Photoconductivity of DLC film deposited by pulsed discharge plasma CVD

DLC films were deposited by a new pulsed DC discharge plasma chemical vapour deposition (CVD) using hydrogen and methane gas mixture. When methane concentration (Cm) i.e. CH₄/(H₂ + CH₄) was increased from 3 to 40%, the graphitization of the carbon film increases as evident from Raman study. When Cm was increased to 30%, DLC film shows photoconducting property. The white light photoconductivity (S = I_l/I_d, where I_l is light current and I_d is dark current) measured with solar simulator under AM 1.5 condition was approximately 20 at room temperature. The photoconductivity was not clear when Cm was lower than 20%. ESR measurements also show that the electron spin density was slightly decreased with decreasing concentration of methane. Thus we can conclude here that at higher concentrations of methane at 30%, Sp² content of the film increases and the DLC film becomes photoconducting.     

Mechanical properties of DLC films prepared inside of micro-holes by pulse plasma CVD

Diamond-like carbon (DLC) films are metastable amorphous carbon materials with superior tribological characteristics. In order to improve wear resistance of micro-extrusion dies with numerous imperceptible holes, DLC films were deposited on the inner wall surface of model dies with holes of 2 and 0.9 mm in diameter, and 20 mm in depth by using pulse plasma CVD method. This paper will discuss how argon gas, deposition pressure and time affect the characteristics of films deposited on the inner wall surface of dies. This micro-coating method can be applied widely for inner wall surface treatment of components with thin holes.     

Deposition of DLC film from adamantane by using pulsed discharge plasma CVD

Diamond like carbon films are deposited on silicon and quartz substrates using adamantane as a sole source of carbon by pulsed discharge plasma chemical vapor deposition. Tauc band gap of such films has been successfully tuned from 1.7eV to 2.9eV. Iodine incorporation is observed to favor the growth of such films and induces disorder in the films. It also brings down in energy the on-set of photon absorption. Such iodine incorporated diamond like carbon films may be interesting candidates for the new coming applications such as for heterojunction photovoltaic devices.     

Microstructure and optical band gap control of DLC film deposited by pulsed discharge plasma CVD

DLC films were deposited on silicon and quartz glass substrates by pulsed discharge plasma chemical vapor deposition (CVD), where the plasma was generated by pulsed DC discharge in H₂–CH₄ gas mixture at about 90 Torr in pressure, and the substrates were located near the plasma. The repetition frequency and duty ratio of the pulse were 800 Hz and 20%, respectively. When CH₄ / (CH₄ + H₂) ratio, i.e. methane concentration (Cm), increased from 3 to 40%, C₂ species in the plasma was increased, and corresponding to the increase of C₂, deposition rate of the film was increased from about 0.2 to 2.4 μm/h. The absorption peaks of sp³C–H and sp²C–H structures were observed in the FT-IR spectra, and the peak of sp²C–H structure was increased with increasing Cm, showing that sp² to sp³ bonding ratio was increased when Cm was increased. Corresponding to these structural changes due to the increase of Cm, optical band gap (Eg) was decreased from 3 to 0.5 eV continuously when Cm was increased from 3 to 40%.     

Effects of iodine doping on optoelectronic properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

We report the effects of iodine (I) doping on the electrical and optical properties of diamond-like carbon (DLC) thin films grown on silicon and quartz substrates by microwave surface wave plasma chemical vapor deposition at low temperature (<100 °C). For film deposition, we used argon gas with methane or camphor dissolved with ethyl alcohol composition as plasma source. The optical gap and photoconductivity measurements of the samples were carried out before and after the iodine doping. The results show that optical gap dropped from 3.4 to 0.9 eV corresponding to nondoping to iodine-doping conditions, respectively. The photovoltaic measurements show that the open-circuit voltage (V_oc) and short-circuit current density (J_sc) of I-doped DLC film deposited on n-type silicon substrate under light illumination (AM1.5, 100 mW/cm²) were approximately 177 mV and 1.15 μA, respectively, and the fill factor was found to be 0.217.     

Influence of substrate treatment on the tribological properties of DLC coatings

Due to the very thin nature of DLC coatings, the substrate must carry the main part of the applied load. If the substrate has insufficient strength to carry the contact load and thus support the coating, plastic deformation will occur, leading to premature failure of the coating. The challenge to improve the properties of hard DLC coatings by thermo-chemical pre-treatment of the substrate has gained much attention in recent years, leading to a new method called duplex treatment. In the present study, a hydrogen-free hard carbon coating deposited on plasma nitrided AISI 4140 steel was investigated with respect to microhardness, residual stress, scratch adhesion and dry sliding wear resistance. The pin-on-disc results showed that nitriding of the substrate improves the wear resistance of the hydrogen-free hard carbon coating as compared to the hardened substrate. The improvement can be related to the increased load carrying capacity of the steel substrate and to improved coating to substrate adhesion.     

Synthesis of nitrogen incorporated diamond-like carbon thin films using microwave surface-wave plasma CVD

Nitrogenated diamond-like (DLC:N) carbon thin films have been deposited by microwave surface wave plasma chemical vapor deposition on silicon and quartz substrates, using argon gas, camphor dissolved in ethyl alcohol composition and nitrogen as plasma source. The deposited DLC:N films were characterized for their chemical, optical, structural and electrical properties through X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Raman spectroscopy, atomic force microscope and current–voltage characteristics. Optical band gap decreased (2.7 to 2.4 eV) with increasing Ar gas flow rate. The photovoltaic measurements of DLC:N / p-Si structure show that the open-circuit voltage (V_oc) of 168.8 mV and a short-circuit current density (J_sc) of 8.4 μA/cm² under light illumination (AM 1.5 100 mW/cm²). The energy conversion efficiency and fill factor were found to be 3.4 × 10^{− 4}% and 0.238 respectively.     

Spinose carbon nanotubes grown on graphitized DLC film by low frequency r.f. plasma-enhanced chemical vapor deposition

Spinose carbon nanotubes (SCNTs) are grown on silicon substrates covered with diamond-like carbon film and iron catalyst film (Fe/DLC/Si structure) by low frequency r.f. plasma-enhanced chemical vapor deposition (LFRF-PECVD). During the pre-treatment of the Fe/DLC/Si substrate, there are three processes happened, namely, iron film spalled to small islands, the DLC film graphitized, and the iron island reacted partially with the graphitized DLC (GDLC), which can be deduced from the Raman spectroscopy and SEM pictures. SCNTs film grew from C₂H₂---H₂ mixture under low plasma density. The good contact of carbon nanotube with GDLC film was acquired by the accumulation of the graphite sheets and the reaction between the iron particles and GDLC film. The homogeneous spines with the length of approximately 15 nm and the thickness of <5 nm burgeoned from the defects at the wall of carbon nanotube and distributed uniformly, which were in fact thin bent or rolled-up graphite sheets.     

Characteristics of carbon-related materials deposited in electron-energy controlled CH4/H2 RF discharge plasmas

The influence of electron temperature T_e on the production of carbon-related materials was investigated in a hollow-type magnetron radio-frequency (RF) CH₄/H₂ plasma. Here, the electron temperature decreased along the plasma column. Since the dissociation of CH₄ is determined by the electron energy in plasmas, the density ratio of radicals CH₂/CH₃ can be varied by the electron temperature. Therefore, the change of the electron temperature is quite important for controlling the characteristics of carbon-related materials. In the experiment, the production of diamond microparticles in low T_e plasma was detected. On the other hand, thin carbon films consisting of graphitic carbons were observed in the high T_e plasma. Therefore, it is shown that control of the electron temperature in the plasma has a key effect on the film quality.     

Argon plasma treatment techniques on steel and effects on diamond-like carbon structure and delamination

We demonstrate alteration in diamond-like carbon (DLC) film structure, chemistry and adhesion on steel, related to variation in the argon plasma pretreatment stage of plasma enhanced chemical vapour deposition. We relate these changes to the alteration in substrate structure, crystallinity and chemistry due to application of an argon plasma process with negative self bias up to 600 V.Adhesion of the DLC film to the substrate was assessed by examination of the spallated fraction of the film following controlled deformation. Films with no pretreatment step immediately delaminated. At 300 V pretreatment, the spallated fraction is 8.2%, reducing to 1.2% at 450 V and 0.02% at 600 V. For bias voltages below 450 V the adhesion enhancement is explained by a reduction in carbon contamination on the substrate surface, from 59 at.% with no treatment to 26 at.% at 450 V, concurrently with a decrease in the surface roughness, R_q, from 31.5 nm to 18.9 nm. With a pretreatment bias voltage of 600 V a nanocrystalline, nanostructured surface is formed, related to removal of chromium and relaxation of stress; X-ray diffraction indicates this phase is incipient at 450 V. In addition to improving film adhesion, the nanotexturing of the substrate prior to film deposition results in a DLC film that shows an increase in sp³/sp² ratio from 1.2 to 1.5, a reduction in surface roughness from 31 nm to 21 nm, and DLC nodular asperities with reduced diameter and increased uniformity of size and arrangement. These findings are consistent with the substrate alterations due to the plasma pretreatment resulting in limitation of surface diffusion in the growth process. This suggests that in addition to deposition phase processes, the parameters of the pretreatment process need to be considered when designing diamond-like carbon coatings.     

Steam plasma reforming of biogas by non-thermal pulsed discharge

The purpose of this study was to develop technology that can convert biogas to synthesis gas (SynGas), a low emission substituted energy, using a non-thermal pulsed plasma method. To investigate the characteristics of the SynGas production from simulated biogas, the reforming characteristics were studied about the variations of pulse frequency, biogas component ratio (C₃H₈/CO₂), vapor flow ratio (H₂O/TFR), biogas velocity and pulse power. A maximum conversion rate of 49.1% was achieved for the biogas when the above parameters were 500 Hz, 1.5, 0.52, 0.32 m/s and 657 W, respectively. Under the above-mentioned reference conditions, the dry basis concentrations of the SynGas were, H₂ 64.5%, CH₄ 8.1%, C₂H₂ 6.7%, C₃H₆ 4.9%, CO 0.8% and C₂H₄ 0.4%. The ratio of hydrogen to the other intermediates in the SynGas (H₂/TTMs) was 3.1.     

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.     

Characteristics of nitrogen doped diamond-like carbon thin films grown by microwave surface-wave plasma CVD

Nitrogen doped diamond-like carbon (DLC:N) thin films were deposited on p-type silicon (p-Si) and quartz substrates by microwave (MW) surface-wave plasma (SWP) chemical vapor deposition (CVD) at low temperature (< 100 °C). For films deposition, argon (Ar: 200 sccm), acetylene (C₂H₂:10 sccm) and nitrogen (N: 5 sccm) were used as carrier, source and doping gases respectively. DLC:N thin films were deposited at 1000 W microwave power where as gas composition pressures were ranged from 110 Pa to 50 Pa. Analytical methods such as X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, FTIR and Raman spectroscopy were employed to investigate the chemical, optical and structural properties of the DLC:N films respectively. The lowest optical gap of the film was found to be 1.6 eV at 50 Pa gas composition pressure.     

Bonding defects and optical band gaps of DLC films deposited by microwave surface-wave plasma CVD

The effects of CH₄ / C₂H₄ flow ratio and annealing temperature on the defect states and optical properties of diamond-like carbon (DLC) films deposited by novel microwave surface-wave plasma chemical vapour deposition (MW SWP CVD) are studied through UV/VIS/NIR measurements, atomic force microscopy, Raman spectroscopy and electron spin resonance analysis. The optical band gap of DLC has been tailored between a relatively narrow range, 2.65–2.5 eV by manipulating CH₄ / C₂H₄ flow ratio and a wide range, 2.5–0.95 by thermal annealing. The ESR spin density varied between 10¹⁹ to 10¹⁷ spins/cm³ depending on the CH₄ / C₂H₄ flow ratio (1 : 3 to 3 : 1). The defect density increased with increasing annealing temperature. Also, there is a strong dependence of spin density on the optical band gap of the annealed-DLC films, and this dependency has been qualitatively understood from Raman spectra of the films as a result of structural changes due to sp³/sp² carbon bonding network. The surfaces of the films are found to be very smooth and uniform (RMS roughness < 0.5 nm).     

Structure and properties of Si and N co-doping on DLC film corrosion resistance

Three species of diamond-like carbon (DLC) film were systematically examined in NaCl solution for their anticorrosion properties. Si&N&H-DLC has better electrochemical characteristics and salt spray corrosion testing results than the substrate and two species DLC films in NaCl solution. Due to the successive growth of Si, N, and H-DLC, there is a well-bonded Si–N interface and the formation of Si oxides. The Si&N&H-DLC film exhibits extremely high charge transfer resistance, exceeding 10⁶ Ω/cm². A salt spray test shows that the Si&N&H-DLC film presents a lower rate in NaCl solution in comparison to the substrate and the other two species of DLC films. As a result, the Si&N&H-DLC film significantly improved the corrosion performance of the substrate.     

A review of diamond synthesis by CVD processes

Diamond has some of the most extreme mechanical, physical and chemical properties of all materials. Within the last 50 years, a wide variety of manufacturing methods have been developed to deposit diamond layers under various conditions. The most common process for diamond growth is the chemical vapor deposition (CVD). Starting from the first publications until the latest results today, a range of different developments can be seen. Comparing the basic conditions and the process parameters of the CVD techniques, the technical limitations are shown. Processes with increased pressure, flow rate and applied power are the general tendency.     

Free-standing diamond films deposited by DC arc plasma jet on graphite substrates with a destroyable Ti interlayer

A destroyable Ti interlayer on graphite substrate was used for fabrication of crack-free free-standing diamond films by high-power DC Arc Plasma Jet. Ti interlayer was arc ion plated on the polycrystalline graphite substrate. The thickness, morphology and composite phase of the Ti interlayer were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Titanium carbide (TiC) was detected in both sides of the interlayer, which played an important role with respect to reasonable adhesion and diamond nucleation. Semi-translucent and crack-free diamond films were obtained and characterized by SEM and Raman spectroscopy. It is shown that the diamond films so obtained have excellent Raman signature. The overall results suggest that plating Ti interlayer on graphite substrate is an effective way to obtain potentially crack-free free-standing diamond films.     

Deposition of diamond film on silicon and quartz substrates located near DC plasma

Deposition of diamond films on to both Si and quartz substrates was succeeded by means of locating the substrate near plasma, and their microstructures were investigated by using SEM and Raman spectroscopy. The plasma was generated by intermittent DC discharge in H₂–CH₄ gas mixture at high gas pressure. The deposition rate of the film was remarkably increased when distance (D) between the substrate and the plasma (discharge electrodes) decreased. When the gas pressure (P_g) was increased from 100 to 250 Torr, the deposition rate was extremely increased and the crystalline quality of the film was improved. The deposition rate, when P_g = 200 Torr and D = 5 mm, was about 2.1 and 1.7 μm/h for Si and quartz substrate, respectively.     

Moisture barrier properties of thin organic-inorganic multilayers prepared by plasma-enhanced ALD and CVD in one reactor

A widely used application of the atomic layer deposition (ALD) and chemical vapour deposition (CVD) methods is the preparation of permeation barrier layers against water vapour. Especially in the field of organic electronics, these films are highly demanded as such devices are very sensitive to moisture and oxygen. In this work, multilayers of aluminium oxide (AlO _x ) and plasma polymer (PP) were coated on polyethylene naphthalate substrates by plasma-enhanced ALD and plasma-enhanced CVD at 80℃ in the same reactor, respectively. As precursor, trimethylaluminium was used together with oxygen radicals in order to prepare AlO _x , and benzene served as precursor to deposit the PP. This hybrid structure allows the decoupling of defects between the single AlO _x layers and extends the permeation path for water molecules towards the entire barrier film. Furthermore, the combination of two plasma techniques in a single reactor system enables short process times without vacuum breaks. Single aluminium oxide films by plasma-enhanced ALD were compared to thermally grown layers and showed a significantly better barrier performance. The water vapour transmission rate (WVTR) was determined by means of electrical calcium tests. For a multilayer with 3.5 dyads of 25-nm AlO _x and 125-nm PP, a WVTR of 1.2 × 10 ⁻³ gm⁻²d⁻¹ at 60℃ and 90% relative humidity could be observed.     

High structural retention during pulsed plasma polymerization of 1H,1H,2H-perfluorododecene: an NMR and TOF-SIMS study

A combined NMR and TOF-SIMS study has been carried out on 1H,1H,2H-perfluorododecene plasma polymers. Pulsed plasma polymerization is found to give rise to a high level of structural retention for the perfluoroalkyl groups, whereas continuous wave conditions lead to monomer fragmentation and cross linking. This investigation provides unequivocal proof that pulsed plasma deposition is a simple and highly effective method for functionalising solid surfaces.