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    Electrodeposited metal sulfide thin films for gas sensing applications
    (4th International Research Symposium on Pure and Applied Sciences, Faculty of Science, University of Kelaniya, Sri Lanka, 2019) Namawardana, D. G. K. K.; Wickramathilaka, P. A. K. Y.; Atapattu, H. Y. R.; De Silva, D. S. M.
    Quantitative measurements of gases are based on a variety of physical or chemical principles. Among them semiconductor gas sensors are best candidates for the development of commercial gas sensors due to their higher specificity and sensitivity. They are mainly based on metal oxide and metal sulfide materials. Due to certain drawbacks of metal oxides, metal sulfides are extensively investigated as novel gas sensing materials. In this study ZnS and CdS were investigated for their gas sensing ability. Both types of thin films were fabricated by electrodeposition using a three electrode electrolytic system consisted of a fluorine doped tin oxide glass substrate (1×3 cm2) as working electrode and a high purity carbon as counter electrode. An aqueous electrolyte containing CdCl2 (0.10 mol/L) and Na2S2O3 (0.01 mol/L) precursors were used for the electrodeposition of CdS material and aqueous electrolyte containing ZnCl2 (0.10 - 0.05 mol/L) and Na2S2O3 (0.01 - 0.05 mol/L) precursors were used for electrodeposition of ZnS material. The CdS depositions were carried out in the cathodic deposition potential (CDP) range of 0.65 to 0.70 V vs. saturated calomel electrode and pH range of 1.5 to 2.0 at a temperature of 55 °C for 30 minutes. The ZnS depositions were carried out in the CDP range of 0.70 to 1.10 V vs. Ag/AgCl reference electrode and pH range of 4.0 to 3.5 at a temperature of 30 °C for 90 minutes. Both types of thin films were characterized for their crystalline structure, surface morphology, and elemental composition by using the techniques of X-ray diffraction spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy respectively and were exposed to various gases namely; NO2, H2S, and LPG. CdS thin films grown at CDP of 0.67 V and pH of 1.5 and ZnS thin films grown at CDP of 1.05 V and pH of 3.7 were found to have notable gas sensing properties. CdS has shown highest resistance variation of 1.2 Ω towards H2S with respect to the initial resistance of 36.0 Ω and ZnS has shown highest resistance variation of 2 Ω with respect to the initial resistance of 26.2 Ω when exposed to NO2 gas at 30 oC. Both CdS and ZnS thin films showed resistance variation of 1.1 Ω and 0.6 Ω towards LPG respectively at 30 oC.
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    Electrodeposited homojunction Cu2O solar cell on FTO substrate
    (Research Symposium on Pure and Applied Sciences, 2018 Faculty of Science, University of Kelaniya, Sri Lanka, 2018) Kafi, F. S. B.; Jayathilaka, K. M. D. C.; Wijesundera, L. B. D. R. P.; Siripala, W.
    Cuprous oxide (Cu2O), an abundant photoactive semiconducting material has optimum optoelectronic properties to develop efficient, inexpensive and eco-friendly solar cells. Even though, it is possible to fabricate Cu2O based hetero or Schottky junction solar cells, it is believed that the reduction of interface strains via application of surface treatments can produce best efficient homojunction Cu2O solar cell. Apart from the homogeneity of a p-n junction, reduction of contact resistances of a solar cell also has a great impact on its overall performance. Previous studies have shown that, annealing and/or sulphidation of thin film Cu2O enhances the surface properties while sulphided p-Cu2O/Au junction exhibits ohmic behavior as well. Thus, in this study possibility of developing efficient thin film homojunction Cu2O solar cell on FTO substrate was tested by improving the surface properties of n- and p-Cu2O thin film layers. n-Cu2O thin film was potentiostatically electrodeposited in a three electrode photoelectrochemical cell, contained 0.1 M sodium acetate and 0.01 M cupric acetate, acetic acid at bath pH value of 6.1 and then, this thin film FTO/n-Cu2O photoelectrode was annealed at temperature of 4000C to form very thin p-Cu2O layer with lower surface defects. Subsequently, for a thicker absorber layer a thin film ptype Cu2O was electrodeposited on annealed FTO/n-Cu2O photoelectrode using a lactate bath, consisted 3 M lactic acid, 0.4 M copper(II) sulphate and 4 M sodium hydroxide at bath pH value of 13.0. Finally, to form ohmic back contact this bi-layer is directly exposed to ammonium sulphide vapor for 8s and sputtered thin film of Au on it. Photoresponses and modulated light induced current-voltage characterization of this final thin film Cu2O homojunction is given the highest VOC and JSC values of 154 mV and 3.905 mA/cm-2 respectively. This result revealed that application of surface treatments to the thin film n-Cu2O and the bi-layers ameliorates surface properties, thereby the optoelectronic properties. Parameterization of surface treatments and improvements in the front contact will further improve this homojunction solar cell.
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    Evaluation of solution parameters for CdCl2 solutions to be used in post-deposition treatments of CdTe thin films in CdS/CdTe solar cells.
    (International Research Symposium on Pure and Applied Sciences, 2017 Faculty of Science, University of Kelaniya, Sri Lanka., 2017) Atapattu, H. Y. R.; Silva, D. S. M. D.; Pathiratne, K. A. S.
    Owing to its high absorption coefficient and the near ideal band gap, CdTe has become one of the topmost solar energy materials available for conversion of solar energy into electricity. It exhibits excellent power conversion efficiencies, when coupled with the CdS window material to form CdS/CdTe heterojunction solar cells. Further, CdCl2 treatment has been identified as one of the promising post-deposition treatments available for achieving drastic improvements in the performance of CdTe material. However, no extensive investigations have yet been carried out to identify suitable solution parameters for the CdCl2 solutions used in the post-deposition treatment process. Hence, the present study was designed to investigate the effect of concentration and pH of CdCl2 solutions used for post-deposition treatments of CdTe material grown on glass/FTO/CdS surfaces. In this study, CdTe layers were potentiostatically electrodeposited on glass/FTO/CdS substrates in electrolytic baths containing 1.0 mol/L CdSO4 and 1.0 mmol/L TeO2 at pH 2.3. A cathodic deposition potential of 650 mV with respect to saturated calomel electrode and temperature of 65 °C at a continuous stirring rate of 60 rpm were maintained through the deposition. At the end of electrodeposition process, all the glass/FTO/CdS/CdTe samples were rinsed in de-ionized water and dried under a high purity nitrogen gas stream and conveyed for the CdCl2 treatment followed by air annealing at 390 °C for 15 min. For CdCl2 treatment, three different CdCl2 concentrations (1.0, 0.5 and 0.1 mol/L) were used. For each concentration, three different pHs; as prepared (5.6, 6.3 and 7.1 for 1.0, 0.5 and 0.1 mol/L CdCl2 solutions respectively), 2.0 and 6.5 at 25 °C were selected. Hence, nine sets of samples with two replicates in each were subjected to the CdCl2 treatment. Once the treatment process was over, samples were inspected for their optical, electrical and morphological properties using the techniques of optical absorption spectroscopy, photo-electrochemical cell studies and scanning electron microscopy. The results revealed that, two solutions; one with 1.0 mol/L CdCl2 solution at pH of 5.6 and the other with 0.1 mol/L CdCl2 solution at pH of 2.0 can be effectively used for the post-deposition treatment of CdTe material for improving its properties and eventually to produce power efficient CdS/CdTe based solar cells with ~80 % efficiency improvement compared to the untreated devices.
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    Optimization of growth parameters of photoactive Cu2ZnSnS4.
    (International Research Symposium on Pure and Applied Sciences, 2017 Faculty of Science, University of Kelaniya, Sri Lanka., 2017) Fernando, W. T. R. S.; Jayathilaka, K. M. D. C.; Wijesundera, R. P.; Siripala, W.
    Cu2ZnSnS4 (CZTS) is a promising candidate for application in low-cost and environmentally friendly thin film solar cells due to its optoelectronics properties. It is a perfect absorber material for photovoltaic applications due to its high absorption coefficient (>10-4 cm-1) and direct optical band gap (1.4 - 1.5 eV). Among the CZTS preparation techniques, electrodeposition of Cu, Sn and Zn stack layers followed by sulphurisation in H2S is an attractive technique because of its simplicity, low cost and easy to control stoichiometry. In this investigation, optimization of growth parameters in order to obtain photoactive CZTS thin films by sulphurisation of electrodeposited Cu, Sn and Zn stack layers has been investigated. Cu thin film was electrodeposited on Mo substrate at –0.89 V Vs Ag/AgCl electrode in an electrochemical cell containing 0.4 M CuSO4, 3 M lactic acid and NaOH at pH 11. Deposition of Sn thin film on Mo/Cu electrode was carried out at -1.2 V Vs Ag/AgCl in an electrochemical cell containing 0.055 M, 2.25 M NaOH and 8 ml of sorbitol. Zn thin film was electrodeposited on Mo/Cu/Sn at -1.2 V Vs Ag/AgCl in an electrochemical cell containing 0.2 M ZnSO4. Deposition parameters of Cu, Sn and Zn have been obtained by voltammograms. In order to grow CZTS, Mo/Cu/Sn/Zn thin film electrodes were annealed at 550 oC for 60 min in H2S. Sulphurisation process was carried out at different temperatures and durations using set of identical Mo/Cu/Sn/Zn thin film electrodes and thereby optimized temperature and duration of the sulpurisation. Atomic ratios of initial Cu, Sn and Zn layers could be crucial parameters in determining properties of CZTS thin films. Therefore, atomic ratios of Cu/Sn/Zn layers were optimized by changing Cu, Sn and Zn deposition duration. Various combinations of deposition durations were carried out and optimized by monitoring the dark and light I-V measurements in a PEC containing 0.1 M sodium acetate. Dark and light I-V characteristics revealed that the best photoactive CZTS films can be grown by depositing Cu for 20 min, Sn for 10 sec and Zn for 10 sec. Results further showed that photoconductivity of CZTS thin films is p-type. It is evident from reflectance measurements that the band gap of the CZTS films is 1.5 eV. In conclusion, it is found that the highest photoactive p-CZTS thin films can be grown by sulphurisation of electrodeposited Cu, Sn and Zn stack layers on Mo substrate using H2S at 550 oC for 60 min. Cu: Sn: Zn ratios of the stack layers are the crucial parameters in determining photoactive CZTS thin films. The methodology developed in this study will be further investigated in order to develop the materials for wider applications.
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    Effect of temperature on photosensitivity of electrodeposited n-Cu2O/p-CuxS thin film junctions
    (Faculty of Science, University of Kelaniya, Sri Lanka, 2016) Madusanka, H.D.P.; Kalubowila, K.D.R.N.; Jayathilaka, K.M.D.C.; Jayanetti, J.K.D.S.
    The purpose of this study was the construction of a standalone microcontroller based ambient light sensing device to interface an ambient light sensor with a temperature correction and to study the effects of temperature on photosensitivity of electrodeposited Cu2O based thin film p-n junction diodes. Environmentally friendly, low cost, nontoxic cuprous oxides have highly acceptable electrical and optical properties. It has a direct energy gap of about 2 eV at room temperature and has a good absorption coefficient. Cuprous oxide has a good mobility for the majority carriers and a diffusion length of the minority carriers is several micrometers. In this study, an electrolytic solution of 0.1M sodium acetate and 0.01M cupric acetate was used to fabricate Cu2O thin films on top of Ti substrates using electrodeposition. Electrodeposition was carried out potentiostatically at a potential of -200 mV with respect to the saturated calomel electrode. A Na2S solution was used to make the n- Cu2O/p-CuxS junction. In order to increase the photocurrent from the fabricated n- Cu2O/p-CuxS junction, the sulphided Cu2O sample was exposed to ammonium sulphide gas. Then the photocurrent of the n-Cu2O/p-CuxS thin film junction was measured by a constructed microcontroller based light sensing device simultaneously monitoring the intensity of light with a luminance meter HS1010. An important observation made in this study was that the photocurrent of the electrodeposited Cu2O/CuxS thin film junctions depended greatly on the variation of temperature during exposure to light. Thus the junction photocurrent was studied by exposing the junctions to light while monitoring the variation in the photocurrent with the temperature using a DS18B20 temperature sensor. The resulting data were plotted using MATLAB software and it was found that the photocurrent of the thin film p-n junction displayed a variation that was very much linear at low intensities of light. The measured output currents obtained from the p-n junctions and the output values obtained from the temperature sensor were used to display the intensity of light with the temperature correction using an electronic circuit.
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    Electrodeposition of CdTe thin films using a two electrode system
    (Faculty of Science, University of Kelaniya, Sri Lanka, 2016) Wedisinghe, K.C.; Atapattu, H.Y.R.; de Silva, D.S.M.
    Cadmium telluride (CdTe) is a promising material for thin film solar cell applications due to its ideal band gap of ~1.5 eV which has the ability to absorb the maximum of the solar spectrum and higher conversion efficiency of sun light. Among the various deposition techniques available to produce CdTe semiconductor material in commercial quantities, electrodeposition has drawn more attention due to its simplicity, scalability and easy control of the material properties through growth parameters; applied potential, temperature, pH and the composition of the bath etc. Since the reference electrode could be a potential impurity source in the conventional three electrode electrolytic system, this study was mainly focused on the use of two electrode electrolytic system to determine suitable deposition potential and pH ranges for growth of CdTe thin film while avoiding the influence of impurities. The two electrode electrolytic cell consisted of, fluorine doped tin oxide coated glass substrate as the working electrode and 99.99% pure carbon electrode as counter electrode was used for the deposition of CdTe thin films. The electrolyte contained analytical grade reagents of 1.25 mol/L CdSO4 and 1.0 mmol/L TeO2 as cadmium and tellurium precursors respectively. Prior to electrodepositions, pH of the electrolytic baths were varied from 2.0 to 2.4 at 25 °C. While changing the cathodic deposition potentials in the range of (1.30 - 1.37) V, the CdTe depositions were carried out stirring the bath at 60 rpm and at the temperature of 65 °C. Following the heat treatment of the samples for 10 minutes at 400 °C in air, the characterization of CdTe thin films was carried out based on optical absorption, photo-electrochemical cell, X-ray diffraction and scanning electron microscopic studies. The results of the study indicate that, CdTe thin films can be successfully grown in the cathodic potential range of (1.34 -1.35) V and at a pH of 2.2 using two electrode electrolytic system.
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    Improvement of p-Cu2O/Au interface by controlling the pH of the electrodeposition bath of Cu2O
    (Faculty of Science, University of Kelaniya, Sri Lanka, 2016) Kafi, F.S.B.; Jayathilekea, K.M.D.C.; Wijesundera, R.P.; Siripala, W.
    Metal-Semiconductor junction studies play a very important role in discovering new junction properties leading to improved electronic devices. Indeed, Schottky junction is among the fundamental structures used in modern optoelectronics and microwave devices. In this regard, low cost and eco-friendly metal-semiconductor devices with inexpensive materials and fabrication techniques are extremely important. Among other materials, p-Cu2O thin films grown by electrodeposition method have attracted as potential candidates for developing Cu2O based low cost Schottky junction devices. In this study, dependence of the p-Cu2O/Au junction properties on the pH of the Cu2O film deposition bath has been investigated for the development of low cost devices. p-Cu2O thin films were potentiostatically electrodeposited in a three electrode electrochemical cell containing 3M lactic acid, 0.4M CuSO4 and NaOH at different pH values. p-Cu2O/Au Schottky junctions were fabricated by sputtering Au on masked Cu2O samples. Dark Capacitance – Voltage measurements (Mott- Schottky plots) of the fabricated devices revealed that a positive shift of 620 mV of the flat band potential against Au for the change in pH of the film deposition bath from 7.0 to 13.0. This positive shift is significant when compared to the positive shift of 350 mV at the p-Cu2O/electrolyte interface observed earlier. The interaction of surface atoms with the electrolyte species at the Cu2O/electrolyte interface and the presence of bare surface atoms at the Cu2O/Au interface might have led to this improvement. The positive shift of the flat band potential manifests that the positive shift in the valence band edge of p-Cu2O relative to the Fermi level of Au increases the barrier height at the p-Cu2O/Au interface. Thus, the study reveals that the barrier height at the p-Cu2O/Au interface can be controlled with the pH of the film deposition both. As observed, dark Current-Voltage measurements on p-Cu2O/Au devices resulted nearly ohmic behavior for low pH values and non ohmic diode behavior for high pH values. This suggests that for high pH values of the film deposition bath of p-Cu2O improved Schottky junctions can be in fabricated with Au, suitable for various device applications such as rectifying circuits, photovoltaics, etc.
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    Growth of CuZnS thin films by sequential electrodeposition and sulphurisation
    (Faculty of Science, University of Kelaniya, Sri Lanka, 2016) Fernando, W.T.R.S.; Jayathilekea, K.M.D.C.; Wijesundera, R.P.; Siripala, W.
    Copper Zinc Sulphide (CuZnS) is a promising new absorber material for solar cell applications. Indeed, this material is very attractive for low cost device applications due to abundance and low cost of the staring materials. Very recently, a CuZnS based solar cell with In2S3 window material has been reported having Voc of 0.41 V, Jsc of 10.6 mA/cm2, FF of 45% and  of 1.94%. This initial finding has proven the possibility of developing this material as a solar energy material. Among the CuZnS preparation techniques, electrodeposition is an attractive technique because of its simplicity, low cost and possibility of making large area thin films. In this study, possibility of growth of CuZnS thin films by sulphurisation of electrodeposited Cu and Zn stack layers using S powder has been investigated. Cu thin film was electrodeposited on Ti substrate at –700 mV Vs Ag/AgCl for 15 min in an electrochemical cell containing 0.05 M sodium acetate and 0.005 M cupric acetate. Deposition of Zn thin film on Ti/Cu electrodes was carried out at -1.2 V Vs Ag/AgCl for 1 min in an electrochemical cell containing 0.2 M ZnSO4. Deposition parameters of Cu and Zn have been obtained by voltammograms. Set of identical Ti/Cu/Zn thin film electrodes having Cu/Zn ratio of 3.2 were prepared by maintaining the respective Cu and Zn thin film deposition durations for studying the sulphurisation process. In order to grow CuZnS, Ti/Cu/Zn thin film electrodes were annealed at different temperatures (400 oC, 450 oC, 500 oC, 550 oC and 600 oC) with different S contents (10 mg, 20 mg, 30 mg, 40 mg and 50 mg) for a duration of 60 min. CuZnS thin films were characterized using dark and light current voltage measurements in a PEC containing 0.1 M sodium acetate to obtain the best sulphurisation condition. Dark and light I-V characteristics revealed that the films annealed at 600 oC with the S content between 10 to 20 mg exhibits photoactivity. Further, photocurrent was always cathodic confirming the formation of p-CuZnS thin films. It was revealed in this preliminary investigation that the best photoactive films could be produced when films are annealed at 600 oC for 60 min in 20 mg S content. We have found, that photoactive p-CuZnS thin films can be grown by employing the technique of annealing electrodeposited Cu and Zn stack layers using S powder. Cu/Zn ratio of the stack layers could be the crucial parameter in determining the structure, conductivity type and resistivity of CuZnS films and therefore the methodology developed in this study could be further investigated, in order to develop the material for wider applications.
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    Electrodeposition of well-adhered CdTe thin films for solar cell applications
    (Faculty of Science, University of Kelaniya, Sri Lanka, 2016) Atapattu, H.Y.R.; de Silva, D.S.M.; Pathiratne, K.A.S.
    Among the second generation thin film photovoltaics, CdS/CdTe based solar cell device is one of the leading contenders for large scale commercialization. Since the CdTe is the crucial absorber material of the foregoing device, it is essential to maintain a well-adhered CdTe layer to obtain high photovoltaic activities. If not, loosened CdTe layers with numerous pinholes can reduce the electrical, optical, structural and morphological properties of the material and hence extinguish the entire activities of CdS/CdTe solar cells. In the present study, an electrodeposition procedure was developed to fabricate welladherent CdTe layers to the substrate using the typical three electrode electrolytic cell. A fluorine doped tin oxide conducting glass substrate (7Ω/sq.) with dimensions of (1×3) cm2 was used as the working electrode in the cell. A saturated calomel electrode and a high purity graphite rod served as reference and counter electrodes respectively. All the electrodepositions were carried out using an aqueous solution containing 1.0 mol/L CdSO4, 1.0 mmol/L TeO2 and 5.5 mmol/L CdCl2. Based on the cyclic voltammetry studies and the stoichiometry of the proposed chemical reaction which forms CdTe material, the possible cathodic deposition potential (CDP) and pH ranges were identified to be in the ranges of 550-710 mV and 1.4-2.4 respectively. Henceforth, CdTe layers were electrodeposited at above mentioned conditions at temperature of 65 °C and subsequently annealed in air at 400 °C for 10 min. Thereafter, by considering the physical appearance of deposited CdTe layers and their adhesiveness upon a high pressure N2 flow, the feasible values for CDP and pH were found to be in the ranges of 590-660 mV and 2.0-2.4 respectively. To further fine-tune the values for CDP and pH, a series of CdTe layers were deposited at above feasible growth conditions and inspected for their electrical, optical, structural and morphological properties using the methods of photo-electrochemical cell, optical absorption spectroscopy, X-ray diffraction and scanning electron microscopy respectively. Results revealed that, the optimum CDP is in the range of 620-660 mV and pH is in the range of 2.1-2.3 to exhibit good photovoltaic qualities.