Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Structural and optical properties of a-Si1−xCx:H films synthesized by dc magnetron sputtering technique

Hydrogenated amorphous SiC films (a-Si_1−xC_x:H) were prepared by dc magnetron sputtering technique on p-type Si(1 0 0) and corning 9075 substrates at low temperature, by using 32 sprigs of silicon carbide (6H-SiC). The deposited a-Si_1−xC_x:H film was realized under a mixture of argon and hydrogen gases. The a-Si_1−xC_x:H films have been investigated by scanning electronic microscopy equipped with an EDS system (SEM-EDS), X-ray diffraction (XRD), secondary ions mass spectrometry (SIMS), Fourier transform infrared spectroscopy (FTIR), UV-vis-IR spectrophotometry, and photoluminescence (PL). XRD results showed that the deposited film was amorphous with a structure as a-Si_0.80C_0.20:H corresponding to 20 at.% carbon. The photoluminescence response of the samples was observed in the visible range at room temperature with two peaks centred at 463 nm (2.68 eV) and 542 nm (2.29 eV). In addition, the dependence of photoluminescence behaviour on film thickness for a certain carbon composition in hydrogenated amorphous SiC films (a-Si_1−xC_x:H) has been investigated.     

The influence of growth parameters on the optical properties and morphology of UHV deposited Ni thin films

Nickel films of different thickness ranging from 15 nm to 350 nm were deposited on glass substrates, at different substrate temperatures (313-600 K) under UHV condition. The nano-structure of the films was obtained, using X-ray diffraction (XRD) and atomic force microscopy (AFM). The nano-strain in these films was obtained using the Warren-Averbach method. Their optical properties were measured by spectrophotometry in the spectral range of 190-2500 nm. Kramers-Kronig method was used for the analysis of the reflectivity curves. The absorption peaks of Ni thin films at ∼1.4 eV (transition between the bands near W and K symmetry points) and ∼5.0 eV (transition from L_2^′ to L₁ upper) are observed, with an additional bump at about 2 eV. The over-layer thickness was calculated to be less than 3.0 nm, using the Transfer Matrix method. The changes in optical data are related to different phenomena, such as different crystallographic orientations of the grains in these polycrystalline films (film texture), nano-strain, and film surface roughness.     

Study of electronic structures for Fe thin films deposited on Si- and C-faces of 4H-SiC substrates by soft X-ray emission spectroscopy

Silicon carbide (SiC) is a candidate material for electronic devices to operate upon crucial environment. Electronic states of silicides and/or carbide/graphite formed in metal/SiC contact system are fundamentally important from the viewpoint of device performance.We study interface electronic structure of iron thin film deposited on silicon (Si)- and carbon (C)-face of 4H-SiC(0 0 0 1) by using a soft X-ray emission spectroscopy (SXES). For specimens of Fe (50 nm)/4H-SiC (substrate) contact systems annealed at 700 and 900 °C, the Si L_2,3 emission spectra indicate different shapes and peak energies from the substrate depending on thermal-treated temperature. The product of materials such as silicides is suggested. Further, from comparison of Si L_2,3 emission spectra between Si- and C-face for the same annealing temperature at 700 °C, it is concluded that the similar silicides and/or ternary materials are formed on the two surfaces. However for those of 900 °C, the film on substrate is composed of the different silicide and/or ternary materials.     

Study of electronic states for V thin films deposited on 6H-SiC substrates by soft X-ray emission spectroscopy

Silicon carbide (SiC) is a candidate material for electronic devices to operate upon crucial environment. Electronic states of silicides and/or carbide/graphite formed in metal/SiC contact system is fundamentally important from the view point of device performance.We study interface electronic structure of vanadium (V) thin-film deposited on 6H-SiC(0 0 0 1) Si-face by using a soft X-ray emission spectroscopy (SXES). For specimens of V(38 nm)/6H-SiC (substrate) contact systems annealed at 850 °C, the Si L_2,3 emission spectra indicate different shapes and peak energies from the substrate. The product of materials such as silicides and/or ternary materials is suggested. Similarly, the C Kα emission spectra show the shape and peak energy characteristic of vanadium carbide including substrate 6H-SiC signal.     

Epitaxially grown ZnO thin films on 6H-SiC(0 0 0 1) substrates prepared by spin coating-pyrolysis

Epitaxially grown ZnO thin film on 6H-SiC(0 0 0 1) substrate was prepared by using a spin coating-pyrolysis with a zinc naphthenate precursor. As-deposited film was pyrolyzed at 500 °C for 10 min in air and finally annealed at 800 °C for 30 min in air. In-plane alignment of the film was investigated by X-ray pole-figure analysis. Field emission-scanning electron microscope, scanning probe microscope, and He-Cd laser (325 nm) was used to analyze the surface morphology, the surface roughness and photoluminescence of the films. In the photoluminescence spectra, near-band-edge emission with a broad deep-level emission was observed. The position of the near-band-edge peak was around 3.27 eV.     

Optical and structural studies on Ba(Mg1/3Ta2/3)O3 thin films obtained by radiofrequency assisted pulsed plasma deposition

Single-phase Ba(Mg_1/3Ta_2/3)O₃ thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of ≈4.72 eV has been obtained.     

Effect of H2 and O2 plasma etching treatment on the surface of diamond-like carbon thin film

In this study, we investigated the surface properties of diamond-like carbon (DLC) films for biomedical applications through plasma etching treatment using oxygen (O₂) and hydrogen (H₂) gas. The synthesis and post-plasma etching treatment of DLC films were carried out by 13.56 MHz RF plasma enhanced chemical vapor deposition (PECVD) system. In order to characterize the surface of DLC films, they were etched to a thickness of approximately 100 nm and were compared with an as-deposited DLC film. We obtained the optimum condition through power variation, at which the etching rate by H₂ and O₂ was 30 and 80 nm/min, respectively. The structural and chemical properties of these thin films after the plasma etching treatment were evaluated by Raman and Fourier transform infrared (FT-IR) spectroscopy. In the case of as-deposited and H₂ plasma etching-treated DLC film, the contact angle was 86.4° and 83.7°, respectively, whereas it was reduced to 35.5° in the etching-treated DLC film in O₂ plasma. The surface roughness of plasma etching-treated DLC with H₂ or O₂ was maintained smooth at 0.1 nm. These results indicated that the surface of the etching-treated DLC film in O₂ plasma was hydrophilic as well as smooth.     

Enhanced luminescent characteristics of laser-ablated GdVO4:Eu thin films by Li-doping

Li-doping has been used to improve luminescent characteristics of thin films. Influence of Li-doping on the crystallization, surface morphology and luminescent properties of GdVO₄:Eu³⁺ films have been investigated. Crystallinity and surface morphology of thin films have been very important factors to determine luminescent characteristics and depended on the deposition conditions. The GdVO₄:Eu³⁺ and Li-doped GdVO₄:Eu³⁺ thin films have been grown using pulsed laser deposition method on Al₂O₃ (0 0 0 1) substrates at a substrate temperature of 600 °C under an oxygen pressure of 13.33-53.33 Pa. The crystallinity and surface morphology of the films were investigated using X-ray diffraction (XRD) and atomic force microscope (AFM), respectively. A broadband incoherent ultraviolet light source with a dominant excitation wavelength of 310 nm and a luminescence spectrometer have been used to measure photoluminescence spectra at room temperature. The emitted radiation was dominated by the red emission peak at 619 nm radiated from the transition of ⁵D₀-⁷F₂ of Eu³⁺ ions. Particularly, the peak intensity of Li-doped GdVO₄ films was increased by a factor of 1.7 in comparison with that of GdVO₄:Eu³⁺ films. The enhanced luminescence results not only from the improved crystallinity but also from the reduced internal reflections caused by rougher surfaces. The luminescent intensity and surface roughness exhibited similar behavior as a function of oxygen pressure.     

Structural studies of evaporated CoxCr1−x/Si (1 0 0) and CoxCr1−x/glass thin films

Series of Co_xCr_1−x thin films have been evaporated under vacuum onto Si (1 0 0) and glass substrates. Chemical composition and interface properties have been studied by modelling Rutherford backscattering spectra (RBS) using SIMNRA programme. Thickness ranges from 17 to 220 nm, and x from 0.80 to 0.88. Simulation of the energy spectra shows an interdiffusion profile in the thickest films, but no diffusion is seen in thinner ones. Microscopic characterizations of the films are done with X-ray diffraction (XRD) measurements. All the samples are polycrystalline, with an hcp structure and show a 〈0 0 0 1〉 preferred orientation. Atomic force microscopies (AFM) reveal very smooth film surfaces.     

Substrate temperature influence on the properties of nanostructured ZnO transparent ultrathin films grown by PLD

Zinc oxide films of 40 nm thickness have been deposited on glass substrates by pulsed laser deposition using an excimer XeCl laser (308 nm) at different substrate temperatures ranging from room temperature to 650 °C. Surface investigations carried out by using atomic force microscopy have shown a strong influence of temperature on the films surface topography. UV-VIS transmittance measurements have shown that our ZnO films are highly transparent in the visible wavelength region, having an average transmittance of ∼90%. The optical band gap of the films was found to be 3.26 eV, which is lower than the theoretical value of 3.37 eV. Besides the normal absorption edge related to the transition between the valence and the conduction band, an additional absorption band was also recorded in the wavelength region around 364 nm (∼3.4 eV). This additional absorption band may be due to excitonic, impurity, and/or quantum size effects. Photoreduction/oxidation in ozone of the ZnO films lead to larger conductivity changes for higher deposition temperature. In conclusion, the ozone sensing characteristics as well as the optical properties of the ZnO thin films deposited by pulsed laser deposition are strongly influenced by the substrate temperature during growth. The sensitivity of the films towards ozone might be enhanced significantly by the control of the films deposition parameters and surface characteristics.     

Fabrication of nanostructured CuInS2 thin films by ion layer gas reaction method

CuInS₂ thin films were prepared by a two-stage ion layer gas reaction (ILGAR) process in which the Cu and In precursors were deposited on glass substrate by using a simple and low-cost dip coating technique and annealed in H₂S atmosphere at different temperatures. The influence of the annealing temperature (250-450 °C) on the particle size, crystal structure and optical properties of the CuInS₂ thin films was studied. Transmission electron microscopy revealed that the particle radii varied in the range 6-21 nm with annealing. XRD and SAED patterns indicated polycrystalline nature of the nanoparticles. The optical band gap (E_g) varied from 1.48 to 1.56 eV with variation of particle size. The variation of Urbach tail with temperature indicated higher density of the defects for the films annealed at lower temperature. From the Raman study, it was observed that the FWHM of the A₁ mode at ∼292 cm⁻¹ corresponding to the chalcopyrite phase of CuInS₂ decreased with increasing annealing temperature.     

A comparative study of the physical properties of Sb2S3 thin films treated with N2 AC plasma and thermal annealing in N2

As-deposited antimony sulfide thin films prepared by chemical bath deposition were treated with nitrogen AC plasma and thermal annealing in nitrogen atmosphere. The as-deposited, plasma treated, and thermally annealed antimony sulfide thin films have been characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, UV-vis spectroscopy, and electrical measurements. The results have shown that post-deposition treatments modify the crystalline structure, the morphology, and the optoelectronic properties of Sb₂S₃ thin films. X-ray diffraction studies showed that the crystallinity of the films was improved in both cases. Atomic force microscopy studies showed that the change in the film morphology depends on the post-deposition treatment used. Optical emission spectroscopy (OES) analysis revealed the plasma etching on the surface of the film, this fact was corroborated by the energy dispersive X-ray spectroscopy analysis. The optical band gap of the films (E_g) decreased after post-deposition treatments (from 2.36 to 1.75 eV) due to the improvement in the grain sizes. The electrical resistivity of the Sb₂S₃ thin films decreased from 10⁸ to 10⁶ Ω-cm after plasma treatments.     

Photoluminescence from C ion-implanted and electrochemical etched Si layers

The microstructural and optical analysis of Si layers emitting blue luminescence at about 431 nm is reported. These structures have been synthesized by C⁺ ion implantation and high-temperature annealing in hydrogen atmosphere and electrochemical etching sequentially. With the increasing etching time, the intensity of the blue peak increases at first, decreases then and is substituted by a new red peak at 716 nm at last, which shows characteristics of the emission of porous silicon. CO compounds are induced during C⁺ implantation and nanometer silicon with embedded structure is formed during annealing, which contributes to the blue emission. The possible mechanism of photoluminescence is presented.     

Synthesis and electrochemical characteristics of Ta-N thin films fabricated by cathodic arc deposition

Ta-N thin films were deposited on AISI 317L stainless steel (SS) substrates by cathodic arc deposition (CAD) at substrate biases of −50 and −200 V. The as-deposited films were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX). The results show that stoichiometric TaN with hexagonal lattice (3 0 0) preferred orientation was achieved at the bias of −200 V. On the other hand, Ta-rich Ta-N thin film deposited at −50 V shows amorphous nature. According to the XPS result, Ta element in the films surface exist in bonded state, including the Ta-N bonds characterized by the doublet (Ta 4f_7/2 = 23.7 eV and Ta 4f_5/2 = 25.7 eV). Electrochemical properties of the Ta-N coated stainless steel systems were investigated using potentiodynamic polarization and electrochemical impedance spectroscope (EIS) in Hank's solution at 37 °C. For the Ta-N coated samples, the corrosion current (i_corr) is two or three orders of magnitude lower than that of the uncoated ones, indicating a significantly improved corrosion resistance. Growth defects in the Ta-N thin films produced by CAD, however, play a key role in the corrosion process, especially the localised corrosion. Using the polarization fitting and the EIS modelling, we compared the polarization resistance (R_p) and the porosity (P) of the Ta-N coatings deposited at different biases. It seems that Ta-N film with comparatively lower bias (−50 V) shows better corrosion behavior in artifical physiological solution. That may be attributed to the effect of ion bombarding, which can be modulated by the substrate bias.     

Structural and photoluminescence characters of SnO2:Sb films deposited by RF magnetron sputtering

The Antimony-doped tin oxide (SnO₂:Sb) films have been prepared on glass substrates by RF magnetron sputtering method. The prepared samples are polycrystalline films with rutile structure of pure SnO₂ and have preferred orientation of (1 1 0) direction. XRD measurement did not detect the existence of Sb₂O₃ phase and Sb₂O₅ phase; Sb ions occupy the site of Sn ions and form the substitution doping. An intensive UV-violet luminescence peak near 392 nm is observed at room temperature. Photoluminescence (PL) properties influenced by sputtering power and annealing for the SnO₂:Sb films are investigated in detail and corresponding PL mechanism is discussed.     

Surface morphology and luminescence characterization of β-FeSi2 thin films prepared by pulsed laser deposition

β-FeSi₂ thin films were prepared on Si (1 1 1) substrates by pulsed laser deposition (PLD) with a sintering FeSi₂ target and an electrolytic Fe target. The thin films without micron-size droplets were prepared using the electrolytic Fe target; however, the surface without droplets was remarkably rougher using the Fe target than using the FeSi₂ target. After deposition at 600 °C and then annealing at 900 °C for 20 h, XRD indicated that the thin film prepared using the Fe target had a poly-axis-orientation, but that prepared using the FeSi₂ target had a one-axis-orientation. The PL spectra of the thin films prepared using the FeSi₂ and Fe targets at a growth temperature of 600 °C and subsequently annealed at 900 °C for 20 h had A-, B- and C-bands. Moreover, it was found that the main peak at 0.808 eV (A-band) in the PL spectrum of the thin films prepared using the FeSi₂ target was the intrinsic luminescence of β-FeSi₂ from the dependence of PL peak energy on temperature and excitation power density.     

Initial study on the structure and photoluminescence properties of SiC films doped with Al

SiC films doped with aluminum (Al) were prepared by the rf-magnetron sputtering technique on p-Si substrates with a composite target of a single crystalline SiC containing several Al pieces on the surface. The as-deposited films were annealed in the temperature range of 400-800 °C under nitrogen ambient. The thin films have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results show that the introduction of Al into films hinders crystalline formation process. And with the increase of annealing temperature, more Si particles are formed in the films, which strongly affect the optical absorption properties. The photoluminescence (PL) spectra of the samples show two peaks at 370 nm and 412 nm. The intensities of the PL peaks are evidently improved after Al doped. We attribute the origin of the two PL peaks to a kind of Si-related defect centres. The obtained results are expected to have important applications in modern optoelectronic devices.     

Crystallization kinetics of amorphous SiC films: Influence of substrate

The crystallization kinetics of amorphous silicon carbide films was studied by means of X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The films were deposited by radio frequency (r.f.) magnetron sputtering on glassy carbon and single crystalline silicon substrates, respectively. TEM micrographs and XRD patterns show the formation of nano-crystalline β-SiC with crystallite sizes in the order of 50 nm during annealing at temperatures between 1200 and 1600 °C. A modified Johnson-Mehl-Avrami-Kolmogorov (JMAK) formalism was used to describe the isothermal transformation of amorphous SiC into β-SiC as an interface controlled, three-dimensional growth processes from pre-existing small crystallites in the order of 10 nm. These pre-existing crystallites are formed in a transient process in the early stages of crystallization. For films deposited on the silicon substrate, the obtained rate constants of crystallite growth obey an Arrhenius behavior with an activation enthalpy of 4.1 ± 0.5 eV in accordance with literature data. Films deposited on glassy carbon show an increased stability of amorphous SiC films, which is reflected in smaller rate constants of crystallite growth of several orders of magnitude at low temperatures and a higher activation enthalpy of 8.9 ± 0.9 eV. A model is proposed, where the faster crystallization of films on silicon substrates can be explained with the presence of superabundant point defects, which diffuse from the substrate into the film and accelerate the incorporation of atoms from the amorphous into the crystalline phase.     

AlF3 film deposited by IAD with end-Hall ion source using SF6 as working gas

A novel and effective process to fabricate high quality fluoride thin films was presented. Aluminum fluoride films deposited by a conventional thermal evaporation with an ion-assisted deposition (IAD) using SF₆ as a working gas at around room temperature were investigated. In this study, the optimal voltage and current, 50 V and 0.25 A, were found according to the optical properties of the films: high refractive index (1.489 at 193 nm), low optical absorption and extinction coefficient (<10⁻⁴ at 193 nm) in the UV range. The physical properties of the film are high packing density and amorphous without columnar structure. It was proved that using SF₆ working gas in IAD process is a good choice and significantly improves the quality of AlF₃ films.