Studies on the structural and electrical properties of spray deposited SnO2:Sb thin films as a function of substrate temperature

Thin films of antimony doped tin oxide (SnO₂:Sb) were prepared by spray pyrolysis technique using SnCl₂ as precursor with the various antimony doping levels ranging from 1 to 4 wt%. The XRD analysis showed that the undoped SnO₂ films grow in (211) preferred orientation whereas the Sb doped films grow in (200) plane. Scanning electron microscopy studies indicated that the surface of the films prepared with lower doping level (1 wt%) consists of larger grains whereas those prepared with higher doping levels (>1 wt%) consist of smaller grains. The sheet resistance has been found to be reduced considerably (2.17 Ω/□) for Sb doped films. To the best of our knowledge this is the lowest sheet resistance obtained for Sb doped SnO₂ thin films.     

Studies on pyrolytically sprayed SnO2 and Sb-SnO2 thin films for LPG sensor applications

Undoped and antimony doped tin oxide thin films of different thicknesses were prepared on mineral glass substrate by spray pyrolysis method via sol-gel route. Both the films show good transmittance in the visible region. Band gap energy of both films lies between 3 to 3.5 eV. X-ray diffraction studies of undoped and antimony doped tin oxide thin films for various annealing temperature show polycrystalline tetragonal structure of SnO₂ with preferred orientation of (110) and (101), respectively and from the XRD data, grain size were also evaluated. AFM images of Undoped and antimony doped tin oxide thin films annealed at 375 °C depict the film thickness and indicate uniform surface pattern without dark pits and with strains of some ups exceeding the specified limit. The prepared films were tested in a specially developed test rig for Liquefied Petroleum Gas detection at different operating temperatures. The response characteristics of the films for LPG detection show maximum sensitivity and minimum response time at the operating temperature 400 °C. Studies indicate that antimony doped tin oxide thin film are one among the suitable candidates for LPG detection with a detection sensitivity and response time (t90) of 11 and 140 seconds, respectively. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Structural, optical and electrical characterization of antimony-substituted tin oxide nanoparticles

Antimony-doped tin oxide (ATO) nanostructures were prepared using chemical precipitation technique starting from SnCl₂, SbCl₃ as precursor compounds. The antimony composition was varied from 5 to 20 wt%. The lower resistance was observed at composition of Sn:95 and Sb:05, when compared with undoped and higher doping concentration of antimony. The average crystalline size of undoped and doped tin oxide was calculated from the X-ray diffraction (XRD) pattern and found to be in the range of 30-11 nm and it was further confirmed from the transmission electron microscopy (TEM) studies. The scanning electron microscopy (SEM) analysis showed that the nanoparticles agglomerates forming spherical-shaped particles of few hundreds nanometers. The samples were further analyzed by energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and electrical resistance measurements.     

Effect of fluorine doping on highly transparent conductive spray deposited nanocrystalline tin oxide thin films

The undoped and fluorine doped thin films are synthesized by using cost-effective spray pyrolysis technique. The dependence of optical, structural and electrical properties of SnO₂ films, on the concentration of fluorine is reported. Optical absorption, X-ray diffraction, scanning electron microscope (SEM) and Hall effect studies have been performed on SnO₂:F (FTO) films coated on glass substrates. The film thickness varies from 800 to 1572 nm. X-ray diffraction pattern reveals the presence of cassiterite structure with (2 0 0) preferential orientation for FTO films. The crystallite size varies from 35 to 66 nm. SEM and AFM study reveals the surface of FTO to be made of nanocrystalline particles. The electrical study reveals that the films are degenerate and exhibit n-type electrical conductivity. The 20 wt% F doped film has a minimum resistivity of 3.8 × 10⁻⁴ Ω cm, carrier density of 24.9 × 10²⁰ cm⁻³ and mobility of 6.59 cm² V⁻¹ s⁻¹. The sprayed FTO film having minimum resistance of 3.42 Ω/cm², highest figure of merit of 6.18 × 10⁻² Ω⁻¹ at 550 nm and 96% IR reflectivity suggest, these films are useful as conducting layers in electrochromic and photovoltaic devices and also as the passive counter electrode.     

Effect of solvent volume on the physical properties of undoped and fluorine doped tin oxide films deposited using a low-cost spray technique

Undoped and fluorine doped tin oxide films were deposited from starting solutions having different values of solvent volume (10-50 ml) by employing a low cost and simplified spray technique using perfume atomizer. X-ray diffraction studies showed that there was a change in the preferential orientation from (2 1 1) plane to (1 1 0) plane as the volume of the solvent was increased. The sheet resistance (R_sh) of undoped SnO₂ film was found to be minimum (13.58 KΩ/□) when the solvent volume was lesser (10 ml) and there was a sharp increase in R_sh for higher values of solvent volume. Interestingly, it was observed that while the R_sh increases sharply with the increase in solvent volume for undoped SnO₂ films, it decreases gradually in the case of fluorine doped SnO₂ films. The quantitative analysis of EDAX confirmed that the electrical resistivity of the sprayed tin oxide film was mainly governed by the number of oxygen vacancies and the interstitial incorporation of Sn atoms which in turn was governed by the impinging flux on the hot substrate. The films were found to have good optical characteristics suitable for opto-electronic devices.     

Effective utilization of spray pyrolyzed CeO2 as optically passive counter electrode for enhancing optical modulation of WO3

Nanocrystalline cerium oxide (CeO₂) thin films were deposited onto the fluorine doped tin oxide coated glass substrates using methanolic solution of cerium nitrate hexahydrate precursor by a simple spray pyrolysis technique. Thermal analysis of the precursor salt showed the onset of crystallization of CeO₂ at 300 °C. Therefore, cerium dioxide thin films were prepared at different deposition temperatures from 300 to 450 °C. Films were transparent (T ~ 80%), polycrystalline with cubic fluorite crystal structure and having band gap energy (Eg) in the range of 3.04–3.6 eV. The different morphological features of the film obtained at various deposition temperatures had pronounced effect on the ion storage capacity (ISC) and electrochemical stability. The larger film thickness coupled with adequate degree of porosity of CeO₂ films prepared at 400 °C showed higher ion storage capacity of 20.6 mC cm^? 2 in 0.5 M LiClO₄ + PC electrolyte. Such films were also electrochemically more stable than the other studied samples. The Ce⁴⁺/Ce³⁺ intervalancy charge transfer mechanism during the bleaching–lithiation of CeO₂ film was directly evidenced from X-ray photoelectron spectroscopy. The optically passive behavior of the CeO₂ film (prepared at 400 °C) is affirmed by its negligible transmission modulation upon Li⁺ ion insertion/extraction, irrespective of the extent of Li⁺ ion intercalation. The coloration efficiency of spray deposited tungsten oxide (WO₃) thin film is found to enhance from 47 to 53 cm² C^? 1 when CeO₂ is coupled with WO₃ as a counter electrode in electrochromic device. Hence, CeO₂ can be a good candidate for optically passive counter electrode as an ion storage layer.     

The role of oxygen vacancy in fluorine-doped SnO2 films

The fluorine-doped tin oxide films (FTO) were prepared with SnCl₂ and SnCl₄ precursors using the spray pyrolysis method. The vibrational feature of oxygen vacancy in FTIR has been identified. The oxygen vacancy plays a role of donor in FTO films, although it becomes inconspicuous with an increase in fluorine concentration in the solution. The substitution of fluorine for oxygen has also been confirmed by FTIR spectrum, and it further indicates the production of fluorine doping is α-SnF₂. The reflectivity shows a close relation with the carrier concentration, suggested by the Drude theory. The discussion of scattering mechanism in FTO films suggests that impurity ions are the main scattering centers for free carriers.     

Characterisation of porous doped ZnO thin films deposited by spray pyrolysis technique

Al or Sn doped ZnO films were deposited by spray pyrolysis using aqueous solutions. The films were deposited on either indium tin oxide coated or bare glass substrates. ZnCl₂, AlCl₃ and SnCl₂ were used as precursors. The effect of ZnCl₂ molar concentration (0.1-0.3 M) and doping percentage (2-4% AlCl₃ or SnCl₂) have been investigated. The main goal of this work being to grow porous ZnO thin films, small temperature substrates (200-300 °C) have been used during the spray pyrolysis deposition. It is shown that, if the X-ray diffraction patterns correspond to ZnO, the films deposited onto bare glass substrate are only partly crystallized while those deposited onto ITO coated glass substrate exhibit better crystallization. The homogeneity of the films decreases when the molar concentration of the precursor increases, while the grain size and the porosity decrease when the Al doping increases. The optical study shows that band tails are present in the absorption spectrum of the films deposited onto bare glass substrate, which is typical of disordered materials. Even after annealing 4 h at 400 °C, the longitudinal resistivity of the films is quite high. This result is attributed to the grain boundary effect and the porosity of the films. Effectively, the presence of an important reflection in the IR region in samples annealed testifies of a high free-carriers density in the ZnO crystallites. Finally it is shown that when deposited in the same electrochemical conditions, the transmission of a polymer film onto the rough sprayed ZnO is smaller than that onto smooth sputtered ZnO.     

Synthesis and characterization of single- and co-doped SnO2 thin films for optoelectronic applications

Doped SnO₂ thin films have been prepared by sputtering from two different targets: antimony doped tin oxide (ATO) and antimony and zinc doped tin oxide (AZTO). In the case of ATO ceramic, the antimony amount only reaches 0.012 mol per formula unit due to its evaporation at high temperature while the presence of Zn²⁺ in AZTO prevents the antimony evaporation, greatly enhances the ceramic density and allows the deposition of thin films with a high deposition rate. Both types of thin films have a dense morphology with a smooth surface and they are polycrystalline. For post-annealed ATO thin films, the Drude model was applied to deduce the carrier concentration, the optical mobility as well as the resistivity. The carrier concentration is around ten times higher for ATO thin films compared to AZTO. The two combined effects (higher carrier concentration and mobility) for ATO thin films doped with 1.2% of Sb lead to the best optoelectronic performances, confirming previous results obtained with ceramics. Nevertheless, we have a better opportunity to modulate the conductivity in the case of AZTO thin films.     

Electrochromic performance of the mixed V2O5–WO3 thin films synthesized by pulsed spray pyrolysis technique

Vanadium pentoxide (V₂O₅) mixed tungsten trioxide (WO₃) thin films have been synthesized by a novel pulsed spray pyrolysis technique (PSPT) on glass and fluorine doped tin oxide (FTO) coated glass substrates at 400 °C. Aqueous solutions of equimolar vanadium chloride and ammonium tungstate were mixed in volume proportions (5%, 10% and 15%) for the deposition of V₂O₅–WO₃ thin films. The structural, morphological, optical and electrochemical properties of V₂O₅–WO₃ thin films were investigated by FT-IR, XRD, SEM, cyclic voltammetry, chronoamperometry and chronocoulometry techniques. The results showed that the electrochemical properties of V₂O₅ were altered by mixing WO₃. All the films exhibited cathodic electrochromism in lithium containing electrolyte (0.5 M LiClO₄ + propylene carbonate (PC)). Maximum coloration efficiency (CE) of about 49 cm² C⁻¹ was observed for the V₂O₅ film mixed with 15% WO₃. The electrochemical stability of the sample was examined and it was found to be stable up to 1000 cycles.     

Structural and electrical properties of fluorine-doped zinc tin oxide thin films prepared by radio-frequency magnetron sputtering

Transparent and conductive thin films of fluorine doped zinc tin oxide (FZTO) were deposited on glass substrates by radio-frequency (RF) magnetron sputtering using a 30 wt% ZnO with 70 wt% SnO₂ ceramic targets. The F-doping was carried out by introducing a mixed gas of pure Ar, CF₄, and O₂ forming gas into the sputtering chamber while sputtering ZTO target. The effect of annealing temperature on the structural, electrical and optical performances of FZTO thin films has been studied. FZTO thin film annealed at 600 °C shows the decrease in resistivity 5.47 × 10⁻³ Ω cm, carrier concentration ∼10¹⁹ cm⁻³, mobility ∼20 cm² V⁻¹ s⁻¹ and an increase in optical band gap from 3.41 to 3.60 eV with increasing the annealing temperatures which is well explained by Burstein–Moss effect. The optical transmittance of FZTO films was higher than 80% in all specimens. Work function (ϕ) of the FZTO films increase from 3.80 eV to 4.10 eV through annealing and are largely dependent on the amounts of incorporated F. FZTO is a possible potential transparent conducting oxide (TCO) alternative for application in optoelectronics.     

Fluorine-doped zinc oxide transparent and conducting electrode by chemical spray synthesis

Highly transparent and conducting fluorine-doped zinc oxide thin films, consisting of spherical nanometer-sized grains, were synthesized onto soda-lime glass substrate by using a chemical spray unit. The effect of fluorine doping concentration in starting solution was investigated. Both doped and undoped films were preferentially oriented along [002] direction. Electrical resistivity decreases from 5.7 x 10^-2 to 8.6 x 10^-3 ohm-cm after 1 at.% fluorine doping, and increases for higher doping concentration. However, surface morphology of films obtained at 3 at.% fluorine doping appeared smooth and uniform. A shift of the edge of the optical transmission in the ultraviolet region as a result of fluorine doping was obtained.     

Preparation and properties of spray-deposited ZnIn2Se4 nanocrystalline thin films

Zinc indium selenide (ZnIn₂Se₄) thin films have been deposited onto amorphous and fluorine doped tin oxide (FTO)-coated glass substrates using a spray pyrolysis technique. Aqueous solution containing precursors of Zn, In, and Se has been used to obtain good quality deposits at different substrate temperatures. The preparative parameters such as substrate temperature and concentration of precursors solution have been optimized by photoelectrochemical technique and are found to be 325 °C and 0.025 M, respectively. The X-ray diffraction patterns show that the films are nanocrystalline with rhombohedral crystal structure having lattice parameter a=4.05 Å. The scanning electron microscopy (SEM) studies reveal the compact morphology with large number of single crystals on the surface. From optical absorption data the indirect band gap energy of ZnIn₂Se₄ thin film is found to be 1.41 eV.     

Prototype electrochromic device and dye sensitized solar cell using spray deposited undoped and ‘Li’ doped V2O5 thin film electrodes

Lithium (Li) (0–5 wt%) doped V₂O₅ thin films were spray deposited at 450 °C onto ITO substrates. Structural analysis using X-ray diffraction and Raman spectroscopy revealed orthorhombic phase of the films. In addition to the V₂O₅ phase, presence of VO₂ peaks due to high deposition temperature is also evident from structural and optical characterization. The non-stoichiometric nature of the films due to loss of the terminal O atom was confirmed from Raman spectroscopy. The direct band gap, indirect bandgap, and phonon energies were also calculated from optical studies. Different charge states of vanadium ions present in the film were identified from X-ray photoelectron spectroscopy study. Results from cyclic voltammetry experiments reflected significant differences between the undoped and Li doped V₂O₅ samples. Transport properties by Hall-effect measured at room temperature indicated significant increase in conductivity, carrier concentration and mobility of V₂O₅ thin films on doping with Li. A Dye Sensitized Solar Cell (DSSC) was fabricated using mobility enhanced 5 wt% Li doped V₂O₅ film as photoanode and its efficiency was found to be 2.7%. A simple electrochromic cell is fabricated using undoped V₂O₅ thin film to demonstrate the colour change.     

Structural transition and blue emission in textured and highly transparent spray deposited Li doped WO3 thin films

The effect of Li (0-5 wt%) doping on the properties of WO₃ thin films deposited using an automated homemade spray pyrolysis unit is studied. Change in structural and optical properties is observed on doping with Li. The XRD patterns shows that undoped WO₃ film has an orthorhombic phase while the Li (1-5 wt%) doped WO₃ films have tetragonal phase. The SEM and AFM images confirm relatively smooth surface of Li doped WO₃ films compared to undoped WO₃ film. Transmission spectra reveal that the transparency of the Li-doped films is much greater than that of undoped film. From the transmission data, the direct, indirect bandgap and phonon energies were calculated. Room temperature photoluminescence spectra showed pronounced blue emission on doping with Li.     

Effects of deposition temperature on the surface roughness and the nonlinear optical susceptibility of sprayed deposited ZnO:Zr thin films

Zirconium doped zinc oxide thin films were deposited by reactive chemical pulverization spray pyrolysis technique on heated glass substrates at 400 °C, 450 °C and 500 °C using zinc and zirconium chlorides as precursors. The effect of zirconium dopant and surface roughness on the nonlinear optical properties was investigated using atomic force microscopy (AFM) and third harmonic generation (THG). The best value of susceptibility χ⁽³⁾ was obtained from the doped films with less roughness. A strong third order nonlinear optical susceptibility χ⁽³⁾ = 20.49 × 10⁻¹² (esu) of the studied films was found for the 5% doped sample at 450 °C.     

Application of Mössbauer spectroscopy to the studies of FeCl3, SnCl4 and SbCl5 doped polypyrrole

Chemically polymerized polypyrrole was chemically doped with FeCl₃, SnCl₄, and SbCl₅. In⁵⁷Fe and¹¹⁹Sn ME studies, samples prepared under rigorously anhydrous conditions show only one type of iron and tin with Mössbauer parameters characteristic of FeCl ₄ ^– and SnCl₅ whereas in¹²¹Sb experiments two types of antimony corresponding to SbCl₃ and SbCl ₆ ^– have been detected.From the temperature dependence of the recoil free fraction the Mössbauer lattice temperatures were estimated as 125 K and 105 K for polypyrrole doped with iron chloride and with tin chloride respectively.     

Investigation of Physical and electrochemical properties of Ni doped CeO2 Thin films: DFT calculation

Undoped and Ni-doped thin films of cerium dioxide have been deposited by spray pyrolysis technique on the glass substrate at the optimized temperature (450 ± 5) °C. Thin films Ce_1-xNi_xO₂ doped by different concentrations of Ni was characterized by X-ray diffraction. Raman analysis showed a peak at 461 ± 1 cm⁻¹ position for the undoped film, which corresponds to the active mode (F_2g mode) of the cubic fluorite structure. SEM images showed that the particles have a uniform spherical shape. EDS data have confirmed all elements (Ce, Ni and O) existence. Optical properties of samples show a decrease in band gap energy with increasing the nickel rate. Cyclic voltammetry indicates that the storage capacity of samples increases as the Ni rate increases. The EIS of CeO₂/ITO electrodes displays a small semicircular at high frequency. The theoretical results obtained using WIEN2k match well with the experimental ones.     

Electrosynthesis and characterization of Fe doped CdSe thin films from ethylene glycol bath

The CdSe and Fe doped CdSe (Fe:CdSe) thin films have been electrodeposited potentiostatically onto the stainless steel and fluorine doped tin oxide (FTO) glass substrates, from ethylene glycol bath containing (CH₃COO)₂·Cd·2H₂O, SeO₂, and FeCl₃ at room temperature. The doping concentration of Fe is optimized by using (photo) electrochemical (PEC) characterization technique. The deposition mechanism and Fe incorporation are studied by cyclic voltammetry. The structural, surface morphological and optical properties of the deposited CdSe and Fe:CdSe thin films have been studied by X-ray diffraction, scanning electron microscopy (SEM) and optical absorption techniques respectively. The PEC study shows that Fe:CdSe thin films are more photosensitive than that of undoped CdSe thin films. The X-ray diffraction analysis shows that the films are polycrystalline with hexagonal crystal structure. SEM studies reveal that the films with uniformly distributed grains over the entire surface of the substrate. The complete surface morphology has been changed after doping. Optical absorption study shows the presence of direct transition and a considerable decrease in bandgap, E_g from 1.95 to 1.65 eV.     

The characteristic investigation of spray coated W incorporated in oxide thin films

W incorporated tin oxide (TO) thin films were grown via spray pyrolysis with various tungsten contents. The films were observed to be polycrystalline tetragonal crystal nature with (301) and (211) preferential planes. From EDX analysis, it was seen the tungsten concentrations in the TO films were slightly higher than ones in the starting solutions. Polyhedron-like and small rod like grains were observed in the SEM images. 3 at % W doped tin oxide film has minimum sheet resistance (44.67 Ohm) and resistivity (3.685 × 10^?3 Ohm cm) values and maximum figure of merit (75.74 × 10^?5 Ohm^?1) value. The optical band gap (E_g) of pure film raised from 3.84 to 3.91 eV with 3 at % W contribution level.