马赛克拼接法制备大尺寸高品质单晶金刚石研究进展

Research progress on preparation of large-size and high-quality single crystal diamond by mosaic splicing method

摘要

单晶金刚石（single crystal diamond，SCD）凭借优异的力学、热学及光电性能，在航空航天、光电子、高功率电子器件及量子技术等领域具有重要应用价值。微波等离子体化学气相沉积（microwave plasma chemical vapor deposition，MPCVD）是制备高质量单晶金刚石的主流方法，但受限于籽晶尺寸以及大面积生长过程中应力累积、缺陷扩展和生长均匀性下降等问题，难以满足英寸级高品质单晶金刚石的规模化制备需求。马赛克拼接法通过多籽晶横向外延生长与界面融合，有效突破了单颗籽晶尺寸限制，为大尺寸单晶金刚石制备提供了新的技术路径。本文综述了近年来马赛克拼接法制备大尺寸高品质单晶金刚石的研究进展，重点分析拼接界面缺陷形成机制、应力演化规律以及台阶流调控对界面融合质量的影响，总结设备优化、籽晶预处理、界面调控及生长参数优化等关键技术。在此基础上，进一步指出未来研究应聚焦于高精度晶向匹配与界面原子级重构技术、低损伤可重复剥离工艺、大面积生长过程中温场-流场-等离子体场协同调控机制，以及原位监测与多尺度表征技术的构建，实现拼接界面缺陷密度降低、残余应力精准调控和生长均匀性提升，为英寸级高品质单晶金刚石晶圆的产业化制备提供理论基础与技术支撑。

Abstract

Single crystal diamond (SCD) possesses excellent mechanical, thermal, photoelectric properties and thus has important application values in aerospace, optoelectronics, high-power electronic devices and quantum technology. Microwave plasma chemical vapor deposition (MPCVD) is the mainstream technique for synthesizing high-quality single crystal diamond. Nevertheless, it is restricted by seed crystal size, as well as the problems of stress accumulation, defect propagation and deteriorated growth during large-area growth, which makes it difficult to realize the large-scale fabrication of inch-sized high-quality single crystal diamond. The mosaic splicing method achieves interfacial fusion via lateral epitaxial growth of multiple seeds, effectively breaking the size limitation of a single seed crystal and offering a new technical route for the preparation of large-size single crystal diamond. This paper reviews the research progress of preparing large-size and high-quality single crystal diamond by the mosaic splicing method in recent years. It mainly analyzes the formation mechanism of defects and the evolution law of stress at splicing interfaces, as well as the influence of step flow regulation on interfacial bonding quality. Key technologies including equipment optimization, seed pretreatment, interfacial regulation and growth parameter optimization are summarized. On this basis, future research priorities are proposed: developing technologies for high-precision crystal orientation matching and atomic-level interfacial reconstruction, exploring low-damage and reusable lift-off processes, establishing the synergistic regulation mechanism of temperature field, flow field and plasma field during large-area growth, and constructingin-situ monitoring and multi-scale characterization techniques. The above research aims to reduce the defect density at splicing interfaces, precisely control residual stress and improve growth uniformity, so as to provide theoretical basis and technical support for the industrial production of inch-sized high-quality single crystal diamond wafers.

关键词

CVD 单晶金刚石 / 马赛克拼接法 / 大尺寸 / 拼接界面调控 / 单晶金刚石应用

Key words

CVD single crystal diamond / mosaic splicing method / large size / bonding interface control / application of single crystal diamond

参考文献

[1] 李一村. MPCVD低缺陷单晶金刚石生长及基础研究[D]. 哈尔滨：哈尔滨工业大学，2023.

[2] LI Y C. Growth and basic research of MPCVD low defect single crystal diamond[D]. Harbin: Harbin Institute of Technology,2023.

[3] PREM ANAND P S . Significance of diamond as a cutting tool in ultra—precision machining process[M]. Vellore:IntechOpen, 2020.

[4] PRASAD K K, SINGH M P, NEGI V S, et al. Ductile machining of single—crystal germanium freeform optics via ultra—precision diamond turning for high—performance infrared imaging systems[J].Precision Engineering, 2025, 96: 380-397.

[5] HA S J, YOON S J, BAEK S Y, et al. A study on the development of sub—micron single—crystal diamond tools for machining diffractive optical elements[J].International Journal of Advanced Manufacturing Technology, 2023, 126(9/10): 4399-4406.

[6] SHI Z, YUAN Q, WANG Y, et al. Optical properties of bulk single—crystal diamonds at 80—1200 K by vibrational spectroscopic methods[J].Materials, 2021, 14(23): 7435.

[7] LU J, ZHANG X, FENG S, et al. Single—crystal diamond nanowires embedded with platinum nanoparticles for high—temperature solar—blind photodetector[J].Nano Micro Letters, 2025, 17(1): 220.

[8] 黑立富，闫雄伯，朱瑞华，等. 金刚石自支撑膜的高温红外透过性能[J].材料工程，2017，45（2）：1-6.

[9] HEI L F, YAN X B, ZHU R H, et al. High—temperature infrared transmission of free—standing diamond films[J].Journal of Materials Engineering, 2017, 45(2): 1-6.

[10] De BOER W, BOL J, FURGERI A, et al. Radiation hardness of diamond and silicon sensors compared[J].Physica Status Solidi (A), 2007, 204(9): 3009.

[11] DODSON J M, BRANDON J R, DHILLON H K, et al. Single crystal and polycrystalline CVD diamond for demanding optical applications[C]//SPIE Proceedings. Orlando, Florida: SPIE, 2011: 80160L.

[12] 孙祁，汪建华，程翀，等. （100）/（111）面金刚石膜抗氧等离子刻蚀能力[J].航空材料学报，2019，39（2）：55-60.

[13] SUN Q, WANG J H, CHENG C, et al. Resistance abilities of (100)/(111)—faceted diamond films against oxygen plasma etching[J].Journal of Aeronautical Materials, 2019, 39(2): 55-60.

[14] ISBERG J, HAMMERSBERG J, JOHANSSON E, et al. High carrier mobility in single—crystal plasma—deposited diamond[J].Science, 2002, 297(5587): 1670-1673.

[15] WANG Y F, WANG W, CHANG X, et al. Hydrogen—terminated diamond field—effect transistor with AlO_x dielectric layer formed by autoxidation[J].Scientific Reports, 2019, 9(1): 5192.

[16] HUANG A Q. New unipolar switching power device figures of merit[J].IEEE Electron Device Letters, 2004, 25(5): 298-301.

[17] BUNDY F P, HALL H T, STRONG H M, et al. Man—made diamonds[J].Nature, 1955, 176(4471): 51-55.

[18] FANG C, JIA X, CHEN N, et al. HPHT synthesis of N―H co—doped diamond single crystals[J].Journal of Crystal Growth, 2016, 436: 34-39.

[19] MATSUMOTO S. Development of diamond synthesis techniques at low pressures[J].Thin Solid Films, 2000, 368(2): 231-236.

[20] ZHANG T, QIN F, ZHANG L, et al. HFCVD synthesis of boron—doped microcrystalline diamonds[J].Journal of Superhard Materials, 2019, 41(3): 143-148.

[21] LU Z P, STACHOWICZ L, KONG P, et al. Diamond synthesis by DC thermal plasma CVD at 1 atm[J].Plasma Chemistry and Plasma Processing, 1991, 11(3): 387-394.

[22] HUANG Y, CHEN L, SHAO S, et al. The 7—in. free—standing diamond thermal conductive film fabricated by DC arc plasma jet CVD with multi—stage magnetic fields[J].Diamond and Related Materials, 2022, 122: 108812.

[23] MOKUNO Y, CHAYAHARA A, YAMADA H, et al. Improving purity and size of single—crystal diamond plates produced by high—rate CVD growth and lift—off process using ion implantation[J].Diamond and Related Materials, 2009, 18(10): 1258-1261.

[24] SCHRECK M, GSELL S, BRESCIA R, et al. Ion bombardment induced buried lateral growth: the key mechanism for the synthesis of single crystal diamond wafers[J].Scientific Reports, 2017, 7(1): 44462.

[25] ISHIGAKI N, YUGO S. Mechanism of diamond epitaxial growth on silicon[J].Diamond and Related Materials, 2000, 9(9/10): 1646-1649.

[26] CHOI U, SHIN H, KWAK T, et al. Growth and characterization of heteroepitaxial (001) and (111) diamond on Ir/sapphire structures[J].Diamond and Related Materials, 2022, 121: 108770.

[27] GSELL S, BAUER T, GOLDFUSS J, et al. A route to diamond wafers by epitaxial deposition on silicon via iridium/yttria—stabilized zirconia buffer layers[J].Applied Physics Letters, 2004, 84(22): 4541-4543.

[28] WEI Q, NIU G, WANG R, et al. Heteroepitaxy of single crystal diamond on Ir buffered KTaO₃ (001) substrates[J].Applied Physics Letters, 2021, 119(9): 092104.

[29] FISCHER M, GSELL S, SCHRECK M, et al. Preparation of 4—inch Ir/YSZ/Si(001) substrates for the large—area deposition of single—crystal diamond[J].Diamond and Related Materials, 2008, 17(7/8/9/10): 1035-1038.

[30] TALLAIRE A, ACHARD J, SILVA F, et al. Growth of large size diamond single crystals by plasma assisted chemical vapour deposition: recent achievements and remaining challenges[J].Comptes Rendus Physique, 2013, 14(2/3): 169-184.

[31] SILVA F, ACHARD J, BRINZA O, et al. High quality, large surface area, homoepitaxial MPACVD diamond growth[J].Diamond and Related Materials, 2009, 18(5/6/7/8): 683-697.

[32] TERAJI T. Chemical vapor deposition of homoepitaxial diamond films[J].Physica Status Solidi (A), 2006, 203(13): 3324-3357.

[33] YAN C, VOHRA Y K, MAO H, et al. Very high growth rate chemical vapor deposition of single—crystal diamond[J].Proceedings of the National Academy of Sciences, 2002, 99(20): 12523-12525.

[34] JANSSEN G, GILING L J. “Mosaic” growth of diamond[J].Diamond and Related Materials, 1995, 4(7): 1025-1031.

[35] WANG W, LIU B, ZHANG L, et al. Heteroepitaxy of diamond semiconductor on iridium: a review[J].Functional Diamond, 2022, 2(1): 215-235.

[36] YAMADA H, CHAYAHARA A, MOKUNO Y, et al. A 2—in. mosaic wafer made of a single—crystal diamond[J].Applied Physics Letters, 2014, 104(10): 102110.

[37] WANG X, DUAN P, CAO Z, et al. Surface morphology of the interface junction of CVD mosaic single—crystal diamond[J].Materials, 2019, 13(1): 91.

[38] LI Y, DAI B, RALCHENKO V G, et al. Growth of single—crystal diamond by microwave plasma CVD with high precursor utilization using cyclic gas injection and control of carbonaceous species content with optical emission spectroscopy[J].Vacuum, 2022, 206: 111529.

[39] ZHENG Y, MUEHLE M, LAI J, et al. Bilayer metal etch mask strategy for deep diamond etching[J].Journal of Vacuum Science and Technology B, 2022, 40(2): 022210.

[40] ZHANG X, PIESHKOV T S, CHEN D, et al. Ion—implantation, epilayer growth, and lift—off of high—quality diamond films[J].Advanced Functional Materials, 2025, 35(40): 2423174.

[41] SUK J, KIM H, LIM W C, et al. Fabrication of thin diamond membranes by using hot implantation and ion—cut methods[J].Applied Physics Letters, 2017, 110(10): 101903.

[42] SUDHEER S K, PILLAI V P M, NAYAR V U. Characterisation of a Q—switched TEM00 Nd: YAG laser for processing single and polycrystalline diamonds[J].Journal of Optoelectronics and Advanced Materials, 2005, 7(2): 1047-1056.

[43] YUAN H, ZHANG C, SONG C, et al. Grain boundary—mediated graphitization of nanocrystalline diamond under nanosecond laser irradiation[J].Diamond and Related Materials, 2025, 155: 112327.

[44] KONONENKO V V, GOLOLOBOV V M, KONOV V I. Latent laser—induced graphitization of diamond[J].Applied Physics A, 2016, 122(3): 258.

[45] MOKUNO Y, CHAYAHARA A, YAMADA H, et al. Improvements of crystallinity of single crystal diamond plates produced by lift—off process using ion implantation[J].Diamond and Related Materials, 2010, 19(2/3): 128-130.

[46] KHMELNITSKY R A, DRAVIN V A, TAL A A, et al. Damage accumulation in diamond during ion implantation[J].Journal of Materials Research, 2015, 30(9): 1583-1592.

[47] GEIS M W, SMITH H I, ARGOITIA A, et al. Large—area mosaic diamond films approaching single—crystal quality[J].Applied Physics Letters, 1991, 58(22): 2485-2487.

[48] GEIS M W. Device quality diamond substrates[J].Diamond and Related Materials, 1992, 1(5): 684-687.

[49] PRYOR R W, GEIS M W, CLARK H R. Growth technique for large area mosaic diamond films[J].MRS Online Proceedings Library, 1992, 242(1): 13-22.

[50] GEIS M W, EFREMOW N N, SUSALKA R, et al. Mosaic diamond substrates approaching single—crystal quality using cube—shaped diamond seeds[J].Diamond and Related Materials, 1994, 4(1): 76-82.

[51] JANSSEN G, SCHERMER J J, GILING L J. Towards large area diamond substrates: the mosaic process[J].MRS Online Proceedings Library, 1995, 416(1): 33-44.

[52] YAMADA H, CHAYAHARA A, MOKUNO Y, et al. Fabrication of 1 inch mosaic crystal diamond wafers[J].Applied Physics Express, 2010, 3(5): 51301.

[53] TANAKA K, OHMAGARI S, TACHIKI M, et al. Characterization of mosaic diamond wafers and hot—filament epilayers by using HR—EBSD technics[J].Diamond and Related Materials, 2022, 123: 108839.

[54] DING S, REN Z, ZHANG J, et al. Influence of the splicing interface of the mosaic single crystal diamond on the H—diamond field—effect transistor performance[J].IEEE Transactions on Electron Devices, 2024: 1-6.

[55] SHU G, DAI B, RALCHENKO V G, et al. Epitaxial growth of mosaic diamond: mapping of stress and defects in crystal junction with a confocal raman spectroscopy[J].Journal of Crystal Growth, 2017, 463: 19-26.

[56] 黎振坤，翁俊，刘繁，等. 马赛克法生长大尺寸单晶金刚石的研究[J].化学工程与装备，2021（10）：7-8.

[57] LI Z K, WENG J, LIU F, et al. Research on growth of large—size single crystal diamond by mosaic method[J].Chemical Engineering & Equipment, 2021(10): 7-8.

[58] LI G, LI D, MU C, et al. Effect of step—flow modulation on the large—size single crystal diamond through mosaic growth[J].Functional Diamond, 2023, 3(1): 2279057.

[59] 华秩彬，张军安，张冠群. 一种用于金刚石生长的衬底以及应用有该衬底的金刚石拼接生长的方法: CN202411182127.X[P].2024—12—06.

[60] 西安交通大学新闻网. [科技自立自强]西安交大王宏兴教授团队实现2英寸异质外延单晶金刚石自支撑衬底量产—西安交通大学新闻网[EB/OL]. [2025—07—08].https://news.xjtu.edu.cn/info/1424/205582.htm.

[61] QU P, JIN P, ZHOU G, et al. Growth of two—inch free—standing heteroepitaxial diamond on Ir/YSZ/Si (001) substrates via laser—patterned templates[J].Journal of Semiconductors, 2024, 45(9): 090501.

[62] JING J, SUN F, WANG Z, et al. Scalable production of ultraflat and ultraflexible diamond membrane[J].Nature, 2024, 636(8043): 627-634.

[63] MATSUSHITA A, FUJIMORI N, TSUCHIDA Y, et al. Evaluation of diamond mosaic wafer crystallinity by electron backscatter diffraction[J].Diamond and Related Materials, 2020, 101: 107558.

[64] GUISE A, BOZZOLO N, BARRAT S, et al. Crystal orientation distribution in highly oriented diamond films investigated by SEM and TEM[J].Diamond and Related Materials, 2006, 15(4/5/6/7/8): 531-535.

[65] MUCHNIKOV A B, RADISHEV D B, VIKHAREV A L, et al. Characterization of interfaces in mosaic CVD diamond crystal[J].Journal of Crystal Growth, 2016, 442: 62-67.

[66] SHIKATA S. Diamond dislocations analysis by X—ray topography[J].Functional Diamond, 2022, 2(1): 175-191.

[67] 张明，于万里，贾晓鹏，等. 合成金刚石晶体缺陷的同步辐射形貌研究[J].材料工程，2009（4）：49-51.

[68] ZHANG M, YU W L, JIA X P, et al. Synchrotron radiation topographic study of crystal defects in synthetic diamond[J].Journal of Materials Engineering, 2009(4): 49-51.

[69] UMEZAWA H, KATO Y, WATANABE H, et al. Characterization of crystallographic defects in homoepitaxial diamond films by synchrotron X—ray topography and cathodoluminescence[J].Diamond and Related Materials, 2011, 20(4): 523-526.

[70] MORA A E, STEEDS J W, BUTLER J E. Relationship between grain boundaries and broad luminescence peaks in CVD diamond films[J].Diamond and Related Materials, 2003, 12(3/4/5/6/7): 310-317.

[71] ZHU X, LIU J, SHAO S, et al. Evolution of growth characteristics around the junction in the mosaic diamond[J].Diamond and Related Materials, 2021, 120: 108640.

[72] TANAKA K, MOKUNO Y, UMEZAWA H, et al. High—spatial resolution analysis of dislocation bundles in homoepitaxial single—crystal diamond by HR—EBSD[J].Diamond and Related Materials, 2025, 156: 112394.

[73] WILSON R G, ZAVADA J M. Secondary ion mass spectrometry of dopant and impurity elements in wide bandgap semiconductors[J].Materials Science and Engineering, 2012, 73(11/12): 101-128.

[74] KAMINSKY F V, SHILOBREEVA S N, BER B Y, et al. Quantification of hydrogen in natural diamond by secondary ion mass spectrometry (SIMS)[J].Doklady Earth Sciences, 2020, 494(1): 699-703.

[75] WANG H A O, CARTIER L E, BAUMGARTNER L P, et al. A preliminary SIMS study using carbon isotopes to separate natural from synthetic diamonds[J].Journal of Gemmology, 2018, 36(1): 38-43.

[76] LLORET F, EON D, BUSTARRET E, et al. Crystalline defects induced during MPCVD lateral homoepitaxial diamond growth[J].Nanomaterials, 2018, 8(10): 814.

[77] ACHARD J, TALLAIRE A, MILLE V, et al. Improvement of dislocation density in thick CVD single crystal diamond films by coupling H₂/O₂ plasma etching and chemo—mechanical or ICP treatment of HPHT substrates[J].Physica Status Solidi (A), 2014, 211(10): 2264-2267.

[78] YAMADA H, CHAYAHARA A, MOKUNO Y, et al. Simulation with an improved plasma model utilized to design a new structure of microwave plasma discharge for chemical vapor deposition of diamond crystals[J].Diamond and Related Materials, 2008, 17(4/5): 494-497.

[79] YAMADA H, CHAYAHARA A, MOKUNO Y, et al. Microwave plasma generated in a narrow gap to achieve high power efficiency during diamond growth[J].Diamond and Related Materials, 2009, 18(2/3): 117-120.

[80] CAO W, MA Z, GAO D, et al. Homoepitaxial lateral growth of single—crystal diamond with eliminating PCD rim and enlarging surface area[J].Vacuum, 2022, 197: 110820.

[81] LI K, ZHANG J, MO P, et al. Optimizing single crystal diamond mosaic growth: a study on seed thickness variation and pre—growth treatment[J].Journal of Crystal Growth, 2025, 649: 127953.

[82] 胡付生，杨明阳，袁其龙，等. 金刚石表面沟槽的横向拼接生长研究[J].硬质合金，2020，37（2）：106-112.

[83] HU F S, YANG M Y, YUAN Q L, et al. Investigation of the transverse splicing growth of grooves on diamond surface[J].Cemented Carbide, 2020, 37(2): 106-112.

[84] 刘俊杰，关春龙，杨国永，等. 拼接法制备单晶金刚石的拼接缝形貌与残余应力[J].中国表面工程，2024，37（6）：247-256.

[85] LIU J J, GUAN C L, YANG G Y, et al. Stitched seam morphology and residual stress of single—crystal diamond prepared by splicing method[J].China Surface Engineering, 2024, 37(6): 247-256.

[86] 宋修曦，马志斌，耿传文，等. 不同温度下同质外延生长单晶金刚石的应力分析[J].人工晶体学报，2018，47（5）：942-947.

[87] SONG X X, MA Z B, GENG C W, et al. Stress analysis of homoepitaxial growth of single crystal diamond at different temperatures[J].Journal of Synthetic Crystals, 2018, 47(5): 942-947.

[88] WANG X, DUAN P, CAO Z, et al. Homoepitaxy growth of single crystal diamond under 300 torr pressure in the MPCVD system[J].Materials, 2019, 12(23): 3953.

[89] SHIVKUMAR G. Analysis of hydrogen plasma in MPCVD reactor[J].Theses and Dissertations Available from Proquest, 2015: 1-99.

[90] CHU G, LI S, GAO J, et al. Evolution of surface morphology and properties of diamond films by hydrogen plasma etching[J].Green Processing and Synthesis, 2023, 12(1): 20228110.

[91] DÍAZ R D. Larger area single crystal diamond substrate formation with a mosaic tiling process[D]. East Lansing:Michigan State University, 2021.

[92] MENG Y, YAN C, LAI J, et al. Enhanced optical properties of chemical vapor deposited single crystal diamond by low—pressure/high—temperature annealing[J].Proceedings of the National Academy of Sciences, 2008, 105(46): 17620-17625.

[93] PAWAR R J. Atomistic simulations of ∑3 [110](111) grain boundary in diamond: structure, stability, and properties[J].International Journal of Quantum Chemistry, 2023, 123(2): 27016.

[94] YANG B, SHEN Q, GAN Z, et al. Improving the edge quality of single—crystal diamond growth by a substrate holder—an analysis[J].Comptes Rendus Physique, 2019, 20(6): 583-592.

[95] 刘金龙，王鹏，乔冠中，等. 一种基于侧面键合拼接生长大尺寸单晶金刚石的方法: CN202210917780.0[P].2024—01—26.

[96] FAN Q H, FERNANDES A, PEREIRA E, et al. Stress—relief behavior in chemical—vapor—deposited diamond films[J].Journal of Applied Physics, 1998, 84(6): 3155-3158.

基金资助

国家重点研发项目(2024YFB3816600)