Lee Seongha, Wolfe Sarah, Torres Jorge, Yun Minhee, Lee Jung-Kun
Department of Mechanical Engineering & Materials Science, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States.
Department of Electrical and Computer Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States.
ACS Appl Mater Interfaces. 2021 Jun 16;13(23):27209-27216. doi: 10.1021/acsami.1c06278. Epub 2021 Jun 3.
Halide perovskite materials such as methylammonium lead iodide (CHNHPbI) have attracted considerable interest for the resistive random-access memory applications, which exploit a dramatic change in the resistance by an external electric bias. In many semiconductor films, the drift, accumulation, and chain formation of defects explain the change in the resistance by an external bias. This study demonstrates that the interface of CHNHPbI with TiO has a significant impact on the formation and rupture of defect chains and causes the asymmetric bipolar resistive switching in the Au/CHNHPbI/TiO/FTO device (FTO = fluorine-doped tin oxide). When a negative bias is applied to the Au electrode, iodine interstitials with the lowest migration activation energy move toward TiO in the CHNHPbI layer and pile up at the CHNHPbI-TiO interface. Under the same condition, oxygen vacancies in the TiO layer also travel to the CHNHPbI-TiO interface and strongly attract iodine interstitials. As a result, a Schottky barrier appears at the CHNHPbI-TiO interface, and the resistance of Au/CHNHPbI/TiO/FTO becomes much larger than that of Au/CHNHPbI/FTO in the high resistance state. The frequency dependence of the capacitance confirms the asymmetric appearance of a large space charge polarization at the CHNHPbI-TiO interface, which causes the unique bipolar resistive switching behavior with the on/off ratio (10) and retention time (>10 seconds) at -0.85 V in Au/CHNHPbI/TiO/FTO film.
卤化物钙钛矿材料,如甲基碘化铅铵(CH₃NH₃PbI₃),因其在电阻式随机存取存储器应用中能利用外部电偏压引起的电阻急剧变化而备受关注。在许多半导体薄膜中,缺陷的漂移、积累和链的形成解释了外部偏压引起的电阻变化。本研究表明,CH₃NH₃PbI₃与TiO₂的界面缺陷链的形成和断裂有重大影响,并导致了Au/CH₃NH₃PbI₃/TiO₂/FTO器件(FTO = 氟掺杂氧化锡)中的不对称双极电阻开关。当向Au电极施加负偏压时,迁移活化能最低的碘间隙原子向CH₃NH₃PbI₃层中的TiO₂移动并堆积在CH₃NH₃PbI₃-TiO₂界面处。在相同条件下,TiO₂层中的氧空位也迁移到CH₃NH₃PbI₃-TiO₂界面并强烈吸引碘间隙原子。结果,在CH₃NH₃PbI₃-TiO₂界面处出现肖特基势垒,在高电阻状态下,Au/CH₃NH₃PbI₃/TiO₂/FTO的电阻比Au/CH₃NH₃PbI₃/FTO的电阻大得多。电容的频率依赖性证实了在CH₃NH₃PbI₃-TiO₂界面处出现了大的空间电荷极化不对称现象,这导致了Au/CH₃NH₃PbI₃/TiO₂/FTO薄膜在-0.85 V时具有开/关比(10)和保持时间(>10秒)的独特双极电阻开关行为。