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Influence of (N,H)-terminated surfaces on stability, hyperfine structure, and zero-field splitting of NV centers in diamond

MetadataDetails
Publication Date2022-02-17
JournalPhysical review. B./Physical review. B
AuthorsWolfgang Körner, Reyhaneh Ghassemizadeh, Daniel F. Urban, Christian ElsÀsser
InstitutionsUniversity of Freiburg, Fraunhofer Institute for Mechanics of Materials
Citations17
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Technical Documentation & Analysis: Influence of (N,H)-Terminated Surfaces on NV Centers in Diamond

Section titled “Technical Documentation & Analysis: Influence of (N,H)-Terminated Surfaces on NV Centers in Diamond”

Analysis of arXiv:2109.12557v2 by Körner et al., focusing on Density Functional Theory (DFT) applied to NV- stability near diamond surfaces.

The research provides critical DFT insights into stabilizing negatively charged Nitrogen-Vacancy (NV-) centers near diamond surfaces, crucial for high-sensitivity quantum sensing.

  • Stability Condition: Stable NV- centers require a minimum nitrogen concentration at the surface. Below approximately 25% N termination, the NV center is unstable and transitions to the neutral NV0 state.
  • Optimized Configuration: Axial NV centers positioned near a flat, 100% N-terminated (111) surface exhibit the highest degree of symmetry preservation and are least influenced by surface proximity, making them the optimal choice for quantum sensing.
  • Bulk Properties Recovery: Functional NV properties (ZFS, HFS) achieve bulk-like values when the NV center is located at least ~8 Å (0.8 nm) below the surface.
  • Surface Orientation Effects: Both (111) and (001) surfaces were studied. The NV orientation (axial vs. basal) has a greater effect on ground state properties than the specific N:H surface ratio.
  • Electronic Integrity: High N termination (positive electron affinity, EA) is necessary to prevent surface states from interfering with the NV electronic levels, ensuring the defect’s deep-lying electronic states remain intact.
  • 6CCVD Value Proposition: 6CCVD specializes in high-purity, oriented SCD and PCD wafers (e.g., (111) and (001)) which serve as the foundation required for manufacturing these precise, ultra-shallow NV sensors.
ParameterValueUnitContext / Research Implication
Critical N Termination (001)approx. 25%%Minimum required N for stable NV- formation.
Critical N Termination (111)approx. 33%%Minimum required N for stable NV- formation.
Formation Energy Stability0.15eVMaximum energy gain observed for NV- formation < 6 Å from surface.
Bulk Property Recovery Distance~8 (approx.)ÅDistance from surface where ZFS properties converge to bulk values.
HFS Disturbance Range~4 (approx.)ÅProximity range where Hyperfine Structure (HFS) is significantly modified.
Bulk ZFS (D0, Experiment)2.872 (± 0.002)GHzReference longitudinal zero-field splitting component.
ZFS Reduction (Surface)Up to 25%%Maximum reduction in D component observed near the surface.
Transversal ZFS (E)0MHzOptimal value for axial NV on 100% N-(111) surface (high symmetry).
Transversal ZFS (E)~10MHzTypical small splitting observed for mixed (N,H) terminations (broken symmetry).
Surface Polarity (H-Terminated)-1.0 to -1.3eVNegative Electron Affinity (EA); destabilizes NV- charge state.
Surface Polarity (N-Terminated)3.2 to 4.0eVPositive Electron Affinity (EA); stabilizes NV- charge state.

The theoretical analysis was performed using advanced Density Functional Theory (DFT) calculations. Key simulation parameters and methodologies include:

  1. Computational Framework: Vienna Ab Initio Simulation Package (VASP) utilizing Projector-Augmented-Waves (PAW) potentials.
  2. Exchange-Correlation: Generalized Gradient Approximation (GGA) as defined by Perdew, Burke, and Ernzerhof (PBE).
  3. Supercell Models: Large atomistic supercells (approx. 1000 atoms total) were constructed to model diamond slabs (finite thickness with two opposing surfaces).
    • (111) Orientation: Modeled with 6 x 6 hexagonal unit cells (13 carbon double layers).
    • (001) Orientation: Modeled with 6 x 6 cubic primitive units (33 carbon monolayers).
  4. Relaxation Criteria: Atomic positions were relaxed until residual forces were less than 0.03 eV/Å, and energy differences between steps were less than 10-5 eV.
  5. Surface Chemistry Simulation: Mixed terminations were studied by varying the N:H ratio (1:3, 1:1, and 1:0, corresponding to 25%, 50%, and 100% nitrogen) for both (111) and (001) surfaces.
  6. NV Positioning: NV centers were investigated at all symmetry-inequivalent positions, varying distance (up to 14 Å) and orientation (axial vs. basal) relative to the surface plane.
  7. ZFS/HFS Calculation: Zero-Field Splitting (ZFS) and Hyperfine Structure (HFS) tensor components (Dij and AIij) were evaluated using VASP subroutines.

This research confirms that the success of shallow NV quantum sensing relies heavily on the quality, orientation, and dopant incorporation capabilities of the base diamond material. 6CCVD is uniquely positioned to supply the foundational materials and custom engineering required to replicate and advance this work.

The study emphasizes the need for high-quality, oriented diamond substrates with controlled nitrogen introduction.

6CCVD MaterialSpecific CapabilityRelevance to Research
Optical Grade SCDHigh purity, extremely low defect density (essential for long T2 coherence).Provides the high-symmetry crystalline lattice necessary to minimize background decoherence.
SCD Wafers (Custom Orientation)Standard (100), (111) available. Custom cuts upon request.Directly addresses the need for specific (111) and (001) surfaces identified as optimal for high-symmetry NV centers.
Controlled N DopingAbility to incorporate controlled nitrogen concentrations during MPCVD growth.Essential precursor for creating NV centers via high-energy implantation or during subsequent high-temperature annealing steps.
Custom Thickness SCDSCD thickness down to 0.1 ”m.Crucial for the thin slab models studied (maximum depth 1.4 nm/14 Å), enabling future experimental realization of ultra-shallow NV systems.

Experimental realization of the NV systems analyzed requires precision manufacturing and integration capabilities that 6CCVD provides in-house.

  • Precision Polishing: Achieving stable, symmetric NV centers close to the surface requires extremely low surface roughness to avoid dynamic surface disturbances (unpaired surface spins).
    • 6CCVD delivers SCD polishing with Ra < 1 nm and PCD polishing with Ra < 5 nm (for inch-size wafers), ensuring the atomically flat surfaces required by this DFT study.
  • Custom Dimensions and Shapes: 6CCVD supports plates and wafers up to 125mm (PCD). We offer custom laser cutting services for precise engineering integration, enabling specific sensor geometries.
  • Thin Film Metalization: Although the paper is theoretical, functional NV sensors require readout electrodes. 6CCVD provides in-house metalization services including deposition of Ti/Pt/Au, Ti/W, Au, Pd, Pt, and Cu, necessary for device integration and magnetic sensing circuitry.

The transition from theoretical optimum (100% N-terminated (111) surface) to experimental realization involves complex material processing, including high-dose implantation and annealing protocols.

  • 6CCVD’s in-house PhD team can assist partners with material selection, orientation optimization, and thickness specifications for projects targeting shallow NV-based quantum magnetometry and solid-state quantum computing.
  • We offer technical consultation regarding nitrogen incorporation control necessary to stabilize the NV- charge state during the required surface termination steps.

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

View Original Abstract

We present a density functional theory analysis of the negatively charged\nnitrogen-vacancy (NV$^-$) defect complex in diamond located in the vicinity of\n(111)- or (100)-oriented surfaces with mixed (N,H)-terminations. We assess the\nstability and electronic properties of the NV$^-$ center and study their\ndependence on the H:N ratio of the surface termination. The formation energy,\nthe electronic density of states, the hyperfine structure and zero-field\nsplitting parameters of an NV$^-$ center are analyzed as function of its\ndistance and orientation to the surface. We find stable NV$^-$ centers with\nbulk-like properties at distances of at least $\sim8$ Angstroem from the\nsurface provided that the surface termination consists of at least 25\%\nsubstitutional nitrogen atoms. Our results indicate that axial NV centers near\na flat 100\% N-terminated (111) surface are the optimal choice for NV-based\nquantum sensing applications as they are the least influenced by the proximity\nof the surface.\n