Structural,Optical and Photoluminescence Study of Nanocrystalline SnO2 Thin Films Deposited by Spray Pyrolysis

Undoped SnO₂ thin films prepared by spray pyrolysis method reveal polycrystalline nature with prominent peaks along (110), (101) and (211) planes. All the films are nanocrystalline with particle size lying in the range of 3·14–8·6 nm calculated by DS formula. Orientation along plane (200) decreases continuously as molar concentration of SnO₂ increases. Dislocation density along plane (110) also decreases as molar concentration increases except 0·4 M SnO₂ thin film. Scanning electron microscopy image of the films contain jelly structures along with agglomerated clusters of particles. SnO₂ synthesized successfully, which confirms by Fourier transform infra-red spectroscopy. The optical transmittance spectra of 0·2 M SnO₂ thin film shows transmittance about 50–60% transmission in visible and near infrared region with a sharp cut off in the ultraviolet region. The transmission decreases in visible and near infrared region as molar concentration increases. Broad UV emission at 398 nm is observed in photoluminescence spectra of the films along with a blue emission, when excited at 250 nm wavelength. Emission intensity randomly changed as SnO₂ molar concentration increases. When excited at 320 nm, one UV and two visible peaks appeared at 385, 460 and 485 nm, respectively.     

Amorphous indium tungsten oxide films prepared by DC magnetron sputtering

Indium-tungsten-oxide (IWO) films were prepared by dc magnetron sputtering at ambient substrate temperature (T_s). Characteristics of the films were compared with those of In₂O₃–SnO₂ (ITO) thin films prepared under the same condition. The sputter-deposited IWO films have entirely amorphous structure with an average transmittance of over 85% in the visible range and exhibit a minimum resistivity of 3.2 × 10^–4cm at W content [W/(In + W)] of 0.57 at.%. An in-situ heating X-ray diffraction measurement have shown that the crystallization temperature of IWO films is higher than those of ITO films (150–160C) and increases with increasing W content. This enabled a smooth amorphous surface of IWO films as compared with a rough surface of partially crystallized ITO films as revealed by an atomic force microscopy. IWO films are useful for transparent electrode of organic light emitting diode and polymer LCDs because of the low resistivity, high transparency and smooth surface obtainable by the conventional dc magnetron sputtering at room temperature.     

Preparation and properties of antimony-doped SnO2 films by thermal decomposition of tin 2-ethylhexanoate

Transparent Sb-doped SnO₂ films were prepared at 600° C on glass substrates by thermal decomposition of tin 2-ethylhexanoate and antimony tributoxide. The films 100 to 300 nm thick, which are composed of fine particles, were very smooth. The films showed no preferred orientation. The minimum resistivity (2.1×10^–2 cm) was attained at a concentration of 8 at% Sb on the substrate precoated with SiO₂. The transmission of these films was about 80% over a wavelength range from 0.4 to 2.0 m.     

Optical and electrical properties of SnO2 films prepared by chemical vapour deposition

Transparent and conducting SnO₂ films are prepared at 500°C on quartz substrates by chemical vapour deposition technique, involving oxidation of SnCl₂. The effect of oxygen gas flow rate on the properties of SnO₂ films is reported. Oxygen with a flow rate from 0·8–1·35 lmin⁻¹ was used as both carrier and oxidizing gas. Electrical and optical properties are studied for 150 nm thick films. The films obtained have a resistivity between 1·72 × 10⁻³ and 4·95 × 10⁻³ ohm cm and the average transmission in the visible region ranges 86–90%. The performance of these films was checked and the maximum figure of merit value of 2·03 × 10⁻³ ohm⁻¹ was obtained with the films deposited at the flow rate of 1·16 lmin⁻¹.     

Subject index

Transparent conducting films of cadmium-tin oxide were prepared by d.c. reactive sputtering from a CdSn alloy target in an ArO₂ atmosphere. The electrical and optical properties of the films were found to depend on the oxygen concentration in the gas mixture. The lowest resistivity obtained was 4 × 10^?4 Ω cm and the average optical transmission was 90% over the visible region. The structure of the films was examined by X-ray diffraction. The thick films exhibited CdSnO₃ (200) or Cd₂SnO₄ (001) and (130) peaks but most of the thin films were amorphous. The post-deposition annealing of the films in an argon atmosphere affected their electrical and optical properties.     

Synthesis and properties of epitaxial SnO2 films deposited on MgO (100) by MOCVD

Epitaxial tin oxide (SnO₂) thin films have been prepared on MgO (100) substrates at 500-600 °C by metalorganic chemical vapor deposition method. Structural and optical properties of the films have been investigated in detail. The obtained films were pure SnO₂ with the tetragonal rutile structure. An in-plane orientation relationship of SnO₂ (110) [010]//MgO (200) [110] between the film and substrate was determined. Two variant structure of SnO₂ were analyzed. The structure of the film deposited at 600 °C was investigated by high-resolution transmission electron microscopy, and an epitaxial structure was observed. The absolute average transmittance of the SnO₂ film at 600 °C in the visible range exceeded 90%. The optical band gap of the film was about 3.93 eV.     

Synthesis of hydrous SnO2 and SnO2-coated TiO2 powders by the homogeneous precipitation method and their characterization

Hydrous SnO₂ and SnO₂-coated TiO₂ powders were synthesized by the homogeneous precipitation method using urea and the products were characterized by X-ray diffraction, thermogravimetry, differential thermal analysis, scanning electron microscopy and energy- dispersive X-ray microanalysis. Electrical conductivities were measured with an impedance analyser. Hydrous SnO₂ powder prepared under conditions without SO ₄ ^2– ions was a bulky product containing 75 wt% of water. The addition of SO ₄ ^2– ions to the solution changed bulky hydrous SnO₂ to a dense product; approximately spherical particles were obtained with an average particle size of 0.14 ± 0.03 m. with 13.5 wt % of absorbed water. Antimony-doped hydrous SnO₂ prepared under conditions with SO ₄ ^2– ions consisted of approximately spherical particles with an average particle size of 0.17 ± 0.04 m with 15.0 wt % of absorbed water. Hydrous SnO₂-coated TiO₂ powders with a good dispersion state and with various Sn/Ti ratios were prepared under conditions with SO ₄ ^2– ions. All the as-prepared coated powders were white, but the products doped with Sb³⁺ ions were turned to pale blue by heat treatment at 600° C for 1 h and their electrical conductivities increased by orders of about 3.0 in comparison with those of the other two.     

Properties of transparent conducting ZnO : Al oxide thin films and their application for molecular organic light-emitting diodes

ZnO : Al (ZAO) films were deposited on glass substrates by a reactive mid-frequency sputtering system. The microstructural, electrical, and optical properties of ZAO films were investigated. It was observed that the polycrystalline film was (0 0 2n) textured with columnar structure. The minimum resistivity was 1.39×10^–4 cm with a carrier concentration of 1.58×10²¹ cm^–3 and a Hall mobility of 28.2 cm² V^–1 s^–1, correspondingly with the c-axis nearly equal to the value of ZnO powder and the minimum mechanical stress therein. The average transmittance of 80.8% in the visible range and infrared reflectance of over 86% in the 1600–4400 cm^–1 interval were obtained. The ZAO films were used as the transparent anodes to fabricate light-emitting diodes, and a luminance efficiency of 2.09 cd A^–1 was measured at a current density of 5.38 A m^–2.     

Preparation and electrical properties of ITO thin films by dip-coating process

Indium tin oxide (ITO) thin films were prepared on quartz glass substrates by a dip-coating process. The starting solution was prepared by mixing indium chloride dissolved in acetylacetone and tin chloride dissolved in ethanol. The ITO thin films containing 0 20 mol% SnO₂ were successfully prepared by heat-treatment at above 400 °C. Chemical stability of sol were investigated by using a FTIR spectrometer. The electrical resistivity of the thin films decreased with increasing heat-treatment temperature, that is carrier concentration increased, and mobility decreased with increasing SnO₂ content. The ITO thin films containing 12 mol% SnO₂ showed the minimum resistivity of =1.2 × 10^–3 ( cm). It also showed high carrier concentration of N=1.2 × 10²⁰(cm^–3) and mobility _H=7.0(cm² V^–1 s^–1).     

Direct patterning of SnO2 composite films prepared with various contents of Pt nanoparticles by photochemical metal-organic deposition

The optical and electrical characteristics of SnO₂ composite films with various contents (0, 0.05, 0.1, 0.2, and 0.3 at.%) of Pt nanoparticles were evaluated. The Pt nanoparticles were synthesized by a methanol reduction method and their average size was controlled to 3 nm using poly(N-vinyl-2-pyrrolidone) as a protecting agent. The lowest resistivity of 2.031 × 10^− 2 Ω cm was obtained in the SnO₂ film containing 0.2 at.% Pt nanoparticles after annealing at 700 °C while its average transmittance in the visible region was 85.24%. The enhanced electrical properties were attributed to the increase of the carrier concentration and crystallinity of the films due to donation from Pt nanoparticles as well as the increased annealing temperature. Meanwhile, the slight degradation of the transmittance was due to scattering from the introduction of Pt nanoparticles and the increased crystallite size due to the increase of the annealing temperature to 700 °C. Well-defined 20-μm wide direct-patterned composite SnO₂ films containing Pt nanoparticles were formed by a simple photochemical metal-organic deposition process involving a photosensitive starting precursor, UV exposure, and removal of the unpatterned area by rinsing with solvent. Based on the results of this study, we suggest that direct-patternable SnO₂ films with Pt nanoparticles can be easily applied to transparent electrodes in electrical devices without requiring an expensive and toxic process such as dry etching.     

Interaction of Pb and Sn with Thin Films of Their Oxides on Single-Crystal Silicon

Experimental data are presented on the interactions between Pb and thin SnO and SnO₂ films and between Sn and thin PbO films during vacuum annealing and subsequent heat treatment in flowing oxygen. The Pb and Sn films were deposited by magnetron sputtering onto single-crystal Si substrates; the SnO and SnO₂ films were produced by heat-treating Sn in flowing oxygen at 470 and 870 K, respectively; and the PbO films were obtained by heat-treating Pb films at 520 K. During annealing of Pb/SnO₂/Si heterostructures at 870 K in a vacuum of 0.33 × 10^–2 Pa, Pb reacts with lead oxides to form PbSnO₃, whereas vacuum annealing of Sn/PbO/Si heterostructures leads to the formation of SnO and Pb metal. The lead stannates forming in vacuum persist during subsequent heat treatment in flowing oxygen at atmospheric pressure at temperatures of up to 1120 K.     

Properties of indium oxide/tin oxide multilayered films prepared by ion-beam sputtering

The preparation and characterization of indium oxide (InO _x )/tin oxide (SnO _y ) multilayered films deposited by ion-beam sputtering are described and compared with indium tin oxide (ITO) films. The structure and the optoelectrical properties of the films are studied in relation to the layered structures and the post-deposition annealing. Low-angle X-ray diffraction analysis showed that most films retained the regular layered structures even after annealing at 500° C for 16 h. As an example, we obtained a resistivity of 6×10^–4 cm and a transparency of about 85% in the visible range at a thickness of 110 nm in a multilayered film of InO _x (2.0 nm)/SnO _y (0.2 nm)×50 pairs when annealed at 300° C for 0.5 h in air. Hall coefficient measurements showed that this film had a mobility of 17 cm² V^–1 sec^–1 and a carrier concentration (electron density) of 5×10²⁰ cm^–3.     

Influence of different process parameters on physical properties of fluorine dopes indium oxide thin films

Fluorine-doped indium oxide films were prepared by the spray pyrolysis technique. The physical properties of these films were investigated with respect to various process parameters, namely variation of dopant concentration (in the solution), deposition temperature (T _s), carrier gas (air) flow rate and the thickness of the film. The best films had a Hall mobility of the order of 28 cm²V^–1 s^–1 and a carrier density of 2.7 × 10²⁰ cm^–3. These films were deposited at T _s=425 °C at an air flow rate of 71 min^–1 for an atomic ratio of fluorine to indium of 72%. The electrical resistivity of these films was of the order of 10^–4 cm and the average transmission in the visible range was found to be 80–90%. The films were polycrystalline, n-type semiconductors with [400] as a preferred orientation. The preferred orientation changes from [400] to [222] depending upon the process parameters.     

Sensor Properties of Pd-Doped SnO2 Films Deposited by Laser Ablation

Polycrystalline SnO₂ and SnO₂ films were surface-doped with palladium using laser ablation. The effect of the energy density of pulsed KrF laser radiation on the plasma generation process and Pd deposition rate was studied, and the depth profiles of Pd in the films were determined. The gas response of the Pd/SnO₂, SnO₂, and Pd/SnO₂ films was studied between 200 and 380°C using a mixture of 1 vol % H₂ with N₂. Surface doping with Pd was found to enhance the hydrogen sensitivity of SnO₂ by two orders of magnitude.     

Preparation of Sb:SnO2 thin films and its effect on opto-electrical properties

The present study focuses on pure and antimony (Sb)-doped tin oxide thin film and its influence on their structural, optical, and electrical properties. Both undoped and Sb-doped SnO₂ thin films have been grown by using simple, inexpensive pyrolysis spray technique. The deposition temperature was optimized to 450 °C. X-ray diffractions pattern have revealed that the films are polycrystalline and have tetragonal rutile-type crystal structure. Undoped SnO₂ films grow along (110) preferred orientation, while the Sb-doped SnO₂ films grow along (200) direction. The size of Sb-doped tin oxide crystals changes from 26.3 to 58.0 nm when dopant concentration is changed from 5 to 25 wt%. The transmission spectra revealed that all the samples are transparent in the visible region, and the optical bandgap varies between 3.92 and 3.98 eV. SEM analysis shows that the surface morphology and grain size are affected by the doping rate. All the films exhibit a high transmittance in the visible region and show a sharp fundamental absorption edge at about 0.38–0.40 nm. The maximum electrical conductivity of 362.5 S/cm was obtained for the film doped with 5 wt% Sb. However, the carrier concentration is increased from 0.708?×?10¹⁸ to 4.058?×?10²⁰ cm³. The electrical study reveals that the films have n-type electrical conductivity and depend on Sb concentration. We observed a decrease in sheet resistance and resistivity with the increase in Sb dopant concentration. For the dopant concentration of 5 wt% of Sb in SnO₂, the Rs and ρ were found minimum with the values of 88.55 (Ω cm^?2) and 2.75 (Ω cm), respectively. We observed an increase in carrier concentration and a decrease in mobility with the addition of Sb up to 25 wt%. The highest figure of merit values 2.5?×?10^–3 Ω^?1 is obtained for the 5wt% Sb, which may be considered potential materials for solar cells' transparent windows.

     

Tin oxide-black molybdenum photothermal solar energy converters

Efficient photothermal solar converters exhibit high solar absorptance and low thermal emittance. The spectral selectivity of both tin oxide (SnO₂) and black molybdenum (BlMo) has been demonstrated in the literature. Tin oxide is transparent in the visible yet becomes reflective in the infrared. Black molybdenum is absorptive in the visible while exhibiting only moderate infrared reflectance, if post-deposition annealing is avoided. Coating BlMo with SnO₂ increases absorptance due to antireflection in the visible and decreases emittance due to the higher infrared reflectance of SnO₂. Typical $\text{SnO}{}_2\text{BlMo}$ stacks exhibit an absorptance of 91 % (of the air mass 2 solar input) and a normal emittance of 13 % (of the 200 C blackbody curve). Both layers are produced under one atmosphere at temperatures as high as 500 C. Exposure of the stacks to air at 400 C for over 48 hours has resulted in no observable optical changes.     

Effect of annealing on the electrical, optical and structural properties of cadmium stannate thin films prepared by spray pyrolysis technique

Polycrystalline thin films of cadmium stannate (Cd₂SnO₄) were deposited by spray pyrolysis method on the Corning substrates at substrate temperature of 525 °C. Further, the films were annealed at 600 °C in vacuum for 30 min. These films were characterized for their structural, electrical and optical properties. The experimental results showed that the post-deposition annealing in vacuum has a significant influence on the properties of the films. The average grain size of the film was increased from 27.3 to 35.0 nm on heat treatment. The average optical transmittance in the visible region (500-850 nm) is decreased from 81.4% to 73.4% after annealing in vacuum. The minimum resistivity achieved in the present study for the vacuum annealed films is the lowest among the reported values for the Cd₂SnO₄ thin films prepared by spray pyrolysis method.     

Fast response time alcohol gas sensor using nanocrystalline F-doped SnO2 films derived via sol–gel method

Pure and fluorine-modified tin oxide (SnO₂) thin films (250–300 nm) were uniformly deposited on corning glass substrate using sol–gel technique to fabricate SnO₂-based resistive sensors for ethanol detection. The characteristic properties of the multicoatings have been investigated, including their electrical conductivity and optical transparency in visible IR range. Pure SnO₂ films exhibited a visible transmission of 90% compared with F-doped films (80% for low doping and 60% for high doping). F-doped SnO₂ films exhibited lower resistivity (0· 12 × 10^???4 Ω  cm) compared with the pure (14·16 × 10^???4 Ω  cm) one. X-ray diffraction and scanning electron microscopy techniques were used to analyse the structure and surface morphology of the prepared films. Resistance change was studied at different temperatures (523–623 K) with metallic contacts of silver in air and in presence of different ethanol vapour concentrations. Comparative gas-sensing results revealed that the prepared F-doped SnO₂ sensor exhibited the lowest response and recovery times of 10 and 13 s, respectively whereas that of pure SnO₂ gas sensor, 32 and 65 s, respectively. The maximum sensitivities of both gas sensors were obtained at 623 K.     

Properties of multilayer transparent conducting oxide films

Multilayered transparent conducting oxide (TCO) film structures have been designed and fabricated to achieve both high conductivity and high transmittance in the visible spectrum. Double-layered TCO structures consisting of Sn-doped CdO and Sn-doped CdIn₂O₄, Cd-rich Cd₂SnO₄, or Ga-doped ZnO are discussed. By optimizing the thickness of the individual layers and the doping levels within those layers, an effective conductivity of 20 600 S/cm and an average transmittance larger than 85% in the 400-700 nm range have been achieved for films epitaxially grown on MgO substrates. Bi-layer films consisting of Sn-doped CdO and Ga-doped ZnO have also been deposited on plastic substrates at room temperature with resistivities of ∼1×10⁻⁴ Ω cm and an average transmittance of 80-85% in the visible range. These properties are attractive for future TCO applications.     

Nanocrystalline sol–gel TiO2–SnO2 coatings: Preparation,characterization and photo-catalytic performance

In this study, preparation of SnO₂ (0–30 mol% SnO₂)–TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process has been investigated. The effects of SnO₂ on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Surface topography and surface chemical state of thin films were examined by atomic force microscopy and X-ray photoelectron spectroscopy. XRD patterns showed an increase in peak intensities of the rutile crystalline phase by increasing the SnO₂ content. The prepared Sn doped TiO₂ photo-catalyst films showed optical absorption in the visible light area exhibited excellent photo-catalytic ability for the degradation of methylene blue under visible light irradiation. Best photo-catalytic activity of Sn doped TiO₂ thin films was measured in the TiO₂–15 mol% SnO₂ sample by the Sn⁴⁺ dopants presented substitution Ti⁴⁺ into the lattice of TiO₂ increasing the surface oxygen vacancies and the surface hydroxyl groups.