Annealing effects of sapphire substrate on properties of ZnO films grown by magnetron sputtering

The annealing effects of sapphire substrates on the quality of epitaxial ZnO films grown by dc reactive magnetron sputtering were studied. The atomic steps formed on (0001) sapphire (α-Al₂O₃) substrates surface by annealing at high temperature were analyzed by atomic force microscopy. Their influence on the growth of ZnO films was examined by X-ray diffraction and photoluminescence measurements. Experimental results indicate that the film quality is strongly affected by annealing treatment of the sapphire substrate surface. The optimum annealing temperature of sapphire substrates for ZnO grown by magnetron sputtering is 1400 °C for 1 h in air. PACS 81.40.Ef; 68.55.Jk; 81.05.Dz; 81.15.Cd     

Effects of crystalline quality on the ultraviolet emission and electrical properties of the ZnO films deposited by magnetron sputtering

The ZnO films were deposited on c-plane sapphire, Si (0 0 1) and MgAl₂O₄ (1 1 1) substrates in pure Ar ambient at different substrate temperatures ranging from 400 to 750 °C by radio frequency magnetron sputtering. X-ray diffraction, photoluminescence and Hall measurements were used to evaluate the growth temperature and the substrate effects on the properties of ZnO films. The results show that the crystalline quality of the ZnO films improves with increasing the temperature up to 600 °C, the crystallinity of the films is degraded as the growth temperature increasing further, and the ZnO film with the best crystalline quality is obtained on sapphire at 600 °C. The intensity of the photoluminescence and the electrical properties strongly depend on the crystalline quality of the ZnO films. The ZnO films with the better crystallinity have the stronger ultraviolet emission, the higher mobility and the lower residual carrier concentration. The effects of crystallinity on light emission and electrical properties, and the possible origin of the n-type conductivity of the undoped ZnO films are also discussed.     

Effect of annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films on sapphire (0 0 0 1) substrates by magnetron sputtering

ZnO thin films were epitaxially grown on sapphire (0 0 0 1) substrates by radio frequency magnetron sputtering. ZnO thin films were then annealed at different temperatures in air and in various atmospheres at 800 °C, respectively. The effect of the annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films are investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL). A strong (0 0 2) diffraction peak of all ZnO thin films shows a polycrystalline hexagonal wurtzite structure and high preferential c-axis orientation. XRD and AFM results reveal that the better structural quality, relatively smaller tensile stress, smooth, uniform of ZnO thin films were obtained when annealed at 800 °C in N₂. Room temperature PL spectrum can be divided into the UV emission and the Visible broad band emission. The UV emission can be attributed to the near band edge emission (NBE) and the Visible broad band emission can be ascribed to the deep level emissions (DLE). By analyzing our experimental results, we recommend that the deep-level emission correspond to oxygen vacancy (V_O) and interstitial oxygen (O_i). The biggest ratio of the PL intensity of UV emission to that of visible emission (I_NBE/I_DLE) is observed from ZnO thin films annealed at 800 °C in N₂. Therefore, we suggest that annealing temperature of 800 °C and annealing atmosphere of N₂ are the most suitable annealing conditions for obtaining high quality ZnO thin films with good luminescence performance.     

Photosensitivity of nanocrystalline ZnO films grown by PLD

We have studied the properties of ZnO thin films grown by laser ablation of ZnO targets on (0 0 0 1) sapphire (Al₂O₃), under substrate temperatures around 400 °C. The films were characterized by different methods including X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). XPS analysis revealed that the films are oxygen deficient, and XRD analysis with θ-2θ scans and rocking curves indicate that the ZnO thin films are highly c-axis oriented. All the films are ultraviolet (UV) sensitive. Sensitivity is maximum for the films deposited at lower temperature. The films deposited at higher temperatures show crystallite sizes of typically 500 nm, a high dark current and minimum photoresponse. In all films we observe persistent photoconductivity decay. More densely packed crystallites and a faster decay in photocurrent is observed for films deposited at lower temperature.     

Effects of sapphire substrates surface treatment on the ZnO thin films grown by magnetron sputtering

The surface treatment effects of sapphire substrate on the ZnO thin films grown by magnetron sputtering were studied. The sapphire substrates properties have been investigated by means of atomic force microscopy (AFM) and X-ray diffraction rocking curves (XRCs). The results show that sapphire substrate surfaces have the best quality by CMP with subsequent chemical etching. The surface treatment effects of sapphire substrate on the ZnO thin films were examined by X-ray diffraction (XRD) and photoluminescence (PL) measurements. Results show that the intensity of (0 0 2) diffraction peak of ZnO thin films on sapphire substrates treated by CMP with subsequent chemical etching was strongest, FWHM of (0 0 2) diffraction peak is the narrowest and the intensity of UV peak of PL spectrum is strongest, indicating surface treatment on sapphire substrate preparation may improve ZnO thin films crystal quality and photoluminescent property.     

Rapid thermal annealing effects on the structural and optical properties of ZnO films deposited on Si substrates

The structural and optical properties of ZnO films deposited on Si substrate following rapid thermal annealing (RTA) have been investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), and photoluminescence (PL) measurements. After RTA treatment, the XRD spectra have shown an effective relaxation of the residual compressive stress, an increase of the intensity and narrowing of the full-width at half-maximum (FWHM) of the (0 0 2) diffraction peak of the as-grown ZnO film. AFM images show roughening of the film surface due to increase of grain size after RTA. The PL spectrum reveals a significant improvement in the UV luminescence of ZnO films following RTA at 800 °C for 1 min.     

Epitaxial ZnO films grown on ZnO-buffered c-plane sapphire substrates by hydrothermal method

ZnO films are hydrothermally grown on ZnO-buffered c-plane sapphire substrates at a low temperature of 70 °C. A radio-frequency (RF) reactive magnetron sputtering has been used to grow the ZnO buffer layers. X-ray diffraction, scanning electron microscopy, and room temperature photoluminescence are carried out to characterize the structure, morphology and optical property of the films. It is found that the films are stress-free. The epitaxial relationship between the ZnO film and the c-plane sapphire substrate is found to be ZnO (0 0 0 1)||Al₂O₃ (0 0 0 1) in the surface normal and in plane. Sapphire treatment, as such acid etching, nitridation, and oxidation are found to influence the nucleation of the film growth, and the buffer layers determine the crystalline quality of the ZnO films. The maximum PL quantum efficiency of ZnO films grown with hydrothermal method is found to be about 80% of single-crystal ZnO.     

Reversible wettability of nanostructured ZnO thin films by sol-gel method

Nanostructured ZnO thin films were deposited on Si(1 1 1) and quartz substrate by sol-gel method. The thin films were annealed at 673 K, 873 K, and 1073 K for 60 min. Microstructure, surface topography, and water contact angle of the thin films have been measured by X-ray diffractometer, atomic force microscopy, and water contact angle apparatus. XRD results showed that the ZnO thin films are polycrystalline with hexagonal wurtzite structure. AFM studies revealed that rms roughness changes from 2.3 nm to 7.4 nm and the grain size grow up continuously with increasing annealing temperature. Wettability results indicated that hydrophobicity of the un-irradiated ZnO thin films enhances with annealing temperature increase. The hydrophobic ZnO surfaces could be reversibly switched to hydrophilic by alternation of UV illumination and dark storage (thermal treatment). By studying the magnitude and the contact angle reduction rate of the light-induced process, the contribution of surface roughness is discussed.     

Properties of ZnO thin films grown on Si substrates by photo-assisted MOCVD

ZnO thin films were grown on (1 0 0) p-Si substrates by Photo-assisted Metal Organic Chemical Vapor Deposition (PA-MOCVD) using diethylzinc (DEZn) and O₂ as source materials and tungsten-halogen lamp as a light source. The effects of tungsten-halogen lamp irradiation on the surface morphology, structural and optical properties of the deposited ZnO films have been investigated by means of atomic force microscope (AFM), X-ray diffraction and photoluminescence (PL) spectra measurements. Compared with the samples without irradiation, the several characteristics of ZnO films with irradiation are improved, including an improvement in the crystallinity of c-axis orientation, an increase in the grain size and an improvement in optical quality of ZnO films. These results indicated that light irradiation played an important role in the growth of ZnO films by PA-MOCVD.     

Pure UV photoluminescence from ZnO thin film by thermal retardation and using an amorphous SiO2 buffer layer

ZnO/SiO₂ thin films were fabricated on Si substrates by E-beam evaporation with thermal retardation. The as-prepared films were annealed for 2 h every 100 °C in the temperature range 400-800 °C under ambient air. The structural and optical properties were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL). The XRD analysis indicated that all ZnO thin films had a highly preferred orientation with the c-axis perpendicular to the substrate. From AFM images (AFM scan size is 1 μm×1 μm), the RMS roughnesses of the films were 3.82, 5.18, 3.65, 3.40 and 13.2 nm, respectively. PL measurements indicated that UV luminescence at only 374 nm was observed for all samples. The optical quality of the ZnO film was increased by thermal retardation and by using an amorphous SiO₂ buffer layer.     

Seebeck and magnetoresistive effects of Ga-doped ZnO thin films prepared by RF magnetron sputtering

In this paper, Ga-doped ZnO (GZO) films were deposited on glass substrates at different substrate temperatures by RF magnetron sputtering. The effect of substrate temperature on the structural, surface morphological properties, Seebeck and magnetoresistive effects of GZO films was investigated. It is found that the GZO films are polycrystalline and preferentially in the [0 0 2] orientation, and the film deposited at 300 °C has an optimal crystal quality. Seebeck and magnetoresistive effects are apparently observed in GZO films. The thermoelectromotive forces are negative. Decreasing substrate temperature and annealing in N₂ flow can decrease carrier concentration. The absolute value of the Seebeck coefficient increases with decreasing carrier concentration. The maximal absolute value of Seebeck coefficient is 101.54 μV/K for the annealed samples deposited at the substrate temperature of 200 °C. The transverse magnetoresistance of GZO films is related to both the magnetic field intensity and the Hall mobility. The magnetoresistance increases almost linearly with magnetic field intensity, and the films deposited at higher substrate temperature have a stronger magnetoresistance under the same magnetic field, due to the larger Hall mobility.     

Structural characterization of supported nanocrystalline ZnO thin films prepared by dip-coating

Nanocrystalline ZnO thin films prepared by the sol-gel dip-coating technique were characterized by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). The structures of several thin films subjected to (i) isochronous annealing at 350, 450 and 550 °C, and (ii) isothermal annealing at 450 °C during different time periods, were characterized. The studied thin films are composed of ZnO nanocrystals as revealed by analysing several GIXD patterns, from which their average sizes were determined. Thin film thickness and roughness were determined from quantitative analyses of AFM images and XR patterns. The analysis of XR patterns also yielded the average density of the studied films. Our GISAXS study indicates that the studied ZnO thin films contain nanopores with an ellipsoidal shape, and flattened along the direction normal to the substrate surface. The thin film annealed at the highest temperature, T = 550 °C, exhibits higher density and lower thickness and nanoporosity volume fraction, than those annealed at 350 and 450 °C. These results indicate that thermal annealing at the highest temperature (550 °C) induces a noticeable compaction effect on the structure of the studied thin films.     

Microstructures and optical properties of Cu-doped ZnO films prepared by radio frequency reactive magnetron sputtering

Pure and Cu-doped ZnO (ZnO:Cu) thin films were deposited on glass substrates using radio frequency (RF) reactive magnetron sputtering. The effect of substrate temperature on the crystallization behavior and optical properties of the ZnO:Cu films have been studied. The crystal structures, surface morphology and optical properties of the films were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer, respectively. The results indicated that ZnO films showed a stronger preferred orientation toward the c-axis and a more uniform grain size after Cu-doping. As for ZnO:Cu films, the full width at half maxima (FWHM) of (0 0 2) diffraction peaks decreased first and then increased, reaching a minimum of about 0.42° at 350 °C and the compressive stress of ZnO:Cu decreased gradually with the increase of substrate temperature. The photoluminescence (PL) spectra measured at room temperature revealed two blue and two green emissions. Intense blue-green luminescence was obtained from the sample deposited at higher substrate temperature. Finally, we discussed the influence of annealing temperature on the structural and optical properties of ZnO:Cu films. The quality of ZnO:Cu film was markedly improved and the intensity of blue peak (∼485 nm) and green peak (∼527 nm) increased noticeably after annealing. The origin of these emissions was discussed.     

The effect of post-annealing on surface acoustic wave devices based on ZnO thin films prepared by magnetron sputtering

Zinc oxide (ZnO) thin films were deposited on unheated silicon substrates via radio frequency (RF) magnetron sputtering, and the post-deposition annealing of the ZnO thin films was performed at 400 °C, 600 °C, 800 °C, and 1000 °C. The characteristics of the thin films were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The films were then used to fabricate surface acoustic wave (SAW) resonators. The effects of post-annealing on the SAW devices are discussed in this work. Resulting in the 600 °C is determined as optimal annealing temperature for SAW devices. At 400 °C, the microvoids exit between the grains yield large root mean square (RMS) surface roughness and higher insertion losses in SAW devices. The highest RMS surface roughness, crack and residual stress cause a reduction of surface velocity (about 40 m/s) and increase dramatically insertion loss at 1000 °C. The SAW devices response becomes very weak at this temperature, the electromechanical coupling coefficient (k²) of ZnO film decrease from 3.8% at 600 °C to 1.49% at 1000 °C.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

Photoemission studies of initial oxidation for ultra-thin zinc film on 6H-SiC(0 0 0 1) surface with synchrotron radiation

The thermal oxidation process of metallic zinc on 6H-SiC(0 0 0 1) surface has been investigated by using atomic force microscopy (AFM), synchrotron radiation photoelectron spectroscopy (SRPES) and XPS methods. The AFM images characterize the surface morphology of ZnO film formed during the thermal oxidation and SRPES record the valence band, Si 2p and Zn 3d spectra at different stages. The O 1s peak is recorded by XPS because of the energy limit of the synchrotron radiation. Our results reveal that the silicon oxides layer of SiC substrate can be reduce by hot metallic zinc atom deposition. The oxygen atoms in the silicon oxides are captured by the zinc atoms to form ZnO_x at the initial stage and as a result, the oxidized SiC surface are deoxidized. After the zinc deposition with the final thickness of 2.5 nm, the sample is exposed in oxygen atmosphere and annealed at different temperatures. According to the evolution of peaks integrated intensities, it is considered that the Zn/SiC system will lose zinc atoms during the annealing in oxygen flux at high temperature due to the low evaporation temperature of pure zinc. After further annealing in oxygen flux at higher temperature, the substrate is also oxidized and finally the interface becomes a stable SiC-SiO_x-ZnO sandwich structure.     

Effect of substrate temperature on the morphology, structural and optical properties of Zn1−xCoxO thin films

Zn_1−xCo_xO thin films with c-axis preferred orientation were deposited on sapphire (0 0 0 1) by pulsed laser deposition (PLD) technique at different substrate temperatures in an oxygen-deficient ambient. The effect of substrate temperature on the microstructure, morphology and the optical properties of the Zn_1−xCo_xO thin films was studied by means of X-ray diffraction (XRD), atomic force microscopy (AFM), UV-visible-NIR spectrophotometer, fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted as substrate temperature rose. The structure of the samples was not distorted by the Co incorporating into ZnO lattice. The surface roughness of all samples decreased as substrate temperature increased. The Co concentration in the film was higher than in the target. Emission peak near band edge emission of ZnO from the PL spectra of the all samples was quenched because the dopant complexes acted as non-radiative centers. While three emission bands located at 409 nm (3.03 eV), 496 nm (2.5 eV) and 513 nm (2.4 eV) were, respectively, observed from the PL spectra of the four samples. The three emission bands were in relation to Zn interstitials, Zn vacancies and the complex of V_O and Zn_i (V_OZn_i). The quantity of the Zn interstitials maintained invariable basically, while the quantity of the V_OZn_i slightly decreased as substrate temperature increased.     

Surface characterization and microstructure of ITO thin films at different annealing temperatures

In this study, the electron beam evaporation method is used to generate an indium tin oxide (ITO) thin film on a glass substrate at room temperature. The surface characteristics of this ITO thin film are then investigated by means of an AFM (atomic force microscopy) method. The influence of postgrowth thermal annealing on the microstructure and surface morphology of ITO thin films are also examined. The results demonstrate that the film annealed at higher annealing temperature (300 °C) has higher surface roughness, which is due to the aggregation of the native grains into larger clusters upon annealing. The fractal analysis reveals that the value of fractal dimension D_f falls within the range 2.16-2.20 depending upon the annealing temperatures and is calculated by the height-height correlation function.     

Effect of substrate annealing on the quality of pulsed laser deposited Zn1−xMgxO thin films

The annealing effects of sapphire substrate before deposition on the quality of epitaxial Zn_1−xMg_xO thin films grown by pulsed laser deposition are reported. Our Experimental results indicate that the surface quality of Zn_1−xMg_xO thin films and hexagonal columnar growth is improved on the annealed sapphire substrate at high temperatures due to formation of atomic terraces on the substrate surface. The photoluminescence signals also increases with the increasing annealing temperature of the substrate.     

Influence of annealing temperature on structural, optical and magnetic properties of Mn-doped ZnO thin films prepared by sol-gel method

Thin films of Zn_1−xMn_xO (x=0.01) diluted magnetic semiconductor were prepared on Si (1 0 0) substrates by the sol-gel method. The influence of annealing temperature on the structural, optical and magnetic properties was studied by X-ray diffraction (XRD), atom force microscopy (AFM), photoluminescence (PL) and SQUID magnetometer (MPMS, Quantum Design). The XRD spectrum shows that all the films are single crystalline with (0 0 2) preferential orientation along c-axis, indicating there are not any secondary phases. The atomic force microscopy images show the surfaces morphologies change greatly with an increase in annealing temperature. PL spectra reveal that the films marginally shift the near band-edge (NBE) position due to stress. The magnetic measurements of the films using SQUID clearly indicate the room temperature ferromagnetic behavior, and the Curie temperature of the samples is above room temperature. X-ray photoelectron spectroscopy (XPS) patterns suggest that Mn²⁺ ions were successfully incorporated into the lattice position of Zn²⁺ ions in ZnO host. It is also found that the post-annealing treatment can affect the ferromagnetic behavior of the films effectively.