Investigation of properties of Cu containing DLC films produced by PECVD process

Copper containing diamond like carbon (Cu-DLC) thin films were deposited on various substrates at a base pressure of 1×10^?3 Torr using a hybrid system involving DC-sputtering and radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD) techniques. The compressive residual stresses of these films were found to be considerably lower, varying between 0.7 and 0.94 GPa and Cu incorporation in these films improve their conductivity significantly. Their structural properties were studied by Raman spectroscopy, atomic force microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction techniques that clearly revealed the presence of Cu in the DLC structure. Raman analysis yields that Cu incorporation in DLC enhances the graphite-like sp² bonding. However, the sp² bonding was found to continuously reduce with the increasing C₂H₂ gas pressure, this may be due to reduction of Cu nanocrystal at the higher pressure. FTIR results inferred various bonding states of carbon with carbon, hydrogen and oxygen. In addition, hydrogen content and sp³ and sp² fractions in different Cu-DLC films were also estimated by FTIR spectra and were correlated with stress, electrical, optical and nano-mechanical properties of Cu-DLC films. The effect of indentation load (4–10 mN) on nano-mechanical properties of these films was also explored.     

Comparison and semiconductor properties of nitrogen doped carbon thin films grown by different techniques

Amorphous carbon nitride (a-CN_x) thin films have been synthesised by three different deposition techniques in an Ar/N₂ gas mixture and have been deposited by varying the percentage of nitrogen gas in the mixture (i.e. the N₂/Ar + N₂ ratio) from 0 to 10%. The variation of the electrical conductivity and the gap values of the deposited films versus the N₂/Ar + N₂ ratio were investigated in relation with their local microstructure. Film composition was analysed using Raman spectroscopy and optical transmission experiments. The observed variation of electrical conductivity and optical properties are attributed to the changes in the atomic bonding structures, which were induced by N incorporation, increasing both the sp² carbon content and their relative disorder. The low N content samples seem to be an interesting material to produce films with interesting properties for optoelectronic applications considering the facility to control the gas composition as a key parameter.     

Electrical conditioning of diamond-like carbon films for the formation of coated field emission cathodes

Diamond-like carbon (DLC) films deposited on different substrates by plasma enhanced chemical vapour deposition were investigated. Bonding states and film quality were characterized by FT-IR spectroscopy. The influence of the power of plasma and the deposition time on the sp²/sp³ ratio as well as the concentration of CH_n bonds was studied. The influence of sp²/sp³ ratio on the formation process of conducting channels in diamond-like carbon films as a result of electrical breakdown was determined. Reproducible increase of diamond-like carbon film conductivity, with initial sp²/sp³ ratio larger than 0.16, was observed after electrical breakdown.     

Nitrogen 1s electron binding energy assignment in carbon nitride thin films with different structures

Carbon nitride thin films deposited by dc unbalanced magnetron sputtering have been analyzed by high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS data show that N 1s binding states depend on substrate temperature (T_s). By comparison with the Raman spectra, N 1s binding states are assigned in which nitrogen atoms are mainly bound to sp² and sp³ carbon atoms at T_s = 100°C, whereas at T_s = 500°C nitrogen atoms are mainly bonded to sp², sp³ and sp¹ carbon atoms.     

Ion-beam analysis of the structure and composition of nanocomposite nc-TiC/a-C:H coatings

The structure and composition of nanocomposite nc-TiC/a-C:H thin films prepared by closed-field unbalanced reactive magnetron sputtering in an argon-acetylene atmosphere have been investigated. The concentrations of carbon and heavier elements have been obtained by Rutherford backscattering and nuclear backscattering. The hydrogen concentration in the films has been determined by elastic recoil detection analysis. Based on the data obtained, a scheme has been proposed to evaluate the C:H matrix mass density and the sp ³ and sp ² fractions in the matrix.     

Substrate effects on the microstructure of hydrogenated amorphous carbon films

In this work, plasma enhanced chemical vapour deposition was used to prepare hydrogenated amorphous carbon films (a-C:H) on different substrates over a wide range of thickness. In order to observe clear substrate effect the films were produced under identical growth conditions. Raman and near edge X-ray absorption fine structure (NEXAFS) spectroscopies were employed to probe the chemical bonding of the films. For the films deposited on silicon substrates, the Raman I_D/I_G ratio and G-peak positions were constant for most thickness. For metallic and polymeric substrates, these parameters increased with film thickness, suggesting a change from a sp³-bonded hydrogenated structure to a more sp² network, NEXAFS results also indicate a higher sp² content of a-C:H films grown on metals than silicon. The metals, which are poor carbide precursors, gave carbon films with low adhesion, easily delaminated from the substrate. The delamination can be decreased/eliminated by deposition of a thin (∼10 nm) silicon layer on stainless steel substrates prior to a-C:H coatings. Additionally we noted the electrical resistivity decreased with thickness and higher dielectric breakdown strength for a-C:H on silicon substrate.     

Study of porous carbon thin films produced by pulsed laser deposition

Amorphous carbon is an interesting material and its properties can be varied by tuning its diamond-like (sp³) fractions. The diamond-like fractions in an amorphous carbon films depends on the kinetic energy of the deposited carbon ions. Porous amorphous carbon thin films were deposited onto silicon substrates at room temperature in a vacuum chamber by Glancing Angle Pulsed Laser Deposition (GAPLD). Krypton fluoride (248 nm) laser pulses with duration of 15 ns and intensities of 1-20 GW/cm² were used. In GAPLD, the angles between the substrate normal and the trajectory of the incident deposition flux are set to be almost 90°. Porous thin films consisting of carbon nanowires with diameters less than 100 nm were formed due to a self-shadowing effect. The kinetic energies of the deposited ions, the deposition rate of the films and the size of the nanowires were investigated. The sp³ fraction of the porous carbon films produced at intensity around 20 GW/cm² were estimated from their Raman spectra.     

含氮氟化类金刚石(FN-DLC)薄膜的研究：(Ⅰ) sp结构与化学键分析

以CF₄，CH₄和N₂为源气体，利用射频等离子体增强化学气相沉积法，在不同功率下制备了含氮氟化类金刚石膜.用俄歇电子能谱、拉曼光谱、X射线光电子能谱和傅里叶变换红外光谱对薄膜的电子结构和化学键进行了表征，并结合高斯分峰拟合方法分析了薄膜中sp²，sp³结构比率.结果表明，制备的薄膜属于类金刚石结构，不同沉积功率下，薄膜内的sp²/sp³值在2.0—9.0之间，随着沉积功率的增加薄膜内sp²的相对含量增加.膜内主要有C—F_x(x=1，2)，C—C，C=C和C≡N等化学键.沉积功率增加，C—C基团增加，膜内F的浓度降低，C—F基团减少，薄膜的关联加强，稳定性提高. 关键词： 含氮氟化类金刚石膜 sp结构 化学键结构 射频功率     

Characterization of sp carbon produced by plasma deposition on gamma-TiAl alloys

Surfaces of two gamma-TiAl alloys, Ti-47%Al-2%Nb-2%Cr (MJ12) and Ti-47%Al-2%Nb-2%Mn + 0.8%TiB₂ (MJ47), were modified by acetylene plasma deposition at −3 kV bias voltage for 0.5-4 h. By using GIXRD and SAED, C (n-diamond), TiC, Al, AlTi, AlTi₂, AlTi₃, Al_0.64Ti_0.36 and Al₂Ti were detected on both alloys. Additional TiB₂ was detected on MJ47. XPS and Raman analyses revealed the presence of sp³ and sp² carbon deposited on the alloy surfaces with their binding energies of 283.9-284.8 eV for MJ12 and 283.9-285.0 eV for MJ47. Both sp³ and sp² contents were increased with the increase in the exposure times. The increasing rate of the first was less than that of the second, due to the stress developed in the films. Moiré fringe and crystallographic planes were detected using TEM. Knoop hardness of the deposited alloys, influenced by sp³ carbon, was increased with the increase in the exposure time. Those of MJ12 and MJ47 with 4 h deposition are 1.88 and 1.57 times of the corresponding untreated alloys, respectively.     

Influence of sp 3 fraction on the field emission properties of tetrahedral amorphous carbon films formed by magnetic filtered plasma stream

Electron field emission properties of tetrahedral amorphous carbon films (ta-C) with various sp³ fractions, [sp³]/([sp²]+[sp³]), prepared by magnetic filtered plasma deposition system, were investigated. The ta-C films were deposited on (100) n-Si wafer with a resistivity of 0.01–0.02 cm in a substrate bias voltage V_b range from +20 V to -80 V. The relative fraction of sp³-bonded carbon in these films was qualitatively and quantitatively estimated by a fitting of the Raman and XPS spectra, respectively. Results show that ta-C films of high sp³ fraction, more than 80%, can be formed with a substrate bias voltage V_b in the range from -10 to -50 V. A remarkably low turn-on field of about 1.7 V/m was observed for these samples. For V_b outside this range, the sp³ fraction is lower. The surface of such ta-C films was found to be smooth and uniform from the images of atomic force microscopy. The sp³ fraction of the sample is believed to be the main factor affecting field emission properties of ta-C films. PACS 79.70; 78.30; 73.90.+f     

Optical and structural characterization of ultrananocrystalline diamond/hydrogenated amorphous carbon composite films deposited via coaxial arc plasma

Ultrananocrystalline diamond/hydrogenated amorphous carbon composite films were deposited in the ambient of hydrogen by coaxial arc plasma deposition. The film compositions and chemical bonding structures were investigated by X-ray diffraction, X-ray photoemission and hydrogen forward scattering spectroscopies. The sp³/(sp²+sp³) ratio and hydrogen content in the film were estimated to be 64% and 35?at.%, respectively. The optical parameters and the optical dispersion profile were determined by using a variable angle spectroscopic ellipsometer at 55°, 65° and 75° angle of incidence in the photon energy range of 0.9–5?eV. Combinations of multiple Gaussian, and Tauc-Lorentz or Cody-Lorentz dispersion functions are used to reproduce the experimental data. Results of ellipsometry showed a refractive index of approximately 2.05 (at 2eV) and optical band gap of 1.63?eV. The imaginary part of dielectric function exhibited a peak at 3.8?eV, which has assigned to π-π* electron transitions. Furthermore, Electron spin resonance measurements implied the existence of dangling bonds, which might have a partial contribution to the optical absorption properties of the deposited films. A correlation between optical parameters and structural profile of the deposited films is discussed.     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

Mechanical properties and platelet adhesion behavior of diamond-like carbon films synthesized by pulsed vacuum arc plasma deposition

Diamond-like carbon (DLC) is an attractive biomedical material due to its high inertness and excellent mechanical properties. In this study, DLC films were fabricated on Ti6Al4V and Si(1 0 0) substrates at room temperature by pulsed vacuum arc plasma deposition. By changing the argon flow from 0 to 13 sccm during deposition, the effects of argon flow on the characteristics of the DLC films were systematically examined to correlate to the blood compatibility. The microstructure and mechanical properties of the films were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) surface analysis, a nano-indenter and pin-on-disk tribometer. The blood compatibility of the films was evaluated using in vitro platelet adhesion investigation, and the quantity and morphology of the adherent platelets was investigated employing optical microscopy and scanning electron microscopy.The Raman spectroscopy results showed a decreasing sp³ fraction (an increasing trend in I_D/I_G ratio) with increasing argon flow from 0 to 13 sccm. The sp³:sp² ratio of the films was evaluated from the deconvoluted XPS spectra. We found that the sp³ fraction decreased as the argon flow was increased from 0 to 13 sccm, which is consistent with the results of the Raman spectra. The mechanical properties results confirmed the decreasing sp³ content with increasing argon flow. The Raman D-band to G-band intensity ratio increased and the platelet adhesion behavior became better with higher flow. This implies that the blood compatibility of the DLC films is influenced by the sp³:sp² ratio. DLC films deposited on titanium alloys have high wear resistance, low friction and good adhesion.     

Preparation and characterization of boron-incorporated amorphous carbon films from a natural source of camphoric carbon as a precursor material

The boron-incorporated amorphous carbon (a-C:B) film has been prepared by pulsed laser deposition (PLD) in high vacuum at room temperature using natural source of camphoric carbon (CC) as a precursor material. The effects of various B weight percentages in the target (Bwt.%) on the properties of a-C:B films have been investigated using standard measurement techniques and discussed. The optical band gap (E_g) is almost unchanged up to 10 Bwt.%, decreased a little, and with decrease of electrical resistivity (ρ) with higher Bwt.%, we considered that the variation of E_g and electrical properties can be related to interstitial doping of B in carbon films through modifications of C-B bonding configurations by rearranging B atoms and the B incorporation induced by doping, which are responsible for the decrease in ρ. The decrease of ρ is considered not due to the graphitization caused by the increase of sp²-bonded carbon. This is further confirmed by the variation of surface morphology (AFM), Raman and FT-IR as the structural and bonding properties of these films was unchanged with B incorporation up to 16 Bwt.%.     

Properties of amorphous carbon nitride prepared by RF reactive sputtering

The local microstructure and optical and electrical properties were investigated of amorphous carbon nitride (a-CN) films deposited by reactive radio-frequency (RF) sputtering. Two series prepared in nitrogen or in a nitrogen and argon mixture were studied. The optical properties were investigated by transmittance/reflectance and photothermal deflection spectroscopies. Combined infrared measurements and Raman scattering spectroscopies were used to investigate the microstructure of a-CN films in terms of nitrogen incorporation within the films and C sp ² content. These experiments were completed by dark electrical conductivity measurements performed in coplanar configuration in the temperature range 50–450?K. The films exhibit semiconductor behaviour and the temperature dependence suggests two types of conduction. An increase in nitrogen incorporation induces an increase with clustering of sp ² phase replacing C=C olefinic groups with aromatic groups.     

Investigation of the electrical properties and stability of HfInZnO thin-film transistors

In this study, amorphous HfInZnO (a-HIZO) thin films and related thin-film transistors (TFTs) were fabricated using the RF-sputtering method. The effects of the sputtering power (50–200 W) on the structural, surface, electrical, and optical properties of the a-HIZO films and the performance and NBIS stability of the a-HIZO TFTs were investigated. The films’ N_e increased and resistivity decreased as the sputtering power increased. The 100 W deposited a-HIZO film exhibited good optical and electrical properties compared with other sputtering powers. Optimization of the 100 W deposited a-HIZO TFT demonstrated good device performance, including a desirable μ_FE of 19.5 cm²/Vs, low SS of 0.32 V/decade, low V_th of 0.8 V, and high I_on/I_off of 10⁷, respectively. The 100 W deposited a-HIZO TFT with Al₂O₃ PVL also exhibited the best stability, with small V_th shifts of -2.2 V during NBIS testing. These high-performance a-HIZO thin films and TFTs with Al₂O₃ PVL have practical applications in thin-film electronics.     

Structural, electrical, and optical properties of ZnInO alloy thin films

Indium zinc oxide (IZO) thin films with different percentages of In content (In/[In+Zn]) are synthesized on glass substrates by magnetron sputtering, and the structural, electrical and optical properties of IZO thin films deposited at different In₂O₃ target powers are investigated. IZO thin films grown at different In₂O₃ target sputtering powers show evident morphological variation and different grain sizes. As the In₂O₃ sputtering power rises, the grain size becomes larger and electrical mobility increases. The film grown with an In₂O₃ target power of 100 W displays the highest electrical mobility of 13.5 cm·V^-1·s^-1 and the lowest resistivity of 2.4 × 10^-3 Ω·cm. The average optical transmittance of the IZO thin film in the visible region reaches 80% and the band gap broadens with the increase of In₂O₃ target power, which is attributed to the increase in carrier concentration and is in accordance with Burstein-Moss shift theory.     

Structural,optical and electrical properties of tin oxide thin films by electrostatic spray deposition

Tin oxide (SnO₂) thin films were deposited by electrostatic spray deposition (ESD). The structural, optical and electrical properties of the films for different solvents were studied. The morphology of the deposited thin films was investigated by scanning electron microscopy. The optical transmission spectra of the films showed 66–75% transmittance in the visible region of spectrum. The electrical resistivity of thin films deposited using the different solvents ranged 1.08 × 10^?3–1.34 × 10^?3 Ω-cm. Overall, EG and PG were good solvents for depositing SnO₂ thin films by the ESD technique with stable cone jet.     

Effect of titanium incorporation on the structural, mechanical and biocompatible properties of DLC thin films prepared by reactive-biased target ion beam deposition method

Amorphous diamond like carbon (DLC) and titanium incorporated diamond like carbon (Ti-DLC) thin films were deposited by using reactive-biased target ion beam deposition method. The effects of Ti incorporation and target bias voltage on the microstructure and mechanical properties of the as-deposited films were investigated by means of X-ray photoelectron spectroscopy, Raman spectroscopy, transmission electron microscopy and nano-indentation. It was found that the Ti content in Ti-DLC films gets increased with increasing target bias voltage. At about 4.2 at.% of Ti, uniform sized well dispersed nanocrystals were seen in the DLC matrix. Using FFT analysis, a facility available in the TEM, it was found that the nanocrystals are in cubic TiC phase. Though at the core, the incorporated Ti atoms react with carbon to form cubic TiC; most of the surface exposed Ti atoms were found to react with the atmospheric oxygen to form weakly bonded Ti-O. The presence of TiC nanocrystals greatly modified the sp³/sp² hybridized bonding ratio and is reflected in mechanical hardness of Ti-DLC films. These films were then tested for their biocompatibility by an invitro cell culturing test. Morphological observation and the cell proliferation test have demonstrated that the human osteoblast cells well attach and proliferate on the surface of Ti incorporated DLC films, suggesting possible applications in bone related implant coatings.     

Optical,photo-acoustic and electrical switching studies of amorphous GeS2 thin films

This paper reports optical, photo-acoustic and electrical switching investigations of GeS₂ amorphous thin films of different thicknesses, deposited on glass substrates in vacuum. The Tauc parameter (B ^1/2) and Urbach energy (E _U) have been determined from the transmittance spectra, to understand the changes in structural disorder; it is found that B ^1/2 increases whereas E _U decreases as the thickness of the films increases. Based on the results, it is suggested that bond re-arrangement, i.e. transformation from homopolar bonds to heteropolar bonds, takes place with increase in thickness. The thermal diffusivity values of GeS₂ thin films also show the presence of a chemically ordered network in the GeS₂ thin films. Further, it is found that these films exhibit memory-type electrical switching. The observed variation in the switching voltages has been understood on the basis of increase in chemical order.