Influence of rapid thermal annealing on structure and interfacial characteristic of ZnO thin films

Highly C‐axis oriented ZnO thin film was manufactured by radio‐frequency magnetron sputtering technique on Si (111) substrate. The main objective was to study the influence of rapid thermal annealing (RTA) temperature on the structure and interfacial characteristic of ZnO thin films. X‐ray diffraction results showed that the ZnO thin films annealed at 600 °C by RTA technique had a perfect C‐axis preferred orientation compared to the other ZnO thin films, and the full width at half maximum of ZnO (002) rocking curve measurements indicted that the RTA‐annealed ZnO thin films possessed better crystal structure. Atom force microscopy displayed that the grain size of RTA‐annealed ZnO thin films was fine and uniform compared with the as‐deposited ZnO thin films, although the grains grew in RTA process and the root meant square roughness was smaller than that of as‐deposited films. High‐resolution transmission electron microscopy showed that there was an obvious amorphous layer between ZnO thin films and Si substrate, but the RTA‐annealed ZnO thin films exhibited larger and denser columnar structure and a preferred orientation with highly c axis perpendicular to the amorphous layer. Copyright © 2012 John Wiley & Sons, Ltd.     

Thickness and temperature‐dependent study of Co/Si interface

Thin films of cobalt (10, 40, and 100 nm) are deposited on Si substrate by electron beam physical vapor deposition technique. After deposition, 4 pieces from each of the wafers of silicon substrate were cut and annealed at a temperature of 200°C, 300°C, and 400°C for 2 hours each, separately. X‐ray diffraction, atomic force microscopy, and transmission electron microscopy (TEM) are used to study the structural and morphological characteristics of the deposited films. To obtain TEM images, Co films are deposited on Cu grids; so far, no such types of TEM images of Co films are reported. Structural studies confirm nanocrystalline nature with hexagonal close packed structure of the deposited Co film at lower thickness, while at higher thickness, film structure transforms to amorphous with lower surface roughness value. The particle sizes in all the cases are in the range of 3 to 5 nm. Micro‐Raman spectroscopy is also used to study the phase formation and chemical composition as a function of thickness and temperature. The results confirm that the grown films are of good quality and free from any impurity. Studies show the silicide formation at the interface during deposition. The appearance of new band at 1550 cm⁻¹ as a result of annealing indicates the structural transformation from CoSi to CoSi₂, which further enhances at higher annealing temperatures.     

Facile synthesis of spray pyrolyzed ZnO/NiO nanocomposites thin films

Abstract

This study reviews ZnO, NiO, and ZnO/NiO nanocomposites thin films deposition using the Spray Pyrolysis Technique (S.P.T). The thin films were deposited onto ordinary glass substrates heated at 500?°C from aqueous solutions of zinc chloride and nickel chloride precursors dissolved in distilled water. The structural, morphological, and optical properties of the ZnO, NiO, and ZnO/NiO thin films have been studied by X-ray diffraction, scanning electron microscopy, Raman spectroscopies, and so on. The optical band gaps are 3.3 and 3.5?eV for ZnO and NiO thin films, respectively obtained by UV–Vis spectroscopy. However, the optical band gaps of ZnO/NiO nanocomposites thin films, are noticeable out of the range (3.4–3.64?eV).     

Substrate temperature effects on the structural,compositional, and electrical properties of VO2 thin films deposited by pulsed laser deposition

The vanadium dioxide (VO₂) thin films were deposited on silicon (100) substrate using the pulsed laser deposition technique. The thin films were deposited at different substrate temperatures (500°C, 600°C, 700°C, and 800°C) while keeping all the other parameters constant. X‐ray diffraction confirmed the crystalline VO₂ (B) and VO₂ (M) phase formation at different substrate temperatures. X‐ray photoelectron spectroscopy analysis showed the presence of V⁴⁺ and V⁵⁺ charge states in all the deposited thin films which confirms that the deposited films mainly consist of VO₂ and V₂O₅. An increase in the VO₂/V₂O₅ ratio has been observed in the films deposited at higher substrate temperatures (700°C and 800°C). Scanning electron microscope micrographs revealed different surface morphologies of the thin films deposited at different substrate temperatures. The electrical properties showed the sharp semiconductor to metal transition behavior with approximately 2 orders of magnitude for the VO₂ thin film deposited at 800°C. The transition temperature for heating and cooling cycles as low as 46.2°C and 42°C, respectively, has been observed which is related to the smaller difference in the interplanar spacing between the as‐deposited thin film and the standard rutile VO₂ as well as to the lattice strain of approximately −1.2%.     

XPS study of the oxidation of nanosize Ni/Si(100) films

The XPS (X-ray photoelectron spectroscopy) study of nickel oxide nanolayers obtained by magnetron sputtering of the metal and its subsequent oxidation in air at different temperatures (400°C and 1000°C) was performed. Silicon(100) was used as a substrate. Surface of the initial Ni/Si structure was shown to contain not only Ni metal, but also the NiO oxide. Annealing at 400°C results in a complete oxidation of the metal film. At a high-temperature annealing (1000°C), nickel interacts both with oxygen and silicon substrate to form NiSi silicide and a composite Ni-Si-O phase in transition layer. Electronconductivity of NiO films is determined by intercrystallite barriers. Activation energies of film electroconductivity in model gases (O₂, Ar, H₂) were found.     

Effect of 120 MeV Au9+ ion irradiation on the structure and surface morphology of ZnO/NiO heterojunction

ZnO/NiO thin films, each of thickness 100 nm, were deposited on Si(100) substrate by pulsed laser deposition method. The resulting heterojunction, ZnO/NiO/Si, was irradiated by 120 MeV Au⁹⁺ ions and characterized by grazing incidence X‐ray diffraction (GIXRD), Raman spectroscopy, and atomic force microscopy (AFM). The GIXRD confirmed the presence of both NiO and ZnO in the samples. Ion irradiation induced suppression of crystalline nature, and the recrystallization of the same occurred at the fluence of 1 × 10¹³ ions cm⁻². The occurrence of most intense band at 302 cm⁻¹ in Raman spectra corresponds to the symmetric stretching vibration of ZnO. The linear shift of stretching mode of ZnO with ion fluence could be associated with the effect of compressive stress in the material. AFM analysis of the films indicated that the rms roughness increased when the film is irradiated at a fluence of 1 × 10¹² ions cm⁻². Beyond this fluence, the value of roughness decreased up to fluence of 1 × 10¹³ ions cm⁻² and increased thereafter. To see the effect of the stress of buffer layer on the surface layer, we calculated the stress for NiO layer with ion fluence form the lattice parameter. Comparing the stress of buffer layer with roughness of surface layer at the given fluence, we can say that the compressive stress in the buffer layer could possibly control the roughness of the surface layer.     

Characterisation and properties of magnetron sputtered nanoscale bi‐layered Ni/Ti thin films and effect of annealing

Single‐bi‐layer of Ni–Ti thin film was deposited using DC and RF magnetron sputtering technique by layer‐wise deposition of Ni and Ti on Si(100) substrate in the order of Ni as the bottom layer and Ti as the top layer. The deposition of these amorphous as‐deposited thin films was followed by annealing at 300 °C, 400 °C, 500 °C, and 600 °C temperature with 1‐h annealing time for each to achieve crystalline thin films. This paper describes the fabrication processes and the novel characterization techniques of the as‐deposited as well as the annealed thin films. Microstructures were analysed using FESEM and HRTEM. Nano‐indentation and AFM were carried out to characterize the mechanical properties and surface profiles of the films. It was found that, for the annealing temperatures of 300 °C to 600 °C, the increase in annealing temperature resulted in gradual increase in atomic‐cluster coarsening with improved ad‐atom mobility. Phase analyses, performed by GIXRD, showed the development of silicide phases and intermetallic compounds. Cross‐sectional micrographs exhibited the inter‐diffusion between the two‐layer constituents, especially at higher temperatures, which resulted either in amorphization or in crystallization after annealing at temperatures above 400 °C. Copyright © 2015 John Wiley & Sons, Ltd.     

50 keV H+ ion beam irradiation of Al doped ZnO thin films: Studies of radiation stability for device applications

Thin films of Al doped ZnO (Al:ZnO) were deposited on two substrates (Si and glass) at room temperature and 300°C using DC magnetron sputtering. These films were bombarded with 50 keV H⁺ beam at several fluences. The pristine and ion beam irradiated films were analysed by X‐ray diffraction, Raman spectroscopy, scanning electron microscopy, and UV‐Vis spectroscopy. The X‐ray diffraction analysis, Hall measurements, Raman and UV‐Vis spectroscopy confirm that the structural and transport properties of Al:ZnO films do not change substantially with beam irradiation at chosen fluences. However, in comparison to film deposited at room temperature, the Al:ZnO thin film deposited at 300°C shows increased transmittance (from 70% to approximately 90%) with ion beam irradiation at highest fluence. The studies of surface morphology by scanning electron microscopy reveal that the ion irradiation yields smoothening of the films, which also increases with ion fluences. The films deposited at elevated temperature are smoother than those deposited at room temperature. In the paper, we discuss the interaction of 50 keV H⁺ ions with Al:ZnO films in terms of radiation stability in devices.     

ZnO thin films prepared on titanium substrate by PLD technique at different substrate temperatures

ZnO thin films were grown by pulsed laser deposition on titanium substrates at different substrate temperatures ranging from 300 to 700 °C. X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS),photoluminescence, and Raman spectroscopy are employed to investigate the change of properties. XRD, XPS, and Raman data showed that the films consisted of TiO₂ at high substrate temperature, which will deteriorate the crystallization quality of ZnO films. The optimum temperature for the growth of ZnO films on the Ti substrate is about 500 °C in this paper. The ZnO films grown on titanium substrate can be used in direct current, microwave, and medical applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Reactive diffusion in W–Mo–Si thin films

This study reports the phase formation in the ternary thin films system Mo–W–Si. The metallic films were deposited onto Si (100) substrate by sputtering. Two kinds of samples were prepared, either by sequential deposition or by co-deposition. The phase formation was investigated by In situ X-ray diffraction measurements from 300 to 900 °C. The influence of the sample preparation, namely sequential deposition and co-deposition, on the mechanism of phase formation has been evidenced.     

Effect of substrate on phase formation and surface morphology of sol-gel lead-free KNbO3, NaNbO3, and K0.5Na0.5NbO3 thin films

Environmentally acceptable lead-free ferroelectric KNbO₃ (KN) or NaNbO₃ (NN) and K_0.5Na_0.5NbO₃ (KNN) thin films were prepared using a modified sol-gel method by mixing potassium acetate or sodium acetate or both with the Nb-tartrate complex, deposited on the Pt/Al₂O₃ and Pt/SiO₂/Si substrates by a spin-coating method and sintered at 650°C. X-ray diffraction (XRD) analysis indicated that the NN and KNN films on the Pt/SiO₂/Si substrate possessed a single perovskite phase, while NN and KNN films on the Pt/Al₂O₃ substrate contained a small amount of secondary pyrochlore phase, as did KN films on both substrates. Scanning electron microscopic (SEM) and atomic force microscopic (AFM) analyses confirmed that roughness R _q of the thin KNN/Pt/SiO₂/Si film (?? 7.4 nm) was significantly lower than that of the KNN/Pt/Al₂O₃ film (?? 15 nm). The heterogeneous microstructure composed of small spherical and larger needle-like or cuboidal particles were observed in the KN and NN films on both substrates. The homogeneous microstructure of the KNN thin film on the Pt/SiO₂/Si substrate was smoother and contained finer spherical particles (?? 50 nm) than on Pt/Al₂O₃ substrates (?? 100 nm). The effect of different substrates on the surface morphology of thin films was confirmed.     

Spectroelectrochemical Evaluation of a ZnO Optically Transparent Electrode Prepared by the Spin‐spray Technique

We present a novel zinc oxide (ZnO) optically transparent electrode (OTE) prepared by the spin‐spray technique for spectroelectrochemistry. The spin‐spray technique can deposit ZnO film at a low cost, high rate deposition, and at a low temperature (<100 °C) in a single step. This new technique provides good optical transparency and electrical conductivity for ZnO. The electrochemical and spectroelectrochemical properties of the ZnO electrode were investigated for varying thicknesses of ZnO using methylene blue as a redox indicator. A ZnO OTE chip that includes three electrodes on a glass chip was developed for thin‐layer spectroelectrochemistry. Moreover, the ZnO films were successfully applied in an electrochemical‐localized surface plasmon resonance (LSPR) method for methylene blue detection by using them as a transparent conducting substrate for loading gold nanoparticles.     

Annealing effect on the structural and magnetic properties of nickel ferrite thin films

Nickel ferrite is a soft magnetic material with inverse spinel structure. Soft ferrite films are used in microwave devices, integrated planar circuits, etc., because of their high resistivity. In this work, thin films of nickel ferrite were deposited on Si (100) substrate by using pulsed laser deposition (PLD) technique. The thickness of the film was measured by surface profilometer and also by X‐ray reflectivity (XRR). The films were annealed at three different temperatures to observe the effect on the structural and magnetic properties of the film. The films were characterised by X‐ray diffraction (XRD), Raman spectroscopy and vibrating sample magnetometer (VSM) to study the structural and magnetic properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Sputter‐deposited Ni/Ti double‐bilayer thin film and the effect of intermetallics during annealing

In the present study, a double bilayer of a Ni/Ti thin film was investigated. A nanoscale NiTi thin film is deposited in a Ni–Ti–Ni–Ti manner to form a double‐bilayer structure on a Si(100) substrate. Ni and Ti depositions were carried out by using d.c. and r.f. power, respectively, in a magnetron sputtering chamber. Four types of bilayers are formed by varying the deposition time of each layer (i.e. 15, 20, 25, and 30 min). The as‐deposited amorphous thin films were annealed at 300, 400, 500, and 600 °C for 1 h to achieve the diffusion in between the layers. Microstructures were analyzed using field‐emission scanning electron microscope and high‐resolution transmission electron microscope. It was found that, with the increase in annealing temperature from 300 to 600 °C, the diffusion at the interface and atomic migration on the surface increase. Cross‐sectional micrographs exhibited the interdiffusion between the two‐layer constituents, especially at higher temperatures, which resulted in diffusion patches along the interface. Phase analyses, performed by grazing incidence X‐ray diffraction, showed the formation of intermetallic compounds with some silicide phases that enhance the mechanical properties. Nanoindentation and atomic force microscopy were carried out to know the mechanical properties and surface profiles of the films. The surface finish is better at higher annealing temperatures. It was found that for annealing temperatures varying from 300 to 600 °C, the increase in annealing temperature resulted in a gradual increase in atomic‐cluster coarsening with improved adatom mobility. Copyright © 2016 John Wiley & Sons, Ltd.     

Nitridation of Niobium Pentoxide Films in Ammonia by Rapid Thermal Processing

The feasibility of niobium oxynitride formation through nitridation of niobium pentoxide films in ammonia by rapid thermal processing (RTP) was investigated. Niobium films 200 and 500 nm thick were deposited by sputtering on Si(100) wafers covered by a 100 nm thick thermally grown SiO₂ layer. These as‐deposited films exhibited distinct texture effects. They were processed in three steps using an RTP system. The as‐deposited niobium films were first nitridated in an ammonia atmosphere at 1000 °C for 1 min and then oxidised in molecular oxygen at temperatures ranging from 400 to 600 °C. Those samples in which a single Nb₂O₅ phase was determined after oxidation were additionally nitridated in ammonia at 1000 °C for 1 min. Investigations show that surface roughness of the samples after oxidation of niobium films first nitridated in ammonia is lower than after direct oxidation of as‐deposited films in oxygen, although the niobium pentoxide phase formed after annealing was the same in both cases. We explain this result as being due to the large expansion of the niobium lattice during the direct oxidation of the niobium film in molecular oxygen and also to the high oxidation rate of the as‐deposited niobium film in oxygen. By incorporation of oxygen in the crystal lattice of niobium and rapid formation of niobium pentoxide, substantial intrinsic stress was built up in the film, frequently resulting in delamination of the film from the substrate. Nitrogen hinders the diffusion of oxygen in nitridated films, which leads to a decrease of the oxidation rate and thus slower formation of Nb₂O₅. Nitridation of the completely oxidised niobium films in ammonia leads to the formation of niobium oxynitride and niobium nitride phases.     

Ultrathin cobalt silicide film formation on Si(100)

The interfacial reaction between ultrathin Co film and substrate Si(100) was studied by in situ XPS using monochromatized Al Kα. When the Co is deposited on Si(100) at room temperature, CoSi₂ is formed during the initial stage of Co deposition and then metallic Co starts to grow sequentially. For 8 ML Co deposition on Si(100) the interfacial reaction layer is relatively thin compared with the pure Co overlayer, which is not involved in the interfacial reaction in depth. The Co layers change rapidly to CoSi layers after annealing at 270°C, and then CoSi₂ layers form after annealing at 540°C for 2 min. The CoSi₂ layers are changed to CoSi₂ islands by post‐annealing at >650°C. Copyright © 2003 John Wiley & Sons, Ltd.     

Effect of Annealing on the Electrical Properties of CuxS Thin Films

Copper sulphide CuS was deposited on three substrates; glass, Indium Tin Oxide (ITO) and Ti by using spray pyrolysis deposition (SPD). After depositing CuS thin films on the substrates at 200 °C, they were annealed at 50, 100, 150, and 200 °C for 1 hour. Structural measurements revealed covellite CuS and chalcocite Cu₂S phases for thin films before and after annealing at 200 °C with changes in intensities, and only covellite CuS phase for thin films after annealing at 50, 100, and 150 °C. Morphological characteristics show hexagonal-cubic crystals for the CuS thin film deposited on glass substrate and plates structures for films deposited on ITO and Ti substrates before annealing, these crystals became bigger in size and there were be oxidation and some agglomerations in some regions with formation of plates for CuS on glass substrate after annealing at 200 °C. For Hall Effect measurements, thin films sheet resistivity and mobility increased after annealing while the carrier concentration decreased. Generally, the thin film deposited on ITO substrate had the lowest resistivity and the highest carrier concentration before and after annealing. The thin film deposited on Ti substrate had the highest mobility before and after annealing, which makes it the best thin film for device performance. The objective of this research is to show the improvement of thin films electrical properties especially the mobility after annealing those thin films.     

Bioactivity and mechanical properties of nickel‐incorporated hydrogenated carbon nanocomposite thin films

In this paper, the influence of nickel incorporation on the mechanical properties and the in vitro bioactivity of hydrogenated carbon thin films were investigated in detail. Amorphous hydrogenated carbon (a‐C:H) and nickel‐incorporated hydrogenated carbon (Ni/a‐C:H) thin films were deposited onto the Si substrates by using reactive biased target ion beam deposition technique. The films' chemical composition, surface roughness, microstructure and mechanical properties were investigated by using XPS, AFM, TEM, nanoindentation and nanoscratch test, respectively. XPS results have shown that the film surface is mainly composed of nickel, nickel oxide and nickel hydroxide, whereas at the core is nickel carbide (Ni₃C) only. The presence of Ni₃C has increased the sp² carbon content and as a result, the mechanical hardness of the film was decreased. However, Ni/a‐C:H films shows very low friction coefficient with higher scratch‐resistance behavior than that of pure a‐C:H film. In addition, in vitro bioactivity study has confirmed that it is possible to grow dense bone‐like apatite layer on Ni/a‐C:H films. Thus, the results have indicated the suitability of the films for bone‐related implant coating applications. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization of silver selenide thin films grown on Cr‐covered Si substrates

Thermal stability of silver selenide thin films formed from the solid‐state reaction of Ag‐Se diffusion couples on Si substrates covered with a thin Cr film, is investigated. Glancing angle X‐ray diffraction (GXRD), XPS, atomic force microscopy (AFM) and Rutherford backscattering spectrometry (RBS) are used to characterize the as‐deposited films and those annealed at 100, 200, 300, and 400 °C. The results reveal the formation of polycrystalline orthorhombic silver selenide films that remain stable without compositional change upon thermal annealing, in marked contrast to the agglomeration exhibited by silver selenide films deposited on Si without Cr film. The improvement in the thermal stability is attributed to compressive stress relief by a grainy morphology with large surface area, the formation of which is promoted by partially oxidized Cr adhesion film. Copyright © 2008 John Wiley & Sons, Ltd.     

Electrochemical fabrication and characterization of p-CuSCN/n-ZnO heterojunction devices

p-CuSCN/n-ZnO heterojunction devices were prepared by depositing CuSCN electrochemically over a ZnO film previously deposited. The compact and smooth surface films of n-ZnO on FTO substrate were deposited electrochemically from a nonaqueous bath. The CuSCN films were characterized by cyclic voltammetry, chronoamperometry, SEM, energy-dispersive X-ray spectroscopy, and XRD measurements. The pure crystalline films of CuSCN with intrinsic trigonal pyramidal morphology over the ZnO films were obtained electrochemically by fixing the SCN/Cu ratio in the electrolytic bath 1.5:1 at 60 °C with ?0.4 V deposition potential. Photocurrent measurements showed the increase of intrinsic surface states or defects in ZnO/CuSCN interface. The I–V characteristic of p-CuSCN/n-ZnO heterojunctions shows good rectification behavior with a rectification ratio of 250 at ±2 V. The value of 2.81 of the ideality factor calculated by fitting the semilogarithmic I–V data with the ideal diode equation revealed the better electrical contact between the smooth ZnO and CuSCN films than that of ZnO nano-rods and CuSCN crystallites.