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P-type CuInSe2 thin films prepared by selenization of one-step electrodeposited precursors

Published online by Cambridge University Press:  31 January 2011

Deliang Wang*
Affiliation:
Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China
*
a) Address all correspondence to this author. e-mail: eedewang@ustc.edu.cn
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Abstract

In this study, p-type CuInSe2 (CIS) films were prepared by selenization of one-step electrodeposited Cu-In-2Se (atomic ratio) precursors. To obtain high-quality, dense, and homogeneous CIS films for solar cell application, the effects of substrate temperatures during selenization and precursor compositions on the final microstructures were systematically investigated. The precursor layers evolved in very different ways under different selenization conditions. The final microstructures and phases of the films depended critically on the precursor compositions, selenization temperature, and the selenization thermal process history. Low melting temperature CuxSe phase, which tended to segregate at the film surface, can efficiently assist the CIS grain growth. Large hexagonal CuSe platelets were formed at a temperature as low as 170 °C in Cu-rich precursor, which acted as an element-transport flux agent at higher temperature under high Se vapor and reacted with In-Se selenide to form CIS at temperatures above 500 °C. Good crystalline quality chalcopyrite CIS film was obtained at a selenization temperature of 550 °C.

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Copyright © Materials Research Society 2009

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References

1Rau, U. and Schock, H.W.: Electronic properties of Cu(In,Ga)Se2 heterojunction solar cells–Recent achievements, current understanding, and future challenges. Appl. Phys. A 69, 131 (1999).CrossRefGoogle Scholar
2Repins, I., Contreras, M.A., Egaas, B., DeHart, C., Scharf, J., Perkins, C.L., To, B., and Noufi, R.: 19.9%-efficient ZnO/CdS/CuInGaSe2 solar cell with 81.2% fill factor. Prog. Photovoltaics Res. Appl. 16, 235 (2008).CrossRefGoogle Scholar
3Lincot, D., Guillemoles, J.F., Taunier, S., Guimard, D., Sicx-Kurdi, J., Chaumont, A., Roussel, O., Ramdani, O., Hubert, C., Fauvarque, J.P., Bodereau, N., Parissi, L., Panheleux, P., Fanouillere, P., Naghavi, N., Grand, P.P., Benfarah, M., Mogensen, P., and Kerrec, O.: Chalcopyrite thin film solar cells by electrodeposition. Sol. Energy 77, 725 (2004).CrossRefGoogle Scholar
4Bhattacharya, R.N., Batchelor, W., Wiesner, H., Hasoon, F., Granata, J.E., Ramanathan, K., Alleman, J., Keane, J., Mason, A., Matson, R.J., and Noufi, R.N.: 14.1% CuIn1–xGaxSe2-based photovoltaic cells from electrodeposited precursors. J. Electrochem. Soc. 145, 3435 (1998).CrossRefGoogle Scholar
5Thouin, L. and Vedel, J.: Electrodeposition and characterization of CuInSe2 thin films. J. Electrochem. Soc. 142, 2996 (1995).CrossRefGoogle Scholar
6Guillen, C. and Herrero, J.: Reaction pathways to CuInSe2 formation from electrodeposited precursors. J. Electrochem. Soc. 142, 1834 (1995).CrossRefGoogle Scholar
7Guillmoles, J.F., Cowache, P., Massaccesi, S., Thouin, L., Sanchez, S., Lincot, D., and Vedel, J.: Solar cells with improved efficiency based on electrodeposited copper indium diselenide thin films. Adv. Mater. 6, 379 (1994).CrossRefGoogle Scholar
8Tzvetkova, E., Stratieva, N., Ganchev, M., Tomov, I., Ivanova, K., and Kochev, K.: Preparation and structure of annealed CuInSe2 electrodeposited films. Thin Solid Films 311, 101 (1997).CrossRefGoogle Scholar
9Guillemoles, J.F., Cowache, P., Lusson, A., Fezzaa, K., Boisivon, F., Vedel, J., and Lincot, D.: One step electrodeposition of CuInSe2: Improved structural, electronic, and photovoltaic properties by annealing under high selenium pressure. J. Appl. Phys. 79, 7293 (1996).CrossRefGoogle Scholar
10Kaelin, M., Rudmann, D., Kurdesau, F., Meyer, T., Zogg, H., and Tiwari, A.N.: CIS and CIGS layers from selenized nanoparticle precursors. Thin Solid Films 431–432, 58 (2003).CrossRefGoogle Scholar
11Taunier, S., Sicx-Kurdi, J., Grand, P.P., Chomont, A., Ramdani, O., Parissi, L., Panheleux, P., Naghavi, N., Hubert, C., Ben-Farah, M., Fauvarque, J.P., Connolly, J., Roussel, O., Mogensen, P., Mahe, E., Guillemoles, J.F., Lincot, D., and Kerrec, O.: Cu(In,Ga)(S,Se)2 solar cells and modules by electrodeposition. Thin Solid Films 480-481, 526 (2005).CrossRefGoogle Scholar
12Noufi, R., Axton, R., Herrington, C., and Deb, S.K.: Electronic properties versus composition of thin films of CuInSe2. Appl. Phys. Lett. 45, 668 (1984).CrossRefGoogle Scholar
13Parretta, A., Addonizio, M.L., Loreti, S., Quercia, L., and Jayaraj, M.K.: An investigation on the growth of thin chalcopyrite CuInSe2 films by selenization of Cu-In alloys in a box. J. Cryst. Growth 183, 196 (1998).CrossRefGoogle Scholar
14Nadenau, V., Braunger, D., Hariskos, D., Kaiser, M., Koble, C., Oberacker, A., Ruckh, M., Ruhle, U., Schaeffler, R., Schmid, D., Walter, T., Zweigart, S., and Schock, H.W.: Solar cells based on CuInSe2 and related compounds: Material and device properties and processing. Prog. Photovoltaics Res. Appl. 3, 363 (1995).CrossRefGoogle Scholar
15Tuttle, J.R., Contreras, M., Bode, M.H., Niles, D., Albin, D.S., Matson, R., Gabor, A.M., Tennant, A., Duda, A., and Noufi, R.: Structure, chemistry, and growth mechanisms of photovoltaic quality thin-film Cu(In,Ga)Se2 grown from a mixed-phase precursor. J. Appl. Phys. 77, 153 (1995).CrossRefGoogle Scholar
16Anderson, T.J., Crisalle, O.D., Li, S.S., and Holloway, P.H.: Future CIS manufacturing technology development, in NREL Report No. SR-520-33997 (2003).Google Scholar
17Givargizov, E.I.: Oriented Crystallization on Amorphous Substrates (Plenum Publishing Corp., New York, 1991).CrossRefGoogle Scholar
18Anderson, T.J., Li, S.S., Crisalle, O.D., and Craciun, V.: Fundamental materials research and advanced process development for thin-film CIS-based photovoltaics, in NREL Report No. SR-520-40568 (2005).Google Scholar
19Gupta, A. and Isomura, S.: Precursor modification for preparation of CIS films by selenization technique. Sol. Energy Mater. Sol. Cells 53, 385 (1998).CrossRefGoogle Scholar
20Folmer, J.C.W., Turner, J.A., Noufi, R., and Cahen, D.: Structural and solar conversion characteristics of the (Cu2Se)x(In2Se3)1-x system. J. Electrochem. Soc. 132, 1319 (1985).CrossRefGoogle Scholar
21Ramakrishna, K.T. Reddy, Forbes, I., Miles, R.W., Carter, M.J., and Dutta, P.K.: Growth of high-quality CuInSe2 films by selenising sputtered Cu–In bilayers using a closed graphite box. Mater. Lett. 37, 57 (1998).CrossRefGoogle Scholar
22Bhattacharyya, D., Forbes, I., Adurodija, F.O., and Carter, M.J.: Formation of CuInSe2 by the selenization of sputtered Cu/In layers. J. Mater. Sci. 32, 1889 (1997).CrossRefGoogle Scholar
23Adurodija, F.O., Carter, M.J., and Hill, R.: Synthesis and characterization of CuInSe2 thin films from Cu, In and Se stacked layers using a closed graphite box. Sol. Energy Mater. Sol. Cells 40, 359 (1996).CrossRefGoogle Scholar
24Hergert, F., Jost, S., Hock, R., and Purwins, M.: A crystallographic description of experimentally identified formation reactions of Cu(In,Ga)Se2. J. Solid State Chem. 179, 2394 (2006).CrossRefGoogle Scholar
25Niki, S., Fons, P.J., Yamada, A., Lacroix, Y., Shibata, H., Oyanagi, H., Nishitani, M., Negami, T., and Wada, T.: Effects of the surface Cu2-xSe phase on the growth and properties of CuInSe2 films. Appl. Phys. Lett. 74, 1630 (1999).CrossRefGoogle Scholar
26Ishii, M., Shibata, K., and Nozaki, H.: Anion distributions and phase transitions in CuS1-xSex(x = 0-1) studied by Raman spectroscopy. J. Solid State Chem. 105, 504 (1993).CrossRefGoogle Scholar
27Wang, D., Wan, L., Bai, Z., and Cao, Y.: Mixed phases in p-type CuInSe2 thin films detected by using micro-Raman scattering spectroscopy. Appl. Phys. Lett. 92, 211912 (2008).CrossRefGoogle Scholar
28Adurodija, F.O., Song, J., Kim, S.D., Kwon, S.H., Kim, S.K., Yoon, K.H., and Ahn, B.T.: Growth of CuInSe2 thin films by high vapor Se treatment of co-sputtered Cu-In alloy in a graphite container. Thin Solid Films 338, 13 (1999).CrossRefGoogle Scholar
29Rincon, C. and Ramirez, F.J.: Lattice vibrations of CuInSe2 and CuGaSe2 by Raman microspectrometry. J. Appl. Phys. 72, 4321 (1992).CrossRefGoogle Scholar
30Tanino, H., Maeda, T., Fujikake, H., Nakanishi, H., Endo, S., and Irie, T.: Raman spectra of CuInSe2. Phys. Rev. B 45, 13323 (1992).CrossRefGoogle ScholarPubMed
31Stanbery, B.J., Kincal, S., Kim, S., Chang, C.H., Ahrenkiel, S.P., Lippold, G., Neumann, H., Anderson, T.J., and Crisalle, O.D.: Epitaxial growth and characterization of CuInSe2 crystallographic polytypes. J. Appl. Phys. 91, 3598 (2002).CrossRefGoogle Scholar
32Nagels, P., Sleeckx, E., Callaerts, R., and Tichy, L.: Structural and optical properties of amorphous selenium prepared by plasmaenhanced CVD. Solid State Commun. 94, 49 (1995).CrossRefGoogle Scholar
33Alvarez-Garcia, J., Barcones, B., Perez-Rodriguez, A., Romano-Rodriguez, A., Morante, J.R., Janotti, A., Wei, S.H., and Scheer, R.: Vibrational and crystalline properties of polymorphic CuInC2 (C=Se,S) chalcogenides. Phys. Rev. B 71, 054303 (2005).CrossRefGoogle Scholar