Exploring High-Spin Color Centers in Wide Band Gap Semiconductors SiC: A Comprehensive Magnetic Resonance Investigation (EPR and ENDOR Analysis).

High-spin defects (color centers) in wide-gap semiconductors are considered as a basis for the implementation of quantum technologies due to the unique combination of their spin, optical, charge, and coherent properties. A silicon carbide (SiC) crystal can act as a matrix for a wide variety of optically active vacancy-type defects, which manifest themselves as single-photon sources or spin qubits. Among the defects, the nitrogen-vacancy centers (NV) are of particular importance. This paper is devoted to the application of the photoinduced electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) techniques at a high-frequency range (94 GHz) to obtain unique information about the nature and properties of NV defects in SiC crystal of the hexagonal 4H and 6H polytypes. Selective excitation by microwave and radio frequency pulses makes it possible to determine the microscopic structure of the color center, the zero-field splitting constant (D = 1.2-1.3 GHz), the phase coherence time (T2), and the values of hyperfine (≈1.1 MHz) and quadrupole (Cq ≈ 2.45 MHz) interactions and to define the isotropic (a = -1.2 MHz) and anisotropic (b = 10-20 kHz) contributions of the electron-nuclear interaction. The obtained data are essential for the implementation of the NV defects in SiC as quantum registers, enabling the optical initialization of the electron spin to establish spin-photon interfaces. Moreover, the combination of optical, microwave, and radio frequency resonant effects on spin centers within a SiC crystal shows the potential for employing pulse EPR and ENDOR sequences to implement protocols for quantum computing algorithms and gates.

Aluminum intercalation behaviours of {[Fe(Tp)(CN)3]2[M(H2O)2]} cyanido-bridged chain compounds in an ionic liquid electrolyte.

As the development of aluminum-ion batteries is still in its infancy, researchers are still dedicated to exploring suitable host materials and investigating their aluminum intercalation behaviours. Here, a series of cyanido-bridged chain compounds with the formula {[FeIII(Tp)(CN)3]2[MII(H2O)2]}n (M = Ni, Co, Mn, Zn, Cu) are studied as cathode electrodes for aluminum-ion batteries with [EMIm]Cl-AlCl3 (1-ethyl-3-methylimidazolium chloride-AlCl3) ionic liquid as the electrolyte. The electrochemical properties suggested Fe3+/Fe2+ to be the redox-active couple during the aluminum intercalation and deintercalation processes of these compounds, and the observed maximum specific capacity obtained by the Fe-Co compound is 200 mA h g-1 despite the rapid specific capacity fading. To gain a deeper understanding of the capacity decay suffered by these compounds, further investigation was conducted to explore the evolution of compounds during the electrochemical measurements. It has been attributed to the following reasons: 1. thermodynamic instability results in the transformation/damage of two of the chain structures (for the Fe-Ni and Fe-Co compounds) during heat treatment on electrodes, a crucial step in electrode preparation; 2. the acidic nature of the electrolyte triggers the destruction of the chain structure, with the appearance of partial reduction of Fe3+ to Fe2+, and a new interaction of the cyano group with aluminum; 3. the high charge density of inserted Al ions makes the chain structure suffer from structural damage during both the charging and discharging processes. The progressive accumulation of trapped intercalated ions hampers their involvement in the reaction, consequently decreasing electrochemical reversibility.

Enlightening the Alkali Ion Role in the Photomagnetic Effect of FeCo Prussian Blue Analogues.

FeCo Prussian blue analogues of general formula AxCoy[Fe(CN)6]z are responsive, non-stoichiometric materials whose magnetic and optical properties can be reversibly switched by light irradiation. However, elucidating the critical influence of the inserted alkali ion, A+, on the material's properties remains complicated due to their complex local structure. Here, by investigating soluble A ⊂ [Fe4-Co4] cyanido cubes (A = K, Rb, and Cs), both accurate structural and electronic information could be obtained. First, X-ray diffraction analyses reveal distinct interactions between the inserted A+ ions and the {Fe4-Co4} box, which impacts the structural distortion in the cubic framework. These distortions vanish, and a displacement of the small K+ ion from a corner toward the center is observed, as a cobalt corner CoIIHS is oxidized to CoIIILS. Second, cyclic voltammetry experiments performed at variable temperatures show distinct splitting of the CoIIHS ⇔ CoIIILS peak potentials for the different A+ cations, which can be qualitatively linked to different thermodynamic (standard potentials) and kinetic (energy barriers) parameters associated with the structural reorganization accompanying this redox-coupled spin state change. Moreover, for the first time, photomagnetism was investigated in frozen solution to avoid effects of intermolecular interactions. The results show that the metastable state is stabilized following the trend K > Rb > Cs. The outcome of these studies suggests that the interaction of the inserted alkali ions with the cyanide cage and the structural changes accompanying the electron transfer impact the stability of the photoinduced state and the relaxation temperature: the smaller the cation, the higher the structural reorganization and the associated energy barrier, and the more stable the metastable state.

Coherent Manipulation with Resonant Excitation and Single Emitter Creation of Nitrogen Vacancy Centers in 4H Silicon Carbide.

Silicon carbide (SiC) has become a key player in the realization of scalable quantum technologies due to its ability to host optically addressable spin qubits and wafer-size samples. Here, we have demonstrated optically detected magnetic resonance (ODMR) with resonant excitation and clearly identified the ground state energy levels of the NV centers in 4H-SiC. Coherent manipulation of NV centers in SiC has been achieved with Rabi and Ramsey oscillations. Finally, we show the successful generation and characterization of single nitrogen vacancy (NV) center in SiC employing ion implantation. Our results highligh the key role of NV centers in SiC as a potential candidate for quantum information processing.

Deterministic placement of ultra-bright near-infrared color centers in arrays of silicon carbide micropillars.

We report the enhancement of the optical emission between 850 and 1400 nm of an ensemble of silicon mono-vacancies (VSi), silicon and carbon divacancies (VCVSi), and nitrogen vacancies (NCVSi) in an n-type 4H-SiC array of micropillars. The micropillars have a length of ca. 4.5 µm and a diameter of ca. 740 nm, and were implanted with H+ ions to produce an ensemble of color centers at a depth of approximately 2 µm. The samples were in part annealed at different temperatures (750 and 900 °C) to selectively produce distinct color centers. For all these color centers we saw an enhancement of the photostable fluorescence emission of at least a factor of 6 using micro-photoluminescence systems. Using custom confocal microscopy setups, we characterized the emission of VSi measuring an enhancement by up to a factor of 20, and of NCVSi with an enhancement up to a factor of 7. The experimental results are supported by finite element method simulations. Our study provides the pathway for device design and fabrication with an integrated ultra-bright ensemble of VSi and NCVSi for in vivo imaging and sensing in the infrared.

Structure and electrochromism of two-dimensional octahedral molecular sieve h'-WO3.

Octahedral molecular sieves (OMS) are built of transition metal-oxygen octahedra that delimit sub-nanoscale cavities. Compared to other microporous solids, OMS exhibit larger versatility in properties, provided by various redox states and magnetic behaviors of transition metals. Hence, OMS offer opportunities in electrochemical energy harnessing devices, including batteries, electrochemical capacitors and electrochromic systems, provided two conditions are met: fast exchange of ions in the micropores and stability upon exchange. Here we unveil a novel OMS hexagonal polymorph of tungsten oxide called h'-WO3, built of (WO6)6 tunnel cavities. h'-WO3 is prepared by a one-step soft chemistry aqueous route leading to the hydrogen bronze h'-H0.07WO3. Gentle heating results in h'-WO3 with framework retention. The material exhibits an unusual combination of 1-dimensional crystal structure and 2-dimensional nanostructure that enhances and fastens proton (de)insertion for stable electrochromic devices. This discovery paves the way to a new family of mixed valence functional materials with tunable behaviors.

Bright room temperature single photon source at telecom range in cubic silicon carbide.

Single-photon emitters (SPEs) play an important role in a number of quantum information tasks such as quantum key distributions. In these protocols, telecom wavelength photons are desired due to their low transmission loss in optical fibers. In this paper, we present a study of bright single-photon emitters in cubic silicon carbide (3C-SiC) emitting in the telecom range. We find that these emitters are photostable and bright at room temperature with a count rate of ~ MHz. Altogether with the fact that SiC is a growth and fabrication-friendly material, our result may be relevant for future applications in quantum communication technology.