担载材料对TiO2薄膜光催化活性的影响

ＴＩＯ２薄膜催化剂光催化治理大气和水污染，具有实际应用的前景，受到科学界的高度重视“－‘’．实验结果发现，担载材料对膜的催化活性有很大影响”’，如采用玻璃、不锈钢。石英作为ＴＩＯ。膜的载体时，由于界面离子扩散作用的不同，使得膜的光催化活性有很大的差异...     

Influence of the substrate type on the microstructural,optical and electrical properties of sol–gel ITO films

Indium tin oxide (ITO) is recognized as the best transparent and conductive material [transparent conducting oxide (TCO)] until now and its properties are dependent on the preparation method. In the present work ITO films with In:Sn atomic ratio 9:1 were prepared by a sol–gel route on different substrates (microscope glass slides, microscope glass covered with one layer of SiO₂ and Si wafers) for TCO applications. The multilayer ITO films were obtained by successive deposition by the dip-coating method and the films were characterized from the structural, morphological, optical, and electrical points of view using X-ray diffraction, scanning electron microscopy, atomic force microscopy, spectroscopic ellipsometry and by Hall effect measurements, respectively. The results showed that the thickness, optical constants and carrier numbers depend strongly on the type of substrate, number of deposited layers and sol concentration. The optical properties of ITO films are closely related to their electrical properties. The enhancement of the conductivity was possible with the increase of crystallite size (which occurred after thermal treatment) and with the reduction of surface roughness.     

担载材料对TiO2薄膜光催化活性的影响

TiO_2 nanocrystalline films were prepared on glass, ITO and p-Si substrates. Degradation of Rhodamine B was used to assess the photocatalytic activity of the films. It was found that photocatalytic activity of TiO2 films on ITO and p-Si are higher than that on glass, and the film grown on ITO is the best. In addition, crystalline phases and surface morphology of TiO_2films were also affected by different substrates. Surface Photovoltage Spectra was used to analyze surface states and energy levels of the films. Separation of photogenerate electrons and holes was promoted due to matching of the energy levels between TiO_2 films and ITO as well as p-Si. High photocatalytic activity was then obtained because more photogenerate electrons and holes took part in photocatalytic reaction on TiO_2 surfaces.     

通过硅烷偶联剂在硅和铟锡氧化物(ITO)表面嫁接寡聚芴分子

通过硅烷偶联剂γ-氨丙基三乙氧基硅烷(3-aminopropyl-triethoxysilane,APTES)的“分子桥梁”作用,采用两种不同的方法,把修饰后的寡聚芴分子键联到硅表面和铟锡氧化物(ITO)表面上。X射线光电子能谱(XPS)、原子力显微镜(AFM)和循环伏安(CV)方法等的表征证实了通过硅烷偶联剂在硅表面和ITO表面嫁接寡聚芴分子可行性。     

Effects of electron transfer between TiO2 films and conducting substrates on the photocatalytic oxidation of organic pollutants

TiO2 films on Al alloy (Al), indium-tin oxide glass (ITO/glass), and glass were prepared by a dip-coating method. ITO is found to have a higher work function, while the work function for Al is lower than that of TiO2 films. An electron transfer is indicated to occur in the interfaces between TiO2 films and conducting substrate Al or ITO, which results in an Ohm contact or Schottky barrier under the transient equilibrium UV radiation conditions. Photocatalytic measurements showed that the TiO2 films on Al have a higher activity for photocatalytic oxidation of C2H4, but the activity for photocatalytic degradation of oleic acid is lower as compared with TiO2 films on glass. Alternatively, TiO2 films on ITO give completely contrary photocatalytic performance to those on Al. These observations could be associated with the electron transfer, in which Al acts as an electron donor and offers electrons to TiO2, allowing photocatalytic oxidation of ethylene to proceed by the photogenerated electrons, while ITO could be an acceptor for the photogenerated electrons, which is beneficial to photocatalytic degradation of oleic acid by the photogenerated holes. This electron-transfer model could be extended to other photocatalytic systems.     

Dense passivating poly(ethylene glycol) films on indium tin oxide substrates

We describe the formation and characterization of surface-passivating poly(ethylene glycol) (PEG) films on indium tin oxide (ITO) glass substrates. PEG chains with a molecular weight of 2000 and 5000 D were covalently attached to the substrates in a systematic approach using different coupling schemes. The coupling strategies included the direct grafting with PEG-silane, PEG-methacrylate, and PEG-bis(amine), as well as the two-step functionalization with aldehyde-bearing silane films and subsequent coupling with PEG-bis(amine). Elemental analysis by X-ray photoelectron spectroscopy (XPS) confirmed the successful surface modification, and XPS and ellipsometry provided values for film thicknesses. XPS and ellipsometry thickness values were almost identical for PEG-silane films but differed by up to 400% for the other PEG layers, suggesting a homogeneous layer for PEG-silane but an inhomogeneous distribution for other PEG coatings on the molecularly rough ITO substrates. Atomic force microscopy (AFM) and water contact angle goniometry confirmed the different degrees of surface homogeneity of the polymer films, with PEG-silane reducing the AFM rms surface roughness by 50% and the water contact angle hysteresis by 75% compared to uncoated ITO. The ability of the PEG layers to passivate the substrate against the nonspecific adsorption of biopolymers was tested using fluorescence-labeled immunoglobulin G and DNA oligonucleotides in combination with fluorescence microscopy. The results indicate a positive relationship between film density and homogeneity on one hand and the ability to passivate against biopolymer adhesion on the other hand. The most homogeneous layers prepared with PEG-silane reduced the nonspecific adsorption of fluorescence-labeled DNA by a factor of 300 compared to uncoated ITO. In addition, the study finds that the ratio of film thicknesses derived by ellipsometry and XPS is a useful parameter to quantify the structural integrity of PEG layers on molecularly rough ITO surfaces. The findings may be applied to characterize PEG or other polymeric films on similarly coarse substrates.     

Surface modification and characterization of indium-tin oxide for organic light-emitting devices

In this work, we used different treatment methods (ultrasonic degreasing, hydrochloric acid treatment, and oxygen plasma) to modify the surfaces of indium-tin oxide (ITO) substrates for organic light-emitting devices. The surface properties of treated ITO substrates were studied by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), sheet resistance, contact angle, and surface energy measurements. Experimental results show that the ITO surface properties are closely related to the treatment methods, and the oxygen plasma is more efficient than the other treatments since it brings about smoother surfaces, lower sheet resistance, higher work function, and higher surface energy and polarity of the ITO substrate. Moreover, polymer light-emitting electrochemical cells (PLECs) with differently treated ITO substrates as device electrodes were fabricated and characterized. It is found that surface treatments of ITO substrates have a certain degree of influence upon the injection current, brightness, and efficiency, but hardly upon the turn-on voltages of current injection and light emission, which are in agreement with the measured optical energy gap of the electroluminescent polymer. The oxygen plasma treatment on the ITO substrate yields the best performance of PLECs, due to the improvement of interface formation and electrical contact of the ITO substrate with the polymer blend in the PLECs.     

On key factors for the fabrication of mesoporous tungsten oxide films from tungstic acid

Thermally stable mesoporous tungsten oxide films (TOFs) were prepared by surfactant templated sol–gel method using tungstic acid as tungsten oxide source. Influence of various experimental conditions on the obtained mesostructures was investigated, including the solvent compositions, addition of hydrogen peroxide, substrates, and aging time, heat treatment, etc. It has been found that the addition of hydrogen peroxide has a significant influence on the flexibility of formed meso-frameworks, and just a small amount can regenerate the degraded coating sol. TOFs were also found to crystallize on ITO coating easier than on bare glass, indicating that the different interactions with the substrates influence the crystallinity of obtained meso-structured TOFs. Film thickness can be adjusted by simply changing the solvent compositions while keeping mesostructures intact. This work clarified several key parameters in delivering well-defined mesostructured TOFs from cheap, moisture-insensitive tungstic acid precursor via the process developed.     

不同波长紫外光照下纳米TiO2薄膜的光致亲水性与循环伏安行为

通过溶胶-凝胶方法分别在ITO和玻璃表面制备了纳米TiO_2薄膜，研究了纳米 TiO_2薄膜在254及365nm的紫外光照射下的循环伏安行为和光致超亲水性。在紫外 光的照射下，TiO_2薄膜电极可表现出两个光电化学过程，纳米TiO_2薄膜的光致超 亲水性转变及两个光电化学过程的速率均取决于紫外光的波长，原因在于纳米 TiO_2薄膜对两种波长的光的吸收率和光子的能量不同。提出了光电化学过程的机 理，认为紫外光照射下纳米TiO_2薄膜的超亲水性变化与产生Ti~(3+)的过程引起的 表面微观结构变化存在的一定的内在联系。     

Order parameters and orientation distributions of solution adsorbed and microcontact printed cytochrome c protein films on glass and ITO

The structure of solution adsorbed and microcontact printed (muCP) cytochrome c (cyt c) films on glass and indium tin oxide (ITO) was investigated using attenuated total reflectance (ATR) and total internal reflectance fluorescence (TIRF) spectroscopies to determine the orientation of the heme groups in the films. The second and fourth order parameters of the heme as well as information on the angle between the absorption and emission dipoles of the heme, gamma, were experimentally determined. The order parameters of the heme are related to the order parameters of the protein molecule using the known angle between the heme plane and the electrostatic dipole moment of the cyt c protein. The effect of the surface roughness of the substrates (glass and ITO) was also taken into account quantitatively using AFM data. Physically possible order parameters were obtained for the heme group in both solution adsorbed and muCP films, but not for the electrostatic dipole moment of the protein. In addition, the experimental values of {cos2 gamma} for immobilized zinc-substituted cyt c are greater than the values of {cos2 gamma} determined in viscous solutions, which could be an indication that the environment of the heme groups changes upon adsorption. The electron transfer behavior of solution adsorbed and muCP films on ITO, determined using electrochemical methods, is compared to their orientation distribution and surface coverage as determined by spectroscopic methods.     

Syntheses and characterization of functionalized polynorbornene dicarboximides for flexible substrates

In this study, we synthesized polynorbornene (PNB) dicarboximides substituted by monochlorophenyl group (PMCPhNDI) and dichlorophenyl group (PDCPhNDI) via ring‐opening polymerization using a ruthenium catalyst and investigated their thermal, mechanical, and optical properties. We also discussed the performance and application of the functionalized PNB dicarboximide films as flexible substrates for organic light‐emitting devices (OLEDs). The polymer films exhibited good optical transparency with an average transmittance of around 97% in the visible light region and good thermal stability with a 5% degradation temperature of >440°C. The polymers were applied for flexible displays, which were coated on indium tin oxide (ITO) thin films using a radio‐frequency planar magnetron sputtering system with changing the deposition substrate temperatures. A flexible OLED that was fabricated on the ITO‐grown polymer substrates exhibited a performance as comparable to the corresponding ITO‐grown glass substrates. Copyright © 2012 John Wiley & Sons, Ltd.     

X-Ray Analysis of Multi-Films for Electrochromic Device Application

Multilayer films based on tungsten oxide (WO₃), ITO (indium tin oxide) and CdS were deposited mainly by reactive dc magnetron sputtering onto glass substrates for electrochromic application. The thin films were analyzed by means of XPS (X-ray photoelectron spectroscopy), GIXD (grazing incidence X-ray diffraction) and XRD (X-ray diffraction). XRD and XPS results confirmed that the films were WO₃, CdS and ITO, respectively. The surface and interface of the CdS/ITO bi-layered film was studied by GIXD in different incidence angles. Detailed results about the amorphous characterization of the films during room temperature growth and post annealing are given.     

Preparation and characterization of dense films of poly(amidoamine) dendrimers on indium tin oxide

Indium tin oxide (ITO) substrates were modified with a layer of poly(amidoamine) (PAMAM) dendrimers to change their surface properties and, in particular, the substrates' work function. The functionalization procedure involved the electrostatic adsorption of positively charged PAMAM dendrimers of generation five onto negatively polarized ITO surfaces. Three different PAMAM dendrimers were used: PAMAM-NH2 and PAMAM-OH with terminal amine and hydroxyl groups, respectively, as well as Q-PAMAM-NH2, which had been prepared from PAMAM-NH2 by quaternization of the dendrimer's terminal and internal amine groups with methyl iodide. The resulting organic films were analyzed by contact angle goniometry, X-ray photoelectron spectroscopy, ellipsometry, and Kelvin probe force microscopy to confirm the presence of a dense layer. A Langmuir isotherm was derived from surface densities of fluorescence-labeled PAMAM-NH2 dendrimers from which we deduced an equilibrium binding constant, K(eq), of (1.3 +/- 0.3) x 10(5) M(-1). Kelvin probe measurements of the contact potential difference revealed a high reduction of the work function from 4.9 eV for bare ITO to 4.3 eV for ITO with a dense film of PAMAM-NH2 of generation five. PAMAM-OH and Q-PAMAM-NH2 resulted in slightly smaller work function changes. This study illustrates that the work function of ITO can be tuned by adlayers composed of PAMAM dendrimers.     

New colorless substrates based on polynorbornene‐chlorinated polyimide copolymers and their application for flexible displays

Novel polynorbornene (PNB)‐polyimide (PI) copolymers were synthesized based on poly(N‐phenyl‐exo‐norbornene‐5,6‐dicarboximide) (PPhNI) and chlorinated PI (BPDA/TCDB). Polynorbornene copolymers (PNCs) with diverse compositions of anhydride were synthesized via ring opening metathesis polymerization (ROMP) of N‐phenyl‐exo‐norbornene‐5,6‐dicarboximide (PhNI) and exo‐7‐oxanorbornene‐5,6‐dicarboxylic anhydride(exo‐NA), followed by copolymerization through a reaction with aromatic dianhydride (3,3′,4,4′‐biphenyltetra‐carboxylic dianhydride, BPDA) and tetrachlorinated diamine (2,2′,5,5′‐tetrachlorobenzidine, TCDB). The copolymer (PNIC) films exhibited good optical transparency with a transmittance of around 70% at 400 nm and a good thermal stability with a glass transition temperature at 276–300 °C. These flexible films also resisted most organic solvents and chemicals, such as methanol, acetone, tetrahydrofuran, N‐methylpyrrolidone, ethyl acetate, hydrochloric acid, sodium hydroxide, and hydrogen peroxide, etc. Indium tin oxide (ITO) coated thin films were prepared at various substrate deposition temperatures with a radio frequency (r.f.) planar magnetron sputtering system. The ITO thin films that were deposited onto the PNIC copolymer substrates had good electrical and optical properties. An organic light‐emitting device (OLED) was fabricated using the PNIC copolymer substrate with a structure of PNIC08/ ITO (anode)/hole‐transporting layer (HTL)/emitting & electron‐transporting layer (EM&ETL)/aluminum (cathode). The flexible OLED fabricated on the ITO‐grown PNIC substrate exhibited a performance that was comparable to corresponding ITO‐grown glass substrates. Therefore, the ITO‐grown PNIC substrate could possibly be a promising candidate as a substrate for flexible displays. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1806–1814, 2010     

Anode Engineering of Highly Efficient Polymer Solar Cells Using Treated ITO

ITO substrates were treated with organic solvent cleaning(OSC), SC1 treatment[V(NH₄OH):V(H₂O₂): V(H₂O)=1:1:5], O₂ plasma and UV ozone, respectively. Combined investigations of atom force microscopy(AFM), water contact angle measurements, ultraviolet photoemission spectroscopy(UPS) and X-ray photoemission spectroscopy(XPS) demonstrated that UV ozone treatment could give rise to the smoothest surface, the most hydrophilic property and the highest work function(WF) of ITO due to the removal of hydrophobic C-O impurity from the ITO surface and the enrichments of more oxygen on the ITO surface. When PEDOT:PSS film[(poly(3,4-ethylenedioxy- thiophene):poly(styrene sulfonate)] was deposited on the ITO substrates treated with UV ozone, it showed a lower root-mean- square roughness in AFM images, a higher transmission in UV-Vis transmission spectra and a higher WF in UPS spectra than the PEDOT:PSS films deposited on the ITO substrates treated by other three methods. As a result, the power conversion efficiency of polymer solar cells(PSCs) based on PTB7:PC₇₁BM as an active layer and ITO treated by UV ozone as an anode can reach 8.48% because of the simultaneously improved short circuit current, open circuit voltage and fill factor compared to the PSCs with ITO treated with other three methods.     

XPS study of the Li intercalation process in sol–gel‐produced V2O5 thin film: influence of substrate and film synthesis modification

We report on the process of lithium intercalation in V₂O₅ thin films deposited onto standard ITO‐coated glass substrates. The films were deposited via a well‐established sol–gel route, and the samples were examined as working electrodes in a range of potentials versus lithium reference electrode. This paper follows up issues arising from parallel spectroscopic characterizations of the films by X‐ray photoelectron spectroscopy (XPS). Specifically, the XPS examination showed that not all of the Li‐ion charge inserted was accounted for by the V(5) to V(4) reduction, but the stoichiometric balance could be maintained only by considering additional oxygens arising from the intercalation procedure, leading to Li₂O formation. In this work, we have examined the possibility that the source of oxygen is the ITO substrate. To this purpose, films of V₂O₅ deposited on silicon substrates have been prepared using the sol–gel process and examined by XPS after electrochemical intercalation/de‐intercalation cycles. We show that in this case a perfect balance between electrochemical charge, inserted Li and reduced vanadium is obtained. A further indication of ITO‐substrate effects was obtained from examination, by the same methods, of some unconventional V₂O₅ films that had been co‐precipitated with a siloxane, designed to provide a template structure. The results obtained from this material imply that a barrier layer is formed at the ITO interface and, therefore, the formation of Li₂O is avoided. The results are discussed in terms of the possible degradation of conventional V₂O₅ on ITO as a result of electrochemically induced interface reactions. Copyright © 2005 John Wiley & Sons, Ltd.     

Oxalic acid sensors based on sol–gel nanostructured TiO<Subscript>2</Subscript> films

Titanium (IV) oxide semiconducting layers were prepared by means of the templated sol–gel method and deposited on conductive ITO substrates. The films were described by a series of techniques involving X-ray diffraction (XRD), Raman spectroscopy, X-ray reflectivity (XRR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and ultraviolet–visible spectroscopy (UV–Vis). The photo-excitation properties of the films were characterized by electrochemical tests and evaluated from the obtained polarization curves. The generated photocurrents were measured in the presence of the hole-scavengers—oxalic acid and formic acid in the electrolyte. It was shown that especially in the case of oxalic acid the developed system can be used as an efficient and simpler concentration sensor. The relationship between values of the generated photocurrent and the layers’ thicknesses was also investigated.     

Use of a precursor solution to fill the gaps between indium tin oxide nanorods, for preparation of three-dimensional CuInGaS2 thin-film solar cells

We have fabricated a three-dimensional (3D) nanostructured indium tin oxide (ITO) film in which the spaces were filled by use of a Cu, In, and Ga precursor solution. This solution has potential for use in bulk heterojunction CuIn _x Ga_1?x S₂ (CIGS) thin-film solar cells. ITO nanorod films ~700 nm thick on glass substrates were synthesized by radio-frequency magnetron sputtering deposition. To ensure complete filling of the gaps in ITO nanorod films, a polymeric binder-free precursor solution was used. In addition, a two-step heating process (oxidation and sulfurization) was used after coating of the precursor solution to make a CIGS absorber film with a minimum of carbon impurities. Superstrate-type solar cell devices with 3D nanostructured films (CIGS–ITO) had a photovoltaic efficiency of 1.11 % despite the absence of a buffer layer (e.g. CdS) between the CIGS and ITO.     

Cu-TiO_2/ITO膜的制备、表征及其光电化学活性的研究

以甲酸作空穴捕获剂,采用直接光还原法将Cu2+沉积到TiO2膜表面制备纳米Cu TiO2/ITO膜.并分别应用紫外可见光漫反射、X 射线衍射、扫描电镜及光开路电压等实验表征.再以甲酸为模型化合物,研究Cu沉积和外加电场对TiO2光催化活性的协同增强作用.结果表明:沉积在TiO2膜表面的铜是以Cu(0)形式存在,Cu沉积对抑制光生电子 空穴的复合有明显的促进作用.于Cu TiO2/ITO膜电极施加适当正偏压,即能明显提高其催化活性.在本文实验条件下,以外加电场和Cu沉积相结合能使TiO2光催化降解甲酸的速率常数增加2.8倍.     

Dielectric and piezoelectric properties of dense and porous PZT films prepared by sol-gel method

PZT films with different microstructure and Zr:Ti ratios were fabricated on ITO/glass and platinized silicon wafer substrates by dip-coating. A dense film of 2% porosity and a porous film of 19% porosity were obtained by repetition of thin and thick coatings, respectively. Development of pores during heating the film was examined and heating process factors were investigated. In the film fabricated on ITO/glass substrates, an existence of non-perovskite and low permittivity layer was confirmed by measurement of film thickness dependence of the dielectric constant. Among the films studied, the film with molar composition of Ti:Zr = 5:5 exhibited the largest dielectric constant and apparent piezoelectric coefficient, d ₃₃, though the values were small. Apparent piezoelectric coefficients of d ₃₃ and g ₃₃ of the porous films were larger than those of the dense films.