Effects of thermal annealing on the optical,spectroscopic, and structural properties of tris (8-hydroxyquinolinate) gallium films grown on quartz substrates

In this study we report the optical, spectroscopic, and structural properties of vacuum deposited tris (8-hydroxyquinolinate) gallium film upon thermal annealing in the temperature range from 85 °C to 255 °C under a flowing nitrogen gas for 10 min. The optical UV–vis–NIR and luminescence spectroscopy measurements were performed to estimate the absorption bands, optical energy gap (E_g), and photoluminescence (PL) of the films. Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) techniques were used to probe the spectroscopic and structural nature of the films. We show that, by annealing the films from 85 °C to 235 °C, it is possible to achieve an enhanced absorption and increased photoluminescence to five times stronger than that of the pristine film. The PL quenching at 255 °C was attributed to the presence of plainer chains allow easy going for excitons to a long distance due to the crystalline region formation of α-Gaq3 polymorph. The reduction in E_g and infrared absorption bands upon annealing were referred to the enhancement in π–π interchain interaction and conformational changes by re-arrangement of the Gaq3 quinolinate ligands, respectively. Stokes shift for the films were observed and calculated. From the differential scanning calorimetry, DSC measurements, higher glass transition temperature was observed for Gaq3 (T_g = 182 °C) compared to that of Alq3 (T_g = 173 °C), which suggests the existence of stronger dipolar interaction in Gaq3 due to the Ga³⁺ cation effect, in comparison to that of Alq3.     

Temperature effect on structure and surface morphology of indium tin oxide films deposited by reactive ion-beam sputtering

Indium tin oxide (ITO) films were deposited by reactive ion-beam sputtering. The relationship among the surface morphology, the resistivity ρ of the films, the substrate temperature T_S and the film thickness t_F was investigated. The heat power from the ion source during the sputtering was 265 W. T_S increased from 30 to 145 °C with an increase of t_F. The films thinner than 187 nm at T_S lower than 120 °C were amorphous, the film surface was as smooth as the substrate. The films deposited at T_S in the range between 135 and 145 °C were polycrystalline. So, the films thicker than 375 nm were in a multilayer structure of a polycrystalline layer on an amorphous layer. The surface of the polycrystalline films became rough. ρ of the films suddenly decreased at t_F of 375 nm, where the structure of the films changed. Next, the amorphous films with t_F of 39 nm were annealed in the atmosphere. The film structure changed to a polycrystalline structure at annealing temperature T_A of 350 °C. However, the surface roughness of all the films was almost same. As a result, the substrate temperature during the sputtering was important for the deposition of the films with a very smooth surface.     

Low cost synthesis of high-Tc superconducting films on metallic substrates via ultrasonic spray pyrolysis

Ultrasonic spray pyrolysis technique has been used to deposit both in situ and ex situ high temperature superconducting films (HTSC) of Y₁Ba₂Cu₃O_x(YBCO) and Bi₂Sr₂CaCu₂O_x (BSCCO) compounds over various substrates. Nitrate precursor solutions are used to deposit films of ∼10 μm thickness. Both low temperature spray with substrate temperature T_s < 500 °C and high temperature deposition with T_s = 550-900 °C are carried out. Superconducting properties of these films are observed to vary with various parameters such as concentration of spray solution, deposition temperature and nature of substrate and annealing process. Best quality films show T_c (R = 0) of 89 K and J_c of ∼4 × 10⁴ A/cm² at 77 K and ∼ 10⁵ A/cm² at 20 K. X-ray diffraction pattern reveals that the films are textured along c-axis. Successful attempt has been made to deposit in situ superconducting films over polycrystalline Ag for coated conductor applications. Various deposition and annealing conditions are optimized to control the diffusion of Ag from substrate to film, which otherwise can segregate into the grain boundaries and make the films non-superconducting.     

Preparation and properties of transparent conductive indium-tin-oxide/polyimide substrates via a sol-gel process

High temperature, flexible and colorless indium-tin-oxide (ITO) coated plastic substrates have been prepared from a series of thermally stable, high glass transition temperature (T_g) and colorless copolyimide films. The copolyimides were synthesized from 3,3′-diaminodiphenylsulfone, 9,9′-bis(4-aminophenyl) fluorene and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride monomers. Their T_gs were around 285-365 °C. The conductive ITO was synthesized by a sol-gel method, and then deposited onto the copolyimide films by a spin coating process. After thermal treatment at 300 °C under a nitrogen/hydrogen mixture gas for 24 h, the resistivity of the ITO film was 10⁻³ Ω cm, and its transmittance was 75% at the visible light region. Scanning electron microscopy and X-ray diffraction were used to observe the surface and morphology of the ITO films. UV-visible spectroscopy and the four-probe method were used to study their optical and electrical properties. The high performance ITO/plastic substrates can be used in the next generation flexible flat panel displays and solar cell.     

Structural and luminescence correlation of annealed Er-ZnO/Si thin films deposited by AACVD process

Er doped ZnO thin films have been synthesized from zinc acetates dihydrate (C₄H₆O₄Zn·2H₂O) and Erbium tris (2,2,6,6-tetramethyl-3,5-heptadionate) (Er(TMHD)₃) by aerosol assisted chemical vapor deposition AACVD atmospheric pressure technique. Films were deposited in the temperature range of [370–500 °C] on Si (1 1 1) substrate. Nano-disk shaped grains were grown on the top of the film surface. The morphology of the as-deposited films was found to be dependent on the substrate temperature. After annealing in air atmosphere, XRD patterns revealed a highly oriented c-axis Er:ZnO films with hexagonal wurtzite structure without any second phase. Under 488 nm excitation, the intra 4f–4f green emission (²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) gradually increased with increasing annealing temperature. Also, the local structure of Er changes to a pseudo-octahedral structure with C_4v symmetry. The ZnO film with 2.504 at.% Er³⁺ doping has the best crystalline structure and the best resolved PL spectra. Using 325 nm excitation, all the samples showed an ultraviolet emission centered at 380 nm originating from a near band EDGE emission and a broad band green emission centered at 520 nm from deep levels. The optical response was correlated with crystallinity of the synthesized thin films.     

Modification of AZO thin-film properties by annealing and ion etching

Effects of annealing and ion etching on the structural, electrical and optical properties of sputtered ZnO:Al (AZO) thin films were investigated. The post-deposition annealing at temperatures T_A = 200-400 °C in the forming gas (80% N₂/20% H₂) for 1 h and ion RF-sputter etching after annealing were used. Ion-sputter etching rate was 7 nm/min. The surface topography changed noticeably after ion-sputter etching: the surface of the sample was rougher (R_a = 33 nm) in comparison with annealed sample only (R_a = 9 nm). After the post-deposition annealing temperature T_A = 400 °C and ion-sputter etching thin films have higher integral transmittance (in the range of λ = 400-1000 nm) than non-etched samples. The figure of merit (F) became higher with increase of annealing temperature and the maximum value was F = 8%/Ω at T_A = 400 °C (R_s = 10 Ω, T_int = 86%).     

Microwave characterization of laser ablated Y1Ba2Cu3O7−x thin films

In the present study we report the measurements of microwave surface resistance (R_s) of YBCO thin films on LaAlO₃ substrate as a function of temperature, thickness and magnetic field by microstrip resonator technique. The T_c(R = 0) of the films is 90 K and J_c > 10⁶ A/cm² at 77 K. The microwave surface resistance has been measured for films of various thicknesses. The value of R_s has been found to be initially decreased with increasing film thickness due to increase in number of defects. A minimum microwave surface resistance has been obtained for film thickness of about 300 nm. The increase of R_s with film thickness above 300 nm is possibly due to degradation of the film microstructure as observed with Atomic Force Microscopy. Temperature dependence of surface resistance has been studied for best quality films. The field induced variations of surface resistance are also investigated by applying dc magnetic field perpendicular to stripline structure and surface of the film. A general linear and square field dependence of R_s at low and high value of fields has been observed with critical field value of 0.4 T which confirms the microwave dissipation induced by flux flow in these resonators at 10 GHz frequency. The hysteresis of R_s in dc field observed for field value above critical field shows the higher value of surface resistance in decreasing field than in increasing field which is in agreement with one state critical model and is a characteristic of homogeneous superconductors.     

Optical and electrical properties of heat-resistant Sb-doped Sn1 − xHfxO2 transparent conducting films

To examine variations in the transparent conducting properties after annealing at high temperatures, 300-nm thick Sb-doped Sn_1 − xHf_xO₂ (x = 0.00-0.10) films were deposited onto silica glass substrates by the RF sputtering method and annealed in air up to 1000 °C at 200 °C increments. After annealing, all the Sb-doped SnO₂ films were transparent and electrically conductive, but large cracks, which decreased the electrical conductivity, were generated in several films due to crystallization or the thermal expansion difference between the film and substrate. Only the film deposited at room temperature in an Ar and O₂ mixed atmosphere did not crack after annealing, and its electrical conductivity exceeded 100 S cm^− 1 even after annealing at 1000 °C in air. Hf-doping blue shifted the fundamental absorption edges in the UV region in the Sb-doped Sn_1 − xHf_xO₂ films. Additionally, the optical transmission at 310 nm, T₃₁₀, increased as the Hf concentration increased, whereas the electrical conductivity was inversely proportional to the Hf concentration. On the other hand, thinner films (150-nm thick) with x = 0.00 showed both a high electrical conductivity over 100 S cm^− 1 and a high transparency T₃₁₀ = 65% after high temperature annealing.     

Effects of hydrogen annealing on the microstructure and optical properties of single-phased Ag2O film deposited using direct-current reactive magnetron sputtering

Single-phased and (111)-oriented Ag₂O film deposited using direct-current reactive magnetron sputtering is annealed using different annealing temperatures (T_a) for 1 h in Ar and H₂ mixture. After hydrogen annealing, a very weak but clear Ag(200) diffraction peak begins to appear, and the Ag₂O diffraction peak weakens at T_a = 175 °C. However, the Ag diffraction peak becomes discernable at T_a = 190 °C. No Ag₂O diffraction peaks but rather Ag diffraction peaks are discerned at T_a = 200 °C. The hydrogen reduction effect can reduce the film's critical thermal decomposition temperature to 175 °C. After hydrogen annealing, the surface of the film evolutes from compact and uniform to osteoporosis, and then to a porous structure. Moreover, the optical properties of the film obviously change at T_a over 190 °C, indicating that the hydrogen reduction can significantly enhance the decomposition of Ag₂O due to H₂ dissociation on the surface followed by gaseous H₂O molecule formation and desorption.     

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.     

Effect of high temperature annealing on the electrical performance of titanium/platinum thin films

In this study, the influence of post deposition annealing steps (PDA) on the electrical resistivity of evaporated titanium/platinum thin films on thermally oxidised silicon is investigated. Varying parameters are the impact of thermal loading with maximum temperatures up to T_PDA = 700 °C and the platinum top layer thickness ranging from 24 nm to 105 nm. The titanium based adhesive film thickness is fixed to 10 nm. Up to post deposition annealing temperatures of T_PDA = 450 °C, the film resistivity is linearly correlated with the reciprocal value of the platinum film thickness according to the size effect. Modifications in the intrinsic film stress strongly influence the electrical material parameter in this temperature regime. At T_PDA > 600 °C, diffusion of titanium into the platinum top layer and its plastic deformation dominate the electrical behaviour, both causing an increase in film resistivity above average.     

Ultra-thin zinc oxide film on Mo(100)

Zinc oxide films on a single crystal Mo(100) substrate were fabricated by annealing the pre-deposited metal Zn films in 10^− 5-10^− 4 Pa O₂ ambience at 300-525 K, and were characterized by in situ Auger electron spectroscopy, electron energy loss spectroscopy, low energy electron diffraction and high-resolution electron energy loss spectroscopy. The results show that the atomic ratio of oxygen to zinc in zinc oxide film is significantly dependent on sample annealing temperature and O₂ pressure. A stoichiometric zinc oxide film has been obtained under ∼10^− 4 Pa O₂ at about 400 K. A redshift of Fuchs-Kliewer phonon energy correlated with surface oxygen deficiency is observed.     

Deterioration and recovery in the resistivity of Al-doped ZnO films prepared by the plasma sputtering

A hot-cathode plasma sputtering technique was used for fabricating the highly transparent and conducting aluminum-doped zinc oxide (AZO) films on glass substrates from a disk-shaped AZO (Al₂O₃: 2 wt.%) target. Under particular conditions where the target voltage was V_T = −200 V and the plasma excitation pressure was P_S = 1.5 × 10⁻³ Torr, the lowest resistivity of 4.2 × 10⁻⁴ Ω cm was obtained at 400 nm, and this was associated with a carrier density of 8.7 × 10²⁰ cm⁻³ and a Hall mobility of 17 cm²/V s. From the annealing experiment of the AZO films in the oxygen and nitrogen gases of the atmospheric pressure it was revealed that both the oxygen vacancies and the grain boundaries in the polycrystalline AZO film played an important role in the electrical properties of the film.     

Formation of gold nanoparticles in silicon suboxide films prepared by plasma enhanced chemical vapour deposition

Nanostructured materials fabricated by dispersing metal particles on the dielectric surface have potential application in the field of nanotechnology. Interfacial metal particles/dielectric matrix interaction is important in manipulating the structural and optical properties of metal/dielectric films. In this work, a thin layer of gold (Au) was sputtered onto the surface of silicon oxide, SiO_x (0.38 < x < 0.68) films which was deposited at different N₂O/SiH₄ flow rate ratios of 5 to 40 using plasma enhanced chemical vapor deposition (PECVD) technique prior to the annealing process at 800 °C. FTIR spectra demonstrate the intensity and full-width at half-maximum (FWHM) of Si-O-Si stretching peaks are significantly dependent on the N₂O/SiH₄ flow-rate ratio, η. The films deposited at low and high N₂O/SiH₄ flow rate ratios are dominated by the oxygen and silicon contents respectively. The size and concentration of Au particles distributed on the surface of SiO_x films are dependent on the N₂O/SiH₄ flow-rate ratio. High concentrations of Au nanoparticles are distributed evenly on the surface of the film deposited at N₂O/SiH₄ flow-rate ratio of 30. Crystallinity and crystallite sizes of Au are enhanced after the thermal annealing process. Appearance of surface plasma resonance (SPR) absorption peaks at 524 nm for all samples are observed as a result of the formation of Au particles. The annealing process has improved SPR peaks for all the as-deposited films. The energy gap of the as-deposited Au/SiO_x films are in the range of 3.58 to 4.38 eV. This energy gap increases after the thermal annealing process except for the film deposited at η = 5.     

Textured surface boron-doped ZnO transparent conductive oxides on polyethylene terephthalate substrates for Si-based thin film solar cells

Textured surface boron-doped zinc oxide (ZnO:B) thin films were directly grown via low pressure metal organic chemical vapor deposition (LP-MOCVD) on polyethylene terephthalate (PET) flexible substrates at low temperatures and high-efficiency flexible polymer silicon (Si) based thin film solar cells were obtained. High purity diethylzinc and water vapors were used as source materials, and diborane was used as an n-type dopant gas. P-i-n silicon layers were fabricated at ~ 398 K by plasma enhanced chemical vapor deposition. These textured surface ZnO:B thin films on PET substrates (PET/ZnO:B) exhibit rough pyramid-like morphology with high transparencies (T ~ 80%) and excellent electrical properties (Rs ~ 10 Ω at d ~ 1500 nm). Finally, the PET/ZnO:B thin films were applied in flexible p-i-n type silicon thin film solar cells (device structure: PET/ZnO:B/p-i-n a-Si:H/Al) with a high conversion efficiency of 6.32% (short-circuit current density J_SC = 10.62 mA/cm², open-circuit voltage V_OC = 0.93 V and fill factor = 64%).     

Annealing effect on cadmium in situ doping of chemical bath deposited PbS thin films

This paper describes the effect of annealing on PbS and Cd-doped PbS thin films prepared by chemical bath deposition at different bath temperatures (T_b). The X-ray diffraction (XRD), optical absorption, scanning electron microscopy, and energy dispersive X-ray (EDX) analyses have been performed to explore the properties of PbS and PbCdS films. From the XRD measurements, the particle size (D) of as-deposited PbS and PbCdS films is estimated to be 22 (27) and 12 (9) nm, respectively, for a T_b of 75 (85) °C. A reduction in D was noticed upon annealing the films at 200 °C, irrespective of the T_b and the doping. The optical band gap energy (E_g) of as-deposited PbS films grown at different T_b is found to be in the range of 1.22-1.42 eV. Doping of PbS with Cd and annealing have led to increase in E_g up to 2.61 (2.66) eV. Optical studies revealed prominent blue shifts in the E_g of as-deposited and annealed films due to quantum confinement effect. The addition of Cd into PbS was confirmed by EDX analysis.     

Influence of magnetic annealing on high-frequency magnetic properties of FeCoNd films

FeCoNd thin film with thickness of 166 nm has been fabricated on silicon (1 1 1) substrates by magnetron co-sputtering and annealed for one hour under magnetic field at different temperatures (T_a) from 200 °C to 700 °C. The As-deposited and annealed FeCoNd film samples at T_a ≤ 500 °C were amorphous while the ones obtained at T_a ≥ 600 °C were crystallized. We found that the perpendicular anisotropy field gradually decreases as the annealing temperature increases from room temperature to 300 °C. A well induced in-plane uniaxial anisotropy is achieved at the annealing temperature between 400 and 600 °C. The variation of the dynamic magnetic properties of annealed FeCoNd films can be well explained by the Landau-Lifshitz equation with the variation of the anisotropy field re-distribution and the damping constant upon magnetic annealing. The magnetic annealing might be a powerful post treatment method for high frequency application of magnetic thin films.     

Grazing incidence X-ray study of Ge-nanoparticle formation in (Ge:SiO2)/SiO2 multilayers

We present the study of formation of Ge-nanoparticles (Ge-NP) in germanosilicate (Ge:SiO₂) multilayer (ML) films under thermal treatment. In anticipation of controllable formation of Ge-NP, ML films were prepared by magnetron deposition at room temperature as 20 bi-layer stacks, each bi-layer comprised of a 7 nm thick layer of (Ge + SiO₂) (molar ratio: 60:40) succeeded by a 7 nm thick layer of pure SiO₂, and then annealed for 1 h, up to T_a = 900 °C. Formation and morphology of Ge-NP were analyzed by combining the information obtained from the grazing incidence small angle X-ray scattering and X-ray diffraction. It was found that precipitation of Ge-NP starts at T_a = 600 °C, while high degree of in-plane confinement and lateral ordering of rather uniform precipitated particles is achieved at T_a =  700-800 °C range. At still higher annealing temperature T_a > 800 °C, volume fraction of precipitated Ge-NP in SiO₂ matrix diminishes due to the out-diffusion of Ge atoms from the film, while Ge-NP are no more well confined to (Ge + SiO₂) layers.     

Structural and electrical properties of BiFeO3 thin films by solution deposition and microwave annealing

Lead-free polycrystalline BiFeO₃ (BFO) thin films were developed using a chemical solution deposition method to deposit the films and the multi-mode 2.45 GHz microwave furnace to optimize the annealing condition of the films. Phase-pure BFO films were obtained at 500 °C-600 °C for 1-5 min with a heating rate of 10 °C/min. The film by microwave annealing (MW) at 550 °C for 5 min exhibited a (012)-preferred orientation with a dense morphology of grain size ~ 294 nm. Its dielectric constant of 96.2, low leakage current density of 2.466 × 10^− 6 A/cm², polarization (2P_r) and coercive field (2E_c) of 0.931 μC/cm² and 57.37 kV/cm, respectively, were improved compared to those by conventional annealing (CA) at the same annealing conditions.     

Effect of thermal annealing on the structural and mechanical properties of amorphous silicon carbide films prepared by polymer-source chemical vapor deposition

We report on the effect of thermal annealing on the structural and mechanical properties of amorphous SiC thin films prepared by means of a polymer-source chemical vapor deposition process. The chemical bondings of the a-SiC:H films were systematically examined by means of Fourier transform infrared spectroscopy (FTIR). The film composition was measured by X-ray photoelectron spectroscopy, while X-ray reflectivity measurements were used to account for the film density variations caused by the post-annealing treatments over the 750-1200 °C range. In addition, their mechanical properties (hardness and Young's modulus) were investigated by using the nano-indentation technique. FTIR measurements revealed that not only the intensity of a-SiC absorption band linearly increases but also its position is found to shift to a higher wave number as a result of annealing. In addition, the bond density of Si―C is found to increase from (101.6-224.5) × 10²¹ bond·cm^− 3 accompanied by a decrease of Si―H bond density from (2.58-0.46)× 10²¹ bond·cm^− 3 as a result of increasing the annealing temperature (T_a) from 750 to 1200 °C. Annealing-induced film densification is confirmed, as the a-SiC film density is found to increase from 2.36 to ∼ 2.75 g/cm^− 3 when T_a is raised from 750 to 1200 °C. In addition, as T_a is increased from 750 to 1200 °C, both hardness and Young's modulus are found to increase from 15.5 to 17.6 GPa and 155 to 178 GPa, respectively. Our results confirm the previously established linear correlation between the mechanical properties of the a-SiC films and their bond densities.