金刚石半导体材料的发展

董卫国; 刘嘉琪; 张钊斌; 孔欣; 崔西会; 贺端威

doi:10.11858/gywlxb.20261113

金刚石半导体材料的发展

doi: 10.11858/gywlxb.20261113

董卫国^1,,
刘嘉琪¹,
张钊斌¹,
孔欣^{2, 3},
崔西会^{2, 3},
贺端威^1,*, ,

1.
四川大学原子与分子物理研究所, 四川成都　610065
2.
中国电子科技集团公司第二十九研究所, 四川成都　610036
3.
四川省宽带微波电路高密度集成工程研究中心, 四川成都　610036

基金项目: 四川省宽带微波电路高密度集成工程研究中心基金类指南项目（BMERC004-2024-09）

详细信息

作者简介:
董卫国（1998－），男，博士研究生，主要从事高压科学及n型金刚石半导体研究.E-mail：2036650041@qq.com

通讯作者:
贺端威（1969－），男，博士，教授，主要从事高压物理、大腔体静高压技术、超硬材料及金刚石半导体研究. E-mail：duanweihe@scu.edu.cn

中图分类号: TN304; O521.2
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出版历程
- 收稿日期: 2026-06-11
- 修回日期: 2026-08-11
- 录用日期: 2026-08-24
- 网络出版日期: 2026-08-12

Development of Diamond Semiconductor Materials

DONG Weiguo^1
,,
LIU Jiaqi¹,
ZHANG Zhaobin¹,
KONG Xin^{2, 3},
CUI Xihui^{2, 3},
HE Duanwei^{1,*
, ,}

1.
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, Sichuan, China
2.
The 29th Research Institute, China Electronics Technology Group Corporation, Chengdu 610036, Sichuan, China
3.
Sichuan Engineering Research Center for High-Density Integration of Broadband Microwave Circuits, Chengdu 610036, Sichuan, China

摘要

摘要: 金刚石因其超宽禁带、高热导率、高击穿场强和优异的载流子迁移率，成为新一代半导体材料的典型代表，受到功率电子、射频通讯、量子信息等领域的广泛关注。本征单晶金刚石是发展金刚石半导体的基石，其杂质浓度需达10⁻⁹（parts per billion，ppb）级且位错密度极低。高温高压（high pressure high temperature，HPHT）法可获得更高的纯度与更好的晶体质量，但受限于尺寸，常作为化学气相沉积（chemical vapor deposition，CVD）外延的基底，以实现大尺寸高质量单晶制备。在掺杂方面，B原子因尺寸与C原子相近（差异仅6.5%），易于进入晶格形成性能优异的p型金刚石，相关器件（如肖特基二极管）已获成功。然而，n型掺杂面临根本挑战：P、S等潜在掺杂原子半径远大于C原子（差异35%～57%），难以掺入并激活。超高压高温热扩散法通过调控原子尺寸差异，有望成为实现浅能级n型掺杂的新途径。表面终端中，氢终端可诱导高迁移率二维空穴气，氧终端则提升界面稳定性，但两者的热稳定窗口（分别约为400、600 ℃）仍低于元素掺杂体系，限制了其在高温高频器件中的应用。因此，突破n型掺杂、提升终端热稳定性、发展大尺寸低成本制备工艺，将是推动金刚石半导体在功率电子、量子信息及高性能传感等领域迈向产业化的关键。本综述对上述问题进行了分析与讨论，并探讨了金刚石半导体的发展前景与困境。
- 金刚石半导体 /
- 化学气相沉积 /
- 高温高压 /
- n型掺杂
Abstract: Diamond has emerged as a quintessential representative of next-generation semiconductor materials, owing to its ultra-wide bandgap, exceptional thermal conductivity, high breakdown field strength, and outstanding carrier mobility. It has thus attracted extensive attention from fields such as power electronics, radio-frequency communications, and quantum information technologies. Intrinsic single-crystal diamond serves as the foundational substrate for diamond semiconductor development, requiring impurity concentrations at the parts per billion (ppb) level and extremely low dislocation densities. While the high-pressure high-temperature (HPHT) method yields material of higher purity and superior crystal quality, its utility is limited by small crystal dimensions. Consequently, HPHT-grown diamond is frequently employed as a substrate for chemical vapour deposition (CVD) homoepitaxy, enabling the preparation of large-area, high-quality single crystals. Regarding doping, the boron (B) atom, with a size difference of merely 6.5% compared to carbon (C), readily incorporates into the diamond lattice, facilitating the production of high-performance p-type diamond. Related devices, such as Schottky barrier diodes, have been successfully demonstrated. In contrast, n-type doping presents a fundamental challenge: potential dopants like phosphorus (P) and sulphur (S) possess atomic radii 35%–57% larger than carbon, making their incorporation and activation within the lattice exceedingly difficult. The ultra-high pressure and high-temperature diffusion method, which modulates this atomic size disparity under extreme pressures (e.g., about 15 GPa), emerges as a promising new pathway towards achieving shallow-level n-type doping. Concerning surface terminations, hydrogen termination induces a high-mobility two-dimensional hole gas (2DHG), whilst oxygen termination enhances interface stability and provides chemical passivation. However, their thermal stability windows (approximately 400 and 600 ℃, respectively) remain inferior to those of substitutionally doped diamond, limiting their application in high-temperature and high-frequency devices. Therefore, breakthroughs in n-type doping, enhanced thermal stability of surface terminations, and the development of large-area, cost-effective fabrication processes are critical to advancing diamond semiconductor technology towards commercialisation in power electronics, quantum technologies, and high-performance sensing. This review aims to analyse and discuss these pivotal issues, exploring both the prospects and the persistent challenges facing diamond semiconductor development.
- diamond semiconductors /
- chemical vapor deposition /
- high temperature and high pressure /
- n-type doping

HTML全文

图 1 CVD合成腔体中的化学反应示意图^[31]

Figure 1. Schematic diagram of chemical reactions in the CVD synthesis chamber^[31]

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图 2 (a) 碳的相图^[34]，(b) HPHT腔体中温度梯度法生长金刚石示意图^[35]

Figure 2. (a) Phase diagram of carbon^[34]; (b) schematic diagram of diamond growth via the temperature gradient method in an HPHT chamber^[35]

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图 3 p型金刚石的杂质能级^[35]

Figure 3. Impurity levels in p-type diamond^[35]

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图 4 n型金刚石的杂质能级^[35]

Figure 4. Impurity levels in n-type diamond^[35]

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图 5 在${V_{\rm{CH}_4}}/{ V_{\rm{H}_2}}$=0.1%和${V_{\rm{CH}_4}}/{ V_{\rm{H}_2}}$=0.2%条件下生长的P掺杂金刚石薄膜中载流子浓度随温度的变化^[95]

Figure 5. Temperature dependence of carrier concentration of P-doped diamond films grown at ${V_{\rm{CH}_4}}/{V_{\rm{H}_2}}$=0.1% and ${V_{\rm{CH}_4}}/{V_{\rm{H}_2}}$=0.2%^[95]

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图 6 基于P掺杂n型金刚石的MOSFET：(a) MOSFET示意图（n⁺金刚石层用于降低源极和漏极的接触电阻，n⁻金刚石层用作沟道）；(b) 金刚石MOSFET的光学图像^[96]

Figure 6. MOSFETs based on phosphorous doped n-type diamond: (a) schematic of the MOSFETs (The n⁺ diamond layer is used to reduce the source and drain contact resistance, and the n⁻ diamond layer serves as the channel); (b) optical image of the diamond MOSFETs^[96]

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表 1 不同单晶金刚石衬底性能汇总

Table 1. Summary of properties of different single-crystal diamond substrates

Method	Crystal quality/ typical size	Purity	Defect density/ cm⁻²	Typical application scenarios	Ref.
HPHT	Single crystal, millimeter-to-centimeter scale, up to 15 carat	N content 0.1–10⁻⁴, Ⅱa <10⁻⁶	10³–10⁵ (Ⅱa, optimized)	High-power devices, quantum, cutting tools, CVD seeding	[37–39]
MPCVD	Single crystal, millimeter-to-centimeter scale, up to 30 mm×30 mm	Impurities<10⁻⁶, N/B/Si well-controlled	10²–10⁴ (high-quality epitaxy)	High-end semiconductors, quantum, optics, epitaxy	[40–41]
HFCVD	Single/polycrystal, millimeter-to-centimeter scale, thick films	Impurities at 10⁻⁶ level, affected by filament	10⁴–10⁶	Large-area films, composite structures, thermal management, some electronics/optics	[42]
Explosion method	Poly/nanocrystalline, micrometer-to- millimeter scale	Higher impurities (N, H, metals, etc.)	10⁶–10⁸	Abrasives, polishing, thermal interface, large-volume industry	[43]

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表 2 P掺杂金刚石性能

Table 2. Properties of P-doped diamond

Doping concentration/ (ion·cm⁻³)	Resistivity/ (Ω·cm)	Mobility/ (cm·²V⁻¹·s⁻¹)	Carrier concentration/ (ion·cm⁻³)	Doping methods	Ref.
2.3×10²⁰	9.26			CVD	[87]
1.2×10²⁰	42			CVD	[88]
1.2×10²⁰	70			CVD	[89]
	3.56×10⁶	313.27	5.59×10⁹	HPHT	[90]
2×10¹⁸		350	1×10¹¹	CVD	[91]
4.8×10¹⁶	1.8×10³		1×10¹³	CVD	[92]
2×10¹⁵		1 060	1×10¹⁰	CVD	[93]
7.07×10¹⁹	0.83	2.78	2.72×10¹⁸	HPHT-TD	[94]

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