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钙钛矿的Rashba效应及其对载流子复合的影响

魏应强 徐磊 彭其明 王建浦

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钙钛矿的Rashba效应及其对载流子复合的影响

魏应强, 徐磊, 彭其明, 王建浦

Rashba effect in perovskites and its influences on carrier recombination

Wei Ying-Qiang, Xu Lei, Peng Qi-Ming, Wang Jian-Pu
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  • 当直接半导体中存在强的自旋轨道耦合作用, 且材料结构不具备中心反演对称性时, Rashba效应将会出现, 从而使自旋简并的能带分裂为具有相反自旋态的两个子能带. 这两个子能带会偏离布里渊区的对称中心位置, 致使半导体呈现出间接带隙的特征. 金属卤化物钙钛矿兼具强的自旋轨道耦合和结构中心反演不对称性, 在Rashba效应研究中展现出巨大的潜力. 本文围绕钙钛矿中Rashba效应的理论研究与实验证明, Rashba效应对载流子复合的影响以及目前Rashba效应研究中出现的争论, 系统地进行回顾与梳理; 针对钙钛矿中Rashba效应的研究现状, 提出了几个目前亟待解决的问题, 并展望了该领域未来的研究方向.
    When there is a strong spin-orbit coupling in some direct semiconductor with an inversion-asymmetric structure, the Rashba effect will exist, splitting the spin-degenerated bands into two sub-bands with opposite spin states. These two sub-bands will deviate from the symmetry center of the Brillouin zone, making the semiconductor an indirect band gap semiconductor. Metal halide perovskites exhibit strong spin-orbit coupling and possess an inversion-asymmetric crystal structure, showing great potential in Rashba effect research. In this review, we systematically review the Rashba effects in perovskites, including the theoretical and experimental studies for demonstrating the Rashba effect in perovskites, the influence of Rashba effect on the carrier recombination, and the current debates concerning the Rashba effect in perovskites. Then, several problems that need to be solved urgently are proposed,they being 1) whether there exists the Rashba effect in the perovskite, 2) whether the Rashba effect can exert a significant influence on carrier recombination, and 3) what the relationship between the Rashba effect and the perovskite stucture is. The prospects are also given for the future research including the study of the Rashba effect in perovskites by various spectral methods and the applications of the Rashba effect in optical-electronic-magnetic devices.
      通信作者: 彭其明, iamqmpeng@njtech.edu.cn ; 王建浦, iamjpwang@njtech.edu.cn
    • 基金项目: 国家重点基础研究发展计划(批准号: 2015CB932200)、国家重点研发计划政府间国际科技创新合作重点专项中国与欧盟合作项目(批准号: 2016YFE0112000)、国家自然科学基金重大研究计划(批准号: 91733302)、国家杰出青年科学基金(批准号: 61725502)、国家自然科学基金青年科学基金(批准号: 11804156)和南京工业大学引进人才科研启动专项经费(批准号: 38274017104)资助的课题.
      Corresponding author: Peng Qi-Ming, iamqmpeng@njtech.edu.cn ; Wang Jian-Pu, iamjpwang@njtech.edu.cn
    • Funds: Project supported by the National Basic Research Program of China (Grant No. 2015CB932200), the Joint Research Program between China and European Union (Grant No. 2016YFE0112000), the Major Research Plan of the National Natural Science Foundation of China (Grant No. 91733302), the National Science Fund for Distinguished Young Scholars,China (Grant No. 61725502), the National Natural Science Foundation of China (Grant No. 11804156), and the Nanjing Tech Start-up Grant, China (Grant No. 38274017104).
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  • 图 1  金属卤化物钙钛矿的晶胞结构[2]

    Fig. 1.  Crystal structure of the metal halide perovskite [2].

    图 2  钙钛矿中Rashba效应对载流子复合的影响示意图[24]

    Fig. 2.  Schematic diagram of the impact of Rashba effect on the carriers recombination in perovskite [24].

    图 3  Rashba效应示意图[47]

    Fig. 3.  Schematic diagram of the Rashba effect [47].

    图 4  (a)具有不同自旋极化的Rashba分裂子带偏离了k空间的Γ[61]; (b)通过调控材料的铁电性改变Rashba分裂子带的自旋螺旋性[57]; (c)通过控制外电场调控自旋分裂子带中的自旋构造[37]

    Fig. 4.  (a) Rashba-splitting sub-bands with different spin polarization deviate from the Γ point in the k space [61]; (b) changing the spin helicity of the Rashba-spliting sub-bands by tuning the ferroelectricity of the material[57]; (c) tuning the spin texture of the spin-splitting sub-bands by controlling the external electric field [37].

    图 5  (a)密度泛函计算表明晶格的扭曲致使钙钛矿成为间接带隙半导体[62]; (b)分子动力学分析指出钙钛矿中的Rashba效应随时间变化[58]; (c)基于分子动力学和冻结声子分析法的研究表明钙钛矿中动态的Rashba效应源自非简谐结构波动[63]; (d) ab initio计算分子动力学、密度泛函理论以及准粒子GW理论的综合分析结果表明钙钛矿中动态Rashba效应来源于材料中热无序导致的势能波动[64]

    Fig. 5.  (a) Density functional calculations show that perovskite becomes an indirect semiconductor due to the lattice distortion[62]; (b) molecular dynamics analysis shows that the Rashba effect in perovskite varies with time[58]; (c) molecular dynamics and frozen phonon analysis show that the dynamic Rashba effect in perovskite originates from the fluctuation of anharmonic structure[63]; (d) the combination analysis of ab initio molecular dynamics, density functional theory and quasiparticle GW theory shows that the dynamic Rashba effect in perovskite originates from the potential energy fluctuation caused by thermal disorder in perovskite [64].

    图 6  (a)高温下钙钛矿中的局域对称性破缺; (b)甲胺的取向与非谐波模式强烈耦合[65]

    Fig. 6.  (a) Local symmetry breaking in perovskite at high temperature; (b) the orientation of methylammonium is strongly coupled to the non-harmonic mode [65].

    图 7  利用圆偏光生电流效应研究钙钛矿中的Rashba效应[36]

    Fig. 7.  Rashba effects in perovskite were studied by measuring the circular photogalvanic effects [36].

    图 8  利用时间分辨微波传导测试研究钙钛矿中的Rashba效应[66]

    Fig. 8.  Studying the Rashba effect in perovskite through time-resolved microwave conductance measurements [66].

    图 9  (a), (b)利用磁光效应研究钙钛矿中的Rashba效应[29]; (c)通过测试高压下的钙钛矿光电性质研究钙钛矿中的Rashba效应[68]; (d)利用电诱导吸收谱和瞬态光谱测试法研究钙钛矿中的Rashba效应[47]

    Fig. 9.  (a), (b) Studying the Rashba effect in perovskite by measuring the magneto-optical effects [29]; (c) studying the Rashba effect in perovskite by measuring the optoelectronic properties of perovskite at high pressure[68]; (d) studying the Rashba effect in perovskite by measuring the electroabsorption spectra and transient spectroscopy [47].

    图 10  利用角分辨光电子能谱研究钙钛矿中的Rashba效应[38]

    Fig. 10.  Studying the Rashba effect in perovskite by angle-resolved photoelectron spectroscopy measurements [38].

    图 11  基于第一性原理计算和Rashba自旋-轨道耦合模型的分析研究钙钛矿中Rashba效应对载流子复合的影响[24]

    Fig. 11.  Studying the influence of Rashba effect on carrier recombination based on the first principle calculations and the Rashba spin-orbit coupling model analyses [24].

    图 12  利用准粒子自洽场GW法研究不同激发密度和不同温度下Rashba效应对钙钛矿中光生载流子辐射复合速率的影响[13]

    Fig. 12.  Studying the influence of the Rashba effect on the radiative recombination rates of photo-generated carriers in perovskite under different excitation densities and temperatures by quasiparticle self-consistent field GW method [13].

    图 13  (a), (b)基于1PE和2PE的瞬态光谱测试研究Rashba效应对钙钛矿表面和内部载流子复合速率的影响[33]; (c)基于瞬态PL研究不同晶粒大小的钙钛矿中Rashba效应对载流子复合的影响[71]

    Fig. 13.  (a), (b) Studying the influences of Rashba effect on the carrier recombination rates on the surface and interior of perovskite by transient spectroscopy measurements based on single-photon (1PE) and two-photon (2PE) excitations [33]; (c) studying the impacts of Rashba effect on the carrier recombination in perovskite with different grain size based on transient PL investigation [71].

    图 14  (a)利用瞬态反射谱研究不同n值的二维钙钛矿中Rashba效应对载流子寿命的影响[72]; (b)利用圆偏振时间分辨光谱研究Rashba效应对钙钛矿中载流子自旋寿命的影响[72]

    Fig. 14.  (a) Studying the influences of Rashba effect on carrier lifetime in two-dimensional perovskite with different n values by using the transient reflection spectroscopy[72]; (b) studying the influences of Rashba effect on spin lifetime of the carriers in the perovskites by circularly polarized time-resolved spectroscopy [72].

    图 15  基于密度泛函理论和时间分辨激光谱法研究不同n值的二维钙钛矿中的Rashba效应对载流子寿命的影响[73]

    Fig. 15.  Studying the influences of Rashba effect on carrier lifetime in two-dimensional perovskite with different n values through density functional theory calculations and time-resolved spectroscopy measurements [73].

    图 16  温度依赖的光谱研究表明钙钛矿是直接带隙半导体[40]

    Fig. 16.  Temperature-dependent spectroscopy measurements indicate that the perovskite is a direct bandgap semiconductor [40].

    图 17  通过吸收-PL谱的对比研究(a)和温度依赖的瞬态PL测试(b)证明钙钛矿是直接带隙半导体[41]

    Fig. 17.  Absorption-PL spectra study (a) and temperature-dependent transient PL measurements (b) show that the perovskite is a direct bandgap semiconductor [41].

    图 18  SHG-RA测量(a)和第一性原理计算(b)的结果表明钙钛矿结构具有中心反演对称性[42]

    Fig. 18.  SHG-RA measurements (a) and first principle calculations (b) show that the structure of perovskite is inversion-symmetric [42]

    图 19  (a)第一性原理计算结果表明虽然钙钛矿中存在Rashba效应, 但载流子复合并不是自旋禁阻的[44]; (b) Rashba效应引起的动量不匹配对载流子复合速率的影响十分微弱[43]

    Fig. 19.  Results of first-principles calculations show that the Rashba effect in perovskite does not lead to the spin forbidden of the carrier recombination [44]; (b) the influence of momentum mismatch caused by the Rashba effect on the carriers recombination is very weak [43].

    图 20  (a)利用Rashba效应产生自旋流; (b)利用Rashba效应构造自旋FET[30]

    Fig. 20.  (a) Generation of spin current by using the Rashba effect; (b) the spin-FET based on the Rashba effect [30].

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出版历程
  • 收稿日期:  2019-05-06
  • 修回日期:  2019-06-13
  • 上网日期:  2019-08-01
  • 刊出日期:  2019-08-05

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