硅酸盐学报

ZnS透明陶瓷的研究进展及其应用

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李家科 ¹ , 郝浩博 ¹^,² , 袁强 ² , 陈鹏辉 ²^,³ , 李江 ²^,³

硅酸盐学报 | 综合评述 2024,52(3): 1082-1099

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硅酸盐学报 |综合评述 2024 , 52 (3) : 1082 -1099

ZnS透明陶瓷的研究进展及其应用

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李家科¹, 郝浩博¹^,², 袁强², 陈鹏辉²^,³, 李江²^,³

作者信息

^1．景德镇陶瓷大学材料科学与工程学院，江西景德镇 333403

^2．中国科学院上海硅酸盐研究所透明陶瓷研究中心，上海 201899

^3．中国科学院大学材料与光电中心，北京 100049

通讯作者:

李江（1977—），男，博士，研究员。

作者简介:

李家科（1973—），男，博士，教授。

Development and Application on ZnS Transparent Ceramics

Jiake LI¹, Haobo HAO¹^,², Qiang YUAN², Penghui CHEN²^,³, Jiang LI²^,³

Affiliations

^1.School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333403, China

^2.Transparent Ceramics Research Center, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China

^3.Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding Author:

LI Jiang (1977-), male, Ph.D., Professor. E-mail: lijiang@mail.sic.ac.cn

LI Jiake (1973-), male, Ph.D., Professor. E-mail: jiakeli.jci@163.com

出版时间: 2024-03-20 doi: 10.14062/j.issn.0454-5648.20230624

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摘要

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硫化锌（ZnS）透明陶瓷在可见光至长波红外波段（0.36~12 μm）都具有很高的透过率，且拥有较好的力学和热学综合性能，在红外窗口、中红外激光增益介质等方面具有广泛的应用。本文梳理了ZnS透明陶瓷的研究进展，并分析了热压烧结、化学气相沉积和放电等离子烧结等制备工艺对ZnS透明陶瓷光学性能和力学性能的影响，对ZnS透明陶瓷的发展进行了总结和展望。

关键词

硫化锌透明陶瓷 / 多光谱硫化锌 / 热压烧结 / 化学气相沉 / 放电等离子烧结 / 中红外激光材料

Abstract

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ZnS is a kind of material with superior optical, mechanical and thermal properties from visible light band to long-wave infrared band (i.e., 0.36-12 μm). It is widely used in infrared imaging, remote sensing, and guidance as well as other photoelectric systems. Also, ZnS is a semiconductor material with the widest band gap (3.6-3.9 eV) in the Ⅱ-Ⅵ group compounds. ZnS materials can have superior luminescence properties by doping divalent transition metals (i.e., Co²⁺, Ni²⁺, Cr²⁺, and Fe²⁺). It is widely used in mid-infrared solid lasers, light-emitting diodes, radar screens and fluorescent lighting.

Compared with ZnS single crystal, polycrystalline ZnS transparent ceramics can be used as main materials in commercial applications due to the advantages like short preparation cycle and easy preparation of coarse grain sizesas. The preparation methods of transparent ZnS ceramics mainly include hot pressing (HP), chemical vapor deposition (CVD), chemical vapor deposition combined with hot isostatic pressing (HIP), and spark plasma sintering (SPS). ZnS transparent ceramics prepared by different methods have certain optical and mechanical properties differences. The transmittance of ZnS ceramics prepared by HP in the visible light band is not as high as that of multi-spectral ZnS ceramics prepared by CVD and HIP post-treatment. However, the oriented grain size of multi-spectral ZnS ceramics is larger. The growth of grain size leads to a significant decrease in the mechanical properties, and the preparation cycle of CVD-prepared ceramics is also longer. Therefore, this review mainly represented development on the optical and mechanical properties of ZnS transparent ceramics prepared by different methods and introduced the application of ZnS transparent ceramics in infrared windows and mid-infrared lasers. In addition, the future development of ZnS transparent ceramics was also prospected.

The physical and chemical properties of ZnS materials were described, including the phase structure, optical properties, and matrix characteristics of ZnS as a divalent transition metal (TM²⁺) doping. The main parameters of ZnS transparent ceramics prepared by different processes were summarized. The application scenarios of ZnS transparent ceramics in infrared window materials and mid-infrared lasers were described. The development of HP-ZnS transparent ceramics, CVD-ZnS transparent ceramics, and SPS-ZnS transparent ceramics applied in infrared windows were represented, and the preparation methods were briefly introduced. The preparation of ZnS transparent ceramics for mid-infrared lasers was introduced. The Cr²⁺ and Fe²⁺ doped ZnS transparent ceramics were discussed, and the spectral characteristics of two different ions in ZnS matrix were analyzed. The preparation of Cr²⁺/Fe²⁺:ZnS transparent ceramics were discussed. In addition, this review also prospected future development of ZnS transparent ceramics in different application fields.

Summary and prospects:

1. Although the long-wave infrared transmittance of HP-ZnS transparent ceramics is close to its theoretical value, the transmittance of its 1 064 nm laser band does not exceed 60%, which makes it difficult to realize the application in dual-mode guidance. Most of the HP-ZnS transparent ceramics still have a certain amount of hexagonal phase and impurities, leading to a decrease in the short-band transmittance of HP-ZnS transparent ceramics.

2. Although the preparation process of CVD-ZnS transparent ceramics is relatively mature, which can be commercialized. The grain size of multi-spectral ZnS transparent ceramics increases to dozens of microns after HIP, resulting in low mechanical properties of the materials and poor corrosion resistance of multi-spectral ZnS.

3. Most SPS-ZnS ceramics are still in the initial stage. Although SPS-ZnS ceramics have an advantage of maintaining small grain size, they have a low relative density and a poor long-wave transmittance of less than 70%.

4. For ZnS transparent ceramics for mid-wave infrared laser, TM²⁺:Ⅱ-Ⅵ can be mainly prepared by a thermal diffusion method. Cr:ZnS achieves a laser output, but Fe:ZnS does not achieve a laser output due to its low optical quality and lack of suitable pump source.

Since the first semitransparent ZnS ceramic was prepared in the 1950s, ZnS transparent ceramics have been extensively studied in the past 70 years. With the increasing demand for infrared imagers and multi-spectral imagers in the fields of national defense, security, and civilian fields such as vehicle night vision systems, there is still a challenge for technological progress and development of ZnS transparent ceramics in the future. In terms of ZnS ceramics for infrared windows, it is necessary to continue to optimize the powder preparation process, improve the chemical purity and phase purity of the powders, and regulate the Zn/S value, combined with HP and HIP to prepare multi-band high-transparent ZnS transparent ceramics. In the future, the mechanical properties of multi-spectral ZnS transparent ceramics can be further improved by coating and other technologies, and its application range can be expanded. The further optimization of the preparation process of SPS-ZnS ceramics is needed. In terms of ZnS transparent ceramics for mid-infrared laser materials, the effective doping concentration and structural uniformity of active ions are improved without reducing the transmittance of the sample, and a further exploration is needed to prepare ZnS ceramics with a high power laser output.

Key words

zinc sulfide transparent ceramics / multi-spectral zinc sulfide / hot-pressing / chemical vapor deposition / spark plasma sintering / mid-infrared laser materials

引用本文

李家科, 郝浩博, 袁强, 陈鹏辉, 李江. ZnS透明陶瓷的研究进展及其应用. 硅酸盐学报, 2024 , 52 (3) : 1082 -1099 . DOI: 10.14062/j.issn.0454-5648.20230624

Jiake LI, Haobo HAO, Qiang YUAN, Penghui CHEN, Jiang LI. Development and Application on ZnS Transparent Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (3) : 1082 -1099 . DOI: 10.14062/j.issn.0454-5648.20230624

基金

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中国科学院国际伙伴计划(121631KYSB20200039)
上海市“一带一路”国际合作项目(20520750200)

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2024年第52卷第3期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230624

接收时间：2023-08-22
首发时间：2026-10-22
出版时间：2024-03-20

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出版历史

收稿日期：2023-08-22
修回日期：2023-10-09

基金

中国科学院国际伙伴计划(121631KYSB20200039)

上海市“一带一路”国际合作项目(20520750200)

作者信息

^1．景德镇陶瓷大学材料科学与工程学院，江西景德镇 333403

^2．中国科学院上海硅酸盐研究所透明陶瓷研究中心，上海 201899

^3．中国科学院大学材料与光电中心，北京 100049

通讯作者:

李江（1977—），男，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230624

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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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