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溶剂对钙钛矿薄膜形貌和结晶性的影响研究

王栋 朱慧敏 周忠敏 王在伟 吕思刘 逄淑平 崔光磊

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溶剂对钙钛矿薄膜形貌和结晶性的影响研究

王栋, 朱慧敏, 周忠敏, 王在伟, 吕思刘, 逄淑平, 崔光磊

Effect of solvent on the perovskite thin film morphology and crystallinity

Wang Dong, Zhu Hui-Min, Zhou Zhong-Min, WangZai-Wei, Lü Si-Liu, Pang Shu-Ping, CuiGuang-Lei
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  • 溶剂对钙钛矿太阳能电池器件有着至关重要的影响. 基于目前常用的N, N-二甲基甲酰胺(DMF)和丁内酯(GBL)溶剂, 一步溶液旋涂技术和介孔电池结构, 制备的钙钛矿薄膜的形貌、结晶性, 以及最终的器件光电转化效率存在较大的差异, 利用DMF作为溶剂, 效率仅为2.8%, 而基于GBL的电池效率可以达到10.1%. 结合SEM, HRTEM, XRD和UV等表征手段, 分析了钙钛矿从DMF溶液和GBL溶液中结晶析出的不同机理, 明确了溶剂跟PbI2的配位作用对钙钛矿的溶解、析出过程的制约作用, 揭示了造成器件效率差异的本质原因.
    Due to their high efficiency and low cost, organic-inorganic hybrid perovskite solar cells are attracting growing interest recently. For the most commonly studied perovskite CH3NH3PbI3, optimization of the morphology and crystallinity of CH3NH3PbI3 thin films can greatly improve the efficiency of perovskite solar cells. A homogenous and uniform perovskite film can prevent direct contact between the hole transport layer and the electron transport layer, and thus can significantly reduce charge recombination. And the high crystallinity perovskite film facilitates fast charge transportation and injection. Various studies have proved that solvent has a critical influence on both the morphology and the crystallinity of perovskite thin films. In this work, we thoroughly studied the influence of the normally used N, N-Dimethylformamide (DMF) and r-butyrolactone (GBL) solvents on perovskite morphology, crystallinity, as well as the solar cells efficiency. When using DMF as the solvent, the efficiency is only 2.8%, while the efficiency of the cell obtained based on GBL can reach 10.1%. SEM and HRTEM are employed to study the morphology and crystallinity of these two kinds of perovskite films. The perovskite film prepared using solvent DMF shows a rough capping layer consisting of strip-like perovskite crystals, and the filling of meso-TiO2 is poor. Compared with DMF, the GBL perovskite film shows a better capping layer structure consisting of large perovskite domains, and the filling of meso-TiO2 is improved as well. This great difference in capping layer morphology and meso-TiO2 filling is one reason for the different performance. Besides morphology, different defect concentrations in these two kinds of perovskite films are another crucial issue. By Combined XRD and UV techniques, the mechanisms how perovskite precipitats from DMF and GBL solutions can be disclosed. In DMF, because of its low spoiling point of 153 ℃, most of DMF solvent volatilize by spin-coating, and an intermediate MOF structure of PbI2: MAI: xDMF is formed. During thermal annealing, the unstable MOF structure breaks down and a large amount of dislocations form in perovskite films, which highly restrict the charge transport. However, the spoil point of GBL (206 ℃) is higher than that of DMF, which makes it hard to be fully volatilized by spin-coating. During the following thermal treatment, the solubility of perovskite is lowered with increasing temperature. So perovskite crystallites precipitate from the GBL first and then gradually grow up with the volatilization of the excess solvent. We finally find that coordination between the solvent and the PbI2 plays a big role on the morphology and the crystallinity of the solution-processed perovskite film, and this is responsible for the difference of the device performance.
    • 基金项目: 国家自然科学基金(批准号: 51202266), 山东省自然科学基金(批准号: ZR2013FZ001)和青岛市应用基础研究基金(批准号: 14-2-4-8-jch)资助的课题.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51202266), the Natural Science Foundation of Shandong Province, China (Grant No. ZR2013FZ001), and the applied fundamental research Program of Qingdao, China (Grant No. 14-2-4-8-jch).
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    Gonzalez-Pedro V, Juarez-Perez E J, Arsyad W S, Barea E M, Fabregat-Santiago F, Mora-Sero I, Bisquert J 2014 Nano lett. 14 888

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    Pang S, Hu H, Zhang J, Lv S, Yu Y, Wei F, Qin T, Xu H, Liu Z, Cui G 2014 Chem. Mater. 26 1485

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    Stranks S D, Eperon G E, Grancini G, Menelaou C, Alcocer M J, Leijtens T, Herz L M, Petrozza A, Snaith H J 2013 Science 342 341

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  • [1]

    Hodes G, Cahen D 2014 Nature Photon. 8 87

    [2]

    Akihiro Kojima K T, Yasuo S, Tsutomu M 2009 J. Am. Chem. Soc. 131 6050

    [3]

    Zhou H, Chen Q, Li G, Luo S, Song T B, Duan H S, Hong Z, You J, Liu Y, Yang Y 2014 Science 345 542

    [4]

    Singh S P, Nagarjuna P 2014 Dalton Trans.43 5247

    [5]

    Chung I, Lee B, He J, Chang R P, Kanatzidis M G 2012 Nature 485 486

    [6]

    Ogomi Y, Morita A, Tsukamoto S, Saitho T, Shen Q, Toyoda T, Yoshino K, Pandey S S, Ma T, Hayase S 2014 J. Phys. Chem. C 118 16651

    [7]

    Shi J, Dong J, Lv S, Xu Y, Zhu L, Xiao J, Xu X, Wu H, Li D, Luo Y, Meng Q 2014 Appl. Phys. Lett. 104 063901

    [8]

    Xiao M, Huang F, Huang W, Dkhissi Y, Zhu Y, Etheridge J, Gray-Weale A, Bach U, Cheng Y-B, Spiccia L 2014 Angew. Chem. Int. Ed. 26 1

    [9]

    Juarez-Perez E J, Wuβler M, Fabregat-Santiago F, Lakus-Wollny K, Mankel E, Mayer T, Jaegermann W, Mora-Sero I 2014 J. Phys. Chem. Lett. 5 680

    [10]

    Chen H, Pan X, Liu W, Cai M, Kou D, Huo Z, Fang X, Dai S 2013 Chem. Commun. 49 7277

    [11]

    Lv S, Han L, Xiao J, Zhu L, Shi J, Wei H, Xu Y, Dong J, Xu X, Li D, Wang S, Luo Y, Meng Q, Li X 2014 Chem. Commun. 50 6931

    [12]

    Lindblad R, Bi D, Park B, Oscarsson J, Gorgoi M, Siegbahn H, Odelius M, Johansson E M J, Rensmo H 2014 J. Phys. Chem. Lett. 5 648

    [13]

    Kumar M H, Yantara N, Dharani S, Graetzel M, Mhaisalkar S, Boix P P, Mathews N 2013 Chem. Commun. 49 11089

    [14]

    Etgar L, Gao P, Xue Z, Peng Q, Chandiran A K, Liu B, Nazeeruddin M K, Grätzel M 2012 J. Am. Chem. Soc. 134 17396

    [15]

    Eperon G E, Burlakov V M, Docampo P, Goriely A, Snaith H J 2014 Adv. Funct. Mater. 24 151

    [16]

    Dualeh A, Tétreault N, Moehl T, Gao P, Nazeeruddin M K, Grätzel M 2014 Adv. Funct. Mater. 24 3250

    [17]

    Carnie M J, Charbonneau C, Davies M L, Troughton J, Watson T M, Wojciechowski K, Snaith H, Worsley D A 2013 Chem. Commun. 49 7893

    [18]

    Burschka J, Pellet N, Moon S J, Humphry-Baker R, Gao P, Nazeeruddin M K, Grätzel M 2013 Nature 499 316

    [19]

    Chen Q, Zhou H, Hong Z, Luo S, Duan H, Wang H H, Liu Y, Li G, Yang Y 2014 J. Am. Chem. Soc. 136 622

    [20]

    Liu M, Johnston M B, Snaith H J 2013 Nature 501 395

    [21]

    Shi J, Luo Y, Wei H, Luo J, Dong J, Lv S, Xiao J, Xu Y, Zhu L, Xu X, Wu H, Li D, Meng Q 2014 ACS Appl. Mater. Interfaces 6 9711

    [22]

    Lv S, Pang S, Zhou Y, Padture N P, Hu H, Wang L, Zhou X, Zhu H, Zhang L, Huang C, Cui G 2014 Phys. Chem. Chem. Phys.16 19206

    [23]

    Hu H, Wang D, Zhou Y, Zhang J, Lv S, Pang S, Chen X, Liu Z, Padture N P, Cui G 2014 RSC Adv. 4 28964

    [24]

    Zhao Y, Zhu K 2014 J. Phys. Chem. C 118 9412

    [25]

    Matteocci F, Razza S, Di Giacomo F, Casaluci S, Mincuzzi G, Brown T M, D'Epifanio A, Licoccia S, Di Carlo A 2014 Phys. Chem. Chem. Phys. 16 3918

    [26]

    Jeon N J, Noh J H, Kim Y C, Yang W S, Ryu S, Seok S I 2014 Nature Mater. 13 897

    [27]

    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

    [28]

    Marchioro A, Teuscher J, Friedrich D, Kunst M, van de Krol R, Moehl T, Grätzel M, Moser J-E 2014 Nature Photon. 8 250

    [29]

    Kim H S, Mora-Sero I, Gonzalez-Pedro V, Fabregat-Santiago F, Juarez-Perez E J, Park N G, Bisquert J 2013 Nature Commun. 4 2242

    [30]

    Gonzalez-Pedro V, Juarez-Perez E J, Arsyad W S, Barea E M, Fabregat-Santiago F, Mora-Sero I, Bisquert J 2014 Nano lett. 14 888

    [31]

    Pang S, Hu H, Zhang J, Lv S, Yu Y, Wei F, Qin T, Xu H, Liu Z, Cui G 2014 Chem. Mater. 26 1485

    [32]

    Stranks S D, Eperon G E, Grancini G, Menelaou C, Alcocer M J, Leijtens T, Herz L M, Petrozza A, Snaith H J 2013 Science 342 341

    [33]

    Dualeh A, Moehl T, Tétreault N, Teuscher J, Gao P, Nazeeruddin M K, Grätzel M 2014 J. Am. Chem. Soc. 8 362

    [34]

    Conings B, Baeten L, De Dobbelaere C, D'Haen J, Manca J, Boyen H G 2013 Adv. Mater. 26 2041

    [35]

    Kazim S, Nazeeruddin M K, Grätzel M, Ahmad S 2014 Angew. Chem. 53 2812

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出版历程
  • 收稿日期:  2014-10-20
  • 修回日期:  2014-11-23
  • 刊出日期:  2015-02-05

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