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Indirect overgrowth as a synthesis route for superior diamond nano sensors

MetadataDetails
Publication Date2020-12-29
JournalScientific Reports
AuthorsChristoph Findler, Johannes Lang, Christian Osterkamp, MiloĆĄ NeslĂĄdek, Fedor Jelezko
InstitutionsCenter for Integrated Quantum Science and Technology
Citations20
AnalysisFull AI Review Included

This research introduces “Indirect Overgrowth” as a superior synthesis route for fabricating shallow, high-coherence nitrogen-vacancy (NV-) diamond nanosensors, overcoming the significant NV loss associated with traditional direct overgrowth methods.

  • Core Value Proposition: Indirect overgrowth enables precise, nanometer-scale depth control of NV- centers while simultaneously achieving tremendously enhanced spin coherence times (T2 and T2*).
  • Mechanism Mitigation: The study identifies NV-to-NVH passivation by hydrogen diffusion during Chemical Vapor Deposition (CVD) as the primary cause of NV loss, successfully mitigating this by performing the CVD capping step before the high-temperature annealing required for NV formation.
  • Coherence Enhancement: The average coherence time (T2,avg) was increased up to five-fold (reaching 100 ”s) by burying the NV centers under a 13 nm diamond capping layer.
  • Depth Control Precision: The method allows tuning the average depth solely by adjusting the overgrowth duration, avoiding the increased damage and broader depth distribution caused by using higher implantation energies alone.
  • Kinetic Insight: Higher nitrogen implantation doses (1012 15N+/cm2) were found to slow down the NV-NVH conversion kinetics, suggesting that implanted nitrogen hinders hydrogen diffusion in the diamond lattice.
  • Depth Confinement: The resulting NV centers maintain a narrow depth distribution, uniformly shifted deeper into the crystal, which is crucial for maintaining high sensitivity while reducing surface noise.
ParameterValueUnitContext
Substrate MaterialElectronic-grade (100) diamond-99.999% 12C enriched
Implantation Species15N+-Used to distinguish from native 14NV centers
Implantation Energy (Low)2.5keVUsed for shallow NV creation
Implantation Energy (High)5.0keVUsed for comparison
Implantation Dose (Medium)101115N+/cm2Primary dose for spin property analysis
Implantation Dose (High)101215N+/cm2Used to study passivation kinetics
CVD Growth Temperature900°CTemperature during capping layer growth
UHV Annealing Temperature1000°CPost-overgrowth step for NV formation
Capping Layer Thicknesses6.5, 13nmAchieved via 1 h and 2 h overgrowth, respectively
Average Growth Rate (2.5 keV)5nm/hNV-calibrated growth rate
Average Growth Rate (5.0 keV)8nm/hNV-calibrated growth rate
Maximum Coherence Time (T2)Up to 100”sAchieved with 13 nm overgrowth (2.5 keV)
Maximum Dephasing Time (T2*)Up to 20”sAchieved after overgrowth
T2*/T2 Ratio15-20%Indicates stable spin environment post-overgrowth
Methane Concentration (Cap)0.05%12CH4 relative to H2 during capping layer growth
Working Pressure (CVD)22.5mbarCVD process parameter

The indirect overgrowth procedure involves three main stages, ensuring the nitrogen is protected from the hydrogen plasma until the NV center is buried and stabilized.

  1. Substrate Preparation and Implantation:

    • Electronic-grade (100) diamond substrates (99.999% 12C enriched) are cleaned using standard acid mixtures (nitric, sulfuric, perchloric acid) in a microwave reactor at 200 °C.
    • The substrates are implanted with 15N+ ions at low energies (2.5 or 5.0 keV) and various doses (109 to 1012 15N+/cm2) using a home-built low-energy ion implanter.
  2. CVD Overgrowth (Capping Layer Deposition):

    • The implanted samples are placed in a home-built microwave plasma CVD reactor.
    • A buffer layer (~150 nm) is grown first (0.2% 12CH4 in H2).
    • The capping layer is grown at 900 °C using ultra-low methane concentration (0.05% 12CH4 in H2) to ensure high purity and slow growth rate (average 6.5 nm/h).
    • The duration of this step (e.g., 1 hour for 6.5 nm, 2 hours for 13 nm) precisely controls the final NV depth.
  3. UHV Annealing and NV Formation:

    • After overgrowth, the samples are annealed in an Ultra High Vacuum (UHV) oven at 1000 °C for 3 hours.
    • This high-temperature step mobilizes vacancies, allowing the implanted nitrogen atoms to combine with carbon vacancies (V) to form the desired NV- centers beneath the protective capping layer.
  4. Characterization:

    • Confocal microscopy (519 nm laser excitation) is used to locate and analyze single NV- centers.
    • Pulsed Optically Detected Magnetic Resonance (ODMR) is used to confirm the 15N nucleus hyperfine splitting (3 MHz) and verify the centers are implantation-induced.
    • Depth distribution and T2* are measured using Nuclear Magnetic Resonance (NMR) sensing of 1H-spins in the immersion oil, utilizing the NV- electron spin as a sensor.
    • T2 (Hahn-echo) measurements are performed to quantify spin coherence enhancement.

The ability to reliably fabricate shallow, high-coherence NV- centers with precise depth control is critical for next-generation quantum sensing devices.

  • Quantum Metrology and Sensing:
    • Nanoscale Magnetic Field Sensing: Used for high-sensitivity detection of magnetic fields from external spins (e.g., in condensed matter physics or material characterization), where sensitivity scales inversely with the distance cubed.
    • Quantum Registers: Intermediate-depth NV- centers (10-30 nm) with long T2 times are favorable for applications involving quantum registers and dipole detection limits.
  • Life Science and Biology:
    • Nanoscale Thermometry: High-precision temperature sensing in living cells (as NV centers are sensitive to temperature changes).
    • NMR/EPR Spectroscopy: Single-spin sensitivity for Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR) spectroscopy of extremely small sample volumes (e.g., proteins or viscous liquids in microfluidic devices).
  • Material Science:
    • Strain and Electric Field Mapping: Sensing local strain and electric fields within materials or devices at the nanoscale.
    • Advanced Defect Engineering: Provides a reliable route for creating other stable color centers (e.g., tin-vacancy centers) by minimizing implantation damage and controlling the defect environment.