Ultrafast-laser-treated poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) electrodes with enhanced conductivity and transparency for semitransparent perovskite solar cells

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is an important organic electrode for solution-processed low-cost electronic devices. However, it requires doping and post-solvent treatment to improve its conductivity, and the chemicals used for such treatments may affect the device fabrication process. In this study, we developed a novel route for exploiting ultrafast lasers (femtosecond and picosecond laser) to simultaneously enhance the conductivity and transparency of PEDOT:PSS films and fabricate patterned solution-processed electrodes for electronic devices. The conductivity of the PEDOT:PSS film was improved by three orders of magnitude (from 3.1 to 1024 S·cm^–1), and high transparency of up to 88.5% (average visible transmittance, AVT) was achieved. Raman and depth-profiling X-ray photoelectron spectroscopy revealed that the oxidation level of PEDOT was enhanced, thereby increasing the carrier concentration. The surface PSS content also decreased, which is beneficial to the carrier mobility, resulting in significantly enhanced electrical conductivity. Further, we fabricated semitransparent perovskite solar cells using the as-made PEDOT:PSS as the transparent top electrodes, and a power conversion efficiency of 7.39% was achieved with 22.63% AVT. Thus, the proposed route for synthesizing conductive and transparent electrodes is promising for vacuum and doping-free electronics.     

Highly Customizable All Solution–Processed Polymer Light Emitting Diodes with Inkjet Printed Ag and Transfer Printed Conductive Polymer Electrodes

Inkjet and transfer printing processes are combined to easily form patterned poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films as top anodes of all solution–processed inverted polymer light emitting diodes (PLEDs) on rigid glass and flexible plastic substrates. An adhesive PEDOT:PSS ink is formulated and fully customizable patterns are obtained using the inkjet printing process. In order to transfer the patterned PEDOT:PSS films, adhesion properties at interfaces during multistep transfer printing processes are carefully adjusted. The transferred PEDOT:PSS film on the plastic substrates shows not only a sheet resistance of 260.6 Ω/□ and a transmittance of 92.1% at 550 nm wavelength but also excellent mechanical flexibility. The PLEDs with spin‐coated functional layers sandwiched between the transferred PEDOT:PSS top anodes and inkjet‐printed Ag bottom cathodes are fabricated. The fabricated PLEDs on the plastic substrates show a high current efficiency of 10.4 cd A^?1 and high mechanical stability. It is noted that because both Ag and PEDOT:PSS electrodes can be patterned with a high degree of freedom via the inkjet printing process, highly customizable PLEDs with various pattern sizes and shapes are demonstrated on the glass and plastic substrates. Finally, with all solution process, a 5 × 7 passive matrix PLED array is demonstrated.     

喷墨印刷沉积的PEDOT/PSS薄膜导电性能

利用压电喷墨印刷技术沉积了PEDOT/PSS有机导电薄膜,研究了退火温度和乙二醇掺杂对薄膜导电性能的影响。实验结果表明:未退火和退火温度为120,140,160℃时,薄膜表面平均粗糙度分别为8.15,4.10,3.36,2.66nm;乙二醇掺杂使导电激活能由未掺杂时的0.096eV减小为0.046eV;电导激活能减小表明PEDOT分子链从低电导率的卷曲构象向高电导率的伸展构象转变;此外,乙二醇掺杂促使PSS与PE-DOT/PSS分离,使团聚的PEDOT/PSS颗粒变小从而分散更均匀,降低了表面粗糙度。     

Semiconducting single-walled carbon nanotubes as interfacial modification layers for organic-Si solar cells

A semiconducting single-walled carbon nanotubes (s-SWCNTs) interlayer between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and n-Si was used for high performance organic-Si hybrid photovoltaic (PV) devices. The s-SWCNTs films with different thickness were utilized to investigate the PV effect on PEDOT:PSS/Si device performance. The surface potential of Si substrate with s-SWCNTs was dramatically reduced, which increased the compatibility between Si and PEDOT:PSS. In addition, s-SWCNTs with good semiconducting properties, guaranteed the charge transfer between Si and PEDOT:PSS. Therein, the electrical contact was dramatically improved with addition of s-SWCNTs interlayer, which led to increased fill factor. A power conversion efficiency (PCE) of 12.14% was achieved with an optimized thickness of s-SWCNTs layer. The s-SWCNTs interface layer was fabricated by a simple solution processed method, which was easily coupled with organic-Si solar cells to enhance the PCE.     

Organic nonpolar nonvolatile resistive switching in poly(3,4-ethylene-dioxythiophene): Polystyrenesulfonate thin film

In this paper, the reproducible nonpolar resistive switching is demonstrated in devices with the sandwiched structure of Au/poly(3,4-ethylene-dioxythiophene): polystyrenesulfonate/Au for nonvolatile memory application. The switching between high resistance state (OFF-state) and low resistance state (ON-state) does not depend on the polarity of the applied voltage bias, which is different from both the WORM characteristics and the bipolar switching characteristics reported before. The resistive ratio between the ON- and OFF-state is on the order of 10³ and increases with the device area decreasing. Both the ON- and OFF-state of the memory devices are stable, showing no significant degradation over 10⁴ s under continuous readout testing. It is proposed that the reduction and oxidation of PEDOT: PSS film might be the switching mechanism.     

Preparation and optical characterization of photosensitive multilayered structures based on polythiophenes and tetracyanoquinodimethane

Organic double layers obtained by electrodeposition of a substituted polythiophene followed by spin-coating of a Tetracyanoquinodimethane (TCNQ) electron acceptor layer, are characterized by means of spectrophotometric measurements carried out in the UV-VIS-IR range. According to the optical data, the electron acceptor molecules reduce to the singly ionized state as a consequence of a charge-transfer reaction that takes place at the interface with the electrodeposited polymer, which acts as an electron donor. Rectifying heterojunctions are obtained by depositing the double layers on the top of monocrystalline silicon wafers, and on the top of monocrystalline silicon wafers coated with electrochemically de-doped poly(3,4-ethylendioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS). Current versus voltage measurements performed in the dark and under halogen light irradiation show that the developed heterojunctions exhibit photosensitive charge transport features, promising in view of photovoltaic applications.     

“Secondary doping” methods to significantly enhance the conductivity of PEDOT:PSS for its application as transparent electrode of optoelectronic devices

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is the most successful conducting polymer in terms of the practical application. It can be dispersed in water and some polar organic solvents, and high-quality PEDOT:PSS films can be readily prepared through solution processing. In addition, PEDOT:PSS is highly transparent in the visible range and has excellent thermal stability. Nevertheless, PEDOT:PSS has a problem of low conductivity. The as-prepared PEDOT:PSS films from its aqueous solution have a conductivity of lower than 1 S cm⁻¹, which severely impedes the application of PEDOT:PSS in various aspects. It has been discovered that the conductivity of as-prepared PEDOT:PSS from its aqueous solution can be significantly enhanced by adding organic compounds like high-boiling point polar organic solvents, ionic liquids and surfactants or through a post-treatment of PEDOT:PSS films with organic compounds, including high-boiling point polar solvents, salts, zwitterions, cosolvents, organic and inorganic acids. Conductivity of more than 3000 S cm⁻¹ was recently observed on PEDOT:PSS films after treated with sulfuric acid. This conductivity is comparable to that of indium tin oxide (ITO), the conventional transparent electrode material of optoelectronic devices. In addition, PEDOT:PSS has high mechanical flexibility while ITO is a brittle material. Thus, PEDOT:PSS is very promising to be the next-generation transparent electrode material. This article reviews the methods to enhance the conductivity of PEDOT:PSS, the mechanisms for the conductivity enhancements and the application of the highly conductive PEDOT:PSS films in polymer light-emitting diodes and polymer solar cells.     

High‐Conductivity Poly(3,4‐ethylenedioxythiophene):Poly(styrene sulfonate) Film and Its Application in Polymer Optoelectronic Devices

The conductivity of a poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film can be enhanced by more than two orders of magnitude by adding a compound with two or more polar groups, such as ethylene glycol, meso‐erythritol (1,2,3,4‐tetrahydroxybutane), or 2‐nitroenthanol, to an aqueous solution of PEDOT:PSS. The mechanism for this conductivity enhancement is studied, and a new mechanism proposed. Raman spectroscopy indicates an effect of the liquid additive on the chemical structure of the PEDOT chains, which suggests a conformational change of PEDOT chains in the film. Both coil and linear conformations or an expanded‐coil conformation of the PEDOT chains may be present in the untreated PEDOT:PSS film, and the linear or expanded‐coil conformations may become dominant in the treated PEDOT:PSS film. This conformational change results in the enhancement of charge‐carrier mobility in the film and leads to an enhanced conductivity. The high‐conductivity PEDOT:PSS film is ideal as an electrode for polymer optoelectronic devices. Polymer light‐emitting diodes and photovoltaic cells fabricated using such high‐conductivity PEDOT:PSS films as the anode exhibit a high performance, close to that obtained using indium tin oxide as the anode.     

PEDOT: Cathode active material with high specific capacity in novel electrolyte system

Poly(3,4-ethylenedioxythiophene) (PEDOT) was chemically synthesized and characterized by FT-IR, XRD, XPS, TGA and organic elemental analysis (EA). The polymer was tested as cathode active material for rechargeable lithium batteries. The cyclic voltammetry (CV) and charge–discharge tests of PEDOT as the cathode active material was investigated in an electrolyte system of LiN(CF₃SO₂)₂/1,2-dimethoxyethane/1,3-dioxopentane (1:2 by weight). The peak discharge capacity of up to 691 mAh/g was obtained during the 1st cycle, and remained above 330 mAh/g after 44 cycles. These results indicate that PEDOT can afford a high specific capacity as a cathode active material. A redox mechanism is tentatively proposed.     

Electroconductive paper prepared by coating with blends of poly(3,4‐ethylenedioxythiophene)/poly(4‐styrenesulfonate) and organic solvents

Electroconductive papers were produced by coating commercial base papers with blends of poly(3,4‐ethylenedioxythiophene)/poly(4‐styrenesulfonate) (PEDOT:PSS) and organic solvents. The bulk conductivities of the coated papers were measured using a four‐probe technique. One‐sided and two‐sided coating gave comparable conductivity levels. The presence of sorbitol and isopropanol in the PEDOT:PSS blends did not enhance the bulk conductivity of the coated paper, and with increasing concentrations of these solvents, the conductivity decreased due to dilution of the conducting component. Samples coated with PEDOT:PSS blends containing N‐methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO) exhibited a higher conductivity than those coated with pure PEDOT:PSS because of their plasticizing effect and conformational changes of PEDOT molecules indicated by the red shift and disappearance of the shoulder peak at about 1442 cm^?1 in the Raman spectra of the coated samples. EDS imaging showed that PEDOT:PSS is distributed throughout the thickness direction of the paper. Contact angle measurements were made to monitor the hydrophilicity of the paper surface and total sulfur analysis was used to determine the amount of PEDOT:PSS deposited onto the paper. The tensile strength of all the paper samples increased slightly after treatment. Thus, it is demonstrated that enhanced bulk conductivity in the order of 10^?3 S/cm can be achieved by using organic conductive materials and surface treatment techniques. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010