Materials Research Express

PAPER

Current transport and capacitance-voltage characteristics of Sb2Se3/n-Si

heterojunction diode prepared by electron beam evaporation
To cite this article: Mahmoud Nasr et al 2019 Mater. Res. Express 6 036405

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 Mater. Res. Express 6 (2019) 036405 https://doi.org/10.1088/2053-1591/aaf3f3

PAPER

Current transport and capacitance-voltage characteristics of

RECEIVED
8 October 2018
Sb2Se3/n-Si heterojunction diode prepared by electron beam
REVISED
9 November 2018
evaporation
ACCEPTED FOR PUBLICATION
26 November 2018
PUBLISHED
Mahmoud Nasr1 , A M Mansour1 and I M El Radaf2
7 December 2018 1
Solid State Physics Department, Physics Research Division, National Research Centre, 33 El-Bohouth St., Dokki, Giza 12622, Egypt
2
Electron Microscope and Thin Films Department, Physics Research Division, National Research Centre, 33 El-Bohouth St., Dokki, Giza
12622, Egypt
E-mail: [email protected]

Keywords: antimony selenide, electron beam, FESEM, diode, ideality factor, photovoltaic

Abstract
The Sb2Se3 thin film was successfully deposited on the n-Si substrate using an electron beam
evaporated technique. The structural investigation was done by means of x-ray diffraction analysis.
The surface morphology and elemental analysis of the synthesized films were studied by FESEM
and EDAX, respectively. The electrical properties of the Sb2Se3/n-Si heterojunction were
considered by current-voltage (I-V) and capacitance-voltage (C-V) measurements. The I-V results
of Sb2Se3/n-Si heterojunction diode show a rectifying behavior. The junction ideality factor, barrier
height, and series resistance values were extracted from the rectifying curves at different
temperatures. The capacitance-voltage results show the abrupt nature of the junction under
consideration.

1. Introduction

The group V–VI compound semiconductors are useful for their frequent applications as infrared
spectroscopy, electronics and optoelectronics [1, 2]. Antimony selenite (Sb2Se3) is a V-VI binary material
which attracts the researcher’s interest owing to their potential applications in photovoltaic and
thermoelectric fields [3–5], besides Li-ion and Na-ion batteries applications [6, 7]. Sb2Se3 is a simple binary
compound [8] that having an orthorhombic structure [9, 10]. Due to its low-band-gap (1.2–1.0 eV) and high
optical absorption coefficient (≈105 cm−1 near the absorption onset) [4, 5], Sb2Se3 can be used as a
photoelectrode for a dual-electrode cell. Sb2Se3 is an earth-abundant, low-toxic, inexpensive compound [5].
Due to its low melting point (600 °C) and high saturated vapor pressure (1200 Pa at 550 °C) [8], it can be
prepared in high-quality polycrystalline thin films at a relatively low temperature [11, 12]. As an intrinsic
p-type semiconductor, Sb2Se3 has a conduction band minimum (CBM) located at −4.15 eV [13]. Thus, it is
suitable for the photocathode manufacturing for hydrogen production. Moreover, Sb2Se3 polycrystalline
thin-film has reached a solar conversion efficiency of about 6% as an evolving photo absorber for solar cells
[4]. This outcome is a promising start-up point to the Shockley−Queisser theoretical maximum efficiency of
about 30% (via a band gap of 1.2–1.0 eV) [13, 14]. Various methods have been used to deposit Sb2Se3 thin
films such as thermal evaporation [4, 15], spin coating [16], electrodeposition [17], solvothermal [18] and
hydrothermal method [19] etc.
However, there are rare reports about Sb2Se3/Si heterojunction due to the difficulty in the growth of a high-
quality layer on Si substrate [20]. So, in this work, Sb2Se3 thin film was deposited onto n-type silicon single
crystal substrates by means of electron beam evaporation to fabricate a p-Sb2Se3/n-Si heterojunction device.
The electrical features of p-Sb2Se3/n-Si junction device were studied by the current voltage and capacitance-
voltage techniques at dark conditions and at different heating temperatures.

© 2018 IOP Publishing Ltd

Mater. Res. Express 6 (2019) 036405 M Nasr et al

Figure 1. Schematic diagram of the Au/p– Sb2Se3/n–Si/Al heterojunction prepared by electron beam evaporation technique.

2. Experimental details

2.1. Materials and preparations

The antimony selenide bulk ingot material was prepared by direct fusion of stoichiometric parentage of the
constituent elements in a vacuum sealed silica tube. Then, p-Sb2Se3 thin film has been evaporated onto n-type
silicon wafers at vacuum pressure 10−5 Pa by electron beam deposition technique. The thickness of the
deposited film was controlled through the evaporation process by quartz crystal thickness monitor. The n-type
single crystal silicon wafer was subjected to etching processing using an HF acid to remove any oxide layer on the
surface of the silicon wafer, then that cleaned with deionized water. Then, the Al electrode has been deposited
onto the back surface of the Si substrate by thermal evaporation technique to form the bottom ohmic contacts.
While the top ohmic electrode was formed by evaporating Au metal onto the Sb2Se3 thin film. The schematic
structure of the resulted device has been represented in figure 1.

2.2. Characterization methods

The structural properties of the Sb2Se3 thin film deposited onto n-Si wafer have been investigated by x-ray
diffraction (XRD, Philips X’ pert MPD, Panalytical, Netherlands) using CuKα radiation (λ=1.540 Å).
The surface morphology images of the Sb2Se3 thin film grown onto a Si substrate was obtained by field-
emission scanning electron microscopy (FESEM, Quanta FEG 250, and FEI, USA). The elemental compositions
of the films were measured by Energy dispersive x-ray unit attached to FESEM.
The dark current-voltage (I-V) characteristics of Au/p-Sb2Se3/n-Si/Al heterojunction at different
temperatures, ranged from 303 to 383 K, were measured by using a high impedance Keithley electrometers
model 617.
The capacitance-voltage (C-V) characteristics of the Au/p-Sb2Se3/n-Si/Al heterojunction were measured at
1 MHz at room temperature by a computerized C-V meter (Model 4108) in dark conditions.

3. Results and discussion

3.1. Structural and morphology results

The x-ray diffraction pattern (XRD) of Sb2Se3/n-Si junction prepared by electron beam evaporator technique is
shown in figure 2. The data was recorded between angles 2θ=10° and 70° respectively. Two peaks with d values
equal to 3.147 and 1.573 corresponding to planes indices (211) and (422) were appeared respectively in
agreement with the standard JCPDS card No. 00-089-0821 of orthorhombic Sb2Se3. The SEM images of the
prepared Sb2Se3 film are shown in figure 3. Figure 3(a) shows a smooth surface with a homogeneous
distribution. With a more magnification power, figure 3(b) shows a clear grains granule along the surface. The
grains average size was found as 20 nm. The elemental composition of the prepared film which was done by
EDAX is provided in figure 4. Fully quantitative analysis features were extracted from the spectrum with the aid
of correction software. The inset table of figure 4, shows the resulted processing analysis of the inspected films.
The attained atomic proportions of the constitutional elements in all inspected films reveal that layers are
approximately stoichiometric. These results provide support for the quality of manufactured films. These results
of XRD and SEM images are close to those found by Li et al [21], Shongalova et al [22], Costa et al [23], and Lai
et al [24].

3.2. Current voltage features

The I-V features of Au/p-Sb2Se3/n-Si/Al junction evaluated at fixed temperatures are plotted in figure 5, the
relatively high values of forwarding current and small values of the reverse current approve the rectifying
contact. The relation out of the forward current natural logarithm and the employed voltage of the junction at
established heating temperatures is drawn in figure 6. At quite low employed voltages (V„0.3 volts), the
relation reveals a linear behavior whilst at larger voltages (0.3<V„2), it reveals a down curvity which

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Mater. Res. Express 6 (2019) 036405 M Nasr et al

Figure 2. X-ray diffraction pattern obtained for the Sb2Se3 thin film deposited on Si substrate.

generally could be produced by the impression of series resistance (Rs) generating typically via the Sb2Se3 film,
n-Si wafer, and wiring resistances.
At a quite low forward voltage, the junction transferring current will be identified by the standard diode
formula [25]:

I = Io (e (qV / nKT ) - 1) (1)

Where q represents the electron charge, V represents the employed voltage throughout the junction, n represents
a factor describing the ideality of a junction, K represents the constant of Boltzmann’s, T represents the absolute
temperature and finally, I0 represents the saturation current in reverse direction written as:

Io = AA*T 2e (qÆB / KT ) (2)

where A represents the junction effective area, A* represents the constant of Richardson which is equal to
120 (A.cm−2.K−2) for n-type silicon [26] and ∅B represents the zero bias effective barrier height.
The factor of junction ideality n and the barrier height are determined from the forward ln I-V plot’s linear
part slope and its lnI axis intercept, respectively. The estimated values of both n and ∅B against absolute
temperature are listed in table 1. The data listed in table 1 shows a decrease of ideality factor and an increase of
the barrier height with heating. This tendency is referenced as the barrier height lateral inhomogeneity. At low
temperatures, electrons are capable to conquer the low energy barriers and the current transfers over the low
barrier heights. When the temperature is raised, further electrons will get an excess energy to conquer higher
barriers. Consequently, the barrier height gets larger with the increase of both the heating temperature and the
employed voltage. The junction provides an ideality factor over the ideal value which always originated from the
series resistance, inhomogeneous barrier height, interfacial states and tunneling [27]. The relation of the ideality
factor versus barrier height for Au/p-Sb2Se3/n-Si/Al junction is sketched in figure 7.
The series resistance, Rs, is actually an important variable for the junction particularly when the voltage
impacts the I-V features of a junction. The Au/p-Sb2Se3/n-Si/Al junction Rs value is identified through the help
of modified Norde’s function [28]:

V KT ⎛⎜ I (V) ⎞⎟
F (V) = - ln (3)
X e ⎝ AA * T 2 ⎠

Where X represents the 1st integer over the ideality factor value. I (V) represent the current. The Rs value at
different heating temperatures is predicted via the next formula [29, 30]:

⎛ k BT ⎞ ⎛ X - m ⎞
Rs = ⎜ ⎟⎜ ⎟ (4)
⎝ e ⎠ ⎝ I (V ) ⎠

where I(Vo) represents the current equivalent to the minimum point voltage of F(V). The barrier height is
predicted by [31, 32]:

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Mater. Res. Express 6 (2019) 036405 M Nasr et al

Figure 3. FESEM micrograph of the Sb2Se3/Si heterojunction, prepared by electron beam evaporation technique at different
magnification powers (a) 25000x and (b) 250000x..

V k T
Æ = F (V ) +  - B (5)
 X e
Where F(Vo) represent the F(V) lowest point and Vo represent the equivalent voltage. Regarding Norde’s
function plotted in figure 8 combined with equations (4) and (5), the series resistance and barrier height
valuations are acquired at preset heating temperatures and are outlined in table 1. It was revealed that a decrease
of series resistance and an increase of the barrier height by raising the heating temperature. It can be seen that the
barrier height acquired via Norde’s function is corresponding to that acquired by I-V outcomes where the
differences between the two results are relying on the differences in calculation techniques.
In the forward direction, the impact of increasing employed voltages on I-V features of the junction is
explored by sketching lnI against lnV as presented in figure 9. The relationship illustrates a linear relation with a
slope of ≈2.5. That outcome implies that the space charge limited current dominated by the exponential trap of

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Mater. Res. Express 6 (2019) 036405 M Nasr et al

Figure 4. EDAX pattern detected for the Sb2Se3 thin film deposited on n-Si substrate.

Figure 5. The I-V characteristics of Au/p-Sb2Se3/n-Si/Al heterojunction diode measured at fixed temperatures.

Figure 6. The variation of the ln(I) with V for Au/p-Sb2Se3/n-Si/Al diode at settled temperatures.

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Mater. Res. Express 6 (2019) 036405 M Nasr et al

Figure 7. The variation of the barrier height with the ideality factor for Au/p-Sb2Se3/n-Si/Al diode.

Figure 8. Nord’s function of Au/p-Sb2Se3/n-Si/Al diode.

Table 1. The values of n and ÆB as a function of

temperature for the p-Sb2Se3/n-Si heterojunction.

I-V F (V)

T (K) n fB (eV) Rs (KΩ) fB (eV)

303 4.68 0.865 278 0.858

323 4.19 0.911 214 0.861
343 3.74 0.956 93 0.867
363 3.08 1.00 40 0.876
483 2.37 1.051 28 0.891

distribution is the conduction mechanism in the present case [33]. This proposes that the conduction operation
of Sb2Se3 film produces an influence to the I-V characteristics of the diode [34].

3.3. Capacitance voltage features

The junction capacitance versus voltage evaluation is accustomed to identifying the barrier height and impurity
concentration. Figure 10 displays the C−2–V feature of Al/n-Si/p-Sb2Se3/Au junction measured at 1 MHz in
dark conditions and at room temperature.

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Mater. Res. Express 6 (2019) 036405 M Nasr et al

Figure 9. lnI–lnV characteristic of higher forward applied voltages region of Au/p-Sb2Se3/n-Si/Al diode.

Figure 10. C−2–V characteristic obtained from Al/n–Si/p– Sb2Se3/Au heterojunction measured at 1-MHz in dark and at room
temperature.

The relationships of C−2 against applied voltage produce straight lines, implies that the junction has an
abrupt character. That habit is generally discussed on the principle of the depletion region width variance with
temperature change [35]. The junction capacitance dependence on the reverse potential for the n-Si/p-Sb2Se3
heterojunction is given by [36–38]:
qNA ND e1 e2 1
C2 = (6)
2(e1 NA + e2 ND ) (Vbi - V )

Where q represent the electronic charge, ε1 represent the Si dielectric constant, ND represents the n-Si donor
concentration, ε2 represent Sb2Se3 layer dielectric constant and NA represent the Sb2Se3 layer acceptor
concentration.
The built-in voltages Vbi of the n–Si/p-Sb2Se3 heterojunction was recognized through extrapolating the
resulted relation line to C−2=0, whilst the net carrier concentration N of the n–Si/Sb2Se3 heterojunction is
evaluated from the slope. The evaluated values of Vbi and N of the Al/n–Si/p-Sb2Se3/Au heterojunction are
recorded in table 2.
The variance of built-in voltages (Vbi) and donor carrier concentration (ND) with temperature for the
Al/n-Si/p-Sb2Se3/Au heterojunction is presented in figure 11. It is obviously noticed that the magnitudes of Vbi
were reduced with raising the temperature whilst the magnitudes of ND has been increased with increasing the
temperature. Actually, the interface density of charges improves by raising the temperature. It has a significant

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Mater. Res. Express 6 (2019) 036405 M Nasr et al

Figure 11. Variation of built in voltages (Vbi) and donor carrier concentration (ND) with temperature for the Al/n-Si/p-Sb2Se3/Au
heterojunction.

Table 2. The evaluated values of Vbi and N of

the Al/n–Si/p– Sb2Se3/Au heterojunction.

T (K) Vbi (V) ND×1018 (cm−3)

303 K 0.54 4.73

323 K 0.48 4.92
343 K 0.41 5.31
363 K 0.35 5.64
383 K 0.29 5.95

impact on the apparent built-in voltage. Evidently, raising the interface density of charges reduces the built-in
voltage. The large interface density of states likewise acts as practical tunneling centers [35, 36, 39].

4. Conclusion

A thin film of Sb2Se3 was successfully evaporated by electron beam deposition on n-type Si. The x-ray diffraction
patterns revealed that the prepared film has an orthorhombic structure and the SEM micrographs showed a fine
smooth homogeneous surface. The EDX investigations revealed a stoichiometric composition. With a
temperature increase, the ideality factor of the prepared junction decrease, the barrier height increases, and the
series resistance decreases. The C−2–V results implied that the junction is of abrupt nature.

ORCID iDs

Mahmoud Nasr https://orcid.org/0000-0001-7716-9048

A M Mansour https://orcid.org/0000-0001-5886-0650
I M El Radaf https://orcid.org/0000-0001-6197-5272

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