Abstract: cu(In,Ga)Se₂ (CIGS) precursor films were deposited on Mo/glass by electrodeposition, and then annealed in Se vapor. The annealing temperature ranged from 450 °C to 580 °C, and two heating rates were selected. The results showed that the crystalline quality of the CIGS films and formation of the Cu-Se compound could be strongly influenced by the selenization temperature and heating rate. Raman spectroscopy and X-ray diffraction (XRD) analysis showed that when the selenization temperature was increased from 450 °C to 550 °C, the amount of binary CuSe phase decreased and the amount of Cu₂Se increased. After annealing at 580 °C, a minimum amount of Cu_2−xSe compounds was obtained and the degree of CIGS film crystallinity was higher than in other samples. The relationship between the properties of the film and the heating rate was studied. XRD and Raman spectra showed a decrease in the Cu_2−xSe phase with increasing heating rate. Scanning electron microscopy (SEM) and XRD showed a remarkable increase in the grain size of CIGS during rapid heating.

退火条件对电沉积制备铜铟镓硒薄膜品质的影响

[1]Adurodija FO, Song J, Kim SD, et al., 1999. Growth of CuInSe₂ thin films by high vapour Se treatment of co-sputtered Cu-In alloy in a graphite container. Thin Solid Films, 338(1-2):13-19.

[2]Ao JP, Yang L, Yan L, et al., 2009. Comparison of the compositions and structures of electrodeposited Cu-poor and Cu-rich Cu(In_1-xGa_x)Se₂ films before and after selenization. Acta Physica Sinica, 58(3):1870-1878.

[3]Basol BM, Kapur VK, 1990. Deposition of CuInSe₂ films by a 2-stage process utilizing e-beam evaporation. IEEE Transactions on Electron Devices, 37(2):418-421.

[4]Bhattacharya RN, Batchelor W, Granata JE, et al., 1998. CuIn_1-xGa_xSe₂-based photovoltaic cells from electrodeposited and chemical bath deposited precursors. Solar Energy Materials and Solar Cells, 55(1-2):83-94.

[5]Birkmire RW, Eser E, 1997. Polycrystalline thin film solar cells: present status and future potential. Annual Review of Materials Science, 27(1):625-653.

[6]Chen CH, Hu HT, Lin FM, et al., 2017. Residual stress analysis and bow simulation of crystalline silicon solar cells. Journal of Zhejiang University-SCIENCE A (Applied Physics & Engineering), 18(1):49-58.

[7]Chen DS, Yang J, Xu F, et al., 2013. Performance improvement of CdS/Cu(In,Ga)Se₂ solar cells after rapid thermal annealing. Chinese Physics B, 22(1):018801.

[8]Contreras MA, Romero MJ, Noufi R, 2006. Characterization of Cu(In,Ga)Se₂ materials used in record performance solar cells. Thin Solid Films, 511-512:51-54.

[9]Delsol T, Samantilleke AP, Chaure NB, et al., 2004. Experimental study of graded bandgap Cu(InGa)(SeS)₂ thin films grown on glass/molybdenum substrates by selenization and sulphidation. Solar Energy Materials and Solar Cells, 82(4):587-599.

[10]Fernandez AM, Bhattacharya RN, 2005. Electrodeposition of CuIn_1-xGa_xSe₂ precursor films: optimization of film composition and morphology. Thin Solid Films, 474(1-2):10-13.

[11]Friedfeld R, Raffaelle RP, Mantovani JG, 1999. Electrodeposition of CuIn_1-xGa_xSe₂ thin films. Solar Energy Materials and Solar Cells, 58(4):375-385.

[12]Hamakawa Y, 2012. Thin-film Solar Cells Next Generation Photovoltaics and Its Applications. Springer-Verlag Berlin Heidelberg, p.167.

[13]Harati M, Jia J, Giffard K, et al., 2010. One-pot electrodeposition, characterization and photoactivity of stoichiometric copper indium gallium diselenide (CIGS) thin films for solar cells. Physical Chemistry Chemical Physics, 12(46):15282-15290.

[14]Izquierdo-Roca V, Saucedo E, Ruiz CM, et al., 2009. Raman scattering and structural analysis of electrodeposited CuInSe₂ and S-rich quaternary CuIn(S,Se)₂ semiconductors for solar cells. Physica Status Solidi (a), 206(5):1001-1004.

[15]Jackson P, Hariskos D, Wuerz R, et al., 2014. Compositional investigation of potassium doped Cu(In,Ga)Se₂ solar cells with efficiencies up to 20.8%. Physica Status Solidi (RRL)-Rapid Research Letters, 8(3):219-222.

[16]Jiang F, Feng J, 2006. Effect of temperature on selenization process of metallic Cu-In alloy precursors. Thin Solid Films, 515(4):1950-1955.

[17]Karg F, Probst V, Harms H, et al., 1993. Novel rapid-thermal-processing for CIS thin-film solar cells. Conference Record of the 23rd IEEE Photovoltaic Specialists Conference, p.441-446.

[18]Kemell M, Ritala M, Saloniemi H, et al., 2000. One-step electrodeposition of Cu_2-xSe and CuInSe₂ thin films by the induced co-deposition mechanism. Journal of the Electrochemical Society, 147(3):1080-1087.

[19]Lakshmikumar ST, Rastogi AC, 1996. Phase evolution in low-pressure Se vapor selenization of evaporated Cu/In bilayer precursors. Journal of Applied Physics, 79(7):3585-3591.

[20]Lincot D, Guillemoles JF, Taunier S, et al., 2004. Chalcopyrite thin film solar cells by electrodeposition. Solar Energy, 77(6):725-737.

[21]Malaquias JC, Steichen M, Dale PJ, 2015. One-step electrodeposition of metal precursors from a deep eutectic solvent for Cu(In,Ga)Se₂ thin film solar cells. Electrochimica Acta, 151:150-156.

[22]Mise T, Nakada T, 2009. Microstructural properties of (In,Ga)₂Se₃ precursor layers for efficient cigs thin-film solar cells. Solar Energy Materials and Solar Cells, 93(6-7):1000-1003.

[23]Panicker MPR, Knaster M, Kroger FA, 1978. Cathodic deposition of CdTe from aqueous-electrolytes. Journal of the Electrochemical Society, 125(4):566-572.

[24]Powalla M, Voorwinden G, Hariskos D, et al., 2009. Highly efficient CIS solar cells and modules made by the co-evaporation process. Thin Solid Films, 517(7):2111-2114.

[25]Rau U, Schock HW, 1999. Electronic properties of Cu(In,Ga)Se₂ heterojunction solar cells–recent achievements, current understanding, and future challenges. Applied Physics A: Materials Science & Processing, 69(2):131-147.

[26]Saji VS, Choi IH, Lee CW, 2011. Progress in electrodeposited absorber layer for CuIn_(1-x)Ga_xSe₂ (CIGS) solar cells. Solar Energy, 85(11):2666-2678.

[27]Sebastian PJ, Calixto ME, Bhattacharya RN, et al., 1999. CIS and CIGS based photovoltaic structures developed from electrodeposited precursors. Solar Energy Materials and Solar Cells, 59(1-2):125-135.

[28]Witte W, Kniese R, Eicke A, et al., 2006. Influence of the GA content on the Mo/Cu(In,Ga)Se₂ interface formation. Conference Record of the IEEE 4th World Conference on Photovoltaic Energy Conversion, p.553-556.

[29]Witte W, Kniese R, Powalla M, 2008. Raman investigations of Cu(In,Ga)Se₂ thin films with various copper contents. Thin Solid Films, 517(2):867-869.

[30]Yamanaka S, Tanda M, Nakada N, et al., 1991. Study of CuInSe₂ formation kinetics in the selenization process by Raman spectroscopy. Japanese Journal of Applied Physics, 30(Part 1, No. 3):442-446.

[31]Yeh MH, Ho SJ, Chen GH, et al., 2016. Toward low-cost large-area CIGS thin film III: effect of Se concentration on crystal growth and defect formation of sequentially electrodeposited CIGS thin films. Solar Energy, 132:547-557.

[32]Zhang HX, Hong RJ, 2016. CIGS absorbing layers prepared by RF magnetron sputtering from a single quaternary target. Ceramics International, 42(13):14543-14547.

[33]Zhang Z, Li J, Wang M, et al., 2010. Influence of annealing conditions on the structure and compositions of electrodeposited CuInSe₂ films. Solid State Communications, 150(47-48):2346-2349.