The influence of seed crystals on the quality of single-crystal diamond produced by a microwave plasma CVD method
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摘要: 采用辽宁瓦房店及山东蒙阴产天然金刚石、俄罗斯高温高压（HPHT）金刚石以及美国Element Six公司CVD金刚石作为种晶，进行红外光谱、激光拉曼光谱、光致发光光谱、XRD摇摆曲线以及原子力显微形貌测试，并选取三类样品各一颗，在相同条件下进行生长实验。测试结果表明，天然金刚石种晶均为IaAB型，定向性好，其内应力及结晶质量差异较大；而HPHT以及CVD金刚石种晶分别为Ib型和Ⅱa型，其生长面与（100）晶向均存在1~2.5度偏差，但晶体结构较天然金刚石好，且内应力及结晶质量差异较小，更加适合作为MPCVD法合成金刚石单晶的种晶。对生长后样品进行了高分辨率激光拉曼光谱测试，并使用光学显微镜及原子力显微镜对样品表面形貌进行了观察。结果表明，在碳氢氮生长体系中，辽宁瓦房店或山东蒙阴产IaAB型天然金刚石种晶由于晶格匹配性较差，容易沉积多晶金刚石，且伴随有微晶石墨和非晶质碳成分；而使用俄罗斯产Ib型HPHT种晶以及美国Element Six产Ⅱa型CVD种晶均能得到优质的CVD金刚石生长层；与HPHT种晶相比，使用CVD种晶得到金刚石生长层的拉曼位移半高宽更窄，非金刚石碳杂质含量更低，结晶质量更好。Abstract: Natural diamonds from Liaoning and Shandong provinces, a HPHT diamond from Russia and a CVD diamond from the Element Six Company in America were selected as seed crystals for the growth of diamonds using the microwave plasma CVD method. The seeds and grown diamonds were characterized by FTIR, Raman spectroscopy, photoluminescence spectroscopy, XRD and AFM. Results indicate that the natural diamonds are type IaAB with a unique orientation and great differences in internal stress and crystalline quality. The HPHT and CVD diamonds are type Ib and type Ⅱa, respectively, with an angular deviation of 1-2.5 degrees and better crystal structure, and are more suitable for the CVD growth of single-crystal diamonds with little variation in internal stress and crystalline quality. The diamond layers grown on the natural IaAB seed crystals from Liaoning and Shandong provinces are polycrystalline with a serious lattice mismatch and impurities of microcrystalline graphite and amorphous carbon while the diamond layers grown on the HPHT type Ib seed crystal from Russia and the CVD type Ⅱa seed crystal from the Element Six Company are both of high quality. Moreover, the diamond layer grown on the CVD seed crystal has a narrower FWHM of the Raman peaks and a lower amount of non-diamond carbon impurity, indicating that it has a better crystalline quality than the diamond layer grown on the HPHT seed crystal.
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Key words:
- Seed crystal /
- Single-crystal diamond /
- Microwave Plasma CVD /
- Growth quality
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Schreck M, Asmussen J, Shikata S, et al. Large-area high-quality single crystal diamond[J]. MRS Bulletin, 2014, 39(06):504-510. Nemanich R J, Carlisle J A, Hirata A, et al. CVD diamond-research, applications, and challenges[J]. MRS Bulletin, 2014, 39(06):490-494. Gicquel A, Hassouni K, Silva F, et al. CVD diamond films:From growth to applications[J].Current Applied Physics, 2001,1(6):479-496. Yamada H, Chayahara A, Mokuno Y, et al. Developments of elemental technologies to produce inch-size single-crystal diamond wafers[J]. Diamond and Related Materials, 2011, 20(4):616-619. Liang Q, Yan C S, Lai J, et al. Large area single-crystal diamond synthesis by 915 MHz microwave plasma-assisted chemical vapor deposition[J]. Crystal Growth & Design, 2014, 14(7):3234-3238. Twitchen D J, Martineau P M, Scarsbrook G A. Coloured diamond[P]. U.S. Patent 8,110,041. 2012-2-7. Scarsbrook G A, Martineau P M, Dorn B S C, et al. Thick single crystal diamond layer method for making it and gemstones produced from the layer[P]. U.S. Patent 7,128,974. 2006-10-31. Yamada H, Chayahara A, Mokuno Y, et al. Uniform growth and repeatable fabrication of inch-sized wafers of a single-crystal diamond[J]. Diamond and Related Materials, 2013, 33:27-31. 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. Silva F, Achard J, Brinza O, et al. High quality, large surface area, homoepitaxial MPACVD diamond growth[J]. Diamond & Related Materials, 2009, 18(5):683-697. Muehle M, Becker M F, Schuelke T, et al. Substrate crystal recovery for homoepitaxial diamond synthesis[J]. Diamond & Related Materials, 2014, 42(2):8-14. Hei L F, Zhao Y, Wei J J, et al. Interface features of the HPHT Ib substrate and homoepitaxial CVD diamond layer[J]. Diamond and Related Materials, 2016, 69:33-39. 吴改, 陈美华, 刘剑红, 等. CVD合成钻石的红外拉曼光谱分析[J]. 矿物学报, 2014(3):411-415. (Wu G, Chen M H, Liu J H, et al. Analysis of CVD synthetic diamond by FTIR and raman spectrometry[J]. Acta Mineralogica Sinica (in Chinese), 2014(3):411-415.) Wang W, D'Haenens-Johansson U F S, Johnson P, et al. CVD synthetic diamonds from gemesis corp[J]. Gems & Gemology, 2012, 48(2):80-97. Willems B, Tallaire A, Barjon J. Exploring the origin and nature of luminescent regions in CVD synthetic diamond[J]. Gems & Gemology, 2011, 47(3). Zaitsev A M. Optical Properties of Diamond:A Data Handbook[M]. Springer Science & Business Media, 2013 Wu G, Chen M H, Liao J. The influence of recess depth and crystallographic orientation of seed sides on homoepitaxial growth of CVD single crystal diamonds[J]. Diamond and Related Materials, 2016, 65:144-151. 廖佳, 陈美华, 吴改, 等. 种晶表面粗糙度及边部形态对MPCVD法生长单晶金刚石的影响[J]. 人工晶体学报, 2015, 2:006. (Liao J, Chen M H, Wu G, et al. Influence of seeds surface roughness and edge appearance on synthesizing single crystal diamond by MPCVD[J]. Journal of Synthetic Crystals (in Chinese), 2015, 2:006.) 刘剑红, 陈美华, 吴改, 等. 金刚石的晶体质量评定探究[J]. 人工晶体学报, 2014, 3:559-564. (Liu J H, Chen M H, Wu G, et al. Study on the evaluation of the crystal quality of diamonds[J]. Journal of Synthetic Crystals (in Chinese), 2014, 3:559-564.) Van Enckevort W J P, Janssen G, Schermer J J, et al. Step-related growth phenomena on exact and misoriented {001} surfaces of CVD-grown single-crystal diamonds[J]. Diamond and Related Materials, 1995, 4(4):250-255. Tyagi P K, Misra A, Unni K N N, et al. Step growth in single crystal diamond grown by microwave plasma chemical vapor deposition[J]. Diamond and Related Materials, 2006, 15(2):304-308. Tallaire A, Achard J, Silva F, et al. Growth of large size diamond single crystals by plasma assisted chemical vapor deposition:recent achievements and remaining challenges[J]. Comptes Rendus Physique, 2013, 14(2):169-184. Ager Ⅲ J W, Veirs D K, Rosenblatt G M. Spatially resolved raman studies of diamond films grown by chemical vapor deposition[J]. Physical Review B, 1991, 43(8):6491. May P W, Smith J A, Rosser K N. 785 nm raman spectroscopy of CVD diamond films[J]. Diamond and Related Materials, 2008, 17(2):199-203. Fukui T, Doi Y, Miyazaki T, et al. Perfect selective alignment of nitrogen-vacancy centers in diamond[J]. Applied Physics Express, 2014, 7(5):055201. Feng Y, Li X Z, Wang E G, et al. Microscopic origin for the orientation dependence of NV centers in chemical-vapor-deposited diamond[J]. Journal of Physics:Condensed Matter, 2014, 26(48):485004. Yiming Z, Larsson F, Larsson K. Effect of CVD diamond growth by doping with nitrogen[J]. Theoretical Chemistry Accounts, 2014, 133(2):1-12. -
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