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.     

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.     

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.     

Preparation of carbon nanotube by rotary CVD on Ni nano-particle precipitated cBN using nickelocene as a precursor

Ni nano-particles were deposited on hexagonal boron nitride (hBN) and cubic boron nitride (cBN) powders by rotary chemical vapor deposition (RCVD) using nickelocene as a precursor. Ni nano-particles precipitated on hBN and cBN powders were about 20 nm and 10 to 50 nm in diameter, respectively. Carbon nanotubes (CNTs) were grown from relatively large Ni particles about 50 nm in diameter on cBN powder, whereas carbon layers surrounded Ni nano-particles on the surface of hBN powders.     

Structural evolution of boron nitride films grown on diamond buffer-layers

Boron nitride films on diamond buffer layers of varying grain size, surface roughness and crystallinity are deposited by the reaction of B₂H₆ and NH₃ in a mixture of H₂ and Ar via microwave plasma-assisted chemical vapor deposition. Various forms of boron nitride, including amorphous α-BN, hexagonal h-BN, turbostratic t-BN, rhombohedral r-BN, explosion E-BN, wurzitic w-BN and cubic c-BN, are detected in the BN films grown on different diamond buffer layers at varying distances from the interface of diamond and BN layers. The c-BN content in the BN films is inversely proportional to the surface roughness of the diamond buffer layers. Cubic boron nitride can directly grow on smooth nanocrystalline diamond films, while precursor layers consisting of various sp²-bonded BN phases are formed prior to the growth of c-BN film on rough microcrystalline diamond films.     

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.     

Plasma-assisted deposition of BN thin films from B(N3)3

Thin boron nitride films have been deposited via plasma-assisted dissociation of the single-source precursor boron triazide. Infrared absorption and X-ray photoelectron spectroscopic studies have shown that the films are composed of sp²-bonded boron nitride, with a B/N ratio very near 1:1. The films are significantly more resistant to degradation in air and contain fewer impurities than those previously grown from dissociation of boron triazide. The film growth mechanism is discussed, along with information on the role ion bombardment plays in the resultant properties of the films.     

溅射气压和沉积时间对c-BN薄膜结构的影响

采用磁控反应溅射方法，在Si(100）衬底上沉积c-BN薄膜，研究了溅射气压和沉积时间对薄膜结构的影响。结果表明，随溅射气压的升高或沉积时间的增加，都是削弱荷能粒子对衬底表面的轰击效果，并导致薄膜中c-BN相含量的减小。     

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.     

Phase formation in the B-BN-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system at high pressures and temperatures: The wettability of the phases with copper-based melts

Multiphase materials, including the B₆N boron subnitride, B₆O boron suboxide, and cBN cubic boron nitride, have been obtained from the initial β-rhombohedral or amorphous boron, hBN hexagonal graphite-like boron nitride and B₂O₃ amorphous boron oxide at a pressure of 8 GPa and temperatures from 2100 to 2900 K in a toroid high-pressure apparatus. The hardness of the resulting materials has been measured. The formation of ternary phases in the B-BN-B₂O₃ system has not been observed. The wettability of the resultant materials with copper-based melts has been studied. An addition of 10 mol % Ti to the copper melt has been found to decrease the contact angle to a value lower than 20 deg.     

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.     

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.     

Thin films of boron nitride grown by CVD

For the first time, thin films of boron nitride were deposited by chemical vapour deposition on to polished silicon and other metal substrates using the inorganic compound H₃BNH₃ (aminodiborane) and ammonia as carrier gas. The substrate temperature was varied from 400 to 600°C. The films were chemically inert and adherent to the substrates. The FTIR spectrum of the film showed B-N-B absorption at 800 cm⁻¹, B-N stretching at 1056 cm⁻¹, and also a weak absorption at 1340cm⁻¹ corresponding to B-N-B bending vibration. Deposited films also exhibited X-ray diffraction pattern with interplanar spacing with (002) plane of hexagonal boron nitride.     

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.     

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.     

Titanium/aluminum diborides in composites produced in the cBN-TiC-Al system by reaction sintering under high pressure

It has been found by X-ray diffraction and structure analyses that in the reaction sintering of cubic boron nitride composites from the cBN+8 % Al+26 % TiC mixture at high pressure and temperature (4.2 GPa, 1750 K) in the binding ceramics composition in addition to AlN, there forms a Ti _x Al_1?x B_2y N_2(1?y) solid solution, in which titanium and aluminum atoms generate a skeleton, whose composition is close to the equimolar one and boron and nitrogen atoms are distributed randomly in graphite-like networks.     

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.     

Materials with extreme properties: Their structuring and applications

This article is a brief review on syntheses of materials with extreme properties and their modification by plasma processes to obtain different morphological structures. First we illustrate general methodologies on preparation of polycrystalline diamond (PD), nanocrystalline diamond (ND), cubic boron nitride (cBN), diamond/cBN multilayer films by low pressure methods. Since cBN synthesis is more challenging, we place more attention to cBN including its growth, structuring and doping. The structural compatibility of cBN and diamond enables the fabrication of multilayer (superlattices); and we describe such an approach to produce composite materials with even more extreme properties. The superior hardness, extreme thermal conductivity and high chemical stability make diamond and cBN well suited for cutting tool and tribological applications. Although doping of these wide bandgap materials for p- and n-type conductivity is difficult, recent works indicate considerable advancement. The combination of high chemical stability and thermal conductivity with attractive electronic properties makes diamond and cBN suitable for construction of high power electronic devices operating in harsh environments. The development of these applications relies on the ability to design patterns and control the film conductivity. We illustrate that despite diamond and cBN are chemically stable and inert against many chemicals, film patterning and device fabrication is possible with the use of plasma processing. Further, we discuss the fundamental issues involved and demonstrate feasibility for the design of practical applications such as deep-ultraviolet (DUV) detectors and surface acoustic wave (SAW) devices. Finally we discuss the existence of other composite materials with extreme properties that have been only barely investigated, and that present promising alternatives for the future commercial applications.     

Cubic boron nitride based metastable coatings and nanocomposites

Various PVD and plasma-assisted CVD methods presently used for the deposition of cubic boron nitride (c-BN) thin films demand adequate conditions relating to ion bombardment of growing films, growth temperature, film stoichiometry, etc. The deposition conditions, often appearing rather apparatus-dependent, can be well categorized according to the fundamental parameters of bombarding ions as well as condensing neutral particles, including their energy and flux ratio, and a few of others like ion mass and incident angle. According to these parameters, various surface kinetic processes and their consequences are discussed particularly in connection with the resulting film phases and stress. Typical c-BN films are known for their extremely high compressive stress and poor adhesion as a result of intensive ion bombardment during deposition. Individual measures attempting to relieve this detrimental stress are briefly summarized. The present paper focuses on magnetron-sputtered, c-BN-based metastable films and nanocomposite films with considerably reduced internal stress in comparison to the usual “pure” c-BN films. Two examples will be shown, namely c-BN/a-C nanocomposite and c-BN:O metastable films, including their deposition details, structure and composition characterization, and mechanical properties. Also illustrated is a growth scheme tailored for the deposition of thick, adhered, cubic-phase dominated, superhard c-BN:O films above 2 µm on silicon substrates.     

用PBⅡ方法在硼膜中注入氮形成BN的结构

用电子束蒸发纯硼,在硅片上沉积不同厚度的硼膜,然后用等离子体基离子注入（ＰＢⅡ）技术在硼膜上主入氮以形成氮化硼（ＢＮ）,用ＸＰＳ分析膜的成分深度分布及化学价态;用傅里叶变换红外（ＦＴＩＲ）透射谱分析膜的结构。氮在膜中呈类似高斯分布,随着注入电压增大,膜的Ｎ／Ｂ比增大且影响氮在膜中的分布,在较高的注入电压时,膜基间产生界面混合,对ＸＰＳＢｌｓ谱进行Ｇａｕｓｓ－ｏｒｅｎｔｚ拟合表明,硼在膜中以ＢＮ及游