High quality nitrogen-doped zinc oxide thin films grown on ITO by sol–gel method

Highly transparent N-doped ZnO thin films were deposited on ITO coated corning glass substrate by sol–gel method. Ammonium nitrate was used as a dopant source of N with varying the doping concentration 0, 0.5, 1.0, 2.0 and 3.0 at%. The DSC analysis of prepared NZO sols is observed a phase transition at 150 °C. X-ray diffraction pattern showed the preferred (002) peak of ZnO, which was deteriorated with increased N concentrations. The transmittance of NZO thin films was observed to be ~88%. The bandgap of NZO thin films increased from 3.28 to 3.70 eV with increased N concentration from 0 to 3 at%. The maximum carrier concentration 8.36×10¹⁷ cm⁻³ and minimum resistivity 1.64 Ω cm was observed for 3 at% N doped ZnO thin films deposited on glass substrate. These highly transparent ZnO thin films can be used as a window layer in solar cells and optoelectronic devices.     

Effect of GZO thickness and annealing temperature on the structural,electrical and optical properties of GZO/Ag/GZO sandwich films

The GZO/Ag/GZO sandwich films were deposited on glass substrates by RF magnetron sputtering of Ga-doped ZnO (GZO) and ion-beam sputtering of Ag at room temperature. The effect of GZO thickness and annealing temperature on the structural, electrical and optical properties of these sandwich films was investigated. The microstructures of the films were studied by X-ray diffraction (XRD). X-ray diffraction measurements indicate that the GZO layers in the sandwich films are polycrystalline with the ZnO hexagonal structure and have a preferred orientation with the c-axis perpendicular to the substrates. For the sandwich film with upper and under GZO thickness of 40 and 30 nm, respectively, it owns the maximum figure of merit of 5.3 × 10⁻² Ω⁻¹ with a resistivity of 5.6 × 10⁻⁵ Ω cm and an average transmittance of 90.7%. The electrical property of the sandwich films is improved by post annealing in vacuum. Comparing with the as-deposited sandwich film, the film annealed in vacuum has a remarkable 42.8% decrease in resistivity. The sandwich film annealed at the temperature of 350 °C in vacuum shows a sheet resistance of 5 Ω/sq and a transmittance of 92.7%, and the figure of merit achieved is 9.3 × 10⁻² Ω⁻¹.     

Epitaxial ZnO thin films grown by pulsed electron beam deposition

In this work, the pulsed electron beam deposition method (PED) is evaluated by studying the properties of ZnO thin films grown on c-cut sapphire substrates. The film composition, structure and surface morphology were investigated by means of Rutherford backscattering spectrometry, X-ray diffraction and atomic force microscopy. Optical absorption, resistivity and Hall effect measurements were performed in order to obtain the optical and electronic properties of the ZnO films. By a fine tuning of the deposition conditions, smooth, dense, stoichiometric and textured hexagonal ZnO films were epitaxially grown on (0001) sapphire at 700 °C with a 30° rotation of the ZnO basal plane with respect to the sapphire substrate. The average transmittance of the films reaches 90% in the visible range with an optical band gap of 3.28 eV. Electrical characterization reveals a high density of charge carrier of 3.4 × 10¹⁹ cm^?3 along with a mobility of 11.53 cm²/Vs. The electrical and optical properties are discussed and compared to ZnO thin films prepared by the similar and most well-known pulsed laser deposition method.     

Properties of nano-ZnO/poly(vinyl alcohol)/poly(ethylene oxide) composite thin films

A series of poly(vinyl alcohol)/nano-ZnO composites were prepared by dispersing nano-ZnO in aqueous solutions containing mixtures of the biodegradable polymers poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO), and composite thin films were prepared by casting. The introduction of nano-ZnO into PVA/PEO mixed solutions significantly decreased the resistivity of the solutions. Ultraviolet absorption, thermal behaviour and visco-elastic properties of the thin films were determined as a function of nano-ZnO content up to 15 wt%. Optimum film properties were obtained with 1 wt% nano-ZnO, higher proportions of nano-ZnO resulting in agglomeration of ZnO particles and deterioration in film properties. The Forouhi and Bloomer model was used for the modelling of ZnO thin films.     

Highly flexible,transparent, conductive and antibacterial films made of spin-coated silver nanowires and a protective ZnO layer

We prepared highly flexible, transparent, conductive and antibacterial film by spin coating a silver nanowire suspension on a poly (ethylene terephthalate) (PET) substrate. The ZnO layer covered the conductive silver nanowire (AgNW) network to protect the metal nanowires from oxidization and enhance both wire-to-wire adhesion and wire-to-substrate adhesion. It is found that the number of AgNW coatings correlates with both the sheet resistance (R_s) and the transmittance of the AgNW/ZnO composite films. An excellent 92% optical transmittance in the visible range and a surface sheet resistance of only 9 Ω sq⁻¹ has been achieved, respectively. Even after bending 1000 times (5 mm bending radius), we found no significant change in the sheet resistance or optical transmittance. The real-time sheet resistance measured as a function of bending radius also remains stable even at the smallest measured bending radius (1 mm). The AgNW/ZnO composite films also show antibacterial effects which could be useful for the fabrication of wearable electronic devices.     

Characteristics of ZnO:In thin films prepared by RF magnetron sputtering

In-doped ZnO (ZnO:In) transparent conductive thin films were deposited on glass substrates by RF magnetron sputtering. The effect of substrate temperature on the structural, electrical and optical properties of the ZnO:In thin films was investigated. It was found that higher temperature improves the crystallinity of the films and promotes In substitution easily. ZnO:In thin films with the best crystal quality were fabricated at 300 °C, which exhibit a larger grain size of 29 nm and small tensile strain of 0.9%. The transmittance of all the films was revealed to be over 85% in the visible range independence of the substrate temperatures and the lowest resistivity of ZnO:In thin films is 2.4×10⁻³ Ω cm.     

Microstructure and characterization of Al-doped ZnO films prepared by RF power sputtering on Al and ZnO targets

Al-doped zinc oxide (AZO) transparent conductive films were prepared on a glass substrate using a magnetron sputtering system with a pure zinc oxide (ZnO) target and a pure Al target sputtered using radio frequency (RF) power. The RF power was set at 100 W for the ZnO target and varied from 20 to 150 W for the Al target. The morphology of the thin films was examined by field-emission scanning electron microscope (FE-SEM), and their composition was analyzed by the equipped energy-dispersive X-ray spectroscopy (EDS). The cross section of the films determined through FE-SEM indicated that their thickness was around 650 nm. EDS analysis revealed that the Al-dopant concentration of the AZO films increased in the following order: 0.85 at.% (20 W) < 1.60 at.% (40 W) < 3.52 at.% (100 W) < 4.34 at.% (150 W). Analysis of the films using X-ray diffractometer (XRD) indicated that all films had a wurtzite structure with a texture of (0 0 2). High-resolution transmission electron microscopy (HRTEM) revealed a number of defects in the films, such as stacking faults and dislocations. Ultraviolet photoelectron spectroscopy (UPS) was used to estimate the optical energy gap (E_g) for the AZO thin films. The energy gap increases from 3.39 to 3.58 eV as the RF power applied to the Al target increase. The electrical resistivity of the films decreased from 3.43 × 10^?2 Ω cm to 3.29 × 10^?3 Ω cm as the RF power increased from 20 to 150 W when a four-point probe was used to investigate. Atomic force microscope (AFM) revealed that the surface roughness of the films increased with increasing RF power. The average optical transmittance of the films was determined by UV–visible spectrometer. The films are suitable for use as transparent conductive oxide films in the optoelectronic industry. A decrease in the electrical resistivity of the film with increasing Al-dopant concentration was ascribed to an increase in the carrier concentration and density of stacking faults in the films.     

AZO/Ag/AZO multilayer films prepared by DC magnetron sputtering for dye-sensitized solar cell application

Ag films were deposited on Al-doped ZnO (AZO) films and coated with AZO to fabricate AZO/Ag/AZO multilayer films by DC magnetron sputtering on glass substrates without heating of glass substrates. The best multilayer films have low sheet resistance of 19.8 Ω/Sq and average transmittance values of 61% in visible region. It was found that the highest figure of merit (F_TC) is 6.9 × 10⁻⁴ Ω⁻¹. For the dye-sensitized solar cell (DSSC) application, the multilayer films were used as transparent conductive electrode (multilayer films/ZnO + Eosin-Y/LiI + I₂/Pt/FTO). The best DSSC based on the multilayer films showed that open circuit voltage (V_oc) of 0.47 V, short circuit current density (J_sc) of 2.24 mA/cm², fill factor (FF) of 0.58 and incident photon-to-current conversion efficiency (η) of 0.61%. It was shown that the AZO/Ag/AZO multilayer films have potential for application in DSSC.     

Comparative study on structural and optical properties of ZnO thin films prepared by PLD using ZnO powder target and ceramic target

Zinc oxide thin films have been obtained in O₂ ambient at a pressure of 1.3 Pa by pulsed laser deposition (PLD) using ZnO powder target and ceramic target. The effect of temperature on structural and optical properties of ZnO thin films was investigated systematically by XRD, SEM, FTIR and PL spectra. The results show that the best structural and optical properties can be achieved for ZnO thin film fabricated at 700 °C using powder target and at 400 °C using ceramic target, respectively. The PL spectrum reveals that the efficiency of UV emission of ZnO thin film fabricated by using powder target is low, and the defect emission of ZnO thin film derived from Zn_i and O_i is high.     

Nonlinear optical properties of erbium doped zinc oxide (EZO) thin films

Undoped and Erbium (Er) doped zinc oxide (EZO) thin films were deposited on glass substrate by sol–gel method using spin coating technique with different doping concentration. EZO films were characterized using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), UV–VIS-NIR transmission and single beam z scan method under illumination of frequency doubled Nd:YAG laser. The deposited films were found to be well crystallized with hexagonal wurtzite structure having a preferential growth orientation along the ZnO (002) plane. A blue-shift was observed in the band gap of EZO films with increasing Er concentration. All the films exhibited a negative value of nonlinear refractive index (n₂) at 532 nm which is attributed to the two photon absorption and weak free carrier absorption. Third order nonlinear optical susceptibility, χ⁽³⁾ values of EZO films were observed in the remarkable range of 10^? 6 esu. EZO (0.4 at.%) sample was found to be the best optical limiter with limiting threshold of 1.95 KJ/cm².     

Structural and optical properties of Mn-doped ZnO nanocrystalline thin films with the different dopant concentrations

The transparent nanocrystalline thin films of undoped zinc oxide and Mn-doped (Zn_1−xMn_xO) have been deposited on glass substrates via the sol–gel technique using zinc acetate dehydrate and manganese chloride as precursor. The as-deposited films with the different manganese compositions in the range of 2.5–20 at% were pre-heated at 100 °C for 1 h and 200 °C for 2 h, respectively, and then crystallized in air at 560 °C for 2 h. The structural properties and morphologies of the undoped and doped ZnO thin films have been investigated. X-ray diffraction (XRD) spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to examine the morphology and microstructure of the thin films. Optical properties of the thin films were determined by photoluminescence (PL) and UV/Vis spectroscopy. The analyzed results indicates that the obtained films are of good crystal quality and have smooth surfaces, which have a pure hexagonal wurtzite ZnO structure without any Mn related phases. Room temperature photoluminescence is observed for the ZnO and Mn-doped ZnO thin films.     

Chemically sprayed ZnO:(F,Zr) thin films: Effect of starting solution ageing time and substrate temperature on the physical properties

Conductive and transparent fluorine and zirconium co-doped zinc oxide [ZnO:(F, Zr)] thin films have been deposited onto sodocalcic glass substrates by the chemical spray technique. The effects of starting solution ageing time and the substrate temperature on the transport, structural, and morphological properties of as-deposited ZnO:(F, Zr) thin films are presented in this paper. A decrease in the electrical resistivity values is observed as the starting solution used is more aged, reaching a minimum resistivity of the order of 1.3×10^?2 Ω cm in samples deposited from a 17-day-aged solution, then increasing in samples deposited from solutions aged beyond this ageing time. According to the characterization results, the surface morphology is dependent on the solution ageing time. The X-ray diffraction patterns reveal that the ZnO:(F, Zr) thin films are polycrystalline in nature, fitting well with a hexagonal wurtzite structure, and showing the (0 0 2) planes as preferential growth in all the deposited films. The average optical transmittance, measured in the near UV–visible region, was of the order of 75% in all the cases.     

The growth of ZnO:Ga:Cu as new TCO film of advanced electrical,optical and structural quality

Because of having similarities in many physical as well as chemical properties to those of Zn, Cu has been strategically used as an effective dopant e.g., Al, Ga, F, etc., to change the optical, electrical and the micro-structural properties of ZnO thin films for obtaining its favorable opto-electronic performance as a transparent conducting oxide suitable for devices. Present study demonstrates the growth of transparent conducting ZnO:Ga:Cu thin films, by low power RF magnetron sputtering at a low substrate temperature (100 °C). Highly crystalline ZnO:Ga:Cu film with preferred c-axis orientation has been obtained demonstrating a high magnitude of transmission ~85% in the visible range and a high electrical conductivity ~40 S cm^–1, facilitated by large crystallite size (~29 nm), introducing reduced grain boundary scattering. XPS O 1S spectrum reveals the presence of a significant fraction of oxygen atoms effectively increasing the optical transparency. Incorporation of Ga and Cu ions into the ZnO matrix promotes violation of the local translational symmetry as suggested by the relaxation of Raman selection rules for the network, evident by the presence of strong (B₁^high–B₁^low) modes which are typically Raman inactive. The consequences of Cu doping has been compared with identically prepared ZnO and ZnO:Ga films.     

Influence of substrate temperature on physical properties of sprayed Zn0.85Mn0.15O films

Zn_1−xMn_xO thin films have been synthesized by chemical spray pyrolysis at different substrate temperatures in the range, 250–450 °C for a manganese composition, x = 15%, on corning 7059 glass substrates. The as-grown layers were characterized to evaluate their chemical and physical behaviour with substrate temperature. The change of dopant level in ZnO films with substrate temperature was analysed using X-ray photoelectron spectroscope measurements. The X-ray diffraction studies revealed that all the films were strongly oriented along the (0 0 2) orientation that correspond to the hexagonal wurtzite structure. The crystalline quality of the layers increased with the increase of substrate temperature up to 400 °C and decreased thereafter. The crystallite size of the films varied in the range, 14–24 nm. The surface morphological studies were carried out using atomic force microscope and the layers showed a lower surface roughness of 4.1 nm. The optical band gap of the films was ∼3.35 eV and the electrical resistivity was found to be high, ∼10⁴ Ω cm. The films deposited at higher temperatures (>350 °C) showed ferromagnetic behaviour at 10 K.     

Preparation and characterization of F doped SnO2 films and electrochromic properties of FTO/NiO films

The dependence of structural and electrical properties of SnO₂ films, prepared using spray pyrolysis technique, on the concentration of fluorine is reported. X-ray diffraction, FTIR and scanning electron microscope (SEM) studies have been performed on SnO₂:F (FTO) films coated on glass substrates. Measured values of Hall coefficient and resistivity are reported. The 7.5 m% of F doped film had a resistivity of 15 × 10⁻⁴ Ω cm, carrier density of 18.7 × 10¹⁹ cm⁻³ and mobility of 21.86 cm² V⁻¹ S⁻¹. The NiO film was coated on an FTO substrate and its electrochromic (EC) behavior was studied and the results are reported and discussed in this paper.     

Synthesis of oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)] and anomalous proton conductivities of the thin films

New proton-conductive polyamide oligomers, oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)], were synthesized to investigate the proton transport properties of bulk and thin films. The obtained oligomers were characterized by the X-ray diffraction, FT-IR spectra, ¹H NMR, Matrix Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrum, and electrical conductivity measurements. The bulk proton conductivity is 3.0 × 10^? 4 S cm^? 1 at the relative humidity (RH) of 80%. The proton conductivity of thin film is relatively higher than that of bulk sample. Thickness dependence of the proton conductivity was observed in these thin films. The maximum proton conductivity of the thin film is 4.0 × 10^? 3 S cm^? 1 at the relative humidity (RH) of 80%, which is higher one order magnitude than that of the bulk sample. The activation energies of bulk and 200 nm thick film are 1.0 and 0.69 eV at the RH of 60%, respectively.     

Structural,electrical and optical properties of sol–gel AZO thin films

Transparent conductive Al-doped zinc oxide (AZO) thin films were prepared by a sol–gel method and their structural, electrical and optical properties were systematically investigated. A minimum resistivity of 4.2 × 10⁻³ Ω cm was obtained for the 650 °C-annealed films doped with 1.0 at.% Al. All films had the preferential c-axis oriented texture according to the X-ray diffraction (XRD) results. Optical transmittance spectra of the films showed a high transmittance of over 85% in the visible region and the optical band gap of the AZO films broadened with increasing doping concentration.     

Photoluminescence studies of ZnO thin films on R-plane sapphire substrates grown by sol–gel method

Zinc oxide (ZnO) thin films on R-plane sapphire substrates were grown by the sol–gel spin-coating method. The optical properties of the ZnO thin films were investigated using photoluminescence. In the UV range, the asymmetric near-band-edge emission was observed at 300 K, which consisted of two emissions at 3.338 and 3.279 eV. Eight peaks at 3.418, 3.402, 3.360, 3.288, 3.216, 3.145, 3.074, and 3.004 eV, which respectively correspond to the free exciton (FX), bound exciton, transverse optical (TO) phonon replica of FX recombination, and first-order longitudinal optical phonon replica of FX and the TO (1LO+TO), 2LO+TO, 3LO+TO, 4LO+TO, and 5LO+TO, were obtained at 12 K. From the temperature-dependent PL, it was found that the emission peaks at 3.338 and 3.279 eV corresponded to the FX and TO, respectively. The activation energy of the FX and TO emission peaks was found to be about 39.3 and 28.9 meV, respectively. The values of the fitting parameters of Varshni's empirical equation were α=4×10^?3 eV/K and β=4.9×10³ K, and the S factor of the ZnO thin films was 0.658. With increasing temperature, the exciton radiative lifetime of the FX and TO emissions increased. The temperature-dependent variation of the exciton radiative lifetime for the TO emission was slightly higher than that for the FX emission.     

Preparation of cadmium stannate films by spray pyrolysis technique

Cadmium stannate thin films were prepared by spray pyrolysis technique using cadmium acetate and tin(II) chloride precursors at substrate temperatures 450 °C and 500 °C. XRD pattern confirms the formation of orthorhombic (1 1 1) cadmium stannate phase for the film prepared at substrate temperature of 500 °C, whereas, films prepared at 450 °C are amorphous. Film formation does not occur at substrate temperature from 300 to 375 °C. SEM images reveal that the surface of the prepared Cd₂SnO₄ film is smooth. The average optical transmittance of ∼86% is obtained for the film prepared at substrate temperature of 500 °C with the film thickness of 400 nm. The optical band gap value of the films varies from 2.7 to 2.94 eV. The film prepared at 500 °C shows a minimum resistivity of 35.6 × 10⁻⁴ Ω cm.     

Preparation and characterization of highly conducting and transparent Al doped CdO thin films by pulsed laser deposition

Highly conducting and transparent aluminum doped CdO thin films were deposited using pulsed laser deposition technique. The effect of growth temperature on structural, electrical, and optical properties was studied. It is observed that the film orientation changes from preferred (1 1 1) plane to (2 0 0) plane with increase in growth temperature. The electrical resistivity of the films was found to increase with increase in growth temperature. The low resistivity of 4.3 × 10⁻⁵ Ω cm and high transparency (∼85%) was obtained for the film grown at 150 °C. The band gap of the films varies from 2.74 eV to 2.84 eV.