SnOx thin films with tunable conductivity for fabrication of p–n homo‐junction

Tin oxide (SnO_x) has been widely used for the fabrication of transparent and flexible devices because of its excellent optical and electronic properties. In this work, we established a methodology for the synthesis of SnO_x thin films with p‐type and n‐type tunable conductivity by direct currecnt (DC) magnetron sputtering. The SnO_x thin films changed from p‐type to n‐type by increasing the relative oxygen partial pressure (ppO₂) from 4.8% to 18.5% and by varying the working pressure between 1.8 and 2.5 mTorr. The SnO_x thin films were annealed at 160°C, 180°C, and 200°C for 30 min to promote the formation of the desired crystalline structures. At the annealing temperature of 180°C in air ambient, the SnO_x thin films showed a tetragonal structure with Sn traces. Having found the optimal conditions, we deposited both types of SnO_x thin films with the same tetragonal structure and similar chemical stoichiometry. Also, the conditions to obtain thin films with the highest mobility values for p‐type (1.10 cm²/Vs) and n‐type (22.20 cm²/Vs) were used for fabricating the device. Finally, the implementation of a SnO_x‐based p–n diode was demonstrated using transparent SnO_x thin films developed in this work, illustrating their potential use in transparent electronics.     

Electrochemical deposition of electrochromic niobium oxide films from an acidic solution of niobium peroxo complexes

Deposition of electrochromic niobium(V) oxide films from an acidic solution of niobium peroxo complexes on a transparent conducting cathode in the form of an SnO₂ film on glass was studied. With an increase in the negative potential of the deposition of niobium(V) oxide films from a solution of niobium peroxo complexes at pH 2.5, the structure and composition of the films changed. A study of the electrochromic properties of Nb₂O₅ films revealed broadening of the bands in the electrochromic coloration spectrum with an increase in the negative potential of the deposition.     

Electrochemical and Electrochromic Properties of Polymer Complex Films Composed of Polytetramethyleneviologen and Poly-[p-Styrenesulfonic Acid] Containing a Conductive Powder

The electrochemical and electrochromic properties of polymer films containing a conductive powder (SnO₂/TiO₂) have been investigated. The films are complexes of polytetramethyleneviologen and poly(p-styrenesulfonic acid). It was found that the coloration (purple) and bleaching rates of the composite films increase markedly with increasing conductive powder content(x). The coloring and bleaching of the composite film with x = 95 wt% were about 7 and 44 times faster, respectively, than those for an equivalent film without conductive powder. This increase in the rate of color change by introduction of a conductive powder was found to be correlated with the apparent diffusion coefficient (D _app) for the diffusionlike charge-transport process within the composite films which increases with increasing x. The D _app for the reduction process of the film with x = 95 wt% was larger by about 3 orders of magnitude than that for the unfilled film.     

Enhancement of thin film tin oxide negative electrodes for lithium batteries

Thin films of pure SnO₂, of the Sn/Li₂O layered structure, and of Sn/Li₂O were fabricated by sputtering method, while a `lithium-reacted tin oxide thin film' was assembled by the evaporation of lithium metal onto a SnO₂ thin film. Film structure and charge/discharge characteristics were compared. The lithium-reacted tin oxide thin film, the Sn/Li₂O layered structure, and the Sn/Li₂O co-sputtered thin films did not show any irreversible side reactions of forming Li₂O and metallic Sn near 0.8 V vs Li/Li⁺. The initial charge retention of the Sn/Li₂O layered structure and Sn/Li₂O co-sputtered thin films was about 50% and a similar value was found for the lithium-reacted tin oxide thin film (more than 60%). Sn/Li₂O layered structure and Sn/Li₂O co-sputtered thin films showed better cycling behavior over 500 cycles than the pure SnO₂ and lithium-reacted tin oxide thin film in the cut-off range from 1.2 to 0 V vs Li/Li⁺.     

Efficient Deposition of Semiconductor Powders for Photoelectrocatalysis by Airbrush Spraying

Powder catalysts were deposited as thin films on transparent conductive oxides (TCO) by means of an airbrush spray coating technique. Photoelectrocatalytic properties of the powder catalysts were characterized using photocurrent spectroscopy at different wavelengths demonstrating on the one hand the stability of the films and on the other hand the electrical connection with the electrode surface. The morphology and thickness of the deposited powder catalyst films on TCO were characterized using scanning electron microscopy. Aiming at photocatalytic water splitting, semiconductor powders like gallium oxide (Ga₂O₃) and zinc oxide (ZnO) were used as test samples to optimize the deposition technique resulting in thin homogeneous layers and good adhesion on the conductive substrate. The proposed airbrush deposition technique of powder catalysts allows closing an experimental gap between microheterogeneous systems and modified electrodes for finding suitable materials for photoelectrochemical water splitting.     

Polymer electrolyte gate dielectric reveals finite windows of high conductivity in organic thin film transistors at high charge carrier densities

Finite regions of high conductivity were observed in both n- and p-channel organic thin film transistors based on polycrystalline organic semiconductor films and a solution-processed, solid polymer electrolyte gate dielectric. The transition from a highly conductive state to a more insulating state with increasing gate bias may be attributed to the realization of carrier densities greater than 1014 charges/cm2 in the semiconductor film.     

Fine pattern fabrication on SnO2:Sb thin films formed by the sol–gel process

The effects of UV irradiation on the properties of Sb⁵⁺ doped gel films were studied, which were prepared from stannic chloride (SnCl₄·5H₂O) and sodium alkoxide (NaOR) modified with benzytone (BzAcH). It was found that the absorption peak at around 335 nm due to the π → π* transition showed the formation of a chelate ring to Sn. The intensity of the absorption band decreased with UV light irradiation at 365 nm from a high‐pressure mercury lamp (250W). This finding showed that the SnO₂:Sb gel films modified with BzAcH were photosensitive to UV light. Additionally, this finding was applied to the fabrication of patterns on the SnO₂:Sb thin films. A gel film was irradiated through a mask and leached in water. Then a positive pattern was formed on the SnO₂:Sb thin films attached to the substrate. After heat treatment, the SnO₂:Sb gel films changed into transparent conductive films with an average conductivity of 1.20 × 10^?2Ω cm and with a transmission of 97.1%. Copyright © 2006 John Wiley & Sons, Ltd.     

Preparation of nano-sized Pt metal particles by photo-assisted deposition (PAD) on transparent Ti-containing mesoporous silica thin film

We have investigated a novel technique for the preparation of nano-sized Pt metals on Ti-containing mesoporous silica (TMS) thin film by photo-assisted deposition (PAD). The transparent TMS thin film was prepared on a quartz plate through sol—gel/spin coating. XRD, UV-Vis and Ti K-edge XAFS measurements revealed the formation of isolated Ti oxide species with a tetrahedral-coordination geometry in the silica framework. Deposition of Pt metal precursor on TMS thin film under UV-light irradiation, followed by reduction with molecular hydrogen, afforded a transparent thin film (Pt/TMS). The formation of highly dispersed nano-sized Pt metals having narrow size distributions was determined by Pd L_III-edge XANES and TEM analysis. The TMS and Pt/TMS thin films have been demonstrated to exhibit a strong hydrophilic property, even before UV irradiation, compared to the common mesoporous silica and TiO₂ thin films. After UV-light irradiation, the contact angle of water droplet on the TMS and Pt/TMS thin films became extremely lower, indicating the appearance of the photo-induced super-hydrophilic property.     

High-resolution transmission electron microscopy investigation of nanostructures in SnO2 thin films prepared by pulsed laser deposition

Pulsed laser deposition (PLD) was used to grow nanocrystalline SnO₂ thin films onto glass substrates. The nanocrystallites and microstructures in SnO₂ thin films grown by PLD techniques have been investigated in detail by using X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The PLD process was carried out at room temperature under a working pressure of about 2×10⁻⁶ mbar. Experimental results indicate that thin films are composed of a polycrystalline SnO₂ and an amorphous SnO phase. In particular, the presence of such an amorphous SnO phase in the thin films greatly limits their practical use as gas-sensing devices. HRTEM observations revealed that SnO₂ nanocrystallites with tetragonal rutile structure embed in an amorphous SnO matrix, which are approximatively equiaxed. These approximatively equiaxed SnO₂ nanocrystallites contain a high density of defects, such as twin boundaries and edge dislocations. The grain growth of SnO₂ thin films may be discussed in terms of the coalescent particle growth mechanism.     

有机、聚合物薄膜电致发光器件的研究进展

有机、聚合物薄膜电致发光器件是近年来国际上的一个研究热点。与无机材料相比, 有机材料具有更高的发光效率和更宽的发光颜色选择范围, 并且具有容易大面积成膜的优越性。本文介绍了有机、聚合物薄膜电致发光器件的结构和制备、发光机理以及有关材料的选择, 并对该研究领域的最新动态、器件的稳定性问题以及应用前景进行了讨论。     

Photoelectrochemical effect with poly(p-phenylene sulfide) films

Poly(p-phenylene sulfide) films coated on conducting SnO₂ and Pt surfaces were found to attain p-type semiconducting properties on electrochemical cycling. Upon illumination of these films with visible light (λ < 500 nm) a photoelectrochemical effect was observed. The performance of a photoelectrochemical cell employing this polymer film coated electrode is discussed.     

Characterization and electrochemical deposition of natural melanin thin films

Melanin is an important class of biological pigments because of its distinct chemical and physical properties. The electrochemical deposition of natural melanin thin films was studied using two different techniques; constant potential and cyclic voltammetry along with a deposition time of five hours. The thin films deposited electrochemically on a fluorine-doped tin oxide conductive glass substrate using the constant potential method, exhibited faster growth rate and better adhesion to the fluorine-doped tin oxide working electrodes than those deposited using the cyclic voltammetry method. The thin films deposited on the fluorine-doped tin oxide conductor glass using the constant potential method were also more homogeneous than those deposited via the cyclic voltammetry technique. The increase of film thickness is related to the increase of electrochemical deposition time. Interestingly, the electrochemical deposition using the constant potential method had the advantage of consuming less electric charge. The physical and chemical structures of the melanin thin films were characterized using ultraviolet–visible absorption spectroscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction analysis. The ultraviolet–visible absorption spectra showed the correlation between the variation of deposition rates of melanin and the type of electrochemical technique employed as well as the thickness of the film. The average thickness of the film is 500 nm which absorb 40% of light in both type of films. The atomic force microscopy images illustrated the homogeneous deposition of the melanin molecules on the fluorine-doped tin oxide conductive glass substrate, indicating that the thickness of the thin films can be controlled. We estimated an average grain size of 14.093 Å. The ease of preparing such thin films of organic materials can open new avenues towards the use of soft conductors, in contrast to the complex preparation of industrial semiconductors.     

Characterization of Tin(IV) Oxide Thin Films Prepared by Atmospheric Pressure Chemical Vapor Deposition of cis‐[SnCl4{OC(H)OC2H5}2]

A new single‐source precursor, [SnCl₄{OC(H)OC₂H₅}₂], prepared by treating tin tetrachloride with ethyl formate (1:2 ratio) was developed for the deposition of tin oxide thin films on glass substrates. The compound [SnCl₄{OC(H)OC₂H₅}₂] is highly volatile and provides very high growth rates (up to 100Å s^?1 at 560 °C) in an atmospheric pressure chemical vapor deposition (APCVD) reactor. More significantly, the compound does not decompose to tin oxide below 320 °C, thereby minimizing the formation of particles in the vapor above the growing tin oxide film. To prepare highly conducting fluorine doped tin oxide (SnO₂:F) films 2,2,2‐trifluoroethyl trifluoroacetate was used as the source of fluoride. High quality SnO₂:F films were deposited at 560 °C with a flow rate of 2 mL fluoride reagent hr^?1; typical film properties are resistivity of 5.9 X 10^?4 Ω cm, Hall mobility of 27.3 cm² V^?1 s^?1, carrier concentration of 3.9 X 10²⁰ cm^?3 and percent transmission ranging from 86 to 88 %. The best films of SnO₂:F possess transparencies as high as 90 % (750 nm), sheet resistances as low as 7 Ω sq^?1 and Haacke's figure of merit as high as 29 X 10^?3 (750 nm). The newly developed APCVD reactor and the chemistry were optimized with respect to structural, electrical and optical properties of the films by adjusting the substrate temperature, gas flow rates and the amount of fluoride present in the vapor stream. Growth rates with respect to deposition time, substrate temperature and flow rates of precursors were found to be similar for both undoped (SnO₂) and doped (SnO₂:F) samples. The SnO₂:F films possess larger grains than the SnO₂ which may account for the lower resistivity and the higher mobility in the SnO₂:F samples.     

Band gap tuning in nanocomposite ZrO2–SnO2 thin film achieved through sol–gel co-deposition method

Transparent SnO₂, nanocomposite ZrO₂–SnO₂ and ZrO₂ thin films were prepared by sol–gel dip-coating technique. X-ray diffraction (XRD) spectra showed a mixture of three phases: tetragonal ZrO₂ and SnO₂ and orthorhombic ZrSnO₄. X-ray photoelectron spectroscopy (XPS) gave Zr 3d, Sn 3d and O 1s spectra of the nanocomposite ZrO₂–SnO₂ thin film which revealed the presence of oxygen vacancies in the nanocomposite ZrO₂–SnO₂ thin film. Scanning electron microscopy (SEM) observations showed that microstructure of the nanocomposite ZrO₂–SnO₂ thin film consists of uniform dispersion of isolated SnO₂ particles in ZrO₂ matrix. The band gap for the ZrO₂ was estimated to be 5.51 eV and that for the nanocomposite ZrO₂–SnO₂ film was 4.9 eV. These films demonstrated the tailoring of band gap values which can be directly employed in tuning the band gap by simply changing the relative concentration of zirconium and tin elements. Photoluminescence (PL) spectra revealed an intense emission peak at 424 nm in the nanocomposite ZrO₂–SnO₂ film which indicate the presence of oxygen vacancies in ZrSnO₄.     

Layered molybdenum oxide thin films electrodeposited from sodium citrate electrolyte solution

Molybdenum oxide thin films were prepared electrochemically onto the selenium predeposited tin oxide-coated glass substrates using 0.22 M sodium citrate (C₆H₅Na₃O₇) solution (pH 8.3) and sodium molybdate as a precursor. Cyclic voltammetry was used to determine the deposition potential effects on molybdenum compound speciation, while quantitative thin film composition was obtained from X-ray photoelectron spectroscopy depth profiles. Thin molybdenum film growth and composition was potential dependant. Predominant molybdenum species was Mo(IV) at all deposition potentials and deposition times. Optical properties of the molybdenum oxide thin films were determined using UV–VIS spectroscopy. The absorption edge varied between 560 and 650 nm, whereas optical band gap values—between 1.79 and 2.19 eV—well within the limits for solar light-induced chemical reactions.     

Photoelectrochemical study of electrodeposited TiO<Subscript>2</Subscript> thin films onto F:SnO<Subscript>2</Subscript> substrates

TiO₂ thin films have been effectively fused onto F:SnO₂ (FTO) substrates via the electrodeposition method. The influence of deposition temperature on the synthesis of F:SnO₂ substrates and relative information of as-deposited and annealed TiO₂ thin films have been studied. Novel TiO₂ microspheres are detected on F:SnO₂ substrates at an optimized electrodeposition potential. Raman bands approve the creation of single-anatase-phase TiO₂. The optimized deposition surroundings show a decrease in the band gap of F:SnO₂ substrates and TiO₂ thin films. The determined photoelectrochemical properties of annealed TiO₂ thin films indicate a fill factor of 51% and power conversion efficiency of 0.15% for application in solar cells.     

Optimization of the synthesis and characterizations of chemical bath deposited Cu2S thin films

Semiconducting copper sulphide (Cu₂S) thin films have been deposited on various substrates (SnO₂:F/glass, glass) by the simple and economical chemical bath deposition technique. The depositions were carried out during a deposition time of about 32.5 min in the pH range of 9.4 to 11. The synthesized Cu₂S thin films were characterized using various techniques without any annealing treatment. X-ray diffraction study shows that Cu₂S films exhibit the best crystallinity for pH = 10.2. For this pH value, Auger electron spectroscopy investigations show that Cu₂S thin films grown on an SnO₂/glass substrate exhibit stochiometric composition with [Cu]/[S] concentrations ratio equal to 2.02. Using the Kelvin method, the work function difference (Ф_material– Ф_probe) for the Cu₂S films deposited on SnO₂/glass substrates at the optimum pH value was found to be equal to 145 meV. Hall measurements confirm the p-type electrical conductivity of the obtained films. The electrical resistivity was of the order of 3.85 × 10⁻⁴ Ω-cm. The transmission and reflection coefficients vary in the range of [35–60] % and [5–15] % respectively, in the visible range, and the band gap energy is about 2.37 eV.     

XPS/EXAFS study of cycleability improved LiMn2O4 thin film cathodes prepared by solution deposition

The influence of Sn substitution in LiMn₂O₄ thin films as a cathode has been studied via solution deposition to improve the electrochemical performance of thin film lithium batteries. LiSn_0.025Mn_1.95O₄ thin films showed the most promising performance, i.e. a high capacity retention of 77% at 10 C after the 500th cycle, due to the increased average Mn valence state. The thin films of LiSn_x/2Mn_2?xO₄ (x ? 0.10) showed significant precipitation of SnO₂ and SnO after the cycling evaluation.     

Observation of Organic Thin Film Surface by Atomic Force Microscopy

The 8-hydroxyquinoline neodymium(Ndq3) organic thin films deposited on the cleaned indium/tin oxide (ITO) at different deposition rates with the same vacuity (133.3×10^-5 Pa) were revealed by atomic force microscopy (AFM). Organic devices with one layer of Ndq3 as the e-type conductive material at different deposition rates sandwiched between ITO and aluminum electrodes have been fabricated. respectively. Evidence suggests that the current-voltage (I-V) characteristics were determined by the uniformity of organic film which was controlled by the deposition conditions.     

Electron Probe Microanalysis of HfO2 Thin Films on Conductive and Insulating Substrates

Quantitative electron probe microanalysis of highly insulating materials is a complicated problem, partially solved by coating samples with grounded thin conductive layers or using novel scanning electron microscopy (SEM) techniques, such as low-voltage and/or variable pressure SEM. In this work, some problems of quantitative X-ray microanalysis of thin HfO₂ films, in particular the possibility to determine mass thickness correlated to the density of the layer material, are discussed. For comparison, Al₂O₃, Ta₂O₅ and TiO₂ films grown onto both semiconductive Si and insulating quartz substrates were also analysed. All the films studied were synthesized by atomic layer deposition method.