Investigation of thermal annealing effects on microstructural and optical properties of HfO2 thin films

In the present paper, we investigate the effect of thermal annealing on optical and microstructural properties of HfO₂ thin films (from 20 to 190 nm) obtained by plasma ion assisted deposition (PIAD). After deposition, the HfO₂ films were annealed in N₂ ambient for 3 h at 300, 350, 450, 500 and 750 °C. Several characterisation techniques including X-ray reflectometry (XRR), X-ray diffraction (XRD), spectroscopic ellipsometry (SE), UV Raman and FTIR were used for the physical characterisation of the as-deposited and annealed HfO₂ thin films. The results indicate that as-deposited PIAD HfO₂ films are mainly amorphous and a transition to a crystalline phase occurs at a temperature higher than 450 °C depending on the layer thickness. The crystalline grains consist of cubic and monoclinic phases already classified in literature but this work provides the first evidence of amorphous-cubic phase transition at a temperature as low as 500 °C. According to SE, XRR and FTIR results, an increase in the interfacial layer thickness can be observed only for high temperature annealing. The SE results show that the amorphous phase of HfO₂ (in 20 nm thick samples) has an optical bandgap of 5.51 eV. Following its transition to a crystalline phase upon annealing at 750 °C, the optical bandgap increases to 5.85 eV.     

Exchange coupling in CoO–Co bilayer

In this work, exchange bias and coercivity enhancement in ferromagnet (FM)–antiferromagnet (AFM) bilayer have been investigated. CoO film (50 nm) was deposited by sputtering with a relatively high oxygen partial pressure. The deposited films were subsequently annealed at varied temperature up to 973 K in the air atmosphere. The CoO film shows a disordered structure in the as-deposited state and an increase of crystallinity after annealing characterized by XRD and Raman spectra. A 40-nm Co film was deposited on the as-deposited CoO and annealed films. The Co–CoO bilayer shows a large exchange bias up to 1600 Oe and relatively high coercivity up to 3200 Oe (H_C−) at 5 K, which is much larger than that of crystalline Co–CoO bilayer films without any treatment. The spin glass behavior combined with increasing crystallinity, surface roughness of CoO after annealing may be attributed to the large exchange bias and high coercivity.     

Characteristics of electron beam evaporated nanocrystalline SnO2 thin films annealed in air

Tin oxide (SnO₂) thin films (about 200 nm thick) have been deposited by electron beam evaporation followed by annealing in air at 350-550 °C for two hours. Optical, electrical and structural properties were studied as a function of annealing temperature. The as-deposited film is amorphous, while all other annealed films are crystalline (having tetragonal structure). XRD suggest that the films are composed of nanoparticles of 5-10 nm. Raman analysis and optical measurements suggest quantum confinement effects that are enhanced with annealing temperature. For instance, Raman peaks of the as-deposited films are blue-shifted as compared to those for bulk SnO₂. Blue shift becomes more pronounced with annealing temperature. Optical band gap energy of amorphous SnO₂ film is 3.61 eV, which increases to about 4.22 eV after crystallization. Two orders of magnitude decrease in resistivity is observed after annealing at 350-400 °C due to structural ordering and crystallization. The resistivity, however, increases slightly with annealing temperature above 400 °C, possibly due to improvement in stoichiometry and associated decrease in charge carrier density.     

Effect of composition and thermal annealing on the absorption and electrical conduction of Se85−xTe15Sbx glasses

The optical absorption of the as-prepared and thermally annealed Se_85−xTe₁₅Sb_x (0≤x≤9) thin films was measured. The mechanism of the optical absorption follows the rule of non-direct transition. The optical energy gap (E₀) decreased from 1.12 to 0.84 eV with increasing Sb content of the as-prepared films from 0 to 9 at.%. The as-prepared Se₇₆Te₁₅Sb₉ films showed an increase in (E₀) with increasing the temperature of annealing in the range above T_g (363 K). The electrical conductivity of the as-prepared and annealed films was found to be of Arrhenius type with temperature in the range 300-360 K. The activation energy for conduction was found to decrease with increasing both the Sb content and temperature of annealing. The results were discussed on the basis of the lone-pair electron effect and of amorphous crystalline transformation.     

Effects of Pb addition and heat treatment on optical properties of thermally evaporated Ge1−xSe2Pbx thin films

Thin chalcogenide films of Ge_1−xSe₂Pb_x (x=0, 0.2, 0.4, 0.6 and 0.8) have been prepared by the thermal evaporation technique, from previously synthesized bulk samples. The X-ray diffraction showed the amorphous nature for the as-deposited films and the partially crystalline for the annealed films. The optical constants (the refractive index, n, and absorption index k) were determined for as-deposited and annealed Ge_1−xSe₂Pb_x films of different thicknesses by using spectrophotometeric measurements of the transmittance and reflectance at normal incidence in the spectral range 200-2500 nm. The obtained values of both n and k were found to be independent of the film thickness. The optical absorption edges are described using both the Urbach rule and the indirect transition. In transparent region, the spectral dependences of refractive index were interpreted in the frame of a single oscillator model.     

Optical and electrical properties of plasma-oxidation derived HfO2 gate dielectric films

High-k gate dielectric HfO₂ thin films have been deposited on Si(1 0 0) by using plasma oxidation of sputtered metallic Hf thin films. The optical and electrical properties in relation to postdeposition annealing temperatures are investigated by spectroscopic ellipsometry (SE) and capacitance-voltage (C-V) characteristics in detail. X-ray diffraction (XRD) measurement shows that the as-deposited HfO₂ films are basically amorphous. Based on a parameterized Tauc-Lorentz dispersion mode, excellent agreement has been found between the experimental and the simulated spectra, and the optical constants of the as-deposited and annealed films related to the annealing temperature are systematically extracted. Increases in the refractive index n and extinction coefficient k, with increasing annealing temperature are observed due to the formation of more closely packed thin films and the enhancement of scattering effect in the targeted HfO₂ film. Change of the complex dielectric function and reduction of optical band gap with an increase in annealing temperature are discussed. The extracted direct band gap related to the structure varies from 5.77, 5.65, and 5.56 eV for the as-deposited and annealed thin films at 700 and 800 °C, respectively. It has been found from the C-V measurement the decrease of accumulation capacitance values upon annealing, which can be contributed to the growth of the interfacial layer with lower dielectric constant upon postannealing. The flat-band voltage shifts negatively due to positive charge generated during postannealing.     

The influence of substrate temperature and annealing on the properties of pulsed laser-deposited YIG films on fused quartz substrate

Yttrium iron garnet (YIG) thin films were deposited on fused quartz substrate at different substrate temperatures (T_s) varying from room temperature (RT) to 850 °C using pulsed laser deposition (PLD) technique. All the films in the as-deposited state were X-ray amorphous and non-magnetic at RT. The film deposited at RT after annealing at temperatures T_a?700 °C showed both X-ray peaks and the magnetic order. The films deposited at higher T_s (500–850 °C) and then annealed at 700 °C resulted in better-quality films with higher 4πM_s value. The highest value of magnetization was for the sample deposited at 850 °C and annealed at 700 °C, which is 68% of the bulk 4πM_s value.     

Magnetic,structural and electrical properties of ordered and disordered Co50Fe50 films

Co₅₀Fe₅₀ films with thickness varying from 100 to 500 Å were deposited on a glass substrate by sputtering process, respectively. Two kinds of CoFe films were studied: one was the as-deposited film, and the other the annealed film. The annealing procedure was to keep the films at 400 °C for 5 h in a vacuum of 5×10⁻⁶ mbar. From the X-ray study, we find that the as-deposited film prefers the CoFe(1 1 0) orientation. Moreover, the body-centered cubic (bcc) CoFe(1 1 0) line is split into two peaks: one corresponding to the ordered body-centered tetragonal (bct) phase, and the other, the disordered bcc phase. After annealing, the peak intensity of the ordered bct phase becomes much stronger, while that of the disordered bcc phase disappears. The annealing has also caused the ordered CoFe(2 0 0) line to appear. When the amount of the ordered bct phase in Co₅₀Fe₅₀ is increased, the saturation magnetization (M_s) and coercivity (H_c) become larger, but the electrical resistivity (ρ) decreases. From the temperature coefficient of resistance (TCR) measurement, we learn that the bct grains in the CoFe film start to grow at temperature 82 °C.     

Influence of N2 flow ratio on the properties of hafnium nitride thin films prepared by DC magnetron sputtering

Hafnium nitride (Hf-N) thin films were deposited on fused silica at different N₂ flow ratio (N₂/N₂ + Ar) using a reactive DC magnetron sputtering system. A gradual evolution in the composition of the films from Hf₃N₂, HfN, to higher nitrides was found through X-ray diffraction (XRD). Films of Hf₃N₂ and HfN show positive temperature coefficients of resistivity, while higher nitride has a negative one. Highly oriented growth of (0 0 1) Hf₃N₂ and NaCl-structure (1 0 0) HfN films were fabricated on fused silica substrate at relatively lower temperature of 300 °C. The electrical resistivity values of both as-deposited and post-deposition annealed films were measured by a four-point probe method. The obtained minimum resistivity of as-deposited film is 20 μΩ cm, and this result shows potential application of HfN films as electrode materials in electronic devices.     

Characterization of chemically deposited ZnSe/SnO2/glass films: Influence of annealing in Ar atmosphere on physical properties

The Zinc Selenide (ZnSe) thin films have been deposited on SnO₂/glass substrates by a simple and inexpensive chemical bath deposition (CBD). The structural, optical and electrical properties of ZnSe films have been characterized by X-ray diffraction (XRD), Energy Dispersive X-ray Analysis (EDAX), optical absorption spectroscopy, and four point probe techniques, respectively. The films have been subjected to different annealing temperature in Argon (Ar) atmosphere. An increase in annealing temperature does not cause a complete phase transformation whereas it affects the crystallite size, dislocation density and strain. The optical band gap (E_g) of the as-deposited film is estimated to be 3.08 eV and decreases with increasing annealing temperature down to 2.43 eV at 773 K. The as-deposited and annealed films show typical semiconducting behaviour, dρ/dT > 0. Interestingly, the films annealed at 373 K, 473 K, and 573 K show two distinct temperature dependent regions of electrical resistivity; exponential region at high temperature, linear region at low temperature. The temperature at which the transition takes place from exponential to linear region strongly depends on the annealing temperature.     

The effects of Si3N4 interlayer on the thermal stability and hardness of Ti/TiNx (x = 0.5-1) nanolayered coatings

The polycrystalline Ti/TiN_x multilayer films were deposited by magnetron sputtering, and the as-deposited multilayer coatings were annealed at 500-800 °C for 2-4 h in vacuum. We investigated the effects of annealing temperature and annealing time on the microstructural, interfacial, and mechanical properties of the polycrystalline Ti/TiN_x multilayer films. It was found that the hardness increased with annealing temperature. This hardness enhancement was probably caused by the preferred crystalline orientation TiN(1 1 1). The X-ray reflectivity measurements showed that the layer structure of the coatings could be maintained after annealing at 500 °C and the addition of the Si₃N₄ interlayer to Ti/TiN_x multilayer could improve the thermal stability to 800 °C.     

Annealing effect on the structural and optical properties of a Cd1−xZnxS thin film for photovoltaic applications

Herein is a report of a study on a Cd_1−xZn_xS thin film grown on an ITO substrate using a chemical bath deposition technique. The as-deposited films were annealed in air at 400 °C for 30 min. The composition, surface morphology and structural properties of the as-deposited and annealed Cd_1−xZn_xS thin films were studied using EDX, SEM and X-ray diffraction techniques. The annealed films have been observed to possess a crystalline nature with a hexagonal structure. The optical absorption spectra were recorded within the range of 350-800 nm. The band gap of the as-deposited thin films varied from 2.46 to 2.62 eV, whereas in the annealed film these varied from 2.42 to 2.59 eV. The decreased band gap of the films after annealing was due to the improved crystalline nature of the material.     

Chemical bath-deposited ZnS thin films: Preparation and characterization

Chemical bath deposition of ZnS thin films from NH₃/SC(NH₂)₂/ZnSO₄ solutions has been studied. The effect of various process parameters on the growth and the film quality are presented. The influence on the growth rate of solution composition and the structural, optical properties of the ZnS thin films deposited by this method have been studied. The XRF analysis confirmed that volume of oxygen of the as-deposited film is very high. The XRD analysis of as-deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results confirmed that the as-deposited films have amorphous Zn(OH)₂. SEM studies of the ZnS thin films grown on various growth phases show that ZnS film formed in the none-film phase is discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular structure with the grain size about 100 nm. There are adsorbed particles on films formed in the saturation phase. Transmission measurement shows that an optical transmittance is about 90% when the wavelength over 500 nm. The band gap (E_g) value of the deposited film is about 3.51 eV.     

Studies on the influence of lithium incorporation in the photoluminescence of Y2O3:Eu thin films

Nanostructured europium-doped yttrium oxide thin films with lithium as a co-dopant were prepared using pulsed laser ablation technique. X-ray diffraction studies of the films indicated amorphous nature of the as deposited films and a transformation to crystalline phase with increase of annealing temperature. In this transformation, lithium co-doped films showed early crystallization. Lithium substitution resulted not only in enhancement of photoluminescence at 612 nm, resulting from ⁵D₀-⁷F₂ transition within europium, but also found to reduce the required processing temperature for intense photoemission. The deviation observed in the value of lattice constant of films annealed at different temperatures is found to be sensitive to annealing temperature. In the light of this, the dependence of photoluminescence intensity on the magnitude of lattice imperfection is also discussed. The morphology and transmittance of the films are also found to be sensitive to annealing process and lithium doping.     

Formation of CdO films from chemically deposited Cd(OH)2 films as a precursor

Formation of cadmium hydroxide at room temperature onto glass substrates from an aqueous alkaline cadmium nitrate solution using a simple soft chemical method and its conversion to cadmium oxide (CdO) by thermal annealing treatment has been studied in this paper. The as-deposited film was given thermal annealing treatment in oxygen atmosphere at 450 °C for 2 h for conversion into cadmium oxide. The structural, surface morphological and optical studies were performed for as-deposited and the annealed films. The structural analyses revealed that as-deposited films consists of mixture of Cd(OH)₂ and CdO, while annealed films exhibited crystalline CdO. From surface morphological studies, conversion of clusters to grains after annealing was observed. The band gap energy was changed from 3.21 to 2.58 eV after annealing treatment. The determination of elementals on surface composition of the core-shell nanoparticles of annealed films was carried out using X-ray photoelectron spectroscopy (XPS).     

On the structure, morphology, and optical properties of chemical bath deposited Sb2S3 thin films

In the present paper, we have reported the room temperature growth of antimony sulphide (Sb₂S₃) thin films by chemical bath deposition and detailed characterization of these films. The films were deposited from a chemical bath containing SbCl₃ and Na₂S₂O₃ at 27 °C. We have analysed the structure, morphology, composition and optical properties of as deposited Sb₂S₃ films as well as those subjected to annealing in nitrogen atmosphere or in air. As-deposited films are amorphous to X-ray diffraction (XRD). However, the diffused rings in the electron diffraction pattern revealed the existence of nanocrystalline grains in these films. XRD analysis showed that upon annealing in nitrogen atmosphere these films transformed into polycrystalline with orthorhombic structure. Also, we have observed that during heating in air, Sb₂S₃ first converts into orthorhombic form and then further heating results in the formation of Sb₂O₃ crystallites. Optical bandgap energy of as deposited and annealed films was evaluated from UV-vis absorption spectra. The values obtained were 2.57 and 1.73 eV for the as-deposited and the annealed films respectively.     

Annealing temperature dependence of Raman scattering in Si/SiO2 superlattice prepared by magnetron sputtering

Si/SiO₂ superlattices were prepared by magnetron sputtering, and the deposition temperature and annealing temperature had a great influence on the superlattice structure. In terms of SEM images, the mean size of Si nanocrystals annealed at 1100 °C is larger than that of nanocrystals annealed at 850 °C. It was found that the films deposited at room temperature are amorphous. With increasing deposition temperature, the amorphous and crystalline phases coexist. With increasing annealing temperature, the Raman intensity of the peak near 470 cm⁻¹ decreases, and the intensity of that at 520 cm⁻¹ increases. Also, on increasing the annealing temperature, the Raman peak near 520 cm⁻¹ shifts and narrows, and asymmetry emerges. A spherical cluster is used to model the nanocrystals in Si/SiO₂ superlattices, and the observed Raman spectra are analyzed by combining the effects of confinement on the phonon frequencies. Raman spectra from a variety of nanocrystalline silicon structures were successfully explained in terms of the phonon confinement effect. The fitted results agreed well with the experimental observations from SEM images.     

Structural and optoelectronic properties of antimony tin sulphide thin films deposited by thermal evaporation techniques

Thin films of SnSb₂S₄ have been prepared on glass substrate by using thermal evaporation techniques. The films were annealed in argon gas at low pressure in sealed glass ampoules at 85 °C, 150 °C, 275 °C and 325 °C. XRD of the films reveal that the low temperature annealed films are poly crystalline while the as deposited films and high annealed films are in amorphous states. There is no adequate variation in the photoconductivity response of the amorphous and crystalline phases. The transmittance of the films is low and having no transmittance below 740 nm. The band gap calculated by ellipsometry technique is in the range of 1.82–3.1 eV. The films have n-type conductivity but the film annealed at 325 °C show p-type conductivity.     

Characterization of Cu additive FePt-C granular films

FePt-C granular films doped with different Cu atomic fractions (x_Cu) were fabricated using facing-target sputtering at room temperature and subsequently annealed at 650 °C. Structural analyses reveal that the as-deposited films are in amorphous state. Appropriate Cu addition (x_Cu = 14) can improve the ordering of L1₀ FePt phase, and excessive Cu doping destroys the formation of ordered L1₀ phase with the appearance of Fe₃C and CuPt phases. Besides, preferential graphitization of amorphous carbon (a-C) occurs near large metal particles upon annealing. Annealing turns the as-deposited superparamagnetic films into ferromagnetic associated with coercivity peaks at x_Cu = 14, drops from ∼11.2 kOe at 5 K to ∼7.2 kOe at 300 K in a 50 kOe field.     

Electronic transport properties and Microstructures of TiO2:Co magnetic semiconductors

TiO₂:Co thin films of high Co concentration were investigated by the high resolution transmission electron microscopy, physical property measurement system and energy dispersive X-ray. The as-deposited films are amorphous magnetic semiconductors and we did not find any Co metal particles in them. The electronic transport process in the low-temperature range below 80 K could be described by the spin-dependent variable-range-hopping process. However, after the samples were annealed at 300 °C, large amounts of Co metal particles were observed to connect each other and the films show a metallic behavior. The origin of ferromagnetism of the thin films is also discussed.