Annealing Studies of CdS Film Grown on ITO Substrate with CBD Method

Abstract CdS material is very important for fabricating electro-optic devices because it has a direct and wide band-gap. Due to its wide band-gap, CdS film can be acted as a window material to develop stable and low-cost solar cell. In recent years, CdS film grown on ITO substrate is usually used to fabricate a high efficiency solar cell. If the CdS thin film was deposited by using chemical bath deposition (CBD) method, the fabrication process was not only simple and inexpensive, but the film thickness also quite uniform. Furthermore, the properties of CdS film will be quite improved through annealing process. In this paper, it is to present the enhancing properties of CdS thin film growth on ITO substrate by varying the annealing temperature and annealing time.

Keywords: Annealing, CdS film, ITO substrate, CBD method, solar cell.

1. Introduction Due to direct and wide band-gap, CdS material is one of for In the important application particular,

using many techniques such as chemical bath deposition (VE), (CBD), spray vacuum pyrolysis,

evaporation

semiconductors electro-optic

electro-deposition (ED), etc. Among these deposition techniques, CBD method is rather simple and inexpensive. It is possible that uniform films with good adherence and reproducibility can be obtained by CBD method[3,4]. In advance, annealing process will improve the structural, electrical, and optical

devices.

heterojunction solar cells with a narrow band-gap base and wide band-gap

window have been investigated in an attempt to develop efficient, stable, and low-cost solar cell. It has been found that CdS can be acted as excellent window for thin-film CdTe solar cell. From the point of view of technology, a high efficient CdS/CdTe solar cell requires a

properties of CdS film to act as an optical window in a solar cell. In addition, Ordaz-Flores et al[5] had been reported that annealing process could improve the quality of CdS/ITO interface. Therefore, the annealing treatments would be an important parameter to develop a higher efficient CdTe solar cell. The aim of this work is to present the properties of CdS thin film growth on ITO substrate varied with annealing temperature and annealing time(Fig. 2). Furthermore, we are going to find the optimal annealing temperature and

conducting substrate for improving cell performance. By using this junction, its solar conversion efficiency can be

reached at 16.5% in the laboratory [1]. It is well known that ITO can be used as both a conductor and an electrode to support the CdS thin film into the heterostructure CdTe/CdS/ITO/glass solar cell[2](Fig. 1). Therefore, CdS film grown on ITO substrate will play an important role in high efficiency solar cell
Incident light

annealing time which can conduct the performance of CdS/ITO layer.

Glass substrate ITO CdS CdTe Fig. 2 Back connect Fig. 1 A typical CdS/CdTe solar cell. The structure of analysis model. ITO CdS Glass substrate

CdS thin films can be deposited by

2

2. Experimental details 2.1 The experimental setup The experimental setup for the chemical bath deposition of CdS thin films is shown in Fig.3. It consists of a water beaker whose temperature was controlled automatically with a magnetic hot plate and temperature controller. Magnetic stirring was utilized to promote ion-by-ion heterogeneous growth on the substrates. The substrates were placed vertically in the solution after being cleaned. The other equipments are pH meter, burette, Teflon holder, etc.
Burett

substrate. It would affect the quality of CdS thin film. 2.3 Preparation of CdS film CdS films were prepared by CBD technique with magnetic agitation.

Briefly, the total volume (1000 ml) of the chemical bath is formed by an aqueous solution containing the following molar concentrations of each react: 0.02M CdSO4, 0.007M thiourea (CS[NH2]2) and ammonia solution (NH3) 25% were used. The reaction mechanism for the

formation of CdS could be understood as follows. Ammonia hydrolyzes in water can give out OH: NH3 + H2O NH4+ + OH (1)

Thermometer

The source of Cd2+:

Reaction solution Solution beaker Substrate Magnetic stirrer Magnetic hot plate

CdSO4

Cd2+ + SO42

(2)

Cd2+ and NH3 form a complex species of cadmium [Cd(NH3)4]2+ (to slowly release Cd2+): Cd2+ + 4NH3 [Cd(NH3)4]2+ (3)

Fig.3 Experimental setup for growing CdS film in solution.

2.2 Cleaning of ITO substrate For our sample, CdS thin film was deposited onto 55 cm ITO substrate. Before deposition, the ITO substrate must be cleaned first with soap and then acetone and isopropyl alcohol, and rinsed with distilled water. This step is
3
2

Then Cd2+ + 2OH Cd(OH)2(S) (4)

Thiourea hydrolyzes in alkaline solution to give S2( The source of S2): SC(NH2)2+2OH S2+CN2H2+2H2O (5)

important before CdS film grown on ITO

Cadmium sulfide is formed: [Cd(NH3)4]2+ + S2CdS(S) + 4NH3 (6)

deionized water ultrasonically to remove any loosely adhered CdS particles on the film surface and then dried in air.

The pH value of chemical bath is 10. The bath temperature was kept at 75C~80C. A lower bath temperature could retard the CdS deposition rate, however, a higher temperature would produce a higher evaporation of chemical bath to make an uncontrollable deposition rate. The ITO substrate was held by Teflon holder when they were immersed vertically in the chemical bath. Good CdS film was reasonably obtained if the temperature and the pH value mentioned above could be

2.3 Annealing To improve the properties of CdS film, the samples were annealed in nitrogen atmosphere. Annealing

temperatures were at 50, 100, 150, 200 C with different annealing time (time of constant annealing temperature) of 5, 10, 15, and 20 min, respectively, as listed in Table 1. After anneal processing, the samples were still left in the nitrogen atmosphere until they came back to room temperature.
Tab.1 Experimental samples fabricated at different annealing conditions. 5 min 50 100 150 200 Sample 1 Sample 5 Sample 9 Sample 13 10 min Sample 2 Sample 6 Sample 10 Sample 14 15 min Sample 3 Sample 7 Sample 11 Sample 15 20 min Sample 4 Sample 8 Sample 12 Sample 16

maintained constant within 20 minutes. Due to evaporation of ammonia, however, ammonia solution was needed to be appropriately and slowly dropped into the bath. Thus, a transparent and pale yellow film will present and highly adhere to the substrate. In order to proceed optical measurement, the CdS film must be removed from one side of the substrate by using HCl solution. By the way, the chemical bath solution was agitated with a magnetic stirrer during deposition. This method is not only producing

2.4 Measurements Measurements of in-plane resistance were made on films deposited on ITO/glass. For low-resistivity films, a four-probe technique was used. Optical properties of the

high-quality CdS film but also is very useful gradients for of avoiding the bath concentration or colloids.

CdS/ITO/glass layer were measured at room temperature by using UV-visible spectrometer (UV-500, LNICAM) in the wavelength range of 190-900 nm.
4

Consequently, the film was washed with

3. Results and discussion 3.1 Electrical properties For CdS film, the variation of its sheet resistance is as a function of annealing temperature and time, as shown in Fig.6. From this figure, it can be observed that the sheet resistance roughly decreased as the temperature and time increased. This result could be
Fig. 6 Sheet resistance of CdS film is as a function of

understood by three major causes resulted by annealing process. The first one is due to the crystalline phase change of CdS film from cubic to hexagonal through thermal treatment. Because the resistance of hexagonal CdS phase is lower than that of cubic. The second is that the increasing of the grain size would lead to the sheet resistance decreased[6]. The last was the stoichiometric change in the film. It is due to increased electron density by reducing the sulfide thought annealing as a result of the reduction of resistance[7]. However, the sheet resistance was

annealing temperature and time.

3.2 Optical properties Optical transmittance layers spectra at of

CdS/ITO/glass

different

annealing temperatures and times are shown in Fig.2. It is known that the optical transmittance of CdS film at the band edge is quite sharp and the band edge shifts towards the higher

wavelength (lower energy region) side through annealing[8]. Through annealing, however, the band edge of as-deposited side located at the higher wavelength would shift to the lower wavelength, as shown in Fig.7. It is perhaps seen that more light can reach to the CdS/CdTe layer since the optical property of ITO substrate was improved by thermal treatment.

increasing as annealing temperature over 200C. Owing to higher temperature cadmium and sulphur would be degraded to affect the overall quality of CdS thin film. In this study, we know that the CdS film on ITO substrate would disappear when the temperature was over 250C.

Therefore, the spectra shift properly be attributed to the CdS films due to annealing. It means that less energy is needed for an electron of CdS films to jump to the conduction band.

Fig. 7 Transmission spectra of CdS/ITO/glass layers for all samples are as-deposited film at different annealing temperatures and times.

Figure

shows

transmittance

spectra at 150C for different times. Their band edges were not shifted and the transmittance increased as the annealing time increased.
Fig. 9 Transmission spectra of CdS/ITO/glass layers for four samples are annealed with 20 min but at different annealing temperatures.

4. Conclusion In this work, properties of the CdS film are certainly improved by annealing process including annealing temperature and annealing time. In other words, annealing process can increase the

conductivity of the CdS film and improve

Fig. 8 Transmission spectra of CdS/ITO/glass layers for four samples are annealed at 150C with different annealing times.

the transmittance of CdS/ITO/glass layers. However, higher temperature would

cause degradation of cadmium and sulphur to indirectly affect the overall 9 shows transmittance

Figure

performance of CdS/CdTe solar cell. In conclusion, the optimum annealing

spectra for different temperatures at 20 min. It can be seen that the higher annealing temperature, the higher

conditions of temperature and time can be considered as 150 C and 20 min which can dominantly conduct the performance of CdS/ITO layer for CdTe solar cell.
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wavelength side the band edge shifts toward. This is consistent with the results reported by O. Zelaya-Angel et al.

5. Acknowledgment The author would like to thank the National Science Council of the Republic of China, Taiwan, for financially

pp.47-54, 1984. [7] P.N. Gibson, M.E. zsan, D. Lincot, P. Cowache, D. Summa, Modelling of the structure of CdS thin films, Thin Solid Films, vol.361362, pp.34-40, 2000. [8] O. Zelaya-Angel, L. Hernandez, O. de Melo, J. J. Alvarado-Gil, R. Lozada-Morales, C. Falcony and H. Vargas, Band-gap shift in CdS: phase transition

supporting this research under Contract No. NSC98-2815-C-155-002-E.

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applications, Solar Energy Materials & Solar Cells, vol.62, pp.275-293, 2000. [4] S. Mahanty, D. Basak, F. Rueda, M. Leon. Optical properties of chemical bath deposited CdS thin films, Electronic Materials, vol.28 (5), pp. 559-562, 1999. [5] A. Ordaz-Flores, P. Bartolo-Prez, R.

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