Synthesis of adhesive c-BN films in pure nitrogen radio-frequency plasma

Cubic boron nitride (c-BN) thin films were prepared at 600 °C by radio-frequency (rf) plasma pulsed laser deposition. All c-BN films prepared in Ar-rich plasma have poor adhesion on Si(100) substrates, but those prepared in pure N₂ plasma can be maintained for more than 5 months without degradation. However, an increase of ion flux at an ion energy similar to that of pure N₂ plasma results in the peeling of c-BN films. Thus, application of pure N₂ plasma with suppressed ion flux can improve c-BN film adhesion. Under such conditions, an extended sp²-bonded interlayer is suspected, with the onset of the c-BN phase being delayed. Suppression of radiative damage in reduced nitrogen ion flux on both the c-BN and h-BN/t-BN phases are important for the adhesive of c-BN films.     

Microstructure of c-BN thin films deposited on diamond films

Diamond films were used as substrates for cubic boron nitride (c-BN) thin film deposition. The c-BN films were deposited by ion beam assisted deposition (IBAD) using a mixture of nitrogen and argon ions on diamond films. The diamond films exhibiting different values of surface roughness ranging from 16 to 200 nm (in R_rms) were deposited on Si substrates by plasma enhanced chemical vapor deposition. The microstructure of these c-BN films has been studied using in situ reflexion electron energy loss spectroscopy analyses at different primary energy values, Fourier transform infrared spectroscopy and high resolution transmission microscopy. The fraction of cubic phase in the c-BN films was depending on the roughness of the diamond surface. It was optimized in the case of the smooth surface presenting no particular geometrical effect for the incoming energetic nitrogen and argon ions during the deposition. The films showed a nanocrystalline cubic structure with columnar grains while the near surface region was sp² bonded. The films exhibit the commonly observed layered structure of c-BN films, that is, a well textured c-BN volume lying on a h-BN basal layer with the (00.2) planes perpendicular to the substrate. The formation mechanism of c-BN films by IBAD, still involving a h-BN basal sublayer, does not depend on the substrate nature.     

Study of stress and infra-red absorption line of BN films containing various fractions of cubic phase

This paper focuses on the stress dependence of infrared absorption lines of BN films synthesized by ion beam assisted deposition (IBAD) and containing various fractions of cubic phase. The compressive stress ranges from −3 to –11 GPa and is found to be conditioned by the content in the c-BN phase. This stress results in a characteristic shift towards high wavenumbers of the IR TO c-BN peak. A frequency shift rate of 3.0±0.5 cm⁻¹/GPa was derived, very close to the one measured for bulk c-BN under hydrostatic pressure. The effect of post-deposition annealing was analyzed. We found the compressive stress to be slightly modified by a post-deposition annealing at 800°C. The resulting relaxation effect is found to be most effective in the c-BN part of mixed films, and in the h-BN one in c-BN rich films (>80% of cubic phase). From the latter observation, the stress level retained initially in the sp²-bonded fraction should reach −10 GPa. This stress level suggests a mechanism involving the rhombohedral form of BN as a precursory phase for c-BN nucleation.     

Selective etching of boron nitride phases

Cubic boron nitride (c-BN) films can be used as hard coatings and for electronic devices due to their outstanding material properties, but the gas phase deposition of c-BN is still a challenging task. Until now it has only been possible to achieve nanocrystalline c-BN layers via physical vapor deposition (PVD) methods with rather weak film qualities. Only a chemical vapor deposition (CVD) process for c-BN can produce high quality films with material properties similar to those of the product achieved by high pressure, high temperature processes (HPHT) conventional routes. Therefore it is essential to tune the individual steps in the CVD process (nucleation, growth and selective etching) in a similar manner to that for diamond CVD to enable continuous growth of c-BN.Since selective etching of hexagonal boron nitride (h-BN) and sp² phases is still a major problem, we investigated the interaction of h-BN and c-BN with different reactive gases — ammonia (NH₃), chlorine (Cl₂), hydrogen chloride (HCl) and boron trifluoride (BF₃) — regarding their etching behaviour and surface stabilisation properties. Etching ratios from ≈10:1 up to 450:1 were found in the temperature range 600–1300°C for the h-BN/c-BN system, clearly indicating a high selectivity due to kinetic effects.The reaction mechanisms will be discussed with respect to the kinetic differentiation of the degradation of c-BN and h-BN (selective etching). The morphological changes and the quality of the remaining BN phases was studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), and infrared and Raman spectroscopy and these indicated a homogeneous decay of the individual phases. Since a homogeneous decay of c-BN resembles the reversed growth, the study of the interaction of both BN phases with reactive gases allowed us to collect more detailed information of the molecular mechanisms involved in the formation of the individual phases. These results will provide new routes for growing c-BN in a CVD process.     

Effects of crystalline quality on the phase stability of cubic boron nitride thin films under medium-energy ion irradiation

To investigate the effect of radiation damage on the stability and the compressive stress of cubic boron nitride (c-BN) thin films, c-BN films with various crystalline qualities prepared by dual beam ion assisted deposition were irradiated at room temperature with 300 keV Ar⁺ ions over a large fluence range up to 2 × 10¹⁶ cm^− 2. Fourier transform infrared spectroscopy (FTIR) data were taken before and after each irradiation step. The results show that the c-BN films with high crystallinity are significantly more resistant against medium-energy bombardment than those of lower crystalline quality. However, even for pure c-BN films without any sp²-bonded BN, there is a mechanism present, which causes the transformation from pure c-BN to h-BN or to an amorphous BN phase. Additional high resolution transmission electron microscopy (HRTEM) results support the conclusion from the FTIR data. For c-BN films with thickness smaller than the projected range of the bombarding Ar ions, complete stress relaxation was found for ion fluences approaching 4 × 10¹⁵ cm^− 2. This relaxation is accompanied, however, by a significant increase of the width of c-BN FTIR TO-line. This observation points to a build-up of disorder and/or a decreasing average grain size due to the bombardment.     

Growth of cubic boron nitride films by ibad and triode sputtering: development of intrinsic stress

Two methods are employed to evidenced the stress behavior in c-BN films. On the one hand, in depth stress profile of c-BN film, deposited by ion beam assisted evaporation, was performed by recording infrared spectra and substrate curvature after reactive ion etching (RIE) steps. It shows a peak of stress up to −17 GPa in the h-BN basal layer and a stress relaxation when the cubic phase appears. On the other hand, dynamic stress profiles of c-BN films deposited by a triode sputtering system, are obtained by recording infrared spectra and substrate curvature after various c-BN deposition times, with the same experimental conditions. Likewise, a peak of stress of −12 GPa is unmistakably observed in the h-BN basal layer followed by a stress release during c-BN nucleation, where an average value of −12 GPa is observed in the c-BN film volume. These results provide a support for the stress model proposed by McKenzie even if along with a minimum stress a high level of densification of the layer is needed.     

c-BN color change with bonded water added into the h-BN–Mg system

Cubic boron nitride (c-BN) crystals were synthesized in conditions of high temperature and high pressure (HTHP) when different kinds of bonded water were respectively added into the system of h-BN–Mg. All bonded water used in this work could reduce the temperature of growing c-BN compared to that in the system of h-BN–Mg. The c-BN color could change from black to yellow when certain amounts of bonded water, such as NiSO₄·6H₂O and CuSO₄·5H₂O, Mg(OH)_2, were added. However, c-BN color remained black no matter how much bonded water, such as NiCl₂·6H₂O, CuCl₂·2H₂O, and SnCl₂·2H₂O, was added. The bonded water can be classified into Chlorine-containing bonded water (Cl-BW) and Chlorine-free bonded water (ClF-BW) according to their different characters and effects on the synthesized c-BN color.     

Effect of the microstructure of graphitic boron nitride on the kinetics of the formation of boron nitride high-pressure phases

Three types of hexagonal boron nitride (h-BN) with graphitic crystal structure having different microstructures were subjected to high pressures (HP) and high temperatures (HT), and the kinetics of the phase transitions to the sp³-hybridized phases (w-BN, c-BN) was studied using in situ synchrotron diffraction. The analysis of the phase transformation kinetics revealed the transformation paths and activation energies E_a of the transformation of h-BN to the high-pressure forms of BN for different microstructures of h-BN. Defect-poor h-BN transforms to metastable wurtzitic BN (w-BN) with E_a ≈ 0.3 eV/at. Defect-rich forms of h-BN transform directly to c-BN, but with a higher activation energy. It was observed that the turbostratic disorder in h-BN retards the phase transition as compared to h-BN containing corrugated basal planes and a low degree of turbostracity. The experimental results are discussed in view of the microstructure changes during the HP/HT treatment and compared to available theoretical phase transition models.     

Characterization of boron nitride film synthesized by helicon wave plasma-assisted chemical vapor deposition

The microstructure of boron nitride film grown on Si (100) at various temperatures by a helicon wave plasma chemical vapor deposition using borazine as a precursor was investigated. The optimum substrate bias voltage for c-BN growth by the employed deposition process ranged from −200 to −400 V. HRTEM images revealed that the film included an interlayer of a-BN and h-BN followed by c-BN layer. A sufficient accumulation of compressive stress is required before c-BN growth. With increasing interlayer thickness and random orientation at high growth temperatures, residual compressive stress seems to decrease owing to an annealing effect. At the initial c-BN growth stage, the congruent growth of hexagonal and cubic phases occurs at low temperatures of 300 and 500°C; however, c-BN growth proceeds only after the formation of h-BN layer at the high temperature of 800°C. The hydrogen content in the BN films synthesized at lower temperatures was ∼8%, while that of the BN film synthesized at 800°C was ∼2.6%. In addition, with increasing the temperature, the decreasing tendency in c-BN IR mode FWHM indicates enhancement of c-BN crystallinity.     

The introducing of fluorine into the deposition of BN: a successful method to obtain high-quality,thick cBN films with low residual stress

Cubic boron nitride films were synthesized on silicon substrates by DC-bias-assisted DC jet chemical vapor deposition in an Ar–N₂–BF₃–H₂ system. By this method, the deposition of cBN at high gas pressure of 50 torr became possible, and the conditions of cBN CVD approached to those of diamond CVD. cBN films with low residual stress (1–2 GPa) and with large crystal size of up to several hundred nanometers were obtained and clear Raman peaks of cBN appeared. Furthermore, the deposition rate was as high as 0.3 μm/min at the initial stage and over 20-μm-thick BN films were obtained for a 3-h deposition. These remarkable improvements are attributed to the preferential etching effect of fluorine to sp² bonds and the decrease of the bombarding energy of ions.     

Synthesis of c-BN films by using a low-pressure inductively coupled BF3–He–N2–H2 plasma

Cubic boron nitride (c-BN) films were synthesized by low-pressure inductively coupled radio-frequency plasma (ICP) chemical vapor deposition (CVD) from a gas mixture of borontrifluoride (BF₃), nitrogen, hydrogen and helium. BN films containing 50–80% cubic phase were obtained under 100 mTorr and at 750–1050 °C of substrate temperature. Substrate bias voltage required to obtain c-BN decreased down to − 20 V with increasing substrate temperature. The adhesion was also improved at high substrate temperatures as compared with those obtained in the B₂H₆–Ar–N₂–H₂ gas system, probably because of the decrease of bombarding energy and chemical effects of fluorine for selective deposition of c-BN.     

Low surface temperature synthesis and characterization of diamond thin films

Polycrystalline diamond films are deposited on p-type Si(100) and n-type SiC(6H) substrates at low surface deposition temperatures of 370–530 °C using a microwave plasma enhanced chemical vapor deposition (MPECVD) system. The surface temperature during deposition is monitored by an IR pyrometer capable of measuring temperature between 250 and 600 °C in a microwave environment. The lower deposition temperature is achieved by using an especially designed cooling stage. The influence of the deposition conditions on the growth rate and structure of the diamond film is investigated. A very high growth rate up to 1.3 μm/h on SiC substrate at 530 °C surface temperature is attributed to an optimized Ar-rich Ar/H₂/CH₄ gas composition, deposition pressure, and microwave power. The structure and microstructure of the films are characterized by X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. A detailed stress analysis of the deposited diamond films of grain sizes between 2 and 7 μm showed a net tensile residual stress and predominantly sp³-bonded carbon in the deposited films.     

Microstructure and mechanical properties of pulsed laser deposited boron nitride films

Boron nitride films were prepared by pulsed laser ablation from a boron nitride target using a KrF-excimer laser, where the growing films were deposited in nitrogen atmosphere or bombarded by a nitrogen/argon ion beam. Films deposited without or at weak ion bombardment (such films will be called l-BN in this paper) are hexagonal with amorphous to turbostratic microstructure (l-BN) and show high adhesive strength to silicon and stainless steel substrates. By using them as intermediate layers, the adhesion of pure cubic boron nitride films (c-BN) can significantly be improved. l-BN films and l-BN/h-BN/c-BN layer systems have been investigated by in-situ ellipsometry, infrared spectroscopy and cross-section and plan-view high-resolution transmission electron microscopy, including diffraction. The mechanical properties, i.e. stress and hardness, of these films and layer systems are presented. l-BN films deposited at higher laser energy densities have compressive stresses as high as 11.5 GPa. Films deposited at lower laser energy densities have stresses in the range of 4.7 to 1.3 GPa and a Vickers hardness in the range of 18.6 to 7.5 GPa depending on substrate temperature and ion bombardment. The compressive stresses of 400 nm thick adherent c-BN films were estimated to be 4.5 GPa.     

Stress and structural properties of diamond-like carbon films deposited by electron beam excited plasma CVD

Diamond-like carbon (DLC) films prepared using CH₄ or C₆H₆ with varying deposition parameters by an electron beam excited plasma CVD system were investigated for the internal stress, dynamic hardness and structural properties such as the film density, total, bonded and unbound hydrogen contents, sp³ ratio and graphite crystallite. From the correlations between internal stress and structural properties, the following conclusions were derived. The fraction of unbound hydrogen to total hydrogen content was the most influential factor for the compressive stress of the DLC films deposited from CH₄. It is suggested that unbound hydrogen may be trapped into the disordered microstructure of graphite crystallites embedded in the network of film. For the DLC films deposited from C₆H₆, it was shown that the compressive stress was correlated with not only the fraction of unbound hydrogen content but also the degree of cross-linking between graphite crystallites in the film.     

Effect of deposition voltage on the microstructure of electrochemically deposited hydrogenated amorphous carbon films

Hydrogenated amorphous carbon (a-C:H) films were deposited on Si substrates by electrolysis in a methanol solution at ambient pressure and a low temperature (50 °C), using various deposition voltages. The influence of deposition voltage on the microstructure of the resulting films was analyzed by visible Raman spectroscopy at 514.5 nm and X-ray photoelectron spectroscopy (XPS). The contents of sp³ bonded carbon in the various films were obtained by the curve fitting technique to the C1s peak in the XPS spectra. The hardness and Young’s modulus of the a-C:H films were determined using a nanoindenter. The Raman characteristics suggest an increase of the ratio of sp³/sp² bonded carbon with increasing deposition voltage. The percentage of sp³-bonded carbon is determined as 33–55% obtained from XPS. Corresponding to the increase of sp³/sp², the hardness and Young’s modulus of the films both increase as the deposition voltage increases from 800 V to 1600 V.     

Dependence of intrinsic stress and structure of ta-C film on ion energy and substrate temperature in model of the non-local thermoelastic peak

In model of the subsurface non-local thermoelastic peak (NTP) the analytical expression for the intrinsic compressive stress arising in thin coating at ion beam deposition or ion-assisted deposition is obtained. Energy dependence of compressive stress in tetrahedral amorphous carbon (ta-C) coating at C⁺ ions deposition compares with experimental data at substrate temperature 300 K and activation energy of interstitial migration. Total temperature and pressure in the NTP of C⁺ ion in ta-C matrix and its position on phase P,T-diagram of carbon depending on ion energy and substrate temperature are determined. The substrate temperature at which transition from sp³-bounded to sp²-bounded structure formation occurs is calculated depending on the ion energy. The calculation results are compared with experimental data.     

Corrosion and tribological properties of ultra-thin DLC films with different nitrogen contents in magnetic recording media

The corrosion spot density and contact–start–stop tribological properties that correlate to mechanical properties, electrical resistivity and lubricant bonded ratio of DLC overcoats on different disks of various surface roughness were investigated. DLC overcoats of hydrogenated carbon (CH) and nitrogenated carbon (CN) films were deposited by ion beam deposition (IBD) and sputter, respectively. Results show that the intensity ratio I(D)/I(G) increases with decreasing IBD-CH film thickness and increasing N₂ concentration of sputtered-CN layer, which implies that the films prepared at higher N₂ concentration contain a relatively lower sp³ bonded carbon. The composite hardness and Young's modulus of DLC films decrease with decreasing IBD-CH thickness and increasing N₂ concentration of sputtered-CN layers. Compared to disk overcoats deposited with only IBD-CH of comparable thickness, the lubricant bonded ratio is dramatically increased from 12 to 30% when the 0.5 nm CN is deposited on IBD-CH film. By increasing the N₂ concentration in the CN layer from 10 to 50 at.%, the electrical resistivity decreased from 3.6 to 0.8 kΩ and the lubricant bonded ratio increased from 30 to 46%. The corrosion spots density of sputtered-CN film surface decreases with increasing N₂ concentration. It is concluded that the dual layer of 1.5 nm IBD-CH/0.5 nm sputtered-CN with 30% N₂ deposition has the best integrated performance of corrosion resistance and CSS tribological properties.     

Substrate temperature effects on the microhardness and adhesion of diamond-like thin films

Diamond-like films were deposited on silicon substrates by r.f. plasma-enhanced chemical vapor deposition from gas methane. In this study, the substrate temperature, T_S, was varied in a wide range from 20 to 370°C while maintaining fixed other important process parameters such as r.f. power (70 W) or pressure (2.5 Pa). The increase of T_S causes an increase of the sp²/(sp²+sp³) bonded carbon ratio and a decrease of the hydrogen content. These changes produce a great modification of the mechanical properties: microhardness, friction coefficient and adhesion. The variations of mechanical properties with T_S correlate well with the sp²/(sp²+sp³) bonded carbon ratio and the hydrogen content in the films showing a gradual transformation of the diamond-like structure into a more sp²-rich one.     

Mechanical properties and thermal stability of SiBCN films prepared by ion beam assisted sputter deposition

The high hardness, exceptional high temperature stability, and oxidation resistance of bulk Si–B–C–N ceramics have led to the expectation that these materials will be good candidates for superior coating materials in high-temperature applications. In this study, SiBCN films were prepared using ion beam assisted sputter (IBAS) deposition, and the mechanical properties and thermal stabilities of the films at 600, 700, and 800 °C in air were investigated. In particular, the effects of the ion beam assist on the properties of the SiBCN films were examined. The SiBCN films were deposited on Si plates by sputtering a target composed of Si + BN + C using a 2-keV Ar⁺ ion beam. A low-energy N₂⁺ and Ar⁺ mixed ion beam irradiated the samples during the sputter deposition. The Si content in the SiBCN films was controlled by changing the Si/(BN + C) ratio of the target. BCN films were also deposited for comparison. The composition and chemical bonding structure of the prepared films were investigated by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. We found that c-BN bonds were formed in the ion-assisted BCN film. The oxide layer thickness on the SiBCN films after thermal annealing decreased due to the IBAS deposition and an increase in the Si content. Ion-assisted SiBCN films annealed at 800 °C showed the highest hardness of 20 GPa.     

A comparative study of composition,structure and elastic properties of boron nitride films deposited by magnetron and ion beam sputtering

Sputtering from hexagonal BN targets, using a conventional magnetron (MS) or ion beam (IBS), produces films consisting of both sp²- and sp³-bonded BN and BN_x. We present here the dependence of BN film composition, structure, morphology and elastic properties on the bias voltage (V_b) applied on the substrate in the case of MS, compared with those of IBS-deposited BN films. The optical properties and the composition of the BN films were examined by spectroscopic ellipsometry (SE), whereas the chemical bonding was identified by Fourier Transform IR SE. The films' structure, morphology and density were also examined by X-ray diffraction and reflectivity and transmission electron microscopy. The elastic properties of the films were studied by nanoindentation techniques. Significant differences were found in composition, chemical bonding and structure of films grown by MS at various bias voltages.