The charge degree of freedom in solid-state defects fundamentally underpins the electronic spin degree of freedom, a workhorse of quantum technologies. Here we measure, analyze, and control charge-state behavior in individual near-surface nitrogen-vacancy (NV) centers in diamond, where NV^{-} hosts the metrologically relevant electron spin. We find that NV^{-} initialization fidelity varies between individual centers and over time; we alleviate the deleterious effects of reduced NV^{-} initialization fidelity via logic-based initialization. Importantly, we also show that NV^{-} can ionize in the dark on experimentally relevant timescales, and we introduce measurement protocols that mitigate the compromising effects of charge conversion on spin measurements. We identify tunneling to a single local electron trap as the mechanism for ionization in the dark, and we develop novel NV-assisted techniques to control and read out the trap charge state. Our understanding and command of the NV's local electrostatic environment will simultaneously guide materials design and provide unique functionalities with NV centers.
The charge degree of freedom in solid-state defects fundamentally underpins the electronic spin degree of freedom, a workhorse of quantum technologies. Here we measure, analyze, and control charge-state behavior in individual near-surface nitrogen-vacancy (NV) centers in diamond, where NV^{-} hosts the metrologically relevant electron spin. We find that NV^{-} initialization fidelity varies between individual centers and over time; we alleviate the deleterious effects of reduced NV^{-} initialization fidelity via logic-based initialization. Importantly, we also show that NV^{-} can ionize in the dark on experimentally relevant timescales, and we introduce measurement protocols that mitigate the compromising effects of charge conversion on spin measurements. We identify tunneling to a single local electron trap as the mechanism for ionization in the dark, and we develop novel NV-assisted techniques to control and read out the trap charge state. Our understanding and command of the NV's local electrostatic environment will simultaneously guide materials design and provide unique functionalities with NV centers.
The charge state stability of nitrogen-vacancy (NV) centers critically affects their application as quantum sensors and qubits. Understanding charge state conversion and equilibration is important not only for NV centers in diamond but also for defects and impurities in wide-bandgap materials in general. The mechanisms by which these centers change charge state upon optical or electronic excitation without the presence of mobile carriers remain unclear. Here, we elucidate this issue for the case of photoionization of NV center ensembles. Using pump-probe spectroscopy, we ionize negatively charged NV centers and monitor the recovery of NV^{-} on timescales of up to several seconds. We find that the recovery rate depends strongly on the concentration of surrounding nitrogen donors. Remarkably, the equilibration dynamics exhibit no discernible dependence on temperature, ruling out thermally activated processes. We develop a multiphonon-assisted electron-tunneling model, supported by density-functional calculations, that explains the measurements and identifies tunneling as the equilibration mechanism. Because tunneling rates depend exponentially on donor separation, the random distribution of nitrogen donors spreads recovery times from nanoseconds to hours or longer.
Nitrogen vacancy (NV) centers in diamond have been identified over the past few years as promising systems for a variety of applications, ranging from quantum information science to magnetic sensing. This relies on the unique optical and spin properties of the negatively charged NV. Many of these applications require shallow NV centers, i.e., NVs that are close (a few nm) to the diamond surface. In recent years there has been increasing interest in understanding the spin and charge dynamics of NV centers under various illumination conditions, specifically under infrared (IR) excitation, which has been demonstrated to have significant impact on the NV centers' emission and charge state. Nevertheless, a full understanding of all experimental data is still lacking, with further complications arising from potential differences between the photodynamics of bulk and shallow NVs. Here we suggest a generalized quantitative model for NV center spin- and charge-state dynamics under both green and IR excitation. We experimentally extract the relevant transition rates, providing a comprehensive model which reconciles all existing experimental results in the literature, except for highly nonlinear regimes. Moreover, we identify key differences between the photodynamics of bulk and shallow NVs, and use them to significantly enhance the initialization fidelity of shallow NVs to the useful negatively charged state.
In recent years, defect centers in wide band gap semiconductors such as diamond, have received significant attention. Defects offer great utility as single photon emitters, nanoscale sensors, and quantum memories and registers for quantum computation. Critical to the utility of these defects, is their charge state. In this dissertation, experiments surrounding the charge state dynamics and the carrier dynamics are performed and analyzed. Extensive studies of the ionization and recombination processes of defects in diamond, specifically, the Nitrogen Vacancy (NV) center, have been performed. Diffusion of ionized charge carriers has been imaged indirectly through the recapture of said carriers by optically active defects such as the NV center and the Silicon Vacancy (SiV) center. With proper understanding of the carrier dynamics, diamond stands to be a strong competitor in the field of spintronics for quantum information processing. Additionally, the understanding of these charge state dynamics is utilized in a novel proof of principle experiment, showing that the NV center defect’s charge state could serve as an ultra-dense 3D memory platform. The NV center has also been used as a nanoscale magnetometer. The high degree of spin polarization and the ease of manipulation of the NV allows us to transfer this polarization to other spins in the diamond and assists in the detection of spins outside of the diamond. Ensembles of Nitrogen Vacancy centers can be used to perform NMR spectroscopy of sample volumes not achievable through traditional methods. The operating mechanisms of the magnetic resonance aspects of the NV center will be discussed in depth. Work surrounding the control and polarization of the NV center’s host nitrogen spin will be covered. The topic of sensitivity and methods to improve that sensitivity will be covered as well.
Although the spin properties of superficial shallow nitrogen-vacancy (NV) centers have been the subject of extensive scrutiny, considerably less attention has been devoted to studying the dynamics of NV charge conversion near the diamond surface. Using multicolor confocal microscopy, here we show that near-surface point defects arising from high-density ion implantation dramatically increase the ionization and recombination rates of shallow NVs compared to those in bulk diamond. Further, we find that these rates grow linearly, not quadratically, with laser intensity, indicative of single-photon processes enabled by NV state mixing with other defect states. Accompanying these findings, we observe NV ionization and recombination in the dark, likely the result of charge transfer to neighboring traps. Despite the altered charge dynamics, we show that one can imprint rewritable, long-lasting patterns of charged-initialized, near-surface NVs over large areas, an ability that could be exploited for electrochemical biosensing or to optically store digital data sets with subdiffraction resolution.
Control of charge-state stability in near-surface quantum defects is critical for nanoscale sensing, yet remains particularly challenging under ultra-high vacuum (UHV), where surface-induced band bending destabilizes the metrologically relevant charge-state. Here, we present a robust and reproducible approach for stabilizing shallowly implanted (< 10 nm deep) nitrogen-vacancy (NV) centers in near-UHV conditions (P = 3×10−9 mbar) based on dielectric interface engineering. Through measurements on individually addressable NV centers, we demonstrate that a TiO2 coating on the diamond suppresses surface-induced electrostatic fields, yielding a 79% increase n NV- population and a 45% enhancement in NV-spin resonance contrast at room temperature. Coherent control measurements further reveal suppressed charge-state conversion dynamics. These results establish dielectric screening as a powerful and reproducible strategy to engineer charge transition energetics of NV centers in scanning-probe-compatible geometries under extreme conditions.
Nitrogen vacancy (NV) centers in diamond exhibit long spin coherence times, optical initialization, and optical spin readout under ambient conditions, making them excellent quantum sensors. However, the conventional scheme for charge state initialization based on off-resonant green excitation results in significant state preparation errors, typically around 30%. One method for improving charge state initialization fidelity is to use multicolor excitation, which has been demonstrated to achieve a near-unity preparation fidelity for bulk NV centers by using a few milliseconds of near-infrared (5 mW) and green (10 μW) excitation. The translation of such schemes to NV centers near the diamond surface with higher efficiency optical pumping would enable myriad tasks in nanoscale sensing. Here, we demonstrate a protocol for efficient charge initialization of shallow NV centers between 5 nm and 15 nm from the diamond surface. By carefully studying the charge dynamics of shallow NV centers, we identify a region of parameter space that allows for near-unity (95%) charge initialization within 300 μs of near-infrared (1 mW) and green (10 μW) excitation. The time to 90% charge initialization can be as fast as 10 μs for 4 mW of near-infrared and 39 μW of green illumination. This fast, efficient charge initialization protocol will enable nanoscale sensing applications where state preparation errors currently prohibit scaling, such as measuring higher-order multi-point correlators.