Synthesis and characterization of a single diamond crystal with a high nitrogen concentration

In this paper,we explore diamond synthesis with a series of experiments using an Fe-Ni catalyst and a P3N5 additive in the temperature range of 1250-1550 ℃ and the pressure range of 5.0-6.3 GPa.We also investigate the influence of nitrogen on diamond crystallization.Our results show that the synthesis conditions(temperature and pressure) increase with the amount of P3N5 additive increasing.The nitrogen impurity can significantly influence the diamond morphology.The diamonds stably grow into strip and lamellar shapes in the nitrogen-rich environment.The Fourier-transform infrared spectrum shows that the nitrogen concentration increases rapidly with the content of P3N5 additive increasing.By spectrum analysis,we find that with the increase of the nitrogen concentration,the Ib-type nitrogen atoms can aggregate in the A-centre form.The highest A-centre nitrogen concentration is approximately 840 ppm.     

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.     

Surface energy and pressure of diamond and silicon nanocrystals

Based on the pair potential of interatomic interaction, we study the dependence of various properties of diamond and silicon nanocrystals with a free surface on size, surface shape, and temperature. A model nanocrystal has the form of a parallelepiped faceted by {100} planes with a square base. The number of atoms N in the nanocrystals is varied from 5 to infinity. The Debye temperature, Gruneisen parameter, specific surface energy, isochoric derivative of specific surface energy with respect to temperature, and surface pressure are calculated as a function of the size and shape of diamond and silicon nanocrystals at temperatures ranging from 20 K to the melting point. The surface pressure P _sf(N) ∼ N ^−1/3 is much lower than the pressure calculated by the Laplace formula for similar nanocrystals for given values of density, temperature, and number of atoms. As the temperature increases from 20 K to the melting point, the isotherm P _sf(N) lowers and changes the shape of the dependence on N; at high temperatures, it goes to the region of extension of small nanocrystals of diamond and silicon.     

A New Dopant of NaN3 for High-Concentration-Nitrogen Diamond Synthesized by HPHT

Nitrogen is successfully doped in diamond by adding sodium azide （NaN3 ） as the source of nitrogen to the graphite and iron powders. The diamond crystals with high nitrogen concentration, 1000-2200ppm, which contain the same concentrations of nitrogen with natural diamond, have been synthesized by using the system of iron-carbon- additive NAN3. The nitrogen concentrations in diamond increase with the increasing content of NAN3. When the content of NaN3 is increased to 0.7-1.3 wt. %, the nitrogen concentration in the diamond almost remains in a nitrogen concentration range from 1250ppm to 2200ppm, which is the highest value and several times higher than that in the diamond synthesized by a conventional method without additive NaN3 under high pressure and high temperature （HPHT） conditions.     

The high pressure synthesis of the graphitic form of C3N4

Abstract

Basing on “ab-initio” calculations, C₃N₄ was claimed to be an ultra-hard material with a bulk-modulus close to that of diamond. Five different structural varieties were announced: the graphitic form, the zinc blende structure, the α and β forms of Si₃N₄ and another form, isostructural with the high pressure variety of Zn₂Si0₄.

Using the same strategy as that developed for diamond or c-BN synthesis, it appears that the graphitic form could be an appropriate precursor for preparing the 3D varieties. Two main problems characterize the C₃N₄ synthesis: (-) the temperature should be reduced in order to prevent nitrogen loss, (-) the reactivity of the precursors should be improved.

Consequently, we have developed a new process using the solvothermal decomposition of organic precursors containing carbon and nitrogen in the presence of a nitriding solvent. The resulting material, with a composition close to C₃N₄, has been characterized by different physico-chemical techniques.     

Autowave synthesis of cast aluminum oxynitrides with a high nitrogen content

Aluminum oxynitrides Al₂₂O₃₀N₂ and Al₂₃O₂₇N₅ and a number of Al-O-N solid solutions with a nitrogen content of 2.3 to 6.5 wt % were prepared from (CrO₃-Al-Al₂O₃-AlN) thermite-type mixtures with a high combustion temperature (2950–3200 K) by using the autowave synthesis method. The synthesis was conducted in a hermetically sealed reactor at an initial nitrogen pressure of 4.0 to 8.0 MPa. The aluminum nitride content was demonstrated to influence the nitrogen content in cast aluminum oxynitrides and on their microstructure and phase composition.     

添加Fe(C5H5)2合成氢掺杂金刚石大单晶及其表征

在Ni₇₀Mn₂₅Co₅-C体系中添加含氢化合物Fe(C₅H₅)₂作为新型氢源, 利用温度梯度法, 在压力为5.5-6.0 GPa、温度为1280-1400 ℃的条件下, 成功合成出氢掺杂的宝石级金刚石大单晶. 通过傅里叶显微红外光谱发现, 随着Fe(C₅H₅)₂添加量的增加, 合成晶体中与氢相关的对应于sp³杂化C-H键的对称伸缩振动和反对称伸缩振动的红外特征峰2850和2920 cm^-1逐渐增强, 而晶体中氮含量却逐渐减少. 通过合成晶体的拉曼光谱分析发现, 金刚石的拉曼峰伴随Fe(C₅H₅)₂的添加向高频偏移, 这表明氢的进入在金刚石内部产生了压应力. 观察扫描电子显微镜图像发现, 在低含量Fe(C₅H₅)₂添加时晶体表面平滑, 而高含量添加时晶体表面缺陷增多, 且呈现出气孔状. 使用新的添加剂Fe(C₅H₅)₂作为氢源, 合成出含氢宝石级金刚石单晶, 丰富了金刚石单晶中对氢的研究内容, 也可为理解天然金刚石的形成机理提供帮助.     

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.     

Effects of Al and Ti/Cu on Synthesis of Type-IIa Diamond Crystals in Ni70Mn25Co5-C System at HPHT

High-quality type-Ⅱa gem diamond crystals are successfully synthesized in a NiToMn25Co5-C system by temperature gradient method （TGM） at about 5.5 GPa and 1560 K. Al and Ti/Cu are used as nitrogen getters respectively. While nitrogen getter Al or Ti/Cu is added into the synthesis system, some inclusions and caves tend to be introduced into the crystals. When Al is added into the solvent alloy, we would hardly gain high-quality type-Ⅱa diamond crystals with nitrogen concentration Nc 〈 1 ppm because of the reversible reaction of Al and N at high pressure and high temperature （HPHT）. Piowever, when Ti/Cu is added into the solvent alloy, high-quality type-Ⅱa diamond crystals with Nc 〈 1 ppm can be grown by decreasing the growth rate of diamonds.     

Formation of N2 C3Πu and B3Πg by dissociative recombination of Ar 2 + in Ar+N2 early afterglow

The hf pulse excited Ar + N₂ mixtures and early afterglow are investigated at total pressures from 266 to 1995 Pa using nitrogen of 0·05–0·5% concentration. The time-resolved intensity of Ar I atomic lines and N₂ (2nd pos., 1st pos. and 1st neg.) band systems exhibit an intense early afterglow (0·3 ms). Both the decay of electron densityn _e and that of molecular Ar ₂ ⁺ ions and enhancement of coefficient of dissociative recombination due to electron temperature decrease after the pulse lead to the formation of characteristic secondary maximum of Ar I spectral line and N₂ molecular band intensities in the momentt _m after cut-off the pulse. The values oft _m(B³_g)>t _m(C³_u)>t _m(Ar I) decrease with increasing total pressure and increase with growing concentration of N₂ in Ar. In the afterglow period the Ar ₂ ⁺ dissociatively recombine in 5p and 4p Ar states. As a result of radiative transitions the metastable Ar (³P_2,0) atoms are formed which consequently due to collisions with N₂ molecules create electronically excited N₂. With increasing nitrogen concentration this effect becomes less pronounced and at concentration of N₂ greater than 0·5% it is negligible.     

Effects of additive NaN_3 on the HPHT synthesis of large single crystal diamond grown by TGM

In this paper,large single crystal diamond with perfect shape and high nitrogen concentration approximately 1671-1742 ppm was successfully synthesized by temperature gradient method (TGM) under high pressure and high temperature (HPHT).The HPHT synthesis conditions were about 5.5 GPa and 1500-1550 K.Sodium azide (NaN3) with different amount was added as the source of nitrogen into the synthesis system of high pure graphite and kovar alloy.The effects of additive NaN3 on crystal growth habit were investigated in detail.The crystal morphology,nitrogen concentration and existing form in synthetic diamond were characterized by means of scanning electron microscope (SEM) and infrared (IR) absorption spectra,respectively.The results show that with an increase of the content of NaN3 added in the synthesis system,the region of synthesis temperature for high-quality diamond becomes narrow,and crystal growth rate is restricted,whereas the nitrogen concentration in synthetic diamond increases.Nitrogen exists in diamond mainly in dispersed form (C-centers) and partially aggregated form (A-centers).The defects occur more frequently on crystal surface when excessive NaN3 is added in the synthesis system.     

Raman and IR study of high-pressure atomic phase of nitrogen

Atomic phase of nitrogen has been studied up to pressure 250 GPa and temperature 3300 K using a shear diamond anvil cell. This phase was synthesized both from azide NaN₃ and molecular N₂. The atomic phase has been interpreted as a cubic gauche (CG) structure by means of Raman and IR absorption spectroscopy procedures. The phase transition to CG begins at pressure 50 GPa and room temperature for NaN₃ and at 127 GPa for N₂. Observed pressure dependencies and degeneration of phonon modes, the selection rules for IR and Raman spectra, as well equilibrium pressure between molecular N₂ and atomic phase of nitrogen agree well with theoretical predictions for CG.     

EPR spectrum of donors in 6H SiC in a broad temperature range

An EPR study of donors in 6H SiC crystals with an uncompensated donor concentration (N _D−N _A) of 2×10¹⁸ to 1×10¹⁶ cm⁻³ performed in the temperature range 4.2 to 160 K at frequencies of 9 and 140 GHz showed that 6H n-SiC samples have two donor states in the gap. One of them originates from nitrogen occupying three inequivalent lattice sites with ionization energies of 150 and 80 meV, and the second is connected with a structural defect lying deeper in the gap than nitrogen. The temperature dependences of donor EPR line intensities have been found to deviate from the Curie law. The observed EPR line-intensity peaks of donors are produced in a temperature-driven successive redistribution of donor electrons between the donor levels. The temperature dependences of EPR line intensities obtained from samples with low donor concentrations were used to determine the valley-orbit splitting of nitrogen in cubic sites. Fiz. Tverd. Tela (St. Petersburg) 40, 1824–1828 (October 1998)     

Spectral and Electrical Properties of a Medium Pressure,Low-Power,RF-Generated Postdischarge Nitrogen Plasma Jet

A method for obtaining a medium pressure (p ～ 1 torr), low power (< 100 W), RF-generated plasma jet, suitable for chemical kinetics studies and technological applications is described. Though various supply gases can be used to create the plasma jet, only results on the properties of a nitrogen jet are given in this paper with an emphasis on some spectral and electrical characteristics. The emission spectra of the nitrogen jet are discussed and spatial distributions of the relative concentration of nitrogen or radical impurities emitting species such as N₂(C³Π_u, v' = 0), NH(A³Π_g, v'=0) in the bulk of the postdischarge plasma are calculated from the intensity of their vibrational bands. Electrical space resolved double probe measurements and the spatial distributions of the electron density and temperature in the plasma jet are also presented. Possible applications are shortly discussed.     

On the surface properties of a nanodiamond

The dependences of the specific surface energy, the surface tension, and the surface pressure on the size, the surface shape, and the temperature of a nanodiamond with a free surface have been investigated using the Mie-Lennard-Jones interatomic interaction potential. The nanocrystal has the form of a parallelepiped faceted by the (100) planes with a square base. The number of atoms N in the nanocrystal varies from 5 to ∞. The isothermal isomorphic dependences of the specific surface energy, its isochoric derivative with respect to the temperature, the surface tension, and the surface pressure on the nanodiamond size have been calculated at temperatures ranging from 20 to 4300 K. According to the results of the calculations, the surface energy under this conditions is positive, which indicates that the nanodiamond cannot be fragmented at temperatures up to 4300 K. The surface pressure for the nanodiamond P _sf (N) ∼ N ^−1/3 is considerably less than the Laplace pressure P _ls (N)^−1/3 ∼ N ^−1/3 for the same nanocrystal at the given values of the temperature, the density, and the number of atoms N. As the temperature increases from 20 to 4300 K, the lowering of the isotherm P _sf (N) is considerably more pronounced than that of the isotherm P _ls (N). At high temperatures, the isotherm P _sf (N) changes the shape of the size dependence and goes to the range of extension of small nanocrystals. It has been demonstrated that the lattice parameter of the nanodiamond can either decrease or increase with a decrease in the nanocrystal size. The most significant change in the lattice parameter of the nanodiamond is observed at temperatures below 1000 K.     

EPR Spectra of Nitrogen in Ultra-Dispersed Diamonds

The analysis of the electron paramagnetic resonance (EPR) line shape of ultra-dispersed diamond (UDD) obtained by conversion of trotyl and hexogen mixture and purified from other phases and metal compounds is carried out. The observed wide line with g = 2.0028 and a line width of 8.7 G is shown to be formed by superposition of three lines with line widths of 15.3, 8.5 and 3 G and with a ratio of integral intensities of 70:30:1. The procedure of decomposition and subtraction of wide lines has revealed the resolved hyperfine structure (HFS) from donor nitrogen with parameters A = 40.8 G and B = 29.2 G. Experimentally obtained dependence of the line width of the exchange line on the concentration of donor nitrogen in synthetic diamonds assumed that variations in line widths of the EPR spectrum components are caused by different local concentration of donor nitrogen due to distribution of nitrogen impurity during crystallization of diamond nanoparticles. EPR spectra of UDD after annealing in vacuum and at high pressures in the range of diamond phase stability are also discussed. At high-pressure annealing above 973 K, the areas with high concentration of defects are graphitized and a narrow Dyson-shape line from conductivity electrons and a resolved HFS from donor nitrogen can be observed without additional treatment of the EPR spectrum.     

NO excitation and thermal non-equilibrium within a flat plate boundary layer in an air plasma

Optical emission spectroscopy experiments are carried out by recording the radiation from the γ transitions of nitrogen monoxide in an air inductively coupled plasma in interaction with a water-cooled metallic flat plate at moderate pressure. The calibrated results allow to derive the vibrational and rotational temperatures of the NO(A ² Σ ⁺) excited state as well as its densities in the free jet and within the boundary layer by comparison with calculated spectra. Those results are compared with previous ones concerning temperatures and densities of the ground states of the majority species (N₂, O₂ and NO) that were obtained by laser techniques. As for the NO(X ² Π) ground state, vibration and rotation of the excited state are found out of equilibrium. The NO(A ² Σ ⁺) excited state is found to be populated by an energy transfer from the metastable N₂( A³\varSigma ⁺_uA^{3}\varSigma ^{+}_{u}). The steady state of the plasma allows using this property to derive N₂( A³\varSigma ⁺_uA^{3}\varSigma ^{+}_{u}) densities and N₂ electronic excitation temperatures. Close to the wall, a production of excited NO by a catalytic process is also considered involving N₂( A³\varSigma ⁺_uA^{3}\varSigma ^{+}_{u}) as source of adsorbed atoms. The present results confirm that the kinetic temperature cannot be compared to the rotational temperature derived from optical emission spectroscopy in such plasma conditions.     

Experimental study of the effect of helium/nitrogen concentration and initial droplet diameter on nonane droplet combustion with minimal convection

In this paper, we study the influence of inert concentration and initial droplet diameter on nonane (C₉H₂₀) droplet combustion in an environment that promotes spherical droplet flames. The oxygen concentration is fixed while the inert is varied between nitrogen and helium. A range of initial droplet diameters (D_o) are examined in each ambient gas: 0.4 mm < D_o < 0.8 mm; and an oxidizing ambiance consisting of 30% oxygen (fixed) and 70% inert (fixed), with the inert in turn composed of mixtures of nitrogen and helium in concentrations of 0, 25, 50, 75, and 100% N₂. The experiments are carried out at normal atmospheric pressure in a cold ambiance (room temperature) under low gravity to minimize the influence of convection and promote spherical droplet flames. For burning within a helium inert (0% N₂), the droplet flames are entirely blue and there is no influence of initial droplet diameter on the local burning rate (K). With increasing dilution by nitrogen, droplet flames show significant yellow luminosity indicating the presence of soot and the individual burning histories show K reducing with increasing D_o. The evolution of droplet diameter D(t) is nonlinear for a given D_o in the presence of either helium or nitrogen inerts indicating that soot formation has little to do with nonlinear burning. A correlation is presented of the data in the form where the effective burning rate, K′, and ε are concentration-dependent. Correlations for these parameters are presented in the paper.     

Preparation of a macrocrystalline pressure calibrant SrB4O7:Sm 2+ suitable for the HP-HT powder diffraction

A new simplified synthesis of monocrystalline chips of SrB₄O₇: Sm²⁺ pressure calibrant, well-suited for the diamond anvil cell (DAC) powder diffraction experiments, is proposed. It consists of ordinary solid-state synthesis of fine-grained SrB₄O₇: Sm²⁺ and subsequent annealing near melting temperature. The obtained material was characterized and tested in HP-HT DAC experiment.     

Two-photon-excited luminescence spectra in diamond nanocrystals

Two-photon-excited luminescence (TEL) spectra have been recorded in the blue (400–500 nm) and near-ultraviolet (300–400 nm) ranges for diamond particles with 4 nm average size, which were obtained by detonation synthesis from explosives. The observed TEL bands are attributed, by comparing the obtained spectra with the impurity luminescence spectra in large diamond crystals, to N2 and N3 defects associated with the presence of nitrogen impurities in diamond. The TEL spectra presented are found to have certain distinguishing features: short-wavelength shift of the maximum and changes in the shape and width of the spectral bands for ultradispersed diamond compared with the spectrum in bulk crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 1110–1112 (June 1999)