本論文係採用助熔劑長晶法來成長非線性光學晶體，並藉由能量散佈光譜(EDS)量測晶體成分比例、單晶X光繞射(XRD)量測晶體結構、粉末X光繞射(PXRD)確定純相製備、拉曼散射光譜(Raman)量測晶體振動型態、傅立葉紅外線光譜(FTIR)量測晶體可穿透範圍、紫外光可見光光譜(UV-visible)量測晶體能隙、粉末二倍頻(PSHG)量測晶體非線性係數。
　　化合物彼此間為等結構關係，晶系為tetragonal P 21c，其中化合物(1)的晶格常數為：a = 13.0397(12) Å, c = 6.3042(12) Å；化合物 (2)的晶格常數為：a = 13.1585(2) Å, c = 6.3520(2) Å；化合物 (3)的晶格常數為：a = 13.5975(14) Å, c = 6.5266(13) Å。結構皆以 [CuGa4Q14]鏈狀區塊組成，其中 [CuGa4Q14]利用CuQ4四面體以共用邊方式相連，再與GaQ4四面體以共用角方式連結而形成；最後 [CuGa4Q14]鏈狀結構與GaQ4四面體利用共用角的方式連結成三維骨架結構；由於化合物(1)、(2)與(3)皆為非對稱中心結構，實驗得知具有二次非線性光學特性。

We have successfully synthesized the new nonlinear materials by using the flux-growth synthesis method.
From the results of XRD, we prove that Ba4CuGa5Q12 (Q = S(1), S/Se(2), Se(3)) belong to space group P-421c. Compound 1 crystallizes in tetragonal P-421c with a =13.5975(14) Å, c = 6.5266(13) Å and adopts a new 3D structure. The CuSe4 and GaSe4 tetrahedra share corners alternatively to form a framework with the noncentro-symmetric characteristic.
According to the powder second harmonic generation signals, we obtain the Ba4CuGa5S9Se3 nonlinear effective coefficient is about 1 times value of the AgGaS2, which is larger than Ba4CuGa5S12 but smaller than Ba4CuGa5S12.
The measurements of FTIR、Raman and UV-Vis spectrum reveal that the transparency range is 2.5μm to 46μm and the energy band gap is Ba4CuGa5S12 (2.82ev) > Ba4CuGa5S9Se3 (2.45eV)> Ba4CuGa5Se12 (1.45eV).

[1] G. Dmitriev, G. G. Gurzadyan, and D. N. Nikogosyan, Handbook of Nonlinear Optical Crystals, Springer in Optical Sciences Vol.64
[2] Qingtian Cu,Qiwei Pan,Xiangwen Wu,Wei Shi,Changshui Fang, Journal of Crystal Growth 212, 605 (2000)
[3] J. D. Feichtner and G. W. Roland, Appl. Opt. 11, 993 (1972)
[4] S. C. Abrahams; J. L. Bernstein, J. Chem. Phy. 1973, 59, 1625.
[5] S. C. Abrahams; J. L. Bernstein, J. Chem. Phy. 1974, 61, 1140.
[6] Jackson, A. G.; Ohmer, M. C.; LeClair, S. R., Infrared Phys. Technol. 1997, 38, 233.
[7] Ueng, H. Y.; Hwang, H. L., Mater. Sci. Eng. 1992, B12, 261.
[8] D. H. Auston, et al., Research on NLO materials: an assesment, Appl. Opt. 26, 211 (1986).
[9] W. R. Cooks, Jr. And Ianinni, Final Technical Report, Project No. FY1457-87-03016, AFWAL/MLPO, Wright-Patterson AFB, OH(1987).
[10] (a) Sheldrick, G. M., SHELXL-97, Program for the solution of Crystal Structure, University of Göttingen, Germany, 1997. (b) Sheldrick, G. M., SHELXL-97, Program for the Refinement of Crystal Structure, University of Göttingen, Germany, 1997.
[11] 汪建銘主編,材料分析,第三版, 出版, 中國材料學會
[12] E. A. Davis and N. F. Mott, Philos. Mag., 22 (1970) 903.
[13] P.A. Franken, A.E. Hill, C.W. Peters, and G. Weinreich, Phys. Rev. Letters., 7, 118 (1961)
[14] P.A. Franken and J.F. Ward, Rev. Mod. Phys., 35, 23 (1963)
[15] N. Bloembergen, Proc. IEEE., 51, 124 (1963)
[16] P.S. Pershan, and E. Wolf, Progress in Optics vol.5, (North-Holland Publishing Co., Amsterdam, 1966)
[17] S. K. Kurtz, T. T. perry, J. Appl. Phys. 39,3798(1968)
[18] Chung, D. Y.; Choi, K. S.; Iordanidis, L.; Schindler, J. L.; Brazis, P. W.; Kannewurf, C. R.; Chen, B., Hu, S.; Uher, C.; Kanatzidis, M. G., Chem. Mater. 1997, 9, 3060.
[19] I. V. Bodnar’ , Semiconductors. 1998, 32, 614.
[20] Isaenko, L.; Yelisseyev, S.; Titov, A.; Petrov, V.; Zondy, J. J.; Krinitsin, P.; Merkulov, A.; Vendenyapin, V.; Smirnova, J., Cryst. Res. Technol., 2003, 38, 379.