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Shallow Nitrogen Vacancy Color Centers in Diamond by Ion Implantation

MetadataDetails
Publication Date2025-06-11
JournalAdvanced Quantum Technologies
AuthorsG. Speranza, Alessandro Cian, B. Perlingeiro CorrĂȘa, Elena Missale, Andrea Pedrielli
InstitutionsFondazione Bruno Kessler, Netherlands Organisation for Applied Scientific Research
AnalysisFull AI Review Included

This research details a controlled fabrication method for creating shallow Nitrogen-Vacancy (NV) color centers in diamond, critical for high-sensitivity quantum sensing applications.

  • Core Achievement: Successful creation of NV defects concentrated in the first 0-30 nm subsurface layer of pure Chemical Vapor Deposition (CVD) diamond, with peak nitrogen concentration confirmed to be within the first 5 nm.
  • Methodology: Broad-beam 30 keV N+ ion implantation was performed through a 100 nm Plasma-Enhanced CVD (PECVD) SiO2 screening layer, which effectively reduced ion penetration depth and suppressed channeling.
  • Depth Control: Oblique incidence (45°) implantation (Sample D2) achieved a shallower projected range (Rp < 2.6 nm) compared to near-normal incidence (7°, Rp < 5 nm), as predicted by SRIM simulations.
  • Charge State Control: Shallower centers (D2) exhibited a higher NV0/NV- ratio (0.9 ± 0.2), confirming increased charge neutralization due to stronger interaction with surface acceptor states.
  • PL Intensity: The near-normal incidence sample (D1) showed significantly higher overall Photoluminescence (PL) intensity (150.2 kcts s-1 average) compared to the shallower D2 sample (16.3 kcts s-1 average).
  • Characterization: Angle-Resolved X-ray Photoelectron Spectroscopy (ARXPS) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) qualitatively confirmed the surface enrichment of nitrogen.
ParameterValueUnitContext
Substrate MaterialElectronic Grade Single CrystalDiamondN background <5 ppb
Screening Layer Thickness100 ± 2nmPECVD SiO2
Implantation Energy30keVN+ ions
Total N+ Fluence9.0 x 1014ions cm-2Applied to SiO2/Diamond
Incidence Angle (D1)7degreesNear-normal
Incidence Angle (D2)45degreesOblique
Annealing Conditions1000°C3 hours, 10-6 mbar vacuum
Predicted N Peak Concentration (D1)~2.0 x 1020at cm-3At diamond surface
Predicted N Projected Range (D2)0-2.6nmShallower distribution
Measured N Depth (ARXPS Max)3.4 (D1) / 3.15 (D2)nmEstimated using Maximum Entropy Method
NV- Zero-Phonon Line (ZPL)~637nmCharged NV state
NV0 Zero-Phonon Line (ZPL)~575nmNeutral NV state
Average PL Intensity (D1)150.2 ± 95.7kcts s-1Confocal PL map (7° incidence)
Average PL Intensity (D2)16.3 ± 8.2kcts s-1Confocal PL map (45° incidence)
NV0/NV- Ratio (D2)0.9 ± 0.2unitlessHigher ratio indicates surface neutralization
Graphitic Layer Thickness (D2)~6AngstromDerived from C 1s ARXPS fitting

The experimental process flow combined simulation, deposition, implantation, etching, and thermal activation, followed by multi-modal characterization:

  1. SRIM Simulation: Used to optimize the combination of 30 keV energy, 100 nm SiO2 thickness, and incidence angles (7° and 45°) to ensure the nitrogen distribution peaked at the diamond surface.
  2. SiO2 Screening Layer Deposition: A 100 nm SiO2 film was deposited on the diamond surface using PECVD to slow down the N+ ions and prevent channeling effects.
  3. N+ Ion Implantation: Broad-beam implantation was performed at 30 keV with a fluence of 9.0 x 1014 ions cm-2, utilizing both near-normal (7°) and oblique (45°) incidence angles to modulate penetration depth.
  4. SiO2 Removal: The screening layer was removed using Hydrofluoric Acid (HF) etching, a process that does not affect the diamond surface polishing.
  5. Thermal Annealing: Samples were annealed at 1000 °C for three hours in a 10-6 mbar vacuum to promote vacancy migration and subsequent trapping by substitutional nitrogen atoms, forming NV centers.
  6. Angle-Resolved XPS (ARXPS): Used to analyze surface composition (C, O, N, Si) and chemical states. Varying the take-off angle allowed for depth profiling, confirming nitrogen enrichment in the topmost surface layers (<4 nm sampling depth).
  7. ToF-SIMS Depth Profiling: Monitored the CN- species profile to confirm the trend of nitrogen concentration decrease within the first 15 nm of the diamond substrate, consistent with SRIM predictions.
  8. PL Spectroscopy: Confocal Raman/PL (515 nm laser, NA 0.9) was used to confirm the formation of both NV- (637 nm ZPL) and NV0 (575 nm ZPL) centers and to quantify the relative NV0/NV- ratio, indicating charge state stability near the surface.

The controlled fabrication of shallow NV centers is foundational for next-generation quantum technologies, particularly those requiring high spatial resolution and sensitivity near a surface.

  • Quantum Sensing (Nano-NMR): Enabling highly efficient coupling between the NV spin and external nuclear spins, allowing for nanotesla-range magnetic field detection and single-molecule Nuclear Magnetic Resonance (NMR) spectroscopy.
  • Solid-State Quantum Computing: Providing precisely localized, spectrally stable qubits (NV- centers) necessary for scalable quantum processors and simulators.
  • Nano-Thermometry: Utilizing the spin properties of shallow NV centers for high-resolution temperature mapping in microelectronic and biological systems.
  • Quantum Communication: Fabricating NV centers with stable optical transitions (lifetime-limited linewidths) for use as quantum repeaters or memory nodes in quantum networks.
  • Advanced Materials Characterization: Serving as a noninvasive, high-resolution magnetic imaging tool (scanning SQUIDs or magnetic force microscopy alternatives) for characterizing novel materials like 2D materials or topological insulators.
  • Deterministic Emitter Fabrication: The screening layer technique provides a pathway toward creating isolated, single NV centers by using extremely low fluence recipes, essential for single-photon source applications.
View Original Abstract

Abstract Recent advancements in quantum technologies are fueled by the ability to engineer materials with specific quantum properties, enabling various applications. The nitrogen‐vacancy (NV) center in diamond is a key system for nanoscale sensors, capable of detecting weak magnetic fields with nanotesla‐range sensitivity. To achieve high spatial resolution and sensitivity, NV centers must be placed near the diamond surface. This study investigates the creation of NV defects in a pure chemical vapor deposition (CVD) diamond single crystal via broad‐beam ion implantation. The implantations are performed through thin (100 nm) SiO 2 layers deposited by plasma‐enhanced CVD (PECVD). Both normal and oblique ion beam incidences are used, with the oblique incidence chosen to reduce the nitrogen ion penetration depth. Simulations show a subsurface NV center distribution, with the highest concentration near the surface; the expected trends are confirmed by angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). This distribution extends to a depth of 30 nm. By adjusting the ion beam incidence angle, NV center density can be modulated. This work contributes to optimizing the fabrication process for shallow color centers through ion implantation using a screening layer.

  1. 2013 - Second Edition, Spin Dynamics: Basics of Nuclear Magnetic Resonance