Effect of annealing atmosphere (Ar vs. air) and temperature on the electrical and optical properties of spin-coated colloidal indium tin oxide films

Colloidal indium tin oxide (ITO) ~6 nm nanoparticles synthesized in-house were deposited by spin coating on fused silica substrates, resulting in high resistivity films due to the presence of passivating organics. These films were annealed at various temperatures ranging from 150 to 750 °C in air and argon atmospheres. The films are very transparent in the as-coated form, and they retain high transparency upon annealing, except the films annealed at 300 °C in argon, which became brown due to incomplete pyrolysis of the organics. Thermogravimetric analysis and Raman characterization showed that the removal of organics increases with an increase in the annealing temperature, and that this removal is more efficient in the oxidizing atmosphere of air, especially in the 300–450 °C temperature range than in Ar. Although ITO defect chemistry suggests that argon annealing should result in higher carrier concentration than air annealing, the faster removal of insulating organics upon annealing in air resulted in significantly lower film resistivity at intermediate annealing temperatures for films annealed in air than in Ar. At higher annealing temperatures, both Ar and air annealing, resulted in comparable film resistivities (the lowest achieved was ~10⁰ Ω cm).     

Zinc vacancy mediated structural phase transition and photoluminescence in nanocrystalline ZnS thin films

Nanocrystalline thin films of zinc sulphide were prepared on glass substrate at various deposition temperatures by thermal evaporation technique. The variation of the structural and optical properties of films deposited at various substrate temperatures was investigated in detailed. X-ray diffraction spectra showed that films deposited at 300 and 400 °C are polycrystalline in nature having cubic and both cubic and wurtzite structure, respectively. However, film deposited at temperature of 200 °C was found to be amorphous in nature. The ultra-violet and visible absorption studies showed that the band gap of films increases with increase in deposition temperatures. Photoluminescence spectra displayed emission near 396 and 444 nm, which arises due to zinc vacancies and sulphur vacancies, respectively and has been correlated to phase transition of the films.     

Pulsed laser deposition of NiTi shape memory alloy thin films with optimum parameters

A series of experiments was carried out to optimize the pulsed laser deposition parameters for the fabrication of high quality NiTi shape memory alloy thin films. Smooth NiTi shape memory alloy thin films were deposited at high growth rate with optimum deposition parameters based on the analysis of the relationships among the morphology of the target surface and the deposited thin film, the laser energy, the target–substrate distance, the thin film composition and its growth rate. Crystal structures and phase transformation temperatures of the annealed Ni_49.7Ti_50.3 thin film were characterized by using X-ray diffraction and differential scanning calorimetry, respectively. The martensitic transformation temperature of the crystallized Ni_49.7Ti_50.3 thin film is found to be lower than room temperature and 27°C lower than that of the NiTi target material. These results are attributed to the refined grain size of the thin film and its composition, which deviates slightly from Ni₅₀Ti₅₀.     

Effects of annealing and deposition temperature on the structural and optical properties of AZO thin films

Al-doped ZnO (AZO) thin films were deposited on p- type Si(100) substrate by r.f magnetron sputtering at 200, 300 and 400 °C substrate temperatures. The deposited films were annealed in air atmosphere for 1 h at temperatures of 700, 800 and 900 °C. The deposition temperature and post-deposition annealing effects on structural and optical properties of the AZO samples were analyzed using X-ray diffraction, atomic force microscope and photoluminescence (PL). After annealing, the value of full width half maximum of the diffraction peaks was decreased as well as, the intensity of visible and strong UV PL emission peaks were increased with temperature. However, the deep-level emission related with zinc point defects was removed by annealing of the samples. Results revealed that all of the as-deposited and annealed AZO films have hexagonal structure along (002) direction and their crystallinity were improved with the increased deposition and post-growth annealing temperatures. In addition, the surface roughness and the particle size of the films were increased with increased deposition and annealing temperatures.     

Annealing effects on the structural and optical properties of growth ZnO thin films fabricated by pulsed laser deposition (PLD)

Annealed ZnO thin film at 300, 350, 400, 450 and 500 °C in air were deposited on glass substrate by using pulsed laser deposition. The effects of annealing temperature on the structural and optical properties of annealed ZnO thin films by grazing incident X-ray diffraction (GIXRD), transmittance spectra, and photoluminescence (PL) were investigated. The GIXRD reveal the presence of hexagonal wurtzite structure of ZnO with preferred orientation (002). The particle size is calculated using Debye–Scherrer equation and the average grain size were found to be in the range 5.22–10.61 ± 0.01 nm. The transmittance spectra demonstrate highly transparent nature of the films in visible region (>70 %). The calculation of optical band gap energy is found to be in the range 2.95–3.32 ± 0.01 eV. The PL spectra shows that the amorphous film gives a UV emission only and the annealed films produce UV, violet, blue and green emissions this indicates that the point defects increased as the amorphous film was annealed.     

Synthesis,characterization and gas sensing performance of SnO<Subscript>2</Subscript> thin films prepared by spray pyrolysis

In this work, SnO₂ thin films were deposited onto alumina substrates at 350°C by spray pyrolysis technique. The films were studied after annealing in air at temperatures 550°C, 750°C and 950°C for 30 min. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical absorption spectroscopy technique. The grain size was observed to increase with the increase in annealing temperature. Absorbance spectra were taken to examine the optical properties and bandgap energy was observed to decrease with the increase in annealing temperature. These films were tested in various gases at different operating temperatures ranging from 50–450°C. The film showed maximum sensitivity to H ₂S gas. The H₂S sensing properties of the SnO₂ films were investigated with different annealing temperatures and H ₂S gas concentrations. It was found that the annealing temperature significantly affects the sensitivity of the SnO₂ to the H ₂S. The sensitivity was found to be maximum for the film annealed at temperature 950°C at an operating temperature of 100°C. The quick response and fast recovery are the main features of this film. The effect of annealing temperature on the optical, structural, morphological and gas sensing properties of the films were studied and discussed.     

Growth of Bi1.5MgNb1.5O7 thin films on Pt/Ti/SiO2/Si substrates by RF magnetron sputtering

In this letter, bismuth magnesium niobate (Bi_1.5MgNb_1.5O₇, BMN) thin films were deposited on Pt/Ti/SiO₂/Si substrates by using radio-frequency magnetron sputtering at various substrate temperatures. Based on the phase compositions and microstructures of these samples, we discussed the nucleation and growth of the BMN thin films and how the substrate temperature influenced these processes. The thin film begins to crystallize at 450 °C, and the annealed films were all composed of the cubic pyrochlore phase with a strong (222)-preferred orientation. The film deposited at 450 °C exhibited a large dielectric constant of 173, and a tunability of 26.6 % was obtained at a max dc bias field of 0.8 MV/cm.     

Effect of deposition temperature and thermal annealing on the dry etch rate of a-C: H films for the dry etch hard process of semiconductor devices

The effect of deposition and thermal annealing temperatures on the dry etch rate of a-C:H films was investigated to increase our fundamental understanding of the relationship between thermal annealing and dry etch rate and to obtain a low dry etch rate hard mask. The hydrocarbon contents and hydrogen concentration were decreased with increasing deposition and annealing temperatures. The I(D)/I(G) intensity ratio and extinction coefficient of the a-C:H films were increased with increasing deposition and annealing temperatures because of the increase of sp² bonds in the a-C:H films. There was no relationship between the density of the unpaired electrons and the deposition temperature, or between the density of the unpaired electrons and the annealing temperature. However, the thermally annealed a-C:H films had fewer unpaired electrons compared with the as-deposited ones. Transmission electron microscopy analysis showed the absence of any crystallographic change after thermal annealing. The density of the as-deposited films was increased with increasing deposition temperature. The density of the 600 °C annealed a-C:H films deposited under 450 °C was decreased but at 550 °C was increased, and the density of all 800 °C annealed films was increased. The dry etch rate of the as-deposited a-C:H films was negatively correlated with the deposition temperature. The dry etch rate of the 600 °C annealed a-C:H films deposited at 350 °C and 450 °C was faster than that of the as-deposited film and that of the 800 °C annealed a-C:H films deposited at 350 °C and 450 °C was 17% faster than that of the as-deposited film. However, the dry etch rate of the 550 °C deposited a-C:H film was decreased after annealing at 600 °C and 800 °C. The dry etch rate of the as-deposited films was decreased with increasing density but that of the annealed a-C:H films was not. These results indicated that the dry etch rate of a-C:H films for dry etch hard masks can be further decreased by thermal annealing of the high density, as-deposited a-C:H films. Furthermore, not only the density itself but also the variation of density with thermal annealing need to be elucidated in order to understand the dry etch properties of annealed a-C:H films.     

Properties of electrochemically deposited CdTe thin films: annealing effect

CdTe thin film have been deposited onto stainless steel and fluorine doped tin oxide coated glass substrates from aqueous acidic bath using electrodeposition technique. The different preparative parameters, such as deposition time, bath temperature, pH of the bath have been optimized by photoelectrochemical (PEC) technique get good quality photosensitive material. The deposited films are annealed at different temperature in presence of air. Annealing temperature is also optimized by PEC technique. The film annealed at 200 °C showed maximum photosensitivity. Different techniques have been used to characterize the as deposited and also annealed (at 200 °C) CdTe thin film. The X-ray diffraction (XRD) analysis showed the polycrystalline nature and a significant increase in the XRD peak intensities is observed for the CdTe films after annealing. Optical absorption shows the presence of direct transition with band gap energy 1.64 eV and after annealing it decreases to 1.50 eV. Energy dispersive analysis by X-ray study for the as-deposited and annealed films showed nearly stoichiometric compound formation. Scanning electron microscopy reveals that spherically shaped grains are more uniformly distributed over the surface of the substrate for the annealed CdTe film. Photovoltaic output characteristics and spectral response of the annealed film have been carried. The fill factor and power conversion efficiency (η) of the cell are found to be 71 and 3.89 %.     

Dielectric properties of lead zirconate titanate thin films seeded with barium strontium titanate nanoparticles

A low temperature synthetic method recently proposed by the authors was applied to the fabrication of lead zirconate titanate (PZT) thin films containing crystalline seeds of barium strontium titanate (BST) nanoparticles. PZT precursor and the BST particles were prepared with complex alkoxide methods. Precursor solution suspending the BST particles was spin-coated on Pt/Ti/SiO₂/Si substrate to film thickness of 500–800 nm at particle concentrations of 0–25.1 mol%, and annealed at various temperatures. Seeding of BST particles prevented the formation of pyrochlore phases, which appeared at temperatures above 400 °C in unseeded PZT films, and induced crystallization of PZT into perovskite structures at 420 °C, which was more than 100 °C below the crystallization temperature of the unseeded PZT films. Measurement of dielectric properties at 1 kHz showed that the 25.1 mol% BST-seeded PZT films annealed at 450 °C had a dielectric constant as high as 300 with a dissipation factor of 0.05. Leakage current density of the film was less than 1×10⁻⁶ A/cm² at applied electric field from 0 to 64 kV/cm.     

Effect of oxidation and annealing temperature on optical and structural properties of SnO2

Tin oxide thin films were deposited on glass substrate with 100 nm thickness of Sn, which was coated by magnetron sputtering followed by thermal oxidation at different temperatures. The effect of oxidation temperature on the optical and structural properties of SnO₂ films were investigated. Higher transmittance, lower absorption and lesser structural defects were obtained at higher temperatures. Optical bandgap increases with temperature, while the Urbach energy showed reduction. The X-ray diffraction studies showed that at lower temperatures (300, 350 °C), a combined phase of SnO and SnO₂ was obtained, while at higher temperatures (400, 450 °C), a nearly polycrystalline SnO₂ film with preferred orientation of (101) was produced. Annealing of the samples at 500–650 °C caused the transmittance and optical bandgap increased, while the absorption decreased. Reduction of the Urbach energy after annealing could be attributed to the reduction of the degree of thermal disorder. AFM studies showed that although the thin films were annealed under similar condition, their roughness was not similar because of different oxidation temperatures, which means that initial oxidation temperature played an important role on surface uniformity of SnO₂ thin films.     

Low temperature deposition of hexagonal BN films by chemical vapour deposition

Transparent hexagonal BN films were deposited onto copper substrates from the reactant gas BCl₃-NH₃-H₂ at temperatures in the range 250–700°C. The lowest deposition temperature of the films was about 250°C. The films deposited at temperatures below 450°C were unstable in moist atmosphere and devitrified; a 20%–30% decrease in weight was observed when these films were heated above 600°C in an argon atmosphere. In contrast, the films deposited at temperatures above 600°C were very stable, decreased in weight by 1%–2% on heating and were stable in air at temperatures below 750°C.     

Influence of deposition temperature on the structure and optical properties of HfO2 thin films

Hafnium oxide (HfO₂) thin films were deposited on Si (001) substrates by electron beam evaporation at various growth temperatures. It was found that the film was amorphous when deposited at temperatures lower than 200°C. It was polycrystalline when deposited at 250°C and 300°C. At temperatures above 400°C, it was grown preferably along the [111] direction. The influence of growth temperature on the surface morphology and optical property was also investigated.     

Optical characterization of ZnO thin films deposited by Sol-gel method

In this paper, ZnO thin film is deposited on Pt/TiO₂/SiO₂/Si substrate using the sol-gel method and the effect of annealing temperature on the structural morphology and optical properties of ZnO thin films is investigated. The ZnO thin films are crystallized by the heat treatment at over 400°C. The ZnO thin film annealed at 600°C exhibits the greatest c-axis orientation and the Full-Width-Half-Maximum (FWHM) of X-ray peak is 0.4360°. A dense ZnO thin film is deposited by the growth of uniform grains with the increase of annealing temperature but when the annealing temperature increases to 700°C, the surface morphology of ZnO thin film becomes worse by the aggregation of ZnO particles. In the results of surface morphology of ZnO thin film using atomic force microscope (AFM), the surface roughness of ZnO thin film annealed at 600°C is smallest, that is, approximately 1.048 nm. For the PL characteristics of ZnO thin film, it is observed that ZnO thin film annealed at 600°C exhibits the greatest UV (ultraviolet) exciton emission at approximately 378 nm, and the smallest visible emission at approximately 510 nm among ZnO thin films annealed at various temperatures. It is deduced that ZnO thin film annealed at 600°C is formed most stoichiometrically, since the visible emission at approximately 510 nm comes from either oxygen vacancies or impurities.     

Preparation of ceria films by spray pyrolysis method

The deposition of CeO₂ films on fused-silica substrates by spray pyrolysis of a water–ethanol solution of a cerium nitrate precursor has been studied. Polycrystalline films have been obtained at a substrate temperature of 300–450°C after annealing of the deposit in air at temperatures in the range 350–500°C. It has been established that the best uniform ceria films with nanometric scale grains are prepared at a substrate temperature of 400°C with 0.5 h annealing of the deposit at 500°C. At lower spraying temperatures large CeO₂ crystallites have been observed on the film surface along with the fine grains. When the substrate temperature exceeds 400°C, numerous cracks caused by thermal stresses appear in the films.     

Structural and electrical properties of RuO2 thin films prepared by rf-magnetron sputtering and annealing at different temperatures

Conductive ruthenium oxide (RuO₂) thin films have been deposited at different substrate temperatures on various substrates by radio-frequency (rf) magnetron sputtering and were later annealed at different temperatures. The thickness of the films ranges from 50 to 700 nm. Films deposited at higher temperatures show larger grain size (about 140 nm) with (200) preferred orientation. Films deposited at lower substrate temperature have smaller grains (about 55 nm) with (110) preferred orientation. The electrical resistivity decreases slightly with increasing film thickness but is more influenced by the deposition and annealing temperature. Maximum resistivity is 861 μΩ cm, observed for films deposited at room temperature on glass substrates. Minimum resistivity is 40 μΩ cm observed for a thin film (50 nm) deposited at 540°C on a quartz substrate. Micro-Raman investigations indicate that strain-free well-crystallized thin films are deposited on oxidized Si substrates.     

Effect of annealing on magnetic properties and silicide formation at Co/Si interface

The interaction of Co (30 nm) thin films on Si (100) substrate in UHV using solid state mixing technique has been studied. Cobalt was deposited on silicon substrate using electron beam evaporation at a vacuum of 4×10^?8 Torr having a deposition rate of about 0·1 Å/s. Reactivity at Co/Si interface is important for the understanding of silicide formation in thin film system. In the present paper, cobalt silicide films were characterized by atomic force microscopy (AFM) and secondary ion mass spectroscopy (SIMS) in terms of the surface and interface morphologies and depth profile, respectively. The roughness of the samples was found to increase up to temperature, 300°C and then decreased with further rise in temperature, which was due to the formation of crystalline CoSi₂ phase. The effect of mixing on magnetic properties such as coercivity, remanence etc at interface has been studied using magneto optic Kerr effect (MOKE) techniques at different temperatures. The value of coercivity of pristine sample and 300°C annealed sample was found to be 66 Oe and 40 Oe, respectively, while at high temperature i.e. 748°C, the hysteresis disappears which indicates the formation of CoSi₂ compound.     

Growth and characterization of shape memory alloy thin films for Si microactuator technologies

NiTi thin film alloys have been grown on Si (1 0 0) substrates by sequential multilayer deposition of Ni and Ti layers followed by metal interdiffusion via annealing. Short-time (5 min) annealing of the deposited layers at 500 °C leads to alloying of Ni and Ti, provided that preferential oxidation of Ti is avoided. This has been achieved by capping the layers with AlN, which constitutes a very efficient barrier preventing oxygen contamination of the film. For uncapped films, annealing has to be performed under high vacuum conditions. The structure of the processed films strongly depends on the temperature and time of the thermal process, obtaining Ni- and Ti-rich phases when the films are annealed at higher temperatures and/or during longer times. As-grown and processed films are analyzed by X-ray diffraction, in-depth Auger electron spectroscopy and X-ray photoelectron spectroscopy techniques. Finally, resistivity measurements show the existence of a phase transition in the films annealed at 600 °C without the capping layers (vacuum furnace). This contrasts with the behavior observed for AlN capped films, where cracking of the film occurs during cooling, which has been attributed to generation of stress in the buried film during the phase transition.     

Large and uniform piezoresponse of BiFe0.995W0.005O3 thin film annealed at 450?°C

BiFe_0.995W_0.005O₃ films were epitaxially deposited on LaNiO₃(100)/Si substrates using a metal organic decomposition process at the annealing temperatures below 500?°C. X-ray diffraction measurement reveals that the film can be well crystallized at an annealing temperature as low as 450?°C. The leakage current analysis indicates that the content of grain boundaries in the films is a dominant factor affecting the leakage currents of the BiFe_0.995W_0.005O₃ films. Well saturated polarization–electric field hysteresis loops can be obtained in all the crystallized BiFe_0.995W_0.005O₃ films due to their low leakage currents. The film annealed at 450?°C exhibits a large remanent piezoelectric coefficient d ₃₃ (128?pm/V), which is comparable to that obtained in the BiFe_0.99W_0.01O₃ film annealed at 500?°C. Additionally, the most uniform piezoresponse can be observed in the BiFe_0.995W_0.005O₃ film annealed at 450?°C among all the crystallized films, which can be explained by the uniform domain structure and effective electric field applied on the film owing to the homogeneous grain size in the film.     

Effect of substrate temperature on properties of Cu(In,Ga, Al)Se<Subscript>2</Subscript> films grown by magnetron sputtering

Cu(In, Ga, Al)Se₂ (CIGAS) thin films were deposited by magnetron sputtering on Si(100) and soda-lime glass substrates at different substrate temperatures, followed by post-deposition annealing at 350 or 520 °C for 5 h in vacuum. Electron probe micro-analysis and secondary ion mass spectroscopy were used to determine the composition of the films and the distribution of Al across the film thickness, respectively. X-ray diffraction analysis showed that the (112) peak of CIGAS films shifts to higher 2θ values with increasing substrate temperature but remains unchanged when the films were annealed at 520 °C for 5 h. Scanning electron microscopy and atomic force microscopy images revealed dense and well-defined grains for both as-deposited and annealed films. However, notable increase in grain size and roughness was observed for films deposited at 500 °C. The bandgap of CIGAS films was determined from the optical transmittance and reflectance spectra and was found to increase as the substrate temperature was increased.