聚苯胺/聚合物透明导电复合膜研究进展

论述了聚苯胺/聚合物透明导电复合膜的制备及性能.原位聚合法、掺杂聚苯胺旋转涂膜法和机械共混浇铸法均可制备透明导电复合膜.所得复合膜具有良好的透明性、导电性、环境稳定性及耐疲劳性能.     

Synthesis and characterization of polyaniline/activated carbon composites and preparation of conductive films

Polyaniline was synthesized via polyaniline/activated carbon (PANI/AC) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/AC composite films were prepared by drop-by-drop and spin coating methods. The electrical conductivities of HCl doped PANI film and PANI/AC composite films were measured according to the standard four-point-probe technique. The composite films exhibited an increase in electrical conductivity over neat PANI. PANI and PANI/AC composites were investigated by spectroscopic methods including UV–vis, FTIR and photoluminescence. UV–vis and FTIR studies showed that AC particles affect the quinoid units along the polymer backbone and indicate strong interactions between AC particles and quinoidal sites of PANI. The photoluminescence properties of PANI and PANI/AC composites were studied and the photoluminescence intensity of PANI/AC composites was higher than that of neat PANI. The increase of conductivity of PANI/AC composites may be partially due to the doping or impurity effect of AC, where the AC competes with chloride ions. The amount of weight loss and the thermostability of PANI and PANI/AC composites were determined from thermogravimetric analysis. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the AC particles were well dispersed and isolated in composite films.     

Fluorine doped gallium tin oxide composite films as transparent conductive oxides on polyethylene terephthalate film prepared by electron cyclotron resonance metal organic chemical vapor deposition

The undoped and fluorine doped gallium tin oxide composite films are prepared by an electron cyclotron resonance metal organic chemical vapor deposition. Characteristics of structural, optical and electrical properties of the fluorine doped gallium tin oxide composite thin films are investigated. The four point probe method, atomic force microscopy and X-ray photoelectron spectroscopy are employed to characterize the composite thin films. UV-visible, X-ray diffraction, scanning electron microscope and Hall measurement performed on fluorine doped gallium tin oxide composite are films deposited on polyethylene terephthalate substrates. The diffraction pattern shows the presence of tetragonal structure with (112) special orientation for fluorine doped gallium tin oxide composite films. The doped composite film on F/Ga + Sn mole ratio of 0.35 is observed the lowest electrical resistivity of 3.35 × 10^− 4 Ω cm.     

Fabrication of transparent conductive carbon nanotubes/polyurethane-urea composite films by solvent evaporation-induced self-assembly (EISA)

Transparent and conductive carbon nanotubes (CNTs)/polyurethane-urea (PUU) composite films were prepared by solvent evaporation-induced self-assembly (EISA). Pristine CNTs were treated with acids (H₂SO₄/HNO₃ = 3:1, v:v), acylated with thionyl chloride, and purified after filtration. These acylated CNTs (0.05 wt.% in dimethylformamide, DMF) were deposited onto the 3-aminopropyl triethoxysilane (APTES)-modified glass substrate by DMF EISA at 100 °C with the withdrawal rate of 3 cm/h. The CNT layers of 200–400 nm thicknesses were transferred to the PUU films by solution casting or resin transfer molding (RTM) at ambient temperature. Optical transmittances of the composite films were 60–75% at 550 nm wavelength and their sheet resistances were 5.2 × 10⁰–2.4 × 10³ kΩ/square, and which varied significantly with type of CNTs and the transferring methods of CNT layers.     

Fabrication of surface silvered polyimide/iron oxide composite films with both superparamagnetism and electrical conductivity

Surface silvered polyimide (PI)/Fe₂O₃ composite films with both superparamagnetic and surface electrically conductive properties have been fabricated by an in situ technique. Iron (III) 2,4-pentanedionate was incorporated into a PI precursor poly(amic acid) solution and thermally decomposed to form iron oxide nanoparticles in the process of thermal imidization, preparing PI/Fe₂O₃ nanocomposite films. The establishment of a silver layer on the PI/Fe₂O₃ film surface involved the steps of chemical etching by the alkaline aqueous solution, ion exchange with silver ions and chemical reduction by glucose. The formed Fe₂O₃ particles of the nano scale endow the film with typical superparamagnetic response. By employing the etching time of only 10 min and a reduction time of no more than 15 min, the well-established silver layers have formed on the upside surface. The corresponding reflectivity and resistivity reached to the value of 76.15% and 0.7 Ω/square respectively.     

Expanded graphite/polyaniline electrical conducting composites: Synthesis, conductive and dielectric properties

Expanded graphite/polyaniline electrical conducting composites were prepared by emulsion polymerization of aniline in the presence of expanded graphite. The phase composition and morphology of the composites were characterized by X-ray diffractometer and scanning electron microscopy, respectively. The electrical conductivities were measured by a four-probe resistivity instrument. The dielectric loss factor was performed on an impedance/material analyzer. The electrical conductivities of the composites were enhanced dramatically to 298.51 S cm^− 1 compared to polyaniline. The composites also showed excellent dielectric loss behavior in the frequency range from 1 MHz to 3 GHz, and the maximum of the dielectric loss factor approximated to 15,000.     

Fabrication of flexible transparent conductive films from long double-walled carbon nanotubes

The fabrication of flexible transparent conducting films (TCFs) is important for the development of the next-generation flexible devices. In this study, we used double-walled carbon nanotubes (DWCNTs) as the starting material and described a fabrication method of flexible TCFs. We have determined in a quantitative way that the key factors are the length and the dispersion states of the DWCNTs as well as the weight-ratios of dispersant polymer/DWCNTs. By controlling such factors, we have readily fabricated a flexible highly transparent (94% transmittance) and conductive (surface resistivity = 320 Ω sq⁻¹) DWCNT film without adding any chemical doping that is often used to reduce the surface resistivity. By applying a wet coating, we have succeeded in the fabrication of large-scale conducting transparent DWCNT films based on the role-to-role method.     

Annealing effect of ZnO/Au/ZnO transparent conductive films

Au intermediate ZnO (ZAZ) thin films were prepared by radio frequency and direct current magnetron sputtering on glass substrates and then vacuum annealed. The thickness of each layer of the ZAZ films was set at 50 nm, 3 nm, and 47 nm, respectively. The structural, electrical, and optical properties of ZAZ films were investigated with respect to the variation of annealing temperature.As-deposited AZO films showed X-ray diffraction peaks corresponding to ZnO (002) and Au (111) planes and those peak intensities increased with post-deposition vacuum annealing. The optical and electrical properties of the films were strongly influenced by post-deposition annealing. Although the optical transmittance of the films deteriorated with an Au interlayer, as-deposited ZAZ films showed a low resistivity of 2.0 × 10⁻⁴ Ω cm, and the films annealed at 300 °C had a lower resistivity of 9.8 × 10⁻⁵ Ω cm. The work function of the films increased with annealing temperature, and the films annealed at 300 °C had a higher work function of 4.1 eV than the films annealed at 150 °C. The experimental results indicate that vacuum-annealed ZAZ films are attractive candidates for use as transparent electrodes in large area electronic applications such as solar cells and large area displays.     

碳纳米管/环氧树脂复合材料的导电性能研究

采用搅拌和高速剪切分散工艺将碳纳米管(CNT)分散在环氧树脂(EP)中,制成CNT/EP复合导电材料,浇成圆形试样.用表面电阻计测量样品的表面电阻检测其导电性,结果显示随着碳纳米管添加量的增加,复合材料的表面电阻不断降低.碳纳米管添加量为5%时,表面电阻从1012Ω下降到106Ω.使用SEM观测了碳纳米管在环氧树脂中的分散情况.     

Carbon nanotube based transparent conductive films: progress,challenges, and perspectives

Developments in the manufacturing technology of low-cost, high-quality carbon nanotubes (CNTs) are leading to increased industrial applications for this remarkable material. One of the most promising applications, CNT based transparent conductive films (TCFs), are an alternative technology in future electronics to replace traditional TCFs, which use indium tin oxide. Despite significant price competition among various TCFs, CNT-based TCFs have good potential for use in emerging flexible, stretchable and wearable optoelectronics. In this review, we summarize the recent progress in the fabrication, properties, stability and applications of CNT-based TCFs. The challenges of current CNT-based TCFs for industrial use, in comparison with other TCFs, are considered. We also discuss the potential of CNT-based TCFs, and give some possible strategies to reduce the production cost and improve their conductivity and transparency.     

超声强制浸润法制备碳纳米纸/聚合物导热复合材料

为实现聚合物基导热复合材料的高效制备，提出了一种利用超声焊接设备实施的超声强制浸润方法。采用真空抽滤方法制备出由碳纳米管(Carbon nanotubes, CNTs)堆叠而成的碳纳米纸(Carbon nanopapers, CNPs), 将CNPs放置在未固化的聚二甲基硅氧烷(Polydimethylsiloxane, PDMS)中，利用超声焊接设备的高频率、高功率超声源进行震荡，凭借超声波的能量传递作用，使液态PDMS逐步浸润到CNPs中。在100℃加热30 min固化后，即得到兼具高柔性和优良导热性能的CNPs/PDMS复合材料。结果表明，相同振幅条件下，CNPs/PDMS复合材料的导热性能随超声处理时长的增加而先上升后下降，并在超声时长为1.9 s时达到最优，热导率达5.781 W/(m·K)。验证了超声强制浸润法高效的制备柔性导热复合材料的可行性。      

Structural, electrical and bending properties of transparent conductive Ga-doped ZnO films on polymer substrates

We investigated the characteristics of highly transparent conductive Ga-doped ZnO (GZO) polycrystalline films of 100 nm thickness deposited on glass and polymer substrates. GZO films were deposited by ion plating with dc-arc discharge. We developed multiple-deposition method to obtain various deposition process temperatures lower than 100 °C. Cross-sectional SEM images show that all the GZO films have columnar structure. Analysis of data obtained by XRD measurements shows that all the GZO films with wurtzite structure exhibit highly (002) orientation perpendicular to the substrate. The resistivity of the GZO films deposited on polyester and glass substrates were 5.0 × 10^-4 Ω · cm. The mechanical bending properties of the GZO films were investigated by comparing the sheet resistance determined before and after a bending test with various bending diameters. For the bending diameter of more than 30 mm, all the GZO films exhibited excellent bending properties with no change in sheet resistance. For the bending diameter of less than 20 mm, we found the sheet resistance affected by the bending. We demonstrated that our multiple-deposition method to achieve different controllable polyester substrate temperatures is highly suitable for improving the bending properties of GZO films.     

Preparation process and properties of LiCoO2/PANI/dodecylbenzenesulfonate composite electrode materials

Composite materials that combine the lithium exchanging material LiCoO₂ and the conductive polymer poly(aniline) (PANI) have been investigated regarding their possible application to electrode materials of lithium batteries. Such composite materials have been prepared by means of polymerization of aniline in acidic suspensions of LiCoO₂ particles. PANI was synthesized by oxidative polymerization of aniline by ammonium persulfate in the presence of sodium dodecylbenzenesulfonate (SDBS) as a micellar template and dopant. The composite material consisted in LiCoO₂ particles dispersed in a continuous matrix of PANI. The ribbon-like morphology of the powdered material was distinctly different of the morphologies of the parent materials. The conductive material had conductivity close to that of PANI because the LiCoO₂ content of the composite material was low. The presence of the poorly conductive inorganic phase caused a significant loss of conductivity, showing that LiCoO₂ blocked electronic transfers between PANI crystallites. Ammonium persulfate caused the loss of lithium from LiCoO₂ when it was used at high concentration in the polymerization recipe. In this case a new phase made of Co₃O₄ formed by chemical decomposition of Li_xCoO₂. Thin films prepared from stable suspensions of composite materials in water show comparable electrical performance to that measured for bulk materials.     

Preparation and properties of p-type transparent conductive Cu-doped NiO films

The NiO-Cu composite films with various Cu contents of 0-18.17 at.% are deposited on a glass substrate. An ultra high electrical resistivity (ρ) is obtained and cannot be detected by a four point probe measurement when the Cu content in the films is lower than 6.97 at.%. The ρ value is reduced significantly to 35.8 Ω-cm as Cu content is increased to 9.18 at.%, and it further decreases to 0.02 Ω-cm when the Cu content further increases to 18.17 at.%. The Hall measurement for all Cu-doped NiO films shows p-type conduction. In addition, the transmittance of NiO films also decreases continuously from 96% to 43% as Cu content increases from 0 to 18.17 at.%. The XRD patterns of Cu-doped NiO films show that only NiO peaks appear and the crystallinity of NiO films degrades as Cu content exceeds 6.97 at.%. A large amount of lattice sites of Ni²⁺ ions in a NiO crystallite is replaced by the Cu⁺ ions that lead to p-type conduction and result in the degradation of crystallinity for NiO-Cu composite films that have a higher Cu content.     

Study of PEDOT conductive polymer films by admittance measurements

In this paper we propose the use of a microwave technique to measure the conductivity of poly(3,4-ethylenedioxythiophene) (PEDOT) films. The PEDOT layers were prepared by electropolymerization from aqueous solutions using both poly(sodium 4-styrene sulphonate) (NaPSS) and sodium dodecyl sulphate (NaDS) acting as monomer solubilizer and dopant for the polymer. The conductive properties of a series of samples produced under different synthesis conditions and characterized by different structures have been investigated by microwave measurements in the frequency range from 40 MHz to 40 GHz by using a Corbino disc geometry. Such technique allows to estimate the mean conductivity of the polymer samples overcoming the limitations of the measuring configurations typically imposed by the conventional d.c. measurements. The morphology of PEDOT films and the structure of polymer chains were studied by scanning electron microscopy (SEM) and Raman spectroscopy, respectively. The correlated morphological, structural and microwave analysis enabled us to evidence several factors that affect the macroscopic scale conductivity of the polymer sample films and to identify the conditions for preparation of PEDOT films with functional properties relevant to technological applications.     

High quality transparent conductive ZnO/Ag/ZnO multilayer films deposited at room temperature

We have fabricated, by simultaneous DC and RF magnetron sputtering, multilayer transparent electrodes having much lower electrical resistance than the widely used transparent conductive oxide electrodes. The multilayer structure consists of three layers (ZnO/Ag/ZnO). Ag films with different film thickness were used as metallic layers. Optimum thicknesses of Ag and ZnO films were determined for high optical transmittance and good electrical conductivity. Several analytical tools such as spectrophotometer, atomic force microscopy, scanning electron microscopy and four-point probe were used to explore the possible changes in electrical and optical properties. A high quality transparent electrode, having resistance as low as 3 Ω/sq and high optical transmittance of 90% was obtained at room temperature and could be reproduced by controlling the preparation process parameters. The electrical and optical properties of ZnO/Ag/ZnO multilayers were determined mainly by the Ag film properties. The performance of the multilayers as transparent conducting materials was also compared using a figure of merit.     

Continuous production of flexible carbon nanotube-based transparent conductive films

Abstract

This work shows a simple, single-stage, scalable method for the continuous production of high-quality carbon nanotube-polymer transparent conductive films from carbon feedstock. Besides the ease of scalability, a particular advantage of this process is that the concentration of nanotubes in the films, and thus transparency and conductivity, can be adjusted by changing simple process parameters. Therefore, films can be readily prepared for any application desired, ranging from solar cells to flat panel displays. Our best results show a surface resistivity of the order of 300 Ω square^-1 for a film with 80% transparency, which is promising at this early stage of process development.     

Continuous production of flexible carbon nanotube-based transparent conductive films

This work shows a simple, single-stage, scalable method for the continuous production of high-quality carbon nanotube-polymer transparent conductive films from carbon feedstock. Besides the ease of scalability, a particular advantage of this process is that the concentration of nanotubes in the films, and thus transparency and conductivity, can be adjusted by changing simple process parameters. Therefore, films can be readily prepared for any application desired, ranging from solar cells to flat panel displays. Our best results show a surface resistivity of the order of 300 Ω square^-1 for a film with 80% transparency, which is promising at this early stage of process development.     

Copper doped nickel oxide transparent p-type conductive thin films deposited by pulsed plasma deposition

Transparent p-type conductive Ni_0.9Cu_0.1O thin films were prepared by pulsed plasma deposition (PPD) method. The effects of substrate temperature and oxygen pressure on the structural, electrical and optical properties of the films were investigated respectively. The film deposited at room temperature exhibits the highest conductivity of 5.17 S cm⁻¹, with an average transmittance of 60% in the visible region. A transparent p-Ni_0.9Cu_0.1O/n-In₂O₃:W (IWO) hetero-junction diode was fabricated exhibiting rectifying current-voltage characteristics.     

Dielectric polymer matrix composite films of CNT coated with anatase TiO2

This study presents the fabrication method and the dielectric property of polymer matrix composite films of carbon nanotube (CNT) coated with TiO₂. The TiO₂ was coated with sol-gel method using titanium (IV) butoxide (TNBT), HO₂ and benzyl-alcohol as the surfactant. The configuration of CNT-TiO₂ hybrid was observed with the field emission scanning electron microscope images. The coated TiO₂ was thermally treated and transformed into the anatase structure to enhance the mechanical strength and get the high insulating property. The anatase structure was proved from the diffraction angles of XRD. The CNT-TiO₂ hybrid was mixed with the epoxy resin using 3-roll-mil and casted into the films using film casting method. The structure of CNT-TiO₂ hybrid was ascertained to be maintained against the high shear stress during the mixing and casting processes. The dielectric property of the composite films was measured following IPC-TM-6550. The dielectric property at 1 GHz of the composite film of 5 wt.% CNT is about 10 and the loss tangent at 1 GHz is about 0.06.