Luminescence of samarium-activated cubic boron nitride

Under high pressure conditions, we have obtained samples of samarium-activated cubic boron nitride in the form of micropowders, ceramic samples, and polycrystals having high-intensity discrete photoluminescence in the red region of the spectrum that is stable in the temperature range 6 K to 300 K and is assigned to internal f-f electronic transitions in the Sm³⁺ ions. The materials obtained on the basis of cBN are intended for use as phosphors and light emitters (sources of red light) having thermal and chemical stability. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 88–93, January–February, 2008.     

Luminescence centers in cubic boron nitride

Complex and multiband photoluminescence spectra for GB and HBN centers in single crystals of cubic boron nitride (cBN) were recorded in the wavelength ranges 385–400 nm and 365–395 nm and the nature of these centers was studied. The use of models involving resonance vibrations and strongly shifted configuration diagrams for the electronic ground state and excited state made it possible to associate formation of the GB-1 center with the presence of tungsten impurity in cBN. It was established that the HBN band in the 300–350 nm range of the cathodoluminescence spectra of cBN polycrystals, single crystals, and micropowders is associated with luminescence centers present in microinclusions of graphite-like boron nitride (hBN). The nature of the hBN band is tentatively interpreted within the model of recombination of donor and acceptor defects in hBN: respectively nitrogen vacancies and carbon atoms in positions substituting for nitrogen. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 241–246, March–April, 2007.     

The electrical properties of sulfur-implanted cubic boron nitride thin films

Cubic boron nitride (c-BN) thin films are deposited on p-type Si wafers using radio frequency (RF) sputtering and then doped by implanting S ions. The implantation energy of the ions is 19 keV, and the implantation dose is between 10 15 ions/cm 2 and 10 16 ions/cm 2 . The doped c-BN thin films are then annealed at a temperature between 400°C and 800 C. The results show that the surface resistivity of doped and annealed c-BN thin films is lowered by two to three orders, and the activation energy of c-BN thin films is 0.18 eV.     

Surface properties of cubic boron nitride thin films

Studying the surface properties of cubic boron nitride (c-BN) thin films is very important to making it clear that its formation mechanism and application. In this paper, c-BN thin films were deposited on Si substrates by radio frequency sputter. The influence of working gas pressure on the formation of cBN thin film was studied. The surface of c-BN films was analyzed by X-ray photoelectron spectroscopy (XPS), and the results showed that the surface of c-BN thin films contained C and O elements besides B and N. Value of N/B of c-BN thin films that contained cubic phase of boron nitride was very close to 1. The calculation based on XPS showed that the thickness of hexagonal boron nitride (h-BN) on the surface of c-BN films is approximately 0.8 nm.     

Phonon spectrum boron nitrideof single-wallednanotubes

Based on a force constant model, we investigated the phonon spectrum and then specific heat of single-walled boron nitride nanotubes. The results show that the frequencies of Raman and infrared active modes decrease with increasing diameter in the low frequency, which is consistent with the results calculated by density functional theory. The fitting formulae for diameter and chirality dependence of specific heat at 300K are given.     

A cubic boron nitride P-N diode: Fabrication in a large-volume press

Abstract

A simple method to determine the temperature of synthesis was proposed. (Mishima et al., to be published) This method utilized the melting of NaCl as an indicator of heater temperature. Applying the method to the fabrication of cBN p-n diodes in a large volume belt-type apparatus, we obtained an UV LED of ～2 mm in size.     

Influence of oxygen on the formation of cubic boron nitride by r.f. magnetron sputtering

Formation of cubic boron nitride by r.f. magnetron sputtering has been studied with O₂ addition to the common working gas Ar/N₂. The chemical and the phase composition were determined with Auger electron spectroscopy sputter depth profiling and Fourier transform infrared spectroscopy. The result shows that oxygen hinders the formation of cBN in sufficient nitrogen-supply, but facilitates the growth of cBN in insufficient nitrogen-supply. With insufficient nitrogen-supply, there exists an optimal oxygen-supply in the working gas that promoted the establishment of the stoichiometric condition in the growing film. O-concentration in the film increases with oxygen-supply in the working gas. cBN forms only when the oxygen concentration is below 5% and c_N/c_B (ratio of concentration of nitrogen atoms and boron atoms) is 1 in the film.     

Luminescence investigations of cubic boron nitride doped with beryllium

The cathodoluminescence and photoluminescence spectra of cubic boron nitride doped with beryllium under high-pressure and high-temperature conditions are investigated. It is revealed that, upon doping of cubic boron nitride with beryllium, the cathodoluminescence spectra exhibit a broad stable band. An increase in the impurity content leads to a shift in the position of the maximum of this band toward the short-wavelength range from ～315 to ～250 nm and to a change in the crystal color from dark yellow to blue. The structure, the intensity, and the position of the band at the maximum are studied as a function of the temperature of the cathodoluminescence measurement. The nature of the band is tentatively interpreted in the framework of the model of recombination at defects of the donor and acceptor types. It is assumed that several overlapping subbands which are associated with differently charged acceptor levels of beryllium are located in the vicinity of the valence band in the electronic structure of the doped cubic boron nitride. It is found that the photoluminescence spectra of single crystals of the doped cubic boron nitride contain three previously unknown zero-phonon lines at energies of 2.135, 2.270, and 2.600 eV.     

X-ray photoelectron spectroscopy study of cubic boron nitride single crystals grown under high pressure and high temperature

The defects, impurities and their bonding states of unintentionally doped cubic boron nitride (cBN) single crystals were investigated by X-ray photoelectron spectroscopy (XPS). The results indicate that nitrogen vacancy (V_N) is the main native defect of the cBN crystals since the atomic ratio of B:N is always larger than 1 before Ar ion sputtering. After sputter cleaning, around 6 at% carbon, which probably comes from the growth chamber, remains in the samples as the main impurity. Carbon can substitute nitrogen lattice site and form the bonding states of CBN or CB, which can be verified by the XPS spectra of C1s, B1s and N1s. The C impurity (acceptor) and N vacancy (donor) can compose the donor-acceptor complex to affect the electrical and optical properties of cBN crystals.     

Preparation and characterization of thick cubic boron nitride films

Cubic boron nitride （c-BN） films are prepared by the radio frequency magnetron sputtering technique. The stresses and crystallinities of the films are estimated by the Fourier transform infrared spectroscopy of c-BN samples, including the peak shifts and varieties of full widths at half maximum. The effects of the B-C-N interlayer and the two-stage deposition method on the c-BN films are investigated. Then the thick and stable c-BN films are prepared by a combination of the two methods. The properties of the interlayer and film are also characterized.     

The near edge structure of cubic boron nitride

We compare the near edge structure (NES) of cubic boron nitride (cBN) measured using both electron energy loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) with that calculated using three commonly used theoretical approaches. The boron and nitrogen K-edges collected using EELS and XAS from cBN powder were found to be nearly identical. These experimental edges were compared to calculations obtained using an all-electron density functional theory code (WIEN2k), a pseudopotential density functional theory code (CASTEP) and a multiple scattering code (FEFF). All three codes were found to reproduce the major features in the NES for both ionisation edges when a core-hole was included in the calculations. A partial core hole (1/2 of a 1s electron) was found to be essential for correctly reproducing features near the edge threshold in the nitrogen K-edge and to correctly obtain the positions of all main peaks. CASTEP and WIEN2k were found to give almost identical results. These codes were also found to produce NES which most closely matched experiment based on χ² calculations used to qualitatively compare theory and experiment. This work demonstrated that a combined experimental and theoretical approach to the study of NES is a powerful way of investigating bonding and electronic structure in boron nitride and related materials.     

六方氮化硼单层中一种(CN)3VB缺陷的第一性原理计算

二维六方氮化硼(hBN)的点缺陷最近被发现可以实现室温下的单光子发射,而成为近年的研究热点.尽管其具有重要的基础和应用研究意义,hBN中发光缺陷的原子结构起源仍然存在争议.本文采用基于密度泛函理论的第一性原理计算,研究hBN单层中一种B空位附近3个N原子被C替代的缺陷(CN)3VB.在hBN的B空位处,3个N原子各自带...     

Diamond and cubic boron nitride under high pressure: Raman scattering,equation of state and high pressure scale

Abstract

The development of the diamond-anvil cell has stimulated Raman-scattering investigation of vibrational modes in covalent crystals. The linear pressure coefficient reported for diamond by Hanfland et at' (2.90 ± 0.05 cm-¹/GPa) agrees to within mutual experimental error with the result of Boppard et aL² (2.87±0.01 cm-¹/GPa). As to cubic boron nitride, the only work by Sanjurjo ef aL3 reports 3.45 ± 0.07 cm-¹/GPa for LO- and 3.39 ± 0.08 cm-¹/GPa for TO- modes. Since no compressibility data are availablel^1?3, the mode Griineisen parameter γ = ‐ δ In γ/δ is defined as y = K/Y·dv/aP and depends on the bulk modulus K and the calibration of the ruby scale. The above papers report y= 0.96 and y=0.95±O.O3fordiamondand γ_Lo=1.21,γTo=1.51 forBN.     

Equation of state of turbostratic boron nitride

Abstract

The lattice parameters of turbostratic boron nitride (tBN) have been measured to 6.1 GPa at room temperature using energy-dispersive powder diffraction with synchrotron radiation. A fit to the experimental p-V data using Birch-Murnaghan equation of state gives values of the tBN bulk modulus 17.5(8) GPa and its pressure derivative ll.4(5). These values point to significantly higher compressibility of turbostratic BN as compared to three-dimensionally ordered graphite-like hexagonal and rhombohedral boron nitride.     

Raman scattering of light in doped cubic boron nitride

The Raman spectra of single crystals of cubic boron nitride (cBN) doped with beryllium and also synthesized in the absence of dopants are investigated. It is shown that the wide bands at 215 and 535 cm^–1 can be registered in the Raman spectra of the ( ) faces of undoped cBN crystals and that the Be impurity penetrates into the cBN crystals predominantly in the direction of these faces. In the spectra of the investigated cBN samples doped with Be, the contour of the TO and LO phonon lines does not take the Fano shape, in contrast to diamond, which can point to an insufficient concentration of the dopant for attaining the Fano interference or to the absence of it in cBN. The wide bands have been investigated on the assumption that they are boson-like and result from small-size disorders in both undoped and doped cBN samples with the sp ³ bond deformed by Be.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 803–809, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Development of superhard materials,sintered diamond and cubic boron nitride

Abstract

Recent advances on the preparation technique of sintered diamond and cubic boron nitride containing small amount of sintering additives having superior thermal and mechanical properties is reviewed. Sintered diamond of lower metallic content (1–5 vol%) shows high hardness (100–150 GPa) and high electrical resistivity (10⁸ ohm-cm) at room temperature. Reaction sintered cubic boron nitride contained 1–3 mole % of magnesium boron nitride shows high thermal conductivity. (7 watt/cm K at RT)     

Thermal phase stability of rhombohedral boron nitride

Abstract

Thermal phase stability of rhombohedra] boron nitride has been studied between 0 and 8 GPa from 300 to 2700 K. Analysis of the data obtained points to the decisive role of kinetic factors in the rBN phase transformations, the structure and dispersity of the samples under study being of great importance. rBN phase transformations in the cBN thermodynamic stability region of the equilibrium p,T phase diagram for boron nitride occur according to Ostwald stepwise principle by the rBN→hBN→(wBN)→cBN scheme.     

Increasing the thermal conductivity of boron nitride and aluminum nitride particle epoxy-matrix composites by particle surface treatments

The thermal conductivity of boron nitride and aluminum nitride particle epoxy-matrix composites was increased by up to 97% by surface treatment of the particles prior to composite fabrication. The increase in thermal conductivity is due to decrease in the filler-matrix thermal contact resistance through the improvement of the interface between matrix and particles. Effective treatments for BN involved acetone, acids (nitric and sulfuric) and silane. The most effective treatment involved silane such that the coating resulted from the treatment amounted to 2.4% of the weight of the treated BN. The effectiveness of a treatment was higher for a larger BN volume fraction. At 57 vol.% BN, the thermal conductivity reached 10.3 W/ m·K. The treatments had little effect on the specific surface area of the BN particles. Silane treatments were also effective for AlN. At 60 vol.% AlN, the thermal conductivity reached 11.0 W/m·K.