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Effect of temperature on the (100) surface features of type Ib and type IIa large single crystal diamonds

MetadataDetails
Publication Date2015-01-01
JournalActa Physica Sinica
AuthorsHe Zhang, Shangsheng Li, Taichao Su, Meihua Hu, Zhou You-Mo
Citations6
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Technical Documentation and Analysis: Temperature Effects on (100) SCD Surface Features

Section titled “Technical Documentation and Analysis: Temperature Effects on (100) SCD Surface Features”

Documentation generated by 6CCVD Material Science Division based on: Zhang He et al. Effect of temperature on the (100) surface features of type Ib and type IIa large single crystal diamonds. Acta Physica Sinica, 64, 198103 (2015).


This paper investigates the relationship between synthesis temperature and surface morphology in High-Pressure High-Temperature (HPHT) synthesized Type Ib (Nitrogen-doped) and Type IIa (Ultra-pure) single-crystal diamonds (SCDs) grown on the (100) face using the Temperature Gradient Method (TGM).

  • Morphology Control: Demonstrated the ability to control crystal habit, transitioning from Plate-like (low T) to Tower-like (medium T) and Spire Tower-like (high T) morphologies by tuning the growth temperature (1250 °C - 1340 °C).
  • Purity Differentiation: Confirmed that Type IIa synthesis requires approximately 30 °C higher temperatures and the use of nitrogen scavengers (Ti/Cu) compared to Type Ib growth under similar conditions.
  • Quality Benchmark: Raman spectroscopy confirmed the superior crystal quality of Type IIa SCD, evidenced by a significantly narrower Full Width at Half Maximum (FWHM) of 5.554 cm-1, compared to Type Ib SCD at 5.842 cm-1.
  • Growth Mechanism: Laser Raman microscopy confirmed a step-flow growth mechanism on the (100) surface, exhibiting preferential carbon precipitation and nucleation at the crystal’s angularity regions over the central face.
  • Rate Dependence: Growth rate was effectively controlled by adjusting the axial temperature gradient, achieving rates between 1.99 mg·h-1 and 4.33 mg·h-1 for crystals measuring 3-4 mm in diameter.

Extracted quantitative data points and performance metrics from the research paper.

ParameterValueUnitContext
Synthesis Pressure5.6GPaFixed HPHT condition
Temperature Range1250 - 1340°CTGM Synthesis range
IIa T Offset vs Ib Tapprox. 30°C higherRequired to achieve comparable morphology
SCD Crystal Size (Diameter)3 to 4mmResultant large single crystals
Maximum Growth Rate4.33mg·h-1Observed for Type Ib (1310 °C, high gradient)
Minimum Growth Rate1.99mg·h-1Observed for Type IIa (1310 °C, low gradient)
Temperature Gradient (Range)18.1 to 36.5°C·mm-1Controlled axial gradient for growth rate tuning
Type Ib Raman Peak Position1331.752cm-1Indicating minor stress/strain deviation
Type Ib FWHM5.842cm-1Quality metric (Higher Nitrogen Content)
Type IIa Raman Peak Position1331.833cm-1Closer to ideal 1332.7 cm-1 standard
Type IIa FWHM (Superior Quality)5.554cm-1Quality metric (Low Nitrogen Content, superior purity)
IIa Synthesis AdditivesTi/CuN/AUsed as nitrogen getters/scavengers

The synthesis employed the High-Pressure High-Temperature Temperature Gradient Method (HPHT-TGM) using a six-side cubic press.

  1. Carbon Source and Seeding: High-purity artificial graphite was used as the carbon source. High-grade, 0.5 mm single-crystal diamond seeds were utilized, with the (100) face selected as the primary growth surface.
  2. Catalyst System: A FeNiMnCo alloy was chosen as the metallic solvent/catalyst for Type Ib diamond growth.
  3. IIa Purity Management: For Type IIa diamond synthesis (requiring ultra-low nitrogen content), Ti/Cu additives were incorporated into the FeNiMnCo catalyst system to function as effective nitrogen scavengers.
  4. Pressure Application: Experiments were conducted under a stable, high-pressure condition of 5.6 GPa.
  5. Temperature Gradient Control (TGM): Temperature gradients ranging from 18.1 °C·mm-1 to 36.5 °C·mm-1 were applied across the chamber (using a combination of a graphite heater and insulation) to drive carbon transport from the hot (carbon source) end to the cooler (seed) end.
  6. Morphology Tuning: Growth temperature was precisely adjusted (1250 °C to 1340 °C) to achieve specific macroscopic morphologies: Plate-like (low T), Tower-like (medium T), and Spire Tower-like (high T).
  7. Characterization: Resultant crystals were analyzed using high-precision weighing (0.1 mg accuracy), optical microscopy, and Laser Raman Spectroscopy (Leica DM 2500 M) for surface step-flow analysis and crystal quality (FWHM measurement).

The research demonstrates the critical role of material purity and growth dynamics in achieving high-quality, large-format SCD. While the paper uses HPHT, 6CCVD specializes in MPCVD, offering far greater control, flexibility, and scalability for advanced diamond applications.

Application AreaMaterial Requirement (Paper)6CCVD Material Solution (MPCVD Advantage)
High Purity/Ultra-Low NType IIa SCD (FWHM 5.554 cm-1, requiring Ti/Cu getters)Optical Grade SCD: 6CCVD achieves comparable or superior purity (sub-ppb nitrogen) routinely via MPCVD, eliminating the need for metallic scavengers and minimizing residual metal inclusion risks.
Doped DiamondType Ib SCD (Nitrogen-doped)N-Doped or B-Doped SCD/PCD: 6CCVD offers precise, controllable gas-phase doping for research into color centers (e.g., NV centers) or customized electrical properties (BDD).
High-Power ElectronicsHigh Thermal Conductivity (Implied by high purity)Thermal Management Grade SCD: Our Type IIa material excels in thermal performance, available in thicknesses up to 500 ”m, ideal for high-power device heat spreaders.
Bulk StructuresLarge single crystals (3-4 mm)Custom Large SCD Plates: 6CCVD produces SCD plates up to 10 mm x 10 mm and large area Polycrystalline Diamond (PCD) wafers up to 125 mm, far surpassing the size limitations demonstrated by HPHT TGM.
Paper Requirement / Research Need6CCVD Customization ServiceTechnical Benefit
Specific Crystal Face ControlPrecision-Oriented SubstratesSCD materials available with highly controlled crystal orientations (e.g., (100) or (111)) with orientation errors held to < 0.5°, essential for epitaxial research and device integration.
Surface Finish for MicroscopyUltra-High Quality PolishingSingle Crystal Diamond (SCD) is polished to achieve surface roughness Ra < 1 nm, ensuring optimal results for high-resolution microscopy and Raman/optical characterization used in this study.
Device IntegrationCustom Metalization ServicesInternal capability for multi-layer metal stack deposition (e.g., Ti/Pt/Au, W, Cu, Pd). This supports the full transition from crystal growth studies to functional device prototypes.
Unique DimensionsLaser Cutting and ShapingCustom shaping, laser cutting, and precise dimensional control ensure the final product fits specialized experimental setups, regardless of complexity.

6CCVD’s in-house team of PhD material scientists and technical engineers are experts in translating fundamental growth physics—like the relationship between temperature gradient, growth rate, and morphology demonstrated in this research—into scalable and repeatable MPCVD recipes. We provide consultation and support for projects requiring controlled doping, specific crystal morphology (e.g., optimizing axial vs. radial growth rates), and precise material selection for similar crystal growth dynamics and quality analysis projects.

For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly. We ship globally (DDU default, DDP available).

View Original Abstract

In this paper, by choosing FeNiMnCo alloy as a catalyst and the (100) face of a seed crystal as the growth face, high quality type Ib and type IIa large diamond single crystals (diameter about 3-4 mm) can be successfully synthesized using temperature gradient method, at 5.6 GPa pressure and different temperatures between 1250-1340 ℃. To control the diamond crystal morphology, the growth temperature should be adjusted. Then the morphology of the synthesized large diamonds is plate-like at low temperatures, tower-like at medium temperatures, and spire tower-like at high temperatures. For the same crystal morphology, the synthetic temperature of type IIa diamond single crystals is about 30 ℃ higher than that of type Ib. The central and angularity regions of the top (100) surface, for the synthesized samples of type Ib and type IIa large diamond single crystals at different temperatures, are examined by laser Raman microscope respectively. It is found that the black lines of the type Ib and type IIa large diamond single crystals become dimmed and dense on the same top surface from center to the edge. It is indicated that the priority growth mechanism is in the angularity regions, compared with the central regions. Namely the solute of carbon is primarily precipitated in the angularity regions of the (100) surface. With increasing synthesis temperature, the black lines on the top surface (100) of type Ib diamond single crystals become gradually denser, and the characteristics of the lines are transformed from irregular distribution to typical dendritic distribution. The reason of the above results is that the rate of carbon deposition (the growth rate of diamond crystal), which is along the direction of the diamond crystal [100], will gradually rise as the synthesis temperature of the crystal is increased. The characteristics of the lines on the top surfaces (100) of type IIa large diamond single crystals, which are synthesized under different temperatures, are similar to that of type Ib. However, the lines on the top (100) surface of type IIa diamonds are not so obvious and denser than that of type Ib diamonds at different synthesis temperatures. Similar characteristics of lines on the top (100) surface of both types of diamond single crystals can be explained by the axis and radial growth rate variation at different temperatures. These different characteristics of the lines are due to the fact that the growth rate of type IIa diamonds is slower than that of type Ib diamonds, and the nitrogen concentrations in type IIa diamonds are lower than those of type Ib diamonds. Finally, the full width at half maximum (5.554 cm-1) of the tower-like type IIa diamond is narrower than that (5.842 cm-1) of tower-like type Ib diamond from the test of Raman spectra. It is shown that the quality of type IIa diamond single crystals is better than that of type Ib.