Fabrication of TiO2 nanotube film by well-aligned ZnO nanorod array film and sol-gel process

High density TiO₂ nanotube film with hexagonal shape and narrow size distribution was fabricated by templating ZnO nanorod array film and sol-gel process. Well-aligned ZnO nanorod array films obtained by aqueous solution method were used as template to synthesize ZnO/TiO₂ core-shell structure through sol-gel process. Subsequently, TiO₂ nanotube array films survived by removing the ZnO nanorod cores using wet-chemical etching. Polycrystalline anatase TiO₂ nanotube films were ∼ 1.5 μm long and ∼ 100 nm in inter diameter with a wall thickness of ∼ 10 nm.     

Effect of annealing temperature on the tribological behavior of ZnO films prepared by sol-gel method

The tribological behavior of zinc oxide (ZnO) films grown on glass and silicon (100) substrates by sol-gel method was investigated. Particularly, the as-coated films were post-annealed at different temperatures in air to investigate the effect of annealing temperature. Crystal structural and surface morphology of the films were measured by X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). XRD patterns and AFM images indicated that the crystallinity and grain size of the films were enhanced and increased, respectively, with temperature. The tribological behavior of films was evaluated by sliding the ZnO films against a Si₃N₄ ball under 0.5 gf normal load using a reciprocating pin-on-plate tribo-tester. The wear tracks of the films were measured by AFM to quantify the wear resistance of the films. The results showed that the wear resistance of the films could be improved by the annealing process. The wear resistance of the films generally increased with annealing temperature. Specifically, the wear resistance of the films was significantly improved when the annealing temperature was higher than 550° C. The increase in the wear resistance is attributed to the increase in hardness and modulus of the film with annealing temperature.     

ZnO thin films prepared by a single step sol-gel process

ZnO thin films were prepared on fused silica from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH ] and isopropanol. Crystallization annealing was performed over the range 500 to 650 °C. X-ray analysis showed that thin films were preferentially orientated along the [002] c-axis direction of the crystal. The films had a transparency of greater than 85% in the visible region for sol-gels with a zinc content of up to 0.7 M and exhibited absorption edges at ∼ 378 nm. The optical band-gap energy was evaluated to be 3.298-3.306 eV. Photoluminescence showed a strong emission centered at ca. 380 nm along with a broad yellow-orange emission centered at ca. 610 nm. Single step sol-gel thin film deposition in the film thickness range from 80 nm to 350 nm was demonstrated. The effect of sol-gel zinc concentration, film thickness and crystallization temperature on film microstructure, morphology and optical transparency is detailed. A process window for single spin coating deposition of c-axis oriented ZnO discussed.     

Activation of phosphorous doping in high quality ZnO thin film grown on Yttria-stabilized zirconia (1 1 1) by thermal treatment

Phosphorous doped (P-doped) ZnO thin films are grown on c-sapphire and Yttria-stabilized zirconia (YSZ) (111) substrates by pulsed laser deposition. Post growth annealing is carried out to activate phosphorous to act as acceptor. The rocking curve of annealed P-doped ZnO films grown on YSZ (111) has full width at half maximum of 0.08°, more than two times narrower than that of the as-grown one. Neutral acceptor bound exciton (A⁰X) is observed from low temperature photoluminescence with estimated activation energy of 11.3 meV. Low carrier concentration of as-grown P-doped ZnO films indicated phosphorous doping creates acceptor states and/or reduced the oxygen vacancies. The carrier concentration of annealed samples is reduced by five order magnitudes from 3.21 × 10¹⁸ cm^− 3 to 1.21-8.19 × 10¹³ cm^− 3. At annealing temperature of 850 °C, the sample has the lowest carrier concentration and highest resistivity. This is an indication that the phosphorous in P-doped ZnO has been activated.     

Control of ZnO thin film surface by ZnS passivation to enhance photoluminescence

To enhance the optical property of zinc oxide (ZnO) thin film, zinc sulfide (ZnS) thin films were formed on the interfaces of ZnO thin film as a passivation and a substrate layer. ZnO and ZnS thin films were deposited by atomic layer deposition (ALD) using diethyl zinc, H₂O, and H₂S as precursors. Investigations by X-ray diffraction and transmission electron microscopy showed that ZnS/ZnO/ZnS multi-layer thin films with clear boundaries were achieved by ALD and that each film layer had its own polycrystalline phase. The intensity of the photoluminescence of the ZnO thin film was enhanced as the thickness of the ZnO thin film increased and as ZnS passivation was applied onto the ZnO thin film interfaces.     

Titanium and zirconium hard coatings on glass substrates prepared by the sol-gel method

In this work innovative antiscratch sol-gel coating films deposited on a soda-lime glass substrate are examined. Sol-gel coatings of different composition (TiO₂, TiO₂/B₂O₃, ZrO₂ and ZrO₂/B₂O₃) were prepared starting from Titanium, Zirconium and Boron alkoxides and from boron oxide. Coatings were obtained at room temperature and at atmospheric pressure by dip-coating using common soda lime silicate glass slides as substrates. Densification was carried out at 550 °C for 2 h in air. The morphology of the coatings has been studied by Atomic Force Microscopy, Scanning Electron Microscopy, and with a profilometer. Roughness grows with thickness and with boron addition. The mechanical properties of the films were evaluated by micro scratch at fixed and variable load. The scratch hardness numbers of ZrO₂ and ZrO₂/B₂O₃ coatings reach 6 GPa (glass value = 1.9 GPa), whereas the best value for the critical load is 16.7 N (glass value = 9 N).     

Effect of annealing temperature on ZnO:Al/p-Si heterojunctions

Al-doped, zinc oxide (ZnO:Al) films with a 1.2 at.% Al concentration were deposited on p-type silicon wafers using a sol-gel dip coating technique to produce a ZnO:Al/p-Si heterojunction. Following deposition and subsequent drying processes, the films were annealed in vacuum at five different temperatures between 550 and 900 °C for 1 h. The resistivity of the films decreased with increasing annealing temperature, and an annealing temperature of 700 °C provided controlled current flow through the ZnO:Al/p-Si heterojunction up to 20 V. The ZnO:Al film deposited on a p-type silicon wafer with 1.2 at.% Al concentration was concluded to have the potential for use in electronic devices as a diode after annealing at 700 °C.     

The effects of post-annealing on the performance of ZnO thin film transistors

In this study, we investigated the effects of a post-annealing process on the performance and stability of zinc oxide thin film transistors fabricated by atomic layer deposition. After the post-annealing process in ambient air at 250 °C for 2 h, the value of the saturation mobility increased from 1.2 to 1.8 cm/Vs, the subthreshold swing decreased from 0.53 to 0.34 V/decade, and the I_on/I_off ratio increased from 3.1 × 10⁶ to 1.7 × 10⁷. The positive bias stability was also enhanced after post-annealing. These results are related to the formation of another phase in which the difference of enthalpy between the semiconductor material and contact metal electrode causes the carrier concentration at the metal/semiconductor interface to increase, leading to decreased contact resistivity. Additionally, internal modification of the semiconductor/dielectric interface and/or improving the semiconductor structure, which is related to a change in the oxidation state of Zn through the incorporation of oxygen and/or hydroxide, can result in improved device performance.     

Microstructural evolution of sol-gel derived ZnO thin films

Zinc oxide thin films, with thicknesses between ∼ 20 and 450 nm, were prepared by spin-coating a sol-gel precursor solution (zinc acetate dihydrate and monoethanolamine in an isopropanol solvent) onto glass substrates, followed by heat treatment at temperatures through 773 K. At 298 and 373 K, the films exhibited the structure of a lamellar ZnO precursor, Layered Basic Zinc Acetate (LBZA). At higher temperatures, LBZA released intercalated water and acetate groups and dehydroxylated to form zinc oxide nanograins with wurtzite structure, which were preferentially oriented in the c-axis direction. Both the degree of the films' c-axis orientation and the topography of their surfaces varied with heat treatment and precursor concentration. For films calcined at 773 K, a minimum of micron-scale surface wrinkles coincided with a maximum in c-axis preference at intermediate concentrations, suggesting that release of mechanical stress during densification of thicker films may have disrupted the ordering process that occurs during heat treatment.     

Synthesis and characterization of (CuO)x(ZnO)1 − x composite thin films with tunable optical and electrical properties

Mixed (CuO)_x(ZnO)_1 − x composite films have been prepared on glass substrates by a sol-gel spin coating method using copper acetate hydrate and zinc acetate dihydrate as precursors. The surface morphology and crystal structure of the films were investigated by field emission scanning electron microscopy and x-ray diffraction, respectively. It was observed that the crystal structure changed from wurtzite (ZnO) to monoclinic (CuO) as the Cu content increased from 0% to 100% in the films. UV-Vis absorption and photoluminescence measurements indicated that the optical properties can be tuned continuously from pure ZnO to pure CuO as the Cu content was increased, following the expected trends for a transition from ZnO to CuO. The resistivity of the films decreased by three orders of magnitude as Cu increased from 0% to 100%. These semiconducting composite oxides with tunable optical and electrical properties have potential applications in electronics and optoelectronics.     

High-temperature-dependent optical properties of ZnO film on sapphire substrate

In order to fabricate fiber-optic temperature sensors based on ZnO film, it is important to study the temperature-dependent optical properties of this material. In this work, we deposited ZnO films on c-plane (0001) sapphire substrate at 250 °C. Atomic force microscope and X-ray diffraction measurements show the smooth surface and high orientation along [0001] of ZnO film, respectively. The high-temperature-dependent optical properties of ZnO film were measured by ultraviolet-visible transmission with temperatures ranging from room-temperature to 300 °C and analyzed by theoretically fitting the optical absorption edge curve. It is observed that the band gap energy red shifts nonlinearly from 3.345 to 3.153 eV with increasing temperature. The sharp absorption edge of ZnO films after annealing at 300 °C is almost consistent with that of the as-deposited sample, indicating an excellent thermal stability and the potential application in fiber-optic temperature sensors.     

Effects of the annealing temperature on the structure and up-conversion photoluminescence of ZnO film

The up-conversion film is being tried to increase the photoelectric conversion efficiency of the silicon solar cell. To improve the efficiency of the photoluminescence film, the effects of the annealing temperature were investigated on the structure and photoluminescence of the ZnO up-conversion film, which was prepared using the sol-gel method and the spin-coating technique. The results show that the organic compounds and water in the ZnO film were completely eliminated when the annealing temperature reached 500?°C. The crystallinity of film is improved and the average grain size continuously increases as increasing the annealing temperature. The transmittance in the wavelength range of 400–2000?nm continuously increases as the annealing temperature increases from 500?°C to 700?°C, whilst it decreases first and then increases as the annealing temperature increases from 800?°C to 1000?°C. When the film is excited with a laser of 980?nm, there are two intense emission bands in the up-conversion emission spectra, 542-nm green light and 660-nm red light, corresponding to Ho³⁺: ⁵S₂/⁵F₄?→?⁵I₈?and ⁵F₅?→?⁵I₈ transitions, respectively. In addition, the intensity of up-conversion luminescence for the film increases first and then decreases with the increase of the annealing temperature. When the annealing temperature is at 900?°C, the film consists of small round compact particles with a high degree of crystallization, reaching maximum up-conversion intensity of the film.     

高质量ZnO薄膜的退火性质研究

在LP－MOCVD中，我们利用Zn(C2H5)2作Zn源，CO2作氧源，在（0002）蓝宝石衬底上成功制备出皮c轴取向高度一致的ZnO薄膜，并对其进行500℃-800℃四个不同温度的退火。利用XRD、吸收谱、光致发光谱和AFM等手段研究了退火对ZnO晶体质量和光学性质的影响。退火后，（0002）ZnO的XRD衍射峰强度显著增强，c轴晶格常数变小，同时（0002）ZnOX射红衍射峰半高宽不断减小表明晶粒逐渐增大，这与AFM观察结果较一致。由透射谱拟合得到的光学带隙退火后变小，PL谱的带边发射则加强，并出现红移，蓝带发光被有效抑制，表明ZnO薄膜的质量得到提高。     

Annealing and partial pressure ratio effects on ZnO films grown by metal-organic chemical vapor deposition using tert-butanol as oxidant

ZnO films were deposited by metal-organic chemical vapor deposition on (0001) sapphire substrates at various partial pressure ratios of oxygen and zinc precursors (R_VI/II). The annealing and the R_VI/II ratio effects on the vibrational and optical properties of ZnO films have been investigated by Micro-Raman scattering and low temperature photoluminescence (PL) spectroscopy. As confirmed by characterizations used in this study, the quality of the ZnO films was improved by thermal annealing at 900 °C in oxygen ambient. Raman spectra of the as-deposited films show a broad band (BB) centered at about 518 cm⁻¹ whose intensity increases when the R_VI/II ratio decreases. After annealing, the intensity ratio of the BB to the E₂ high (E₂^H) peak decreases rapidly with increasing the annealing time (t_an). The vibrational properties of the annealed films grown at R_VI/II = 1 need only 1 h to be improved in contrast to those of films grown in Zn-rich condition, which need 4 h. From the E₂^H mode frequency, the residual stress in both the as-grown and the annealed films has been estimated. Micro-Raman measurements show that as-grown films are under a compressive stress which vanishes upon annealing and is not strongly dependent on t_an for t_an up to 1 h. PL spectra show that sharp donor bound exciton and A-free exciton emissions are observed for the as-deposited films grown at R_VI/II ≥ 0.5 and are enhanced after annealing for 1 h. However, in ZnO films grown in Zn-rich condition these emissions are absent and a t_an = 4 h is needed to annihilate non-radiative recombination centers and improve their luminescent efficiency.     

Growth mechanism and characterization of ZnO: Al multi-layered thin films by sol-gel technique

In this study, transparent conductive Al-doped ZnO films were deposited by the sol-gel method. The growth mechanism of the film microstructure and its influences on the electrical properties were discussed. It was found that dopant and solution concentration affected the nucleation behavior considerably. The preferred growth orientation of ZnO crystallite was restrained by the film itself. The repeated dip-coating processes did not enable the crystallite size to grow obviously, but it could allow crystallite and atoms to find the suitable positions and therefore led to a better film quality. Consequently, this process led to an electrical resistivity of 7.08 × 10^− 3 Ω cm and a high transmittance of over 80% in the visible region. The best sample was obtained for an Al concentration of 1 at.% and at 600 °C for pre- and post-heat treatment.     

Thickness dependency of sol-gel derived ZnO thin films on gas sensing behaviors

ZnO thin films were fabricated by a sol-gel method using Zn(CH₃COO)₂·2H₂O as starting material in order to prepare an acetone gas sensor. A homogeneous and stable solution was prepared by dissolving the zinc acetate in a solution of ethanol and monoethanolamine. The sol-gel solution is coated on alumina substrates with various thicknesses by spin coating technique and heat treated to grow crystalline ZnO thin films. The effect of thickness on physical and electrical properties of as deposited ZnO thin films has been studied. The as deposited ZnO thin films were characterized by X-ray diffraction spectroscopy, field emission scanning electron microscopy and atomic force microscopy. The root mean square surface roughness factors increase with thickness of the films and found 3.9, 6.6, 9.0, and 11.28 nm for 80-, 220-, 450- and 620-nm-thin films respectively. The activation energies of the films are calculated from the resistance temperature characteristics. The sensitivities of the ZnO films towards the acetone gas were determined at an operating temperature of 200 °C. The sensitivity towards acetone vapor is strongly depending on surface morphology of the ZnO thin films.     

Microstructural and optical properties of Ga-doped ZnO semiconductor thin films prepared by sol-gel process

Transparent thin films of Ga-doped ZnO (GZO), with Ga dopant levels that varied from 0 to 7 at.%, were deposited onto alkali-free glass substrates by a sol-gel process. Each spin-coated film was preheated at 300 °C for 10 min, and then annealed at 500 °C for 1 h under air ambiance. The effects of Ga dopant concentrations on crystallinity levels, microstructures, optical properties, and electrical resistivities of these ZnO thin films were systematically investigated. Photoluminescence spectra of GZO thin films were examined at room temperature. XRD results revealed that the undoped ZnO thin films exhibited a preferred orientation along the (002) plane and that the ZnO thin films doped with Ga showed degraded crystallinity. Experimental results also showed that Ga doping of ZnO thin films could markedly decrease surface roughness, improve transparency in the visible range, and produce finer microstructures than those of undoped ZnO thin films. The most promising films for transparent thin film transistor (TTFT) application produced in this study, were the 3 and 5 at.% Ga-doped ZnO thin films, both of which exhibited an average transmittance of 90.6% and an RMS roughness value of about 2.0 nm.     

Anomalous behavior in ZnMgO thin films deposited by sol-gel method

The magnesium doped zinc oxide is a promising optical material to enhance the luminescence for possible application in solid state lighting. Magnesium doped zinc oxide thin films (Zn_0.85Mg_0.15O) were deposited by sol-gel route on p-type silicon and annealed at different temperatures in oxygen environment for an hour. The doping of magnesium in zinc oxide was confirmed by X-Ray diffraction and the samples were found to have wurtzite crystal structure with (002) preferred orientation. The films were characterized by Hall-effect, atomic force microscopy, UV-VIS spectroscopy, photoluminescence (PL) and work function measurements. The different studies exhibited an anomalous behavior for the film annealed at 900 °C. The Hall effect, work function measurements and UV-VIS spectroscopy indicated that the resistivity, work function and optical band gap increased as a function of annealing temperature (from 300 °C to 700 °C) however these parameters were found to decrease for the films annealed above 700 °C. The particle size increased with the annealing but for the samples annealed at 900 °C, the shape of the grains changed and became elongated like fibers as observed by the atomic force microscopy. The PL measurements displayed the existence of oxygen vacancies defects for the samples annealed at and above 600 °C. The possible mechanism for this anomaly has been discussed in this work.     

Microstructure and gas-sensing properties of sol-gel ZnO thin films

The paper presents the properties of zinc oxide thin films deposited on glass substrate via dip-coating technique. Zinc acetate dehydrate, ethanol and monoethanol amine were used as starting materials and N₂ gas was used as thermal annealing atmosphere for film crystallization. The effect of withdrawal speed on the crystalline structure, morphology, zinc and nitrogen chemical states, optical, electrical and gas-sensing properties of the thin films has been investigated using X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, optical transmittance and photoreduction-ozone reoxidation data.     

High quality c-axis oriented thin ZnO film obtained at very low pre-heating temperature

Highly oriented ZnO thin film has been obtained at a very low pre-heating temperature, with the spin-coating sol-gel technique. The dependence of the c-axis orientation on the pre-heating temperature has been studied with experimental design and response surface techniques to optimize the deposition process with respect to c-axis orientation, and surface uniformity. The optimization variables selected for this study are: pre-heating temperature, spin-coating speed and number of coating layers. The films are probed with X-ray diffraction and electron microscopy.