Surface Morphological and Nanomechanical Properties of PLD-Derived ZnO Thin Films

This study reports the surface roughness and nanomechanical characteristics of ZnO thin films deposited on the various substrates, obtained by means of atomic force microscopy (AFM), nanoindentation and nanoscratch techniques. ZnO thin films are deposited on (a- and c-axis) sapphires and (0001) 6H-SiC substrates by using the pulsed-laser depositions (PLD) system. Continuous stiffness measurements (CSM) technique is used in the nanoindentation tests to determine the hardness and Young’s modulus of ZnO thin films. The importance of the ratio (H/E _film) of elastic to plastic deformation during nanoindentation of ZnO thin films on their behaviors in contact-induced damage during fabrication of ZnO-based devices is considered. In addition, the friction coefficient of ZnO thin films is also presented here.     

Band structure and thermoelectric properties of inkjet printed ZnO and ZnFe2O4 thin films

The band structure and thermoelectric properties of inkjet printed ZnO and ZnFe₂O₄ thin films have been investigated. The bulk pellets were prepared by a solid-state method and thin films were deposited using an inkjet printing method. Multiple print cycles were required to fabricate homogeneous films and the composition of the thin films can be varied by varying the relative amounts of liquid deposited. It was possible to obtain high thermoelectric properties of ZnO by controlling the ratios of dopant added and the temperature of the heat treatments. XRD analysis showed that the fabricated samples have a wurtzite structure and an additional ZnAl₂O₄ phase was formed with increasing Al content and sintering temperature. It was found that the band gap of Al doped ZnO becomes smaller with increasing Al content and thus the electrical conductivity of Al_x doped ZnO (x=0.04) thin films showed the highest electrical conductivity (114.10 S/cm). The ZnFe₂O₄ samples were compared against the ZnO samples. The formation of single phase cubic spinel structure of the sintered ZnFe₂O₄ samples was found and confirmed by X-ray diffraction technique. Secondary phase Fe₂O₃ was also detected for compositions with Zn (x≤0.4). Finally, we want to report that the electrical conductivity of Zn_xFe_3−xO₄ was lower than the conductivity of the Al-doped ZnO.     

The dielectric properties and optical propagation loss of c-axis oriented ZnO thin films deposited by sol–gel process

The c-axis oriented ZnO thin films were prepared on various substrates by sol–gel processes. The stability of solution was examined through solvent and stabilizer. The c-axis orientation and grain size of films were increased with increasing of heat treatment temperature. The optical propogation losses of ZnO films deposited SiO₂/Si(111) substrates were measured using end-coupling method. The losses result in the scattering of the interface of ZnO/SiO₂, and the ZnO grain. Dielectric constant and resistivity of thin films deposited on Pt/SiO₂/Si(111) substrates are, respectively, in the range of 7–13 and 1.7×10⁴9.8×10⁵Ω cm.     

Microstructure and ferroelectric properties of Ta-doped Bi3.25La0.75Ti3O12/ZnO thin film capacitors

Ta-doped Bi_3.25La_0.75Ti₃O₁₂(BLTT)/ZnO films were fabricated on Pt(111)/Ti/SiO₂/Si substrates by a magnetron sputtering method. Firstly, ZnO crystal thin films were grown on the substrates by a reactive sputtering method. Then, BLTT thin films were deposited on the ZnO layers at room temperature and post-annealed at 600 °C. The micromorphology, ferroelectric and dielectric properties of BLTT/ZnO films were analyzed. The XRD analysis shows that ZnO buffer layer significantly reduces the crystallization temperature of BLTT thin film. The TEM results show that lamellar BLTT grains are grown on ZnO layer at a certain angle with few elements diffusion at the interface of ZnO phase and Bi₄Ti₃O₁₂ phase. The ferroelectric properties indicate that BLTT/ZnO films exhibit different remanent polarization and coercive fields under electric field with different directions. The novel mechanism of tailoring ferroelectric properties may open new possibilities for designing special ferroelectric devices.     

STRUCTURAL AND OPTICAL PROPERTIES OF ZNO THIN FILMS PREPARED BY DIFFERENT SOL-GEL PROCESSES

ZnO thin films were prepared on quartz glass substrates by different sol-gel methods using a spin-coating technique. The structural and optical properties of ZnO thin films were studied by X-ray diffraction (XRD) and transmission spectra analysis. The results show that different factors such as Zn²⁺ concentration, solvent, sol stabilizer, pre-heat treatment temperature, and annealing temperature have a great impact on the structural and optical properties of ZnO thin films.     

Effect of structural defects,surface roughness on sensing properties of Al doped ZnO thin films deposited by chemical spray pyrolysis technique

In this article, the gas sensing properties of Al-doped ZnO thin films have been reported where the nanocrystalline ZnO based thin films were well deposited by a simple and inexpensive ‘chemical spray pyrolysis (CSP)’ technique. Films have been found to be uniform, pinhole free and well adherent to the substrate. The morphology, structures, and surface roughness of the deposited Al-doped ZnO thin films were studied by various types of characterization techniques. In addition, the authors have observed that the sensor response and selectivity towards CO gas is improved by the Al doping at a low operating temperature. XRD results showed that the obtained films are nanocrystalline in nature with hexagonal wurtzite phase. Further, the annealed films were used for detection of CO in the air and maximum response was observed at 175 °C. The improvement in sensor response of Al-doped ZnO thin films to CO gas attributed to the defect chemistry, crystallite size and surface roughness.     

Influence of water content in mixed solvent on surface morphology,wettability, and photoconductivity of ZnO thin films

ZnO thin films have been synthesized by means of a simple hydrothermal method with different solvents. The effect of deionized water content in the mixed solvents on the surface morphology, crystal structure, and optical property has been investigated by scanning electron microscopy, X-ray diffraction, and UV-Vis spectrophotometer. A large number of compact and well-aligned hexagonal ZnO nanorods and the maximal texture coefficient have been observed in the thin film, which is grown in the mixed solvent with x = 40%. A lot of sparse, diagonal, and pointed nanorods can be seen in the ZnO thin film, which is grown in the 40-mL DI water solution. The optical band gap decreases firstly and then increases with the increase of x. Reversible wettability of ZnO thin films were studied by home-made water contact angle apparatus. Reversible transition between hydrophobicity and hydrophilicity may be attributed to the change of surface chemical composition, surface roughness and the proportion of nonpolar planes on the surface of ZnO thin films. Photocurrent response of ZnO thin films grown at different solvents were measured in air. The response duration of the thin film, which is grown in the solvent with x = 40%, exhibits a fast growth in the beginning but cannot approach the saturate current value within 100 s. The theoretical mechanism for the slower growth or decay duration of the photocurrent has been discussed in detail.     

Fabrication and properties of ZnO/GaN heterostructure nanocolumnar thin film on Si (111) substrate

Zinc oxide thin films have been obtained on bare and GaN buffer layer decorated Si (111) substrates by pulsed laser deposition (PLD), respectively. GaN buffer layer was achieved by a two-step method. The structure, surface morphology, composition, and optical properties of these thin films were investigated by X-ray diffraction, field emission scanning electron microscopy, infrared absorption spectra, and photoluminiscence (PL) spectra, respectively. Scanning electron microscopy images indicate that the flower-like grains were presented on the surface of ZnO thin films grown on GaN/Si (111) substrate, while the ZnO thin films grown on Si (111) substrate show the morphology of inclination column. PL spectrum reveals that the ultraviolet emission efficiency of ZnO thin film on GaN buffer layer is high, and the defect emission of ZnO thin film derived from Zn_i and V_o is low. The results demonstrate that the existence of GaN buffer layer can greatly improve the ZnO thin film on the Si (111) substrate by PLD techniques.     

Effects of NIR annealing on the characteristics of al-doped ZnO thin films prepared by RF sputtering

Aluminum-doped zinc oxide (AZO) thin films have been deposited on glass substrates by employing radio frequency (RF) sputtering method for transparent conducting oxide applications. For the RF sputtering process, a ZnO:Al₂O₃ (2 wt.%) target was employed. In this paper, the effects of near infrared ray (NIR) annealing technique on the structural, optical, and electrical properties of the AZO thin films have been researched. Experimental results showed that NIR annealing affected the microstructure, electrical resistance, and optical transmittance of the AZO thin films. X-ray diffraction analysis revealed that all films have a hexagonal wurtzite crystal structure with the preferentially c-axis oriented normal to the substrate surface. Optical transmittance spectra of the AZO thin films exhibited transmittance higher than about 80% within the visible wavelength region, and the optical direct bandgap (E_g) of the AZO films was increased with increasing the NIR energy efficiency.     

Preparation of Nanostructured ZnO Thin Films Using Magnetron Sputtering for the Gas Sensors Applications

ZnO is one of the most promising transparent conducting oxide materials, which widely used in thin film gas sensors. In this research, the dependence of the thermal oxidation time on structural, morphological and gas sensing properties of ZnO thin films is investigated. ZnO nanostructures are synthesized by using DC magnetron sputtering for deposition of pure zinc layers on glass substrates and then thermal oxidation of deposited zinc layers to produce zinc oxide (ZnO) thin films. Obtained results from X-ray diffraction revealed that the degree of crystallinity and the average grain size of the ZnO deposited thin films enhance with increasing the thermal oxidation time. Surface topography and growth behavior of ZnO thin films have important role in optimization of gas sensing properties of these films. In this study, scanning electron microscopy and atomic force microscopy have been used to investigate the effective parameters related to the surface topography of the films. Obtained results from these analyzes revealed that the surface topography of ZnO deposited samples strongly depend on thermal oxidation time. Also the effect of thermal oxidation time on the performance of ZnO gas sensors is investigated. The results indicated that the ethanol gas sensing properties of ZnO samples improve with decreasing the size of grains.     

High-quality c-axis oriented non-vacuum Er doped ZnO thin films

Preparation, growth, structure and optical properties of high-quality c-axis oriented non-vacuum Er doped ZnO thin films were studied. Zn_1−xEr_xO (x=0.0, 0.01, 0.02, 0.04, and 0.05) precursor solutions were prepared by sol–gel synthesis using Zn, and Er based alkoxide which were dissolved into solvent and chelating agent. Zn_1−xEr_xO thin films with different Er doping concentration were grown on glass substrate using sol–gel dip coating. Thin films were annealed at 600 °C for 30 min, and tried to observe the effect of doping ratio on structural and optical properties. The particle size, crystal structure, surface morphologies and microstructure of all samples were characterized by X-Ray diffraction (XRD) and Scanning Electron Microscope (SEM). The UV–vis spectrometer measurements were carried out for the optical characterizations. The surface morphology of the Zn_1−xEr_xO films depend on substrate nature and sol–gel parameters such as withdrawal speed, drying, heat treatment, deep number (film thickness) and annealing condition. Surface morphologies of Er doped ZnO thin films were dense, without porosity, uniform, crack and pinhole free. XRD results showed that, all Er doped ZnO thin films have a hexagonal structure and (002) orientation. The optical transmittance of rare earth element (Er) doped ZnO thin films were increased. The Er doped ZnO thin films showed high transparency (>85) in the visible region (400–700 nm).     

The ultraviolet emission mechanism of ZnO thin film fabricated by sol–gel technology

ZnO thin films were successfully deposited on SiO₂/Si substrate by sol–gel technology. The as-grown ZnO thin films were annealed under an ambient atmosphere from 600 to 900 °C by rapid thermal annealing (RTA) process. X-ray diffraction and scanning electron microscopy analyses reveal the physical structures of ZnO thin films. From PL measurement, two ultraviolet (UV) luminescence bands were obtained at 375 and 380 nm, and the intensity became stronger when the annealing temperature was increased. The strongest UV light emission appeared at annealing temperature of 900 °C. The chemical bonding state in ZnO films was investigated by using X-ray photoelectron spectrum. The mechanism of UV emission was also discussed.     

Electrospray deposition of in-situ UV-photoactivated polyimide films

In electrospray deposition, a precursor solution, composed of a solute material in a volatile carrier solvent, is atomized into a spray of charged microdroplets under the influence of a strong electric field. As the droplets are in-flight, the carrier solvent evaporates, leaving behind the solute material that can be delivered to a target surface to create a film. In this work, we employ electrospray deposition to create films of UV-photosensitive polyimide. Films were deposited using in-situ UV exposure, where the in-flight droplets and deposited material were exposed to UV during deposition. The characteristics of these films were compared to films exposed to UV only after deposition (referred to as post-UV exposure). The microstructure of the deposited films was notably different for the two exposure modes, in which the in-situ UV exposed films have a wavy/dimpled surface, compared to the flat and smooth surface of the post-UV exposed films. However, thermogravimetric analysis and Fourier transform infrared spectroscopy showed that the UV activation of the in-situ UV and post-UV exposed films was nearly identical. Breakdown testing was conducted to evaluate the dielectric strength of the films. Overall, the in-situ UV and post-UV exposed films exhibited similar breakdown strengths of approx. 430–450 V/μm. The use of in-situ UV exposure cuts in half the processing time for producing thin polyimide films.     

Deposition of F-doped ZnO transparent thin films using ZnF2-doped ZnO target under different sputtering substrate temperatures

Highly transparent and conducting fluorine-doped ZnO (FZO) thin films were deposited onto glass substrates by radio-frequency (RF) magnetron sputtering, using 1.5 wt% zinc fluoride (ZnF₂)-doped ZnO as sputtering target. Structural, electrical, and optical properties of the FZO thin films were investigated as a function of substrate temperature ranging from room temperature (RT) to 300°C. The cross-sectional scanning electron microscopy (SEM) observation and X-ray diffraction analyses showed that the FZO thin films were of polycrystalline nature with a preferential growth along (002) plane perpendicular to the surface of the glass substrate. Secondary ion mass spectrometry (SIMS) analyses of the FZO thin films showed that there was incorporation of F atoms in the FZO thin films, even if the substrate temperature was 300°C. Finally, the effect of substrate temperature on the transmittance ratio, optical energy gap, Hall mobility, carrier concentration, and resistivity of the FZO thin films was also investigated.     

Tailoring of polar and nonpolar ZnO planes on MgO (001) substrates through molecular beam epitaxy

ABSTRACT: Polar and nonpolar ZnO thin films were deposited on MgO (001) substrates under different deposition parameters using oxygen plasma-assisted molecular beam epitaxy (MBE). The orientations of ZnO thin films were investigated by in situ reflection high-energy electron diffraction and ex situ X-ray diffraction (XRD). The film roughness measured by atomic force microscopy evolved as a function of substrate temperature and was correlated with the grain sizes determined by XRD. Synchrotron-based X-ray absorption spectroscopy (XAS) was performed to study the conduction band structures of the ZnO films. The fine structures of the XAS spectra, which were consistent with the results of density functional theory calculation, indicated that the polar and nonpolar ZnO films had different electronic structures. Our work suggests that it is possible to vary ZnO film structures from polar to nonpolar using the MBE growth technique and hence tailoring the electronic structures of the ZnO films.PACS: 81; 81.05.Dz; 81.15.Hi.     

Preparation and characterization of Al-doped ZnO piezoelectric thin films grown by pulsed laser deposition

Undoped and Al-doped ZnO (AZO) thin films (Al: 3, 5 at%) using a series of high quality ceramic targets have been deposited at 450 ºC onto glass substrates using PLD method. The used source was a KrF excimer laser (248 nm, 25 ns, 2 J/cm²). The study of the obtained thin films has been accomplished using X-ray diffraction (XRD), M-lines spectroscopy and Rutherford backscattering spectroscopy (RBS). XRD patterns have shown that the films crystallize in a hexagonal wurtzite type structure with a highly c-axis preferred (002) orientation, and the grain sizes decrease from 37 to 25 nm with increasing Al doping. The optical waveguiding properties of the films were characterized by means of the prism-coupling method. The distinct M-lines of the guided transverse magnetic (TM) and transverse electric (TE) modes of the ZnO films waveguide have been observed. The M-lines device has allowed determination of the accurate values of refractive index and thickness of the studied ZnO and AZO thin films. An evaluation of experimental uncertainty and calculation of the precision of the refractive index and thickness were developed on ZnO films. The RBS results agree with XRD and m-lines spectroscopy measurements.     

ELECTROSTATIC SOL–SPRAY DEPOSITION OF NANOSTRUCTURED CERAMIC THIN FILMS

Electrospraying has been developed into an electrostatic spray deposition technique for the deposition of ceramic thin films. The cone-jet spraying mode appears to be the most preferable for this purpose, and the domain where the cone-jet mode exists was found to depend strongly on the nozzle design. A nozzle with a large diameter and a tilted outlet widens the windows for both the applied high DC voltage and the flow rates of a precursor liquid keeping the cone-jet mode intact. The results of three nozzle designs are compared, one of which has been selected for feeding two different precursor liquids simultaneously. With three relevant sols as precursor liquids, nanostructured thin films of ZnO, ZrO₂, and Al₂O₃ have been deposited. Their morphologies are dependent on the preparation of the precursor sols and the deposition temperature. Highly porous films were obtained by using a high deposition temperature and a sol prepared from a metal alkoxide or a metal acetate.     

Optical and Structural Characteristics of Nanocrystalline ZnO:Cd Ceramics

Nanostructured cadmium (Cd) doped ZnO ceramic thin films were deposited on glass substrates by the sol-gel spin coating method and characterized by X-ray diffraction (XRD), scanning electron microscopy and UV-VIS-NIR spectrophotometry. The XRD analysis showed that thin films were crystalline with hexagonal wurtzite structure. The preferred orientation of un-doped and Cd-doped ZnO thin films lies along the (002) plane. FESEM images revealed that the morphology consists of spherical, non-spherical and partly cylindrical structures. The results of EDX showed that Cd was doped into the ZnO structure. The UV-Vis transmittance spectra showed that substitution of Cd into ZnO leads to bandgap narrowing. The Urbach energy increases with the increase in Cd concentration. The prepared nanostructured cadmium (Cd) doped ZnO ceramic thin films can be used in electronic device technologies.     

Effect of thermal treatment on the electrical properties of the sol–gel-derived (Zr,Sn)TiO4 thin films

The effect of heating temperatures on the electrical properties of sol–gel-derived (Zr,Sn)TiO₄ thin films deposited on a p-type (1 0 0) Si substrate was studied. The leakage currents of films with two different heating temperatures chosen to burn-out the solvent as a function of applied voltage were measured at different temperatures. The activation energies obtained from the Arrhenius plot of the leakage current density versus measured temperature for (Zr,Sn)TiO₄ films were then extracted. Additionally, microstructures of films with two different heating temperatures chosen to burn-out the solvent were analyzed by a conductive atomic force microscope (AFM) and an X-ray diffraction (XRD). Finally, the conductive mechanisms of leakage current and leakage current correlated to microstructures were also discussed.     

Transparent semiconductor zinc oxide thin films deposited on glass substrates by sol–gel process

Transparent semiconductor ZnO thin films were spin-coated onto alkali-free glass substrates by a sol–gel process. The influence of ZnO sols synthesized via different solvents (2-ME, EtOH or IPA) on the surface morphologies, microstructures, optical properties and resistivities of the obtained films were investigated. The as-coated films were annealed in ambient air at 500 °C for 1 h. X-ray diffraction results showed all polycrystalline ZnO thin films to have preferred orientation along the (0 0 2) plane. The surface morphologies, optical transmittances and resistivity values of the sol–gel derived ZnO thin films depended on the solvent used. The ZnO thin films synthesized with IPA as the solvent exhibited the highest average transmittance 92.2%, an RMS roughness of 4.52 nm and a resistivity of 1.5 × 10⁵ Ω cm.