Substrate bias effect on structure of tetrahedral amorphous carbon films by Raman spectroscopy

Diamond-like carbon (DLC) films form a critical protective layer on magnetic hard disks and their reading heads. Now tetrahedral amorphous carbon films (ta–C) thickness of 2 nm are becoming the preferred means due to the highly sp³ content. In this paper, Raman spectra at visible and ultraviolet excitation of ta–C films have been studied as a function of substrate bias voltage. The spectra show that the sp³ content of 70 nm thick DLC films increases with higher substrate bias, while sp³ content of 2 nm ultra-thin films falls almost linearly with bias increment. And this is also consistent with the hardness measurement of 70 nm thick films. We proposed that substrate bias enhances mixing between the carbon films and either the Si films or Al₂O₃TiC substrate such that thin films contain less sp³ fraction. These mixing bonds are longer than C–C bonds, which inducing the hardness decreasing of ultra-thin DLC films with bias. But for 70 nm DLC, the effect of mixing layer can be negligible by compared to bias effect with higher carbon ion energy. So sp³ content will increase for thick films with substrate bias.     

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.     

Electronic and bonding properties of Fe- and Ni based hydrogenated amorphous carbon thin films by X-ray absorption, valence-band photoemission and Raman spectroscopy

Electronic and bonding properties of Me-based hydrogenated amorphous carbon (a-CH:Me, Me = Fe, Ni) thin films have been studied by X-ray absorption near-edge structure (XANES), valence-band photoemission (VB-PES) and Raman spectroscopy. Raman and XANES results show enhancement of the content of sp³-rich diamond-like carbon (DLC) by doping with Fe and Ni. The VB-PES spectrum of a-CH:Fe shows emergence of a prominent feature due to states of sp³-bonded clusters, indicating that a-CH:Fe induced enhancement of DLC structure. The nano-indentation measurement reveals that a-CH:Fe has a greatly enhanced hardness, while electrical resistance measurement shows that a-CH:Me reduces resistivity.     

Influence of bias voltage on diamond like carbon (DLC) film deposited on polyethylene terephthalate (PET) film surfaces using PECVD and its blood compatibility

In this paper, diamond like carbon (DLC) films were coated on polyethylene terephthalate (PET) film substrate as a function of biasing voltage using plasma enhanced chemical vapour deposition. The surface morphology of the DLC films was analyzed by scanning electron microscopy and atomic force microscopy. The chemical state and structure of the films were analyzed by X-ray photoelectrons spectroscopy and Raman spectroscopy. The micro hardness of the DLC films was also studied. The surface energy of interfacial tension between the DLC and blood protein was investigated using contact angle measurements. In addition, the blood compatibility of the films was examined by in vitro tests. For a higher fraction of sp³ content, maximum hardness and surface smoothness of the DLC films were obtained at an optimized biasing potential of ? 300 V. The in vitro results showed that the blood compatibility of the DLC coated PET film surfaces got enhanced significantly.     

Effects of thermal annealing and Si incorporation on bonding structure and fracture properties of diamond-like carbon films

The effects of thermal annealing and Si incorporation on the structure and properties of diamond-like carbon (DLC) films were investigated. As-deposited DLC film (DLC) and Si incorporated DLC film (Si-DLC), both with and without thermal annealing, were analyzed for bonding structure, residual stress, film thickness, elastic modulus and fracture properties using Raman spectroscopy, wafer curvature, nanoindentation, four-point bend fracture testing, and X-ray photoelectron spectroscopy (XPS). Raman spectroscopy clearly showed that thermal annealing of DLC films promotes more sp² bonding character, whereas Si incorporation into the films promotes more sp³ bonding character. Interfacial fracture energies, film hardness and elastic modulus, and residual film stress were all found to vary strongly with the degree of sp³ bonding in the DLC film. These changes in mechanical properties are rationalized in terms of the degree of three dimensional inter-links within the atomic bond network.     

Effect of substrate bias voltage on the properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

Diamond-like carbon (DLC) thin films were deposited on silicon and ITO substrates with applying different negative bias voltage by microwave surface wave plasma chemical vapor deposition (MW SWP-CVD) system. The influence of negative bias voltage on optical and structural properties of the DLC film were investigated using X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. Optical band gap of the films decreased from 2.4 to 1.7 with increasing negative bias voltage (0 to − 200 V). The absorption peaks of sp³ CH and sp² CH bonding structure were observed in FT-IR spectra, showing that the sp²/sp³ ration increases with increasing negative bias voltage. The analysis of Raman spectra corresponds that the films were DLC in nature.     

Microstructure and mechanical properties of Mo/DLC nanocomposite films

Mo-doped diamond-like carbon (Mo/DLC) films were deposited on stainless steel and Si wafer substrates via unbalanced magnetron sputtering of molybdenum combined with inductively coupled radio frequency (RF) plasma chemical vapor deposition of CH₄/Ar. The effects of Mo doping and sputtering current on the microstructure and mechanical properties of the as-deposited films were investigated by means of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, atomic force microscopy (AFM), and nano-indentation. It was found that Mo doping led to increase in the content of sp² carbon, and hence decreased the hardness and elastic modulus of Mo/DLC films as compared with that of DLC films. The content of Mo in the films increased with the increasing sputtering current, and most of Mo reacted with C atoms to form MoC nanocrystallites at a higher sputtering current. Moreover, the Mo-doped DLC films had greatly decreased internal stress and increased adhesion to the substrate than the DLC film, which could be closely related to the unique nanocomposite structure of the Mo-doped films. Namely, the Mo/DLC film was composed of MoC nanoparticles embedded in the cross-linked amorphous carbon matrix, and such a kind of nanostructure was beneficial to retaining the loss of hardness and elastic modulus.     

Electrochemical characterization of diamond like carbon thin films

Diamond-like carbon (DLC) thin films were deposited from pure graphite target by DC magnetron sputtering method. Experimental parameters, i.e., substrate temperature and negative bias voltage, have been changed to finely tune the chemical bonding property (sp²/sp³) of the as-deposited DLC films. The as-deposited DLC films were characterized as anode materials for Li–ion batteries and special attentions were paid to the effects of sp²/sp³ ratio on the electrochemical properties of the DLC films. The results indicated that a high fraction of sp² bonding in the DLC films is preferred for high lithium storage capacity, flat and low charge voltage plateau, and long cycling retention.     

Characterization of hydrogen-free diamond-like carbon film deposited on cyclic olefin copolymer

In this study, the feasibility of the diamond-like carbon (DLC) film as a viable component for cyclic olefin copolymer (COC) substrate overcoat was assessed. Featured by its advanced physical and chemical properties such as high hardness, chemical stability, and wide band-gap optical transparency, the hydrogen-free DLC exhibits promising characteristics as the overcoat for flexible substrates or other TFT components. Ultra smooth, DLC thin films were synthesized by using a filter arc deposition (FAD) system and a cathodic arc evaporation (CAE) system. Raman spectroscopy, ESCA, Nano-Indentation, and electron microscopy were used to characterize the electronic, morphological, and microstructure properties of the DLC coatings. Results indicate that the device-quality DLC needs to be synthesized at lower substrate bias potential to retain high sp³/sp² ratio. The bending tests demonstrated a 30-fold improvement of the DLC-protected COC over that of the unprotected COC. Water vapor permeability tests demonstrated a 25-fold improvement of the DLC-protected COC over that of unprotected COC.     

Long-term stability of hydrogenated DLC coatings: Effects of aging on the structural,chemical and mechanical properties

Long-term stability is an essential condition for the commercial use of protective coatings, yet often remains overlooked in the literature. Here we report the effects of long-term environmental aging on the properties of hydrogenated diamond-like carbon (DLC) films. A range of DLC coatings produced by plasma-enhanced chemical vapor deposition were first thoroughly characterized and then stored for three years before the second set of analysis. Raman spectroscopy showed that the films exhibited excellent structural stability during aging, observing no sign of sp³ to sp² conversion. Similarly, the hardness and smoothness of the DLC coatings remained unchanged, despite the observed relaxation of their intrinsic stress with time. However, X-ray photoelectron spectroscopy analyses provided evidence of aging-induced surface oxidation, which was confirmed by reduced hydrophobicity (water contact angle dropped to 65°). Overall, these findings suggest that DLC possesses a suitable long-term stability when exposed to environmental conditions.     

Sp content in ta-C films vs pulse bias width to the substrate: A correlative structural analysis

Tetrahedral amorphous carbon (ta-C) films were studied with and without applying fixed pulse bias and frequency at variable pulse widths in double bent Filtered Cathodic Vacuum Arc (FCVA) system. Both from Raman and X-ray photoelectron spectroscopy (XPS) analyses it has been observed that the ratio of sp³/sp² is maximal at pulse width of 15 µs with fixed pulse bias 3 kV and frequency 200 Hz. Increasing or decreasing pulse width from this threshold value accompanies the decreasing sp³ content in the film. It is also observed that with applying pulse bias width at said frequency and bias voltage G peak position was shifted to lower values and after reaching a minimum at 15 µs G peak position shifted to higher wave numbers. At the 15 µs pulse width, 3 kV bias voltage and 200 Hz frequency we have formed ta-C films with maximum sp³ content. This study clearly suggests that it is possible to tune the ta-C film's most important properties such as percentage of sp³ content, internal stress, and hardness by applying pulse width at particular frequency and bias voltage.     

Changes in chemical bonding of diamond-like carbon films by atomic-hydrogen exposure

We have deposited unhydrogenated diamond-like carbon (DLC) films on Si substrate by pulsed laser deposition using KrF excimer laser, and investigated the effects of atomic-hydrogen exposure on the structure and chemical bonding of the DLC films by photoelectron spectroscopy (PES) using synchrotron radiation and Raman spectroscopy. The fraction of sp³ bonds at the film surface, as evaluated from C1s spectra, increased at a substrate temperature of 400 °C by atomic-hydrogen exposure, whereas the sp³ fraction decreased at 700 °C with increasing exposure time. It was found that the sp³ fraction was higher at the surfaces than the subsurfaces of the films exposed to atomic hydrogen at both the temperatures. The Raman spectrum of the film exposed to atomic hydrogen at 400 °C showed that the clustering of sp² carbon atoms progressed inside the film near the surface even at such a low temperature as 400 °C.     

Electrochemical characteristics of lithium metal anodes with diamond like carbon film coating layer

To overcome the poor electrochemical characteristics of lithium metal anodes due to the dendrite formations, diamond like carbon (DLC) films were deposited onto the surface of lithium metal by radio frequency-plasma enhanced chemical vapor deposition (CVD) technique using acetylene gas as carbon precursor. The substrate temperature was selected as the main experimental parameter to control the bonding characteristic (sp²/sp³ ratio) of the films. The presence of diamond like structures was confirmed by Raman and Fourier transform infra red spectroscopy. The DLC coated lithium metal was then characterized as an anode material for lithium secondary batteries. The results showed that the DLC coated lithium metal anodes exhibited better electrochemical characteristics in terms of higher specific capacity and smaller interfacial impedance. These improved characteristics were attributed to the presence of DLC film coating which might suppress the dendrite's formation by protecting the lithium metal surface from the direct contact with the electrolyte.     

Properties of diamond-like carbon films on crystalline quartz and lithium niobate

One-micron thick DLC films are deposited on Y-X cut quartz and Y-cut lithium niobate substrates using a plasma-enhanced CVD technique. From the Raman spectra, we find that the films have a small intensity ratio of ‘D’ to ‘G’ peak, indicating a high carbon sp³/sp² ratio and high hardness characteristic. The effect of accelerating a surface acoustic wave by the DLC films has been confirmed by comparing two delayed signals from two near-by delay lines. One was coated with the DLC, while the other was kept as the free quartz or lithium niobate surfaces. It is observed that the one-micron thick DLC films are able to speed up SAW by 2.4% (at 198 MHz) for DLC/quartz and 2.5% (at 430 MHz) for DLC/lithium niobate samples, respectively.     

Effects of diamond-like carbon in TPD-Alq3 doped PVK organic light-emitting devices

Effects of an ultrathin (~ 1 nm) diamond-like carbon (DLC) layer in single-layer organic light-emitting devices (OLEDs) that consist of ITO/(TPD-Alq₃ doped PVK)/Al were investigated. DLC layers deposited by using Nd:YAG laser at laser wavelengths of 355 nm were high in sp³ content and resistivity (DLC_UV) while that of 1064 nm laser were lower in sp³ content and resistivity (DLC_IR), as characterized by Raman spectroscopy and resistivity measurements. Although emission were obtained for all the devices, only the device of ITO/DLC_UV/(TPD-Alq₃ doped PVK)/Al exhibited enhanced current density and brightness with lower turn-on voltage as compared to a standard device. Devices of ITO/DLC_IR/(TPD-Alq₃ doped PVK)/Al and ITO/(TPD-Alq₃ doped PVK)/DLC_UV/Al showed poor current and brightness characteristics but failed at higher applied voltage. The enhance performance of device with high resistivity/sp³ DLC film suggests the mechanisms of barrier reduction by sufficiently thin insulating layer which increase the probability of tunneling of carriers at ITO and PVK interface.     

Structure and mechanical properties of oxygen doped diamond-like carbon thin films

In this study, structure and mechanical properties of doped diamond-like carbon (DLC) films with oxygen were investigated. A mixture of methane (CH₄), argon (Ar) and oxygen (O₂) was used as feeding gas, and the RF-PECVD technique was used as a deposition method. The thin films were characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (RS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and a combination of elastic recoil detection analysis and Rutherford backscattering (ERDA-RBS). Nano-indentation tests were performed to measure hardness. Also, the residual stress of the films was calculated by Stoney equation. The XPS and ERDA-RBS results indicated that by increasing the oxygen in the feeding gas up to 5.6 vol.%, the incorporation of oxygen into the films' structure was increased. The ratio of sp² to sp³ sites was changed by the variation of oxygen content in the film structure. The sp²/sp³ ratios are 0.43 and 1.04 for un-doped and doped DLC films with 5.6 vol.% oxygen in the feeding gas, respectively. The Raman spectroscopy (RS) results showed that by increasing the oxygen content in doped DLC films, the amount of sp² CC aromatic bonds was raised and the hydrogen content reduced in the structure. The attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the decrease of hydrogen content and the increase the ratio of CC aromatic to olefinic bonds. Hardness and residual stress of the films were raised by increasing the oxygen content within the films' structure. The maximum hardness (19.6 GPa) and residual stress (0.29 GPa) were obtained for doped DLC films, which had the maximum content of oxygen in structure, while the minimum hardness (7.1 GPa) and residual stress (0.16 GPa) were obtained for un-doped DLC films. The increase of sp³ CC bonds between clusters and the decrease of the hydrogen content, with a simultaneous increase of oxygen in the films' structure is the reason for increase of hardness and residual stress.     

Mechanical properties of DLC films prepared in acetylene and methane plasmas using electron cyclotron resonance microwave plasma chemical vapor deposition

Diamond-like carbon (DLC) films were deposited on silicon using methane and acetylene plasma induced by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MPCVD). The mechanical properties of DLC films were characterized by micro-Raman system, atomic force microscope, tribometer, nano-indenter used for both hardness and nano-scratch test measurements. The mechanical properties of both DLC films, prepared in methane and acetylene plasmas, respectively, strongly depended on the kinetic energy of impinging particles. The deposition at −120 V substrate bias gave rise to DLC films with the best mechanical properties for both methane and acetylene plasmas. The hardness measurements with variable indentation depth showed the characteristic changes in hardness values implying elastic deformations of supporting substrates. The maximum hardness value of DLC^M films was 20 GPa while that of DLC^A films was 28 GPa. However, the hardness dropped when DLC films were prepared at substrate biases more negative than −120 V due to the thermal graphitization. The improvement in DLC properties usually provided the films with smaller hydrogen content and higher density of sp³ bondings. These parameters were engineered through controlling the deposition parameters. Particularly, the bombardment of growing DLC films by energetic ions showed to be extremely important to yield films with lower internal stress.     

Piezoresistive properties of diamond like carbon films containing copper

In the present study diamond like carbon films containing copper (DLC:Cu) were deposited by reactive magnetron sputtering. Direct current (DC) sputtering and high power pulsed magnetron sputtering (HIPIMS) were used. The influence of the composition and structure on piezoresistive properties of DLC:Cu films was investigated. Structure of DLC:Cu films was investigated by Raman scattering spectroscopy and transmission electron microscopy (TEM). Chemical composition of the films was studied by using energy-dispersive X-ray spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS). Particularly analysis of XPS O1s spectra revealed oxidation of Cu nanoparticles. Piezoresistive gauge factor of DLC:Cu films was in 3–6 range and decreased with the increase of copper atomic concentration. Tendency of the decrease of the gauge factor of DLC:Cu films with the increased D/G peak area ratio (decreased sp³/sp² carbon bond ratio) was observed. It was found that resistance (R) of DLC:Cu films decreased with the increase of Cu atomic concentration by logarithmic law. It is shown that a quasilinear increase of piezoresistive gauge factor with log(R) is in good accordance with percolation theory. Temperature coefficient of resistance (TCR) of DLC:Cu films was negative and decreased with copper amount in Cu atomic concentrations ranging up to ~ 40%. Very low TCR values (zero TCR) were observed only for DLC:Cu films with low gauge factor that was close to the gauge factor of the metallic strain gauges. Role of some possible mechanisms: copper amount as well as Cu cluster size on the value of gauge factor is discussed.     

Structural and mechanical properties of DLC films prepared by bipolar PBII&D

In the present study, diamond-like carbon (DLC) films were prepared by bipolar plasma based ion implantation and deposition (PBII&D), and the structural and mechanical properties of the DLC films deposited on Si substrates were evaluated by Raman spectroscopy. In the PBII&D processing, the positive and negative pulse voltages were varied from 1 to 3 kV and from ? 1 to ? 15 kV, respectively. With an increase in the pulse voltages, the Raman G-peak position and I(D) / I(G) ratio increased, and the G-peak full width at half maximum (FWHM(G)) decreased, indicating graphitization of the DLC films. In the low wavenumber regime, the FWHM(G) increases when the G-peak shifts to higher wavenumbers, reaching a maximum value at around 1540 cm^? 1, and then decreases. This behavior was due to the structural changes occurring in the DLC films with an increase in the wavenumber. DLC to polymer-like carbon (PLC) transition occurred in the low wavenumber regime, and DLC to graphite-like carbon (GLC) transition occurred in the high wavenumber regime. Further, two different trends were observed in the relationship between the mechanical properties (hardness, elastic modulus, and internal stress) of the DLC films and the FWHM(G), originating from the structural change from DLC to GLC and PLC.     

The effect of negative bias pulse on the bonding configurations and properties of DLC films prepared by PBII with acetylene

The effect of negative bias pulse applied to substrate on the bonding configurations and properties of diamond-like carbon (DLC) films prepared by plasma-based ion implantation (PBII) with acetylene were investigated. The research results show that as the plasma density is 10⁹ cm⁻³ and the negative bias pulses applied to substrate decrease from 50 to 10 kV, the Raman spectra of the carbon films all possess the most dominant characterizations of typical a-C:H [J. Robertson, Mater. Sci. Eng., R 37 (2002) 129-281.], the positions and FWHM for G and D peaks vary no distinguished, but the ratio ID/IG decreases monotonically, as the negative bias pulse decreasing to 5 kV, the Raman spectrum possesses rather strong photoluminescence characterized the polymer-like phase. The variation of Raman spectra for plasma density 10⁸ cm⁻³ is analogous to that of the plasma density 10⁹ cm⁻³. The binding energies of XPS C1s peak decrease from the side of diamond peak to the side of graphite peak with the increasing of negative bias pulse from 10 to 50 kV monotonously, the sp³ content in the films increases with the decreasing in the negative bias pulse. With the increasing of negative bias pulse from 0 to 50 kV, the surface electric resistance of the films decreases monotonously, but the surface nanohardness at first increases with the increasing of the negative bias pulse from 0 to 10 kV, then decreases with the increasing of the negative bias pulse from 10 to 50 kV monotonously. These properties of the films are corresponding to the bonding configurations of the films. The reason for the highest sp³ fractions of the a-C:H films formed at higher effective ion energy per C atom in PBII is discussed in this paper.