AFM study of the surface morphology of L-CVD SnO2 thin films

In this paper we present the results of Atomic Force Microscopy (AFM) characterisation of the surface morphology of the L-CVD SnO₂ thin films prepared by L-CVD technology and studied after exposure to air, dry air oxidation, and ion beam profiling. The L-CVD SnO₂ thin films after air exposure have a very smooth surface morphology with an average surface roughness (RMS) smaller than 0.5 nm, and average and maximal grain heights of about 1 and 2 nm, respectively. After dry air oxidation the L-CVD SnO₂ thin films exhibit an average surface roughness (RMS), as well as the average and maximal grain height, increased by one order of magnitude. Finally, after the ion beam profiling the L-CVD SnO₂ thin films exhibit an evidently disordered structure with a lot of craters. These experiments showed that the L-CVD SnO₂ thin films exhibit a very high quality surface morphology, what can be useful for solar cells and gas sensors application.     

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.     

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.     

Structural and optoelectronic properties of indium doped SnO2 thin films deposited by sol gel technique

Indium doped tin oxide (SnO₂:In) thin films were deposited on glass substrates by sol–gel dip coating technique. X-ray diffraction pattern of SnO₂:In thin films annealed at 500 °C showed tetragonal phase with preferred orientation in T (110) plane. The grain size of tin oxide (SnO₂) in SnO₂:In thin films are found to be 6 nm which makes them suitable for gas sensing applications. AFM studies showed an inhibition of grain growth with increase in indium concentration. The rms roughness value of SnO₂:In thin films are found to 1 % of film thickness which makes them suitable for optoelectronic applications. The film surface revealed a kurtosis values below 3 indicating relatively flat surface which make them favorable for the production of high-quality transparent conducting electrodes for organic light-emitting diodes and flexible displays. X-ray photoelectron spectroscopy gives Sn 3d, In 3d and O 1s spectra on SnO₂:In thin film which revealed the presence of oxygen vacancies in the SnO₂:In thin film. These SnO₂:In films acquire n-type conductivity for 0–3 mol% indium doping concentration and p type for 5 and 7 mol% indium doping concentration in SnO₂ films. An average transmittance of >80 % (in ultra-violet–Vis region) was observed for all the SnO₂:In films he In doped SnO₂ thin films demonstrated the tailoring of band gap values. Photoluminescence spectra of the films exhibited an increase in the emission intensity with increase in indium doping concentration which may be due structural defects or luminescent centers, such as nanocrystals and defects in the SnO₂.     

Optical properties of SnO2:F films deposited by atmospheric pressure CVD

Atmospheric pressure chemical vapor deposition (APCVD) system, designed for the deposition of F-doped SnO₂ thin films, is compatible with industrial requirements such as high process speed, scaling to wide substrate widths and low costs. Precise method for measuring the optical absorptance in the spectral range 300–1700 nm combines transmittance, reflectance and photothermal deflection (PDS) spectra measured on the same spot of the sample immersed in the transparent liquid with a relatively high index of refraction. The effects of the film thickness, doping gas addition and the susceptor temperature on the optical absorptance and electrical resistivity of the TCO films are assessed. We show that the doping gas concentration and the susceptor temperature influence both the incorporation ratio of dopants into SnO₂ film as well as the defect concentration. The SnO₂ films growth at optimum APCVD conditions have thickness 0.7 µm, average surface roughness about 40 nm, sheet electrical resistance 10 Ω/sq and the optical absorption 1% at 500 nm and about 5% at 1000 nm.     

Gas sensitivity of metal oxide mixed tin oxide films prepared by spray pyrolysis

Various kinds of SnO₂ films, modified with the addition of iron, antimony, copper, titanium, manganese, nickel, cobalt or calcium oxides, were fabricated by using the spray pyrolysis technique and their gas-sensing characteristics were studied. From electrical measurements in air, the relative sensitivity towards inflammable gas of these SnO₂-based film sensors was compared. It was observed that SnO₂-based films of higher electrical resistance had a tendency to have higher sensitivity towards ethanol than the SnO₂-based films of lower resistance. The addition of p-type metal oxides, such as NiO and MnO, to the SnO₂ matrix was found to be effective in increasing the sensitivity towards inflammable gas.     

Nanocrystalline SnO2 and Au:SnO2 thin films prepared by direct current magnetron reactive sputtering

Nanocrystalline pure and gold doped SnO₂(Au:SnO₂) films were prepared on unheated glass substrates by dc magnetron reactive sputtering and, subsequently, the as deposited films were annealed in air. The films structure, surface morphology, photoluminescence, electrical and optical properties were investigated. After annealing the as deposited SnO₂ films, crystallinity increased and the surface roughness decreased. The intensity of PL peaks increases sharply with the annealing temperature. The optical transmittance of the films was around 89% after annealing the as deposited SnO₂ films at 450 °C. The as deposited Au:SnO₂ films show better crystallinity than the as deposited SnO₂ films, the average grain size was around 4.4 nm. The emission peaks of Au:SnO₂ films are slightly blue shifted as compare to undoped SnO₂ films. The Au:SnO₂ films show the lowest electrical resistivity of 0.001 Ωcm with optical transmittance of 76%, after annealing at 450 °C.     

Effect of substrate type, dopant and thermal treatment on physicochemical properties of TiO2–SnO2 sol–gel films

Thin nanocrystalline TiO₂–SnO₂ films (0–50 mol% SnO₂) were prepared on quartz and stainless steel substrates by sol–gel coating method. The obtained films were investigated by XRD, Raman spectroscopy and XPS. The size of the nanocrystallites was determined by XRD–LB measurements. We ascertained that the increase of treatment temperature and concentration of SnO₂ in the films favour the crystallization of rutile phase. The substrate type influences more substantially the phase composition of the TiO₂–SnO₂ films. It was established that a penetration of elements took place from the substrate into the films. TiO₂ films deposited on quartz substrate include a Si which stabilizes anatase phase up to 600 °C. The films which are deposited on stainless steel substrate and treated at 700 °C show the presence of significant quantity of rutile phase. This phenomenon could be explained by the combined effect of Sn dopant as well as Fe and Cr, which also are penetrated in the films from the steel substrate. The titania films doped up to 10 mol% SnO₂ on stainless steel possess only 12–17 nm anatase crystallites, whereas the TiO₂–(10–50 mol%) SnO₂ films contain very fine grain rutile phase (4 nm).     

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.     

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.     

Gas sensing selectivity of oxygen-regulated SnO2 films with different microstructure and texture

The selectivity of gas sensing materials is increasingly important for their applications. The oxygen-regulated SnO₂ films with (110) and (101) preferred orientation were obtained through magnetron sputtering, followed by annealing treatment. Their micro-structure, surface morphology and gas response were investigated by advanced structural characterization and property measurement. The results showed that the as-prepared (110)-oriented SnO₂ film was oxygen-rich and had more adsorption sites while the as-prepared (101)-oriented SnO₂ film was oxygen-poor and more sensitive to de-oxidation. H₂ gas sensitivity, response speed, selectivity between H₂ and CO of the (110)-orientated SnO₂ film was superior to that of the (101)-orientated SnO₂ film. After treated at high temperature and high vacuum, the reduction of gas-sensing properties of the annealed (110) SnO₂ film was much more than that of the annealed (101) SnO₂ film. The lattice oxygen was responsible for the difference in gas-sensing response between (110) and (101)-oriented SnO₂ films under oxygen regulation. This work indicated the gas-sensing selectivity of the different crystal planes in SnO₂ film, providing a significant reference for design and extension of the related materials.     

The effect of Au and Pt nanoclusters on the structural and hydrogen sensing properties of SnO2 thin films

Au and Pt nanoparticle modified SnO₂ thin films were prepared by the sol-gel method on glass substrates targeting sensing applications. Structural and morphological properties of these films were studied using X-ray Diffraction and Scanning Electron Microscopy. It was proved that the films crystallized in tetragonal rutile SnO₂ crystalline structure. Scanning Electron Microscopy observations showed that the metallic clusters' dimensions and geometry depend on the kind of the metal (Au or Pt) while SnO₂ films surface remains almost the same: nanostructured granular very smooth. Optical properties of the films were studied using UV-visible spectroscopy. The modified SnO₂ films were tested as hydrogen sensors. The response of SnO₂, SnO₂-Au and SnO₂-Pt thin films against hydrogen was investigated at different operating temperatures and for different gas concentrations. The addition of metal nanoparticles was found to decrease the detection limit and the operating temperature (from 180 °C to 85 °C), while increasing the sensing response signal.     

SnO2–Au nanocomposite synthesized by successive ionic layer deposition method: Characterization and application in gas sensors

A possibility of synthesizing the SnO₂–Au nanocomposite by the successive ionic layer deposition (SILD) method is demonstrated in this article. It is shown that as a result of successive treatments in solutions of Sn(OH)_xF_yCl_z and HAuCl₄ the SnO₂–Au nanocomposite with a Sn/Au ratio varying from 1:1 to 6:1 can be formed on the surface of substrates. It is found that the value of this ratio depends on the concentration of F ions in solution. The gold in the indicated composite is in the metallic state. The growth of the SnO₂–Au composite takes place through the formation of 3-D precipitates, which form a continuous film after 13 deposition cycles. As a result, a layer with averaged thickness of up to 20 nm is formed on the surface. Nanocomposite films, even after treatment at an annealing temperature T_an ∼ 600 °C, have finely dispersed structure. The size of the Au clusters incorporated in the SnO₂ matrix is in the range from 3 to 15 nm. Gas sensing characteristics of SnO₂ films modified by SnO₂–Au nanocomposites are discussed as well. It is shown that surface modification by SnO₂–Au nanocomposites can be used for improving operating characteristics of conductometric SnO₂-based gas sensors.     

Preparation of nanocrystalline SnO2 thin films used in chemisorption sensors by pulsed laser reactive ablation

Nanocrystalline SnO₂ thin films were fabricated by pulsed laser reactive ablation using a metallic Sn target. Oxidation of Sn to SnO₂ occurred principally on the substrate surface and was negligible during transportation of Sn atoms in the ablated plume from the target to the film. Therefore, the substrate temperature was the most important parameter to influence the phase constitution of the films. When the substrate temperature was higher than the melting point of metal Sn (230 °C), SnO₂ phase was obtained. Otherwise the films were β-Sn dominant. X-ray diffraction and transmission electron microscopy techniques were used to determine the grain size in the films, which was in the range 10–30 nm, depending upon the substrate temperature and the subsequent annealing. For chemisorption performance, films with a thickness up to 24 nm showed a higher sensitivity than the films 38 nm and 96 nm thick. Excellent chemisorption properties have been achieved on the very thin nanocrystalline films. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and CO gas-sensing behavior of Au-doped SnO2 sensors

A study on the low-temperature CO gas sensors based on Au/SnO₂ thick film was reported. Au/SnO₂ powders, with different Au loading from 0.36 to 3.57 wt%, were prepared by a deposition-precipitation method. Thick films were fabricated from Au/SnO₂ powders. The Au/SnO₂ thick-film sensors exhibited high sensitivity to CO gas at relatively low operating temperature (83-210 °C). We also reported the effect of the Au loading in Au/SnO₂ on the CO gas sensing behavior. The optimal Au loading in as-prepared Au/SnO₂ was 2.86 wt%.     

SnO2:Cu films doped during spray pyrolysis deposition: The reasons of the gas sensing properties change

The influence of Cu doping on electrophysical, structural and gas sensing properties of the SnO₂ films deposited by spray pyrolysis was considered in this paper. It was shown that the addition of Cu in SnO₂ even in small concentrations was accompanied by strong changes in the SnO₂-based gas sensors performances. The reasons of observed changes were discussed. The conclusion was made that the decrease of response of heavy doped SnO₂:Cu-based gas sensors was mainly connected with both structural disordering of heavy doped SnO₂:Cu metal oxide, and the appearance of the fine dispersed phase formed in the SnO₂ matrix.     

On the correlation between morphology and gas sensing properties of RGTO SnO2 thin films

In this paper, we present the results of studies on optimalisation of morphology of the SnO₂ thin films grown by RGTO technique for application as gas sensor structures. The Sn thin films were grown on Si(111) wafer and Al₂O₃ ceramic plate heated in the range 235-295 °C and subsequently oxidized in dry oxygen atmosphere at high temperature, up to 700 °C. Our studies confirmed that the highest surface coverage of Sn droplets can be reached for the substrate temperature of about 265 °C leading to the highest surface-to-volume ratio of SnO₂ thin films. It was in a good correlation to the optimal gas sensor response and sensor sensitivity of RGTO SnO₂ thin films to nitrogen dioxide NO₂.     

Influence of thickness on H2 gas sensor properties in polycrystalline SnO x films prepared by ion-beam sputtering

Amorphous SnO _x films were deposited on sintered alumina substrates by ion-beam sputtering. They were annealed at 500° C for 2 h in air and polycrystalline films with thickness varying from about 1 to 700 nm were prepared. Film-sensor properties against 0.47% H₂ gas were measured as a function of thickness and the operating temperature for 150 to 350° C. The film thickness exhibiting a sensitivity maximum increased gradually with temperature. The optimum thickness shifted from 7 nm at 150° C to 175 nm at 350° C. Highly sensitive films lay in a narrow thickness range of 60 to 180 nm and films thinner or thicker than this were relatively insensitive at 300 and 350°C. A model was proposed to interpret the sensitivity behaviour in terms of thickness and grain-boundary effect.     

Preparation and ethanol sensing properties of the superstructure SnO2/ZnO composite via alcohol-assisted hydrothermal route

Self-assembled superstructure of SnO₂/ZnO composite was synthesized by using alcohol-assisted hydrothermal method gas sensing properties of the material were investigated by using a static test system. The structure and morphology of the products were characterized by X-ray diffraction (XRD) and field-emission scanning electron microscope (FE-SEM). The diameter of the SnO₂ nanorods was about 40 nm with a length of about 300 nm, SnO₂ nanorods and ZnO nanosheets interconnect each other to form a superstructure. The gas sensing properties of superstructure SnO₂/ZnO composite with different content of ZnO were investigated. Furthermore, the superstructure SnO₂/ZnO composite sensor is characterized at different operating temperatures and its long-term stability in response to ethanol vapor is tested over a period of 3 months.     

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.