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Counting vacancies and nitrogen-vacancy centers in detonation nanodiamond

MetadataDetails
Publication Date2016-01-01
JournalNanoscale
AuthorsShery L. Y. Chang, Amanda S. Barnard, Christian Dwyer, Chris Boothroyd, Rosalie K. Hocking
InstitutionsErnst Ruska Centre, Forschungszentrum JĂŒlich
Citations40
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Technical Analysis and Documentation: N-V Center Engineering in Diamond

Section titled “Technical Analysis and Documentation: N-V Center Engineering in Diamond”

This document analyzes the research paper, Counting vacancies and nitrogen-vacancy centers in detonation nanodiamond, focusing on the implications for advanced material engineering. It highlights how 6CCVD’s specialized MPCVD diamond capabilities address the challenges of controlling defects for quantum and bio-technology applications.


The research confirms the critical role of vacancy concentration in maximizing functional Nitrogen-Vacancy (N-V) center formation, a foundational requirement for solid-state qubits and fluorescent biomarkers.

  • Core Finding: Vacancies were successfully detected and quantified (0.4-1.3 at%) in Detonation Nanodiamond (DND) using simulation-aided Electron Energy-Loss Spectroscopy (EELS).
  • Defect Quantification: The combined experimental (EELS) and theoretical (DFT/SCC-DFTB) approach predicted that approximately 20% of the observed vacancies form the desirable N-V centers.
  • Material Challenge: DND, due to its size (<4 nm) and structural complexity (planar faults, fullerene-like surfaces), presents an inconsistent host for scalable N-V engineering.
  • 6CCVD Solution: 6CCVD specializes in high-purity Single Crystal Diamond (SCD) and precise doping, offering superior, large-area substrates necessary for controlled, repeatable defect engineering (e.g., through gas doping or post-growth ion implantation) required for high-coherence quantum applications.
  • Methodology Insight: The study validated EELS/DFT as a robust method for quantifying and differentiating point defects (V vs. N-V), offering a powerful QC tool applicable to all MPCVD diamond processes.

ParameterValueUnitContext
DND Particle Size<4nmMaterial studied (Detonation Nanodiamond)
Observed Vacancy Concentration Range0.4-1.3at%Estimated using EELS/DFT analysis
Measured Nitrogen (N) Concentration3 ± 0.2at%Used as input for N-V formation modeling
Predicted N-V Formation Probability~20%Fraction of vacancies expected to form N-V pairs
TEM Accelerating Voltage80kVChosen to operate below the diamond knock-on threshold
TEM Spatial Resolution1ÅAchieved using Cs- and Cc-corrected PICO TEM
Diamond Lattice Spacing (311)1.07ÅUsed to verify structural resolution
Isolated Vacancy (V C1) EELS Peak282.4eVSimulated Carbon K-edge pre-peak energy
N-V Pair (N-V C1) EELS Peak282.8eVSimulated Carbon K-edge pre-peak energy

The quantification of vacancies relied on a highly integrated experimental and theoretical approach, essential for point-defect engineering in nanocrystalline materials.

  1. Atomic-Resolution Imaging: High-resolution Transmission Electron Microscopy (HRTEM) using a Cs- and Cc-aberration-corrected PICO TEM (80 kV) was employed to image DND structure, identify fullerene-like surfaces and planar defects (twins), and verify minimal beam damage.
  2. High-Resolution EELS Acquisition: Electron Energy-Loss Spectroscopy (EELS) was performed on the DND to collect the Carbon K-edge spectrum, confirming pre-peaks (A, B, C) indicative of defects and surface features.
  3. Density Functional Theory (DFT) Simulation: First-principles calculations (using CASTEP and OptaDOS) modeled the Carbon K-edge spectra for specific point defects (isolated vacancy V and N-V pair) in the diamond lattice to guide the interpretation of EELS peak A.
  4. Vacancy Quantification Formula: The concentration (f) was determined by normalizing the intensity of Peak A ($I_{exp}^{A}$) against the Carbon K-edge intensity ($I_{exp}^{C K-edge}$) and scaling this ratio by a reference value derived from simulated perfect and defected unit cells ($I_{ref}^{A} / I_{ref}^{C K-edge}$).
  5. Nitrogen Concentration Measurement: The N concentration (3 ± 0.2 at%) was independently measured using N-K edge spectra, providing crucial input parameters for kinetic modeling.
  6. N-V Formation Modeling: Density-Functional Tight-Binding (SCC-DFTB) simulations utilized the measured N and vacancy concentrations to statistically predict the probability of N-V pair formation (~20%) based on particle size and defect energetics.

The research highlights the intrinsic difficulty in controlling defect populations in Detonation Nanodiamond (DND). Quantum information and advanced biotechnology require uniform, scalable, and high-coherence N-V centers, which are best hosted in high-purity, bulk Single Crystal Diamond (SCD) grown via MPCVD, not DND powder.

6CCVD provides the necessary materials and engineering expertise to transition this fundamental defect research into scalable device platforms.

Research Requirement/Challenge6CCVD MPCVD Diamond SolutionTechnical Capability
Pristine Host Material (Need for high-purity, structural integrity for high coherence N-V qubits).Optical Grade SCD Wafers. Provides the stable, lowest-defect host lattice essential for stable quantum emitters and minimizing decoherence.SCD wafers with ultra-low nitrogen content and superior polish (Ra < 1nm) suitable for precise implantation/doping. Available up to 500 ”m thickness.
Controlled Defect Generation (Need to control both N and V concentrations precisely).Tailored Doping & Post-Processing Readiness. 6CCVD delivers material ready for either highly controlled in situ Nitrogen Doping (N-SCD) or post-growth Ion Implantation (V creation).Material engineering expertise to adjust growth recipes (temperature, gas flow) for targeted nitrogen incorporation or supply pristine substrates for external MeV implantation campaigns.
Scalable Substrate Size (DND is sub-4 nm powder; commercial integration requires large wafers).Large-Area Substrates (SCD & PCD). Supports device scale-up for optical and thermal applications.SCD plates available up to 10mm thickness; Polycrystalline Diamond (PCD) wafers up to 125mm diameter, ideal for sensor integration and thermal management.
Device Integration (Need metal contacts for electrical interfacing or quantum gates).Custom Metalization Services. Facilitates easy transition from research material to integrated device architecture.Internal deposition and patterning of standard metal stacks (Au, Pt, Pd, Ti, W, Cu) for ohmic and Schottky contacts, as specified by the customer’s device geometry.
Polishing and Finish (Need defect-free surfaces for integration and minimizing surface recombination).Sub-Nanometer Polishing. Ensures ideal surface finish for epitaxial integration, optical coupling, and reduced surface defects that trap vacancies.Standard SCD surface finish Ra < 1nm; Inch-size PCD wafers polished to Ra < 5nm.

6CCVD’s in-house PhD team provides expert consultation on material selection, doping strategies, and substrate preparation for advanced quantum information technology projects. We specialize in providing application-specific diamond solutions—from high-purity SCD for N-V center engineering to heavy Boron-Doped Diamond (BDD) films for electrochemical sensing.

For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly.

View Original Abstract

Detonation nanodiamond particles (DND) contain highly-stable nitrogen-vacancy (N-V) centers, making it important for quantum-optical and biotechnology applications. However, due to the small particle size, the N-V concentrations are believed to be intrinsically very low, spawning efforts to understand the formation of N-V centers and vacancies, and increase their concentration. Here we show that vacancies in DND can be detected and quantified using simulation-aided electron energy loss spectroscopy. Despite the small particle size, we find that vacancies exist at concentrations of about 1 at%. Based on this experimental finding, we use ab initio calculations to predict that about one fifth of vacancies in DND form N-V centers. The ability to directly detect and quantify vacancies in DND, and predict the corresponding N-V formation probability, has a significant impact to those emerging technologies where higher concentrations and better dispersion of N-V centres are critically required.