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

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

Study on the structure and optical property of Zn1−xCuxO sol–gel thin films on quartz substrate

Zn_1−xCu_xO thin films (x=0, 1.0, 3.0, 5.0%) are prepared on quartz substrate by sol–gel method. The structure and morphology of the samples are investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results show that Cu ions were effectively penetrated into the ZnO crystal lattices with substitutional and interstitial impurities to form stable solid solutions without changing the polycrystalline wurtzite structure. Two peaks at 420 nm (2.95 eV, violet), 485 nm (2.56 eV, blue) have been observed from the photoluminescence (PL) spectra of the samples. It is concluded that the violet peak may correspond to the exciton emission; the blue emission corresponds to the electron transition from the bottom of the conduction band to the acceptor level of zinc vacancy. The optical test shows that the optical band gap E_g is decreased with the increase amount of Cu doping in ZnO. The band gap decrease from 3.40 eV to 3.25 eV gradually. It is also found that the transmission rate is increased rapidly with the increase of Cu ions concentration.     

Characteristics of filtered vacuum arc deposited ZnO-SnO2 thin films on room temperature substrates

ZnO, SnO₂ and zinc stannate thin films were deposited using filtered vacuum arc deposition (FVAD) system on commercial microscope glass and UV fused silica substrates (UVFS) at room temperature (RT). The structural and morphological analyses were performed using X-ray diffraction (XRD) and Atomic Force Microscopy (AFM), respectively. XRD patterns of ZnO films deposited at RT had strongly c-axis orientation, whereas SnO₂ and zinc stannate films had amorphous structure as they did not have any defined patterns. Average crystalline size and surface grain size of ZnO films were ∼16 nm, as determined from diffraction line broadening and AFM images, respectively. Optical constants in the 250-1100 nm wavelength range were determined by variable angle spectroscopic ellipsometry and transmission measurements. The transmission of the deposited films in the VIS was 80-90%, affected by interference. The refractive indices and the extinction coefficients of deposited ZnO, SnO₂ and zinc stannate films were in the range 1.87-2.15 and 0.02-0.04, depending on wavelengths and deposition parameters. The optical band gap (E_g) was determined by the dependence of the absorption coefficient on the photon energy at short wavelengths. Its values for ZnO, SnO₂ and zinc stannate were in the range 3.25-3.30 eV, 3.60-3.98 eV and 3.43-3.52 eV, respectively, depending on the deposition pressure.     

Effects of the substrate and oxygen partial pressure on the microstructures and optical properties of Ti-doped ZnO thin films

Ti-doped ZnO (ZnO:Ti) thin films were deposited on the glass and Si substrates using radio frequency reactive magnetron sputtering. The effects of substrate on the microstructures and optical properties of ZnO:Ti thin films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer. The structural analyses of the films indicated that they were polycrystalline and had a hexagonal wurtzite structure on different substrates. When ZnO:Ti thin film was deposited on Si substrate, the film had a c-axis preferred orientation, while preferred orientation of ZnO:Ti thin film deposited on glass substrate changed towards (1 0 0). Finally, we discussed the influence of the oxygen partial pressures on the structural and optical properties of glass-substrate ZnO:Ti thin films. At a high ratio of O₂:Ar of 18:10 sccm, the intensity of (0 0 2) diffraction peak was stronger than that of (1 0 0) diffraction peak, which indicated that preferred orientation changed with the increase of O₂:Ar ratios. The average optical transmittance with over 93% in the visible range was obtained independent of the O₂:Ar ratio. The photoluminescence (PL) spectra measured at room temperature revealed four main emission peaks located at 428, 444, 476 and 527 nm. Intense blue-green luminescence was obtained from the sample deposited at a ratio of O₂:Ar of 14:10 sccm. The results showed that the oxygen partial pressures had an important influence for PL spectra and the origin of these emissions was discussed.     

Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

Effect of substrate temperature on the structural and optical properties of ZnO and Al-doped ZnO thin films prepared by dc magnetron sputtering

ZnO and Al-doped ZnO(ZAO) thin films have been prepared on glass substrates by direct current (dc) magnetron sputtering from 99.99% pure Zn metallic and ZnO:3 wt%Al₂O₃ ceramic targets, the effects of substrate temperature on the crystallization behavior and optical properties of the films have been studied. It shows that the surface morphologies of ZAO films exhibit difference from that of ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (0 0 2). The optical transmittance and photoluminescence (PL) spectra of both ZnO and ZAO films are obviously influenced by the substrate temperature. All films exhibit a transmittance higher than 86% in the visible region, while the optical transmittance of ZAO films is slightly smaller than that of ZnO films. More significantly, Al-doping leads to a larger optical band gap (E_g) of the films. It is found from the PL measurement that near-band-edge (NBE) emission and deep-level (DL) emission are observed in pure ZnO thin films. However, when Al was doped into thin films, the DL emission of the thin films is depressed. As the substrate temperature increases, the peak of NBE emission has a blueshift to region of higher photon energy, which shows a trend similar to the E_g in optical transmittance measurement.     

Physical properties of ZnO thin films deposited by spray pyrolysis technique

Thin films of ZnO have been prepared on glass substrates at different thicknesses by spray pyrolysis technique using 0.2 M aqueous solution of zinc acetate. X-ray diffraction reveals that the films are polycrystalline in nature having hexagonal wurtzite type crystal structure. The resistivity at room temperature is of the order 10⁻² Ω cm and decreased as the temperature increased. Films are highly transparent in the visible region. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for a sprayed film is also reported. Optical bandgap, E_g, has been reported for the films. A shift from E_g = 3.21 eV to 3.31 eV has been observed for deposited films.     

Effects of thermal oxidation temperature on vacuum evaporated tin dioxide film

In order to investigate the effect of thermal oxidation temperature on tin dioxide (SnO₂), tin dioxide films were obtained on quartz substrates by vacuum evaporation of tin metal. The films were characterized by X-ray diffraction (XRD) analyses, scanning electron microscopy (SEM), temperature dependent electrical resistivity measurement and optical absorption spectroscopy. The SEM images showed that the films are dense, continuous and are composed of nanoparticles and particle sizes are increased after thermal oxidation. From the X-ray measurement results, the films indicated two strong reflection peaks of tetragonal structure in the orientations of (1 0 1) and (2 0 0) at 2θ = 33.89° and 37.95°, respectively. Intensity of the peaks increased with increasing thermal oxidation temperature. We found resistivity values of about 10⁻⁴ Ω-cm. Optical absorption spectra of the films in the UV–Vis spectral range revealed that optical band gap (E_g) value of the films increases with increasing thermal oxidation temperature.     

Structural, optical and magnetic properties of (ZnO)1−x(MnO2)x thin films deposited at room temperature

The structural, magnetic and optical properties of (ZnO)_1−x(MnO₂)_x (with x = 0.03 and 0.05) thin films deposited by pulsed laser deposition (PLD) were studied. The pellets used as target, sintered at different temperatures ranging from 500 °C to 900 °C, were prepared by conventional solid state method using ZnO and MnO₂ powders. The observation of non-monotonic shift in peak position of most preferred (1 0 1) ZnO diffraction plane in XRD spectra of pellets confirmed the substitution of Mn ions in ZnO lattice of the sintered targets. The as-deposited thin film samples are found to be polycrystalline with the preferred orientation mostly along (1 1 0) diffraction plane. The UV-vis spectroscopy of the thin films revealed that the energy band gap exhibit blue shift with increasing Mn content which could be attributed to Burstein-Moss shift caused by Mn doping of the ZnO. The deposited thin films exhibit room temperature ferromagnetism having effective magnetic moment per Mn atom in the range of 0.9-1.4μ_B for both compositions.     

Properties of ZnO thin films deposited on (glass,ITO and ZnO:Al) substrates

ZnO thin films were deposited on glass, ITO (In₂O₃; Sn) and on ZnO:Al coated glass by spray pyrolysis. The substrates were heated at 350 °C. Structural characterization by X-ray diffraction (XRD) measurements shows that films crystallize in hexagonal structure with a preferential orientation along (0 0 2) direction. XRD peak-shift analysis revealed that films deposited on glass substrate (−0.173) were compressive, however, films deposited onto ITO (0.691) and on ZnO:Al (0.345) were tensile. Scanning electron microscopies (SEM) show that the morphologies of surface are porous in the form of nanopillars. The transmittance spectra indicated that the films of ZnO/ITO/glass and ZnO/ZnO:Al/glass exhibit a transmittance around 80% in the visible region. An empirical relationship modeled by theoretical numerical models has been presented for estimating refractive indices (n) relative to energy gap. All models indicate that the refractive index deceases with increasing energy band gap (E_g).     

Realization of p-ZnO thin films by GaP codoping

An attempt has been made to realize p-ZnO by directly doping (codoping) GaP into ZnO thin films. GaP codoped ZnO thin films of different concentrations (1, 2 and 4 mol%) have been grown by RF magnetron sputtering. The grown films on sapphire substrate have been characterized by X-ray diffraction (XRD), Hall measurement, Photoluminescence (PL) and Energy dispersive spectroscopy (EDS) to validate the p-type conduction. XRD result shows that all the films have been preferentially oriented along (0 0 2) orientation. The decrease of full-width at half maximum (FWHM) with increase in GaP doping depicts the decrease in native donor defects. Hall measurement shows that among the three films, 2 and 4 mol% GaP doped ZnO shows p-conductivity due to the sufficient amount of phosphorous incorporation. It has been found that low resistivity (2.17 Ωcm) and high hole concentration (1.8×10¹⁸ cm⁻³) for 2% GaP codoped ZnO films due to best codoping. The red shift in near-band-edge (NBE) emission and donar-acceptor-pair (DAP) and neutral acceptor bound recombination (A°X) observed by room temperature and low temperature (10 K) PL, respectively, well acknowledged the formation of p-ZnO. The incorporated phosphorous in the film has been also confirmed by EDS analysis.     

Structural and photoluminescent properties of Ni doped ZnO nanorod arrays prepared by hydrothermal method

Self-assembled Ni-doped zinc oxide (Zn_1−xNi_xO, x = 0.05, 0.10, 0.15, i.e., ZnNiO, nominal composition) nanorod arrays vertically grown on the ZnO seed layer covered glass along [0 0 1] direction were synthesized by hydrothermal method. Their images and structures have been characterized by scan electron microscope (SEM), X-ray diffraction (XRD) and Raman spectra, showing that Ni doping is beneficial to the formation of ZnO nanorods with hexagonal cross section and the enhancement of ZnO crystal quality. X-ray photoemission spectroscopy (XPS) study further demonstrated that Ni atoms were successfully doped into ZnO lattices. The photoluminescence (PL) spectra of ZnNiO samples show near bandedge emission (NBE) peaks at about 380 nm at a low excitation power and the NBE peak position redshifts while its intensity continuously increases with the increase of Ni doping concentration. With the excitation power increasing, the NBE peak redshifts from 380 nm to about 400 nm for ZnNiO nanorod arrays. The NBE mechanisms for ZnNiO nanorod arrays have been discussed, which is helpful for understanding their room temperature ferromagnetisms.     

Influence of sputter-etching of substrate on the microstructural and optical properties of ZnO films deposited by RF magnetron sputtering

ZnO films were prepared using radio frequency magnetron sputtering on Si(1 1 1) substrates that were sputter-etched for different times ranging from 10 to 30 min. As the sputter-etching time of the substrate increases, both the size of ZnO grains and the root-mean-square (RMS) roughness decrease while the thickness of the ZnO films shows no obvious change. Meanwhile, the crystallinity and c-axis orientation are improved by increasing the sputter-etching time of the substrate. The major peaks at 99 and 438 cm⁻¹ are observed in Raman spectra of all prepared films and are identified as E₂(low) and E₂(high) modes, respectively. The Raman peak at 583 cm⁻¹ appears only in the films whose substrates were sputter-etched for 20 min and is assigned to E₁(LO) mode. Typical ZnO infrared vibration peak located at 410 cm⁻¹ is found in all FTIR spectra and is attributed to E₁(TO) phonon mode. The shoulder at about 382 cm⁻¹ appearing in the films whose substrates were sputter-etched for shorter time (10-20 min) originates from A₁(TO) phonon mode. The results of photoluminescence (PL) spectra reveal that the optical band gap (Eg) of the ZnO films increases from 3.10 eV to 3.23 eV with the increase of the sputter-etching time of the substrate.     

Effects of rf power on surface-morphological, structural and electrical properties of aluminium-doped zinc oxide films by magnetron sputtering

Aluminium-doped zinc oxide (ZnO:Al) films were prepared by magnetron sputtering at different radio-frequency powers (P_rf) of 50, 100, 150 and 200 W. The properties of the films were characterised by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Raman microscopy, and spectrophotometry with the emphasis on the evolution of compositional, surface-morphological, optical, electrical and microstructural properties. XPS spectra showed that within the detection limit the films are chemically identical to near-stoichiometric ZnO. AFM revealed that root-mean-square roughness of the films has almost linear increase with increasing P_rf. Optical band gap E_gopt of the films increases from 3.31 to 3.51 eV when P_rf increases from 50 to 200 W. A widening E_gopt of the ZnO:Al films compared to the band gap (∼3.29 eV) of undoped ZnO films is attributed to a net result of the competition between the Burstein-Moss effect and many-body effects. An electron concentration in the films was calculated in the range of 3.73 × 10¹⁹ to 2.12 × 10²⁰ cm⁻³. Raman spectroscopy analysis indicated that well-identified peaks appear at around 439 cm⁻¹ for all samples, corresponding to the band characteristics of the wurtzite phase. Raman peaks in the range 573-579 cm⁻¹ are also observed, corresponding to the A₁ (LO) mode of ZnO.     

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.     

Room temperature transparent conducting oxides based on zinc oxide thin films

Doped zinc oxide thin films are grown on glass substrate at room temperature under oxygen atmosphere, using pulsed laser deposition (PLD). O₂ pressure below 1 Pa leads to conductive films. A careful characterization of the film stoichiometry and microstructure using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) concludes on a decrease in crystallinity with Al and Ga additions (≤3%). The progressive loss of the (0 0 2) orientation is associated with a variation of the c parameter value as a function of the film thickness and substrate nature. ZnO:Al and ZnO:Ga thin films show a high optical transmittance (>80%) with an increase in band gap from 3.27 eV (pure ZnO) to 3.88 eV and 3.61 eV for Al and Ga doping, respectively. Optical carrier concentration, optical mobility and optical resistivity are deduced from simulation of the optical data.     

Effect of doping on structural,optical and electrical properties of nanostructure ZnO films deposited onto a-Si:H/Si heterojunction

We investigated the structural; optical and electrical properties of ZnO thin films as the n-type semiconductor for silicon a-Si:H/Si heterojunction photodiodes. The ZnO film forms the front contact of the super-strata solar cell and has to exhibit good electrical (high conductivity) and optical (high transmittance) properties. In this paper we focused our attention on the influence of doping on device performance. The results show that the X-ray diffraction (XRD) spectra revealed a preferred orientation of the crystallites along c-axis. SEM images show that all films display a granular, polycrystalline morphology and the ZnO:Al exhibits a better grain uniformity. The transmittance of the doped films was found to be higher when compared to undoped ZnO. A low resistivity of the order of 2.8 × 10⁻⁴ Ω cm is obtained for ZnO:Al using 0.4 M concentration of zinc acetate. The photoluminescence (PL) spectra exhibit a blue band with two peaks centered at 442 nm (2.80 eV) and 490 nm (2.53 eV). It is noted that after doping the ZnO films a shift of the band by 22 nm (0.15 eV) is recorded and a high luminescence occurs when using Al as a dopant. Dark I–V curves of ZnO/a-Si:H/Si structure showed large difference, which means there is a kind of barrier to current flow between ZnO and a-Si:H layer. Doping films was applied and the turn-on voltages are around 0.6 V. Under reverse bias, the current of the ZnO/a-Si:H/Si heterojunction is larger than that of ZnO:Al/a-Si:H/Si. The improvement with ZnO:Al is attributed to a higher number of generated carriers in the nanostructure (due to the higher transmittance and a higher luminescence) that increases the probability of collisions.     

Optical properties of ZnO and ZnO:Ce layers grown by spray pyrolysis

In this paper, zinc oxide (ZnO) and cerium-doped zinc oxide (ZnO:Ce) films were deposited by reactive chemical pulverization spray pyrolysis technique using zinc and cerium chlorides as precursors. The effects of Ce concentration on the structural and optical properties of ZnO thin films were investigated in detail. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) measurements. All deposited ZnO layers at the temperature 450 °C are polycrystalline and indicate highly c-axis oriented structure. The dimension of crystallites depends on incorporation of Ce atoms into the ZnO films. The photoluminescence spectra of the films have been studied as a function of the deposition parameters such as doping concentrations and post grows annealing. Photoluminescence spectra were measured at the temperature range from 13 K to 320 K.     

Effects of hydrogen flow on properties of hydrogen doped ZnO thin films prepared by RF magnetron sputtering

The hydrogen doped ZnO (ZnO:H) thin films were deposited on quartz glass substrates by radio frequency magnetron sputtering. The doping characteristics of ZnO:H thin films with varied hydrogen flow ratio were investigated. At low hydrogen flow ratio (H₂/(H₂+Ar)≤0.02), the ZnO:H thin films exhibited dominant (002) peaks from X-ray diffraction and the lattice constants became smaller. The particles were mainly a columnar structure. The particles’ size became smaller, and the island-like structure appeared on the thin films surface. In addition, the low resistivity properties of ZnO:H thin films was ascribed to the increase of the carriers concentration and carriers mobility; When the hydrogen flow ratio was more than 0.02 (M≥0.02), two absorption bands at 1400–1800 cm^?1 and 3200–3900 cm^?1 were observed from the FT-IR spectra, which indicated that the ZnO:H thin films had typical Zn–H bonding, O–H bonding (hydroxyl), and Zn–H–O bonding (like-hydroxyl). The scanning electron microscope (SEM) results show that a large number of hydroxyl agglomeration formed an island-like structure on the thin films surface. The absorption peak at about 575 cm^?1 in the Raman spectra indicated that oxygen vacancies (V_O) defects were produced in the process of high hydrogen doping. In this condition, the low resistivity properties of ZnO:H thin films were mainly due to the increasing electron concentration resulted from V_O. Meanwhile, the Raman absorption peaks at approximately 98 cm^?1 and 436 cm^?1 became weaker, and the (002) XRD diffraction peak quenched and the lattice constants increased, which shows that the ZnO:H thin films no longer presented a typical ZnO hexagonal wurtzite structure. With the increasing of hydrogen flow ratio, the optical transmittance of ZnO:H thin films in the ultraviolet band show a clear Burstein–Moss shift effect, which further explained that electron concentration was increased due to the increasing V_O with high hydrogen doping concentration. Moreover, the optical reflectance of the thin films decreased, indicating the higher roughness of the films surface. It was noteworthy that etching effect of H plasma was obvious in the process of heavy hydrogen doping.     

Photomodulated reflectance study on optical property of InN thin films grown by reactive gas-timing rf magnetron sputtering

The photoreflectance (PR) spectroscopy has been applied to investigate the band-gap energy (E_g) of indium nitride (InN) thin films grown by rf magnetron sputtering. A novel reactive gas-timing technique applied for the sputtering process has been successfully employed to grow InN thin films without neither substrate heating nor post annealing. The X-ray diffraction (XRD) patterns exhibit strong peaks in the orientation along (0 0 2) and (1 0 1) planes, corresponding to the polycrystalline hexagonal-InN structure. The band-gap transition energy of InN was determined by fitting the PR spectra to a theoretical line shape. The PR results show the band-gap energy at 1.18 eV for hexagonal-InN thin films deposited at the rf powers of 100 and 200 W. The high rf sputtering powers in combination with the gas-timing technique should lead to a high concentration of highly excited nitrogen ions in the plasma, which enables the formation of InN without substrate heating. Auger electron spectroscopy (AES) measurements further reveal traces of oxygen in these InN films. This should explain the elevated band-gap energy, in reference to the band-gap value of 0.7 eV for pristine InN films.