在本研究中，我們利用多元醇法(polyol route)製備出具有單一黃銅礦晶相結構的CuIn1-xBxS2(CIBS)奈米粒子，x介於0.1~0.5之間。CuIn1-xBxS2奈米粉體使用氯化銅(CuCl2)、氯化銦(InCl3)、氧化硼(B2O3)及硫元素(S)藥品製備。合成出的奈米粒子其晶粒大小約介於20~85nm之間。
經由X光晶體繞射儀(X-Ray diffraction)、拉曼光譜儀(Raman spectroscopy)等其他分析來確認材料的性質，並且透過調整CIBS奈米粒子中的氯化銦與氧化硼的成分比，控制銦與硼的比例及不同溫度等參數下，形成最佳的CIBS粉體。

In this study, we report the synthesis in solution of phase pure nanocrystals of chalcopyrite CuIn1-xBxS2 with x ranged from 0.1~0.5. CuIn1-xBxS2 nanocrystals were synthesized from copper chlorides, indium chlorides, boric anhydride and sulfur. The nanocrystals ranging from 20 to 85 nm in diameter were synthesized in solution.
The characteristics of the material could be confirmed by X-Ray diffraction, Raman spectroscopy and the other analysis methods, and the more good CIBS powder could be made by controlling the reaction temperatures and the In-B ratio from the In reactant and the B reactant, respectively.

[1] D. Lidgate, “Green energy,” Engineering science and eduction joural, 1, p.221-227. (1992)
[2] Michael Grätzel, “Photoelectrochemical cells,” Nature, 414, p338-344. (2001)
[3] K. Zweibel, “Harnessing solar Power: The photovoltaics challenge,” Plenum : New York, p.235-253. (1990)
[4] 邱秋燕, 廖曰淳, 郭豐綱, “低成本銅銦鎵硒(CIGS)太陽電池技術發展” 工業材料, 276, p.58-68. (2009)
[5] A.S. Kindyak, V.V. Kindyak, V.F. Gremenok, “Energy-gap variations in thin laser-deposited Cu(In,Ga)Se2 films,” Materials Letters., 28, p.273-275. (1996)
[6] Arturo Morales-Acevedo, “Effective absorption coefficient for graded band-gap semiconductors and the expected photocurrent density in solar cells,” Solar Energy Materials & Solar cells., 93, P.41-44. (2009)
[7] M. A. Contreras, M. J. Romero, R. Noufi, “Characterization of Cu(In,Ga)Se2 materials used in record performance solar cells,” Thin Solid Films., 511-512, p.51-54. (2006)
[8] Stephen J. Fonash, “Solar Cell Device Physics,” Academic Press., p.78. (1981)
[9] M.A.Contreras, K. Ramanathan, J. AbuShama, F. Hasoon, D.L. Young, B. Egass, and R. Noufi,“SHORT COMMUNICATION: ACCELERATED PUBLICATION: Diode Characteristics in State-of-the-Art ZnO/CdS/Cu(In1−xGax)Se2 Solar Cells,” Prog. Photovolt: Res. Appl., 13, p.209-216. (2005)
[10] Philip Jackson, Dimitrios Hariskos, Erwin Lotter, Stefan Paetel, Roland Wuerz, Richard Menner, Wiltraud Wischmann and Michael Powalla,“New world record efficiency for Cu(In,Ga)Se2 thin-film solar cells beyond 20%,” Prog. Photovolt: Res. Appl., 19, p.894-897. (2011)
[11] J.H. Yun, R.B.V. Chalapathy, J.C.Lee, J. Song, and K.H. Yoon, “Formation of CuIn1-xAlxSe2 Thin Films by Selenization of Metallic Precursors in Se Vapor,” Solid State Phenomena, 124-126, p.975-978. (2007)
[12] 徐如人, 龐文琴, “無機合成與製備化學” 五南圖書出版股份有限公司, p.733-742. (2004)
[13] 林琬蓉, “FePt合金粒子之製備與性質研究” 國立成功大學材料科學研究所碩士論文, p.5-8. (2007)
[14] C. B. Murray, D. J. Noms, and M. G. Bawendi, “Synthesis and characterization of nearly monodisperse CdE (E=S, Se, Te) semiconductor nanocrystallites,” J. Am. Chem. Soc., 115, p.8706-8715. (1993)
[15] 利宗倫, “以溶熱法合成Ⅰ-Ⅲ-Ⅵ 族CuInS2奈米 粒子及其特性探討” 國立成功大學化學工程研究所碩士論文, p.12-13. (2008)
[16] L. S. Li, N. Pradhan, Y. Wang, and X. Peng, “High quality ZnSe and ZnS nanocrystals formed by activating zinc carboxylate precursors,” Nano Letters., 4, p.2261-2264. (2004)
[17] M. A. Hines, G. S. Philippe, “Bright UV-blue luminescent colloidal ZnSe nanocrystals,” J. Phys. Chem. B, 102, p. 3655–3657. (1998)
[18] L. Qu, Z. A. Peng, and X. Peng, “Alternative routes toward high quality CdSe nanocrystals,” Nano Letters, 1, p.333-337. (2001)
[19] W. W. Yu, L. Qu, W. Guo, and X. Peng, “Experimental determination of the extinction coefficient of CdTe, CdSe, and CdS nanocrystals,” Chem. Mater, 15, p.2854-2860. (2003)
[20] W. W. Yu and X. Peng, “Formation of high-quality CdS and other II-VI semiconductor nanocrystals in noncoordinating solvents: tunable reactivity of monomers,” Angew. Chem. Int. Ed, 41, p.2368-2371. (2002)
[21] Z. A. Peng and X. Peng, “Nearly monodisperse and shape - controlled CdSe nanocrystals via alternative routes: nucleation and growth,” J. Am. Chem. Soc, 124, p.3343-3353. (2002).
[22] W. W. Yu, Y. A. Wang, and X. Peng, “Formation and stability of size-, shape-, and structure-controlled CdTe nanocrystals: ligand effects on monomers and nanocrystals,” Chem. Mater, 15, p. 4300-4308. (2003)
[23] N. Gaponik, D. V. Talapin, A. L. Rogach, K. Hoppe, E. V. Shevchenko, A. Kornowski, A. Eychmüller, H. Weller, “Thiol-capping of CdTe nanocrystals: an alternative to organometallic synthetic routes,” J. Phys. Chem. B, 106, p. 7177-7185. (2002)
[24] M. Shim, G. S. Philippe, “Organic-capped ZnO nanocrystals: synthesis and n-type character,” J. Am. Chem. Soc., 123, p.11651-11654. (2001)
[25] Dr. Rodney J. Soukup, Natale J. Ianno, Chad A. Kamler , Jiři Olejníček, Scott A. Darveau, and Christopher L. Exstrom, “Thin Films of CuInxB1-xSe2 as Absorbers for CIBS Solar Cells,” ECS Meet. Abstr., MA2009-02, p.761. (2009)
[26] F. O. Adurodija, et. al., “Growth of CuInSe2 thin films by high vapour Se treatment of co-sputtered Cu-In alloy in a graphite container,” Thin Solid Films, 338, p.13-19. (1999)
[27] R. J. Soukup, et. al., “Reaction Pathway Insights into the Solvothermal Preparation of Culn1-xGaxSe2 Nanocrystalline Materials,” Proc. 33 rd IEEE Photovoltaic Specialists Conference, 978-1-4244-1641-7/08, paper 191. (2008)
[28] M. Marudachalam, H. Hichri, RW Birkmire, and JM Schultz, “Preparation of homogeneous Cu(InGa)Se2 films by selenization of metal precursors in H2Se atmosphere,” Appl. Phys. Lett., 67, p.3978-3980. (1995)
[29] Lin-Jer Chen, Jiunn-Der Liao, Yu-Ju Chuang, and Yaw-Shyan Fu, “Synthesis and　Characterization of Cu(InxB1-x)Se2 Nanocrystals　for Low-Cost Thin Film Photovoltaics,” J. Am. Chem. Soc., 133, p.3704-3707. (2011)
[30] Y. G. Chun, K. H. Kim, K. H. Yoon, “Synthesis of CuInGaSe2 nanoparticles by solvothermal route,” Thin Solid Films., 480-481, p.46-49. (2005)
[31] K. H. Kim, Y. G. Chun, M. Kaiser, B. O. Park, K. H. Yoon, “Synthesis of CuInSe2 and CuInGaSe2 nanoparticles by solvothermal route,” Materials Science., 449-452, p.273-276. (2004)
[32] C. H. Chang, J. M. Ting, “Phase, morphology, and dimension control of CIS powders prepared using a solvothermal process,” Thin Solid Films., 517, p.4174-4178. (2009)
[33] M. G. Panthani, V. Akhavan, B. Goodfellow, J. P. Schmidtke, L. Dunn, A. Dodabalapur, P. F. Barbara, B. A. Korgel, “Synthesis of CuInS2, CuInSe2, and Cu(InxGa1-x)Se2 (CIGS) nanocrystal “inks” for printable photovoltaics,” J. AM. Chem. SOC, 130, p.16770-16777. (2008)
[34] H. Grisaru, O. Palchik, A. Gedanken, “Microwave-assisted polyol synthesis of CuInTe2 and CuInSe2 nanoparticles,” Inorg. Chem., 42, p.7148-7155. (2003)
[35] J. Tang, S. Hinds, S. O. Kelley, E. H. Sargent, “Synthesis of colloidal CuGaSe2, CuInSe2, and Cu(InGa)Se2 nanoparticles,” Chem. Mater., 20, p.6906-6910. (2008)
[36] S. Ahn, K. Kim, Y. Chun, K. Yoon, “Nucleation and growth of Cu(In,Ga)Se2 nanoparticles in low temperature colloidal process,” Thin Solid Films., 515, p.4036-4040. (2007)
[37] Yunbin He, “CuInS2 Thin Films for Photovoltaic:RF Reactive Sputter Deposition and Characterization,” Justus-Liebig-Universität Gießen Dissertation, p.1-119. (2003)
[38] S.-H.Wei and A. Zunger, “Predicted band-gap pressure coefficients of all diamond and zinc-blende semiconductors: Chemical trends,” Phys. Rev. B., 60, p.5404-5411. (1999)
[39] S.H. Wei, L.G. Ferreira, and A. Zunger, “First-principles calculation of the order-disorder transition in chalcopyrite semiconductors,” Phys.Rev.B., 45, p.2533-2536. (1992)
[40] Wei S.H., Zhang S.B., and Zunger A., “Band structure and stability of zinc-blende-based semiconductor polytypes,” Phys.Rev.B, 59, R2478-2481 (1999)
[41] Alvarez-Garcia J, Pérez-Rodríguez A, Barcones B., Romano-Rodríguez A and Morante J.R., Scheer R., Janotti A. and Wei S.H., “Polymorphism in CuInS2 epilayers: origin of additional Raman modes,” Appl. Phys. Lett., 80, p.562-564. (2002)
[42] J.J.M. Binsma, L.J. Giling, J. Bloem, “Phase relations in the system Cu2S-In2S3,” Journal of Crystal Growth, 50, p.429-436. (1980)
[43] Krunksa M, Bijakina O, Varema T, Mikli V, Mellikov E, “Structural and optical properties of sprayed CuInS2 films,” Thin Solid Films, 338, p.125-130. (1999)
[44] S.C. Abrahams, J.L. Bernstein, “Piezoeletric nonlinear optic CuGaS2 and CuInS2 crystal structure: Sublattice distortion in AⅠBⅢCⅥ2 and AⅡBⅣCⅤ2 type chalcopyrites,” J. Chem. Phys., 59, p.5415-5422. (1973)
[45] A. Rockett and R. W. Birkmire, “CuInSe2 for photovoltaic applications,” J. Appl. Phys., 70, p.81-97. (1991)
[46] H.J. Lewerenz, “Development of copperindiumdisulfide into a solar material,” Sol. Energy Mater. Sol. Cells, 83, p.395-407. (2004)
[47] F. Abou-Elfotouh, D. J. Dunlavy, T. J. Coutts, “Intrinsic defect states in CuInSe2 single crystals,” Solar Cells, 27, p.237-245. (1989)
[48] A. Slaoui and R. T. Collins, “Advanced inorganic materials for photovoltaics,” MRS Bull., 32, p.211-218. (2007)
[49] P. D. Paulson, M. W. Haimbodi, S. Marsillac, R. W. Birkmire and W. N. Shafarman, “CuIn1-xAlxSe2 thin films and solar cells,” J. Appl. Phys., 91, p.10153-10156. (2002)
[50] I. Repins, M. A. Contreras, B. Egaas, C. DeHart, J. Scharf, C. L. Perkins, B. To and R. Noufi, “19.9%-efficient ZnO/CdS/CuInGaSe2 solar cell with 81.2% fill factor,” Progr. Photovolt.: Res. Appl., 16, p.235-239. (2008)
[51] S. Marsillac, P. D. Paulson, M. W. Haimbodi, R. W. Birkmire and W. N. Shafarman, “High-efficiency solar cells based on Cu(InAl)Se2 thin films,” Appl. Phys. Lett., 81, p.1350-1352. (2002)
[52] S.H. Wei and A. Zunger, “Band offsets and optical bowings of chalcopyrites and Zn-based II-VI alloys,” J. Appl. Phys., 78, p.3846-3856. (1995)
[53] N.J.Ianno, R.J. Soukup, T. Santero, C. Kamler, J. Huguenin-Love, S.A. Darveau, J. Olejnicek, and C. Exstrom, “Copper-Indium-Boron-Diselenide Absorber Materials,” Mater. Res. Soc. Symp. Proc., 1012, Y03-21-Y03-26. (2007)
[54] 林麗娟, “X光繞射原理及其應用”工業材料, 86, p.100-109. (1994)
[55] S. Ahn, C. Kim, Y. Chun, J. Yun, J. Lee, “Effects of heat treatments on the properties of Cu(In,Ga)Se2 nanoparticles,” Solar Energy Materials & Solar Cells., 91, p.1836-1841. (2007)
[56] S. Ahn, K. H. Kim, J. H. Yun, K. H. Yoon, “Effects of selenization conditions on densification of Cu(In,Ga)Se2 (CIGS) thin films prepared by spray deposition of CIGS nanoparticles,” Journal of Applied Physics., 105, p.113533-113533-7. (2009)
[57] Q. Guo, G. M. Ford, H. W. Hillhouse and R. Agrawal, “Sulfide Nanocrystal Inks for Dense Cu(In1−xGax)(S1−ySey)2 Absorber Films and Their Photovoltaic Performance,” Nano Lett., 9(8), p.3060-3065. (2009)
[58] D. Pan, X. Wang, Z. H. Zhou, W. Chen, C. Xu and Y. Lu, “Synthesis of Quaternary Semiconductor Nanocrystals with Tunable Band Gaps,” Chem. Mater., 21, p.2489-2493. (2009)
[59] Gebicki W, Igalson M, Zajac W and Trykozko R, “Growth and characterisation of CuAlxInl-xSe2 mixed crystals,” J. Phys. D: Appl. Phys., 23, p.964-965. (1990)
[60] Bodnar I. V., Tsyrelchuk I. N. and Victorov I .A., “Preparation and analysis of the CuAlxInl-xSe2 solid solutions,” J. Mater. Sci. Lett., 13, p.762-764. (1994)
[61] B. J. Stanbery, “Copper Indium Selenides and Related Materials for Photovoltaic Devices,” Crit. Rev. Solid State Mat. Sci., 27(2), p.73-113. (2002)
[62] B. D. Cullity, “Elements of Xray Diffraction”, Addison Wesley, p284. (1978)
[63] J. Llanos, A. Buljan, C. Mujica and T. J. Ramirez, “Electron transfer and electronic structure of KCuFeS2,” J. Alloys Compd., 234, p. 40-42. (1996)
[64] E. P. Domashevskayaa, V. V. Gorbachev, V. A. Terekhova, V. M. Kashkarova, E. V. Panfilova and A. V. Shchukarev, “XPS and XES emission investigations of d–p resonance in some copper chalcogenides,” J. Electron Spectrosc. Relat. Phenom., 114-116, p. 901-908. (2001)
[65] T. T. Xu, J. G. Zheng, N. Wu, A. W. Nicholls, J. R. Roth, D. A. Dikin, and R. S. Ruoff, “Crystalline Boron Nanoribbons: Synthesis and Characterization,” Nano Lett., 4 (5), p.963-968. (2004)
[66] D. Q. Yang and E. Sacher, “Core/Shell Formation of Gold Nanoparticles Induced on Exposure to N, N-Dimethylformamide: Chemical and Morphological Changes,” J. Phys. Chem. C, 111, p. 14320-14326. (2007)
[67] L.L. kazmerski, “Photovoltaics: A review of cell and module technologies,” Renewable and sustainable energy review, 1, p.71-171. (1997)
[68] I.V. Bodnar, L.V. Golubev, V.G. Plotnichenko, E.A. Smolyaninova, “Raman Scattering in CuGaSe2,” Phys. Status Solidi B, 105, K111- K114. (1981)
[69] C. Guillen, J. Herrero, M.t. Gutierrez, F. Briones, “Structure, morphplogy and optical properties of CuInS2 thin films prepared by modulated fiux deposition,” Thin Solid Films, 480, p.19-23. (2005)
[70] B. Barcones, A. Pérez-Rodríguez, L. Calvo-Barrio, A. Romoano-Rodríguez, J.R. Morante, E.Rudigier, I.Luck, J.Djordjevic, R. Scheer, “In situ and ex situ characterization of thermally induced crystallization of CuInS2 thin films for solar cell,” Thin Solid Films, 408-481, p.362-366. (2005)
[71] J. Álvarez-García, J. Marcos-Ruzafa, A. Pérez-Rodríguez , A. Romano-Rodríguez, J.R. Morante , R. Scheer, “MicroRaman scattering from polycrystalline CuInS2 films,” Thin Solid Films, 361-362, p.208-212. (2000)
[72] D. Papadimitriou, N. Esser, and C. Xue, “Structural properties of chalcopyrite thin films studied by Raman spectroscopy,” phys. stat. sol. (b), 242, p.2633-2643. (2005)
[73] J. Olejníček , C.A. Kamler , A. Mirasano , A.L. Martinez-Skinner , M.A. Ingersoll , C.L. Exstrom ,S.A. Darveau , J.L. Huguenin-Love , M. Diaz , N.J. Ianno , R.J. Soukup, “A non-vacuum process for preparing nanocrystalline CuIn1-xGaxSe2 materialsinvolving an open-air solvothermal reaction,” Solar Energy Materials and Solar Cells, 94, p.8-11. (2010)
[74] S. Theodoropoulou, D. Papadimitriou, N. Rega, S. Siebentritt, M.Ch. Lux-Steiner, “Raman and photoreflectance study of CuIn1-xGaxSe2 epitaxial layers,” Thin Solid Films, 511-512, p.690-694. (2006)
[75] S. Roy, P. Guha, S.N. Kundu, H. Hanzawb, S. Chaudhuri, A.K. Pal, “Characterization of Cu(In,Ga)Se2 films by Raman scattering,” Mater. Chem. Phys., 73, p.24-30. (2002)