甲胺铅碘钙钛矿物性及制备过程的分子模拟

doi:10.11949/j.issn.0438-1157.20171410

化工学报 ›› 2018, Vol. 69 ›› Issue (6): 2380-2387.DOI: 10.11949/j.issn.0438-1157.20171410

甲胺铅碘钙钛矿物性及制备过程的分子模拟

陈超, 赵伶玲, 王镜凡

东南大学能源与环境学院, 能源热转换及其过程测控教育部重点实验室, 江苏南京 210096

收稿日期:2017-10-24 修回日期:2017-12-13 出版日期:2018-06-05 发布日期:2018-06-05
通讯作者: 赵伶玲
基金资助:
国家自然科学基金项目（51376045）。

Molecular simulation of physical properties and preparation of CH₃NH₃PbI₃

CHEN Chao, ZHAO Lingling, WANG Jingfan

Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy & Environment, Southeast University, Nanjing 210096, Jiangsu, China

Received:2017-10-24 Revised:2017-12-13 Online:2018-06-05 Published:2018-06-05
Supported by:
supported by the National Natural Science Foundation of China (51376045).

摘要/Abstract

摘要：

应用分子动力学方法分析了甲胺铅碘晶体的结构特征与机械性质等相关物性，模拟了用蒸气沉积法在TiO₂基底上制备甲胺铅碘晶体的过程，探讨了生成的PbI₄^2-、PbI₅^3-和PbI₄^6-多面体的排布方式，结合周围CH₃NH₃⁺的分布筛选出满足结构要求的初生晶核，分析了前驱盐配比对甲胺铅碘初生晶核产量的影响。结果表明，在拉伸过程中，甲胺铅碘晶体经历弹性形变、塑性形变以及断裂三个阶段，拟合计算得到的弹性模量与实验值符合较好；大部分初生晶核以PbI₅^3-金字塔的结构存在。前驱盐配比对各系统中PbI_x多面体的总含量影响较小，但对其中排布有效的PbI_x结构以及初生晶核的产量影响较大，二者产量随着配比PbI₂∶CH₃NH₃I的增加而迅速减小，这一关系与研究者发现的实验现象相符。

关键词: 杂化钙钛矿, 分子模拟, 结晶, 前驱盐配比, 太阳能, 蒸气沉积法

Abstract:

Molecular dynamics simulation is used to investigate the structure characteristics and mechanical properties, and to discuss the vapor deposition of MAPbI₃ on the TiO₂ substrate under a temperature of 300 K and three precursor compositions of PbI₂:CH₃NH₃I=1:2, 1:1 and 2:1, respectively. During the preparation processes, three polyhedral groups including PbI₄^2- tetrahedra, PbI₅^3- pyramids and PbI₆^4- octahedra are produced. After classifying their arrangements and analyzing the distribution of CH₃NH₃⁺ cations, early CH₃NH₃PbI₃ nuclei consisting of well-connected PbI_x (x=4, 5 or 6) polyhedral clusters and sufficient amounts of surrounding CH₃NH₃⁺ cations were identified. The influence on early nuclei from the precursor compositions of PbI₂:CH₃NH₃I were discussed. The results show that the calculated values of elastic modulus is in good agreement with the experimental results. The PbI₅^3- pyramids dominate over other polyhedral groups during the vapor deposition simulations. Meanwhile, even though the total amounts of polyhedra have a small dependence on the precursor compositions, the populations of the well-connected clusters and the early nuclei decrease rapidly with increasing the PbI₂:CH₃NH₃I ratio. This is in consistent with the experimental finding which to some degree, adding more CH₃NH₃I will optimize the device performance.

Key words: hybrid perovskite, molecular simulation, crystallization, precursor composition, solar energy, vapor deposition

中图分类号:

TQ021.9

陈超, 赵伶玲, 王镜凡. 甲胺铅碘钙钛矿物性及制备过程的分子模拟[J]. 化工学报, 2018, 69(6): 2380-2387.

CHEN Chao, ZHAO Lingling, WANG Jingfan. Molecular simulation of physical properties and preparation of CH₃NH₃PbI₃[J]. CIESC Journal, 2018, 69(6): 2380-2387.

参考文献 30

[1]	GAO P, GRATZEL M, NAZEERUDDIN M K. Organohalide lead perovskites for photovoltaic applications[J]. Energy & Environmental Science, 2014, 7(8):2448-2463.
[2]	KOJIMA A, TESHIMA K, SHIRAI Y, et al. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells[J]. Journal of the American Chemical Society, 2009, 131(17):6050-6051.
[3]	HODES G. Perovskite-based solar cells[J]. Science, 2013, 342(6156):317-318.
[4]	LEE S W, KIM S, BAE S, et al. UV degradation and recovery of perovskite solar cells[J]. Scientific Reports, 2016, 6:38150.
[5]	ETGAR L, GAO P, XUE Z, et al. Mesoscopic CH3NH3PbI3/TiO2 heterojunction solar cells[J]. Journal of the American Chemical Society, 2012, 134(42):17396-17399.
[6]	IM J H, LEE C R, LEE J W, et al. 6.5% efficient perovskite quantum-dot-sensitized solar cell[J]. Nanoscale, 2011, 3(10):4088-4093.
[7]	LEE M M, TEUSCHER J, MIYASAKA T, et al. Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites[J]. Science, 2012, 338(6107):643-647.
[8]	WERNER J, WENG C H, WALTER A, et al. Efficient monolithic perovskite/silicon tandem solar cell with cell area > 1 cm2[J]. The Journal of Physical Chemistry Letters, 2016, 7(1):161-166.
[9]	YANG W S, NOH J H, JEON N J, et al. High-performance photovoltaic perovskite layers fabricated through intra-molecular exchange[J]. Science, 2015, 348(6240):1234-1237.
[10]	NREL. Efficiency chart[EB/OL].[2017-04-14]. https://www.nrel.gov/pv/assets/images/efficiency-chart.png.
[11]	BURSCHKA J, PELLET N, MOON S J, et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells[J]. Nature, 2013, 499(7458):316-319.
[12]	LIU M, JOHNSTON M B, SNAITH H J. Efficient planar heterojunction perovskite solar cells by vapour deposition[J]. Nature, 2013, 501(7467):395-398.
[13]	CHEN Q, ZHOU H, HONG Z, et al. Planar heterojunction perovskite solar cells via vapor-assisted solution process[J]. Journal of the American Chemical Society, 2014, 136(2):622-625.
[14]	WU Y, ISLAM A, YANG X, et al. Retarding the crystallization of PbI2 for highly reproducible planar-structured perovskite solar cells via sequential deposition[J]. Energy & Environmental Science, 2014, 7(9):2934-2938.
[15]	VERLET L. Computer "experiments" on classical fluids (Ⅰ):Thermody-namical properties of Lennard-Jones molecules[J]. Physical Review, 1967, 159(1):98.
[16]	OMINGUES G, VOLZ S, JOULAIN K, et al. Heat transfer between two nanoparticles through near field interaction[J]. Physical Review Letters, 2005, 94(8):085901.
[17]	MATTONI A, FILIPPETTI A, SABA M I, et al. Methylammonium rotational dynamics in lead halide perovskite by classical molecular dynamics:the role of temperature[J]. The Journal of Physical Chemistry C, 2015, 119(30):17421-17428.
[18]	MATSUI M, AKAOGI M. Molecular dynamics simulation of the structural and physical properties of the four polymorphs of TiO2[J]. Molecular Simulation, 1991, 6(4/5/6):239-244.
[19]	LI P, ROBERTS B P, CHAKRAVORTY D K, et al. Rational design of particle mesh Ewald compatible Lennard-Jones parameters for +2 metal cations in explicit solvent[J]. Journal of Chemical Theory and Computation, 2013, 9(6):2733-2748.
[20]	MCDONALD N A, DUFFY E M, JORGENSEN W L. Monte Carlo investigations of selective anion complexation by a bis (phenylurea) p-tert-butylcalix
[4]	arene[J]. Journal of the American Chemical Society, 1998, 120(20):5104-5111.
[21]	RAPP A K, CASEWIT C J, COLWELL K, et al. UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations[J]. Journal of the American Chemical Society, 1992, 114(25):10024-10035.
[22]	NOS S. A unified formulation of the constant temperature molecular dynamics methods[J]. The Journal of Chemical Physics, 1984, 81(1):511-519.
[23]	HOOVER W G. Canonical dynamics:equilibrium phase-space distributions[J]. Physical Review A, 1985, 31(3):1695-1697.
[24]	DARDEN T, YORK D, PEDERSEN L. Particle mesh Ewald:an N·log(N) method for Ewald sums in large systems[J]. The Journal of Chemical Physics, 1993, 98(12):10089-10092.
[25]	AKTULGA H M, FOGARTY J C, PANDIT S A, et al. Parallel reactive molecular dynamics:numerical methods and algorithmic techniques[J]. Parallel Computing, 2012, 38(4):245-259.
[26]	FRENKEL D, SMIT B. Understanding molecular simulation second edition from algorithms to applications computational science series vol 1[M]//Understanding Molecular Simulation:From Algorithms to Applications. San Francisco, Academic Press, Inc. 2001:66.
[27]	TREACY M J, EBBESEN T, GIBSON J. Exceptionally high Young's modulus observed for individual carbon nanotubes[J]. Nature, 1996, 381(6584):678-695.
[28]	HUMPHREY W, DALKE A, SCHULTEN K. VMD:visual molecular dynamics[J]. Journal of Molecular Graphics, 1996, 14(1):33-38.
[29]	WELLER M T, WEBER O J, HENRY P F, et al. Complete structure and cation orientation in the perovskite photovoltaic methylammonium lead iodide between 100 and 352 K[J]. Chemical Communications, 2015, 51(20):4180-4183.
[30]	RAKITA Y, COHEN S R, KEDEM N K, et al. Mechanical properties of APbX3 (A=Cs or CH3NH3; X=I or Br) perovskite single crystals[J]. MRS Communications, 2015, 5(4):623-629.

甲胺铅碘钙钛矿物性及制备过程的分子模拟

Molecular simulation of physical properties and preparation of CH₃NH₃PbI₃

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	叶展羽, 山訸, 徐震原. 用于太阳能蒸发的折纸式蒸发器性能仿真[J]. 化工学报, 2023, 74(S1): 132-140.
[2]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[3]	宋明昊, 赵霏, 刘淑晴, 李国选, 杨声, 雷志刚. 离子液体脱除模拟油中挥发酚的多尺度模拟与研究[J]. 化工学报, 2023, 74(9): 3654-3664.
[4]	胡建波, 刘洪超, 胡齐, 黄美英, 宋先雨, 赵双良. 有机笼跨细胞膜易位行为的分子动力学模拟研究[J]. 化工学报, 2023, 74(9): 3756-3765.
[5]	赵佳佳, 田世祥, 李鹏, 谢洪高. SiO₂-H₂O纳米流体强化煤尘润湿性的微观机理研究[J]. 化工学报, 2023, 74(9): 3931-3945.
[6]	齐聪, 丁子, 余杰, 汤茂清, 梁林. 基于选择吸收纳米薄膜的太阳能温差发电特性研究[J]. 化工学报, 2023, 74(9): 3921-3930.
[7]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[8]	傅予, 刘兴翀, 王瀚雨, 李海敏, 倪亚飞, 邹文静, 雷月, 彭永姗. F₃EACl修饰层对钙钛矿太阳能电池性能提升的研究[J]. 化工学报, 2023, 74(8): 3554-3563.
[9]	陈吉, 洪泽, 雷昭, 凌强, 赵志刚, 彭陈辉, 崔平. 基于分子动力学的焦炭溶损反应及其机理研究[J]. 化工学报, 2023, 74(7): 2935-2946.
[10]	董明, 徐进良, 刘广林. 超临界水非均质特性分子动力学研究[J]. 化工学报, 2023, 74(7): 2836-2847.
[11]	刘远超, 蒋旭浩, 邵钶, 徐一帆, 钟建斌, 李耑. 几何尺寸及缺陷对石墨炔纳米带热输运特性的影响[J]. 化工学报, 2023, 74(6): 2708-2716.
[12]	顾浩, 张福建, 刘珍, 周文轩, 张鹏, 张忠强. 力电耦合作用下多孔石墨烯膜时间维度的脱盐性能及机理研究[J]. 化工学报, 2023, 74(5): 2067-2074.
[13]	李辰鑫, 潘艳秋, 何流, 牛亚宾, 俞路. 基于碳微晶结构的炭膜模型及其气体分离模拟[J]. 化工学报, 2023, 74(5): 2057-2066.
[14]	苏晓丹, 朱干宇, 李会泉, 郑光明, 孟子衡, 李防, 杨云瑞, 习本军, 崔玉. 湿法磷酸半水工艺考察与石膏结晶过程研究[J]. 化工学报, 2023, 74(4): 1805-1817.
[15]	张生安, 刘桂莲. 高效太阳能电解水制氢系统及其性能的多目标优化[J]. 化工学报, 2023, 74(3): 1260-1274.

甲胺铅碘钙钛矿物性及制备过程的分子模拟

Molecular simulation of physical properties and preparation of CH3NH3PbI3

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

Molecular simulation of physical properties and preparation of CH₃NH₃PbI₃