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近年来, 铅基卤素钙钛矿因其制备工艺简单、载流子扩散距离长以及离子迁移速率快等优点而被应用于阻变存储器. 然而, 铅基卤素钙钛矿结构中的铅对人类健康与环境保护存在威胁, 限制了铅基卤素钙钛矿在数据存储领域的实际应用. 研究者们针对铅基钙钛矿铅毒性的问题展开了一系列研究. 其中, 非铅卤素钙钛矿因不含铅而被认为是最有前景的下一代新型阻变存储介质材料. 最近几年, 锡基、铋基、锑基和铜基等非铅卤素钙钛矿被引入阻变存储器领域. 本文系统地综述了非铅卤素钙钛矿材料及其阻变性能, 归纳了非铅卤素钙钛矿的阻变性能及其阻变机理, 指出了非铅卤素钙钛矿材料应用于阻变存储器存在的关键问题, 为进一步研究非铅钙钛矿阻存储器提供了参考.With the rapid development of the information age, the demand for information storage capacity and miniaturization of memory units has been being increased. However, the commonly used silicon-based flash memory has nearly approached to its physical limit. The resistive switching random access memory (ReRAM) has become one of the promising candidates for the next-generation non-volatile memory due to its simple structure, fast operation speed, excellent flexibility, and long endurance. Recently, we witnessed that the lead halide perovskites, as hot star materials, have been widely used in optoelectronic fields owning to their advantages of low cost, excellent photoelectric properties, and solution process ability. Moreover, the lead halide perovskite has been successfully used as the active layer in ReRAM device because of its tunable bandgap, long charge carrier diffusion length, fast ion migration, and high charge carrier mobility. Whereas the toxicity of lead in halide perovskite is a very horrible problem in lead halide perovskite-based ReRAM devices. The lead-free halide perovskite is considered to be the most promising material for perovskite-based ReRAM devices because it does not contain lead element. Most recently, a large number of scientists from different groups have begun to study lead-free perovskite-based ReRAM devices. For example, tin, bismuth, antimony, and copper-based halide perovskite materials have been utilized in ReRAM devices and exhibited excellent resistance switching (RS) performances. Here in this paper, the recent development of lead-free perovskite and its RS performance are reviewed, including lead-free halide perovskite materials, RS performances, and RS mechanisms of lead-free perovskite-based ReRAM. Finally, the key problems and development prospects of lead-free perovskite-based ReRAM are also presented, which provides a fundamental step towards developing the RS performance based on lead-free halide perovskites.
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Keywords:
- lead-free halide perovskite /
- resistive switching random access memory /
- resistance switching performance /
- mechanism of resistance switching
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图 2 CsSnBr3非铅钙钛矿材料阻变性能 (a) Pt/CsSnBr3/Pt/PET阻变存储器结构示意图; (b)电流-电压(I-V )特性曲线; (c)耐受性[48]
Fig. 2. Resistive switching performance of CsSnBr3 lead-free halide perovskite: (a) Schematic of Pt/CsSnBr3/Pt/PET resistive switching device; (b) typical current-voltage (I-V ) curve; (c) endurance performance[48].
图 3 CsSnI3非铅钙钛矿材料及其阻变性能 (a) CsSnI3晶体结构; (b)阻变存储器结构; (c)器件的截面SEM图; Ag/CsSnI3/Pt/Ti/SiO2/Si器件的(d) I-V特性曲线、(e)耐受性和(f)高低阻态保持特性; Au/CsSnI3/Pt/Ti/SiO2/Si器件的(g) I-V特性曲线、(h)耐受性和(i) 50个不同元器件高低阻态[49]
Fig. 3. Resistive switching performance of CsSnI3 lead-free perovskite: (a) CsSnI3 crystal structure; (b) schematic of the Ag or Au/PMMA/CsSnI3/Pt/SiO2/Si vertical stack structure; (c) cross-sectional SEM image of the device; (d) the typical I-V curves, (e) endurance performance, and (f) retention characteristics of low resistances state (LRS) and high resistance state (HRS) of the Ag/PMMA/CsSnI3/Pt devices; (g) the typical I-V curves, (h) endurance performance, and (i) HRS and LRS of 50 different cells of the Au/PMMA/CsSnI3/Pt devices[49].
图 6 铋基非铅卤素钙钛矿阻变存储器 (a) Au/A3Bi2I9/Pt/Ti/SiO2/Si器件结构示意图; (b) Rb3Bi2I9阻变存储器截面SEM图; (c) Cs3Bi2I9阻变存储器截面SEM图; Rb3Bi2I9阻变存储器的(d) I-V特性曲线、(e)耐受性和(f)保持特性; Cs3Bi2I9阻变存储器的(g) I-V特性曲线、(h)耐受性和(i)保持特性[52]
Fig. 6. The Bi-based perovskite resistance random access memory (ReRAM) devices: (a) Schematic of Au/A3Bi2I9/Pt/Ti/SiO2/Si based ReRAM devices; (b) the cross-section SEM image of Rb3Bi2I9 based ReRAM device; (c) the cross-section SEM image of Cs3Bi2I9 based ReRAM device; (d) the typical I-V curve, (e) endurance, and (f) retention of Rb3Bi2I9 based ReRAM; (g) the typical I-V curve, (h) endurance, and (i) retention of Cs3Bi2I9 based ReRAM[52].
图 9 Au/Cs2AgBi2Br6/ITO 器件在不同恶劣环境下的I-V特性曲线 (a)相对湿度(RH) 10%—80%; (b)温度范围为303—453 K; (c)酒精灯外焰加热10 s; (d)在60Co射线照射下曝露, 总剂量高达5 × 105 rad(SI)[55]
Fig. 9. I-V characteristics of Au/Cs2AgBi2Br6/ITO device in different harsh environments: (a) 10%—80% relative humidity; (b) temperature range from 303 to 453 K; (c) burnt by luminous cone of alcohol lamp for 10 s; (d) exposed under 60Co γ-ray irradiation with a total dose as high as 5 × 105 rad (SI)[55].
图 10 (a) Ag/PMMA/MA3Sb2Br9/ITO阻变存储器结构示意图; (b) MA3Sb2Br9晶体结构; (c) MA3Sb2Br9薄膜截面SEM图; MA3Sb2Br9基阻变存储器的(d) I-V特性曲线、(e)耐久性和(f)保持时间; (g)依赖于连续脉冲的长期增强(LTP)和长期抑制(LTD)现象; (h)突触前和突触后突峰(用于模拟突峰时间依赖性可塑性(STDP)); (i) STDP行为[58]
Fig. 10. (a) Schematic device structure of Ag/PMMA/MA3Sb2Br9/ITO ReRAM; (b) crystal structure of MA3Sb2Br9; (c) cross-sectional SEM image; (d) I-V characteristics, (e) endurance, and (f) retention time of MA3Sb2Br9 based memristors; (g) long-term potentiation (LTP) and long-term depression (LTD) depending on consecutive pulses; (h) presynaptic and postsynaptic spikes for emulating spike timing dependent plasticity (STDP); (i) STDP behavior of an MA3Sb2Br9 memristor[58].
图 11 (a) Cs3Cu2I5非铅钙钛矿晶体结构; Cs3Cu2I5阻变存储器的(b)垂直结构示意图和(c)循环测试; (d)模拟神经突触示意图; (e)线性增强和线性抑制; (f)美国国家标准技术研究院数据库(MNIST)训练数据识别精度[65]
Fig. 11. (a) Cs3Cu2I5 crystal structure; (b) vertical stack structure schematic and (c) cycle tests of the Ag/PMMA/Cs3Cu2I5/ITO memristor; (d) schematic of synapses; (e) linear potentiation and depression; (f) successful recognition accuracy monitored while training the data set from Modified National Institute of Standards and Technology (MNIST)[65].
图 13 (a) Au/PMMA/CsSnI3/Pt器件界面型机理示意图[49]; (b)电场作用下, p型钙钛矿层中锡空位的积累引起的耗尽宽度变化[49]; (c)界面型机理示意图
Fig. 13. (a) Schematic of the interface-type switching mechanism in the Au/PMMA/CsSnI3/Pt device[49]; (b) depletion width variation in the p-type perovskite layer according to the accumulation of Sn vacancies under an electric field[49]; (c) the schematic illustration of interface-type switching mechanism in the switching layer
表 1 基于非铅卤素钙钛矿的阻变存储器的阻变性能
Table 1. Resistive switching performance of resistive switching memory parameters based on lead-free halide perovskites.
器件结构 设置/重置电压/V 开/关比 耐受性/次 保持特性/s Pt/CsSnBr3/Pt/PET[48] 0.2/–0.15 105 50 104 Ag/PMMA/CsSnI3/Pt/Ti/SiO2/Si[49] 0.15/–0.3 104 600 7 × 103 Au/Cs3Bi2I9/Pt/Ti/SiO2/Si[52] –0.5/0.1 107 400 103 Au/Rb3Bi2I9/Pt/Ti/SiO2/Si[52] –0.5/0.09 107 100 103 Al/CsBi3I10/ITO[54] –1.7/0.9 103 100 104 Au/Cs2AgBiBr6/ITO[55] –3.4/2 102 103 105 Au/Cs3Bi2I9/ITO[66] –0.5/0.3 102 103 104 Ag/PMMA/MA3Sb2Br9/ITO[58] 2.5/–0.5 102 300 104 Ag/PMMA/Cs3Cu2I5/ITO[65] –1/0.75 102 100 104 -
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