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Depth-dependent decoherence caused by surface and external spins for NV centers in diamond

MetadataDetails
Publication Date2017-12-29
JournalPhysical review. B./Physical review. B
AuthorsWenlong Zhang, Jian Zhang, Junfeng Wang, Fupan Feng, Shengran Lin
InstitutionsChinese Academy of Sciences, University of Science and Technology of China
Citations23
AnalysisFull AI Review Included

Technical Analysis and Commercial Solutions Brief: Depth-Dependent NV Decoherence

Section titled “Technical Analysis and Commercial Solutions Brief: Depth-Dependent NV Decoherence”

6CCVD Reference Document: QST-2017-NV-Decoherence-Depth


This research establishes a critical quantitative relationship between the depth of negatively charged Nitrogen-Vacancy (NV) centers in diamond and their spin coherence time ($T_2$), particularly when interacting with external spin baths. The findings are essential for optimizing ultra-shallow NV sensors required for nanoscale magnetic and electric field detection.

  • Core Achievement: Demonstrated the capability to track the $T_2$ coherence time of the exact same single NV center as its depth was precisely reduced step-by-step using nanoscale ICP RIE etching. This eliminates variables associated with internal adjacent environments.
  • Material Requirement: Experiments required high-purity, electronic-grade Single Crystal Diamond (SCD) with extremely low nitrogen ([N]<5ppb) and carbon-13 ([13C]=1.1%) impurity concentrations to maximize initial $T_2$.
  • Characteristic Depth Found: Identified a characteristic depth ($d_0 \approx 6$ nm) where external spins (nuclear or electronic) cause the relatively strongest decoherence, providing a design threshold for optimizing shallow NV sensor performance.
  • Methodology: NV centers were formed via 50 keV N2+ ion implantation, annealed at 1050 °C, and progressively brought closer to the surface via highly controlled, efficient Inductively Coupled Plasma Reactive Ion Etching (ICP RIE) at a rate of 11.8 $\pm$ 1 nm/min.
  • External Spin Effects: Measured decoherence influence from external nuclear spins (immersion oil) and external electronic spins (Cu2+ solution), confirming that electronic spins cause stronger decoherence, especially near the characteristic depth.
  • Commercial Relevance: Validates the critical necessity of ultra-high quality SCD substrates and precision nanoscale etching for the next generation of solid-state quantum sensing devices.

ParameterValueUnitContext
Diamond GradeElectronic Grade (100)N/ASubstrate orientation
Substrate Dimensions2 x 2 x 0.5mm3Sample size
Nitrogen Impurity ([N])< 5ppbSpecified purity from Element Six
Carbon-13 Isotope ([13C])1.1%Natural abundance spin bath
Implantation Energy50keVN2+ molecule energy for NV creation
Implantation Fluence0.65 x 101114N2+ per cm2Nitrogen dose
Annealing Temperature1050°CRequired temperature for NV formation
Annealing Environment2 x 10-5PaHigh vacuum condition
Etching MethodICP RIEN/AOxford PlasmaPro NGP80 machine
ICP Power200WRIE plasma parameter
Chamber Pressure30mTorrRIE process parameter
Gas Flow (Oxygen)10sccmO2 flow rate
Gas Flow (Argon)5sccmAr flow rate
Average Etching Rate11.8 $\pm$ 1nm/minHighly controlled removal rate
Characteristic Depth ($d_0$)~6nmDepth for minimum coherence time ratio (strongest external decoherence)
Magnetic Field (B)55 $\pm$ 5GApplied field for spin measurement (paralleling NV center axes)
Coherence Time (Deep NV)214.1”sInitial $T_{2,air}$ at $d \sim 38$ nm
Coherence Time (Shallow NV)6.84”sFinal $T_{2,air}$ at $d \sim 2$ nm

The highly precise depth profiling and NV tracking relied on specialized material preparation and controlled plasma etching:

  1. Substrate Preparation:

    • Used electronic-grade (100) SCD (2 x 2 x 0.5 mm3) with low impurities ([N]<5ppb, [13C]=1.1%).
    • Coated surface with 300 nm Polymethyl Methacrylate (PMMA).
  2. NV Center Patterning and Formation:

    • Electron beam lithography was used to pattern arrays of 60 nm diameter apertures and 2 ”m wide vacant strips (serving as position markers) onto the PMMA mask.
    • Ion implantation performed using 50 keV N2+ through the mask.
  3. Post-Implantation Processing:

    • Annealing conducted at 1050 °C in high vacuum (2 x 10-5 Pa) for 2 hours to activate NV centers.
    • Thermal oxidation (430 °C in air for 2 h) and rigorous acid cleaning (sulfuric, nitric, perchloric acid 1:1:1) at 200 °C were performed to remove surface contaminants.
  4. Controlled Depth Etching (ICP RIE Recipe):

    • Plasma etching performed using an Oxford PlasmaPro NGP80 reactor.
    • Recipe: 200 W ICP power, 30 mTorr chamber pressure, 10 sccm O2, and 5 sccm Ar.
    • The etching rate was precisely calibrated (11.8 $\pm$ 1 nm/min) using AFM analysis to ensure accurate depth control.
  5. Spin Decoherence Measurement:

    • Fluorescence images (using position marks) tracked the exact same NV center through multiple etching steps (0 nm, 20 nm, 44 nm, etc.).
    • Spin echo measurements were conducted before ($T_{2,air}$) and after applying external spin baths (T2,oil or T2,Cu2+) at each depth interval.

The findings in this paper underscore the critical role of ultra-pure, precisely manufactured diamond substrates in advancing quantum technology, particularly in achieving shallow, high-coherence NV centers for robust sensing applications. 6CCVD is uniquely positioned to supply materials that meet or exceed the demanding specifications required for this research.

To replicate or extend this research, the highest quality diamond material is paramount. 6CCVD recommends:

  • Optical Grade Single Crystal Diamond (SCD): Required for achieving maximum initial $T_2$ coherence times. Our SCD wafers feature superior crystal quality necessary for post-processing steps like ion implantation and annealing.
  • Ultra-Low Nitrogen/Low [13C] Substrates: 6CCVD focuses on MPCVD growth capable of delivering SCD with impurity levels commensurate with or better than the commercial electronic grade material used in the study, ensuring high spin coherence.
  • Precision Polishing (Surface Engineering): The paper highlights the dependence of decoherence on surface spins. 6CCVD provides SCD polishing down to Ra < 1 nm, which is essential for maximizing the performance and predictability of ultra-shallow NV centers (d < 10 nm).

6CCVD’s in-house capabilities directly address the manufacturing challenges implied by this cutting-edge research:

Requirement from Paper/Field6CCVD Specific CapabilityTechnical Advantage
Custom Wafer SizePlates/wafers up to 125 mm (PCD), and large format SCD.Supports scale-up from lab samples (2x2 mm3) to industrial, inch-sized quantum devices.
Precise Depth ControlSCD Thickness control from 0.1 ”m up to 500 ”m.Ideal for manufacturing substrates with precisely tailored active layers or specialized membranes.
Electrode Integration (Future Devices)Full internal metalization capability: Au, Pt, Pd, Ti, W, Cu.Enables direct integration of quantum devices with on-chip microwave and control electrodes (e.g., for applying RF fields or mitigating electric field noise).
Patterning & IsolationCustom laser cutting and patterning services.Allows creation of the micro-scale mesas, trenches, or protected reference areas required for targeted ICP RIE etching and high-density NV arrays.

The discovery of the characteristic depth ($d_0$) depending on surface spin density ($\sigma$) requires careful material selection and surface preparation. 6CCVD’s in-house PhD team can provide specialized technical consultation covering:

  • Optimizing substrate selection (e.g., nitrogen concentration, crystal orientation) for specific Quantum Sensing projects.
  • Consulting on surface treatments and cleaning protocols to minimize $\sigma$ and thus lower $d_0$, enabling more sensitive External Spin Detection projects (e.g., detecting electronic spins in biological samples or materials science).
  • Guidance on material requirements for high-temperature Annealing processes (up to 1200 °C) post-implantation.

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

View Original Abstract

By efficient nanoscale plasma etching, the nitrogen-vacancy (NV) centers in diamond were brought to the sample surface step by step successfully. At each depth, we used the relative ratios of spin coherence times before and after applying external spins on the surface to present the decoherence, and investigated the relationships between depth and ratios. The values of relative ratios declined and then rised with the decreasing depth, which was attributed to the decoherence influenced by external spins, surface spins, discrete surface spin effects and electric field noise. Moreover, our work revealed a characteristic depth at which the NV center would experience relatively the strongest decoherence caused by external spins in consideration of inevitable surface spins. And the characteristic depth was found depending on the adjacent environments of NV centers and the density of surface spins.