XPS study of the surface chemistry of L-CVD SnO2 thin films after oxidation

In this paper we present the results of XPS study of the surface chemistry of L-CVD SnO₂ thin films onto Si(100) before and after subsequent additional oxidation. Moreover, the ageing effect was also studied in order to check the influence of ambient oxidation. As-deposited L-CVD SnO₂ thin films exhibit evident nonstoichiometry with the relative concentration [O]/[Sn] equal to 1.29 ± 0.1. After in situ oxidation at high temperature (800 K) the relative concentration [O]/[Sn] increases to 1.95 ± 0.05 which corresponds to the almost stoichiometric SnO₂. Almost the same relative concentration [O]/[Sn] of L-CVD SnO₂ thin films has been obtained after long term exposure to air. The oxidation states of L-CVD SnO₂ thin films in both cases were confirmed by the shape analysis of corresponding XPS O1s and Sn3d_5/2 peaks using the decomposition procedure. For the as-deposited L-CVD SnO₂ thin films a mixture of SnO and SnO₂ was observed, while for the oxidized L-CVD SnO₂ thin films the domination of SnO₂ was determined.     

X-ray photoelectron spectroscopy and thermal desorption spectroscopy comparative studies of L-CVD SnO2 ultra thin films

In this paper we present the results of comparative studies of the chemical stability of L-CVD SnO₂ ultra thin films (20 nm) deposited on the atomically clean Si(100) substrate after their subsequent in situ hydrogenation and oxidation, and then after air exposure. For the control of surface chemistry of these films we used in a comparative way the X-ray Photoemission Spectroscopy (XPS) combined with ion depth profiling (DP XPS) and Thermal Desorption Spectroscopy (TDS). Our XPS experiments showed that the L-CVD SnO₂ ultrathin films after subsequent in situ hydrogenation and oxidation consist of strongly nonstoichiometric layer at the top of Si dioxide substrate. After subsequent air exposure they were covered with undesired 3 monolayers of C contamination and various forms of oxygen. During the TDS procedure a two-step desorption of molecular hydrogen (H₂), water vapor (H₂O), carbon dioxide (CO₂) and atomic oxygen (O) at the temperatures of ~ 530 K and 600 K was observed, respectively. The TDS results were in a good correlation with evident decreasing of the relative concentration of C contaminations, as well as variation of nonstoichiometry of the L-CVD SnO₂ ultra thin films as determined by XPS combined with ion depth profiling.     

Local surface morphology and chemistry of SnO2 thin films deposited by rheotaxial growth and thermal oxidation method for gas sensor application

In this paper experimental results of a comparative X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS) study of the crystalline structure, the local morphology, and the surface and in-depth chemistry of SnO₂ thin films obtained by Rheotaxial Growth and Thermal Oxidation (RGTO) method are presented. XRD rules out even a minor presence of a coexisting SnO phase. AFM and SEM show a fractal like morphology of nanograins (20 nm typical size) agglomerated in clusters of crystallites with a bimodal size distribution. XPS shows that the surface of the SnO₂ crystallites is slightly under-stoichiometric as expected from the oxygen deficient termination of their facets. Noteworthy, as evidenced by XPS depth profiles, there are no significant changes of the surface chemistry of the RGTO film with argon ion sputtering.     

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 deposition temperature on structure and morphology of nanostructured SnO2 films synthesized by pulsed laser deposition

Nanostructured tin oxide thin films were deposited on the Si (100) substrate using the pulsed laser deposition technique at different substrate temperatures (300, 450 and 600 °C) in an oxygen atmosphere. The structure and morphology of the as-deposited films indicate that the film crystallinity and surface topography are influenced by the deposition temperature by changing from an almost amorphous to crystalline microstructure and smoother topography at a higher substrate temperature. The photoluminescence measurement of the SnO₂ films shows three stable emission peaks centered at respective wavelengths of 591, 554 and 560 nm with increasing deposition temperature, contributed by the oxygen vacancies.     

Microstructural study of SnO2 thin layers deposited on sapphire by sol-gel dip-coating

Tin oxide (SnO₂) films have been grown onto (006) sapphire substrates by sol-gel dip-coating using tin alkoxide solutions. It is shown, using grazing-incidence X-ray diffraction, reciprocal space mapping and atomic force microscopy, that thermal annealing at 500 °C induces the crystallization of SnO₂ in the rutile-type phase. Further annealing treatments at temperatures lower than 1100 °C give rise to slow grain growth controlled by surface diffusion, whereas rapid grain growth (controlled by an evaporation-condensation mechanism) takes place at temperatures higher than 1100 °C. Concomitantly, the film splits into isolated islands and a fibre texture occurs at higher temperatures.     

Role of surface properties of MoO3-doped SnO2 thin films on NO2 gas sensing

The role of surface morphology of MoO₃-doped SnO₂ thin film on the gas sensing properties is analyzed. SnO₂ thin films doped with 1, 3, 5 and 10 wt% MoO₃ are prepared by sol-gel spin coating process. Structural and morphological properties are studied using glancing angle X-ray diffractometer, atomic force microscopy, transmission electron microscopy and high resolution transmission electron microscopy. Energy dispersive X-ray analysis and X-ray photoelectron spectroscopy studies are used for chemical analysis. A good correlation is found between the characteristics of the surface and gas sensing properties of these films. MoO₃ addition is found responsible for increase in acidic nature of films which in turn increases their sensitivity and selectivity towards NO₂ gas.     

Morphology and microstructure of textured SnO2 thin films obtained by spray pyrolysis and their effect on electrical and optical properties

Tin dioxide thin films on glass substrate with different Zn doping levels were obtained by spray pyrolysis. Their microstructure, preferred crystallographic orientation, electrical and optical properties were extensively studied. The characterization techniques employed were scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X-ray diffraction, electrical conductivity and optical transmission measurements. It was found that the material obtained has a nano-scale texture which characteristic size and orientation strongly depend on the Zn doping level. Doping-induced variations in texture and structure modify both the electrical and optical properties of films (namely, refractive index and transparency). The results obtained are relevant for potential applications of the studied films in gas sensing and photoconductive devices.     

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.     

Structural and morphological characterization of Pr and Er-containing SiO2-P2O5 sol-gel thin films

Present work is focused on obtaining and characterization of sol-gel thin films belonging to SiO₂-P₂O₅-Er₂O₃ (I) and SiO₂-P₂O₅-Pr₂O₃ (II) systems. The films have been obtained by spin coating technique for three rotation speeds: 2000, 3500 and 5000 rpm. The deposition of the films was performed at different periods of time, i.e. 24 h, 96 h, 120 h, 144 h and 168 h after instant preparation of the precursor sols. FTIR (Fourier transform infrared spectroscopy) and Raman characterization aimed at investigating the structural changes that occurred in silicophosphate network in dependence on the spin rate of the substrate as well as on the time period elapsed since the sol preparation till the deposition day. FTIR spectra recorded in the 400-4000 cm⁻¹ range revealed Si-O-Si, P-O-P and Si-O-P vibration modes and optical phonons specific for OH units. Raman spectra collected in the 100-4000 cm⁻¹ range put in evidence stretching, bending and mixed vibration modes specific for silicophosphate network as well as rare-earth ion peaks specific to certain electronic transitions. Morphological investigation made by AFM (atomic force microscopy) on Er and Pr-doped silicophosphate sol-gel films evidenced specific features depending on the parameters mentioned above and SEM (scanning electron microscopy) analysis revealed micron sphere structural units, exfoliation of the films and micro cracks.     

Studies on chemically deposited CuInSe2 thin films

Nanocrystalline thin films of CuInSe₂ have been prepared by chemical bath deposition technique at temperatures below 60 °C. X-ray diffraction of the films confirmed the identity of CuInSe₂ and with largely broadened peaks indicated the nanocrystalline nature of the films. Images from scanning electron microscope represented spherical nanoparticles.     

Nanoscale study by piezoresponse force microscopy of relaxor 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 and 0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 thin films grown on platinum and LaNiO3 electrodes

Relaxor 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (70/30 PMN-PT) and 0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ (90/10 PMN-PT) thin films have been grown by RF-sputtering on platinum (Pt) and lanthanum nickelate (LaNiO₃) bottom electrodes. For both electrodes, macroscopic measurements evidence lower coercive fields, remnant polarizations and piezoelectric coefficients d₃₃ for 90/10 PMN-PT films compared to 70/30 PMN-PT films. For both compositions, coercive fields and remnant polarizations are lower for films grown on LaNiO₃ compared to on Pt while piezoelectric coefficients d₃₃ are higher. For each electrode and composition, a similar behavior is revealed for electromechanical activity at the nanoscale when measuring local piezoelectric hysteresis loops; on the other hand, the voltages required for switching the domains are the highest for 90/10 PMN-PT films grown on LaNiO₃. The existence of large grain boundaries in the films grown on Pt and the presence of local random fields with polar nano-domains for the 90/10 composition could explain the differences measured in domains switching properties at the macroscale and nanoscale levels.     

The influence of the additives composition and concentration on the properties of SnOx thin films used in photocatalysis

The aim of this study is to investigate the influence of different organic additives on the surface properties of SnO_x thin films used for photocatalytic degradation of methylene blue. The films were obtained by anodic oxidation of tin substrate in electrolyte solutions containing green additives based on hydrophobic and hydrophilic maleic anhydride copolymers. The hydrophobic copolymer leads to the formation of thin films with increased specific area which generates a larger interfacial area between the layers and the dye solution. The consequence is an improvement in the photocatalytic efficiency: up to 16% compared to less than 5% for samples electrodeposited without polymer. The hydrophilic copolymer presence in the electrolyte solution leads to higher grain size and lower surface energy which significantly reduce the photocatalytic properties of the layers. The use of copolymers can be a tool for enhancing the surface roughness and film's wettability and thus the photodegradation efficiency.     

Nanopatterns of ABA triblock copolymer thin films formed on water surface

Nanopatterns of hydrophobic triblock copolymer SEBS thin films formed on a water surface by using drop spreading casting and dilute solution casting methods have been studied. It is found that the surface morphologies of thin films, as well as the spreading behavior of polymer solutions on water, depend strongly on the selectivity of the solvent and the functional group which interacts with the water subphase. The resulting nanopatterns were examined in terms of the relative interaction parameter (Δχ) and the copolymer volume fraction (?) in the solution, based on the physics of solvent annealing and evaporation.     

TiO2 coated SnO2 nanosheet films for dye-sensitized solar cells

TiO₂-coated SnO₂ nanosheet (TiO₂-SnO₂ NS) films about 300 nm in thickness were fabricated on fluorine-doped tin oxide glass by a two-step process with facile solution-grown approach and subsequent hydrolysis of TiCl₄ aqueous solution. The as-prepared TiO₂-SnO₂ NSs were characterized by scanning electron microscopy and X-ray diffraction. The performances of the dye-sensitized solar cells (DSCs) with TiO₂-SnO₂ NSs were analyzed by current-voltage measurements and electrochemical impedance spectroscopy. Experimental results show that the introduction of TiO₂-SnO₂ NSs can provide an efficient electron transition channel along the SnO₂ nanosheets, increase the short current density, and finally improve the conversion efficiency for the DSCs from 4.52 to 5.71%.     

Influence of Si(1 0 0) surface pretreatment on the morphology of TiO2 films grown by atomic layer deposition

The effect of water plasma treatment of both hydrophobic and hydrophilic Si(1 0 0) surfaces has been studied using infrared spectroscopy to monitor the various surface species present. Exposure to a water plasma results in a significant increase in the concentration of H-bonded hydroxyls and hydrides. Both atomic force microscopy (AFM) and cross-sectional transmission electron microscopy (XTEM) of TiO₂ films deposited by atomic layer deposition at 300 °C, show that the morphology of the films is dependent on the nature of the initial surface. XTEM of the early stages of growth showed that coatings on hydrophilic substrates deposited as initially amorphous and continuous films, which crystallised with further growth. However, the hydrophobic substrate produced island growth of small, crystalline grains. AFM images of 23-nm thick films showed that films deposited on hydrophobic and hydrophilic Si consisted of 35–100 and 150–350 nm crystallites, respectively. A film on water plasma treated Si, closely resembled that on the hydrophilic surface, indicating that hydroxyl groups are responsible for directing the film growth.     

Microstructure and electrical properties of RuO2-CeO2 composite thin films

RuO₂-CeO₂ composite thin films are deposited on various Si substrates by a radiofrequency magnetron sputtering technique. Compacted polycrystalline pellets of the nanostructured CeO₂-RuO₂ composite system are used as standard samples for comparative electrical analyses. All films and composite samples are analyzed by X-ray diffraction and transmission electron microscopy. Electrical measurements of radiofrequency sputtering of thin films are performed as a function of the RuO₂ fraction and of the temperature (between 25 and 400 °C). A nonlinear variation in the electrical conductivity of the RuO₂-CeO₂ composite thin films as a function of the RuO₂ volume fraction (Φ) is observed and discussed. It is interpreted in terms of a power law (in (Φ − Φc)^m ), where m and Φc are parameters characteristic of the distribution of the conducting phase in a composite medium.     

Preparation and super-hydrophilic properties of TiO2/SnO2 composite thin films

SnO₂-TiO₂ composite thin films were fabricated on soda-lime glass with sol-gel technology. By measuring the contact angle of the film surface and the degradation of methyl orange, we studied the influence of SnO₂ doping concentration, heat-treatment temperature and film thickness on the super-hydrophilicity and photocatalytic activity of the composite films. The results indicate that the doping of SnO₂ into TiO₂ can improve their hydrophilicity and photocatalytic activity, and the composite film with 1-5 mol% SnO₂ and heat-treated at 450°C is of super-hydrophilicity. The optimal SnO₂ concentration for the photocatalytic activity is 10 mol% and larger film thickness is helpful to reduce the contact angle of the composite films.     

Photoinduced changes in the surface morphology of As50Se50 chalcogenide glass films

The photoinduced changes in the surface morphology of As₅₀Se₅₀ chalcogenide glass films are observed using atomic force microscopy. The thin film samples, on single crystal silicon or a microscope glass slide as substrate, were exposed to laser light of wavelength λ=632 or 685 nm. The results show nucleation and gradual growth of micrometer size pyramids that grow with laser irradiation, ultimately covering 15% of exposed area in 20 min. The rate of growth of a given pyramid slows down with time until it ceases to grow on reaching a height of several 100 nm. The maximum height of these faceted pyramids is 1 μm, sometimes even larger than the film thickness, which cannot be understood from the reported photoinduced expansion. A photoinduced oxidation is suspected, in which As atoms in the surface layer move to the sites of pyramids. These observations raise new questions about the impact of ambient atmosphere on photodarkening and other photoinduced effects in chalcogenide glasses.     

Characterization of the surface of bio-ceramic thin films

The biocompatibility and corrosion resistance of orthopaedic and dental implants are determined by their material composition and surface microstructural properties such as surface roughness, grain size, etc. Thin films of bio-inert materials such as oxides of Ti, Al, Zr, and bio-active materials such as hydroxy-apatite (Ca₁₀(PO₄)₆(OH)₂), compounds of calcium and phosphorous oxides are more attractive as bio-ceramic films because of their biocompatibility being higher, and toxicity being lower than those of the other materials. In this study, we mainly focused on characterization of the surface of bio-ceramics using atomic force microscopy (AFM). These films having a thickness of about 500 nm, had been processed using ion-beam sputter deposition, and ion-beam-assisted sputter deposition methods. Investigation of the surface of the films by AFM shows that irradiation with oxygen ions in the energy range of 3 keV increases the surface roughness. A detailed study of the grain size and roughness of several experimental cases of TiO₂ thin films showed that the films contained columnar grains with mean size of about 100 × 100 nm² grown in the z direction with a height of a few nanometers.