Ethylene glycol assisted hydrothermal synthesis of flower like ZnO architectures

We describe a simple route to flower like ZnO architectures, based on the decomposition of zinc acetate precursor in water-ethylene glycol solution at 140-160 °C for 1d through hydrothermal method. The PXRD pattern reveals that the ZnO crystals are of hexagonal wurtzite structure. Ethylene glycol plays a key role on the morphology control of ZnO crystals. The SEM images of ZnO products prepared at 140 °C and 160 °C mainly exhibit flower like architecture composed of many rods. Whereas, the product prepared at 180 °C shows bunches accompanying a few number of free rods. TEM results reveal that the rods resemble swords with decrease in size from one end to another. From Raman spectrum, the peaks at 437 cm^− 1, 382 cm^− 1 and 411 cm^− 1 correspond to E₂ (high), A₁ (TO) and E₁ (TO) of ZnO crystals respectively. The photoluminescence spectrum exhibits strong UV emission at ~ 397 nm, which comes from recombination of exciton. The possible mechanism for the formation of flower like ZnO architecture is proposed.     

Room temperature ferromagnetism in chemically synthesized ZnO rods

We report structural and magnetic properties of pure ZnO rods using x-ray diffraction (XRD), magnetization hysteresis (M−H) loop and near edge x-ray fine structure spectroscopy (NEXAFS) study at O K edge. Sample of ZnO was prepared by co-precipitation method. XRD and selective area electron diffraction measurements infer that ZnO rods exhibit a single phase polycrystalline nature with wurtzite lattice. Field emission transmission electron microscopy, field emission scanning electron microscopy micrographs infers that ZnO have rod type microstructures with dimension 200 nm in diameter and 550 nm in length. M-H loop studies performed at room temperature display room temperature ferromagnetism in ZnO rods. NEXAFS study reflects absence of the oxygen vacancies in pure ZnO rods.     

Structures, varistor properties, and electrical stability of ZnO thin films

In this letter, we report the structures, varistor properties, and electrical stability of ZnO thin films deposited by the gas discharge activated reaction evaporation (GDARE) technique. The X-ray diffraction (XRD) and atomic force microscopy (AFM) measurements showed that the thin films thus prepared have polycrystalline structures with the preferred orientation along the (002) plane whose surface consists of ZnO aggregates with sizes of 50-200 nm. The ZnO thin films deposited by GDARE and annealed at 250 °C for 2 h have strong nonlinear varistor-type I-V characteristics. The nonlinear coefficient (α) of a single-layered ZnO thin film sample was 33 and that of a triple-layered sample obtained by the many-time deposition was 62. The varistor voltages (V_1mA) of the two samples are found rather close each other. Under a DC bias of 0.75 V_1mA and a temperature of 150 °C these thin films exhibit good electrical stability with a degradation rate coefficient K_T of 0.05 mA/h^1/2.     

Influence of substrate temperature on N-doped ZnO films deposited by RF magnetron sputtering

Nitrogen-doped ZnO films were deposited by RF magnetron sputtering in 75% of N₂ / (Ar + N₂) gas atmosphere. The influence of substrate temperature ranging from room temperature (RT) to 300 °C was analyzed by X-ray diffractometry (XRD), spectrophotometry, X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS) and Hall measurements setup. The XRD studies confirmed the hexagonal ZnO structure and showed that the crystallinity of these films increased with increasing substrate temperature (T_s). The optical studies indicate the average visible transmittance in the wavelength ranging 500-800 nm increases with increasing T_s. A minimum transmittance (9.84%) obtained for the films deposited at RT increased with increasing T_s to a maximum of 88.59% at 300 °C (500-800 nm). Furthermore, it was understood that the band gap widens with increasing T_s from 1.99 eV (RT) to 3.30 eV (250 °C). Compositional analyses (XPS and SIMS) confirmed the nitrogen (N) incorporation into the ZnO films and its decreasing concentration with increasing T_s. The negative sign of Hall coefficients confirmed the n-type conducting.     

Hierarchical nanostructures of ZnO obtained by spray pyrolysis

A two step spray pyrolysis deposition method was applied in order to grow ZnO nanorod core/ZnO shell hierarchical nanostructures with various surface morphologies, such as a highly organised platelet network on the side facets of the ZnO rod and bundles of nanoneedles on the top plane of the rod. First, well-shaped ZnO nanorods with lengths of ca. 1 μm and average diameters of 150–300 nm were deposited from zinc chloride (ZnCl₂·2H₂O) aqueous solutions onto TCO/glass substrates. Then, zinc acetate (Zn(CH₃COO)₂·2H₂O) solution was pulverised over the surface of the sprayed ZnO nanorods at a growth temperature of approximately 330 °C within 6–10 min. The obtained structures were characterised by high resolution SEM, UV–VIS and XRD. To estimate the surface areas and photocatalytic ability of the bare rods and hierarchical structures, their adsorption ability and activity of photocatalytic oxidation of doxycycline were measured. It was found that the surface area of hierarchical structures comprised of a network of platelets is at least 4 times larger than that of a bare rod. The structural and morphological properties of sprayed hierarchical structures largely depend on the spraying rate of the zinc acetate solution and on the ZnO nanorod top plane shape.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

Influence of seed layers on the vertical growth of ZnO nanowires

We synthesized vertically aligned ZnO nanowires on SiO₂ wafer <100> using the Au, ZnO and Au/ZnO seed layers through the physical vapor deposition process. The growth direction of ZnO nanowire was controlled by using the three different seed layers. From the XRD results, we observed the highest intensity of the (002) peak on the Au/ZnO seed layer among the three seed layers. The SEM images show that all of the ZnO nanowires have an average diameter of about 100 ~ 200 nm and a length of about 5 μm, and the nanowires grown on the Au/ZnO seed layer are oriented the most perpendicularly to the substrate surface. From the PL analysis, we observed that the intensity of broad emissions at 400-600 nm relating the green emission for the ZnO nanowires on the Au/ZnO seed layer was much weaker than that for the ZnO nanowires on the ZnO seed layer. The experiment results indicate that the selection of seed layers is important to grow nanowires vertically for the application of nanoscale devices.     

Characterization of gallium-nitrogen co-doped zinc oxide thin films prepared by RF diode sputtering

We investigated the possibility of achieving p-type zinc oxide (ZnO) by RF diode sputtering and gallium-nitrogen co-doping. ZnO:Ga:N thin films were prepared with a different N₂ content in Ar/N₂ working gas, ranging from 0 to 100%, and at a varying substrate temperature, from room temperature (RT) to 300 °C. A hole conduction with maximum carrier concentration of 2.6 × 10¹⁸ cm⁻³, mobility of 2 cm²/Vs and resistivity of 1.5 Ω cm resulted from deposition at RT with 100% N₂. It arose from N incorporation and formation of N_O acceptors. In the secondary ion mass spectrometry (SIMS) depth profiles of the co-doped films were observed NO/NO₂ negative ions. Average transmittance (including Corning glass substrate) across the visible spectrum varied (60 ÷ 66%) with increasing nitrogen content (50 ÷ 100% N₂). As the substrate temperature increased (RT - 300 °C), highly transparent (T ∼72-83%) and conductive (electron concentrations of 10¹⁷-10¹⁹ cm⁻³) n-type ZnO:Ga:N films were attained. Reduction of optical band gap (E_g) (∼3.13-3.08 eV) was observed for co-doped ZnO films. Atomic force microscopy (AFM) images revealed that the films grown at RT have roughness of approximately 5.3 nm while roughness of those grown at 300 °C is approximately 3.9 nm.     

Transparent, amorphous and organics-free ZnO thin films produced by chemical solution deposition at 150 °C

We have studied the low-temperature processing of ZnO by chemical solution deposition. A transparent, stable precursor solution prepared from zinc acetate dihydrate dissolved in 2-methoxyethanol was spin-coated on SiO_x/Si, soda-lime glass and polymer substrates and heated at 150 °C. Selected thin films deposited on SiO_x/Si were additionally heated at 450 °C.Microstructural and chemical analyses showed that the thin films heated at 150 °C in air were amorphous, contained no organic residues and had a root mean square roughness of 0.7 nm. The films deposited on SiO_x/Si and heated at 450 °C were crystallised and consisted of randomly oriented grains with a diameter of about 20 nm. All thin films were transparent, exhibiting a transmission of over 80% in the visible range. The resistivity of the 120-nm thick ZnO films processed at 150 °C was 57 MΩ cm and upon heating at 450 °C it decreased to 1.9 kΩ cm.     

Properties of nanocrystalline zinc oxide thin films prepared by thermal decomposition of electrodeposited zinc peroxide

Zinc peroxide thin films were electrodeposited from aqueous solution at room temperature using H₂O₂ as the oxidation agent. Nanocrystalline zinc oxide thin films were then obtained from thermal decomposition of zinc peroxide thin films. The grain sizes of ZnO through thermal decomposition of ZnO₂ at 200 °C, 300 °C and 400 °C were estimated from the peak width of ZnO(110) obtained from X-ray diffraction and were 6.3 nm, 9.1 nm and 12.9 nm, respectively. The optical properties of zinc oxide thin films have been studied. The photoluminescence results indicate that ZnO thin films have low Stokes blue shift (about 110 meV) and low oxygen vacancies.     

Phase determination of filtered vacuum arc deposited TiO2 thin films by optical modeling

Thin films of TiO₂ were produced using filtered vacuum arc deposition. Arc currents were 275, 300, 325 A, and the oxygen pressure during deposition was 0.93 Pa. The substrates were glass microscope slides, at temperatures of 25 °C (RT), 200 °C, and 400 °C. Film thickness was in the range 100 to 250 nm, depending on the deposition conditions. Film structure and chemical composition were determined using XRD and XPS analyses, respectively. As-deposited films were amorphous, except to two samples that were found to be crystalline (deposited with 300 A, 325 A at 400 °C), and the crystalline phase was close to that of anatase. All of the films were partially crystallized by annealing in air at 450 °C for 1 h. The O:Ti atomic concentration ratio was in the range 1.6:1-2:1, independent of deposition conditions. The optical parameters, refractive index and the extinction coefficient of the films were determined using variable angle spectroscopic ellipsometry. In addition, the optical transmission of the films were determined in the UV-VIS and IR regions. The average optical transmission in the VIS spectrum was 70-85%, affected by the interference in the film with 90% maxima and 60% minima. The refractive index at λ = 550 nm was in the range 2.4 to 2.7, depending on the deposition conditions and annealing. Using the semi-empirical model of Wemple and DiDomenico for the dielectric function below the interband absorption edge of ionic and covalent solids, the dispersion energy parameters of TiO₂ (E_o, E_d) were calculated. The underlying structural order of the amorphous films was inferred by comparing the dispersion energy parameters of the amorphous films with those of crystalline TiO₂. As expected, the refractive index of the amorphous films depended on the underlying phase of the film. The optical analyses indicated that the underlying phase of the amorphous films deposited on RT substrates was close to anatase, whereas the underlying phase of the amorphous films deposited on 400 °C substrates and annealed at 450 °C for 1 h consisted of both anatase and rutile. Thus, although the XRD analyses could not indicate the underlying phase of the amorphous films, it could be determined by the optical analyses.     

Deposition of WNxCy thin films for diffusion barrier application using the dimethylhydrazido (2) tungsten complex (CH3CN)Cl4W(NNMe2)

Tungsten nitride carbide (WN_xC_y) thin films were deposited by chemical vapor deposition using the dimethylhydrazido (2⁻) tungsten complex (CH₃CN)Cl₄W(NNMe₂) (1) in benzonitrile with H₂ as a co-reactant in the temperature range 300 to 700 °C. Films were characterized using X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy and four-point probe to determine film crystallinity, composition, atomic bonding, and electrical resistivity, respectively. The lowest temperature at which growth was observed from 1 was 300 °C. For deposition between 300 and 650 °C, AES measurements indicated the presence of W, C, N, and O in the deposited film. The films deposited below 550 °C were amorphous, while those deposited at and above 550 °C were nano-crystalline (average grain size < 70 Å). The films exhibited their lowest resistivity of 840 µΩ-cm for deposition at 300 °C. WN_xC_y films were tested for diffusion barrier quality by sputter coating the film with Cu, annealing the Cu/WN_xC_y/Si stack in vacuum, and performing AES depth profile and XRD measurement to detect evidence of copper diffusion. Films deposited at 350 and 400 °C (50 and 60 nm thickness, respectively) were able to prevent bulk Cu transport after vacuum annealing at 500 °C for 30 min.     

ZnO nanostructured film deposition using the separated pulsed laser deposition (SPLD) assisted by electric and magnetic drift motion

We have developed the separated pulsed laser deposition (SPLD) technique to prepare high quality ZnO based films exhibiting uniform and droplet-free properties. This SPLD consists of an ablation chamber and a deposition chamber which can be independently evacuated under different ambient gases.The gas species and the pressures in both chambers can be arbitrarily chosen for the specific deposition such as nanostructured films and nanoparticles. The ablation chamber is a stainless steel globe and the deposition chamber is a quartz tube connected to a metallic conic wall with an orifice. We used a KrF excimer laser with λ = 248 nm and 25 ns pulse duration. The different gas conditions in two chambers allow us to realize optimal control of the plasma plume, the gas phase reaction and the film growth by applying the bias voltage between the conic wall and the substrate under the magnetic field. We can expect that at appropriate pressures the electric and magnetic field motion (E × B azimuthal drift velocity) gives significant influences on film growth.We have deposited ZnO thin films at various pressures of ablation chamber (Pab) and deposition chamber (Pd). The deposition conditions used here were laser fluence of 3 J/cm², laser shot number of 30,000, Pab of 0.67-2.67 Pa (O₂ or Ar), Pd of 0.399-2.67 Pa (O₂), and substrate temperature of 400 °C. Particle-free and uniform ZnO films were obtained at Pab of 0.67 Pa (Ar) and Pd of 1.33 Pa (O₂). The ZnO film showed high preferential orientation of (002) plane, optical band gap of 2.7 eV, grain size of 42 nm and surface roughness of 1.2 nm.     

Bilayer Cr/Au contacts on n-GaN

Cr/Au (40/65 nm) metal layers have been deposited by thermal evaporation onto n-GaN epitaxial layers grown by metal-organic chemical-vapour deposition (MOCVD) on a sapphire substrate. The samples have been annealed at 400, 700 and 900 °C for 10 min in vacuum. Techniques of TEM, EDS, HRTEM, FESEM, XRD and I-V characteristics have been used to characterize the micro-, and nanostructure, morphology, composition and electrical properties of the contacts before and after annealing. A binary phase of Cr₃Ga₄ and Au₇Ga₂ were identified at the interface of the n-GaN/Cr/Au contacts after annealing in vacuum at 700 and 900 °C. Current-voltage characterizations showed that the as-deposited and annealed Cr/Au contacts are rectifying up to 600 °C. After heat treatment in vacuum at 700 °C and 900 °C the Cr/Au contacts were linear.     

Synthesis of hierarchical ZnO nanobelts via Zn(OH)F intermediate using ionic liquid-assistant microwave irradiation method

ZnOHF nanobelts (NBs) were synthesized under microwave irradiation in the presence of ionic liquid, 1,2,3-trimethyl-imidazole tetrafluoroborate. The ranges of width, length and thickness of the NBs are ca. 500-800 nm, several micrometers and 100 nm, respectively. Porous polycrystal ZnO NBs with hierarchical structure were obtained after careful heat treatment of the intermediate ZnOHF at 400 °C for 2 h. The structural characters of the ZnO NBs were investigated by XRD, SEM, TEM, HRTEM and XPS measurements, and their absorption and photoluminescence properties were studied as well. The characterization results support the proposed reaction mechanism that the hierarchical ZnO NBs were produced via ZnOHF intermediate and subsequent removal of one of its decomposition products, ZnF₂, by hot water. This may be a facile method to fabricate porous ZnO NBs with hierarchical structure.     

Heat treatment effects on the formation of lanthanum-modified lead zirconate titanate thin films

The microstructural and compositional properties of lanthanum-modified lead zirconate titanate (PLZT) thin films deposited on platinum coated Si substrates by RF magnetron sputtering have been studied. The heat treatment processes of substrate heating during deposition and post deposition furnace and rapid thermal annealing were compared as processes for obtaining the desired pervoskite phase. PLZT thin films deposited with in-situ substrate heating showed little evidence of micro-cracking. The XRD data obtained showed the formation of pervoskite phase at 550 °C and indicated the suppression of the pyrochlore phase for increasing temperatures. The RBS analysis revealed a film thickness of 140 nm and composition of (Pb_0.91La_0.09)(Zr_0.6Ti_0.4)O₃. Deposition performed with in-situ substrate heating at 650 °C resulted in highly (110) pervoskite orientated thin films with an average grain size around 160 to 200 nm and an RMS roughness of 3 nm.     

Fabrication and characterization of Ga-doped ZnO nanowire gas sensor for the detection of CO

We demonstrate an efficient CO sensor using Ga-doped ZnO (GZO) nanowires (NWs). Various GZO NWs are synthesized with Au catalysts on sapphire substrates by hot-walled pulse laser deposition. The deposition temperature of ZnO NWs was in the range of 800-900 °C. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) characterizations indicate that the obtained NWs have the well-crystallized hexagonal structure with customized Ga-doping concentration of 0-5 wt.%. The NWs have the diameter of about 50 nm and the length of about 8 µm. After depositing the Ag electrodes on both sides of the NW cluster, the resistance change is checked with the exposure to CO gas in the self-designed gas chamber that can facilitate the detection of the resistance change and the control of gas flow as well as temperature. The detected resistance modulations are 1.0 kΩ and 83.2 kΩ in the cases of 3 wt.% GZO and pure ZnO NW clusters, respectively, indication that we successfully customize the sensitivity of the gas sensors by controlled doping.     

A ZnO nanorod based layered ZnO/64° YX LiNbO3 SAW hydrogen gas sensor

A zinc oxide (ZnO) nanorod based surface acoustic wave (SAW) sensor has been developed and investigated towards hydrogen (H₂) gas. The ZnO nanorods were deposited onto a layered ZnO/64° YX LiNbO₃ substrate using a liquid solution method. Micro-characterization results revealed that the diameters of ZnO nanorods are around 100 and 40 nm on LiNbO₃ and Au (metallization for electrodes), respectively. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 200 °C and 300 °C. The study showed that the sensor responded with highest frequency shift at 265 °C. At this temperature, stable baseline and fast response and recovery were observed.     

Deposition of nanocrystalline ZnO by wire explosion technique and characterization of the films' properties

ZnO films deposited on glass, quartz and Al on silicon mono-crystal Si (100) substrates by using the wire explosion technique were investigated by X-ray diffraction (XRD), UV–VIS spectroscopy, scanning electron (SEM) and atomic force microscopy (AFM) measurements. X-ray diffraction measurements have shown that ZnO films are mainly composed of (100), (002) and (101) orientation crystallites. The post-deposition thermal treatment at 600 °C temperature in air has shown that the composite of Zn/ZnO film was fully oxidized to ZnO film. The XRD spectra of the film deposited in oxygen atmosphere at room temperature present high intensity dominating peak at 2h = 36, 32° corresponding to the (101) ZnO diffraction peak. The small fraction of the film (7%) corresponds to the (002) peak intensity at 2h = 34, 42°. This result indicates the good crystal quality of the film and hexagonal wurtzite-type structure deposited by zinc wire explosion. The optical absorption spectra shows the bands at 374, 373 and 371 nm corresponding to deposition conditions. The SEM analysis shows that ZnO films presented different morphologies from fractal network to porous films depending on deposition conditions. AFM analysis revealed the grain size ranges from 50 nm to 500 nm. The nanoneedles up to 300 nm in length were found as typical structures in the film. It was demonstrated that the wire explosion technique is a feasible method to produce ZnO crystalline thin films and nanostructures.     

Synthesis of size-tunable ZnO nanorod arrays from NH3·H2O/ZnNO3 solutions

Well-aligned crystalline ZnO nanorod arrays were fabricated via an aqueous solution route with zinc nitrate and ammonia as precursors. Dip-coating was firstly utilized to form a ZnO film on ITO substrate as a seed layer for subsequent growth of ZnO nanorods. The effects of NH₃·H₂O/ZnNO₃ molar ratio, ZnNO₃ concentration, growth temperature and time on nanorod morphology were respectively investigated. It was found that the size of nanorod is mainly determined by the molar ratio and concentration. XRD demonstrates that ZnO nanorods are wurtzite crystal structures preferentially orienting in the direction of the c-axis. SEM confirms that ZnO nanorods grew up perpendicular to the substrate. The diameter and length were tunable in a broad range from 80 nm to 500 nm and 250 nm up to 8 μm, respectively. The aspect ratio changed from 3 to 17 mainly dependent on composition of the aqueous solution.