碳离子注入金刚石制备氮空位色心的机理

何健; 贾燕伟; 屠菊萍; 夏天; 朱肖华; 黄珂; 安康; 刘金龙; 陈良贤; 魏俊俊; 李成明

doi:10.7498/aps.71.20220794

摘要

金刚石中浅表层氮空位色心在磁探测、量子传感等方面表现出优异的灵敏度和分辨率. 相比于其他制备方法, 低能碳离子注入具有要求金刚石纯度低、不引入新的杂质原子等优点, 但其氮空位色心的形成机理尚不明确. 本文采用低能碳离子注入和真空退火工艺在金刚石浅表层创建氮空位色心, 并通过拉曼光谱、X射线光电子能谱以及正电子湮没分析, 揭示了碳离子注入金刚石制备氮空位色心的机理. 结果表明: 碳离子注入金刚石在950 ℃真空退火后呈现出显著的氮空位色心发光. 碳离子注入后金刚石浅表层表现出晶格畸变与非晶碳的损伤区, 并产生了碳-空位簇缺陷(包裹碳原子的空位簇). 在真空退火过程中损伤区通过畸变区的恢复与非晶碳区的固相外延逐步转变为金刚石结构, 并伴随着碳-空位簇缺陷的不断解离. 在850 ℃和900 ℃退火条件下损伤区结构得到部分修复, 而在950 ℃ 退火时损伤层基本恢复, 同时伴随碳空位簇解离的单空位与代位氮原子结合, 形成了氮空位色心.

关键词:

Abstract

The shallow nitrogen-vacancy center of diamond exhibits excellent sensitivity and resolution in the magnetic detection and quantum sensing areas. Compared with other methods, low-energy carbon ion implantation does not need high-purity diamond nor introduce new impurity atoms, but the formation mechanism of nitrogen-vacancy center is not clear. In this work, shallow nitrogen-vacancy centers are created in the diamond by low energy carbon ion implantation and vacuum annealing, and the transformation mechanism of nitrogen-vacancy centers in diamond is studied by Raman spectroscopy, X-ray photoelectron spectroscopy, and positron annihilation analysis. The results show that shallow nitrogen-vacancy centers can be obtained by carbon ion implantation combined with vacuum annealing. After implantation, superficial layer of diamond shows the damage zone including lattice distortion and amorphous carbon, and carbon-vacancy cluster defects (carbon atoms are surrounded by vacancy clusters) are generated. In the vacuum annealing process, the damaged area gradually transforms into the diamond structure through the recovery of the distortion area and the solid-phase epitaxy of the amorphous carbon area, accompanied by the continuous dissociation of carbon-vacancy cluster defects. When samples are annealed at 850 and 900 ℃, the structure of the damaged area is partially repaired. While annealing at 950 ℃, not only the damaged layer is basically recovered, but also nitrogen atoms capture the single vacancy obtained by the dissociation of carbon vacancy clusters, forming the nitrogen-vacancy centers.

Keywords:

作者及机构信息

1.
北京科技大学新材料技术研究院, 北京　100083

2.
北京科技大学顺德研究生院, 佛山　528399

通信作者: 刘金龙, liujinlong@ustb.edu.cn ; 李成明, chengmli@mater.ustb.edu.cn

基金项目: 国家磁约束核聚变发展研究专项资助(批准号: 2019YFE03100200)、北京自然科学基金(批准号: 4192038)和核探测与核电子学国家重点实验室项目(批准号: SKLPDE-KF-202202)资助的课题.

Authors and contacts

1.
Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China

2.
Shunde Graduate School, University of Science and Technology Beijing, Foshan 528399, China

Corresponding author: Liu Jin-Long, liujinlong@ustb.edu.cn ; Li Cheng-Ming, chengmli@mater.ustb.edu.cn

Funds: Project supported by the National Magnetic Confinement Fusion Science Program of China (Grant No. 2019YFE03100200), the Natural Science Foundation of Beijing, China (Grant No. 4192038), and the State Key Laboratory of Particle Detection and Electronics Program of China (Grant No. SKLPDE-KF-202202).

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参考文献

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施引文献

图 1 碳离子注入金刚石的深度及损伤的SRIM模拟

Fig. 1. SRIM simulation of depth and damage of carbon ion implantation in diamond.

下载: 全尺寸图片幻灯片

图 2 金刚石在碳离子注入前后的拉曼光谱及 PL 光谱　(a) 原始金刚石拉曼光谱; (b) 原始金刚石的PL光谱; (c) 碳离子注入后金刚石的拉曼光谱; (d) 碳离子注入后金刚石的PL光谱

Fig. 2. Raman spectra and PL spectra of the sample before and after implantation: (a) Raman spectrum of original sample; (b) PL spectrum of original sample; (c) Raman spectra of sample after implantation; (d) PL spectrum of sample after implantation.

下载: 全尺寸图片幻灯片

图 3 (a) 不同温度退火后金刚石表面的拉曼光谱; (b) 不同温度退火后金刚石表面的PL光谱

Fig. 3. (a) Raman spectra of diamond surfaces after annealing at different temperatures; (b) PL spectra of diamond surfaces after annealing at different temperatures.

下载: 全尺寸图片幻灯片

图 4 离子注入后金刚石的XPS图谱及其退火后的XPS图谱　(a) 注入金刚石的XPS谱; (b) S1 (850 ℃)退火金刚石的XPS谱; (c) S2 (900 ℃)金刚石的XPS谱; (d) S3 (950 ℃)金刚石的XPS谱

Fig. 4. XPS spectra of samples after ion implantation and its XPS spectra after annealing: (a) XPS spectra of implanted sample; (b) XPS spectra of the sample annealed at 850 ℃; (c) XPS spectra of the sample annealed at 900 ℃; (d) XPS spectra of the sample annealed at 950 ℃.

下载: 全尺寸图片幻灯片

图 5 金刚石碳离子注入及退火后多普勒展宽谱　(a) 金刚石碳离子注入及退火后S-E分布曲线; (b) 金刚石碳离子注入及退火后W-E分布曲线

Fig. 5. Doppler broadening spectra after diamond carbon ion implantation and annealing: (a) S-E curves after carbon ion implantation and annealing; (b) W-E curves after carbon ion implantation and annealing.

下载: 全尺寸图片幻灯片

图 6 金刚石碳离子注入及退火后W-S参数变化

Fig. 6. Changes of W-S parameters after diamond carbon ion implantation and annealing.

下载: 全尺寸图片幻灯片

表 1 XPS谱的拟合结果

Table 1. Fitting results of XPS spectra.

Samples
C-ions S1(850 ℃) S2(900 ℃) S3(950 ℃)

μ(sp²) 91.5% 53.5% 25.3% 13.6%
μ(sp³) 8.5% 46.5% 74.7% 86.4%

下载: 导出CSV

[1]	Solyom A, Flansberry Z, Tschudin M A, Leitao N, Pioro-Ladrière M, Sankey J C, Childress L I 2018 Nano Lett. 18 6494 Google Scholar
[2]	Casola F, Van Der Sar T, Yacoby A 2018 Nat. Rev. Mater. 3 17088 Google Scholar
[3]	Feng F, Zhang W, Zhang J, Lou L, Zhu W, Wang G 2019 Eur. Phys. J. 73 202 Google Scholar
[4]	Kim D, Ibrahim M I, Foy C, Trusheim M E, Han R, Englund D R 2019 Nat. Electron. 2 284 Google Scholar
[5]	Chen M, Meng C, Zhang Q, Duan C, Shi F, Du J 2018 Natl. Sci. Rev. 5 346 Google Scholar
[6]	Schmitt S, Gefen T, Stürner F M, Unden T, Wolff G, Müller C, Scheuer J, Naydenov B, Markham M, Pezzagna S, Meijer J 2017 Science 356 832 Google Scholar
[7]	Barbiero M, Castelletto S, Zhang Q, Chen Y, Charnley M, Russell S, Gu M 2020 Nanoscale 12 8847 Google Scholar
[8]	Ninio Y, Waiskopf N, Meirzada I, Romach Y, Haim G, Yochelis S, Banin U, Bar-Gill N 2021 ACS Photonics 8 1917 Google Scholar
[9]	Perona Martínez F, Nusantara A C, Chipaux M, Padamati S K, Schirhagl R 2020 ACS Sensors 5 3862 Google Scholar
[10]	Zhang C, Yuan H, Zhang N, Xu L X, Li B, Cheng G D, Wang Y, Gui Q, Fang J C 2017 J. Phys. D: Appl. Phys. 50 505104 Google Scholar
[11]	Watanabe A, Nishikawa T, Kato H, Fujie M, Fujiwara M, Makino T, Yamasaki S, Herbschleb E D, Mizuochi N 2021 Carbon 30 294 Google Scholar
[12]	Ishiwata H, Nakajima M, Tahara K, Ozawa H, Iwasaki T, Hatano M 2017 Appl. Phys. Lett. 24 043103 Google Scholar
[13]	Momenzadeh S A, Stohr R J, De Oliveira F F, Brunner A, Denisenko A, Yang S, Reinhard F, Wrachtrup J 2015 Nano Lett. 15 165 Google Scholar
[14]	Bourgeois E, Londero E, Buczak K, Hruby J, Gulka M, Balasubramaniam Y, Wachter G, Stursa J, Dobes K, Aumayr F, Trupke M 2017 Phys. Rev. B 95 041402 Google Scholar
[15]	Monticone D G, Quercioli F, Mercatelli R, Soria S, Borini S, Poli T, Vannoni M, Vittone E, Olivero P 2013 Phys. Rev. B 88 155201 Google Scholar
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[18]	Van Dam S B, Walsh M, Degen M J, Bersin E, Mouradian S L, Galiullin A, Ruf M, IJspeert M, Taminiau T H, Hanson R, Englund D R 2019 Phys. Rev. B 99 161203 Google Scholar
[19]	Orwa J O, Santori C, Fu K M, Gibson B, Simpson D, Aharonovich I, Stacey A, Cimmino A, Balog P, Markham M, Twitchen D 2011 J. Appl. Phys. 109 083530 Google Scholar
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[21]	Ohno K, Joseph Heremans F, de las Casas C F, Myers B A, Alemán B J, Bleszynski Jayich A C, Awschalom D D 2014 Appl. Phys. Lett. 105 052406 Google Scholar
[22]	Healey A J, Stacey A, Johnson B C, Broadway D A, Teraji T, Simpson D A, Tetienne J P, Hollenberg L C 2020 Phys. Rev. Mater. 4 104605 Google Scholar
[23]	Woods, G S, Van Wyk J A, Collins A T 1990 Philos. Mag. 62 589
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[25]	张礼红, 成斌, 张杰, 张丽娟, 郭卫峰, 刘建党, 张礼楠, 叶邦角 2021 中国科学: 物理学力学天文学 42 1217 Google Scholar Zhang L H, Cheng B, Zhang J, Zhang L J, Guo W F, Liu J D, Zhang L N, Ye B J 2021 Sci. Chin. Sin. :Phys. , Mech. Astron. 42 1217 Google Scholar
[26]	张鹏, 秦秀波, 于润升, 李玉晓, 曹兴忠, 王宝义 2012 郑州大学学报 44 5 Google Scholar Zhang P, Qin X B, Yu R S, Li Y X, Cao X Z, Wang B Y 2012 J. Zhengzhou Univ. 44 5 Google Scholar
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[28]	Crocombette J P, Van Wambeke C 2019 EPJ Nucl. Sci. Technol. 5 9 Google Scholar
[29]	Khomich A A, Khmelnitskii R A, Poklonskaya O N, Averin A A, Bokova-Sirosh S N, Poklonskii N A, Ralchenko V G, Khomich A V 2019 J. Appl. Spectrosc. 86 597 Google Scholar
[30]	Uedono A, Ujihira Y, Ikari A, Haga H, Yoda O 1993 Hyperfine Interacts. 79 615 Google Scholar
[31]	Uedono A, Wei L, Tanigawa S, Suzuki R, Ohgaki H, Mikado T, Kametani H, Akiyama H, Yamaguchi Y, Koumaru M 1993 Jpn. J. Appl. Phys. 32 3682 Google Scholar
[32]	Uedono A, Kitano T, Watanabe M, Moriya T, Komuro N, Kawano T, Tanigawa S, Suzuki R, Ohdaira T, Mikado T 1997 Jpn. J. Appl. Phys. 36 969 Google Scholar
[33]	王锐, 胡晓君 2014 物理学报 63 148102 Google Scholar Wang R, Hu X J 2014 Acta Phys. Sin. 63 148102 Google Scholar
[34]	Uedono A, Mori K, Morishita N, Itoh H, Tanigawa S, Fujii S, Shikata S 1999 J. Phys. Condens. Matter 11 4925 Google Scholar
[35]	Guagliardo P, Byrne K, Chapman J, Sudarshan K, Samarin S, Williams J 2013 Diamond Relat. Mater. 37 37 Google Scholar
[36]	王凯悦, 郭睿昂, 王宏兴 2020 物理学报 69 127802 Google Scholar Wang K Y, Guo R A, Wang H X 2020 Acta Phys. Sin. 69 127802 Google Scholar
[37]	胡远超, 曹兴忠, 李玉晓, 张鹏, 靳硕学, 卢二阳, 于润升, 魏龙, 王宝义 2015 物理学报 64 247804 Google Scholar Hu Y C, Cao X Z, Li Y X, Zhang P, Jin S X, Lu E Y, Yu R S, Wei L, Wang B Y 2015 Acta Phys. Sin. 64 247804 Google Scholar
[38]	田雪芬, 刘翔, 龚敏, 张培源, 王康, 邓爱红 2021 金属学报 57 121 Google Scholar Tian X F, Liu X, Gong M, Zhang P Y, Wang K, Deng A H 2021 Acta Metall. Sin. 57 121 Google Scholar
[39]	Selim F A 2021 Mater Charact. 174 110952 Google Scholar
[40]	Siemek K, Dryzek J, Mitura-Nowak M, Lomygin A, Schabikowski M 2020 Nucl. Instrum. Methods Phys. Res., Sect. B 465 73 Google Scholar
[41]	Agulló-Rueda F, Gordillo N, Ynsa M D, Maira A, Cañas J, Ramos M A 2017 Carbon 123 334 Google Scholar

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碳离子注入金刚石制备氮空位色心的机理