Low temperature annealing effects on the structure and optical properties of ZnO films grown by pulsed laser deposition

ZnO thin films were deposited on glass substrates at room temperature (RT) ∼500 °C by pulsed laser deposition (PLD) technique and then were annealed at 150-450 °C in air. The effects of annealing temperature on the microstructure and optical properties of the thin films deposited at each substrate temperature were investigated by XRD, SEM, transmittance spectra, and photoluminescence (PL). The results showed that the c-axis orientation of ZnO thin films was not destroyed by annealing treatments; the grain size increased and stress relaxed for the films deposited at 200-500 °C, and thin films densified for the films deposited at RT with increasing annealing temperature. The transmittance spectra indicated that E_g of thin films showed a decreased trend with annealing temperature. From the PL measurements, there was a general trend, that is UV emission enhanced with lower annealing temperature and disappeared at higher annealing temperature for the films deposited at 200-500 °C; no UV emission was observed for the films deposited at RT regardless of annealing treatment. Improvement of grain size and stoichiometric ratio with annealing temperature can be attributed to the enhancement of UV emission, but the adsorbed oxygen species on the surface and grain boundary of films are thought to contribute the annihilation of UV emission. It seems that annealing at lower temperature in air is an effective method to improve the UV emission for thin films deposited on glass substrate at substrate temperature above RT.     

Influence of substrate temperature on N-doped ZnO films deposited by RF magnetron sputtering

Nitrogen-doped ZnO films were deposited by RF magnetron sputtering in 75% of N₂ / (Ar + N₂) gas atmosphere. The influence of substrate temperature ranging from room temperature (RT) to 300 °C was analyzed by X-ray diffractometry (XRD), spectrophotometry, X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS) and Hall measurements setup. The XRD studies confirmed the hexagonal ZnO structure and showed that the crystallinity of these films increased with increasing substrate temperature (T_s). The optical studies indicate the average visible transmittance in the wavelength ranging 500-800 nm increases with increasing T_s. A minimum transmittance (9.84%) obtained for the films deposited at RT increased with increasing T_s to a maximum of 88.59% at 300 °C (500-800 nm). Furthermore, it was understood that the band gap widens with increasing T_s from 1.99 eV (RT) to 3.30 eV (250 °C). Compositional analyses (XPS and SIMS) confirmed the nitrogen (N) incorporation into the ZnO films and its decreasing concentration with increasing T_s. The negative sign of Hall coefficients confirmed the n-type conducting.     

The effects of substrate temperature on the structure and properties of ZnO films prepared by pulsed laser deposition

ZnO thin films were prepared by pulsed laser deposition (PLD) on glass substrates with growth temperature from room temperature (RT) to 500 °C. The effects of substrate temperature on the structural and optical properties of ZnO films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission spectra, and RT photoluminescence (PL) measurements. The results showed that crystalline and (0 0 2)-oriented ZnO films were obtained at all substrate temperatures. As the substrate temperature increased from RT to 500 °C, the ratio of grain size in height direction to that in the lateral direction gradually decreased. The same grain size in two directions was obtained at 200 °C, and the size was smallest in all samples, which may result in maximum E_g and E₀ of the films. UV emission was observed only in the films grown at 200 °C, which is probably because the stoichiometry of ZnO films was improved at a suitable substrate temperature. It was suggested that the UV emission might be related to the stoichiometry in the ZnO film rather than the grain size of the thin film.     

Study of plasma enhanced chemical vapor deposition of ZnO films by non-thermal plasma jet at atmospheric pressure

Plasma enhanced chemical vapor deposition using a non-thermal plasma jet was applied to deposition of ZnO films. Using vaporized bis(octane-2,4-dionato)zinc flow crossed by the plasma jet, the deposition rate was as high as several tens of nm/s. From the results of infrared spectra, the films deposited at the substrate temperature T_sub = 100 °C contained a significant amount of carbon residue, while the films prepared at T_sub = 250 °C showed less carbon fraction. The experimental results confirmed that the plasma jet decomposed bis(octane-2,4-dionato)zinc in the gaseous phase and on the substrate, and that there should be the critical T_sub to form high-quality ZnO films in the range from 100 to 250 °C.     

Scaling behavior and structure transition of ZrO2 films deposited by RF magnetron sputtering

ZrO₂ thin films were deposited onto Si wafers and glass slides by reactive rf magnetron sputtering with varying conditions of substrate temperature (T_s). Structural analysis was carried out using high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM). The scaling behavior of the AFM topographical profiles was analyzed using one-dimensional power spectral density method (1DPSD). Morphological and structural evolution of ZrO₂ films have been studied in relation to T_s. With substrate temperatures ranging from RT to 550 °C, the structural transition of the films is a-ZrO₂ (below 250 °C) → m-ZrO₂ with a little a-ZrO₂ (450 °C) → m-ZrO₂ with a little t-ZrO₂ (550 °C). The roughness exponent α is 1.53 ± 0.02, 1.04 ± 0.01, 1.06 ± 0.05, 1.20 ± 0.03 for ZrO₂ thin films deposited at RT, 250 °C, 450 °C, and 550 °C, respectively. Quantitative surface characterization by spatially resolved 1DPSD analyses identified three different growth mechanisms of surface morphology for ZrO₂ thin films deposited at RT, 250∼450 °C and 550 °C. The evolution and interactions of surface roughness and microstructure are discussed in terms of surface diffusion, grain growth, and flux shadowing mechanisms.     

Correlation study between structural, magnetic and transport properties of annealed Co thin films

This paper presents structural, magnetization and transport properties measurements carried out on as-deposited Co (400 Å) thin film as well as samples annealed in the temperature range 100-500 °C in steps of 100 °C for 1 h. The samples used in this work were deposited on float glass substrates using ion beam sputtering technique. The magnetization measurements carried out using MOKE technique, clearly indicates that as-deposited as well as annealed samples up to 500 °C show well saturation magnetization with applied magnetic field. The as-deposited sample shows coercivity value (H_c) of 26 Oe, and it is increased to 94 Oe for 500 °C-annealed sample. A minimum coercivity value of 15 Oe is obtained for 200 °C annealed sample. The XRD measurements of as deposited films show microcrystalline nature of Co film, which becomes crystalline with increase in annealing temperature. The corresponding resistivity measurements show gradual decrease in resistivity. AFM technique was employed to study the surface morphology of as deposited film as well as annealed thin films. Observed magnetization, and resistivity behaviour is mainly attributed to the (i) change in crystal structure (ii) increase in grain size and (iii) stress relaxation due to the annealing treatment.     

Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

Effect of Ag doping on the performance of ZnO thin film transistor

Ag-doped zinc oxide (SZO) thin film transistors (TFTs) have been fabricated using a back-gate structure on thermally oxidized and heavily doped p-Si (100) substrate. The SZO thin films were deposited via pulsed laser deposition (PLD) from a 1, 3, and 5 wt.% Ag-doped ZnO (1SZO, 3SZO, and 5SZO, respectively) target using a KrF excimer laser (λ, 248 nm) at oxygen pressure of 350 mTorr. The deposition carried out at both room-temperature (RT) and 200 °C. The SZO thin films had polycrystalline phase with preferred growth direction of (002) as well as a wurtzite hexagonal structure. Compare with ZnO thin films, the SZO thin films were characterized by confirming the shift of (002) peak to investigate the substitution of Ag dopants for Zn sites. The as-grown SZO TFTs deposited at RT and 200 °C showed insulator characteristics. However the SZO TFTs annealed at 500 °C showed good n-type TFT performance because Ag was diffused from Zn lattice site and bound themselves at the high temperature, and it caused generation of electron carriers. The post-annealed 5SZO TFT deposited at 500 °C exhibited a threshold voltage (V_th) of 11.5 V, a subthreshold swing (SS) of 2.59 V/decade, an acceptable mobility (μ_SAT) of 0.874 cm²/V s, and on-to-off current ratios (I_on/off) of 1.44 × 10⁸.     

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.     

Influence of annealing temperature on the structural, mechanical and wetting property of TiO2 films deposited by RF magnetron sputtering

TiO₂ films have been deposited on silicon substrates by radio frequency magnetron sputtering of a pure Ti target in Ar/O₂ plasma. The TiO₂ films deposited at room temperature were annealed for 1 h at different temperatures ranging from 400 °C to 800 °C. The structural, morphological, mechanical properties and the wetting behavior of the as deposited and annealed films were obtained using Raman spectroscopy, atomic force microscopy, transmission electron microscopy, nanoindentation and water contact angle (CA) measurements. The as deposited films were amorphous, and the Raman results showed that anatase phase crystallization was initiated at annealing temperature close to 400 °C. The film annealed at 400 °C showed higher hardness than the film annealed at 600 °C. In addition, the wettability of film surface was enhanced with an increase in annealing temperature from 400 °C to 800 °C, as revealed by a decrease in water CA from 87° to 50°. Moreover, the water CA of the films obtained before and after UV light irradiation revealed that the annealed films remained more hydrophilic than the as deposited film after irradiation.     

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.     

Characterization of nanostructures of ZnO and ZnMnO films deposited by successive ionic layer adsorption and reaction method

ZnO and ZnMnO thin films were obtained by the successive ionic layer adsorption and reaction (SILAR) method. All thin films were deposited on glass microscope slide. A precursor solution of 0.1 M of ZnCl₂ complexed with ammonium hydroxide and water close to boiling point (92 °C) as a second solution was used for the ZnO films. An uncomplexed bath comprised of 0.1 M ZnCl₂, 0.1 M MnCl_2, and a second solution of 0.1 ml of NH₄OH with water close to boiling point was used for the ZnMnO films. The film samples were deposited by the SILAR method and annealed at 200 °C for 15 min. These samples were characterized using X-Ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive Spectroscopy (EDS), and Atomic Force Microscope. Atomic absorption was used to determine quantitatively the amount of Mn incorporated into the films. According to the XRD patterns these films were polycrystalline with wurtzite hexagonal structure. The morphology of the ZnO films constituted by rice-like and flower-like structures changed significantly to nanosheet structures with the Mn incorporation. The Mn inclusion in a ZnO structure was less than 4% according to the results from EDS, XRD, and atomic absorption.     

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%).     

Effects of thermal annealing on the performance of Al/ZnO nanorods/Pt structure ultraviolet photodetector

ZnO nanorod arrays were fabricated on ZnO coated glass substrate by hydrothermal method. Schottky barrier ultraviolet photodetectors (PDs) were obtained by sputtering Pt electrode and evaporating Al electrode on the top of ZnO nanorod arrays with thermal treatment. It is illustrated that Schottky contacts at the electrode/ZnO NRs interface were formed at the annealing temperature of 300 °C and above. When annealing temperature was up to 300 °C, the performance of the PDs was improved with the great decrease of response and recovery times. At the forward bias of 2 V, the Schottky contact PDs showed the biggest responsivity and the best detectivity at the annealing temperature of 300 °C. For annealing temperature at 300 °C and above, the responsivity decreases with increasing annealing temperature and the ratio of detectivity (D₂₅₄^* to D₅₄₆^*) was calculated as high as 10³ for all PDs annealed at 300 °C and above.     

The properties of transparent semiconductor Zn1 − xTixO thin films prepared by the sol-gel method

Transparent semiconductor thin films of Zn_1 − xTi_xO (0 ≦ x ≦ 0.12) were deposited on alkali-free glass substrates by the sol-gel method. The effects of Ti addition on the crystallization, microstructure, optical properties and resistivity of ZnO thin films were investigated. The as-coated films were preheated at 300 °C, and then annealed at 500 °C in air ambiance. X-ray diffraction results showed all polycrystalline Zn_1 − xTi_xO thin films with preferred orientation along the (002) plane. Ti incorporated within the ZnO thin films not only decreased surface roughness but also increased optical transmittance and electrical resistivity. In the present study, the Zn_0.88Ti_0.12O film exhibited the best properties, namely an average transmittance of 91.0% (an increase of ~ 12% over the pure ZnO film) and an RMS roughness value of 1.04 nm.     

Preparation and characterization of pulsed laser deposited CdTe thin films at higher FTO substrate temperature and in Ar + O2 atmosphere

Pulsed laser deposition (PLD) is one of the promising techniques for depositing cadmium telluride (CdTe) thin films. It has been reported that PLD CdTe thin films were almost deposited at the lower substrate temperatures (<300 °C) under vacuum conditions. However, the poor crystallinity of CdTe films prepared in this way renders them not conducive to the preparation of high-efficiency CdTe solar cells. To obtain high-efficiency solar cell devices, better crystallinity and more suitable grain size are needed, which requires the CdTe layer to be deposited by PLD at high substrate temperatures (>400 °C). In this paper, CdTe layers were deposited by PLD (KrF, λ = 248 nm, 10 Hz) at different higher substrate temperatures (T_s). Excellent performance of CdTe films was achieved at higher substrate temperatures (400 °C, 550 °C) under an atmosphere of Ar mixed with O₂ (1.2 Torr). X-ray diffraction analysis confirmed the formation of CdTe cubic phase with a strong (1 0 0) preferential orientation at all substrates temperatures on 60 mJ laser energy. The optical properties of CdTe were investigated, and the band gaps of CdTe films were 1.51 eV and 1.49 eV at substrate temperatures of 400 °C and 550 °C, respectively. Scanning electron microscopy (SEM) showed an average grain size of 0.3–0.6 μm. Thus, under these conditions of the atmosphere of Ar + O₂ (15 Torr) and at the relatively high T_s (500 °C), an thin-film (FTO/PLD-CdS (100 nm)/PLD-CdTe (~1.5 μm)/HgTe: Cu/Ag) solar cell with an efficiency of 6.68% was fabricated.     

Transparent, amorphous and organics-free ZnO thin films produced by chemical solution deposition at 150 °C

We have studied the low-temperature processing of ZnO by chemical solution deposition. A transparent, stable precursor solution prepared from zinc acetate dihydrate dissolved in 2-methoxyethanol was spin-coated on SiO_x/Si, soda-lime glass and polymer substrates and heated at 150 °C. Selected thin films deposited on SiO_x/Si were additionally heated at 450 °C.Microstructural and chemical analyses showed that the thin films heated at 150 °C in air were amorphous, contained no organic residues and had a root mean square roughness of 0.7 nm. The films deposited on SiO_x/Si and heated at 450 °C were crystallised and consisted of randomly oriented grains with a diameter of about 20 nm. All thin films were transparent, exhibiting a transmission of over 80% in the visible range. The resistivity of the 120-nm thick ZnO films processed at 150 °C was 57 MΩ cm and upon heating at 450 °C it decreased to 1.9 kΩ cm.     

Role of substrate temperature on the structural, morphological and optical properties of CuGaSe2 thin films grown by Pulsed Electron Deposition technique

CuGaSe₂ (CGS) thin films were grown on uncoated and Mo-coated soda lime glass by Pulsed Electron Deposition (PED) technique at substrate temperatures comprised between 25 °C and 475 °C. X-ray diffraction analysis reveals that CGS samples exhibit a noteworthy crystal quality even at low growth temperature, T_g = 100 °C, whereas the out-of-plane preferential orientation of CGS chalcopyrite phase switches from < 220 > to < 112 > by increasing the substrate temperature. Annealing treatments seem to enhance the crystallinity of the film and to release the residual strain energy. Visible/near-infrared absorbance spectra show a monotonic decrease of CGS optical bandgap (from 1.75 to 1.65 eV) by enhancing the substrate temperature. Yet the morphology of CGS films strongly depends on T_g, which promotes the formation of larger columnar grains perpendicular to the growth plane. Grain dimensions of ~ 2 μm are achieved when CGS films are grown at high temperature (> 400 °C) on Mo-coated glass. The results indicate that PED is a promising growth technique for achieving good-quality CGS that can be useful as absorber layers in thin film solar cells.     

Influence of oxygen pressure on the structural, electrical and optical properties of VO2 thin films deposited on ZnO/glass substrates by pulsed laser deposition

The influence of oxygen pressure on the structural and electrical properties of vanadium oxide thin films deposited on glass substrates by pulsed laser deposition, via a 5-nm thick ZnO buffer, was investigated. For the purposes of comparison, VO₂ thin films were also deposited on c-cut sapphire and glass substrates. During laser ablation of the V metal target, the oxygen pressure was varied between 1.33 and 6.67 Pa at 500 °C, and the interaction and reaction of the VO₂ and the ZnO buffer were studied. X-ray diffraction studies showed that the VO₂ thin film deposited on a c-axis oriented ZnO buffer layer under 1.33 Pa oxygen had (020) preferential orientation. However, VO₂ thin films deposited under 5.33 and 6.67 Pa were randomly oriented and showed (011) peaks. Crystalline orientation controlled VO₂ thin films were prepared without such expensive single crystal substrates as c-cut sapphire. The metal-insulator transition properties of the VO₂/ZnO/glass samples were investigated in terms of electrical conductivity and infrared reflectance with varying temperatures, and the surface composition was investigated by X-ray photoelectron spectroscopy.     

Porous nanostructured ZnO films deposited by picosecond laser ablation

Porous nanostructured polycrystalline ZnO films, free of large particulates, were deposited by picosecond laser ablation. Using a Zn target, zinc oxide films were deposited on indium tin oxide (ITO) substrates using a picosecond Nd:YVO₄ laser (8 ps, 50 kHz, 532 nm, 0.17 J/cm²) in an oxygen atmosphere at room temperature (RT). The morpho-structural characteristics of ZnO films deposited at different oxygen pressures (150–900 mTorr) and gas flow rates (0.25 and 10 sccm) were studied. The post-deposition influence of annealing (250–550 °C) in oxygen on the film characteristics was also investigated. At RT, a mixture of Zn and ZnO formed. At substrate temperatures above 350 °C, the films were completely oxidized, containing a ZnO wurtzite phase with crystallite sizes of 12.2–40.1 nm. At pressures of up to 450 mTorr, the porous films consisted of well-distinguished primary nanoparticles with average sizes of 45–58 nm, while at higher pressures, larger clusters (3.1–14.7 μm) were dominant, leading to thicker films; higher flow rates favored clustering.