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6CCVD Research

Diamonds from the Mir Pipe (Yakutia) - Spectroscopic Features and Annealing Studies

At a Glance

Section titled “At a Glance”
MetadataDetails
Publication Date2021-03-31
JournalCrystals
AuthorsMariana I. Rakhmanova, Andrey Komarovskikh, Yuri N. Palyanov, Alexander A. Kalinin, O. P. Yuryeva
InstitutionsNikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences
Citations11
AnalysisFull AI Review Included

Executive Summary

Section titled “Executive Summary”
  • Material Characterization: 21 colorless octahedral diamonds from the Mir pipe (Yakutia) were analyzed using IR, PL, and EPR spectroscopies, classifying them into Type IIa, IaAB, and IaB based on nitrogen content (up to 1900 ppm) and aggregation state (10-90% B-center aggregation).
  • Unique Type IIa Defect: Type IIa diamonds exhibited a characteristic 418 nm double peak (417.4 + 418.7 nm), hypothesized to be the nickel-boron (Ni-B) defect (NIRIM5/NOL1).
  • Defect Thermal Stability: Step-by-step annealing (600-1700 °C) was performed to map the transformation kinetics of intrinsic and impurity-related defects.
  • Low-Temperature Annihilation: The 563.5 nm center was completely annealed out at 600 °C, attributed to interstitial carbon vacancy annihilation.
  • High-Temperature Transformation: HPHT treatment at 1500 °C induced the formation of 558.5 nm and 576 nm centers, defects characteristic of superdeep diamonds, suggesting the Yakutian samples experienced high effective storage temperatures.
  • Dislocation Mobility: The dislocation-related 490.7 nm center, correlating with an EPR signal, annealed out completely at 1700 °C, reflecting thermally activated diffusion of dislocations.
  • Growth History Implication: The low intensity or absence of nickel-related centers in Type IaAB diamonds, combined with IR data, suggests multiple, distinct episodes of diamond formation at varying temperatures.

Technical Specifications

Section titled “Technical Specifications”
ParameterValueUnitContext
Sample Weight Range5.4-55.0mgOctahedral diamond crystals studied
Total Nitrogen Content (Ntotal)< 1 to approx. 1900ppmRange across Type IIa and Type I samples
Nitrogen Aggregation (%B)10-90%Range for Type Ia diamonds
IR Measurement Range700-4000cm-1Bruker VERTEX 80 spectrometer
IR Resolution0.5cm-1Standard measurement resolution
Platelet Peak Absorption (Max)Up to 7.2cm-1Observed in high nitrogen content samples
EPR g-factor (Common Spectrum)2.0032-Single line, correlated with 490.7 nm PL
EPR Peak-to-Peak Width0.32-0.36mTCommon single line spectrum
Low-T Annealing Duration2hoursTreatments at 600 °C and 1000 °C (ambient pressure)
HPHT Annealing Pressure6.0GPaTreatments at 1500 °C and 1700 °C (BARS apparatus)
HPHT Annealing Duration1.5hoursTreatments at 1500 °C and 1700 °C
563.5 nm Center Annealing T600°CComplete annihilation (interstitial C vacancy)
676.5 nm Center Annealing T1500°CComplete annihilation
613 nm Center Annealing T1700°CComplete annihilation
490.7 nm Center Annealing T1700°CComplete annihilation (dislocation diffusion)

Key Methodologies

Section titled “Key Methodologies”

The study utilized a combination of high-resolution spectroscopy and controlled step-by-step annealing to analyze defect transformation kinetics:

  1. Sample Preparation: Four representative diamond crystals (Type IIa, IaAB, IaB) were selected, and two opposite octahedral faces were polished to allow for consistent spectroscopic measurements before and after annealing.
  2. Infrared (IR) Spectroscopy: Used to quantify total nitrogen content (Ntotal) and the degree of nitrogen aggregation (%B), allowing for classification and correlation with the Taylor diagram (1050-1300 °C isotherms).
  3. Photoluminescence (PL) Spectroscopy: Performed at 80 K using 313 nm, 405 nm, and 532 nm excitation to identify specific zero-phonon lines (ZPLs) associated with nickel, nitrogen, boron, and vacancy defects (e.g., 418 nm, 490.7 nm, 563.5 nm, NV centers).
  4. Electron Paramagnetic Resonance (EPR): Measured at 80 K and 300 K (X and Q bands) to detect paramagnetic centers, including P1 (single substitutional nitrogen) and P2 (N3V complex), and the dislocation-related 490.7 nm signal.
  5. Low-Temperature Annealing: Samples were treated in a graphite crucible at ambient pressure for 2 hours at 600 °C and 1000 °C to study initial defect mobility (e.g., vacancy migration and GR1 annihilation).
  6. High-Pressure High-Temperature (HPHT) Annealing: Samples were treated using a split-sphere multi-anvil apparatus (BARS) at 6.0 GPa for 1.5 hours at 1500 °C and 1700 °C to simulate deep mantle conditions and induce high-energy defect transformations (e.g., N3 formation, dislocation annealing, and the appearance of superdeep diamond defects).

Commercial Applications

Section titled “Commercial Applications”

The detailed understanding of defect formation and thermal stability in natural diamonds is crucial for several high-technology sectors:

  • Quantum Technology (Qubit Manufacturing):
    • Controlled formation of Nitrogen-Vacancy (NV) centers (observed at 1000 °C annealing) is essential for creating high-quality solid-state qubits used in quantum computing and sensing applications (e.g., magnetic field, temperature, and strain sensing).
  • High-Power Electronics and Heat Sinks:
    • The characterization of low-nitrogen Type IIa diamonds, which possess superior thermal conductivity, informs the selection of optimal natural material for use as high-performance heat spreaders and substrates in high-frequency/high-power devices.
  • Advanced Material Sourcing and Authentication:
    • The identification of specific defect signatures (like the 558.5 nm and 576 nm centers induced by high effective storage temperatures) provides valuable spectroscopic fingerprints for geological provenance studies and distinguishing natural diamonds based on their deep mantle history.
  • Defect Engineering and Material Processing:
    • The established annealing recipes (e.g., 600 °C for 563.5 nm removal, 1700 °C for dislocation annealing) enable precise thermal post-processing to tailor the optical and electronic properties of diamond materials for specific industrial requirements.
  • High-Temperature/High-Pressure Research:
    • The use of the BARS apparatus and the study of defect behavior under 6 GPa pressure provide fundamental data relevant to the synthesis of industrial HPHT diamonds and the development of materials stable under extreme conditions.
View Original Abstract

For this study, 21 samples of colorless octahedral diamonds (weighing 5.4-55.0 mg) from the Mir pipe (Yakutia) were investigated with photoluminescence (PL), infrared (IR), and electron paramagnetic resonance (EPR) spectroscopies. Based on the IR data, three groups of diamonds belonging to types IIa, IaAB, and IaB were selected and their spectroscopic features were analyzed in detail. The three categories of stones exhibited different characteristic PL systems. The type IaB diamonds demonstrated dominating nitrogen-nickel complexes S2, S3, and 523 nm, while they were less intensive or even absent in the type IaAB crystals. The type IIa diamonds showed a double peak at 417.4 + 418.7 nm (the 418 center in this study), which is assumed to be a nickel-boron defect. In the crystals analyzed, no matter which type, 490.7, 563.5, 613, and 676.3 nm systems of various intensity could be detected; moreover, N3, H3, and H4 centers were very common. The step-by-step annealing experiments were performed in the temperature range of 600-1700 °C. The treatment at 600 °C resulted in the 563.5 nm system’s disappearance; the interstitial carbon vacancy annihilation could be considered as a reason. The 676.5 nm and 613 nm defects annealed out at 1500 °C and 1700 °C, respectively. Furthermore, as a result of annealing at 1500 °C, the 558.5 and 576 nm centers characteristic of superdeep diamonds from São Luis (Brazil) appeared. These transformations could be explained by nitrogen diffusion or interaction with the dislocations and/or vacancies produced.

Tech Support

Section titled “Tech Support”

Original Source

Section titled “Original Source”

References

Section titled “References”
  1. 2015 - Specific features of diamonds from promising areas of Sibirian platform [Crossref]
  2. 1966 - The origin of types I, II diamonds and reasons for their different physical properties
  3. 2017 - Nature of Type IaB Diamonds from the Mir Kimberlite Pipe (Yakutia): Evidence from Spectroscopic Observation [Crossref]
  4. 2015 - The Characteristic Photoluminescence and EPR Features of Superdeep Diamonds (SĂŁo-Luis, Brazil) [Crossref]
  5. 1982 - The Kinetics of the Aggregation of Nitrogen Atoms in Diamond [Crossref]
  6. 2015 - Multiple Growth Events in Diamonds with Cloudy Microinclusions from the Mir Kimberlite Pipe: Evidence from the Systematics of Optically Active Defects [Crossref]
  7. 2006 - Directional Chemical Variations in Diamonds Showing Octahedral Following Cuboid Growth [Crossref]

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