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Charge state dynamics and optically detected electron spin resonance contrast of shallow nitrogen-vacancy centers in diamond

MetadataDetails
Publication Date2020-08-18
JournalPhysical Review Research
AuthorsZhiyang Yuan, Mattias Fitzpatrick, Lila V. H. Rodgers, Sorawis Sangtawesin, Srikanth Srinivasan
InstitutionsPrinceton University
Citations39
AnalysisFull AI Review Included

Technical Documentation & Analysis: Shallow NV Center Charge State Dynamics

Section titled “Technical Documentation & Analysis: Shallow NV Center Charge State Dynamics”

This research highlights the critical dependence of shallow Nitrogen-Vacancy (NV) center performance on the diamond surface environment, a key challenge for nanoscale quantum sensing applications.

  • Surface Sensitivity: Optically Detected Electron Spin Resonance (OD-ESR) contrast degrades significantly for NV centers within < 10 nm of the diamond surface due to surface-mediated charge state dynamics.
  • Charge State Instability: The degradation is driven by two factors: increased steady-state neutral NV (NV0) population (increasing background fluorescence) and fast charge conversion rates (Γion, Γrec) that compete with spin dynamics.
  • Contamination Impact: Sample F, exhibiting persistent boron contamination (4% of surface monolayer via XPS), showed drastically lower OD-ESR contrast (< 0.3) and short coherence times (T2 < 4 ”s) compared to cleaner samples.
  • Kinetic Interference: Fast charge conversion rates (up to ~20 MHz) were observed in unstable samples, comparable to the NV spin polarization rate, leading to a loss of spin information during initialization and readout.
  • Material Imperative: The study underscores that achieving stable, high-contrast NV quantum sensors requires ultra-high purity diamond substrates and rigorous, contamination-free surface engineering and termination protocols.

Data extracted from the research paper and supplemental material, focusing on critical experimental parameters and results.

ParameterValueUnitContext
Critical NV Depth Region< 10nmRegion where OD-ESR contrast degradation is most pronounced.
Implantation Energy (Sample F, B)1.5keVLowest energy used, targeting shallow NV centers.
Implantation Energy (Sample A, C, D, E)3keVHigher energy used for comparison samples.
High-Temperature Annealing1200°CVacuum annealing for surface damage removal.
NV Creation Annealing800°CVacuum annealing post-implantation.
Oxygen Termination Annealing440 - 460°CUsed to create well-ordered oxygen-terminated surfaces.
Surface Boron Contamination (Sample F)4%Estimated surface monolayer percentage (via XPS).
Typical OD-ESR Contrast (Sample F)< 0.3N/ASignificantly degraded contrast due to surface effects.
Spin Coherence Time (Sample F)< 4”sShort T2 times observed in unstable samples.
Max Charge Conversion Rate (Γion, Sample F)~20MHzRate comparable to spin polarization, causing dynamic contrast loss.
Excited State Lifetime (ES0 τ, typical)10 - 13nsIntrinsic NV parameter used in rate equation model.

The following steps were critical in preparing the diamond samples and characterizing the shallow NV centers:

  1. Substrate Polishing: Electronic grade diamond was scaife polished to an RMS roughness of < 1 nm.
  2. Pre-Etch & Annealing: Inductively-coupled plasma reactive ion etching (ICP-RIE) followed by high-temperature vacuum annealing at 1200 °C to remove subsurface damage.
  3. Chemical Cleaning: Triacid cleaning (Sulfuric, Nitric, Perchloric) to remove amorphous carbon and contaminants.
  4. Ion Implantation: Nitrogen ion implantation at energies of 1.5 keV or 3 keV to create shallow vacancies.
  5. NV Activation: Post-implantation vacuum annealing at 800 °C to activate the NV centers.
  6. Surface Termination: Oxygen annealing at 440 °C - 460 °C to create well-ordered oxygen-terminated surfaces, followed by Piranha cleaning.
  7. Characterization: X-ray photoelectron spectroscopy (XPS) was used to confirm surface contamination (e.g., Boron 1s peak) and confocal microscopy was used for time-resolved Photoluminescence (PL) and OD-ESR measurements.

This research demonstrates that the success of shallow NV quantum sensing hinges on material purity and precise surface control—areas where 6CCVD provides industry-leading solutions.

Research Requirement/Challenge6CCVD Solution & CapabilityTechnical Advantage for Quantum Sensing
Challenge: Surface contamination (Boron, charge traps) leading to NV0 population and poor contrast.Applicable Material: High Purity Optical Grade SCD (Single Crystal Diamond).Our MPCVD process yields ultra-low impurity levels, minimizing background defects and ensuring the stability of the desired NV- charge state necessary for high OD-ESR contrast.
Requirement: Ultra-smooth surfaces (Ra < 1 nm) essential for stable shallow NV centers and subsequent termination.Polishing Services: SCD polishing to Ra < 1 nm standard; Inch-size PCD polishing to Ra < 5 nm.Provides the pristine surface required to mitigate surface reconstruction and minimize the density of surface charge traps, extending T2 coherence times.
Requirement: Substrates optimized for precise shallow ion implantation (1.5 keV to 3 keV).Custom Dimensions & Thickness: SCD plates available from 0.1 ”m to 500 ”m thick, and substrates up to 10 mm. Custom wafers up to 125 mm (PCD).We supply high-quality, stress-minimized substrates tailored for subsequent high-energy processing steps (implantation and high-temperature annealing up to 1200 °C).
Requirement: Integrated electrical contacts for microwave delivery during OD-ESR measurements.Custom Metalization: Internal capability for deposition of Au, Pt, Pd, Ti, W, and Cu.Enables direct integration of microwave antennas or electrodes onto the diamond surface, streamlining the fabrication of functional quantum devices.
Requirement: Consultation on optimal surface termination (e.g., Oxygen, Hydrogen) to stabilize NV-.Engineering Support: 6CCVD’s in-house PhD team provides consultation on material selection and post-processing protocols for similar Shallow NV Quantum Sensing projects.We assist researchers in selecting the optimal material and surface treatment to maximize NV- yield and minimize charge state conversion rates (Γion, Γrec).

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

View Original Abstract

Nitrogen-vacancy (NV) centers in diamond can be used for nanoscale sensing\nwith atomic resolution and sensitivity; however, it has been observed that\ntheir properties degrade as they approach the diamond surface. Here we report\nthat in addition to degraded spin coherence, NV centers within nanometers of\nthe surface can also exhibit decreased fluorescence contrast for optically\ndetected electron spin resonance (OD-ESR). We demonstrate that this decreased\nOD-ESR contrast arises from charge state dynamics of the NV center, and that it\nis strongly surface-dependent, indicating that surface engineering will be\ncritical for nanoscale sensing applications based on color centers in diamond.\n