Hybrid laser—magnetron technology for carbon composite coating

Hybrid laser- magnetron deposition system was developed and tested for study of carbon based thin film coatings. Various geometrical configurations and deposition conditions were tested. Films of TiC, TiCN, and SiC were synthesized. Films were fabricated in argon (TiC), in argon/nitrogen (TiCN), or in argon/hydrogen ambient (SiC films). Film properties were studied by SEM, XRD, GDOES, and XPS. Smooth, homogeneous film over the area of 9 cm² were prepared. Crystalline TiC films were grown at room substrate temperature.     

Hybrid pulsed laser deposition and Si-surface-micromachining process for integrated TiC coatings in moving MEMS

Titanium carbide (TiC) is one of the preferred coatings for improving the performance of macroscopic moving mechanical components due to its established wear-resistance. Pulsed laser deposition (PLD) is an excellent method for depositing TiC, because unlike any other deposition process for TiC, PLD offers the capability of producing high-quality films even at room temperature. Using a modified PLD technique, especially designed for the deposition of particulate-free films, TiC coatings have been deposited at room temperature on silicon (Si) and on several types of thin films typically employed for fabricating microelectromechanical systems (MEMS). Our results demonstrate that TiC coatings also offer a high wear-resistance to Si surfaces, which in turn has led to our application of TiC to “moving” Si MEMS devices. The performance of moving Si MEMS devices is limited by their poor operational lifetimes, which have been attributed to the excessive wear at sliding Si interfaces. The work presented here describes a hybrid process, whereby PLD is used in conjunction with a user-friendly Si surface micromachining scheme for inserting wear-resistant TiC coatings between critical sliding Si interfaces in MEMS devices. This paper describes the properties of PLD-TiC for MEMS and the hybrid PLD-surface micromachining process for the integration of TiC coatings into Si MEMS. Received: 23 January 2003 / Accepted: 8 February 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +1-310/563-7614, E-mail: gouri.radhakrishnan@aero.org     

Spectroscopic characterization of TiCx films produced by pulsed laser deposition in CH4 environments

Titanium carbide (TiC_x) thin films were grown on (1 0 0)-Si substrates by a pulsed laser deposition (PLD) method using a Ti target in methane gas. The films are characterized in situ by Auger (AES), electron energy loss (EELS) and X-ray photoelectron spectroscopies (XPS). It was found that the reaction between the ablated Ti species and CH₄ in the plasma plume influenced the C:Ti ratio. XPS numerical fitting for the C 1s transition revealed three Gaussians components. The main component, binding energy of 282.8 eV, is assigned to C making bonds with Ti, like in stoichiometric TiC. The second component, binding energy of 284.9 eV, is assigned to C---C bonds. A third component is found for films deposited at pressures higher than 25 mTorr at 286.5 eV. A post-deposition thermal treatment demonstrates that the Ti---C and C---C peaks are very stable, whereas, the third peak tends to decrease for temperatures higher than 200 °C. It is assumed that this last component is due to carbonyl complexes remnant in films. Finally, it can be concluded that the titanium carbide films processed by PLD is a chemically inhomogeneous material; mostly composed of sub-stoichiometric TiC and particulates of segregated carbon.     

Pulsed-laser deposition of particulate-free TiC coatings for tribological applications

Hybrid bearings comprising ceramic or ceramic-coated steel balls and steel raceways can provide good fatigue life and resistance to wear. One of the coating materials that has received serious consideration in hybrid systems is titanium carbide (TiC). At present, the commercially available process for the deposition of TiC involves the heating of steel substrates to fairly high temperatures (>900 °C). The high-temperature process involves considerable costs and complexities that are associated with the post-deposition heat treatment and repolishing of the coated steels for bearing applications. Pulsed-laser deposition (PLD) is ideally suited to deposit TiC coatings on bearing steels at room temperature. However, it is well known that codeposition of particulates has been one of the most challenging problems of PLD. This is especially of concern when dealing with hard coatings for tribological applications. Here we describe a novel and extremely simple method of depositing high-quality, particulate-free TiC coatings on bearing steel surfaces that uses PLD. The method relies on a new non-line-of-sight deposition that uses a permanent magnet and prevents particulates from arriving at the substrate. The surface roughness of TiC films deposited on steels by way of this technique has an extremely low root mean square value of 1.6 nm. The TiC films have been extensively characterized for their morphology, chemical composition, and mechanical properties with scanning electron and atomic force microscopy, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and nanoindentation. Time-resolved emission has been used for the in situ characterization of the laser-ablated TiC plume and has resulted in the identification of various plume species as a function of laser parameters. The spectroscopic results are correlated to film growth and to our modified PLD method.     

Effect of process parameters on the mechanical properties of carbon nitride thin films synthesized by plasma assisted pulsed laser deposition

We present an investigation of the effect of the process parameters, namely deposition pressure and laser intensity, on the growth and mechanical properties of carbon nitride (CN_x) thin films synthesized by plasma assisted pulsed laser deposition. Deposition at high remote plasma pressure (200 mTorr) enhances both growth rate and nitrogen incorporation (up to 40 at.%), but nano-indentation measurements indicate that these films are very soft and have poor mechanical properties. At low remote plasma pressure (0.5 mTorr), the nitrogen content varies from 24 to 16 at.% with increasing laser intensity as the films become much harder and more elastic, with hardness and Youngs modulus values reaching 24 GPa and 230 GPa, respectively. These effects are explained in terms of a thermalization of the laser plasma at 200 mTorr and indicate that plasma activation of nitrogen does not provide any particular benefit to the film properties when deposition is performed at high pressure. However, at low pressure, the benefit of plasma activation is evidenced through enhanced nitrogen incorporation in the films while preserving the highly energetic species in the ablation plume. Such conditions lead to the synthesis, at room temperature, of hard and elastic films having properties close to those of fullerene-like CN_x. PACS 81.15.Fg; 81.05.Gc; 68.60.Bs     

激光制备类金刚石膜技术研究

现有技术制备的类金刚石(DLC)膜由于含氢、硬度低、内应力大、附着力差等特点,严重限制了其光学工程应用.激光法是近年发展的一种制备DLC膜的新方法,相比其他制备方法具有诸多优点.综合分析了激光制备DLC膜过程中,激光波长、脉宽、功率密度、衬底温度和偏压等因素对薄膜质量的影响规律.采用氧气氛辅助沉积、元素掺杂和双波长激光...     

Adjusting chemical bonding of hard amorphous CSixNy thin films by N*-plasma-assisted pulsed laser deposition

Hard amorphous carbon silicon nitride thin films have been grown by pulsed laser deposition (PLD) of various carbon silicon nitride targets by using an additional nitrogen RF plasma source on [100] oriented silicon substrates at room temperature. The influence of the number of laser shots per target site on the growth rate and film surface morphology was studied. Up to about 30 at. % nitrogen and up to 20 at. % silicon were found in the films by Rutherford backscattering spectroscopy (RBS) and X-ray photoelectron spectroscopy (XPS). The XPS of the films showed a clear correlation of binding energy to the variation of PLD parameters. The films show a universal hardness value up to 23 GPa (reference value for silicon substrate 14 GPa) in dependence on target composition and PLD parameters. The results emphasise the possibility of variation of chemical bonding and corresponding properties, such as nanohardness, of amorphous CSi_xN_y thin films by the plasma-assisted PLD process.     

Comparative study of titanium carbide and nitride coatings grown by cathodic vacuum arc technique

Titanium nitride (TiN), titanium carbide (TiC) thin films and TiC/TiN bilayers have been deposited on AISI 304 stainless steel substrates by plasma assisted physical vapor deposition technique—reactive pulsed vacuum arc method. The coatings were characterized in terms of crystalline structure, microstructure and chemical nature by X-ray diffraction and X-ray photoelectron spectroscopy, respectively. Tribological behavior was investigated using ball on disc technique. The average coefficient of friction was measured, showing lower values for the TiN/TiC bilayer. Dynamic wear curves were performed for each coating, observing a better wear resistance for TiN/TiC bilayers, compared to TiN and TiC monolayers. On the other hand, the TiCN formation in the TiN/TiC bilayer was observed, being attributed to the interdiffusion between TiN and TiC at the interface. Moreover, the substrate temperature influence was analysing observing a good behavior at T_S = 115 °C.     

TiN growth on Si by hybrid radical beam PLD

High-quality (good crystallinity and stoichiometry) titanium nitride (TiN) thin films were grown on Si(100) substrates by pulsed laser deposition (PLD) using a high-purity titanium target (99.99%) and nitrogen radical beam. The crystallinity, chemical composition, and depth profiles of the grown films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Rutherford backscattering spectroscopy (RBS), respectively. The XRD pattern indicated that the preferred growth of TiN(200) with an orientation parallel to the Si(100) direction was obtained and the nitrogen radical drastically improved crystallinity compared with that grown in ambient nitrogen gas. RBS spectra indicated that the combination of PLD and the nitrogen radical beam suppressed silicidation at the interface between the Si substrate and TiN thin film during growth. The XPS analysis revealed that this method achieved the synthesis of stoichiometric TiN films.     

Electrical and optical properties of indium tin oxide thin films grown by pulsed laser deposition

Indium tin oxide (ITO) thin films (200-400 nm in thickness) have been grown by pulsed laser deposition (PLD) on glass substrates without a post-deposition anneal. The electrical and optical properties of these films have been investigated as a function of substrate temperature and oxygen partial pressure during deposition. Films were deposited at substrate temperatures ranging from room temperature to 300 °C in O₂ partial pressures ranging from 0.1 to 100 mTorr. For 300 nm thick ITO films grown at room temperature in oxygen pressure of 10 mTorr, the electrical conductivity was 2.6᎒^-3 Q^-1cm^-1 and the average optical transmittance was 83% in the visible range (400-700 nm). For 300 nm thick ITO films deposited at 300 °C in 10 mTorr of oxygen, the conductivity was 5.2᎒^-3 Q^-1cm^-1 and the average transmittance in the visible range was 87%. Atomic force microscopy (AFM) measurements showed that the RMS surface roughness for the ITO films grown at room temperature was ~7 Å, which is the lowest reported value for the ITO films grown by any film growth technique at room temperature.     

Optical properties of aluminium nitride films obtained by pulsed laser deposition: an ellipsometric study

Aluminium nitride (AlN) films obtained by pulsed laser deposition (PLD) at different low ambient nitrogen pressure have been optically investigated by spectral ellipsometry within the 300–800 nm wavelength range, Sellmeier and Wemple–DiDomenico approximation approaches have been applied for the ellipsometric data analysis. Optical parameters such as refractive index and single oscillator energies of deposited films were estimated and their dependence on the N₂ pressure was studied. The obtained refractive index values of AlN films are around 2 in a wide wavelength region above 400 nm and suggest the growth of a polycrystalline structure. The relatively low (<3.4 eV) threshold energies indicate the formation of a defective and disordered structure, formed during the deposition process. PACS 78.20.-e; 78.20.Ci; 78.66.Fd     

Synthesis and characterization of laser ablated TiNi films

TiNi thin films with BaTiO₃ and PbZr_0.52Ti_0.48O₃ (PZT) as buffer layers were deposited on Si(100) substrates by the pulsed laser deposition (PLD) method. Buffer layers (BaTiO₃ and PZT) were deposited at 600 °C in oxygen (O₂) environment and TiNi films were deposited on the top of the buffer layer in presence of 15 mTorr nitrogen (N₂) at various deposition temperatures (50, 300, and 500 °C). Synthesis and characterization of TiNi films were investigated from the crystallographic point of view by using X-ray diffractometer (XRD) and atomic force microscope (AFM) techniques. It is found that buffer layer of BaTiO₃ and PZT have improved the crystallinity of TiNi films deposited at higher temperatures. The TiNi/PZT film was uniform compared to TiNi/BaTiO3 film with the exception of agglomerates that appeared throughout the layer.     

Inverse pulsed laser deposition

Since the advent of pulsed laser deposition (PLD), several different target-substrate arrangements have been proposed. Besides the most common on-axis PLD, several off-axis geometries were studied, mainly to protect the substrate from the agglomerated species (clusters, droplets, particulates) of the plasma plume, which are detrimental to the homogeneity of films. Recently we introduced a novel geometry, termed inverse pulsed laser deposition (IPLD), in which the substrate is placed parallel to and slightly above the target plane. In this paper we summarize our results on this new geometry, and show how it can extend the perspectives of pulsed laser deposition, e.g., by improving the surface morphology of the films. Effects of ambient pressure are presented and exemplified on metallic and compound IPLD films, including Ti, CN _x , and Ti-oxides. AFM topographic images are used to prove that under optimized conditions IPLD is capable of growing compact and smooth films that are superior to PLD ones. A special—but easy-to-implement—IPLD arrangement is also introduced that considerably improves the homogeneity of IPLD films. In this geometry, the properties (e.g., deposition rate and roughness) of the films grown in the 1–25 Pa pressure domain are examined.     

Relationship between the photoluminescence and conductivity of undoped ZnO thin films grown with various oxygen pressures

The pulsed laser deposition (PLD) technique is used to deposit undoped ZnO thin films on glass substrates at 150 °C with different oxygen pressures of 40, 80, 100 and 150 mTorr. X-ray diffraction (XRD) and atomic force microscopy (AFM) studies indicated that the obtained ZnO thin films were hexagonal wurtzite-type structures with strong (0 0 2) c-axis orientation. The relationship between photoluminescence and the conductivity of the ZnO thin films grown by pulsed laser deposition at various oxygen pressures was also discussed. The intensity of the deep-level-emission (DLE) and conductivity generally increased as the oxygen pressure decreased. The intensity of DLE peak was generally proportional to the conductivity. The band gap energy values, determined from transmittance spectra, were around 3.30-3.34 eV, and decreased when the oxygen pressure increased.     

Correlation between structural and mechanical properties of PbTiO3 thin films grown by pulsed-laser deposition

Tetragonal lead titanate (PbTiO₃, PT) thin films are grown on (1 0 0) MgO substrate by pulsed-laser deposition (PLD) for expected applications in integrated optics. The realisation of outstanding and reliable devices into integrated circuits requires sufficient mechanical resistance despite that the obtained PT films display interesting waveguiding properties associated with low optical losses. Two mechanical properties characteristic of elasticity and hardness of PT films are studied. The elastic modulus (E or Young's modulus) and the hardness (H) are measured by the nanoindentation technique. These mechanical properties are correlated to the crystalline quality of PT/MgO thin films. The films show epitaxial relationship with the MgO substrate and the orientation of crystallites perpendicularly to the surface substrate may be the consequence of a growth process along c-axis, a-axis or both. Differences on curves plotting hardness and elastic modulus as a function of indentation depth are observed as the curves are less dispersed for the films mainly c-axis oriented.     

Influence of deposition pressure and power on characteristics of RF-Sputtered Mo films and investigation of sodium diffusion in the films

Mo films deposited by DC sputtering are widely used as back contact in CIGS and CZTS based thin film solar cells. However, there have been only a few studies on the deposition of Mo films by RF sputtering method. In this context, Mo films on SLG substrates were prepared as a function of deposition pressure and power by using RF magnetron sputtering method to contribute to this shortcoming. Mo films were deposited at 250 °C substrate temperature by using 20, 15, 10 mTorr Ar pressures at 120 W RF power and 10 mTorr Ar pressure at 100 W RF power. Structural, morphological and reflectivity properties of RF-sputtered Mo films were clarified by XRD, AFM, FE-SEM and UV–Vis measurements. In addition, due to sodium incorporation from SLG substrate to the absorber layer through Mo back contact layer is so essential in terms of improving the conversion efficiency values of CIGS and CZTS thin film solar cell devices, the effects of Na diffusion in the films were analyzed with SIMS depth profile. The electrical properties of the films such as mobility, carrier density and resistivity were determined by Hall Effect measurements. It was found that Mo films prepared at 120 W, 10 mtorr and 250 °C substrate temperature and then annealed at 500 °C for 30 min, had resistivity as low as 10⁻⁵ Ω cm, as well as higher amount of Na incorporation than other films.     

Fabrication of LiNbO3 thin films by pulsed laser deposition and investigation of nonlinear properties

Thin films of LiNbO₃ were deposited by pulsed-laser deposition (PLD). Crystalline and transparent films were deposited on a sapphire substrate at 400 °C, in 100 mTorr of oxygen, with a fluence lower than 1.2 J/cm². Droplet free films were deposited with low ablation laser fluence by the eclipse method, and waveguide losses were 15.9 dB/cm and 3.1 dB/cm. Subsequently, second-harmonic generation (SHG) was achieved by waveguide mode phase matching. The center wavelength of the matching spectrum was 853 nm, and the full width at half maximum (FWHM) was 19 nm. PACS 42.70.Mp; 52.38.Mf; 68.55.Jk; 77.84.Dy; 81.15.-z     

TiCN thin films grown by reactive crossed beam pulsed laser deposition

In this work, we used a crossed plasma configuration where the ablation of two different targets in a reactive atmosphere was performed to prepare nanocrystalline thin films of ternary compounds. In order to assess this alternative deposition configuration, titanium carbonitride (TiCN) thin films were deposited. Two crossed plasmas were produced by simultaneously ablating titanium and graphite targets in an Ar/N₂ atmosphere. Films were deposited at room temperature onto Si (100) and AISI 4140 steel substrates whilst keeping the ablation conditions of the Ti target constant. By varying the laser fluence on the carbon target it was possible to study the effect of the carbon plasma on the characteristics of the deposited TiCN films. The structure and composition of the films were analyzed by X-ray Diffraction, Raman Spectroscopy and non-Rutherford Backscattering Spectroscopy. The hardness and elastic modulus of the films was also measured by nanoindentation. In general, the experimental results showed that the TiCN thin films were highly oriented in the (111) crystallographic direction with crystallite sizes as small as 6.0 nm. It was found that the hardness increased as the laser fluence was increased, reaching a maximum value of about 33 GPa and an elastic modulus of 244 GPa. With the proposed configuration, the carbon content could be easily varied from 42 to 5 at.% by changing the laser fluence on the carbon target.     

不同生长条件下BiFeO_3薄膜的显微拉曼光谱研究

使用显微拉曼散射技术观察了用脉冲激光沉积方法(PLD)在不同的生长条件下制备的BiFeO3薄膜的拉曼光谱,并且研究了薄膜的结构以及不同的生长条件对薄膜的结构和微结构的影响。与BiFeO3粉末的拉曼光谱比较,我们发现在N2气氛中,在LaNiO3缓冲层上沉积的BiFeO3薄膜具有单一的三方相和最完整的晶格结构。     

Transition of crystalline orientation of yttria-stabilized zirconia films grown by pulsed laser deposition

We have synthesized 5 wt. %-yttria-stabilized zirconia (YSZ) films on stainless steel and glass substrates by pulsed laser deposition (PLD) at substrate temperatures between 60 and 600 °C and oxygen pressures from 0.1 to 1000 mTorr. While highly (101)-oriented tetragonal YSZ films are obtained at intermediate oxygen pressures, near complete (001)-oriented tetragonal films are achieved at lower oxygen pressures, with a full width at half maximum X-ray peak of only 0.4°. The results can be attributed to surface energy-induced orientation; that is, the lowest surface energy plane of the YSZ films changes from (101) plane at intermediate pressures to the (001) plane at lower oxygen pressures due to surface relaxation. PACS 81.15.Fg; 83.85.Hf; 68.55.jm