Effect of Cr and V dopants on the chemical stability of AZO thin film

The effect of the dopants of Cr and V on the optoelectronic properties of AZO thin film by pulsed DC magnetron sputtering has been investigated. We also use HCl and KOH solutions to conduct the chemical stability of AZO:Cr:V thin film. The experimental results show that the optimum AZO optoelectronic properties without Cr and V doping obtain the resistivity of 9.87 × 10⁻⁴ Ω cm, optical transmittance of 84% and surface roughness rms value of 2.6 nm. The chemical stability of AZO will increase after Cr and V doping. Under the added V = 0.19 wt.%, Cr = 0.56 wt.%, AZO:Cr:V thin film showed 52% increased chemical stability and 128% decrease in surface roughness after etching (the resistivity was 3.62 × 10⁻³ Ω cm and optical transmittance 81%). From the experimental results, the higher resistivity obtained after KOH etching compared with after HCl etching. The reason is that the Zn/Al ratio will reduce after etching and cause the AZO film carrier density to reduce as well. However, the optical transmittance obtained after KOH etching will be higher than that after HCl etching. This is because that a better surface roughness after KOH etching obtained than after HCl etching.     

Deposition of quasi-crystal Al-doped ZnO thin films for photovoltaic device applications

Quasi-crystal aluminum-doped zinc oxide (AZO) films were prepared by in situ radio frequency (RF) magnetron sputtering (sputtering without annealing) on glass substrates. The influence of deposition parameters on the optoelectronic and structural properties of the in situ deposited quasi-crystal AZO films was investigated in order to compare resulting samples. X-ray diffraction (XRD) patterns show that the quasi-crystal AZO thin films have excellent crystallization improved with increase of the RF power and substrate temperature, with an extremely preferential c-axis orientation exhibit sharp and narrow XRD pattern similar to that of single-crystal. Field emission scanning electron microscopy (FESEM) images show that quasi-crystal AZO thin films have uniform grains and the grain size increase with the increase of RF power and substrate temperature. Craters of irregular size with the columnar structure are observed in the quasi-crystal AZO thin films at a lower substrate temperature while many spherical shaped grains appeared at a higher substrate temperature. The average optical transmittance of all the quasi-crystal AZO films was over 85% in the 400-800 nm wavelength range. The resistivity of 4.176 × 10⁻⁴ Ω cm with the grain size of 76.4891 nm was obtained in the quasi-crystal AZO thin film deposited at 300 °C, under sputtering power of 140 W.     

The enhanced conductivity and stability of AZO thin films with a TiO2 buffer layer

Aluminum doped zinc oxide (AZO) films were substitutes of the SnO₂:F films on soda lime glass substrate in the amorphous thin-film solar cells due to good properties and low cost. In order to improve properties of AZO films, the TiO₂ buffer layer had been introduced. AZO films with and without TiO₂ buffer layer were deposited on soda lime glass substrates by r.f. magnetron sputtering. Subsequently, one group samples were annealed in vacuum (0.1 Pa) at 500 °C for 120 s using the RTA system, and the influence of TiO₂ thickness on the properties of AZO films had been discussed. The XRD measurement results showed that all the films had a preferentially oriented (0 0 2) peak, and the intensity of (0 0 2) peak had been enhanced for the AZO films with TiO₂ buffer layer. The resistivity of TiO₂ (3.0 nm)/AZO double-layer film is 4.76×10⁻⁴ Ω cm with the maximum figure merit of 1.92×10⁻² Ω⁻¹, and the resistivity has a remarkable 28.7% decrease comparing with that of the single AZO film. The carrier scattering mechanism of TiO₂ (3.0 nm)/AZO double-layer film had been described by Hall measurement in different temperatures. The average transmittance of all the films exceeded 92% in the visible spectrum. Another group samples were heat treated in the quartz tube in air atmosphere, and the effect of TiO₂ thickness on thermal stability of AZO films had been discussed.     

Dependence of resistivity on structure and composition of AZO films fabricated by ion beam co-sputtering deposition

The correlation between the resistivity and the structure/composition in the aluminum doped zinc oxide (AZO) films fabricated by the ion beam co-sputtering deposition at room temperature was investigated. The various compositions of AZO films were controlled by the sputtered area ratio of Al to Zn target. The structure, Al concentrations and resistivities of the as-deposited films were determined by X-ray diffractometer (XRD), energy dispersive spectrometer (EDS) and four-point probe station, respectively. The lowest resistivity of the deposited film was 5.66 × 10⁻⁴ Ω-cm at the 0.7 wt.% aluminum concentration. The most intense ZnO (0 0 2) diffraction peak, the largest grain size, the longest mean free path, and the highest free carrier concentration in the film result in the lowest resistivity of 5.66 × 10⁻⁴ Ω-cm at room temperature; simultaneously, the thermal stability of the resistivity of the AZO film as a function of the sample temperature was investigated. Below 200 °C the film's resistivity was almost kept at a fixed value and the lowest resistivity of 4.64 × 10⁻⁴ Ω-cm at 247 °C was observed.     

Optical and electrical characteristics of Al-doped ZnO thin films prepared by aqueous phase deposition

Transparent conducting Al-doped ZnO (AZO) thin films have been deposited by sol-gel route. Starting from an aqueous solution of zinc acetate by adding aluminum chloride as dopant, a c-axis oriented polycrystalline ZnO thin film 100 nm in thickness could be spin-coated on glass substrates via a two-step annealing process under reducing atmosphere. The effects of thermal annealing and dopant concentration on the structural, electrical and optical properties of AZO thin films were investigated. The post-treated AZO films exhibited a homogenous dense microstructure with grain sizes less than 10 nm as characterized by SEM photographs. The annealing atmosphere has prominent impact on the crystallinity of the films which will in turn influence the electrical conductivity. By varying the doping concentrations, the optical and electrical properties could be further adjusted. An optimal doping concentration of Al/Zn = 2.25 at.% was obtained with minimum resistivity of 9.90 × 10⁻³ Ω-cm whereas the carrier concentration and mobility was 1.25 × 10²⁰ cm⁻³ and 5.04 cm² V⁻¹ s⁻¹, respectively. In this case, the optical transmittance in the visible region is over 90%.     

The effect of heating rate on the structural and electrical properties of sol-gel derived Al-doped ZnO films

Al-doped ZnO (AZO) films are prepared by sol-gel method with a proper annealing procedure. For the first time, we find that the heating rate which is normally neglected during the post annealing process plays a significant role in improving AZO properties. The AZO film with nanorod structure is obtained by using a rapid heating rate. The AZO nanorods can provide a faster conduction pathway for charge transport due to the high crystal quality and thus enhance the conductivity of the film significantly. After hydrogen treatment, the AZO nanorod film exhibits a minimum resistivity of 1.4 × 10⁻³ Ω cm. This approach to the preparation of AZO nanorods by a simple rapid annealing process may be helpful for the development of sol-gel-derived TCO films.     

Characteristics of ZnO:Al thin films co-doped with hydrogen and fluorine

Fluorine and hydrogen co-doped ZnO:Al (AZO) films were prepared by radio frequency (rf) magnetron sputtering of ZnO targets containing 1 wt.% Al₂O₃ on Corning glass at substrate temperature of 150 °C with Ar/CF₄/H₂ gas mixtures, and the structural, electrical and optical properties of the as-deposited and the vacuum-annealed films were investigated. In as-deposited state, films with fairly low resistivity of 3.9-4 × 10⁻⁴ Ω cm and very low absorption coefficient below 900 cm⁻¹ when averaged in 400-800 nm could be fabricated. After vacuum-heating at 300 °C, the minimum resistivity of 2.9 × 10⁻⁴ Ω cm combined with low absorption loss in visible region, which enabled the figure of merit to uplift as high as 4 Ω⁻¹, could be obtained for vacuum-annealed film. It was shown that, unlike hydrogenated ZnO films which resulted in degradation upon heating in vacuum at moderately high temperature, films with fluorine addition could yield improved electrical properties mostly due to enhanced Hall mobility while preserving carrier concentration level. Furthermore, stability in oxidizing environment could be improved by fluorine addition, which was ascribed to the filling effect of dangling bonds at the grain boundaries. These results showed that co-doping of hydrogen and fluorine into AZO films with low Al concentration could be remarkably compatible with thin film solar cell applications.     

High work function of Al-doped zinc-oxide thin films as transparent conductive anodes in organic light-emitting devices

Deposition of Al-doped ZnO (AZO) films with various film thicknesses on glass substrates was performed to investigate the feasibility of using AZO films as anode electrodes in organic light-emitting devices (OLEDs). The electrical resistivity of the AZO films with a 180-nm thickness was 4.085 × 10⁻² Ω cm, and the average optical transmittance in the visible range was 80.2%. The surface work function for the AZO films, determined from the secondary electron emission coefficients obtained with a focused ion beam, was as high as 4.62 eV. These results indicate that AZO films grown on glass substrates hold promise for potential applications as anode electrodes in high-efficiency OLEDs.     

Transparent conductive and near-infrared reflective Cu-based Al-doped ZnO multilayer films grown by magnetron sputtering at room temperature

Cu-based Al-doped ZnO multilayer films were deposited on glass substrates by DC magnetron sputtering at room temperature. Three kinds of multilayer structures (AZO/Cu, AZO/Cu/AZO, and Cu/AZO) were designed for comparison, and the effects of the Cu layer thickness on photoelectrical properties of the multilayer films were investigated. The results revealed that the transparent-conductive property and near-infrared reflectance of the films are closely correlated with the Cu layer thickness, and among the three structures, AZO/Cu bi-layer films exhibited preferable photoelectrical properties. The AZO/Cu bi-layer film with a Cu layer thickness of 7 nm displayed the highest figure of merit of 4.82 × 10⁻³ Ω⁻¹, with a low sheet resistance of 21.7 Ω/sq and an acceptable visible transmittance of 80%. The near infrared reflectance above 50% can be simultaneously obtained. The good performance of the coatings indicates that they are promising for coated glasses, thin film solar cells and heat-reflectors.     

Selective wet etching of Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> phase-change thin films in thermal lithography with tetramethylammonium

In this paper, we study Ge₂Sb₂Te₅ phase-change film as a promising inorganic photoresist using organic alkaline: tetramethylammonium hydroxide (TMAH) solution, instead of inorganic alkali or acid as etchant. The basic etching properties are investigated by prior and posterior annealing Ge₂Sb₂Te₅ films. Selectivity is found to be dependent on concentration of TMAH. There is a good selectivity in the 25% TMAH solution, in which the amorphous state is etched away, whereas the crystalline state remains. The etching rate decreases when the concentration of TMAH is diluted; and an opposite selectivity, compared with 25% TMAH solution, is observed in the 0.125% TMAH solution. Selective etching with laser crystallization in different power levels is also studied, and an excellent wet selectivity in the 25% TMAH solution is obtained. The remaining crystalline lines are observed by atomic force microscopy. The surface roughness after etching is at a good level. The selective wet-etching mechanism is also discussed.     

Effects of post-annealing on structural, optical and electrical properties of Al-doped ZnO thin films

Aluminum-doped zinc oxide (AZO) films were deposited at 400 °C by radio-frequency magnetron sputtering using a compound AZO target. The effects of annealing atmospheres as well as hydrogen annealing temperatures on the structural, optical and electrical properties of the AZO films were investigated. It was found that the electrical resistivity varied depending on the atmospheres while annealing in air, nitrogen and hydrogen at 300 °C, respectively. Comparing with that for the un-annealed films, the resistivity of the films annealed in hydrogen decreased from 9.8 × 10⁻⁴ Ω cm to 3.5 × 10⁻⁴ Ω cm, while that of the films annealed in air and nitrogen increased. The variations in electrical properties are ascribed to both the changes in the concentration of oxygen vacancies and adsorbed oxygen at the grain boundaries. These results were clarified by the comparatively XPS analyzing about the states of oxygen on the surface of the AZO films. There was great increase in electrical resistivity due to the damage of the surfaces, when AZO films were annealed in hydrogen with a temperature higher than 500 °C, but high average optical transmittance of 80-90% in the range of 390-1100 nm were still obtained.     

Influence of substrate temperature and post-treatment on the properties of ZnO:Al thin films prepared by pulsed laser deposition

Highly transparent conductive Al₂O₃ doped zinc oxide (AZO) thin films have been deposited on the glass substrate by pulsed laser deposition technique. The effects of substrate temperature and post-deposition annealing treatment on structural, electrical and optical properties of AZO thin films were investigated. The experimental results show that the electrical resistivity of films deposited at 240 °C is 6.1 × 10⁻⁴ Ω cm, which can be further reduced to as low as 4.7 × 10⁻⁴ Ω cm by post-deposition annealing at 400 °C for 2 h in argon. The average transmission of AZO films in the visible range is 90%. The optical direct band gap of films was dependent on the substrate temperature and the annealing treatment in argon. The optical direct band gap value of AZO films increased with increasing annealing temperature.     

Boron doped ZnO thin films fabricated by RF-magnetron sputtering

By using the radio frequency-magnetron sputtering (RF-MS) method, both pure ZnO and boron doped ZnO (ZnO:B) thin films were deposited on glass substrates at ambient temperature and then annealed at 450 °C for 2 h in air. It is found that both ZnO and ZnO:B thin films have wurtzite structure of ZnO with (0 0 2) preferred orientation and high average optical transmission (≥80%). Compared with the resistivity of 6.3 × 10² Ω cm for ZnO film, both as-deposited and annealed ZnO:B films exhibit much lower resistivity of 9.2 × 10⁻³ Ω cm and 7.5 × 10⁻³ Ω cm, respectively, due to increase in the carrier concentration. Furthermore, the optical band gaps of 3.38 eV and 3.42 eV for as-deposited and annealed ZnO:B films are broader than that of 3.35 eV for ZnO film. The first-principles calculations show that in ZnO:B thin films not only the band gap becomes narrower but also the Fermi level shifts up into the conduction band with respect to the pure ZnO film. These are consistent with their lower resistivities and suggest that in the process of annealing some substituted B in the lattice change into interstitial B because of its smaller ion radius and this transformation widens the optical band gap of ZnO:B thin film.     

Influence of deposition temperature on the crystallinity of Al-doped ZnO thin films at glass substrates prepared by RF magnetron sputtering method

Al-doped ZnO (AZO) transparent conducting films were successfully prepared on glass substrates by RF magnetron sputtering method under different substrate temperatures. The microstructural, electrical and optical properties of AZO films were investigated in a wide temperature range from room temperature up to 350 °C by X-ray Diffraction (XRD), Field-Emission Scanning Electron Microscopy (FESEM), High-Resolution Transmission Electron Microscopy (HRTEM), Hall measurement, and UV–visible meter. The nature of AZO films is polycrystalline thin films with hexagonal wurtzite structure and a preferred orientation along c-axis. The crystallinity and surface morphologies of the films are strongly dependent on the growth temperature, which in turn exerts a great effect on microstructural, electrical and optical properties of the AZO films. The atomic arrangement of AZO film having an wurtzite structure was indeed identified by the HRTEM as well as the Selected Area Electron Diffraction (SAED). The defect density of AZO film was investigated by HRTEM. The film deposited at 100 °C exhibited the relatively well crystallinity and the lowest resistivity of 3.6 × 10⁻⁴ Ω cm. The average transmission of AZO films in the visible range is all over 85%. More importantly, the low-resistance and high-transmittance AZO film was also prepared at a low temperature of 100 °C.     

Surface textured ZnO:Al thin films by pulsed DC magnetron sputtering for thin film solar cells applications

Transparent conducting thin films of ZnO:Al (Al-doped ZnO, AZO) were prepared via pulsed DC magnetron sputtering with good transparency and relatively lower resistivity. The AZO films with 800 nm in thickness were deposited on soda-lime glass substrates keeping at 473 K under 0.4 Pa working pressure, 150 W power, 100 μs duty time, 5 μs pulse reverse time, 10 kHz pulse frequency and 95% duty cycle. The as-deposited AZO thin films has resistivity of 6.39 × 10⁻⁴ Ω cm measured at room temperature with average visible optical transmittance, T_total of 81.9% under which the carrier concentration and mobility were 1.95 × 10²¹ cm⁻³ and 5.02 cm² V⁻¹ s⁻¹, respectively. The films were further etched in different aqueous solutions, 0.5% HCl, 5% oxalic acid, 33% KOH, to conform light scattering properties. The resultant films etched in 0.5% HCl solution for 30 s exhibited high T_total = 78.4% with haze value, H_T = 0.1 and good electrical properties, ρ = 8.5 × 10⁻⁴ Ω cm while those etched in 5% oxalic acid for 150 s had desirable H_T = 0.2 and relatively low electrical resistivity, ρ = 7.9 × 10⁻⁴ Ω cm. However, the visible transmittance, T_total was declined to 72.1%.     

The role of oxygen and hydrogen partial pressures on structural and optical properties of ITO films deposited by reactive rf-magnetron sputtering

Sn doped In₂O₃ films are deposited by rf-magnetron sputtering at 300 °C under Ar, Ar + O₂ and Ar + H₂ gas ambients. For the film prepared under argon ambient, electrical resistivity 6.5 × 10⁻⁴ Ω cm and 95% optical transmission in the visible region have been achieved optimizing the power and chamber pressure during the film deposition. X-ray diffraction spectra of the ITO film reveal (2 2 2) and (4 0 0) crystallographic planes of In₂O₃. With the introduction of 1.33% oxygen in argon, (2 2 2) peak of In₂O₃ decreases and resistivity increases for the deposited film. With further increase of oxygen in the sputtering gas mixture crystallinity in the film deteriorates and both the peaks disappeared. On the other hand, when 1.33% hydrogen is mixed with argon, the resistivity of the deposited film decreases to 5.5 × 10⁻⁴ Ω cm and the crystallinity remains almost unchanged. In case of reactive sputtering, the deposition rate is lower compared to that in case of non-reactive sputtering. HRTEM and first Fourier patterns show the highly crystalline structure of the samples deposited under Ar and Ar + H₂ ambients. Crystallinity of the film becomes lower with the introduction of oxygen in argon but refractive index increases from 1.86 to 1.9. The surface morphology of the ITO films have been studied by high resolution scanning electron microscopy.     

Optimization of the optical and electrical properties of electron beam evaporated aluminum-doped zinc oxide films for opto-electronic applications

Aluminum-doped zinc oxide (AZO) thin films have been deposited by electron beam evaporation technique on glass substrates. The structural, electrical and optical properties of AZO films have been investigated as a function of annealing temperature. It was observed that the optical properties such as transmittance, reflectance, optical band gap and refractive index of AZO films were strongly affected by annealing temperature. The transmittance values of 84% in the visible region and 97% in the NIR region were obtained for AZO film annealed at 475 °C. The room temperature electrical resistivity of 4.6×10⁻³ Ω cm has been obtained at the same temperature of annealing. It was found that the calculated refractive index has been affected by the packing density of the thin films, whereas, the high annealing temperature gave rise to improve the homogeneity of the films. The single-oscillator model was used to analyze the optical parameters such as the oscillator and dispersion energies.     

Transparent conducting molybdenum-doped zinc oxide films deposited by RF magnetron sputtering

A new transparent conducting oxide (TCO) film with low resistivity and high transmittance in the visible range, molybdenum-doped zinc oxide (MZO), was successfully prepared by RF magnetron sputtering method on glass substrates at room temperature. The structural, electrical, and optical properties as a function of film thickness were investigated. All the samples have a preferred orientation with the (0 0 2) planes parallel to the substrates. The resistivity initially decreases and then shows an increase with the increase of the film thickness. When the thickness is 400 nm, the film has its best crystallinity and lowest resistivity 9.2 × 10⁻⁴ Ω cm with a Hall mobility of 30 cm² V⁻¹ s⁻¹ and a carrier concentration of 2.3 × 10²⁰ cm⁻³. The average transmittance in the visible range exceeds 84% for all thickness films.     

Effect of Al incorporation on the structural,morphological, optoelectronic and transport properties of PbS thin films

Doping of PbS thin films with different metal atoms produce considerable changes in structural and material properties that make them useful in the technology of thin film devices. The goal of this work is to study the effects of doping on the structural, morphological, optoelectronic and transport properties of PbS thin films as a function of Al³⁺ concentration. Thin films of pure and Al doped PbS nanoparticles are prepared on soda lime glass substrates by chemical bath deposition technique. The Al content in aqueous solution is varied from 0 to 20 mg. XRD analysis of the films revealed significant enhancement in crystallinity and crystallite size up to an optimum concentration of doping. Films are polycrystalline with crystallite size 19–32 nm, having face centered cubic structure. The optical band gap energy exhibits a decreasing trend and is shifted from 2.41 to 1.34 eV with increasing Al content. The room temperature conductivity of the as-deposited PbS films is in the range of 0.78×10⁻⁸ to 0.67×10⁻⁶(Ω cm)⁻¹ with a maximum for optimum Al content. The Al doped PbS thin film, which we synthesize with optimum Al concentration of 15 mg is found to be a most suitable material for solar control coating applications.     

Structural, optical and electrical characterization of highly conducting Mo-doped In2O3 thin films

Highly conducting and transparent thin films of molybdenum-doped indium oxide were deposited on quartz by pulsed laser deposition. The effect of growth temperature and oxygen partial pressure on the structural, optical and electrical properties was studied. We find that the film transparency depends on the growth temperature. The average transmittance of the films grown at different temperatures is in range of 48-87%. The X-ray diffraction results show that the films grown at low temperature are amorphous while the films grown at higher temperature are crystalline. Electrical properties are found to be sensitive to both the growth temperature and oxygen pressure. Resistivity of the films decreases from 1.3 × 10⁻³ Ω cm to 8.9 × 10⁻⁵ Ω cm while mobility increases from 9 cm²/V s to 138 cm²/V s as the growth temperature increases from room temperature to 700 °C. However, with increase in oxygen pressure, resistivity increases but the mobility decreases after attaining a maximum. The temperature-dependent resistivity measurements show transition form semiconductor to metallic behavior. The film grown at 500 °C under an oxygen pressure of 1.0 × 10⁻³ mbar is found to exhibit high mobility (250 cm²/V s), low resistivity (6.7 × 10⁻⁵ Ω cm), and relatively high transmittance (∼90%).