Structural, optical and electrical properties of N-doped ZnO thin films prepared by thermal oxidation of pulsed filtered cathodic vacuum arc deposited ZnxNy films

In this study, N-doped ZnO thin films were fabricated by oxidation of Zn_xN_y films. The Zn_xN_y thin films were deposited on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) using metallic zinc wire (99.999%) as a cathode target in pure nitrogen plasma. The influence of oxidation temperature, on the electrical, structural and optical properties of N-doped ZnO films was investigated. P-type conduction was achieved for the N-doped ZnO obtained at 450 °C by oxidation of Zn_xN_y, with a resistivity of 16.1 Ω cm, hole concentration of 2.03 × 10¹⁶ cm⁻³ and Hall mobility of 19 cm²/V s. X-ray photoelectron spectroscopy (XPS) analysis confirmed the incorporation of N into the ZnO films. X-ray diffraction (XRD) pattern showed that the films as-deposited and oxidized at 350 °C were amorphous. However, the oxidized films in air atmosphere at 450-550 °C were polycrystalline without preferential orientation. In room temperature photoluminescence (PL) spectra, an ultraviolet (UV) peak was seen for all the samples. In addition, a broad deep level emission was observed.     

The influence of plasma power on the temperature-dependant conductivity and on the wet chemical etch rate of sputter-deposited alumina thin films

Aluminum oxide (Al₂O₃) thin films are synthesized by reactive d.c. magnetron sputter deposition on silicon substrates. The impact of varying plasma power P_p (i.e. 400 to 1000 W) and of thin film temperatures T up to 540 °C on the electrical performance are evaluated, as these dielectric layers with a thickness of 450 nm are targeted as potential candidates for high temperature sensor applications. From 150 °C to 500 °C, the current-voltage measurements show a leakage current behavior according to the Poole-Frenkel electron emission with an activation energy of 1.16 eV. At T > 500 °C, the conductivity increases above average, in respect to the extrapolated Poole-Frenkel behavior at T < 500 °C, most probably due to the migration of charged ions, such as Ar⁺, incorporated into the film during deposition. Basically, samples synthesized at higher plasma levels show an enhanced electrical insulation behavior. This result is supported by measurements applying optical ellipsometry as well as by the determination of the wet chemical etching behavior in phosphoric-based acid at different bath temperatures. At higher plasma power, the refractive index shows a slight tendency to increase, staying, however, below the value of single-crystalline Al₂O₃. In contrast, the etch rate decreases by a factor of 1.5 at samples deposited at 1000 W when lowering the temperature of the etchant from 90 °C to 60 °C. These results indicate an enhanced film density at higher P_p values as the microstructure of the Al₂O₃ films is X-ray amorphous independent of plasma power and post-deposition annealing temperatures up to 650 °C.     

Annealing driven performance and optical effects in nanocrystalline SnO2 thin films induced by pulsed delivery

Tin dioxide thin films were prepared successfully by pulsed laser deposition techniques on glass substrates. The thin films were then annealed for 30 min from 50 °C to 550 °C at 50 °C intervals. The influence of the annealing temperature on the microstructure and optical properties of SnO₂ thin films was investigated using X-ray diffraction, optical transmittance and reflectance measurements. Various optical parameters, such as optical band gas energy, refractive index and optical conductivity were calculated from the optical transmittance and reflectance data recorded in the wavelength range 300-2500 nm. We found that the SnO₂ thin film annealed at temperatures up to 400 °C is a good window material for solar cell application. Our experimental results indicated that SnO₂ thin films with the high optical quality could be synthesized by pulsed laser deposition techniques.     

Preparations and characterizations of polycrystalline PbSe thin films by a thermal reduction method

Polycrystalline PbSe thin films were deposited on Si substrates by a thermal reduction method with the carbon as the reducing agent. The X-ray diffraction (XRD) spectra show that the deposited thin films predominately crystallize with the rock-salt structures above the evaporation temperature of 600 °C, and the PbSe thin film has the optimal crystal quality at 900 °C. The scanning electron microscopy (SEM) measurements reveal that the PbSe thin film with carbon addition has uniform crystal grain sizes and dense microstructure, while the thin film without carbon consists of loosely distributed and widely size-ranged crystal grains. The optical transmittance spectrum shows that the direct band gap of the PbSe film is about 0.256 eV. By the introduction of element S, PbSe_1−xS_x (0 ≤ x ≤ 1.0) thin films could be prepared, but excess amount of S additions (>20 at.%) would cause phase segregations between PbSe and PbS phases. The deposition method presented in this paper may be useful for mass-producing polycrystalline lead chalcogenide thin films in the future.     

Photoelectrochemical investigations of cadmium sulphide (CdS) thin film electrodes prepared by spray pyrolysis

Polycrystalline cadmium sulphide (CdS) thin films have been prepared by spraying a mixture of an equimolar aqueous solutions of cadmium chloride and thiourea on preheated fluorine doped tin oxide (FTO) coated glass substrates at different substrate temperatures. The cell configurations n-CdS/1 M (NaOH + Na₂S + S)/C were used for studying the capacitance-voltage (C-V) characteristics in dark, current-voltage (I-V) characteristics in dark and under illumination, photovoltaic power output and spectral response characteristics of the as deposited thin films. Photoelectrochemical study shows that as deposited CdS thin films exhibits n-type of conductivity. The spectral response characteristics of the films at room temperature show a prominent sharp peak at 500 nm leading to optical bandgap energy of 2.48 eV. It is found that fill factor and efficiency are maximum for photoelectrode deposited at 300 °C. This is due to low resistance; high flat band potential, maximum open circuit voltage as well as maximum short-circuit current. The measured values of efficiency (η) and fill factor (FF) are found to be 0.17% and 0.38 respectively for film deposited at 300 °C.     

Constitution, microstructure, and battery performance of magnetron sputtered Li-Co-O thin film cathodes for lithium-ion batteries as a function of the working gas pressure

Li-Co-O thin film cathodes have been deposited onto Si and stainless steel substrates by RF magnetron sputtering from a ceramic LiCoO₂ target at various working gas pressures from 0.15 to 25 Pa. Composition, crystal structure and thin film morphology were examined and properties such as intrinsic stress, conductivity and film density were determined. As-deposited films at 0.15 Pa as well as in the range between 5 Pa and 10 Pa working gas pressure showed a nanocrystalline metastable rocksalt structure with disordered cation arrangement and were nearly stoichiometric. To induce a cation ordering the films were annealed in a furnace at temperatures between 100 and 600 °C for 3 h in argon/oxygen atmosphere (Ar:O₂ = 4.5:5) of 10 Pa. This cation ordering process was observed by XRD and Raman spectroscopy. For the films deposited at 10 Pa gas pressure an annealing temperature of 600 °C leads to the formation of the high temperature phase HT-LiCoO₂ with a layered structure. The Raman spectrum of the films deposited at 0.15 Pa and annealed at 400 °C indicates the formation of the low temperature phase LT-LiCoO₂ with a cubic spinel-related structure, which is assumed to be stabilized due to high compressive stress in the film. The electrochemical characterisation of annealed thin film cathodes revealed that the discharge capacity strongly depends on the crystal structure. Thin Li-Co-O films with a perfect layered HT-LiCoO₂ structure showed the highest discharge capacities.     

Fabrication and characterization of ITO thin films on heat-resistant transparent flexible clay films

Transparent conductive indium tin oxide (ITO) thin films were deposited on transparent flexible clay films with heat resistant and high gas barrier properties by rf magnetron sputtering. The electrical, structural, and optical properties of these films were examined as a function of deposition temperature. A lowest resistivity of 4.2 × 10^− 4 Ωcm and an average transmittance more than 90% in the visible region were obtained for the ITO thin films fabricated at deposition temperatures more than 300 °C. It was found that ITO thin films with low resistivity and high transparency can be achieved on transparent flexible clay film using conventional rf magnetron sputtering at high temperature, those characteristics are comparable to those of ITO thin films deposited on a glass substrate.     

Fabrication of GdBa2Cu3O7−x films by TFA-MOD process

GdBa₂Cu₃O_7−x (GdBCO) films have been deposited on LaAlO₃ (LAO) (0 0 l) single crystal substrates by trifluoroacetate metal organic deposition (TFA-MOD) method. The effects of oxygen partial pressure and firing temperature on microstructure and critical properties of GdBCO films were discussed. The phase formation, texture and microstructure of films were characterized by X-ray diffraction and scanning electron microscopy. The oxygen partial pressure was considered to play a great role for formation of impurity phase and a-axis oriented grains. The degree of c-axis orientation was also influenced by the firing temperature. The highly c-axis oriented GdBCO film obtained at 815 °C under an oxygen partial pressure of 100 ppm has a high performance critical current density J_c (77 K, self field) = 1.8 MA/cm².     

Structural and optical properties of electrodeposited ZnO thin films on conductive RuO2 oxides

ZnO thin films were grown on the 150 nm-thick RuO₂-coated SiO₂/Si substrates by electrochemical deposition in zinc nitrate aqueous solution with various electrolyte concentrations and deposition currents. Crystal orientation and surface structure of the electrodeposited ZnO thin films were characterized by X-ray diffraction (XRD) and scanning electron microscopy, respectively. The XRD results show the as-electrodeposited ZnO thin films on the RuO₂/SiO₂/Si substrates have mixed crystallographic orientations. The higher electrolyte concentration results in the ZnO thin films with a higher degree of c-axis orientation. Moreover, the use of an ultra-thin 5 nm-thick ZnO buffer layer on the RuO₂/SiO₂/Si substrate markedly improves the degree of preferential c-axis orientation of the electrodeposited ZnO crystalline. The subsequent annealing in vacuum at a low temperature of 300 °C reduces the possible hydrate species in the electrodeposited films. The electrodeposited ZnO thin films on the 5 nm-thick ZnO buffered RuO₂/SiO₂/Si substrates grown in 0.02 M electrolyte at −1.5 mA with a subsequent annealing in vacuum at 300 °C had the best structural and optical properties. The UV to visible emission intensity ratio of the film can reach 7.62.     

Variation of microstructure and composition of the Cr2AlC coating prepared by sputtering at 370 and 500 °C

Cr₂AlC coating was deposited at 370 and 500 °C by D.C. magnetron sputtering from an as-synthesized bulk Cr₂AlC target. The phase composition and preferential orientation of the coating were investigated using XRD, and the microstructure of the coating was characterized by TEM. Results indicated that Cr₂AlC coating with a strong (110) preferential orientation could be obtained. The coating microstructure was clearly affected by the deposition temperature. At 370 °C, the deposited coating possessed a triple-layered structure with an α-(Cr, Al)₂O₃ inner layer, an amorphous intermediate layer and a crystalline Cr₂AlC outer layer. However, the coating deposited at 500 °C had a single-layered structure consisting of crystalline Cr₂AlC layer. The growth mechanism of the Cr₂AlC coating at different deposition temperatures is discussed.     

Effect of annealing temperature on the structure and optical properties of sputtered TiO2 films

TiO₂ thin films were deposited by DC reactive magnetron sputtering. Some TiO₂ thin films samples were annealed for 5 min at different temperatures from 300 to 900 °C. The structure and optical properties of the films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and ultraviolet-visible (UV-vis) spectrophotometry, respectively. The influence of the annealing temperature on the structure and optical properties of the films was investigated. The results show that the as-deposited TiO₂ thin films are mixtures of anatase and rutile phases, and possess the column-like crystallite texture. With the annealing temperature increasing, the refractive index and extinction coefficient increase. When the annealing temperature is lower than 900 °C, the anatase phase is the dominant crystalline phase; the weight fraction of the rutile phase does not increase significantly during annealing process. As the annealing temperature rises to 900 °C, the rutile phase with the large extinction coefficient becomes the dominant crystalline phase, and the columnar structure disappears. The films annealed at 300 °C have the best optical properties for the antireflection coatings, whose refractive index and extinction coefficient are 2.42 and 8 × 10⁻⁴ (at 550 nm), respectively.     

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.     

Effects of growth temperature on structure and electrical properties of dielectric (Ba,Sr)TiO3 capacitors with transparent conducting oxide electrodes

200 nm-thick BST thin films were grown on Zr-doped In₂O₃/SrTiO₃ (1 0 0) substrates at 550-750 °C. X-ray diffraction results show that the as-deposited BST films were polycrystalline with random crystallographic orientations. X-ray diffraction patterns reveal that the BST film grown at 650 °C had the best crystalline quality of all the deposition temperatures. Atomic force microscopy and secondary ion mass spectrometry showed that the surface and interface structures of the BST films became rough as the growth temperature increased. The BST film grown at 650 °C showed the best electrical properties, with a dielectric constant of 420 at 1 MHz, dielectric tunability of 32.1%, dielectric loss of 0.015 at 300 kV/cm, and a mean optical transmittance in visible wavelength of 71.3%.     

Application of Bu2Sn(acac)2 for the deposition of nanocrystallite SnO2 films: Nucleation, growth and physical properties

High-quality uniform SnO₂ thin films were successfully prepared by pulsed-spray evaporation chemical vapor deposition (PSE-CVD) method, using a cost-efficient precursor of ⁿBu₂Sn(acac)₂. The volatility and stability of ⁿBu₂Sn(acac)₂ were studied through thermogravimetric-differential thermal (TG-DTA) analysis and mass spectrometry, indicating the good adaptability for the CVD process. Deposition of SnO₂ films was made in the range of 250-450 °C to investigate the effect of substrate temperature on their structural and physical properties. The film growth activation energy changes from 66.5 kJ/mol in the range of 250-330 °C to 0 kJ/mol at 330-450 °C, suggesting the change of the rate-limiting step from surface kinetics to diffusion control. All films possess the rutile-type tetragonal structure, while a change of preferred orientation from (1 1 0) to (1 0 1) plane is observed upon the increase of the deposition temperature. The different variation of the nucleation and growth rates with the deposition temperature is proposed to explain the observed unusual change of crystallite size. A significant deterioration of the electrical conductivity was observed upon the increase of the deposition temperature, which was tentatively attributed to the non-specific decomposition of the precursor at high temperature leading to carbon contamination. Optical measurements show transparencies above 80% in the visible spectral range for all films, while band gap energy increases from 4.02 eV to 4.08 eV when the deposition temperature was raised from 250 °C to 450 °C.     

High temperature tribological characterisation of TiAlSiN coatings produced by cathodic arc evaporation

This study reports on the wear properties at medium-high temperatures of TiAlSiN films deposited by cathodic arc evaporation on hot work steel substrates. The chemical composition and microstructure of the coatings were characterised by glow discharge optical emission spectroscopy, scanning electron microscopy and X-ray diffraction. The mechanical properties, i.e. hardness and elastic modulus were evaluated by nanoindentation, and the adhesion of the coatings was tested by scratch tests. Coatings with stoichiometries of Ti_0.31Al_0.1Si_0.06N_0.53 and Ti_0.23Al_0.12Si_0.09N_0.55 exhibit microstructures consisting of solid solutions of (Ti,Al,Si)N, where Al and Si replace Ti atoms. These films show high hardness and good adhesion strength to the hot work steels. Conversely, coatings with a stoichiometry of Ti_0.09Al_0.34Si_0.02N_0.55 show a wurtzite-like microstructure, low hardness and poor adhesion strength.The wear rates of the coatings were investigated by ball-on-disc experiments at room temperature, 200 °C, 400 °C and 600 °C, using alumina balls as counter surfaces. At room temperature, the films show wear rates of the same order of magnitude of TiN and TiAlN coatings. On the other hand, the wear rates of solid solution (Ti,Al,Si)N coatings measured at 200, and 400 °C are one order of magnitude smaller than those measured at room temperature due to the formation of oxide-containing tribofilms on the wear tracks. At 600 °C the wear rates increase but still keep smaller than those measured at room temperature, although this effect can be influenced by the softening of the steel substrates by over-tempering. EDS analyses revealed that, between 200 °C and 400 °C, the oxidation of the coating occurs only at the contact zone between the film and the counterpart body due to the sliding process.     

Doping and annealing effects on ZnO:Cd thin films by sol-gel method

In this article, ZnO:Cd films were successfully deposited on glass substrates by a sol-gel technique. The influence of doping concentration and annealing temperature effects was carefully investigated. All films exhibited c-axis preferential orientation and optical transparency with visible transmittance >80%. The minimum room temperature resistivity of 0.0341 Ω cm was obtained with 10 at.% Cd doping under 600 °C annealing temperature. The optical band gap of ZnO:Cd film was reduced as Cd doping concentration increased, while the band gap increased with the increase of annealing temperature.     

P-type transparent conducting SnO2:Zn film derived from thermal diffusion of Zn/SnO2/Zn multilayer thin films

Highly transparent, p-type conducting SnO₂:Zn thin films are prepared from the thermal diffusion of a sandwich structure of Zn/SnO₂/Zn multilayer thin films deposited on quartz glass substrate by direct current (DC) and radio frequency (RF) magnetron sputtering using Zn and SnO₂ targets. The deposited films were annealed at various temperatures for thermal diffusion. The effect of annealing temperature and time on the structural, electrical and optical performances of SnO₂:Zn films was studied. XRD results show that all p-type conducting films possessed polycrystalline SnO₂ with tetragonal rutile structure. Hall effect results indicate that the treatment at 400 °C for 6 h was the optimum annealing parameters for p-type SnO₂:Zn films which have relatively high hole concentration and low resistivity of 2.389 × 10¹⁷ cm^− 3 and 7.436 Ω cm, respectively. The average transmission of the p-type SnO₂:Zn films was above 80% in the visible light range.     

Ultrathin films of co-sputtered CrZrx alloys on polymeric substrates

This experimental study combines the research topics of ultrathin films on polymeric substrates with binary transition metal alloys. Chrome zirconium (CrZr_x), ca. 60 nm, was co-sputtered onto pre-coated polymeric substrates having a glass transition temperature below 150 °C. As a consequence of this, the ultrathin films are deposited under vacuum at temperatures below 100 °C, over time frames of only 1 to 2 min. For the ultrathin CrZr_x alloy films we report the coexistence of the body centred cubic and Ω-hexagonally close packed phase within a narrow Zr concentration range. The influence of this atomic structure, in combination with the electron structure of the ultrathin CrZr_x film, on the optical and mechanical performance is investigated. Results show the change in structure with elemental composition correlates with variations in the molecular orbital filling of the atoms, thus yielding changes in the optical reflectivity and the resistance to abrasion.     

Combustion chemical vapour deposition of Al2O3 films: Effect of temperature on structure, morphology and adhesion

Alumina films were synthesized on Si(100) substrates at different temperatures in the range of 600 to 900 °C using open atmosphere combustion chemical vapour deposition (C-CVD) technique. A custom made premixed-diffusion type burner with an extra coaxial oxygen inlet close to the burner mouth enabled variation of deposition temperature from 600 to 900 °C in steps of 100 (± 10) °C. The presence of γ- and θ-alumina phases were observed in films synthesized in the temperature range of 600-800 °C, whereas at 900 °C single phase θ-alumina films were obtained. Adherent coatings were obtained at temperatures ≥ 700 °C. The grain size and roughness of the films increased with deposition temperature. The films underwent two types of adhesion failures, a continuous ductile perforation and a tensile type hertzian crack due to the presence of interfacial oxide layer, during scratch test. The presence of SiO₂ interfacial layer between substrate and film was discerned from ellipsometric studies.     

Characterization of nanostructured Cr2Nx/Cu multilayers deposited by reactive DC magnetron sputtering

Nitride/metal nanostructured multilayers of Cr₂N_x/Cu were deposited by reactive DC magnetron sputtering with various bilayer periods (2.5-30 nm) and substrate temperatures (25-400 °C). All films had a total thickness of about 470 nm and the overall chemical composition of the chromium nitride layers was close to Cr₂N_0.8. The deposited films were characterized by Rutherford Backscattering (RBS), low-angle X-ray reflectivity (XRR), high-angle X-ray diffraction (XRD) and transmission electron microscopy (TEM). The hardness and elastic modulus were measured by nanoindentation. The films deposited at 25 °C had a well-defined multilayer structure and the chromium nitride layers were found to crystallize into N-deficient fcc CrN_0.4 with traces of hexagonal Cr₂N_0.8. The layers were strongly textured with fcc CrN_0.4[002] and Cu[002] oriented along the growth direction — the fcc CrN_0.4 and Cu grains growing with a cube-on-cube relationship. The measured hardness values were about 8 GPa, and showed no dependence on the bilayer period. Higher deposition temperatures caused the multilayer structure to degrade, and at 400 °C the films were better described as non-textured nanocomposites with the chromium nitride crystallized entirely into the equilibrium hexagonal Cr₂N_0.8 structure. Hardness values of the high-temperature films in the range of 4-8 GPa were measured. Multilayer films deposited at 25 °C were found to be thermally stable against post-deposition annealing at temperatures up to about 400 °C. Annealing at 500 °C caused severe structural changes — the fcc CrN_0.4 phase transformed into hexagonal Cr₂N_0.8 accompanied by degradation of the periodic multilayer structure. The hardness decreased from the originally 8 GPa to about 5 GPa upon annealing.