Conductivity enhancement of conjugated polymer after HCl-methanol treatment

Polymer conductivity is key factor to improve the performance of the electronic and photonic devices. Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) films were soaked into 0.03, 0.14, 0.41, and 1.13 M concentrations of HCl-methanol solution for 10, 20, 30, 40, 50, 60, and 70 min. The resulting films were investigated using Fourier transform infrared (FTIR) spectrometry, conductivity measurements, and field emission scanning electron microscopy. The characteristic FTIR absorption peaks of poly(4-styrenesulfonate) (PSS) of the films decreased as the soaking time increased. While PSS absorption peaks appeared in the HCl-methanol soaking solution and increased with the soaking time. The conductivity of PEDOT:PSS film was approximately 1.20 × 10^− 6 S/cm before soaking in the HCl-methanol solution. The conductivity of PEDOT:PSS was enhanced nearly three orders of magnitude after soaking the films into the HCl-methanol solvent. The surface of PEDOT:PSS film was initially very smooth. However, numerous humps appeared on the surface of the films after soaking PEDOT:PSS film into the HCl-methanol solution for 10, 20, and 30 min. The number of humps was reduced and disappeared thereafter.     

Vacuum vapour phase polymerised poly(3,4-ethyelendioxythiophene) thin films for use in large-scale electrochromic devices

Large-scale electrochromic devices were manufactured using vacuum vapour phase polymerised (VPP) poly(3,4-ethylenedioxythiophene) (PEDOT). Homogeneous 3,4-ethylenedioxythiophene (EDOT) and water vapour distribution within the large 115 L VPP chamber is paramount for the reproducible synthesis of high conductivity PEDOT thin films. Obtaining these conditions, however, was not trivial. The issue was resolved by synthesising PEDOT under vacuum, however, this altered the dynamics of the polymerisation process. As a result, surfactant addition, monomer and water vapour distribution, monomer and chamber temperature, and polymerisation times were all systematically investigated. Controlling these parameters has resulted in PEDOT with conductivity exceeding 1100 S · cm⁻¹, with a best of 1485 S · cm⁻¹, and electrochromic devices with an optical switch of Δ%Tx ≥ 50%. The resulting high conductivity and optical range are due to long undisrupted PEDOT polymer chains coupled with low levels of oligomers within the matrix.     

Fabrication of conducting poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) thin films by ultrasonic spray-assisted mist deposition method

Transparent conducting polymer, poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) thin films were fabricated by a vapor-deposition technique, ultrasonic spray-assisted mist deposition method. The thickness was well controlled from 40 to 600 nm, keeping reasonable conductivity of 300-450 S/cm. The films with thickness less than 180 nm have high (> 80%) transmission over a wide (270-800 nm) spectral region. In addition, formation of ring-dot electrode pattern with a hard-mask was demonstrated, achieving lithography-less patterning. The results encourage that this deposition method is developed as an actual process technology of transparent electrodes in devices.     

Enhancement of poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonate) properties by poly(vinyl alcohol) and doping agent as conductive nano-thin film for electronic application

In this work, the integration of the useful concepts of polymer blending and doping agent to simultaneously improve various properties of poly(3,4-ethylene dioxy thiophene) poly(styrene sulfonate) (PEDOT:PSS) nano-thin films was shown. According to the polymer-blending concept, insulating poly(vinyl alcohol) (PVA) has a good deal of potential to be utilized as a filler to improve the critical properties of the PEDOT:PSS matrix, especially conductivity, wettability, and thermal and mechanical properties. At the appropriate amount of PVA, 0.08 wt%, it acts as a binder to improve the connection network between PEDOT:PSS chains, leading to a maximum conductivity of 1.18 S/cm, and also providing a good contact angle of 8.8°. The transmission of the films decreased with increasing PVA content; however, all specimens still showed excellent transmittance values of more than 80 %. The thermal stability and the resistance to abrasion of the nano-thin conductive films were improved by strong covalent bonds between PVA and PSS, which were verified by TGA and a scratching test, respectively. In addition, the relationship of PEDOT:PSS properties versus various amounts of insulating PVA for practical usage for specific electronic fields were shown. Use of the doping agent quinoxaline was aimed to particularly enhance the conductivity of PEDOT:PSS. The highest conductivity (2.75 S/cm) was achieved when 0.5 wt% quinoxaline was added into 0.08 wt% PVA/PEDOT:PSS while the other properties were not significantly altered.     

Conductive polymer PEDOT:PSS back contact for CdTe solar cell

Two types of superstrate glass/ITO/CdS/CdTe PV structures were prepared by high vacuum evaporation technique with (i) activation of CdS layer and CdS/CdTe bi-layer structure step-by-step and (ii) activation of CdS/CdTe bi-layer structure. The activation was performed by annealing the structures with CdCl₂ in air at 400 °C for 15 min. Main conditions for CdS and CdTe thin films deposition and following treatment were selected from the literature data with the purpose to prepare and compare complete CdTe solar cells with standard p + Cu_xTe back contact and conductive polymer poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid (PEDOT:PSS) back contact. Obtained layers and structures were characterized using the XRD, SEM and I-V methods. Both the methods of activation treatment give comparable results from the point of view PV properties of complete solar cells. It was found that highly conductive PEDOT:PSS intermediate layer can significantly improve the back contact characteristics of CdTe. However these hybrid structures need to be further optimized to compete successfully with conventional inorganic back contacts in complete CdTe solar cells.     

Enhanced conductivity in iodine doped polyaniline thin film formed by thermal evaporation

Thermal evaporation technique was employed to deposit pristine and iodine doped polyaniline (PANI) thin films on glass substrates. PANI was synthesized by the chemical oxidation method. Iodine doping was carried out by evaporation. The polymer synthesized was characterized by Thermo Gravimetric Analysis (TGA), Fourier Transform Infra Red (FTIR) and Ultraviolet-Visible (UV-VIS) spectroscopy. The evaporation temperature was optimized from TGA measurements. The thin film was deposited in vacuum at 1.33 × 10^− 4 Pa by thermal evaporation of PANI. The polymer film was characterized by FTIR and UV-VIS spectroscopy. The surface morphology of the films was studied by field emission scanning electron microscopy. The resistivity was measured by van der Pauw technique. The conductivity of the doped films was seen to increase with the iodine concentration and many fold increase in conductivity was observed in comparison to the pristine films. The increase in conductivity is due to the generation of polaron band in the band gap upon iodine doping.     

Fabrication of flexible conductive films derived from poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) (PEDOT:PSS) on the nonwoven fabrics substrate

In this research, conducting poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) (PEDOT:PSS) aqueous dispersion was synthesized at first via chemical oxidative polymerization and followed by mixing it with poly(styrene-r-butyl acrylate) P(St-BA) aqueous latex, creating a conductive material with outstanding stretchability. The elastic conductive composite were then film formed on the glass and poly(ethylene terephthalate) (PET) nonwoven fabric substrate by spin coating and dip coating, respectively. Composite films with various contents of PEDOT:PSS polymer (10–100 wt.%) had been prepared. From the conductivity measurements, the conductivity was still kept as high as 88 S cm⁻¹ even the PEDOT:PSS content was lowered to 10 wt.%. Furthermore, the elasticity of conductive films on the PET-nonwoven fabric substrate was evaluated by the 180° bending test repeating 100 times. With introducing soft P(St-BA) material in the PEDOT:PSS phase, the surface resistance increased merely 3–6 times after bending 100 times, while the surface resistance for pure PEDOT:PSS film could reach 18–20 times.     

Properties of PEDOT:PEG/ZnO/p-Si heterojunction diode

The zinc oxide (ZnO) and poly(3,4-ethylenedioxythiophene) bis-poly(ethyleneglycol) (PEDOT:PEG) films were deposited on p-Si substrate by sputter and spin coating methods, respectively. An organic/inorganic heterojunction diode having PEDOT:PEG/ZnO on p-Si substrate was fabricated. The barrier height (BH) and the ideality factor values for the device were found to be 0.82 ± 0.01 eV and 1.9 ± 0.01, respectively. It has been seen that the value of BH is significantly larger than those of conventional Au/p-Si metal–semiconductor contacts. The PEDOT:PEG/ZnO/p-Si heterostructure exhibits a non-ideal I–V behavior with the ideality factor greater than unity that could be ascribed to the interfacial layer, interface states and series resistance. The modified Norde's function combined with conventional forward I–V method was used to extract the parameters including the barrier height and series resistance. At the same time, the physical properties of ZnO and PEDOT:PEG films deposited by sputter and spin coating technique, respectively, were investigated at room temperature. The obtained results indicate that the electrical parameters of the diode are affected by structural properties of ZnO film and PEDOT:PEG organic film.     

Polymeric anodes from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) for 3.5% efficient organic solar cells

We present highly efficient indium tin oxide free polymer solar cells based on poly-(3-hexylthiophene-2,5-diyl) and C₆₁-bis-butric-acid-methyl-ester (P3HT:bisPCBM) comprising a polymeric anode from highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) formulations. The film conductivity was optimized by various additives. We found conductivities of almost 600 S/cm upon the addition of dimethylsulfoxide. The wetting properties of different PEDOT:PSS formulations were investigated by contact angle measurements. The optimized high conductivity in combination with the good film forming properties allow for the fabrication of highly efficient organic solar cells with an external power conversion efficiency of 3.5% with PEDOT:PSS as polymeric anode.     

Significant vertical phase separation in solvent-vapor-annealed poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) composite films leading to better conductivity and work function for high-performance indium tin oxide-free optoelectronics

In the present study, a novel polar-solvent vapor annealing (PSVA) was used to induce a significant structural rearrangement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films in order to improve their electrical conductivity and work function. The effects of polar-solvent vapor annealing on PEDOT:PSS were systematically compared with those of a conventional solvent additive method (SAM) and investigated in detail by analyzing the changes in conductivity, morphology, top and bottom surface composition, conformational PEDOT chains, and work function. The results confirmed that PSVA induces significant phase separation between excess PSS and PEDOT chains and a spontaneous formation of a highly enriched PSS layer on the top surface of the PEDOT:PSS polymer blend, which in turn leads to better 3-dimensional connections between the conducting PEDOT chains and higher work function. The resultant PSVA-treated PEDOT:PSS anode films exhibited a significantly enhanced conductivity of up to 1057 S cm(-1) and a tunable high work function of up to 5.35 eV. The PSVA-treated PEDOT:PSS films were employed as transparent anodes in polymer light-emitting diodes (PLEDs) and polymer solar cells (PSCs). The cell performances of organic optoelectronic devices with the PSVA-treated PEDOT:PSS anodes were further improved due to the significant vertical phase separation and the self-organized PSS top surface in PSVA-treated PEDOT:PSS films, which can increase the anode conductivity and work function and allow the direct formation of a functional buffer layer between the active layer and the polymeric electrode. The results of the present study will allow better use and understanding of polymeric-blend materials and will further advance the realization of high-performance indium tin oxide (ITO)-free organic electronics.     

Electrical and physicochemical properties of Poly(3,4-ethylenedioxythiophene)-based organic-inorganic hybrid conductive thin films

Conductive polymer coating precursors were prepared using poly (3, 4-ehtylenedioxythiophene) (PEDOT) and three kinds of silane precursors (Q type, T type, and bridged T type) through an in-situ organic/inorganic hybrid sol-gel process. The spin-coated precursor films on Poly(ethyleneterephthalate) substrate exhibited fairly good surface resistance (~ 10⁴ Ω/□), transparency (~ 80%) and pencil hardness (2 - 4 H). The solvent resistance of the film using 2, 5-bis (triethoxysilyl)-3, 4-ethylenedioxythiophene (BTES-EDOT) was excellent as compared with the films that used silane precursors due to a high degree of BTES-EDOT crosslinking in the hybrid film. Moreover, EDOT moiety in the BTES-EDOT molecule may contribute to homogeneous dispersion of the PEDOT in the organic-inorganic hybrid film.     

The thermoelectric performance of carbon black/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) composite films

Carbon black/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (CB/PEDOT:PSS) composite films have been prepared by a spin-coating method. The morphology of the composite films was investigated by field emission scanning electron microscopy and atomic force microscopy. The thermoelectric properties of CB/PEDOT:PSS composite films were measured at room temperature. As the content of CB increased from 0 to 11.16 wt%, the electrical conductivity of the composite films first increased sharply and then decreased, while the Seebeck coefficient increased slowly. A highest power factor of 0.96 μWm^?1 K^?2 was obtained.     

Morphological characterization and analytical application of poly(3,4-ethylenedioxythiophene)-Prussian blue composite films electrodeposited in situ on platinum electrode chips

Electrochemical in situ preparation and morphological characterization of inorganic redox material-organic conducting polymer coatings as thin films on platinum electrodes are presented. Composite inorganic-organic coatings consist of Prussian blue (PB) and [poly(3,4-ethylenedioxythiophene)] (PEDOT), and PEDOT organic polymers doped with ferricyanide (PEDOT-FeCN). The PEDOT coating deposited from an aqueous solution containing the 3,4-ethylenedioxythiophene monomer and LiClO₄ as supporting electrolyte was used as a “reference” material (PEDOT-ClO₄). The composite coatings were prepared by electrochemical methods on platinum electrode chips, which consist of a 150 nm Pt layer deposited on 100-oriented standard 3″ silicon wafers. Electrochemical behavior of the composite inorganic-organic coatings is based mainly on inorganic component redox reactions. Different surface properties of the composite materials were studied. Thus, the roughness of the deposited films was measured by both atomic force microscopy (AFM) and profilometry, leading to roughness values ranging from 3 nm to 217 nm for PEDOT-ClO₄, and PEDOT-FeCN and PEDOT-PB coatings, respectively. AFM and Scanning Electron Microscopy pictures were also produced to characterize the film morphologies, and revealed a granular pattern of the deposited inorganic component inside the organic polymer matrix. Moreover, the adhesion properties of the composites were studied by AFM and proved to be very different from one material to the other depending on the film structure. The electrochemical responses of these composite coatings to H₂O₂ reduction were also investigated using chronoamperometry. A linear response over a concentration range from 1 × 10^− 4 to 1 × 10^− 5 M and a detection limit of 10 μM were obtained.     

Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (3,4-ethylenedioxythiophene)-few walled carbon nanotube (PEDOT-FWCNT) nanocomposite based thin films for Schottky diode application

Transparent, conductive films of poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (3,4-ethylenedioxythiophene)-few walled carbon nanotube (PEDOT-FWCNT) nanocomposite were synthesized by in-situ oxidative polymerization and investigated for their Schottky diode property. The prepared films were characterized by UV–Vis spectroscopy, thermal gravimetric analysis (TGA), surface resistivity, cyclic voltametery, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). SEM reveals the formation of homogeneous and adhesive polymer films while HRTEM confirms the uniform wrapping of polymer chains around the nanotube walls for PEDOT-FWCNT film. Improved thermal stability, conductivity and charge storage property of PEDOT in the presence of FWCNT is observed. Among different compositions, 5 wt. % of FWCNT is found to be optimum with sheet resistance and transmittance of 500 Ω sq⁻¹ and 77%, respectively. Moreover, the electronic and junction properties of polymer films were studied and compared by fabricating sandwich type devices with a configuration of Al/PEDOT or PEDOT-FWCNT nanocomposite/indium tin oxide (ITO) coated glass. The measured current density-voltage characteristics show typical rectifying behavior for both configurations. However, enhanced rectification ratio and higher forward current density is observed in case of PEDOT-FWCNT based Schottky diode. Furthermore, reliability test depicts smaller hysteresis effect and better performance of PEDOT-FWCNT based diodes.     

Thermal characterization of screen printed conductive pastes for RFID antennas

Thermal resistance is an essential aspect of electronic circuits designing. It leads to unexpected changes in electronic components during their work. In this study, new materials for screen printed RFID tag's antennas were characterized in terms of their resistance to thermal exposure. Polymer materials containing silver flakes, silver nanopowder, carbon nanotubes or conductive polymer PEDOT:PSS were elaborated and used for antenna printing on flexible materials. In order to verify their long term susceptibility to damages caused by the changing environmental conditions, the temperature cycling test was used in three different temperature ranges: +65 °C, −12 °C, −40 °C/+85 °C (3 h in each temp., dwell time 1 h). The highest durability to thermal exposure exhibited the paste with carbon nanotubes dispersed in poly(methyl methacrylate) PMMA and the lowest one – the paste with conductive polymer PEDOT:PSS.     

On the mechanism of conductivity enhancement in plasma treated poly(3,4-ethylenedioxythiophene) films

The conductive poly(3,4-ethylenedioxythiophene): p-toluene sulfonate (PEDOT : PTS) films were prepared by gas-phase polymerization using CVD technique. PEDOT : PTS films with better electrical performance were produced by the additional doping with O₂ plasma after vapor phase polymerization. The mechanism for this conductivity enhancement is studied through surface structural analyses using Raman and X-ray photoelectron spectroscopy (XPS). The increase in conductivity is likely to be due to the generation of new functional groups such as carboxyl and hydroxyl groups that are acted as a dopant and the removal of the impurities on PEDOT: PTS surface with plasma treatment.     

溴掺杂对PEDOT/PSS薄膜性能的影响及机理研究

为改善聚乙撑二氧噻吩∶聚（对苯乙烯磺酸）根阴离子（PEDOT/PSS）薄膜的光学及电学性能,采用共混-旋涂法在石英玻片上制备出溴掺杂的PEDOT/PSS透明导电膜,并就其掺杂导电机理进行了探讨.结果表明：经微量溴掺杂后的PEDOT/PSS薄膜,其透光性能与导电性能均得到提高;质量分数6%溴掺杂条件下,薄膜透光率为95....     

Morphology and growing of nanometric multilayered films formed by alternated layers of poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole)

Multilayered nanometric films formed by alternated layers of conducting poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole) doped with perchlorate anions (ml-PEDOT/PNMPy) have been prepared using a layer-by-layer electrodeposition technique combined with a very small polymerization time. The mechanisms of formation and growth of the resulting multilayered systems have been investigated using Atomic Force Microscopy (AFM), and compared with those obtained for the corresponding homopolymers, which were prepared using identical experimental conditions. Furthermore, the local conductivity, electroactivity and electrostability have been also examined. Analyses of the morphology, topography and roughness of the surfaces indicate that the formation and growth of the multilayered films strongly depend on the number of layers as well as on the chemical nature of the conducting polymer. Interestingly, AFM reflects that the formation and growth of the ml-PEDOT/PNMPy films are significantly different from those of PEDOT and PNMPy homopolymers. The electrical and electrochemical properties of the systems under study are fully consistent with the proposed mechanisms. Results evidenced that multilayered systems formed by two conducting polymers are more advantageous from a technological point of view than the corresponding copolymers.     

Conductivity enhancement of PEDOT:PSS thin film using roll to plate technique and its characterization as a Schottky diode

The conductivity of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) was improved by pressing the PEDOT:PSS thin film using roll to plate system. PEDOT:PSS thin film was deposited on polyethylene terephthalate using electrohydrodynamics atomization technique. The physico-chemical properties of the pressed thin film at different loads were compared with an un-pressed sample. The electrical properties show that the film conductivity has been increased by four times. An optimized pressing load was found to have good conductivity and transmittance of the thin film. A hybrid device (PEDOT:PSS/F8BT/ZnO/Ag) was fabricated using layer by layer method with PEDOT:PSS as anode. The I–V characterization showed that the device with pressed PEDOT:PSS showed higher current densities. The results give a promising future of PEDOT:PSS in electronics device applications using printed electronics techniques.     

Hydrogen storing and electrical properties of hyperbranched polymers-based nanoporous materials

Hydrogen storage and electrical properties of different hyperbranched polymer systems beside a nanocomposite are studied. The polymers examined are aliphatic hyperbranched poly urea (P-Urea), polyamide amine (PAMAM) and polyamide amine/vanadium oxide (PAMAM/VO_x) nanocomposite. At 80 K and up to 20 bar hydrogen pressure, the hydrogen storage capacity of hyperbranched P-Urea reached 1.6 wt%, 0.9 wt% in case of PAMAM and 0.6 wt% for VO_x. The hydrogen storage capacity significantly enhanced when PAMAM and VO_x form a nanocomposite and increased up to 2 wt%. At 298 K and up to 20 bar, all the samples did not show measurable hydrogen uptake. Electrical properties of the samples are also investigated; the measurements showed complete insulating behavior at hydrogenation measuring temperature. These investigations ensure that the polymer conductivity does not play a role in hydrogen uptake, also hyperbranched polymers are promising materials for hydrogen storage.