硅酸盐学报

用于喷墨打印的Cu₂Se墨水的制备及表征

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陈小雨 ¹ , 张骐昊 ² , 叶佳意 ³ , 王连军 ¹ , 江莞 ¹^,³

硅酸盐学报 | 第14届无机非金属材料专题研讨会专题—研究论文 2025,53(4): 778-784

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硅酸盐学报 |第14届无机非金属材料专题研讨会专题—研究论文 2025 , 53 (4) : 778 -784

用于喷墨打印的Cu₂Se墨水的制备及表征

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陈小雨¹, 张骐昊², 叶佳意³, 王连军¹, 江莞¹^,³

作者信息

^1．东华大学先进纤维材料全国重点实验室，东华大学材料科学与工程学院，中国上海 201620

^2．卡尔斯鲁厄理工学院，光技术研究所，德国卡尔斯鲁厄 76131

^3．东华大学功能材料研究中心，中国上海 201620

通讯作者:

叶佳意（1977—），女，博士，高级工程师；

王连军（1974—），男，博士，教授。

作者简介:

陈小雨（2001—），女，硕士研究生。

Preparation and Characterization of Cu₂Se Ink for Inkjet Printing

Xiaoyu CHEN¹, Qihao ZHANG², Jiayi YE³, Lianjun WANG¹, Wan JIANG¹^,³

Affiliations

^1.State Key Laboratory for Advanced Fibers Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China

^2.Light Technology Institute, Karlsruhe Institute of Technology, Karlsruhe 76131, Germany

^3.Institute of Functional Materials, Donghua University, Shanghai 201620, China

Corresponding Author:

YE Jiayi (1977-), female, Ph.D., Senior engineer. E-mail: jiayiye@dhu.edu.cn;

WANG Lianjun (1974-), male, Ph.D., Professor. wanglj@dhu.edu.cn

CHEN Xiaoyu (2001-), female, Master candidate. E-mail: aoe1211@126.com

出版时间: 2025-04-20 doi: 10.14062/j.issn.0454-5648.20240760

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摘要

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相较于传统块体热电器件，柔性热电薄膜器件展现出更高的集成密度、更快的响应时间和更小的体积，这使得它们在现代电子器件中具有更灵活的应用场景，充分契合当前科技发展的趋势。然而，传统的Cu₂Se薄膜制备方法在图案精确化和微型化设计方面存在一定的局限性，限制了其在高性能微型器件中的应用。喷墨打印技术则能够有效弥补这些不足，提供更为灵活的制备方案。通过探索不同的合成方法制备Cu₂Se纳米粉体，并研究其在不同溶液中的分散效果，成功开发出适用于喷墨打印的Cu₂Se墨水。这一工作为后续制备Cu₂Se热电薄膜及其温差电转换器件奠定了基础，推动了柔性热电材料在实际应用中的发展。

关键词

硒化亚铜 / 喷墨打印 / 热电 / 墨水

Abstract

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Introduction

With the rapid development of portable and wearable microelectronics, flexible thermoelectric materials have attracted much attention due to their ability to enable self-powered devices via utilizing the temperature difference between the skin and the environment. However, the scarcity of tellurium resources and its high toxicity pose some challenges to the commercial application of tellurium-based thermoelectric materials. It is thus critical to develop high-performance, low-cost, and non-toxic alternatives for flexible thermoelectric films. Copper(I) selenide (i.e., Cu₂Se), as a representative liquid-like thermoelectric material, has attracted recent attention. Cu₂Se is an intrinsic p-type semiconductor composed of abundant, low-cost, and non-toxic elements, thus offering significant advantages in the field of sustainable energy. The existing studies report the fabrication of high-performance Cu₂Se thin films using conventional preparation techniques. However, these processes face significant limitations in pattern refinement and miniaturization, hindering their application in the fabrication of micro-thermoelectric devices. Inkjet printing technology, as a low-cost, efficient, and high-precision digital printing process, offers a promising solution to these challenges. This technique enables the preparation of complex patterns without masks or templates and is suitable for a variety of substrate materials. Therefore, this study was to prepare Cu₂Se nanopowders and explore their dispersion properties in different solvents to develop Cu₂Se inks suitable for inkjet printing technology, thereby offering insights into the preparation of flexible thermoelectric films and their application in next-generation wearable devices.

Methods

Cu₂Se nanoparticles were synthesized by the following methods. In method 1 (i.e., hydrothermal method), 5 mmol copper chloride, 2.5 mmol selenium powder, 0.05 mol sodium hydroxide were mixed with 50 mL deionized water, and continuously stirred at room temperature for 20 min, and then a certain amount of hydrazine hydrate solution was added, and the mixture was transferred to 100 mL PPL-stainless steel autoclave. Subsequently, the sealed autoclave reactor was heated at 180 ℃ for 20 h and then naturally cooled to room temperature. The precipitate at the bottom of the reactor was centrifuged at 10 000 r/min and washed with ethanol and distilled water for several times to obtain Cu₂Se powder. In method 2 (i.e., hydrothermal method), 1 mmol of selenium dioxide and 2 mmol of copper acetate were mixed with 65 mL of deionized water, and then stirred at room temperature until there was no sediment. Afterwards, hydrazine hydrate was slowly added and stirred for 10 min. The mixture was transferred to 100 mL PPL-stainless steel autoclave, and then the sealed autoclave reactor was heated at 180 ℃ for 24 h. After cooling to room temperature, the resulting sediment was collected and centrifugally cleaned. The content of hydrazine hydrate was changed by the control variable method in the synthesis process to investigate its effect on the morphology. In method 3 (i.e., wet synthesis), 1.54 g polyvinylpyrrolidone (PVP) was dispersed in 77 mL deionized water, followed by 1.92 mmol selenium dioxide (9.6 mL) and 11.52 mmol ascorbic acid (28.8 mL) solutions and stirred for 15 min. Afterwards, 3.84 mmol cupric sulfate pentahydrate (9.6 mL) and 15.36 mmol -ascorbic acid (38.4 mL) solution were added successively. The solution was magnetically stirred at room temperature for 16 h. After washing with deionized water for several times, Cu₂Se core-shell nanoparticles were collected by centrifugation at 11 000 r/min.

For Cu₂Se ink configuration, the prepared Cu₂Se powder was dispersed in deionized water and ethanol by an ultrasonic dispersion method. After ultrasonic treatment for 1 h, the dispersion effect was analyzed.

Results and discussion

Cu₂Se nanoparticles are prepared by the three methods, and the crystal structure of the synthesized products is verified by the XRD patterns. The morphology and size of Cu₂Se particles prepared by different methods are different. In method 1, Cu₂Se powder prepared under alkaline conditions has a flake structure with a particle size of more than 10 μm, which does not meet the size requirements of inkjet printing. In method 2, under the influence of different contents of hydrazine hydrate, the synthesized powders show a large irregular flake structure (~500 nm) and small granular structure, and the particle size does not decrease significantly. The particle size of the powder is reduced when PVP is introduced into the subsequent synthesis process, indicating that the particles do not continue to grow into sheets during the synthesis process due to the coating of PVP, but remain small and irregular nanoparticles, and the particles are still agglomerated, which can cause a nozzle clogging in the subsequent printing process. In method 3, Cu₂Se particles synthesized by the wet method are spherical with a particle size of approximately 40 nm, and uniform in sizes without particle agglomeration, which can meet the requirements of material size for inkjet printing.

Cu₂Se particles synthesized by the wet method and dispersed under ultrasound in ethanol show a well-dispersion, and the particles in ink do not settle significantly after placing for a period of time, showing a good stability and suitable for inkjet printing.

Conclusions

Cu₂Se particles were prepared by the three methods for Cu₂Se ink suitable for inkjet printing, respectively, and nano-sized particles of Cu₂Se with uniform particle size and non-agglomeration were prepared by the wet method. The effective dispersion and stability of Cu₂Se particles were mainly attributed to the coating of PVP on the surface of the particles, improving the solubility of the particles in ethanol, effectively preventing the particle aggregation. This study could provide a foundation for the subsequent development of high-performance Cu₂Se thermoelectric thin films and their microdevices.

Key words

copper(I) selenide / inkjet printing / thermoelectric / ink

引用本文

陈小雨, 张骐昊, 叶佳意, 王连军, 江莞. 用于喷墨打印的Cu₂Se墨水的制备及表征. 硅酸盐学报, 2025 , 53 (4) : 778 -784 . DOI: 10.14062/j.issn.0454-5648.20240760

Xiaoyu CHEN, Qihao ZHANG, Jiayi YE, Lianjun WANG, Wan JIANG. Preparation and Characterization of Cu₂Se Ink for Inkjet Printing[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (4) : 778 -784 . DOI: 10.14062/j.issn.0454-5648.20240760

基金

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国家自然科学基金(U23A20685)
上海市教委科研创新项目(2021-01-07-00-03-E00110)
上海市科委国际科技合作项目(23520710300)

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2025年第53卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240760

接收时间：2024-11-29
首发时间：2026-10-22
出版时间：2025-04-20

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出版历史

收稿日期：2024-11-29
修回日期：2024-12-16

基金

国家自然科学基金(U23A20685)

上海市教委科研创新项目(2021-01-07-00-03-E00110)

上海市科委国际科技合作项目(23520710300)

作者信息

^1．东华大学先进纤维材料全国重点实验室，东华大学材料科学与工程学院，中国上海 201620

^2．卡尔斯鲁厄理工学院，光技术研究所，德国卡尔斯鲁厄 76131

^3．东华大学功能材料研究中心，中国上海 201620

通讯作者:

叶佳意（1977—），女，博士，高级工程师；

王连军（1974—），男，博士，教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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