Large Room Temperature Bulk DNP of $^{13}$C via P1 Centers in Diamond

TL;DR

This study demonstrates large room-temperature DNP enhancements of bulk $^{13}$C in diamond using P1 centers, enabling improved NMR sensitivity at ambient conditions.

Contribution

It presents the first large-scale room-temperature DNP of bulk $^{13}$C in diamond via P1 centers at 3.34 T, with detailed spectral analysis and enhancement techniques.

Findings

Achieved over 100-fold DNP enhancement of $^{13}$C signals.

Identified multiple DNP mechanisms including Overhauser and solid effect.

Frequency-chirped excitation improves enhancements and spectral features.

Abstract

We use microwave-induced dynamic nuclear polarization (DNP) of the substitutional nitrogen defects (P1 centers) in diamond to hyperpolarize bulk $^{13}$C nuclei in both single crystal and powder samples at room temperature at 3.34 T. The large ($>100$-fold) enhancements demonstrated correspond to a greater than 10,000 fold improvement in terms of signal averaging of the 1\% abundant $^{13}$C spins. The DNP was performed using low-power solid state sources under static (non-spinning) conditions. The DNP spectrum (DNP enhancement as a function of microwave frequency) of diamond powder shows features that broadly correlate with the EPR spectrum. A well-defined negative Overhauser peak and two solid effect peaks are observed for the central ($m_I=0$) manifold of the $^{14}$N spins. Previous low temperature measurements in diamond had measured a positive Overhauser enhancement in this manifold. Frequency-chirped millimeter-wave excitation of the electron spins is seen to significantly improve the enhancements for the two outer nuclear spin manifolds ($m_I = \pm 1$) and to blur some of the sharper features associated with the central manifolds. The outer lines are best fit using a combination of the cross effect and a truncated cross effect -- which is known to mimic features of an Overhauser effect. Similar features are also observed in experiments on single crystal samples. The observation of all of these mechanisms in a single material system under the same experimental conditions is likely due to the significant heterogeneity of the high pressure, high temperature (HPHT) type Ib diamond samples used. Large room temperature DNP enhancements at fields above a few Tesla enable spectroscopic studies with better chemical shift resolution under ambient conditions.