Relative fraction of sp bonding in boron incorporated amorphous carbon films determined by X-ray photoelectron spectroscopy

Boron incorporated amorphous carbon (a-C:B) films were deposited by a filtered cathodic vacuum arc system using various percentage of boron mixed graphite cathodes. X-ray photoelectron spectroscopy (XPS) was employed to determine the properties of the films as a function of boron concentration. Deconvolutions of the XPS C 1s core level spectra were carried out using four different components. The relative fraction of sp³ bonding was then evaluated from the area ratio of the peaks at 285.0, 284.1 eV which were individually attributed to sp³ C-C, sp² CC hybridizations. The results showed that the sp³ content of a-C:B film decreases from 73.8 to 58.6% for the films containing boron from 0.59 to 2.13 at.%, and then gradually reduced to 42.5% at a slower rate with boron concentration up to 6.04 at.%. Furthermore, a series of a-C:B films with fixed boron content (2.13 at.%) were prepared to identify the relationship between sp³ bonding and substrate bias. It was found that the fraction of sp³ bonding increased from 50.28% at the bias voltage of 0 V and reached a maximum value of 66.3% at −150 V. As the bias voltage increased up to −2000 V, the sp³ content decreased sharply to 43.9%.     

Evaluation of microstructures and mechanical properties of diamond like carbon films deposited by filtered cathodic arc plasma

Diamond-like carbon (DLC) films were deposited by a cathodic arc plasma evaporation (CAPD) process, using a mechanical shield filter combined with a magnetic filter with enhanced arc structure at substrate-bias voltage ranging from − 50 to − 300 V. The film characteristics were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM). The mechanical properties were investigated by using a nanoindentation tester, scratch test and ball on disc wear test. The Raman spectra of the films showed that the wavenumber ranging from 900 to 1800 cm^− 1 could be deconvoluted into 1140 cm^− 1, D band and G band. The bias caused a significant effect on the sp³ content which was increased with the decreasing of I_D/I_G ratio. The XPS spectra data of the films which were etched by H⁺ plasma indicated the sp³ content are higher than those of the as-deposited DLC films. This implied that there is a sp²-rich layer present on the surface of the as-deposited DLC films. The nanoindentation hardness increased as the maximum load increased. A 380 nm thick and well adhered DLC film was successfully deposited on WC-Co substrate above a Ti interlayer. The adhesion critical load of the DLC films was about 33 N. The results of the wear tests demonstrated that the friction coefficient of the DLC films was between 0.12 and 0.2.     

Growth and characterization of stoichiometric BCN films on highly oriented pyrolytic graphite by radiofrequency plasma enhanced chemical vapor deposition

Hexagonal boron carbonitride (h-BCN) hybrid films have been synthesized on highly oriented pyrolytic graphite by radiofrequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane as a single-source molecular precursor. The films were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopic measurements. XPS measurement showed that the B atoms were bonded to C and N atoms to form the sp²-B-C-N atomic hybrid chemical environment. The atomic composition estimated from the XPS of the typical sample was found to be almost B₁C₁N₁. NEXAFS spectra of the B K-edge and the N K-edge had the peaks due to the π* and σ* resonances of sp² hybrid orbitals implying the existence of the sp² hybrid configurations of h-BCN around the B atoms. The G band at 1592 and D band at 1352 cm^− 1 in the Raman spectra also suggested the presence of the graphite-like sp²-B-C-N atomic hybrid bonds. The films consisted of micrometer scale crystalline structure of around 10 µm thick has been confirmed by the field emission scanning electron microscopy.     

Chemical states of carbon in amorphous boron carbide thin films deposited by radio frequency magnetron sputtering

Boron carbide thin films were deposited by radio frequency (RF) magnetron sputtering and characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and high resolution transmission electron microscopy. The results reveal that the structure of thin films deposited at substrate temperatures lower than 350 °C is amorphous. We found that there are four chemical states for carbon in amorphous boron carbide thin films deposited by RF magnetron sputtering. One is the segregated carbon in form of the graphitic inclusions in the thin film identified by Raman spectroscopy and Raman mapping using two strong peaks at ~ 1360 cm^− 1 and ~ 1590 cm^− 1, but the XPS results show that the graphitic inclusions do not connect to the substrate directly. On the surface the carbon forms C=O bonds characterized by the peak of C1s core level at 285.0 eV besides B-C bonds in the boron carbide with the peak of C1s being at 282.8 eV. The detailed analysis of B-C bonds in the boron carbide shows that there are two states for carbon atoms in B-C bonds: in the C-B-C models with C1s peak at 282.3 eV and in the icosahedra with C1s peak at 283.3 eV.     

Mechanical properties and thermal stability of nitrogen incorporated diamond-like carbon films

The nitrogen incorporated diamond-like carbon films were deposited on Si (100) substrates by arc ion plating (AIP) under different N₂ content in the gas mixture of Ar and N₂. The influence of N₂ content on the film microstructure and mechanical properties was studied by atomic force microscopy, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and nanoindentation. It was found that the hardness (H), elastic modulus (E), elastic recovery (R) and plastic resistance parameter (H/E) decrease with increasing the nitrogen content. The decrease of mechanical properties of DLC films resulted from nitrogen incorporation was associated with total sp³ carbon bond content and N-sp³C bond content. The structural modification as well as mechanical properties of the annealed nitrogen incorporated diamond-like carbon films was investigated as a function of annealing temperature. Raman spectra indicate that the I_D/I_G ratio starts to increase and G peak position shifts upward at the annealing temperature over 500 °C. The hardness and elastic modulus of thermally annealed nitrogen incorporated DLC films decreased slightly at lower annealing temperature and then significantly decreased at higher annealing temperature. The strong covalent bonding between C and N atoms is expected to be effective on their thermal stability enhancement.     

Structural and surface energy analysis of nitrogenated ta-C films

Surface and bulk properties of the Filtered Cathodic Vacuum Arc prepared nitrogenated tetrahedral amorphous carbon (ta-C:N) films were characterized by X-ray Photoelectron Spectroscopy (XPS), Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS), Raman spectroscopy, Atomic Force microscopy and contact angle techniques. An increase in the Nitrogen (N) content of the films is accompanied by a reduction in the sp³ fraction, confirmed via the deconvolution of the C 1 s XPS spectra. Critical Raman parameters such as peak position and peak width of the G band, defect ratio, I_D/I_G and skewness of the G line were analyzed as a function of N content. ToF-SIMS showed the variance of chemical composition with the increase in the sputtering depth. While some amount of incorporated oxygen and hydrogen were observed for all films; for high N content ta-C:N films signature of CN bonds was evident. Surface energies (both polar and dispersive components) for these ta-C:N films were analyzed in a geometric mean approach. Contact angle measurements using both deionized water and ethylene glycol reveal that upon the insertion of nitrogen into ta-C films, the initial change in the contact angle is sharp, followed by a gradual decrease with subsequent increase in N content. The variation of contact angle with increasing N content corresponds to an increase of the total surface energy with an increase of the polar component and a decrease of the dispersive component.     

Ramanspektroskopische Charakterisierung von ultra‐dünnen Kohlenstoff‐Schutzschichten für die Magnetspeichertechnologie

Raman‐spectroscopy is a standard tool for structural characterization of ultra‐thin (<10 nm) amorphous carbon films which are used as protective overcoats in the magnetic storage industry. It provides powerful information on the bonding structure of the films. The Raman‐spectra of amorphous carbons are dominated by the D‐ and G‐bands at around 1350 cm^‐1 – 1600 cm^‐1 whose position and intensity are used for interpreting the carbon bonding. Several carbon films have been investigated using green (λ = 514.5 nm) and ultraviolet (λ = 244 nm) laser‐light. The dispersion of the G‐peak is the most crucial of parameters to describe the internal structure of the films since it distinguishes between graphite‐ and diamond‐like carbon. A high G‐peak‐dispersion corresponds to a high sp³‐fraction. These information are not available by single wavelength investigations due to the so called hysteresis effect causing the Raman‐spectra of different samples accidentally to look similar albeit having a different internal structure. The dual‐method we are here introducing avoids the hysteresis effect and provides good estimations on the sp³‐content and the mass density of different carbon systems. Furthermore, UV‐Raman analysis leads to quantification of the nitrogen content of nitrogen‐doped carbon layers by using the relative intensity of the 2200 cm^‐1 band in the UV‐spectrum. The great advantage of ramanspectroscopic investigations is its celerity. Acquisition times are seldom higher than 1.5 min. Additionally, Raman‐spectroscopy is a non‐destructive tool which leaves the investigated samples undamaged for further processing and makes it an attractive method for insitu‐analysis in the magnetic storage industry.     

Effect of bias voltage on growth property of Cr-DLC film prepared by linear ion beam deposition technique

Cr-containing diamond-like carbon films were deposited on silicon wafers by a combined linear ion beam and DC magnetron sputtering. The influence of the bias voltage on the growth rate, atomic bond structure, surface topography and mechanical properties of the films were investigated by SEM, XPS, Raman spectroscopy, AFM, and nano-indentation. It was shown that the chromium concentration of the films increased with negative bias voltage and that a carbide phase was detected in the as-deposited films. The surface topography of the films evolved from a rough surface with larger hillocks reducing to form a smoother flat surface as the bias voltage increased from 0 to −200 V. The highest hardness and elastic modulus were obtained at a bias voltage of about −50 V, while the maximum sp³ bonding fraction was acquired at −100 V. It was suggested that the mechanical properties of the films not only depended on the sp³ bonding fraction in the films but also correlated with the influence of Cr doping and ion bombardment.     

Thickness dependent electronic structure of ultra-thin tetrahedral amorphous carbon (ta-C) films

Microstructural properties of ultrathin (1-10 nm) tetrahedral amorphous carbon (ta-C) films are investigated by Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, X-ray Photoelectron Spectroscopy, Raman spectroscopy and Atomic Force Microscopy (AFM). The CK-edge NEXAFS spectra of 1 nm ta-C films provided evidence of surface defects (C―H bonds) which rapidly diminish with increasing film thickness. A critical thickness for stabilization of largely sp³ matrix structure distorted by sp² sites is observed via the change of π*C═C peak behavior. Meanwhile, an increase in the film thickness promotes an enhancement in sp³ content, the film roughness remains nearly constant as probed by spectroscopic techniques and AFM, respectively. The effect of thickness on local bonding states of ultrathin ta-C films proves to be the limiting factor for their potential use in magnetic and optical storage devices.     

Characterization of boron-doped diamond-like carbon prepared by radio frequency sputtering

Instead of the sophisticated deposition processes and boron sources reported in literature, the study used the radio frequency magnetron sputtering method to prepare boron-doped diamond-like carbon (DLC) films with p-type conduction. The adopted sputtering targets were composed of boron pellets buried in a graphite disc. The undoped DLC films prepared exhibited n-type conduction, based on the Hall-effect measurement. For boron content ≥ 2.51 at.%, the films showed semiconductor behavior converted from n-type to p-type conduction after annealing at 450 °C. B-DLC films with a boron content of 5.91 at.% showed a maximum carrier concentration of 1.2 × 10¹⁹ cm⁻³, a mobility of 0.4 cm²/V s, and an electrical resistivity of 1.8 Ω cm. The results of XPS and Raman spectra indicated that the motion of boron atoms was thermally activated during post-annealing, helping promote the formation of C-B bonds in the films. Moreover, the doping of boron in DLC films decreased sp³ bonding and facilitated carbon atoms to form sp² bonding and graphitization.     

Effect of ambient gaseous environment on the properties of amorphous carbon thin films

Amorphous carbon films have been deposited by filtered cathodic jet carbon arc technique under different gaseous environments. Scanning electron microscope and atomic force microscope studies have been performed on the deposited films for the surface morphological studies. The morphology of the deposited film changes with the change in gas environment. X-ray photoelectron spectroscopic (XPS) and Raman studies have been carried out on the deposited samples for the evaluation of the chemical bonding of carbon atoms with the ambient gas atoms. The sp³ and sp² contents have been evaluated from the XPS studies and found to be dependent on the gaseous environment. The film deposited under hydrogen environment has the highest value of the sp³ content (54.6 at.%) whereas the film deposited under helium environment has the lowest value of sp³ content (37 at.%). For the evaluation of the electrical and mechanical properties of the deposited films, the electrical conductivity and nanoindentation measurements have been performed on the deposited films. It has been observed that the film deposited under helium environment has the highest electrical conductivity and the lowest hardness (∼15 GPa) value whereas film deposited under hydrogen environment has the highest hardness (∼21 GPa) and the lowest conductivity.     

Theoretical and spectroscopic investigations on the structure and bonding in B-C-N thin films

In this study, we have synthesized boron, carbon, and nitrogen containing films using RF sputter deposition. We investigated the effects of deposition parameters on the chemical environment of boron, carbon, and nitrogen atoms inside the films. Techniques used for this purpose were grazing incidence reflectance-Fourier-transform infrared spectroscopy (GIR-FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). GIR-FTIR experiments on the B-C-N films deposited indicated presence of multiple features in the 600 to 1700 cm^− 1 range for the infrared (IR) spectra. Analysis of the IR spectra, XPS and the corresponding EELS data from the films has been done in a collective manner. The results from this study suggested even under nitrogen rich synthesis conditions carbon atoms in the B-C-N films prefer to be surrounded by other carbon atoms rather than boron and/or nitrogen. Furthermore, we have observed a similar behavior in the chemistry of B-C-N films deposited with increasing substrate bias conditions. In order to better understand these results, we have compared and evaluated the relative stability of various nearest-neighbor and structural configurations of carbon atoms in a single BN sheet using DFT calculations. These calculations also indicated that structures and configurations that increase the relative amount of C-C bonding with respect to B-C and/or C-N were energetically favorable than otherwise. As a conclusion, carbon tends to phase-segregate in to carbon clusters rather than displaying a homogeneous distribution for the films deposited in this study under the deposition conditions studied.     

Tunnelling through diamond-like carbon nanofilms deposited by electron-beam-induced deposition

The tunnelling properties in metal/diamond-like carbon (DLC)/semiconductor junctions and structural characteristics of thin DLC films produced using different electron beam conditions were studied. We show that under the same electron dose conditions, thicker DLC films were obtained using lower accelerating voltages (2 kV) than when using higher accelerating voltage (20 kV). However, under the settings used the thicker films showed worse insulating performance than the thinner films. We attribute this effect to the variation of tunnelling barrier height in DLC deposited using different accelerating voltages. DLC films with a tunnelling barrier height of up to 3.12 eV were obtained using a 20 kV electron-beam, while only 0.73 eV was achieved for 2 kV DLC films. The X-ray photoemission spectra of the C 1s core level in these films reveal components at 284.4 ± 0.1 eV and 285 ± 0.1 eV, which were identified as the sp² and sp³ hybrid forms of carbon. The sp³/sp² concentration ratio increased with increasing electron beam accelerating voltage. We show how this effect is responsible for the barrier height variation.     

Characterization of amorphous hydrogenated carbon films deposited by MFPUMST at different ratios of mixed gases

Amorphous hydrogenated carbon films (a-C:H) on p-type (100) silicon wafers were prepared with a middle frequency pulsed unbalanced magnetron sputtering technique (MFPUMST) at different ratios of methane–argon gases. The band characteristics, mechanical properties as well as refractive index were measured by Raman spectra, X-ray photoelectron spectroscopy (XPS), nano-indentation tests and spectroscopic ellipsometry. It is found that the sp ³ fraction increases with increasing Ar concentration in the range of 17–50%, and then decreases when Ar concentration exceeds 50%. The nano-indentation tests reveal that nano-hardness and elastic modulus of the films increase with increasing Ar concentration in the range of 17–50%, while decreases with increasing Ar concentration from 50% to 86%. The variations in the nano-hardness and the elastic modulus could be interpreted due to different sp ³ fractions in the prepared a-C:H films. The variation of refractive index with wavelength have the same tendency for the a-C:H films prepared at different Ar concentrations, they decrease with increasing wavelength from 600 to 1700 nm. For certain wavelengths within 600–1700 nm, refractive index has the highest value at the Ar concentration of 50%, and it is smaller at the Ar concentration of 86% than at 17%. The results given above indicate that ratio of mixed gases has a strong influence on bonding configuration and properties of a-C:H films during deposition. The related mechanism is discussed in this paper.     

Deposition of crystalline C3N4 films via microwave plasma chemical vapour deposition

Crystalline carbon nitride films have been synthesized on polycrystalline Ni substrates by a microwave plasma chemical vapour deposition technique, using a mixture of N₂, CH₄ and H₂ as precursor. Scanning electron microscopy shows that the film consisted of perfect crystals of short and long hexagonal bars, tetragonal bars and irregular particles. From the X-ray photoelectron spectroscopy (XPS) data, a maximum N/C ratio of 1.0 was achieved in the films. The XPS spectra of the film typically showed three peaks in the C 1s core spectrum (centered at 284.78, 285.94, and 287.64 eV) and two peaks in the N 1s core level spectrum (centered at 398.35 and 400.01 eV). This indicates that there are two types of C–N bonds; N is bonded to sp²- or sp³-coordinated C atoms in the as-deposited film. The X-ray diffraction pattern indicates that the film is composed of α-, β-, pseudocubic, graphitic C₃N₄ and an unidentified phase. A series of intense sharp Raman peaks were observed in the range of 100–1500 cm^− 1. These peaks match well with the calculated Raman frequencies of α- and β-C₃N₄, revealing the formation of α- and β-C₃N₄ phase.     

Bonding structure and optical properties of a-CNx:H films deposited in CH4-NH3 system

Hydrogenated amorphous carbon nitride (a-CN_x:H) films were deposited by plasma enhanced chemical vapor deposition (PECVD) in CH₄-NH₃ system. The chemical composition and bonding configuration were investigated by XPS and FTIR. The results indicated that both sp²CN and sp³CN bonds generally increased with the increase of the nitrogen concentration, and the N atoms bonded to C atoms through CN, CN and CN bonds. Remarkably, for FTIR spectra, two peaks (2125 and 2200 cm⁻¹) were obviously observed, corresponding to CN bond which was found to predominantly exist in the isonitrile structure. As more nitrogen atoms were incorporated, the optical band gap was found to vary from 1.8 to 2.5 eV. Finally, the conduction mechanisms were discussed at low and high temperature, respectively.     

XPS and IR study of carbon thin films prepared under negative substrate DC voltage bias

Hydrogenated amorphous carbon (a-C:H) thin films were prepared on glass substrates at different applied DC voltage bias by the HF-CVD method. Other factors of deposition were kept constant. The IR and XPS spectra of the films were obtained. By the deconvolution of the IR and XPS spectra sp³/sp² ratio calculated. The sp³/sp² ratio varies nonlinearly with bias voltage and it has a minimum and maximum in the 0–70 V range of the bias voltage.     

Broad band photoluminescence studies of diamond layers grown by hot-filament CVD

Photoluminescence and Raman spectroscopy were employed to investigate the broad band luminescence in thin diamond films grown on a silicon substrate by the HF CVD technique. The broad band luminescence with a maximum emission at 1.8–2 eV observed for CVD diamonds is characteristic for amorphous carbon with sp²-hybridized carbon bonds. As was shown by the Raman spectroscopy our diamond layer contained certain amounts of amorphous carbon phase and diamond nanocrystals which were the source of an additional energy state within the diamond energy gap. The experimental results precluded the possibility of broad band luminescence being due to the electron–lattice interaction. The amorphous carbon and diamond nanocrystals admixture in polycrystalline diamond layer introduced a defect state in the energy gap not in the form of point defects but rather in the form of a line or extended defects. In consequence these extended defects were responsible for the broad PL spectrum in the CVD diamond films.     

Low-temperature plasma-enhanced chemical vapor deposition of hard carbon films

Carbon films were prepared by the plasma-enhanced chemical vapor deposition method from methane gas under different regimes of a growing film surface ion bombardment. Ion energy and ion flux was measured for different deposition regimes and were controllably and independently varied for deposition of different film samples. The structure of the films deposited was studied by Raman scattering spectroscopy. It was found that ion bombardment of the growing film surface is a key factor in hard carbon films deposition. A correlation between the sp³ hybridized carbon fraction content with both ion energy and ion flux was found. The maximum sp³ hybridized carbon fraction content was achieved for films deposited under maximum ion energy and ion flux conditions. Additionally, a dependence of the film properties on the substrate material and on the final film thickness was observed.     

Synthesis of HDLC films from solid carbon

Diamond-like carbon (DLC) films were synthesized on silicon substrates from solid carbon by a very low power (60 W) microwave plasma chemical vapor deposition (MPCVD) reaction of a mixture of 90–70% helium and 10–30% hydrogen. It is proposed that He⁺ served as a catalyst with atomic hydrogen to form an energetic plasma. The average hydrogen atom temperature of a helium-hydrogen plasma was measured to be up to 180–210 eV versus 3 eV for pure hydrogen. Bombardment of the carbon surface by highly energetic hydrogen formed by the catalysis reaction may play a role in the formation of DLC. The films were characterized by time of flight secondary ion mass spectroscopy (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. TOF-SIMS identified the coatings as hydride by the large H⁺ peak in the positive spectrum and the dominant H^– in the negative spectrum. The XPS identification of the H content of the CH coatings as a novel hydride corresponding to a peak at 49 eV has implications that the mechanism of the DLC formation may also involve one or both of selective etching of graphitic carbon and the stabilization of sp ³-bonded carbon by the hydrogen catalysis product. Thus, a novel H intermediate formed by the plasma catalysis reaction may enhance the stabilization and etching role of H used in past methods.