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有机-无机杂化的卤素钙钛矿材料在2009年首次应用在光伏器件中, 而后有关此类型太阳能电池的报道数量呈井喷式增长. 至2014年5月钙钛矿电池光电转化效率已接近20%, 已超过有机及染料敏化太阳能电池的效率, 且有望达到单晶硅太阳能的水平, 成为光伏发电领域中的希望之星. 在钙钛矿电池中, 电子传输材料与吸收层的电子选择性接触对提高光电转化效率起到重要作用, 尤其在正置结构器件中, 电子传输层的介观结构直接影响钙钛矿的生长情况. 同时, 电子传输层的化学性质及其界面也会对电池的稳定性和寿命产生影响. 本文总结了电子传输材料在该类电池中的研究现状和热点, 并按材料的化学组分不同, 将电子传输材料分为三类: 金属氧化物、有机小分子和复合材料, 详细地介绍了电子传输材料在钙钛矿太阳能电池中的作用和近来的最新进展.Ever since the first organic-inorganic hybrid halogen perovskite solar cell was first used as a photo-voltaic material in 2009, reports on this type of solar cell have grown exponentially over the years. Up till May 2014, the photo-energy conversion efficiency of the perovskite solar cell have already achieved an efficiency approaching 20%. Surpassing the efficiency achieved by organic and dye synthesized solar cell, the perovskite solar cell is in good hope of reaching the efficiency compatible with that of mono-crystalline silicon solar cell, thus it is going to be the star in photo-voltaic industry. In a perovskite solar cell, the film-formation and electron-mobility in the electron transfer layer can dramatically affect its efficiency and life-span. Especially in the up-right structured device, the mesoscopic structures of the electron-transfer layer will directly influence the growth of the perovskite layer. The present researches of electron transport materials mainly focus on three aspects: (1) How to improve the instability in mesoporous TiO2-mesosuperstructured solar cells, that arises from light-induced desorption of surface-adsorbed oxygen. (2) How to obtain TiO2 or other electron transport materials at low temperature (sub 150 ℃) in order to be applicatable in flexible devices. (3) How to substitute the mesoporous TiO2 or compact TiO2 transport layer by organic or composite materials. This article devides the materials that are used to make the electron-transfer layer into three distinct groups according to their chemical composition: i.e. metal oxides, organic small molecules, and composite materials, and introduces about the role they play and the recent development of them in constructing the perovskite solar cell.
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[1] Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050
[2] Im J H, Lee C R, Lee J W, Park S W, Park N G 2011 Nanoscale 3 4088
[3] Kim H S, Lee C R, Im J H, Lee K B, Moehl T, Marchioro A, Moon S J, Humphry-Baker R, Yum J H, Moser J E, Graätzel M, Park N G 2012 Sci. Rep. 2 591
[4] Burschka J, Pellet N, Moon S J, Humphry-Baker R, Gao P, Nazeeruddin M K, Graätzel M 2013 Nature 499 316
[5] Liu M Z, Johnston M B, Snaith H J 2013 Nature 501 395
[6] Zhou H P, Chen Q, Li G, Luo S, Song T B, Duan H S, Hong Z R, You J B, Liu Y S, Yang Y 2014 Science 345 542
[7] Service R F 2014 Science 344 458
[8] Lee M M, Teuscher J, Miyasaka T, Murakami T N, Snaith H J 2012 Science 338 643
[9] Ogomi Y, Morita A, Tsukamoto S, Saitho T, Fujikawa N, Shen Q, Toyoda T, Yoshino K, Pandey S S, Ma T, Hayase S 2014 J. Phys. Chem. Lett. 5 1004
[10] Ma Y Z, Wang S F, Zheng L L, Lu Z L, Zhang D F, Bian Z Q, Huang C H, Xiao L X 2014 Chin. J. Chem. 32 957
[11] Grinberg I, West D V, Torres M, Gou1 G, Stein D M, Wu L, Chen G, Gallo E M, Akbashev A R, Davies P K, Spanier J E, Rappe A M 2013 Nature 503 509
[12] Tanaka K, Takahashi T, Ban T, Kondo T, Uchida K 2003 Solid State Commun. 127 619
[13] Wu S K, Wang P F 2010 Organic Electronics (Beijing: Chemical industry press) pp32-36 (in Chinese) [吴世康, 汪鹏飞 2010 有机电子学概论 (北京: 化学工业出版社)第32–35页]
[14] Kim H S, Im S H, Park N G 2014 J. Phys. Chem. C 118 5615
[15] Loi M A, Hummelen J C 2013 Nat. Mater. 12 1087
[16] Ball J M, Lee M M, Hey A, Snaith H J 2013 Energy Environ. Sci. 6 1739
[17] Wang Q, Shao Y C, Dong Q F, Xiao Z G, Yuan Y B, Huang J S 2014 Energy Environ. Sci. 7 2359
[18] Xiao Z G, Bi C, Shao Y C, Dong Q F, Wang Q, Yuan Y B, Wang C G, Gao Y L, Huang JS 2014 Energy Environ. Sci. 7 2619
[19] Xiao Z G, Dong Q F, Bi C, Shao Y C, Yuan Y B, Huang JS 2014 Adv. Mater. 26 6503
[20] Snaith H J, Abate A, Ball J M, Eperon G E, Leijtens T, Noel N K, Stranks S D, Wang J T-W, Wojciechowski K, Zhang W 2014 J. Phys. Chem. Lett. 5 1511
[21] Jeon N J, Noh J H, Kim Y C, Yang W S, Ryu S, Seok II S 2014 Nat. Mater. 13 897
[22] Hou Q Y, Wu Y, Zhao C W 2013 Acta Phys. Sin. 62 237101 (in Chinese) [侯清玉, 乌云, 赵春旺 2013 物理学报 62 237101]
[23] Gill W D 1972 J. Appl. Phys. 43 5033
[24] Wehrenfennig C, Eperon G E, Johnston M B, Snaith H J, Herz L M 2014 Adv. Mater. 26 1584
[25] Stranks S D, Eperon G E, Grancini G, Menelaou C, Alcocer M J P, Leijtens T, Herz L M, Petrozza A, Snaith H J 2013 Science 342 341
[26] Xing G, Mathews N, Sun S, Lim S S, Lam Y M, Grätzel M, Mhaisalkar S, Sum T C 2013 Science 342 344
[27] Etgar L, Gao P, Xue Z S, Peng Q, Chandiran A K, Liu B, Nazeeruddin M K, Graätzel M 2012 J. Am. Chem. Soc. 134 17396
[28] Abu Laban W, Etgar L 2013 Energy Environ. Sci. 6 3249
[29] Aharon S, Gamliel S, El Cohen B, Etgar L 2014 PCCP 16 10512
[30] Aharon S, El Cohen B, Etgar L 2014 J. Phys. Chem. C 118 17160
[31] Yella A, Heiniger L P, Gao P, Nazeeruddin M K, Graätzel M 2014 Nano Lett. 14 2591
[32] Schwanitz K, Weiler U, Hunger R, Mayer T, Jaegermann W 2007 J. Phys. Chem. C 111 849
[33] Bisquert J, Fabregat-Santiago F, Mora-Sero I, Garcia-Belmonte G, Barea E M, Palomares E 2008 Inorg. Chim. Acta 361 684
[34] Henderson M A, Epling W S, Perkins C L, Peden C H F, Diebold U 1999 J. Phys. Chem. B 103 5328
[35] Leijtens T, Eperon G E, Pathak S, Abate A, Lee M M, Snaith H J 2013 Nat.Commun. 4 2885
[36] Bach U, Lupo D, Comte P, Moser J E, Weissortel F, Salbeck J, Spreitzer H, Graätzel M 1998 Nature 395 583
[37] Apgar B A, Martin L W 2014 Cryst. Growth Des. 14 1981
[38] Nakamura I, Negishi N, Kutsuna S, Ihara T, Sugihara S, Takeuchi E 2000 J. Mol. Catal. A-Chem. 161 205
[39] Eperon G E, Burlakov V M, Goriely A, Snaith H J 2014 ACS Nano 8 591
[40] Chen Q, Zhou H P, Hong Z R, Luo S, Duan H S, Wang H H, Liu Y S, Li G, Yang Y 2014 J. Am. Chem. Soc. 136 622
[41] Wojciechowski K, Saliba M, Leijtens T, Abate A, Snaith H J 2014 Energy Environ. Sci. 7 1142
[42] Conings B, Baeten L, Jacobs T, Dera R, D'Haen J, Manca J, Boyen H G 2014 APL Mater. 2 081505
[43] Pournami P V, Marykutty T, George K C 2012 J. Appl. Phys. 112 104308
[44] Docampo P, Ball J M, Darwich M, Eperon G E, Snaith H J 2013 Nat. Commun. 4 2761
[45] Small C E, Chen S, Subbiah J, Amb C M, Tsang S W, Lai T H, Reynolds J R, So F 2012 Nat. Photonics 6 115
[46] Kim H S, Lee J W, Yantara N, Boix P P, Kulkarni S A, Mhaisalkar S, Graätzel M, Park N G 2013 Nano Lett. 13 2412
[47] Dharani S, Mulmudi H K, Yantara N, Trang P T T, Park N G, Graetzel M, Mhaisalkar S, Mathews N, Boix P P 2014 Nanoscale 6 1675
[48] Tang H, Prasad K, Sanjines R, Schmid P E, Levy F 1994 J. Appl. Phys. 75 2042
[49] Zhang Q F, Dandeneau C S, Zhou X Y, Cao G Z 2009 Adv. Mater. 21 4087
[50] Ariyanto N P, Abdullah H, Syarif J, Yuliarto B, Shaari S 2010 Funct. Mater. Lett. 3 303
[51] Keis K, Magnusson E, Lindström H, Lindquist S, Hagfeldt A A 2002 Sol. Energy Mater. Sol. Cells 73 51
[52] Goncalves A S, Goes M S, Fabregat-Santiago F, Moehl T, Davolos M R, Bisquert J, Yanagidad S, Nogueirac A F, Bueno P R 2011 Electrochim. Acta 56 6503
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[54] Kumar M H, Yantara N, Dharani S, Graätzel M, Mhaisalkar S, Boix P P, Mathews N 2013 Chem. Commun. 49 11089
[55] Liu D, Kelly T L 2014 Nat. Photonics 8 133
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[57] Zheng H D, Tachibana Y, Kalantar-zadeh K 2010 Langmuir 26 19148
[58] Mahmood K, Swain BS, Kirmania A R, Amassian A 2014 J. Mater. Chem. A DOI: 10.1039/C4TA04883K
[59] Sakai N, Miyasaka T, Murakami T N 2013 J. Phys. Chem. C 117 10949
[60] Oh L S, Kim D H, Lee J A, Shin S S, Lee J W, Park I J, Ko M J, Park N G, Pyo S G, Hong K S, Kim J Y 2014 J. Phys. Chem. C 118 22991
[61] Yong S M, Nikolay T, Ahn B T, Kim D K 2013 J. Alloys Compd. 547 113
[62] Haddon R C, Perel A S, Morris R C, Palstra T T M, Hebard A F, Fleming R M 1995 Appl. Phys. Lett. 67 121
[63] Kobayashi S, Takenobu T, Mori S, Fujiwara A, Iwasa Y 2003 Appl. Phys. Lett. 82 4581
[64] Jeng J Y, Chiang Y F, Lee M H, Peng S R, Guo T F, Chen P, Wen T C 2013 Adv. Mater. 25 3727
[65] Liang P W, Liao C Y, Chueh C C, Zuo F, Williams S T, Xin X K, Lin J J, Jen A K Y 2014 Adv. Mater. 26 3748
[66] Wang Q, Shao Y C, Dong Q F, Xiao Z G, Yuan Y B, Huang J S 2014 Energy Environ. Sci. 7 2359
[67] Gao Z, Qu B, Xiao L X, Chen Z J, Zhang L P, Gong Q H 2014 Appl. Phys. Lett. 104 103301
[68] Qu B, Gao Z, Yang H S, Xiao L X, Chen Z J, Gong Q H 2014 Appl. Phys. Lett. 104 043305
[69] 2006 Nano Lett 6 755
[70] Savenije T J, Huijser A, Vermeulen M J W, Katoh R 2008 Chem. Phys. Lett. 461 93
[71] Fravventura M C, Deligiannis D, Schins J M, Siebbeles L D A, Savenije T J 2013 J. Phys. Chem. C 117 8032.
[72] Mei A Y, Li X, Liu L F, Ku Z L, Liu T F, Rong Y G, Xu M, Hu M, Chen J Z, Yang Y, Graätzel M, Han H W 2014 Science 345 295
[73] Ogomi Y, Kukihara K, Qing S, Toyoda T, Yoshino K, Pandey S, Momose H, Hayase S 2014 ChemPhysChem 15 1062
[74] Abrusci A, Stranks S D, Docampo P, Yip H L, Jen A K-Y, Snaith H J 2013 Nano Lett. 1 3
[75] Ito S, Tanaka S, Manabe K, Nishino H 2014 J. Phys. Chem. C 118 16995
[76] Wang J T-W, Ball J M, Barea E M, Abate A, Alexander-Webber J A, Huang J, Saliba M, Mora-Sero I, Bisquert J, Snaith H J 2014 Nano Lett. 14 724
[77] Miyauchi M 2007 J. Phys. Chem. C 111 12440
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