Mechanism of nucleation and growth of cubic boron nitride thin films

The mechanism and the crystallography of the nucleation and growth of cubic boron nitride (c-BN) films deposited on 〈100〉-oriented silicon substrate by RF bias sputtering have been studied by means of cross-sectional high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Both methods provide experimental information showing no sp²-bonded BN layer formation in the subsurface region of c-BN phase. This is clear evidence for layer-by-layer homoepitaxial growth of cubic boron nitride without graphitic monolayers in the near-surface region of the film. The turbostratic boron nitride (t-BN) consists of thin sub-layers, 0.5–2 nm thick, growing in such a way that a sub-layer normal is almost parallel to the growth direction. t-BN also comprises a large volume fraction of the grain boundaries with high interface energies. The present result and the finding by Shtansky et al. [Acta Mater. 48, 3745 (2000)], who showed that an individual sub-layer consists of parallel lamellae in both the hexagonal +h-BN) and rhombohedral (r-BN) configurations, demonstrate that high intrinsic stress in the films is due to the complex structure of sp²-bonded BN. The crystallography of c-BN films indicates heteroepitaxial nucleation of cubic phase on the graphitic BN structural precursor. The present results are consistent with stress-induced c-BN formation.     

Mechanism of nucleation and growth of cubic boron nitride thin films

The mechanism and the crystallography of the nucleation and growth of cubic boron nitride (c-BN) films deposited on 100-oriented silicon substrate by RF bias sputtering have been studied by means of cross-sectional high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Both methods provide experimental information showing no sp²-bonded BN layer formation in the subsurface region of c-BN phase. This is clear evidence for layer-by-layer homoepitaxial growth of cubic boron nitride without graphitic monolayers in the near-surface region of the film. The turbostratic boron nitride (t-BN) consists of thin sub-layers, 0.5–2 nm thick, growing in such a way that a sub-layer normal is almost parallel to the growth direction. t-BN also comprises a large volume fraction of the grain boundaries with high interface energies. The present result and the finding by Shtansky et al. [Acta Mater. 48, 3745 (2000)], who showed that an individual sub-layer consists of parallel lamellae in both the hexagonal (h-BN) and rhombohedral (r-BN) configurations, demonstrate that high intrinsic stress in the films is due to the complex structure of sp²-bonded BN. The crystallography of c-BN films indicates heteroepitaxial nucleation of cubic phase on the graphitic BN structural precursor. The present results are consistent with stress-induced c-BN formation.     

Facile synthesis of cubic boron nitride nanoparticles from amorphous boron by triple thermal plasma jets at atmospheric pressure

Cubic boron nitride (c-BN) is a superhard material, with hardness value comparable to that of diamond. c-BN is used in a wide range of industrial applications, including tool, abrasives, and refractory. The hardness of c-BN can be improved by decreasing the particle size to the nanoscale; however, the simultaneous application of high pressure (～8 GPa) and temperature (>2,500 K) is required to synthesize the c-BN crystal structure. In this study, we effectively synthesized c-BN nanoparticles from amorphous boron using a triple direct current (DC) thermal plasma jet system at atmospheric pressure. The injection of nitrogen as plasma forming gas generated reactive nitridation species. The average particle size of the synthesized c-BN was 22 nm, and the major crystal structure is the (1 1 1) cubic phase. We carried out a numerical simulation for a thermal fluid, to confirm the high temperature and velocity fields of the plasma jets that formed inside the reactor as the flow rate of plasma forming gas was adjusted. A high production yield of 51% was achieved using amorphous boron at a feed rate of 190 mg/min and the c-BN nanoparticles exhibited high crystallinity without requiring pre-and post-processing.     

水热条件下氮化硼枝蔓晶的形成

利用水热方法合成了氮化硼枝蔓晶,根据X射线衍射(XRD),傅立叶红外吸收(FTIR)测试确定了产物的物相组成,X射线能谱仪(XPS)也证明了枝蔓晶的立方氮化硼成分,同时,利用透射电镜(TEM)和选取电子衍射(SAED)的测试结果分析了枝蔓晶的形貌和表面特征,另外,本文结合负离子配位多面体理论探讨了枝蔓晶的形成机理.     

渗硼注氮复合处理表面硬化层研究

采用渗硼工艺和新型的等离子体源氮离子注入技术对Cr12MoV钢进行复合处理 ,获得了高硬度的表面硬化层。用XPS对硬化层进行相分析和性能试验 ,结果表明 :硬化层主要由立方氮化硼 (C BN)和FeB组成 ,硬化层具有很高的硬度和耐磨性     

Hydrochloric Acid-Promoted Synthesis of cBN via Hydrothermal Route

Single phase crystalline cubic boron nitride （cBN） with high yield was prepared by hydrothermal route at low temperature, using hydrochloric acid （HCI） as the promoter. The promotion effect of HCI on the synthesis of cBN is briefly discussed.     

Parameter spaces for the nucleation and the subsequent growth of cubic boron nitride films

The data existing in the literature about the deposition of cubic boron nitride thin films were reviewed critically in order to establish the parameter spaces of c-BN nucleation and growth. The ion energy E_i, the flux ratio F (=incoming ions/incoming boron atoms), the ion mass m_i, (or the ratio Ar/N₂, respectively), and the substrate temperature T_s, had already been identified as the decisive parameters which are, however, interdependent. Earlier data collections on c-BN deposition had shown that, irrespective of the deposition technique used, a well-defined c-BN region exists in the F/E_i parameter space, in which the deposition of c-BN is possible. Similar regions exist in the F/m_i and F/T_s parameter spaces. The present collection extends these older diagrams considerably, especially to the low energy region. From this extention it can be concluded that the momentum transfer concepts proposed in the literature fail to explain the data. Furthermore, the older collections were considered valid for nucleation and growth likewise. However, in recent years data have been published showing that the boundaries of the c-BN regions are different for nucleation and growth. After successful nucleation, subsequent growth can occur either at reduced ion bombardment (either energy or flux ratio or ion mass) and also at reduced temperatures. The existing data for this parameter reduction have been collected in this paper. It will be shown that the growth depends in a similar way as the nucleation on the (interdependent) ion bombardment parameters but no longer on temperature. This means that the nucleation and growth of c-BN are based on different, although in both cases ion-induced, mechanisms.     

Molecular dynamics study of deposition mechanism of cubic boron nitride

We have performed molecular dynamics simulations of bombardment of graphitic boron nitride (gBN) by energetic boron and nitrogen particles in order to examine the roles of ion bombardment in ion/plasma-assisted deposition of cubic boron nitride (cBN) thin films. We have found that the interaction of the energetic particles with gBN creates four-fold coordinated local structures (sp³-formation) inside gBN. We have also found that clusters of sp³-formations are created as a result of successive bombardment, some of which have cBN-like structures. On the basis of these results, we propose an atomic-scale model of cBN nucleation in which successive sp³-formation converts gBN into cBN.     

用水热方法合成氮化硼过程中反应原料种类的影响

利用选相原位合成方法制备了立方氮化硼(cBN),研究了硼源和氮源种类对产物物相的影响.利用X射线衍射(XRD)、红外吸收光谱(FTIR)、透射电子显微镜(TEM)、选区电子衍射(SAED)以及高分辨透射电子显微镜(HRTEM)对样品进行了表征.结果表明:如果利用硼酸作为反应原料,可以在优化的条件下得到纯相cBN;当硼酸被硼酸铵取代时,制备的样品变成了六方氮化硼(hBN)和cBN的混合物.另一方面,用三聚氰胺取代部分NaN3作为氮源时,样品几乎是纯相的hBN.对上述结果进行了简要分析,并在此基础上给出了水热合成氮化硼过程中反应原料的选择原则.     

Variation of residual stress in cubic boron nitride film caused by hydrogen addition during unbalanced magnetron sputtering

The effect of hydrogen on compressive residual stress of cubic boron nitride (cBN) was investigated. The deposition was performed by unbalanced magnetron sputtering of a hexagonal boron nitride (hBN) target connected to radio-frequency electric power of 400 W. Up to 2 sccm of hydrogen was added to a gas mixture of argon and nitrogen flowing at 9 and 1 sccm, respectively. The compressive stress rapidly decreased from 10.5 GPa to 3 GPa, with increasing hydrogen flow up to 1.0 sccm. The cBN fraction in these films, however, remained over 60%, with only a trivial decrease with increasing hydrogen. This reduction was discussed in terms of the relation between the penetration probabilities of hydrogen and argon ions into the film, which was main origin of compressive residual stress of the hBN layer.     

New approach in depositing thick, layered cubic boron nitride coatings by oxygen addition—structural and compositional analysis

Cubic boron nitride (c-BN) can be produced by PVD and PA-CVD techniques by intensive ion bombardment leading to highly stressed films limiting its use in industrial applications. Various attempts have been undertaken to reduce the compressive stress of c-BN thin films. A significant reduction in compressive stress and a substantially improved adhesion was achieved by a new coating concept consisting of a two-step adhesion-promoting base layer, a compositional-graded nucleation layer obtained by a stepwise decrease of the oxygen content in the Ar/N₂/O₂ atmosphere and a low-stressed c-BN:O top layer with controlled oxygen addition. The four-layer c-BN:O film with a thickness of 3 μm was deposited by unbalanced radio frequency magnetron sputtering of a hot-pressed hexagonal boron nitride target on silicon substrates. The adhesion layer was deposited in a mixed Ar/O₂ atmosphere of 0.26 Pa with a stepwise increased nitrogen gas flow and a subsequent increase of the ion energy by increasing the substrate bias from 0 to − 250 V. The c-BN nucleation was gradually initiated by decreasing the O₂ gas flow. The present study was focused on the investigation of the morphology, the microstructure on the nanoscale, and the bonding structure using scanning electron microscopy (SEM), Fourier-Transmission infra-red spectroscopy (FTIR), high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) employing analytical scanning transmission electron microscopy (ASTEM). The HRTEM images revealed a four-layer coating consisting of a gradual nucleation of t-BN, on which a gradual nucleation of c-BN was achieved by decreasing the oxygen gas flow.     

Enhanced deposition of cubic boron nitride films on roughened silicon and tungsten carbide-cobalt surfaces

We report the influence of substrate surface roughness on cubic boron nitride (cBN) film deposition under low-energy ion bombardment in an inductively coupled plasma. Silicon and cemented tungsten carbide-cobalt (WC-Co) surfaces are roughened by low-energy ion-assisted etching in a hydrogen plasma, followed by deposition in a fluorine-containing plasma. Infrared absorption coefficients are measured to be 22,000 cm⁻¹ and 17,000 cm⁻¹ for sp²-bonded BN and cBN phases, respectively, for our films. For the silicon substrates, the film growth rate and the cBN content in the film increase with increasing the surface roughness, while the amount of sp²BN phase in the film shows only a small increase. A larger surface roughness of the substrate results in a smaller contact angle of water, indicating that a higher surface free energy of the substrate contributes to enhancing growth of the cBN film. For the WC-Co substrates, the film growth rate and the cBN content in the film increase similarly by roughening the surface.     

The structure formation in reaction sintering of cubic boron nitride submicron and nanosized powders with aluminum at the stage of high-pressure infiltration

Porosity, phase composition, and structure of samples produced from submicron and nano-metric cBN powders high-pressure infiltrated with aluminum (at a pressure of 2.5 GPa and a temperature of 1300 K) have been studied. It has been found that a special feature of the nanopowder consolidation under these p, T parameters is the formation of local volumes of different densities, which is responsible for the complexity of the infiltration, causes an increase of the closed porosity and gradients of stresses by volume, and thus, the cBN → hBN deformation phase transformation and the crack initiation as the temperature and pressure decrease. It has been shown that to obtain a homogeneous infiltration structure, the initial cBN powders with a small concentration of nanosized fractions, when nanoparticles do not form aggregates of different densities but are distributed on the surfaces of larger particles, can be promising.     

Investigation of Ti coatings on cubic boron nitride (cBN) grits by discharge treatment in spark plasma sintering system

The Ti coatings on cubic boron nitride (cBN) grits were prepared by discharge treatment on a mixture of Ti powders and cBN grits in spark plasma sintering system. The uniform and full coatings with a thickness of ～1.2 μm were prepared at 850 °C for 60 min, which were constituted with TiB₂, TiN, and Ti phases. The compressive fracture strength and toughness impact of the Ti-coated cBN grits were 11.6% and 7.4% higher than the cases of the pristine ones, respectively. With the aid of Ti coatings, the interface bonding strength between cBN grits and Fe-based matrix was improved by 335 MPa in the Fe-based matrix/cBN composites.     

Mass spectrometric study of low-pressure inductively coupled plasma for chemical vapor deposition of cubic boron nitride films

Chemical species in plasma are crucial for understanding the mechanism of cubic boron nitride film vapor phase deposition and controlling the film structure. In this study, the plasma condition for cubic boron nitride deposition by low-pressure inductively coupled plasma-enhanced chemical vapor deposition using B₂H₆, N₂, and Ar as reactant gases has been diagnosed by a quadrupole mass spectrometer with an ion energy analyzer. The ionization potentials of B_XH_Y (X=1–2, Y=0–6) decomposed from B₂H₆ have been measured to be between 11.6 and 18.9 eV. B₂H₆ was totally ionized to B⁺ together with small amounts of BH⁺, BH₂⁺ and B₂H_Y⁺ in plasma above the 2 kW input power. N₂ was only partially ionized, and the degree of ionization increased with increasing Ar partial pressure. Neutral species under the present plasma environment were N₂, Ar and He, but N and H were not detected even by appearance mass spectrometry. Our results demonstrate that the main sources for cubic boron nitride formation are ions produced in plasma. The interaction between N₂ and the growth surface suppresses the cubic boron nitride formation by enhancing the tBN growth, and this surface interference can be reduced by introducing Ar into the system.     

Catalytic effect of water on the synthesis of cubic BN

The transition pressure and temperature of graphitic hexagonal boron nitride to the dense cubic form is drastically reduced by the presence of water in the starting material. A water content of about 40 wt% reduces these conditions to about 50 kb and 600°C. Cubic BN obtained under such conditions is extremely small in crystal size, which was estimated by the broadening of x-ray powder diffraction lines.     

One-pot hydrothermal synthesis of uniformly cubic Co3O4 nanocrystals

Cubic Co₃O₄ nanocrystals (NCs) were synthesized by a one-pot hydrothermal reaction in the presence of the oxidant KClO₃ and the capping reagent polyvinylpyrrolidone (PVP). The as-prepared Co₃O₄ NCs were uniformly cubic with sharp edges and good crystallinity and showed flat surfaces with {100} facets. The capped PVP could be removed without losing cubic shape by heating the NCs at 300 °C.     

A hydrothermal method to prepare the spherical ZnS and flower-like CdS microcrystallites

The spherical ZnS and flower-like CdS microcrystallites are prepared by a convenient hydrothermal process through the reactions of Zn(CH₃COO)₂·2H₂O or Cd(CH₃COO)₂·2H₂O with S and NaH₂PO₂·H₂O in aqueous solution at 180 °C for 12 h. Powder X-ray diffraction (XRD) is used to confirm the cubic phases of the ZnS and CdS microcrystallites. Their chemical compositions are characterized by X-ray photoelectron spectroscopy (XPS). Scanning electron microscope (SEM) images show the morphologies of the as-synthesized ZnS and CdS. The photoluminescence spectra (PL) exhibit their optical properties.