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.     

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.     

CuO-PAA hybrid films: Chemical synthesis and supercapacitor behavior

We report the synthesis of CuO-Poly (acrylic) acid (PAA) hybrid thin films by a cost-effective spin coating technique for supercapacitor application. Coated films were annealed at 300, 400 and 500 °C, to study the annealing effect on the supercapacitor behavior. Further films were characterized by X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform-Raman spectroscopy (FT-Raman) and Fourier transform-Infrared spectroscopy (FT-IR) techniques. Energy dispersive spectroscopy (EDS) shows the formation of amorphous blend of CuO and Cu₂O phases at 300 °C. Further, films annealed at 400 and 500 °C exhibit polycrystalline phase pure CuO with monoclinic structure. The scanning electron microscopy (SEM) micrographs show the transition of island-like structure to CuO crystals surrounded by PAA grafted composite ring with increase in annealing temperature. The possible growth mechanism of PAA and CuO bonding is discussed. Cyclic voltammetry (CV) is employed to calculate the specific capacitance (C_sp) in 1 M H₂SO₄ electrolyte. It is observed that the C_sp increases from 41 to136 F g⁻¹ with increase in annealing temperature.     

A facile process to prepare copper oxide thin films as solar selective absorbers

Copper oxide thin films as solar selective absorbers were conveniently prepared by one-step chemical conversion method. X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis-NIR spectra and Fourier transform infrared (FTIR) spectra were employed to characterize the composition, structure and optical properties of thin films. The results indicated that the composition, structure and optical properties of thin films were greatly influenced by reaction temperature, time and concentration of NaOH. When reaction temperature was fixed at 40 °C, the as-prepared films consist of pure cubic Cu₂O. The surface morphology of thin films was changed from square-like structure (reaction time ≤ 25 min) to porous belt-like structure (reaction time ≥ 30 min) with the elongation of reaction time. While for thin films prepared at 60 °C and 80 °C, single Cu₂O was observed after 5 min reaction. When reaction time is longer than 5 min, CuO appears and the content of CuO is increasing with the elongation of reaction time. With the increase of reaction temperature, the belt-like structure was easily formed for 60 °C/10 min and 80 °C/5 min. Decreasing concentration of NaOH also could result in the formation of CuO and porous belt-like structure. Simultaneously, the film thickness is increasing with the increase of reaction time, temperature and concentration. Films containing CuO with belt-like structure exhibited high absorptance (>0.9), and the emissivity of films increased with elongation of reaction time. Combination of the composition, structure and optical properties, it can be deduced that the porous belt-like structure like as a light trap can greatly enhance absorbance (α), while the composition, thickness and roughness of thin films can greatly influence the emissivity (?). The highest photo-thermal conversion efficiency was up to 0.86 (α/? = 0.94/0.08) for thin films prepared at 80 °C/5 min, which proved that the CuO_x thin films can be served as high performance solar selective absorbers.     

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).     

Preparation of p-type CdS thin films and in situ dark conductivity in vacuum deposited CdS:Cu films

CdS:Cu thin films were prepared using a vacuum co-evaporation technique. The Hall measurements indicate that the conductivity characteristic of CdS thin films transformed from highly compensated in as-grown or weakly annealed materials to p-type conductive in strongly annealed materials. X-ray diffraction spectra show that as-deposited thin films were the hexagonal phase of CdS except the presence of copper for high Cu doping and the diffraction peaks of Cu disappeared after annealing. From the X-ray photoelectron spectroscopy we found the ionization of Cu atoms and the formation of an acceptor level. In situ dark conductivity in vacuum as-deposited CdS:Cu was performed in the temperature range between 27 and 250 °C. An abnormal temperature dependence of conductivity was observed in medium and heavily Cu-doped films. The formation of a p-type material at a certain temperature was also studied by the hot probe measurements, which indicates a complex compensation process in the Cu-doped CdS films.     

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.     

Post-annealing influence on properties of N-In codoped ZnO thin films prepared by ion beam enhanced deposition method

N-In codoped ZnO thin films were prepared by ion beam enhanced deposition method (IBED) and were annealed in nitrogen and oxygen ambient after deposition. The influence of post-annealing on structure, electrical and optical properties of thin films were investigated. As-deposited and all post-annealed samples showed preferential orientation along (0 0 2) plane. Electrical property studies indicated that the as-deposited ZnO film showed p-type with a sheet resistance of 67.5 kΩ. For ZnO films annealed in nitrogen with the annealing temperature increasing from 400 to 800 °C, the conduction type of the ZnO film changed from p-type to n-type. However, for samples annealed in oxygen the resistance increased sharply even at a low annealing temperature of 400 °C and the conduction type did not change. Room temperature PL spectra of samples annealed in N₂ and in O₂ showed UV peak located at 381 and 356 nm, respectively.     

Chemical synthesis of p-type nanocrystalline copper selenide thin films for heterojunction solar cells

Nanocrystalline thin films of copper selenide have been grown on glass and tin doped-indium oxide substrates using chemical method. At ambient temperature, golden films have been synthesized and annealed at 200 °C for 1 h and were examined for their structural, surface morphological and optical properties by means of X-ray diffraction (XRD), scanning electron microscopy and UV-vis spectrophotometry techniques, respectively. Cu_2−xSe phase was confirmed by XRD pattern and spherical grains of 30 ± 4 - 40 ± 4 nm in size aggregated over about 130 ± 10 nm islands were seen by SEM images. Effect of annealing on crystallinity improvement, band edge shift and photoelectrochemical performance (under 80 mW/cm² light intensity and in lithium iodide electrolyte) has been studied and reported. Observed p-type electrical conductivity in copper selenide thin films make it a suitable candidate for heterojunction solar cells.     

Effect of substrate bias voltages on the diffusion barrier properties of Zr-N films in Cu metallization

Zr-N diffusion barriers were deposited on the Si substrates by rf reactive magnetron sputtering under various substrate bias voltages. Cu films were subsequently sputtered onto the Zr-N films by dc pulse magnetron sputtering without breaking vacuum. The Cu/Zr-N/Si specimens were then annealed up to 650 °C in N₂ ambient for an hour. The effects of deposition bias on growth rate, film resistivity, microstructure, and diffusion barrier properties of Zr-N films were investigated. An increase in negative substrate bias resulted in a decrease in deposition rate together with a decrease in resistivity. It was found that the sheet resistances of Cu/Zr-N(−200 V)/Si contact system were lower than those of Cu/Zr-N(−50 V)/Si specimens after annealing at 650 °C. Cu/Zr-N(−200 V)/Si contact systems showed better thermal stability so that the Cu₃Si phase could not be detected.     

Effect of post-annealing temperature on the microstructure and magnetic properties of Ce:YIG thin films deposited on Si substrates

Amorphous Ce₁Y₂Fe₅O₁₂ (Ce:YIG) thin films deposited on single crystal Si(1 0 0) and thermally oxidized Si(1 0 0) substrates by pulsed laser deposition were annealed in the temperature range of 700-1000 °C in air. The annealing temperature dependence of microstructure and magnetic properties of Ce:YIG films was studied using X-ray diffraction combined with vibrating sample magnetometer. The results show that single phase of polycrystalline Ce:YIG thin films can be obtained by the post-annealing of as-deposited films at the temperature of 700 °C. However, two steps of phase segregation of Ce:YIG occur as the post-annealing temperature increases: at first, Ce:YIG is decomposed into YIG and non-magnetic CeO₂ when annealed at 800 °C; then YIG continues to be decomposed forming Fe₂O₃ when the temperature is increased up to 900 °C. Consequently, the saturation magnetization of Ce:YIG films decreases first and then increases with the post-annealing temperature going up, which indicates that the saturation magnetization of Ce:YIG films is mainly related to the phase composition of the films. Meanwhile, the presence of SiO₂ buffer layer can significantly enhance the saturation magnetization of Ce:YIG films.     

The thermoluminescence properties of CdS films under nitrogen atmosphere

Chemically deposited cadmium sulphide (CdS) films have been grown on glass at 60 °C and annealed at nitrogen atmosphere at different temperatures. The as-deposited film shows a mix phase of cubic and hexagonal. Once the film subjected to annealing the hexagonal phase becomes dominant and the crystal size increases due to these changes optical band gap energy decreases from 2.44 to 2.28 eV. The electrical conductivity increases depending on temperature and the film annealed at 423 K shows the highest conductivity. Thermoluminescence (TL) intensity of the films was measured after irradiating the films with ⁹⁰Sr/⁹⁰Y β-source and the trap depths were calculated after the TL curves deconvoluted by using the computer glow curve deconvolution (CGCD) method. It is observed that the as-deposited film has three different trap depths, at around 0.257, 0.372, and 0.752 eV corresponding to 383, 473, and 608 K, respectively.     

Atom beam sputtered Mo2C films as a diffusion barrier for copper metallization

The saddle field fast atom beam sputtered (ABS) 50 nm thick molybdenum carbide (Mo₂C) films as a diffusion barrier for copper metallization were investigated. To study the diffusion barrier properties of Mo₂C films, the as-deposited and annealed samples were characterized using four probes, X-ray diffraction, field enhanced scanning electron microscopy, energy dispersive X-ray analysis, atomic force microscopy and Rutherford back scattering techniques. The amorphous structure of the barrier films along with presence of carbon atoms at the molybdenum carbide-silicon interface is understood to reduce effective grain boundaries and responsible for increased thermal stability of Cu/Mo₂C/Si structure. The lowest resistivity of the as-deposited molybdenum carbide barrier films was ∼29 μΩ cm. The low carbon containing molybdenum carbide was found thermally stable up to 700 °C, therefore can potentially be used as a diffusion barrier for copper metallization.     

Annealing induced microstructural evolution of electrodeposited electrochromic tungsten oxide films

A significant influence of microstructure on the electrochromic and electrochemical performance characteristics of tungsten oxide (WO₃) films potentiostatically electrodeposited from a peroxopolytungstic acid (PPTA) sol has been evaluated as a function of annealing temperature. Powerful probes like X-ray diffractometry (XRD), transmission electron microscopy (TEM), UV-vis spectrophotometry, multiple step chronoamperometry and cyclic voltammetry have been employed for the thin film characterization. The as-deposited and the film annealed at 60 °C are composed of nanosized grains with a dominant amorphous phase, as well as open structure which ensues from a nanoporous matrix. This ensures a greater number of electroactive sites and a higher reaction area thereby manifesting in electrochromic responses superior to that of the films annealed at higher temperatures. The films annealed at temperatures ≥250 °C are characterized by a prominent triclinic crystalline structure and a hexagonal phase co-exists at temperatures ≥400 °C. The deleterious effect on the electrochromic properties of the film with annealing is ascribed to the loss of porosity, densification and the increasing crystallinity and grain size. Amongst all films under investigation, the film annealed at 60 °C exhibits a high transmission modulation (ΔT ∼ 68%) and coloration efficiency (η ∼ 77.6 cm² C⁻¹) at λ = 632.8 nm, charge storage capacity (Q_ins ∼ 21 mC cm⁻²), diffusion coefficient (6.08 × 10⁻¹⁰ cm² s⁻¹), fast color-bleach kinetics (t_c ∼ 275 s and t_b ∼ 12.5 s) and good electrochemical activity, as well as reversibility for the lithium insertion-extraction process upon cycling. The remarkable potential, which the film annealed at 60 °C has, for practical “smart window” applications has been demonstrated.     

Structural and optoelectronic properties of vacuum evaporated SnS thin films annealed in argon ambient

In this work, 650 nm polycrystalline SnS thin films were grown by thermal evaporation of high purity tin sulfide powder at 250 °C substrate temperature, followed by post deposition annealing at 200 °C and 300 °C for 2, 4 and 6 h, and at 400 °C for 2 and 4 h in argon ambient. The XRD pattern of the as-deposited and annealed SnS films led to the conclusion that the as-deposited films were polycrystalline in nature with preferentially oriented along (1 1 1) direction. The direct bandgap of all the films was found to be observed between 1.33 and 1.53 eV. Except for annealing at 400 °C all the films were nearly stoichiometric in nature, suggesting lower rate of desulfurization at that ambient. However, higher annealing temperature has resulted in the segregation of tin phase. All the films showed good absorption in the visible range. The as-deposited and annealed films showed p-type conductivity. Hall measurement revealed the carrier concentration and mobility ranging from 10¹⁵ to 10¹⁶ cm⁻³ and 0.8 to 31.6 cm² V⁻¹ s⁻¹ respectively. The photoconductivity measurements of all the SnS films were carried out by recording the lowering of resistance of the respective films with time under illumination.     

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.     

Investigation of p-type behavior in Ag-doped ZnO thin films by E-beam evaporation

Ag-doped ZnO (ZnO:Ag) thin films were grown on glass substrates by E-beam evaporation technique. The structural, electrical and optical properties of the films were investigated as a function of annealing temperature. The films were subjected to post annealing at different temperatures in the range of 350-650 °C in an air ambient. All the as grown and annealed films at temperature of 350 °C showed p-type conduction. The films lost p-type conduction after post annealing treatment temperature of above 350 °C, suggesting a narrow post annealing temperature window for the fabrication of p-type ZnO:Ag films. ZnO:Ag film annealed at 350 °C revealed lowest resistivity of 7.25 × 10⁻² Ω cm with hole concentration and mobility of 5.09 × 10¹⁹ cm⁻³ and 1.69 cm²/V s, respectively. Observation of a free-to-neutral-acceptor (e,A^o) and donor-acceptor-pair (DAP) emissions in the low temperature photoluminescence measurement confirms p-type conduction in the ZnO:Ag films.     

Effect of annealing temperature on the decomposition of reactively sputtered Ag2Cu2O3 films

Ag₂Cu₂O₃ films were deposited on glass substrates by reactive sputtering of a composite silver-copper target. The deposited films were annealed in air at 100, 200 and 300 °C. The structure of the films was studied using X-ray diffraction (XRD), their surface morphology was characterised using scanning electron microscopy (SEM) and their electrical resistivity at room temperature was measured using the four point probe method. The 100 °C annealing did not modify either the film structure or the film morphology. On the other hand, Ag₂Cu₂O₃ films were partially decomposed into Ag and CuO after a 200 °C annealing. The decomposition was complete for a 300 °C annealing. The evolution of the film surface morphology as a function of the annealing temperature was discussed in connection to the evolution of the molar volume of the phases constituting the films.     

Oxidation and contact resistance of Sn-Ag coated superconducting strands for the Large Hadron Collider (LHC)

The oxides formed on the Sn-Ag coated Large Hadron Collider (LHC) superconducting cables during a 200 °C heat treatment in air are described and the oxide composition is compared with the interstrand contact resistance (R_C). The analysis of more than 250 interstrand contact areas shows that the higher the average Cu content with respect to the Sn content in the oxide, the higher is R_C. During the 200 °C heat treatment, Sn in the coating is transformed into a Cu₃Sn layer, on which an oxide grows that consists essentially of a thin outermost layer of CuO on top of Cu₂O, similar to the oxide structure formed on bare Cu. The underlying Cu₃Sn layer acts as an O diffusion barrier that prevents O diffusion into the Cu bulk during the subsequent cable heat treatment under high pressure. On contact zones where the Cu₃Sn layer is not formed during the 200 °C heat treatment mainly Sn oxide grows and R_C is comparatively low.     

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.