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Optical hyperpolarization of nitrogen donor spins in bulk diamond

MetadataDetails
Publication Date2017-02-14
JournalPhysical review. B./Physical review. B
AuthorsM. Loretz, H. Takahashi, Takuya F. Segawa, J. M. Boss, Christian L. Degen
InstitutionsETH Zurich
Citations17
AnalysisFull AI Review Included

Technical Documentation: Hyperpolarized Diamond Materials for DNP

Section titled “Technical Documentation: Hyperpolarized Diamond Materials for DNP”

Source Paper: Optical hyperpolarization of nitrogen donor spins in bulk diamond (Loretz et al., 2016/2022)

6CCVD Ref: Hyperpolarization of P1 Centers for Enhanced Dynamic Nuclear Polarization (DNP)


This study successfully demonstrates a critical step toward enhancing the efficiency of diamond-based Dynamic Nuclear Polarization (DNP) devices by hyperpolarizing bulk substitutional nitrogen (P1) defects.

  • Mechanism Demonstrated: Hyperpolarization of P1 centers (N°) achieved through optical pumping of Nitrogen-Vacancy (NVÂŻ) centers coupled via rapid cross-relaxation at an energy level matching condition ($B = 51 \text{ mT}$).
  • Performance Metrics: Achieved a substantial P1 spin polarization of 0.9%, corresponding to a robust enhancement factor of 25x relative to the thermal Boltzmann polarization.
  • Material Utilization: This approach leverages the high concentration of P1 centers (up to 77 ppm), which act as an abundant resource for high electronic spin polarization in bulk diamond.
  • Application Relevance: Hyperpolarized P1 centers form a useful resource for charge state conversion processes, significantly increasing the efficiency and feasibility of room-temperature, diamond-based DNP systems for high-sensitivity NMR.
  • Technical Challenge: The observed polarization enhancement unexpectedly saturates at very low laser intensities (~10 mW/mmÂČ), indicating the necessity of advanced defect engineering and pulsed excitation schemes to overcome charge state conversion limitations.

The following critical parameters and performance metrics were extracted from the experimental data, focusing on Chip A.

ParameterValueUnitContext
Magnetic Bias Field (B)51mTRequired for NV¯/N° cross-relaxation matching
Optical Pumping Wavelength532nmCW Green Laser Illumination
Maximum N° (P1 Center) Polarization0.9%Achieved at 300 mW laser power
N° Polarization Enhancement Factor25N/AEnhancement over Boltzmann polarization
Maximum NVÂŻ Polarization3.5%Achieved at 300 mW laser power
NVÂŻ Polarization Enhancement Factor103N/AEnhancement over Boltzmann polarization
Material UsedType Ib HPHT DiamondN/ABulk diamond material
N° (P1 Center) Density (Chip A)77ppm1020 cm-3 density achieved
NVÂŻ Center Density (Chip A)9ppmTotal density post-irradiation/annealing
Anomalous Saturation Threshold~10mW/mm2Polarization ceases to increase above this intensity
Annealing Temperature850°CRequired step for defect formation
Operating Temperature~200KAchieved via cold N2 gas flow
Chip Dimensions (Lateral)3 x 3mm2Used in the EPR setup
Chip Thickness (Chip A)0.3mmSample thickness

The experiment relied on precise material preparation, controlled defect creation, and low-frequency EPR spectroscopy.

  1. Diamond Selection: High-nitrogen (Type Ib) diamond chips grown by High-Pressure/High-Temperature (HPHT) synthesis were selected, featuring exposed (100) surfaces.
  2. Defect Creation: Samples were irradiated using a 2 MeV electron beam for a total duration of 30 h to 40 h to create vacancies, which subsequently formed NV and P1 centers upon annealing.
  3. Post-Irradiation Annealing: Annealing was performed in high vacuum at 850°C for 2 h to mobilize vacancies and convert P1 centers into NV centers (while retaining high P1 concentrations).
  4. EPR Setup: In situ Electron Paramagnetic Resonance (EPR) spectroscopy was conducted at 51 mT using a custom-built low-frequency setup (1.44 MHz) utilizing an inductively coupled loop gap resonator.
  5. Magnetic Field Orientation: The diamond crystal was precisely oriented (35° tilt, 45° rotation) to align the magnetic field along one of the [111] crystal axes, maximizing the efficiency of the optical pumping mechanism for aligned NV centers.
  6. Optical Pumping and Cooling: CW 532 nm laser light (up to 1 W) was directed onto the diamond surface. Absorptive heating was managed by flowing cold nitrogen gas (~200 K) over the chip.
  7. Polarization Transfer: Hyperpolarization was achieved by driving the cross-relaxation process between the optically pumped NV¯ centers (ms = 0 $\leftrightarrow$ ms = -1 transition) and the substitutional nitrogen defects (N°).

6CCVD provides the engineered diamond platforms required to replicate, optimize, and scale this groundbreaking work in hyperpolarization and quantum technologies. Our Microwave Plasma Chemical Vapor Deposition (MPCVD) materials offer enhanced control over crystal purity, orientation, and defect concentration compared to the HPHT material used in the study.

Applicable Materials & Requirements6CCVD Solution & CapabilityEngineering and Sales Advantage
Type Ib Material Replication (High N content, 77 ppm)High-Nitrogen SCD & PCD (Custom Doped)We offer highly controlled nitrogen incorporation during MPCVD growth, providing far greater spatial uniformity and repeatable P1 concentrations compared to bulk HPHT. This ensures consistent defect creation post-irradiation.
Precise Dimensions (3 x 3 mm2, 0.3 mm thickness)Custom Dimensions & Thickness Control6CCVD delivers SCD plates (0.1 ”m - 500 ”m) and PCD wafers up to 125 mm lateral size. We can provide materials pre-cut or laser-etched to fit specific EPR/DNP resonator geometries.
Superior Crystal Quality & Orientation ([100] surface used)High-Purity SCD (Ra < 1 nm Polishing)To minimize surface traps (which affect charge state conversion), we provide ultra-low roughness SCD (Ra < 1 nm) and precision-oriented crystals, including standard [100] and optimized [111] cuts.
Mitigating Saturation / Charge State ControlBoron-Doped Diamond (BDD) WafersThe saturation is linked to charge state conversions (NVÂŻ $\leftrightarrow$ NV°, N° $\leftrightarrow$ Nâș). Integrating BDD material into the device stack allows for electrical tuning of the Fermi level, which can suppress or mitigate undesirable charge state conversions, thereby increasing the maximum achievable polarization.
Future DNP Integration (Surface transfer / spin labels)Custom Metalization CapabilitiesFor advanced DNP devices requiring integrated control structures or micro-coils, we offer in-house metalization services, including Au, Pt, Pd, Ti, W, and Cu deposition, crucial for creating reliable surface interfaces and electrodes.
Scale-Up and Volume RequirementsGlobal Shipping & Supply ChainWe support academic and commercial partners with reliable, DDU or DDP global shipping of high-volume and custom diamond orders, reducing logistical burden for international research teams.

Engineering Support: 6CCVD’s in-house PhD team specializes in optimizing defect creation protocols (nitrogen insertion and post-growth processing) necessary for maximizing the T1 and T2 coherence times required for efficient bulk hyperpolarization and subsequent transfer in Dynamic Nuclear Polarization (DNP) projects.

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

View Original Abstract

We report hyperpolarization of the electronic spins associated with\nsubstitutional nitrogen defects in bulk diamond crystal. Hyperpolarization is\nachieved by optical pumping of nitrogen vacancy centers followed by rapid cross\nrelaxation at the energy level matching condition in a 51 mT bias field. The\nmaximum observed donor spin polarization is 0.9 \% corresponding to an\nenhancement by 25 compared to the thermal Boltzmann polarization. A further\naccumulation of polarization is impeded by an anomalous optical saturation\neffect that we attribute to charge state conversion processes. Hyperpolarized\nnitrogen donors may form a useful resource for increasing the efficiency of\ndiamond-based dynamic nuclear polarization devices.\n