High-rate deposition of Sb-doped SnO2 films by reactive sputtering using the impedance control method

SnO₂ films doped with Sb (ATO) were deposited both on unheated glass substrates and on glass substrates that had been heated at 200 °C by reactive sputtering of an Sb-Sn alloy target with a plasma control unit (PCU) and mid-frequency (mf, 50 kHz) unipolar pulsing. The PCU feedback system monitors the oxidation states of target surface by detecting the sputtering cathode voltage (impedance control method). The mf pulse wave is approximately square-shaped; this helps to reduce arcing on the target when high power density is applied on the cathode. In case of the ATO depositions on the heated substrate at 200 °C in the “transition region” of reactive sputtering, the deposition rate was 280 nm/min, the lowest resistivity of the ATO films was 4.6 × 10^− 3 Ω cm and the optical transmittance was over 80% in the visible region of light.     

An alternative fluorine precursor for the synthesis of SnO2:F by spray pyrolysis

An alternative, non-toxic precursor was employed for the synthesis of SnO₂:F transparent conducting oxide. The performance of benzenesulfonyl fluoride (BSF) as F source for spray pyrolysis was investigated. Its decomposition and the actual incorporation of fluorine in the tin oxide matrix were confirmed by X-ray photoelectron spectroscopy while its effect on the electrical properties was investigated by resistance and Hall measurements. Results were compared with respect to samples grown using a common fluorine source (NH₄F), a commercial available sample and a sample grown by spray pyrolysis at an independent laboratory. We show that BSF leads to actively doped conductive SnO₂ with good carrier mobility, though the fluorine incorporation rate and hence overall conductivity of the films is lower than for fluorine precursors commonly used in spray pyrolysis.     

Effect of density and thickness on H2-gas sensing property of sputtered SnO2 films

Undoped and Pd-doped SnO₂ films were deposited under various conditions for the investigation of the effect of Pd doping, porosity, and thickness on their H₂ gas sensing properties. The temperature of the substrate and the pressure of the discharge gas were varied. All films formed were composed of columns with thicknesses between 20 and 30 nm. The film density decreased as the discharge gas pressure increased and the substrate temperature decreased. It showed values between 4.2×10³ and 7.0×10³ kg/m³ depending on the deposition condition. Low film density and Pd doping resulted in high sensitivity and fast response. The largest sensitivity was observed for a Pd-doped film with a low density of 4.7×10³ kg/m³ and a thickness of 20 nm.     

H2S sensing property of porous SnO2 sputtered films coated with various doping films

Pure SnO₂ films and Ag-, Cu-, Pt-, and Pd-doped SnO₂ films were investigated for H₂S sensing properties. SnO₂ films were deposited by DC magnetron sputtering at various substrate temperatures and discharge gas pressures. As the discharge gas pressure increased and the substrate temperature decreased, the film became porous. Doping with Cu or Ag film improved the sensitivity, and the highest sensitivity was obtained in the porous SnO₂ film coated with an Ag film 16 nm thick. According to the X-ray diffraction (XRD) pattern, Ag deposited on SnO₂ film transformed to Ag₂S upon exposure to H₂S. When the Ag-doped film sensor was operated at a low temperature, the sensitivity was extremely high, but the recovery was insufficient. By increasing the operation temperature, the recovery was improved but the sensitivity decreased.     

Characterizations of SnO2 and SnO2:Sb thin films prepared by PECVD

Structural characterizations of tin oxide (SnO₂) thin films, deposited by plasma-enhanced chemical vapor deposition (PECVD), were investigated with scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results show that the films are porous, the crystalline structure transforms from crystalline to amorphous phase as deposition temperature changes from 500°C to 200°C, and the chemical component is non-stoichiometric (Sn:O is 1.0716 prepared at 450°C with a value of O₂ flow 3.5 l/min). Sheet resistance of the thin films decreases with increasing of deposition temperature. Whereas, sheet resistance increases with increasing of oxygen flow. Tin oxide doped with antimony (SnO₂:Sb) thin films prepared by same method have a better selectivity to alcohol than to carbon monoxide; the maximum sensitivity is about 220%. The gas-sensing mechanism of SnO₂ thin films is commentated.     

Large scale F-doped SnO2 coating on glass by spray pyrolysis

Large scale F-doped SnO₂ coating was carried out on a glass production line by a cheap in-house spray pyrolysis coater. The coater was installed on glass annealing lehr which has a width of ∼2 m. The solution for film formation consisted of SnCl₄·5H₂O and NH₄F dissolved in a solvent. The solution was sprayed by pressure spray nozzles downward to underneath hot glass sheet. The coating was done for 150 s where the glass temperature was in a range of 430-450 °C. The total length of the coated glass was ∼10 m. It was found by sheet resistance measurement that the coating started non-uniformly and then it covered the entire width of glass when spraying time approached 150 s. The lowest sheet resistance of the coated glass was 0.8 kΩ/□ where the film thickness was ∼80 nm which corresponds to film resistivity of ∼6.4 × 10^− 3 Ω-cm.     

Structure and thermal properties of transparent conductive nanoporous F:SnO2 films

The nanoporous F:SnO₂ materials prepared for the purpose of dye-sensitized solar cells (DSCs) application are composed of SnCl₄ (98.0%) and HF (48-51%), produce with a NH₄OH aqueous solution with sol-gel method as a catalyst. Acetylene black is needed to make nano-porous from FTO heated until 120 °C that will change it from sol to gel and with that 2 phase sintering with 500 °C and 550 °C can be predicted to produce nano-materials. The preferred orientation indicates (110), (101), (211) for SnO₂ and (200) for fluorine, respectively. The main IR features include resonances at 660, 620 and 540 cm^− 1. From the FE-SEM results, the mean pore size of the sample is range of 16-38 nm. Finally, the nanoporous F:SnO₂ film used for TCO layer of dye-sensitized solar cells (DSCs) exhibited an energy conversion efficiency of about 1.83% at light intensity of 100 mW/cm².     

Hydrogen sensing properties of Pd-doped SnO2 sputtered films with columnar nanostructures

Pd-doped SnO₂ sputtered films with columnar nanostructures were deposited using reactive magnetron sputtering at the substrate temperature of 300 °C and the discharge gas pressures of 1.5, 12, and 24 Pa. Structural characterization by means of X-ray diffraction and scanning electron microscopy shows that the films composed of columnar nanograins have a tetragonal SnO₂ structure. The films become porous as the discharge gas pressure increases. Gas sensing measurements demonstrate that the films show reversible response to H₂ gas. The sensitivity increases as the discharge gas pressure increases, and the operating temperature at which the sensitivity shows a maximum is lowered. The highest sensitivity defined by (R_a − R_g) / R_g, where R_a and R_g are the resistances before and after exposure to H₂, 84.3 is obtained for the Pd-doped film deposited at 24 Pa and 300 °C upon exposure to 1000 ppm H₂ gas at the operating temperature of 200 °C. The improved gas sensing properties were attributed to the porosity of columnar nanostructures and catalytic activities of Pd doping.     

Fast response detection of H2S by CuO-doped SnO2 films prepared by electrodeposition and oxidization at low temperature

Fast response detection of H₂S by CuO-doped SnO₂ films prepared was prepared by a simple two-step process: electrodeposition from aqueous solutions of SnCl₂ and CuCl₂, and oxidization at 600 °C. The phase constitution and morphology of the CuO-doped SnO₂ films were characterized by X-ray diffraction and scanning electron microscopy. In all cases, a polycrystalline porous film of SnO₂ was the product, with the CuO deposited on the individual SnO₂ particles. Two types of CuO-doped SnO₂ films with different microstructures were obtained via control of oxidation time: nanosized CuO dotted island doped SnO₂ and ultra-uniform, porous, and thin CuO film coated SnO₂. The sensor response of the CuO doped SnO₂ films to H₂S gas at 50–300 ppm was investigated within the temperature range of 25–125 °C. Both of the CuO-doped SnO₂ films show fast response and recovery properties. The response time of the ultra-uniform, porous, and thin CuO coated SnO₂ to H₂S gas at 50 ppm was 34 s at 100 °C, and its corresponding recovery time was about 1/3 of the response time.     

Porous SnO2 sputtered films with high H2 sensitivity at low operation temperature

Undoped and Pd-doped SnO₂ films were deposited at various substrate temperatures and discharge gas pressures using reactive magnetron sputtering. Structural factors of the films, such as crystallite size, grain size, and film density, were systematically investigated. The main objectives of this study are to clarify the operation temperature dependence of the H₂ sensitivity of these films as well as to clarify the dominant structural factor in the determination of the sensitivity. The operation temperature at which the sensitivity defined by (R_a−R_g)/R_g, where R_a and R_g are the resistances before and after exposure to H₂, showed a maximum decreased with decreasing film density. The highest sensitivity of 4470 was obtained for a Pd-doped film with the lowest density of 3.1 g/cm³ at 100 °C. It was found that the sensitivity correlated with film density rather than with crystallite size and grain size. The high sensitivity of a Pd-doped porous film at a low temperature was discussed in relation to the Schottky-barrier-limited transport as well as the chemical and electronic effects of Pd.     

ZnO sputter coating on SnO2 nanowires: Effects of thin coating and subsequent thermal annealing

The structural and optical properties of SnO₂–ZnO core–shell nanowires were studied and the effects of thermal annealing were investigated. As-prepared SnO₂–ZnO core–shell nanowires exhibited a smooth and continuous shell layer along the nanowire, with a thickness in the range of 5–10 nm. While the thin ZnO shell layer disappeared after annealing at 800 °C, this did not occur after annealing at 600 °C. The as-fabricated SnO₂–ZnO core–shell nanowires exhibited yellow emission, presumably from the core SnO₂ nanowires. The UV emission from ZnO shell layer was obtained by annealing at 600 °C, whereas it was removed by annealing at 800 °C.     

SnO2:Ga thin films as oxygen gas sensor

Ga-doped SnO₂ thin films deposited by spray pyrolysis were investigated as oxygen gas sensors. Gallium was added to the films to enhance the catalytic activity of the surface’s film to oxygen. Film resistance was studied in an environment of dry air loaded with oxygen in excess at partial pressures in the range from 0 to 8.78×10³ Pa. The best sensitivity lies close to partial pressures of 133.3 Pa. Film sensitivity reach a maximum at 350 °C. For this temperature and a doping concentration of 3 at.% of Ga in the starting solution, a sensitivity up to 2.1 was obtained.     

Effect of Li doping on the structural, optical and electrical properties of spray deposited SnO2 thin films

Studies on spray deposited transparent conducting Li doped SnO₂ thin films are scarce. Li (0 to 5 wt.%) doped SnO₂ thin films spray deposited onto glass substrates at 773 K in air from chloride precursors were studied for their structural, optical and temperature dependent electrical behaviors. X-ray diffraction patterns indicated single phase with polycrystalline nature. Systematic variation in surface morphology on Li doping was examined by scanning electron microscopy and atomic force microscopy. Film thickness, optical band gap (direct and indirect), sheet resistance and figure of merit were computed from spectral transmittance and temperature dependent resistivity data. Lithium doping was found to decrease the value of sheet resistance by an order in magnitude. Activation energy was computed from temperature dependent electrical resistivity data measured in the range 300 to 448 K. The 4 wt.% Li doped SnO₂ film was found to have a high value of figure of merit among other films. The results are discussed.     

An investigation of super-hydrophilic properties of TiO2/SnO2 nano composite thin films

A sol-gel dip coating technique was used to fabricate TiO₂/SnO₂ nano composite thin films on soda-lime glass. The solutions of SnO₂ and TiO₂ were mixed with different molar ratios of SnO₂:TiO₂ as 0, 3, 4, 6, 8, 9, 10.5, 13, 15, 19.5, 25 and 28 mol.% then the films were prepared by dip coating of the glasses. The effects of SnO₂ concentration, number of coating cycles and annealing temperature on the hydrophilicity of films were studied using contact angle measurement. The films were characterized by means of scanning electron microscopy, X-ray diffraction and atomic force microscopy measurements. The nano composite thin films fabricated with 8 mol.% of SnO₂, four dip coating cycles and annealing temperature of 500 °C showed super-hydrophilicity.     

Nanocrystalline SnO2 and In2O3 as materials for gas sensors: The relationship between microstructure and oxygen chemisorption

The correlations between microstructure of nanocrystalline TCO SnO₂ and In₂O₃ and parameters of oxygen chemisorption are analyzed. Nanocrystalline SnO₂ and In₂O₃ were prepared by wet chemical method. The sample's microstructure was characterized by TEM, XRD and low-temperature nitrogen adsorption. Electrical properties of TCO were studied at 200-400 °C depending on the oxygen partial pressure. Increase of TCO grain size leads to the increase of the fraction of atomic forms of chemisorbed oxygen at the fixed temperature. It could be due to the decrease of surface barrier resulting in the decrease of activation energy of dissociation of molecular ion O_2(ads)⁻.     

Fabrication of highly conductive Ta-doped SnO2 polycrystalline films on glass using seed-layer technique by pulse laser deposition

We discuss the fabrication of highly conductive Ta-doped SnO₂ (Sn_1 − xTa_xO₂; TTO) thin films on glass by pulse laser deposition. On the basis of the comparison of X-ray diffraction patterns and resistivity (ρ) values between epitaxial films and polycrystalline films deposited on bare glass, we proposed the use of seed-layers for improving the conductivity of the TTO polycrystalline films. We investigated the use of rutile TiO₂ and NbO₂ as seed-layers; these are isostructural materials of SnO_2, which are expected to promote epitaxial-like growth of the TTO films. The films prepared on the 10-nm-thick seed-layers exhibited preferential growth of the TTO (110) plane. The TTO film with x = 0.05 on rutile TiO₂ exhibited ρ  = 3.5 × 10^− 4 Ω cm, which is similar to those of the epitaxial films grown on Al₂O₃ (0001).     

Transparent conducting Nb-doped anatase TiO2 (TNO) thin films sputtered from various oxide targets

Transparent conducting Nb-doped anatase TiO₂ (TNO) epitaxial films were sputtered from TiO₂-, Ti₂O₃-, and Ti-based targets at various oxygen partial pressures (Po₂). Using the TiO₂- and Ti₂O₃-based targets, highly conductive films showing a resistivity (ρ) of ~ 3 × 10^− 4 Ω cm could be formed without postdeposition treatment. In the case of the TNO films formed from the Ti-based target, reductive annealing had to be carried out at a temperature of 600 °C to achieve similar resistivity values. Thus, the use of oxide targets is preferable to obtain as-grown transparent conducting TNO films. In particular, the Ti₂O₃-based target is practically advantageous, because it offers a wide range of optimal Po₂ values at which ρ values of the order of 10^− 4 Ω cm are achievable.     

CO sensing with SnO2 thick film sensors: role of oxygen and water vapour

The paper investigates the gas response of nanocrystalline SnO₂ based thick film sensors upon exposure to carbon monoxide (CO) in changing water vapour (H₂O) and oxygen (O₂) backgrounds. The sensing materials were undoped, Pt- and Pd-doped SnO₂. We found that in the absence of oxygen, the sensor signal (defined as the ratio between the resistance in the background gas, R₀ and the resistance in the presence of the target gases, R, namely R₀/R) have the highest values. These values are higher for doped materials than for the undoped ones. The presence of humidity increases dramatically the sensor signal of the doped materials. In the presence of oxygen, the sensor signal decreases significantly for all sensor materials. The results indicate that there is a competitive adsorption between O₂ and H₂O related surface species and, as a result, different sensing mechanisms can be observed for CO.     

Silicon doped SnO2 films for liquid petroleum gas sensor

Silicon doped SnO₂ films were synthesized by sputtering SnO₂ layer onto glass substrates with appropriate amount of silicon sputtered onto them. The bilayer structures were subjected to rapid thermal annealing for the incorporation of Si in SnO₂ matrix. The films thus obtained were characterized by measuring optical and microstructural properties. Liquid petroleum gas (LPG) sensing properties were also investigated. FTIR and Raman studies were also carried out on these films, both, before and after LPG exposure.     

Optical properties of sputter deposited transparent and conducting TiO2:Nb films

Transparent and conducting thin films of TiO₂:Nb were prepared on glass by reactive dc magnetron sputtering in Ar + O₂. Post-deposition annealing in vacuum at 450 °C led to good electrical conductivity and optical transparency. The optical properties in the sub-bandgap region were in good agreement with Drude free electron theory, which accounts for intraband absorption. The band gap of the films was found to be in the range of 3.3 to 3.5 eV and signifies the onset of interband absorption. Electrical conductivities in the 10^− 3 Ω cm range were obtained both from dc electrical measurements and from analysis of the optical measurements.