Cu-Mn-I固溶体薄膜制备及其p型透明导电性质调控

doi:10.15541/jim20250022

无机材料学报 ›› 2025, Vol. 40 ›› Issue (9): 1022-1028.DOI: 10.15541/jim20250022

Cu-Mn-I固溶体薄膜制备及其p型透明导电性质调控

王亮君¹(), 欧阳玉昭¹, 赵俊亮², 杨长¹()

1.华东师范大学电子科学系, 极化材料与器件教育部重点实验室, 上海类脑智能材料与器件研究中心, 上海 200241
2.上海半人马企业发展集团有限公司, 上海 201306

收稿日期:2025-01-15 修回日期:2025-02-13 出版日期:2025-09-20 网络出版日期:2025-03-19
通讯作者: 杨长, 教授. E-mail: cyang@phy.ecnu.edu.cn
作者简介:王亮君(1998-), 男, 博士研究生. E-mail: 1134420548@qq.com
基金资助:
国家自然科学基金(62074056);国家自然科学基金(62474066);中央高校基本科研业务费专项资金;上海市白玉兰人才计划浦江项目(2023PJD028)

Cu-Mn-I Solid Solution Thin Films: Preparation and Control of p-type Transparent Conductive Properties

WANG Liangjun¹(), OUYANG Yuzhao¹, ZHAO Junliang², YANG Chang¹()

1. Shanghai Center of Brain-inspired Intelligent Materials and Devices, Key Laboratory of Polar Materials and Devices (MOE), Department of Electronics, East China Normal University, Shanghai 200241, China
2. Shanghai Berma Enterprise Development Group Co., Ltd., Shanghai 201306, China

Received:2025-01-15 Revised:2025-02-13 Published:2025-09-20 Online:2025-03-19
Contact: YANG Chang, professor. E-mail: cyang@phy.ecnu.edu.cn
About author:WANG Liangjun (1998-), male, PhD candidate. E-mail: 1134420548@qq.com
Supported by:
National Natural Science Foundation of China(62074056);National Natural Science Foundation of China(62474066);Fundamental Research Funds for the Central Universities;Shanghai Pujiang Programme(2023PJD028)

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的应用价值。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)的增加, 薄膜晶粒尺寸逐渐减小, 并且出现明显的晶粒团聚现象。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0.017~2.5 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较高数量级。与传统n型半导体掺杂规律不同, 引入高价态锰离子未显著影响材料的p型导电特性, 这可能源于锰取代亚铜离子后形成的非完全离域电子态。本研究表明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型导电性的情况下在较大范围内实现材料组分的宽域调控, 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, exhibits unique performance advantages. Firstly, the material can be fabricated at room temperature while maintaining excellent visible light transparency. Secondly, 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 0.017 to 2.5 Ω·cm, while the hole carrier concentration remains stable at a high order of magnitude of 10¹⁸-10¹⁹ cm^-3. Unlike the n-type doping behavior observed in traditional semiconductors, 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 study 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型透明导电性质调控[J]. 无机材料学报, 2025, 40(9): 1022-1028.

WANG Liangjun, OUYANG Yuzhao, ZHAO Junliang, YANG Chang. Cu-Mn-I Solid Solution Thin Films: Preparation and Control of p-type Transparent Conductive Properties[J]. Journal of Inorganic Materials, 2025, 40(9): 1022-1028.

图/表 5

图1 Cu1-xMnxI薄膜的SEM照片(a~e)和Cu0.95Mn0.05I薄膜的元素面分布图(f~h)

Fig. 1 SEM images of Cu1-xMnxI thin films (a-e) and elemental distribution mappings of Cu0.95Mn0.05I thin films (f-h)

图2 Cu1-xMnxI薄膜晶体结构分析

Fig. 2 Crystal structure analyses of Cu1-xMnxI thin films (a) XRD patterns; (b) Localized magnified patterns of diffraction peak (111); (c) Schematic diagram of manganese ions replacing copper ions; (d) Dependence of grain size and FWHM on x

图3 Cu1-xMnxI薄膜光学带隙分析

Fig. 3 Analyses of optical bandgap of Cu1-xMnxI thin films (a) UV-Vis transmission spectra; (b) Tauc plots; (c) Dependence of Eg on x; (d) Schematic diagram of the influence of donor energy levels on Eg. Colorful figures are available on website

图4 Cu1.00I和Cu0.95Mn0.05I薄膜的XPS图谱

Fig. 4 XPS spectra of Cu1.00I and Cu0.95Mn0.05I thin films (a) XPS survey spectra; (b) High-resolution Mn2p XPS spectra of Cu0.95Mn0.05I films; (c, d) High-resolution I3d (c) and Cu2p (d) XPS spectra of Cu1.00I and Cu0.95Mn0.05I thin films

图5 Cu1-xMnxI薄膜电阻率、载流子浓度以及迁移率与x之间的关系

Fig. 5 Dependence of x on resistivity, carrier density, and mobility in Cu1-xMnxI thin films

参考文献 29

[1]	LIU A, ZHU H H, KIM M G, et al. Engineering copper iodide (CuI) for multifunctional p-type transparent semiconductors and conductors. Advanced Science, 2021, 8(14): 2100546.
[2]	THOMAS G. Invisible circuits. Nature, 1997, 389(6654): 907.
[3]	KAWAZOE H, YASUKAWA M, HYODO H, et al. P-type electrical conduction in transparent thin films of CuAlO₂. Nature, 1997, 389(6654): 939.
[4]	UEDA K, HASE T, YANAGI H, et al. Epitaxial growth of transparent p-type conducting CuGaO₂ thin films on sapphire (001) substrates by pulsed laser deposition. Journal of Applied Physics, 2001, 89(3): 1790.
[5]	YANAGI H, HASE T, IBUKI S, et al. Bipolarity in electrical conduction of transparent oxide semiconductor CuInO₂ with delafossite structure. Applied Physics Letters, 2001, 78(11): 1583.
[6]	KUDO A, YANAGI H, HOSONO H, et al. SrCu₂O₂: a p-type conductive oxide with wide band gap. Applied Physics Letters, 1998, 73(2): 220.
[7]	RAGHUPATHY R K M, KÜHNE T D, FELSER C, et al. Rational design of transparent p-type conducting non-oxide materials from high-throughput calculations. Journal of Materials Chemistry C, 2018, 6(3): 541.
[8]	YANG C, KNEIß M, LORENZ M, et al. Room-temperature synthesized copper iodide thin film as degenerate p-type transparent conductor with a boosted figure of merit. Proceedings of the National Academy of Sciences, 2016, 113(46): 12929.
[9]	GENG F J, WANG L J, STRALKA, et al. (111)-oriented growth and acceptor doping of transparent conductive CuI:S thin films by spin coating and radio frequency-sputtering. Advanced Engineering Materials, 2023, 25(11): 2201666.
[10]	YANG J L, JIANG X L, RUAN S Y, et al. Highly weak-light sensitive and dual-band switchable photodetector based on CuI/Si unilateral heterojunction. Journal of Inorganic Materials, 2024, 39(9): 1063.
[11]	GRUNDMANN M, SCHEIN F L, LORENZ M, et al. Cuprous iodide - a p-type transparent semiconductor: history and novel applications. Physica Status Solidi A, 2013, 210(9): 1671.
[12]	GRUNDMANN M. Karl Bädeker (1877-1914) and the discovery of transparent conductive materials. Physica Status Solidi A, 2015, 212(7): 1409.
[13]	CHEN D, WANG Y, LIN Z, et al. Growth strategy and physical properties of the high mobility p-type CuI crystal. Crystal Growth & Design, 2010, 10(5): 2057.
[14]	JUN T, KIM J, SASASE M, et al. Material design of p-type transparent amorphous semiconductor, Cu-Sn-I. Advance Materials, 2018, 30(12): 1706573.
[15]	YANG C, SOUCHAY D, KNEIß M, et al. Transparent flexible thermoelectric material based on non-toxic earth-abundant p-type copper iodide thin film. Nature Communications, 2017, 8: 16076.
[16]	ZENG G X, DOU W, GAN X M, et al. Low-voltage solution-processed Na_xCu_1-_xI thin-film transistors for mimicking synaptic plasticity. Applied Physical Letters, 2024, 124(12): 123508.
[17]	JIANG G G, DOU W, GAN X M, et al. Low-voltage solution- processed p-type Mg-doped CuI thin film transistors with NAND logic function. Applied Physical Letters, 2023, 122(21): 213501.
[18]	GHAZAL N, MADKOUR M, NAZEER A A, et al. Electrochemical capacitive performance of thermally evaporated Al-doped CuI thin films. RSC Advance, 2021, 11(62): 39262.
[19]	MIRZA A S, VISHAL B, DALLY P, et al. Cs-doped and Cs-S co-doped CuI p-type transparent semiconductors with enhanced conductivity. Advanced Functional Materials, 2024, 34(30): 2316144.
[20]	MUDE N N, BUKKE R N, JIANG J. Transparent, p-channel CuISn thin-film transistor with field effect mobility of 45 cm²·V^-1·s^-1 and excellent bias stability. Advanced Materials Technologies, 2022, 7(8): 2101434.
[21]	TAREY R D, RAJU T A. A method for the deposition of transparent conducting thin films of tin oxide. Thin Solid Films, 1985, 128(3/4): 181.
[22]	LIU A, ZHU H H, PARK W T, et al. Room-temperature solution-synthesized p-type copper(I) iodide semiconductors for transparent thin-film transistors and complementary electronics. Advanced Materials, 2018, 30(34): 1802379.
[23]	STRELCHUNK V, KOLOMYS O, RARATA S, et al. Raman submicron spatial mapping of individual Mn-doped ZnO nanorods. Nano Epress, 2017, 12: 1.
[24]	ZI M, LI J, ZHANG Z C, et al. Effect of deposition temperature on transparent conductive properties of γ-CuI film prepared by vacuum thermal evaporation. Physica Status Solidi A, 2015, 212(7): 1466.
[25]	SUNG S Y, KIM S Y, JO K M, et al. Fabrication of p-channel thin-film transistors using CuO active layers deposited at low temperature. Applied Physical Letters, 2010, 97(22): 222109.
[26]	KYKYNESHI R, MCINTYRE D H, TATE J, et al. Electrical and optical properties of epitaxial transparent conductive BaCuTeF thin films deposited by pulsed laser deposition. Solid State Sciences, 2008, 10(7): 921.
[27]	ZAKUTAYEV A, MCINTYRE D H, SCHNEIDER G, et al. Tunable properties of wide-band gap p-type BaCu(Ch_1-_xCh_x′)F (Ch=S, Se, Te) thin-film solid solutions. Thin Solid Films, 2010, 518(19): 5494.
[28]	YANG C, KNEIß M, SCHEIN F L, et al. Room-temperature domain-epitaxy of copper iodide thin films for transparent CuI/ZnO heterojunctions with high rectification ratios larger than 10⁹. Scientific Reports, 2016, 6: 21937.
[29]	YANG C, ROSE E, YU W L, et al. Controllable growth of copper iodide for high-mobility thin films and self-assembled microcrystals. ACS Applied Electronic Materials, 2020, 2(11): 3627.

Cu-Mn-I固溶体薄膜制备及其p型透明导电性质调控

Cu-Mn-I Solid Solution Thin Films: Preparation and Control of p-type Transparent Conductive Properties

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