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.     

Synthesis and characterization of TiC and TiCN coatings

Thin film coatings of titanium carbide (TiC) and titanium- carbo-nitride (TiCN) were deposited on Si(100) substrates using the pulsed laser deposition (PLD) method. The PLD method is a unique process for depositing high-quality thin films with novel microstructure and properties. Mechanical properties of TiCN are found to be dependent on the nitrogen ambient during deposition. For nitrogen ambient pressure of 20 mTorr the TiCN has hardness values close to TiN hardness values, whereas for nitrogen ambient pressure of 5 mTorr the hardness values of the TiCN films are comparable to the hardness values of the TiC films.     

Microstructure and electrical properties of textured Sr0.51Ba0.48La0.01Nb2O6 thin films

Sr_0.51Ba_0.48La_0.01Nb₂O₆ (SBLN) thin films were prepared on platinized silicon substrates by pulsed laser deposition (PLD) combined with annealing technique. The preferred orientation, surface morphology, composition, and interfacial properties of the SBLN thin films were characterized by X-ray diffraction, atomic force microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, and automatic spreading resistance measurement. The ferroelectric properties were confirmed by P - E hysteresis loops. The frequency variation of the dielectric constant was measured as well.     

Preparation of the Ni-P composite coating co-deposited by nano TiC particles and evaluation of it's corrosion property

In current research, low carbon steel plates were coated by Ni-P electroless method. The effect of adding different concentrations (ranging from 0.01 g/l to 0.5 g/l) of TiC nano-sized particles to the plating bath on deposition rate, surface morphology and corrosion behavior of Ni-P-TiC composite coatings were investigated. The surface morphology and the relevant structure were evaluated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Corrosion behavior of the coated steel was evaluated by electrochemical impedance spectroscopy (EIS) and polarization techniques. The results showed that addition of TiC nano-particles to Ni-P electroless bath not only changes the surface morphology of Ni-P coating, but also improves corrosion resistance of the steel in comparison with TiC free Ni-P electroless coating. In addition, the deposition rate of coating was also affected by incorporation of TiC particles. It was also found that improvement in corrosion resistance largely depends on the phosphorous and TiC concentrations on the coatings.     

The effect of oxygen rf discharge on pulsed laser deposition of oxide films

In this work final results on TiO₂ film deposition by Plasma Assisted Pulsed Laser Deposition (PAPLD) with an rf biased substrate are presented. In previous work it has been shown that PAPLD is an improvement over conventional PLD for the elimination of particulates in high refractive index thin film deposition. This paper will give a comparison between conventional PLD and PAPLD on the stoichiometry, morphology, and optical properties of deposited TiO₂ films. It will be demonstrated that oxygen rf discharge during the PLD process makes incorporation of oxygen into the depositing films extremely effective. This effect of the rf discharge allows operation of the PLD process at a lower oxygen background pressure while enhancing the deposition rate. Also, the production of a good quality TiO₂ film by PAPLD using a pure metal titanium target will be shown. PACS 79.20.Ds; 52.80.Pi     

LiFePO4 thin films grown by pulsed laser deposition: Effect of the substrate on the film structure and morphology

Well crystallized and homogeneous LiFePO₄/C (LFPO) thin films have been grown by pulsed laser deposition (PLD). The targets were prepared by the sol-gel process at 600 °C. The structure of the polycrystalline powders was analyzed with X-ray powder diffraction (XRD) data. The XRD patterns were indexed having a single phase olivine structure (Pnma). LFPO thin films have been deposited on three different substrates: aluminum (Al), stainless steel (SS) and silicon (Si) by pulsed laser deposition (PLD). The structure of the films was analyzed by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). It is found that the crystallinity of the thin films depends on the substrate temperature which was set at 500 °C. When annealed treatments were used, secondary phases were found, so, one step depositions at 500 °C were made.Stainless steel is demonstrated to be the best choice to act as substrate for phosphate deposition. LiFePO₄ thin films grown on stainless steel plates exhibited the presence of carbon, inducing a slight conductivity enhancement that makes these films promising candidates as one step produced cathodes in Li-ion microbatteries.     

Stoichiometry issues in pulsed-laser deposition of alloys grown from multicomponent targets

We have examined the degree of congruent transfer in pulsed-laser deposition (PLD) of alloy thin films in phases that are stable over a wide range of compositions. SiGe films were deposited by PLD onto high-purity glassy carbon substrates. We analyzed the average composition of these films using Rutherford backscattering spectrometry (RBS), and results show that the deposited films have a higher relative concentration of Ge than the initial targets. We infer that the noncongruent transfer is due to differential scattering in the plume itself. Additionally, the local composition of the particulates was measured by the use of microprobe analysis, and observations of a sintered target of Si and Ge powders and a solidified target of melted Si and Ge were compared. We found that the sintered target produces particulates with a wide range of compositions, whereas the solidified target produces five times fewer particulates with a tighter distribution of compositions. In contrast with the average composition of the films, the average composition of the particulates is the same as that of the targets. These results are discussed in terms of the microstructure of the targets and the melting process at the surface. The implications of these observations for composition determination by laser ablation are discussed.     

Nanocrystalline growth and diagnostics of TiC and TiB2 hard coatings by pulsed laser deposition

Nanocrystalline coatings of TiC and TiB₂ were grown by pulsed laser deposition on Si(100) and on X155 steel at low substrate temperatures ranging from 40 °C to 650 °C. A pulsed KrF excimer laser was used with the deposition chamber at a base pressure of 10^-6 mbar. The morphology and structure of the films, studied with SEM, XRD, and TEM, showed that nanocrystalline films with a fine morphology of TiC and TiB₂ were deposited with a grain size of 10 nm-70 nm at all substrate temperatures. The growth of the polycrystalline coatings possessed a columnar morphology with a 𘜄¢ preferred orientation. The hardness of the coatings was determined to be 40 GPa and the elastic modulus, 240 GPa. The composition and the kinetics of the plume produced during the pulsed laser deposition of TiC and TiB₂ was studied under film growth conditions. The mass analysis of ions of the ejected material was performed by time-of-flight mass spectroscopy (TOF-MS) and showed the presence of Ti⁺ and C⁺ during TiC ablation and B⁺, B₂⁺, and Ti⁺ during TiB₂ ablation. The kinetic energies (KE) of the ions depended on the laser fluence which was between 0.5 eV and 340 eV. The kinetic energy and the evolution of the plasma was studied with a streak camera. The velocity of the plasma was of the order of 10⁶ cm/sec and was linearly dependent on the energy fluence of the laser. The emission spectroscopy of the plasma plume confirmed the atomic neutral and single excited species of Ti. These results show that coating growth basically occurs by the recombination of the ionic species at the surface of the substrate.     

Ultra-fast laser ablation and deposition of TiO2

In this work we report on the properties of the ablation plume and the characteristics of the films produced by ultra-fast pulsed laser deposition (PLD) of TiO₂ in vacuum. Ablation was induced by using pulses with a duration of ≈300 fs at 527 nm. We discuss both the composition and the expansion dynamics of the TiO₂ plasma plume, measured by exploiting time- and space-resolved emission spectroscopy and gated imaging. The properties of the TiO₂ nanoparticles and nanoparticle-assembled films were characterized using different techniques, i.e. environmental scanning electron microscopy (ESEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). It is suggested that most of the material decomposes in the form of nanoparticles.     

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.     

Diamond deposition on siliconized stainless steel

Silicon diffusion layers in AISI 304 and AISI 316 type stainless steels were investigated as an alternative to surface barrier coatings for diamond film growth. Uniform 2 μm thick silicon rich interlayers were obtained by coating the surface of the steels with silicon and performing diffusion treatments at 800 °C. Adherent diamond films with low sp² carbon content were deposited on the diffused silicon layers by a modified hot filament assisted chemical vapor deposition (HFCVD) method. Characterization of as-siliconized layers and diamond coatings was performed by energy dispersive X-ray analysis, scanning electron microscopy, X-ray diffraction and Raman spectroscopy.     

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.     

Bioglass thin films for biomimetic implants

Pulsed laser deposition (PLD) method was used to obtain bioglass (BG) thin film coatings on titanium substrates. An UV excimer laser KrF* (λ = 248 nm, τ = 25 ns) was used for the multi-pulse irradiation of the BG targets with 57 or 61 wt.% SiO₂ content (and Na₂O-K₂O-CaO-MgO-P₂O₅ oxides). The depositions were performed in oxygen atmosphere at 13 Pa and for substrates temperature of 400 °C. The PLD films displayed typical BG of 2-5 μm particulates nucleated on the film surface or embedded in. The PLD films stoichiometry was found to be the same as the targets. XRD spectra have shown, the glass coatings obtained, had an amorphous structure. One set of samples, deposited in the same conditions, were dipped in simulated body fluids (SBFs) and subsequently extracted one by one after several time intervals 1, 3, 7, 14 and 21 days. After washing in deionized water and drying, the surface morphology of the samples and theirs composition were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), IR spectroscopy (FTIR) and energy dispersive X-ray analysis (EDX). After 3-7 days the Si content substantially decreases in the coatings and PO₄³⁻ maxima start to increase in FTIR spectra. The XRD spectra also confirm this evolution. After 14-21 days the XRD peaks show a crystallized fraction of the carbonated hydroxyapatite (HAP). The SEM micrographs show also significant changes of the films surface morphology. The coalescence of the BG droplets can be seen. The dissolution and growth processes could be assigned to the ionic exchange between BG and SBFs.     

Nanosecond laser ablation for pulsed laser deposition of yttria

A thermal model to describe high-power nanosecond pulsed laser ablation of yttria (Y₂O₃) has been developed. This model simulates ablation of material occurring primarily through vaporization and also accounts for attenuation of the incident laser beam in the evolving vapor plume. Theoretical estimates of process features such as time evolution of target temperature distribution, melt depth and ablation rate and their dependence on laser parameters particularly for laser fluences in the range of 6 to 30 J/cm² are investigated. Calculated maximum surface temperatures when compared with the estimated critical temperature for yttria indicate absence of explosive boiling at typical laser fluxes of 10 to 30 J/cm². Material ejection in large fragments associated with explosive boiling of the target needs to be avoided when depositing thin films via the pulsed laser deposition (PLD) technique as it leads to coatings with high residual porosity and poor compaction restricting the protective quality of such corrosion-resistant yttria coatings. Our model calculations facilitate proper selection of laser parameters to be employed for deposition of PLD yttria corrosion-resistive coatings. Such coatings have been found to be highly effective in handling and containment of liquid uranium.     

Current state-of-the-art of pulsed laser deposition of optical waveguide structures: Existing capabilities and future trends

Pulsed laser deposition (PLD) has now reached a stage of maturity where the growth of thin films is routine. All that is required is a pulsed ultra-violet (UV) wavelength laser, a vacuum chamber, a target, and a substrate placed in near proximity to the plasma plume. Whether the film that you grow is the film that you need, and whether the thickness, uniformity, optical quality, stoichiometry, degree of crystallinity, orientation and much more is what is desired is another question entirely. PLD is both a science and an art and there are many tricks-of-the-trade that need to be considered to ensure that materials grown are the materials wanted. This paper discusses the practicalities of PLD systems, target geometries, heating regimes for successful epitaxial growth of crystalline films, the problem of particulates, laser sources to use, and in the context of our most recent PLD system, the number of independent lasers and targets used. We show that the use of multiple targets permits a combinatorial approach, whereby stoichiometry can be adjusted to grow designer materials, and in particular multilayer systems, ideally suited for active optical waveguides, a truly demanding end application where optical quality and in-plane losses must be reduced to an absolute minimum.     

Nanostructured high valence silver oxide produced by pulsed laser deposition

Among silver oxides, Ag₄O₄, i.e. high valence Ag(I)Ag(III) oxide, is interesting for applications in high energy batteries and for the development of antimicrobial coatings. We here show that ns UV pulsed laser deposition (PLD) in an oxygen containing atmosphere allows the synthesis of pure Ag₄O₄ nanocrystalline thin films, permitting at the same time to control the morphology of the material at the sub-micrometer scale. Ag₄O₄ films with a crystalline domain size of the order of tens of nm can be deposited provided the deposition pressure is above a threshold (roughly 4 Pa pure O₂ or 20 Pa synthetic air). The formation of this particular high valence silver oxide is explained in terms of the reactions occurring during the expansion of the ablated species in the reactive atmosphere. In particular, expansion of the PLD plasma plume is accompanied by formation of low stability Ag-O dimers and atomic oxygen, providing reactive species at the substrate where the film grows. Evidence of reactive collisions in the expanding ablation plume is obtained by analysis of the plume visible shape in inert and reactive atmospheres. In addition, we show how the dimensionless deposition parameter L, relating the target-to-substrate distance to the ablation plume maximum expansion length, can be used to classify different growth regimes. It is thus possible to vary the stoichiometry and the morphology of the films, from compact and columnar to foam-like, by controlling both the gas pressure and the target-to-substrate distance.     

Mg-Al layered double hydroxides (LDHs) and their derived mixed oxides grown by laser techniques

Layered double hydroxides (LDHs) have been widely studied due to their applications as multifunctional materials, catalysts, host materials, anionic exchangers, adsorbents for environmental contaminants and for the immobilization of biological materials. As thin films, LDHs are good candidates for novel applications as sensors, corrosion resistant coatings or components in electro optical devices. For these applications, lamellar orientation-controlled film has to be fabricated.In this work, the successful deposition of LDH and their derived mixed oxides thin films by laser techniques is reported. Pulsed laser deposition (PLD) and matrix assisted pulsed laser evaporation (MAPLE) were the methods used for thin films deposition. The ability of Mg-Al LDHs as a carrier for metallic particles (Ag) has been considered. Frozen targets containing 10% powder in water were used for MAPLE, while for PLD the targets consisted in dry-pressed pellets.The structure and the surface morphology of the deposited films were examined by X-ray Diffraction, Atomic Force Microscopy, Scanning Electron Microscopy and Secondary Ion Mass Spectrometry.     

Microstructure and tribological properties of TiN, TiC and Ti(C, N) thin films prepared by closed-field unbalanced magnetron sputtering ion plating

TiN, TiC and Ti(C, N) films have been respectively prepared using closed-field unbalanced magnetron sputtering ion plating technology, with graphite target serving as the C supplier in an Ar-N₂ mixture gas. Bonding states and microstructure of the films are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) in combination with transmission electron microscopy (TEM). The friction coefficients are measured by pin-on-disc test and the wear traces of deposited films are observed by optical microscope. Results show that the TiN film and Ti(C, N) film exhibit dense columnar structure while the TiC film exhibits a mixed microstructure of main nanocrystallite and little amorphous phases. The Ti(C, N) film has the highest microhardness value and the TiC film has the lowest. Because of small amount of pure carbon with sp² bonds existing in the film, the friction coefficients of Ti(C, N) and TiC multilayer films are lower than that of TiN film. In addition, the multilayer structure of films also contributes visually to decrease of friction coefficients. The TiC film has extremely low friction coefficient while the wear ratio is the highest in all of the films. The results also show that the Ti(C, N) film has excellent anti-abrasion property.     

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.