Optical and microstructural properties of diamond-like carbon films grown by pulsed laser deposition

Diamond-like carbon films have been fabricated using 308 nm excimer laser ablation in vacuum followed by deposition at temperatures between 77 K and 573 K. Optical band gap energies are obtained from UV/optical spectroscopy. Raman spectra and X-ray photoelectron spectra (XPS) show that the sp³/(sp² + sp³) ratio in these films is in excess of 0.7 in films deposited at 77 K and 300 K. This ratio decreases to 0.2 in films deposited at 573 K. It is found that films deposited at cryogenic temperatures consist of a matrix structure assembled from embedded nanometer clusters, while films deposited at 300 K or higher temperature are amorphous and atomically flat. Microstructural features in cryogenic films are discussed in relation to the mechanism of deposition and possible phase transitions during assembly of these films.     

Effects of hydrogen on the properties of Si-incorporated diamond-like carbon films prepared by pulsed laser deposition

We have deposited unhydrogenated and hydrogenated Si-incorporated DLC (Si-DLC) films by pulsed laser deposition using KrF excimer laser, and systematically examined the structure and the mechanical and tribological properties of the films. Hydrogenated Si-DLC films were prepared by atomic-hydrogen irradiation during deposition. The Si/(Si+C) ratio in DLC films increased by atomic-hydrogen irradiation during deposition, indicating that the hydrogen etching is more effective for C atoms compared with Si atoms. The formation of Si–C bonds in the films and silicon oxides only at the surfaces was confirmed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. It was found that the atomic-hydrogen irradiation led to the formation of Si–H bonds to prevent the surface oxidation of the Si-DLC films. The scratch tests revealed that the critical loads of the films deposited with hydrogen were higher than those of the films deposited without hydrogen. We found that the moderately hydrogen-irradiated Si-DLC films tended to have higher wear resistance than the unhydrogenated Si-DLC films.     

Parametric studies of diamond-like carbon by pulsed Nd:YAG laser deposition

This paper presents the results, analysis and discussions of parametric studies of diamond-like carbon (DLC) thin films by pulsed Nd:YAG laser deposition. Effects on the DLC properties and growth rate were investigated by varying the deposition parameters, namely the laser wavelength and fluence, substrate and temperature. For characterization, visible Raman spectroscopy, current-voltage measurement, optical interferometry, and optical absorption technique were employed. Comparisons were made with previous work by other workers who had also employed pulsed Nd:YAG lasers. The results also supported the subplantation mechanism for DLC formation.     

Electrical and optical properties of diamond-like carbon films deposited by pulsed laser ablation

Pulsed laser ablation of a graphite target was carried out by ArF excimer laser deposition at a laser wavelength of 193 nm and fluences of 10 and 20 J/cm² to produce diamond-like carbon (DLC) films. DLC films were deposited on silicon and quartz substrates under 1 × 10^? 6 Torr pressure at different temperatures from room temperature to 250 °C. The effect of temperature on the electrical and optical properties of the DLC films was studied. Laser Raman Spectroscopy (LRS) showed that the DLC band showed a slight increase to higher frequency with increasing film deposition temperature. Spectroscopic ellipsometry (SE) and ultraviolet–visible absorption spectroscopy showed that the optical band gap of the DLC films was 0.8–2 eV and decreased with increasing substrate temperature. These results were consistent with the electrical resistivity results, which gave values for the films in the range 1.0 × 10⁴–2.8 × 10⁵ Ω cm and which also decreased with deposition temperature. We conclude that at higher substrate deposition temperatures, DLC films show increasing graphitic characteristics yielding lower electrical resistivity and a smaller optical band gap.     

Effect of temperature on sulfur-doped diamond-like carbon films deposited by pulsed laser ablation

In this study, S-DLC films were deposited using pulsed laser ablation of a novel sulfur-graphite (SG) mixture target using an ArF excimer laser (193 nm). The SG targets were made by mixing sulfur and graphite powders at different sulfur molar percentages from 0% to 25%. The S-DLC films were deposited at room temperature, 150 °C and 250 °C. The optical and electronic properties of the doped films were studied. Laser Raman spectroscopy indicated increased graphitic behavior with temperature but decreased with higher sulfur content. Spectroscopic ellipsometry analyses found that the optical band-gap energy, extinction coefficient and reflective index, clearly depended on deposition temperature and sulfur content. Hall Effect measurements indicated n-type carrier with concentration in the range of 1 × 10¹⁴ to 2 × 10¹⁷ cm^− 3, strongly depended upon the deposition temperature and amount of sulfur.     

Structural characterization of diamond-like carbon films for ultracold neutron applications

We have produced hydrogen-free diamond-like carbon (DLC) films by vacuum arc deposition for use as wall coating material in ultracold neutron (UCN) applications. The sp³ fraction, the main quality factor for DLC used in UCN applications, was varied from 0.4 to 0.9, the coating thickness between 10 nm and 120 nm. The samples were characterized by using X-ray Absorption Near-Edge Spectroscopy (XANES), X-ray induced Photoelectron Spectroscopy (XPS), Laser induced surface Acoustic Waves (LAwave), cold neutron reflectometry and Raman spectroscopy at visible excitation wavelength. We observe reasonable agreement between the different results for film thicknesses below 20 nm. For larger thickness, we find that the surface-sensitive methods XPS and XANES yield smaller sp³ fractions (by up to 20%) than the bulk-sensitive LAwave, being consistent with the assumption of a lower-density surface layer on a nominal-density bulk layer.     

The properties of fluorine-containing diamond-like carbon films prepared by pulsed DC plasma-activated chemical vapour deposition

Diamond-like carbon films containing up to 23.1 at. % of fluorine (F-DLC), were deposited onto silicon substrates by low-frequency, pulsed DC, plasma-activated, chemical vapour deposition (PACVD). The influence of fluorine on plasma current density, deposition rate, composition, bonding structure, surface energy, hardness, stress and biocompatibility was investigated and correlated with the fluorine content. X-ray photoelectron spectroscopy (XPS) analysis revealed the presence C–C, C–CF and C–F for F-DLC films with a low fluorine concentration (1.5–12.1 at. %), however for films with a higher fluorine content (23.0 at. %) an additional peak due to CF₂ bonding was detected. The addition of fluorine into the DLC film resulted in lower stress and hardness values. The reduction in these values was attributed to the substitution of strong C=C by weaker C–F bonds which induces a decrease in hardness. Ion scattering spectrometery (ISS) measurements revealed the presence of fluorine atoms in the outmost layer of the F-DLC films and there was no evidence of surface oxygen contamination. The water contact angle was found to increase with increasing fluorine content and has been attributed to the change of the bonding nature in the films, in particularly increasing CF and CF₂ bonds. Biocompatibility tests performed using MG-63 osteoblast-like cell cultures indicated homogeneous and optimal tissue integration for both the DLC and the F-DLC surfaces. This pulsed-PACVD technique has been shown to produce biocompatible DLC and F-DLC coatings with a potential for large area applications.     

Fast deposition of diamond-like hydrogenated carbon films

Diamond-like hydrogenated carbon films have been formed at low temperatures using methane and acetylene as precursor gases. The source used was of a cascaded arc type employing Ar and Ar/H₂ as carrier gases. Energies of ion species and ion densities in the plasma were measured with a mass energy probe and a Langmuir probe.The films produced were characterized in terms of sp³ content, refractive index, relative hydrogen content, hardness and adhesion. The variation of these parameters is presented as functions of precursor gas flow, process pressure, and surface temperature.Deposition rates up to 30 nm/s have been achieved using acetylene as precursor gas at substrate temperatures below 100 °C. Experiments with acetylene showed deposition rates seven times greater than with methane. The typical sp³ content of 55–78% in the films was determined by X-ray-Excited Auger Electron Spectroscopy (XAES) technique. The hardness and reduced modulus were determined by nanoindentation. Preliminary Atomic Force Microscopy (AFM) studies of the films showed a roughness below 3 nm (R_a).     

Highly conductive nanoclustered carbon:nickel films grown by pulsed laser deposition

An enhancement by 5 orders of magnitude of the electrical conductivity of nanoclustered carbon films is reported by incorporation of metallic atoms, but without significant morphological changes. Films were deposited by 248 nm pulsed laser ablation of both a pyrolytic graphite target and a mixed carbon–nickel (C:Ni) target, and structural analysis revealed that similar film morphologies were obtained when deposition was carried out using either target. Compositional analysis demonstrated a preferential incorporation of nickel over carbon in the resulting films (cf. the composition of the target). This non-stoichiometric transfer was also observed for films grown by 193 nm laser ablation of the C:Ni target, for which the enhancement was more pronounced, indicating that the ablation mechanism and the subsequent transfer are important in determining the eventual film composition.     

Ferroelectric thin films obtained by pulsed laser deposition

We review our significant results concerning pulsed laser deposition (PLD) of some ferroelectric compounds: (i) lead magnesium niobate Pb(Mg_1/3Nb_2/3)O₃ (PMN); (ii) lead magnesium niobate–lead titanate Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT), with variable PT contents; (iii) La-doped lead zirconate titanate (Pb_1 − xLa_x)(Zr_0.65Ti_0.33)O₃ (PLZT); and (iv) Nb-doped lead zirconate titanate Pb_0.988(Zr_0.52Ti_0.48)_0.976Nb_0.024O₃ (PNZT). A parametric study has been performed in order to evidence the influence of the deposition parameters (laser wavelength, laser fluence, oxygen pressure, substrate type and temperature, RF power discharge addition, etc.) on the film properties and to identify the best growing conditions. Techniques including atomic force microscopy (AFM), X-ray diffraction (XRD), scanning electron microscopy (SEM), secondary ions mass spectroscopy (SIMS), transmission electron microscopy (TEM), electrical and ferroelectric hysteresis measurements have been used for layer characterization.     

Diamond-like carbon thin films prepared by ECR argon plasma assisted pulsed laser deposition

Diamond-like carbon films were prepared by pulsed laser ablation of graphite target in argon plasma produced from electron cyclotron resonance (ECR) microwave discharge and analyzed by Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The analysis shows that the films prepared with argon plasma assistance have different chemical structure compared with the films prepared in vacuum without plasma assistance. The structure of the films prepared with plasma assistance depends strongly on the bias voltages applied on the substrate. Surface morphology observation shows that the films prepared with argon plasma assistance have a smoother surface than the films prepared without plasma assistance. The re-sputtering of the growing film due to the bombardment of the plasma stream results in reduction of the deposition rate. The ablation plumes during film preparation with and without plasma assistance were examined through optical emission spectroscopy. In vacuum, emission lines from mono-atomic carbons and carbon ions dominate the plume emission. In argon plasma, the plume emission exhibits different behavior in its temporal and spatial evolution. It is initially dominated by strong lines from mono-atomic carbons and carbon ions and then evolves to consist mainly of emissions from C₂ molecules superposed on a featureless continuum. It is also found that the emission intensity of the C₂ molecules as well as the continuum varies with the bias voltages.     

液相沉积类金刚石膜的沉积机理研究

根据电化学的相关理论,提出了钛合金表面液相沉积DLC膜的反应机理,给出了可能电极过程,认为膜是通过甲基阳离子的亲电取代反应而不断生长。讨论了氢原子对金刚石结构的稳定作用,并解释了实验条件对膜结构和性能的影响。     

Preparation and characterization of YAG:Ce thin phosphor films by pulsed laser deposition

We report the use of YAG:Ce phosphor as the raw material to make thin and transparent phosphor films with pulsed laser deposition including the effects of heating temperature, target–substrate distances, annealing times, and annealing atmosphere on the YAG:Ce³⁺ phosphor film crystal types and spectral properties. The results indicated that at a coating temperature of 350°C, the YAG:Ce³⁺ phosphor film had the best crystallinity with an intact film and maximum fluorescence emission. The crystallinity and fluorescence emission intensity of the film gradually decreased as a function of increasing target–substrate distances. As the annealing time increased, the crystallinity and the fluorescence emission intensity of the film first increased and then decreased. The film made with 5 h of annealing had the best crystallinity and the highest fluorescence emission intensity. The crystallinity of the film annealed under air was higher than that made under nitrogen; the fluorescence intensity of the film under air was slightly lower than the film under nitrogen. The emission peak of the prepared film was at 523 nm when excited at 450 nm. This is slightly blue‐shifted versus the emission of commercial phosphor powders. This study offers a theoretical basis for the development of transparent phosphor films.     

Preparation and characterization of Al-doped ZnO piezoelectric thin films grown by pulsed laser deposition

Undoped and Al-doped ZnO (AZO) thin films (Al: 3, 5 at%) using a series of high quality ceramic targets have been deposited at 450 ºC onto glass substrates using PLD method. The used source was a KrF excimer laser (248 nm, 25 ns, 2 J/cm²). The study of the obtained thin films has been accomplished using X-ray diffraction (XRD), M-lines spectroscopy and Rutherford backscattering spectroscopy (RBS). XRD patterns have shown that the films crystallize in a hexagonal wurtzite type structure with a highly c-axis preferred (002) orientation, and the grain sizes decrease from 37 to 25 nm with increasing Al doping. The optical waveguiding properties of the films were characterized by means of the prism-coupling method. The distinct M-lines of the guided transverse magnetic (TM) and transverse electric (TE) modes of the ZnO films waveguide have been observed. The M-lines device has allowed determination of the accurate values of refractive index and thickness of the studied ZnO and AZO thin films. An evaluation of experimental uncertainty and calculation of the precision of the refractive index and thickness were developed on ZnO films. The RBS results agree with XRD and m-lines spectroscopy measurements.     

Preparation and microstructure properties of tetrahedral amorphous carbon films by pulsed laser deposition using camphoric carbon target

The properties of tetrahedral amorphous carbon (ta-C) films grown by pulsed laser deposition (PLD) using camphoric carbon (CC) target and their respective effects of diamond percentages by weight in the target (Dwt.%) are discussed. Scanning electron microscopy (SEM), atomic force microscopy (AFM), Visible-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicated that the Dwt.% noticeably modified the sp³ bonds content and the morphology of the ta-C films. The optical gap (E_g) and electrical resistivity (ρ) increase with Dwt.% up to 1.6 eV and 5.63×10⁷ (Ω cm), respectively, for the ta-C films deposited using target with higher of 50 Dwt.%. We found that the Dwt.% has modified the surface morphological, structural, bonding and physical properties of the camphoric carbon films.     

Phase transformation of diamond-like carbon/silver composite films by sputtering deposition

This study fabricated hydrogenated diamond-like carbon/silver bioceramic films on glass substrates using radio frequency magnetron sputtering with a single silver target in an atmosphere of Ar/CH4 mixture. The effects of applied power on the composition and microstructure of bioceramic film were evaluated. A phase transformation, amorphous diamond-like carbon → nano-silver precipitation → nano-silver growth in the amorphous diamond-like carbon matrix was observed during sputtering. The film growth rate, surface roughness, silver content and size of silver nanoclusters in the films all increased with the silver target power due to the higher flux of sputtered silver species toward the substrate.     

Optical properties of ultrananocrystalline diamond/amorphous carbon composite films prepared by pulsed laser deposition

Ultrananocrystalline diamond (UNCD)/amorphous carbon (a-C) composite thin films were grown in ambient hydrogen by pulsed laser deposition using a graphite target, and their optical properties were determined by optical absorption spectroscopy and Raman scattering spectroscopy. Three optical bandgaps exist. Two bandgaps are indirect and their values were estimated to be 1.0 eV and 5.4 eV; these bandgaps correspond to the a-C surrounding the UNCDs and the UNCDs respectively. The third bandgap is direct and has a value of 2.2 eV, which significantly contributes to a large absorption coefficient, (10⁶ cm^− 1 at 3.0 eV). Possible origins of the third bandgaps are the grain boundaries (GBs) between the UNCDs and the a-C since they are specific to the UNCD/a-C composite films. The infrared absorption spectrum and the Raman scattering spectrum revealed the incorporation of hydrogen in the GBs. The hydrogen incorporated in the GBs might also have some influence on the appearance of the direct bandgap and its value.     

Synthesis of carbon-rich hafnia thin films by pulsed laser deposition

Carbon-rich ceramics are an emerging class of materials with attractive high-temperature properties, including resistance to crystallization, dense microstructure, and low porosity. We explored direct synthesis of carbon-rich hafnia, which is known to form as a compact interlayer in the oxide scales of oxidized hafnium carbide. The material was synthesized by pulsed laser deposition, using pure HfO₂ targets in C₂H₂ background gas at low pressures. Stable films up to 700 nm thick and with high molar fractions (～0.1–0.45) of carbon were obtained. The predominant chemical bonding of Hf and O atoms is that of oxygen-deficient HfO₂, while carbon is present in elemental or hydrogenated forms. Annealing at 600 °C leads to loss of most of the hydrogen from the films, which is accompanied by enhanced sp² bonding of carbon. The films have amorphous, compact, and finely grained microstructure. Carbon molar fractions higher than ～0.2 inhibit microcrystallinity to at least 600 °C.     

Ultra-low density carbon foams produced by pulsed laser deposition

We report on the manufacturing of ultra-low density carbon foam produced by pulsed laser deposition. Mean mass density, morphology and structure were investigated within a broad range of process parameters. We have been able to obtain carbon foam layers having tunable mean density and thickness in the range 1–1000 mg/cm³ and 5–80 μm, respectively. Surface uniformity has been achieved over ∼1 μm² areas with mean pore size around 10 nm. The morphological/structural properties have been investigated by means of quartz crystal microbalance, scanning electron microscopy and Raman spectroscopy. Based on these results, this work shows how pulsed laser deposition can be exploited as a versatile tool for the deposition of carbon foams with tunable and tailored density, thickness and uniformity.     

Very hard ZrC thin films grown by pulsed laser deposition

Thin ZrC films were grown on (1 0 0) Si substrates at temperatures from 30 to 500 °C by the pulsed laser deposition technique. Auger electron spectroscopy investigations found that films contained oxygen concentration below 2.0 at%, while X-ray photoelectron spectroscopy investigations showed that oxygen is bonded in an oxy-carbide type of compound. The films’ mass densities, estimated from X-ray reflectivity curve simulations, and crystallinity improved with the increase of the substrate temperature. Williamson–Hall plots and residual-stress measurements using the modified sin² ψ method for grazing incidence X-ray diffraction showed that the deposited films are nanostructured, with crystallite sizes from 6 to 20 nm, under high micro-stress and compressive residual stress. Nanoindentation investigations found hardness values above 40 GPa for the ZrC films deposited at substrate temperatures higher than 300 °C. The high density of the deposited films and the nm-size crystallites are the key factors for achieving such high hardness values.