Effect of composition on mechanical behaviour of diamond-like carbon coatings modified with titanium

In this study, diamond-like carbon (DLC) films modified with titanium were deposited by plasma decomposition of metallorganic precursor, titanium isopropoxide in CH₄/H₂/Ar gas atmosphere. The obtained films were composed of amorphous titanium oxide and nanocrystalline titanium carbide, embedded in an amorphous hydrogenated (a-C:H) matrix. The TiC/TiO₂ ratio in the DLC matrix was found to be dependent on the deposition parameters. The dependence of the films chemical composition on gas mixture and substrate temperature was investigated by X-ray photoelectron spectroscopy, whereas the crystallinity of TiC nanoparticles and their dimension were evaluated by X-ray diffraction. The size of TiC crystallites varied from 10 to 35 nm, depending on the process parameters. The intrinsic hardness of 10-13 GPa, elastic modulus of 170-200 GPa and hardness-to-modulus ratio of obtained coatings were measured by the nanoindentation technique. Obtained results demonstrated a correlation of mechanical properties with the chemical composition and the ratio of amorphous/crystalline phases in the films. In particular, the formation of nanocrystalline TiC with atomic concentration not exceeding 10% and with grain size between 10 nm and 15 nm resulted in significantly enhanced mechanical properties of composite material in comparison with ordinary DLC films.     

Characteristics of a well-adherent nanocrystalline diamond thin film grown on titanium in Ar/CH4 microwave CVD plasma

The fabrication of a well-adherent diamond film on titanium and its alloys is always problematical due to the different thermal expansion coefficients of the two materials, the complex nature of the interlayer formed during diamond deposition, and the difficulty in achieving very high nucleation density. In this work, well-adherent and smooth nanocrystalline diamond (NCD) thin film is successfully deposited on pure titanium substrate by microwave plasma-assisted chemical vapor deposition (MWPCVD) method in Ar/CH₄ environment. It is found that the average grain size is less than 20 nm with a surface roughness value as low as 12 nm. Morphology, surface roughness, diamond crystal orientation and quality are obtained by characterizing the sample with field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy, respectively. Detailed experimental results and mechanisms for NCD film deposition are discussed.     

A study of titanium thin films in transmission laser micro-joining of titanium-coated glass to polyimide

Electron beam evaporation (EB-PVD) and cathodic arc physical vapor deposition (CA-PVD) techniques were used for the preparation of titanium (Ti) thin films onto Pyrex borosilicate 7740 glass wafers and the deposited films were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. The microstructure and surface morphology of the films were studied as a function of the film deposition techniques. Film properties such as, adherence, microstructure and roughness were interconnected to the laser joint strength between Ti coated glass wafers and polyimide films. Ti thin films on glass had a natural oxide layer on the surface as found from XPS. AFM study showed the formation of a uniform Ti coating consisted of packed crystallites with average size of 35 nm by EB-PVD. The root-mean-square surface roughness of the films was 1-2 nm. Whereas, films prepared by CA-PVD had crystallites with an average size of 120 nm and defects in the form of macro-particles which is a common attribute of this deposition system. The surface roughness of the film was 125 nm. The laser joint strength was found to be influenced by the Ti film quality on the glass substrate.     

Structural study of Si1 − xGex nanocrystals embedded in SiO2 films

We have investigated the structural properties of Si_1 − xGe_x nanocrystals formed in an amorphous SiO₂ matrix by magnetron sputtering deposition. The influence of deposition parameters on nanocrystal size, shape, arrangement and internal structure was examined by X-ray diffraction, Raman spectroscopy, grazing incidence small angle X-ray scattering, and high resolution transmission electron microscopy. We found conditions for the formation of spherical Si_1 − xGe_x nanocrystals with average sizes between 3 and 13 nm, uniformly distributed in the matrix. In addition we have shown the influence of deposition parameters on average nanocrystal size and Ge content x.     

Effect of high temperature annealing on the electrical performance of titanium/platinum thin films

In this study, the influence of post deposition annealing steps (PDA) on the electrical resistivity of evaporated titanium/platinum thin films on thermally oxidised silicon is investigated. Varying parameters are the impact of thermal loading with maximum temperatures up to T_PDA = 700 °C and the platinum top layer thickness ranging from 24 nm to 105 nm. The titanium based adhesive film thickness is fixed to 10 nm. Up to post deposition annealing temperatures of T_PDA = 450 °C, the film resistivity is linearly correlated with the reciprocal value of the platinum film thickness according to the size effect. Modifications in the intrinsic film stress strongly influence the electrical material parameter in this temperature regime. At T_PDA > 600 °C, diffusion of titanium into the platinum top layer and its plastic deformation dominate the electrical behaviour, both causing an increase in film resistivity above average.     

Optical and structural properties of nanocrystalline anatase (TiO2) thin films prepared by non-aqueous sol-gel dip-coating

Anatase (TiO₂) thin films were grown by non-aqueous sol-gel dip-coating using titanium (IV) n-butoxide as precursor and 1-butanol as solvent. High withdrawal speed of 4.7 mm/s in dip-coating resulted in defect free films of 100 nm average film thickness after subsequent heat treatments. According to scanning electron microscope and X-ray diffraction measurements, the films consisted of nanocrystalline anatase with 30 nm mean crystallite size. Refractive index n(λ) and extinction coefficient k(λ) were determined over the wavelength range from 200 to 1650 nm. The optical band gap of the film material was approximately 3.2 eV. The results showed very similar optical characteristics to those that are accomplished with chemically more reactive aqueous sol-gel processes. Furthermore, it was found that in addition to porosity, coordination number of Ti atoms to nearest oxygen neighbors is likely to have a significant role in explaining differences of optical properties between bulk anatase and thin film materials of the present work.     

Native oxide consumption during the atomic layer deposition of TiO2 films on GaAs (100) surfaces

The consumption of the surface native oxides is studied during the atomic layer deposition of TiO₂ films on GaAs (100) surfaces. Films are deposited at 200 °C from tetrakis dimethyl amido titanium and H₂O. Transmission electron microscopy data show that the starting surface consists of ~2.6 nm of native oxide and X-ray photoelectron spectroscopy indicates a gradual reduction in the thickness of the oxide layer as the thickness of the TiO₂ film increases. Approximately 0.1-0.2 nm of arsenic and gallium suboxide is detected at the interface after 250 process cycles. For depositions on etched GaAs surfaces no interfacial oxidation is observed.     

Mechanical and ellipsometry measurements of thin TiN layer prepared by PIII

Titanium nitrides have good mechanical, biomedical and optical properties, therefore they are used to harden and protect cutting and sliding surfaces and as a non-toxic exterior for bio-medical applications. Nitrogen plasma immersion implantation (PIII), in which the diffusion of nitrogen from low pressure r.f. plasma is combined with the implantation of nitrogen ions at energies up to 30 kV, is an effective tool for nitriding titanium and titanium alloys. In this work, samples of pure titanium were nitrided by PIII at different negative high voltage pulses. The properties and the characteristics of the processed samples were evaluated using X-ray diffraction (XRD), Auger electron spectroscopy (AES), ball-on-disk type tribometer, surface profilemeter, and ellipsometry measurements. The results show that, the wear resistance of the untreated sample in comparison to the PIII treated samples is extremely poor and the friction coefficient for the PIII treated samples is decreased to the half value in comparison to the untreated titanium, this attributed to the formation of the solid solution titanium α-Ti(N) and the cubic TiN phases. Ellipsometric measurements were carried out on the PIII treated samples at different negative high voltage pulses. A three layers model was used to fit the calculated data to the experimental ellipsometric spectra. The thickness, surface roughness and refractive index increase with increasing the negative high voltage pulses. The refractive index at 550 nm increases from 1.83 to 2.09 as the negative high voltage pulses increases from 10 to 30 kV.     

Templated synthesis of nanosized mesoporous carbons

Mesoporous carbon materials formed by nanosized particles have been synthesized by means of a nanocasting technique based on the use of mesostructured silica materials as templates. We found that the modification of the chemical characteristics of the surfactant employed allows mesostructured silica materials with particle sizes <100 nm to be synthesised. The mesoporous carbons obtained from these silica materials retain the structural properties of the silica used as template and consequently they have a particle size in the 20-100 nm range. These carbons exhibit large BET surfaces areas (up to 1300 m² g⁻¹) and high pore volumes (up to 2.5 cm³ g⁻¹), a framework confined porosity made up of uniform mesopores (3.6 nm) and an additional textural porosity arising from the interparticle voids between the sub-micrometric particles. The main advantage of nanometer-sized mesoporous carbons in relation to the micrometer-sized carbons is that they have enhanced mass transfer rates, which is important for processes such as adsorption or catalysis.     

Synthesis and photoluminescence of ultra-pure germanium nanoparticles

We have used aerosol deposition to synthesize defect and micro-strain free, ultra-pure germanium nanoparticles. Transmission electron microscopy images show a core-shell configuration with highly crystalline core material. Powder X-ray diffraction measurements verify the presence of highly pure, nano-scale germanium with average crystallite size of 30 nm and micro-strain of 0.058%. X-ray photoelectron spectroscopy demonstrates that GeO_x (x ? 2) shells cover the surfaces of the nanoparticles. Under optical excitation, these nanoparticles exhibit two separate emission bands at room temperature: a visible emission at 500 nm with 0.5-1 ns decay times and an intense near-infrared emission at 1575 nm with up to ∼20 μs lifetime.     

Initiated chemical vapor deposition of pH responsive poly(2-diisopropylamino)ethyl methacrylate thin films

Poly(2-(diisopropylamino)ethyl methacrylate) (PDPAEMA) thin films were deposited on low temperature substrates by initiated chemical vapor deposition (iCVD) method using tertbutyl peroxide as an initiator. Very high deposition rates up to 38 nm/min were observed at low filament temperatures due to the use of the initiator. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy show the formation of PDPAEMA films with high retention of tertiary amine functionality which is responsible for pH induced changes in the wetting behavior of the surfaces. As-deposited PDPAEMA thin films on flat Si surface showed a reversible switching of water contact angle values between 87° and 28°; after successive treatments of high and low pH water solutions, respectively. Conformal and non-damaging nature of iCVD allowed to functionalize fragile and rough electrospun poly(methyl methacrylate) fiber mat surfaces by PDPAEMA, which creates a surface with a switching behavior between superhydrophobic and approaching superhydrophilic with contact angle values of 155 ± 3°and 22 ± 5°, respectively.     

Etching processes of transparent carbon nanotube thin films using laser technologies

Carbon nanotubes (CNTs) have potential as a transparent conductive material with good mechanical and electrical properties. However, carbon nanotube thin film deposition and etching processes are very difficult to pattern the electrode. In this study, transparent CNT film with a binder is coated on a PET flexible substrate. The transmittance and sheet resistance of carbon nanotube film are 84% and 1000 Ω/□, respectively. The etching process of carbon nanotube film on flexible substrates was investigated using 355 nm and 1064 nm laser sources. Experimental results show that carbon nanotube film can be ablated using laser technology. With the 355 nm UV laser, the minimum etched line width was 20 μm with a low amount of recast material of the ablated sections. The optimal conditions of laser ablation were determined for carbon nanotube film.     

Structural and surface property study of sputter deposited transparent conductive Nb-doped titanium oxide films

We have investigated structural and surface property of transparent conductive Nb-doped titanium oxides (TNO) thin film with high conductivity of 10⁻⁴ Ω cm order which were made by RF-magnetron sputtering at high deposition rates followed by an annealing in vacuum. The grain sizes of TNO evaluated by atomic force microscope were found to become larger by annealing at temperature higher than 500 °C. The measured work functions of the TNO films using ultra-violet light photoelectron spectroscopy were 5.02-5.47 eV, and depended on TNO grain size and on the amount of surface weakly bound oxygen that was estimated from peak area intensities of O(1 s) X-ray photoelectron spectra.     

Influence of calcination ambient and film thickness on the optical and structural properties of sol-gel TiO2 thin films

Influence of both calcination ambient and film thickness on the optical and structural properties of sol-gel derived TiO₂ thin films have been studied. X-ray diffraction results show that prepared films are in an anatase form of TiO₂. Films calcined in argon or in low vacuum (∼2 × 10⁻¹ mbar) are found to be smaller in crystallite size, more transparent at low wavelength region of ∼300-450 nm, denser, have higher refractive index and band gap energy compared to air-calcined films. Scanning electron microscopic study reveals that surfaces of TiO₂ films calcined in argon or in low vacuum are formed by densely packed nano-sized particulates. Presence of voids and signs of agglomeration can be seen clearly in the surface microstructure of air-calcined films. In the thickness range ∼200-300 nm, band gap energy and crystallite size of TiO₂ films remain practically unaffected with film thickness but refractive index of thinner film is found to be marginally higher than that of thicker film. In this work, it has been shown that apart from temperature and soaking time, partial pressure of oxygen of the ambient is also an important parameter by which crystallite size, microstructure and optical properties of the TiO₂ films may be tailored during calcination period.     

Formation of PTFE-like films in CF4 microwave plasmas

The study focuses on the deposition of films from pure CF₄ using low pressure microwave plasmas (MW) on polystyrene substrate with a subsequent examination of the resulting surfaces. It is generally accepted, that the F/C-ratio of the precursor molecule plays an important role for the outcome of a low pressure plasma process, or the balance between fluorocarbon deposition and material etching. Surprisingly, thin film formation could be observed using MW gas discharges in CF₄, a typical etching gas. Coatings with a thickness of at least 10 nm are formed. The films are polytetrafluoroethylene (PTFE)-like, characterized by an F/C-ratio of 1.8, and a hydrophobic surface with a water contact angle of 110°.     

AFM surface analysis of ZnO layers prepared by pulsed laser deposition at different oxygen pressures

Polycrystalline thin films of zinc oxide were deposited by pulsed laser deposition onto silicon substrates at different oxygen partial pressures in the range of 1-35 Pa. For ablation of the sintered zinc oxide target a pulsed Nd:YAG laser was used. Other processing parameters such as laser pulse energy, pulse repetition rate, substrate temperature and deposition pressure were identical. The effect of oxygen pressure on the structural properties of the films was systematically studied by using atomic force microscopy. The surface morphology, average roughness S_a, root mean square S_q, and mean size of grains on selected places with 2 × 2 μm² area of prepared samples were evaluated. Detailed structural analysis confirmed that partial oxygen pressure leads to the modification of surface morphology. Mean grain size in height and lateral direction decreases with raising oxygen pressure from 1 to 5 Pa while the further increase of oxygen pressure from 5 to 35 Pa results in grain size enlargement. The zinc oxide film formed at oxygen partial pressure 5 Pa shows smallest values of evaluated parameters (S_a = 0.6 nm, S_q = 0.7 nm and mean size of grains 50 nm).     

High transparent polyimide/titania multi-layer anti-reflective hybrid films

In this study, polyimide-titania hybrid thin films (6FDA-6FpDA-4ABA/TiO₂, PIT) were prepared from soluble fluorine-containing polyimide and titanium butoxide. The soluble polyimide with carboxylic acid terminal groups (6FDA-6FpDA-4ABA-COOH) was synthesized from the precursor s 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4′-(hexafluoroisopropylidene) dianiline (6FpDA), and 4-aminobenzoic acid (4ABA). Such end groups undergo a condensation reaction with titanium butoxide to provide organic-inorganic bonding and thus prevent macrophase separation. The titania content in the hybrid films was varied from 0 to 90 wt.% (PIT0-PIT90). The effects of TiO₂ content on the hybrid film properties and the optimum operating conditions were also investigated. TGA and DSC analysis showed that the decomposition temperature of polyimide was about 468 °C. T_d increased as the titania content in hybrid thin films increased. HRTEMM and XRD results indicated the formation of nanocrystalline-titania domains of around 4-11 nm in the hybrid films. AFM, SEM, TEM, and XRD results indicated the formation of well-dispersed nanocrystalline-titania. FTIR spectra indicated that the amidization was complete and that a cross-linked Ti-O-Ti network had formed. UV-vis and n&k analysis showed that the prepared hybrid films had high refractive index (1.931) and good optical properties. Moreover, the prepared polyimide/titania hybrid thin films were further applied to develop a three layer antireflective (AR) coating on glass and PMMA substrates. The results showed that the average reflectance of the AR coating on the glass and PMMA substrates was 0.5% and 0.8%, respectively. The transparency at 550 nm was greater than 90% for both AR coatings.     

Single-step synthesis of MWCNT/ZnO nanocomposite using co-chemical vapor deposition method

Single-step synthesis of MWCNT and ZnO nanocomposite was conducted by co-chemical vapor deposition method. Electron microscopic analysis revealed that the fabricated nanostructures consisted of MWCNTs with a diameter of 60-70 nm which were coated with ZnO nanoparticles with an average size of 20-30 nm. The growth of ZnO nanoparticles took place after the formation of MWCNTs. EDS and XRD analyses could confirm the high crystallinity of ZnO deposited on the MWCNT surface. In comparison with pristine MWCNTs and ZnO nanoparticles, the UV absorption of MWCNT/ZnO nanocomposite was changed through modification with ZnO nanoparticles.     

Magnetite surface morphology during hematite reduction with CO/CO2 at 1073 K

The morphology of the magnetite phase that formed during the hematite/magnetite reduction process was studied. A very dense hematite ore of very high grade iron content (Fe = 69%) was used. Annealed ore specimens of about 2 g and 5 × 5 × 1 mm size were polished and reduced with 20%CO-80%CO₂ gaseous mixtures of total gas flow rate 1 L/min at 1073 K. The morphological observation of the surface of the specimens and its cross-section after reduction was detected by SEM. The initial formation of magnetite phase nuclei was detected as needles in shape. These needles of about 500-1000 nm diameter and length 10-15 μm come in a random distribution in the reduced surfaces. These needles are accumulated after forming a large centered area of a porous magnetite phase inside each surface grain.     

Aerosol based fabrication of a Cu/polymer and its application for electromagnetic interference shielding

The effect of a catalytic surface activation on the electromagnetic interference shielding of Cu deposited polymer substrates was investigated. The surface of polymer substrates was catalytically activated by different methods respectively adopted Pd aerosol nanoparticles and Sn-Pd wet chemical processes. Although both activations initiated the deposition of Cu on the substrates, differences such as morphology (Pd aerosol: ~80 nm vs Sn-Pd: ~ 140 nm, in Cu grain size) and composition (Pd aerosol: Cu and Pd vs Sn-Pd: Cu, Pd, Sn, and Cl) of Cu deposits were presented. Specimens activated using Pd aerosol nanoparticles showed a higher range of shielding effectiveness by about 4-10 dB than those activated by Sn-Pd processes in 2-18 Ghz frequencies.