Effects of substrate parameters on structure and optical properties of ZnO thin films fabricated by pulsed laser deposition

Highly oriented zinc oxide thin films have been grown on quartz, Si (1 1 1) and sapphire substrates by pulsed laser deposition (PLD). The effect of temperature and substrate parameter on structural and optical properties of ZnO thin films has been characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), optical transmission spectra and PL spectra. The experimental results show that the best crystalline thin films grown on different substrate with hexagonal wurtzite structure were achieved at growth temperature 400–500 °C. The growth temperature of ZnO thin film deposited on Si (1 1 1) substrate is lower than that of sapphire and quartz. The band gaps are increasing from 3.2 to 3.31 eV for ZnO thin film fabricated on quartz substrate at growth temperature from 100 to 600 °C. The crystalline quality and UV emission of ZnO thin film grown on sapphire substrate are significantly higher than those of other ZnO thin films grown on different substrates.     

Epitaxial growth of non-polar m-plane ZnO thin films by pulsed laser deposition

Non-polar ZnO thin films were deposited on m-plane sapphire substrates by pulsed laser deposition at various temperatures from 300 to 700 °C. The effects of growth temperature on surface morphology, structural, electrical, and optical properties of the films were investigated. All the films exhibited unique m-plane orientation indicated by X-ray diffraction and transmission electron microscopy. Based on the scanning electron microscopy and atomic force microscopy, the obtained films had smooth and highly anisotropic surface, and the root mean square roughness was less than 10 nm above 500 °C. The maximum electron mobility was ～18 cm²/V s, with resistivity of ～0.26 Ω cm for the film grown at 700 °C. Room temperature photoluminescence of the m-plane films was also investigated.     

Annealing effect on the photoluminescence properties of ZnO nanorod array prepared by a PLD-assistant wet chemical method

Well-aligned ZnO nanorod arrays were synthesized by a wet chemical method on the glass substrate with ZnO thin film as seed layer prepared by pulsed laser deposition. The effect of annealing temperature on the luminescence characteristics was investigated. As the annealing temperature increased, the photoluminescence properties show a general enhancing tendency. The nanorod array with high ultraviolet emission and negligible visible light emission (designated by the photoluminescence intensity ratio of ultraviolet to visible emission of 66.4) is obtained by annealing the sample at 700 °C for 1 h. Based on the results of X-ray photoelectron spectroscopy and photoluminescence spectra, the mechanisms of visible emission were discussed.     

Annealing induced reorientation of crystallites in Sn doped ZnO films

Tin doped ZnO thin films were prepared by employing a simplified spray pyrolysis technique using a perfume atomizer and subsequently annealed under different temperatures from 350 °C to 500 °C in steps of 50 °C. The structural, optical, electrical, photoluminescence and surface morphological properties of the as-deposited films were studied and compared with that of the annealed films. The X-ray diffraction studies showed that as-deposited film exhibits preferential orientation along the (0 0 2) plane and it changes in favour of (1 0 0) plane after annealing. The increase in crystallite size due to annealing is explained on the basis of Ostwald ripening effect. It is found that the optical transmittance and band gap increases with increase in annealing temperature. A slight decrease in resistivity caused by annealing is discussed in correlation with annealing induced defect modifications and surface morphology.     

Formation of F-doped ZnO transparent conductive films by sputtering of ZnF2

Fluorine-doped ZnO transparent conductive thin films were successfully deposited on glass substrate by radio frequency magnetron sputtering of ZnF₂. The effects of rapid thermal annealing in vacuum on the optical and electrical properties of fluorine-doped ZnO thin films have been investigated. X-ray diffraction spectra indicate that no fluorine compounds, such as ZnF₂, except ZnO were observed. The specimen annealed at 500 °C has the lowest resistivity of 6.65 × 10^? 4 Ω cm, the highest carrier concentration of 1.95 × 10²¹ cm^? 3, and the highest energy band gap of 3.46 eV. The average transmittance in the visible region of the F-doped ZnO thin films as-deposited and annealed is over 90%.     

Oxygen plasma power dependence on ZnO grown on porous silicon substrates by plasma-assisted molecular beam epitaxy

ZnO thin films were deposited on porous silicon by plasma-assisted molecular beam epitaxy using different radio frequency power settings. Optical emission spectrometry was applied to study the characteristics of the oxygen plasma, and the effects of the radio frequency power on the properties of the ZnO thin films were evaluated by X-ray diffraction, scanning electron microscopy, and photoluminescence. The grain sizes for radio frequency powers of 100, 200, and 300 W were 46, 48, and 62 nm, respectively. In addition, the photoluminescence intensities of the ultraviolet and the visible range increased at 300 W, because the density of the atomic oxygen transitions increased. The quality of the ZnO thin films was enhanced, but the deep-level emission peaks increased with increasing radio frequency power. The structural and optical properties of the ZnO thin films were improved at the radio frequency power of 300 W. Moreover, the optical properties of the ZnO thin films were improved with porous silicon, instead of Si.     

Characteristics of Al-doped c-axis orientation ZnO thin films prepared by the sol–gel method

Transparent conducting ZnO thin films doped with Al have been prepared by sol–gel method, which were characterized by X-ray diffraction, atomic force microscopy and ultra-violet spectrometer. The films showed a hexagonal wurtzite structure and high preferential c-axis orientation. The optical transmittance spectra of the films showed the transmittance higher than 85% within the visible wavelength region. A minimum resistivity of 6.2 × 10⁻⁴ Ω cm was obtained for the film doped with 1.5 mol.% Al, preheated at 300 °C for 15 min and post-heated at 530 °C for 1 h.     

Producing CuO and ZnO composite thin films using the spin coating method on microscope glasses

In this work, we have presented a new route to produce pure ZnO and composite ZnO-CuO thin films. In the process we have started with pure ZnO thin films and ended up with CuO by doping Cu in various percentages, ranging from 0% to 100%. We have managed to attain crystal phases in all doping concentrations. All the produced thin films have been crystallized at the annealing temperatures of 600 and 700 °C for 6 h. The X-ray diffraction (XRD) spectra have been performed to see the formation of crystal phases of all pure ZnO and composite ZnO-CuO thin films. These give insight that the two crystal phases related to ZnO and CuO stayed together within the thin film matrices, which were produced in different doping concentrations, i.e. nZnO + mCuO (0 ≤ n, m ≤ 100%). The scanning electron microscopy (SEM) micrographs and UV–vis absorption spectra have also been taken to elucidate the structure and composition of the all films.     

Effect of solvents on the synthesis of nano-size zinc oxide and its properties

The effect of the solvents on particle size and morphology of ZnO is investigated. The optical properties of nano ZnO were studied extensively. During this study, zinc oxalate was prepared in aqueous and organic solvents using zinc acetate and oxalic acid as precursors. The thermo-gravimetric analysis (TGA/DTA) showed formation of ZnO at 400 °C. Nano-size zinc oxide was obtained by thermal decomposition of aqueous and organic mediated zinc oxalate at 450 °C. The phase purity was confirmed by XRD and crystal size determined from transmission electron microscopy (TEM) was found to be 22–25 nm for the aqueous and 14 –17 nm in organic mediated ZnO. Scanning electron microscope (SEM) also revealed different nature of surfaces and microstructures for zinc oxide obtained in aqueous and organic solvents. The UV absorption spectra showed sharp absorption peaks with a blue shift for organic mediated ZnO, due to monodispersity and lower particle size. Sharp peaks and absence of any impurity peaks in photoluminescence spectra (PLS) complement the above observations.     

Deposition of nanocrystalline ZnO by wire explosion technique and characterization of the films' properties

ZnO films deposited on glass, quartz and Al on silicon mono-crystal Si (100) substrates by using the wire explosion technique were investigated by X-ray diffraction (XRD), UV–VIS spectroscopy, scanning electron (SEM) and atomic force microscopy (AFM) measurements. X-ray diffraction measurements have shown that ZnO films are mainly composed of (100), (002) and (101) orientation crystallites. The post-deposition thermal treatment at 600 °C temperature in air has shown that the composite of Zn/ZnO film was fully oxidized to ZnO film. The XRD spectra of the film deposited in oxygen atmosphere at room temperature present high intensity dominating peak at 2h = 36, 32° corresponding to the (101) ZnO diffraction peak. The small fraction of the film (7%) corresponds to the (002) peak intensity at 2h = 34, 42°. This result indicates the good crystal quality of the film and hexagonal wurtzite-type structure deposited by zinc wire explosion. The optical absorption spectra shows the bands at 374, 373 and 371 nm corresponding to deposition conditions. The SEM analysis shows that ZnO films presented different morphologies from fractal network to porous films depending on deposition conditions. AFM analysis revealed the grain size ranges from 50 nm to 500 nm. The nanoneedles up to 300 nm in length were found as typical structures in the film. It was demonstrated that the wire explosion technique is a feasible method to produce ZnO crystalline thin films and nanostructures.     

Influence of the molar concentration and substrate temperature on fluorine-doped zinc oxide thin films chemically sprayed

The effect of both the molar concentration of the starting solution and the substrate temperature on the electrical, morphological, structural and optical properties of chemically sprayed fluorine-doped zinc oxide (ZnO:F) thin films deposited on glass substrates is analyzed in this work. All the starting solutions employed were aged for 10 days before the deposition. The results show that as the molar concentration increases, a decrease in the electrical resistivity values is obtained, reaching the minimum resistivity in films ZnO:F deposited from a 0.4 M solution at 500 °C. A further increase in the molar concentration leads to a very slight increase in the resistivity. On the other hand, as the substrate temperature is increased, the resistivity decreases and a tendency towards to minimum value is evidenced; taking the molar concentration as parameter, minimum values are reached at 500 °C. The obtaining of ZnO:F thin films, with a resistivity as low as 7.8 × 10^− 3 Ω cm (sheet resistance of 130 Ω/□ and film thickness of 600 nm) measured in as-deposited films is reported here for the first time. The concurrent effect of the high molar concentration of the starting solution, the substrate temperature values used, and the ageing of the starting solution, which might cause polymerization of the zinc ions with the fluorine species, enhance the electrical properties. The structure of the films is polycrystalline, with a (002) preferential growth. Molar concentration rules the surface morphology as at low concentration an hexagonal and porous structure is developed changing to a uniform compact and small grain size surface in the films deposited with the high molar concentrations.     

Effects of the sulfidation temperature on the structure,composition and optical properties of ZnS films prepared by sulfurizing ZnO films

Nanocrystalline ZnS films have been prepared by sulfidation of the reactive magnetron sputtered ZnO films. The structure, composition and optical properties of the sulfurized ZnO films as a function of the sulfidation temperature (T_S) have been systematically studied. It is found that at T_S ⩾ 400 °C ZnO is completely converted to ZnS with the hexagonal structure. The ZnS films have a strongly (0 0 2) preferred orientation and an optical transparency of about 80% in the visible region. In addition, at T_S < 444.6 °C (boiling point of sulfur), some residual sulfur decomposed from H₂S gas can adhere to the sulfurized film surface while at T_S = 580 °C a S/Zn ratio much higher than the ideal stoichiometric proportion of ZnS is obtained for the ZnS films. ZnS films with a minimum XRD FWHM value of 0.165° and a good S/Zn ratio of 0.99 are obtained at a temperature of 500 °C indicating the ZnS films to be suitable for use in the thin film solar cells.     

Photoluminescent properties of LiInO2 nanocrystals

Synthesis and luminescence properties of LiInO₂ nanocrystals by the sol–gel process were investigated. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence spectroscopy and absorption spectra. The well-crystallized tetragonal LiInO₂ can be obtained by heat treatment above 600 °C from XRD. The excitation wavelengths at about 246 nm were associated with charge transfer between In and O with In³⁺ ions in octahedral coordination. The PL spectra excited at 246 nm have a broad and strong emission band maximum at 391 nm, corresponding to the self-activated luminescence. The optical absorption spectra of the 600 °C sample exhibited the band gap energies of 3.7 eV.     

Transparent amorphous zinc oxide thin films for NLO applications

This review focuses on the growth and optical properties of amorphous zinc oxide (ZnO) thin films. A high quality ZnO films fabricated by dip-coating (sol–gel) method were grown on quartz and glass substrates at temperature equal to 350 K. The amorphous nature of the films was verified by X-ray diffraction. Atomic Force Microscopy was used to evaluate the surface morphology of the films. The optical characteristics of amorphous thin films have been investigated in the spectral range 190–1100 nm. Measurement of the polarized optical properties was shows a high transmissivity (80–99%) and low absorptivity (<5%) in the visible and near infrared regions at different angles of incidence. Linear optical properties were investigated by classic and Time-Resolved Photoluminescence (TRPL) measurements. Photoluminescence spectrum exhibits a strong ultraviolet emission while the visible emission is very weak. An innovative TRPL technique has enabled the measurement of the photoluminescence decay time as a function of temperature. TRPL measurements reveal a multiexponential decay behavior typical for amorphous thin films. Second and third harmonic generation measurements were performed by means of the rotational Maker fringe technique using Nd:YAG laser at 1064 nm in picosecond regime for investigations of the nonlinear optical properties. The obtained values of second and third order nonlinear susceptibilities were found to be high enough for the potential applications in the optical switching devices based on refractive index changes. Presented spectra confirm high structural and optical quality of the investigated zinc oxide thin films.     

Structural and functional properties of ZnO thin films grown on Si substrates by air assisted USP method from non-aqueous solutions at low-temperature

In this work, we deals with the processing and characterization of transparent conducting ZnO thin films on p-type Silicon substrates (1 0 0) by air assisted Ultrasonic Spray Pyrolysis (USP) method. The thin films from different Zn acetate precursor solution concentrations (0.1, 0.2, 0.3 and 0.4 M) were deposited at several temperatures (400, 450 and 500 °C) with thickness from ～100 to ～500 nm. The effects of precursor solution concentration, deposition time and temperature on the structural, morphological, optical, and electrical properties of ZnO films were studied by X-ray Diffraction (XRD), Atomic Force Microscopy (AFM), UV–Vis-NIR spectroscopy, and Hall Effect techniques, respectively. It has been shown that on the ZnO film surface, the preferred orientation, the average crystallite size, the electrical resistivity and the RMS surface roughness depend on the substrate temperature. The grown films have showed a good adhesion and an excellent optical transmission of about 80–95% within the visible range (400–800 nm) and a direct band gap from 3.35 to 3.23 eV with the increase of the substrate temperature and the deposition time. All the PL spectra have exhibited a typical green-yellow emission band. Additionally photovoltaic (PV) activities of n-ZnO/p-Si heterostructures fabricated are investigated.     

Effect of substrate temperature on the properties of pyrolytically deposited nitrogen-doped zinc oxide thin films

The effect of substrate temperature (T_s) on the properties of pyrolytically deposited nitrogen (N) doped zinc oxide (ZnO) thin films was investigated. The T_s was varied from 300 °C to 500 °C, with a step of 50 °C. The positive sign of Hall coefficient confirmed the p-type conductivity in the films deposited at 450 °C and 500 °C. X-ray diffraction studies confirmed the ZnO structure with a dominant peak from (1 0 0) crystal plane, irrespective of the variation in T_s. The presence of N in the ZnO structure was evidenced through X-ray photoelectron spectroscopy (XPS) analysis. The obtained high N concentration reveals that the 450 °C is the optimal T_s. Atomic force microscope (AFM) analysis showed that the surface roughness was increased with the increasing T_s until 400 °C but then decreased. It is found that the transmittance of the deposited films is increased with the increasing T_s. The optical band gap calculated from the absorption edge showed that the films deposited with T_s of 300 °C and 350 °C possess higher values than those deposited at higher T_s.     

Morphology and crystal quality investigation of hydrothermally synthesized ZnO micro-rods

Micro-structural and room and low temperature photoluminescence response of undoped one-dimensional ZnO were investigated. ZnO rods of different morphology and size were synthesized by controlling growth parameters through hydrothermal technique. The phase and microstructure analysis were carried out by X-ray diffraction and scanning electron microscopy. The room and low temperature photoluminescence spectra of the samples were studied. Near band edge sharp exciton emission peaks and broad defect-related peaks were observed. The ratio of band edge emission to deep level emission was controlled by tuning the initial concentration, pH and reaction time period. Optimal growth condition for growth of micro-rods with improved crystal quality was obtained with initial Zn²⁺ concentration of 0.5 M, at reaction temperature of 120 °C, pH of 9.9 and in a reaction time period of 6 h.     

New natively textured surface Al-doped ZnO-TCOs for thin film solar cells via magnetron sputtering

Natively textured surface aluminum doped zinc oxide (ZnO:Al) thin films were directly deposited via pulsed direct current (DC) reactive magnetron sputtering on glass substrates. During the reactive sputtering process, the oxygen gas flow rate was varied from 8.5 sccm to 11.0 sccm. The influences of oxygen flow rate on the structural, electrical and optical properties of naturally textured ZnO:Al TCO thin films with milky surface were investigated in detail. Gradual oxygen growth (GOG) technique was developed in the reactive sputtering process for textured ZnO:Al thin films. The light-scattering ability and optical transmittance of the natively textured ZnO:Al TCO thin films can be improved through gradual oxygen growth method while maintaining a low sheet resistance. Typical natively textured ZnO:Al TCO thin film with crater-like surface exhibits low sheet resistance (R_s ～ 4 Ω), high transmittance (T_a > 85%) in visible optical region and high haze value (12.1%).     

Fabrication and characterization of tetrapod-like ZnO nanostructures prepared by catalyst-free thermal evaporation

Tetrapod-like ZnO nanostructures were fabricated on ZnO-coated sapphire (001) substrates by two steps: pulsed laser deposition (PLD) and catalyst-free thermal evaporation process. First, the ZnO films were pre-deposited on sapphire (001) substrates by PLD. Then the ZnO nanostructures grew on ZnO-coated sapphire (001) substrate by the simple thermal evaporation of the metallic zinc powder at 900 °C in the air without any catalysts. The pre-deposited ZnO films by PLD on the substrates can provide growing sites for the ZnO nanostructures. The as-synthesized ZnO nanostructures were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectrum (FTIR). The results show that the tetrapod-like ZnO nanostructures are highly crystalline with the wurtzite hexagonal structure. Photoluminescence (PL) spectrum of as-synthesized nanostructures exhibits a UV emission peak at ～ 389 nm and a broad green emission peak at ～ 513 nm. In addition, the growth mechanism of ZnO nanostructures is also briefly discussed.     

Low temperature preparation and characterization of CdTiO3 nanoplates

An alternative low cost method was proposed for the low temperature (600 °C) preparation of CdTiO₃ nanoplates, using low-melting-point Cd(NO₃)₂ · 4H₂O and high-reactive-activity TiO₂ nanocrystals as the reactants. The structure, composition, specific surface area, thermal stability and optical properties of the as-synthesized products were characterized by X-ray diffraction, energy dispersive X-ray spectroscopy, field emission scanning electron microscopy, Brunauer–Emmett–Teller surface area analysis, UV–vis absorption and room temperature photoluminescence spectra. The as-synthesized CdTiO₃ nanoplates were thermally stable at temperatures ≤ 900 °C, and their phase changed from ilmenite to perovskite when heated in air at 1000 °C for 2 h. Besides, they exhibited a strong and broad visible light emission in the range of about 470–750 nm upon laser excitation at 325 nm, enabling their use as a luminescent material.