Cu-Mn-I固溶体薄膜制备及其p型透明导电性质的调控

doi:10.15541/jim20250022

摘要/Abstract

摘要： 在光电子器件领域, 具有可控电学参数的p型透明半导体材料具有重要应用价值。但以CuI为代表的该类材料在制备工艺与掺杂调控方面仍存在显著技术瓶颈。本研究通过锰阳离子掺杂, 成功制备出具有可调电学特性的新型p型透明半导体材料, 为透明电子学发展提供了新思路。采用反应磁控溅射技术制备的Cu_1-_xMn_xI固溶体薄膜展现出独特的性能优势。首先, 该材料可以在室温条件下制备, 并保持优异的可见光透明性。其次, 随着锰掺杂量x值的增加, 薄膜晶粒尺寸逐渐减小, 伴随掺杂浓度提升观察到明显的晶团聚集现象。通过X射线光电子能谱分析, 揭示了薄膜中锰离子以Mn²⁺和Mn³⁺混合价态存在。电学性能表征显示, 薄膜电阻率可在0.02~2.50 Ω·cm区间实现两个数量级的可控调节, 同时空穴载流子浓度稳定维持在10¹⁸~10¹⁹ cm^-3的较高值。与传统半导体n型掺杂规律不同, 高价态锰离子的引入未显著影响材料的p型导电特性, 可能源于锰取代亚铜离子后形成的非完全离域电子态。该发现表明CuI半导体的空穴导电特性不易受高价锰离子掺杂的影响, 有望在保持良好p型导电的情况下在较大范围内实现材料组分宽域调控, 为开发CuI基多功能透明电子器件提供了重要材料基础。

关键词: Cu_1-_xMn_xI, 透明p型半导体, 可控p型导电性

Abstract: In the field of optoelectronic devices, p-type transparent semiconductor materials with controllable electrical properties hold significant application value. CuI, as a representative material, still faces considerable technical challenges in terms of preparation processes and doping control. This study successfully developed a new p-type transparent semiconductor material with adjustable electrical properties through manganese cation doping, offering a new approach for the advancement of transparent electronics. The Cu_1-_xMn_xI solid solution film, prepared via reactive magnetron sputtering, demonstrates unique performance advantages. First, the material can be fabricated at room temperature while maintaining excellent visible light transparency. Second, as the manganese doping concentration (x) increases, the grain size of the film gradually decreases, and pronounced crystal cluster aggregation is observed at higher doping concentrations. X-ray photoelectron spectroscopy analysis reveals that manganese ions in the film exist in a mixed valence state of Mn²⁺ and Mn³⁺. Electrical performance characterization shows that the resistivity of the film can be tuned over two orders of magnitude, ranging from 0.02 to 2.5 Ω·cm, while the hole carrier concentration remains stable at a high level of 10¹⁸-10¹⁹ cm^-³. Unlike the n-type doping behavior observed in traditional semiconductors, the introduction of high-valent manganese ions does not significantly affect the p-type conductivity of the material. This is likely due to the partially localized electronic state formed when manganese replaces cuprous ions. This discovery suggests that the hole conductivity of CuI semiconductors is not easily affected by high-valent manganese ion doping, enabling a wide range of compositional adjustments while maintaining stable p-type conductivity. This provides a valuable material basis for the development of CuI-based multifunctional transparent electronic devices.

Key words: Cu_1-_xMn_xI, transparent p-type semiconductor, controllable p-type resistivity

中图分类号:

TQ174

王亮君, 欧阳玉昭, 赵俊亮, 杨长. Cu-Mn-I固溶体薄膜制备及其p型透明导电性质的调控[J]. 无机材料学报, DOI: 10.15541/jim20250022.

WANG Liangjun, OUYANG Yuzhao, ZHAO Junliang, YANG Chang. Preparation of Cu-Mn-I Solid Solution Thin Films and Control of Their p-type Transparent Conductive Properties[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250022.

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