单晶金刚石异质外延生长过程中的位错行为及其控制工艺研究进展

WANG Wei-hua; WANG Yang; SHU Guo-yang; FANG Shi-shu; HAN Jie-cai; DAI Bing; ZHU Jia-qi

doi:10.1016/S1872-5805(21)60096-3

单晶金刚石异质外延生长过程中的位错行为及其控制工艺研究进展

doi: 10.1016/S1872-5805(21)60096-3

王伟华^1,,
王杨¹,
舒国阳¹,
房诗舒¹,
韩杰才¹,
代兵^{1, 2, ,},
朱嘉琦^{1, 3, ,}

1.
哈尔滨工业大学，特种环境复合材料技术国家级重点实验室，黑龙江哈尔滨 150001
2.
哈工大机器人（中山）无人装备与人工智能研究院，广东中山 528521
3.
哈尔滨工业大学，微系统与微结构制造教育部重点实验室，黑龙江哈尔滨 150001

基金项目: 国家重点研发计划项目（2020YFA0709700，2016YFE0201600），国家杰出青年基金项目（51625201），国家自然科学基金项目（52072087），广东省重点研发计划项目（2020B010169002）

详细信息

通讯作者:
代　兵，讲师. E-mail：daib@hit.edu.cn

朱嘉琦，教授. E-mail：zhujq@hit.edu.cn

中图分类号: TQ127.1⁺1
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出版历程
- 收稿日期: 2021-07-04
- 修回日期: 2021-08-31
- 网络出版日期: 2021-11-13
- 刊出日期: 2021-12-01

Recent progress on controlling dislocation density and behavior during heteroepitaxial single crystal diamond growth

WANG Wei-hua^1
,,
WANG Yang¹,
SHU Guo-yang¹,
FANG Shi-shu¹,
HAN Jie-cai¹,
DAI Bing^{1, 2
, ,},
ZHU Jia-qi^{1, 3
, ,}

1.
National Key Laboratory of Special Environment Composite Technology, Harbin Institute of Technology, Harbin 150001, China
2.
HRG Institute (Zhongshan) of Unmanned Equipment & AI, Zhongshan 528521, China
3.
Key Laboratory of Micro-systems and Micro-structures Manufacturing Ministry of Education, Harbin Institute of Technology, Harbin 150001, China

More Information

Author Bio:
王伟华，博士研究生. E-mail：weihuawang2011@163.com

Corresponding author: DAI Bing, Lecturer. E-mail: daib@hit.edu.cn; ZHU Jia-qi, Professor. E-mail: zhujq@hit.edu.cn

摘要

摘要: 位错是异质外延单晶金刚石合成过程中的重要线缺陷，而降低位错密度是金刚石在电子器件领域上应用的显著挑战。本文以降低Ir衬底上异质外延金刚石膜中位错密度为目标，首先对该过程中的位错产生、类型、表征等进行阐释，然后从理论与工艺相结合的角度总结了加剧位错反应（增加外延层厚度，偏轴衬底生长）、除去已有位错（横向外延过度生长，悬挂-横向外延生长，图形化形核生长）及其他方法（三维生长法、金属辅助终止法、采用金字塔型衬底法）在降低金刚石位错密度方面的最新进展，随后结合经典的大失配异质外延半导体体系降低位错的理论，提出了衬底图形化技术、超晶格缓冲层技术和柔性衬底技术等可通过抑制引入位错来进一步降低位错密度的研究方向，最后对本领域的发展现状和未来展望进行了总结。
- 单晶金刚石 /
- 异质外延 /
- 位错控制 /
- 横向外延过度生长 /
- 衬底图形化
Abstract: Dislocations are considered crucial linear defects in the synthesis of heteroepitaxial single crystal diamond. Minimizing the dislocation density is a significant challenge for using diamond in electronics. This especially holds for diamond growth on iridium substrates with a large lattice constant difference of 7.1%. We first discuss several aspects of dislocations in heteroepitaxial diamond nucleation and growth, including their generation, types and characterization. Next, methods to reduce dislocation density are summarized, including increasing dislocation reactions (increasing the diamond film thickness and off-axis substrate growth), removing dislocations (conventional epitaxial lateral growth, pendeoepitaxial lateral growth and patterned nucleation growth), and other methods (three-dimensional growth, metal-assisted termination and using a pyramidal substrate). The dislocation density has been reduced to 6×10⁵ cm⁻², based on the use of a micrometric laser-pierced hole array, a method similar to patterned nucleation growth. To further reduce dislocation density and improve crystal quality, proposed ways of controlling the introduction of dislocations (substrate patterning, buffer layer and compliant substrate methods) are highlighted.
- Single crystal diamond /
- Heteroepitaxy /
- Dislocation reduction /
- Epitaxial lateral growth /
- Substrate patterning

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FIG. 1033. FIG. 1033.

FIG. 1033..

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Figure 1. Dislocation behaviors during diamond heteroepitaxy. (A) Lattice mismatch at the interface between diamond and iridium substrates^[7]; (B) Diamond epitaxial growth on iridium substrates^[26,29]; (C) Dislocation propagation and types at the interface from WBDF images^[35]and (D) Dislocation density comparison between heteroepitaxial diamond and other single crystal diamonds^[7]. Reprinted from Power Electronics Device Applications of Diamond Semiconductors, Diamond and Related Materials, Applied Physics Letters with permission from Elsevier, AIP Publishing.

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Figure 2. Methods to reduce dislocation density and improve crystal quality and their underlying mechanisms. (A1) Increasing film thickness^[37], (A2) Off-axis growth^[35], (B1) ELO method^[58], (B2) PENDEO-ELO method^[58,65], (B3) PNG method^{[ 62]}, (C1) Substrate patterned method^[73], (C2) Buffer method/virtual substrate^[74] and (C3) Compliant substrate method^[76]. Note: the dashed regions represent the future trend, and the solid boxes describe the reported methods. Reprinted from Applied Physics Letters, Physica Status Solidi (a) applications and materials science, Japanese Journal of Applied Physics with permission from AIP Publishing, John Wiley and Sons, The Japan Society of Applied Physics.

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Figure 3. Other methods used to reduce dislocations during the homoepitaxial growth stage. (A) Three-dimensional growth method^[68], (B) Metal-assisted termination method^{[69, 70]}, (C) The pyramid substrate method^{[71, 72]}. Reprinted from Physica Status Solidi (a) applications and materials science, Applied Physics Letters, Diamond and Related Materials with permission from John Wiley and Sons, AIP Publishing, Elsevier.

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Figure 4. Dislocation reduction and crystal quality improvement with diamond film thickness after adopting different methods. Note:A1:increasing the thickness;A2:off-axis substrate growth;B1:conventional ELO method;B2:PENDEO-ELO method;B3: Patterned nucleation growth.^{[26, 37,39,40, 60-66]}

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Table 1. Dislocation reduction and crystal quality improvement for different methods.

Substrate		Diamond film thickness	Dislocation reduction methods	Etch pit density	Raman shift	FWHM of Raman characteristic peak	Tilt(400)/ Twsit(311)	Refs.
Ir/MgO		75 μm	With PNG	/	1334.7 cm⁻¹	/	0.14°/none	[64]
Ir/MgO		80 nm	With PNG	10^10-11 cm⁻²	/	/	/	[63]
Ir/MgO		5 μm	With PNG	10⁹ cm⁻²	/	/	/	[63]
Ir/MgO		20 μm	With ELO	/	1332±1 cm⁻¹	5 cm⁻¹	/	[60]
Ir/Al₂O₃		70 μm	With ELO	7×10⁷ cm⁻²	/	/	/	[51, 58, 65]
		2/10 μm	With ELO	/		10 cm⁻¹/ 5cm⁻¹
		2/10 μm	Without ELO	/		15±1cm⁻¹/15 cm⁻¹
Ir/MgO		<12 μm	With PNG	/	1333 cm⁻¹	2.73 cm⁻¹	/	[62]
		<12 μm	Without PNG		1334 cm⁻¹	7.87 cm⁻¹
		0~15 μm			/	10-20 cm⁻¹
		>45 μm			/	2.8 cm⁻¹
Ir/MgO		100 μm	Grid PNG	/	/	/	0.064°/0.043°	[61]
		60 μm	Grid PNG	9×10⁶ cm⁻²	1332 cm⁻¹	1.9 cm⁻¹	0.077°/0.082°
		60 μm	Without Grid PNG	10⁸ cm⁻²	1334 cm⁻¹	3.0-4.7 cm⁻¹	0.17°/0.51°
Heteroepitaxial diamond substrate		300 μm	laser-pierced hole array growth similar with PNG	6×10⁵ cm⁻²	/	/	/	[66]
Ir/YSZ/Si		1.6 mm	Increasing film thickness	4×10⁷ cm⁻²	/	/	0.064°/0.12°	[26]
Ir/YSZ/Si		0-1 mm	Increasing film thickness	>10¹⁰cm⁻²-<10⁸ cm⁻²	/	>10 cm⁻¹-1.86 cm⁻¹	/	[37]
Ir/MgO		50 μm	Increasing film thickness	5×10⁸ cm⁻²	/	/	/	[40]
Ir/YSZ/Si4°- 8° off-axis		2.4-4 μm	Off-axis growth	/	/	8 cm⁻¹-11 cm⁻¹	0.4°-0.6°/none	[39]
Ir/YSZ/Si4° off-axis	[110]	1.62 mm	Off-axis growth	1×10⁸ cm⁻²-1×10⁹ cm⁻²	/	1.52 cm⁻¹-4.33 cm⁻¹	/	[48]

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