Long-lived Spin Research Articles

Bridging the Gap: From Homogeneous to Heterogeneous Parahydrogen-induced Hyperpolarization and Beyond.

Demonstration of parahydrogen-induced polarization effects in hydrogenations catalyzed by heterogeneous catalysts instead of metal complexes in a homogeneous solution has opened an entirely new dimension for parahydrogen-based research, demonstrating its applicability not only for the production of catalyst-free hyperpolarized liquids and gases and long-lived non-equilibrium spin states for potential biomedical applications, but also for addressing challenges of modern fundamental and industrial catalysis including advanced mechanistic studies of catalytic reactions and operando NMR and MRI of reactors. This essay summarizes the progress achieved in this field by highlighting the research contributed to it by our colleague and friend Kirill V. Kovtunov whose scientific career ended unexpectedly and tragically at the age of 37. His role in this research was certainly crucial, further enhanced by a vast network of his contacts and collaborations at the national and international level.

Coupling light to a nuclear spin gas with a two-photon linewidth of five millihertz.

Nuclear spins of noble gases feature extremely long coherence times but are inaccessible to optical photons. Here, we realize a coherent interface between light and noble-gas spins that is mediated by alkali atoms. We demonstrate the optical excitation of the noble-gas spins and observe the coherent back action on the light in the form of high-contrast two-photon spectra. We report on a record two-photon linewidth of 5 ± 0.7 mHz above room temperature, corresponding to a 1-min coherence time. This experiment provides a demonstration of coherent bidirectional coupling between light and noble-gas spins, rendering their long-lived spin coherence accessible for manipulations in the optical domain.

Magnetization Lifetimes Prediction and Measurements Using Long-Lived Spin States in Endogenous Molecules

Nuclear magnetization storage in biologically-relevant molecules opens new possibilities for the investigation of metabolic pathways, provided the lifetimes of magnetization are sufficiently long. Dissolution-dynamic nuclear polarization-based spin-order enhancement, sustained by long-lived states can measure the ratios between concentrations of endogenous molecules on a cellular pathway. These ratios can be used as meters of enzyme function. Biological states featuring intracellular amino-acid concentrations that are depleted or replenished in the course of in-cell or in-vivo tests of drugs or radiation treatments can be revealed. Progressing from already-established long-lived states, we investigated related spin order in the case of amino acids and other metabolites featuring networks of coupled spins counting up to eight nuclei. We detail a new integrated theoretical approach between quantum chemistry simulations, chemical shifts, J-couplings information from databanks, and spin dynamics calculations to deduce a priori magnetization lifetimes in biomarkers. The lifetimes of long-lived states for several amino acids were also measured experimentally in order to ascertain the approach. Experimental values were in fair agreement with the computed ones and prior data in the literature.

Robust transformation of singlet order into heteronuclear magnetisation over an extended coupling range

Several important NMR procedures involve the conversion of nuclear singlet order into heteronuclear magnetisation, including some experiments involving long-lived spin states and parahydrogen-induced hyperpolarisation. However most existing sequences suffer from a limited range of validity or a lack of robustness against experimental imperfections. We present a new radio-frequency scheme for the transformation of the singlet order of a chemically-equivalent homonuclear spin pair into the magnetisation of a heteronuclear coupling partner. The proposed radio-frequency (RF) scheme is called gS2hM (generalized singlet-to-heteronuclear magnetisation) and has good compensation for common experimental errors such as RF and static field inhomogeneities. The sequence retains its robustness for homonuclear spin pairs in the intermediate coupling regime, characterised by the in-pair coupling being of the same order of magnitude as the difference between the out-of-pair couplings. This is a substantial improvement to the validity range of existing sequences. Analytical solutions for the pulse sequence parameters are provided. Experimental results are shown for two test cases.

Silicon-Integrated Telecommunications Photon-Spin Interface

Long-distance entanglement distribution is a vital capability for quantum technologies. An outstanding practical milestone towards this aim is the identification of a suitable matter-photon interface which possesses, simultaneously, long coherence lifetimes and efficient telecommunications-band optical access. In this work, alongside its sister publication, we report upon the T center, a silicon defect with spin-selective optical transitions at 1326 nm in the telecommunications O-band. Here we show that the T center in $^{28}$Si offers electron and nuclear spin lifetimes beyond a millisecond and second respectively, as well as optical lifetimes of 0.94(1) $\mu$s and a Debye-Waller factor of 0.23(1). This work represents a significant step towards coherent photonic interconnects between long-lived silicon spins, spin-entangled telecom single-photon emitters, and spin-dependent silicon-integrated photonic nonlinearities for future global quantum technologies.

In vitro singlet state and zero-quantum encoded magnetic resonance spectroscopy: Illustration with N-acetyl-aspartate.

Magnetic resonance spectroscopy (MRS) allows the analysis of biochemical processes non-invasively and in vivo. Still, its application in clinical diagnostics is rare. Routine MRS is limited to spatial, chemical and temporal resolutions of cubic centimetres, mM and minutes. In fact, the signal of many metabolites is strong enough for detection, but the resonances significantly overlap, exacerbating identification and quantification. Besides, the signals of water and lipids are much stronger and dominate the entire spectrum. To suppress the background and isolate selected signals, usually, relaxation times, J-coupling and chemical shifts are used. Here, we propose methods to isolate the signals of selected molecular groups within endogenous metabolites by using long-lived spin states (LLS). We exemplify the method by preparing the LLSs of coupled protons in the endogenous molecules N-acetyl-L-aspartic acid (NAA). First, we store polarization in long-lived, double spin states, followed by saturation pulses before the spin order is converted back to observable magnetization or double quantum filters to suppress background signals. We show that LLS and zero-quantum coherences can be used to selectively prepare and measure the signals of chosen metabolites or drugs in the presence of water, inhomogeneous field and highly concentrated fatty solutions. The strong suppression of unwanted signals achieved allowed us to measure pH as a function of chemical shift difference.

Multiplexed Single Photons from Deterministically Positioned Nanowire Quantum Dots

Solid-state quantum emitters are excellent sources of on-demand indistinguishable or entangled photons and can host long-lived spin memories, crucial resources for photonic quantum information applications. However, their scalability remains an outstanding challenge. Here we present a scalable technique to multiplex streams of photons from multiple independent quantum dots, on-chip, into a fiber network for use off-chip. Multiplexing is achieved by incorporating a multi-core fiber into a confocal microscope and spatially matching the multiple foci, seven in this case, to quantum dots in an array of deterministically positioned nanowires. First, we report the coherent control of the emission of biexciton-exciton cascade from a single nanowire quantum dot under resonant two-photon excitation. Then, as a proof-of-principle demonstration, we perform parallel spectroscopy on the nanowire array to identify two nearly identical quantum dots at different positions which are subsequently tuned into resonance with an external magnetic field. Multiplexing of background-free single photons from these two quantum dots is then achieved. Our approach, applicable to all types of quantum emitters, can readily be scaled up to multiplex $>100$ quantum light sources, providing a breakthrough in hardware for photonic based quantum technologies. Immediate applications include quantum communication, quantum simulation, and quantum computation.

Defect Engineering for Quantum Grade Rare-Earth Nanocrystals.

Nanostructured systems that combine optical and spin transitions offer new functionalities for quantum technologies by providing efficient quantum light-matter interfaces. Rare-earth (RE) ion-doped nanoparticles are promising in this field as they show long-lived optical and spin quantum states. However, further development of their use in highly demanding applications, such as scalable single-ion-based quantum processors, requires controlling defects that currently limit coherence lifetimes. In this work, we show that a post-treatment process that includes multistep high-temperature annealing followed by high-power microwave oxygen plasma processing advantageously improves key properties for quantum technologies. We obtain single crystalline Eu3+:Y2O3 nanoparticles (NPs) of 100 nm diameter, presenting bulk-like inhomogeneous line widths (Γinh) and population lifetimes (T1). Furthermore, a significant coherence lifetime (T2) extension, up to a factor of 5, is successfully achieved by modifying the oxygen-related point defects in the NPs by the oxygen plasma treatment. These promising results confirm the potential of engineered RE NPs to integrate devices such as cavity-based single-photon sources, quantum memories, and processors. In addition, our strategy could be applied to a large variety of oxides to obtain outstanding crystalline quality NPs for a broad range of applications.

Strain-controlled spin-splitting in the persistent spin helix state of two-dimensional SnSe monolayer

Abstract Recently, ferroelectric materials have attracted much attention in the field of spintronics since they enable to manipulation of spin splitting and spin textures via electric control of electric polarization. Here, two-dimensional ferroelectric SnSe monolayer (ML) comprises a promising candidate for spintronics since it has large and switchable in-plane electric polarization. However, the application of strain strongly modifies the electronic properties of the SnSe ML, which is expected to significantly affect the properties of the spin-splitting bands. By using fully-relativistic density-functional theory calculations, we predict that a strongly anisotropic spin splitting is observed in the energy bands near both the conduction band minimum (CBM) and valence band maximum (VBM), which can be effectively tuned by applying a small uniaxial in-plane strain. We demonstrate that these spin-splitting bands exhibit a unidirectional out-of-plane spin configuration in the momentum space, giving rise to a long-lived persistent spin helix (PSH) state. Importantly, a giant spin splitting (up to 245 meV) is achieved under the uniaxial in-plane tensile strain without losing the nature of the PSH state, thus offering a possibility for realizing efficient spintronic devices enabling operation at room temperature.

Using Photoexcited Core/Shell Quantum Dots To Spin Polarize Appended Radical Qubits.

The synthetic tunability, flexibility, and rich spin physics of semiconductor quantum dots (QDs) make them promising candidates for quantum information science applications. However, the rapid spin relaxation observed in colloidal quantum dots limits their functionality. In the current work, we demonstrate a method to harness photoexcited spin states in QDs to produce long-lived spin polarization on an appended organic ligand molecule. We present a system composed of CdSe/CdS core/shell QDs, covalently linked to naphthalenediimide (NDI) electron-accepting molecules. The electron transfer dynamics from photoexcited QDs to the appended NDI ligands is explored as a function of both shell thickness and number of NDIs per QD. Transient EPR spectroscopy shows that the photoexcited QDs strongly spin polarize the NDI radical anion, which is interpreted in the context of both the radical pair and the triplet mechanisms of spin polarization. This work serves as an initial step toward using photoexcited QDs to strongly spin polarize organic radicals having long spin relaxation times to serve as spin qubits in quantum information science applications.

Spin-phonon relaxation from a universal ab initio density-matrix approach

Designing new quantum materials with long-lived electron spin states urgently requires a general theoretical formalism and computational technique to reliably predict intrinsic spin relaxation times. We present a new, accurate and universal first-principles methodology based on Lindbladian dynamics of density matrices to calculate spin-phonon relaxation time of solids with arbitrary spin mixing and crystal symmetry. This method describes contributions of Elliott-Yafet and D’yakonov-Perel’ mechanisms to spin relaxation for systems with and without inversion symmetry on an equal footing. We show that intrinsic spin and momentum relaxation times both decrease with increasing temperature; however, for the D’yakonov-Perel’ mechanism, spin relaxation time varies inversely with extrinsic scattering time. We predict large anisotropy of spin lifetime in transition metal dichalcogenides. The excellent agreement with experiments for a broad range of materials underscores the predictive capability of our method for properties critical to quantum information science.

Preparation of Long-Lived States in a Multi-Spin System by Using an Optimal Control Method.

The lifetime Ts of a long-lived nuclear spin state (LLS) could be much longer than the longitudinal order T1 . Many spin systems were used to produce long-lived states, including two or more homonuclear spins that couple to each other. For multiple homonuclear spins with rather small chemical shift difference, normally it is difficult to selectively control the spins and then to prepare a LLS. Herein, we present a scheme that prepares different spin orders in a multi-spin system by using optimal control and numerical calculation. By experimentally measuring the lifetime of the states, we find that for a three-spin physical system, although there are many forms of state combinations with different spin orders, each component has its own lifetime.

Sensing Individual Nuclear Spins with a Single Rare-Earth Electron Spin.

Rare-earth related electron spins in crystalline hosts are unique material systems, as they can potentially provide a direct interface between telecom band photons and long-lived spin quantum bits. Specifically, their optically accessible electron spins in solids interacting with nuclear spins in their environment are valuable quantum memory resources. Detection of nearby individual nuclear spins, so far exclusively shown for few dilute nuclear spin bath host systems such as the nitrogen-vacancy center in diamond or the silicon vacancy in silicon carbide, remained an open challenge for rare earths in their host materials, which typically exhibit dense nuclear spin baths. Here, we present the electron spin spectroscopy of single Ce^{3+} ions in a yttrium orthosilicate host, featuring a coherence time of T_{2}=124 μs. This coherent interaction time is sufficiently long to isolate proximal ^{89}Y nuclear spins from the nuclear spin bath of ^{89}Y. Furthermore, it allows for the detection of a single nearby ^{29}Si nuclear spin, native to the host material with ∼5% abundance. This study opens the door to quantum memory applications in rare-earth ion related systems based on coupled environmental nuclear spins, potentially useful for quantum error correction schemes.

Spin-locked transport in a two-dimensional electron gas

Spin-orbit interactions in solids have inspired innovative physics for spin-based technologies. One such example is the persistent spin helix, where spin-orbit interactions from the semiconductor lattice are balanced with those in asymmetric quantum wells, to create long-lived spin textures. Spin transport in the presence of the momentum-dependent spin-orbit interactions lead to Larmor precession and subsequent dephasing that challenges the design of current spin-based information processing devices. We demonstrate that external magnetic fields can be applied to overcome this issue for spin-polarized charge carriers transported by in-plane electric fields. A frame of reference picture is introduced to describe the emergence and dynamics of the polarization-locked spin-wave packet after optical excitation. Applying well-matched magnetic fields maintains the persistent spin-helix profile regardless of whether the frame of reference is in motion or not. Monte Carlo simulations allow this traveling persistent spin-helix concept to be extended to a proposed spin Hall-effect transistor to ease design requirements.

Unveiling Valley Lifetimes of Free Charge Carriers in Monolayer WSe2.

We report on nanosecond-long, gate-dependent valley lifetimes of free charge carriers in monolayer WSe2, unambiguously identified by the combination of time-resolved Kerr rotation and electrical transport measurements. While the valley polarization increases when tuning the Fermi level into the conduction or valence band, there is a strong decrease of the respective valley lifetime consistent with both electron-phonon and spin-orbit scattering. The longest lifetimes are seen for spin-polarized bound excitons in the band gap region. We explain our findings via two distinct, Fermi-level-dependent scattering channels of optically excited, valley-polarized bright trions either via dark or bound states. By electrostatic gating we demonstrate that the transition-metal dichalcogenide WSe2 can be tuned to be either an ideal host for long-lived localized spin states or allow for nanosecond valley lifetimes of free charge carriers (>10 ns).

Spin-cooling of the motion of a trapped diamond.

Observing and controlling macroscopic quantum systems has long been a driving force in quantum physics research. In particular, strong coupling between individual quantum systems and mechanical oscillators is being actively studied1-3. Whereas both read-out of mechanical motion using coherent control of spin systems4-9 and single-spin read-out using pristine oscillators have been demonstrated10,11, temperature control of the motion of a macroscopic object using long-lived electronic spins has not been reported. Here we observe a spin-dependent torque and spin-cooling of the motion of a trapped microdiamond. Using a combination of microwave and laser excitation enables the spins of nitrogen-vacancy centres to act on the diamond orientation and to cool the diamond libration via a dynamical back-action. Furthermore, by driving the system in the nonlinear regime, we demonstrate bistability and self-sustained coherent oscillations stimulated by spin-mechanical coupling, which offers the prospect of spin-driven generation of non-classical states of motion. Such a levitating diamond-held in position by electric field gradients undervacuum-can operate as a 'compass' with controlled dissipation and has potential use in high-precision torque sensing12-14, emulation of the spin-boson problem15 and probing of quantum phase transitions16. In the single-spin limit17 and using ultrapure nanoscale diamonds, it could allow quantum non-demolition read-out of the spin of nitrogen-vacancy centres at ambient conditions, deterministic entanglement between distant individual spins18 and matter-wave interferometry16,19,20.

Rotational-permutational dual-pairing and long-lived spin order.

Quantum systems in contact with a thermal environment experience coherent and incoherent dynamics. These drive the system back toward thermal equilibrium after an initial perturbation. The relaxation process involves the reorganization of spin state populations and the decay of spin state coherences. In general, individual populations and coherences may exhibit different relaxation time constants. Particular spin configurations may exhibit exceptionally long relaxation time constants. Such spin configurations are known as long-lived spin order. The existence of long-lived spin order is a direct consequence of the symmetries of the system. For nuclear spin systems, rotational and permutational symmetries are of fundamental importance. Based on the Schur-Weyl duality theorem, we describe a theoretical framework for the study of rotational and permutational dual-symmetries in the context of long-lived spin order. Making use of the proposed formalism, we derive refined bounds on the number on long-lived spin populations and coherences for systems exhibiting rotational-permutational dual-symmetries.

Transform-Limited Photons From a Coherent Tin-Vacancy Spin in Diamond.

Solid-state quantum emitters that couple coherent optical transitions to long-lived spin qubits are essential for quantum networks. Here we report on the spin and optical properties of individual tin-vacancy (SnV) centers in diamond nanostructures. Through cryogenic magneto-optical and spin spectroscopy, we verify the inversion-symmetric electronic structure of the SnV, identify spin-conserving and spin-flipping transitions, characterize transition linewidths, measure electron spin lifetimes, and evaluate the spin dephasing time. We find that the optical transitions are consistent with the radiative lifetime limit even in nanofabricated structures. The spin lifetime is phonon limited with an exponential temperature scaling leading to T_{1}>10 ms, and the coherence time, T_{2}^{*} reaches the nuclear spin-bath limit upon cooling to 2.9K. These spin properties exceed those of other inversion-symmetric color centers for which similar values require millikelvin temperatures. With a combination of coherent optical transitions and long spin coherence without dilution refrigeration, the SnV is a promising candidate for feasable and scalable quantum networking applications.

Emergence of the giant out-of-plane Rashba effect and tunable nanoscale persistent spin helix in ferroelectric SnTe thin films

A non-vanishing electric field inside a non-centrosymmetric crystal transforms into a momentum-dependent magnetic field, namely, a spin–orbit field (SOF). SOFs are of great use in spintronics because they enable spin manipulation via the electric field. At the same time, however, spintronic applications are severely limited by the SOF, as electrons traversing the SOF easily lose their spin information. Here, we propose that in-plane ferroelectricity in (001)-oriented SnTe thin films can support both electrical spin controllability and suppression of spin dephasing. The in-plane ferroelectricity produces a unidirectional out-of-plane Rashba SOF that can host a long-lived helical spin mode known as a persistent spin helix (PSH). Through direct coupling between the inversion asymmetry and the SOF, the ferroelectric switching reverses the out-of-plane Rashba SOF, giving rise to a maximally field-tunable PSH. Furthermore, the giant out-of-plane Rashba SOF seen in the SnTe thin films is linked to the nano-sized PSH, potentially reducing spintronic device sizes to the nanoscale. We combine the two ferroelectric-coupled degrees of freedom, longitudinal charge and transverse PSH, to design intersectional electro-spintronic transistors governed by non-volatile ferroelectric switching within nanoscale lateral and atomic-thick vertical dimensions.

A simple and cost-efficient technique to generate hyperpolarized long-lived 15N-15N nuclear spin order in a diazine by signal amplification by reversible exchange.

Signal Amplification by Reversible Exchange (SABRE) is an inexpensive and simple hyperpolarization technique that is capable of boosting nuclear magnetic resonance sensitivity by several orders of magnitude. It utilizes the reversible binding of para-hydrogen, as hydride ligands, and a substrate of interest to a metal catalyst to allow for polarization transfer from para-hydrogen into substrate nuclear spins. While the resulting nuclear spin populations can be dramatically larger than those normally created, their lifetime sets a strict upper limit on the experimental timeframe. Consequently, short nuclear spin lifetimes are a challenge for hyperpolarized metabolic imaging. In this report, we demonstrate how both hyperpolarization and long nuclear spin lifetime can be simultaneously achieved in nitrogen-15 containing derivatives of pyridazine and phthalazine by SABRE. These substrates were chosen to reflect two distinct classes of 15N2-coupled species that differ according to their chemical symmetry and thereby achieve different nuclear spin lifetimes. The pyridazine derivative proves to exhibit a signal lifetime of ∼2.5 min and can be produced with a signal enhancement of ∼2700. In contrast, while the phthalazine derivative yields a superior 15 000-fold 15N signal enhancement at 11.7 T, it has a much shorter signal lifetime.