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.     

Influence of annealing temperature on the properties of ZnO thin films deposited by thermal evaporation

ZnO thin films were deposited by thermal evaporation of a ZnO powder. The as-deposited films are dark brown, rich zinc and present a low transmittance. Then, these films were annealed in air atmosphere at different temperatures between 100 and 400 °C. Their microstructure and composition were studied using XRD and RBS measurements respectively. By increasing the temperature, it was found that film oxidation starts at 250 °C. XRD peaks related to ZnO appear and peaks related to Zn decrease. At 300 °C, zinc was totally oxidised and the films became totally transparent. The electrical conductivity measurement that were carried out in function of the annealing temperature showed the transition from highly conductive Zn thin film to a lower conductive ZnO thin film. The optical gap (E_g) was deduced from the UV-vis transmittance, and its variation was linked to the formation of ZnO.     

Effects of rapid thermal annealing on structural, magnetic and optical properties of Ni-doped ZnO thin films

XPS depth profiles were used to investigate the effects of rapid thermal annealing under varying conditions on the structural, magnetic and optical properties of Ni-doped ZnO thin films. Oxidization of metallic Ni from its metallic state to two-valence oxidation state occurred in the film annealed in air at 600 °C, while reduction of Ni²⁺ from its two-valence oxidation state to metallic state occurred in the film annealed in Ar at 600 and 800 °C. In addition, there appeared to be significant diffusion of Ni from the bottom to the top surface of the film during annealing in Ar at 800 °C. Both as-deposited and annealed thin films displayed obvious room temperature ferromagnetism (RTFM) which was from metallic Ni, Ni²⁺ or both with two distinct mechanisms. Furthermore, a significant improvement in saturation magnetization (M_s) in the films was observed after annealing in air (M_s = 0.036 μ_B/Ni) or Ar (M_s = 0.033 μ_B/Ni) at 600 °C compared to that in as-deposited film (M_s = 0.017 μ_B/Ni). An even higher M_s value was observed in the film annealed in Ar at 800 °C (M_s = 0.055 μ_B/Ni) compared to that at 600 °C mainly due to the diffusion of Ni. The ultraviolet emission of the Ni-doped ZnO thin film was restored during annealing in Ar at 800 °C, which was also attributed to the diffusion of Ni.     

Effect of post-annealing on the properties of copper oxide thin films obtained from the oxidation of evaporated metallic copper

Thin films of copper oxide were obtained through thermal oxidation (100-450 °C) of evaporated metallic copper (Cu) films on glass substrates. The X-ray diffraction (XRD) studies confirmed the cubic Cu phase of the as-deposited films. The films annealed at 100 °C showed mixed Cu-Cu₂O phase, whereas those annealed between 200 and 300 °C showed a single cubic Cu₂O phase. A single monoclinic CuO phase was obtained from the films annealed between 350 and 450 °C. The positive sign of the Hall coefficient confirmed the p-type conductivity in the films with Cu₂O phase. However, a relatively poor crystallinity of these films limited the p-type characteristics. The films with Cu and CuO phases show n-type conductivity. The surface of the as-deposited is smooth (RMS roughness of 1.47 nm) and comprised of uniformly distributed grains (AFM and SEM analysis). The post-annealing is found to be effective on the distribution of grains and their sizes. The poor transmittance of the as-deposited films (<1%) is increased to a maximum of ∼80% (800 nm) on annealing at 200 °C. The direct allowed band gap is varied between 2.03 and 3.02 eV.     

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 ZnO-SnO2 thin film composites prepared by pulsed laser deposition

Thin films of ZnO-SnO₂ composites have been deposited on Si(1 0 0) and glass substrates at 500 °C by pulsed laser ablation using different composite targets with ZnO amount varying between 1 and 50 wt%. The effect of increasing ZnO-content on electrical, optical and structural properties of the ZnO-SnO₂ films has been investigated. X-ray diffraction analysis indicates that the as-deposited ZnO-SnO₂ films can be both crystalline (for ZnO <1 wt%) and amorphous (for ZnO ≥ 10 wt%) in nature. Atomic force microscopy studies of the as-prepared composite films indicate that the surfaces are fairly smooth with rms roughness varying between 3.07 and 2.04 nm. The average optical transmittance of the as-deposited films in the visible range (400-800 nm), decreases from 90% to 72% for increasing ZnO concentration in the film. The band gap energy (E_g) seems to depend on the amount of ZnO addition, with the maximum obtained at 1 wt% ZnO. Assuming that the interband electron transition is direct, the optical band gap has been found to be in the range 3.24-3.69 eV for as-deposited composite films. The lowest electrical resistivity of 7.6 × 10⁻³ Ω cm has been achieved with the 25 wt% ZnO composite film deposited at 500 °C. The photoluminescence spectrum of the composite films shows a decrease in PL intensity with increasing ZnO concentration.     

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).     

Effect of H2 and O2 plasma etching treatment on the surface of diamond-like carbon thin film

In this study, we investigated the surface properties of diamond-like carbon (DLC) films for biomedical applications through plasma etching treatment using oxygen (O₂) and hydrogen (H₂) gas. The synthesis and post-plasma etching treatment of DLC films were carried out by 13.56 MHz RF plasma enhanced chemical vapor deposition (PECVD) system. In order to characterize the surface of DLC films, they were etched to a thickness of approximately 100 nm and were compared with an as-deposited DLC film. We obtained the optimum condition through power variation, at which the etching rate by H₂ and O₂ was 30 and 80 nm/min, respectively. The structural and chemical properties of these thin films after the plasma etching treatment were evaluated by Raman and Fourier transform infrared (FT-IR) spectroscopy. In the case of as-deposited and H₂ plasma etching-treated DLC film, the contact angle was 86.4° and 83.7°, respectively, whereas it was reduced to 35.5° in the etching-treated DLC film in O₂ plasma. The surface roughness of plasma etching-treated DLC with H₂ or O₂ was maintained smooth at 0.1 nm. These results indicated that the surface of the etching-treated DLC film in O₂ plasma was hydrophilic as well as smooth.     

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.     

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.     

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.     

Determination of photocatalytic activity in amorphous and crystalline titanium oxide films prepared using plasma-enhanced chemical vapor deposition

Hydro-oxygenated amorphous titanium oxide (a-TiO_x:OH) films were prepared by plasma-enhanced chemical vapor deposition (PECVD) using precursors of titanium tetraisopropoxide (TTIP) and oxygen. The influences of chemical states and crystal quality on the photocatalytic activity were systematically investigated in the as-deposited and post-annealed films. The degree of the photocatalytic activity was deeply correlated with the porosity related to the hydroxyl (OH) groups in the as-deposited amorphous film. The crystallized anatase structures was observed from the 200 °C-deposited a-TiO_x:OH film after a post-annealing treatment at 400 °C. The photocatalytic activity related to the film with anatase structure was markedly superior to that of an amorphous film with porous structures. The larger the crystal size of the anatase structure, the higher the photocatalytic activity obtained. At elevated annealed temperatures, the inferior anatase structure due to the crystalline transformation led to a low photocatalytic activity. It was concluded that the photocatalytic activity of an amorphous TiO_x film prepared using PECVD was determined by the porosity originating from the functional OH groups in the film, whereas the crystalline quality of anatase phase in the annealed poly-TiO_x film was crucial to the photocatalytic activity.     

Transmission electron microscopy studies of HfO2 thin films grown by chloride-based atomic layer deposition

Detailed transmission electron microscopy characterization of HfO₂ films deposited on Si(1 0 0) using atomic layer deposition has been carried out. The influence of deposition temperature has been investigated. At 226 °C, a predominantly quasi-amorphous film containing large grains of cubic HfO₂ (a₀ = 5.08 Å) was formed. Grain morphology enabled the nucleation sites to be determined. Hot stage microscopy showed that both the cubic phase and the quasi-amorphous phase were very resistant to thermal modification up to 500 °C. These observations suggest that nucleation sites for the growth of the crystalline cubic phase form at the growing surface of the film, rather homogeneously within the film. The films grown at higher temperatures (300-750 °C) are crystalline and monoclinic. The principal effects of deposition temperature were on: grain size, which coarsens at the highest temperature; roughness with increases at the higher temperatures due to the prismatic faceting, and texture, with texturing being strongest at intermediate temperatures. Detailed interfacial characterization shows that interfacial layers of SiO₂ form at low and high temperatures. However, at intermediate temperatures, interfaces devoid of SiO₂ were formed.     

Magnetic properties and domain structures of FeSiB thin films

Smooth Fe₇₈Si₁₀B₁₂ thin films were prepared by r.f. sputtering with the very slow deposition rate of 0.59 nm/min. The as-deposited films were not fully amorphous, instead α-Fe(Si) nanocrystallites were found to be embedded in the amorphous matrix. The saturation magnetostriction λ_s of the as-deposited film is about 6.5 × 10⁻⁶. After annealing at 540 °C for 1 h in an ultrahigh vacuum (4.5 × 10⁻⁵ Pa), the fraction of α-Fe(Si) crystalline phase largely increased, and correspondingly the λ_s decreased to 4.5 × 10⁻⁷. Ripple domain structures were observed in the as-deposited film, while dense stripe domains were observed in the annealed sample, characterized by a very narrow domain width of 80 nm. (1 1 0) texture and island-like configuration of α-Fe(Si) nanocrystallites formed by the annealing treatment are responsible for the perpendicular anisotropy. For the as-deposited film, the magnetization curves increased linearly with the increase of the magnetic field, and showed the very small hysteresis. On the other hand, the annealed sample clearly showed a very steep jump near the origin, which is due to the switch process of the dense stripe domain.     

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.     

Nanostructure of photocatalytic TiO2 films sputtered at temperatures below 200 °C

The article reports on correlations between the process parameters of reactive pulsed dc magnetron sputtering, physical properties and the photocatalytic activity (PCA) of TiO₂ films sputtered at substrate surface temperature T_surf ≤ 180 °C. Films were deposited using a dual magnetron system equipped with Ti (Ø50 mm) targets in Ar + O₂ atmosphere in oxide mode of sputtering. The TiO₂ films with highly photoactive anatase phase were prepared without a post-deposition thermal annealing. The decomposition rate of the acid orange 7 (AO7) solution during the photoactivation of the TiO₂ film with UV light was used for characterization of the film PCA. It was found that (i) the partial pressure of oxygen pO₂ and the total sputtering gas pressure p_T are the key deposition parameters influencing the TiO₂ film phase composition that directly affects its PCA, (ii) the structure of sputtered TiO₂ films varies along the growth direction from the film/substrate interface to the film surface, (iii) ∼500 nm thick anatase TiO₂ films with high PCA were prepared and (iv) the structure of sputtered TiO₂ films is not affected by the substrate surface temperature T_surf when T_surf < 180 °C. The interruption of the sputtering process and deposition in long (tens of minutes) pulses alternating with cooling pauses has no effect on the structure and the PCA of TiO₂ films and results in a decrease of maximum value of T_surf necessary for the creation of nanocrystalline nc-TiO₂ film. It was demonstrated that crystalline TiO₂ films with high PCA can be sputtered at T_surf ≤ 130 °C. Based on obtained results a phase zone model of TiO₂ films was developed.     

Excimer laser processing of ZnO thin films prepared by the sol-gel process

ZnO thin films were prepared on soda-lime glass from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH] and isopropanol. The deposited films were dried at 50 and 300 °C. X-ray analysis showed that the films were amorphous. Laser annealing was performed using an excimer laser. The laser pulse repetition rate was 25 Hz with a pulse energy of 5.9 mJ, giving a fluence of 225 mJ cm⁻² on the ZnO film. Typically, five laser pulses per unit area of the film were used. After laser processing, the hexagonal wurtzite phase of zinc oxide was observed from X-ray diffraction pattern analysis. The thin films had a transparency of greater than 70% in the visible region. The optical band-gap energy was 3.454 eV. Scanning electron microscopy and profilometry analysis highlighted the change in morphology that occurred as a result of laser processing. This comparative study shows that our sol-gel processing route differs significantly from ZnO sol-gel films prepared by conventional furnace annealing which requires temperatures above 450 °C for the formation of crystalline ZnO.     

ZnO thin films on Si(1 1 1) grown by pulsed laser deposition from metallic Zn target

ZnO thin films with highly c-axis orientation have been fabricated on p-type Si(1 1 1) substrates at 400 °C by pulsed laser deposition (PLD) from a metallic Zn target with oxygen pressures between 0.1 and 0.7 mbar. Experimental results indicate that the films deposited at 0.3 and 0.5 mbar have better crystalline and optical quality and flatter surfaces than the films prepared at other pressures. The full width at half maximum (FWHM) of (0 0 0 2) diffraction peak decreases remarkably from 0.46 to 0.19° with increasing annealing temperature for the film prepared at 0.3 mbar. In photoluminescence (PL) spectra at room temperature, the annealed film at 700 °C exhibits a smaller ultraviolet (UV) peak FWHM of 108 meV than the as-grown film (119 meV). However, an enhanced deep-level emission is observed. Possible origins to above results are discussed.     

Microstructural and electrochromic properties of tungsten oxide thin films produced by surfactant mediated electrodeposition

By electrochemically controlling the structure of the surface aggregates, the grain microstructure has been optimized to yield mesoporous thin films of tungsten oxide (WO₃) at the electrode-electrolyte interface in a peroxotungstate sol in the presence of a structure-directing agent (Triton) at room temperature. Apart from the dominant ultrafine nanocrystallites and pores (5-10 nm), well-developed abutting grains (25-100 nm) and nanofibrils also constitute an integral part of the film matrix. X-ray photoemission spectra reveal the as-deposited film (WO_3−x) to be constituted by a high proportion of W⁶⁺ states with a low oxygen deficiency (x = 0.02). A relatively high W⁵⁺ content in the film, upon intercalation of 18 mC cm⁻² charge translates into a large coloring efficiency (η_VIS ∼ 70 cm² C⁻¹) and transmission modulation. At a lithium intercalation level of 22 mC cm⁻², in addition to W⁵⁺ and W⁶⁺ states, the film also comprises of W⁴⁺ states. The extremely fast color-bleach kinetics (3 and 2 s, respectively, for a 50% change in transmittance) shown by the as-deposited WO₃ film are repercussions of the mesopore morphology, the multiple nanostructures and the sixfold channels of its hexagonal modification. The film shows a high cycling stability as the switching times do not show any significant decline even after 3500 repetitive cycles. Coloration efficiency over the solar and photopic regions and current density for lithium intercalation for the as-deposited film are superior to that observed for the films annealed at 100, 250 and 500 °C. The abysmal electrochromic response of the annealed films is a consequence of surface defects like cracks and uncontrolled densification and pore shrinkage.     

Optical properties of In2O3 oxidized from InN deposited by reactive magnetron sputtering

Unintentionally doped and zinc-doped indium nitride (U-InN and InN:Zn) films were deposited on (0 0 0 1) sapphire substrates by radio-frequency reactive magnetron sputtering, and all samples were then treated by annealing to form In₂O₃ films. U-InN and InN:Zn films have similar photon absorption characteristics. The as-deposited U-InN and InN:Zn film show the absorption edge, ∼1.8-1.9 eV. After the annealing process at 500 °C for 20 min, the absorption coefficient at the visible range apparently decreases, and the absorption edge is about 3.5 eV. Two emission peaks at 3.342 eV (371 nm) and 3.238 eV (383 nm) in the 20 K photoluminescence (PL) spectrum of In₂O₃:Zn films were identified as the free-exciton (FE) or the near band-to-band (B-B) and conduction-band-to-acceptor (C-A) recombination, respectively.