Excimer laser processing of ZnO thin films prepared by the sol-gel process

ZnO thin films were prepared on soda-lime glass from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH] and isopropanol. The deposited films were dried at 50 and 300 °C. X-ray analysis showed that the films were amorphous. Laser annealing was performed using an excimer laser. The laser pulse repetition rate was 25 Hz with a pulse energy of 5.9 mJ, giving a fluence of 225 mJ cm⁻² on the ZnO film. Typically, five laser pulses per unit area of the film were used. After laser processing, the hexagonal wurtzite phase of zinc oxide was observed from X-ray diffraction pattern analysis. The thin films had a transparency of greater than 70% in the visible region. The optical band-gap energy was 3.454 eV. Scanning electron microscopy and profilometry analysis highlighted the change in morphology that occurred as a result of laser processing. This comparative study shows that our sol-gel processing route differs significantly from ZnO sol-gel films prepared by conventional furnace annealing which requires temperatures above 450 °C for the formation of crystalline ZnO.     

Photosensitive sol-gel preparation and direct micro-patterning of c-oriented ZnO film

Using zinc acetate as the raw material, isopropanol as the solvent, and monoethanolamine as the stabilizer, photosensitive ZnO sol is prepared by chemical modification with the acetylacetone. Chelate rings of acetylacetone with zinc ions are formed in the ZnO sol and its corresponding gel films. Irradiation of the gel film by a UV lamp in air leads to the decomposition of the chelate ring. Using the photosensitivity of the gel films, ZnO gel patterns can be obtained by selective irradiation followed by leaching in organic solvents. After the patterned ZnO gel film is preheated at 500 °C, and fired at 600 °C, c-oriented ZnO patterned films are obtained.     

The enhancement of humidity sensing performance based on Eu-doped ZnO

In this work, a high performance impedance-type humidity sensor based on Europium-doped ZnO with abundant surface oxygen vacancy defects was synthesized by sol-gel method. Response of the Eu-doped ZnO with different molar ratio were investigated by exposing them to humidity environments in wide range of 11–95% RH at room temperature. The Eu-doped ZnO (2?mol%) exhibits a three orders impedance change, along with short response/recovery time (5?s/19?s), low hysteresis and best linearity. Complex impedance spectra indicates that dopant Eu can enhance humidity sensing performance of ZnO, which is resulted from the introduction of Eu³⁺ ions into ZnO structure to produce more defects of surface oxygen vacancy and more active sites on the surface of ZnO. The results show that this is a feasible method to achieve high humidity sensing performance by Eu doped ZnO, which make it a promising candidate for humidity sensing materials and broaden the use of ZnO materials.     

Observation of ZnO nanoparticles outside pores of nano Zn4O(C8H4O4)3 metal-organic framework

It was recognized that ZnO can be formed during synthesizing nano Zn₄O(C₈H₄O₄)₃ metal-organic framework (nano MOF-5). Furthermore, it is generally accepted that the ZnO is dispersed inside the pores of MOF-5. However, herein, the measurements of X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) showed that the crystal particle sizes of ZnO in MOF-5 are in the range of 5-18 nm, which are larger than the pore size of MOF-5 (1.3 nm). This clearly demonstrates that those ZnO nanoparticles are located outside the pores of MOF-5.     

Enhancing the crystallinity and surface roughness of sputtered TiO2 thin film by ZnO underlayer

TiO₂ and TiO₂/ZnO double layer films were sputtered on glass substrates. It was found that a thin ZnO underlayer is helpful for tailoring the microstructure and surface morphology of the TiO₂ film. By applying a 70-nm-thick ZnO underlayer, a TiO₂ thin film of 100 nm in thickness with well crystallized anatase phase and rough surface was successfully fabricated without heating the substrate. Relatively high photo-catalytic activity and good hydrophilic properties were observed in such TiO₂/ZnO double layer films.     

Modification in structural and optical properties of ZnO, CeO2 doped Al2O3-PbO-B2O3 glasses

The structural and optical analysis of glasses is carried out by XRD, FTIR, density and UV visible spectroscopic measurement techniques. XRD results have confirmed the glassy nature of the samples. The FTIR spectral analysis reveals that with the combined presence of ZnO and CeO₂ contents in Al₂O₃-PbO-B₂O₃ glasses, more BO₃ groups are transformed into BO₄. The optical analysis reveals that optical band gap energy decreases more for CeO₂-ZnO-Al₂O₃-PbO-B₂O₃ glasses (from 2.28 to 1.84 eV). The presence of CeO₂ and ZnO in the glass samples causes more compaction of the borate network due to the formation of more BO₄ groups and the presence of ZnO₄ groups, which results an increase in density, refractive index and decrease of molar volume.     

Enhanced antibacterial performance of hybrid semiconductor nanomaterials: ZnO/SnO2 nanocomposite thin films

The nano-sized coupled oxides ZnO/SnO₂ thin films in a molar ratio of 2:1 (Z2S), 1:1 (ZS) and 1:2 (ZS2) were prepared using sol-gel dip coating method and characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-vis spectroscopy. Escherichia coli (E. coli, ATCC 25922) was selected as a model for the Gram-negative bacteria to evaluate antibacterial property of composite samples compared with single ZnO (Z) and single SnO₂ (S) films. The antibacterial activity has been studied applying the so-called antibacterial drop test under UV illumination. The bactericidal activity was estimated by relative number of bacteria survived calculated from the number of viable cells which form colonies on the nutrient agar plates. The influence of the SnO₂-ZnO nanocomposite composition on the structural features and on the antibacterial properties of the thin films are reported and discussed. It is found that all coatings exhibited a high antibacterial activity. The coupled oxide photocatalyst Z2S has better photocatalytic activity to bacteria inactivation than ZS, ZS2, Z and S films. Furthermore, nanostructured films were active even in the absence of irradiation.     

Elucidating surface properties of dry-etched ZnO using H2/CH4 and H2/CH4/Ar plasma

This paper reports a study of reactive ion etching (RIE) of n-ZnO in H₂/CH₄ and H₂/CH₄/Ar gas mixtures. Variables in the experiment were gas flow ratios, radio-frequency (rf) plasma power, and total pressure. Structural and electrical parameters of the etched surfaces and films were determined. Both the highest surface roughness and highest etching rate of ZnO films were obtained with a maximum rf power of 300 W, but at different gas flow ratios and working pressures. These results were expected because increasing the rf power increased the bond-breaking efficiency of ZnO. The highest degree of surface roughness was a result of pure physical etching by H₂ gas without mixed CH₄ gas. The highest etching rate was obtained from physical etching of H₂/Ar species associated with chemical reaction of CH₄ species. Additionally, the H₂/CH₄/Ar plasma treatment drastically decreased the specific contact and sheet resistance of the ZnO films. These results indicated that etching the ZnO film had roughened the surface and reduced its resistivity to ohmic contact, supporting the application of a roughened transparent contact layer (TCL) in light-emitting diodes (LEDs).     

Impedance studies of Sb doped SnO2 thin film prepared by sol gel process

Antimony-doped tin oxide thin films have a range of technological applications as conductive coatings, and sol-gel processing seems to offer some advantages over other coating techniques. In this study antimony-doped tin oxide (ATO) thin films have been prepared by the sol-gel dip-coating (SGDC) process, using tin (II) chloride dehydrate (SnCl₂, 2H₂O) and antimony (III) chloride (SbCl₃) as host and dopant precursors respectively. The structure of the (ATO) powders was analysed by X-ray diffraction (XRD) and the microstructure of the thin films by atomic force microscopy (AFM). These investigations show that the structure is tetragonal rutile type and that an increase in Sb-doping decreases the crystallite size of the (ATO) particles. To analyze the impedance spectroscopy data, the Nyquist (Z″ vs. Z′) plots as well as the representation of imaginary (Z″) and real (Z′) parts of impedance vs. frequency were used. The Nyquist plots suggest that only the grain boundaries are responsible in the conduction mechanism of the material. From the variation of lnσ vs. inverse of absolute T we have deduced the activation energy found to be 0.87 eV.     

Realization of controllable etching for ZnO film by NH4Cl aqueous solution and its influence on optical and electrical properties

ZnO films were deposited on c-plane Al₂O₃ substrates by pulsed laser deposition. The etching treatments for as-grown ZnO films were performed in NH₄Cl aqueous solution as a function of NH₄Cl concentration and etching time. It was found that NH₄Cl solution is an appropriate candidate for ZnO wet etching because of its controllable and moderate etching rate. The influence of etching treatment on the morphology, optical and electrical properties of the ZnO films has been investigated systematically by means of X-ray diffraction, atomic force microscope, photoluminescence and Hall effect. The results indicated that the surface morphology and optical properties of the films were highly influenced by etching treatment.     

Sol-gel synthesis of iron(III) oxyhydroxide nanostructured monoliths using Fe(NO3)3·9H2O/CH3CH2OH/NH4OH ternary system

Iron(III) oxyhydroxide xerogels were prepared through sol-gel technology, using iron(III) nitrate nonahydrate as precursor, ethanol as solvent and ammonium hydroxide as gelation agent. This base is used for propylene oxide substitution, which was the gelation agent in previous works. Synthesis of a gel using NH₄OH as a gelation agent is an innovative result with this type of precursor, since with metal salts the addition of a strong base commonly results in precipitation of the solid. The gel synthesis was achieved by controlling the base addition time. The dried material has a residual amount of organic impurities, in contrast with the significant amount detected in xerogels prepared using propylene oxide. The iron phase prevailing in the produced xerogels can be defined as γ-FeO(OH) (lepidocrocite), according to FTIR and Mössbauer analyses. The xerogels are formed by large clusters of well connected nanocrystallites of this phase. XRD revealed a crystalline phase retained inside the iron oxyhydroxide amorphous structure, which corresponds to NH₄NO₃ and results from the combination of NO₃⁻ and NH₄⁺ ions in solution. The produced xerogel has a promising composition to be an oxidizing composite for the energetic materials area.     

Experimental study of Love-wave immunosensors based on ZnO/LiTaO3 structures

Experimental study of Love-mode immunosensors based on structures of ZnO/36°YX-LiTaO₃ is presented, in which the ZnO films with c-axis (0 0 2) orientation have been successfully grown on the 36°YX-LiTaO₃ substrates by RF magnetron sputtering technique. Then the Love-mode immunosensors based on the ZnO/36°YX-LiTaO₃ structures and monitoring antibody-antigen immunoreactions in aqueous solutions in real time are fabricated. The experimental results show that the optimal thickness of ZnO layers is about 1.20 μm in the structures deposited on 36°YX-LiTaO₃ substrates, which is much less than that of SiO₂ overlayers about 6 μm. The antibody-antigen immunoreaction experiments also show that the frequency shifts of the sensors with 1.33 μm ZnO films are proportional to the concentration of antigen in solution as the concentration range less than 100 μg/ml.     

High-performance Zinc-Tin-Oxide thin film transistors based on environment friendly solution process

Zinc-Tin-Oxide (ZTO) thin films were fabricated using a simple and eco-friendly sol-gel method and their application in thin film transistors (TFTs) was investigated. Annealing temperature has a crucial influence on the structure and electrical properties of sol-gel ZTO thin films. The ZTO thin films annealed at 300–600?°C revealed smooth and uniform surfaces with amorphous state, in addition, a high optical transparency over 90% of the ZTO films in the visible range was obtained. The electrical performance of ZTO TFTs showed obvious dependence on annealing temperature. The ZTO TFTs annealed at 500?°C showed a high carrier mobility of 5.9?cm²/V, high on/off current ratio (I_on/off) of 10⁶-10⁷, and threshold voltage (V_th) of 1.03?V. To demonstrate the application of sol-gel ZTO films in low-power display fields, we also fabricated ZTO TFTs with a solution-processed high-permittivity (high-k) ZrTiO_x dielectric layer. The ZTO/ZrTiO_x TFTs showed high mobility of 17.9?cm²/V and I_on/off of 10⁵-10⁶?at a low operation voltage of 3?V, indicating that Indium-free ZTO thin films would be potential candidates for low cost, high performance oxide TFT devices.     

The gas response enhancement from ZnO film for H2 gas detection

ZnO thin films were prepared by thermal oxidation of Zn metal at 400 °C for 30 and 60 min. The XRD results showed that the Zn metal was completely converted to ZnO with a polycrystalline structure. The sensors had a maximum response to H₂ at 400 °C and showed stable behavior for detecting H₂ gases in the range of 40 to 160 ppm. The film oxidized for 60 min in oxygen flow exhibited higher response than that of the 30 min oxidation which was approximately 4000 for 160 ppm H₂ gas concentration. The sensing mechanism was modeled according to the oxygen-vacancy model.     

Co3O4-ZnO hierarchical nanostructures by electrospinning and hydrothermal methods

A new hierarchical nanostructure that consists of cobalt oxide (Co₃O₄) and zinc oxide (ZnO) was produced by the electrospinning process followed by a hydrothermal technique. First, electrospinning of a colloidal solution that consisted of zinc nanoparticles, cobalt acetate tetrahydrate and poly(vinyl alcohol) was performed to produce polymeric nanofibers embedding solid nanoparticles. Calcination of the obtained electrospun nanofiber mats in air at 600 °C for 1 h, produced Co₃O₄ nanofibers with rough surfaces containing ZnO nanoparticles (i.e., ZnO-doped Co₃O₄ nanofibers). The rough surfaced nanofibers, containing ZnO nanoparticles (ZnNPs), were then exploited as seeds to produce ZnO nanobranches using a specific hydrothermal technique. Scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were employed to characterize the as-spun nanofibers and the calcined product. X-ray powder diffractometery (XRD) analysis was used to study the chemical composition and the crystallographic structure.     

Optical and electrical properties of p-type ZnO fabricated by NH3 plasma post-treated ZnO thin films

In this paper, a simple method is reported to obtain nitrogen-doped p-ZnO film. In this method NH₃ plasma, generated in a plasma-enhanced chemical vapor deposition system, was employed to treat ZnO thin film. By Hall-effect measurement, a p-type conductivity was observed for the treated film with the hole density of 2.2 × 10¹⁶ cm⁻³. X-ray photoelectron spectroscopy (XPS) results confirmed that nitrogen was incorporated into ZnO film during the treatment process to occupy the oxygen positions. In low temperature photoluminescence spectra, an emission peak corresponding to acceptor-donor pair was observed. From this emission peak we calculated the N-related acceptor binding energy to be 130 meV.     

Evolution of Zn based high purity phases under NH3 gas atmosphere and their PL properties

We report here the evolution of zinc based high purity phases with novel morphologies such as Zn₃N₂ hollow structures, ZnO nanowires and nanopowders, as well as metallic Zn layered hexagonal microparticles at progressively increased reaction temperature of 600 °C, 700 °C, 800 °C under NH₃ gas atmosphere using Zn powder precursor and keeping all other experimental parameters unchanged. Growth mechanism for Zn₃N₂ obtained by nitridation, ZnO by oxidation and Zn microparticles via thermal evaporation & condensation process are discussed briefly. The as-synthesized products were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM). Photoluminescence (PL) studies have revealed very interesting and infrequently observed emission bands at 378 and 661 nm for Zn₃N₂, 359 and 396 nm for ZnO as well as 389 nm for Zn polyhedral microparticles.     

Characteristics and heterostructure of metal-doped TiO2/ZnO nanocatalysts

In this study, Ag or Al-doped TiO₂/ZnO heterostructure nanocatalysts were prepared using a sol-gel method for photocatalysis to evaluate the degradability. The photocatalytic behavior was evaluated by the degradation of methylene blue (MB) under ultraviolet (UV) light irradiation. Photocatalytic studies suggested that 1 mol% Ag-doped TiO₂/ZnO (TiO₂/ZnO = 0.75/0.25) heterostructure nanocatalysts showed higher photocatalytic activity, and that the degradation efficiency can reach 83% in 4 h, 14% higher than that for pure TiO₂. Finally, the photocatalysis mechanism for the Ag-doped TiO₂/ZnO heterostructure nanocatalysts is discussed.     

Spectroscopic study of ZnO doped CeO2-PbO-B2O3 glasses

Glass samples of compositions xZnO-xCeO₂-(30−x)PbO-(70−x)B₂O₃ with x varying from 2% to 10% mole fraction are prepared by the melt quench technique. The structural and optical analysis of glasses is carried out by XRD, FTIR, density and UV-visible spectroscopic measurement techniques. The FTIR spectral analysis indicates that with the addition of ZnO contents in glass network, structural units of BO₃ are transformed into BO₄. It has been observed in our previous work that band gap decreases from 2.89 to 2.30 eV for CeO₂-PbO-B₂O₃ glasses with cerium content varying from 0% to 10% [Gurinder Pal Singh, Davinder Paul Singh, Physica B 406(3) (2011) 640-644]. With the incorporation of zinc in CeO₂-PbO-B₂O₃ glasses, the optical band gap energy decreases further from 2.38 to 2.03 eV. This causes more compaction of the borate network, which results in an increase of density (3.39-4.02 g/cm³). Transmittance shows that ZnO in glass samples acts as a reducing agent thathelps to convert Ce⁴⁺→Ce³⁺ ions.     

Shape alterations of ZnO nanocrystal arrays fabricated from NH3·H2O solutions

Well-aligned crystalline ZnO nanorod arrays were synthesized via an aqueous solution route with ammonia and zinc nitrate as inorganic precursors. ZnO crystalline seed films were firstly coated on ITO substrates for epitaxial growth of rods through sol-gel processing and heat treatment. SEM, TEM, SAED and XRD were utilized to characterize morphologies and structures of ZnO crystals. Heterogeneous nucleation is crucial for rod growth. A broad scope of pH favorable for heterogeneous nucleation was disclosed at zinc concentration from 0.04 to 0.1 M in the inorganic system due to the complex reaction of ammonia with Zn²⁺. Elevation of initial zinc concentration or pH promoted growth rate of rods and enlarged rod size. ZnO nanorods were transformed to nanotubes, nanosheets and rods with blanket-like shaped surface mainly by secondary pH adjustment. All ZnO nanocrystals are wurtzite structure preferentially oriented in c-axis direction.