Thermal history of diamond from Arkhangelskaya and Karpinsky-I kimberlite pipes
At a Glance
Section titled âAt a Glanceâ| Metadata | Details |
|---|---|
| Publication Date | 2022-07-26 |
| Journal | Journal of Mining Institute |
| Authors | E. A. Vasilev, G. Yu. Kriulina, Victor Garanin |
| Institutions | Institute of Mineralogy, Saint Petersburg Mining University |
| Citations | 7 |
| Analysis | Full AI Review Included |
Technical Documentation & Analysis: Thermal History of Natural Diamond
Section titled âTechnical Documentation & Analysis: Thermal History of Natural DiamondâThis document analyzes the research paper âThermal history of diamond from Arkhangelskaya and Karpinsky-I kimberlite pipesâ to provide technical specifications and highlight how 6CCVDâs advanced MPCVD diamond materials and services can support and extend this critical research into defect engineering and thermal history simulation.
Executive Summary
Section titled âExecutive SummaryâThis research provides a detailed spectroscopic and morphological analysis of natural diamonds, focusing on nitrogen defect aggregation and thermal historyâa core area of expertise for 6CCVD.
- Core Achievement: Identification of three distinct diamond populations based on growth conditions, post-growth evolution, and unique thermal histories characterized by extremely low natural annealing temperatures/durations.
- Defect Focus: Extensive use of IR and PL spectroscopy to quantify key defects, including the N3 nitrogen-vacancy center, Bâ band, and hydrogen-containing defects (N3VH, 3107 cm-1 band).
- Nitrogen Concentration: The majority of crystals exhibit a tightly clustered total nitrogen concentration (Ntot) between 800 and 1400 ppm, with very low nitrogen aggregation (NBs < 20%).
- Morphology Correlation: Octahedral habit crystals are statistically linked to the presence of the N3 system, indicating a specific tangential growth mechanism and complex dissolution history.
- Methodological Requirement: The study necessitates high-purity, low-strain diamond material for accurate defect quantification and the ability to produce thin plates for non-destructive zoning analysis.
- 6CCVD Value Proposition: 6CCVD offers custom, high-ppurity Single Crystal Diamond (SCD) with precise, controlled nitrogen doping (Ntot) and post-growth thermal annealing services to replicate and simulate the complex thermal histories observed in these natural samples.
Technical Specifications
Section titled âTechnical SpecificationsâThe following hard data points were extracted from the research methodology and results, focusing on material characteristics and spectroscopic parameters.
| Parameter | Value | Unit | Context |
|---|---|---|---|
| Total Samples Analyzed | 650 | Crystals | From Arkhangelskaya (350) and Karpinsky-I (300) pipes |
| Crystal Size Range | 3 - 5 | mm | Samples used for comprehensive spectroscopic study |
| IR Spectrometer Resolution | 2 | cm-1 | Used for Ntot and NBs calculation |
| UV-Vis Spectral Range | 200 - 800 | nm | Used for N3 defect quantification |
| Low-T PL Measurement Temperature | 77 | K | Used for detailed defect system analysis (S2, S3, H3) |
| Ntot Concentration Range (Karpinsky-I) | 600 - 1400 | ppm | Range for most crystals |
| Ntot Concentration Range (Arkhangelskaya) | 900 - 1050 | ppm | Maximum frequency range |
| Nitrogen Aggregation (NBs) | < 20 | % | Characteristic of the majority of samples |
| N3 Defect Detection Frequency (Arkhangelskaya) | 47 | % | Detected in absorption spectra |
| Bâ Band Detection Frequency (Karpinsky-I) | 78 | % | Detected in absorption spectra |
| Minimum N3 Absorption Coefficient | 0.01 | cm-1 | Detection limit for the zero-phonon N3 line (415 nm) |
Key Methodologies
Section titled âKey MethodologiesâThe study relied on advanced spectroscopic techniques to characterize the structural defects and thermal history of the natural diamond samples.
- Morphological and Habit Analysis: 650 crystals were non-destructively studied to classify growth forms (octahedra, cuboids, dodecahedroids) and identify dominant growth mechanisms (tangential {111} vs. normal {100}).
- Fourier Transform Infrared (FTIR) Spectroscopy: IR absorption spectra were recorded at 2 cm-1 resolution (Bruker VERTEX-70) to determine the total nitrogen concentration (Ntot) and the degree of nitrogen aggregation (NBs, proportion of B defects) using established proportionality coefficients.
- Hydrogen and Bâ Defect Quantification: Specific absorption coefficients for the Bâ band ($\alpha_{Bâ}$) and the 3107 cm-1 band ($\alpha_{3107}$), associated with the N3VH hydrogen-nitrogen defect, were measured to assess low-temperature hydrogen-containing defects.
- UV-Vis Absorption Spectroscopy: Spectra were recorded (Shimadzu UV-2550) in the 200-800 nm range to quantify the N3 nitrogen-vacancy defect system, specifically measuring the absorption coefficient at the 415 nm zero-phonon line ($\alpha_{N3}$).
- Photoluminescence (PL) Spectroscopy: PL spectra were recorded using a Horiba FL-3 spectrometer at room temperature (excitation 350 nm, 450 nm) and at low temperature (77 K, excitation 488 nm, 787 nm lasers) to identify active luminescence centers (e.g., N3, S2, S3 systems) and correlate them with nitrogen aggregation state.
6CCVD Solutions & Capabilities
Section titled â6CCVD Solutions & CapabilitiesâThe research highlights the critical role of precise defect control, nitrogen concentration, and thermal history in determining diamond properties. 6CCVDâs MPCVD capabilities are ideally suited to replicate, control, and extend these findings for advanced scientific and engineering applications.
Applicable Materials
Section titled âApplicable MaterialsâTo replicate the material characteristics and defect profiles studied in this paper, 6CCVD recommends the following custom MPCVD diamond solutions:
| Material Type | Key Feature | Application Relevance | 6CCVD Capability |
|---|---|---|---|
| Nitrogen-Doped SCD | Controlled Ntot (800-1400 ppm) | Simulating Type Ia natural diamond growth conditions and defect aggregation kinetics. | Precise gas flow control allows Ntot tuning from < 1 ppm up to 1500 ppm. |
| Optical Grade SCD | High Purity, Low Birefringence | Essential for high-resolution spectroscopic analysis (IR, PL, UV-Vis) of defect centers (N3, N3VH). | SCD plates available with Ra < 1 nm polishing, ensuring minimal scattering loss. |
| Custom Annealed SCD | Controlled Thermal History | Simulating the natural annealing process (A-B transformation) and stabilizing specific defect states (e.g., N3, Bâ centers). | In-house high-pressure/high-temperature (HPHT) annealing services for precise thermal simulation. |
| Polycrystalline Diamond (PCD) | Large Area Substrates | For scaling up research into large-area sensing or optical applications derived from defect physics. | PCD wafers available up to 125 mm diameter, with thicknesses up to 500 ”m. |
Customization Potential
Section titled âCustomization PotentialâThe paper noted the difficulty in studying crystal zoning without making diamond plates, a destructive process. 6CCVD eliminates this barrier by providing materials engineered for non-destructive analysis:
- Custom Dimensions and Thickness: We provide SCD plates and wafers in custom dimensions, with thicknesses ranging from 0.1 ”m up to 500 ”m, allowing researchers to obtain thin sections for detailed zoning analysis (e.g., cathodoluminescence or micro-IR mapping) without destructive cutting.
- Growth Orientation Control: The research emphasizes the difference between {111} (octahedral) and {100} (cuboid) growth mechanisms. 6CCVD offers SCD grown on both (100) and (111) substrates to isolate and study the spectroscopic characteristics of defects formed under specific growth regimes.
- Metalization Services: Should this research transition into quantum sensing or electronic device fabrication utilizing specific nitrogen-vacancy centers (e.g., NV-), 6CCVD offers internal metalization capabilities, including Au, Pt, Pd, Ti, W, and Cu contacts, applied directly to the diamond surface.
Engineering Support
Section titled âEngineering Supportâ6CCVDâs in-house PhD team specializes in defect engineering and thermal kinetics in MPCVD diamond. We can assist researchers working on similar projects involving:
- Defect Stabilization: Optimizing post-growth annealing recipes to stabilize specific nitrogen-hydrogen defects (like N3VH) or control the A-to-B aggregation stage, crucial for simulating the complex thermal history observed in natural diamonds.
- Material Selection for Spectroscopy: Consulting on the optimal material grade (e.g., low-strain SCD vs. high-N PCD) required to achieve the high spectral resolution necessary for distinguishing narrow defect lines (e.g., 3050, 3144, 3154 cm-1 bands).
- Replication of Natural Growth Conditions: Designing MPCVD recipes that mimic the low-temperature, high-hydrogen environments suggested by the presence of specific hydrogen-related defects in the natural samples.
Call to Action: For custom specifications or material consultation regarding defect engineering, thermal simulation, or advanced spectroscopic materials, visit 6ccvd.com or contact our engineering team directly.
View Original Abstract
This work studies and compares the main morphological, structural, and mineralogical features of 350 diamond crystals from the Karpinsky-I and 300 crystals of the Arkhangelskaya kimberlite pipes. The share of crystals of octahedral habit together with individual crystals of transitional forms with sheaf-like and splintery striation is higher in the Arkhangelskaya pipe and makes 15 %. The share of cuboids and tetrahexahedroids is higher in the Karpinsky-I pipe and stands at 14 %. The share of dodecahedroids in the Arkhangelskaya and Karpinsky-I pipes are 60 % and 50 %, respectively. The indicator role of the nitrogen-vacancy N3 center active in absorption and luminescence is shown. Crystals with the N3 absorption system have predominantly octahedral habit or dissolution forms derived from the octahedra. Their thermal history is the most complex. Absorption bands of the lowest-temperature hydrogen-containing defects (3050, 3144, 3154, 3188, 3310 cmâ1, 1388, 1407, 1432, 1456, 1465, 1503, 1551, 1563 cmâ1), are typical for crystals without N3 system, where in the absorption spectra nitrogen is in the form of low-temperature A and C defects. The above mentioned bands are registered in the spectra of 16 % and 42 % of crystals from the Arkhangelskaya and Karpinsky-I pipes, respectively. The diamond of the studied deposits is unique in the minimum temperature (duration) of natural annealing. Based on a set of features, three populations of crystals were distinguished, differing in growth conditions, post-growth, and thermal histories. The established regularities prove the multi-stage formation of diamond deposits in the north of the East European Platform and significant differences from the diamonds of the Western Cisurals. The results suggest the possibility of the existence of primary deposits dominated by diamonds from one of the identified populations.