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有机-无机杂化钙钛矿材料与其他半导体材料相比具有高的缺陷容忍率, 在太阳能电池、发光二极管、低阈值激光器等领域有重要的应用前景. 通常情况下, 钙钛矿材料是通过溶液法合成的, 这种方法虽然可以得到性能优异的钙钛矿器件, 但同时也会在合成过程中产生大量缺陷. 尽管目前在理论和实验上对钙钛矿材料的缺陷做了很多研究, 但对单个缺陷附近的束缚激子发光问题的研究较少. 本文通过共聚焦显微系统研究了低温(4.2 K)下单根钙钛矿纳米线的荧光光谱, 观测到来自于缺陷周围束缚激子的窄线宽和高强度的荧光峰, 同时观测到了磁场下的塞曼分裂和抗磁现象, 并通过施加矢量磁场发现了束缚激子的g因子存在各向异性. 单个束缚态激子的磁光性质的研究为深入理解束缚激子在量子光源以及自旋电子学中的应用提供了依据.Hybrid organic-inorganic perovskites show large potential applications in solar cells, light emitting diodes and low threshold lasers because of the high tolerance of defects compared with other semiconductor materials. Normally they have been synthesized by dilution method, generating a device with high performance, but they also introduce lots of defects. So far, investigations have been done intensively on ensemble defects both in theory and experiment, but single-defect related trapped excitons are yet to be explored. In this work, we prepared high-quality CH3NH3PbBr3 perovskite nanowires with the length of about 1 μm and the width of several hundred nanometers by “reverse” ligand assisted reprecipitation method, and performed the magneto-photoluminescence measurement of different trapped excitons in single perovskite nanowires at a low temperature with a standard confocal microscopic system. The photoluminescence (PL) peak with narrow linewidth has been observed from trapped excitons with high luminescence intensity and the trapped excitons can be coupled with phonons in different ways. Both Zeeman splittings and diamagnetic effects have been observed in single trapped excitons under the magnetic field, and we found that the different trapped excitons have different Zeeman splittings and diamagnetic effects which is caused by the different defects near the trapped excitons. At the same time, we have extracted the g-factor of the trapped excitons under different magnetic field angles. The extracted exciton g-factors show anisotropic, which can be ascribed to the limitation of the lattice structure of the perovskite and the trapped exciton wave-function anisotropy under a vector magnetic field. Our results demonstrate that trapped excitons with narrow linewidth have very good luminescence properties and studying the magneto-optical properties from single trapped excitons can provide a deep understanding of trapped excitons in perovskites for applications in quantum light sources and spintronics. Furthermore, our results can also provide a possibility to control the electron spin in single-trapped-excitons-based hybrid organic-inorganic perovskites by manipulating the g-factor through an applied vector magnetic field, which promotes the application of the perovskite-based spintronics.
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Keywords:
- perovskite nanowire /
- magneto-optical spectroscopy /
- g-factor anisotropy /
- diamagnetic effect
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图 1 低温矢量磁场共聚焦测量系统示意图. 442 nm的激发光通过光纤耦合到测量系统, 激发样品后, 样品发出的荧光通过收集光路耦合至光纤, 最后被光谱仪和探测器记录信号. 图1左下角是
$ {\rm{C}}{{\rm{H}}_3}{\rm{N}}{{\rm{H}}_3}{\rm{PbB}}{{\rm{r}}_3} $ 纳米线样品的SEM图, 图中的比例尺为1 μmFig. 1. Schematic diagram of the confocal microscope measurement system with a vector magnetic field at low temperature(4 K). The excitation laser with the wavelength of 442 nm is coupled to the measurement system through an optical fiber, the PL of the sample is coupled out to the system through another optical fiber when the sample is excited by the laser, the PL signals are collected by a spectrometer and CCD detector. A SEM image of
$ {\rm{C}}{{\rm{H}}_3}{\rm{N}}{{\rm{H}}_3}{\rm{PbB}}{{\rm{r}}_3} $ nanowire is shown in the left bottom of Fig. 1, the scale bar is 1 μm.
图 2 低温(4.2 K)下不同纳米线的典型荧光光谱随激发功率的变化 (a) 能量在2.25 eV附近的发光峰来自纳米线的自由激子发光, 其低能方向出现的不规则且线宽较宽的是束缚激子峰, 这些束缚激子峰随着激光功率的增加峰值能量不稳定; (b) 自由激子峰及线宽较窄的束缚激子峰, 随着激发功率的变化, 这些束缚激子峰的位置相对稳定; (c) 束缚激子峰及其在低能方向的声子伴线, 声子能量为9.5 meV; (d)束缚激子峰及其高能方向的热极化子峰, 声子能量为5.4 meV
Fig. 2. Power dependent PL spectra of different nanowires at 4.2 K: (a) PL spectra from free excitons and defect states with broader linewidth; (b) PL spectra from free excitons and defect states with narrow linewidth; (c) PL spectra from trapped exciton and its phonon replica at lower energy side with a phonon energy of 9.5 meV; (d) PL spectra from trapped excitons and hot polarons at higher energy side with a phonon energy of 5.4 meV.
图 3 低温下不同纳米线在磁场下的荧光光谱 (a) 自由激子(FX)在磁场下无塞曼分裂, 束缚激子(TX)在磁场下有塞曼分裂; (b) 自由激子和束缚激子在磁场下均无塞曼分裂; (c)束缚激子在磁场下有塞曼分裂, 无抗磁现象; (d) 束缚激子在磁场下有塞曼分裂, 有抗磁现象
Fig. 3. PL spectra as a function of magnetic field at low temperature: (a) The peak of free excitons is not effected by the magnetic field while Zeeman splitting is observed for trapped excitons; (b) no splitting observed for both free excitons and trapped excitons; (c) the trapped excitons with a Zeeman effect but not diamagnetic effect; (d) the trapped excitons with both Zeeman effect and diamagnetic effect.
图 4 (a)纳米线的荧光光谱随磁场的变化, 零磁场下的两个峰来自于不同的束缚激子; (b) (c)不同束缚激子在磁场下的塞曼分裂; (d) (e) 不同束缚激子在磁场下的抗磁行为
Fig. 4. (a) PL spectra of trapped excitons as a function of magnetic field; (b) (c) g factors of different trapped excitons; (d) (e) the diamagnetic shifts of different trapped excitons.
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[1] Huang J S, Shao Y C, Dong Q F 2015 J. Phys. Chem. Lett. 6 3218
Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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