CH<sub>3</sub>NH<sub>3</sub>多聚体的形成对有机-无机杂化钙钛矿太阳能电池性能的影响

张翱; 张春秀; 张春梅; 田益民; 闫君; 孟涛

doi:10.7498/aps.70.20210353

摘要

采用第一性原理在MP2/aug-cc-PVTZ 水平下优化得到CH₃NH₃多聚体的几何构型, 发现多聚体中CH₃NH₃沿C-N轴取向, 多聚体随着CH₃NH₃数量增加有收缩趋势, 这有利于无机框架的结构稳定, 多聚体的总偶极矩随着CH₃NH₃数量线性增加, 这导致了CH₃NH₃PbI₃异质结的强极化. CH₃NH₃多聚体中未配对电子分布在每个CH₃NH₃的NH₃-端, 轨道能量在–4.4—–3.2 eV之间. 计算静电势矢量场发现CH₃NH${}_3^+ $具有强亲电性, NH₃-端比CH₃-端有更强的亲电性, CH₃NH₃单体和CH₃NH₃多聚体具有弱亲电性和亲核性, CH₃NH₃多聚体的形成有效地减少CH₃NH₃与无机[PbI₃]^–框架之间的非谐振声子振动模式, 这有利于提高CH₃NH₃PbI₃异质结中载流子传输. 电场作用下CH₃NH₃五聚体中未配对电子通过量子跃迁机制沿着C-N轴发生转移, 施加不同方向电场电子的转移效率是不一样的, 转移电子数量随着电场强度增加而增加, 通过这样的跃迁机制在外电场作用下电子很容易注入CH₃NH₃PbI₃形成CH₃NH₃多聚体. 这些计算结果将有助于更深刻地理解有机-无机杂化钙钛矿太阳能电池高光电转换效率的根源.

关键词:

Abstract

CH₃NH₃PbI₃ is one of the most promising candidates for high-performance hybrid organic-inorganic perovskite solar cells. The CH₃NH₃PbI₃ single crystal and polycrystalline thin film exhibit the unique features of long carrier lifetimes and diffusion lengths, however, their carrier mobilities are in fact rather modest in a range from 1 cm²·V^–1·s^–1 to 100 cm²·V^–1·s^–1. Experimentally, the temperature dependence of mobility is described as T^–1.3 to T^–1.6 due to the acoustic phonon scattering. To be sure, the rotating CH₃NH${}_3^+ $ cations are disadvantageous to the carrier transport and performance for CH₃NH₃PbI₃ solar cells. The effect of the rotating CH₃NH${}_3^+ $ cations on high-performance CH₃NH₃PbI₃ solar cells remains an open question. The Gaussian 09 software has been utilized to optimize the geometrical structures of CH₃NH₃ dimer, trimer, tetramer, and pentamer in isolated state at the MP2 level with using the cc-PVTZ basis set. For CH₃NH₃ polymer, the mean distance between two centroids of neighboring CH₃NH₃ decreasing with the number of CH₃NH₃ is slightly smaller than the lattice constant 6.28 Å of tetragonal CH₃NH₃PbI₃, which is advantageous to structural stability and higher structural order of inorganic [PbI3]^– framework. It signifies that the long range order of electrically neutral CH₃NH₃ is easily formed for room-temperature CH₃NH₃PbI₃. The total dipole moment linearly increases with the number of CH₃NH₃ for CH₃NH₃ polymer, and attains a large value 19.7 Debye for CH₃NH₃ pentamer, which may be the origin of strong polarization in CH₃NH₃PbI₃ heterojunction. The molecular orbitals of five unpaired electrons for CH₃NH₃ pentamer are distributed around NH₃-sides of five different CH₃NH₃ pentamers respectively, and these orbital energies are in a range from –4.4 eV to –3.2 eV. The unpaired electrons in CH₃NH₃ polymer have an electrostatic attraction on the CH₃-side of neighboring CH₃NH₃, which is the key cause of forming the ordered CH₃NH₃ polymer. Hence it can be inferred that the orbital energies of unpaired electrons are getting closer when the longer range order of CH₃NH₃ are formed in room-temperature CH₃NH₃PbI₃ through the interfacial electron injection. The vector field map of electrostatic potential (ESP) shows that CH₃NH${}_3^+ $ has strong electrophilic character, and the NH₃-side has a stronger electrophilic character than CH₃-side, however, CH₃NH₃ monomer and polymer have weak electrophilic and nucleophilic character. Thus, the forming of CH₃NH₃ polymer at the CH₃NH₃PbI₃ heterojunction leads the organic and inorganic portions to be decoupled, which can effectively reduce the anharmonic phonon modes. Under an applied electric field, the unpaired electrons in CH₃NH₃ pentamer can transfer along the C-N axis through the hopping mechanism. According to these results, we can draw three useful conclusions below. i) The electrons under an applied electric field are easily injected into the CH₃NH₃PbI₃ material through the heterojunction, the CH₃NH₃ polymer is easily formed, and the unpaired electrons in polymer are transferred between two neighboring CH₃NH₃ through hopping mechanism. ii) The decoupling between organic CH₃NH₃ and inorganic [PbI3]^– framework can effectively reduce the anharmonic phonon modes, which can lead the carrier scattering decrease and the efficiency of carrier separation and transport to improve; iii) The ordered CH₃NH₃ polymer at the CH₃NH₃PbI₃ heterojunction can enhance the order of inorganic [PbI3]^– framework. Our researches may help to further understand the origin of high power conversion efficiency (PCE) for hybrid organic-inorganic perovskite solar cells.

Keywords:

作者及机构信息

1.
北京印刷学院基础部, 北京　102600

2.
北京交通大学理学院, 微纳材料及应用研究所, 北京　100044

通信作者: 孟涛, tmeng@bigc.edu.cn

基金项目: 国家自然科学基金(批准号: 11605012)、北京市教委科研计划(批准号: KM202010015008)和国家自然科学基金青年科学基金(批准号: 51802014)资助的课题

Authors and contacts

1.
Department of Science, Beijing Institute of Graphic Communication, Beijing 102600, China

2.
Institute of Applied Micro-Nano Materials, School of Science, Beijing Jiaotong University, Beijing 100044, China

Corresponding author: Meng Tao, tmeng@bigc.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11605012), the Project of Beijing Municipal Education Commission, China (Grant No. KM202010015008), and the Young Scientists Fund of the National Natural Science Foundation of China (Grant No. 51802014)

文章全文 : translate this paragraph

参考文献

[1]	Zhang W, Eperon G E, Snaith H J 2016 Nat. Energy 1 16048 Google Scholar
[2]	Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050 Google Scholar
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[23]	Frisch M J, Trucks G W, Schlegel H B, et al. 2009 Gaussian 09 (Revision C.01) (Wallingford: Gaussian, Inc.)
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施引文献

图 1 在MP2/Aug-cc-PVTZ水平下优化CH₃NH₃二聚体、三聚体、四聚体、五聚体的邻近两个分子质心之间的平均距离和电偶极矩

Fig. 1. Mean distance between two centroids of neighboring molecules and dipole moments for optimized CH₃NH₃ dimer, trimer, tetramer, and pentamer at MP2/Aug-cc-PVTZ level.

下载: 全尺寸图片幻灯片

图 2 在MP2/Aug-cc-PVTZ水平下　(a)优化的CH₃NH₃多聚体未配对电子的分子轨道能, (b) 优化的CH₃NH₃五聚体的分子轨道等值面图和轨道能量, 红色和蓝色分别表示正相和负相

Fig. 2. (a) The molecular orbital energies of unpaired electrons for optimized CH₃NH₃ polymer, and (b) the molecular orbitals isosurface map and energies of unpaired electrons of optimized CH₃NH₃ pentamer at MP2/Aug-cc-PVTZ level. Red and blue colors correspond to positive and negative phases, respectively.

下载: 全尺寸图片幻灯片

图 3 在MP2/Aug-cc-PVTZ水平下优化的　(a) CH₃NH${}_3^+ $, (b) CH₃NH₃, (c) CH₃NH₃五聚体的静电势矢量场图, 蓝色的轮廓线表示范德瓦耳斯表面, 红色的箭头表示对应坐标处的电场

Fig. 3. Vector field map of ESP for optimized (a) CH₃NH${}_3^+ $, (b) CH₃NH₃, and (c) CH₃NH₃ pentamer at MP2/Aug-cc-PVTZ level. The blue contour line and red arrow represent van der Waals surface and electric field at corresponding position, respectively.

下载: 全尺寸图片幻灯片

图 4 在MP2/Aug-cc-PVTZ水平下, 在优化的CH₃NH₃五聚体中通过RDG方法图形化CH₃NH₃之间的相互作用

Fig. 4. Weak interaction between two adjacent CH₃NH₃ in optimized CH₃NH₃ pentamer at MP2/Aug-cc-PVTZ level is visualized by RDG method.

下载: 全尺寸图片幻灯片

图 5 (a)优化的CH₃NH₃几何构型; 施加沿x-轴 (b) 正向和 (c) 负向的不同外电场作用下的电荷位移曲线

Fig. 5. (a) Optimized configuration of CH₃NH₃ pentamer; charge displacement curve under external electric field along the (b) positive and (c) negative x-axis with different strengths of electric field.

下载: 全尺寸图片幻灯片

[1]	Zhang W, Eperon G E, Snaith H J 2016 Nat. Energy 1 16048 Google Scholar
[2]	Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050 Google Scholar
[3]	Ding H, Li B, Zareen S, Li G, Tu Y, Zhang D, Cao X, Xu Q, Yang S, Tait S L, Zhu J 2020 ACS Appl. Mater. Interfaces 12 28861 Google Scholar
[4]	Breternitz J, Lehmann F, Barnett S A, Nowell H, Schorr S 2020 Angew. Chem. Int. Ed. 59 424 Google Scholar
[5]	Herz L M 2016 Annu. Rev. Phys. Chem. 67 65 Google Scholar
[6]	Bi Y, Hutter E M, Fang Y, Dong Q, Huang J, Savenije T J 2016 J. Phys. Chem. Lett. 7 923 Google Scholar
[7]	Ponseca C S, Savenije T J, Abdellah M, Zheng K, Yartsev A, Pascher T, Harlang T, Chabera P, Pullerits T, Stepanov A, Wolf J P, Sundströ V 2014 J. Am. Chem. Soc. 136 5189 Google Scholar
[8]	Chen Y, Yi H T, Wu X, Haroldson R, Gartstein Y N, Rodionov Y I, Tikhonov K S, Zakhidov A, Zhu Z Y, Podzorov V 2016 Nat. Commun. 7 12253 Google Scholar
[9]	He J L, Fang W H, Long R, Prezhdo O V 2020 J. Am. Chem. Soc. 142 14664 Google Scholar
[10]	Li W W, Man Z Y, Zeng J T, Zheng L Y, Li G R, Kassiba A 2020 J. Phys. Chem. C 124 13348 Google Scholar
[11]	Brenner T M, Egger D A, Rappe A M, Kronik L, Hodes G, Cahen D 2015 J. Phys. Chem. Lett. 6 4754 Google Scholar
[12]	Dong Q, Fang Y, Shao Y, Mulligan P, Qiu J, Cao L, Huang J 2015 Science 347 967 Google Scholar
[13]	Shi D, Adinolfi V, Comin R, Yuan M, Alarousu E, Buin A, Chen Y, Hoogland S, Rothenberger A, Katsiev K, Losovyj Y, Zhang X, Dowben P A, Mohammed O F, Sargent E H, Bakr O M 2015 Science 347 519 Google Scholar
[14]	Mei Y, Zhang C, Vardeny Z V, Jurchescu O D 2015 MRS Commun. 5 297 Google Scholar
[15]	Savenije T J, Ponseca C S, Kunneman L, Abdellah M, Zheng K, Tian Y, Zhu Q, Canton S E, Scheblykin I G, Pullerits T, Yartsev A, Sundstrom V 2014 J. Phys. Chem. Lett. 5 2189 Google Scholar
[16]	Karakus M, Jensen S A, D’Angelo F, Turchinovich D, Bonn M, Canovas E 2015 J. Phys. Chem. Lett. 6 4991 Google Scholar
[17]	Oga H, Saeki A, Ogomi Y, Hayase S, Seki S 2014 J. Am. Chem. Soc. 136 13818 Google Scholar
[18]	He Y, Galli G 2014 Chem. Mater. 26 5394 Google Scholar
[19]	Wang Y, Zhang Y, Zhang P, Zhang W 2015 Phys. Chem. Chem. Phys. 17 11516 Google Scholar
[20]	Whalley L D, Skelton J M, Frost J M, Walsh A 2016 Phys. Rev. B 94 220301 Google Scholar
[21]	Monahan D M, Guo L, Lin J, Dou L, Yang P, Fleming G R 2017 J. Phys. Chem. Lett. 8 83211
[22]	Ma J, Wang L W 2017 Nano Lett. 17 3646 Google Scholar
[23]	Frisch M J, Trucks G W, Schlegel H B, et al. 2009 Gaussian 09 (Revision C.01) (Wallingford: Gaussian, Inc.)
[24]	Murray J S, Brinck T, Lane P, Paulsen K, Politzer P 1994 J. Mol. Struct. Theochem. 307 55 Google Scholar
[25]	Lefebvre C, Rubez G, Khartabil H, Boisson J C, Contreras-García J, Hénon E 2017 Phys. Chem. Chem. Phys. 19 17928 Google Scholar
[26]	Belpassi L, Infante I, Tarantelli F, Visscher L 2008 J. Am. Chem. Soc. 130 1048 Google Scholar
[27]	Zhang A, Chen Y L, Zhang C X, Yan J 2019 Chin. Phys. Lett. 36 026701 Google Scholar
[28]	张翱, 陈云琳, 闫君, 张春秀 2018 物理学报 67 106701 Google Scholar Zhang A, Chen Y L, Yan J, Zhang C X 2018 Acta Phys. Sin. 67 106701 Google Scholar
[29]	张翱, 张春秀, 陈云琳, 张春梅, 孟涛 2020 物理学报 69 118801 Google Scholar Zhang A, Zhang C X, Chen Y L, Zhang C M, Meng T 2020 Acta Phys. Sin 69 118801 Google Scholar

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CH₃NH₃多聚体的形成对有机-无机杂化钙钛矿太阳能电池性能的影响