Structural and optical properties of ZnO and Al-doped ZnO microrods obtained by spray pyrolysis method using different solvents

ZnO and Al-doped ZnO microrods were obtained by spray pyrolysis method using different solvents such as methanol and propanol. The effect of the type of solvent in the starting solution on the structural, morphological and optical properties of the samples was investigated. X-ray diffraction patterns showed that the undoped and Al-doped ZnO microrods exhibited hexagonal crystal structure with a preferred orientation along (0 0 2) direction. Surface morphology of the samples obtained by scanning electron microscopy revealed that undoped and Al-doped ZnO microrods grew as quasi-aligned hexagonal shaped microrods with diameters varying between 0.7 and 1.3 μm irrespective of solvents used. Optical studies indicated that microrods had a low transmittance (≅30%) and the band gap increased from 3.24 to 3.26 eV upon Al doping. Photoluminescence measurements indicated the existence of two emission bands in the spectra: one sharp ultraviolet luminescence at ∼383 nm and one broad visible emission ranging from 420 to 580 nm.     

ZnO nanorods/plates on Si substrate grown by low-temperature hydrothermal reaction

The zinc oxide (ZnO) nanorods/plates are obtained via hydrothermal method assisted by etched porous Al film on Si substrate. The products consist of nanorods with average diameter of 100 nm and nanoplates with thickness of 200-300 nm, which are uniformly distributed widely and grown perpendicularly to the substrate. The ZnO nanoplates with thickness of 150-300 nm were grown on Si substrate coated with a thin continuous Al film (without etching) in the same aqueous solution. The growth mechanism and room temperature photoluminescence (PL) properties of ZnO nanorods/plates and nanoplates were investigated. It is found that the introduction of the etched Al film plays a key role in the formation of ZnO nanorods/plates. The annealing process is favorable to enhance the UV PL emissions of the ZnO nanorods/plates.     

Catalyst-free synthesis and luminescence of aligned ZnO nanorods

Quasi-aligned undoped ZnO nanorods with diameter in the range 100–300 nm and length of several micrometers have been grown catalyst-free on Si(1 0 0) wafer in a one-step process by direct heating of Zn powders. All nanowires are single crystals and are aligned vertically to the substrate surface with c-axis preferred orientation. XRD, HRTEM and Raman studies revealed that the ZnO nanorods have wurtzite phase, are highly crystalline and well aligned with the lattice parameters a=0.32 nm and c=0.52 nm. The PL spectra measured at different temperatures are dominated by excitonic emission at 380 nm and less intense below band gap emission band centered at 520 nm.     

Characterisation of porous doped ZnO thin films deposited by spray pyrolysis technique

Al or Sn doped ZnO films were deposited by spray pyrolysis using aqueous solutions. The films were deposited on either indium tin oxide coated or bare glass substrates. ZnCl₂, AlCl₃ and SnCl₂ were used as precursors. The effect of ZnCl₂ molar concentration (0.1-0.3 M) and doping percentage (2-4% AlCl₃ or SnCl₂) have been investigated. The main goal of this work being to grow porous ZnO thin films, small temperature substrates (200-300 °C) have been used during the spray pyrolysis deposition. It is shown that, if the X-ray diffraction patterns correspond to ZnO, the films deposited onto bare glass substrate are only partly crystallized while those deposited onto ITO coated glass substrate exhibit better crystallization. The homogeneity of the films decreases when the molar concentration of the precursor increases, while the grain size and the porosity decrease when the Al doping increases. The optical study shows that band tails are present in the absorption spectrum of the films deposited onto bare glass substrate, which is typical of disordered materials. Even after annealing 4 h at 400 °C, the longitudinal resistivity of the films is quite high. This result is attributed to the grain boundary effect and the porosity of the films. Effectively, the presence of an important reflection in the IR region in samples annealed testifies of a high free-carriers density in the ZnO crystallites. Finally it is shown that when deposited in the same electrochemical conditions, the transmission of a polymer film onto the rough sprayed ZnO is smaller than that onto smooth sputtered ZnO.     

Mole-controlled growth of Y-doped ZnO nanostructures by hydrothermal method

We investigated the mole-controlled growth of Y-doped ZnO (YZO) nanostructures by the hydrothermal synthesis techniques. Through controlling the aqueous solution's mole concentration, we could modify the morphological and structural properties of YZO. The shape of YZO becomes a nanometer-sized rod when using a relatively low mole concentration, whereas the morphology is changed to be flat and mosaic when using a relatively high mole concentration. Since the aqueous solution's mole concentration decides the amount of hydroxide, we ascribe the mole-controlled morphological changes to the alteration of chemical potential during the hydrothermal chemical reaction.     

Hydrogen-free spray pyrolysis chemical vapor deposition method for the carbon nanotube growth: Parametric studies

Spray pyrolysis chemical vapor deposition (CVD) in the absence of hydrogen at low carrier gas flow rates has been used for the growth of carbon nanotubes (CNTs). A parametric study of the carbon nanotube growth has been conducted by optimizing various parameters such as temperature, injection speed, precursor volume, and catalyst concentration. Experimental observations and characterizations reveal that the growth rate, size and quality of the carbon nanotubes are significantly dependent on the reaction parameters. Scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy techniques were employed to characterize the morphology, structure and crystallinity of the carbon nanotubes. The synthesis process can be applied to both semiconducting silicon wafer and conducting substrates such as carbon microfibers and stainless steel plates. This approach promises great potential in building various nanodevices with different electron conducting requirements. In addition, the absence of hydrogen as a carrier gas and the relatively low synthesis temperature (typically 750 °C) qualify the spray pyrolysis CVD method as a safe and easy way to scale up the CNT growth, which is applicable in industrial production.     

Cathodoluminescent and nonlinear optical properties of undoped and erbium doped nanostructured ZnO films deposited by spray pyrolysis

We have deposited zinc oxide (ZnO) and erbium doped zinc oxide (ZnO:Er) thin films on heated glass substrates using spray pyrolysis technique. The effect of erbium dopant on structural, morphological, luminescent and nonlinear optical properties was studied. The deposited films have been analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), ex situ compositional analysis (ESCA), profilometry, cathodoluminescence (CL) and third harmonic generation (THG) measurements. All films were polycrystalline, having a preferential growth orientation along the ZnO (0 0 2) plane, with a corresponding average crystallite size of less than 41 nm. Addition of erbium can effectively control the film surface morphology and its cathodoluminescent properties. The films containing low erbium concentration show a uniform surface covered with hexagonal shaped grains and a strong UV light emission intensity as well as TH response. In contrast, when the erbium doping ratio exceeds 3%, a porous surface with columnar textural growth becomes more pronounced, and a substantial reduction of the cathodoluminescent and TH response. A strong TH signal was obtained for the film with good crystalline quality at the concentration of 2%. Third order nonlinear optical susceptibility (χ^〈3〉) values of the studied materials were in the remarkable range of 10⁻¹² esu.     

Homogeneous ZnO Nanoparticles by Flame Spray Pyrolysis

Zinc oxide (ZnO) nanoparticles were made by flame spray pyrolysis (FSP) of zinc acrylate–methanol–acetic acid solution. The effect of solution feed rate on particle specific surface area (SSA) and crystalline size was examined. The average primary particle diameter can be controlled from 10 to 20nm by the solution feed rate. All powders were crystalline zincite. The primary particle diameter observed by transmission electron microscopy (TEM) was in agreement with the equivalent average primary particle diameter calculated from the SSA as well as with the crystalline size calculated from the X-ray diffraction (XRD) patterns for all powders, indicating that the primary particles were rather uniform in diameter and single crystals. Increasing the solution feed rate increases the flame height, and therefore coalescence and/or surface growth was enhanced, resulting in larger primary particles. Compared with ZnO nanoparticles made by other processes, the FSP-made powder exhibits some of the smallest and most homogeneous primary particles. Furthermore, the FSP-made powder has comparable BET equivalent primary particle diameter with but higher crystallinity than sol–gel derived ZnO powders.     

Effect of different dopant elements (Al,Mg and Ni) on microstructural,optical and electrochemical properties of ZnO thin films deposited by spray pyrolysis (SP)

In the present work we studied the influence of the dopant elements and concentration on the microstructural and electrochemical properties of ZnO thin films deposited by spray pyrolysis. Transparent conductive thin films of zinc oxide (ZnO) were prepared by the spray pyrolysis process using an aqueous solution of zinc acetate dehydrate [Zn(CH₃COO)₂·2H₂O] on soda glass substrate heated at 400 ± 5 °C. AlCl₃, MgCl₂ and NiCl₂ were used as dopant. The effect of doping percentage (2–4%) has been investigated. Afterwards the samples were thermally annealed in an ambient air during one hour at 500 °C. X-ray diffraction showed that films have a wurtzite structure with a preferential orientation along the (0 0 2) direction for doped ZnO. The lattice parameters a and c are estimated to be 3.24 and 5.20 ?, respectively. Transmission allowed to estimate the band gaps of ZnO layers. The electrochemical studies revealed that the corrosion resistance of the films depended on the concentration of dopants.     

Sensing of LPG with nanostructured zinc oxide thin films grown by spray pyrolysis technique

Nanostructured zinc oxide thin films were prepared by spray pyrolysis technique using Zn(NO₃)₂·6H₂O as the precursor solution. The resulting films were investigated by X-ray diffraction and scanning electron microscopy to know crystal structure, size of crystallites and surface morphology. The films have been found to be polycrystalline zinc oxide, possessing hexagonal wurtzite crystal structure and nanocrystallite with grain size of approximately 30-35 nm. The LPG sensing performance of the films has been investigated at various concentrations of LPG in air at operating temperatures varying from 225 to 400 °C. At 325 °C the maximum responses of 46.3% and 48.9% have been observed, respectively, for concentrations of 0.8 and 1 vol% of LPG in air (1 vol% of LPG in air corresponds to 50% LEL of LPG in air). The recovery time has been found to be less than the response time for all concentrations of LPG. A possible reaction mechanism of LPG sensing has been proposed.     

Nanocrystalline ZnO film deposited by ultrasonic spray on textured silicon substrate as an anti-reflection coating layer

A ZnO thin film was successfully synthesized on glass, flat surface and textured silicon substrates by chemical spray deposition. The textured silicon substrate was carried out using two solutions (NaOH/IPA and Na₂CO₃). Textured with Na₂CO₃ solution, the sample surface exhibits uniform pyramids with an average height of 5 μm. The properties and morphology of ZnO films were investigated. X-ray diffraction (XRD) spectra revealed a preferred orientation of the ZnO nanocrystalline film along the c-axis where the low value of the tensile strain 0.26% was obtained. SEM images show that all films display a granular, polycrystalline morphology. The morphology of the ZnO layers depends dramatically on the substrate used and follows the contours of the pyramids on the substrate surface. The average reflectance of the textured surface was found to be around 13% and it decreases dramatically to 2.57% after deposition of a ZnO antireflection coating. FT-IR peaks arising from the bonding between Zn–O are clearly represented using a silicon textured surface. A very intense photoluminescence (PL) emission peak is observed for ZnO/textured Si, revealing the good quality of the layer. The PL peak at 380.5 nm (UV emission) and the high-intensity PL peak at 427.5 nm are observed and a high luminescence occurs when using a textured Si substrate.     

Photoluminescence and photoelectrochemical properties of nanocrystalline ZnO thin films synthesized by spray pyrolysis technique

A simple and inexpensive spray pyrolysis technique (SPT) was employed for the synthesis of nanocrystalline zinc oxide (ZnO) thin films onto soda lime glass and tin doped indium oxide (ITO) coated glass substrates at different substrate temperatures ranging from 300 °C to 500 °C. The synthesized films were polycrystalline, with a (0 0 2) preferential growth along c-axis. SEM micrographs revealed the uniform distribution of spherical grains of about 80-90 nm size. The films were transparent with average visible transmittance of 85% having band gap energy 3.25 eV. All the samples exhibit room temperature photoluminescence (PL). A strong ultraviolet (UV) emission at 398 nm with weak green emission centered at 520 nm confirmed the less defect density in the samples. Moreover, the samples are photoelectrochemically active and exhibit the highest photocurrent of 60 μA, a photovoltage of 280 mV and 0.23 fill factor (FF) for the Zn₄₅₀ films in 0.5 M Na₂SO₄ electrolyte, when illuminated under UV light.     

Fabrication of ZnO nanorod array-based photodetector with high sensitivity to ultraviolet

Large scale densely packed and vertically oriented ZnO nanorod arrays were grown on F-doped SnO₂ (FTO) substrates through a simple hydrothermal synthesis route. Based on the arrays of hexagonal ZnO nanorod with size of 60100 nm in diameter, and 1.5 μm in length, a prototypical photoelectrical device was fabricated for ultraviolet detection, showing good reproducibility and a large photocurrent of around 6.71 mA at the applied voltage of 0.4 V. The large photocurrent and the ohmic I–V characteristics of the ZnO nanorods under the illumination could be ascribed to the decrease of the barrier height among the ZnO nanorods and the Schottky barrier between the nanorods and the Au electrodes and, in particular, to the accumulation of conduction electrons, resulted from the neutralization between photogenerated holes and negatively charged oxygen ions. The photoresponse curve is well fitted to an exponential curve with the relaxation time constant of 9 s in rising edge and 90 s in decaying one, representing the accumulation of conduction electrons. These well-aligned ZnO nanostructures of high quality could be easily fabricated by a cost-effective chemical route and used for constructing nanoscale devices with excellent performances.     

Spray deposition of highly transparent fluorine doped cadmium oxide thin films

The cadmium oxide (CdO) and F:CdO films have been deposited by spray pyrolysis method using cadmium acetate and ammonium fluoride as precursors for Cd and F ions, respectively. The effect of temperature and F doping on the structural, morphological, optical and Hall effect properties of sprayed CdO thin films was investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), optical absorption and electrical measurement techniques. TGA and DTA studies, indicates the formation of CdO by decomposition of cadmium acetate after 250 °C. XRD patterns reveal that samples are polycrystalline with cubic structure and exhibits (2 0 0) preferential orientation. Considerable broading of (2 0 0) peak, simultaneous shifting of corresponding Bragg's angle have been observed with respect to F doping level. SEM and AFM show the heterogeneous distribution of cubical grains all over the substrate, which are randomly distributed. F doping shifts the optical gap along with the increase in the transparency of CdO films. The Hall effect measurement indicates that the resistivity and mobility decrease up to 4% F doping.     

PL and EL characterizations of ZnO:Eu, Li films derived by sol-gel process

ZnO:Eu³⁺, Li⁺ films prepared by the dip-coating method were characterized by photoluminescence (PL) and electroluminescence (EL). When the ZnO:Eu³⁺, Li⁺ films were excited using UV light with energy corresponding to the band-to-band excitation of the host matrix, the PL spectra showed emissions from both ZnO and Eu³⁺ ions, while their EL spectra showed emissions only from Eu³⁺ ions, and no emission from ZnO could be detected. It is found that the EL emission intensity B is dependent on the applied voltage, B=B_o exp(−bV^−1/2). With increasing frequency, the EL intensity dramatically increases at lower frequencies (<1000 Hz), and then increases gradually at higher frequencies (>1000 Hz).     

Pulsed laser deposited ZnO/ZnO:Li multilayer for blue light emitting diodes

Thin films of ZnO, Li doped ZnO (ZLO) and multilayer of ZnO and ZLO (ZnO/ZLO) were grown on silicon and corning glass substrates by pulsed laser deposition technique. Single phase formation and the crystalline qualities of the films were analyzed by X-ray diffraction and Li composition in the film was investigated to be 15 wt% by X-ray photoelectron spectroscopy. Raman spectrum reveals the hexagonal wurtzite structure of ZnO, ZLO and ZnO/ZLO multilayer and confirms the single phase formation. Films grown on corning glass shows more than 80% transmittance in the visible region and the optical band gaps were calculated to be 3.245, 3.26 and 3.22 eV for ZnO, ZLO and ZnO/ZLO, respectively. An efficient blue emission was observed in all films which were grown on silicon (1 0 0) substrate by photoluminescence (PL). PL measurements at different temperatures reveal that the PL emission intensity of ZnO/ZLO multilayer was weakly dependent on temperature as compared to the single layers of ZnO and ZLO and the wavelength of emission was independent of temperature. Our results indicate that ZnO/ZLO multilayer can be used for the fabrication of blue light emitting diodes.     

Radio frequency plasma enhanced chemical vapor based ZnO thin film deposition on glass substrate: A novel approach towards antibacterial agent

In the present study, the structural, optical and antibacterial properties of ZnO thin films are reported. ZnO thin films are deposited on borosilicate glass substrates by radio frequency plasma enhanced chemical vapor deposition (PECVD) using oxygen as process gas. The crystallinity of the deposited films is improved upon annealing at 450 °C in air for 1.5 h and the polycrystalline nature of the films is further confirmed by selected area electron diffraction. The particle size of the annealed film (thickness 476 nm) is found to be ∼34 nm from the transmission electron microscopic observation. Energy dispersive X-ray spectrum indicates the stoichiometric deposition of ZnO films. The films are highly transparent (transmittance >85%) in the visible region of electromagnetic spectrum. The films exhibit excellent antibacterial effect towards the growth of Escherichia coli and Pseudomonas aeruginosa.     

Influence of Al doping on microstructure,morphology, optical and photoluminescence properties of pyrolytic ZnO thin films prepared in an ambient atmosphere

Zinc oxide (ZnO) and aluminium (Al) doped zinc oxide (AZO) thin films have been fabricated by spray pyrolysis technique in normal atmospheric condition. Samples of different Al-concentrations (0–5% Al) were deposited at 350 °C onto glass substrate to study the structural, morphological, optical and photoluminescence properties. X-ray diffraction study confirms that the films are polycrystalline having hexagonal structure. SEM images show that the films have rope and tube like morphology. Optical properties, such as transmittance, optical band gap, extinction coefficient, refractive index, optical conductivity, dielectric constants and electron energy loss functions were analyzed and discussed. Results show that the optical parameters have been changed significantly with Al-doping concentration. The photoluminescence spectra indicate that the PL peaks originated from deep level emissions (DLE) with different intensities for ZnO and Al-doped ZnO films.     

On single doping and co-doping of spray pyrolysed ZnO films: Structural, electrical and optical characterisation

In this paper we present studies on ZnO thin films (prepared using Chemical Spray pyrolysis (CSP) technique) doped in two different ways; in one set, ‘single doping’ using indium was done while in the second set, ‘co-doping’ using indium and fluorine was adopted. In the former case, effect of in-situ as well as ex-situ doping using In was analyzed. Structural (XRD studies), electrical (I-V measurements) and optical characterizations (through absorption, transmission and photoluminescence studies) of the films were done. XRD analysis showed that, for spray-deposited ZnO films, ex-situ doping using Indium resulted in preferred (0 0 2) plane orientation, while in-situ doping caused preferred orientation along (1 0 0), (0 0 2), (1 0 1) planes; however for higher percentage of in-situ doping, orientation of grains changed from (0 0 2) plane to (1 0 1) plane. The co-doped films had (0 0 2) and (1 0 1) planes. Lowest resistivity (2 × 10⁻³ Ω cm) was achieved for the films, doped with 1% Indium through in-situ method. Photoluminescence (PL) emissions of ex-situ doped and co-doped samples had two peaks; one was the ‘near band edge’ emission (NBE) and the other was the ‘blue-green’ emission. But interestingly the PL emission of in-situ doped samples exhibited only the ‘near band edge’ emission. Optical band gap of the films increased with doping percentage, in all cases of doping.     

Characterization of nitrogen-doped ZnO thin films grown by plasma-assisted pulsed laser deposition on sapphire substrates

The crystalline, optical and electrical properties of N-doped ZnO thin films were measured using X-ray diffraction, photoluminescence and Hall effect apparatus, respectively. The samples were grown using pulsed laser deposition on sapphire substrates coated priorly with ZnO buffer layers. For the purpose of acceptor doping, an electron cyclotron resonance (ECR) plasma source operated as a low-energy ion source was used for nitrogen incorporation in the samples. The X-ray diffraction analyses indicated some deterioration of the ZnO thin film with nitrogen incorporation. Temperature-dependent Van der Pauw measurements showed consistent p-type behavior over the measured temperature range of 200–450 K, with typical room temperature hole concentrations and mobilities of 5×10¹⁵ cm⁻³ and 7 cm²/V s, respectively. Low temperature photoluminescence spectra consisted of a broad emission band centered around 3.2 eV. This emission is characterized by the absence of the green deep-defect band and the presence of a band around 3.32 eV.