Thickness influence on surface morphology and ozone sensing properties of nanostructured ZnO transparent thin films grown by PLD

Transparent zinc oxide (ZnO) thin films with a thickness from 10 to 200 nm were prepared by the PLD technique onto silicon and Corning glass substrates at 350 °C, using an Excimer Laser XeCl (308 nm). Surface investigations carried out by atomic force microscopy (AFM) and X-ray diffraction (XRD) revealed a strong influence of thickness on film surface topography. Film roughness (RMS), grain shape and dimensions correlate with film thickness. For the 200 nm thick film, the RMS shows a maximum (13.9 nm) due to the presence of hexagonal shaped nanorods on the surface. XRD measurements proved that the films grown by PLD are c-axis textured. It was demonstrated that the gas sensing characteristics of ZnO films are strongly influenced and may be enhanced significantly by the control of film deposition parameters and surface characteristics, i.e. thickness and RMS, grain shape and dimension.     

Room-temperature deposition of transparent conducting Al-doped ZnO films by RF magnetron sputtering method

Transparent conductive Al-doped zinc oxide (AZO) films with highly (0 0 2)-preferred orientation were deposited on quartz substrates at room temperature by RF magnetron sputtering. Optimization of deposition parameters was based on RF power, Ar pressure in the vacuum chamber, and distance between the target and substrate. The structural, electrical, and optical properties of the AZO thin films were investigated by X-ray diffraction, Hall measurement, and optical transmission spectroscopy. The 250 nm thickness AZO films with an electrical resistivity as low as 4.62 × 10⁻⁴ Ω cm and an average optical transmission of 93.7% in the visible range were obtained at RF power of 300 W, Ar flow rate of 30 sccm, and target distance of 7 cm. The optical bandgap depends on the deposition condition, and was in the range of 3.75-3.86 eV. These results make the possibility for light emitting diodes (LEDs) and solar cells with AZO films as transparent electrodes, especially using lift-off process to achieve the transparent electrode pattern transfer.     

Structural and morphological characterization of TiO2 nanostructured films grown by nanosecond pulsed laser deposition

TiO₂ has attracted a lot of attention due to its photocatalytic properties and its potential applications in environmental purification and self cleaning coatings, as well as for its high optical transmittance in the visible-IR spectral range, high chemical stability and mechanical resistance. In this paper, we report on the growth of TiO₂ nanocrystalline films on Si (1 0 0) substrates by pulsed laser deposition (PLD). Rutile sintered targets were irradiated by KrF excimer laser (λ = 248 nm, pulse duration ∼30 ns) in a controlled oxygen environment and at constant substrate temperature of 650 °C. The structural and morphological properties of the films have been studied for different deposition parameters, such as oxygen partial pressure (0.05-5 Pa) and laser fluence (2- 4 J/cm²). X-ray diffraction (XRD) shows the formation of both rutile and anatase phases; however, it is observed that the anatase phase is suppressed at the highest laser fluences. X-ray photoelectron spectroscopy (XPS) measurements were performed to determine the stoichiometry of the grown films. The surface morphology of the deposits, studied by scanning electron (SEM) and atomic force (AFM) microscopies, has revealed nanostructured films. The dimensions and density of the nanoparticles observed at the surface depend on the partial pressure of oxygen during growth. The smallest particles of about 40 nm diameter were obtained for the highest pressures of inlet gas.     

Effect of substrate temperature on structure and electrical resistivity of laser-ablated IrO2 thin films

IrO₂ thin films were prepared on Si(1 0 0) substrates by laser ablation. The effect of substrate temperature (T_sub) on the structure (crystal orientation and surface morphology) and property (electrical resistivity) of the laser-ablated IrO₂ thin films was investigated. Well crystallized and single-phase IrO₂ thin films were obtained at T_sub = 573-773 K in an oxygen partial pressure of 20 Pa. The preferred orientation of the laser-ablated IrO₂ thin films changed from (2 0 0) to (1 1 0) and (1 0 1) depending on T_sub. With the increasing of T_sub, both the surface roughness and crystallite size increased. The room-temperature electrical resistivity of IrO₂ thin films decreased with increasing T_sub, showing a low value of (42 ± 6) × 10⁻⁸ Ω m at T_sub = 773 K.     

Optical characterization of PLD grown nitrogen-doped TiO2 thin films

Nitrogen-doped TiO₂ thin films were prepared by pulsed laser deposition (PLD) by ablating metallic Ti target with pulses of 248 nm wavelength in reactive atmospheres of O₂/N₂ gas mixtures. The layers were characterized by UV-VIS spectrophotometry and variable angle spectroscopic ellipsometry with complementary profilometry for measuring the thickness of the films. Band gap and extinction coefficient values are presented for films deposited at different substrate temperatures and for varied N₂ content of the gas mixture. The shown tendencies are correlated to nitrogen incorporation into the TiO_2-xN_x layers. It is shown that layers of significantly increased visible extinction coefficient with band gap energy as low as 2.89 eV can be obtained. A method is also presented how the spectroscopic ellipsometric data should be evaluated in order to result reliable band gap values.     

Effects of H2 ambient annealing in fully 0 0 2-textured ZnO:Ga thin films grown on glass substrates using RF magnetron co-sputter deposition

Gallium doped zinc oxide (ZnO:Ga) thin films were grown on glass substrates using RF magnetron co-sputtering, followed by H₂ ambient annealing at 623 K to explore a possibility of steady and low-cost process for fabricating transparent electrodes. While it was observed that the ZnO:Ga thin films were densely packed c-axis oriented self-textured structures, in the as-deposited state, the films contained Ga₂O₃ and ZnGa₂O₄ which had adverse effect on the electrical properties. On the other hand, post-annealing in H₂ ambient improved the electrical properties significantly via reduction of Ga₂O₃ and ZnGa₂O₄ to release elemental Ga which subsequently acted as substitutional dopant increasing the carrier concentration by two orders of magnitude. Transmittance of the ZnO:Ga thin films were all over 90% that of glass while the optical band gap varied in accordance with the carrier concentrations due to changes in Fermi level. Experimental observation in this study suggests that transparent conductive oxide (TCO) films based on Ga doped ZnO with good electrical and optical properties can be realized via simple low-cost process.     

Structural and optical characterization of undoped, doped, and clustered ZnO thin films obtained by PLD for gas sensing applications

The synthesis by pulsed laser deposition technique of zinc oxide thin films suitable for gas sensing applications is herein reported. The ZnO targets were irradiated by an UV KrF^* (λ = 248 nm, τ_FWHM ∼7 ns) excimer laser source, operated at 2.8 J/cm² incident fluence value, whilst the substrates consisted of SiO₂(0 0 1) wafers heated at 150 °C during the thin films growth process. The experiments were performed in an oxygen dynamic pressure of 10 Pa. Structural and optical properties of the thin films were investigated. The obtained results have demonstrated that the films are c-axis oriented. Their average transmission in the visible-infrared spectral region was found to be about 85%. The equivalent refractive indexes and extinction coefficients were very close to those of the tabulated reference values. Doping with 0.5% Au and coating with 100 pulses of Au clusters caused but a very slight decrease (with a few percent) of both transmission and refractive index values. The coatings with the most appropriate optical properties as waveguides have been selected and their behavior was tested for butane sensing.     

Structural and optical properties of ZnO thin films prepared by sol-gel method with different thickness

In this work, ZnO thin films with different thickness were prepared by sol-gel method on glass substrates and the structural and optical properties of these films were studied by X-ray diffractometer, atomic force microscope, UV-visible spectrophotometer, ellipsometer and fluorophotometer, respectively. The structural analyses show that all the samples have a wurtzite structure and are preferentially oriented along the c-axis perpendicular to the substrate surface. The growth process of highly c-axis oriented ZnO thin films derived from sol-gel method is a self-template process. With the increase of film thickness, the structural disorder decreases and the crystalline quality of the films is gradually improved. A transition of crystal growth mode from vertical growth to lateral growth is observed and the transition point is found between 270 and 360 nm thickness. The optical analyses show that with the increase of film thickness, both the refractive index and ultraviolet emission intensity are improved. However, the transmittance in the visible range is hardly influenced by the film thickness, and the averages are all above 80%.     

The influence of Mn content on luminescence properties in Mn-doped ZnO films deposited by ultrasonic spray assisted chemical vapor deposition

Mn-doped ZnO (Zn_1−xMn_xO, 0 ≤ x ≤ 0.1) films are prepared by an ultrasonic spray assisted chemical vapor deposition method. X-ray diffraction and Raman scattering show that all the Zn_1−xMn_xO films are good wurtzite structures without any impurity phases. Cathodoluminescence spectra show that ultraviolet emission and green luminescence can be observed. The intensity of ultraviolet emission decreases with the increment of x, while the intensity of green luminescence increases with the increment of x when x ≤ 0.02. However, when x (x > 0.02) is further increased, the intensity of green luminescence decreases gradually, and the green luminescence disappears when x is above 0.075. We consider that the change of the luminescence is related to the competition between the radiative recombination and the non-radiative recombination.     

Post-deposition atomic terraces growth of ZnO thin films deposited on epi-GaN templates

We demonstrate how growth processes affect on ZnO film properties, which are to be essential guides to prevent defect formation in order to synthesize reproducible high quality ZnO films. First, we reveal that deposition at a low temperature is indispensable to transfer underlying GaN atomic terraces to ZnO surface. As the film thickness is increased, however, the terraces disappear to develop island morphology. It is found that the thick film surface is smoothed to the extent that atomic terraces can be seen after an appropriate thermal treatment. Adverse effects associated with high annealing temperatures are then demonstrated as evidenced by cracks formation, increased yellow cathode-luminescence and intermixing at the interface.     

Thermal stability of SiGe films on an ultra thin Ge buffer layer on Si grown at low temperature

The thermal stability of SiGe films on an ultra thin Ge buffer layer on Si fabricated at low temperature has been studied. The microstructure and morphology of the samples were investigated by high-resolution X-ray diffraction, Raman spectra and atomic force microscopy, and using a diluted Secco etchant to reveal dislocation content. After thermal annealing processing, it is observed that undulated surface, threading dislocations (TDs) and stacking faults (SFs) appeared at the strained SiGe layer, which developed from the propagation of a misfit dislocation (MD) during thermal annealing, and no SFs but only TDs formed in strain-relaxed sample. And it is found that the SiGe films on the Ge layer grown at 300 °C has crosshatch-free surface and is more stable than others, with a root mean square surface roughness of less than 2 nm and the threading dislocation densities as low as ∼10⁵ cm⁻². The results show that the thermal stability of the SiGe films is associated with the Ge buffer layer, the relaxation extent and morphology of the SiGe layer.     

Effect of aging time of ZnO sol on the structural and optical properties of ZnO thin films prepared by sol-gel method

In this work, ZnO thin films were prepared by sol-gel method and the effect of aging time of ZnO sol on the structural and optical properties of the films was studied. The structural characteristics of the samples were analyzed by an atomic force microscope and an X-ray diffractometer. The optical properties were studied by a UV-vis spectrophotometer and a fluorophotometer. The results show that the ZnO thin film prepared by the as-synthesized ZnO sol had relatively poor crystalline quality, low optical transmittance in the visible range and relatively weak ultraviolet emission performance. After the as-synthesized ZnO sol was aged for 24 h, the degree of the preferred crystal orientation along the c-axis of the ZnO thin film prepared by this aged sol was improved. At the same time, this film had a very smooth surface with uniform grains and both its visible range transmittance and ultraviolet emission intensity were obviously increased. These results suggest that appropriate aging of ZnO sol is very important for the improvement of structural and optical quality of ZnO thin films derived from sol-gel method.     

Optical and electrical properties of PbTe films grown by laser induced evaporation of pressed PbTe pellets

A simple and cheap method has been developed for the deposition of lead telluride thin films on glass substrates by pulsed Nd:YAG laser evaporation of lead telluride pellets made of high purity Pb and Te powders.Preliminary characterization of the crystallographic and optical properties of the films has been performed as a function of the substrate temperature.The influence of deposition conditions on the sheet resistance of these thin films has been studied. Both deposition temperature, nitrogen pressure during deposition, and addition of Ga and As impurities in the source pellets have been considered.     

Photosensitivity of nanocrystalline ZnO films grown by PLD

We have studied the properties of ZnO thin films grown by laser ablation of ZnO targets on (0 0 0 1) sapphire (Al₂O₃), under substrate temperatures around 400 °C. The films were characterized by different methods including X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). XPS analysis revealed that the films are oxygen deficient, and XRD analysis with θ-2θ scans and rocking curves indicate that the ZnO thin films are highly c-axis oriented. All the films are ultraviolet (UV) sensitive. Sensitivity is maximum for the films deposited at lower temperature. The films deposited at higher temperatures show crystallite sizes of typically 500 nm, a high dark current and minimum photoresponse. In all films we observe persistent photoconductivity decay. More densely packed crystallites and a faster decay in photocurrent is observed for films deposited at lower temperature.     

Atomic force microscopy study of thermal stability of silver selenide thin films grown on silicon

Silver selenide thin films were grown on silicon substrates by the solid-state reaction of sequentially deposited Se and Ag films of suitable thickness. Transmission electron microscopy and particle-induced X-ray emission studies of the as-deposited films showed the formation of single phase polycrystalline silver selenide from the reaction of Ag and Se films. Atomic force microscopy images of the as-deposited and films annealed at different temperatures in argon showed the film morphology to evolve into an agglomerated state with annealing temperature. The results indicate that when annealed above 473 K, silver selenide films on silicon become unstable and agglomerate through holes generated at grain boundaries.     

Surface morphology of highly mismatched InSb films grown on GaAs substrates by molecular beam epitaxy

InSb films on GaAs(001) substrates with and without GaAs buffer layer have been grown by molecular beam epitaxy. Rather than surface undulations, aligned ripples and pyramidal hillocks along the orthogonal 〈110〉 directions were observed on the surface of InSb films. Both the preferential growth and the termination of ripples were proved to be related to strain‐driven mass transport. A model was proposed to elucidate the formation of the hillocks, which are more efficient to relax strain than ripples. Due to the strain relaxation through hillocks with small bases predominantly, the surfaces of the InSb films grown without a GaAs buffer layer are smoother than those of films grown with a GaAs buffer layer. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The influence of substrate on the properties of Er2O3 films grown by magnetron sputtering

The structural properties and the room temperature luminescence of Er₂O₃ thin films deposited by RF magnetron sputtering have been studied. Films characterized by good morphological properties have been obtained by using a SiO₂ interlayer between the film and the Si substrate. The evolution of the properties of the Er₂O₃ films due to rapid thermal annealing processes in O₂ ambient performed at temperatures in the range 800-1200 °C has been investigated in details. The existence of well-defined annealing conditions (temperature of 1100 °C or higher) allowing to avoid the occurrence of extensive chemical reactions with the oxidized substrate has been demonstrated and an increase of the photoluminescence (PL) intensity by about a factor of 40 with respect to the as deposited material has been observed. The enhanced efficiency of the photon emission process has been correlated with the longer lifetime of the PL signal. The same annealing processes are less effective when Er₂O₃ is deposited on Si. In this latter case interfacial reactions and pit formation occur, leading to a material characterized by stronger non-radiative phenomena that limit the PL efficiency.     

Photocatalytic property of TiO2 thin films sputtered-deposited on unheated substrates

TiO₂ films deposited on unheated substrates of alumina silicate glass by rf. (13.56 MHz) magnetron sputtering in the mixture of O₂ and Ar gases have been studied with X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and optical spectroscopy. Structural and optical properties of TiO₂ films deposited at different O₂ concentrations and total pressures have been analyzed. Photocatalytic properties of TiO₂ films were characterized by following the degradation of methylene blue molecules under UV irradiation. It was found that the rate of methylene blue decomposition strongly depends on morphology and crystallinity of the deposited films, namely on the content of the anatase phase and on the size of the anatase grains. The best photocatalytic activity was found on TiO₂ films consisting of pure anatase phase with the size of grains of about 450 Å. With the help of those films a thin film reactor for water purification has been designed and tested.     

Morphology and photoluminescence properties of zinc oxide films grown by pulsed laser deposition

Zinc oxide films with different morphologies have been grown by pulsed laser deposition, varying substrate temperature and oxygen pressure. At low oxygen pressure and low substrate temperature continuous films with different roughness have been obtained, while at high substrate temperature a film with sparse hexagonal pyramids has been observed. Increasing the oxygen pressure the film became rougher and at 100 Pa a rod-array has been deposited. The columns of this rod-array grew along the wurtzite c-axis perpendicularly to the substrate surface as proved by X-ray diffraction measurements. Near to the sample borders the columns were slightly tilted towards the center of the sample. The possible growth mechanisms giving rise to the different morphologies have been discussed. Low-temperature photoluminescence measurements allowed to get information about the film quality, showing the variations of the excitonic peak and two defect bands (green and violet-blue) with the different deposition parameters.     

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.