XPS and X-ray diffraction studies of aluminum-doped zinc oxide transparent conducting films

Aluminum-doped zinc oxide transparent conducting films are prepared by spray pyrolysis at different dopant concentrations. These films are subsequently characterized by X-ray diffractometric and X-ray photoelectron spectroscopic (XPS) techniques. The results are compared with those obtained from pure zinc oxide films prepared under identical conditions. X-ray diffraction measurements show an increase in lattice parameters (c and a) for aluminum-doped films while their ratio remains the same. This study also indicates that within the XPS detection limit the films are chemically identical to pure zinc oxide. However, a difference in the core-electron line shape of the Zn 2p_3/2 photoelectron peaks is predicted. An asymmetry in Zn 2p_3/2 photoelectron peaks has been observed for aluminium-doped films. The asymmetry parameters evaluated from core-electron line-shape analysis yield a value of the order of 0.04±0.01. The value is found to lie between those obtained for pure zinc oxide and has been attributed to the presence of excess zinc in the films.     

Atomic Vapor Depositions of Ti-Ta-O thin films for Metal-Insulator-Metal applications

Atomic Vapor Deposition technique was applied for the depositions of Ti-Ta-O oxide films for Metal-Insulator-Metal capacitors used in back-end of line for Radio Frequency applications. Composition, crystallinity, thermal stability and electrical properties were studied. Ti-Ta-O films, with the ratio of Ta/Ti ~ 1.5, deposited at 400 °C on TiN electrodes, were amorphous and possessed a dielectric constant of 50 with low voltage linearity coefficients and leakage currents densities as low as 10^− 7 A/cm² at 1 V. The films, deposited on Si wafers, were amorphous up to the annealing temperature of 700 °C and crystallized in orthorhombic Ta₂O₅ phase at higher temperatures.     

Phosphonate-anchored thin films on titanium and niobium oxide surfaces: Fabrication and characterization

Phosphonate-anchored thin films form on various metal oxide substrates. This paper compares structural details of these covalently anchored films on the oxidized surfaces of titanium, niobium and a Ti45Nb alloy. This is made possible by a sample configuration wherein the alkylphosphonates are coated onto a thin film of metal which is sputtered onto a double-side-polished silicon wafer and then oxidized. Samples are flat and reflective and are suitable for ellipsometry, wetting measurements, X-ray Photoelectron Spectroscopy, Atomic Force Microscopy, and Fourier Transform Infrared-Attenuated Total Reflectance Spectroscopy. Deposition from heated tetrahydrofuran produces ordered films with measurable differences among deposition protocols and among metal oxide substrates. These substrates enable identification of the mildest deposition procedures that still provide uniform, robust surface coatings.     

Second harmonic generation in self-assembled ZnO microcrystallite thin films

The second-order non-linear susceptibility components were measured using 1.064 μm incident light for ZnO thin films of various thicknesses from 24.4 to 283 nm self-assembled on sapphire substrates by laser molecular beam epitaxy. It was found that the values of the non-linear susceptibility for the films are almost the same as those of bulk material, except the samples with thicknesses ranging from 35 to 64.8 nm, which show a large enhancement effect. For the sample with a thickness of 44.4 nm, the second-order non-linear susceptibility components were found to be approximately 14.7 pm/v for d₃₁, 15.2 pm/v for d₁₅, and −83.7 pm/v, a value approximately 14 times that of the bulk material, for d₃₃. The second-order non-linear coefficient enhancement in the thin films may be resulted from the microcrystallite structures.     

Influence of VI/II ratios on the growth of ZnO thin films on sapphire substrates by low temperature MOCVD

We investigated the structural, electrical, and optical properties of ZnO thin films grown at different VI/II ratios on sapphire substrates by metalorganic chemical vapor deposition. Transmission electron microscopy and X-ray diffraction revealed the epitaxial nature with a reduced dislocation density of the ZnO films grown at increased VI/II ratios. The carrier concentration of the films increased to 4.9 × 10¹⁸ cm^− 3 and their resistivity decreased to 1.4 × 10^− 1 Ω cm at a VI/II ratio of 513.4 μmol/min. The ZnO films also showed good optical transmittance (> 80%) in the visible and near-infrared wavelength regions. The room temperature PL revealed a strong band-edge emission with a weak deep level emission, suggesting the good crystalline quality of the ZnO films on the sapphire substrates. Furthermore, the intensity ratio of the band-edge emission to the deep-level emission (I_UV/I_Vis) increased with increasing VI/II ratio.     

Preparation of crystalline beta barium borate thin films on Sr-doped alpha barium borate substrates by liquid phase epitaxy

Thin films of beta barium borate have been prepared by liquid phase epitaxy on Sr²⁺-doped -BaB₂O₄ (-BBO, the high temperature phase of barium borate) (001) and (110) substrates. The results of X-ray diffraction indicate that the films show highly (00l) preferred orientation on (001)-oriented substrates while the films grown on (110) substrates are textured with (140) orientation. The crystallinity of these films was found to depend on growth temperature, rotation rate, dip time and orientation of substrate. Growth conditions were optimized to grow films with (00l) orientation on (001) substrates reproducibly. The films show second harmonic generation of 400 nm light upon irradiation with 800 nm Ti: Sapphire femtosecond laser light.     

Characterization of nanostructures of ZnO and ZnMnO films deposited by successive ionic layer adsorption and reaction method

ZnO and ZnMnO thin films were obtained by the successive ionic layer adsorption and reaction (SILAR) method. All thin films were deposited on glass microscope slide. A precursor solution of 0.1 M of ZnCl₂ complexed with ammonium hydroxide and water close to boiling point (92 °C) as a second solution was used for the ZnO films. An uncomplexed bath comprised of 0.1 M ZnCl₂, 0.1 M MnCl_2, and a second solution of 0.1 ml of NH₄OH with water close to boiling point was used for the ZnMnO films. The film samples were deposited by the SILAR method and annealed at 200 °C for 15 min. These samples were characterized using X-Ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive Spectroscopy (EDS), and Atomic Force Microscope. Atomic absorption was used to determine quantitatively the amount of Mn incorporated into the films. According to the XRD patterns these films were polycrystalline with wurtzite hexagonal structure. The morphology of the ZnO films constituted by rice-like and flower-like structures changed significantly to nanosheet structures with the Mn incorporation. The Mn inclusion in a ZnO structure was less than 4% according to the results from EDS, XRD, and atomic absorption.     

Effect of the substrate temperature on zirconium oxynitride thin films deposited by water vapour-nitrogen radiofrequency magnetron sputtering

ZrN_x films were deposited by radiofrequency reactive magnetron sputtering technique in nitrogen and water vapour atmosphere varying the working temperature from room temperature to 600 °C. The films' physical properties were investigated using X-ray diffraction, Secondary Ion Mass Spectroscopy, Atomic Force Microscopy and Transmission Electron Microscopy. It was found that the increase of temperature caused a decrease in the oxygen incorporation and a transition from cubic phase of Zr₂ON₂ to ZrN one. The formation of nanosized crystalline particles dispersed in the amorphous matrix was observed.     

Transparent conducting indium oxide thin films grown by low-temperature metal organic chemical vapor deposition

We have grown indium oxide thin films on silicon substrates at low temperature by metal organic chemical vapor deposition. Polycrystalline film growth could only be obtained at temperatures below 400 °C. Above 400 °C, metallic indium deposition dominated. We have investigated the effect of substrate temperature and reactor pressure on the film growth and structural properties in the range of 250-350 °C and 5 ^? 10³-4 ^? 10⁴ Pa. The film grown at 300 °C exhibited a resistivity of about 3.6 × 10^− 3 Ω cm and a maximal optical transmittance of more than 95% in the visible range. The film showed an optical band gap of about 3.6 eV.     

Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

Sputter deposition of ZnO thin films at high substrate temperatures

ZnO thin films have been deposited on GaN and ZnO substrates at substrate temperatures up to 750 °C by radio-frequency sputtering using ZnO ceramic targets in pure argon or in a mixture of argon and oxygen. By optimizing the sputter parameters, such as sputtering power, Ar/O₂ sputtering gas ratio and temperature of the substrates high quality films were obtained as judged from the X-ray rocking curve half width and luminescence line width. The crystallinity of the ZnO films increases with increasing substrate temperature. Yet there are distinct differences between films grown on GaN templates and on O- and Zn-polar ZnO substrates.     

Refractive indices of textured indium tin oxide and zinc oxide thin films

The refractive indices of textured indium tin oxide (ITO) and zinc oxide (ZnO) thin films were measured and compared. The ITO thin film grown on glass and ZnO buffered glass substrates by sputtering showed distinct differences; the refractive index of ITO on glass was about 0.05 higher than that of ITO on ZnO buffered glass in the whole visible spectrum. The ZnO thin film grown on glass and ITO buffered glass substrates by filtered vacuum arc also showed distinct differences; the refractive index of ZnO on glass was higher than that of ZnO on ITO buffered glass in the red and green region, but lower in the blue region. The largest refractive index difference of ZnO on glass and ITO buffered glass was about 0.1 in the visible spectrum. The refractive index variation was correlated with the crystal quality, surface morphology and conductivity of the thin films.     

Indium doped zinc oxide thin films obtained by electrodeposition

Indium doped ZnO thin films were obtained by co-electrodeposition (precursor and dopant) from aqueous solution. XRD analysis showed typical patterns of the hexagonal ZnO structure for both doped and undoped films. No diffraction peaks of any other structure such as In₂O₃ or In(OH)₃ were found. The incorporation of In into the ZnO film was verified by both EDS and XPS measurements. The bandgap energy of the films varied from 3.27 eV to 3.42 eV, increasing with the In concentration in the solution. This dependence was stronger for the less cathodic potentials. The incorporation of In into the film occurs as both, an In donor state in the ZnO grains and as an amorphous In₂O₃ at the grain boundaries.     

The incorporation of preformed metal nanoparticles in zinc oxide thin films using aerosol assisted chemical vapour deposition

The feasibility of Aerosol Assisted Chemical Vapour Deposition (AA-CVD) has been investigated for the growth of zinc oxide (ZnO) films containing preformed metal nanoparticles. The deposition parameters were first established for ZnO thin films, by varying the heating configuration, substrate temperature and deposition time. Films were characterised using Scanning Electron Microscopy and X-Ray Diffraction. As-deposited films, grown at 250 °C, were mostly amorphous and transformed to highly crystalline Wurtzite ZnO at higher substrate temperatures (400-450 °C). A change in the preferential orientation of the films was observed upon changing (i), the substrate temperature or (ii), the heating configuration. Following this, the applicability of the AA-CVD process for the incorporation of preformed nanoparticles (platinum and gold) in ZnO thin films was investigated. It was found that surface agglomeration occurred, such that the ZnO films were capped with an inhomogeneous coverage of the metal. These layers were characterised using Transmission Electron Microscopy and Electron Diffraction. A possible mechanism for the formation of these metal surface clusters is presented.     

Femtosecond laser deposited zinc oxide film and its optical properties

Zinc oxide (ZnO) thin films have been grown on Si (100) substrates using a femto-second pulsed laser deposition (fsPLD) technique. The effects of substrate temperature and laser energy on the structural, surface morphological and optical properties of the films are discussed. The X-ray diffraction results show that the films are highly c-axis oriented when grown at 80 °C and (103)-oriented at 500 °C. In the laser energy range of 1.0 mJ-2.0 mJ, the c-axis orientation increases and the mean grain size decreases for the films deposited at 80 °C. The field emission scanning electron microscopy indicates that the films have a typical hexagonal structure. The optical transmissivity results show that the transmittance increases with the increasing substrate temperature. In addition, the photoluminescence spectra excited with 325 nm light at room temperature are studied. The structural properties of ZnO films grown using nanosecond (KrF) laser are also discussed.     

Nitrogen-doped p-type ZnO thin films and ZnO/ZnSe p-n heterojunctions grown on ZnSe substrate by radical beam gettering epitaxy

We investigate the p-type doping in ZnO prepared by the method of radical beam gettering epitaxy using NO gas as the oxygen source and nitrogen dopant. Secondary ion mass spectroscopy measurements demonstrate that N is incorporated into ZnO film in concentration of about 8 × 10¹⁸ cm^− 3. The hole concentration of the N-doped p-type ZnO films was between 1.4 × 10¹⁷ and 7.2 × 10¹⁷ cm^− 3, and the hole mobility was 0.9-1.2 cm²/Vs as demonstrated by Hall effect measurements. The emission peak of 3.312 eV is observed in the photoluminescence spectra at 4.2  of N-doped p-type ZnO films, probably neutral acceptor bound. The activation energy of the nitrogen acceptor was obtained by temperature-dependent Hall-effect measurement and equals about 145 meV. The p-n heterojunctions ZnO/ZnSe were grown on n-type ZnSe substrate and have a turn-on voltage of about 3.5 V.     

Monocrystalline zinc oxide films grown by atomic layer deposition

In the present work we report on the monocrystalline growth of (00.1) ZnO films on GaN template by the Atomic Layer Deposition technique. The ZnO films were obtained at temperature of 300 °C using dietylzinc (DEZn) as a zinc precursor and deionized water as an oxygen precursor. High resolution X-ray diffraction analysis proves that ZnO layers are monocrystalline with rocking curve FWHM of the 00.2 peak equals to 0.07°. Low temperature photoluminescence shows a sharp and bright excitonic line with FWHM of 13 meV.     

Radio frequency sputtered zinc oxide thin films with application to metal-semiconductor-metal photodetectors

Zinc oxide (ZnO) films were successfully deposited on silicon, silicon dioxide, and glass substrates by radio frequency magnetron sputtering at different deposition conditions. Field emission scanning electron microscopy, X-ray photoelectron spectroscopy, transmission and photoluminescence measurements were employed to analyze the effect of the deposition conditions and the postdeposition annealing treatment on the surface morphology, structure, chemical deposition and optical properties of ZnO thin films. It was found that the thickness of ZnO films decreased with increased ratio of oxygen/argon and increased temperature. The crystalline and stoichiometric quality of the film was improved by depositing at high temperature and low pressure. Crystals formed more tightly and uniformly with heat treatment under air ambient. The dark current of the ZnO metal-semiconductor-metal photodetector was reduced from 3.06 μA to 96.5 nA at 5 V after postdeposition annealing when compared with that of as-deposited ZnO. Its magnitude was found to be at least two orders lower than that of the as-deposited sample.     

Transparent conductive indium-doped zinc oxide films prepared by atmospheric pressure plasma jet

Atmospheric-pressure plasma processing has attracted much interest for industrial applications due to its low cost, high processing speed and simple system. In this study, atmospheric-pressure plasma jet technique was developed to deposit indium-doped zinc oxide films. The inorganic metal salts of zinc nitrate and indium nitrate were used as precursors for Zn ions and In ions, respectively. The effect of different indium doping concentration on the morphological, structural, electrical and optical properties of the films was investigated. Grazing incidence X-ray diffraction results show that the deposited films with a preferred (002) orientation. The lowest resistivity of 1.8 × 10^− 3 Ω cm was achieved with the 8 at.% indium-doped solution at the substrate temperature of 200 °C in open air, and average transmittance in the visible region was more than 80%.     

Amorphous structure and electrical performance of low-temperature annealed amorphous indium zinc oxide transparent thin film transistors

The effect of low-temperature (200 °C) annealing on the threshold voltage, carrier density, and interface defect density of amorphous indium zinc oxide (a-IZO) thin film transistors (TFTs) is reported. Transmission electron microscopy and x-ray diffraction analysis show that the amorphous structure is retained after 1 h at 200 °C. The TFTs fabricated from as-deposited IZO operate in the depletion mode with on-off ratio of > 10⁶, sub-threshold slope (S) of ~ 1.5 V/decade, field effect mobility (μ_FE) of 18 ± 1.6 cm²/Vs, and threshold voltage (V_Th) of − 3 ± 0.7 V. Low-temperature annealing at 200 °C in air improves the on-current, decreases the sub-threshold slope (1.56 vs. 1.18 V/decade), and increases the field effect mobility (μ_FE) from 18.2 to 23.3 cm²/Vs but also results in a V_Th shift of − 15 ± 1.1 V. The carrier density in the channel of the as-deposited (4.3 × 10¹⁶ /cm³) and annealed at 200 °C (8.1 × 10¹⁷ /cm³) devices were estimated from test-TFT structures using the transmission line measurement methods to find channel resistivity at zero gate voltage and the TFT structures to estimate carrier mobility.