Abstract
All-inorganic zero-dimensional (0D) tetrahedrite (Cu12Sb4S13, CAS) quantum dots (QDs) have attracted extensive attention due to their excellent optical properties, bandgap tunability, and carrier mobility. In this paper, various sized CAS QDs (5.1, 6.7, and 7.9 nm) are applied as a switching layer with the structure F:SnO2 (FTO)/CAS QDs/Au, and in doing so, the nonvolatile resistive-switching behavior of electronics based on CAS QDs is reported. The SET/RESET voltage tunability with size dependency is observed for memory devices based on CAS QDs for the first time. Results suggest that differently sized CAS QDs result in different band structures and the regulation of the SET/RESET voltage occurs simply and effectively due to the uniform size of the CAS QDs. Moreover, the presented memory devices have reliable bipolar resistive-switching properties, a resistance (ON/OFF) ratio larger than 104, high reproducibility, and good data retention ability. After 1.4 ×106 s of stability testing and 104 cycles of quick read tests, the change rate of the ON/OFF ratio is smaller than 0.1%. Furthermore, resistive-witching stability can be improved by ensuring a uniform particle size for the CAS QDs. The theoretical calculations suggest that the space-charge-limited currents (SCLCs), which are functioned by Cu 3d, Cu 3p and S 3p to act as electron self-trapping centers due to their quantum confinement and form conduction pathways under an electric field, are responsible for the resistive-switching effect. This paper demonstrates that CAS QDs are promising as a novel resistive-switching material in memory devices and can be used to facilitate the application of next-generation nonvolatile memory.
摘要
全无机零维Cu12 Sb4 S13 量子点因其优异的光学性能、带隙可 调性和载流子迁移率而受到广泛关注. 本文首次报道了Cu12 Sb4 S13 量子点的阻变存储特性, 构建的FTO/Cu12 Sb4 S13 QDs/Au阻变存储 器具有良好的可再现性和可靠的双极性电阻开关特性. 量子点的 写入/擦除电压具有尺寸依赖性, 通过控制Cu12 Sb4 S13 量子点的尺寸 调控其能带结构进而调控写入/擦除电压, 实现了器件的写入/擦除 电压的有效调控. 同时, 器件具有较大开/关比(大于104), 优异的保 持性和耐久性. 在保持1.4×106 s和经过104 次快速读取后, 阻变性能 变化率小于0.1%. 性能稳定性的提升也得益于更加均一的量子点 尺寸, 因此可通过制备尺寸均匀的量子点来提升器件稳定性. 理论 计算表明Cu12 Sb4 S13 量子点的阻变机理由空间电荷限制电流机制占主导, 在电场作用下, Cu3d、Cu 3p 和S 3p 作为电子自俘获中心进 行电子的俘获与去俘获, 从而改变了Cu12 Sb4 S13 量子点的阻值. 结果 表明, Cu12 Sb4 S13 量子点可作为一种新型的阻性开关材料, 在数据存 储器件中具有巨大的应用潜力, 有望促进下一代非易失性存储器 的发展与应用.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (51572205, 11674258 and 51802093), the Joint Fund of Ministry of Education for Equipment Pre-research the Fundamental Research (6141A02022262), the Excellent Dissertation Cultivation Funds of Wuhan University of Technology (2018-YS-001) and the Fundamental Research Funds for the Central Universities (2019-zy-007).
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Author contributions Wang Z and Liu Y, Shen J and Chen W, Miao J and Zhou J designed the experiment. Wang Z, Li A and Liu K prepared the CAS QDs, characterized the SEM, AFM, XRD, EDS, electrical features of all the films and theoretical calculation of all devices. Wang Z and Liu Y prepared the manuscript. Chen W, Miao J and Zhou J helped revise the manuscript. The final version of the manuscript was approved by all authors.
Conflict of interest The authors declare that they have no conflict of interest.
Zhiqing Wang is a master student in the School of Material Science and Engineering, Wuhan University of Technology (WUT). He obtained his bachelor’s degree in materials science and engineering in June 2017 from WUT, China. His research interest is the application of quantum dot materials as resistive-switching materials for memory devices.
Yueli Liu is a professor in the State Key Laboratory of Silicate Materials for Architectures and School of Material Science and Engineering, WUT. He received his PhD degree in materials physics and chemistry in 2006 from Wuhan University, China. His research interests lie in photocatalytic and photovoltaic devices, gas sensors, metal oxide nanomaterials and quantum dots.
Jing Zhou is a professor of materials science and engineering at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing and School of Material Science and Engineering, WUT. She received her PhD degree in materials science in 2005 from WUT, China. Her research interests lie in the preparation, structure and properties of functional materials.
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Wang, Z., Liu, Y., Shen, J. et al. Resistive-switching tunability with size-dependent all-inorganic zero-dimensional tetrahedrite quantum dots. Sci. China Mater. 63, 2497–2508 (2020). https://doi.org/10.1007/s40843-020-1380-5
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DOI: https://doi.org/10.1007/s40843-020-1380-5