Fabrication and characterization of fluorine-doped thin oxide thin films and nanorod arrays via spray pyrolysis

This paper reports the synthesis and characterization of fluorine-doped tin oxide (FTO) thin films via intermittent spray pyrolysis utilizing a solution mixture of tin chloride pentahydrate and ammonia fluoride. Utilizing the same solution, nanorod arrays were fabricated via template-based growth. Uniform and crack-free FTO films over 20×20 mm with a thickness up to 900 nm have been routinely achieved; such FTO films demonstrate electrical resistivity as low as 2.2×10^-4 Ω cm as well as good optical transparency ranging from 75 to 85%. In addition, FTO nanorods were fabricated using template-filling methods at a temperature of 440 °C. The nanorods have a diameter of ∼160–250 nm, appear to be comprised of small nanoparticles 5–10 nm in size, and have a resistivity value of 4×10^-1 Ω cm. PACS 81.07.-b; 73.61.-r; 81.16.Be     

Room-temperature deposition of transparent conductive Al-doped ZnO thin films using low energy ion bombardment

Al-doped zinc oxide (AZO) films are prepared on quartz substrates by dual-ion-beam sputtering deposition at room temperature (∼25°C). An assisting argon ion beam (ion energy E _i =0–300 eV) directly bombards the substrate surface to modify the properties of AZO films. The effects of assisted-ion beam energy on the characteristics of AZO films were investigated in terms of X-ray diffraction, atomic force microscopy, Raman spectra, Hall measurement and optical transmittance. With increasing assisting-ion beam bombardment, AZO films have a strong improved crystalline quality and increased radiation damage such as oxygen vacancies and zinc interstitials. The lowest resistivity of 4.9×10⁻³Ω cm and highest transmittance of above 85% in the visible region were obtained under the assisting-ion beam energy 200 eV. It was found that the bandgap of AZO films increased from 3.37 to 3.59 eV when the assisting-ion beam energy increased from 0 to 300 eV.     

CO2 laser-induced crystallization of sol–gel-derived indium tin oxide films

Indium tin oxide (ITO) thin films prepared by the sol–gel method have been deposited by the dip-coating process on silica substrates. CO₂ laser is used for annealing treatments. The electrical resistivity of sol–gel-derived ITO thin films decreased following crystallization after exposure to CO₂ laser beam. The topological and electrical properties of the irradiated surfaces have been demonstrated to be strongly related to the coating solution and to the laser processing parameters. Optimal results have been obtained for 5 dip-coating layers film from 0.4 mol/l solution irradiated by 0.6 W/m² laser power density. In this case, homogeneous and optically transparent traces were obtained with a measured sheet resistance of 1.46×10² Ω/□.     

Structural, optical and electrical properties of tin oxide thin film deposited by APCVD method

Tin oxide (SnO₂) thin films have been grown on glass substrates using atmospheric pressure chemical vapour deposition (APCVD) method. During the deposition, the substrate temperature was kept at 400°C–500°C. The structural properties, surface morphology and chemical composition of the deposited film were studied by X-ray diffraction (XRD), scanning electron microscope (SEM) and Rutherford back scattering (RBS) spectrum. XRD pattern showed that the preferred orientation was (110) having tetragonal structure. The optical properties of the films were studied by measuring the transmittance, absorbance and reflectance spectra between λ = 254 nm to 1400 nm and the optical constants were calculated. Typical SnO₂ film transmits ∼ 94% of visible light. The electrical properties of the films were studied using four-probe method and Hall-voltage measurement experiment. The films showed room temperature conductivity in the range 1.08 × 10² to 1.69 × 10² Ω⁻¹cm⁻¹.     

Structural,electrical and optical properties of boron doped ZnO thin films using LSMCD method at room temperature

Zn_1−x B _x O (0≤x≤0.04) thin films were deposited by the liquid source misted chemical vapor deposition (LSMCD) method. The thin films were polycrystalline with grain sizes of 16 nm to 22 nm. The structural, optical, and electrical properties were investigated by X-ray diffraction, UV-visible spectrophotometry, Raman spectroscopy, and Hall effect measurement. Also scanning electron (SEM) and atomic force microscopy (AFM) techniques were used in order to determine the morphological and topological characteristics of the films. The optimal result of Zn_1−x B _x O films was obtained at x=0.02, with a low resistivity of ≈10⁻² Ω cm, and a high transmittancy of 85% in the visible light spectrum (300 nm ∼ 800 nm).     

Fabrication of cuprous and cupric oxide thin films by heat treatment

Cuprous oxide (Cu₂O) and cupric oxide (CuO) thin films were prepared by thermal oxidation of copper films coated on indium tin oxide (ITO) glass and non-alkaline glass substrates. The formation of Cu₂O and CuO was controlled by varying oxidation conditions such as, oxygen partial pressure, heat treatment temperature, and oxidation time. The microstructure, crystal direction, and optical properties of copper oxide films were measured with X-ray diffraction, atomic force microscopy, and optical spectroscopy. The results indicated that the phase-pure Cu₂O and CuO films were produced in the oxidation process. Optical transmittance and reflectance spectra of Cu₂O and CuO clearly exhibited distinct characteristics related to their phases. The electrical properties indicated that these films formed ohmic contacts with Cu and ITO electrode materials. Multilayers of Cu₂O/CuO were fabricated by choosing the oxidation sequence. The experimental results in this paper suggest that the thermal oxidation method can be employed to fabricate device quality Cu₂O and CuO films that are up to 200–300 nm thick.     

Development of conductive transparent indium tin oxide (ITO) thin films deposited by direct current (DC) magnetron sputtering for photon-STM applications

Highly conductive and transparent indium tin oxide (ITO) thin films, each with a thickness of 100 nm, were deposited on glass and Si(100) by direct current (DC) magnetron sputtering under an argon (Ar) atmosphere using an ITO target composed of 95% indium oxide and 5% tin oxide for photon-STM use. X-ray diffraction, STM observations, resistivity and transmission measurements were carried out to study the formation of the films at substrate temperatures between 40 and 400 °C and the effects of thermal annealing in air between 200 and 400 °C for between1 and 5 h. The film properties were highly dependent on deposition conditions and on post-deposition film treatment. The films deposited under an Ar atmosphere pressure of ∼1.7×10^-3 Torr by DC power sputtering (100 W) at substrate temperatures between 40 and 400 °C exhibited resistivities in the range 3.0–5.7×10^-5 Ω m and transmissions in the range 71–79%. After deposition and annealing in air at 300 °C for 1 h, the films showed resistivities in the range 2.9–4.0×10^-5 Ω m and transmissions in the range 78–81%. Resistivity and transmission measurements showed that in order to improve conductive and transparent properties, 2 h annealing in air at 300 °C was necessary. X-ray diffraction data supported the experimental measurements of resistivity and transmission on the studies of annealing time. The surface roughness and film uniformity improve with increasing substrate temperature. STM observations found the ITO films deposited at a substrate temperature of 325 °C, and up to 400 °C, had domains with crystalline structures. After deposition and annealing in air at 300 °C for 1 h the films still exhibited similar domains. However, after deposition at substrate temperatures from 40 °C to 300 °C, and annealing in air at 300 °C for 1 h, the films were shown to be amorphous. More importantly, the STM studies found that the ITO film surfaces were most likely to break after deposition at a substrate temperature of 325 °C and annealing in air at 300 °C for 2 or 3 h. Such findings give some inspiration to us in interpreting the effects of annealing on the improvement of conductive and transparent properties and on the transition of phases. In addition, correlations between the conductive/transparent properties and the phase transition, the annealing time and the phase transition, and the conductive/transparent properties and the annealing time have been investigated. Received: 10 July 2000 / Accepted: 27 October 2000 / Published online: 9 February 2001     

Electrical responses and dielectric relaxations in giant permittivity NaCu3Ti3TaO12 ceramics

Conductive and highly transparent indium tin oxide (ITO) thin films were prepared on photosensitive glass substrates by the combination of sol–gel and spin-coating techniques. First, the substrates were coated with amorphous Sn-doped indium hydroxide, and these amorphous films were then calcined at 550^∘C to produce crystalline and electrically conductive ITO layers. The resulting thin films were characterized by means of scanning electron microscopy, UV-Vis spectroscopy, X-ray photoelectron spectroscopy and spectroscopic ellipsometry. The measurements revealed that the ITO films were composed of spherical crystallites around 20 nm in size with mainly cubic crystal structure. The ITO films acted as antireflection coatings increasing the transparency of the coated substrates compared to that of the bare supports. The developed ITO films with a thickness of ∼170–330 nm were highly transparent in the visible spectrum with sheet resistances of 4.0–13.7 kΩ/sq. By coating photosensitive glass with ITO films, our results open up new perspectives in micro- and nano-technology, for example in fabricating conductive and highly transparent 3D microreactors.     

Novel type of indium oxide thin films sputtering for opto-electronic applications

Transparent conductive oxide (TCO) thin films play a significant role in recent optical technologies. Displays of various types, photovoltaic systems, and opto-electronic devices use these films as transparent signal electrodes. They are used as heating surfaces and active control layers. Oxides of TCO materials such as: tin, indium, zinc, cadmium, titanium and the like, exhibit their properties. However, indium oxide and indium oxide doped with tin (ITO) coatings are the most used in this technology.In this work, we present conductive transparent indium oxide thin films which were prepared using a novel triode sputtering method. A pure In₂O₃ target of 2 in. in diameter was used in a laboratory triode sputtering system. This system provided plane plasma discharge at a relatively low pressure 0.5-5 mTorr of pure argon. The substrate temperature was varied during the experiments from room temperature up to 200 °C. The films were deposited on glass, silicon, and flexible polyimide substrates. The films were characterized for optical and electrical properties and compared with the indium oxide films deposited by magnetron sputtering.     

Pulsed laser deposition of conductive metallo-dielectric optical filters

We describe the fabrication by room-temperature pulsed laser deposition of a transparent conductor comprising alternating layers of silver and aluminum oxide, forming a metallo-dielectric filter. Transmittances of 0.7 over specific wavelength bands were achieved with resistivities as low as 6.0×10^-6 Ω cm, almost two orders of magnitude lower than that of the best single-substrate thin films, such as indium tin oxide. The resistivity can be predicted without adjustable parameters and designed using a simple parallel-circuit model; the optical properties are well described by standard matrix transmission calculations. This demonstrates that pulsed laser deposition may be used to fabricate prototypes of high-quality transparent conductors with predictable properties for conducting windows where low-temperature deposition is critical, as in organic light-emitting diodes and for non-linear optical films. Received: 10 June 2001 / Accepted: 9 August 2001 / Published online: 20 December 2001     

Electrical and optical properties of indium tin oxide thin films grown by pulsed laser deposition

Indium tin oxide (ITO) thin films (200-400 nm in thickness) have been grown by pulsed laser deposition (PLD) on glass substrates without a post-deposition anneal. The electrical and optical properties of these films have been investigated as a function of substrate temperature and oxygen partial pressure during deposition. Films were deposited at substrate temperatures ranging from room temperature to 300 °C in O₂ partial pressures ranging from 0.1 to 100 mTorr. For 300 nm thick ITO films grown at room temperature in oxygen pressure of 10 mTorr, the electrical conductivity was 2.6᎒^-3 Q^-1cm^-1 and the average optical transmittance was 83% in the visible range (400-700 nm). For 300 nm thick ITO films deposited at 300 °C in 10 mTorr of oxygen, the conductivity was 5.2᎒^-3 Q^-1cm^-1 and the average transmittance in the visible range was 87%. Atomic force microscopy (AFM) measurements showed that the RMS surface roughness for the ITO films grown at room temperature was ~7 Å, which is the lowest reported value for the ITO films grown by any film growth technique at room temperature.     

A simplified reactive thermal evaporation method for indium tin oxide electrodes

Indium tin oxide (ITO) films approximately 120 nm thick were deposited onto unheated glass substrates by using reactive thermal evaporation (RTE) and in situ post-evaporation annealing in oxygen. We show that this simplified method can be used to produce high quality ITO thin films with low electrical resistivity (10⁻³ Ω cm) and high transmittance (approximately 80% at 550 nm). The refractive index is approximately 2.0 and the direct optical band gap of the films (above 3.0 eV) is in good agreement with previously reported values. Since this deposition method does not require heating the substrates or furnace annealing at high temperatures, it can be advantageous when it is necessary to decrease the thermal budget on underlying devices or layers.     

Transparence and electrical properties of ZnO-based multilayer electrode

Three-layered ZnO/Ag–Ti/ZnO structures were prepared using both the sol-gel technique and DC magnetron sputtering. This study focuses on the electrical and optical properties of the ZnO/Ag–Ti/ZnO multilayers with various thicknesses of the Ag–Ti layer. The ZnO thin film prepared by the sol–gel method was dried at 300°C for 3 minutes, and a fixed thickness of 20 nm was obtained. The thickness of the Ag–Ti thin film was controlled by varying the sputtering time. The Ag–Ti layer substantially reduced the electrical resistivity of the sol–gel-sprayed ZnO thin films. The sheet resistance of the Ag–Ti layer decreased dramatically and then became steady beyond a sputtering time of 60 s. The sputtering time of Ag–Ti thin film deposition was determined to be 60 s, taking into account the optical transmittance. Consequently, the transmittance of the ZnO/Ag–Ti/ZnO multilayer films was 71% at 550 nm and 60% at 350 nm. The sheet resistance was 4.2 Ω/sq.     

The origin of haze in CVD tin oxide thin films

The origin of haze was investigated in antimony-doped tin oxide thin films, and in double-stack thin films of fluorine-doped tin oxide/antimony-doped tin oxide, both deposited by chemical vapor deposition onto soda-lime–silica float glass substrates. These transparent conductive oxide thin films are of great importance in the production of solar control architectural glazing units. Therefore, understanding the origins of haze is necessary to the development of coated, IR-reflecting glass windows with low overall haze levels. Haze measurements of as-prepared and polished samples were correlated with surface roughness and concentration of internal hole defects. Surface roughnesses were evaluated by atomic force microscopy, and characterized by estimated RMS values. In thin tin oxide films (<2000 Å) internal hole defects caused haze, while in thick tin oxide films (>4000 Å) surface roughness was the primary source of haze.     

Real-time measurement of oxidation dynamics of sub-stoichiometric tungsten oxide films by pulsed laser deposition

In this study WO _x films were deposited by laser ablation of ultra-pure (5N) tungsten trioxide targets onto SiO₂ or silicon substrates at 250°C temperature, 100 mTorr oxygen partial pressure and 1×10⁻⁵ Torr vacuum. Surface chemical states and compositions of the deposits were determined by X-ray photoelectron spectroscopy. The results showed that deposits in oxygen partial pressure contain W⁶⁺ with x∼3.1, while vacuum-deposited films have different W states with various percentage distributions as W⁴⁺>W⁵⁺>W⁶⁺>W⁰, and x∼1. We used fast electrical resistance measurement as a probe to study the deposition process. Film resistance as a function of deposition time in vacuum revealed some microsecond fluctuations modulated on the time variation curve of electrical resistance. We attribute these data to surface absorption and desorption of oxygen during layer deposition. Finally, the effect of the laser beam on the target’s structure, surface morphology and chemical state was studied. Our results revealed that in spite of structural variation by laser irradiation, the O/W ratio remained about 3.     

Impurity effects on the laser-induced crystallization of thin amorphous silicon film on glass substrate

Crystallization of 100 nm thick amorphous silicon (a-Si) films deposited on glass substrates was carried out using a dual-green-laser method. Depending on a-Si deposition method, either low-pressure chemical vapor deposition (LPCVD) or plasma-enhanced chemical vapor deposition (PECVD), the density of impurities such as Al, K, and Na within the a-Si thin films significantly varied. For the high impurity case of LPCVD, grains of 200–300 nm in size were obtained, whereas for the PECVD case a maximum grain size of about 4 μm was achieved, satisfying the requirements for applications in commercial TFT devices. These results confirm that for the use of glass substrates in polycrystallization of a-Si, controlling the impurity density during substrate preparation is critical.     

Structural, electrical and optical properties of TiO2 doped WO3 thin films

TiO₂ doped WO₃ thin films were deposited onto glass substrates and fluorine doped tin oxide (FTO) coated conducting glass substrates, maintained at 500 °C by pyrolytic decomposition of adequate precursor solution. Equimolar ammonium tungstate ((NH₄)₂WO₄) and titanyl acetyl acetonate (TiAcAc) solutions were mixed together at pH 9 in volume proportions and used as a precursor solution for the deposition of TiO₂ doped WO₃ thin films. Doping concentrations were varied between 4 and 38%. The effect of TiO₂ doping concentration on structural, electrical and optical properties of TiO₂ doped WO₃ thin films were studied. Values of room temperature electrical resistivity, thermoelectric power and band gap energy (E_g) were estimated. The films with 38% TiO₂ doping in WO₃ exhibited lowest resistivity, n-type electrical conductivity and improved electrochromic performance among all the samples. The values of thermoelectric power (TEP) were in the range of 23-56 μV/K and the direct band gap energy varied between 2.72 and 2.86 eV.     

SnO2 thin films grown by pulsed Nd:YAG laser deposition

SnO₂ thin films have been deposited on glass substrates by pulsed Nd:YAG laser at different oxygen pressures, and the effects of oxygen pressure on the physical properties of SnO₂ films have been investigated. The films were deposited at substrate temperature of 500°C in oxygen partial pressure between 5.0 and 125 mTorr. The thin films deposited between 5.0 to 50 mTorr showed evidence of diffraction peaks, but increasing the oxygen pressure up to 100 mTorr, three diffraction peaks (110), (101) and (211) were observed containing the SnO₂ tetragonal structure. The electrical resistivity was very sensitive to the oxygen pressure. At 100 mTorr the films showed electrical resistivity of 4×10⁻² Ω cm, free carrier density of 1.03×10¹⁹ cm⁻³, mobility of 10.26 cm² V⁻¹ s⁻¹ with average visible transmittance of ∼87%, and optical band gap of 3.6 eV.     

Hydrothermal synthesis of CdS meso-structures: effects of Zn dopant on optical and photovoltaic properties

Un- and Zn-doped CdS films were synthesized on fluorine (F)-doped tin oxide (FTO) coated glass substrates by hydrothermal method as photovoltaic applications. X-ray diffraction (XRD) patterns clearly indicated hexagonal wurtzite structures in nature for all of the CdS samples. Scanning electron microscopy (SEM) results showed spherical- and flower-like morphologies with micron- and nano-size. The effects of doping on the optical and photovoltaic properties were also investigated using UV–Vis, Raman spectroscopy and J–V plots.     

Characterization of SnO2 obtained from the thermal oxidation of vacuum evaporated Sn thin films

Tin oxide has been prepared by thermal oxidation of evaporated tin thin films onto pyrex glass substrates. Films oxidation was achieved in air at a temperature of 600 °C with varied duration from 20min to 3 h. Structural, optical and electrical properties of the films were characterized by means of X-ray diffraction, UV–vis spectroscopy and electrical resistivity measurements respectively. The X-ray analysis revealed the transformation of Sn into SnO₂ with preferential orientation along (101) plans. No intermediate phases such as SnO and Sn₃O₄ were evidenced. It was also found that the SnO₂ crystallites orientation changed with the annealing time due to the strain energy effect. Both band gap energy and electrical resistivity decrease with annealing time due to the crystalline quality improvement and films densification. We have noticed that oxidation at 600 °C for 3 h leads to transparent and conductive films with suitable properties for photovoltaic applications.