Suppressed ion migration in halide perovskite nanocrystals by simultaneous Ni2+ doping and halogen vacancy filling
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摘要: 卤化铅钙钛矿(LHPs)由于具有优异的光电性能和制备成本低等优点，已成为新一代光电器件的有力候选材料。然而，缺陷造成的离子迁移会导致LHPs纳米晶的晶体结构解离分解。因此，稳定性成为LHPs实际应用中亟待解决的问题。本文旨在研究镍离子替位掺杂及卤素空位填补对CsPbBr3纳米晶中的离子迁移抑制作用。通过离子迁移活化能的测定和高分辨透射电镜的原位观察，分析了前驱体掺杂剂对加强LHPs稳定性的作用原理。首先，选用乙酰丙酮镍和溴化镍作为掺杂剂，合成了掺杂LHPs纳米晶。其次，通过吸收-荧光光谱，X射线衍射，X射线光电子衍射，透射电子显微镜等测试手段对掺杂样品的光学及化学组成进行分析。最后，通过纳米晶薄膜电导率的温度依赖关系计算出其离子迁移活化能，并结合高分辨电镜原位观察纳米晶在高能电子束辐照下的形貌演变过程，揭示了不同掺杂剂对合成掺杂LHPs稳定性的影响。实验结果表明：Ni2+掺杂CsPbBr3样品的离子迁移活化能相较本征CsPbBr3样品（0.07 eV）有显著提升，其中乙酰丙酮镍掺杂样品的离子迁移活化能为0.238 eV，溴化镍掺杂样品的离子迁移活化能为0.487 eV。另外，电子束辐照测试表明溴化镍掺杂钙钛矿晶体表现出更高的结构稳定性，这主要归因于掺杂的Ni2+对卤素的强结合和卤素填补空位缺陷的协同钝化作用。Ni2+掺杂和卤素空位填充协同可以有效抑制卤化物钙钛矿纳米晶体中的离子迁移。Abstract: Lead Halide Perovskites(LHPs) are promising candidates for next-generation optoelectronic application. However, defect-induced ion migration causes phase degradation in LHP nanocrystals. Therefore, material stability has become an urgent problem that impedes practical applications. In this paper, we aim to study the influence of doping cations on inhibiting the migration of halogen ions in perovskite nanocrystals. Through the measurement of ion migration activation energy and in-situ high-resolution transmission electron microscope technology, the effect of precursor dopants on the stability of LHPs were analyzed. Firstly, we synthesized two types of LHP nanocrystals with high crystal quality using nickel acetylacetonate and nickel bromide as precursor dopants, respectively. Secondly, the optical properties and component elements of the doped samples were analyzed by absorption-fluorescence spectroscopy, X-ray diffraction, X-ray photoelectron diffraction, and transmission electron microscopy. Finally, the ion migration activation energies of various LHP films were measured using temperature-dependent ion conductivity tests, and the influence of the precursor dopants on the stability of as-synthesized doped LHPs was compared with the results from high-resolution electron microscopy. The results showed that the activation energies of the doped CsPbBr3 samples were significantly improved compared to the intrinsic CsPbBr3 sample (0.07 eV), which were determined to be 0.238 eV for nickel acetylacetonate and 0.487 eV for nickel bromide. In addition, the electron irradiation experiments showed that the nickel bromide-doped perovskite nanocrystals exhibited higher structural stability. This is due to the strong bonding of doped Ni2+ to halogen and the synergistic passivation effect of halogen filling vacancy defects. It can be concluded that Ni2+ doping and halogen vacancy filling can effectively inhibit ion migration in halide perovskite nanocrystals.
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图 1 钙钛矿样品的结构和性能。（a, b）为溴化镍掺杂（NiBr2-doped）CsPbBr3纳米晶的吸收光谱和发射光谱。(c, d) 乙酰丙酮镍掺杂（Ni(acac)2-doped））CsPbBr3纳米晶吸收光谱和发射光谱。（e, f, g）分别为未掺杂，乙酰丙酮镍掺杂及溴化镍掺杂CsPbBr3纳米晶体TEM图像。(h) 掺Ni的CsPbBr3纳米晶与本征CsPbBr3的XPS图谱。 (i,k)分别为NiBr2-doped、Ni(acac)2-doped CsPbBr3纳米晶的XRD图谱，在图的底部显示了斜方CsPbBr3结构。（j, l）分别为Ni(acac)2-doped、NiBr2-doped CsPbBr3纳米晶的高分辨XRD谱(110)（JCPDS No.18-0364）
Figure 1. Structures and properties of LHPs. Absorption spectra and PL spectra of CsPbBr3 nanocrystals doped with NiBr2 (a, b) and Ni(acac)2 (c,d). (e, f, g) TEM images of Ni-doped and undoped CsPbBr3 nanocrystals. (h) XPS spectra of Ni-doped and undoped CsPbBr3 nanocrystals. (i, k) XRD patterns of NiBr2-doped, Ni(acac)2-doped and undoped CsPbBr3 nanocrystals. JCPDS No.18-0364 of the orthorhombic CsPbBr3 structure are indicated at the bottom of each figure. (j, l) High-resolution XRD spectra (110) of NiBr2-doped, Ni(acac)2-doped and undoped CsPbBr3 nanocrystals
图 2 电子束辐照实验结果及原理图
Figure 2. Experimental results of electron beam irradiation and corresponding schematic diagram
图 3 活化能测试示意图及测试结果。（a）活化能测试示意图，图中t1和t2指光电流和暗电流分别拟合得到的光/暗电流的驰豫时间。（b）不同温度暗电流变化（NiBr2掺杂10%），插图显示以电流弛豫时间为横坐标的半对数暗电流曲线（lnA）。（c）阿伦尼乌斯关系式活化能(Ea)计算结果。（d）不同掺杂样品的活化能 (x代表实际含量)
Figure 3. Schematic diagram of activation energy test and test results. (a) Schematic diagram of activation energy test. t1 and t2 in the figure refer to the relaxation time of the light/dark currents fitted by the photocurrent and dark current, respectively. (b) The dark current changes at different temperatures (NiBr2 doping 10%). The inset shows the semilog dark current (lnA) curve as function with the current relaxation time. (c) Activation energy (Ea) caculated by formla (1). (d) Activation energy of different doped samples (x is the actual content)
图 4 掺杂与空位填补原理图。（a）掺杂锚定；（b）空位填补
Figure 4. Schematic diagram of doping and vacancy filling. (a) Doping anchoring; (b) vacancy filling
表 1 使用ICP-MS测试的掺杂含量
Table 1. Doping content tested by ICP-MS
乙酰丙酮镍掺杂 溴化镍掺杂 名义含量 实际含量* 名义含量 实际含量 5% 0.07 5% 0.11 10% 0.12 10% 0.14 12% 0.13 12% 0.17 15% 0.20 15% 0.21 20% 0.23 20% 0.25 *：表示ICP-MS测定的CsPb1−xNixBr3中Ni掺杂的实际含量 
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