
3.6. Photoconductivity studies
The photoconductivity of In4Se3: Sn samples are studied using two
probe method. For ohmic contact, silver paste is applied on the film
(6) surface with an illumination area of 1 cm2. A constant bias of 10 V is
applied across the film surface to stabilize the current. After the stabi-
lization period, the current values are recorded in the following se-
quences. 60 s in dark, 60 s under illumination and 60 s in dark. The time
evolution of photoconductivity of In4Se3: Sn films are shown in Fig. 11.
It is observed that when the samples are exposed to light, the
photocurrent increases rapidly and reaches to a saturation value. The
conductivity is found to decay rapidly when the light is switched off. In
(7) the present case photoconductivity decay follows exponential law with
decay time constant τd. Photoconductivity decay of the prepared sam-
ples is shown in the inset of Fig. 11. The decay time constant τd is
evaluated from the exponential fit to the experimental data points
(represented as solid red curve). The photosensitivity S in the samples
is determined using the relation
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R. Anuroop and B. Pradeep Materials Science in Semiconductor Processing 98 (2019) 19–28

Fig. 7. (a) Full scan XPS survey spectrum of Sample C. High resolution XPS spectra of (b) In 3d (c) Se 3d (d) Sn 3d and (e) O 1s in sample C.

Table 8 I
S =
Elemental composition of In4Se3: Sn samples from XPS analysis. Idark (8)
Name Atomic compositions (at%)
where I = Ilight Idark . The amount of photocurrent generated per unit
In Se Sn time/unit illumination intensity will give the Photoresponsivity R of
the material [59].
Sample A 56.26 43.74 0
Sample B 54.89 43.44 1.67
Sample C 55.43 42.12 2.45 I
R =
PS (9)

Table 9
Binding energies calculated from In 3d5/2, Sn 3d5/2, Se 3d and O 1s peaks of In4Se3: Sn Samples.
Name Binding Energy (eV)

In 3d5/2 Sn 3d5/2 Se 3d O 1s

Sample A 444.14 444.93 – – – 53.73 531.5

Sample B 444.11 444.92 484.46 485.69 486.43 53.71 529.81 531.54
Sample C 444.24 445 484.27 485.61 486.27 53.78 529.50 531.23

25
R. Anuroop and B. Pradeep
Fig. 8. Transmission spectrum of In4Se3: Sn samples.
where P is the intensity of incident illumination (100 mW/cm2), S is
the effective illumination area. The evaluated time constants, photo-
sensitivity and photoresponsivity are shown in Table 10.
The results show that the prepared samples are photosensitive with
Sample C showing the highest photoresponsivity. This is due to the
increase in carrier concentration due to doping, which resulted in an
increase of photogenerated carriers. Similar results have also been re-
ported for Sn doped β–Ga2O3 thin films [60].
Fig. 9. Tauc plot of (a) Sample A, (b) Sample B and (c) Sample C.
26
Materials Science in Semiconductor Processing 98 (2019) 19–28
Fig. 10. Variation of 1 with 2
of the prepared samples.
Depending on the method of preparation, the traps are created in
thin films due to surface states, point defects, localized stress or the
impurities [61]. The trap depth E can be evaluated from the probability
p of an electron escaping from the trap using the relation [62,63].
p = se E / kT
(10)
here s , E, k and T are frequency factor (attempt to escape frequency)
which is of the order of 109 per second at room temperature, trap depth,
R. Anuroop and B. Pradeep Materials Science in Semiconductor Processing 98 (2019) 19–28

Fig. 11. Time evolution of photoconductivity of (a) Sample A, (b) Sample B and (c) Sample C.

Table 10 the formation of SnIn3+ or SnIn+ donor level. Room temperature pho-
Photoconductivity parameters of In4Se3: Sn samples. toconductivity measurements suggest that the decay follows ex-
Name Decay time Sensitivity S Responsivity Rλ Trap depth E
ponential function with single time constant. Our study shows that Sn
τd (s) (10−6AW−1) (eV) doping in In4Se3 enhances the photoresponsivity significantly. This at-
tractive optoelectronic properties of Sn doped In4Se3 films imply a
Sample A 0.84 0.44 15.9 0.534 potential for optoelectronic device applications.
Sample B 1.12 0.51 107.3 0.542
Sample C 0.41 0.30 274.6 0.516
Acknowledgment

Boltzmann constant and absolute temperature respectively. The prob- Anuroop R would like to thank University Grants Commission
ability p is calculated using the relation (UGC), Govt. of India F:25-1/2013-14(BSR)/5-22/2007 (BSR) for fi-
nancial assistance in the form of Basic Scientific Research fellowship
I = I0 e pt (11) (UGC-BSR Fellowship).
where I is the photocurrent at any instant of time and I0 is the current at
Appendix A. Supplementary data
the moment of interruption of light. The p values are determined from
the decay portion of the photoconductivity curve. Here it is assumed
Supplementary data to this article can be found online at https://
that E and s are temperature independent, the electrons freed from the
doi.org/10.1016/j.mssp.2019.03.020.
traps undergo radiative transition only and are not re-trapped again
[63]. The trap depth corresponding to different dopant concentration in
References
the prepared samples is shown in Table 10.

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4. Conclusions
Using reactive evaporation technique, thin films of In4Se3 and Sn
doped In4Se3 are deposited on to ultrasonically cleaned glass substrate.
X-ray diffraction studies and FESEM analysis confirms that all samples
are polycrystalline. The prepared samples show direct allowed transi-
tion. A slight increase in the optical band gap energy of Sample C is
successfully explained by Burstein-Moss effect. In all prepared samples
a single activation process is observed. Among the prepared samples,
Sample C exhibits lowest resistivity. This improvement is attributed to
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