Photoluminescence of ZnO nanostructures grown by the aqueous chemical growth technique

Zinc oxide nanostructured films were grown by the aqueous chemical growth technique using equimolar aqueous solutions of zinc nitrate and hexamethylenetetramine as precursors. Silicon(100) and glass substrates were placed in Pyrex glass bottles with polypropylene autoclavable screw caps containing the precursors described above, and heated at 95 C for several hours. X-ray diffraction 2θ/θ scans showed that the only crystallographic phase present was the hexagonal wurtzite structure. Scanning electron microscopy showed the formation of flowerlike ZnO nanostructures, consisting of hexagonal nanorods with a diameter of a few hundred nanometers. The photoluminescence spectra of the ZnO nanostructures were recorded at 18–295 K using a cw He–Cd laser (325 nm) and a pulsed laser (266 nm). The ZnO nanostructures exhibit an ultraviolet emission band centered at 3.192 eV in the vicinity of the band edge, which is attributed to the well-known excitonic transition in ZnO.     

Photoluminescence study of pure and Li-doped ZnO thin films grown by sol-gel technique

The effect of annealing atmosphere, temperature and aging on the photoluminescence of pure and Li-doped ZnO thin films has been investigated. Annealing the pure ZnO in N₂ and He above 800 °C results in green emission centered at ca. 500 nm; however annealing in air red-shifts the green emission to 527 nm. The visible emission of the Li-doped ZnO is found to be largely dependent on the annealing atmosphere. Warm-white photoluminescence with a broad emission band covering nearly the whole visible spectrum is obtained for the Li-doped ZnO films annealed in helium. The substitutional and interstitial extrinsic point defects created by lithium doping may mediate the relative concentration of the intrinsic defects and thereby tune the intrinsic-defect-related visible emission. The enhanced intensity ratio of near-band-edge ultraviolet emission to deep-level visible emission with aging time may be ascribed to both in-diffusion of oxygen from air and self-diffusion of oxygen interstitials to heal the oxygen vacancies during the aging process.     

Investigation of electronic and optical properties in Al−Ga codoped ZnO thin films

Electronic and optical properties of Al−Ga codoped ZnO thin films were investigated by post-annealing. The lowest resistivity of the Al-Ga codoped ZnO films was observed from the 450 °C-annealed sample. The Fermi-level shift of the Al−Ga codoped ZnO film was ∼0.6 eV from x-ray photoelectron spectroscopy, and the widening of optical-bandgap in the Al−Ga codoped ZnO film was ∼0.3 eV. The correlations of optical-bandgap with Fermi-level shift and conduction band filling were suggested by schematic band diagrams.     

Effect of mesh patterning with UV pulsed-laser on optical and electrical properties of ZnO/Ag-Ti thin films

In this study, the ZnO/Ag-Ti structure for transparence conducting oxide (TCO) is investigated by optimizing the thickness of the Ag-Ti alloy and ZnO layers. The Ag-Ti thin film is deposited by DC magnetron sputtering and its thicknesses is well controlled. The ZnO thin film is prepared by sol-gel method using zinc acetate as cation source, 2-methoxiethanol as solvent and monoethanolamine as solution stabilizer. The ZnO film deposition is performed by spin-coating technique and dried at 150 °C on Corning 1737 glass. Due to the conductivity of ZnO/Ag-Ti is dominated by Ag-Ti, the sheet resistance of ZnO/Ag-Ti decrease dramatically as the thickness of Ag-Ti layer increases. However, the transmittances of ZnO/Ag-Ti become unacceptable for TCO application after the thickness of Ag-Ti layer beyond 6 nm. The as-deposited ZnO/Ag-Ti structure has the optical transmittance of 83% @ 500 nm and the low resistivity of 1.2 × 10⁻⁵ Ω-cm. Furthermore, for improving the optical and electrical properties of ZnO/Ag-Ti, the thermal treatment using laser is adopted. Experimental results indicate that the transmittance of ZnO/Ag-Ti is improved from 83% to 89% @ 500 nm with resistivity of 1.02 × 10⁻⁵ Ω-cm after laser drilling. The optical spectrum, the resistance, and the morphology of the ZnO/Ag-Ti will be reported in the study.     

Photoluminescence and resonant Raman scattering in N-doped ZnO thin films

A combination of studies on photoluminescence and resonant Raman scattering in N-doped ZnO thin films were carried out at room temperature. In the photoluminescence spectra, a transformation of radiative recombination mechanism from free-exciton to donor-acceptor-pair transition was observed. An enhancement of resonant Raman scattering processes as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed in the Raman spectra. Also, the nature of the 1LO phonon underwent a transformation from a pure A₁(LO) mode to a quasimode with mixed A₁ and E₁ symmetry. The underlying mechanisms accounting for the influences of N doping on the optical properties of ZnO were related to the incorporation of extrinsic defects in the crystal lattice.     

Growth and characterization of thin ZnO films deposited on glass substrates by electrodeposition technique

Electrodeposition technique was used in order to produce nanometric zinc oxide films on glass insulating substrates. The effect of electrolyte concentration and applied current density on the formation and growth of electrodeposited Zn thin films in aqueous solutions of ZnSO₄ were studied. After a thermal oxidation, a characterization of the structural morphology of the films deposited was carried out by optical microscopy (OM), atomic force microscopy (AFM), scanning electron microscopy (SEM) and by grazing incidence X-rays diffraction (GIXD). These characterization techniques show that the grains size of the films after oxidation at temperature 450 °C is between 5 and 15 nm, as well as the structure is polycrystalline nature with several orientations. UV/vis spectrophotometry confirms that it is possible to obtain transparent good ZnO films with an average transmittance of approximately 80% within the visible wavelength region, as well as the optical gap of obtained ZnO films is 3.17 eV.     

Effects of annealing on properties of ZnO thin films prepared by electrochemical deposition in chloride medium

The development of cost-effective and low-temperature synthesis techniques for the growth of high-quality zinc oxide thin films is paramount for fabrication of ZnO-based optoelectronic devices, especially ultraviolet (UV)-light-emitting diodes, lasers and detectors. We demonstrate that the properties, especially UV emission, observed at room temperature, of electrodeposited ZnO thin films from chloride medium (at 70 °C) on fluor-doped tin oxide (FTO) substrates is strongly influenced by the post-growth thermal annealing treatments. X-ray diffraction (XRD) measurements show that the films have preferably grown along (0 0 2) direction. Thermal annealing in the temperature range of 150-400 °C in air has been carried out for these ZnO thin films. The as-grown films contain chlorine which is partially removed after annealing at 400 °C. Morphological changes upon annealing are discussed in the light of compositional changes observed in the ZnO crystals that constitute the film. The optical quality of ZnO thin films was improved after post-deposition thermal treatment at 150 °C and 400 °C in our experiments due to the reducing of defects levels and of chlorine content. The transmission and absorption spectra become steeper and the optical bandgap red shifted to the single-crystal value. These findings demonstrate that electrodeposition have potential for the growth of high-quality ZnO thin films with reduced defects for device applications.     

Enhancement of surface morphology and optical properties of nanocolumnar ZnO films

Nanocolumnar ZnO films were prepared by electrodeposition (ED) on a glass substrate covered with a conductive layer of thin oxide doped with fluorine (FTO). After deposition the samples were annealed in oxidizing or reducing atmosphere, at temperatures between 100 to 500 C, in order to follow the evolution of optical properties and morphology. The optical properties of these films were studied by means of photoluminescence spectroscopy (PL) and the morphology by scanning electron microscopy (SEM). Films annealed at 300 C exhibit a higher ultraviolet emission peak, originating from exciton transitions. A green band related to deep-level emission centered at 500 nm, shows a drastic increase at 500 C. These results are independent of the annealing atmosphere. An increase of coalescence is also observed after annealing at 500 C. These results are explained taking into account the contribution of different point defects.     

Growth of transparent conducting nano-structured In doped ZnO thin films by pulsed DC magnetron sputtering

Transparent conducting nano-structured In doped zinc oxide (IZO) thin films are deposited on corning 7059 glass substrates by bipolar pulsed DC magnetron sputtering with variation of pulsed frequency and substrate temperature. Highly c-axis oriented IZO thin films were grown in perpendicular to the substrate on the 30 kHz and 500 °C. The IZO films exhibited surface roughness of 3.6 nm similar to the commercial ITO and n-type semiconducting properties with electrical resistivity (carrier mobility) of about 5 × 10⁻³ Ω cm (14 cm²/V s). The optical characterization showed high transmittance of over 85% in the UV-vis region and exhibited the absorption edge of near 350 nm. In micro-Raman spectra, the origin of two additional modes is attributed to the host lattice defect due to the addition of In dopant. These results suggest that the IZO film can possibly be applied to make transparent conducting electrodes for flat panel displays.     

Photoluminescence observations of hydrogen incorporation and outdiffusion in ZnO thin films

ZnO thin films were deposited with the addition of H₂ to the reaction gas using the atmospheric-pressure metal organic chemical vapor deposition method. The incorporation and outdiffusion of hydrogen in ZnO films were investigated by comparing the intensity of the hydrogen-related bound-exciton peak (I₄: 3.363 eV) in the photoluminescence spectrum. The intensity of I₄ peak was found to be the strongest in the ZnO film deposited at 680 °C with H₂ present. However, for the ZnO films prepared at the same temperature 680 °C but without H₂ present and at the higher temperature of 900 °C with H₂ present, respectively, the I₄ peak was just a minor shoulder of another bound-exciton peak (I₈: 3.359 eV). The intensity of I₄ peak in the ZnO films deposited with H₂ present was found to decrease with the increasing of annealing temperature. These results suggest that it is difficult for hydrogen to incorporate into ZnO thin films grown at high temperatures even in the hydrogen-present ambient.     

Characterization of nitrogen-doped ZnO thin films grown by plasma-assisted pulsed laser deposition on sapphire substrates

The crystalline, optical and electrical properties of N-doped ZnO thin films were measured using X-ray diffraction, photoluminescence and Hall effect apparatus, respectively. The samples were grown using pulsed laser deposition on sapphire substrates coated priorly with ZnO buffer layers. For the purpose of acceptor doping, an electron cyclotron resonance (ECR) plasma source operated as a low-energy ion source was used for nitrogen incorporation in the samples. The X-ray diffraction analyses indicated some deterioration of the ZnO thin film with nitrogen incorporation. Temperature-dependent Van der Pauw measurements showed consistent p-type behavior over the measured temperature range of 200–450 K, with typical room temperature hole concentrations and mobilities of 5×10¹⁵ cm⁻³ and 7 cm²/V s, respectively. Low temperature photoluminescence spectra consisted of a broad emission band centered around 3.2 eV. This emission is characterized by the absence of the green deep-defect band and the presence of a band around 3.32 eV.     

Effects of deposition temperatures and annealing conditions on the microstructural, electrical and optical properties of polycrystalline Al-doped ZnO thin films

Al-doped ZnO (AZO, ZnO:Al₂O₃ = 98:2 wt%) films are deposited on different substrates by an RF magnetron sputtering and subsequently annealed at three different conditions to investigate the microstructural, electrical, and optical properties. X-ray diffraction and scanning electron microscope results show that all the samples are polycrystalline and the samples rapid-thermal-annealed at 900 °C in an N₂ ambient contain larger grains compared to the furnace-annealed samples. It is shown that the sample deposited at room temperature on the sapphire gives a resistivity of 5.57 × 10⁻⁴ Ω cm when furnace-annealed at 500 °C in a mixture of N₂:H₂ (9:1). It is also shown that the Hall mobility vs. carrier concentration (μ-n) relation is divided into two groups, depending on the annealing conditions, namely, either rapid-thermal annealing or furnace annealing. The relations are described in terms of either grain boundary scattering or ionized impurity scattering mechanism. In addition, the samples produce fairly high transmittance of 91-96.99% across the wavelength region of 400-1100 nm. The optical bandgaps of the samples increase with increasing carrier concentration.     

Synthesis of submicron rhombic ZnO rods via ZnOHF intermediate using electrodeposition route

ZnOHF submicron rods with the rhombus-like shape were successfully prepared by a low-temperature aqueous electrodeposition route. By further adjusting the experimental parameters including the electrolyte concentration, temperature, the electrodeposition potential, and the duration, the morphologies of ZnOHF films can further be controlled; accordingly, ZnO films with different morphologies were also obtained by calcining ZnOHF intermediate at 400 °C for 2 h. Based on the experimental results, a plausible mechanism for the conversion from ZnOHF to ZnO crystals was proposed. The surface morphology and microstructure of the products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and the optical property of the samples was investigated by room-temperature photoluminescence (PL) spectra as well. The PL spectra confirmed that ZnOHF and ZnO exhibited emission band centered at 413 nm and 382 nm in UV region, respectively.     

Morphology and photoluminescence study of electrodeposited ZnO films

ZnO films on ITO substrates and Au coated ITO substrates were fabricated by using electrodeposition technique. We carried out the experiments by adjusting the concentration of solution, potential, substrate, and temperature. The effect of temperature on the growth of the film has been examined. SEM images have shown that there are several kinds of grown competitions for the deposition of ZnO films, but three kinds of them are dominant. One is the discrete hexagonal column structure, the other is the pentagonal structure, and the third one is of well-oriented hexagonal columns with well-aligned structure. The explanation on the grown competition is discussed. ZnO hexagonal column structures with well-aligned and well-perpendicular to the surface were successfully obtained on Au/ITO substrate in aqueous solvent of electrolyte. Clearly the main columns in the film were obtained by increasing the temperature. Its photoluminescence (PL) study at low temperature exhibited the optical properties as wurtzite ZnO and indicated the existence of macrocrystalline ZnO. A better quality of ZnO columnar structures after annealing was demonstrated from PL analysis and discussion on the existence of 370 nm, 384 nm and 639 nm in the emission bands before and after annealing.     

Photoluminescence and photoelectrochemical properties of nanocrystalline ZnO thin films synthesized by spray pyrolysis technique

A simple and inexpensive spray pyrolysis technique (SPT) was employed for the synthesis of nanocrystalline zinc oxide (ZnO) thin films onto soda lime glass and tin doped indium oxide (ITO) coated glass substrates at different substrate temperatures ranging from 300 °C to 500 °C. The synthesized films were polycrystalline, with a (0 0 2) preferential growth along c-axis. SEM micrographs revealed the uniform distribution of spherical grains of about 80-90 nm size. The films were transparent with average visible transmittance of 85% having band gap energy 3.25 eV. All the samples exhibit room temperature photoluminescence (PL). A strong ultraviolet (UV) emission at 398 nm with weak green emission centered at 520 nm confirmed the less defect density in the samples. Moreover, the samples are photoelectrochemically active and exhibit the highest photocurrent of 60 μA, a photovoltage of 280 mV and 0.23 fill factor (FF) for the Zn₄₅₀ films in 0.5 M Na₂SO₄ electrolyte, when illuminated under UV light.     

用非水二甲基溶液作电解液电沉积ZnO纳米晶薄膜

用含ZnCl2的二甲基亚砚溶液做电解液可在Si衬底上电化学沉积纳米晶薄膜。薄膜的粒径尺寸为8.9nm，样品的光致发光谱以紫外发射峰为主。分析表明用本文介绍的方法可以制备高质量的不含-OH的ZnO纳米晶薄膜。     

Influence of negative ion resputtering on Al-doped ZnO thin films prepared by mid-frequency magnetron sputtering

Al-doped ZnO (AZO) films were deposited on glass substrates by mid-frequency magnetron sputtering with a ceramic ZnO:Al₂O₃ (98 wt%:2 wt%) target. The origin of the high resistivity of the films at the substrate position facing the erosion area of the target was investigated. The results indicate a preferential resputtering of Zn atoms caused by the negative ions, which leads to an increase of the oxygen/metal ratio in the films. Then more Al oxides form and result in the decrease of Al_Zn (the main donor in the films) concentration in the films. Thus the free carrier concentration decreases badly. This is the main mechanism responsible for the high resistivity.     

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.     

Structure and properties of GZO thin films grown on ZnO buffer layers

Thin gallium-doped zinc oxide (in GZO the Ga₂O₃ contents are approximately 3 wt%) films having different ZnO buffer layers were deposited using radio frequency (rf) magnetron sputtering. The use of a grey-based Taguchi method to determine the processing parameters of ZnO buffer layer deposition has been studied by considering multiple performance characteristics. A Taguchi method with an L₉ orthogonal array, signal-to-noise (S/N) ratio, and analysis of variance (ANOVA) is employed to investigate the performance characteristics in the deposition operations. The effect and optimization of ZnO buffer deposition parameters (rf power, sputtering pressure, thickness, and annealing) on the structure, morphology, electrical resistivity, and optical transmittance of the GZO films are studied. Annealing treatment and reduction in thickness resulted in a decrease in root-mean-square (RMS) surface roughness of the ZnO buffer layer. Using the optimal ZnO buffer layer obtained by the application of the grey-based Taguchi method, the electrical resistivity of GZO films was decreased from 2.94×10⁻³ to 9.44×10⁻⁴ Ω cm and the optical transmittance in the visible region was slightly increased from 84.81% to 85.82%.     

Photoluminescence in SiCGe thin films grown on 6H-SiC

Intense visible luminescence is observed at room temperature from SiCGe films on 6H-SiC (0 0 0 1) substrate. The PL intensity increases rapidly under the UV laser excitation during the first 2 h. This phenomenon may be explained by an effect similar to the Steabler-Wronski effect in hydrogenated amorphous Silicon. High density of defects such as double phase boundaries and stacking faults are observed by TEM characterization, which produce the quasidefects and accelerate the effect.