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利用六面顶压机, 在5.8 GPa, 1300 ℃的高温高压条件下, 以Fe59Ni25Co16合金作为触媒, 系统地开展了Li3N添加金刚石单晶的生长研究. 首先, 考察了Li3N添加比例对金刚石单晶生长的影响. 研究结果表明, 随着Li3N添加比例的逐渐增加, 金刚石单晶的颜色逐渐由黄绿色、绿色、深绿色向墨绿色过渡, 其形貌逐渐由六面体、六八面体向八面体过渡, 且单晶的生长速度随Li3N添加比例的增加而减小. 其次, 借助傅里叶红外(FTIR)光谱测试, 揭示了金刚石单晶的氮含量随着Li3N添加比例的增加而增大, 并验证了提高金刚石生长压力可实现对金刚石单晶氮含量的提升. 再次, 结合拉曼(Raman)光谱测试, 阐述了金刚石单晶的拉曼特征峰随着Li3N添加比例的增加而逐渐向低能端移动, 这与金刚石单晶的内应力随晶体内氮含量的增加而增大有关. 最后, 通过光致发光光谱(PL)测试, 验证了本研究实现了具有NV–色心金刚石单晶的高温高压制备. 另外, PL光谱测试结果同时表明, 当金刚石中的氮含量不低于4.93×10–4时, 晶体内部NV–色心的零声子线强度会随着晶体氮含量的增加而显著降低.In the paper, under 5.8 GPa and 1300 ℃, the Li3N doped diamond single crystals were synthesized in a cubic anvil high pressure and high temperature apparatus. Firstly, Fe59Ni25Co16 alloy was used as the catalyst, high-purity Li3N powder was used as the additive, industrial high-purity graphite powder was used as the carbon source, and the (100) crystal orientation of industrial grade diamond single crystal with good crystalline quality was used as the growth direction of diamond single crystal, the effect of Li3N addition ratio on the growth of diamond single crystals was systematically investigated with a growth time of 20 h. The research results indicate that with the increase of Li3N addition ratio, the color of diamond single crystals gradually transitions from yellow green, green, and dark green to dark green, and their morphology gradually transitions from hexahedron, hexahedron to octahedron. Moreover, the growth rate of single crystals decreases with the gradual increase of Li3N addition ratio, which can be attributed to the phenomenon of upward movement in the “V-shaped region” of diamond single crystal growth with the gradual increase of Li3N addition ratio in the P-T phase diagram of carbon. Secondly, using Fourier transform infrared (FTIR) spectroscopy, it was revealed that the nitrogen content of diamond single crystals increases with the increase of Li3N addition ratio, and increasing the diamond growth pressure can achieve the increase in the nitrogen content of diamond single crystals.
Fig. 5 shows FTIR spectra of diamond crystals synthesized under different Li3N addition ratios. When the weight percent of Li3N added to the catalyst is 0.55%, the nitrogen content of the grown diamond single crystal is 8.92×10–4. Thirdly, Raman spectroscopy testing revealed that the Raman characteristic peak of diamond single crystals gradually shifts towards the low-energy end with the increase of Li3N addition ratio, which is related to the increase of internal stress in diamond single crystals. Finally, the PL spectroscopy test results showed that this study achieved high temperature and high pressure preparation of diamond single crystals with NV– color centers, and the zero phonon line intensity of NV– color centers in the single crystals significantly decreased with the increase of crystal nitrogen content.Fig. 7 shows PL spectra of diamond crystals synthesized under different Li3N addition ratios.
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Keywords:
- high temperature and high pressure /
- diamond single crystals /
- catalyst /
- Li3N
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图 1 金刚石单晶的生长组装示意图. ①叶蜡石块; ②白云石衬管; ③触媒合金; ④金刚石单晶; ⑤导电钢帽; ⑥石墨加热管; ⑦碳素源; ⑧晶体生长容器; ⑨晶种; ⑩导电紫铜片
Fig. 1. Sample assembly to treat synthesis diamond single crystals. ① Synthetic block of pyrophyllite; ② dolomite lining tube; ③ catalyst alloy; ④ diamond single crystal; ⑤ conductive steel cap; ⑥ graphite heating tube; ⑦ carbon source; ⑧ crystal growth container; ⑨ seed crystals; ⑩ conductive copper sheet.
图 2 5.8 GPa下不同Li3N添加质量含量金刚石单晶的光学显微照片 (a) 0.25% Li3N; (b) 0.35% Li3N; (c) 0.45% Li3N; (d) 0.55% Li3N
Fig. 2. Optical micrographs of diamond single crystals with different weight percent Li3N addition ratios under 5.8 GPa: (a) 0.25% Li3N; (b) 0.35% Li3N; (c) 0.45% Li3N; (d) 0.55% Li3N.
图 3 Li3N添加金刚石单晶生长“V形区”上移示意图. (a)低Li3N添加的“V形区”; (b)高Li3N添加的“V形区”
Fig. 3. Schematic diagram of the upward movement of the “V-shaped region” with Li3N doped diamond growth. (a) V-shaped region with low Li3N addition; (b) V-shaped region with high Li3N addition
图 4 不同压力及Li3N添加比例下生长金刚石单晶的光学显微照片 (a)5.8 GPa, 0.60%; (b) 5.6 GPa, 0.07%; (c) 5.6 GPa, 0.08%
Fig. 4. Optical micrographs of diamond single crystals grown under different pressures and Li3N addition ratios: (a) Under 5.8 GPa, for 0.60% Li3N; (b) under 5.6 GPa, for 0.07% Li3N; (c) under 5.6 GPa, for 0.08% Li3N.
图 5 不同Li3N添加比例金刚石单晶的微区红外光谱 (a) S6; (b) S1; (c) S2; (d) S3; (e) S4
Fig. 5. FTIR spectra of diamond crystals synthesized under different Li3N addition ratios: (a) S6; (b) S1; (c) S2; (d) S3; (e) S4.
图 6 不同Li3N添加比例金刚石单晶的Raman光谱测试结果 (a) S1; (b) S2; (c) S3; (d) S4
Fig. 6. Raman spectra of diamond crystals synthesized under different Li3N addition ratios: (a) S1; (b) S2; (c) S3; (d) S4.
图 7 不同Li3N添加比例金刚石单晶的PL光谱 (a) S1; (b) S2; (c) S3; (d) S4
Fig. 7. PL spectra of diamond crystals synthesized under different Li3N addition ratios: (a) S1; (b) S2; (c) S3; (d) S4.
表 1 Li3N添加金刚石单晶的生长条件及晶体品质特征
Table 1. Growth conditions and crystal quality of Li3N doped diamond single crystals.
样品 压力
/GPa温度
/℃Li3N添加比例
/%生长速度
/(mg·h–1)晶体品质 S1 5.8 1300 0.25 1.85 六面体, 无包裹体及表面凹坑 (图2(a)) S2 5.8 1300 0.35 1.65 六-八面体, 少量包裹体, 无表面凹坑(图2(b)) S3 5.8 1300 0.45 1.36 近八面体, 无包裹体及表面凹坑 (图2(c)) S4 5.8 1300 0.55 0.89 八面体, 无包裹体及表面凹坑 (图2(d)) S5 5.8 1300 0.60 0.27 八面体, 表面存在沟壑状缺陷 (图4(a)) S6 5.6 1300 0.07 0.15 六八面体, 晶种附近较多包裹体 (图4(b)) S7 5.6 1300 0.08 0.09 六面体, 边缘出现较大尺寸孪晶 (图4(c)) 
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表 2 Li3N添加金刚石单晶的氮含量
Table 2. Nitrogen contents of Li3N doped diamond single crystals.
序号 Li3N添加质量
含量/%C心N含量
NC/×10–6金刚石样品 a 0.07 356 S6 b 0.25 493 S1 c 0.35 616 S2 d 0.45 770 S3 e 0.55 892 S4
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表 3 Li3N添加金刚石单晶的内应力σh
Table 3. Internal stress of Li3N doped diamond single crystals.
序号 拉曼峰值/cm–1 △γ/cm–1 内应力σh/MPa a 1330.92 1.08 375 b 1330.81 1.19 413 c 1330.77 1.23 427 e 1330.50 1.50 521
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