Structural and optical properties of ZnO nanopowder prepared by microwave-assisted synthesis

We report the characterization of nano-size zinc oxide (ZnO) powder synthesized via microwave-assisted heating of Zn(CH₃COO)₂·2H₂O and NaHCO₃ solution with deionized water (DI water) as the solvent. The as-synthesized ZnO powder was calcined at temperatures from 400 to 800 °C for 8 h. The X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) spectra revealed pure wurtzite structure for the ZnO nanopowder (NP) calcined at 800 °C. Scanning electron microscopy (SEM) images showed increasing size ZnO NP with uniform size distribution with increase in calcination temperature. Significant UV emission at about 373 nm has been observed in the photoluminescence (PL) spectra of the as-synthesized and calcined ZnO NP. Our results showed enhanced PL intensity with a reduced full-width at half-maximum (FWHM) for ZnO NP synthesized at higher calcination temperature.     

Photoluminescence of thermal-annealed nanocolumnar ZnO thin films grown by electrodeposition

Nanostructured zinc oxide thin films formed by partially oriented hexagonal columns with dimensions of about 100 nm × 300 nm have been prepared by cathodic electrodeposition on conducting glass substrates. After subsequent thermal annealing in air at different temperatures (100-500 °C), structural information on the films was obtained by means of non-resonant Raman spectroscopy. Increasing the annealing temperature leads to a higher degree of crystallinity. The photoluminescence activity of the samples (at low temperature) also improves for increasing annealing temperatures in two ways: increasing the intensity of the near-band edge emission and decreasing the width of the excitonic peak. No emission band in the visible is detected, which attests the high quality of the ZnO nanocolumnar films.     

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.     

Preparation and characterization of ZnO thin films prepared by thermal oxidation of evaporated Zn thin films

In this paper, the experimental results regarding some structural, electrical and optical properties of ZnO thin films prepared by thermal oxidation of metallic Zn thin films are presented.Zn thin films (d=200–400 nm) were deposited by thermal evaporation under vacuum, onto unheated glass substrates, using the quasi-closed volume technique. In order to obtain ZnO films, zinc-coated glass substrates were isochronally heated in air in the 300–660 K temperature range, for thermal oxidation.X-ray diffraction (XRD) studies revealed that the ZnO films obtained present a randomly oriented hexagonal nanocrystalline structure. Depending on the heating temperature of the Zn films, the optical transmittance of the ZnO films in the visible wavelength range varied from 85% to 95%. The optical band gap of the ZnO films was found to be about 3.2 eV. By in situ studying of the temperature dependence of the electrical conductivity during the oxidation process, the value of about 2×10⁻² Ω⁻¹ m⁻¹ was found for the conductivity of completely oxidized ZnO films.     

Superhydrophobic and transparent ZnO thin films synthesized by spray pyrolysis technique

Superhydrophobic and transparent zinc oxide (ZnO) thin films were deposited by a simple and cost effective spray pyrolysis technique (SPT) onto the glass substrates at 723 K from an aqueous zinc acetate precursor solution. The solution concentration was varied from 0.1 to 0.4 M and its effect on structural, morphological, wetting and optical properties of ZnO thin films was studied. The synthesized films were found to be polycrystalline, with preferential growth along c-axis. A slight improvement in the crystallite size and texture coefficient is observed as the concentration of the solution is increased. SEM micrographs show the uniform distribution of spherical grains of about 60-80 nm grain size. The films were specular and highly transparent with average transmittance of about 85%. The spectrum shows sharp absorption band edge at 381 nm, corresponding to optical gap of 3.25 eV. The samples of texture coefficient less than 90% and roughness less than 75 nm are hydrophobic and above these values they become superhydrophobic in nature. The hydrophobicity coupled with high transmittance is of great importance in commercial application such as transparent self-cleaning surfaces, anti-fog, anti-snow, fluid microchips and microreactors.     

Structural and optical characteristics of spin-coated ZnO thin films

Zinc oxide (ZnO) thin films were deposited onto glass substrates by spin-coating method, from a precursor solution containing zinc acetate, ethanol and ammonium hydroxide. After deposition, the films were heated at a temperature of 100 °C in order to remove unwanted materials. Finally, the films were annealed at 500 °C for complete oxidation. X-ray diffraction showed that ZnO films were polycrystalline and have a hexagonal (wurtzite) structure. The crystallites are preferentially oriented with (0 0 2) planes parallel to the substrate surface. The films have a high transparency (more than 75%) in the spectral range from 450 nm to 1300 nm. The analysis of absorption spectra shows the direct nature of band-to-band transitions. The optical bandgap energy ranges between 3.15 eV and 3.25 eV.Some correlations between the processing parameters (spinning speed, temperature of post deposition heat treatment) and structure and optical characteristics of the respective thin films were established.     

Structural and morphological properties of thin ZnO films grown by pulsed laser deposition

The pulsed laser deposition technique was used to produce zinc oxide thin films onto silicon and Corning glass substrates. Homogeneous surfaces exhibiting quite small Root Mean Square (RMS) roughness, consisting of shaped grains were obtained, their grain diameters being 40-90 nm at room temperature and at 650 °C growth respectively. Films were polycrystalline, even for growth at room temperature, with preferential crystallite orientation the (0 0 2) basal plane of wurtzite ZnO. Temperature increase caused evolution from grain to grain agglomeration structures, improving crystallinity. Compressive to tensile stresses transition with temperature was found while the lattice constant decreased.     

The influence of annealing temperature on the slip plane activity and optical properties of nanostructured ZnO films

The zinc oxide films were prepared by the sol-gel method on the ordinary glass substrates. The activity of slip systems were evaluated by X-ray diffraction line broadening analysis using convolution multiple whole profile (CMWP) fitting procedures. It was found that in all temperatures the 〈a〉 type dislocations is dominating and its fraction increases with the rise of annealing temperature in the range of 350-600 °C. The investigation on the optical properties of films showed that the optical band gap energy increases linearly with the annealing temperature and crystallite size but decreases with the lattice strain.     

Characterisation of porous doped ZnO thin films deposited by spray pyrolysis technique

Al or Sn doped ZnO films were deposited by spray pyrolysis using aqueous solutions. The films were deposited on either indium tin oxide coated or bare glass substrates. ZnCl₂, AlCl₃ and SnCl₂ were used as precursors. The effect of ZnCl₂ molar concentration (0.1-0.3 M) and doping percentage (2-4% AlCl₃ or SnCl₂) have been investigated. The main goal of this work being to grow porous ZnO thin films, small temperature substrates (200-300 °C) have been used during the spray pyrolysis deposition. It is shown that, if the X-ray diffraction patterns correspond to ZnO, the films deposited onto bare glass substrate are only partly crystallized while those deposited onto ITO coated glass substrate exhibit better crystallization. The homogeneity of the films decreases when the molar concentration of the precursor increases, while the grain size and the porosity decrease when the Al doping increases. The optical study shows that band tails are present in the absorption spectrum of the films deposited onto bare glass substrate, which is typical of disordered materials. Even after annealing 4 h at 400 °C, the longitudinal resistivity of the films is quite high. This result is attributed to the grain boundary effect and the porosity of the films. Effectively, the presence of an important reflection in the IR region in samples annealed testifies of a high free-carriers density in the ZnO crystallites. Finally it is shown that when deposited in the same electrochemical conditions, the transmission of a polymer film onto the rough sprayed ZnO is smaller than that onto smooth sputtered ZnO.     

ZnO nanostructured thin films grown by pulsed laser deposition in mixed O2 / Ar background gas

We report on the properties of ZnO nanostructured thin films grown on either bare or gold patterned a-plane sapphire substrates. The pulsed laser deposition technique was used to deposit all the films at a temperature of 700 C in a mixture of oxygen and argon under a total pressure of 35 Pa. SEM surface characterizations typically showed pyramidal nanostructures with hexagonal symmetry and a coverage density strongly dependent on the O₂ partial pressure. For the patterned samples, wall-like structures of nanoneedles were observed. For all samples, x-ray diffraction results confirmed the high crystalline quality of the nanostructures, with the rocking curve widths of the (0002) reflection as low as 0.09. Similarly, photoluminescence results at room temperature testified to the high optical quality of the material.     

ZnO films grown by laser ablation with and without oxygen CVD

In the present work we have studied the properties of zinc oxide (ZnO) thin films grown by laser ablation of ZnO targets under different substrate temperature and background oxygen conditions. The ZnO layers were deposited with a Pulsed Laser Deposition (PLD) system on pre-nitrided (0001) sapphire (Al₂O₃), using the base line of a Nd:YAG laser at 1064 nm. The films were characterized by different structural and optical methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), optical transmission spectroscopy, and steady-state photoluminescence (PL). XRD analysis with rocking curves and θ–2θ scans indicates preferential growth along the c-axis direction with a full width at half maximum (FWHM) smaller than 1.5. Low-temperature photoluminescence (PL) showed strong excitonic emission near 3.36 eV between 9 and 65 K.     

Structural and morphological study of ZnO thin films electrodeposited on n-type silicon

In this work, we report on the electrodeposition of ZnO thin films on n-Si (1 0 0) and glass substrates. The influence of the deposition time on the morphology of ZnO thin films was investigated. The ZnO thin films were characterized by X-ray diffraction (XRD), energy dispersive X-ray (EDS) and scanning electron microscopy (SEM). The results show a variation of ZnO texture from main (0 0 2) at 10 min to totally (1 0 1) at 15 min deposition time. The photoluminescence (PL) studies show that both UV (∼382 nm) and blue (∼432 nm) luminescences are the main emissions for the electrodeposited ZnO films. In addition, the film grown at 15 min indicates an evident decrease of the yellow-green (∼520 nm) emission band comparing with that of 10 min. Finally, transmittance spectra show a high transmission value up to 85% in the visible wavelength range. Such results would be very interesting for solar cells applications.     

Electrical and optical properties of ZnO thin films prepared by magnetron rf sputtering—influence of Al, Er and H

The influence of Al, Er and H in ZnO thin films (ZnO:Al, ZnO:Er and ZnO:H) deposited by magnetron sputtering at different substrate temperatures, T_s, on their optical, structural and electrical properties was investigated. X-ray diffraction (XRD) analyses show an improvement of the crystalline structure with increasing T_s. The optical band gap, , of the films, from transmission and reflection spectra, ranged from 3.27 to 3.41 eV. The Urbach band tail width was also calculated. Incorporation of Al and Er resulted in a reduced and an increased resistivity, ρ, respectively, and an increase in the Urbach tail width in both cases. However, sputtering in an Ar+H₂ gas mixture led to an increase in ρ and an improvement in the structural order of the films. A discussion of the influence of T_s and of Al, Er and H on the properties is presented.     

Structural and optical properties of ZnO and Al-doped ZnO microrods obtained by spray pyrolysis method using different solvents

ZnO and Al-doped ZnO microrods were obtained by spray pyrolysis method using different solvents such as methanol and propanol. The effect of the type of solvent in the starting solution on the structural, morphological and optical properties of the samples was investigated. X-ray diffraction patterns showed that the undoped and Al-doped ZnO microrods exhibited hexagonal crystal structure with a preferred orientation along (0 0 2) direction. Surface morphology of the samples obtained by scanning electron microscopy revealed that undoped and Al-doped ZnO microrods grew as quasi-aligned hexagonal shaped microrods with diameters varying between 0.7 and 1.3 μm irrespective of solvents used. Optical studies indicated that microrods had a low transmittance (≅30%) and the band gap increased from 3.24 to 3.26 eV upon Al doping. Photoluminescence measurements indicated the existence of two emission bands in the spectra: one sharp ultraviolet luminescence at ∼383 nm and one broad visible emission ranging from 420 to 580 nm.     

Cathodoluminescent and nonlinear optical properties of undoped and erbium doped nanostructured ZnO films deposited by spray pyrolysis

We have deposited zinc oxide (ZnO) and erbium doped zinc oxide (ZnO:Er) thin films on heated glass substrates using spray pyrolysis technique. The effect of erbium dopant on structural, morphological, luminescent and nonlinear optical properties was studied. The deposited films have been analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), ex situ compositional analysis (ESCA), profilometry, cathodoluminescence (CL) and third harmonic generation (THG) measurements. All films were polycrystalline, having a preferential growth orientation along the ZnO (0 0 2) plane, with a corresponding average crystallite size of less than 41 nm. Addition of erbium can effectively control the film surface morphology and its cathodoluminescent properties. The films containing low erbium concentration show a uniform surface covered with hexagonal shaped grains and a strong UV light emission intensity as well as TH response. In contrast, when the erbium doping ratio exceeds 3%, a porous surface with columnar textural growth becomes more pronounced, and a substantial reduction of the cathodoluminescent and TH response. A strong TH signal was obtained for the film with good crystalline quality at the concentration of 2%. Third order nonlinear optical susceptibility (χ^〈3〉) values of the studied materials were in the remarkable range of 10⁻¹² esu.     

Crystal orientation control of polycrystalline TiN thin films using ZnO under layers deposited by magnetron sputtering

The effect of ZnO under layers on crystal growth of TiN thin films was investigated. TiN single layers and double-layered ZnO/TiN thin films were deposited on soda-lime-silicate glass substrates by magnetron sputtering. XRD analysis indicated that TiN single layers exhibited {1 1 1} preferred orientation on glass substrates; on the other hand, the TiN thin films with {1 0 0} preferred orientation were obtained using ZnO under layers and crystallized better than the TiN single layers. This crystal orientation change of TiN thin films should come from heteroepitaxial-like growth because the TiN{1 0 0} and ZnO{0 0 1} crystal lattice planes have similar atomic arrangements. Besides, the possible mismatch between TiN and ZnO atomic arrangements was estimated to be 7.8%. Furthermore, the resistivity and optical absorbance of TiN thin films decreased when they were deposited on ZnO under layers. It can be considered that electrical and optical properties should be improved due to the well-crystallization of TiN thin films using ZnO under layers.     

Deposition and characterization of sputtered ZnO films

Zinc oxide thin films were deposited by radio frequency magnetron sputtering at room temperature using a metallic zinc target in a gas mixture of argon and oxygen. Plasma power, oxygen /argon gas ratio, gas pressure, and substrate temperature were varied, and an experimental design method was used to optimize these deposition parameters by considering their interdependence. Crystalline structures and film stresses were examined. Post-deposition rapid thermal annealing was also carried out to observe its effects on the film properties. Statistical analysis was then used to find the optimal sputtering conditions. Results indicated that plasma power and gas pressure have the largest effects on film crystallization and stress and that postdeposition annealing can be used to improve the quality of the film properties.     

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.