Influence of thickness and crystalline structure on thermal and optical properties of ZnO thin films

Measurements of the temperature dependence of refractive index of ZnO thin films and thermal diffusivity using photothermal deflection technique are presented. Thin film thickness and surface homogeneity were found to be the effective parameters on optical and thermal properties of the thin films. High refractive index gradient with temperature was found for films of a nonuniform distribution and gathered in clusters, and a high predicted value for thermal diffusivity. Optical properties of the thin films revealed that films with disorder in the deposition and gathered clusters showed poor transmittance in visible region with a pronounced peak in the near IR, and also a reduction in the band gap. A detailed parametric analysis using analytical solution of one-dimensional heat equation had been performed. A discontinuity in the temperature elevation at the ZnO-glass interface was found.     

Structural and optical properties of nanocrystalline ZnO thin films synthesized by the citrate precursor route

Nanocrystalline zinc oxide (ZnO) thin films have been deposited by spin-coating polymeric precursors synthesized by the citrate precursor route using ethylene glycol and citric acid as chelating agents. The ZnO thin films were annealed in air at different temperatures for 10 min. The films were characterized by different structural and optical techniques, including X-ray diffraction (XRD), atomic force microscopy (AFM), optical transmission spectroscopy, and photoluminescence (PL). The thermal decomposition of polymeric precursor was studied by thermogravimetric analysis (TGA). XRD analysis with grazing incidence and rocking curves indicate that the ZnO films are polycrystalline with preferential orientation along the c-axis direction with a full-width at half-maximum (FWHM) of 0.31° for 600 °C-annealed samples. On annealing, the texturing in films increased along with a decrease in FWHM. AFM micrographs illustrate that the ZnO films are crack-free with well-dispersed homogeneous and uniformly distributed spherical morphology. The synthesized ZnO thin films have transparency >85% in the visible region exhibiting band edge at 375 nm, which becomes sharper with anneal. Room temperature PL spectra of these films show strong ultraviolet (UV) emission around 392 nm with an increase in intensity with annealing temperature, attributed to grain growth. Deconvolution of the PL spectra reveals that there is coupling of free excitons with higher orders of longitudinal optical (LO) phonon replicas leading to a broad asymmetric near-band-edge peak.     

The influence of oxygen on the optical properties of RF-sputtered zinc oxide thin films

In this article, we investigate the effects of oxygen partial pressure in the deposition chamber on the optical properties of zinc oxide (ZnO) thin films; in particular, we examine the variation of the refractive index with oxygen flux.ZnO thin films were deposited by radio-frequency (RF) magnetron sputtering and studied by means of X-ray diffraction (XRD) and spectroscopic ellipsometry (SE). We have found a preferential c-axis growth of ZnO films, with slightly variable deposition rates from 2.6 to 3.8 Å/s. Conversely, the refractive index exhibits, from ultraviolet (UV) to near infrared (IR), a considerable and almost linear variation when the oxygen flux value in the deposition chamber varies from 0 to 10 sccm.     

Influence of substrate activation process on structural and optical properties of ZnS thin films

ZnS thin films were deposited on glass substrates by a chemical bath deposition method using a substrate activation process in which aluminum ions become “contaminants” that act as a nucleation center for active components within the deposition solution. The structure and morphology results demonstrate that the films have a ZnS sphalerite crystal structure with a particle size less than 15 nm, and the films consist of small homogeneous grains. The effects of the substrate activation process on the band gap energies and donor-acceptor pair luminescence process were also investigated. A green emission centered at 502 nm was produced due to donor-acceptor transitions from the aluminum acceptor to the ionized and substitution aluminum centers (Al³⁺).     

AlN缓冲层对ZnO薄膜质量的影响

采用脉冲激光沉积法以AlN为缓冲层在Si(100)衬底上制备了ZnO薄膜,并测量了样品的XRD谱、SEM图和PL谱.结果表明,AlN缓冲层可以提高Si衬底上外延生长ZnO薄膜的晶体质量.改变缓冲层的生长温度(50～500 ℃)所制备样品的测量结果表明,较低温度下生长的AlN缓冲层有利于制备高质量的ZnO外延层薄膜,其中AlN缓冲层生长温度为100 ℃时外延生长ZnO薄膜晶体质量最好.     

Effect of strain on the structural and optical properties of Cu-N co-doped ZnO thin films

Polycrystalline ZnO thin films co-doped with Cu and N have been obtained by chemical bath deposition. Introduction of Cu and N causes the change of strained stress in ZnO films, which subsequently affects the structural and optical properties. The dependence of structural and optical properties of the ZnO films on lattice strained stress is investigated by XRD measurement, SEM, PL spectrum, optical reflection and Raman spectrum. The result of photoluminescence of Cu-N co-doped ZnO films indicates that the UV emission peaks shift slightly towards higher energy side with decrease in tensile strain and vise versa. The blue-shift of the absorption edge and up-shift of E2 (high) mode of the films can be observed in the optical reflection and Raman spectra.     

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.     

Effect of precursors on structure, optical and electrical properties of chemically deposited nanocrystalline ZnO thin films

Nanocrystalline ZnO thin films were chemically deposited on glass substrates using two different precursors namely, zinc sulphate and zinc nitrate. XRD studies confirm that the films are polycrystalline zinc oxide having hexagonal wurtzite structure with crystallite size in the range 25-33 nm. The surface morphology of film prepared using zinc sulphate exhibits agglomeration of small grains throughout the surface with no visible holes or faulty zones, while the film prepared using zinc nitrate shows a porous structure consisting of grains with different sizes separated by empty spaces. The film prepared using zinc sulphate shows higher reflectance due to its larger refractive index which is related to the packing density of grains in the film. Further, the film prepared using zinc sulphate is found to have normal dispersion for the wavelength range 550-750 nm, whereas the film prepared using zinc nitrate has normal dispersion for the wavelength range 450-750 nm. The direct optical band gaps in the two films are estimated to be 3.01 eV and 3.00 eV, respectively. The change in film resistance with temperature has been explained on the basis of two competing processes, viz. thermal excitation of electrons and atmospheric oxygen adsorption, occurring simultaneously. The activation energies of the films in two different regions indicate the presence of two energy levels - one deep and one shallow near the bottom of the conduction band in the bandgap.     

Dependence of film thickness on the structural and optical properties of ZnO thin films

ZnO thin films are prepared on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) at room temperature. Optical parameters such as optical transmittance, reflectance, band tail, dielectric coefficient, refractive index, energy band gap have been studied, discussed and correlated to the changes with film thickness. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. Films with optical transmittance above 90% in the visible range were prepared at pressure of 6.5 × 10⁻⁴ Torr. XRD analysis revealed that all films had a strong ZnO (0 0 2) peak, indicating c-axis orientation. The crystal grain size increased from 14.97 nm to 22.53 nm as the film thickness increased from 139 nm to 427 nm, however no significant change was observed in interplanar distance and crystal lattice constant. Optical energy gap decreased from 3.21 eV to 3.19 eV with increasing the thickness. The transmission in UV region decreased with the increase of film thickness. The refractive index, Urbach tail and real part of complex dielectric constant decreased as the film thickness increased. Oscillator energy of as-deposited films increased from 3.49 eV to 4.78 eV as the thickness increased.     

Structural and optical properties of Mn-doped ZnO nanocrystalline thin films with the different dopant concentrations

The transparent nanocrystalline thin films of undoped zinc oxide and Mn-doped (Zn_1−xMn_xO) have been deposited on glass substrates via the sol–gel technique using zinc acetate dehydrate and manganese chloride as precursor. The as-deposited films with the different manganese compositions in the range of 2.5–20 at% were pre-heated at 100 °C for 1 h and 200 °C for 2 h, respectively, and then crystallized in air at 560 °C for 2 h. The structural properties and morphologies of the undoped and doped ZnO thin films have been investigated. X-ray diffraction (XRD) spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to examine the morphology and microstructure of the thin films. Optical properties of the thin films were determined by photoluminescence (PL) and UV/Vis spectroscopy. The analyzed results indicates that the obtained films are of good crystal quality and have smooth surfaces, which have a pure hexagonal wurtzite ZnO structure without any Mn related phases. Room temperature photoluminescence is observed for the ZnO and Mn-doped ZnO thin films.     

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.     

Effect of Li incorporation on the structural and optical properties of ZnO

This paper presents the structural and optical properties of the as-prepared and lithium-doped ZnO at different percentages of Li incorporation (5%–15%) in ZnO. Effect of doping with various percentages of Li at a particular annealing temperature of 600 C is studied. The samples are characterized by X-ray diffraction, absorption spectroscopy, photoluminescence and Raman spectroscopy. The X-ray diffraction and micro-Raman spectroscopy confirm that the lithium substituted zinc and retains the wurtzitic structure of the lattice. Such substitutional Li in ZnO gives rise to shallow acceptor levels and contributes to the p-type conductivity. From the results of the absorption spectroscopy we observed the evidence of shallow levels upon doping and we also determined the bandgap of the materials which is found to be 3.36 eV. Photoluminescence studies reveal that no deep level is formed. The electrical measurements show that the Li-doped samples are p-type in nature and this is due to substitutional Li.     

Influence of Al-doping on the structure and optical properties of ZnO films

Al-doped ZnO (ZnO:Al) thin films with c-axis preferred orientation were deposited on glass substrates using the radio frequency reactive magnetron sputtering technique. The effect of Al concentrations on the microstructure and the luminescence properties of the ZnO:Al thin films were studied by atomic force microscopy (AFM), X-ray diffraction (XRD), and fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted by appropriate Al concentrations; the photoluminescence spectra (PL) of the samples were measured at room temperature. Strong blue peak located at 437 nm (2.84 eV) and two weak green peaks located at about 492 nm (2.53 eV) and 524 nm (2.37 eV) were observed from the PL spectra of the four samples. The origin of these emissions was discussed. In addition, absorption and transmittance properties of the samples were researched by UV spectrophotometer; the UV absorption edge shifted to a shorter wavelength first as Al was incorporated, and then to a longer wavelength with the increasing Al concentrations. The optical band gaps calculated based on the quantum confinement model are in good agreement with the experimental values.     

Effects of rapid thermal annealing on structural, magnetic and optical properties of Ni-doped ZnO thin films

XPS depth profiles were used to investigate the effects of rapid thermal annealing under varying conditions on the structural, magnetic and optical properties of Ni-doped ZnO thin films. Oxidization of metallic Ni from its metallic state to two-valence oxidation state occurred in the film annealed in air at 600 °C, while reduction of Ni²⁺ from its two-valence oxidation state to metallic state occurred in the film annealed in Ar at 600 and 800 °C. In addition, there appeared to be significant diffusion of Ni from the bottom to the top surface of the film during annealing in Ar at 800 °C. Both as-deposited and annealed thin films displayed obvious room temperature ferromagnetism (RTFM) which was from metallic Ni, Ni²⁺ or both with two distinct mechanisms. Furthermore, a significant improvement in saturation magnetization (M_s) in the films was observed after annealing in air (M_s = 0.036 μ_B/Ni) or Ar (M_s = 0.033 μ_B/Ni) at 600 °C compared to that in as-deposited film (M_s = 0.017 μ_B/Ni). An even higher M_s value was observed in the film annealed in Ar at 800 °C (M_s = 0.055 μ_B/Ni) compared to that at 600 °C mainly due to the diffusion of Ni. The ultraviolet emission of the Ni-doped ZnO thin film was restored during annealing in Ar at 800 °C, which was also attributed to the diffusion of Ni.     

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.     

Growth of Ga-doped ZnO films with ZnO buffer layer by sputtering at room temperature

Gallium-doped zinc oxide films have been grown on glass substrates with and without ZnO buffer layers by r.f. magnetron sputtering at room temperature. In this approach, the grey relational Taguchi method analysis is adopted to solve the coating process with multiple deposition qualities. Optimal coating parameters can then be determined by using the gray relational grade as a performance index. The GZO coating parameters (r.f. power, sputtering pressure, O₂/(Ar+O₂) flow-rate ratios, and deposition time) are optimized, by taking into account the multiple performance characteristics (structural, morphological, deposition rate, electrical resistivity, and optical transmittance). The results indicate that with the grey relational Taguchi method, the electrical resistivity of GZO films is reduced from 9.23×10⁻³ to 5.77×10⁻³ Ω cm and optical transmittance increases from 79.42% to 82.95%, respectively. The ZnO buffer layer can reduce the electrical resistivity of GZO films from 5.77×10⁻³ to 2.38×10⁻³ Ω cm. It can be anticipated that room temperature deposition enables film deposition onto polymeric substrates for flexible optoelectronic devices.     

Effect of solution concentrations on crystal structure,surface topographies and photoluminescence properties of ZnO thin films

Zinc oxide thin films were deposited on silicon substrates via hydrothermal method. Microstructures, surface topographies and optical properties of ZnO thin films were systematically investigated by X-ray diffraction, atomic force microscopy and fluorescence spectrophotometer. The mean grain size and surface roughness of the thin films decrease first and then increase with increasing the concentration of zinc nitrate hexahydrate. The photoluminescence spectra of ZnO thin films, excited by the 240, 320, 360, 380 and 400 nm excitation wavelength, were investigated in detail. Based on our analysis, it can be noted that mechanisms of the ultraviolet, violet and blue emissions are attributed to the transitions from the localized levels below the conduction band, zinc vacancy, interstitial zinc and extended interstitial zinc levels to the valance band, respectively. Blue–violet emissions of ZnO have great potential in light emitting and biological fluorescence labeling applications.     

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.     

Thickness effect on the evolution of morphology and optical properties of ZnO films

N-Al co-doped ZnO films with various thicknesses were deposited on glass substrates by ultrasonic spray pyrolysis (USP). The crystalline microstructure, morphology, distribution of elements and photoluminescence properties of ZnO films were characterized by X-ray diffraction (XRD), field emission scanning microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and photoluminescence (PL) spectroscopy. The XRD and FESEM results show that with the increase of film thickness the grain size increases and the grain shape changes from regular hexagonal sheet-like to wedge-shaped, even pyramidal. The PL spectra illustrate that there is an obvious red-shift for the emission center from ultraviolet to blue region, and the intensities of defects emissions increase with the increase of thickness. In addition, the electrical properties are proved to be strongly affected by film thickness.     

Influence of films thickness and structure on the photo-response of ZnO films

ZnO thin films were grown using Successive Ionic Layer Adsorption and Reaction (SILAR) method on glass substrates at room temperature. Annealing temperatures and film thickness effect on the structural, morphological, optical and electrical properties of the films were studied. For this as-deposited films were annealed at 200, 300, 400 and 500 °C for 30 min in oxygen atmosphere. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies showed that the films are covered well with glass substrates and have good polycrystalline structure and crystalline levels. The film thickness effect on band gap values was investigated and band gap values were found to be within the range of 3.49-3.19 eV. The annealing temperature and light effect on electrical properties of the films were investigated and it was found that the current increased with increasing light intensity. The resistivity values were found as 10⁵ Ω-cm for as-deposited films from electrical measurements. The resistivity decreased decuple with annealing temperature and decreased centuple with light emission for annealed films.