Growth and characterization of non-polar ZnO thin films by pulsed laser deposition

Non-polar ZnO thin films were fabricated on r-plane sapphire substrates by pulsed laser deposition at various temperatures from 100 to 500 °C. The effects of the substrate temperature on structural, morphological and optical properties of the films were investigated. Based on the X-ray diffraction analysis, the ZnO thin films grown at 300, 400 and 500 °C exhibited the non-polar (a-plane) orientation and those deposited below 300 °C exhibited polar (c-plane) orientation. In the optical properties of non-polar ZnO films, there were two photoluminescence peaks detected. The peaks (near-band edge emission, blue emission) are due to electron transitions from band-to-band and shallow donor level to valence band, respectively.     

Effect of the variation of temperature on the structural and optical properties of ZnO thin films prepared on Si (1 1 1) substrates using PLD

ZnO thin films were prepared on Si (1 1 1) substrates at various temperatures from 250 to 700 °C using pulsed laser deposition (PLD) technique in order to investigate the structural and optical properties of the films. The structural and morphological properties of the films were investigated by XRD and SEM measurements, respectively. The quality of the films was improved with the increase of the temperature. By XRD patterns, the FWHMs of the (0 0 2) peaks of the ZnO films became narrower when the temperatures were above 500 °C. The FWHMs of the peaks of (0 0 2) of the films were as narrow as about 0.19° when films were grown at 650 and 700 °C. This indicates the superior crystallinity of the films. The optical properties of the films were studied by photoluminescence spectra using a 325 nm He-Cd laser. The two strongest UV peaks were found at 377.9 nm from ZnO films grown at 650 and 700 °C. This result is consistent with that of the XRD investigation. Broad bands in visible region from 450 to 550 nm were also observed. Our works suggest that UV emissions have close relations with not only the crystallinity but also the stoichiometry of the ZnO films.     

Effect of laser repetition frequency on the structural and optical properties of ZnO thin films by PLD

ZnO thin films were grown on Si (1 1 1) substrates by pulsed laser deposition (PLD) at various laser repetition frequency in order to investigate the structural and optical properties of the films. The optical properties of the films were studied by photoluminescence spectra using a 325 nm He-Cd laser. The structural properties of the films were investigated by XRD measurement. The results suggest that films grown at 5 Hz have excellent UV emission and high-quality crystallinity. Laser repetition frequency can affect the structural and optical properties obviously. In addition, the thickness of all samples is about 200 nm and is not as expected that the film thickness was in direct proportion to laser repetition frequency. The authors think that one laser pulse is not corresponding to one growth instantaneousness. There is a growth ambience containing essential components and partial pressure in the work cavity.     

Influence of target to substrate distance on the sputtered CuCl film properties

CuCl is a potential candidate for UV optoelectronic devices due to its superior optical properties and lattice matching with Si. Stoichiometric CuCl thin films of polycrystalline nature were grown by RF magnetron sputtering technique. The effect of varying the target to substrate distance on the compositional, structural and optoelectronic properties of the sputtered films was analysed. A critical target to substrate distance (d_ts) was observed and the film properties were clearly different above and below this distance. Based on the film properties, the optimum spacing of d_ts = 6 cm was found to yield stoichiometric and high optical quality films. The existence of more than one chemical bonding state was identified in nonstoichiometric, chlorine rich, films by analysing the Cu 2p_3/2 core level XPS spectra. Chlorine rich samples were found to show a noticeable emission from deep levels at ∼ 515 nm in cathodoluminescence (CL) spectroscopy. An exciton mediated sharp UV luminescence (385 nm) emission was realized at room temperature in the stoichiometric CuCl thin films.     

Femtosecond laser deposited zinc oxide film and its optical properties

Zinc oxide (ZnO) thin films have been grown on Si (100) substrates using a femto-second pulsed laser deposition (fsPLD) technique. The effects of substrate temperature and laser energy on the structural, surface morphological and optical properties of the films are discussed. The X-ray diffraction results show that the films are highly c-axis oriented when grown at 80 °C and (103)-oriented at 500 °C. In the laser energy range of 1.0 mJ-2.0 mJ, the c-axis orientation increases and the mean grain size decreases for the films deposited at 80 °C. The field emission scanning electron microscopy indicates that the films have a typical hexagonal structure. The optical transmissivity results show that the transmittance increases with the increasing substrate temperature. In addition, the photoluminescence spectra excited with 325 nm light at room temperature are studied. The structural properties of ZnO films grown using nanosecond (KrF) laser are also discussed.     

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.     

Transparent conductive ZnO:B films deposited by magnetron sputtering

This paper focuses on the preparation of boron doped ZnO (ZnO:B) films prepared by nonreactive mid-frequency magnetron sputtering from ceramic target with 2 wt.% doping source. Adjusting power density, ZnO:B film with low resistivity (1.54 × 10^− 3 Ω cm) and high transparency (average transparency from 400 to 1100 nm over 85%) was obtained. Different deposition conditions were introduced as substrate fixed in the target center and hydrogen mediation. Hall mobility increased from 11 to above 26 cm²/V·s, while carrier concentration maintained almost the same, leading to low resistivity of 6.45 × 10^− 4 Ω cm. Transmission spectra of ZnO:B films grown at various growth conditions were determined using a UV-visible-NIR spectrophotometer. An obvious blue-shift of absorption edge was obtained while transmittances between 600 nm and 1100 nm remained almost the same. Optical band baps extracted from transmission spectra showed irregular enhancement due to the Burstein-Moss effect and band gap renormalization. Photoluminescence spectra also showed a gradual increase at UV emission peak due to free exciton transition near band gap. We contributed this enhancement in both optical band gap and UV photoluminescence emission to the lattice structure quality melioration.     

Oxygen pressure and measurement temperature dependence of defects related bands in zinc oxide films

The ZnO films were fabricated by pulsed laser deposition at various oxygen pressure on single crystal silicon substrate. The structural and optical properties were investigated at various measurement temperature. The results showed that all the films have good c-axis preferred orientation. The different defects in films were fabricated which can be caused by various oxygen pressure. The films deposited at 1 Pa oxygen pressure have the most intense and narrow UV emission, and did not exhibit the deep band emission at the various measurement temperature. With the decrease of measurement temperature, the V_O-, O_i- and O_Zn-related band energy decreases, which is opposed to the V_Zn-related defects, meanwhile, the intensity of O_i-related emission peak has a sharp increase.     

Effect of cadmium oxide incorporation on the microstructural and optical properties of pulsed laser deposited nanostructured zinc oxide thin films

CdO doped (doping concentration 0, 1, 3 and 16 wt%) ZnO nanostructured thin films are grown on quartz substrate by pulsed laser deposition and the films are annealed at temperature 500 °C. The structural, morphological and optical properties of the annealed films are systematically studied using grazing incidence X-ray diffraction (GIXRD), energy dispersive X-ray analysis (EDX), scanning electron microscopy (SEM), atomic force microscopy (AFM), Micro-Raman spectra, UV–vis spectroscopy, photoluminescence spectra and open aperture z-scan. 1 wt% CdO doped ZnO films are annealed at different temperatures viz., 300, 400, 500, 600, 700 and 800 °C and the structural and optical properties of these films are also investigated. The XRD patterns suggest a hexagonal wurtzite structure for the films. The crystallite size, lattice constants, stress and lattice strain in the films are calculated. The presence of high-frequency E₂ mode and the longitudinal optical A₁ (LO) modes in the Raman spectra confirms the hexagonal wurtzite structure for the films. The presence of CdO in the doped films is confirmed from the EDX spectrum. SEM and AFM micrographs show that the films are uniform and the crystallites are in the nano-dimension. AFM picture suggests a porous network structure for 3% CdO doped film. The porosity and refractive indices of the films are calculated from the transmittance and reflectance spectra. Optical band gap energy is found to decrease in the CdO doped films as the CdO doping concentration increases. The PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. The 16CdZnO film shows an intense deep green PL emission. Non-linear optical measurements using the z-scan technique indicate that the saturable absorption (SA) behavior exhibited by undoped ZnO under green light excitation (532 nm) can be changed to reverse saturable absorption (RSA) with CdO doping. From numerical simulations the saturation intensity (I_s) and the effective two-photon absorption coefficient (β) are calculated for the undoped and CdO doped ZnO films.     

Ellipsometric study of nanostructured carbon films deposited by pulsed laser deposition

When depositing carbon films by plasma processes the resulting structure and bonding nature strongly depends on the plasma energy and background gas pressure. To produce different energy plasma, glassy carbon targets were ablated by laser pulses of different excimer lasers: KrF (248 nm) and ArF (193 nm). To modify plume characteristics argon atmosphere was applied. The laser plume was directed onto Si substrates, where the films were grown. To evaluate ellipsometric measurements first a combination of the Tauc-Lorentz oscillator and the Sellmeier formula (TL/S) was applied. Effective Medium Approximation models were also used to investigate film properties. Applying argon pressures above 10 Pa the deposits became nanostructured as indicated by high resolution scanning electron microscopy. Above ~ 100 and ~ 20 Pa films could not be deposited by KrF and ArF laser, respectively. Our ellipsometric investigations showed, that with increasing pressure the maximal refractive index of both series decreased, while the optical band gap starts with a decrease, but shows a non monotonous course. Correlation between the size of the nanostructures, bonding structure, which was followed by Raman spectroscopy and optical properties were also investigated.     

Correlations between optical properties, microstructure, and processing conditions of Aluminum nitride thin films fabricated by pulsed laser deposition

Aluminum nitride (AlN) films were deposited using pulsed laser deposition (PLD) onto sapphire (0001) substrates with varying processing conditions (temperature, pressure, and laser fluence). We have studied the dependence of optical properties, structural properties and their correlations for these AlN films. The optical transmission spectra of the produced films were measured, and a numerical procedure was applied to accurately determine the optical constants for films of non-uniform thickness. The microstructure and texture of the films were studied using various X-ray diffraction techniques. The real part of the refractive index was found to not vary significantly with processing parameters, but absorption was found to be strongly dependent on the deposition temperature and the nitrogen pressure in the deposition chamber. We report that low optical absorption, textured polycrystalline AlN films can be produced by PLD on sapphire substrates at both low and high laser fluence using a background nitrogen pressure of 6.0 × 10^− 2 Pa (4.5 × 10^− 4 Torr) of 99.9% purity.     

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.     

Laser-induced amorphization and crystallization on Se80Te20−xPbx thin films

Thin films of glassy alloys of a-Se₈₀Te_20−xPb_x (x=2, 6 and 10) was crystallized in a specially designed sample holder under a vacuum of 10⁻² Pa. The amorphous and crystallized films were induced by pulse laser (wavelength: 337.1 nm, frequency: 10 Hz, pulse duration: 4 ns and pulse energy: 0.963 mJ). After laser irradiation on amorphous and crystalline films: optical band gaps were measured. Crystallization and amorphization of chalcogenide films is accompanied by the change in the optical band gap. The change in optical energy gap could be determined by identification of the transformed phase. This change in the optical band gap may be due to the increase in the grain size and the reduction in the disorder of the system.     

Optical and structural characteristics of ZnO thin films grown by rf magnetron sputtering

Nanostructured ZnO thin films on Pyrex glass substrates were deposited by rf magnetron sputtering at different substrate temperatures. Structural features and surface morphology were studied by X-ray diffraction and atomic force microscopy analyses. Films were found to be transparent in the visible range above 400 nm, having transparency above 90%. Sharp ultraviolet absorption edges around 370 nm were used to extract the optical band gap for samples of different particle sizes. Optical band gap energy for the films varied from 3.24 to 3.32 eV and the electronic transition was of the direct in nature. A correlation of the band gap of nanocrystalline ZnO films with particle size and strain was discussed. Photoluminescence emission in UV range, which is due to near band edge emission is more intense in comparison with the green band emission (due to defect state) was observed in all samples, indicating a good optical quality of the deposited films.     

Fabrication of highly oriented (002) ZnO film on glass by sol-gel method

In this study high quality (002) ZnO films were deposited on glass substrate by a sol-gel spin coating process. The as-coated films were post-annealed at different temperatures in air to investigate the effect of annealing temperature in particular. The chemical composition of the precursor sol and the intermediates produced in the films heating process were analyzed by thermo gravimetric analysis/differential thermal analysis (TGA/DTA). The microstructure and its optical properties of ZnO films were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), ultraviolet-visible spectroscopy (UV-Vis) and photoluminescence. TGA/DTA showed that a significant weight loss occurred at around 200-300 °C and the weight stabilized at 300 °C. An extremely sharp (002) diffracted peak in XRD patterns indicated the high preference in crystallinity of these films. FESEM micrographs revealed that the films were filled with particulates with size ranging from 10 to 25 nm as post annealing temperature increased from 400 to 500 °C and turned into porous films at 600 °C. UV-Vis has shown that the films were highly transparent under visible light and had a sharp absorption edge in the ultraviolet region at 380 nm. The measured optical band gap values of the ZnO thin films were around 3.24-3.26 eV. Photoluminescence spectra revealed a strong UV emission centered at about 390 nm corresponding to the near-band-edge emission with a weak defect-related emission at about 520 nm. The intensity of UV emission increased with the annealing temperature. This may be attributed to a higher quality ZnO film while annealed at higher temperature.     

Effect of precursor concentration on structural and optical properties of ZnO microrods by spray pyrolysis

ZnO films have been prepared by spray pyrolysis technique on glass substrate at 500 °C. Zinc Chloride has been used as a precursor. Effect of precursor concentration on structural and optical properties has been investigated. Homogenous films are obtained with precursor concentration rating between 0.1 M and 0.4 M. X-ray diffraction patterns show that ZnO films are polycrystalline with (002) plane as preferential orientation. Field emission scanning electron microscopy images show that ZnO films consist of microrods that their length increases with increasing precursor concentration and tallest microrods obtain by spraying precursor with 0.3 M concentration. The optical transmittance spectrum shows that transmittance increases with decreasing of the concentration and transmittance reaches to a maximum value of about 80% for the visible region ZnO films prepared with 0.1 M. Photoluminescence spectra at room temperature show an ultraviolet emission at 3.21 eV that can be related to band gap and two visible emissions at 2.88 eV and 2.38 eV.     

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

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

Effect of process parameters on the growth and properties of impurity-doped zinc oxide transparent conducting thin films by RF magnetron sputtering

Zinc oxide transparent conducting thin films co-doped with aluminum and ruthenium were grown on polyethylene terephthalate substrates at room temperature using RF magnetron sputtering. The crystal growth and physical properties of the films were investigated with respect to the variation of discharge power density from 1.5 to 6.1 W/cm² and sputtering pressure from 0.13 to 2.0 Pa. X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) showed that the films grown with 3.6 W/cm² power density and sputtering pressure of 0.4 Pa had the best crystallinity and larger pyramid-like grains. The optimized electrical resistivity had a lowest measured value of about 9 × 10⁻⁴ Ω cm. The low carrier mobilities of the films (3-8.9 cm² V⁻¹ s⁻¹) have been discussed in terms of what is believed to be the dominant effect of ionized impurity scattering, but in addition chemisorption of oxygen on the film surface and effect of grain boundaries are also thought to be significant. The transmittances of the films in the visible range are greater than 80%, while the optical band gaps are in the order of 3.337-3.382 eV.     

Optical and structural properties of Cu-doped β-Ga2O3 films

The intrinsic and Cu-doped β-Ga₂O₃ films were grown on Si and quartz substrates by RF magnetron sputtering in an argon and oxygen mixture ambient. The effects of the Cu doping and the post thermal annealing on the optical and structural properties of the β-Ga₂O₃ films were studied. The surface morphology, microstructure, optical transmittance, optical absorption, optical energy gap and photoluminescence of the β-Ga₂O₃ films were significantly changed after Cu-doping. After post thermal annealing, Polycrystalline β-Ga₂O₃ films were obtained, the transmittance decreased. After Cu-doping, the grain size decreased, the crystal quality deteriorated and the optical band gap shrunk. The UV, blue and green emission bands were observed and discussed. The UV and blue emission were enhanced and a new blue emission peak centred at 475 nm appeared by Cu-doping.     

Effects of annealing atmosphere on thermoelectric signals from ZnO films

Zinc oxide epilayer films were grown on vicinal cut sapphire substrates by pulsed laser deposition with in situ annealing oxygen pressures varied from 0 to 10 × 10³ Pa. The best crystalline quality was obtained for ZnO layer with annealing oxygen pressure of 6 × 10³ Pa. Laser induced thermoelectric voltage (LITV) were observed along the tilting angle orientation of the substrate when the pulsed KrF excimer laser of 248 nm were irradiated on the films. The largest LITV signal was measured for the film grown at 6 × 10³ Pa annealing oxygen pressure. According to the measured LITV signals, Seebeck anisotropy was evaluated and was found to range from 3 to 12 μV/K for ZnO films annealed at different oxygen pressures from 2 to 10 × 10³ Pa. It is suggested that oxygen ambient plays an important role in the electronic properties of the ZnO films.