Effect of Al concentrations on the electrodeposition and properties of transparent Al-doped ZnO thin films

Al-doped zinc oxide (AZO) thin films are prepared on polycrystalline fluorine-doped tin oxide-coated conducting glass substrates from nitrates baths by the electrodeposition process at 70 °C. The electrochemical, morphological, structural and optical properties of the AZO thin films were investigated in terms of different Al concentration in the starting solution. It was found that the carrier density of AZO thin films varied between ?3.11 and ?5.56 × 10²⁰ cm^?3 when the Al concentration was between 0 and 5 at.%. Atomic force microscopy images reveal that the concentration of Al has a very significant influence on the surface morphology and roughness of thin AZO. X-ray diffraction spectra demonstrate preferential (002) crystallographic orientation having c-axis perpendicular to the surface of the substrate and average crystallites size of the films was about 33–54 nm. With increasing Al doping, AZO films have a strong improved crystalline quality. As compared to pure ZnO, Al-doped ZnO exhibited lower crystallinity and there is a shift in the (002) diffraction peak to higher angles. Due to the doping of Al of any concentration, the films were found to be showing >80 % transparency. As Al concentration increased the optical band gap was also found to be increase from 3.22 to 3.47 eV. The room-temperature photoluminescence spectra indicated that the introduction of Al can improve the intensity of ultraviolet (UV) emission, thus suggesting its greater prospects in UV optoelectronic devices. A detailed comparison and apprehension of electrochemical, optical and structural properties of ZnO and ZnO:Al thin films is done for the determination of optimum concentration of Al doping.     

Quantum dot sensitized aluminium doped and copper doped ZnO nanostructure based solar cells

Aluminium doped and copper doped ZnO nanostructured thin films have been prepared using simple solgel dip coating method. The X-ray diffraction pattern results revealed that the prepared Al and Cu doped ZnO sample exhibits hexagonal structure. The average crystallite size of pure ZnO, Al doped ZnO and Cu doped ZnO samples were found to be 29, 26 and 15 nm, respectively. The optical band gap of ZnO, Al doped ZnO and Cu doped ZnO thin films was found to be 3.27, 3.29, and 3.20 eV respectively. Solar cells have been fabricated using CdS quantum dots sensitized ZnO nanostructured thin films and the efficiency of the fabricated Al doped and Cu doped ZnO solar cells were 1.37 and 1.29 % respectively.     

Influence of Fe dopant concentration and annealing temperature on the structural and optical properties of ZnO thin films deposited by sol–gel method

Nanostructured Fe doped ZnO thin films were deposited onto glass substrates by sol–gel spin coating method. Influence of Fe doping concentration and annealing temperature on the structural, compositional, morphological and optical properties were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV–Vis spectroscopy and photoluminescence (PL) measurements. XRD analysis showed that all the films prepared in this work possessed a hexagonal wurtzite structure and were preferentially oriented along the c-axis. Pure ZnO thin films possessed extensive strain, whereas Fe doped films possessed compressive strain. In the doped films, least value of stress and strain was observed in the 0.5 at.% Fe doped thin film, annealed at 873 K. Average crystallite size was not significantly affected by Fe doping, but it increased from 15.57 to 17.79 nm with increase in annealing temperature from 673 to 873 K. Fe ions are present in +3 oxidation state as revealed by XPS analysis of the 0.5 at.% Fe doped film. Surface morphology is greatly affected by changes in Fe doping concentration and annealing temperature which is evident in the SEM images. The increase in optical band gap from 3.21 to 3.25 eV, with increase in dopant concentration was attributed to Moss–Burstein shift. But increase in annealing temperature from 673 to 873 K caused a decrease in band gap from 3.22 to 3.20 eV. PL spectra showed emissions due to excitonic combinations in the UV region and defect related emissions in the visible region in all the investigated films.     

Influence of Al concentration on structural and optical properties of Al-doped ZnO thin films

Undoped ZnO and Al-doped zinc oxide (ZnO:Al) thin films with different Al concentrations were prepared onto Si (100) substrate by pulsed filtered cathodic vacuum arc deposition system at room temperature. The influence of doping on the structural and optical properties of thin films was investigated. The preferential (002) orientation was weakened by high aluminum doping in films. Raman measurement was performed for the doping effects in the ZnO. Atomic force microscopy images revealed that the surface of undoped ZnO film grown at RT was smoother than that of the Al-doped ZnO (ZnO:Al) films. The reflectance of all films was studied as a function of wavelength using UV–Vis–NIR spectrophotometer. Average total reflectance values of about 35 % in the wavelength range of 400–800 nm were obtained. Optical band gap of the films was determined using the reflectance spectra by means of Kubelka–Munk formula. From optical properties, the band gap energy was estimated for all films.     

Nonlinear optical investigations on Al doping ratio in ZnO thin film under pulsed Nd:YAG laser irradiation

In the present study, it has been reported on the effect of Al doping on linear and nonlinear optical properties of ZnO thin films synthesized by spray pyrolysis method. The structural properties of ZnO thin films with different Al doping levels (0–4 wt%) were analyzed using X-ray diffraction (XRD). The results obtained from XRD analysis indicated that the grain size decreased as the Al doping value increased. The UV–Vis diffused refraction spectroscopy was used for calculation of band gap. The optical band gap of Al-doped ZnO (AZO) thin films is increased from 3.26 to 3.31 eV with increasing the Al content from 0 to 4 wt%. The measurements of nonlinear optical properties of AZO thin films have been performed using a nanosecond Nd:YAG pulse laser at 532 nm by the Z-scan technique. The undoped ZnO thin film exhibits reverse saturation absorption (RSA) whereas the AZO thin films exhibit saturation absorption (SA) that shows RSA to SA process with adding Al to ZnO structure under laser irradiation. On the other hand, all the films showed a self-defocusing phenomenon because the photons of laser stay on below the absorption edge of the ZnO and AZO films. The third-order nonlinear optical susceptibility, χ⁽³⁾, of AZO thin films, was varied from of the order of 10^?5–10^?4 esu. The results suggest that AZO thin films may be promising candidates for nonlinear optical applications.     

Enhancement in the electrical and antibacterial properties of sprayed ZnO films by simultaneous doping of Mg and F

Undoped and Doubly (Magnesium + Fluorine) doped zinc oxide (ZnO:Mg:F) thin films with different Mg doping levels (4, 8, 12 and 16 at.%) and constant F doping level (20 at.%) were fabricated by employing a simplified spray pyrolysis technique. The antibacterial and certain physical properties of the films were studied as a function of Mg doping level. All the films exhibited hexagonal wurtzite structure with preferential orientation along the (002) plane. A lesser electrical resistivity was achieved in the present study than earlier reports of ZnO:Mg films thanks to the simultaneous doping of F with Mg in ZnO films. From the optical studies, it was observed that, all the films showed good transparency (≈85 %) with significant enhancement in the optical band gap with Mg doping level. The obtained PL spectra were well corroborated with the structural and optical studies. Further, it was also found that the antibacterial activity of doubly doped ZnO films was enhanced remarkably by the increasing incorporation of Mg concentration.     

Influence of Al doping on the structural,morphological and opto-electrical properties of spray deposited lead sulfide thin films

This paper reports the synthesis of Al-doped PbS (PbS:Al) thin films by spray pyrolysis technique on glass substrates. Al doping concentration is varied as 0, 2, 4, 6 and 8 at.% in undoped PbS. Undoped and doped films exhibit cubic crystal structure with a (2 0 0) preferential orientation. The 2θ value of the doped films shifts towards higher Bragg angles confirming a contraction in their unit cell volume. The crystallite size values determined using the Scherrer formula decreased from 27.88 to 25.79 nm with increase in Al doping concentration. EDX spectra confirmed the presence of Al in the doped films. Increased transparency and blue shift in the optical band gap is observed with Al doping. The resistivity range of all the films were found to be in the order of 10² Ω-cm. Increased transparency, widened band gap and decreased resistivity observed make PbS:Al films suitable for tandem solar cells which uses multilayered pn junctions.     

The effects of the aluminium concentration on optical and electrical properties of AZO thin films as a transparent conductive layer

In this paper, we studied the effects of the aluminium dopant concentration on the optical and electrical properties of aluminium doped zinc oxide (AZO) thin films grown on soda-glass substrates by a simple chemical method. The amount of aluminium in the compound was varied from 0 to 5 atomic percent (at.%), and the typical thickness of the films produced was about 300 nm. The thin films were characterized by scanning electron microscopy and X-ray diffraction to investigate the morphology and crystallinity of the samples. The optical properties of the thin films were studied by UV–Vis spectroscopy to determinate absorption, transmittance, and the diffuse reflectance. In addition, the photoluminescence properties of the thin films, excited with a 320 nm UV laser beam, were investigated. The effects of the aluminium concentration on these optical properties are discussed. The films with 2 and 5 % doping had excellent optical transmittance (~85–90 %) in the 400–1100 nm wavelength range. The photoluminescence spectra of the AZO films revealed UV near band edge emission peaks in the 378–401 nm range and an oxygen-vacancy related peak around 471 nm. The addition of aluminium changed the band gap of zinc oxide from 3.29 to 3.41 eV, and the appearance of a new level was observed in the band gap at the higher aluminium doping concentrations. The AZO thin films showed good conductivity (in the order of 10^?2 Ω cm) which allows their use as transparent electrodes. Moreover, the AZO thin films were stable in open air for 30 days.     

Structural and optical characterization of Al-doped ZnO films prepared by thermal oxidation of evaporated Zn/Al multilayered films

Aluminum-doped zinc oxide (ZnO:Al) thin films (t = 68–138 nm) were prepared by thermal oxidation in air flow, at 720 K, of the multilayered metallic Zn/Al thin stacks deposited in vacuum onto glass substrates by physical vapor deposition. The effect of Al content (3.7–8.2 at.%) on the structural (crystallinity, texture, stress, surface morphology) and optical (transmittance, absorbance, energy band gap) characteristics of doped ZnO thin films was investigated. The X-ray diffraction spectra revealed that the Al-doped ZnO films have a hexagonal (wurtzite) structure with preferential orientation with c-axis perpendicular to the substrate surface. A tensile residual stress increasing with Al content was observed. The films showed a high transmittance (about 90%) in the visible and NIR regions. The optical band gap value was found to decrease with Al content from 3.22 eV to 3.18 eV. The results are discussed in correlation with structural characteristics and Al content in the films.     

Nitrogen effect on spin-coated ZnO-based p–n homojunctions: structural,optical and electrical characteristics

In this work, ZnO:Al–N/ZnO:Al and ZnO:Ag–N/ZnO:Al homojunctions were deposited by means of spin coating method using precursors obtained by sol gel chemistry. The optical, structural and electrical properties of spin coated undoped and M-doped ZnO thin films (M?=?Al, Ag–N and Al–N) using ammonium hydroxide as a nitrogen source are reported. The films showed the wurtzite type structure with a c-axis (002) preferential orientation. The films showed a surface morphology consisting of wrinkles, which were constituted of nanocrystals in the range of ～?20 nm. The thin films were highly transparent in the visible region of the electromagnetic spectrum. The optical band gap of the films was close to 3.30 eV. Hall Effect measurements indicated that undoped and Al doped ZnO thin films showed an n-type conductivity, whereas ZnO:Al–N and ZnO:Ag–N thin films exhibited p-type conductivity, probably related to the formation of dual acceptor complexes related to nitrogen. Two types of p–n homojunctions (ZnO:Al–N/ZnO:Al and ZnO:Ag–N/ZnO:Al) were fabricated by means of sol–gel spin-coating method. In both cases, a rectifying behavior was observed, as revealed by current–voltage measurements.     

Preparation of nanocrystalline Mg doped CdSe thin films and their optical,photoluminescence, electrical and structural characterization

Phosphors used are mostly rare earth doped complex structures. A simple and unique material system of CdSe:Mg nanocrystalline thin films, which efficiently absorb UV (235 nm) and emit broad spectrum of green-yellow region has been prepared by chemical bath deposition method with average particle size of 52.3 nm, measured using AFM images. The optical absorption studies found that CdSe thin film has direct optical band gap, \({E_g}\) of 2.62 eV that shows a blue shift of 0.88 eV compared to the bulk \({E_g}\) value. Optical, electrical, structural and morphological properties were studied by UV–Vis–NIR spectrophotometer, photoluminescence (PL) emission spectra, dc two-probe method, X-ray diffraction (XRD), and atomic force microscope (AFM). Measured electrical resistivity decreased with increase of doping concentration. Activation energy was also calculated. The results confirm that the CdSe:Mg thin films are in the pure cubic phase. The magnesium concentrations also affect the nanocrystalline nature of the CdSe thin films. The optical band gap and surface roughness of CdSe thin films mostly decrease with 5% doping of Mg. The effect of Mg doping on refractive index, extinction coefficient and other optical parameters was also investigated.     

Investigation of the substrate effect for Zr doped ZnO thin film deposition by thermionic vacuum arc technique

ZnO is a fundamental wide band gap semiconductor. Especially, doped elements change the optical properties of the ZnO thin film, drastically. Doped ZnO semiconductor is a promising materials for the transparent conductive oxide layer. Especially, Zr doped ZnO is a potential material for the high performance TCO. In this paper, ZnO semiconductors were doped with Zr element and microstructural, surface and optical properties of the Zr doped ZnO thin films were investigated. Zr doped ZnO thin films were deposited thermionic vacuum arc (TVA) technique. TVA is a rapid and high vacuum deposition method. A glass, polyethylene terephthalate and Si wafer (111) were used as a substrate material. Zr doped ZnO thin films deposited by TVA technique and their substrate effect investigated. As a results, deposited thin films has a high transparency. The crystal orientation of the films are in polycrystal formation. Especially, substrate crystal orientation strongly change the crystal formation of the films. Substrate crystal structure can change the optical band gap, microstructural properties and deposited layer formation. According to the atomic force microscopy and field emission scanning electron microscopy measurements, all deposited layer shows homogeneous, compact and low roughness. The band values of the deposited thin film were approximately found as to be 3.1–3.4 eV. According to the results, Zr elements created more optical defect and shifted to the band gap value towards to blue region.     

Hydrothermal derived nanostructure rare earth (Er,Yb)-doped ZnO: structural,optical and electrical properties

The structural, optical and electrical properties of undoped and rare-earth (Er, Yb) doped zinc oxide (ZnO) nanopowder samples synthesized by hydrothermal method were investigated. The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive spectroscopy. The optical properties of undoped and rare-earth (Er, Yb) doped ZnO were carried out with UV–visible diffuse reflectance spectroscopy techniques. XRD results reveal that Yb and Er doped ZnO nanopowders have single phase hexagonal (Wurtzite) structure without any impurities. SEM analysis indicate that dopants with different radii affected the surface morphology of ZnO nanostructures. The optical band gap of all samples were calculated from UV–Vis diffuse reflectance spectroscopy data. We have obtained band gap values of undoped, Er and Yb doped ZnO as 3.24, 3.23, 3.22 eV, respectively. Electrical characterization of the samples were made in the 280–350 K temperature range using Van der Pauw method based on Hall effect measurement. The carrier concentrations decreased for both Er and Yb doping while the Hall mobility and electrical resistivity increased with Yb, Er doping compared to undoped ZnO nanopowder at room temperature. The temperature dependent resistivity measurements of Er doped ZnO showed a metal–semiconductor transition at about 295 K, while Yb doped ZnO showed characteristic semiconductor behavior.     

Optical and structural properties of Mg doped ZnO thin films by chemical bath deposition method

The chemical bath deposition method has often been employed to successfully deposit pure and Mg doped ZnO thin films on a glass substrate. The impact of Mg creates a strained stress in ZnO films affecting its structural and optical properties. XRD patterns revealed that all thin films possess a polycrystalline hexagonal wurtzite structure and Mg doped ZnO thin films (002) plane peak position is shifted towards a lower angle due to Mg doping. From the SEM image, it is understood that the Mg doped ZnO thin films are uniformly coated and are seen as dense rods like pillers deposited over the film. The energy dispersive X-ray analysis confirmed the presence of Mg in doped ZnO thin films. The transmittance spectra exhibit that it is possible for Mg doping to enhance ZnO thin films. The optical energy gap of the films was assessed by applying Tauc’s law and it is observed to show an increasing tendency with an improvement in Mg doping concentrations. The optical constants such as reflectance, index of refraction, extinction coefficient and optical conductivity are determined by using transmission at normal incidence of light by using wavelength range of 200–800 nm. In PL spectra, the band edge emission shifted to the blue with increasing amount of Mg doping.     

Synthesis, structural and optical properties of Ni-doped ZnO micro-spheres

Ni doped ZnO nanoparticles were synthesized by a simple chemical method at low temperature with Ni:Zn atomic ratio from 0 to 5 %. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and nickel acetate tetrahydrate followed by heat treatment at 65 °C under refluxing using methanol as a solvent. X-ray diffraction analysis reveals that the Ni-doped ZnO crystallizes in a wurtzite structure with crystal size of 4–11 nm. These nanocrystals self-aggregated themselves into hollow spheres of size of 600–170 nm. High resolution transmission electron microscopy image shows that each sphere is made up of numerous nanoparticles of average diameter 4 nm. The XRD patterns, Scanning electron microscopy and transmission electron microscopy micrographs of doping of Ni in ZnO are confirmed the formation of micro-spheres. Furthermore, the UV–vis. spectra and photoluminescence spectra of the Ni-doped ZnO nanoparticles were also investigated. The band gap of the nanoparticles can be tuned in the range of 3.55–3.36 eV by the use of the dopants. The observed red shift in the band gap from UV–visible analysis and near band edge UV emission with Ni doping may be considered to be related to the incorporation of Ni ions into the Zn site of the ZnO lattice.     

Sn doping effects on properties of ZnO thin films deposited by RF magnetron sputtering using a powder target

In the present study, tin doped ZnO thin films (ZnO:Sn) at different contents (0–3 wt%) were deposited onto glass substrates by RF magnetron sputtering using a powder compacted target at room temperature. The effect of Sn concentration on the structural, optical and electrical properties of the ZnO:Sn thin films were investigated. The X-ray diffraction analysis shows that the pure ZnO thin film exhibits a strong intensity of the (002) peak indicating a preferential orientation along the c-axis. For Sn doped ZnO thin films, there is a change in the orientation from the (002) plane to the (101) one. The undoped ZnO thin films have transmittance 85% in the visible range and slightly increased for 0.5 wt% of Sn, while it get decreased with further increasing the Sn doping concentration. The optical band gap energy get increased with increasing the doping concentration. Moreover, the electrical conductivity and conduction mechanism are also studied by impedance spectroscopy in the frequency range of 1KHz–13 MHz at various temperatures (633–743 K). The AC conductivity in ZnO thin films increased with angular frequency. The frequency exponent S decreases with increasing temperature. Such behavior suggests that the correlated barrier hopping (CBH) model may be suitable to explain the conduction mechanism in ZnO thin films. The activation energy values calculated from angular frequency and DC conductivity are in good agreement confirming that the conduction mechanism is thermally activated by hopping between localized states.     

Structure and optical properties of ZnO:V thin films with different doping concentrations

A series of ZnO thin films doped with various vanadium concentrations were prepared on glass substrates by direct current reactive magnetron sputtering. The results of the X-ray diffraction (XRD) show that the films with doping concentration less than 10 at.% have a wurtzite structure and grow mainly along the c-axis orientation. The residual stress, estimated by fitting the XRD diffraction peaks, increases with the doping concentration and the grain size also has been calculated from the XRD results, decreases with increasing the doping concentration. The surface morphology of the ZnO:V thin films was examined by SEM. The optical constants (refractive index and extinction coefficient) and the film thickness have been obtained by fitting the transmittance. The optical band gap changed from 3.12 eV to 3.60 eV as doping concentration increased from 1.8 at.% to 13 at.% mol. All the results have been discussed in relation with doping concentration.     

Variation of optical band gap in anodically grown nanocrystalline ZnO thin films at room temperature—effect of electrolyte concentrations

Zinc oxide thin films were deposited by electrochemical oxidation of Zinc at room temperature using high purity Zn as anode, Pt cathode, a calomel reference electrode and an aqueous electrolytic solution of oxalic acid. A range of 0.3, 0.1, 0.05, and 0.01 M electrolyte concentrations were used during anodization. Glancing angle X-ray diffraction and field emission scanning electron microscope were used to determine the crystallinity and the surface morphology respectively of the deposited ZnO thin films. The variation of the molar concentration of the electrolyte during anodic oxidation had a significant effect on the optical band gap of ZnO thin film. There was an increase in band gap with the decreasing concentrations of oxalic acid and a highest bandgap of 4.20 eV was obtained by using 0.05 M oxalic acid electrolyte. An apparent blue shift of band gap was further confirmed by Photoluminescence spectra.     

Investigation of the some physical properties of Ge-doped ZnO thin films deposited by thermionic vacuum arc technique

We exhibit the first nano-crystalline Ge–ZnO thin films deposited on glass and PET substrates by a thermionic vacuum arc technique. The effect of Ge doping on the structural, morphological and optical properties of ZnO:Ge films were investigated. An X-ray diffraction (XRD), atomic force microscopy, field emission scanning electron microscopy (FESEM) and UV–Vis spectrophotometer were used for the analysis. XRD patterns show the polycrystalline structure of the films in the range of 20°–80°. The roughness value for the ZnO:Ge on PET substrate was increased due to agglomeration of the grains. The results are in a good agreement with the FESEM images. Using Filmetrics F20 tool, the thickness values of the deposited thin films were obtained as 60 and 80 nm on glass and PET substrates, respectively. The optical properties of the films such as transmittance, absorbance, refractive index, and reflectance were determined. The band gap values were obtained as to be 3.43 and 3.38 eV glass and PET substrates, respectively. It was found that band gap variation of ZnO is very small with Ge doping.     

Structural,Transport and Optical Properties of Boron-doped Zinc Oxide Nanocrystalline

The paper has reported the structural,transport and optical properties of boron doped zinc oxide(ZnO:B) thin films grown on glass substrate by sol-gel spin coating process.It is observed from the analysis of the X-ray diffraction(XRD) results that the crystalline quality of the films is improved with increasing B concentration.A crystallite size of ～17 nm is obtained for B doped films.A minimum resistivity of 7.9×10-4 Ω.cm is obtained at 0.6 at.% of B concentration in the ZnO:B films.Ionized and intragrain cluster scattering are found to dominate the scattering mechanism in ZnO:B films.Optical interference pattern in transmittance spectra shows good homogeneity with a transparency of ～88% in the visible region.The band gap of the films is increased from 3.24 to 3.35 eV with increasing B concentration.Band gap widening is analyzed in terms of Burstein-Moss shift.The origin of the broad band photoluminescence(PL) spectra is explained in terms of the intragrain cluster scattering.