Thin Solid Films 518 (2010) 72227224

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

Electrochemical deposition of CdSe/CdTe multilayer nanorods for hybrid solar cell

Seong-Hun Kim a, Ju-Young Lee a, Wone-Keun Han b, Jae-Ho Lee a,
a b

Dept. of Materials Science & Engineering, Hongik University, 72-1 Sangsu-dong, Mapo-gu, Seoul 121-791, Republic of Korea Dept. of Science, Hongik University, 72-1 Sangsu-dong, Mapo-gu, Seoul 121-791, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
CdSe and CdTe are composite semiconductor materials used in hybrid solar cell due to their high absorption coefcients. CdSe and CdTe have different band gaps, 1.74 eV and 1.45 eV respectively and then they can absorb solar energy in a wider range of wavelength compare to the silicon solar cell. In this research, CdSe and CdTe nanorods were fabricated using electrochemical deposition in an anodic aluminum oxide template. The electrodeposition behaviors of CdSe and CdTe were investigated using cyclic voltammetric technique. The deposition potentials of CdSe and CdTe were obtained through cyclic voltammetric technique. The effects of Te and Se ion concentration in the electrolyte on the composition of the deposits were investigated to obtain 1:1 atomic ratio. Structures of layered CdSe/CdTe nanorods were analyzed with FESEM and EDS. 2010 Elsevier B.V. All rights reserved.

Available online 7 May 2010 Keywords: CdSe CdTe Cyclic voltammetry Nanorods Electrodeposition

1. Introduction The demands for the eco-friendly energy techniques, such as solar cell, geothermal energy, and wind power were increased due to the shortage of fossil fuel and environmental crisis. Solar cell is the forerunner among eco-friendly energy techniques and has been used for decades. Most of solar cells are bulk silicon solar cells, however the cost of silicon is the burden for solar cell industry. There were many researches on the modied types of solar cell. Hybrid solar cell is one of the possible candidates to lower the cost of solar cell than bulk silicon solar cell. Thin lms of cadmium telluride and cadmium selenide, which belong to the IIVI groups of semiconductors were used in photovoltaic solar cell [1,2]. They are direct energy band gap materials with high absorption coefcient. CdTe and CdSe thin lms were fabricated by ALD, sputtering, MOCVD, chemical spraying, electrodeposition and etc [38]. To achieve the high conversion efciency, the sequential of layers which can absorb wide range of spectrum were deposited. And also nanorods can enhance electron/hole movement and reduce recombination [9]. In this research, multilayer nanorods with CdSe and CdTe with electrodeposition method were investigated. Cyclic voltammetry method shows the basic electrochemical mechanism for the electrodeposition of CdSe and CdTe.

wafer. The counter electrode was mesh type platinum and the reference electrode was an Ag/AgCl electrode. The electrolytes were prepared by dissolving TeO2, CdSO4 in distilled water. The pH of the solution was adjusted with H2SO4 20 ml/l. The lms were deposited from the solution of various concentrations. The cyclic voltammetric measurements were carried out in a potentiostat/galvanostat Model 273A EG&G. For the CdTe and CdSe nanorods anodic aluminum oxide (AAO) was used as a template. Titanium and copper were deposited in series on AAO by sputtering method to give the conductive layer for the electrodeposition. For sequential deposition of CdSe and CdTe, modied cell was designed to control the supply of different electrolytes. The schematic diagram of the multilayer electrodeposition system is shown in Fig. 1. The compositions of the electrolytes were 0.2 M CdSO41 mM H2SeO3 and 0.2 M CdSO40.5 mM TeO2. The pH of all solutions was adjusted between 0.6 and 1 with H2SO4 20 ml/l. Potential was xed at0.6 V (vs. Ag/AgCl) to obtain 1:1 ratio of CdTe and CdSe. The morphologies and compositions of deposits were analyzed with FESEM and EDS. CdSe/CdTe multilayer nanorods in AAO template were obtained after dissolving AAO template in 1 M NaOH for 40 min.

3. Results and discussion 2. Experimental procedure Voltammograms were obtained using a Flat Cell. The substrate material was gold thin lm on copper and titanium deposited silicon
Corresponding author. Tel.: +82 2 320 1483. E-mail address: jhlee@hongik.ac.kr (J.-H. Lee). 0040-6090/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2010.04.079

Cyclic voltammogram was obtained from the electrolyte containing 0.2 M CdSO4 and 0.5 103 M TeO2. Fig. 2(a) shows the cyclic voltammogram. The potential was changed between +1 V and1 V (vs. Ag/AgCl) and scan rate was 100 mV/s. Two cathodic peaks and two anodic peaks were observed. One large cathodic peak was observed at 0.8 V and another small cathodic peak was observed at 0.2 V enlarged inset of cyclic voltammogram in Fig. 2(a). Two anodic

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Fig. 1. Schematic diagram of modied designed cell for multilayer deposition.

Fig. 2. Deposition behavior in 0.2 M Cd0.5 mM Te (a) cyclic voltammogram (b) EDS analysis.

Fig. 3. Deposition behavior in 0.2 M Cd3 mM Se (a) cyclic voltammogram (b) EDS analysis.

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Fig. 4. Morphology of CdSe/CdTe multilayer nanorods.

0.1 V to 0.6 V however Cd deposition was dominant at 0.7 V. CdSe and CdTe multilayer were fabricated by repeating UPD processes. One cycle was consisted of CdSe UPD followed by distilled water washing and CdTe UPD followed by distilled water washing. Total 8 cycles of UPD processes were repeated. Fig. 4 shows CdSe/CdTe multilayer nanorods using potentiostat and modied designed cell at 0.6 V after dissolving AAO template in 1 M NaOH solution. Fig. 5 shows the EDS results of multilayer nanorods before dissolving AAO template. The white region on the top is the CdSe/CdTe multilayer and the gray region is AAO. Cd, Se and Te were detected from EDS analysis. Since the thickness of CdSe and CdTe was not uniform inside the AAO template, the discrete EDS results were not shown and then the mixed signal of elements was detected. Se was richer than Te in multilayer nanorods. At0.6 V, the deposition rate of CdSe was higher than that of CdTe. 4. Conclusions

peaks were observed at 0.4 V and 0.6 V. Reactions at three peaks were explained as follows [10]: Peak 1: Cd2+ + 2e Cd Peak 2: Cd Cd2+ + 2e Peak 3: Te Te4+ + 4e The potential of CdTe deposition is between 0.22 V and 0 V. It is called under potential deposition (UPD). At UPD, CdTe was deposited by following reaction Cd
2

It is possible to deposit CdSe/CdTe nanorods by electrodeposition method for the solar cell. The cyclic voltammetry can reveal the intermediate electrochemical reaction at different potentials in CdSe and CdTe deposition. The condition for the electrodeposition of 1:1 atomic composition of CdSe and CdTe was determined with the use of cyclic voltammetry and analysis of the deposits. Acknowledgement This work was supported by KOSEF Grant No R01-2007-000-20757-0 and New & Renewable Energy R&D program (2008-N-PV08-P-09) under the Korea Ministry of Commerce, Industry and Energy (MOCIE). References
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Te

6e CdTe

Fig. 2(b) shows EDS results of CdTe deposition for 20 min at each potential from 0.1 V to 0.7 V(vs. Ag/AgCl). The ratio of Cd to Te was analyzed at different potentials. The ratio of Cd to Te was maintained between 1 and 0.6 from 0.1 V to 0.6 V, however Cd deposition was dominant at 0.7 V. Fig. 3(a) shows cyclic voltammogram of CdSe electrodeposition on the gold surface. According to Natarajan the deposition of CdSe may be attributed to the following reactions [11]: Peak 1: Cd2+ + 2e Cd Peak 2: H2SeO3 + 4H+ + 4e Se + 3H2O Peak 3: Cd + H2SeO3 + 4H+ + 4e CdSe + 3H2O Fig. 3(b) shows the EDS results with CdSe deposition for 20 min at each potential from0.1 V to0.7 V. The ratio of Cd to Se was analyzed at different potentials. The ratio of Cd to Se was maintained about 1 from

Fig. 5. EDS results of CdSe/CdTe multilayer nanorods.