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甲胺铅碘钙钛矿物性及制备过程的分子模拟

陈超1 赵伶玲1 王镜凡1

(1.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)

【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Ti O2基底上制备甲胺铅碘晶体的过程,探讨了生成的Pb I42-、Pb I53-和Pb I64-多面体的排布方式,结合周围CH 3NH3+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Pb I53-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Pb I2∶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;

【DOI】

【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 Chao1 ZHAO Lingling1 WANG Jingfan1

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

【Abstract】Molecular dynamics simulation WAs 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 PbI42− tetrahedra, PbI53− pyramids and PbI64− octahedra are produced. After their arrangements were classified and the distribution of CH3NH3+ cations was analyzed, the early CH3NH3PbI3 nuclei consisting of well-connected PbIx (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 was discussed. The results show that the calculated values of elastic modulus is in good agreement with the experimental results. The PbI53− 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 that adding more CH3NH3I will optimize the device performance to some extent.

【Keywords】 hybrid perovskite; molecular simulation; crystallization; precursor composition; solar energy; vapor deposition;

【DOI】

【Funds】 National Natural Science Foundation of China (51376045);

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This Article

ISSN:0438-1157

CN: 11-1946/TQ

Vol 69, No. 06, Pages 2380-2387+2331

June 2018

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Article Outline

Abstract

  • Introduction
  • 1 Study object and method
  • 2 Results and discussion
  • 3 Conclusion
  • References