溶剂热法合成六方氮化硼纳米晶的影响因素研究

以Li_3N和BBr3为原料,采用溶剂热法在220 ℃合成了h-BN纳米晶,研究了反应时间、表面活性剂和诱导晶粒对产物的影响.研究结果表明:反应产物主要为h-BN,同时含有少量c-BN,随着反应时间从12 h延长至36 h,晶粒尺寸从20 nm增大至80 nm;十二烷基苯磺酸钠的引入可以控制产物颗粒尺寸在10 nm左右,并且使球形度得到提高;以h-AlN为诱导晶粒时,产物中六方相含量增加,并且出现了h-BN纳米棒.     

Flow of space-charge-limited currents in cubic boron nitride

Current-voltage characteristics of polycrystal cubic nitride samples are studied at various temperatures. The samples were undoped crystals obtained by the method of direct phase transformation of pyrolytic graphite-like boron nitride and crystals doped with sulfur to obtain n-type conductivity. The current-voltage characteristics consist of three different parts: linear and quadratic segments and the region of dramatic increase in the current, which indicates the existence of space-charge-limited currents. The activation energy, E_t, and concentration of the trapping centers, N_t, are determined. The experimental data obtained allowed us to calculate, for the first time, the mobility and concentration of free carrier in the conduction band. Possible mechanisms giving rise to a dramatic increase in are made the current on the current-voltage characteristics are discussed.     

Formation and Properties of Boron Nitride Nanocapsules with Metals and Semiconductor Nanoparticles

Abstract

Boron nitride nanocapsules with gold, iron oxide and germanium nanoparticles were produced. High-resolution electron microscopy and electron energy-loss spectroscopy showed the gold, iron oxide and germanium nanoparticles were encapsulated in the boron nitide sheets. Weak peaks of photoluminescence spectrum were observed from the nanocapsules with germanium nanoparticles. The present work indicates that the boron nitide nanocapsules with conducting, magnetic and semiconductor nanoparticles can be produced by are melting method, and models for the formation mechanism and nano-structures of the boron nitide nanocapsule were proposed.     

Dependence of RF power on the phase transformation for boron nitride films deposited on graphite at room temperature

Cubic boron nitride (cBN) thick films deposited on mainly c-axis-oriented graphite substrate at room temperature and zero bias by radio frequency (RF) magnetron sputtering were studied. In the growth process, RF power plays a key role in determining the content of cubic phase in films, while the conventional substrate heating and biasing have been neglected. With increase in RF power, the dominated content of films converts from explosion boron nitride (eBN) to cBN. The transformation mechanism has been discussed. The unique structural properties of the “soft” graphite are favorable to propose simple conditions for growing “hard” cBN films. Furthermore, the optical band gap of BN films having ∼90% cubic phase is of ∼5.8 eV obtained from ultraviolet–visible optical transmission measurement. The electron field emission examination shows that cBN film on graphite has a high emission current density of 2.8×10⁻⁵ A/cm² at an applied field of ∼30 V/μm.     

溶剂热合成氮化硼纳米晶过程中氮源种类的影响

以NaNH2和BC l3为原料,利用溶剂热方法合成了六方氮化硼纳米微晶,并用红外吸收光谱(FTIR)、X射线粉末衍射(XRD)方法分析了微粒的结构,利用透射电子显微镜(TEM)观测了BN微粒的粒度和微观形貌。与早期用L i3N为氮源合成的氮化硼(产物中具有较多纳米棒)相比,本文中制备的氮化硼纳米晶主要呈球形,颗粒粒度明显增大,而且产率有较大幅度的提高。     

石墨烯及石墨烯/氮化硼的电子结构特性研究

化学气相沉积法生长的单层石墨烯具有卓越的力学、热学和电学特性,成为新一代纳米器件的首选材料。对石墨烯电子特性的理论研究有利于推动纳米器件的发展与应用。本文基于密度泛函理论与非平衡格林函数相结合的方法,系统地研究了石墨烯及石墨烯/氮化硼的电子结构特性。结果表明,在高对称K点,带隙为零。在50~400 K范围内,由于费米面的电声子散射作用,单层石墨烯的迁移率随着温度增加呈现显著下降趋势。此外,通过对不同层间距的石墨烯/氮化硼结构的能带、态密度、电子密度等特性分析,发现随着层间距增加,能带间隙减小,导带与价带间的能量差减小。随着原子个数的增加,石墨烯/氮化硼超胞结构与原胞结构的带隙开度变化规律一致,这对石墨烯基器件的结构设计具有一定的指导意义。     

Structural characteristics of the boron nitride sphalerite modification synthesized in a shock wave

Crystallography Reports - The real structure of ultradispersed powders of sphalerite boron nitride synthesized under shock compression has been studied by X-ray diffraction. The lattice microstrain...     

The effect of local centers on conduction and luminescence of boron nitride

Energetic and kinetic characteristics of charge carrier trapping and recombination centres in graphite-like boron nitride produced by gas-phase deposition are discussed. Local levels in X-ray excited PBN are studied using the method of thermally activated spectroscopy of luminescence and conduction, and their position in the band gap is determined from the temperature dependences of the diffusive current and depolarization current. Acceptor and donor level models for different PBN are developed. Their influence on conduction and on luminescence is determined. The scheme of hole-electron transitions by luminescence is suggested. The carbon influence on the nature of the defects creating local levels is discussed.     

X-ray diffraction study of the effects of boron on occurrence of deformation faults in Ni3Al alloy

Ni₃Al and Ni₃Al alloys containing varying amounts of boron in L1₂ phase were prepared. All the samples were suitably annealed and then cold-worked by hand filing. X-ray diffraction data are collected on annealed and cold-worked samples. The deformation fault probabilities have been evaluated by two methods, viz. peak shift analysis of powder pattern X-ray reflections of annealed and cold-worked samples, and lattice parameter change between annealed and corresponding cold-worked samples. The values obtained by both the methods are in reasonable agreement. It has been found that the deformation fault probability of Ni₃Al and Ni₃Al containing boron alloys are very high compared to Ag and Cu base alloys. Further the deformation fault probability of Ni₃Al is more sensitive to boron addition. It has been found that at least 1.22 at. % of boron goes into the Ni₃Al lattice.     

Ordering of carbon atoms in boron carbide structure

Boron carbide crystals have been obtained in the entire compositional range according to the phase diagram by self-propagating high-temperature synthesis (SHS). Based on the results of X-ray diffraction investigations, the samples were characterized by the unit-cell metric and reflection half-width in the entire range of carbon concentrations. A significant spread in the boron carbide unit-cell parameters for the same carbon content is found in the data in the literature; this spread contradicts the structural concepts for covalent compounds. The SHS samples have not revealed any significant spread in the unit-cell parameters. Structural analysis suggests that the spread of parameters in the literary data is related to the unique process of ordering of carbon atoms in the boron carbide structure.     

Effect of Li2CO3 on formation temperature of hBN by modified O'Connor model

This study is interested in the effect of lithium carbonate on the formation of hexagonal boron nitride (hBN) by means of the available experimental methods including TGA, XRD, FTIR, SEM and HR‐TEM. hBN samples were synthesized at the 1450 °C with different molar ratios of lithium carbonate by modified O'Connor routine. The crystalline hBN formation tended to improve with the increment of the Li₂CO₃ concentration level (especially after more 20 %). The dopant quantity decreased the residual stresses due to the presence of possible relaxation mechanisms along with the nanocrystal structure, even favored by XRD experimental findings regarding the enhancement of crystal plane alignments, crystallite sizes and lattice parameters. As for the FTIR surveys, the Li₂CO₃ foreign impurities strengthened more and more the covalent bonds between boron and nitrogen atoms. At the same time, the samples with 40 % lithium carbonate were annealed at the varied temperatures of 1000, 1150, 1300 and 1450 °C to determine the optimum annealing temperature. The XRD+FTIR investigations indicated that the degree of hexagonality improved with the increased annealing temperature. Similarly, the surface morphology confirmed not only the formation of regularity and flaky hexagonal BN structures, but also the strengthening of covalent bonds between the atoms.     

Mössbauer and X-ray studies of the kinetics of crystallization in glassy Fe---B alloys

X-ray crystallography and Mössbauer spectroscopy were used to investigate the crystallization of the amorphous Fe_100−xB_x alloys, 14 x 20 annealed at 615 K. As a result of the heat treatment, the formation of crystalline -Fe and Fe₃B were observed. Variations in the values of the isomer shift and the orientation of the axis of magnetization indicate changes in the iron-boron bonding and the local atomic arrangement.

Formation of the -Fe phase was determined as a function of boron concentration and annealing time. Crystallization rates of that phase were observed to be dependent on boron concentration and on the annealing time. The average hyperfine field of the untreated samples was observed to increase till x = 17 after which it decreased. This is explained in terms of the Invar behavior of Fe₈₃B₁₇. The anomalous crystallization of Fe₈₆B₁₄ is proposed to be due to the existence of interstitial-like boron sites in a near bcc short range atomic structure.     

Study of mechanical stability of suspended bridge devices used as pH sensors

This study presents the processing of micro-bridges used in suspended gate field effect transistor. Micro mechanical structures were processed using different materials. To ensure the mechanical stability, boron doped polysilicon films, showing positive mechanical stress, had to be embedded between two negatively stressed silicon nitride layers. These micro-bridges are used as suspended gate with a gap as low as 500 nm in the field effect transistor process. The pH sensitive membrane is a silicon nitride layer. The device characteristics are sensitive to any electrical charge in the air-gap because of the local high electrical field. It is then possible to detect any charge variation with higher sensitivity than the one reached using other non electrical technique. For example the present structure was used as pH sensor with a sensitivity five times greater than the ISFET usual Nernstian response.     

Effect of Boron Doping in Bi-based 2223 Superconductors

Samples with the stoichiometric composition Bi_2−xPb_xSr₂Ca₂Cu_3−yB_yO_z (x = 0.3, y = 0.2, 0.25, 0.3, 0.4) ceramics were prepared by a solid state reaction method. The samples were annealed at 850 °C for 100 hours (treatment A), and the other at 850 °C for 200 hours (treatment B). From the X-ray diffraction data of a ceramic sample it is revealed that all the samples were mixed phases of 2212 and 2223. The variation of the lattice parameters with the dopant level are represented. From the D.C. four-probe electrical resistivity data it was found that for the samples subjected to treatment B the T_c(0) values were higher than those with treatment A. The A.C. susceptibility data were collected by change in the inductance method. The effect of boron doping on the phase formation and T_c(0) is presented and the volume fraction of the phases estimated from the X-ray data. The presence of boron in the samples was confirmed by the inductive coupled plasma method. The microstructure of the samples was studied by scanning electron microscopy.     

立方氮化硼薄膜的气相沉积及过渡层对其附着性能的影响

本文采用非平衡磁控溅射物理气相沉积工艺,在单晶硅基片上合成了立方氮化硼薄膜,并且通过采用过渡层提高了立方氮化硼薄膜的附着力,过渡层分别是碳化硼(B4C)薄膜以及碳化硼(B4C)薄膜与B-C—N梯度层的复合层(B4C／B—C—N)。同时,不同过渡层的存在使立方氮化硼薄膜的剥落机理产生变化。     

Transport Properties of Epoxy-Binary Filler Composites

This paper presents the results of changes in electrical resistivity and thermal conductivity of polymer composites (CMs) with two-component filler. It is shown that thermal conductivity of epoxy CMs strongly depends on structural and morphological characteristics of carbon fillers. The synergistic effect in electrical and thermal conductivities of the studied CMs is observed upon addition of boron nitride BN. The presence of a sufficiently large number of BN particles in CMs promotes a more efficient formation of chains of carbon filler and reduces thermal (electrical) contact resistance between the filler particles by decreasing the distance between particles of the filler.     

Synthesis of highly ordered hBN in presence of group I/IIA carbonates by solid state reaction

This comprehensive study declares experimentally the effects of IA/IIA metal carbonates on the formation of hexagonal boron nitride (hBN) with the aid of the available experimental methods as regards Fourier transform infrared spectroscopy (FT‐IR), powder X‐ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (TEM). hBN is synthesized in the existence of the metal carbonates at the low temperature by modified O'Connor method. The experimental findings of FT‐IR and XRD investigations show that the addition of metal carbonates affects considerably the crystallization of hBN powder during the synthesis process. The presence of the high concentration level of the additions improves harshly the crystallinity. In this respect, the graphitization index deduced from the XRD patterns reduces with the enhancement in the amount of the dopant content. At the same time, the differentiation between the products is analyzed by the SEM surveys. According to the results, the materials synthesized by the Li₂CO₃ powder exhibit both the tubular form and rod‐like while the other samples prepared by the CaCO₃ chemical dopant display the homogeneous plates. Even, the TEM images confirm the nanowires and nanotubes structures such as multi‐walled cylindrical, bamboo nanotubes in all the materials studied in this work.     

Effect of boron on the crystallization of amorphous Si–(B–)C–N polymer-derived ceramics

Amorphous Si–(B–)C–N polymer-derived ceramics (PDCs) with a boron content ranging from 0 to 8.3 at.%, were synthesized by thermolysis of boron-modified poly(methylvinylsilazane). Correlation of the boron content and the thermal stability of these materials in the course of annealing were investigated using high temperature thermal gravimetric analysis (HT-TGA). Furthermore, the initial crystallization of the as-thermolyzed amorphous ceramics was studied by X-ray diffraction (XRD) measurements. The increase of boron content promotes the crystallization of SiC, and inhibits the crystallization of Si₃N₄. Moreover, the ratio of α-Si₃N₄/β-Si₃N₄ in crystalline ceramic decreases with increasing boron content. Thermodynamic modeling proves the influence of boron content on driving force for crystallization. The available thermodynamic model of amorphous Si–C–N domains, nano-crystalline silicon nitride, and nano-crystalline silicon carbide treated as the separated phases has been used to interpret these results.     

SiCN薄膜在Si衬底上的沉积

本文采用微波等离子体化学气相沉积(MPCVD)系统,在单晶Si衬底上制备出了SiCN薄膜.所采用的源气体为高纯CH4和N2,而Si源来自于Si衬底、SiH4和Si棒.用场发射扫描电镜(SEM)、X射线光电子能谱(XPS)和X射线衍射谱(XRD)对样品进行了表征与分析.结果表明,外加Si源、高的衬底温度、高流量N2有助于提高样品的成膜质量.所得到SiCN样品是新型的六方结构三元化合物.     

氨气流量对富硅SiNx薄膜结构及其光学特性的影响

采用等离子体增强化学气相沉积技术,以NH3、SiH4和N2为反应气体制备富硅-氮化硅薄膜.在优化了其它沉积参数条件下,研究氨气流量对富硅-氮化硅薄膜的结构和光学性质的影响.利用傅立叶变换红外光谱、紫外可见光谱和X射线衍射谱分析了薄膜的键合情况、带隙结构.结果表明,随着NH3流量的增大,薄膜中的Si-N键和N-H键增强,Si-H键减小并向高波数方向移动,薄膜逐渐由非晶SiNx相向小晶粒Si3 N4相转变.同时随着NH3流量的增大,薄膜的光学带隙逐渐展宽,微观结构的有序度降低.XRD图谱分析表明薄膜内的平均晶粒尺寸也随着氨气流量的增加而在逐渐增大.结合以上结果分析,适当增加NH3流量有助于薄膜由非晶SiNx向包含小晶粒的Si3 N4转变.