A New EPR Data on the MA1 and NIRIM8 (NP1) Phosphorus-Related Centers in Synthetic 1b Diamonds

Microdiamonds grown under high-pressure and high-temperature conditions from a P–C medium at different temperatures have been studied by electron paramagnetic resonance (EPR). Two paramagnetic centers P1 and MA1 were observed in microdiamonds grown at 1,873 K. Analysis of weak lines around these centers suggests that they may be due to ¹³C hyperfine structure (HFS) of the MA1 center. The calculated s/p hybridization parameter for this carbon atom (C₁) was similar to that for the undistorted lattice. At a growth temperature of 1,973 K, in addition to MA1 and P1, a new center, labeled NP1, with HFS from nitrogen and phosphorus atoms and with EPR parameters similar to NIRIM 8 was identified. The NP1 (NIRIM8) centers have an electron spin S = 1/2. We propose that nitrogen–phosphorus defects are created through subsequent migration of nitrogen atoms towards phosphorus atoms upon increasing of the growth.     

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.     

Mössbauer study of Fe in 3C-SiC following 57Mn implantation

Our investigations on substitutional and interstitial Fe in the group IV semiconductors, from ⁵⁷Fe Mössbauer measurements following ⁵⁷Mn implantation, have been continued with investigations in 3C-SiC. Mössbauer spectra were collected after implantation and measurement at temperatures from 300 to 905 K. Following comparison with Mössbauer parameters for Fe in Si, diamond and Ge, four Fe species are identified: two due to Fe in tetrahedral interstitial sites surrounded, respectively, by four C atoms (Fe_i.C) or four Si atoms (Fe_i,Si) and two to Fe in (or close to) defect free or implantation damaged substitutional sites. An annealing stage at 300–500 K is evident. Above 600 K the Fe_i,Si fraction decreases markedly, reaching close to zero intensity at 905 K. This is accompanied by a corresponding increase in the Fe_i,C fraction.     

Magnetism and the magnetocaloric effect in PrMn1.6Fe0.4Ge2

The magnetic and magnetocaloric properties of PrMn_1.6Fe_0.4Ge₂around the ferromagnetic transitions T _C ^inter ~ 230 K and T _C ^Pr ~ 30 K have been investigated by magnetisation, ⁵⁷Fe Mössbauer spectroscopy and electron paramagnetic resonance (EPR) measurements over the temperature range 5–300 K. The broad peaks in magnetic entropy around T_C ^inter (intralayer antiferromagnetism of the Mn sublattice to canted ferromagnetism) and T_C ^Pr (onset of ferromagnetic order of Pr sublattice in addition to ferromagnetically ordered Mn sublattice) are typical of second order transitions with maximum entropy values of -ΔS _M ~ 2.0 J/kg K and -ΔS _M ~ 2.2 J/kg K respectively for ΔB = 0–6 T. The EPR signal around T = 48 K of g value g ~ 0.8 is consistent with paramagnetic free ion Pr^3?+?. Below T_C ^Pr ~ 30 K the g value increases steadily to g ~ 2.5 at 8 K as saturation of the Pr^3?+? ion is approached. The EPR measurements indicate additional effects in this system below T ~ 20 K with the appearance of EPR signals of low g value g ~ 0.6.     

EPR study of the transformations in nickel containing centres at heated synthetic diamonds

Electron paramagnetic resonance (EPR) was used to investigate the transformation of as grown nickel and nitrogen defects at the annealing of synthetic diamonds, obtained by the temperature gradient method. Structural models and formation mechanisms of the seven nickel containing paramagnetic centres (NE1-NE7) in synthetic diamonds are discussed. A common structural fragment of NE1-NE4 centres is a double semivacancy, in centre of which Ni⁺ ion is located. The NE6, NE7 centres are proved to operate as shallow electronic traps. The effects observable for NE5 centres are supposed due to an internal electronic transformation in them. The problem of charge compensators for nickel ions is also discussed. The features observable in the charge transfer processes under X-ray irradiation for nickel and nitrogen containing centres suggest that donor nitrogen serves as a bulk charge compensator for substitutional nickel and NE1 centres.     

A novel use of hyperfine structure in the electron paramagnetic resonance of interacting pairs of paramagnetic defects in diamond

It is the hyperfine structure of ¹⁴N and ¹³C in the electron paramagnetic resonance (EPR) spectrum which indicates that the unpaired electron of a single substitutional nitrogen atom in diamond is in one of the four anti-bonding N-C orbitals. We show that, for diamonds containing a very high concentration of nitrogen, the hyperfine structure of interacting pairs of nitrogen atoms indicates that for close neighbours there are unique orientations of the constituent N-C bonds, while at larger distances the orientations are random. This revised version was published online in August 2006 with corrections to the Cover Date.     

Room Temperature High-Field Spin Dynamics of NV Defects in Sintered Diamonds

Sintered oriented nanodiamond arrays with the extremely high concentrations of the nitrogen-vacancy (NV) centers (up to 10³ ppm) were investigated by the W-band (94 GHz) electron spin echo electron paramagnetic resonance techniques. The NV centers were fabricated by the high-pressure high-temperature sintering of detonation nanodiamonds (DND) without the post or prior irradiation of the samples. The processes of polarization and recovery of the equilibrium population of the spin sublevels by optical and microwave pulses have been examined at room temperature in high magnetic fields corresponding to the fine-structure transitions for the NV defects at 94 GHz (3,250–3,450 mT). A long spin coherence time of 1.6 μs and spin–lattice relaxation time of 1.7 ms were measured. The results were compared with those obtained on the NV centers fabricated by the irradiation and subsequent annealing of the commercially available bulk diamonds. It was shown that the relaxation characteristics of the NV defects were similar in the both types of the samples despite the extremely high concentrations of NV defects and isolated nitrogen donors in the sintered DND.     

Matrix Isolation Infrared Spectroscopic and Density Functional Theory Study of the 1:1 Complex of Bromocyclohexane with NH3: Evidence for a Weak C–H–N Hydrogen Bond

ABSTRACT

The hydrogen-bonded bromocyclohexane–ammonia complex has been isolated and characterized for the first time in argon matrices at 16 K. Coordination of the proton adjacent to the Br substituent on the cyclohexane ring to the amino nitrogen was evidenced by distinct blue shifts of bending modes involving the H-C₁–Br unit. In particular, C–C₁–Br, H–C₁–Br, and C–C₁–H bending modes produced blue shifts ranging from 2.8 to 12.2 cm^?1. Density Functional Theory (DFT) calculations at the B3LYP/6–31 + G(d, p) level yield an essentially linear Br–C₁–H–NH₃ hydrogen bond with a C-H–N distance of 2.412 Å and a hydrogen bond energy of 2.95 kcal/mol.     

The measurement of cone length and range in etched plastics

Abstract

Group V impurities implanted at 400 keV into silicon have been detected in substitutional lattice positions by EPR. Three samples of VFZ, p-type 1200–1500 ohm-cm silicon from the same ingot were implanted with As⁷⁵, Sb¹²¹, and Sb¹²³, respectively. The EPR spectrum of each implanted substitutional impurity was observed after annealing the lattice damage. Only the isotope implanted in each sample was seen. Since only those donors which are electrically active can be observed, this technique measures the electrically active fraction of the implanted species. Upon annealing to 970°C, most of the antimony was active whereas only about 1/5 of the arsenic was observed. Comparisons with backscattering results indicate that between 350 and 600°C, ～95 per cent of the implanted antimony is substitutional but ～0 per cent is electrically active. The increase in electrical activity at 600°C is due to the rise of the Fermi level to the donor level as the residual lattice damage anneals. The paramagnetic damage centers observed were those also seen in oxygen-implanted silicon, Si-P3 and Si-Pl, but the Si-P3 center was not as well resolved and grows upon annealing to 200°C.     

Identification of substitutional and interstitial Fe in 6H-SiC

Iron impurities on interstitial (Fe_i) and substitutional sites (Fe_S) in SiC have been detected by ⁵⁷Fe emission Mössbauer spectroscopy following implantation of radioactive ⁵⁷Mn⁺ parent ions. At temperatures <900 K two Fe_i species are found, assigned to quasi-tetrahedral interstitial sites surrounded by, respectively, four C (Fe_i,C) or Si atoms (Fe_i,Si). Above 900 K, the Fe_i,Si site is proposed to “transform” into the Fe_i,C site by a single Fe_i jump during the lifetime of the Mössbauer state (T _1/2?=?100 ns). Fe_i,C and substitutional Fe_S sites are stable up to >1,070 K.     

Investigation of structure and magnetic characteristics of Ni-implanted AlGaN films

The structural, valence of elements and magnetic characteristics of Ni-implanted Al_0.5Ga_0.5N films, deposited on Al₂O₃ substrates by metalorganic chemical vapor deposition (MOCVD), were reported. Ni ions were implanted into Al_0.5Ga_0.5N films by Metal Vapor Arc (MEVVA) sources under the energy of 100 keV for 3 h. The films were annealed at 900 K in the furnace for the transference of Ni ions from interstitial sites to substitutional sites in AlGaN and activating the Ni³⁺ ions. Characterizations were carried out in situ using X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS) and Vibrating sample magnetometer (VSM), indicating that the films have wurtzite structure without forming a secondary phase after annealing. Ni ions were successfully implanted into substitutional sites of Al_0.5Ga_0.5N films and the chemical bonding states of Ni³⁺ is Ni–N. The apparent hysteresis loops prove the films exhibited ferromagnetism at 300 K. The room temperature (RT) M_s and H_c obtained were approximately 0.22 emu/g and 32.97 Oe, respectively. From the first-principles calculation, A total magnetic moment of 2.86 μB per supercell is calculated: the local magnetic moment of NiN₄ tetrahedron, 2.38 μB, makes the primary contribution. The doped Ni atom hybridizes with its four nearby N atoms in NiN₄ tetrahedron, then N atoms are spin polarized and couple with Ni atom with strong magnetization, which result in ferromagnetism. Therefore, the p-d exchange mechanism is responsible for ferromagnetism in Ni-doped AlGaN. It is expected that the room temperature ferromagnetic Ni-doped Al_0.5Ga_0.5N films can make it possible to the applications for the spin electric devices.     

彩色金刚石中过渡金属离子的谱学研究

过渡金属镍、钴和铁是高温高压法合成金刚石的常用触媒,已有研究表明：采用镍、钴作触媒所合成的金刚石中存在镍、钴离子,部分天然金刚石含有镍离子;镍、钴离子以替代方式或间隙形式进入金刚石的晶格,并能与杂质氮形成复合体。为了探寻彩色金刚石中过渡金属离子存在的谱学标志,确定镍、钴离子在彩色金刚石中的赋存状态,文章对6颗彩色天然与合成金刚石进行了扫描电镜-能谱、显微红外光谱、光致发光谱、电子顺磁共振谱(EPR)等测试研究。结果表明天然与合成的样品都具有与镍、钴有关的发光中心与EPR结构：包括西澳的蓝灰色天然金刚石中与镍有关的884.6 nm等发光中心,以及天然变色金刚石中与钴有关的发光中心。对各种谱学测试结果的综合分析,得出样品中存在镍、钴离子并与杂质氮形成各种Ni-N或Co-N复合体的结论,其中在天然金刚石中发现钴离子在该领域研究中尚属首次。     

Formation of Fe i –B pairs in silicon at high temperatures

We report on the detection of Fe _i –B pairs in heavily B doped silicon using ⁵⁷Fe emission Mössbauer spectroscopy following implantation of radioactive ⁵⁷Mn⁺ parent ions (T _1/2?=?1.5 min) at elevated temperatures >?850 K. The Fe _i –B pairs are formed upon the dissociation of Fe _i –V pairs during the lifetime of the Mössbauer state (T _1/2?=?100 ns). The resulting free interstitial Fe_i diffuses over sufficiently large distances during the lifetime of the Mössbauer state to encounter a substitutional B impurity atom, forming Fe _i –B pairs, which are stable up to ～1,050 K on that time scale.     

Influence of C60 Aggregation on Pseudorotation in the Excited Triplet State Probed by Multifrequency Time-Resolved EPR

The influence of C₆₀ aggregation on time-resolved (TR) electron paramagnetic resonance (EPR) of C₆₀ in the excited triplet state was investigated by multifrequency EPR techniques. Temperature-independent X-band (9.7 GHz) TR-EPR spectra were observed in a fresh toluene solution, while temperature-dependent ones were reported in literatures. The experimental spectra in this study indicated that the pseudorotation of pristine C₆₀ in frozen toluene solution is not frozen out even at lower temperatures. Careful investigations of TR-EPR and its decay kinetics demonstrated that the pseudorotation can be affected by C₆₀ aggregation. A comparison between X- and W-band (94.9 GHz) results indicated that the aggregation can be accelerated by a capillary effect. Three decay constants were extracted from the analysis of the decay kinetics. The fastest component was ascribed to the pseudorotation, which was independent of temperature in the range of 10–40 K. The temperature dependences of the decay kinetics showed that the pseudorotation is not affected by C₆₀ aggregation at higher temperatures.     

Annealing of point defects in p-type germanium after electron irradiation at liquid nitrogen temperature

Annealing of radiation induced defects in p-type germanium was studied by measuring Hall coefficient and conductivity. The dopant was gallium or indium. It was concluded that the annealing stage between 80° and 140°K is caused by migration of the vacancy to the sink of an impurity atom. In this stage the vacancy migrates to a substitutional impurity atom and makes an association. The activation energy of the stage was found tO be 0.1 ev ad it is regarded to be that of the vacancy migration. The model for the annealing stage which occurs in the range 220 to 270°K is proposed as follows: An interstitial impurity atom migrates to a substitutional impurity atom and makes an association. From the activation energy of the stage, the migration energy of the interstitial impurity atom was concluded to be about 0.4 eV for gallium and 0.7 eV for indium atoms.     

Phenomena associated with diffusion of trivalent iron in amethyst quartz

In natural amethyst crystals from different locations changes in the EPR, optical and infrared spectra were measured as a function of annealing temperature. After heating to 650°C for two hours the concentration of Fe(III) on substitutional sites with alkali ions as charge compensators is equal in all crystals irrespective of its initial concentration. Establishment of a heterogeneous equilibrium due to formation of iron oxide particles (presumably Fe₂O₃) previously characterized by their EPR and optical spectra is thus confirmed. Initially unequal distributions of Fe(III) among the three equivalent sites of the quartz structure also become equal under this treatment. From comparison with literature data for MnCl₂ precipitates in NaCl the average particle size can be estimated to be about 100 nm allowing an estimate of the diffusion coefficient of Fe(III) at 650°C. In one amethyst with a high concentration of hydrogen a large amount of the substitutional Fe(III) is charge compensated by hydrogen. Thermal destruction of these centers does not correlate with the intensities of infrared absorption bands in the OH stretching vibration region.     

EPR and Magnetization Studies of Polymer-Derived Fe-Doped SiCN Nanoceramics Annealed at Various Temperatures: Blocking Temperature,Superparamagnetism and Size Distributions

X-band EPR spectra on SiCN ceramics, doped with Fe(III) ions, annealed at 800 °C, 1000 °C, 1100 °C, 1285 °C, and 1400 °C have been simulated to understand better their magnetic properties, accompanied by new magnetization measurements in the temperature range of 5–400 K for zero-field cooling (ZFC) and field cooling (FC) at 100C. The EPR spectra reveal the presence of several kinds of Fe-containing nanoparticles with different magnetic properties. The maxima of the temperature variation of ZFC magnetization were exploited to estimate (i) the blocking temperature, which decreased with annealing temperature of the samples and (ii) the distribution of the size of Fe-containing nanoparticles in the various samples, which was found to become more uniform with increasing annealing temperature, implying that more homogenous magnetic SiCN/Fe composites can be fabricated by annealing at even higher temperatures than 1400 °C to be used as sensors. The hysteresis curves showed different behaviors above (superparamagnetic), below (ferromagnetic), and about (butterfly shape) the respective average blocking temperatures, 〈T_B〉. An analysis of the coercive field dependence upon temperature reveals that it follows Stoner–Wohlfarth model for the SiCN/Fe samples annealed above 1100 °C, from which the blocking temperatures was also deduced.     

An Electron Paramagnetic Resonance Study of the Orbital Ordering Compound MgTi<Subscript>2</Subscript>O<Subscript>4</Subscript>

We report the electron paramagnetic resonance (EPR) studies of MgTi₂O₄ in the 300–140 K range. Above the transition temperature T _t (~258 K), the EPR results indicate that MgTi₂O₄ is paramagnetic. The parameters of the EPR spectra show an anomalous change at T _t. The clear EPR lines can be observed in temperature between T _t and 220 K. Besides that the EPR intensity, g value, and EPR linewidth increase with decreasing temperature; in temperature range below 220 K, no clear EPR line can be detected. The EPR spectra results demonstrate that magnetic spin-singlet state and the orbital density wave of MgTi₂O₄ system are formed gradually with decreasing temperature at low temperature range.     

Incommensurate Phases of the MgSiF6·6H2O Crystals: EPR and Group-Theoretical Studies

The group-theoretical study of the structural phase transition to incommensurate state of MgSiF₆·6H₂O crystals, revealed by the electron paramagnetic resonance (EPR) method, as well as analysis of the EPR results, are presented. The consideration of temperature dependences of Mn²⁺ admixture ion EPR spectrum symmetry and parameters leads to the conclusion that at T _i1 = 370 ± 0.3 K they undergo second-order structural phase transition to incommensurately modulated state, the order parameter of this transition may be the angle of [Mg(H₂O)₆]²⁺ octahedra rotation around crystal C ₃ axis. At temperature decreasing below T _i1 the gradual transformation of plane-wave modulation of lattice displacements into soliton mode occurs, which is interrupted by the first-order phase transition at T _i2 = 343 ± 0.3 K accompanied by abrupt decrease in modulation amplitude. At T _c = 298.5 ± 0.3 K the first-order improper ferroelastic phase transition into monoclinic phase occurs. The group-theoretical analysis of the phase transition at T _i1 in the investigated crystals, carried out for the first time, has shown that the existence of the incommensurately modulated phase is conditioned by the fundamental reasons (presence of Lifshitz invariant). The conclusions of this analysis on the nature of order parameter, the structural motifs of incommensurate phase and the possible character of temperature evolution of the structure are in agreement with the EPR investigation data.     

Studying the effect of hydrogen on diamond growth by adding C10H10Fe under high pressures and high temperatures

In this paper, hydrogen-doped industrial diamonds and gem diamonds were synthesized in the Fe–Ni–C system with C₁₀H₁₀Fe additive, high pressures and high temperatures range of 5.2–6.2?GPa and 1250–1460°C. Experimental results indicate similar effect of hydrogen on these two types of diamonds: with the increasing content of C₁₀H₁₀Fe added in diamond growth environment, temperature is a crucial factor that sensitively affects the hydrogen-doped diamond crystallization. The temperature region for high-quality diamond growth becomes higher and the morphology of diamond crystal changes from cube-octahedral to octahedral. The defects on the {100} surfaces of diamond are more than those on the {111} surfaces. Fourier transform infrared spectroscopy (FTIR) results indicate that the hydrogen atoms enter into the diamond crystal lattice from {100} faces more easily. Most interestingly, under low temperature, nitrogen atoms can also easily enter into the diamond crystal lattice from {100} faces cooperated with hydrogen atoms.