1. bookVolume 39 (2021): Issue 2 (June 2021)
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2083-134X
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16 Apr 2011
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Optoelectronics applications of electrodeposited p- and n-type Al2Se3 thin films

Published Online: 02 Sep 2021
Volume & Issue: Volume 39 (2021) - Issue 2 (June 2021)
Page range: 166 - 171
Received: 20 Feb 2021
Accepted: 25 Feb 2021
Journal Details
License
Format
Journal
eISSN
2083-134X
First Published
16 Apr 2011
Publication timeframe
4 times per year
Languages
English
Introduction

In recent times, compound semiconductor materials, such as cadmium telluride (CdTe), zinc oxide (ZnO), zinc sulfide (ZnS), lead sulfide (PbS), aluminum selenide (Al2Se3), and cadmium selenide (CdSe) to mention a few, have experienced renewed scientific attention as they form the bedrock of many scalable technologies [1]. Among the compound semiconductors, aluminum selenide (Al2Se3) thin films are the most infrequently described despite their potential in optoelectronic applications [2]. Aluminum (Al) as an elemental semiconductor has been extensively studied because of its ease of growth, promising optical and electrical properties, and abundance in the earth's crust, after oxygen and silicon [2,3,4]. Although compound semiconductor has more functionalities than elemental semiconductor [5,6,7], compound semiconductors also possess more functionalities than their respective components. In addition, compound semiconductors with selenium as a constituent portend viable nanomaterials in energy conversion solar cells and sensor devices [2, 8,9,10]. Al2Se3 has also been described as a perfect window layer material that is capable of forming a suitable heterojunction with absorber layer materials such as cadmium telluride and lead sulfide. The suitability of this material in the formation of heterostructure-based optoelectronic devices necessitate the study of junction-based Al2Se3. Compound semiconductor materials based thin films have been synthesized by various deposition techniques [11,12,13]. Among all the synthesis routes, the electrodeposition (ED) technique plays a significant role in the synthesis of cost-effective nanomaterials for nanodevice applications [14,15,16,17]. This method allows tunability and control of nanomaterials’ properties by changing the preparative parameters of the solution, such as ionic concentration (electrolyte), pH value, temperature, deposition time, and cathodic voltage [18,19,20].

To our knowledge, researchers over the years have paid little to no attention to the electrical conduction type of Al2Se3, especially when the cathodic potential varies. In this work, the focus is directed toward the possibility of fabrication of both p-and n-type Al2Se3 without the inclusion of external dopants. It is believed that most nanodevices are p-n junction-based devices; therefore n-type and p-type Al2Se3 will be of commercial value in the fabrication of single material-based junction devices such as diodes.

Material and method

The film of Al2Se3 sourced from the solution of high-grade aluminum chloride (AlCl2, 99%) and selenium dioxide (SeO2, 99%) without further purification were subject to ED on a thoroughly degreased conducting fluorine-doped tin oxide (FTO)/substrate of 2.3 by 4 cm2 dimension. The formation of electrolytic bath of Al2Se3 contained 29 g of AlCl2 and 0.9 g of SeO2. The admixed solution of 400 mL in a 500 mL beaker was magnetically stirred for 2 h to ensure homogeneous solution and the acidic level was tested and adjusted using both pH probe (pH = 2.5) and ammonium solution, since the synthesis technique used is favored by acidic medium [20]. Different films of Al2Se3 at a bath temperature of 90 °C in 15 min were achieved potentiostatically in two-electrode configurations; graphite was used as a counter electrode (cathode) and carbon as a reference electrode (anode) by the variation of cathodic potential and duration of deposition, respectively. The film's optical properties and electrical conductivity type were achieved using ultraviolet-visible spectroscopy at wavelength range 200–900 nm and photoelectrochemical cells (PEC) measurements. Thin-film thickness, optical properties, and electrical conductivity type were obtained using Eqs (1)–(4) [21, 22].

T=JtMρnF T = {{JtM} \over {\rho nF}}

The film thickness as illustrated in Table 1 is denoted as T, J is the current density of the electrodeposited Al2Se3, t is the deposition time, ρ is the density of Al2Se3, n is the total number of electrons transferred per ion of the deposited material, F is the faraday's constant with a numerical value of 96,485 C · mol−1, and M is the molar weight of the deposited Al2Se3. (αhv)=A(hvEg)n (\alpha hv) = A{\left( {hv - {E_g}} \right)^n} where α is absorption coefficient, is photon energy, A is a constant usually equal to one, Eg is the energy band gap, and n is the transition between the valence band and conduction band, which is 0.5 for direct and 1 for indirect transition. k=αλ4π=αλ12.57 k = {{\alpha \lambda } \over {4\pi }} = {{\alpha \lambda } \over {12.57}} where α is absorption coefficient, k is extinction coefficient, and 4π carries a numeric value of 12.57. PECSignal=VLVD PEC\;Signal = {V_L} - {V_D} where VL is voltage under illumination and VD is voltage under dark.

Measured material properties as a function of deposition time and cathodic potential based on UV and PEC results.

Semiconductor type and energy band gaps

As time of deposition increases As voltage increases

Time (min) Type Eg (eV) Cathodic potential (mV) Type Eg (eV)
3 N 3.30 1,000 P 3.23
6 N 3.19 1,100 I-Intrinsic 3.20
9 N 2.83 1,200 N 3.00
12 N 2.79 1,300 N 2.96
15 N 2.70 1,400 N 2.95

PEC, photoelectrochemical cells.

Results and discussion
Optical properties of junction-based electrodeposited Al2Se3

The optical properties of the electrodeposited aluminum selenide as a function of optimized time of deposition and cathodic potential are shown in Figures 1–4. From Figure 1, it can be seen that material energy band gaps are not only dependent on films’ thickness but also a function of preparative parameters, as there is a noticeable decrease in the energy band gap as time (3.30–2.70 eV) and voltage (3.23–2.95 eV) increase. The energy bang gaps values obtained as both time and voltage increase are determined by the extrapolation of the linear part of the energy band gap graphs. The changes in the film's bandgap are a result of optical properties’ dependence on particle dimension, causing the quantum conferment effect [13]. However, such preparative parameters reveal significant improvement in the built-in electric field, as the slope of the energy band diagram is well defined [19, 23]. The absorbance spectra of Al2Se3 thin films deposited at varied times and voltage as depicted in Figure 4 clearly showed a decrease in the absorbance with an increase in the wavelength. From Figure 2, two absorption bands are observed. The first absorption band (Figure 2(A)) is an indication of Al2Se3 band edge peak close to quantum dot in the visible region that indicates blue shift [3]. The second absorption band, as shown in Figure 2(B), revealed maximum absorption in the infrared region of the spectrum, which suggests that the film is a good radiation detection material [24]. The absorption characteristic revealed the suitability of Al2Se3 as a good buffer/window material in optoelectronics applications. Figure 3 reveals the transmittance characteristic of the film as a function of wavelength, time of deposition, and cathodic potential. High transmittance peaks as observed in Figure 3(A and B), with values >80%, make the films a good receptive surface to any absorber layer [25]. There is a reflection of radiation light in the films as depicted in Figure 4, which is an indication that reflection of light occurs within the electromagnetic region. Such transition in reflectance revealed the potential of the films as good anti-reflection coating suitable for optoelectronic applications.

Fig. 1

The energy band gap of Al2Se3 at varied (A) time of deposition and (B) cathodic potential.

Fig. 2

Absorption spectra as a function of wavelength at varied (A) time and (B) voltage (B).

Fig. 3

Percentage of transmittance of Al2Se3 as a function of wavelength at varied (A) time and (B) voltage.

Fig. 4

Reflection spectra as a function of wavelength at varied (A) time and (B) voltage.

Optical constant of junction-based electrodeposited Al2Se3

Figures 5 and 6 showed that there is a relatively low absorption edge within the visible region. However, a good absorption edge was observed in the film deposited at various cathodic potentials, which suggests a variation of cathodic potential as a good preparative procedure in the fabrication of optoelectronics materials using the ED technique. The Al2Se3 layers grown at varied cathodic potentials and times of deposition, respectively, have the highest extinction values within the visible to the near-infrared wavelength region.

Fig. 5

Absorption coefficient as a function of wavelength at varied (A) time and (B) voltage.

Fig. 6

Extinction coefficient as a function of wavelength at varied (A) time and (B) voltage.

Electrical conductivity type of electrodeposited Al2Se3

To ascertain the conductivity type of electrode-posited aluminum selenide and suggest possible preparative parameters to the realization of semiconductor type, a PEC measurement was carried out, which was achieved by forming a liquid junction between the substrate and the electrolyte. Figure 7(A) shows the electrical conductivity type span with the negative region, despite the variation in deposition time resulting in n-type material. The PEC signal, measured under conditions of darkness and illumination as depicted in Figure 7(B), revealed the transition from p-type to n-type. At low cathodic voltages, the PEC signal falls within the positive region indicating p-type Al2Se3. As the cathodic voltages increased >1,100 mV, the PEC signal transited to the negative region showing n-type Al2Se3. However, one can conclude that the film's conductivity type transition depends only on the variation of growth voltage and not on the time of deposition (Table 2). Our observation affirms that the film electrical conductivity type cannot be tuned under the influence of time variation but requires post-heat-treatment in accordance with previous researches [17, 23, 25,26,27].

Fig. 7

PEC signal as a function of growth voltage for glass/FTO/Al2Se3 layers at varied (A) time and (B) voltage. FTO, fluorine-doped tin oxide; PEC, photoelectrochemical cells.

Film thickness values with the variation in the time of deposition and cathodic potential.

Film thickness as the time of deposition increases Film thickness as the cathodic potential increases

Time (min) Thickness (nm) Cathodic potential (mV) Thickness (nm)
3 193 1,000 234
6 233 1,100 344
9 399 1,200 522
12 476 1,300 714
15 592 1,400 773
Conclusion

The achievement of junction-based electrode-posited aluminum selenide revealed the potential of the films in optoelectronics applications. The result obtained in the optical phenomena and constants suggests cathodic potential and time of deposition as good preparative parameters in the tunability of optical properties of electrodeposited Al2Se3 thin films. The film energy bandgap varied from 3.23 eV to 2.95 eV as cathodic voltage increases, and from 3.3 eV to 2.7 eV as the time of deposition increases, respectively. The other optical properties with relatively low absorbance, averagely high reflectance, and high transmittance indicate the viability of junction-based electrodeposited Al2Se3 as good buffer/window layers in solar cell device architecture. The absorption and extinction coefficient showed a sharper absorption edge and higher extinction coefficient edge in the visible region of the electromagnetic spectrum. The films possess excellent optical constant, which helps in the selection of good window layer materials capable of providing a receptive surface for absorber layers in the fabrication of junction-based optoelectronics devices. The successful fabrication of p-type and n-type Al2Se3 suggests cathodic potential as an optimized preparative procedure in the ED technique.

Fig. 1

The energy band gap of Al2Se3 at varied (A) time of deposition and (B) cathodic potential.
The energy band gap of Al2Se3 at varied (A) time of deposition and (B) cathodic potential.

Fig. 2

Absorption spectra as a function of wavelength at varied (A) time and (B) voltage (B).
Absorption spectra as a function of wavelength at varied (A) time and (B) voltage (B).

Fig. 3

Percentage of transmittance of Al2Se3 as a function of wavelength at varied (A) time and (B) voltage.
Percentage of transmittance of Al2Se3 as a function of wavelength at varied (A) time and (B) voltage.

Fig. 4

Reflection spectra as a function of wavelength at varied (A) time and (B) voltage.
Reflection spectra as a function of wavelength at varied (A) time and (B) voltage.

Fig. 5

Absorption coefficient as a function of wavelength at varied (A) time and (B) voltage.
Absorption coefficient as a function of wavelength at varied (A) time and (B) voltage.

Fig. 6

Extinction coefficient as a function of wavelength at varied (A) time and (B) voltage.
Extinction coefficient as a function of wavelength at varied (A) time and (B) voltage.

Fig. 7

PEC signal as a function of growth voltage for glass/FTO/Al2Se3 layers at varied (A) time and (B) voltage. FTO, fluorine-doped tin oxide; PEC, photoelectrochemical cells.
PEC signal as a function of growth voltage for glass/FTO/Al2Se3 layers at varied (A) time and (B) voltage. FTO, fluorine-doped tin oxide; PEC, photoelectrochemical cells.

Film thickness values with the variation in the time of deposition and cathodic potential.

Film thickness as the time of deposition increases Film thickness as the cathodic potential increases

Time (min) Thickness (nm) Cathodic potential (mV) Thickness (nm)
3 193 1,000 234
6 233 1,100 344
9 399 1,200 522
12 476 1,300 714
15 592 1,400 773

Measured material properties as a function of deposition time and cathodic potential based on UV and PEC results.

Semiconductor type and energy band gaps

As time of deposition increases As voltage increases

Time (min) Type Eg (eV) Cathodic potential (mV) Type Eg (eV)
3 N 3.30 1,000 P 3.23
6 N 3.19 1,100 I-Intrinsic 3.20
9 N 2.83 1,200 N 3.00
12 N 2.79 1,300 N 2.96
15 N 2.70 1,400 N 2.95

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