Hyper-polarization of nuclear spins is crucial for advancing nuclear magnetic resonance (NMR) and quantum information technologies, as nuclear spins typically exhibit extremely low polarization at room temperature due to their small gyro-magnetic ratios. A promising approach to achieving high nuclear spin polarization is transferring the polarization of electron to nuclear spin. The nitrogen-vacancy (NV) center in diamond has emerged as a highly effective medium for this purpose, and various hyper-polarization protocols have been developed. Among these, the pulsed polarization (PulsePol) method has been extensively studied due to its robustness against static energy shifts of the electron spin. In this study, we introduce a sequential polarization protocol and identify a series of magic and digital sequences for hyper-polarizing nuclear spins. Notably, we demonstrate that some of these magic sequences exhibit significantly greater robustness compared to the PulsePol protocol in the presence of finite half $π$ pulse duration of the protocol. This enhanced robustness positions our protocol as a more suitable candidate for hyper-polarizing nuclear spins species with large gyromagnetic ratios and also ensures better compatibility with high-efficiency readout techniques at high magnetic fields. Additionally, the generality of our protocol allows for its direct application to other solid-state quantum systems beyond the NV center.
Hyper-polarization of nuclear spins is crucial for advancing nuclear magnetic resonance (NMR) and quantum information technologies, as nuclear spins typically exhibit extremely low polarization at room temperature due to their small gyro-magnetic ratios. A promising approach to achieving high nuclear spin polarization is transferring the polarization of electron to nuclear spin. The nitrogen-vacancy (NV) center in diamond has emerged as a highly effective medium for this purpose, and various hyper-polarization protocols have been developed. Among these, the pulsed polarization (PulsePol) method has been extensively studied due to its robustness against static energy shifts of the electron spin. In this study, we introduce a sequential polarization protocol and identify a series of magic and digital sequences for hyper-polarizing nuclear spins. Notably, we demonstrate that some of these magic sequences exhibit significantly greater robustness compared to the PulsePol protocol in the presence of finite half π pulse duration of the protocol. This enhanced robustness positions our protocol as a more suitable candidate for hyper-polarizing nuclear spins species with large gyromagnetic ratios and also ensures better compatibility with high-efficiency readout techniques at high magnetic fields. Additionally, the generality of our protocol allows for its direct application to other solid-state quantum systems beyond the NV center.
Abstract Hyperpolarization of nuclear spins is crucial for advancing nuclear magnetic resonance and quantum information technologies, as nuclear spins typically exhibit extremely low polarization at room temperature due to their small gyromagnetic ratios. A promising approach to achieving high nuclear spin polarization is transferring the polarization of electrons to nuclear spins. The nitrogen-vacancy (NV) center in diamond has emerged as a highly effective medium for this purpose, and various hyperpolarization protocols have been developed. Among these, the pulsed polarization (PulsePol) method has been extensively studied due to its robustness against static energy shifts of the electron spin. In this work, we present a novel polarization protocol and uncover a family of magic sequences for hyperpolarizing nuclear spins, with PulsePol emerging as a special case of our general approach. Notably, we demonstrate that some of these magic sequences exhibit significantly greater robustness compared to the PulsePol protocol in the presence of finite half π pulse duration of the protocol, Rabi and detuning errors. This enhanced robustness positions our protocol as a more suitable candidate for hyper-polarizing nuclear spins species with large gyromagnetic ratios and also ensures better compatibility with high-efficiency readout techniques at high magnetic fields. Additionally, the generality of our protocol allows for its direct application to other solid-state quantum systems beyond the NV center.
PulsePol is an elegantly designed pulse-sequence-based quantum control scheme that enables polarization transfer between electron and nuclear spins, for example, in nitrogen-vacancy (NV) centers. However, previous analyses of PulsePol assumed very strong, near-ideal, instantaneous microwave pulses, which is rarely achievable at higher magnetic fields. We revisit the PulsePol scheme under finite-pulse constraints and show that its performance significantly degrades due to finite-pulse effects. Using bimodal Floquet theory, we identify the symmetry-breaking mechanism responsible for this deterioration in fidelity. By phase adjustment, we reestablish the proper symmetry of the interaction-frame spin Hamiltonian, leading to a sequence called Q-PulsePol, where "Q" reflects the restored quadrature symmetry. Our results demonstrate robustness to finite-pulse effects and improved polarization transfer efficiency, establishing Q-PulsePol as a practical and reliable scheme for bulk hyperpolarization of nuclear spins in solids using a single-mode (zero-quantum or double-quantum) transfer. This work bridges idealized quantum control with realistic pulse engineering, establishing design rules for spin-based quantum control protocols.
Diamond-based quantum sensors have enabled high-resolution NMR spectroscopy at the microscale in scenarios where fast molecular motion averages out dipolar interactions among target nuclei. However, in samples with low-diffusion, ubiquitous dipolar couplings challenge the extraction of relevant spectroscopic information. In this work we present a protocol that enables the scanning of nuclear spins in dipolarly-coupled samples at high magnetic fields with a sensor based on nitrogen vacancy (NV) ensembles. Our protocol is based on the synchronized delivery of radio frequency (RF) and microwave (MW) radiation to eliminate couplings among nuclei in the scanned sample and to efficiently extract target energy-shifts from the sample's magnetization dynamics. In addition, the method is designed to operate at high magnetic fields leading to a larger sample thermal polarization, thus to an increased NMR signal. The precision of our method is ultimately limited by the coherence time of the sample, allowing for accurate identification of relevant energy shifts in solid-state systems.
Microwave-Free 13C Hyperpolarization of Diamond Particles Enabled by Magic Angle Spinning and NV Centers
Nuclear hyperpolarization from optically pumped color centers in solids offers an alternative to conventional microwave-driven dynamic nuclear polarization (DNP). Diamond can host the nitrogen vacancy (NV) center, whose ground spin state can be readily polarized by light at room temperature, making diamond a candidate platform for nuclear hyperpolarization. We report 13C nuclear hyperpolarization in randomly oriented diamond particles with sizes ranging from 0.2 to 2 μm, both at natural 13C abundance (1.1 %) and at 20 % isotopic enrichment, at magnetic fields of 7.1 T and 9.4 T. The protocol combines optical illumination with magic angle spinning (MAS) and does not require microwave irradiation. By investigating the nuclear polarization as a function of the MAS frequency between 0 and 6 kHz at the magnetic field of 7.1 T, we find maximum light-induced polarization enhancements of 280-fold for the isotopically enriched sample and 411-fold for the natural abundance sample. Under continuous illumination, steady-state absolute 13C polarization levels above 0.1 % are reached. A model involving optical pumping of NV centers and spin dynamics near level anticrossings (LACs) in three-spin clusters formed by NV, a substitutional nitrogen (P1) and 13C is used to describe these findings. The protocol strongly mitigates the effect of the anisotropy of the NV spin Hamiltonian, allowing more than 99.9% of NV orientations to participate in the polarization transfer process. These results represent a first step toward transferring nuclear polarization from diamond particles to external nuclei, with potential applications in sensitive and high-resolution NMR at room temperature.
A negatively-charged nitrogen-vacancy (NV) center in diamond is a promising system for quantum computation and quantum information. It has the diamond structure with a substitutional nitrogen atom and a neighboring vacancy. An electron spin in the NV center has an exceptionally long coherence time at room temperature. Thus the NV center has a potential to realize a room-temperature quantum computer which is more efficient than a classical computer. In this dissertation, we focus on the nitrogen nuclear spin as well as the electron spin in the NV center. Every NV center has the nitrogen nuclear spin. Because of the long coherence time of the nitrogen nuclear spin, it is a good candidate for a quantum memory. Thus it is important to prepare the nitrogen nuclear spin qubit in a given pure state for quantum computation. We provide a theoretical understanding of the popular nuclear spin initialization technique. Furthermore, we propose an optimal condition for the initialization of the nitrogen nuclear spin by including the local strain in the NV center. We expect that this optimal condition can improve the purity of the nuclear spin initialization. We also propose an efficient quantum measurement protocol for the hyperfine interaction between the electron spin and the ¹⁵N nuclear spin in the NV center. A precise knowledge of the hyperfine interaction is important to reduce an error in a coherent control of the ¹⁵N nuclear spin. In this protocol, a sequence of quantum operations with successively increasing duration is utilized to estimate the hyperfine interaction with successively higher precision approaching the quantum metrology limit. Unlike common quantum metrological methods, this protocol does not need the preparation of the nuclear spin in a pure state. In the presence of realistic operation errors and electron spin decoherence, we show the overall precision of our protocol still surpasses the standard quantum limit
PulsePol is an elegantly designed pulse-sequence-based quantum control scheme that enables polarization transfer between electron and nuclear spins. However, previous analyses of PulsePol assumed very strong, close to ideal, instantaneous microwave pulses, which is rarely achievable as one goes to higher magnetic fields. We revisit the PulsePol scheme under finite-pulse constraints and show that its performance significantly degrades because of finite-pulse effects. Using bimodal Floquet theory, we identify the symmetry-breaking mechanism responsible for this deteriorating fidelity. By phase adjustment, we reestablish the proper symmetry of the interaction-frame spin Hamiltonian—leading to a sequence called Q-PulsePol, where ‘Q’ reflects the restored quadrature symmetry. Our results demonstrate robustness to finite-pulse effects and improved polarization transfer efficiency, establishing Q-PulsePol as a practical and reliable scheme for bulk hyperpolarization of nuclear spins in solid-state using a single-mode (zero-quantum or double-quantum) transfer. This work bridges idealized quantum control with realistic pulse engineering, establishing design rules for spin-based quantum-control protocols.