Nitrogen Aggregation Induced by High-Pressure High-Temperature Pretreatment and Its Effect on the Apparent Charge-State Ratio of NV Centers in Diamond
-
摘要: 针对高温高压（high-pressure high-temperature, HPHT）法合成的Ⅰb型金刚石中氮空位（nitrogen vacancy，NV）色心形成及电荷态调控问题，比较了初始替位氮含量（C心氮）、电子辐照、真空退火和HPHT预处理对NV色心发光行为的影响。选取2组不同C心氮含量的HPHT金刚石单晶样品，通过电子辐照、600～
1000 ℃真空退火以及5 GPa、1100 ～1900 ℃的HPHT预处理，结合红外吸收光谱、Raman光谱和光致发光光谱分析氮聚集、晶格状态及NV色心发光响应。结果表明：高氮样品更易形成明显的NV相关发光，低氮样品中辐照空位更易以GR1色心形式保留；随着真空退火温度升高，中性态NV0和负电态NV−发光整体增强，但NV−相对于NV0的表观发光响应整体下降。HPHT预处理本身未直接生成大量NV色心，但可促进氮聚集，并改变后续辐照和退火过程中NV−/NV0的表观电荷态比。结果表明，HPHT预处理可作为调控辐照前缺陷初态及后续NV色心电荷态比的前置工艺。Abstract: Formation of nitrogen-vacancy (NV) centers and their apparent charge-state response in high-pressure high-temperature (HPHT) type-Ⅰb diamond were investigated. Effects of the initial substitutional nitrogen content (C-center nitrogen), electron irradiation, vacuum annealing, and HPHT pretreatment on the photoluminescence (PL) behavior of NV centers were compared. Two groups of HPHT diamond single crystals with different C-center nitrogen contents were subjected to electron irradiation, vacuum annealing (600−1000 ℃), and HPHT pretreatment (5 GPa,1100 −1900 ℃). Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, and photoluminescence spectroscopy were employed to analyze nitrogen aggregation, lattice state, and NV-related photoluminescence responses. The results show that high-nitrogen samples exhibit more pronounced NV-related emission, whereas irradiation-induced vacancies in the low-nitrogen samples tend to remain as GR1 centers. As the vacuum annealing temperature increases, the overall emission intensities of NV0 and NV− increase, while the apparent photoluminescence response of NV− relative to NV0 generally decreases. HPHT pretreatment does not directly generate a large number of NV centers but promotes nitrogen aggregation and modifies the apparent NV−/NV0 charge-state ratio during subsequent irradiation and annealing. These results indicate that HPHT pretreatment can serve as a preceding processing parameter for regulating the initial defect state before irradiation and the subsequent apparent charge-state ratio of NV centers. -
图 1 采用辐照-退火工艺处理的样品的光学照片
Figure 1. Optical photographs of the sample processed with irradiation and vacuum annealing
图 2 采用辐照-退火工艺处理的样品的Raman光谱：(a) 全谱图，(b)
1332.00 cm−1处的局部放大图Figure 2. Raman spectra of samples treated by irradiation and vacuum annealing: (a) full spectrum; (b) localized magnified view at
1332.00 cm−1
图 3 辐照-退火处理后样品的PL光谱
Figure 3. PL spectra of samples treated by irradiation and vacuum annealing
图 4 HPHT预处理后未辐照样品A的FTIR光谱（右图为
1000 ～1500 cm−1区间的局部放大图）Figure 4. FTIR spectra of sample A after HPHT pretreatment before electron irradiation (The right panel shows the enlarged region of
1000 −1500 cm−1.)
图 5 采用HPHT预处理后、电子辐照前样品A的(a) Raman光谱及
1332.00 cm−1处局部放大图以及(b) PL光谱Figure 5. Raman and PL spectra of sample A before electron irradiation after HPHT pretreatment: (a) Raman spectra and a local magnification at
1332.00 cm−1; (b) PL spectra
图 6 采用HPHT预处理-辐照-退火工艺处理的样品的光学照片
Figure 6. Optical images of samples subjected to HPHT pretreatment-irradiation-vacuum annealing process
图 7 采用HPHT预处理-辐照-退火处理的样品的(a) Raman光谱及
1332.00 cm−1处局部放大图以及(b) PL光谱Figure 7. Raman and PL spectra of samples treated by HPHT pretreatment, electron irradiation and vacuum annealing: (a) Raman spectra and a local magnification at
1332.00 cm−1; (b) PL spectra表 1 辐照-真空退火样品的残余应力及表观电荷态比
Table 1. Residual stress and apparent charge-state ratio of samples treated by irradiation and vacuum annealing
Sample Ta/℃ $ {\sigma }_{\text{h}} $/GPa $ {R}_{i} $ Sample Ta/℃ $ {\sigma }_{\text{h}} $/GPa $ {R}_{i} $ A0 −0.291 2.31 B0 −0.283 0.17 A1 0.101 4.36 B1 0.085 0.76 A600 600 0.931 57.57 B600 600 0.405 2.21 A700 700 0.611 14.53 B700 700 0.550 1.66 A800 800 0.451 3.35 B800 800 0.617 0.89 A900 900 0.449 0.71 B900 900 0.416 0.06 A1000 1000 0.353 0.33 B1000 1000 0.418 0.03 
下载: 导出CSV
表 2 HPHT预处理-辐照-真空退火样品的残余应力及表观电荷态比
Table 2. Residual stress and apparent charge-state ratio of samples treated by HPHT pretreatment, electron irradiation and vacuum annealing
Sample Tp/℃ Ta/℃ $ {\sigma }_{\text{h}} $/GPa $ {R}_{i} $ Sample Tp/℃ Ta/℃ $ {\sigma }_{\text{h}} $/GPa $ {R}_{i} $ A800 800 0.451 3.35 AVA600 1900 600 0.355 3.39 APA1100 1100 800 0.964 0.47 AVA700 1900 700 0.383 1.15 APA1300 1300 800 0.606 0.51 AVA800 1900 800 0.310 2.58 APA1500 1500 800 0.416 0.85 AVA900 1900 900 0.370 0.44 APA1700 1700 800 0.470 1.45 AVA1000 1900 1000 0.389 0.58
下载: 导出CSV
-
[1] PEZZAGNA S, NAYDENOV B, JELEZKO F, et al. Creation efficiency of nitrogen-vacancy centres in diamond [J]. New Journal of Physics, 2010, 12(6): 065017. doi: 10.1088/1367-2630/12/6/065017 [2] DOHERTY M W, MANSON N B, DELANEY P, et al. The nitrogen-vacancy colour centre in diamond [J]. Physics Reports, 2013, 528(1): 1–45. doi: 10.1016/j.physrep.2013.02.001 [3] EDMONDS A M, D’HAENENS-JOHANSSON U F S, CRUDDACE R J, et al. Production of oriented nitrogen-vacancy color centers in synthetic diamond [J]. Physical Review B, 2012, 86(3): 035201. doi: 10.1103/PhysRevB.86.035201 [4] KATSUMI R, TAKADA K, JELEZKO F, et al. Recent progress in hybrid diamond photonics for quantum information processing and sensing [J]. Communications Engineering, 2025, 4(1): 85. doi: 10.1038/s44172-025-00398-2 [5] JU Z P, LIN J J, SHEN S, et al. Preparations and applications of single color centers in diamond [J]. Advances in Physics: X, 2021, 6(1): 1858721. doi: 10.1080/23746149.2020.1858721 [6] BALASUBRAMANIAN G, LAZARIEV A, ARUMUGAM S R, et al. Nitrogen-vacancy color center in diamond—emerging nanoscale applications in bioimaging and biosensing [J]. Current Opinion in Chemical Biology, 2014, 20: 69–77. doi: 10.1016/j.cbpa.2014.04.014 [7] SHI Z Y, GAO W, WANG Q, et al. Current sensor based on diamond nitrogen-vacancy color center [J]. Chinese Physics B, 2023, 32(7): 070704. doi: 10.1088/1674-1056/acc3fe [8] NUNN N, TORELLI M D, AJOY A, et al. Beauty beyond the eye: color centers in diamond particles for imaging and quantum sensing applications [J]. Reviews and Advances in Chemistry, 2022, 12(1): 1–21. doi: 10.1134/S2634827622010044 [9] RODGERS L V H, HUGHES L B, XIE M Z, et al. Materials challenges for quantum technologies based on color centers in diamond [J]. MRS Bulletin, 2021, 46(7): 623–633. doi: 10.1557/s43577-021-00137-w [10] AHARONOVICH I, NEU E. Diamond nanophotonics [J]. Advanced Optical Materials, 2014, 2(10): 911–928. doi: 10.1002/adom.201400189 [11] TALLAIRE A, BRINZA O, HUILLERY P, et al. High NV density in a pink CVD diamond grown with N2O addition [J]. Carbon, 2020, 170: 421–429. doi: 10.1016/j.carbon.2020.08.048 [12] 王芳, 马宗敏, 赵敏, 等. 金刚石集群NV色心的光谱特征及浓度定量分析 [J]. 光谱学与光谱分析, 2017, 37(5): 1477–1481. doi: 10.3964/j.issn.1000-0593(2017)05-1477-05WANG F, MA Z M, ZHAO M, et al. Spectral characteristics and concentration quantitative analysis of NV center ensembles in diamond [J]. Spectroscopy and Spectral Analysis, 2017, 37(5): 1477–1481. doi: 10.3964/j.issn.1000-0593(2017)05-1477-05 [13] ZHANG X M, WANG S Y, SHI Y B, et al. Quantitative analysis of spectral characteristics and concentration of ensembles of NV− centers in diamond [J]. Diamond and Related Materials, 2017, 76: 21–26. doi: 10.1016/j.diamond.2017.03.020 [14] NUNN N, MILIKISIYANTS S, DANILOV E O, et al. Electron irradiation-induced paramagnetic and fluorescent defects in type Ⅰb high pressure-high temperature microcrystalline diamonds and their evolution upon annealing [J]. Journal of Applied Physics, 2022, 132(7): 075106. doi: 10.1063/5.0103313 [15] LOSERO E, GOBLOT V, ZHU Y C, et al. Creation of NV centers in diamond under 155 MeV electron irradiation [J]. Advanced Physics Research, 2024, 3(2): 2300071. doi: 10.1002/apxr.202300071 [16] LAWSON S C, FISHER D, HUNT D C, et al. On the existence of positively charged single-substitutional nitrogen in diamond [J]. Journal of Physics: Condensed Matter, 1998, 10(27): 6171–6180. doi: 10.1088/0953-8984/10/27/016 [17] NIE Y, LI S S, HU Q, et al. Effects of high pressure and high temperature annealing on the characteristics of HPHT diamonds with high nitrogen content [J]. Optical Materials, 2023, 137: 113538. doi: 10.1016/j.optmat.2023.113538 [18] BREEDING C M, SHIGLEY J E. The “type” classification system of diamonds and its importance in gemology [J]. Gems & Gemology, 2009, 45(2): 96–111. doi: 10.5741/GEMS.45.2.96 [19] SHINEI C, MIYAKAWA M, ISHII S, et al. Equilibrium charge state of NV centers in diamond [J]. Applied Physics Letters, 2021, 119(25): 254001. doi: 10.1063/5.0079687 [20] VINS V, YELISSEYEV A, TERENTYEV S, et al. Specifics of high-temperature annealing of brown CVD single crystal diamonds at graphite-stable and diamond-stable conditions [J]. Diamond and Related Materials, 2021, 118: 108511. doi: 10.1016/j.diamond.2021.108511 [21] ZHENG L P, XIAO X, ZHOU C L, et al. HTHP-induced color transition and NV center engineering in MPCVD single-crystal diamond: defect mechanism and quantum-mechanical property synergy [J]. Diamond and Related Materials, 2026, 165: 113625. doi: 10.1016/j.diamond.2026.113625 [22] POLO M C, CIFRE J, SÁNCHEZ G, et al. Pulsed laser deposition of diamond from graphite targets [J]. Applied Physics Letters, 1995, 67(4): 485–487. doi: 10.1063/1.114544 [23] CATLEDGE S A, VOHRA Y K, LADI R, et al. Micro-Raman stress investigations and X-ray diffraction analysis of polycrystalline diamond (PCD) tools [J]. Diamond and Related Materials, 1996, 5(10): 1159–1165. doi: 10.1016/0925-9635(96)00534-1 [24] STEEDS J W, KOHN S. Annealing of electron radiation damage in a wide range of Ⅰb and Ⅱa diamond samples [J]. Diamond and Related Materials, 2014, 50: 110–122. doi: 10.1016/j.diamond.2014.09.012 [25] DEÁK P, ARADI B, KAVIANI M, et al. Formation of NV centers in diamond: a theoretical study based on calculated transitions and migration of nitrogen and vacancy related defects [J]. Physical Review B, 2014, 89(7): 075203. doi: 10.1103/PhysRevB.89.075203 [26] GROTZ B, HAUF M V, DANKERL M, et al. Charge state manipulation of qubits in diamond [J]. Nature Communications, 2012, 3(1): 729. doi: 10.1038/ncomms1729 [27] COLLINS A T. The Fermi level in diamond [J]. Journal of Physics: Condensed Matter, 2002, 14(14): 3743–3750. doi: 10.1088/0953-8984/14/14/307 -
下载:
计量
- 文章访问数: 352
- HTML全文浏览量: 130
- PDF下载量: 51
