Room-temperature deposition of transparent conducting Al-doped ZnO films by RF magnetron sputtering method

Transparent conductive Al-doped zinc oxide (AZO) films with highly (0 0 2)-preferred orientation were deposited on quartz substrates at room temperature by RF magnetron sputtering. Optimization of deposition parameters was based on RF power, Ar pressure in the vacuum chamber, and distance between the target and substrate. The structural, electrical, and optical properties of the AZO thin films were investigated by X-ray diffraction, Hall measurement, and optical transmission spectroscopy. The 250 nm thickness AZO films with an electrical resistivity as low as 4.62 × 10⁻⁴ Ω cm and an average optical transmission of 93.7% in the visible range were obtained at RF power of 300 W, Ar flow rate of 30 sccm, and target distance of 7 cm. The optical bandgap depends on the deposition condition, and was in the range of 3.75-3.86 eV. These results make the possibility for light emitting diodes (LEDs) and solar cells with AZO films as transparent electrodes, especially using lift-off process to achieve the transparent electrode pattern transfer.     

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.     

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.     

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.     

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.     

Study on the electrical and optical properties of Ag/Al-doped ZnO coatings deposited by electron beam evaporation

A layer of silver was deposited onto the surface of glass substrates, coated with AZO (Al-doped ZnO), to form Ag/AZO film structures, using e-beam evaporation techniques. The electrical and optical properties of AZO, Ag and Ag/AZO film structures were studied. The deposition of Ag layer on the surface of AZO films resulted in lowering the effective electrical resistivity with a slight reduction of their optical transmittance. Ag (11 nm)/AZO (25 nm) film structure, with an accuracy of ±0.5 nm for the thickness shows a sheet resistance as low as 5.6 ± 0.5 Ω/sq and a transmittance of about 66 ± 2%. A coating consisting of AZO (25 nm)/Ag (11 nm)/AZO (25 nm) trilayer structure, exhibits a resistance of 7.7 ± 0.5 Ω/sq and a high transmittance of 85 ± 2%. The coatings have satisfactory properties of low resistance, high transmittance and highest figure of merit for application in optoelectronics devices including flat displays, thin films transistors and solar cells as transparent conductive electrodes.     

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.     

Near infrared to UV dielectric functions of Al doped ZnO films deposited on c-plane sapphire substrate using pulsed laser deposition

Transparent conducting polycrystalline Al-doped ZnO (AZO) films were deposited on sapphire substrates at substrate temperatures ranging from 200 to 300 °C by pulsed laser deposition (PLD). X-ray diffraction measurement shows that the crystalline quality of AZO films was improved with increased substrate temperature. The electrical and optical properties of the AZO films have been systematically studied via various experimental tools. The room-temperature micro-photoluminescence (µ-PL) spectra show a strong ultraviolet (UV) excitonic emission and weak deep-level emission, which indicate low structural defects in the films. A Raman shift of about 11 cm⁻¹ is observed for the first-order longitudinal-optical (LO) phonon peak for AZO films when compared to the LO phonon peak of bulk ZnO. The Raman spectra obtained with UV resonant excitation at room temperature show multi-phonon LO modes up to third order. Optical response due to free electrons of the AZO films was characterized in the photon energy range from 0.6 to 6.5 eV by spectroscopic ellipsometry (SE). The free electron response was expressed by a simple Drude model combined with the Cauchy model are reported.     

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.     

Influence of Au thickness on the optical and electrical properties of transparent and conducting TiO2/Au/TiO2 multilayer films

Au-intermediate TiO₂/Au/TiO₂ (TAT) multilayer films were deposited by RF magnetron sputtering onto glass substrates. Changes in the optical and electrical properties of the films were investigated with respect to the thickness of the Au interlayer.The observed optical and electrical properties were dependent on the thickness of the Au interlayer. The resistivity decreased to 3.3 × 10⁻⁴ Ω cm for TiO₂ films with a 20 nm-thick Au interlayer and the optical transmittance was also influenced by the Au interlayer. Although optical transmittance deteriorated as Au thickness increased, TiO₂ films with a 5 nm-thick Au interlayer showed a relatively high optical transmittance of 80% at a wavelength of 550 nm. In addition, since a TAT film with a 5 nm-thick Au interlayer showed a relatively high work function value, it is an alternative candidate for use as a transparent anode in OLEDs and flat panel displays.     

Pulsed Nd:YAG laser depositions of ITO and DLC films for OLED applications

Indium-tin oxide (ITO) films deposited on heated and non-heated glass substrates by a pulsed Nd:YAG laser at 355 nm and ∼2.5 J/cm² were used in the fabrication of simple organic light-emitting diodes (OLEDs), ITO/(PVK + Alq₃ + TPD)/Al. The ITO was deposited on heated glass substrates which possessed resistivity as low as ∼3 × 10⁻⁴ Ω cm, optical transmission as high as ∼92% and carrier concentration of about ∼5 × 10²⁰ cm⁻³, were comparable to the commercial ITO. Substrate heating transformed the ITO microstructure from amorphous to polycrystalline, as revealed by the XRD spectrum. While the polycrystalline ITO produced higher OLED brightness, it was still lower than that on the commercial ITO due to surface roughness. A DLC layer of ∼1.5 nm deposited on this ITO at laser fluence of >12.5 J/cm² improved its device brightness by suppressing the surface roughness effect.     

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%.     

Microstructural and surface property variations due to the amorphous region formed by thermal annealing in Al-doped ZnO thin films grown on n-Si (1 0 0) substrates

X-ray diffraction (XRD) patterns revealed that the as-grown and annealed Al-doped ZnO (AZO) films grown on the n-Si (1 0 0) substrates were polycrystalline. Transmission electron microscopy (TEM) images showed that bright-contrast regions existed in the grain boundary, and high-resolution TEM (HRTEM) images showed that the bright-contrast regions with an amorphous phase were embedded in the ZnO grains. While the surface roughness of the AZO film annealed at 800 °C became smoother, those of the AZO films annealed at 900 and 1000 °C became rougher. XRD patterns, TEM images, selected-area electron diffraction patterns, HRTEM images, and atomic force microscopy (AFM) images showed that the crystallinity in the AZO thin films grown on the n-Si (1 0 0) substrates was enhanced resulting from the release in the strain energy for the AZO thin films due to thermal annealing at 800 °C. XRD patterns and AFM images show that the crystallinity of the AZO thin films annealed at 1000 °C deteriorated due to the formation of the amorphous phase in the ZnO thin films.     

Preparation of ZnO-doped Al films by spray pyrolysis technique

Al-doped zinc oxide (AZO) thin films have been prepared by spray pyrolysis (SP) technique of zinc acetate and aluminium nitrate, and the effect of thickness on structural and optical properties has been investigated. The structural and optical characteristics of the AZO films were examined by X-ray diffraction (XRD) and double-beam spectrophotometry. These films, deposited on glass substrates at an optimal substrate temperature (T_S = 450 °C), have a polycrystalline texture with a hexagonal structure. Transmission measurements showed that for visible wavelengths, the AZO films have an average transmission of over 90%. The optical parameters have been calculated. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for the sprayed films is also reported. Optical band gap of AZO is 3.30 and 3.55 eV, respectively, depending on the film thicknesses.     

The effect of SiO2 buffer layer on the electrical and structural properties of Al-doped ZnO films deposited on soda lime glasses

In this paper, the influence of SiO₂ buffer layer on electrical and structural properties of AZO films on soda lime glasses has been investigated. The results showed that the Hall mobility and carrier concentration of AZO films deposited on soda lime glasses at high temperature could be enhanced by introducing SiO₂ layers. The optical absorption edges of AZO films with SiO₂ buffer layer are blue shifted compared with that of buffer layer free due to the increase of carrier concentration. SiO₂ layers prepared at 400 °C more effectively suppress the diffusion of Na atoms into AZO films compared with that prepared at room temperature. On the other hand, the in-plane stress dependence of optical band gap is linear for AZO films deposited on quartz glass substrates, but is deviated from linearity in the case of soda lime glass substrates.     

Effective barrier height and work function of Mg:Ag thin films with a low Mg concentration acting as cathodes in high-efficiency organic light emitting devices

Organic molecular-beam deposition (OMBD) of Mg:Ag thin films with a low Mg concentration on tris(8-hydroxyquinolino) aluminum (Alq₃) layers at room temperature was performed to investigate the feasibility of using Mg:Ag thin films as cathode electrodes in organic light-emitting devices (OLEDs). The effective barrier height of the Mg:Ag (5:95) thin films grown on the Alq₃ layers, determined from the current-voltage measurements, was as low as 0.22 eV. The work function of the Mg:Ag (5:95) thin film, determined from the secondary electron emission coefficients obtained by using focused ion beam, was 4.12 eV. These results indicate that Mg:Ag (5:95) thin films with a low Mg concentration grown by using the OMBD method hold promise for potential applications as cathode electrodes in high-efficiency OLEDs.     

Formation of TiN-Ir particle films using pulsed-laser deposition and their electrolytic properties in producing hypochlorous acid

Using sintered TiN and TiN-Ir (Ir contents: 5.9-14.2 at.%) targets, pulsed-laser deposition (PLD) was carried out to produce thin films composed of nanoparticles and particulates in the presence of nitrogen gas. The size (2-100 nm) of the produced crystalline TiN nanoparticles increased as nitrogen pressure was increased in the range from 1.33 to 1.33 × 10² Pa. At a pressure of 1.33 × 10³ Pa, amorphous TiN nanoparticles combined in the form of chains. Large Ir particulates with diameters of up to 2 μm were particularly prominent in TiN-Ir films. Size distributions of the Ir particulates were dependent on ablation laser wavelength; that is, the diameter decreased at laser wavelength shortened. The TiN-Ir films with different Ir contents and morphologies on Ti substrates were evaluated as electrolysis electrodes for water disinfection. The highest current efficiency was 0.45%, which is comparable to that of conventional Ti-Pt electrodes, for a chloride-ion concentration of 9 mg dm⁻³.     

Effects of hydrogen flux on the properties of Al-doped ZnO films sputtered in Ar + H2 ambient at low temperature

Al-doped ZnO (AZO) transparent conductive thin films were grown by magnetron sputtering with AZO (98 wt.% ZnO, 2 wt.% Al₂O₃) ceramic target in Ar + H₂ ambient at a relatively low temperature of 100 °C. To investigate the dependence of crystalline and properties of as-grown AZO films on the H₂-flux, X-ray diffraction (XRD), X-ray photoemission spectrometer (XPS), Hall and transmittance spectra measurements were employed to analyze the AZO samples deposited with different H₂-flux. The results indicate that H₂-flux has a considerable influence on the transparent conductive properties of AZO films. The resistivity of 4.15 × 10⁻⁴ Ω cm and the average transmittance of more than 94% in the visible range were obtained with the optimal H₂-flux of 1.0 sccm. Such a low temperature growing method present here may be especially useful for some low-melting point photoelectric devices and substrates.     

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.     

Properties of ITO–AZO bilayer thin films prepared by magnetron sputtering for applications in thin-film silicon solar cells

In this paper we study the electro-optical behavior and the application of indium–tin oxide (ITO) and aluminum-doped zinc oxide (AZO) bilayer thin films for silicon solar cells. ITO–AZO bilayer thin films were deposited on glass substrates using radio-frequency magnetron sputtering. The experimental results show that a decrease in the electrical resistivity of the ITO–AZO bilayer thin films has been achieved without significant degradation of optical properties. In the best case the resistivity of the bilayer films reached a minimum of 5.075×10^?4 Ω?cm when the thickness of the AZO buffer layer was 12 nm. The ITO–AZO bilayer films were applied as the front electrodes of amorphous silicon solar cells and the short-circuit current density of the solar cells was considerably increased.