EPR study of the peculiarities of incorporating transition metal ions into the diamond structure

In this paper previously obtained data is reviewed and new data is discussed about nickel-containing centers in diamonds. These data are used to suggest interpretation of new data about cobalt-containing centers and to understand the influence of iron on the defects in diamonds grown in the iron system. A newly discovered nickel-nitrogen center has three nitrogen atoms in the first neighbor sphere around the double semi-vacancy and looks like the N3 (P2) center. In diamonds grown in the cobalt system two new types of cobalt-containing centers were found (NLO2 and NWO1). Both centers have electron spinS=1/2 and hyperfine structure from one cobalt ion (I=7/2 with natural abundance 100%). A case can be made for a double semi-vacancy structure for these defects. Special growth of diamond in the system enriched in¹⁵N decreased the line width down to 0.6 G, but gave no direct evidence of the existence of nitrogen in the defect structure. Asymmetrical shapes of the lines in the electron paramagnetic resonance (EPR) spectra of cobalt-containing centers with opposite signs in low and high magnetic field parts of spectra are due to very sensitive spin-Hamiltonian parameters of these defects to the lattice distortions. Annealing of cobalt-containing crystals at 2600 K produces the disappearance of all cobalt-containing EPR spectra, probably due to the capture of an additional nitrogen atom and the creation of a 3d⁶ diamagnetic state. In diamonds grown in the iron system with a high content of nitrogen there is evidence of an influence of ferromagnetic inclusion on the exchange interaction between substitutional nitrogen as an additional channel of indirect exchange interaction.     

Hyperfine interactions of muonium and hydrogen in semiconductors: Cluster calculations

The electronic structure of muonium (Mu) located at different interstitial sites of the silicon crystal is calculated by the complete neglect of differential overlap (CNDO) and intermediate neglect of differential overlap (INDO) methods. Calculations of the electronicg- and hyperfine interaction tensors of the impurity atom are performed. The results obtained are compared with the experimental properties of both “normal” (Mu′) and “anomalous” (Mu^*) muonium centers. It is shown that the most likely dynamic model for Mu′ is that in which neutral Mu diffuses rapidly in the silicon lattice, whereas for Mu^* it is the model wherein interstitial Mu is located at the bond-center site. A correlation is made between the characteristics of the hydrogen-bearing Si-AA9 center, recently observed by EPR in a silicon crystal, and those of Mu^*. The Si-AA9 center is shown to be a hydrogen-bearing paramagnetic analogue of the Mu^* center.     

Mechanochemical penetration of helium atoms into Pd84.5-Si15.5 and Ni78-Si8-B14 eutectic amorphous films extended in liquid 3He and 4He

The penetration of helium atoms into amorphous films extended to fracture in liquid helium has been investigated. It is found that helium atoms penetrate into the eutectic alloy films Pd_84.5-Si_15.5 in ³He (T=0.5 K) and Ni₇₈-Si₈-B₁₄ in ⁴He (T=4.2 K). The spectra of helium liberation from these materials after deformation are obtained upon dynamic (4–5 K/min) annealing at T=293–1323 K. The maximum amount of helium is observed in the regions of local plastic microshears running across the whole width of films and also in the sample regions containing fracture macrocracks and isolated groups of slip bands. The spectra of helium liberation from different regions of destroyed samples show several peaks that correlate with the temperatures of crystallization and melting of the studied films. The data obtained are interpreted within the model of mechanochemical penetration of helium atoms through the dynamically excited dislocation-like defects, which are typical of the amorphous films under consideration.     

Analysis of dynamic dislocation-assisted penetration of helium into tin and cadmium deformed by stretching in liquid helium

Curves describing the liberation of helium from Sn single crystals deformed by stretching in liquid ³He and ⁴He and from Cd polycrystals in ⁴He are analyzed. It is found that the stress-strain diagrams for Sn are in qualitative agreement with the concentration of helium in the samples. The peaks in the amount of He liberated from Cd and Sn at temperatures both below and above the melting point are found to be of different types. The reasons for this difference are investigated, and the assumption concerning the existence of a chemical bond between helium atoms and structural defects of the metals under investigation is formulated.     

Dynamic diffusion of helium into various types of solids during their deformation and dispersion

Quantitative relations governing the penetration of helium atoms into various types of solids in the course of their plastic deformation in liquid ³He (T = 0.6–1.8 K) and ⁴He (T = 4.2 K) and dispersion in gaseous helium at 300 K were obtained and analyzed. Experiments were carried out on metals with different lattice types, ionic single crystals, amorphous alloys, and barite and titanium dioxide powders dispersed in helium. Curves illustrating helium extraction from deformed specimens under dynamic annealing were obtained. The temperature range of helium extraction was found to correlate with the melting temperature and the initial and deformed structures of a material, which determine the number and character of helium traps present in the material. The dependence of helium penetration intensity on the type of defects forming under plastic deformation for various materials, as well as the formation of chemical bonds of helium atoms to the defected structure of these materials, is discussed.     

Role of atomic inelastic collisions in a Cs-He steady state discharge

The population of various excited states and the electron temperature in a mixture of cesium vapor and helium have been measured spectroscopically in a stationary electrical discharge where helium atoms remain in their ground state. An equilibrium between the populations of highly excited cesium levels was observed to be characterized by a Boltzmann temperature equal to the gas temperature. It is concluded that the populations of these high levels are more influenced by Cs¹+He inelastic collisions than by Cs¹+e collisions when [He]/[e]?10⁶. The influence of the helium atoms has also been observed on the relation between electron temperature and electron density.     

The energy of thermal electrons in electron beam created helium discharges

We have measured the electron energy of the thermal group of electrons in both longitudinal and transverse electron beam created helium glow discharges. The measurement technique employs the ratio of intensities of spectral lines in the 2s³S?np³P He I series. Values of kT_e between 0.07 and 0.11 eV were obtained. These energies are typical of the beam-generated electric field free plasmas. The competitive loss of helium ions by recombination and by charge transfer in a He?Hg electron beam created plasma is calculated. The results are applied to the Hg⁺ laser pumping scheme using a electron beam created He?Hg plasma.     

EPR of trivalent iron centers in SrF<Subscript>2</Subscript>: Fe crystals

Paramagnetic centers of three types are found in SrF₂: Fe(0.2 at. %) crystals. Two types are observed in the untreated crystals, and the third type appears only in the crystals irradiated by x-rays. The EPR spectra of one type of centers in a nonirradiated crystal and of the centers that appear after irradiation are described by the orthorhombic Hamiltonians with an effective spin S _eff = 5/2. In both cases, the centers are observed at 4.2 and 77 K. The principal axes of the spin Hamiltonians for them are along the 〈001〉, 〈1 \(\overline 1 \) 0〉, and 〈110〉 axes. However, the fine-structure parameters of their EPR spectra differ significantly. An analysis of the superhyperfine structure (SHFS) of the EPR spectra shows that the radiation center forms through substitution of a Fe²⁺ ion for a Sr²⁺ cation. Under x-ray irradiation, the Fe²⁺ ion transforms into the Fe³⁺(⁶ A _1g ) state and is displaced to an off-center position along the C ₂ axis of its coordination cube. The absence of a SHFS in the EPR spectra of the orthorhombic centers in a nonirradiated crystal makes it impossible to determine their molecular structure unambiguously. The most probable model is proposed for this structure. The EPR spectra of centers of the third type were observed only at 4.2 K, and the structure of these centers was not studied.     

Highly heterogeneous distributions of gadolinium impurities in Pb1 − x Gd x Te crystals when x > 0.005

Two types of Gd³⁺ impurity centers are identified in heavily doped narrow-gap PbTe semiconductor by means of EPR at a frequency of 9.3 GHz and temperature T = 4.2 K. Magnetic properties of both centers have cubic symmetry, but their EPR spectra are characterized with different fine structure constants. The origin of the centers and their characteristics are discussed.     

EPR parameters and defect structures of the off-center Ti ion on the Sr site in neutron-irradiated SrTiO3 crystal

The EPR parameters (g factors and hyperfine structure constants A) for the tetragonal Ti³⁺ center in cubic phase and the rhombic Ti³⁺ center in tetragonal phase in the neutron-irradiated SrTiO₃ crystals are calculated from the third-order perturbation formulas of EPR parameters for d¹ ions. These low-symmetry Ti³⁺ centers in both phases of SrTiO₃ are due to the Ti³⁺ ion at “off center” on the Sr²⁺ site. From the calculation, the defect models (including the direction and magnitude of the Ti³⁺ off-center displacement) of the two Ti³⁺ centers in SrTiO₃ are estimated and the EPR parameters of both Ti³⁺ centers are reasonably explained on the basis of the defect models. The results are discussed.     

Domain structure and phase transitions of LiKSO4:EPR of SO−4 centers

Analysis of the EPR of SO⁻₄ centers in LiKSO₄ crystals indicates that the SO⁻₄ centers are associated with local positive-ion vacancies. Twin-domains of the 〉110〈 types are observed to be temperature-dependent. The anomaly at 215 K on cooling is associated with a sudden growth of the twins and the anomaly at 190 K is associated with a p6₃ to p6₃P6,mc structural phase transition.     

Positron and deuteron depth profiling in helium-3-implanted electrum-like alloy

In spite of previous extensive studies, the helium behavior in metals still remains an issue in microelectronics as well as in nuclear technology. A gold-silver solid solution (Au₆₀Ag₄₀: synthetic gold-rich electrum) was chosen as a relevant model to study helium irradiation of heavy metals. After helium-3 ion implantation at an energy ranging from 4.2 to 5.6 MeV, nuclear reaction analysis (NRA) based on the ³He(d,p)⁴He reaction, was performed in order to study the thermal diffusion of helium atoms. At room temperature, NRA data reveal that a single Gaussian can fit the He-distribution, which remains unchanged after annealing at temperatures below 0.45 of the melting point. Slow positron implantation spectroscopy, used to monitor the fluence dependence of induced defects unveils a positron saturation trapping, which occurs for He contents of the order of 50-100 appm, whereas concentrations larger than 500 appm seem to favor an increase in the S-parameter of Doppler broadening. Moreover, at high temperature, NRA results clearly show that helium long range diffusion occurs, though, without following a simple Fick law.     

EPR study of radiation-induced defects in carbonate-containing hydroxyapatite annealed at high temperature

Radiation-induced (γ or UV) paramagnetic defects in carbonate-containing hydroxyapatite (HAP) annealed at high (600–950 °C) temperature were studied by EPR. The complex spectra reveal the presence of different paramagnetic species. Their contributions were found to be strongly dependent on the annealing temperature as well as microwave power, thus, by the adjustment of experimental conditions some of the components can be eliminated that allowed to record EPR spectra caused by no more than two types of paramagnetic defects. All experimental spectra were analyzed using computer simulation. The parameters of the paramagnetic defects detected were determined, and the centers models were discussed. It was found that high-temperature annealing influences essentially the formation of radiation-induced defects in HAP. The СО₃³⁻, О⁻ centers and oxygen vacancy V_O⁻ were shown to be the main stable γ-induced defects in the HAP annealed at high temperatures. New paramagnetic defect with the parameters g_|| = 2.002, g_⊥ = 2.0135 was detected and tentatively identified as an O-related radical. The γ-induced EPR response from СО₃³⁻ radicals was found to be more intense than response from CO₂⁻ in non-annealed HAP. UV-irradiation was found to create smaller amounts of paramagnetic defects in comparison with γ-rays. Besides, oxygen vacancy V_O⁻ was not observed, while two other centers (СО₃⁻ and the center of unknown nature) appear in the UV-induced EPR spectra.     

Pulsed EPR spectroscopy of Gd3+ centers in Ca1−x R x F2+x (R=La, Y) mixed crystals

A study of Gd³⁺ centers in Ca_1?x R _x F_2+x (R=La, Y) crystals using pulsed EPR spectroscopy is presented. The echo-induced EPR (ESE-EPR) spectrum shows, besides the signal of slightly perturbed cubic Gd³⁺ centers, a broad signal at g≈2 due to Gd³⁺ centers at low symmetry sites. To describe the effects of R³⁺ ions on the EPR Gd³⁺, a model, including cubic and linear R³⁺?2F _i ^? centers, is developed. Its predictions are compared with the experimental results. The composition dependence of the EPR signal due to slightly perturbed cubic Gd³⁺ centers in mixed Ca_1?x R _x F_2+x crystals is explained taking into account the different clustering tendency in La and Y crystals. Moreover, the formation of mixed clusters involving R³⁺ and Gd³⁺ ions is proposed for both series of samples. A greater clustering trend is found in the Y crystals than in the La ones. Gd³⁺ ions are found to be a “non innocent” paramagnetic probe for structural studies in these mixed crystals.     

Electron paramagnetic resonance of hydrogen in silicon

A review of the investigations by means of electron paramagnetic resonance (EPR) of hydrogen and hydrogen-related defects in crystalline silicon is presented. The main features of the EPR center Si-AA9 (bond-centered hydrogen), which is known as the hydrogenic analogue of the anomalous muonium (Mu^*) in silicon, are discussed. It was found that the process of annealing the AA9 center is characterized by an activation energy, E = 0.48 ± 0.04 eV with a second-order pre-exponential factor, K₀ = (1.25 ± 2.5) × 10^-7 cm³/s.

A detailed investigation by EPR of the defect (Si-AA1), which we identify as the hydrogen-related shallow donor in a positive charge state, is also presented. In particular it is shown that the H-related shallow donor is a helium-like center and its wave function has C_2v symmetry. Moreover, the main features of the series of EPR spectra in silicon characteristic for the implantation of hydrogen are presented.     

Observation of the spin polarization of Cs atoms during optical orientation of metastable helium atoms in alkali-helium plasma

We are the first to experimentally observe a magnetic-resonance signal of 6² S _1/2 Cs atoms by absorption of light from a helium lamp that was used to optically orient metastable 2³ S ₁ He atoms. The amplitude of the cesium signal proved to be almost three orders of magnitude lower than the amplitude of the magnetic resonance of 2³ S ₁ He atoms. Particular features of the creation and observation of the collisional polarization of cesium under conditions of alkali-helium plasma have been discussed.     

Dissymmetrization in X-irradiated RbTiOPO4 crystal

Electron paramagnetic resonance has been used to study the hole and electron paramagnetic centers formed in X-irradiated RbTiOPO₄, the crystals of the KTP family. X-irradiation of RbTiOPO₄ crystals at 77 K produced an oxygen hole center and four different trivalent titanium electron centers I₁, II, III and IV. Theg-tensors, their principal values and axes for the defects were calculated and compared with those for KTiOPO₄ centers. X-irradiation at 300 K produced another two oxygen hole centers and three electron centers I₁, I₂ and II. EPR spectra of the center II revealed dissymmetrization, i.e., irregular distribution of growth defects, between the physically equivalent sites lowering the point group symmetry of the local environment of paramagnetic centers Ti³⁺.     

Electronic excitations in BeAl<Subscript>2</Subscript>O<Subscript>4</Subscript>, Be<Subscript>2</Subscript>SiO<Subscript>4</Subscript>, and Be<Subscript>3</Subscript>Al<Subscript>2</Subscript>Si<Subscript>6</Subscript>O<Subscript>18</Subscript> crystals

Low-temperature (T = 7 K) time-resolved selectively photoexcited luminescence spectra (2–6 eV) and luminescence excitation spectra (8–35 eV) of wide-bandgap chrysoberyl BeAl₂O₄, phenacite Be₂SiO₄, and beryl Be₃Al₂Si₆O₁₈ crystals have been studied using time-resolved VUV spectroscopy. Both the intrinsic luminescence of the crystals and the luminescence associated with structural defects were assigned. Energy transfer to impurity luminescence centers in alexandrite and emerald was investigated. Luminescence characteristics of stable crystal lattice defects were probed by 3.6-MeV accelerated helium ion beams.     

On the nature of photoluminescence and EPR centers in glassy Ge2S3in terms of positron annihilation

The results of positron annihilation studies are discussed together with photoluminescence (PL) and EPR data for similar samples. The correlation between changes in e⁺-annihilation lifetime parametors, PL and EPR characteristics under doping of Ge₂S₃ glass with metals confirms the idea that these effects are related to point charged defects. The results obtained permit concluding that these defects (charged dangling bonds in the EPR and “fatigue of PL” cases) are situated at the boundaries of microinclusions. PL centers are probably associated with internal structure of the inclusions.     

Electron paramagnetic resonance in mixed crystals (BaF<Subscript>2</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript> activated by Ce<Superscript>3+</Superscript> ions

The electron paramagnetic resonance (EPR) spectra of mixed crystals (BaF₂)_{1?x? y}(LaF₃)_x(CeF₃)_y (y = 0.001 = 0.1%, x = 0–0.02) are investigated in a magnetic field H‖C₄ at a frequency of 9.5 GHz. The angular dependence of the EPR spectrum is measured for the sample with x = 0.02. The lines attributed to Ce³⁺ impurity centers with tetragonal symmetry and g factors (g_‖ = 0.75, g_⊥ = 2.4) close to those measured for the KY₃F₁₀: Ce³⁺ compound are separated in the complex EPR spectrum. The assumption is made that the aforementioned impurity centers are cubooctahedral clusters of the La₆F₃₇ type in which one of the La³⁺ ions is replaced by the Ce³⁺ ion.