卤化物钙钛矿光电阻变机理研究进展

doi:10.15541/jim20230132

无机材料学报 ›› 2023, Vol. 38 ›› Issue (9): 1005-1016.DOI: 10.15541/jim20230132

所属专题：【能源环境】钙钛矿(202310)；【信息功能】神经形态材料与器件(202310)

卤化物钙钛矿光电阻变机理研究进展

郭华军¹^,²(), 安帅领²^,³, 孟婕²^,³, 任书霞³, 王文文², 梁子尚¹^,², 宋佳钰²^,³, 陈恒彬²^,³, 苏航²^,³, 赵晋津²()

1.石家庄铁道大学机械工程学院, 石家庄 050043
2.河北师范大学化学与材料科学学院, 河北省无机纳米材料重点实验室, 石家庄 050024
3.石家庄铁道大学材料科学与工程学院, 石家庄 050043

收稿日期:2023-03-16 修回日期:2023-05-23 出版日期:2023-09-20 网络出版日期:2023-06-16
通讯作者: 赵晋津, 教授. E-mail: jinjinzhao2012@163.com
作者简介:郭华军(1983-), 男, 博士研究生. E-mail: ghjfriend@foxmail.com
基金资助:
国家自然科学基金(U2130128);国家自然科学基金(11772207);河北省教育厅自然科学基金(ZD2020192);河北省市场监管局科技计划(2023ZC03);中央引导地方科技发展资金(216Z4302G);河北省创新能力提升计划(22567604H);京津冀基础研究合作专项(H2022205047);京津冀基础研究合作专项(22JCZXJC00060);京津冀基础研究合作专项(E3B33911DF);河北师范大学博士科研启动基金(L2023B18)

Research Progress of Photoelectric Resistive Switching Mechanism of Halide Perovskite

GUO Huajun¹^,²(), AN Shuailing²^,³, MENG Jie²^,³, REN Shuxia³, WANG Wenwen², LIANG Zishang¹^,², SONG Jiayu²^,³, CHEN Hengbin²^,³, SU Hang²^,³, ZHAO Jinjin²()

1. School of Mechanical Engineering, Shijiazhuang Tiedao University, Shijiazhuang 050043, China
2. Hebei Key Laboratory of Inorganic Nano-materials, College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024, China
3. School of Materials Science and Engineering, Shijiazhuang Tiedao University, Shijiazhuang 050043, China

Received:2023-03-16 Revised:2023-05-23 Published:2023-09-20 Online:2023-06-16
Contact: ZHAO Jinjin, professor. E-mail: jinjinzhao2012@163.com
About author:GUO Huajun (1983-), male, PhD candidate. E-mail: ghjfriend@foxmail.com
Supported by:
National Natural Science Foundation of China(U2130128);National Natural Science Foundation of China(11772207);Natural Science Foundation of Hebei Education Department(ZD2020192);Hebei Administration for Market Supervision Science and Technology Project List(2023ZC03);Central Government Guiding Local Science and Technology Development Project(216Z4302G);Innovation Capability Improvement Plan Project of Hebei Province(22567604H);Basic Research Cooperation Special Foundation of Beijing-Tianjin-Hebei Region(H2022205047);Basic Research Cooperation Special Foundation of Beijing-Tianjin-Hebei Region(22JCZXJC00060);Basic Research Cooperation Special Foundation of Beijing-Tianjin-Hebei Region(E3B33911DF);Ph.D Scientific Research Start-up Fund of Hebei Normal University(L2023B18)

摘要/Abstract

摘要：

阻变器作为一种基于可逆、非易失、阻态突变的信息存储和处理器件, 是解决传统存储器的内在物理限制和冯·诺依曼架构瓶颈问题的核心电子元器件之一, 受到了广泛关注。卤化物钙钛矿具有快速的载流子迁移特性和优异的光电转换性能, 作为阻变功能层赋予光电阻变存储器优异的阻变性能。因此, 近年来卤化物钙钛矿基阻变器的存储和计算应用研究发展迅速。然而, 目前对于卤化物钙钛矿的光电阻变机理尚未形成统一认识。基于此, 本文分析了卤化物钙钛矿阻变存储器的工作机理, 对比分析了卤化物钙钛矿基光电阻变器导电细丝和能级匹配调控特性, 总结了其各种机理的制约因素, 揭示了导电细丝在光场和电场作用下重复形成和断裂, 以及阻变器中卤化物钙钛矿功能层和其他功能层之间肖特基势垒改变, 主导卤化物钙钛矿光电阻变器的开关比、阈值(Set/Reset)电压和阻变器性能稳定性, 并进一步展望卤化物钙钛矿基光电阻变器在新型人工智能仿生突触、存内运算、机器视觉的应用。

关键词: 导电细丝, 能级匹配, 卤化物钙钛矿, 存内运算, 机器视觉, 综述

Abstract:

As a reversible, non-volatile, and resistive state mutation information storage and processing device, the resistive switching (RS) memory is expected to solve the inherent physical limitations of the traditional memory and von Neumann bottleneck, and has received widespread attention. Taking advantage of rapid carrier migration characteristics and excellent photoelectric conversion performance, halide perovskite optoelectronic RS memory devices present excellent resistive switching performance. In recent years, researches on storage and computing applications of the halide perovskite RS memory developed unprecedentedly; whereas, the working mechanisms of halide perovskite RS memory still remain unclear. This review analyzes the working mechanism of halide perovskite RS memory, compares the regulation characteristics of conduction filaments (CFs) and energy level matching (ELM), summarizes the constraints of various mechanisms, reveals the repeated formation and dissolution of CFs under light illumination and electric field, as well as Schottky barrier between the perovskite transfer layer and other layer, dominates the On/Off ratio, threshold (Set/Reset) voltage and performance stability of halide perovskite optoelectronic RS memory, and prospects the applications of halide perovskite RS memory in artificial intelligence bionic synapses, in-memory computing, and machine vision.

Key words: conductive filament, energy level matching, halide perovskite, in-memory computing, machine vision, review

中图分类号:

TM546

郭华军, 安帅领, 孟婕, 任书霞, 王文文, 梁子尚, 宋佳钰, 陈恒彬, 苏航, 赵晋津. 卤化物钙钛矿光电阻变机理研究进展[J]. 无机材料学报, 2023, 38(9): 1005-1016.

GUO Huajun, AN Shuailing, MENG Jie, REN Shuxia, WANG Wenwen, LIANG Zishang, SONG Jiayu, CHEN Hengbin, SU Hang, ZHAO Jinjin. Research Progress of Photoelectric Resistive Switching Mechanism of Halide Perovskite[J]. Journal of Inorganic Materials, 2023, 38(9): 1005-1016.

图/表 6

图1 卤化物钙钛矿阻变器的机理及其应用

Fig. 1 Schematic diagram of mechanisms and applications of halide perovskite RS devices

图2 3D钙钛矿阻变器的导电细丝[19,27,30⇓-32,37,41-42]

Fig. 2 CFs of 3D perovskite RS device[19,27,30⇓-32,37,41-42] (a) Illustration of Au/CsPbBr3/ITO RS device structure[27]; (b) I−V response of Al/CsPbClxBr3−x/ITO/PET RS device in semilogarithmic scale[41]; (c) Alignment of bromide vacancies and silver atoms in On state of ITO/Cs2AgBiBr6/Au RS device[42]; (d) Pb element oxidation and reduction peaks at cyclic voltammetry (CV) curve of Al@MAPbI3/Al; (e) Pb metallic filaments formation in Set process and dissolution in the Reset process[30]; (f) Perovskite thickness-dependent competition between metallic and iodine vacancy CFs of Ag/MAPbI3/FTO RS device[37]; (g) Hybrid filaments formation and dissolution of Ag/CsPbBr3 QDs:GO/ITO device[19]; (h) Intensity of Cu element on switched and unswitched Cu/MA3Bi2I9/ITO devices[31]; (i) Band diagram of Ag/PMMA/CsPbI3/Pt device and thermally activated Ag ions hopping in CsPbI3[32]; (j) Schematic diagram of ITO/Cs2AgBiBr6/Au RS device; (k) Atomic force microscope images of CFs in Off (left) and On (right) states of Fig 2(j); (l) Element distributions of Br and Ag in Off and On states in Fig 2(j)[42]. ITO: Indium-tin oxide; PET: Polyethylene terephthalate; MA: Methylammonium; QDs: Quantum dots; GO: Graphene oxide; PMMA: Poly(methylmethacrylate)

图3 二维结构(2D)卤化物钙钛矿阻变器的导电细丝[44-45]

Fig. 3 CFs of 2D halide perovskite RS device[44-45] (a) CFs mechanism of FTO/[(TZ-H)2(PbBr4)]n/Ag device; (b) I-V curve with conduction mechanism in semilogarithmic scale under positive-voltage sweep at 30 ℃ with inset showing schematic illustration of FTO/[(TZ-H)2(PbBr4)]n/Ag device structure; (c) I-V curves of FTO/[(TZ-H)2(PbBr4)]n/Ag device at different temperatures[45]; (d) Ternary resistive switching I-V curves of Al/MA2PbI2 (SCN)2/ITO device; (e) I-V curve with conduction mechanism in semilogarithmic scale with inset showing schematic illustration of Al/MA2PbI2 (SCN)2/ITO device structure; (f) CFs mechanism of Al/MA2PbI2 (SCN)2/ITO device[44]. Colorful figures are available on website

图4 光照下钙钛矿阻变器的导电细丝[51-52]

Fig. 4 CFs of perovskite RS device under light illumination[51-52] (a) CFs formation and dissolution of ITO/Ag/MAPbI3 quantum wires/Al device under light illumination[51]; (b) Dynamic bending fatigue I-V curves of mica/AgNWs@AZO/PEDOT:PSS/CsPbBr3 device under light illumination; (c) Three-dimensional tomography images of PEDOT: PSS/CsPbBr3 nanocrystal overlaid by Kelvin-probe force microscopy (KPFM) signals under (c1) dark condition and (c2) light illumination, and statistical variations of (c3) height and (c4) surface potential from Figs. (c1, c2); (d) Hybrid filaments formation and dissolution of mica/AgNWs@AZO/PEDOT:PSS/CsPbBr3 device under light illumination[52]. PEDOT: Poly(3,4-ethylenedioxythiophene); PSS: Poly(styrenesulfonate). Colorful figures are available on website

图5 钙钛矿阻变器的能级匹配[60⇓⇓⇓-64]

Fig. 5 Energy level matching of perovskite RS device[60⇓⇓⇓-64] (a) Energy level matching and the formation and dissolution of corresponding CFs of Ag/PMMA@CsPbI3/FTO device[60]; (b) Depletion width varied in p-type perovskite CsSnI3 layer due to Sn vacancies under an electric field[61]; (c) Schottky barrier formed at MAPbI3/TiO2 interface and resulting asymmetry I-V curve of Au/MAPbI3/TiO2/FTO device[62]; (d) RS loops of Al/Cs0.05(FAxMA1−x)0.95PbIyBr3−y/TiO2/FTO structure under dark condition and light illumination; (e) Depletion region at Cs0.05(FAxMA1−x)0.95PbIyBr3−y/TiO2 interface in low resistance state (LRS) and high resistance state (HRS) under illumination[63]; (f) Light-induced RS behaviours of Ni/ZnO/CsPbBr3/FTO device[64]. Colorful figures are available on website

图6 钙钛矿阻变器的应用[24,30,79,83,86,92-93]

Fig. 6 Application of perovskite-based RS devices[24,30,79,83,86,92-93] (a) CsPbBr3 quantum dots based phototransistor emulating human visual systems[92]; (b) MAPbI3 based synaptic transistor emulating a biological synapse[79]; (c) AgBiI4 used in artificial sensory neuron system emulating biological tactile sensing system[93]; (d) Schematic illustration of Ag/SrTiO3/CsPbBr3/Au device structure; (e) Photodetector, photomemory, memory mode and breakdown of Ag/SrTiO3/CsPbBr3/Au device[83]; (f, g) Schematic illustration of woven fibrous crosspoint RS devices with the architecture of Al@MAPbI3/Al[30]; (h) Al/CH3NH3SnCl3/polyvinyl alcohol/ITO/PET devices achieving logic “OR” and “AND” gate[86]; (i) Physical unclonable functions (memPUFs) of PrPyr[PbI3] RS devices[24]. PrPyr[PbI3]: Propyl pyridinium lead iodide

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卤化物钙钛矿光电阻变机理研究进展

Research Progress of Photoelectric Resistive Switching Mechanism of Halide Perovskite

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