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离子注入对ZnTe:O中间带光伏材料的微观结构及光学特性的影响

甄康 顾然 叶建东 顾书林 任芳芳 朱顺明 黄时敏 汤琨 唐东明 杨燚 张荣 郑有炓

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离子注入对ZnTe:O中间带光伏材料的微观结构及光学特性的影响

甄康, 顾然, 叶建东, 顾书林, 任芳芳, 朱顺明, 黄时敏, 汤琨, 唐东明, 杨燚, 张荣, 郑有炓

Effect of oxygen implantation on microstructural and optical properties of ZnTe:O intermediate-band photovoltaic materials

Zhen Kang, Gu Ran, Ye Jian-Dong, Gu Shu-Lin, Ren Fang-Fang, Zhu Shun-Ming, Huang Shi-Min, Tang Kun, Tang Dong-Ming, Yang Yi, Zhang Rong, Zheng You-Dou
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  • Ⅱ-VI和Ⅲ-V族高失配合金半导体是新型高效中间带太阳电池的优选材料体系, 但中间带的形成及其能带调控等关键问题仍未得到有效解决. 采用氧离子注入方式,在非平衡条件下对碲化锌(ZnTe)单晶材料实现了等电子掺杂, 深入研究了离子注入对ZnTe:O材料的微观结构和光学特性的影响. 研究表明: 注入合适浓度的氧离子(2.5×1018 cm-3)将会形成晶格应变, 并诱导1.80 eV (导带下0.45 eV)中间带的产生; 而较高浓度(2.5×1020 cm-3)的氧离子会导致ZnTe注入层表面非晶化, 并增强与锌空位相关的深能级(~1.6 eV)发光. 时间分辨光致发光结果显示, 离子注入诱导形成的中间带主要是和氧等电子陷阱束缚的局域激子发光有关, 载流子衰减寿命较长 (129 ps). 因此, 需要降低晶格紊乱度和合金无序, 实现电子局域态向扩展态的转变, 从而有效调控中间带能带结构.
    Group Ⅱ-VI and Ⅲ-V highly mismatched alloys are promising material systems in the application of high efficiency intermediate-band solar cell (IBSC), however, the key issues including band engineering of intermediate band still remain challenging. In this study, ZnTe:O alloys have been produced by isoelectric oxygen implantation into ZnTe single crystal, and the influences of implantation on the microstructural and optical properties of ZnTe:O have been investigated in detail. It is found that a proper dose of oxygen ions can lead to a compressive strain in the lattice and induce the formation of intermediate band located on the energy level of ~ 0.45 eV below the conduction band. While a high dose of oxygen ions causes ZnTe surface layer to become amorphous and enhances the deep level emission around 1.6 eV, which is related to Zn vacancies. Results of resonant Raman and time-resolved photoluminescence spectra indicate that implantation induced intermediate band is related to the localized exciton emission bound to oxygen isoelectric trap, and the associated photo excited carriers have a relatively long decay time. This suggests that the reduction of lattice distortion and alloy disorder may be needed for converting localized states of the intermediate band into extended states, which is crucial to realize high efficiency ZnTe:O based IBSCs.
    • 基金项目: 国家重点基础研究发展计划(批准号:2011CB302003)、国家自然科学基金(批准号:61025020,60990312,61274058,61322403,61271077,11104130,11104134)、江苏省自然科学基金(批准号:BK2011437,BK2011556,BK20130013)、江苏省高等学校优势学科发展项目和澳大利亚研究基金会创新项目(批准号:DP1096918)资助的课题.
    • Funds: Project supported by the National Basic Research Program of China (Grant No. 2011CB302003), the National Natural Science Foundation of China (Grant Nos. 61025020, 60990312, 61274058, 61322403, 61271077, 11104130, 11104134), the Natural Science Foundation of Jiangsu Province, China (Grant Nos. BK2011437, BK2011556, BK20130013), the Priority Academic Development Program of Higher Education Institutions of Jiangsu Province, China, and the Australian Research Council Discovery Project (Grant No. DP1096918).
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    Luque A, Marti A 2011 Nat. Photon. 5 137

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    Felici M, Polimeni A, Capizzi M, Nabetani Y, Okuno T, Aoki K, Kato T, Matsumoto T, Hirai T 2006 Appl. Phys. Lett. 88 101910

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    Moon S R, Kim J H, Kim Y 2012 J. Phys. Chem. C 116 10368

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    Tanaka T, Miyabara M, Nagao Y, Saito K, Guo Q, Nishio M, Yu K M, Walukiewicz W 2013 Appl. Phys. Lett. 102 052111

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    Yu K M, Walukiewicz W, Wu J, Beeman J W, Ager Ⅲ J W, Haller E E, Miotkowski I, Ramdas A K, Becla P 2002 Appl. Phys. Lett. 80 1571

    [19]

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    [20]

    Zhang Q, Zhang J, Utama M, Peng B, Mata M, Arbiol J, Xiong Q H 2012 Phys. Rev. B 85 085418

    [21]

    Larramendi E M, Berth G, Wiedemeier V, Husch K P, Zrenner A, Woggon U, Tschumak E, Lischka K, Schikora D 2010 Semicond. Sci. Technol. 25 075003

    [22]

    Ye J D, Tripathy S, Ren F F, Sun X W, Lo G Q, Teo K L 2009 Appl. Phys. Lett. 94 011913

    [23]

    Schmidt R L, Mccombe B D, Cardona M 1975 Phys. Rev. B 11 746

    [24]

    Wang R P, Xu G, Jin P 2004 Phys. Rev. B 69 113303

    [25]

    Sato K, Adachi S 1993 J. Appl. Phys. 73 926

    [26]

    Yu Y M, Nam S G, Lee K S, Choi Y D, Byungsung O 2001 J. Appl. Phys. 90 807

    [27]

    Biao Y, Azoulay, George M A, Burger A, Collins W E, Silberman E, Su C H, Volz M E, Szofran F R, Gillies D C 1994 J. Cryst. Growth 138 219

    [28]

    Norris C B 1982 J. Appl. Phys. 53 5172

    [29]

    Norris C B 1980 J. Appl. Phys. 51 1998

    [30]

    Shigaura G, Ohashi M, Ichinohe Y, Kamamori M, Kimura Na, Kimura No, Sawada T, Suzuki K, Imai K 2007 J. Cryst. Growth 301–302 297

    [31]

    Wei S H, Zhang S B 2002 Phys. Rev. B 66 155211

    [32]

    Carvalho A, Oberg S, Briddon P R 2011 Thin Solid Films 519 7468

    [33]

    Holst J C, Hoffmann A, Rudloff D, Bertram F, Riemann T, Christen J, Frey T, As D J, Schikora D, Lischka K 2000 Appl. Phys. Lett. 76 2832

    [34]

    Bartel T, Dworzak M, Strassburg M, Hoffmann A, Strittmatter A, Bimberg D 2004 Appl. Phys. Lett. 85 1946

  • [1]

    Luque A, Marti A 1997 Phys. Rev. Lett. 78 5514

    [2]

    Luque A, Marti A, Stanley C 2012 Nat. Photon. 6 146

    [3]

    Luque A, Marti A 2011 Nat. Photon. 5 137

    [4]

    Walukiewicz W, Shan W, Yu K M, Ager Ⅲ J W, Haller E E, Miotkowski I, Seong M J, Alawadhi H, Eamdas A K 2000 Phys. Rev. Lett. 85 1552

    [5]

    Wu J, Walukiewicz W, Yu K M, Ager Ⅲ J W, Haller E E, Hong Y G, Xin H P, Tu C W 2002 Phys. Rev. B 65 241303

    [6]

    Yu K M, Walukiewicz W, Wu J, Shan W, Beeman J W, Scarpulla M A, Dubon O D, Becla P 2003 Phys. Rev. Lett. 91 246403

    [7]

    Wang W M, Alvwer S L, varPhillips J D 2009 Appl. Phys. Lett. 95 011103

    [8]

    Wu K P, Gu S L, Ye J D, Tang K, Zhu S M, Zhou M R, Huang Y R, Zhang R, Zheng Y D 2013 Chin. Phys. B 22 107103

    [9]

    Wang W M, Alvwer S L, varPhillips J D, Metzger W K 2009 Appl. Phys. Lett. 95 261107

    [10]

    Seong M J, Miotkowski I, Ramdas A K 1998 Phys. Rev. B 58 7734

    [11]

    Hopfield J J, Thomas D G, Lynch R T 1966 Phys. Rev. Lett. 17 312

    [12]

    Felici M, Polimeni A, Capizzi M, Nabetani Y, Okuno T, Aoki K, Kato T, Matsumoto T, Hirai T 2006 Appl. Phys. Lett. 88 101910

    [13]

    Moon S R, Kim J H, Kim Y 2012 J. Phys. Chem. C 116 10368

    [14]

    Tanaka T, Miyabara M, Nagao Y, Saito K, Guo Q, Nishio M, Yu K M, Walukiewicz W 2013 Appl. Phys. Lett. 102 052111

    [15]

    Cuthbert D, Thomas D G 1967 Phys. Rev. 154 763

    [16]

    Pak S W, Suh J Y, Lee D U, Kim E K 2012 Jpn. J. Appl. Phys. 51 01AD04

    [17]

    Merz J L 1971 J. Appl. Phys. 42 2463

    [18]

    Yu K M, Walukiewicz W, Wu J, Beeman J W, Ager Ⅲ J W, Haller E E, Miotkowski I, Ramdas A K, Becla P 2002 Appl. Phys. Lett. 80 1571

    [19]

    Pine A S, Dresselh G 1971 Phys. Rev. B 4 356

    [20]

    Zhang Q, Zhang J, Utama M, Peng B, Mata M, Arbiol J, Xiong Q H 2012 Phys. Rev. B 85 085418

    [21]

    Larramendi E M, Berth G, Wiedemeier V, Husch K P, Zrenner A, Woggon U, Tschumak E, Lischka K, Schikora D 2010 Semicond. Sci. Technol. 25 075003

    [22]

    Ye J D, Tripathy S, Ren F F, Sun X W, Lo G Q, Teo K L 2009 Appl. Phys. Lett. 94 011913

    [23]

    Schmidt R L, Mccombe B D, Cardona M 1975 Phys. Rev. B 11 746

    [24]

    Wang R P, Xu G, Jin P 2004 Phys. Rev. B 69 113303

    [25]

    Sato K, Adachi S 1993 J. Appl. Phys. 73 926

    [26]

    Yu Y M, Nam S G, Lee K S, Choi Y D, Byungsung O 2001 J. Appl. Phys. 90 807

    [27]

    Biao Y, Azoulay, George M A, Burger A, Collins W E, Silberman E, Su C H, Volz M E, Szofran F R, Gillies D C 1994 J. Cryst. Growth 138 219

    [28]

    Norris C B 1982 J. Appl. Phys. 53 5172

    [29]

    Norris C B 1980 J. Appl. Phys. 51 1998

    [30]

    Shigaura G, Ohashi M, Ichinohe Y, Kamamori M, Kimura Na, Kimura No, Sawada T, Suzuki K, Imai K 2007 J. Cryst. Growth 301–302 297

    [31]

    Wei S H, Zhang S B 2002 Phys. Rev. B 66 155211

    [32]

    Carvalho A, Oberg S, Briddon P R 2011 Thin Solid Films 519 7468

    [33]

    Holst J C, Hoffmann A, Rudloff D, Bertram F, Riemann T, Christen J, Frey T, As D J, Schikora D, Lischka K 2000 Appl. Phys. Lett. 76 2832

    [34]

    Bartel T, Dworzak M, Strassburg M, Hoffmann A, Strittmatter A, Bimberg D 2004 Appl. Phys. Lett. 85 1946

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  • 收稿日期:  2014-05-28
  • 修回日期:  2014-07-24
  • 刊出日期:  2014-12-05

离子注入对ZnTe:O中间带光伏材料的微观结构及光学特性的影响

  • 1. 南京大学电子科学与工程学院, 南京 210093;
  • 2. Department of Electronic Materials Engineering, Research School of Physics and Engineering, the Australian National University, Canberra 2601, Australia
    基金项目: 国家重点基础研究发展计划(批准号:2011CB302003)、国家自然科学基金(批准号:61025020,60990312,61274058,61322403,61271077,11104130,11104134)、江苏省自然科学基金(批准号:BK2011437,BK2011556,BK20130013)、江苏省高等学校优势学科发展项目和澳大利亚研究基金会创新项目(批准号:DP1096918)资助的课题.

摘要: Ⅱ-VI和Ⅲ-V族高失配合金半导体是新型高效中间带太阳电池的优选材料体系, 但中间带的形成及其能带调控等关键问题仍未得到有效解决. 采用氧离子注入方式,在非平衡条件下对碲化锌(ZnTe)单晶材料实现了等电子掺杂, 深入研究了离子注入对ZnTe:O材料的微观结构和光学特性的影响. 研究表明: 注入合适浓度的氧离子(2.5×1018 cm-3)将会形成晶格应变, 并诱导1.80 eV (导带下0.45 eV)中间带的产生; 而较高浓度(2.5×1020 cm-3)的氧离子会导致ZnTe注入层表面非晶化, 并增强与锌空位相关的深能级(~1.6 eV)发光. 时间分辨光致发光结果显示, 离子注入诱导形成的中间带主要是和氧等电子陷阱束缚的局域激子发光有关, 载流子衰减寿命较长 (129 ps). 因此, 需要降低晶格紊乱度和合金无序, 实现电子局域态向扩展态的转变, 从而有效调控中间带能带结构.

English Abstract

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