Effect of deposition temperature on structural, surface, optical and magnetic properties of pulsed laser deposited Al-doped CdO thin films

The objective of this work is to study the influence of deposition temperature on structural, surface, optical and magnetic properties of the Al doped CdO thin films prepared by pulsed laser deposition (PLD) technique. KrF excimer laser (λ = 248 nm, τ_l = 20 ns, ν = 10 Hz, ?_l = 2.5 J/cm²) was employed for the deposition of thin films. It is observed by XRD results that films grown at room temperature and 100 °C show preferential growth along (1 1 1) and (2 0 0) directions while high temperatures (200-400 °C) lead to preferential growth along the (2 0 0) direction only. The optical constants (n, k, α, and optical band gap energy) of films measured by spectroscopic ellipsometry show strong dependence upon deposition temperature. M-H loop of films, measured by vibrating sample magnetometer, deposited at 25 °C and 100 °C show paramagnetic nature while films deposited at temperatures (200-400 °C) exhibit ferromagnetic character. Scanning electron micrographs show degraded elongated grains at lower deposition temperatures, while smooth and compact surface is observed for films deposited at higher deposition temperatures.     

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.     

Structural, optical and electrical properties of In-doped Cd2SnO4 thin films by spray pyrolysis method

Preparation of highly conducting and transparent In-doped Cd₂SnO₄ thin film by spray pyrolysis method at a substrate temperature of 525 °C is reported. In-doping concentration is varied between 1 and 5 wt.%. The effect of In-doping on structural, optical and electrical properties was investigated using different techniques such as X-ray diffraction, atomic force microscopy, optical transmittance and Hall measurement. X-ray diffraction studies revealed that the films are polycrystalline with cubic crystal structure. The undoped and In-doped Cd₂SnO₄ films exhibit excellent optical transparency. The average optical transmittance is ∼87% in the visible range for 3 wt.% In-doping. Further In-doping widens the optical band gap from 2.98 ± 0.1 eV to 3.04 ± 0.1 eV. A minimum resistivity of 1.76 ± 0.2 × 10⁻³ Ω cm and maximum carrier concentration of 9.812 ± 0.4 × 10¹⁹ cm⁻³ have been achieved for 1 wt.% In-doping in Cd₂SnO₄ thin films.     

Yttria-stabilized zirconia thin films deposited by pulsed-laser deposition and magnetron sputtering

Yttria-stabilized zirconia (YSZ, ZrO₂:Y₂O₃) was deposited on (100) silicon by two physical vapor deposition techniques: pulsed laser deposition (PLD) and reactive magnetron sputtering (RMS). PLD thin films were grown on silicon substrates at 500 °C from the ablation of a 8YSZ ceramic target by a KrF excimer laser. RMS thin films were obtained by direct current magnetron sputtering of a Zr/Y metallic target in an oxygen/argon atmosphere. The deposition rate of the PLD technique using an UV excimer laser delivering pulses at a repetition rate of 40 Hz was found two orders of magnitude lower than the RMS method one. Both techniques led to the growth of crystalline films with a (111) preferential orientation. PLD films were dense and featureless whereas RMS ones exhibited well defined but compact columnar structure. Growth of a YSZ film of about 1 μm covering a rough and porous commercial anode support (NiO-YSZ cermet) was successfully carried out with both methods.     

Defect evolution of nanocrystalline SnO2 thin films induced by pulsed delivery during in situ annealing

The microstructural defects of nanocrystalline SnO₂ thin films prepared by pulsed laser deposition have been investigated using transmission electron microscopy, high-resolution transmission electron microscopy and Raman spectroscopy. Defects inside nanocrystalline SnO₂ thin films could be significantly reduced by in situ annealing SnO₂ thin films at 300 °C for 2 h. High-resolution transmission electron microscopy showed that the stacking faults and twins were annihilated upon in situ annealing. In particular, the inside of the SnO₂ nanoparticles demonstrated perfect lattices free of defects after in situ annealing. Raman spectra also confirmed that the in situ annealed specimen was almost defect-free. By using in situ annealing, defect-free nanocrystalline SnO₂ thin films can be prepared in a simple and practical way, which holds the promise for applications as transparent electrodes and solid-state gas sensors.     

Epitaxial 0.65PbMg1/3Nb2/3O3-0.35PbTiO3 (PMN-PT) thin films grown on LaNiO3/CeO2/YSZ buffered Si substrates

Ferroelectric PMN-PT thin films with a thickness of 600 nm were epitaxially grown on buffered Si (0 0 1) substrates at a substrate temperature that ranged from 550 to 700 °C using pulsed laser deposition (PLD). LaNiO₃ (LNO) electrode thin films with a resistivity of ∼1900 μΩ cm were epitaxially grown on CeO₂/YSZ buffered Si (0 0 1) substrates. The PMN-PT thin films grown at 600 °C on LNO/CeO₂/YSZ/Si substrates had a pure perovskite and epitaxial structure. The PMN-PT films exhibited a high dielectric constant of about 1818 and a low dissipation factor of 0.04 at a frequency of 10 kHz. Polarization-electric-field (P-E) hysteresis characteristics, with a remnant polarization of 11.1 μC/cm² and a coercive field of 43 kV/cm, were obtained in the epitaxial PMN-PT films.     

Microstructure and grain growth kinetics of nanocrystalline SnO2 thin films prepared by pulsed laser deposition

The isothermal grain growth of SnO₂ thin films prepared by pulsed laser deposition techniques was investigated at Si (100) substrate temperatures between 300 and 450 °C with 50 °C intervals for different annealing times. X-ray diffraction patterns proved that the average grain sizes are in the range of 2.4–27.8 nm. The grain growth data were analyzed using two different models. The first model, assuming normal grain growth as that in conventional polycrystalline materials, yields large grain growth exponent (n) and extremely low activation energy (Q). Although it can describe the evolution of grain sizes, it fails to give satisfactory physical interpretation of n and Q, both beyond the theoretical predictions. The second model is based on the structural relaxation of the interface component in nanocrystalline materials. In this case, the ordering of distorted interfaces by structural relaxation proceeds with grain growth. This structure relaxation model not only describes the evolutions of grain growth well, but also makes reasonable attribution of the low activation energy to the short-range rearrangement of atoms in the interface region as well.     

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.     

Epitaxial growth of tin ferrite thin films using pulsed laser deposition technique

Epitaxial thin films of tin ferrite (SnFe₂O₄) were deposited on (0 0 2) oriented strontium titanate (SrTiO₃) substrate using pulsed laser deposition method. The quality and epitaxial nature of the films were investigated by X-ray diffraction technique. The phi scan of the film and the substrate shows four folds symmetry indicating cube-on-cube epitaxial growth of the film on the substrate. The optical bandgap of the film was estimated to be 2.6 eV using optical transmittance data. Magnetic measurements indicate that the coercive field and remnant magnetization of the film decrease with increase in temperature. The presence of hysteresis loop in M vs. H plot at room temperature indicates the ferromagnetic nature of the film.     

Effect of annealing on pulsed laser deposited zirconium oxide thin films

Zirconium oxide thin films were deposited using pulsed laser ablation from a ceramic ZrO₂ target on unheated substrates. Subsequently, the films were annealed in air in the temperature range 400-800 °C. The films were characterized by X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and optical spectroscopy to investigate the variation of the structural, chemical, and optical properties upon annealing. As-deposited films were amorphous and had a large surface density of ablated particles. Annealing resulted in the growth of monoclinic nano-crystalline, uniform, and transparent films that were slightly sub-stoichiometric. The annealed films were compact and had high values of the refractive index. Extinction coefficients were small, and may be related to the presence of defects. The films exhibited the presence of an indirect band gap, related to defects, and a direct band gap, related to fundamental absorption.     

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.     

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%.     

Synthesis and characterization of Cu2ZnSnS4 thin films grown by PLD: Solar cells

As-deposited and annealed Cu₂ZnSnS₄ (CZTS) thin films have been synthesized onto Mo coated glass substrates at different deposition times using pulsed laser deposition (PLD) technique. The effect of deposition time (film thickness) and annealing onto the structural, morphological, compositional and optical properties of CZTS thin films have been investigated. The polycrystalline CZTS thin films with tetragonal crystal structure have been observed from structural analysis. FESEM and AFM images show the smooth, uniform, homogeneous and densely packed grains and increase in the grain size after annealing. The internal quantitative analysis has been carried out by XPS study which confirms the stoichiometry of the films. The optical band gap of CZTS films grown by PLD is about 1.54 eV, which suggests that CZTS films can be useful as an absorber layer in thin film solar cells. Device performance for deposited CZTS films has been studied.     

Effect of lanthanum doping on linear and nonlinear-optical properties of Bi3TiNbO9 thin films

Lanthanum doped Bi₃TiNbO₉ thin films (LBTN-x, La³⁺ contents x = 5%, 15%, 25% and 35 mol.%) with layered perovskite structure were fabricated on fused silica by pulsed laser deposition method. Their linear and nonlinear optical properties were studied by transmittance measurement and Z-Scan method. All films exhibit good transmittance (>55%) in visible region. For lanthanum doping content are x = 5%, 15% and 25 mol.%, the nonlinear absorption coefficient of LBTN-x thin films increases with the La³⁺ content, then it drops down at x = 35 mol.% when the content of La³⁺ in (Bi₂O₂)²⁺ layers is high enough to aggravate the orthorhombic distortion of the octahedra. We found that, 25 mol.% is the optimal La³⁺ content for LBTN-x thin films to have the largest nonlinear absorption coefficient making the LBTN-x film a promising candidate for absorbing-type optical device applications.     

Structural, optical and electrical properties of CuIn5S8 thin films grown by thermal evaporation method

Stoichiometric compound of copper indium sulfur (CuIn₅S₈) was synthesized by direct reaction of high purity elemental copper, indium and sulfur in an evacuated quartz tube. The phase structure of the synthesized material revealed the cubic spinel structure. The lattice parameter (a) of single crystals was calculated to be 10.667 Å. Thin films of CuIn₅S₈ were deposited onto glass substrates under the pressure of 10⁻⁶ Torr using thermal evaporation technique. CuIn₅S₈ thin films were then thermally annealed in air from 100 to 300 °C for 2 h. The effects of thermal annealing on their physico-chemical properties were investigated using X-ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM), optical transmission and hot probe method. XRD studies of CuIn₅S₈ thin films showed that as-deposited films were amorphous in nature and transformed into polycrystalline spinel structure with strong preferred orientation along the (3 1 1) plane after the annealing at 200 °C. The composition is greatly affected by thermal treatment. From the optical transmission and reflection, an important absorption coefficient exceeds 10⁴ cm⁻¹ was found. As increasing the annealing temperature, the optical energy band gap decreases from 1.83 eV for the as-deposited films to 1.43 eV for the annealed films at 300 °C. It was found that CuIn₅S₈ thin film is an n-type semiconductor at 300 °C.     

Study of post annealing influence on structural, chemical and electrical properties of ZTO thin films

Zinc-Tin-Oxide (ZTO) thin films were deposited on glass substrate with varying concentrations (ZnO:SnO₂; 100:0, 90:10, 70:30 and 50:50 wt.%) at room temperature by flash evaporation technique. These deposited ZTO films were annealed at 450 °C in vacuum. These films were characterized to study the effect of annealing and addition of SnO₂ concentration on the structural, chemical and electrical properties. The XRD analysis indicates that crystallization of the ZTO films strongly depends on the concentration of SnO₂ and post annealing where annealed films showed polycrystalline nature. Atomic force microscopy (AFM) images manifest the surface morphology of these ZTO thin films. The XPS core level spectra of Zn(2p), O(1s) and Sn(3d) have been deconvoluted into their Gaussian component to evaluate the chemical changes, while valence band spectra reveal the electronic structures of these films. A small shift in Zn(2p) and Sn(3d) core level towards higher binding energy and O(1s) core level towards lower binding energy have been observed. The minimum electrical resistivity (ρ ≈ 3.69 × 10⁻² Ω-cm), maximum carrier concentration (n ≈ 3.26 × 10¹⁹ cm⁻³) and Hall mobility (μ ≈ 5.2 cm² v⁻¹ s⁻¹) were obtained for as-prepared ZTO (50:50) film thereafter move towards lowest resistivity (ρ ≈ 1.12 × 10⁻³ Ω-cm), highest carrier concentration (n ≈ 2.96 × 10²⁰ cm⁻³) and mobility (μ ≈ 18.8 cm² v⁻¹ s⁻¹) for annealed ZTO (50:50) thin film.     

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.     

Filtered vacuum arc deposition of undoped and doped ZnO thin films: Electrical, optical, and structural properties

Filtered vacuum (cathodic) arc deposition (FVAD, FCVD) of metallic and ceramic thin films at low substrate temperature (50-400 °C) is realized by magnetically directing vacuum arc produced, highly ionized, and energetic plasma beam onto substrates, obtaining high quality coatings at high deposition rates. The plasma beam is magnetically filtered to remove macroparticles that are also produced by the arc. The deposited films are usually characterized by their good optical quality and high adhesion to the substrate. Transparent and electrically conducting (TCO) thin films of ZnO, SnO₂, In₂O₃:Sn (ITO), ZnO:Al (AZO), ZnO:Ga, ZnO:Sb, ZnO:Mg and several types of zinc-stannate oxides (ZnSnO₃, Zn₂SnO₄), which could be used in solar cells, optoelectronic devices, and as gas sensors, have been successfully deposited by FVAD using pure or alloyed zinc cathodes. The oxides are obtained by operating the system with oxygen background at low pressure. Post-deposition treatment has also been applied to improve the properties of TCO films.The deposition rate of FVAD ZnO and ZnO:M thin films, where M is a doping or alloying metal, is in the range of 0.2-15 nm/s. The films are generally nonstoichiometric, polycrystalline n-type semiconductors. In most cases, ZnO films have a wurtzite structure. FVAD of p-type ZnO has also been achieved by Sb doping. The electrical conductivity of as-deposited n-type thin ZnO film is in the range 0.2-6 × 10^− 5 Ω m, carrier electron density is 10²³-2 × 10²⁶ m^− 3, and electron mobility is in the range 10-40 cm²/V s, depending on the deposition parameters: arc current, oxygen pressure, substrate bias, and substrate temperature. As the energy band gap of FVAD ZnO films is ∼ 3.3 eV and its extinction coefficient (k) in the visible and near-IR range is smaller than 0.02, the optical transmission of 500 nm thick ZnO film is ∼ 0.90.     

Low temperature sputter deposition of SnOx:Sb films for transparent conducting oxide applications

SnO_x:Sb films have been prepared by reactive dc magnetron sputtering from a metallic target, with the aim of evaluating the potential of SnO_x:Sb as an attractive low-cost alternative to In₂O₃:Sn (ITO) for TCO applications. The deposition was performed without any additional heating of the substrates. The films were subsequently analysed regarding their optical, electrical and structural properties. Our results show that there is only a narrow process window for the sputter deposition of transparent and conducting tin oxide films at low temperature. A sharp minimum in resistivity of 4.9 mΩ cm is observed at an oxygen content of approximately 17% in the sputtering gas. Under these deposition conditions, the SnO₂:Sb films turn out to be both highly transparent and crystalline. At lower oxygen content (10-15%) the SnO_x:Sb films are substoichiometric, as revealed by Rutherford backscattering, and show a low transmission and high resistivity due to numerous defects and the presence of the SnO phase. At higher oxygen content (> 17%) excess oxygen is incorporated into the films, which is attributed to an increase of oxygen ion bombardment. This leads to a degradation of the electrical properties and a decrease of the density of the films, whilst the optical transmittance slightly improves.     

Elaboration and characterization of Al doped ZnO nanorod thin films annealed in hydrogen

ZnO thin films doped with Al concentrations of 1.0, 2.0, 3.0, 4.0, 5.0 at% were prepared by a sol-gel spin-coating method on glass substrates and respectively annealed at 550 °C for 2 h in hydrogen and air. The X-ray diffraction and selected-area electron diffraction results confirm that the Al doped ZnO thin films are of wurtzite hexagonal ZnO. The scanning electron microscope results indicate that the Al doped ZnO nanorod thin films can be got by annealing in hydrogen rather than in air. The optical properties reveal that the Al doped ZnO thin films have obviously enhanced transmittance in the visible region. The electrical properties show that the resistivity of 1.0 at% Al doped ZnO thin films has been remarkably reduced from 0.73 Ω m by annealing in air to 3.2 × 10⁻⁵ Ω m by annealing in hydrogen. It is originated that the Al doped ZnO nanorod thin films annealed in hydrogen increased in electron concentration and mobility due to the elimination of adsorbed oxygen species, and multicoordinated hydrogen.