Control Of Spin State Research Articles

Probing the electronic ground state of the nitrogen-vacancy center in nanodiamonds at room temperature

The color centers in diamonds are promising candidates in the context of quantum information science, quantum computation, and spin-based quantum sensors due to their spin-dependent optical transitions. The manipulation and optical readout of electronic spin state is measured using a technique known as optically detected magnetic resonance (ODMR). Here, we discuss the indigenous development of ODMR setup to coherently manipulate and precise readout of spin state of nitrogen-vacancy centers (NV) in nanodiamond at room-temperature. The study involves the confocal mapping of an ensemble of NV centers to measure spin state-dependent optical transition by applying an optical excitation and microwave field simultaneously. The spin state control appears as a dip at 2.87 GHz in the measured emission intensity spectra as a function of microwave frequency. An ODMR contrast of 3.4 % is achieved at the NV center emission maximum of 660 nm and an inhomogeneous dephasing time of 0.03 microseconds. We find an inherent small split in the ODMR dip which is induced by local strain in nanodiamonds. The split becomes stronger while applying an external magnetic field, which forms the basis of NV center-based magnetometry. The results are useful for spin-based microwave-optical quantum transducers, quantum sensing, and quantum memory devices.

Chirality-Induced Spin Selectivity Enables New Breakthrough in Electrochemical and Photoelectrochemical Reactions.

To facilitate the transition from a carbon-energy-dependent society to a sustainable society, conventional engineering strategies, which encounter limitations associated with intrinsic material properties, should undergo the paradigm shift. From a theoretical viewpoint, the spin-dependent feature of oxygen evolution reaction (OER) reveals the potential of a spin-polarization strategy in enhancing the performance of electrochemical (EC) reactions. The chirality-induced spin selectivity (CISS) phenomenon attracts unprecedented attention owing to its potential utility in achieving novel breakthroughs. This paper starts with the experimental results aimed at enhancing the efficiency of the spin-dependent OER focusing on the EC system based on the CISS phenomenon. The applicability of spin-polarization to EC system is verified through various analytical methodologies to clarify the theoretical groundwork and mechanisms underlying the spin-dependent reaction pathway. The discussion is then extended to effective spin-control strategies in photoelectrochemical system based on the CISS effect. Exploring the influence of spin-state control on the kinetic and thermodynamic aspects, this perspective also discusses the effect of spin polarization induced by the CISS phenomenon on spin-dependent OER. Lastly, future directions for enhancing the performance of spin-dependent redox systems are discussed, including expansion to various chemical reactions and the development of materials with spin-control capabilities.

Controlling Reactivity through Spin Manipulation: Steric Bulkiness of Peroxocobalt(III) Complexes.

The intrinsic relationship between spin states and reactivity in peroxocobalt(III) complexes was investigated, specifically focusing on the influence of steric modulation on supporting ligands. Together with the previously reported [CoIII(TBDAP)(O2)]+ (2Tb), which exhibits spin crossover characteristics, two peroxocobalt(III) complexes, [CoIII(MDAP)(O2)]+ (2Me) and [CoIII(ADDAP)(O2)]+ (2Ad), bearing pyridinophane ligands with distinct N-substituents such as methyl and adamantyl groups, were synthesized and characterized. By manipulating the steric bulkiness of the N-substituents, control of spin states in peroxocobalt(III) complexes was demonstrated through various physicochemical analyses. Notably, 2Ad oxidized the nitriles to generate hydroximatocobalt(III) complexes, while 2Me displayed an inability for such oxidation reactions. Furthermore, both 2Ad and 2Tb exhibited similarities in spectroscopic and geometric features, demonstrating spin crossover behavior between S = 0 and S = 1. The steric bulkiness of the adamantyl and tert-butyl group on the axial amines was attributed to inducing a weak ligand field on the cobalt(III) center. Thus, 2Ad and 2Tb are an S = 1 state under the reaction conditions. In contrast, the less bulky methyl group on the amines of 2Me resulted in an S = 0 state. The redox potential of the peroxocobalt(III) complexes was also influenced by the ligand field arising from the steric bulkiness of the N-substituents in the order of 2Me (-0.01 V) < 2Tb (0.29 V) = 2Ad (0.29 V). Theoretical calculations using DFT supported the experimental observations, providing insights into the electronic structure and emphasizing the importance of the spin state of peroxocobalt(III) complexes in nitrile activation.

Room Temperature Dynamics of an Optically Addressable Single Spin in Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) hosts pure single-photon emitters that have shown evidence of optically detected electronic spin dynamics. However, the electrical and chemical structures of these optically addressable spins are unknown, and the nature of their spin-optical interactions remains mysterious. Here, we use time-domain optical and microwave experiments to characterize a single emitter in h-BN exhibiting room temperature optically detected magnetic resonance. Using dynamical simulations, we constrain and quantify transition rates in the model, and we design optical control protocols that optimize the signal-to-noise ratio for spin readout. This constitutes a necessary step toward quantum control of spin states in h-BN.

Coherent Microwave, Optical, and Mechanical Quantum Control of Spin Qubits in Diamond

AbstractDiamond has emerged as a highly promising platform for quantum network applications. Color centers in diamond fulfill the fundamental requirements for quantum nodes: they constitute optically accessible quantum systems with long‐lived spin qubits. Furthermore, they provide access to a quantum register of electronic and nuclear spin qubits and they mediate entanglement between spins and photons. All these operations require coherent control of the color center's spin state. This review provides a comprehensive overview of the state‐of‐the‐art, challenges, and prospects of such schemes, including high‐fidelity initialization, coherent manipulation, and readout of spin states. Established microwave and optical control techniques are reviewed, and moreover, emerging methods such as cavity‐mediated spin–photon interactions and mechanical control based on spin–phonon interactions are summarized. For different types of color centers, namely, nitrogen–vacancy and group‐IV color centers, distinct challenges persist that are subject of ongoing research. Beyond fundamental coherent spin qubit control techniques, advanced demonstrations in quantum network applications are outlined, for example, the integration of individual color centers for accessing (nuclear) multiqubit registers. Finally, the role of diamond spin qubits in the realization of future quantum information applications is described.

Efficient Green Spin Light-Emitting Diodes Enabled by Ultrafast Energy- and Spin-Funneling in Chiral Perovskites.

Introducing molecular chirality into perovskite crystal structures has enabled the control of carrier spin states, giving rise to circularly polarized luminescence (CPL) in thin films and circularly polarized electroluminescence (CPEL) in LEDs. Spin-LEDs can be fabricated either through a spin-filtering layer enabled by chiral-induced spin selectivity or a chiral emissive layer. The former requires a high degree of spin polarization and a compatible spinterface for efficient spin injection, which might not be easily integrated into LEDs. Alternatively, a chiral emissive layer can also generate circularly polarized electroluminescence, but the efficiency remains low and the fundamental mechanism is elusive. In this work, we report an efficient green LED based on quasi-two-dimensional (quasi-2D) chiral perovskites as the emitting layer (EML), where CPEL is directly produced without separate carrier spin injection. The optimized chiral perovskite thin films exhibited strong CPL at 535 nm with a photoluminescence quantum yield (PLQY) of 91% and a photoluminescence dissymmetry factor (glum) of 8.6 × 10-2. Efficient green spin-LEDs were successfully demonstrated, with a large EL dissymmetry factor (gEL) of 7.8 × 10-2 and a maximum external quantum efficiency (EQE) of 13.5% at room temperature. Ultrafast transient absorption (TA) spectroscopic study shows that the CPEL is generated from a rapid energy transfer accompanied by spin transfer from 2D to 3D perovskites. Our study not only demonstrates a reliable approach to achieve high performance spin-LEDs but also reveals the fundamental mechanism of CPEL with an emissive layer of chiral perovskites.

Spin-state regulation by secondary coordination sphere for improved oxygen evolution activity of LaCo1-xNixO3 perovskite

The evolution of oxygen evolution reaction (OER) remains a pivotal challenge in the realm of oxygen electrocatalysis. Recently, the proposition of regulating spin states has emerged as a novel avenue for enhancing the efficiency of electrocatalytic reactions. Presently, accurately modulating the metal active center into immediate spin (IS) remains a formidable challenge. Here, our research has achieved a breakthrough in precise spin state control and catalytic performance enhancement of Co3+ through the utilization of Ni-substituted LaCo1-xNixO3 perovskite. This achievement is primarily attributed to the fine regulation of both the secondary coordination sphere (SCS) and primary coordination sphere (PCS), i.e., Co6-y-[Co]-Niy (y = 0–6) and Co-O lengths, respectively. Our findings reveal that LaCo7/9Ni2/9O3 consisted of the SCS (y ≤ 2) with the eg1 fillings of IS Co3+ exhibits an optimal OER activity. Additionally, adjusting the Co-O bond length in PCS to approximately 1.89 Å proves to be more conducive to the transition of Co3+ spin states from high spin (HS) and low spin (LS) to IS. These discoveries present new approach to precisely modulating the spin state, offering promising prospects for the development of high-efficiency OER catalysts.

Light-Controlled Multiconfigurational Conductance Switching in a Single 1D Metal-Organic Wire.

Precise control of multiple spin states on the atomic scale presents a promising avenue for designing and realizing magnetic switches. Despite substantial progress in recent decades, the challenge of achieving control over multiconfigurational reversible switches in low-dimensional nanostructures persists. Our work demonstrates multiple, fully reversible plasmon-driven spin-crossover switches in a single π-d metal-organic chain suspended between two electrodes. The plasmonic nanocavity stimulated by external visible light allows for reversible spin crossover between low- and high-spin states of different cobalt centers within the chain. We show that the distinct spin configurations remain stable for minutes under cryogenic conditions and can be nonperturbatively detected by conductance measurements. This multiconfigurational plasmon-driven spin-crossover demonstration extends the available toolset for designing optoelectrical molecular devices based on SCO compounds.

Engineering Spin Polarization of the Surface-Adsorbed Fe Atom by Intercalating a Transition Metal Atom into the MoS2 Bilayer for Enhanced Nitrogen Reduction.

The precise control of spin states in transition metal (TM)-based single-atom catalysts (SACs) is crucial for advancing the functionality of electrocatalysts, yet it presents significant scientific challenges. Using density functional theory (DFT) calculations, we propose a novel mechanism to precisely modulate the spin state of the surface-adsorbed Fe atom on the MoS2 bilayer. This is achieved by strategically intercalating a TM atom into the interlayer space of the MoS2 bilayer. Our results show that these strategically intercalated TM atoms can induce a substantial interfacial charge polarization, thereby effectively controlling the charge transfer and spin polarization on the surface Fe site. In particular, by varying the identity of the intercalated TM atoms and their vacancy filling site, a continuous modulation of the spin states of the surface Fe site from low to medium to high can be achieved, which can be accurately described using descriptors composed of readily accessible intrinsic properties of materials. Using the electrochemical dinitrogen reduction reaction (eNRR) as a prototypical reaction, we discovered a universal volcano-like relation between the tuned spin and the catalytic activity of Fe-based SACs. This finding contrasts with the linear scaling relationships commonly seen in traditional studies and offers a robust new approach to modulating the activity of SACs through interfacial engineering.

Spin-State Control of Shallow Single NV Centers in Hydrogen-Terminated Diamond.

The ability to control the charge and spin states of nitrogen-vacancy (NV) centers near the diamond surface is of pivotal importance for quantum applications. Hydrogen-terminated diamond is promising for long spin coherence times and ease of controlling the charge states due to the low density of surface defects. However, it has so far been challenging to create negatively charged single NV centers with controllable spin states beneath a hydrogen-terminated surface because atmospheric adsorbates that act as acceptors induce surface holes. In this study, we optically detected the magnetic resonance of shallow single NV centers in hydrogen-terminated diamond through precise control of the nitrogen implantation fluence. Furthermore, we found that the probability of detecting the resonance was enhanced by reducing the surface acceptor density through passivation of the hydrogen-terminated surface with hexagonal boron nitride without air exposure. This control method opens up new opportunities for using NV centers in quantum applications.

Quantum Logic Enhanced Sensing in Solid-State Spin Ensembles.

We demonstrate quantum logic enhanced sensitivity for a macroscopic ensemble of solid-state, hybrid two-qubit sensors. We achieve over a factor of 30 improvement in the single-shot signal-to-noise ratio, translating to an ac magnetic field sensitivity enhancement exceeding an order of magnitude for time-averaged measurements. Using the electronic spins of nitrogen vacancy (NV) centers in diamond as sensors, we leverage the on-site nitrogen nuclear spins of the NV centers as memory qubits, in combination with homogeneous and stable bias and control fields, ensuring that all of the ∼10^{9} two-qubit sensors are sufficiently identical to permit global control of the NV ensemble spin states. We find quantum logic sensitivity enhancement for multiple measurement protocols with varying optimal sensing intervals, including XY8 and DROID-60 dynamical decoupling, as well as correlation spectroscopy, using an applied ac magnetic field signal. The results are independent of the nature of the target signal and broadly applicable to measurements using NV centers and other solid-state spin ensembles. This work provides a benchmark for macroscopic ensembles of quantum sensors that employ quantum logic or quantum error correction algorithms for enhanced sensitivity.

Magnetic nanodoping: Atomic control of spin states in cobalt doped silver clusters

Magnetic nanodoping: Atomic control of spin states in cobalt doped silver clusters

Electric control of spin states in frustrated triangular molecular magnets

Frustrated triangular molecular magnets are a very important class of magnetic molecules since the absence of inversion symmetry allows an external electric field to couple directly with the spin chirality that characterizes their ground state. The spin-electric coupling in these molecular magnets leads to an efficient and fast method of manipulating spin states, making them an exciting candidate for quantum information processing. The efficiency of the spin-electric coupling depends on the electric dipole coupling between the chiral ground states of these molecules. In this paper, we report on first-principles calculations of spin-electric coupling in $\{V_3\}$ triangular magnetic molecule. We have explicitly calculated the spin-induced charge redistribution within the magnetic centers that is responsible for the spin-electric coupling. Furthermore, we have generalized the method of calculating the strength of the spin-electric coupling to calculate any triangular spin 1/2 molecule with $C_3$ symmetry and have applied it to calculate the coupling strength in $\{V_{15}\}$ molecular magnets.

Wigner-molecularization-enabled dynamic nuclear polarization

Multielectron semiconductor quantum dots (QDs) provide a novel platform to study the Coulomb interaction-driven, spatially localized electron states of Wigner molecules (WMs). Although Wigner-molecularization has been confirmed by real-space imaging and coherent spectroscopy, the open system dynamics of the strongly correlated states with the environment are not yet well understood. Here, we demonstrate efficient control of spin transfer between an artificial three-electron WM and the nuclear environment in a GaAs double QD. A Landau–Zener sweep-based polarization sequence and low-lying anticrossings of spin multiplet states enabled by Wigner-molecularization are utilized. Combined with coherent control of spin states, we achieve control of magnitude, polarity, and site dependence of the nuclear field. We demonstrate that the same level of control cannot be achieved in the non-interacting regime. Thus, we confirm the spin structure of a WM, paving the way for active control of correlated electron states for application in mesoscopic environment engineering.

A Noble-Metal-Free Spintronic System with Proximity-Enhanced Ferromagnetic Topological Surface State of FeSi above Room Temperature.

Strongly spin-orbit coupled states at metal interfaces, topological insulators, and 2D materials enable efficient electric control of spin states, offering great potential for spintronics. However, there are still materials challenges to overcome, including the integration into advanced silicon electronics and the scarce resources of constituent heavy elements of those materials. Through magneto-transport measurements and first-principles calculations, here robust spin-orbit coupling (SOC)-induced properties of a ferromagnetic topological surface state in FeSi and their controllability via hybridization with adjacent materials are demonstrated. In comparison to the case of its naturally oxidized surface, the ferromagnetic transition temperature is greatly increased beyond room temperature and the effective SOC strength is almost doubled at the surface in proximity to a wide-bandgap fluoride insulator. Those enhanced magnetic properties enable room-temperature magnetization switching, being applicable to spin-orbit torque based spintronic devices. Realization of strong SOC in the noble-metal-free silicon-based compound will accelerate spintronic applications.

Unveiling the Decisive Factor for the Sharp Transition in the Scanning Tunneling Spectroscopy of a Single Nickelocene Molecule.

Scanning tunneling microscopy (STM) has been utilized to realize the precise measurement and control of local spin states. Experiments have demonstrated that when a nickelocene (Nc) molecule is attached to the apex of an STM tip, the dI/dV spectra exhibit a sharp or a smooth transition when the tip is displaced toward the substrate. However, what leads to the two distinct types of transitions remains unclear, and more intriguingly, the physical origin of the abrupt change in the line shape of dI/dV spectra remains unclear. To clarify these intriguing issues, we perform first-principles-based simulations on the STM tip control process for the Cu tip/Nc/Cu(100) junction. In particular, we find that the suddenly enhanced hybridization between the d orbitals on the Ni ion and the metallic bands in the substrate leads to Kondo correlation overwhelming spin excitation, which is the main cause of the sharp transition in the dI/dV spectra observed experimentally.

Regulating Magnetic Behavior of Fe in Hematene by Defects to Improve Oxygen Evolution Reaction.

Two-dimensional hematene is earth-abundant and exhibits easy modulation with unique electronic properties, suggesting a promising role as an electrocatalyst for oxygen evolution reaction (OER). In this Letter, we propose a strategy to regulate the magnetic behavior of Fe atoms in hematene by introducing structural defects to enhance its OER activity. Hematene is proved to be thermodynamically stable at electrolyte pH values ≥3 under the OER working potential according to the Pourbaix diagram. Among all the defective structures, the most stable DVFe1-O defect exhibits superior OER activity, which originates from the unique spin state of the active Fe atom. We further propose a novel descriptor of the magnetic moment difference on active Fe to efficiently evaluate the OER activity. We believe that our strategy of combining the defect modulation in the geometric structure and spin-state control in the electronic configuration could provide a guideline to design highly active Fe-based electrocatalysts.

Photochemical spin-state control of binding configuration for tailoring organic color center emission in carbon nanotubes

Incorporating fluorescent quantum defects in the sidewalls of semiconducting single-wall carbon nanotubes (SWCNTs) through chemical reaction is an emerging route to predictably modify nanotube electronic structures and develop advanced photonic functionality. Applications such as room-temperature single-photon emission and high-contrast bio-imaging have been advanced through aryl-functionalized SWCNTs, in which the binding configurations of the aryl group define the energies of the emitting states. However, the chemistry of binding with atomic precision at the single-bond level and tunable control over the binding configurations are yet to be achieved. Here, we explore recently reported photosynthetic protocol and find that it can control chemical binding configurations of quantum defects, which are often referred to as organic color centers, through the spin multiplicity of photoexcited intermediates. Specifically, photoexcited aromatics react with SWCNT sidewalls to undergo a singlet-state pathway in the presence of dissolved oxygen, leading to ortho binding configurations of the aryl group on the nanotube. In contrast, the oxygen-free photoreaction activates previously inaccessible para configurations through a triplet-state mechanism. These experimental results are corroborated by first principles simulations. Such spin-selective photochemistry diversifies SWCNT emission tunability by controlling the morphology of the emitting sites.

Inverse Faraday effect in Mott insulators

The inverse Faraday effect (IFE), where a static magnetization is induced by circularly polarized light, offers a promising route to ultrafast control of spin states. Here we study the IFE in Mott insulators using the Floquet theory. We find two distinct IFE behavior governed by the inversion symmetry. In the Mott insulators with inversion symmetry, we find that the effective magnetic field induced by the IFE couples ferromagnetically to the neighboring spins. While for the Mott insulators without inversion symmetry, the effective magnetic field due to IFE couples antiferromagnetically to the neighboring spins. We apply the theory to the spin-orbit coupled single- and multiorbital Hubbard model that is relevant for the Kitaev quantum spin liquid material and demonstrate that the magnetic interactions can be tuned by light.

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(II) and cobalt(II) complexes.

Control of the spin state of metal complexes is important because it leads to a precise control over the physical properties and the chemical reactivity of the metal complexes. Currently, controlling the spin state in metal complexes is challenging because a precise control of the properties of the secondary coordination sphere is often difficult. It has been shown that non-covalent interactions in the secondary coordination sphere of transition metal complexes can enable spin state control. Here we exploit this strategy for fluorinated triazole ligands and present mononuclear CoII and FeII complexes with "click"-derived tripodal ligands that contain mono-fluorinated benzyl substituents on the backbone. Structural characterization of 1 and 2 at 100 K revealed Co-N bond lengths that are typical of high spin (HS) CoII complexes. In contrast, the Fe-N bond lengths for 3 are characteristic of a low spin (LS) FeII state. All complexes show an intramolecular face-to-face non-covalent interaction between two arms of the ligand. The influence of the substituents and of their geometric structure on the spin state of the metal center was investigated through SQUID magnetometry, which revealed spin crossover occurring in compounds 1 and 3. EPR spectroscopy sheds further light on the electronic structures of 1 and 2 in their low- and high-spin states. Quantum-chemical calculations of the fluorobenzene molecule were performed to obtain insight into the influence of fluorine-specific interactions. Interestingly, this work shows that the same fluorinated tripodal ligands induce SCO behavior in both FeII and CoII complexes.