Inverted EPR signal from nitrogen defects in a synthetic diamond single crystal at room temperature

Electron paramagnetic resonance (EPR) in diamond single crystals was studied. The crystals were grown using apparatuses of the “split-sphere” type in a Ni-Fe-C system using the temperature gradient method with a subsequent high-temperature high-pressure treatment. It was found that, after the high-temperature high-pressure treatment of a diamond sample, the EPR signal from the lattice defects containing nitrogen atoms became inverted with the growth of the microwave power in an H₁₀₂ resonator. In a constant polarizing magnetic field, when the microwave power applied to the diamond was low, a resonance absorption by the nitrogen defects took place, whereas, when the microwave power was high, an emission was observed. The inversion of the EPR lines of a single nitrogen atom substituting for a carbon atom at a diamond lattice site could be caused by the presence of a nickel atom with an uncompensated magnetic moment at the adjacent tetrahedral interstitial site. In synthetic diamond crystals that were not subjected to high-temperature high-pressure treatment, the inversion of the EPR signal from nitrogen atoms (P1 centers, nitrogen in the C form) was absent.     

Influence of annealing treatment on as-grown Ib-type diamond crystal at a high temperature and high pressure

In this paper,we report on the influence of annealing treatment on as-grown Ib-type diamond crystal under high pressure and high temperature in a china-type cubic anvil high-pressure apparatus.Experiments are carried out at a pressure of 7.0 GPa and temperatures ranging from 1700 C to 1900 C for 1 h.Annealing treatment of the diamond crystal shows that the aggregation rate constant of nitrogen atoms in the as-grown Ib-type diamond crystal strongly depends on diamond morphology and annealing temperature.The aggregation rate constant of nitrogen remarkably increases with the increase of annealing temperature and its value in octahedral diamond is much higher than that in cubic diamond annealed at the same temperature.The colour of octahedral diamond crystal is obviously reduced from yellow to nearly colorless after annealing treatment for 1 h at 1900 C,which is induced by nitrogen aggregation in a diamond lattice.The extent of nitrogen aggregation in an annealed diamond could approach approximately 98% indicated from the infrared absorption spectra.The micro-Raman spectrum reveals that the annealing treatment can improve the crystalline quality of Ib-type diamond characterized by a half width at full maximum at first order Raman peak,and therefore the annealed diamond crystals exhibit nearly the same properties as the natural IaA-type diamond stones of high quality in the Raman measurements.     

Optical and paramagnetic properties of natural diamonds implanted with hydrogen ions

We used IR spectroscopy and electron spin resonance (ESR) to investigate defect reconstruction processes occurring in diamond crystals due to their implantation with H⁺ ions with energies of 65–350 keV and subsequent isochronous annealing in the temperature range 250–1550°C. We found that most of the hydrogen in diamonds implanted with protons is in an IR-inactive state. Magnetic hysteresis related to radiation defects in diamond is observed for the first time at room temperature using ESR. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 485–490, July–August, 2007.     

氮掺杂金刚石{100}晶面的缺陷发光特性

氮是金刚石中最常见的杂质之一, 其对金刚石的缺陷发光具有重要的影响. 氮可以与金刚石中的本征缺陷形成复合缺陷. 本文首先利用阴极射线发光照片(CL)对一个高温高压合成的氮掺杂金刚石进行表征, 发现{100}晶面为蓝色, 然后利用透射电子显微镜(TEM)对该晶面进行电子辐照及后续退火处理, 以引入本征点缺陷进而形成含氮的复合缺陷, 并利用低温光致发光光谱(PL光谱)表征其缺陷发光特性, 发现该晶面主要以氮-空位复合缺陷(NV中心)发光为主, 并伴随着较弱的503 nm发光. 关键词： 金刚石 缺陷 发光     

Effects of a carbon convection field on large diamond growth under high-pressure high-temperature conditions

Large diamond crystals were successfully synthesized by a FeNi-C system using the temperature gradient method under high-pressure high-temperature conditions. The assembly of the growth cell was improved and the growth process of diamond was investigated. Effects of the symmetry of the carbon convection field around the growing diamond crystal were investigated systematically by adjusting the position of the seed crystal in the melted catalyst/solvent. The results indicate that the morphologies and metal inclusion distributions of the synthetic diamond crystals vary obviously in both symmetric and non-symmetric carbon convection fields with temperature. Moreover, the finite element method was applied to analyze the carbon convection mode of the melted catalyst/solvent around the diamond crystal. This work is helpful for understanding the growth mechanism of diamond.     

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba（N3）2

Additive Ba(N 3) 2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure (about 6.0 GPa) by employing the temperature gradient method.Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus.The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated.It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets.The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra.The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form,and the aggregated nitrogen concentration in diamond increases with temperature and duration.In addition,it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature.Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy.Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress,whereas diamond crystals heavily doped with the addition of Ba(N 3) 2 display the tensile stress.     

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.     

Low-temperature phase transition in α′-(BEDT-TTF)2IBr2 single crystals detected by the ESR method

A hysteresis of electron spin resonance spectra, which indicates a first-order phase transition, has been revealed in α′-(BEDT-TTF)₂IBr₂ single crystals in the temperature range 15–30 K. Two lines corresponding to the high-temperature and low-temperature phases have been observed in the ESR spectra.     

Interaction of Muons with H2/H3-Centres in Diamond

We report on transverse field muon spin rotation measurements on a nitrogen-rich type Ia diamond, both before and after the conversion of some of the aggregated nitrogen centres to nitrogen-vacancy complexes known as H2/H3-centres. The prompt fractions f and the spin relaxation rates λ were determined for the diamagnetic (μ_d) and the paramagnetic (Mu_T) states in the temperature range 10–300 K. The production of the nitrogen-vacancy complexes had little effect on the parameters of the Mu_T state for which f and λ remained unchanged at approximately 30% and 4 μs⁻¹, respectively. For the μ_d state, on the other hand, the formation of the H2/H3-centres resulted in an increase of the prompt fraction from 10(2)% to 20(3)%, and (for the first time) the spin relaxation rate showed a non-zero value of 0.020(3) μs⁻¹. These results show evidence of strong μ_d interactions with the nitrogen-vacancy complexes in diamond, and suggest a more complex structure for this state than a bare μ⁺. This revised version was published online in September 2006 with corrections to the Cover Date.     

Effects of carbon convection field on large diamond growth under high-pressure high-temperature conditions

Large diamond crystals were successfully synthesized by FeNi-C system using temperature gradient method under high-pressure high-temperature conditions. The assembly of the growth cell was improved and the growth process of diamond was investigated. Effects of the symmetry of carbon convection field around the growing diamond crystal were investigated systematically by adjusting the position of seed crystal in the melted catalyst/solvent. The results indicate that morphologies and metal inclusion distributions of the synthetic diamond crystals vary obviously in both symmetric and non-symmetric carbon convection fields with temperature. Moreover, finite element method was applied to analyze carbon convection mode of the melted catalyst/solvent around the diamond crystal. This work is helpful for understanding the growth mechanism of diamond.     

Synthesis of industrial diamonds using FeNi alloy powder as catalyst

Synthesis of diamond single crystals in Fe80Ni20 C system was carried out in a cubic anvil high-pressure and high-temperature apparatus. This paper reports that the surface morphology and inclusion distribution of the grown diamonds had been observed. It finds that the inclusions in cubic and octahedral diamonds radiated along certain crystal orientation, while the inclusion distribution in cubo-octahedral diamond seemed independent of crystal orientation. By using scanning electron microscope, the surface morphology of the three shapes of diamonds was observed. The results of Mossbauer spectrum indicated that there were iron-inclusions FeaC and Fe-Ni alloy in the diamonds. According to the Fe-C phase diagram, FeaC should have formed during the quenching process. Nickel might have an inhibitory effect on the formation of Fe3C.     

氮氢共掺杂金刚石中氢的典型红外特征峰的表征

所有天然Ia型金刚石红外光谱中都存在3107 cm-1特征峰,而在金属触媒直接合成的金刚石红外光谱中没有检测出3107 cm-1特征峰.本文在6.3 GPa,1500?C条件下,通过Fe70Ni30触媒中添加P3N5直接合成出具有3107 cm-1特征峰的氮氢共掺杂的金刚石.红外光谱分析表明,合成的金刚石中氢有两种存在形式:一种对应着乙烯基团C=CH2中C—H键的伸缩振动(3107 cm-1)和弯曲振动(1450 cm-1)的吸收峰,另一种对应着sp3杂化C—H键的对称伸缩振动(2850 cm-1)和反对称伸缩振动(2920 cm-1)的吸收峰.通过分析发现,3107 cm-1吸收峰与金刚石中聚集态的氮原子有关,当金刚石中没有聚集态的氮元素时,即使氮含量高也不会出现3107 cm-1峰;并且2850和2920 cm-1附近的吸收峰比3107 cm-1附近的吸收峰更为普遍存在.这说明sp3杂化C—H键比乙烯基团的C—H键更广泛存在于金刚石中,从两者的峰值看,天然金刚石中的氢杂质主要以乙烯基团C=CH2存在.3107 cm-1吸收峰与聚集态的氮原子的这种存在关系为天然金刚石形成机制的研究提供了一种新思路,同时较低的合成条件也可能为氢与其他元素共掺杂合成具有n型半导体特性的金刚石提供一个较理想的合成环境.     

Electron spin resonance detection and identification of nitrogen centers in nanodiamonds

Individual nitrogen centers N⁰ and nitrogen pairs N ₂ ⁺ have been detected and identified in natural diamond nanocrystals by means of the high-frequency electron spin resonance method. The N⁰ nitrogen centers have been observed in synthetic diamond nanocrystallites with a size of less than 10 nm produced by high-temperature high-pressure sintering of detonation nanodiamonds. Thus, the possibility of the stable state of impurity nitrogen atoms in diamond nanoparticles has been demonstrated.     

Magnetooptical microwave spectroscopy of the coherent magnetic state in the mixed valence compound SmB6 in the frequency range 40–120 GHz

In undoped pure single crystals of the mixed valence compound SmB₆ anomalous ESR absorption is observed in the frequency range v=40–120 GHz at temperatures of 1.8–4.2 K. The ESR for the case of the coherent ground state consists of two components corresponding to g-factors g ₁=1.907±0.003 and g ₂=1.890±0.003. The amplitude of both ESR lines strongly depends on temperature in the temperature range studied: the amplitude of the first line with g=g ₁ increases and the amplitude of the second line decreases with temperature. A model based on consideration of intrinsic defects in the SmB₆ crystalline lattice, with a densit ∼10¹⁵−10¹⁶ cm⁻³, is suggested as an explanation for the anomalous ESR-behavior. In the frequency range v>70 GHz at T=4.2 K, in addition to the main ESR lines, a new magnetic resonance with a hysteretic field dependence is discovered. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 10, 707–712 (25 November 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Muon/Muonium in an Isotopically Pure 13C Diamond

A preliminary study of the diamagnetic (μ_d) and the paramagnetic (Mu _T ) states in a synthetic ¹³C diamond has been performed using the Transverse Field Muon Spin Rotation method. This system could be used to verify the quantum diffusion behaviour observed before, however, with a more reliable extraction of the hopping rate. The results were obtained in an applied magnetic field of 7.5 mT and at sample temperatures of 10 K, 100 K and 200 K. The prompt fraction, f, of the μ_d state remains constant at 22(5)% in the range 10–200 K; that of the Mu _T state increases from 53(10)% at 10 K to 78(10)% at 200 K. The fractions of the two states add to 100% at 200 K, suggesting non-population of the bond-centred state, Mu_BC, which is often observed in other diamond samples. The μ_d state has a spin relaxation rate of 0.20(5) μs⁻¹, in contrast to the zero value obtained in type II diamond samples. This indicates appreciable interaction of the μ_d state with the ¹³C atoms. The Mu _T state has a large spin relaxation rate ranging from 3.0(5) μs⁻¹ at 10 K to 7.0(5) μs⁻¹ at 200 K, consistent with values obtained in diamond samples with defects. This work is part of ongoing studies of muon/muonium-defect interactions in diamonds. This revised version was published online in September 2006 with corrections to the Cover Date.     

Spin-spin and spin-lattice relaxation of nitrogen in electron irradiated and annealed synthetic diamond

Transient nutation ESR spectroscopy has been used to study the broadening of isolated lines in the triplet of P1 nitrogen centers in disperse synthetic diamond bombarded by electrons and annealed at 670–1070 K. On the basis of measurements of the spin-spin relaxation time, it was established that at nitrogen concentrations up to 1.2×10¹⁹ cm⁻³ the homogeneous line width is caused by dipole interaction between the nitrogen atoms and exchange interactions make no contribution. Fiz. Tverd. Tela (St. Petersburg) 40, 1235–1237 (July 1998)     

Magnetic Properties of a New Er(III) Macrobicyclic Complex Studied by EPR

The macrobicyclic ligands of a Schiff base form complexes with various lanthanide metal cations, where the lanthanide ion can be coordinated in the mono- or binuclear systems. As a result of the Schiff-base condensation, a new erbium cryptate complex has been synthesized and investigated by electron paramagnetic resonance EPR technique. The measurements in the 3.9–300 K temperature range confirmed the presence of the 1:1 macrobicyclic Schiff base–Er³⁺ complex. Computer simulations of the registered EPR spectra have revealed the existence of low-symmetry crystal field at the Er(III) site. The complicated EPR spectra of Er(III) complex with an effective spin S = 1/2 in low magnetic fields (<200 mT) were observed only below 60 K. At 5 K the anisotropic g-factors and the integrated intensity reached local maximum values. In the 5–13 K temperature range the line width and g-factors remained constant, while the integrated intensity strongly decreased with increasing temperature. Above 13 K a strong increase of g _y -factor and ΔB _y line width was observed. The observed peak in integrated intensity indicates that the EPR signal is produced by the excited state that lies 6.3 K above the nonmagnetic ground state. Authors' address: Sławomir M. Kaczmarek, Institute of Physics, Szczecin University of Technology, Al. Piastów 48, 70-310 Szczecin, Poland     

Superconductivity in the Ti-D system under pressure

The pressure dependence of the superconducting transition temperature in TiD_0.74 has been measured up to 30 GPa in a diamond high-pressure chamber. It is found that the deuteride TiD_0.74 becomes a superconductor at pressures corresponding to the transition to the high-pressure ζ phase, with a transition temperature that increases from 4.17 to 4.43 K in the interval P=14–30 GPa. The value extrapolated to atmospheric pressure T _c (0)=4.0 K is significantly lower than the superconducting transition temperature (T _c =5.0 K) measured earlier in the metastable state obtained by quenching TiD_0.74 under pressure. It is assumed that the significant difference of the extrapolated value from the superconducting transition temperature in the metastable state after quenching under pressure is caused by a phase transition on the path from the stability region of the ζ phase under pressure to the region of the metastable state at atmospheric pressure. Fiz. Tverd. Tela (St. Petersburg) 40, 2153–2155 (December 1998)     

Conference summary on the first international workshop on advanced superhard materials

Composite diamond anvils have been developed for high-pressure/high-temperature measurements of diamond anvil cells. The anvils are fabricated using single-crystal chemical vapor deposition (CVD) from previously used and/or slightly damaged anvils made of natural or synthetic diamond. These composite anvils can be fabricated to possess optical characteristics at least comparable to conventional diamond anvils, whereas the single-crystal CVD portion is more durable because of its enhanced toughness relative to natural diamond. The viability of such anvils is demonstrated in measurements on hydrogen at megabar pressures and high temperature.