Structure and electronic tunability of acene alkylamine based layered hybrid organic-inorganic perovskites from first principles
Structure and electronic tunability of acene alkylamine based layered hybrid organic-inorganic perovskites from first principles
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基于第一原理的并苯烷基胺基层状杂化有机-无机钙钛矿的结构和电子可调性
DOI：
10.1103/physrevmaterials.7.084601
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发表时间：
2023
影响因子：
3.4
通讯作者：
Blum, Volker
中科院分区：
文献类型：
--
作者：
Song, Ruyi;Liu, Chi;Kanai, Yosuke;Mitzi, David B.;Blum, Volker
利用第一性原理密度泛函理论（DFT）研究了12种低聚丙烯酸衍生物[苯基甲基铵（PMA）、萘基甲基铵（NMA）、蒽基甲基铵（AMA）和四基甲基铵（TMA）]和卤化铅（and阴离子）组成的层状有机-无机杂化钙钛矿，发现它们具有广泛、合理的带隙可调性、量子阱类型和自旋依赖的能带性质。从以前的合成中已知六种化合物，并用于设计可能的低能结构的计算搜索空间。在已知的六种化合物中，确定了(的精细化结构，并提出了(的新低能结构。接下来应用基于DFT的搜索方法来预测六个未知化合物的可能结构。从自旋轨道耦合杂化DFT计算预测的所有12种化合物的能级显示可调谐的I型量子阱排列，前沿轨道位于无机组分上，有机组分上，或两者上，由阳离子和阴离子选择控制。一些结构自发地打破局部和全局反转对称性，导致导带的强自旋分裂[高达0.12 eV的[]]，并显示出自旋相关输运性质和未来自旋电子和可调热学应用的潜力。
Twelve layered hybrid organic-inorganic perovskites combining oligoacene derivatives [phenylmethylammonium (PMA), naphthylmethylammonium (NMA), anthrylmethylammonium (AMA), and tetrylmethylammonium (TMA)] and lead halides (, andanions) are investigated by first-principles density functional theory (DFT), showing broad, rational tunability of band gap, quantum well type, and spin-dependent energy band properties. Six compounds are known from previous syntheses and are used to devise a computational search space for likely low-energy structures. Among the six known compounds, a refined structure is identified for (and a new, lower-energy structure is suggested for (. The DFT based search methodology is next applied to predict the likely structures for the six unknown compounds. Computationally predicted energy levels for all 12 compounds from spin-orbit coupled hybrid DFT reveal tunable type I quantum well alignments, with frontier orbitals located on the inorganic component, on the organic component, or on both, as controlled by cation and anion selection. Several structures spontaneously break local and global inversion symmetry, causing strong spin splitting of the conduction bands [up to 0.12 eV for (] and showing potential for spin-dependent transport properties and future spintronic and tunable chiroptical applications.