Effect of annealing on molybdenum doped indium oxide thin films RF sputtered at room temperature

Thin films of molybdenum doped indium oxide (IMO) were deposited on glass at room temperature using an in-built three-source RF magnetron sputtering. The films were studied as a function of oxygen volume percentage (O₂ vol. %; ranging from 0.0 to 17.5%) in the sputtering chamber. The as-deposited amorphous films were crystallized on post-annealing. The as-deposited films are low conducting and Hall coefficients were undetectable; whereas post-annealed films possess fairly high conductivity. The lowest transmittance (11.96% at 600 nm) observed from the films deposited without oxygen increased to a maximum of 88.01% (3.5 O₂ vol. %); whereas this transmittance was decreased with the increasing O₂ vol. % to as low as 81.04% (15.6 O₂ vol. %); a maximum of 89.80% was obtained from the films annealed at 500 °C in open air (3.5 O₂ vol. %). The optical band gap of 3.80 eV obtained from the films deposited without oxygen increased with increasing O₂ vol. % to as high as 3.91 eV (17.5 O₂ vol. %). A maximum of 3.92 eV was obtained from the films annealed at 300 °C in N₂:H₂ gas atmosphere (17.5 O₂ vol. %).     

The effect of annealing on Al-doped ZnO films deposited by RF magnetron sputtering method for transparent electrodes

In this study, transparent conducting Al-doped zinc oxide (AZO) films with a thickness of 150 nm were prepared on Corning glass substrates by the RF magnetron sputtering with using a ZnO:Al (Al₂O₃: 2 wt.%) target at room temperature. This study investigated the effects of the post-annealing temperature and the annealing ambient on the structural, electrical and optical properties of the AZO films. The films were annealed at temperatures ranging from 300 to 500 °C in steps of 100 °C by using rapid thermal annealing equipment in oxygen. The thicknesses of the films were observed by field emission scanning electron microscopy (FE-SEM); their grain size was calculated from the X-ray diffraction (XRD) spectra using the Scherrer equation. XRD measurements showed the AZO films to be crystallized with strong (002) orientation as substrate temperature increases over 300 °C. Their electrical properties were investigated by using the Hall measurement and their transmittance was measured by UV-vis spectrometry. The AZO film annealed at the 500 °C in oxygen showed an electrical resistivity of 2.24 × 10^− 3 Ω cm and a very high transmittance of 93.5% which were decreased about one order and increased about 9.4%, respectively, compared with as-deposited AZO film.     

Effects of heat treatment on properties of ITO films prepared by rf magnetron sputtering

Indium tin oxide (ITO) films were deposited on glass substrates by rf magnetron sputtering using a ceramic target (In₂O₃-SnO₂, 90-10 wt%) without extra heating. The post annealing was done in air and in vacuum, respectively. The effects of annealing on the structure, surface morphology, optical and electrical properties of the ITO films were studied. The results show that the increase of the annealing temperature improves the crystallinity of the films, increases the surface roughness, and improves the optical and electrical properties. The transmittance of the films in visible region is increased over 90% after the annealing process in air or in vacuum. The resistivity of the films deposited is about 8.125×10⁻⁴ Ω cm and falls down to 2.34×10⁻⁴ Ω cm as the annealing temperature is increased to 500°C in vacuum. Compared with the results of the ITO films annealed in air, the properties of the films annealed in vacuum is better.     

Effect of annealing on the electrical, optical and structural properties of cadmium stannate thin films prepared by spray pyrolysis technique

Polycrystalline thin films of cadmium stannate (Cd₂SnO₄) were deposited by spray pyrolysis method on the Corning substrates at substrate temperature of 525 °C. Further, the films were annealed at 600 °C in vacuum for 30 min. These films were characterized for their structural, electrical and optical properties. The experimental results showed that the post-deposition annealing in vacuum has a significant influence on the properties of the films. The average grain size of the film was increased from 27.3 to 35.0 nm on heat treatment. The average optical transmittance in the visible region (500-850 nm) is decreased from 81.4% to 73.4% after annealing in vacuum. The minimum resistivity achieved in the present study for the vacuum annealed films is the lowest among the reported values for the Cd₂SnO₄ thin films prepared by spray pyrolysis method.     

Characterization of nanocrystalline indium tin oxide thin films prepared by ion beam sputter deposition method

Indium tin oxide (ITO) thin films were deposited on glass substrates by ion beam sputter deposition method in three different deposition conditions [(i) oxygen (O₂) flow rate varied from 0.05 to 0.20 sccm at a fixed argon (1.65 sccm) flow rate, (ii) Ar flow rate changed from 1.00 to 1.65 sccm at a fixed O₂ (0.05 sccm) flow rate, and (iii) the variable parameter was the deposition time at fixed Ar (1.65 sccm) and O₂ (0.05 sccm) flow rates]. (i) The X-ray diffraction (XRD) patterns show that the ITO films have a preferred orientation along (400) plane; the orientation of ITO film changes from (400) to (222) direction as the O₂ flow rate is increased from 0.05 to 0.20 sccm. The optical transmittance in the visible region increases with increasing O₂ flow rate. The sheet resistance (R_s) of ITO films also increases with increasing O₂ flow rate; it is attributed to the decrease of oxygen vacancies in the ITO film. (ii) The XRD patterns show that the ITO film has a strong preferred orientation along (222) direction. The optical transmittance in the visible spectral region increases with an increase in Ar flow rate. The R_s of ITO films increases with increasing Ar flow rate; it is attributed to the decrease of grain size in the films. (iii) A change in the preferred orientations of ITO films from (400) to (222) was observed with increasing film thickness from 314 to 661 nm. The optical transmittance in the visible spectral region increases after annealing at 200 °C. The R_s of ITO film decreases with the increase of film thickness.     

Optical recording characteristics of molybdenum oxide films prepared by pulsed laser deposition method

Molybdenum-oxide (MoO₃)films were deposited on glass substrates (Corning #7059 with an area of 26 × 38 mm²) by pulsed laser deposition using an ArF excimer laser. It was found that after annealing at 340 °C for 10 min, the film thickness became 2.3 times that (approximately 30 nm) of the as-deposited film thickness. The difference in the transmittance, ΔT, between the annealed state and the as-deposited state was about 40% at a wavelength of 400 nm. X-ray diffraction spectra indicated that oxygen was absorbed into the MoO₃ films through the annealing process. From revolution testing of 30 nm-thick MoO₃ films without a protective layer deposited on a polycarbonate DVD-R disk substrate (120 mm?, 0.6 mm thickness), a write peak-power dependence of carrier-to-noise ratio (CNR) (recording on-land, at λ = 406 nm, NA = 0.65) of the 3T signal (58.5 MHz) was measured at a linear velocity of 5 m/s and a read power of 0.6 mW. Consequently, CNR near 50dB was obtained in the wide write-power margin ΔP of 7 mW (at peak powers between 3.5 and 10.5 mW). From SEM observations, it was recognized that bits of 0.25-0.30 μm size, corresponding to a storage capacity of 7-10GB/in² in the case of NA = 0.65, were formed. For the sample structure with an Al₂O₃ protective layer of ~ 20 nm thickness, a CNR near 50dB was obtained in the peak-power margin ΔP of 12 mW (at peak powers between 6.0 and 18.0 mW). Larger values of the CNR can be obtained if the film thickness of each layer including both the active and protective layers is optimized.     

Structural, electrical and optical studies of SILAR deposited cadmium oxide thin films: Annealing effect

Successive ionic layer adsorption and reaction (SILAR) method has been successfully employed for the deposition of cadmium oxide (CdO) thin films. The films were annealed at 623 K for 2 h in an air and changes in the structural, electrical and optical properties were studied. From the X-ray diffraction patterns, it was found that after annealing, H₂O vapors from as-deposited Cd(O₂)_0.88(OH)_0.24 were removed and pure cubic cadmium oxide was obtained. The as-deposited film consists of nanocrystalline grains of average diameter about 20-30 nm with uniform coverage of the substrate surface, whereas for the annealed film randomly oriented morphology with slight increase in the crystallite size has been observed. The electrical resistivity showed the semiconducting nature with room temperature electrical resistivity decreased from 10⁻² to 10⁻³ Ω cm after annealing. The decrease in the band gap energy from 3.3 to 2.7 eV was observed after the annealing.     

Optical properties of tungsten oxide thin films by non-reactive sputtering

Tungsten oxide thin films were grown on glass substrates by RF sputtering at room temperature using a tungsten trioxide target for several values of the argon pressure (P_Ar). The structural and morphological properties of these films were studied using X-ray diffraction and atomic force microscopy. The as-deposited films were amorphous irrespective of the argon pressure, and crystallized in a mixture of hexagonal and monoclinic phases after annealing at a temperature of 350 °C in air. Surface-roughness increased by an order of magnitude (from 1 nm to 20 nm) after thermal treatment. The argon pressure, however, had a strong influence on the optical properties of the films. Three different regions are clearly identified: deep blue films for P_Ar ≤ 2.67 Pa with low transmittance values, light blue films for 2.67 Pa < P_Ar < 6 Pa with intermediate transmittance values and transparent films for P_Ar ≥ 6 Pa with high transmittance values. We suggest that the observed changes in optical properties are due to an increasing number of oxygen vacancies as the growth argon pressure decreases.     

Optical properties and hydrophilic behaviors of TaOxNy thin films with and without rapid thermal annealing

TaO_xN_y thin films were prepared using DC reactive sputtering of Ta target with the variation of (O₂ + N₂)/Ar ratio, followed by rapid thermal annealing (RTA) at 800 °C for 5 min. During RTA, the amorphous structure of the as-deposited films would transform to crystallized phases that might contain either TaON, or Ta₂O_5, or both. With the increase of (O₂ + N₂)/Ar ratio, Ta₂O₅ phase becomes more dominant, while TaON was formed in an opposite way. Elemental analysis also shows the same trend. Hydrophilicity and optical properties of these films were found to be dependent on phases formed after annealing. The optical band gap was measured and calculated to be in the range of 2.43 eV (510 nm) to 3.94 eV (315 nm). The films with low band gap values exhibited super hydrophilicity behavior under visible light irradiation, mainly due to their light absorption had been extended to visible light range. Clearly, it was due to the existence of TaON phase.     

Study of surface morphology and optical properties of Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> thin films with annealing

Nb₂O₅ films have been deposited on variety of substrates using the sol-gel dip coating technique. As-deposited films on all substrates are amorphous. Films were annealed under controlled ambience at 300, 400 and 600°C for 5 h. As-deposited films on glass substrate show uniform surface structure. The crystal structure and surface topography are found to depend strongly on the annealing temperature and nature of the substrates. The average grain size of 40 nm is observed in films annealed at 300°C. On annealing at 400°C increasing grain size and resulting fusing of them, enhanced surface roughness. Films deposited on NaCl substrates crystallized into a stable monoclinic phase and those deposited on single crystal Si substrates crystallized into hexagonal phase after annealing at 600°C. The as-deposited films show very high transmittance (>90%) in the visible region. The optical band gap is observed to increase from 4.35 eV when the films are in amorphous state to 4.87 eV on crystallization.     

Properties of transparent conducting oxides formed from CdO alloyed with In2O3

The structure, optical and electrical properties of transparent conducting oxide films depend greatly on the methods of preparation, heat treatment, type and level of dopant. Thin films of (CdO)_1−x(In₂O₃)_x have been grown by electron beam evaporation technique for different concentrations of In₂O₃ (x = 0, 0.05, 0.1, 0.15 and 0.2). Increase of doping led to increased carrier concentration as derived from optical data and hence to increased electrical conductivity, which degraded the transparency of the films. An improvement of the electrical and optical properties of Cadmium indium oxide (CdIn₂O₄) has been achieved by post-deposition annealing. A resistivity value of 7 × 10^− 5 Ω cm and transmittance of 92% in the near infrared region and 82% in the visible region have been obtained after annealing at 300 °C for 90 min in air.     

Influence of post-annealing temperature on the properties exhibited by ITO, IZO and GZO thin films

In this work we present a study on the effect of annealing temperatures on the structural, morphological, electrical and optical characteristics of gallium doped zinc oxide (GZO), indium zinc oxide (IZO) and indium-tin-oxide (ITO) films. GZO and IZO films were deposited at room temperature by r.f. magnetron sputtering, whereas the ITO films were commercial ones purchased from Balzers. All films were annealed at temperatures of 250 and 500 °C in open air for 1 h. The GZO and ITO films were polycrystalline. The amorphous structure of as-deposited IZO films becomes crystalline on high temperature annealing (500 °C). The sheet resistivity increased with increase in annealing temperature. GZO films showed an increase of 6 orders of magnitude. The optical transmittance and band gap of as-deposited films varied with annealing. The highest transmittance (over 95 %) and maximum band gap (3.93 eV) have been obtained for ITO films.     

Effects of oxygen flow ratios and annealing temperatures on Raman and photoluminescence of titanium oxide thin films deposited by reactive magnetron sputtering

Titanium oxide (TiO_x) thin films were deposited on the Si(100) substrates by direct-current reactive magnetron sputtering at 3-15 % oxygen flow ratios (FO₂% = FO₂/(FO₂ + FAr) × 100%), and then annealed by rapid thermal annealing (RTA) at 350-750 °C for 2 min in air. The phase, bonding and luminescence behaviors of the as-deposited and annealed TiO_x thin films were analyzed by X-ray diffraction (XRD), Raman spectroscopy and photoluminescence (PL) spectroscopy, respectively. The as-deposited TiO_x films were amorphous from XRD and showed weak Raman intensity. In contrast, the distinct crystalline peaks of anatase and rutile phases were detected after RTA at 550-750 °C from both XRD and Raman spectra. A mixture of anatase and rutile phases was obtained by RTA at 3 FO₂% and its amount increased with annealing temperature. Only the anatase phase was detected in the 6-15 FO₂% specimens after RTA. The PL spectra of all post-annealed TiO_x films showed a broad peak in visible light region. The PL peak of TiO_x film at 3 FO₂% at 750 °C annealing can be fitted into two Gaussian peaks at ~ 486 nm (2.55 eV) and ~ 588 nm (2.11 eV) which were attributed to deep-level emissions of oxygen vacancies in the rutile and anatase phases, respectively. The peak around 550 nm was observed at 6-15 FO₂% which is attributed to electron-hole pair recombination from oxygen vacancy state in anatase phase to valence band. The variation of intensity of PL peaks is concerned with the formation of the rutile and anatase phases at different FO₂% and annealing temperatures.     

In situ and ex situ investigation on the annealing performance of the ZnO film grown by ion beam deposition

The effects of the post-annealing treatment on the properties of the ZnO thin films deposited by ion beam sputtering have been investigated. By using in situ X-ray diffraction technique, an overview of the crystallization behavior of the ZnO film during the annealing process was obtained. It was found that the whole process can be divided into three regions. The improvement of the film’s crystallinity performance mainly occurs within the annealing temperature ranging from 300 to 600 °C. Both in situ and ex situ XRD results show the shift of the ZnO (002) peak towards high angle with the increasing annealing temperature, which is attributed to the variation of the stress in the film. The stress is mainly caused by the intrinsic stress which is affected by the oxygen deficiency in the film. The oxygen deficiency is sensitive to the annealing ambient. The film annealed in the O₂ ambient has less oxygen deficiency and higher resistivity. All the ZnO films deposited on the glass substrates have an optical transmittance over 85% in the visible region. Our results show that the ZnO films deposited using ion beam sputtering exhibit good thermal stability and high performance after annealing.     

Effect of annealing temperature on the properties of IZO films and IZO based transparent TFTs

This work shows the effect of the annealing temperature and atmosphere on the properties of r.f. magnetron sputtered indium-zinc oxide (IZO) thin-films of two types: one a conductive film (as-deposited, room temperature) that exhibits a resistivity of 3.5 × 10^− 4 Ω cm; the other, a semiconductor film with a resistivity ∼ 10² Ω cm. The annealing temperatures were changed between 125 and 500 °C. Crystallization of the more conductive films was already noticeable at temperatures around 400 °C. Three different annealing atmospheres were used — vacuum, air and oxygen. For the conductive films, only the oxygen atmosphere was critical, leading to an increase of the electrical resistivity of more than one order of magnitude, for temperatures of 250 °C and above. Concerning the semiconductor films, both temperature and atmosphere had a strong effect on the film's properties, and the resistivity of the annealed films was always considerably smaller than the as-deposited films. Finally, some results of the application of these films to transparent TFTs are shown.     

Effect of Cu dopant on microstructure and phase transformation of ZnTiO3 thin films prepared by radio frequency magnetron sputtering

Cu doped zinc titanate (ZnTiO₃) films were prepared using radio frequency magnetron sputtering. Subsequent annealing of the as-deposited films was performed at temperatures ranging from 600 to 900 °C. It was found that the as-deposited films were amorphous and contained 0.84 at.% Cu. This was further confirmed by the onset of crystallization that took place at annealing temperatures 600 °C. The phase transformation for the as-deposited films and annealed films was investigated in this study. The results showed that Zn₂Ti₃O₈, ZnTiO₃, and TiO₂ can coexist at 600 °C. When annealed at 700 °C, the results revealed that mainly the hexagonal ZnTiO₃ phase formed, accompanied by minority amounts of TiO₂ and Zn₂Ti₃O₈. Unlike pure zinc titanate films, this result showed that the Zn₂Ti₃O₈ phase can be stable at temperatures above 700 °C. Moreover, Cu addition in zinc titanate thin film could result in the decomposition of hexagonal (Zn,Cu) TiO₃ phase at 800 °C. When the Cu content was increased in zinc titanate thin films from 0.84 at.% to 2.12 at.%, there were only two phases; Zn₂Ti₃O₈ and ZnTiO₃, coexisting at temperatures between 700 and 800 °C. This result indicated that a greater presence of Cu dopants in zinc titanate thin films leads to the existence of the Zn₂Ti₃O₈ phase at higher temperatures.     

Annealing studies on the structural and optical properties of electrodeposited CdO thin films

Cadmium oxide (CdO) thin films were electrodeposited on indium doped tin oxide glass substrates from aqueous solution and subsequently annealed at higher temperatures up to 600 °C in air, oxygen and inert gas ambients, respectively. The effect of annealing on the morphology, crystalline quality and optical properties of CdO films was investigated. The CdO films were polycrystalline in nature and the grain size strongly depended on the annealing temperature as well as annealing ambient. CdO films were highly transparent in the visible region of the spectrum. The transmittance of the films decreased with increasing annealing temperatures in all the three ambients. Optical bandgap of the nanocrystalline CdO films varied in the range of 2.20–2.54 eV.     

Rapid thermal annealed Al-doped ZnO film for a UV detector

A low-resistive Al-doped ZnO (AZO) film was achieved by rapid thermal annealing. A co-sputtering method was used in the initial growth of AZO films and a rapid annealing process was performed on the as-deposited AZO film under N₂ atmosphere for 3 min. An as-deposited AZO film had an optical transmittance of 84.78% at 550 nm and a resistivity of 7.8 × 10^− 3 Ω cm. A rapid annealing process significantly improved the optical transmittance and electrical resistivity of the AZO film to 99.67% and 1 × 10^− 3 Ω cm, respectively. The structural changes of the AZO films were investigated by X-ray diffraction and transmission electron microscopy. The high quality AZO film was used to fabricate a metal-semiconductor-metal (MSM) structure for a UV detector. The MSM device provided a stable current of 25 μA at a bias of 2 V in a dark condition. Under UV illumination, the MSM device was highly responsive to UV light uniformly and repeatedly, and it enhanced the current by 80% at 45 μA. This rapid thermal annealing process may provide a useful method to fabricate quality AZO films for photoelectric applications with a low thermal budget.     

Preparation of highly transparent conductive Al-doped ZnO thin films and annealing effects on properties

Aluminum-doped ZnO (ZAO) thin films were deposited on fused quartz substrates by radio frequency sputtering in pure argon ambient at 450 °C. Effects of in situ annealing temperature and annealing atmosphere on microstructure, electrical and optical properties of ZAO films have been investigated. Results showed that as-grown film without annealing treatments attained lowest resistivity of 1.1 × 10⁻⁴Ω cm. And all films performed high average transmittance greater than 90% in visible region. X-Ray diffraction (XRD), photoluminescence (PL), X-ray photoelectron spectroscopy (XPS) were utilized to characterize the microstructure properties of films. XRD results indicated that as-grown film had higher crystalline quality and larger grain size than annealed films. Al atoms replaced Zn efficiently to provide electrons stable in all samples. PL spectra revealed that high annealing temperature and oxygen atmosphere would generate more Zn vacancy (V_Zn) and oxide antisite defect (O_Zn), respectively and composition content results from XPS provided supports to this.     

Atomic layer deposition and post-deposition annealing of PbTiO3 thin films

Lead titanate thin films were deposited by atomic layer deposition on Si(100) using Ph₄Pb and Ti(O-i-Pr)₄ as metal precursors and O₃ and H₂O as oxygen sources. The influence of the Ti : Pb precursor pulsing ratio on the film growth, stoichiometry and quality was studied at two different temperatures, i.e. 250 and 300 °C. Uniform and stoichiometric films were obtained using a Ti : Pb precursor pulsing ratio of 1 : 10 at 250 °C or 1 : 28 at 300 °C. The as-deposited films were amorphous but the crystalline PbTiO₃ phase was obtained by rapid thermal annealing at 600-900 °C both in N₂ and O₂ ambient. Thin PbTiO₃ films were visually uniform and roughness values for as-deposited and annealed films were observed by atomic force microscopy.