Hexagonal diamond formation on steel substrates by negative bias microwave plasma enhanced chemical vapor deposition

This paper reports for the first time the synthesis of hexagonal diamond thin films on high-speed steel substrates by multi-mode microwave plasma enhanced chemical vapor deposition. Before deposition of the films, the substrate surface was treated by scratching with diamond powder. The deposited films were characterized by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy. The XRD patterns of (100) and (101) planes and the Raman peaks at ~ 1317-1322 cm^− 1 were observed, confirming the formation of hexagonal diamond phase in the prepared films. The effects of voltage bias on the phase formation, microstructure and hardness of the films were also studied by setting the voltage to 0, − 70, − 150 and − 190 V. The highest hardness of 23.8 GPa was found in the film having clusters of size about 550 nm deposited under a bias voltage of − 150 V. These clusters were built up of grains of size about 14 nm.     

Influence of growth temperature on the optical and structural properties of ultrathin ZnO films

This study investigates the effect of growth temperature on the optical and structural properties of ultrathin ZnO films on the polished Si substrate. Thickness of the ultrathin ZnO films deposited by atomic layer deposition (ALD) method was about 10 nm. Photoluminescence (PL), X-ray diffraction (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM) techniques were used to measure the properties of ultrathin ZnO films. Experimental results showed that the ultrathin ZnO film deposited at 200 °C had excellent ultraviolet emission intensity, and the average roughness of the film surface was about 0.26 nm.     

Cathodic arc plasma deposition of nano-multilayered ZrN/AlSiN thin films

Thin films of ZrN/AlSiN were deposited on SKD 11 tool steel substrate using Zr and AlSi cathodes in an Ar/N₂ gas mixture in a cathodic arc plasma deposition system. The influence of the AlSi cathode arc current and the substrate bias voltage on the mechanical and structural properties of the films was investigated. X-ray diffraction, electron probe micro-analysis, high resolution transmission electron microscopy, nanoindentation and profilometry were used to characterize the films. The ZrN/AlSiN thin films had a multilayered structure by rotating the substrate in which nano-crystalline ZrN layers alternated with amorphous AlSiN layers. The hardness of the films increased as the AlSi cathode arc current was raised from 35 to 40 A, and then decreased with a further increase of the current. The hardness of the films increased with the increase of the bias voltage from − 50 to − 100 V. Further increase in the bias voltage decreased the hardness. The films exhibited a maximum hardness of 38 GPa. With the increase of bias voltage, the residual stress of the films correlated well with the hardness.     

Layer formation by resputtering in Ti-Si-C hard coatings during large scale cathodic arc deposition

This paper presents the physical mechanism behind the phenomenon of self-layering in thin films made by industrial scale cathodic arc deposition systems using compound Ti-Si-C cathodes and rotating substrate fixture. For the as-deposited films, electron microscopy and energy dispersive X-ray spectrometry reveals a trapezoid modulation in Si content in the substrate normal direction, with a period of 4 to 23 nm dependent on cathode configuration. This is caused by preferential resputtering of Si by the energetic deposition flux incident at high incidence angles, when the substrates are facing away from the cathodes. The Ti-rich sub-layers exhibit TiC grains with sizes up to 5 nm, while layers with high Si-content are less crystalline. The nanoindentation hardness of the films increases with decreasing layer thickness.     

Deposition of dense and smooth Ti films using ECR plasma-assisted magnetron sputtering

We report high quality Ti films grown in a novel electron cyclotron resonance (ECR) plasma-assisted magnetron sputtering (PMS) deposition system. The films are compared with films deposited by conventional direct current (DC) magnetron sputtering. Using ECR-PMS, the argon plasma bombardment energy and Ti film deposition rate can be controlled separately, with the substrate bias voltage under feedback control. Results from SEM, AFM, XRD and PAS (scanning electron microscopy, atomic force microscopy, X-ray diffraction and positron annihilation spectroscopy) show that the properties of Ti films prepared by ECR-PMS are greatly improved compared with conventional sputtering. SEM and AFM confirmed that ECR-PMS Ti films have a dense, smooth, mirror-like surface. Increasing the substrate bias of the ECR plasma from − 23 V to − 120 V while keeping a fixed sputtering bias voltage of − 40 V, the intensity of the (100) reflection of Ti film was a little strengthened, but (002) remained strongly preferred orientation. The XRD peak broadening of ECR-PMS Ti films is more than for conventional magnetron sputtering, due to grain refinement induced by Ar ion bombardment. Doppler broadening of PAS analysis reveals that the Ti films have fewer vacancy defects compared with films prepared by the conventional magnetron.     

Process–structure–property relations of micron thick Gd2O3 films deposited by reactive electron-beam physical vapor deposition (EB-PVD)

Thick polycrystalline gadolinium oxide (Gd₂O₃) films up to 11 μm in thickness were deposited via reactive electron beam-physical vapor deposition (EB-PVD) on silicon (111) substrates for use in neutron radiation detection. The effects of coating thickness, substrate temperature, and oxygen flow on film structural, electrical and optical properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), capacitance–voltage (C–V) measurements, and ultraviolet–visible (UV–Vis) spectroscopy. Films were characterized as either monoclinic or mixed monoclinic and cubic phase depending on deposition parameters. Increasing the deposition temperature resulted in increased film crystallinity and cubic phase volume while decreasing the O₂ flow rate resulted in increased volume of the monoclinic phase. Evidence of a thickness dependent crystallography is also presented. Electrical property measurements showed thin film dielectric constant could be tailored between 12 and 20 at 1 MHz frequency by decreasing the oxygen flow rate at deposition temperatures of 250 °C which is attributed to an increased presence of the monoclinic phase and increased film density. Band gap values were calculated from transmission measurements and ranged between 5.44 and 5.96 eV.     

From nanowires to cubes of CdO: Ethanol gas response

The cadmium oxide (CdO) thin films have been synthesized by chemical bath deposition (CBD) method from an aqueous cadmium acetate solution for different time periods. The effect of film thickness on structural, morphological and wettability properties have been investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and contact angle measurements. The chemically deposited CdO thin films were polycrystalline with face centered cubic crystal structure. The average crystallite size was found to be in the range of 28-31 nm. An interesting morphological transition from nanowires to microcubes was observed with change in deposition time from 25 to 100 h at room temperature. The deposited CdO films exhibit excellent sensing properties against ethanol at 673 K. The 0.8239 μm thick films comprising nanowires deposited for 75 h showed the better ethanol gas performance as compared to other films.     

Synthesis of nanostructured CuxS thin films by chemical route at room temperature and investigation of their size dependent physical properties

Nanostructured semiconductors show very interesting physical properties than bulk crystal due to size effects that arises because of quantum confinement of the electronic states. Using cupric acetate and sodium thiosulphate as cationic and anionic precursor, nanostructured Cu₂S thin films were successfully prepared at room temperature by chemical bath deposition technique. By varying the deposition time from 9 to 24 h, the Cu₂S films of thickness 70-233 nm were prepared. The different characterization methods such as X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption and electrical resistivity measurement techniques were used to investigate size dependent properties of Cu₂S thin films. As thickness increases, the hexagonal covellite phase of CuS observed at thickness 70 nm gets converted to monoclinic chalcosite phase of Cu₂S. The resistivity and activation energy is found to be thickness dependent. The optical band-gap energy increases from 2.48 to 2.90 eV as thickness decreases from 233 to 70 nm. The influence of film thickness on carrier concentration, mobility and thermo-emf is reported.     

Synthesis and characterization of spray deposited PdO-NiO-SDC composite anode material for potential application in IT-SOFC

The synthesis of mixed conducting PdO-NiO-SDC composite films has been reported for the first time by a simple and cost effective spray pyrolysis technique. The films were deposited at low substrate and annealing temperatures of 350 °C and 500 °C, respectively. The structure, morphology and electrical properties of the films were studied by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray analysis (EDAX), atomic force microscopy (AFM) and impedance spectroscopy (IS). The substrate and annealing temperatures were optimized for obtaining nano-crystalline, porous, adherent and composite films with PdO, NiO and SDC phases. Films showed good microstructure with sufficient porosity and good connectivity of the deposited material. Crystallite size of the deposited material was found to be in the range of 7-9 nm. The deposited film showed high oxygen ion conductivity, 3.94 × 10⁻¹ S cm⁻¹ at 350 °C. Due to their nano-crystalline, porous and composite nature the spray deposited PdO-NiO-SDC films may have high three phase boundary area and hence can be considered as an anode for intermediate temperature solid oxide fuel cells.     

High-repetition rate pulsed laser deposition of ZrC thin films

ZrC thin films were grown on (100) Si substrates by the pulsed laser deposition (PLD) technique using a high-repetition rate excimer laser working at 40 Hz. The substrate temperature during depositions was set at 300 °C and the cooling rate was 5 °C/min. X-ray diffraction investigations showed that the films were crystalline. Films deposited under residual vacuum or 2 × 10^− 3 Pa of CH₄ atmosphere exhibited a (200)-axis texture, while those deposited under 2 × 10^− 2 Pa of CH₄ atmosphere were found to be equiaxed. The surface elemental composition of as-deposited films, analyzed by Auger electron spectroscopy (AES), showed the usual high oxygen contamination of carbides. Once the topmost − 3-5 nm region was removed, the oxygen concentration rapidly decreased, being around 3-4% only in bulk. Scanning electron microscopy (SEM) investigations showed a smooth, featureless surface morphology, corroborating the roughness values below 1 nm (rms) obtained from simulations of the X-ray reflectivity (XRR) curves. From the same simulations we also estimated films mass density values of around 6.32-6.57 g/cm³ and thicknesses that correspond to a deposition rate of around 8.25 nm/min. Nanoindentation results showed a hardness of 27.6 GPa and a reduced modulus of 228 GPa for the best quality ZrC films deposited under an atmosphere of 2 × 10^− 3 Pa CH₄.     

LiCoO2 cathode thin film fabricated by RF sputtering for lithium ion microbatteries

Thin films of lithium cobalt oxide were deposited on Pt or Pt/Ti/quartz glass substrates by radio frequency (RF) magnetron sputtering at the substrate temperatures from room temperature to 500 °C. As the substrate temperature increased, the film structure changed from amorphous structure to crystallinity with a strong (003) texture as characterized by X-ray diffraction. The surface morphology and cross-section were observed using scanning electron microscopy. It was found that the films tended to crack at a high substrate temperature. Charge-discharge tests of these films were conducted and compared. The different electrochemical characteristics of these films were attributed to the modified crystallography, morphology, and thermal stress. The LiCoO₂ film deposited at 400 °C showed a well-defined 4.0 V voltage plateau on charge and a 3.9 V plateau on discharge, and delivered 54.5 μAh/cm² μm at the first discharge capacity, with good cycling performance, giving evidence that such films could be used as the thin film cathodes for lithium microbatteries.     

Structural and optical study of samarium doped cerium oxide thin films prepared by electron beam evaporation

Samarium doped cerium oxide films were grown on the glass substrate using e-beam deposition technique and then characterized using different techniques: X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy and UV-visible spectroscopy measurements. XRD analysis shows that all the films have cubic structure and the crystallite size decreases from 18 to 13 nm as the samarium (Sm) concentration increases. The FE-SEM images indicate that all the films have columnar growth. UV-visible measurements reflect that the films have high transparency (>80%) in the visible region. From the Raman spectra, we have observed two peaks at 466 and 565 cm⁻¹. The peak at 466 cm⁻¹ is assigned to the F_2g mode of cerium oxide (CeO₂) whereas the peak at 565 cm⁻¹ is due to the presence of the oxygen vacancies. The increase in the intensity of the peak at 565 cm⁻¹ indicates that the oxygen vacancy increases with Sm doping.     

Microstructures and mechanical properties evaluation of TiAlN/CrSiN multilayered thin films with different bilayer periods

The Ti_0.45Al_0.55N/Cr_0.75Si_0.25N nanoscale multilayered coatings were deposited periodically by a bipolar asymmetric pulsed DC reactive magnetron sputtering technique. The structures and bilayer period of multilayer coatings were characterized by an X-ray diffractometer. The surface and cross-sectional morphologies of thin films were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. The surface roughness of thin films was explored by atomic force microscopy (AFM). A nanoindenter, a micro Vickers hardness tester and pin-on-disk wear tests were used to evaluate the hardness, fracture toughness and tribological properties of the thin films, respectively. Six coatings with bilayer period ranges from 6 nm to 40 nm were produced in this work. It was observed that the hardness increased with increasing bilayer period and reached the maximum at 12 nm and then leveled off at periods larger than 12 nm. An optimal hardness, and plastic deformation resistance, as well as adequate tribological behaviors were found on the coating with a critical bilayer period of 12 nm.     

Dielectric barrier discharge assisted chemical vapor deposition of boron nitride phosphide films on a quartz substrate

Boron nitride phosphide films were deposited on a quartz substrate by dielectric barrier discharge assisted chemical vapor deposition. From results of X-ray photoelectron and UV-Vis absorption spectral measurements, the chemical composition of the films may be defined as BN_1 − xP_x, where the mole number (x) is variable between 0.25-0.58, through modifying the PH₃ flow rate in the film deposition process, and the corresponding optical band gap may be modulated between 4.17-3.25 eV. From measurements of X-ray diffraction and high resolution transmission electron microscopy, an amorphous matrix embedded with a hexagonal crystalline phase of BNP with a crystal lattice spacing of 0.35 nm and a textured pattern is observed. The BN_1 − xP_x films are smooth, well-adhered to the quartz substrate, and display dark resistivities on the order of 10¹¹ Ω cm and ultraviolet light photo/dark conductivity ratios higher than 10³, with negligible sensitivity in the visible region, indicating a potential application in visible/blind UV detectors.     

Effect of Ag nanoparticle size on the plasmonic photocatalytic properties of TiO2 thin films

Photocatalytic TiO₂ films combined with Ag nanoparticles (NPs) embedded-SiO₂ films were fabricated by means of a RF magnetron sputtering and subsequent rapid thermal annealing (RTA). X-ray diffraction results show that the TiO₂ films have anatase phase when annealed at 500 °C. The Ag NPs were formed by deposition and subsequent annealing at 600 °C. Scanning electron microscopy (SEM) results show that the density of the NPs decreases with increasing Ag film thickness. For example, the average NP diameter varies from ~ 19.3 to ~ 55.9 nm as the film thickness increases from 2 to 12 nm. Transmittance measurements show that as the Ag NP size decreases, the plasmonic peaks shift towards the shorter-wavelength region and become narrower. It is further shown that under UV-illumination (352 nm), all the TiO₂ films with the Ag NPs show higher methylene blue decomposition rates compared to the TiO₂ only films and the TiO₂ films with Ag NP (a 7 nm-thick Ag film) show the best decomposition rate among the samples possibly due to the combined effects of optimized localized field amplification and radiative efficiency.     

Preparation and characterization of CoFe2O4 powders and films via the sol-gel method

The CoFe₂O₄ (CFO) starting precursor solutions were prepared by two sol-gel methods. The XRD results show that the second sol-gel method is a better method to obtain CFO materials with high purity. The CFO precursor solutions prepared by the second sol-gel method were spin-coated onto the Pt/Ti/SiO₂/Si substrate to obtain CFO films. With the increase of annealing temperature, the relative amounts of secondary phases in CFO films are decreased. When annealed at 700 °C, CFO films are almost composed of the main phase and the substrate phase without secondary phases. The CFO film is crack-free and has compact structure without any pore. The thickness of CFO film is about 49 nm. The starting precursor solution with the concentration of 0.15 mol L⁻¹ is better for preparing CFO films. The CFO films with nano-scaled film thicknesses have better magnetic properties than the CFO powders.     

High quality TbMnO3 films deposited on YAlO3

High quality thin films of TbMnO₃ were grown by pulsed laser deposition on orthorhombicYAlO₃ (1 0 0). The interface and surface roughness of a 55 nm thick film were probed by X-ray reflectometry and atomic force microscopy, yielding a roughness of 1 nm. X-ray diffraction revealed untwinned films and a small mosaic spread of 0.04° and 0.2° for out-of-plane and in-plane reflections, respectively. This high degree of epitaxy was also confirmed by Rutherford backscattering spectrometry. Using polarized neutron diffraction we could identify a magnetic structure with the propagation vector (0 0.27 0), identical to the bulk magnetic structure of TbMnO₃.     

Structural, optical and hydrophilic properties of nanocrystalline TiO2 ultra-thin films prepared by pulsed dc reactive magnetron sputtering

TiO₂ ultra-thin (15 nm) films were deposited on silicon wafers (100) and glass slides by pulsed dc reactive magnetron sputtering in an ultra-high vacuum (UHV) system. The effects of substrate temperature, from room temperature to 400 °C, on structural, optical, and hydrophilic properties of the obtained films have been investigated. The structure of the films was characterized by grazing-incidence X-ray diffraction, high-resolution transmission electron microscopy, and atomic force microscopy. The optical properties were determined by UV-vis spectrophotometer and spectroscopic ellipsometry. The hydrophilic properties of the films, after exposed to ultraviolet illumination, were analyzed from contact angle measurements. The results suggested that the substrate temperature at 300 °C was critical in the crystalline phase transformation from amorphous to anatase in the TiO₂ films. The obtained films exhibited good qualities in the optical properties, in addition to excellent photo-induced hydrophilic activities.     

Investigation of Niobium oxynitride thin films deposited by reactive magnetron sputtering

Niobium oxynitride films were deposited using reactive magnetron sputtering of a niobium target in an Ar/O₂/N₂ atmosphere with fixed nitrogen flux in direct current (DC) and pulsed modes. For the DC sputtering mode the deposition rate was found to be twice as high as for the pulsed mode at lower oxygen to nitrogen ratios (O/N). Morphology investigation by scanning electron microscopy and atomic force microscopy showed that the coatings are getting very smooth with increasing oxygen content (average roughness R_a < 0.4 nm at oxygen contents > 40 at.%). X-ray diffraction measurements revealed that the niobium oxynitride films are X-ray amorphous for oxygen contents > 40 at.%. The electrical conductivity of the coatings was studied by the 4 point-probe method and was found to decrease with increasing oxygen content. Optical properties of Nb-O-N films were analysed by spectroscopic ellipsometry and transmission spectroscopy. The refractive index of transparent and semi-transparent films was found to be in the range of 2.3 and 2.6 (at 633 nm). The experimental results will be discussed with respect to the O/N ratios (range 1.2 < O/N < ∞) or the oxygen content (range 33.7 at.% < O < 67.3 at.%) in the films as measured by Rutherford backscattering spectroscopy and particle induced X-ray emission.     

Microwave assisted chemical bath deposited polyaniline films for supercapacitor application

In the present investigation, we are reporting the first time synthesis of polyaniline (PANI) thin films by microwave assisted chemical bath deposition (MW-CBD) method on the stainless steel substrate. The PANI thin films are prepared by the oxidation of aniline in the domestic microwave oven working with frequency 2.45 GHz. The PANI thin films are characterized for their structural, morphological and optical studies by means of X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and UV-vis spectrophotometer. The wettability study is carried out by measuring the contact angle. The supercapacitive behavior of PANI electrode is studied in 0.5 M H₂SO₄ using cyclic voltammetric (CV) measurements. The X-ray diffraction pattern showed the films are amorphous. Morphological study revealed PANI thin film is well covered over the entire substrate surface with less overgrown fine spherical granules. The optical band gap of PANI thin film is found to be 2.5 eV. The hydrophilic nature of the PANI thin films is observed from water contact angle measurement. A maximum specific capacitance is found to be 753 F g⁻¹ at the scan rate of 5 mV s⁻¹.