EPR and ENDOR Studies of Shallow Donors in SiC

Recent progress in the investigation of the electronic structure of the shallow nitrogen (N) and phosphorus (P) donors in 3C–, 4H– and 6H–SiC is reviewed with focus on the applications of magnetic resonance including electron paramagnetic resonance (EPR) and other pulsed methods such as electron spin echo, pulsed electron nuclear double resonance (ENDOR), electron spin-echo envelope modulation and two-dimensional EPR. EPR and ENDOR studies of the ²⁹Si and ¹³C hyperfine interactions of the shallow N donors and their spin localization in the lattice are discussed. The use of high-frequency EPR in combination with other pulsed magnetic resonance techniques for identification of low-temperature P-related centers in P-doped 3C–, 4H– and 6H–SiC and for determination of the valley–orbit splitting of the shallow N and P donors are presented and discussed.     

Self-Trapped Excitons in Ionic-Covalent Silver Halide Crystals and Nanostructures: High-Frequency EPR, ESE, ENDOR and ODMR Studies

Silver halides have unique features in solid state physics because their properties are considered to be of borderline nature between ionic and covalent bonding. In AgCl, the self-trapped hole (STH) is centered and partly trapped in the cationic sublattice, forming an Ag²⁺ ion inside of a (AgCl₆)^4? complex as a result of the Jahn–Teller distortion. The STH in AgCl can capture an electron from the conduction band forming the self-trapped exciton (STE). Recent results of a study of STE by means of high-frequency electron paramagnetic resonance, electron spin echo, electron–nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) are reviewed. The properties of the STE in AgCl crystals, such as exchange coupling, the ordering of the triplet and singlet sublevels, the dynamical properties of the singlet and triplet states, and the hyperfine interaction with the Ag and Cl (Br) nuclei are discussed. Direct information about the spatial distribution of the wave function of STE unpaired electrons was obtained by ENDOR. From a comparison with the results of an ENDOR study of the shallow electron center and STH, it is concluded that the electron is mainly contained in a hydrogen-like 1s orbital with a Bohr radius of 15.1 ± 0.6 Å, but near its center the electron density reflects the charge distribution of the hole. The hole of the STE is virtually identical to an isolated STH center. For AgCl nanocrystals embedded into the KCl crystalline matrix, the anisotropy of the g-factor of STE and STH was found to be substantially reduced compared with that of bulk AgCl crystals, which can be explained by a considerable suppression of the Jahn–Teller effect in nanoparticles. A study of ODMR in AgBr nanocrystals in KBr revealed spatial confinement effects and allowed estimating the nanocrystal size from the shape of the ODMR spectra.     

Yb：YAG晶体中的色心

在用引上法生长的Ｙｂ：ＹＡＧ晶体中，存在一个独特的色心，其吸收带位于３７５ｎｍ的６２５ｎｍ，随着Ｙｂ２Ｏ３掺杂浓度的增加，色心浓度增加，探讨了晶体生长过程中色心形成机理。高强γ射线辐照Ｙｂ：ＹＡＧ晶体，诱导大量色心的形成。晶体中的 对激发态Ｙｂ＾３＋离子的荧光寿命具有流淬火效应，因此，Ｙｂ：ＹＡＧ激光晶体需要经高温退火，消除色心的影响。     

Optical Absorption Study on the Conversion and Restoration of Color Centers in Pure KCI Crystals

The conversion and restoration processes of colour centers in pure KCI crystals were studied by optical absorption measurements. When the sample is heated the aggregative centers in it begin to dissolve to F centers, and the opposite process will take place, i.e. F centers will aggregate to form F₂, F₃, F₄centers if the samples are cooled down. It was found that the conversion and restoration processes are dependent on the annealing temperature and time. In our experiment, the samples were treated at various temperatures and time. In addition the restoration process for the 350°C treated sample was studied live. We found that the higher the annealing temperature is the slower the restoration in the samples proceed, and the conversion process maintained for a few minutes even after annealing treatment.     

EPR and ENDOR Investigation of Rhodosemiquinone in Bacterial Reaction Centers Formed by B-Branch Electron Transfer

In photosynthetic bacteria, light-induced electron transfer takes place in a protein called the reaction center (RC) leading to the reduction of a bound ubiquinone molecule, Q_B, coupled with proton binding from solution. We used electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) to study the magnetic properties of the protonated semiquinone, an intermediate proposed to play a role in proton coupled electron transfer to Q_B. To stabilize the protonated semiquinone state, we used a ubiquinone derivative, rhodoquinone, which as a semiquinone is more easily protonated than ubisemiquinone. To reduce this low-potential quinone we used mutant RCs modified to directly reduce the quinone in the Q_B site via B-branch electron transfer (Paddock et al. in Biochemistry 44:6920–6928, 2005). EPR and ENDOR signals were observed upon illumination of mutant RCs in the presence of rhodoquinone. The EPR signals had g values characteristic of rhodosemiquinone (g _x  = 2.0057, g _y  = 2.0048, g _z  ~ 2.0018) at pH 9.5 and were changed at pH 4.5. The ENDOR spectrum showed couplings due to solvent exchangeable protons typical of hydrogen bonds similar to, but different from, those found for ubisemiquinone. This approach should be useful in future magnetic resonance studies of the protonated semiquinone.     

Defects in Nanodiamonds: Application of High-Frequency cw and Pulse EPR,ODMR

Different aspects of applications of electron paramagnetic resonance (EPR) based techniques including high frequency (HF) electron spin echo (ESE), electron-nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) approaches to study diamond nanostructures are examined.     

Group III Acceptors with Shallow and Deep Levels in Silicon Carbide: ESR and ENDOR Studies

Results of investigations of Group III acceptors (B, Al, and Ga) in crystals of silicon carbide using the most informative electron spin resonance and electron nuclear double resonance methods are presented. Structural models of the acceptors with shallow and deep levels are considered. In addition to the data obtained earlier, studies using high-frequency magnetic resonance were obtained, which allowed revealing orthorhombic deviations from the axial symmetry for the deep acceptors; theoretical analysis explains experimentally found shifts of g factors for the deep acceptors arising due to the orthorhombic deviations, which appear probably due to the Jahn–Teller effect.     

A New Method of Growing AlN,GaN, and AlGaN Bulk Crystals Using Hybrid SiC/Si Substrates

Physics of the Solid State - The main principles of a new method of growing bulk single-crystal AlN, AlGaN, and GaN films with thickness from 100 μm and more on silicon substrates with a...     

着色KCl和KBr晶体色心的光谱特性及其零声子跃迁

详细研究了不同温度下着色ＫＣｌ晶体Ｒ２心和７５６．６ｎｍ零声子线以及着色ＫＢｒ晶体Ｒ２心零声子线的产生．利用恰当的热处理，可产生和增强零声子线，并给出了相应的物理解释．     

EPR and ENDOR investigations of Ge,Sn and Pb impurities in CdSe

Electron paramagnetic resonance (EPR) experiments of light activated Ge, Sn and Pb impurities in wurtzite type CdSe crystals are presented. These²S_1/2 centres exhibit a large hyperfine structure which shows a variation with temperature. 25 shells of neighbour nuclei are resolved for CdSeSn by means of the Electron nuclear double resonance (ENDOR) technique. All shells belong to one of three distinct shell symmetries of the lattice thus confirming a high symmetry defect. Additional Sn respectively Ge related spectra are described and interpreted as complex centres correlated with lithium.     

Observation of the triplet metastable state of shallow donor pairs in AlN crystals with a negative-U behavior: a high-frequency EPR and ENDOR Study

Theoretical predictions about the n-type conductivity in nitride semiconductors are discussed in the light of results of a high-frequency EPR an ENDOR study. It is shown that two types of effective-mass-like, shallow donors with a delocalized wave function exist in unintentionally doped AlN. The experiments demonstrate how the transformation from a shallow donor to a deep (DX) center takes place and how the deep DX center can be reconverted into a shallow donor forming a spin triplet and singlet states.     

Room-Temperature Level Anticrossing and Cross-Relaxation Spectroscopy of Spin Color Centers in SiC Single Crystals and Nanostructures

A sharp variation of the near infrared photoluminescence intensity for spin-3/2 color centers in hexagonal (4H-, 6H-) and rhombic (15R-) SiC polytypes in the vicinity of level anticrossing (LAC) and cross-relaxation in an external magnetic field at room temperature are observed. This effect can be used for a purely all-optical sensing of the magnetic field with nanoscale spatial resolution. A distinctive feature of the LAC signal is a weak dependence on the magnetic field direction that allows monitoring of the LAC signals in the nonoriented systems, such as powder materials, without need to determine the nanocrystal orientation in the sensing measurements. Furthermore, an LAC-like signal is also observed for the spin color centers (NV centers) in diamond in low magnetic fields with only marginal dependence on the magnetic field direction. This effect is enabled to detect weak magnetic fields using nanodiamond samples in the form of disordered mixture. In addition, the optically detected magnetic resonance and LAC techniques are suggested to serve as a simple method to determine the local stress in nanodiamonds under ambient conditions.     

Preservation of endometallofullerene La@C82 in polycarbonate: EPR, ENDOR, and NMR studies

On embedding in poly(bisphenol A carbonate) film, La@C₈₂ has featured the exclusive stability against oxygen for more than 1 year's storage of the polymer films on air. The EPR spectral parameters of La@C₈₂ have occurred to be sensitive to the segmental mobility and the phase transition of the polymer from the glassy to the high-elasticity state. Furthermore, the intense matrix ¹H-electron nuclear double resonance (ENDOR) signal discovered in this system testifies the partial transfer of the electron spin density outside the fullerene cage onto the polymer protons. The ¹³⁹La NMR spectrum of the same suggests that La@C₈₂ forms nanoparticles, in which the metal atoms strongly interact with the delocalized electrons. The “spin-leakage” of the fullerene shell, along with the tendency of endohedral fullerenes (EMF) to form nanoparticles, is worth consideration in sight of their applications in material sciences.     

Transformation of Radiation-Induced Molecular Point Defects and Color Centers in LiF Crystals under Influence of Light

Physics of the Solid State - The influences of UV light and integral light pulses from lamps on γ-irradiated LiF crystals with impurities of hydroxyl and magnesium ions have been investigated....     

晶体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱研究

在强场耦合图像中,采用双自旋-轨道耦合(SO)参量模型建立了过渡族3d2(3d8)离子的三角对称下全组态光谱能级和电子顺磁共振(EPR)公式.与经典的晶体场理论(仅考虑中心金属离子的自旋-轨道耦合作用)相比较,该公式还包括了配体离子的自旋-轨道耦合作用的贡献,这一模型在应用于计算共价性较强的晶体光谱和电子顺磁共振谱可得到合理的结果.作为验证,用完全对角化方法研究了品体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱,结果表明,理论与实验很好地符合.建立的全组态谱能级和电子顺磁共振公式为更精确地计算光谱和电子顺磁共振谱提供了一条可行方法.     

EPR, Optical Absorption and Superposition Model Study of Fe3+-Doped Ammonium Dihydrogen Phosphate Single Crystals

X-band electron paramagnetic resonance (EPR) studies are carried out on Fe³⁺ ions doped in ammonium dihydrogen phosphate (ADP) single crystals at room temperature. The crystal field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations. The obtained values of spin Hamiltonian and zero-field parameters of the Fe³⁺ ion in ADP are: g = 1.994 ± 0.002, |D| = (220 ± 5) × 10^?4 cm^?1 and a = (640 ± 5) × 10^?4 cm^?1. On the basis of EPR data, the site symmetry of the Fe³⁺ ion in the crystal is discussed. The Fe³⁺ ion enters the lattice substitutionally replacing the NH₄ ⁺ sites. The optical absorption of the crystal is also studied at room temperature in the wavelength range of 195–925 nm. The energy values of different orbital levels are calculated. The observed bands are assigned as transitions from the ⁶ A _1g (S) ground state to various excited quartet levels of the Fe³⁺ ion in a cubic crystalline field. From the observed band positions, Racah interelectronic repulsion parameters (B and C), cubic crystal field splitting parameter (D _q ) and Trees correction are calculated. There values are: B = 970, C = 1,923, D _q  = 1,380 cm^?1 and α = 90 cm^?1, respectively. On the basis of EPR and optical data, the nature of bonding in the crystal is discussed. The zero-field splitting (ZFS) parameters are also determined theoretically using B _kq parameters estimated from the superposition model. The values of ZFS parameters thus obtained are |D| = (213 ± 5) × 10^?4 cm^?1 and |E| = (21 ± 5) × 10^?4 cm^?1.     

Tryptophan radicals as reaction intermediates in versatile peroxidases: Multifrequency EPR, ENDOR and density functional theory studies

Versatile peroxidases are a new class of ligninolytic enzymes secreted by fungi from the group of white-rot basidiomycetes. Versatile peroxidase (VP) is a structural hybrid between lignin and manganese peroxidase. This hybrid combines the catalytic properties of the two above peroxidases being able to catalyze Mn(II)-dependent and Mn(II)-independent reactions. A long-range electron transfer mechanism has been inferred for the oxidation of big substrate molecules starting from an exposed tryptophan to the heme cofactor. A neutral tryptophan radical has been identified in VP fromBjerkandera adusta andPleurotus eryngii, after H₂O₂ activation and assigned to a specific tryptophan residue using multifrequency electron paramagnetic resonance and electron-nuclear double resonance spectroscopy. Comparative density functional theory calculations were performed for tryptophan neutral and cation radical species, considering also the effect of the polar environment surrounding the radical. The functional role of the radicals is discussed in the context of mechanistic models for VP.     

Pulse EPR, ENDOR, and ELDOR Study of Anionic Flavin Radicals in Na+-Translocating NADH:Quinone Oxidoreductase

The Na⁺-translocating nicotinamide adenine dinucleotide (NADH):quinine oxidoreductase (Na⁺–NQR) is a component of respiratory chain of various bacteria and it generates a redox-driven transmembrane electrochemical Na⁺ potential. It contains four different flavin prosthetic groups, including two flavin mononucleotide (FMN) residues covalently bound to the subunits NqrB and NqrC. Na⁺–NQR from Vibrio harveyi was poised at different redox potentials to prepare two samples, containing either both FMN_NqrB and FMN_NqrC or only FMN_NqrB in a paramagnetic state. These two samples were comparatively studied using pulse electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR), and electron-electron double resonance (ELDOR) spectroscopy. The echo-detected EPR spectra and electron spin relaxation properties were very similar for flavin radicals in both samples. The splitting of the outer peaks in the proton ENDOR spectra, assigned to the C(8α) methyl protons, allows to identify both radicals as anionic flavosemiquinones. The mean interspin distance of 20.7 Å between these radicals was determined by pulse ELDOR experiment, which allows to estimate the edge-to-edge distance (r _e) between these flavin centers as: 11.7 Å < r _e < 20.7 Å. The direct electron transfer between FMN_NqrB and FMN_NqrC during the physiological turnover of the Na⁺–NQR complex is suggested.