ITO-free transparent conductive films based on carbon nanomaterials with metal grid for liquid crystal displays

Carbon nanomaterials with metal grids were used as transparent conductive electrodes for liquid crystal displays (LCDs) to develop an indium tin oxide (ITO)-free device. We prepared LCDs with CNTs and graphene electrodes; however, the working voltage of the device with the CNT electrodes was high. The device with graphene electrodes had good performance, but not as good as devices with ITO electrodes. To improve the device performance, we applied a metal grid to the carbon nanomaterial to create low sheet-resistance transparent electrodes. The device with the graphene and metal grid transparent electrodes had a threshold voltage as low as 0.23 V/µm, which is similar to that of typical LCDs with ITO electrodes. The results show that a hybrid transparent conductive film with graphene and metal grid could be an alternative to ITO for developing ITO-free LCDs.     

Ultrathin transparent conductive films of polymer-modified multiwalled carbon nanotubes

Deposition of multiwalled carbon nanotubes modified by poly(2-vinylpyridine) (CNT-g-P2VP) from aqueous dispersions at low pH is an effective method to prepare homogeneous ultrathin films with a tunable CNTs density. A percolation threshold of 0.25 mug/cm2 and a critical exponent alpha = 1.24 have been found from dc conductivity measurements. The sheet resistance value agrees with the percolation theory for 2D films. According to AFM and electrical measurements, even when only 5% of the surface is covered by CNT-g-P2VPs, the sheet resistance is of the order of 1 MOmega/sq, which indicates that conductivity is imparted by a network of an ultralow density. When the film transmittance decreases down to approximately 70% at 550 nm, the occupied surface area is approximately 15% and sheet resistance falls down to approximately 90 kOmega/sq. These data show that undesired in-plane clustering does not occur upon the dispersion casting of the films and that high-quality networks of CNT-g-P2VPs are built up. The electrosteric stabilization of the CNT-g-P2VP dispersions in water at low pH is at the origin of this desired behavior. Although the multiwalled CNT films prepared in this work are less conductive and less transparent than the SWNTs films, they could find applications, e.g., in touch screens, reflective displays, EMI shielding, and static charge dissipation.     

Free-standing highly conductive transparent ultrathin single-walled carbon nanotube films

Transparent and conductive single-walled carbon nanotube (SWNT) films are of great importance to a number of applications such as optical and electronic devices. Here, we describe a simple approach for preparing free-standing highly conductive transparent SWNT films with a 20-150 nm thickness by spray coating from surfactant-dispersed aqueous solutions of SWNTs synthesized by an improved floating-catalyst growth method. After the HNO(3) treatment, dipping the SWNT films supporting on glass substrates in water resulted in a quick and nondestructive self-release to form free-standing ultrathin SWNT films on the water surface. The obtained films have sufficiently high transmittance (i.e., 95%), a very low sheet resistance (i.e., ～120 Ω/sq), and a small average surface roughness (i.e., ～3.5 nm for a displayed 10 × 10 μm area). Furthermore, the floating SWNT films on the water surface were easily transferred to any substrates of interest, without intense mechanical and chemical treatments, to preserve their original sizes and network structures. For example, the transferred SWNT films on poly(ethylene terephthalate) films are mechanically flexible, which is a great advantage over conventional indium-tin oxide (ITO) and therefore strongly promise to be "post ITO" for many applications.     

Achievement of highly conductive p-type transparent NdCuOS film with Cu deficiency and effective doping

Future advanced invisible or transparent electronics necessitate the need to overcome the well-known challenge in achieving high-performance p-type transparent semiconducting oxides (TSOs). Here, we report our success in achieving an outstanding p-type TSO thin film NdCuOS, which is the best performing p-type TSO reported to date based on the figure of merit (FoM) according to the best of our knowledge. In this work, we designed a novel chemical solution method to prepare the highly performing NdCuOS films with different doping elements. Our success in using a chemical solution method to grow semiconducting NdCuOS demonstrates that highly conductive oxychalcogenide films are possible to be prepared by a solution method. Such a solution method is facile, economically efficient, and scalable. Among our NdCuOS films with different dopants, we find that Mg-doped NdCuOS film demonstrates a very high p-type conductivity of 52.1 S cm^?1 and optical transmittance of 54.3% with a huge FoM value of 1706 μS. This surpassed all the other p-type films reported so far in terms of FoM. Strong photoluminescence peaks at 3.0 eV are observed for our films, indicating their great potential applications for UV or blue light LED and other devices. The science behind such a successful achievement of high-performance p-type NdCuOS film is analyzed and discussed. A transparent p-n diode with very low leakage current (9.12  μA at ?3 V) and turn-on voltage (1.1 V) is successfully fabricated, and it demonstrates a good device performance.     

UV cured transparent films including non‐aqueous conductive microgels

UV cured transparent films containing non‐aqueous conductive microgels coated with poly(aniline)/dodecyl benzenesulfonic acid(DBSA) were obtained. The conductive microgels were prepared by interface polymerization of aniline/DBSA in the presence of non‐aqueous polymeric microgels. The electrical conductivity and the particle size of the prepared conductive microgel were 0.5 S/cm and 58 nm, respectively. The prepared conductive microgels were easily blended with a UV curable coating formulation, and then were cured to make highly optically transparent films. For the UV cured film containing about 35 wt% of the conductive microgels, a surface resistance in the range of 10⁷ to 10⁸ Ω/square was obtained. In a polar cosolvent, such as NMP and m‐cresol, the critical volume was shifted to the lower range, with a value of 10 wt%. The UV cured films containing the conductive microgels exhibited good electrical stability against the thermal aging and humidity. Copyright © 2002 John Wiley & Sons, Ltd.     

Preparation of transparent conductive multilayered films using active pentafluorophenyl ester modified multiwalled carbon nanotubes

A mutilayered film was prepared by layer-by-layer (LBL) assembly of active ester modified multiwalled carbon nanotubes (MWCNTs) and poly(allylamine hydrochloride) (PAH). For this purpose, carboxylic groups on the surface of the oxidized MWCNTs were converted to the acyl chlorides by their reaction with thionyl chloride. Subsequent reaction of the acyl chlorides with pentafluorophenol formed the active esters. These active ester modified MWCNTs (MWCNTs-COOC 6F 5) were air-stable and moisture resistant, but showed a high reactivity toward primary or secondary amines resulting in amide bonds. For the preparation of a multilayered film, the surface of a quartz slide was first activated and sacrificial double layers of PAH and poly(sodium 4-styrene sulfonate) (PSS) were deposited. Subsequently, LBL assembly of MWCNTs-COOC 6F 5 and PAH was then conducted on these double layers [(PAH/PSS) 2]. In the process of the assembly, a reaction occurred between the active ester on the surface of MWCNTs and the amine groups of polyallylamine yielding amide bonds, which resulted in a mechanically stable thin film. A free-standing film was obtained after dissolving the sacrificial layer [(PAH/PSS) 2] in a concentrated aqueous NaOH solution. The surface resistance of the multilayered film with 20 bilayers decreased to around 10 kOmega while remaining a reasonable transparency (70% at 500 nm).     

Anti-scratch and transparency properties of transparent conductive carbon nanotube films improved by incorporating polyethoxysiloxane

Transparent conductive films of single-walled carbon nanotubes (SWCNTs) were fabricated by a simple method to significantly enhance anti-scratch and transparency properties by the incorporation of polyethoxysiloxane (PES). The reasons for changes in the mechanical properties and transmittance were investigated through the reflection property and morphology of thin films. With the incorporation of PES, the sheet resistance of the SWCNT thin film remained unchanged after the anti-scratch test. It was found that the transmittance of the thin films suddenly increased when the thickness of the PES layer was ca 100 nm. Although the PES incorporation resulted in a slight increase in the sheet resistance, the experimental results revealed that the sheet resistance of the SWCNT thin films with PES was lower than that of films without PES for the same transmittance due to the increase of the transmittance caused by the PES incorporation. We have demonstrated that the sheet resistance was halved at a transmittance of ～86% due to PES incorporation. SWCNT thin films with PES showed better electrical properties than those without PES after a bend test.     

Highly transparent and conductive thin films fabricated with nano-silver/double-walled carbon nanotube composites

This study develops a technique for enhancing the electrical conductivity and optical transmittance of transparent double-walled carbon nanotube (DWNT) film. Silver nanoparticles were modified with a NH(2)(CH(2))(2)SH self-assembled monolayer terminated by amino groups and subsequent surface condensation that reacted with functionalized DWNTs. Ag nanoparticles were grafted on the surface of the DWNTs. The low sheet resistance of the resulting thin conductive film on a polyethylene terephthalate (PET) substrate was due to the increased contact areas between DWNTs and work function by grafting Ag nanoparticles on the DWNT surfaces. Increasing the contact area between DWNTs and work function improved the conductivity of the DWNT-Ag thin films. The prepared DWNT-Ag thin films had a sheet resistance of 53.4 Ω/sq with 90.5% optical transmittance at a 550 nm wavelength. After treatment with HNO(3) and annealing at 150 °C for 30 min, a lower sheet resistance of 45.8 Ω/sq and a higher transmittance of 90.4% could be attained. The value of the DC conductivity to optical conductivity (σ(DC)/σ(OP)) ratio is 121.3.     

Cost-effective dye-sensitized solar cells consisting of two metal foils instead of transparent conductive oxide glass

A cost-effective structure for dye-sensitized solar cells (DSSCs) without using transparent conductive oxide (TCO) is reported. Instead of high-cost F/SnO(2) glass (FTO-glass) or woven metal mesh, a Ti foil and a perforation-patterned stainless steel (StSt) foil are introduced as the substrates for a counter-electrode and a photo-electrode, respectively.     

Formation process of indium oxide transparent conducting films via thermal decomposition

Indium 2-ethylhexanoate monohydroxide, In(OH)(O₂CCH(CH₂CH₃)(CH₂)₃CH₃)₂, is a precursory material to fabricate In₂O₃-based transparent conducting films by dip-coating process. Formation process of indium oxide transparent conducting films was investigated using an ultra-low acceleration voltage FE-SEM. The nanostructure change of the precursory layer was observed during the electron beam irradiation in vacuum. A flat and homogeneous surface of the as-coated layer changed to porous and net-work like nanostructure after 80 s; the pore diameter increased and the pore distance decreased although the number of pores remained unchanged. These processes were interpreted as the preliminary step to form porous films composed of nm-sized inter-linked oxide particles as reported in the previous papers by the authors.     

过渡金属电解水催化剂的非金属掺杂研究进展

过渡金属基材料成本相对较低,催化性能较为优异,是在全水分解领域最有希望替代贵金属基电催化剂的候选材料之一,但有限的活性位点、相对较差的电导率等因素限制了其广泛应用。非金属元素掺杂能够调节主体材料电子结构,优化吸附能,从而对过渡金属基电催化剂的活性与稳定性产生积极影响,缩减其与贵金属材料性能差距。本文总结了近年来非金属元素改性在过渡金属基电催化材料中的相关研究,系统综述了非金属元素掺杂的方法和不同非金属元素的掺杂效果,从物理化学性质的改变和电子结构的变化多角度分析了非金属元素改性对过渡金属基材料的影响,最后对非金属元素掺杂过渡金属基电催化剂的未来发展方向作出了展望。     

Effect of transition metal doping and carbon doping on thermoelectric properties of YB66 single crystals

We have been investigating the high-temperature thermoelectric properties of some novel rare earth borides with a structure containing B₁₂ icosahedra. Doping effects on the TE properties in such systems were investigated for the first time. A series of Nb-doped YB₆₆ and C-doped YB₆₆ single crystals were grown by the floating zone method. The Nb-doped compounds have approximate chemical formulas ranging from YNb_0.30B₆₆ to YNb_0.33B₆₆ while the C-doped compound has a formula of YB₆₆C_0.6. The effect of Nb-doping on the thermoelectric properties was not monotonic and appears to be complex. As a result of Nb-doping, the room temperature resistivity and the characteristic temperature T₀ were considerably reduced. At room temperature the power factor of the Nb-doped YB₆₆ sample with 89% site occupancy was three times greater than that of non-doped YB₆₆. However, in the important high-temperature region, the non-doped sample actually exhibited the highest power factor for . Furthermore, owing to a structural feature of YB₆₆, thermal conductivity actually increases with doping of transition metals. Taking into account all the thermoelectric properties, transition metal doping of YB₆₆ is therefore not suitable for our purposes. On the other hand, doping of carbon, which is assumed not to go into the same sites as the transition metals, yielded a lowering of the thermal conductivity. Furthermore, contrary to Nb-doping, carbon doping did not result in a reversal of the relative magnitude of resistivity at extremely high temperatures and therefore, an increase in the figure of merit of factor 2 was realized at 1000 K.     

Preparation of conductive,flexible and transparent films by in situ deposition of polypyrrole nanoparticles on polyethylene terephthalate

In this study polypyrrole (PPy) nanoparticles were deposited as a thin film on the modified surface of polyethyleneterephthalate (PET) by in situ chemical polymerization in the presence of sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (DBSNa) and mixture of them as the surfactant. The surface of PET was modified by KOH before deposition and was investigated for conductivity and adhesion of PPy nanoparticles to PET. Resulting conductive flexible films were characterized by UV–Vis spectroscopy, fieldemission scanning electron microscopy, contact angle measurements and four-point-probe technique for conductivity. Direct morphological observation (FESEM) and electrical measurements indicated that the morphology, conductivity and the nature of deposited PPy films depend on surfactant, surface modification of PET and monomer concentration. In optimized process condition, uniform conductive films of PPy were obtained with good adhesion to PET.     

Synthesis of highly conductive EDOT copolymer films via oxidative chemical in situ polymerization

Poly(3,4‐ethylenedioxythiophene)s (PEDOT) represent a class of conjugated polymers that can be potentially used as an electrode material for flexible organic electronics due to their superior conductivity and transparency. In this study, we demonstrate that the conductivity of a PEDOT containing copolymer film can be further enhanced by the oxidative chemical in situ copolymerization of a liquid film spun coated from monomer mixture (3,4‐ethylenedioxythiophene (EDOT) and 3‐thienyl ethoxybutanesulfonate (TEBS)), oxidant (iron(III) p‐toluenesulfonate (Fe(OTs)₃)), weak base (imidazole), and solvent (methanol). We investigated that the effect of the processing parameters such as the molar ratios TEBS/EDOT, IM/EDOT, and Fe(OTs)₃/EDOT on the surface morphology, optical property, and the conductivity of the resulting copolymer films. These parameters have been optimized to achieve conductivities for the copolymer films as high as 170 S/cm compared with a conductivity of 30 S/cm for the pure PEDOT film synthesized using the same fabrication method. This conductivity enhancement for the copolymer films was found to be resulted from the fact that the addition of TEBS monomer reduces the copolymerization rate, leading to the formation of much more uniform film surface without defects and copolymers of higher molecular weight which increase the conductivity of the resulting copolymer film. The composition of two monomers in the copolymer film is not related to the variation of conductivity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1662–1673, 2008     

Generation and characterization of supported films of transition metal and rare earth metal oxide catalysts

Summary The generation of catalytically relevant metal and/or metal oxide compounds supported on silica fibres is described. The systems investigated are Ni^o, Cu^o, Cu^o/ZnO, as well as perovskite-type La/Fe, La/Ni and La/Mn oxide phases. Ultrasound-aided generated vapours containing dissolved metal salt precursors are transferred onto preheated quartz fibres and transformed into the catalytically relevant phases by subsequent calcination. Analytical SEM and X-ray diffraction reveals the presence of differently crystalline, rough surfaces. The influence of the precursor salt and the conditions of calcination on the formation of the supported catalysts is discussed.     

Effect of the perfluoroalkyl groups on the preparation of carbon-based transparent and conductive thin films from silylated graphite oxides

Carbon-based transparent thin films were prepared from the pyrolysis of silylated graphite oxide containing perfluoroalkyl groups. The saturated amount of n-hexadecylamine molecules which accommodated between the layers of silylated graphite oxide containing larger pefluoroalkyl groups was smaller than that observed for silylated graphite oxide without perfluoroalkyl groups. The resulting intercalation compounds were dispersed in a chloroform/cyclohexane solution and precursor thin films were obtained by a cast method. The sheet resistance of the obtained carbon-based films was about 5 times smaller than that of the films prepared from silylated graphite oxide prepared with the analogous hydrocarbon substituents. The spectroscopic measurements indicated that the number of defects within the carbon layers was larger, however, that of carbon atoms participating π-conjugating system was larger. This probably ascribed to the active fluorine species formed as the result of thermal decomposition of perfluoroalkyl groups. The latter was responsible for the lower sheet resistance of carbon-based thin films.     

Toward transparent molecular wires: electron and energy transfer in transition metal derivatized conducting polymers

A great deal of research has concentrated on long range electron and energy transport in transition metal-based systems, including molecular donor-acceptor assemblies, electron and energy transfer cascades, dendrimers, and derivatized polymer systems. In an effort to improve efficiencies for electron and energy transport over large distances, several groups have now turned to conjugated systems. Several challenges exist to incorporating conducting materials/polymers in the study of photoinduced electron and energy transfer: solubility and processibility of the materials, thermal stability and limitations on direct spectroscopic characterization due to band gap absorptions. We have prepared a new series of conducting materials that provides for direct incorporation of chromophores and electrophores within the backbone of a conducting polymer. Energy transfer dynamics between conducting polymer bridges and porphyrin or metal-to-ligand charge transfer (MLCT) chromophores can be controlled through intermolecular interactions in solid vs solution samples. We have also developed a methodology to incorporate transmissive benzothiophene-type polymers such as polyisothianaphthene (PITN) within a copolymer assembly. These new materials are now being used to investigate long range electronic coupling and have potential applications that range from artificial photosynthesis to light emitting diodes.     

Coordination chemistry and functionalization of white phosphorus via transition metal complexes

The chemistry of phosphorus is nowadays rivaling that of carbon in terms of complexity and diversity. This tutorial review highlights the state-of-the-art in the field of metal-mediated activation and functionalization of white phosphorus. Particular attention is given to an illustration of the coordination abilities of the intact molecule as well as the disaggregating and reaggregating metal-mediated processes resulting in different polyphosphorus ligands from P(1) to P(12). The metal-promoted P-C and P-H bond forming processes are also reviewed showing that an ecoefficient catalytic protocol for transforming P(4) into high value organophosphorus compounds is a concrete possibility for chemical companies.This tutorial review deals with the activation and functionalization of white phosphorus in the coordination sphere of transition metal complexes. Particular attention is given to the coordination abilities of the intact molecule as well as to the disaggregating and reaggregating metal-mediated processes yielding various polyphosphorus ligands from P(1) to P(12). The metal-promoted processes for P-C and P-H bond formation are also reviewed showing that an ecoefficient catalytic protocol for transforming P(4) into high value organophosphorus compounds offers good opportunities for chemical companies.