Effect of Al dopant concentration on structural,optical and photoconducting properties in nanostructured zinc oxide thin films

Thin films of undoped and doped ZnO, with different Al concentrations (1–5 wt%) were deposited onto glass substrates, by the sol–gel spin coating method. Grazing incidence X-ray diffraction (GIXRD) studies confirmed the nature of films as poly-crystalline, with typical hexagonal wurtzite structure. The films showed variation in crystallite size and change in relative intensities, upon different Al doping concentrations. The surface morphology of the films examined using FE-SEM, showed the grain size becoming smaller upon Al doping. The influence of Al with different concentrations, onto ZnO on the optical absorption and transmittance was studied using UV–Vis–NIR spectrophotometer in the wavelength range 300–2500 nm. The UV absorption shifted towards shorter wavelength upon Al doping. The average transmittance in the visible region increased for Al doped films up to 1–2 wt% and decreased for other concentration. The dark and photo conductivity measurements of the films indicated increase in the current values upon doping up to 1–2 wt% of Al and decreased for further concentrations. The rise and decay time measured from the photoresponse study, indicate larger values of rise time for the doped films compared to undoped ZnO. However, the film with 1–2 wt% doping of Al showed better response within the doping concentration. The thermal activation energy obtained from temperature-dependant conductivity showed decrease in the value upon Al doping up to 2 wt% and increased beyond this concentration in the temperature range 300–400 K.     

Electronic and chemical properties of ZnO in inverted organic photovoltaic devices

Photo-conversion efficiency of inverted polymer solar cells incorporating pulsed laser deposited ZnO electron transport layer have been found to significantly increase from 0.8% to up to 3.3% as the film thickness increased from 4 nm to 100 nm. While the ZnO film thickness was found to have little influence on the morphology of the resultant ZnO films, the band structure of ZnO was found to evolve only for films of thickness 25 nm or more and this was accompanied by a significant reduction of 0.4 eV in the workfunction. The films became more oxygen deficient with increased thickness, as found from X-ray photoelectron spectroscopy (XPS) and valence band XPS (VBXPS). We attribute the strong dependence of device performance to the zinc to oxygen stoichiometry within the ZnO layers, leading to improvement in the band structure of ZnO with increased thickness.     

Effects of annealing temperature of aqueous solution-processed ZnO electron-selective layers on inverted polymer solar cells

We investigate the effects of ZnO annealing temperature (T_A) on the performance of inverted polymer solar cells with ZnO electron-selective layers deposited by spin coating aqueous solutions of an ammine-hydroxo zinc complex. The inverted solar cells based on poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester with T_A as low as 80 °C exhibit power-conversion efficiencies of 3.6%, which is equal to those of devices with higher T_A. Characterizations of the ZnO films using X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, grazing incidence wide-angle X-ray scattering, and optical transmittance measurements show that the abrupt improvement of device performance from T_A = 60 to 80 °C is due to the improvement of energy-level alignment arising from the increases in the relative amount and the crystallinity of ZnO.     

The effects of carrier gas and substrate temperature on ZnO films prepared by ultrasonic spray pyrolysis

ZnO films were deposited on glass substrates in the temperature range of 350–470 °C under an atmosphere of compressed air or nitrogen (N₂) by using ultrasonic spray pyrolysis technique. Structural, electrical and optical properties of the ZnO films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical two-probe and optical transmittance measurements. The ZnO films deposited in the range of 350–430 °C were polycrystalline with the wurtzite hexagonal structure having preferred orientation depending on the substrate temperature. The ZnO films deposited below 400 °C had a preferred (100) orientation while those deposited above 400 °C mostly had a preferred (002) orientation. The resistivity values of ZnO films depended on the types of carrier gas. The ZnO thin films deposited under N₂ atmosphere in the range of 370–410 °C showed dense surface morphologies and resistivity values of 0.6–1.1 Ω-cm, a few orders of magnitude lower than those deposited under compressed air. Hydrogen substition in ZnO possibly contributed to decreasing resistivity in ZnO thin films deposited under N₂ gas. The Hall measurements showed that the behavior of ZnO films deposited at 410 °C under the N₂ atmosphere was n-type with a carrier density of 8.9–9.2×10¹⁶ cm^-3 and mobility of ～70 cm²/Vs. ZnO thin films showed transmission values at 550 nm wavelength in a range of 70–80%. The values of band gaps extrapolated from the transmission results showed bandgap shrinkage in an order of milli electron volts in ZnO films deposited under N₂ compared to those deposited under compressed air. The calculation showed that the bandgap reduction was possibly a result of carrier–carrier interactions.     

Organic photovoltaic cells with vertically aligned crystalline molecular nanorods

We demonstrate the growth of vertically aligned nanorod arrays of copper phthalocyanine (CuPc) using the oblique angle deposition technique in high vacuum. High density nanorods with diameters down to 20 nm have been achieved with either stationary or rotational substrates. X-ray diffraction reveals the polycrystalline nature of the CuPc nanorods. Photovoltaic cells have been fabricated by spin-coating [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) onto the CuPc nanorod films to form the active region, and scanning electron micrographs show excellent infiltration of PCBM molecules into the gaps between the CuPc nanorods. A maximum power conversion efficiency of η_p = (1.8 ± 0.1)% under 1 sun AM 1.5G illumination has been achieved in a device with ～40 nm long CuPc nanorods deposited on a 20 nm thick flat CuPc film, approximately twice of that of optimized bilayer CuPc/PCBM devices.     

Influence of Sn content on properties of ZnO:SnO2 thin films deposited by ultrasonic spray pyrolysis

The present work is devoted to the preparation of zinc oxide (ZnO): tin oxide (SnO₂) thin films by ultrasonic spray technique. A set of films are deposited using a solution formed with zinc acetate and tin chloride salts mixture with varied weight ratio R=[Sn/(Zn+Sn)]. The ratio R is varied from 0 to 100% in order to investigate the influence of Sn concentration on the physical properties of ZnO:SnO₂ films. The X rays diffraction (XRD) analysis indicated that films are composed of ZnO and SnO₂ distinct phases without any alloys or spinnel phase formations. The average grain size of crystallites varies with the ratio R from 17 to 20 nm for SnO₂ and from 24 to 40 nm for ZnO. The obtained films are highly transparent with a transmission coefficient equal to 80%. An increase in Sn concentration increases both the effective band gap energy from 3.2 to 4.01 eV and the photoluminescence intensity peak assigned defects to SnO₂. The films electrical characterization indicated that films are resistive. Their resistivities vary between 1.2×10² and 3.3×10⁴ (Ω cm). The higher resistivity is measured in film deposited with a ratio R equal to 50%.     

Deposition of aluminum oxide-doped zinc oxide transparent nano-films on glass substrates for electrostatic discharge applications

Aluminum oxide-doped zinc oxide (ZnO:Al₂O₃) transparent thin films were deposited by DC magnetron sputtering on glass substrates; film thickness can be correlated with deposition time. The effect of ZnO:Al₂O₃ film thickness on electrical properties, ultraviolet (UV) transmission, surface morphology and structure, solvent resistance, and scratch hardness was investigated. The surface roughness and crystallite size of deposited films increased from 0.75 to 2.22 nm and from 14 to 57 nm, respectively, as the film thickness was increased from 18 to 112 nm. In contrast, the percent UV transmission (% T) of ZnO:Al₂O₃ deposited glass plates at a wavelength of 365 nm increased when the film thickness was decreased. The electrical properties of nano-film deposited glass plates such as electrical resistance, tribo-charge voltage, and decay time were in the range of electrostatic discharge (ESD) specifications. The ZnO:Al₂O₃ nano-film deposited glass substrate possessed good acetone and iso-propanol resistance as well as high scratch hardness. This work opens up the possibility of using the ZnO:Al₂O₃ transparent ultra-thin film on glass substrate in ESD applications based on their excellent properties in terms of the relatively thin and adjustable ZnO:Al₂O₃ film thickness needed.     

Processing temperature dependent morphological and optical properties of ZnO nanorods

Zinc Oxide (ZnO) nanorods were synthesized by thermal decomposition of zinc acetate dihydrate at various processing temperatures. The morphology of samples, examined using transmission electron microscopy and field emission scanning electron microscopy, revealed large variations in length and diameter of nanorods. As temperature was increased from 300 °C to 450 °C, ZnO nanocrystal morphology changed from wire-like to rod-like. This morphology change is a result of competition between nucleation and growth rate in the vapor–solid growth mechanism of nanorods. Photoluminescence spectrum of the nanorods showed both band edge emission as well as native defect related visible emission. Relative intensity of UV and visible emission indicated crystal quality of the nanorods, the ratio increased upto 400 °C and deteriorated at higher processing temperature. It is argued that process induced defects dominate at processing temperatures ≤400 °C, whereas equilibrium concentration of native defects is high at temperatures >400 °C.     

Influence of In doping on the structural,optical and acetone sensing properties of ZnO nanoparticulate thin films

Indium-doped zinc oxide (ZnO) nanoparticle thin films were deposited on cleaned glass substrates by spray pyrolysis technique using zinc acetate dihydrate [Zn(CH₃COO)₂ 2H₂O] as a host precursor and indium chloride (InCl₃) as a dopant precursor. X-ray diffraction results show that all films are polycrystalline zinc oxide having hexagonal wurtzite structure. Upon In doping, the films exhibit reduced crystallinity as compared with the undoped film. The optical studies reveal that the samples have an optical band gap in the range 3.23–3.27 eV. Unlike the undoped film, the In-doped films have been found to have the normal dispersion for the wavelength range 450–550 nm. Among all the films investigated, the 1 at% In-doped film shows the maximum response 96.8% to 100 ppm of acetone in air at the operating temperature of 300 °C. Even at a lower concentration of 25 ppm, the response to acetone in this film has been found to be more than 90% at 300 °C, which is attributed to the smaller crystallite size of the film, leading to sufficient adsorption of the atmospheric oxygen on the film surface at the operating temperature of 300 °C. Furthermore, In-doped films show the faster response and recovery at higher operating temperatures. A possible reaction mechanism of acetone sensing has been explained.     

ZnO thin Films with blue emission grown using chemical spray pyrolysis

Photoluminescence in the characteristic blue-green region of the spectrum was emitted by zinc oxide (ZnO) thin films grown by chemical spray pyrolysis. We have been able to optimize spray rate and substrate temperature to obtain ZnO thin films with emission centered at ～383 nm and ～517 nm, respectively. We also observed that Al-doped ZnO films resulted in improved radiative efficiency of the near-band-edge emission; optimized Al-doped spray deposited thin films emitted only blue light.     

Top illuminated organic photodetectors with dielectric/metal/dielectric transparent anode

The top illuminated organic photodetectors (OPDs) with a Dielectric/Metal/Dielectric (DMD) transparent anode are fabricated. The transparent electrode is composed of molybdenum trioxide (MoO₃)/silver (Ag)/MoO₃ layers and zinc oxide (ZnO)/aluminum (Al) is used for bottom cathode. The optimized DMD electrode has an optical transmittance of 85.7% at the wavelength of 546 nm and sheet resistance of ∼6 Ω/sq. The fabricated OPDs exhibit a high detectivity and wide range linearity.     

Effect of pH on the properties of electrochemically prepared ZnO thin films

Zinc Oxide (ZnO) thin films have been electrochemically deposited on fluorine doped tin oxide (FTO) coated glass substrates from an aqueous electrolyte. Deposition potential −0.96 V was optimized by cyclic voltammetry experiment for slow scan rate 5 mV/s with moderate agitation of electrolyte. The effect of pH on the electrodeposition of ZnO is studied by cyclic voltammetry, X-ray diffraction (XRD), scanning electron microscopy (SEM), optical spectroscopy and photoelectrochemical I-t transient characteristics. It is revealed that the pH of the electrolyte has significant influence on the surface morphology and structural properties. Highly crystalline ZnO layers with hexagonal crystal structure deposited for all pH of the solutions. A systematic shift observed in the reflections (002) and (101) is correlated with an effective tensile strain developed in the crystal lattice. A remarkable improvement in the crystallinity was noticed in the as-deposited ZnO samples with increasing pH and upon heat treatment. Optical direct band gap ~ 3.26–3.33 eV and transmittance ~70 −80% was measured by optical spectroscopy. PL measurement showed the band edge emission at 375–382 nm and a visible light emission at 410–550 nm. The intensities of emission peaks are found to be affected by the pH of bath. The compact, densely packed and well adherent thin films of ZnO electrodeposited in zinc nitrate bath for pH 2.0, 3.5 and 6.0. The surface morphology has been changed from granular to disc shaped and finally a large hexagonal sheets were obtained with an increase in the pH of bath. Nearly stoichiometric ZnO thin films are electrodeposited at −0.96 V versus Ag/AgCl reference electrode for pH 6.0. The photoelectrochemical (PEC) measurement (I-t transient curve) shows the enhancement in photocurrent with increasing the pH of zinc nitrate solution. After heat treatment the photocurrent is increased by 54%, 98% and 130% in the samples deposited from 2.0, 3.5 and 6.0 pH of the bath. I-V measurements were further confirmed the current enhancement in all samples after heat treatment.     

Structural,surface morphology and optical properties of sputter-coated CaCu3Ti4O12 thin film: Influence of RF magnetron sputtering power

This study focusses on the investigation of RF power variations (100–300 W) effects on structural, morphological and optical properties of CaCu₃Ti₄O₁₂ thin film deposited on ITO/glass substrate in a non-reactive atmosphere (Ar). The increase of RF power from 100 W to 300 W led to evolution of (112), (022), (033), and (224) of CCTO XRD peaks. The results indicated that all the films were polycrystalline nature with cubic structure. The crystallite size increased from 20 nm to 25 nm with increasing RF power. FESEM revealed that the films deposited were uniform, porous with granular form, while the grain size increased from 30 to 50 nm. AFM analysis confirmed the increment in surface roughness from 1.6 to 2.3 nm with increasing film grain size. Besides, optical transmittance values decreased to minimum 70% with increasing RF power while optical energy bandgap increased from 3.20 eV to 3.44 eV. Therefore, favorable CCTO thin film properties can be possibly obtained for certain application by controlling RF magnetron sputtering power.     

Tuning optical,electrical and magnetic properties of fiber structured ZnO film by deposition temperature and precursor concentration

Highly transparent ZnO films were deposited on glass substrates using zinc acetate solution through cost effective spray pyrolysis method. A comprehensive study was carried out to understand the effects of deposition temperature and precursor concentrations on structure, surface morphology, optical, electrical and magnetic properties of the deposited films. All deposited films were polycrystalline in nature with hexagonal wurtzite structure. The films were preferentially oriented along (1 0 1) plane up to 723 K beyond which orientation changed to (0 0 2) plane. Irrespective of precursor concentration used, the films deposited at 673 K and 723 K showed fibrous structure. The films deposited at higher temperature led to enhanced transmittance and optical energy band gap. With higher precursor concentrations the transmittance decreased while the band gap increased. Photoluminescence studies revealed the presence of various defects leading to emission in the visible region apart from band to band transition near UV region. Lowest electrical resistivity was obtained for films deposited at 723 K which is of the order 10² Ω cm. At room temperature, all deposited films were diamagnetic while they were paramagnetic at 5 K.     

Low temperature Solution-Processed ZnO film on flexible substrate

Transparent conductive ZnO films were directly deposited on unseeded polyethersulfone (PES) substrates with a spin-spray method using aqueous solution at a low substrate temperature of 85 °C. All ZnO films were crystalline with wurtzite hexagonal structure and impurity phases were not detected. ZnO films deposited without citrate ions in the reaction solution had a rod array structure. In contrast, ZnO films deposited with citrate ions in the reaction solution had a continuous, dense structure. The transmittance of the ZnO films was improved from 11.9% to 85.3% as their structure changed from rod-like to continuous. After UV irradiation, the ZnO films with a continuous, dense structure had a low resistivity of 9.1×10⁻³ Ω cm, high carrier concentration of 2.7×10²⁰ cm⁻³ and mobility of 2.5 cm² V⁻¹ s⁻¹.     

ZnO nano-ridge structure and its application in inverted polymer solar cell

We report a unique nano-ridge structure of zinc oxide (ZnO) and its application in high performance inverted polymer solar cells. The ZnO nano-ridge structure was formed by a sol–gel process using a ramp annealing method. As the solvent slowly evaporated due to the low heating rate, there was sufficient time for the gel particles to structurally relax and pile up, resulting in a dense and undulated film. Nano-ridges with peak as high as 120 nm and valley to valley distance of about 500 nm were formed. This film provided an effective hole blocking layer and also an increased interfacial area for electron collection. An inverted bulk heterojunction polymer solar cell was fabricated using the ZnO nano-ridge film as the electron collecting layer. The device showed a high power conversion efficiency of 4.00%, an improvement of about 25% over similar solar cells made with a planar film of ZnO nanoparticles.     

Effect of thickness on the structural,optical and electrical properties of RF magnetron sputtered GZO thin films

Gallium-doped zinc oxide (GZO) thin films with very high conductivity and transparency were successfully deposited by RF magnetron sputtering at a substrate temperature of 400 °C. The dependence of the film properties over the thickness was investigated. X-ray diffraction (XRD) results revealed the polycrystalline nature of the films with hexagonal wurtzite structure having preferential orientation along [001] direction normal to the substrate. The lowest resistivity obtained from electrical studies was 5.4×10⁻⁴ Ω cm. The optical properties were studied using a UV–vis spectrophotometer and the average transmittance in the visible region (400–700 nm) was found to be 92%, relative to the transmittance of a soda–lime glass reference for a GZO film of thickness 495 nm and also the transparency of the films decreases in the near IR region of the spectra. The mobility of the films showed a linear dependence with crystallite size. GZO film of thickness 495 nm with the highest figure of merit indicates that the GZO film is suitable as an ideal transparent conducting oxide (TCO) material for solar cell applications.     

Surfactant free hydrothermally derived ZnO nanowires,nanorods, microrods and their characterization

ZnO nanowires, nanorods and microrods have been prepared by an organic-free hydrothermal process using ZnSO₄ and NaOH/NH₄OH solutions. The powder X-ray diffraction (PXRD) patterns reveal that the ZnO nano/microrods are of hexagonal wurtzite structure. The Fourier transform infrared (FT-IR) spectrum of ZnO powder shows only one significant spectroscopic band at around 417 cm^?1 associated with the characteristic vibrational mode of Zn–O bonding. The thickness 75–300 nm for ZnO nanorods and 0.2–1.8 μm for microrods are identified from SEM/TEM images. UV–visible absorption spectra of ZnO nano/microrods show the blue shift. The UV band and green emission observed in photoluminescence (PL) spectra are due to free exciton emission and singly ionized oxygen vacancy in ZnO. Finally, the mechanism for organic-free hydrothermal synthesis of the ZnO nano/microrods is discussed.     

Properties of cobalt-doped zinc oxide thin films grown by pulsed laser deposition on glass substrates

Undoped and cobalt-doped zinc oxide (CZO) polycrystalline piezoelectric thin films (Co: 3, 5 at.%) using a series of high quality ceramic targets have been deposited at 450 °C onto glass substrates using a pulsed laser deposition method. The used source was a KrF excimer laser (248 nm, 25 ns, 2 J∕cm²). X-ray diffraction patterns showed that the Co-doped ZnO films crystallize in a hexagonal wurtzite type structure with a strong (0 orientation, and the grain sizes calculated from these patterns decrease from 37 to 31 nm by increasing Co doping. The optical waveguiding properties of the films were characterized by using a 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. With the aim of study the optical properties of the ZnO films, an accurate refractive index and thickness measurement apparatus was set up, which is called M-lines device. An evaluation of experimental uncertainty and calculation of the precision of the refractive index and thickness were developed on ZnO films. The optical transmittance spectra showed a good transparency in the visible region. Calculated optical band gap varying from 3.23 to 3.37 eV when the content of Co doping increases from 0 to 5 at.%.     

Study on the thermal stability of Ga-doped ZnO thin film: A transparent conductive layer for dye-sensitized TiO2 nanoparticles based solar cells

Generally, optoelectronic devices are fabricated at a high temperature. So the stability of properties for transparent conductive oxide (TCO) films at such a high temperature must be excellent. In the paper, we investigated the thermal stability of Ga-doped ZnO (GZO) transparent conductive films which were heated in air at a high temperature up to 500 °C for 30 min. After heating in air at 500 °C for 30 min, the lowest sheet resistance value for the GZO film grown at 300 °C increased from 5.5 Ω/sq to 8.3 Ω/sq, which is lower than 10 Ω/sq. The average transmittance in the visible light of all the GZO films is over 90%, and the highest transmittance is as high as 96%, which is not influenced by heating. However, the transmittance in the near-infrared (NIR) region for the GZO film grown at 350 °C increases significantly after heating. And the grain size of the GZO film grown at 350 °C after annealing at 500 °C for 30 min is the biggest. Then dye-sensitized TiO2 NPs based solar cells were fabricated on the GZO film grown at 350 °C (which exhibits the highest transmittance in NIR region after heating at 500 °C for 30 min) and 300 °C (which exhibits the lowest sheet resistance after heating at 500 °C for 30 min). The dye-sensitized solar cell (DSSC) fabricated on the GZO film grown at 350 °C exhibits superior conversion efficiency. Therefore, transparent conductive glass applying in DSSCs must have a low sheet resistance, a high transmittance in the ultraviolet–visible–infrared region and an excellent surface microstructure.