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.     

Synthesis of nanostructured films from template electrodeposition technique

In this report, the use of a simple and versatile technique of templated electrodeposition through colloidal templates to produce nanostructured films of Pt and Au with regular submicron spherical holes arranged in a hexagonal close-packed structure is described. The templates were produced by self assembly of a monodispersed suspension of polystyrene spheres on gold substrates using capillary forces. The self assembly process was modified through the chemical modification of the gold substrate with cysteamine thiol. Films of Pt and Au were prepared by electrochemical deposition through the template. The electrochemical deposition charge and the current time curve were used to control the film height with a precision of approximately 10 nm. The colour of the nanostructured films changed as the film thickness was changed. On the other hand, high surface area of the nanostructured Pt film on top of the gold substrate was calculated using electrochemical cyclic voltammogram. About 55 roughness factor was obtained. SAXS measurements showed strong scattering at low angles indicating the presence of a well-ordered mesostructure.     

Nanoscale conductivity mapping of hybrid nanoarchitectures: ultrathin poly(o-phenylenediamine) on mesoporous manganese oxide ambigels

We use conductive-probe atomic force microscopy (CP-AFM) to characterize and image hybrid electrode structures comprising mesoporous manganese oxide (MnO2) ambigel nanoarchitectures coated with an ultrathin (<10 nm) electrodeposited layer of poly(o-phenylenediamine), PPD. Native MnO2 ambigel films, supported on indium tin oxide (ITO) substrates, exhibit spatially uniform conductivity that correlates well with the topography of the MnO2 film, confirming that the nanoscopic oxide network is effectively wired to the underlying ITO substrate. Following the self-limiting electrodeposition of the PPD coating onto the high-surface-area (>200 m2 g(-1)) MnO2 ambigel, the resulting hybrid structures display an approximately 20-fold reduction in conductivity, as determined from CP-AFM measurements. The CP-AFM imaging studies confirm that the ultrathin, insulating PPD layer conformally and homogeneously coats the conductive nanoarchitecture. CP-AFM imaging of PPD-MnO2 hybrid electrodes following electrochemical cycling in an aqueous acid electrolyte reveals that the ultrathin PPD coating serves as an effective barrier to the electrolyte, protecting the underlying MnO2 nanoarchitecture from electrochemical dissolution.     

Surface enhanced raman scattering of aromatic thiols adsorbed on nanostructured gold surfaces

In this paper we describe the use of a simple and versatile technique of templated electrodeposition through polystyrene sphere templates to produce nanostructured films of gold with regular submicron spherical holes arranged in a hexagonal close-packed structure. The templates were produced by self assembly of a monodispersed suspension of polystyrene spheres on gold substrates using capillary forces. The self assembly process was modified through the chemical modification of the gold substrate with cysteamine thiol. Films of gold were prepared by electrochemical deposition through the template. The electrochemical deposition charge and the current time curve were used to control the film height with a precision of approximately 10 nm. The colour of the nanostructured films changed as the film thickness was changed. Surface enhanced Raman Scattering spectra were recorded and used to identify very low concentrations of aromatic thiol molecules, 4-Nitrobenzenethiol (4-NBT) and 4-Aminobenzenethiol (4-ABT), adsorbed on the surface of the nanostructured gold substrates.      

Power reflectivity from surface films

The admittance technique is used to solve Maxwell's equations for an inhomogenous system consisting of a surface liquid film of low-absorbing (insulating) material on a metallic aluminium substrate. The power reflectivity spectrum in σ and π polarisation is easily discernible and is amplified to full scale for most angles of incidence. The reflectivity spectrum is very sensitive to the thickness of the liquid film and to the angle of incidence. This provides scope for using this technique to detect thin films of polymer material on metal substrates, oxide films, interfaces and so on.     

不同导电基底对TiO2薄膜光致亲水性的影响

分别在导电铝合金片(Al)和具有阳极氧化铝层的非导电铝片(AAO/Al), 以及铟锡氧化物导电玻璃(ITO/glass)和普通非导电玻璃(glass)表面通过提拉法制备出TiO2/Al和TiO2/AAO/Al, 以及TiO2/ITO/glass和TiO2/glass两组TiO2薄膜样品, 通过测试紫外光照下水滴接触角的变化考察TiO2薄膜的光致亲水性. 结果表明, 相对于TiO2/Al2O3/Al, 基底导电的TiO2/Al表现出较好的光致亲水性能; 而相对于TiO2/glass, 基底导电的TiO2/ITO/glass表现出较差的光致亲水性能. 分析认为, Al和ITO两导电基底和TiO2薄膜间的不同电子转移方向影响TiO2薄膜的光致亲水性能, Al片提供电子给TiO2有助于提高以光生电子为主要初级活性物种的光致亲水性, 而ITO接受TiO2的光生电子, 导致光致亲水性的下降.     

Electrochemical fabrication of two-dimensional palladium nanostructures as substrates for surface enhanced Raman scattering

Two-dimensional palladium (Pd) nanostructures have been fabricated by electrochemical deposition of Pd onto an indium tin oxide glass substrate modified with a thin flat film of polypyrrole or a nanofibril film of polyaniline. The experimental results demonstrated that the morphology of Pd nanoparticles strongly depended on the properties of conducting polymers and the conditions of electrochemical deposition. Two-dimensional nanostructures composed of flower-like (consisting of staggered nanosheets) or pinecone-like Pd nanoparticles were successfully synthesized. They can be used as substrates for surface-enhanced Raman scattering after partly decomposing the polymer components by heating in air, and the enhancement factor of the substrate composed of flower-like Pd nanoparticles was measured to be as high as 105 for 4-mercaptopyridine.     

Highly conducting and transparent sprayed indium tin oxide

Spray pyrolysis process has been used to deposit highly transparent and conducting films of tin doped indium oxide onto glass substrates. The electrical, optical and structural properties have been investigated as a function of various deposition parameters namely dopant concentrations, temperature and nature of substrates. X-ray diffraction patterns have shown that deposited films are polycrystalline without second phases and have preferred orientation [400]. Indium tin oxide layers with small resistivity value around 7.10⁻⁵Ω.cm and transmission coefficient in the visible and near IR range of about 85–90 % have been easily obtained.     

Pattern recognition in oxides thin-film electrodeposition: Printed circuits

A novel method for a low-voltage electrodeposition of insulating oxide sol–gel thin films on complex conducting patterns is described. By this method gold meshes and printed chips were selectively coated with titania and zirconia thin films. This method solves a classical problem in the thin-films world: dip-coating, spin-coating, spraying without masks—all cannot be used for selective coating of a complex conductive pattern, because these methods do not differentiate between conducting vs non-conducting areas. The newly developed method provides an electrochemical pattern recognition, which solves this problem.     

TiO2纳米片/巢状分级结构纳米阵列薄膜的制备及其在染料敏化太阳能电池中的应用

采用水热合成法在氟掺杂二氧化锡(FTO)导电玻璃基底上得到TiO2纳米阵列薄膜,并进一步通过NaOH溶液水热处理制备了由巢状纳米阵列及纳米片覆盖层构成的TiO2纳米阵列分级结构一体化薄膜.采用场发射扫描电镜(FE-SEM),X射线衍射(XRD),紫外-可见(UV-Vis)漫反射光谱和吸收光谱技术对TiO2薄膜的结构和性质进行表征.FE-SEM结果表明:分级结构TiO2薄膜膜厚为1.5μm,薄膜由一层纳米片覆盖层(约0.2μm高)和一层巢状纳米阵列层(约1.3μm高)组成.XRD谱图表明TiO2薄膜为锐钛矿相.UV-Vis光谱显示分级结构TiO2薄膜具有较强的光捕获能力和染料吸附能力.TiO2纳米片/巢状分级结构纳米阵列薄膜作为光阳极,可有效地提高染料敏化太阳能电池的光电转换效率,其短路电流(Jsc)为7.79mA·cm-2,开路电压(Voc)为0.80V,填充因子(FF)为0.40,光电转换效率(η)为2.48%,其光电转换效率较TiO2纳米阵列薄膜提高了近10倍.     

Tin oxide coating on polytetrafluoroethylene films in aqueous solutions

Polytetrafluoroethylene (PTFE) films were successfully coated with tin oxide in aqueous solutions. Tin oxide was crystallized in the solution and formed nanocrystal coatings on the polymer films. The coatings consisted of SnO₂ and SnO crystals. They were assemblies of tin oxide nanosheet of about 10 to 50 nm in size and about 5 nm in thickness. The nanocrystal films can be exfoliated from the PTFE substrates. Tin oxide nanocrystal films had a rough liquid surface and a dense substrate‐side surface. Transparency of PTFE films coated with tin oxide was same as that of bare PTFE films in the range from 400 to 800 nm. The PTFE films coated with tin oxide nanocrystals can be pasted on desired substrates. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of polymerization media on the nanoscale conductivity and current-voltage characteristics of chemically synthesized polyaniline films

A current sensing atomic force microscope (CS-AFM) was used to probe the conducting homogeneity and band structures of fully doped polyaniline (PANI) films prepared from in situ chemical polymerization/deposition of aniline on indium tin oxide in various inorganic acids. The charge transport properties of PANI films depend on the film thickness as well as polymerization medium. Fluctuations in conductivity are observed on all acid-doped PANI films and the conducting homogeneity was dependent on the film thickness: the conductivity of thick film is more uniform. The current-voltage (I-V) characteristics of all thick (>200 nm) films displayed a metal-like behavior and conductivity as high as 40 S/cm was detected in high conducting regions of film thicker than 400 nm. Whereas thin (<120 nm) films revealed insulating, semiconducting, and semimetal conducting, wide distribution in conductivity and interband distances (estimated from the I-V ordI/dV-V curves) was found. The interband distances is 0-1.35, 0-1.0, and 0-0.78 eV for thin PANI film prepared from HCl(aq), HClO(4)(aq), and H2SO4(aq), respectively. PANI film (260 nm) prepared from H2SO4(aq) revealed fiberlike morphology, and compared to PANI films prepared from HCl(aq) and HClO4(aq) with similar thickness, it has higher average nanoscale conductivity but lower bulk conductivity. This result could be direct evidence which supports that the bulk conductivity of PANI depended on the carriers hopping between the conducting domains.     

Substrates for flexible electronics: A practical investigation on the electrical,film flexibility,optical, temperature,and solvent resistance properties

Designing and developing flexible electronics requires a thorough investigation of the substrates available for the fabrication of devices. Here, we present a practical study on a variety of significant substrates: polyethylene terephthalate (PET), its heat‐stabilized (HS) derivative, HS‐PET, and polyethylene naphthalate (PEN) plastic insulating films; indium tin oxide (ITO)‐coated ITO/PEN and ITO/PET transparent conducting films; rigid ITO/glass and FTO/glass substrates; stainless steel and titanium foils. We put the substrates through a range of tests these actually undergo during device fabrication to determine their optical, mechanical flexibility (under different types of tensile and compressive stress bending with and without a PEDOT:PSS conducting polymer layer), solvent resistance, stability to temperature treatment (conductivity and deformation), and to UV irradiation. We highlight issues and propose solutions to improve substrate response. The results and thresholds extracted reveal limitations and windows of opportunity useful for the designer of flexible optoelectronics in determining manufacturing processes and the final applications under everyday operation. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Sol–Gel Coating of Thin Display Glasses - Problems and Remedy

Evaporation cooling is an inevitable but often neglected concomitant effect of sol–gel dip coating and related techniques, which is responsible for occasional coating problems. The phenomenon, however, emerges mostly for thin substrates of less than 1 mm thickness as the heat capacity of the substrate - the main source of heat for the evaporation - is reduced. The cooling of the substrate results in a reduced evaporation rate and an increased humidity in the surroundings of the film, leading to demixing of liquid components and an uncontrolled hydrolysis. The resulting coatings exhibit a hazy and cloudy appearance with crater-like structures in the micron range and consequently, functional properties such as the electrical conductivity of ATO coatings (antimony-doped tin oxide, SnO₂:Sb) are unsatisfactory. Among a variety of measures to overcome this cooling problem, a moderate heating of the coating liquid to only 25_°C was found to be the method of choice to obtain high quality sol–gel thin films on substrates with a thickness down to 0.4 mm as required for display applications. This slight modification of the dip coating processing helps to reduce the susceptibility of the wet film to humidity and to improve the coating quality and the reproducibility in general - both on thin and thick substrates.     

Localized surface plasmon resonance interfaces coated with poly[3-(pyrrolyl)carboxylic acid] for histidine-tagged peptide sensing

The paper reports on a novel localized surface plasmon resonance (LSPR) substrate architecture for the immobilization and detection of histidine-tagged peptides. The LSPR interface consists of an ITO (indium tin oxide) substrate coated with gold nanostructures. The latter are obtained by thermal deposition of a thin (2 nm thick) gold film followed by post-annealing at 500 °C. The LSPR interface was coated with poly[3-(pyrrolyl)carboxylic acid] thin films using electrochemical means. The ability of the LSPR interfaces coated with poly[3-(pyrrolyl)carboxylic acid] to chelate copper ions was investigated. Once loaded with metal ions, the modified LSPR interface was able to bind specifically to histidine-tagged peptides. The binding process was followed using LSPR.     

Unusual catalytic properties of nanostructured nickel films obtained by laser electrodispersion

Nanostructured nickel films deposited by laser electrodispersion onto a silicon (semiconducting) or thermally oxidized silicon (insulating) substrate show a remarkably high catalytic activity (of the order of 10³–10⁴ (mol product) (mol Ni)^?1 h^?1) in the isomerization of chlorinated hydrocarbons and olefin hydrogenation. The special properties of the laser-deposited films are likely due to the small size (2.5 nm), developed surface, and amorphism of the nickel particles, as well as to highly active, charged particles appearing on the insulating substrate. The latter result from thermal fluctuations of electrons between closely spaced particles. In a film deposited on silicon covered with a natural oxide layer, a significant role is also played by charge redistribution between the substrate and metal particles.     

Process optimization and characterization of thin films of SrFeO3-x by the pechini method

Nanostructured coatings have recently attracted increasing interest because of the possibilities of synthesizing materials with unique physical-chemical properties. Highly sophisticated surface related properties, such as optical, magnetic, electronic, catalytic, mechanical, chemical and tribological properties can be obtained by advanced nanostructured coatings, making them attractive for various industrial applications. In this report we describe our efforts at developing methodology for the fabrication of SrFeO_3-x based thin films using a modified Pechini method. Thin films of SrFeO_3-x were fabricated using spin coating and a drop coating method developed in-house on Al₂O₃ and Si- substrates. The films annealed at 600°C for one hour show a perovskite phase. The grain size increases with increase in annealing temperature. The influence of various variables such as metal to chelant ratio, drying control reagents, calcination conditions, substrate type and mode of film formation were studied using XRD, optical microscopy, SEM and AFM.     

Electroless deposition of poly(2-alkoxyaniline)s

The in situ deposition of poly(2-alkoxyaniline)s onto oxide surfaces is reported. It is demonstrated that the identity of the substrate can have a pronounced effect on the polymerization rate of these substituted polyanilines. Poly(2-alkoxyaniline)s deposit efficiently onto indium-doped tin oxide (ITO), but deposition onto quartz proceeds slowly. The critical stage in the deposition process is shown to be polymerization of the adsorbed oligomeric species. When this polymerization process is catalyzed by the surface, polymer growth is enhanced, and we find that conducting substrates mediate this apparent catalytic process. We demonstrate selective deposition by growing poly(2-alkoxyaniline) adlayers onto patterned ITO/quartz substrates.     

Microstructure and performance of AZO thin films prepared by sol–gel processing

Al-doped zinc oxide (AZO) films were prepared by a wet-chemical coating technique, their microstructure and crystal growth were characterized as a function of the single layer thickness. When similar final thicknesses are attained by more multiple subsequent coating-firing cycles, film porosity is reduced from over 14 to 2 %. Simultaneously the AZO crystallite size is increased from approximately 23 to 60 nm, a preferential c-axis oriented growth is observed. Different substrates (soda-lime glass, soda-lime glass with a SiO₂ barrier coating, borosilicate glass and alkali-free display glass) were used and the resulting AZO films were compared. It is found that the substrate composition primarily affects grain growth and subsequently the electrical performance of the AZO films.     

Electrochemical stability of self-assembled alkylphosphate monolayers on conducting metal oxides

Alkylphosphate self-assembled monolayers (SAMs) were prepared on Nb-doped SrTiO(3) (Nb-STO) conducting metal oxide substrates. Unlike thiols on gold, the alkylphosphate SAMs on Nb-STO exhibited an electrochemical stability over a wide voltage range from -2 to 2 V. Cyclic voltammetry showed that the SAM modification inhibited the electrochemical activity of the underlying conducting substrate with an efficiency dependent on the chain length. Impedance spectroscopy showed that SAM-modified Nb-STO substrates have a significantly higher resistance than bare substrates.