Cu_2Sn(S,Se)_3薄膜的溶液法制备及其光电性能研究
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摘要
采用低廉、简便及易于控制元素组成的溶液法在钠钙玻璃和钼玻璃基底上沉积Cu-Sn-S前驱体膜,随后在N_2保护下硒化获得到Cu_2Sn(S,Se)_3薄膜,并通过调控前驱薄膜的硒化退火温度,实现了对薄膜形貌、物相结构、电学及光学性能的有效调制.研究结果表明,适当的硒化退火温度,如480℃,可得到表面平整、结晶度高、晶粒致密和双层结构(上层大、下层小晶粒)的Cu_2Sn(S,Se)_3薄膜,其带隙为1.28 eV,载流子浓度可低至6.780×10~(17) cm~(-3),迁移率高达18.19 cm~2·V~(-1)·S~(-1),可用于薄膜太阳能电池的光吸收层.
In this work,Cu-Sn-S precursor film was prepared on a soda lime glass and molybdenum glass substrate by solution method,and then a Cu_2Sn(S,Se)_3 film was obtained by selenization of the precursor under N_2 protection.The morphology,phase,optical and electrical properties of Cu_2Sn(S,Se)_3 films were effectively controlled by adjusting the annealing temperature of the precursor films.It is found that,under an appropriate annealing temperature of 480 ℃ in the selenization process,Cu_2Sn(S,Se)_3 film with double-layer structure show a flat surface,high crystallinity,dense grains and a direct band-gap of 1.28 eV.Furthermore,its carrier concentration can be reduced to 6.780×10~(17) cm~(-3) and the mobility can be as high as 18.19 cm~2·V~(-1)·S~(-1),which is suitable for the optical absorption layer of thin-film solar cells.
In this work,Cu-Sn-S precursor film was prepared on a soda lime glass and molybdenum glass substrate by solution method,and then a Cu_2Sn(S,Se)_3 film was obtained by selenization of the precursor under N_2 protection.The morphology,phase,optical and electrical properties of Cu_2Sn(S,Se)_3 films were effectively controlled by adjusting the annealing temperature of the precursor films.It is found that,under an appropriate annealing temperature of 480 ℃ in the selenization process,Cu_2Sn(S,Se)_3 film with double-layer structure show a flat surface,high crystallinity,dense grains and a direct band-gap of 1.28 eV.Furthermore,its carrier concentration can be reduced to 6.780×10~(17) cm~(-3) and the mobility can be as high as 18.19 cm~2·V~(-1)·S~(-1),which is suitable for the optical absorption layer of thin-film solar cells.
引文
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[2] WU L,CHEN S Y,FAN F J,et al.Polytypic nanocrystals of Cu-based ternary chalcogenides:colloidal synthesis and photoelectrochemical properties[J].J Am Chem Soc,2016,138(17):5576.
[3] ALDAKOV D,LEFRSNCOIS A,REISS P.Ternary and quaternary metal chalcogenide nanocrystals:synthesis,properties and applications[J].Journal of Materials Chemistry C,2013,1(24):3756.
[4] ZHENG X F,LIU Y F,SUN Y,et al.Bandgap engineering of Cu2Sn(S,Se)3 semiconductor nanocrystals and their applications in thin film solar cell[J].Journal of Alloys and Compounds,2017,728:322.
[5] KIM K M,TAMPO H,SHIBATA H,et al.Growth and characterization of coevaporated Cu2SnSe3 thin films for photovoltaic applications[J].Thin Solid Films,2013,536:111.
[6] CHANDRA G H ,KUMAR O L,RAO R P,et al.Influence of substrate and selenization temperatures on the growth of Cu2SnSe3 films[J].Journal of Materials Science,2011,46(21):6952.
[7] BABU G S,KUMAR Y K,REDDY Y B K,et al.Growth and characterization of Cu2SnSe3 thin film[J].Materials Chemistry and Physics,2006,96(2/3):442.
[8] WIBOWO R A,JUUNG W H,AL-FARUQI M H,et al.Crystallization of Cu2ZnSnSe4 compound by solid state reaction using elemental powders[J].Materials Chemistry and Physics,2010,124(2):1006.
[9] SHI X Y,Xi L L,FAN J ,et al.Cu-Se bond network and thermoelectric compounds with complex diamondlike structure[J].Chemistry of Materials,2010,22(22):6029.
[10] Li Y Y,LIU G H,Li J T,et al.High thermoelectric performance of In-doped Cu2SnSe3 prepared by fast combustion synthesis[J].New Journal of Chemistry,2016,40(6):5394.
[11] 张伟,陈顺礼,汪渊.Cu/Sn比率对Cu2SnSe3 薄膜若干物理性质的影响[J].功能材料,2012,43(5):630.
[12] KUO D H,HAUNG W D,HUANG Y S,et al.Single-step sputtered Cu2SnSe3 films using the targets composed of Cu2Se and SnSe2[J].Thin Solid Films,2010,518(24):7218.
[13] XU L,DONALD T M.Thermoelectric properties of Mn-doped Cu2SnSe3[J].Journal of Electronic Materials,2011,41(6):1554.
[14] KIM K M,SHINHO K,HITOSHI T,et al.Narrow-bandgap Cu2Sn1-xGexSe3 thin film solar cell[J].Materials Letters,2015,158:205.
[15] BASAK A,ANUP M,UDAI P S.Post-growth annealing effect on the performance of Cu2SnSe3 solar cells[J].Materials Research Express,2018,5(10):105505
[16] 刘仪柯,唐雅琴,伍玉娇.热注射法合成 Cu2SnSe3纳米晶及其光电转换性能[J].人工晶体学报,2017,46(12):2348.
[17] JEONG J,CHUNG H,JU Y C,et al.Colloidal synthesis of Cu2SnSe3 nanocrystals[J].Materials Letters,2010,64(19):2043.
[18] LIU G H,CHEN K X,Li J T,et al.Combustion synthesis of Cu2SnSe3 thermoelectric materials[J].Journal of the European Ceramic Society,2016,36(6):1407.
[19] 马瑞,李宇洋,刘光华.Se位掺杂对燃烧合成Cu2SnSe3热电性能的影响[J].陶瓷学报,2017,38(4):466.