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Identification and Reversible Optical Switching of NV+ Centers in Diamond

MetadataDetails
Publication Date2025-03-30
JournalAdvanced Functional Materials
AuthorsMarcel Dickmann, Lucian Mathes, Ricardo Helm, Vassily Vadimovitch Burwitz, Werner Egger
InstitutionsHelmholtz-Zentrum Dresden-Rossendorf, Technical University of Munich
Citations1
AnalysisFull AI Review Included

This research successfully identifies and characterizes the positively charged nitrogen-vacancy (NV+) center, often referred to as the ‘dark state’, in diamond using advanced positron annihilation spectroscopy (PAS).

  • NV+ Detection and Switching: NV+ centers, which are optically inactive and do not trap positrons, were indirectly detected by observing their light-induced charge transition to the positron-trapping neutral state (NV0).
  • Quantified Transition Energy: The threshold photon energy required for the NV+ to NV0 charge transition was experimentally determined to be 1.234(8) eV.
  • Metastability Confirmed: The light-induced NV0 state was found to be metastable, decaying back to the initial NV+ state when stored in complete darkness.
  • Decay Time Constant: The characteristic decay time (t1/e) for the NV0 state to revert to NV+ in darkness was quantified as 1.73(22) h.
  • Methodological Advancement: The study validates the use of Positron Annihilation Spectroscopy (PALS) combined with in situ monochromatic light illumination as a unique tool for investigating charge dynamics in deep-level defects like NV centers.
  • Engineering Relevance: This precise knowledge of NV+ properties and charge switching dynamics is critical for developing robust quantum circuits and long-lived quantum data storage devices based on diamond NV centers.
ParameterValueUnitContext
Sample MaterialSingle crystal CVD diamondN/A(100) orientation, low impurities (N < 5 ppb, B < 1 ppb).
N+ Implantation Energy0.5MeVUsed to create NV centers.
N+ Implantation Fluence1.0 ¡ 1014cm-2Chosen to achieve high NV concentration.
Post-Implantation Annealing1200°CPerformed for 2 h to activate NV centers.
NV+ to NV0 Transition Energy1.234(8)eVExperimentally determined threshold photon energy.
NV0 Decay Time (t1/e)1.73(22)hCharacteristic decay time back to NV+ in darkness.
Experimental Positron Lifetime (NV0/NV-)145(12)psLifetime component observed after annealing and switching.
DFT Calculated Positron Lifetime (NV0)141psCalculated lifetime for a positron trapped in a neutral NV center.
DFT Calculated Positron Lifetime (NV-)139psCalculated lifetime for a positron trapped in a negative NV center.
PALS Illumination Wavelength940nmCorresponds to 1.3 eV photons used for switching.
PALS Illumination Intensity2.5 ¡ 1015photons s-1cm-2Nominal intensity used during in situ PALS measurements.
  1. Sample Preparation (Implantation and Annealing):

    • Single crystal CVD diamond was irradiated with 0.5 MeV N+ ions at a fluence of 1.0 ¡ 1014 cm-2 at room temperature.
    • The sample was subsequently annealed at 1200 °C for 2 h to mobilize vacancies and form NV centers (N-V complexes).
  2. Positron Annihilation Lifetime Spectroscopy (PALS):

    • PALS was performed using the Mono-energetic Positron Spectroscopy (MePS) setup at the ELBE facility (HZDR).
    • Measurements were conducted at 4 keV and 12 keV positron implantation energies, corresponding to mean depths of 82 nm and 596 nm, respectively, to probe different defect regions.
    • PALS spectra were analyzed using a free-fit model to extract distinct lifetime components (τi) and their intensities (Ii), which were correlated with DFT calculations for specific defect types (bulk, NV0, NV-, vacancy clusters).
  3. Density Functional Theory (DFT) Calculations:

    • Two-Component Density Functional Theory (TC-DFT) using the ABINIT software package was employed.
    • Calculations determined the theoretical positron lifetimes for bulk diamond, mono-vacancies (V1), di-vacancies (V2), vacancy clusters (Vn), and NV centers (NV0, NV-) to aid experimental interpretation.
  4. In Situ Light Illumination and Spectroscopy:

    • Doppler-Broadening Spectroscopy (DBS): Used a 12 keV positron beam to measure the S parameter (lineshape parameter) as a function of illuminating photon energy (1.1 - 1.4 eV).
    • Threshold Determination: A sharp step-like increase in the S parameter identified the NV+ to NV0 charge transition threshold at 1.234 eV.
    • Decay Measurement: The sample was illuminated (e.g., 1.25 eV photons) and then measured in complete darkness to monitor the time-dependent decrease of the S parameter, yielding the decay time of the metastable NV0 state.

The precise characterization and control of the NV+ state are crucial for advancing diamond-based quantum technologies:

  • Quantum Data Storage and Memory: NV+ centers can be used as spin coherence storage for long-lived nuclear spin states due to the absence of an electronic spin. This enables high-fidelity, long-entanglement times necessary for quantum memory elements.
  • Scalable Quantum Computing: The ability to individually switch single NV centers between NV+ and NV-/NV0 states using light or bias voltage provides a novel scheme for building fully scalable quantum computers.
  • Quantum Networks: Controlled charge state switching is fundamental for initializing, reading out, and coupling NV centers, which are essential components in quantum network nodes.
  • Defect Engineering in Diamond: The methodology provides a powerful non-optical technique for characterizing deep-level defects, allowing material engineers to optimize implantation and annealing recipes to maximize the yield of specific NV charge states (NV+, NV0, or NV-) required for target applications.
  • High-Purity Diamond Substrates: The findings inform the required Fermi level control (e.g., through boron doping) necessary to stabilize the NV+ state in high-purity CVD diamond used for advanced quantum devices.
View Original Abstract

Abstract Positive nitrogen‐vacancy centers (NV + ) in diamond are predicted to exist in conjunction with neutral (NV 0 ) and negative (NV − ) centers. However, the existence of NV + has only been indirectly inferred through a shift of the Fermi level. Evidence of NV + coexisting with NV 0 and NV - in diamond has not yet been observed. In this paper, positron annihilation spectroscopy in combination with in situ light illumination is applied, in order to investigate the presence of NV + centers in nitrogen implanted and subsequently annealed diamond. Switching of NV + to NV 0 centers is observed with a threshold photon energy of 1.234(8) eV. In complete darkness, a decay of NV 0 centers with a decay time of 1.73(22) h can be detected. In conclusion, previously converted NV 0 centers are metastable and partially decay in darkness, leading to the reformation of NV + centers.