Gold Nanoparticle and Gold Nanorod Embedded PEDOT:PSS Thin Films as Organic Thermoelectric Materials

We report the thermoelectric properties of organic–inorganic hybrid thin films composed of conductive polymer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and inorganic gold nanomaterials. Two kinds of material with different shapes, namely rod-shaped gold nanorods (AuNRs) and spherical gold nanoparticles (AuNPs), were used in this study. The PEDOT:PSS/AuNR hybrid films showed an enhancement in electrical conductivity (σ ≈ 2000 S cm^?1) and concurrently a decrease in the Seebeck coefficient (S ≈ 12 μV K^?1) with increase in the AuNR concentration. This behavior indicates the presence of the hybrid effect of AuNR on the thermoelectric properties. From scanning electron microscopy (SEM) observation of the highly concentrated PEDOT:PSS/AuNR hybrid films, the formation of a percolated structure of AuNRs was confirmed, which probably contributed to the large enhancement in σ. For the highly concentrated PEDOT:PSS/AuNP films, a dense distribution of AuNPs in the film was also observed, but this did not lead to a major change in the σ value, probably due to the less conductive connections between NPs. This suggests that one-dimensional particles with larger aspect ratio (rods and wires) are favorable nanocomponents for development of highly conductive hybrid materials.     

Simultaneous Increases in Electrical Conductivity and Seebeck Coefficient of PEDOT:PSS Films by Adding Ionic Liquids into a Polymer Solution

The electrical conductivity and Seebeck coefficient of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films were simultaneously improved by adding an ionic liquid (IL) into a polymer solution of the polymers. The maximum electrical conductivity of such a PEDOT:PSS/IL film reached 174 S cm⁻¹, more than an order of magnitude higher than that of pure PEDOT:PSS film, and the maximum Seebeck coefficient was up to 30 μV K⁻¹, more than twice the value for pure PEDOT:PSS film. This behavior is different from conventional thermoelectric (TE) materials, whose TE properties are strongly correlated, such as increasing electrical conductivity with increasing carrier concentration, usually resulting in a logarithmic decrease in Seebeck coefficient. Atomic force microscopy images of the PEDOT:PSS/IL films indicated that the ILs induced formation of a particular three-dimensional structure of highly conducting PEDOT grains, resulting in improvement of the TE performance of PEDOT:PSS films.     

The Thermoelectric Performance of Poly(3,4-ethylenedi oxythiophene)/Poly(4-styrenesulfonate) Thin Films

The thermoelectric performance of synthetic conductive polymers, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), is explored. The effects of the dielectric solvent, dimethyl sulfoxide (DMSO), and of the ratio of PEDOT to PSS in the polymeric PEDOT/PSS thin films were studied systematically. Within the parameter range studied in this work, the variation of electrical conductivity overwhelmed the variation of the Seebeck coefficient, and the optimal power factor is basically determined by the highest electrical conductivity, because the Seebeck coefficient remains small over a wide range of DMSO concentrations and PEDOT:PSS ratios.     

Surface plasmon spectroscopy of thin composite films of Au nanoparticles and PEDOT:PSS conjugated polymer

We studied the effect of Au nanoparticles (NPs) on optical properties of composite films of poly(3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) mixed with Au NPs of 20, 40 and 60 nm in diameter by surface plasmon resonance (SPR) spectroscopy. The excitation wavelength of SPR redshifts with increasing the concentration of Au NPs in the Au/PEDOT:PSS composite films. The SPR spectra were simulated by using transfer matrix method (TMM) and effective medium approximation (EMA). The SPR wavelength redshift was ascribed to the film thickness increase of Au/PEDOT:PSS composites rather than effective permittivity variation of the composite films induced with Au NPs inclusion.     

Thermoelectric Performance of Poly(3,4-Ethylenedioxy-thiophene)/Poly(Styrenesulfonate) Pellets and Films

The thermoelectric performance of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) pellets and free-standing PEDOT/PSS films, prepared from PEDOT/PSS solution containing the additives dimethyl sulfoxide or ethylene glycol, have been systematically investigated. It has been found that the electrical conductivity of free-standing PEDOT/PSS films is invariably much higher than that of PEDOT/PSS pellets, while there is no distinct change in the Seebeck coefficient. The highest electrical conductivity of a free-standing PEDOT/PSS film can be up to 300 S cm⁻¹, five to six times higher than that of PEDOT/PSS pellets (55 S cm⁻¹). The thermal conductivity was measured over a wide temperature range, indicating that PEDOT/PSS has extremely low thermal conductivity. The figure of merit (ZT) of free-standing PEDOT/PSS films with good environmental stability can be up to 10⁻², an order of magnitude higher than that of pressed PEDOT/PSS pellets (10⁻³).     

Enhanced power factor of poly (3,4-ethyldioxythiophene):poly (styrene sulfonate) (PEDOT:PSS)/RTCVD graphene hybrid films

The thermoelectric generator has been an attractive alternative power source to operate a wireless sensor node. Usually, inorganic compounds are most often used in thermoelectric devices, and hence, are extensively studied due to their superior thermoelectric performance. We have investigated a novel interfacial technique to fabricate a hybrid film of highly conductive PEDOT:PSS (poly 3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) and graphene. Organic materials PEDOT doped with PSS exhibits outstanding electrical properties due to its high conductivity, low bandgap, and energy migration. Furthermore, we utilized graphene fabricated by rapid thermal chemical vapor deposition (RTCVD) as a thermoelectric material. Our results show that the interfacial technique between substrate and hybrid film could be clearly improved due to the UV plasma treatment. The thermoelectric hybrid film of PEDOT:PSS and RTCVD graphene (P/RTG) exhibited an enhanced power factor of 56.28 μW m⁻¹ K⁻² with a Seebeck coefficient of 54.0 μV K⁻¹.     

Organic Semiconductors for Thermoelectric Applications

The thermoelectric performance of thin films fabricated from two commercially available, highly conductive polymer formulations based on poly (3,4-ethylendioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) was investigated. In order to enhance the electrical conductivity, the high-boiling solvent dimethyl sulfoxide (DMSO) was added. By changing the content of DMSO the electrical conductivity was increased by a factor of two without changing the Seebeck coefficient or the thermal conductivity. We achieved ZT = 9.2 × 10⁻³ at room temperature upon the addition of 5 vol.% DMSO to the PEDOT:PSS formulation.     

Highly stretchable organic thermoelectrics with an enhanced power factor due to extended localization length

Wearable electronics, as a new form of ubiquitous technology, require a sustainable self-powering system with an enhanced mechanical durability. In this report, we demonstrate a conducting polymer based stretchable thermoelectric performance with a synergetic effect of an enhanced power factor due to electron delocalization. The fluorosurfactant treatment of poly(3,4-ethylene dioxythiophene):poly(styrenesulphonate) (PEDOT:PSS) films induced a significant dedoping effect with an enhanced Seebeck coefficient and a morphological change into an elongated lamellar structure. Such structural transformation led to a reduced transport dimensionality with strongly extended electron delocalization yielding a simultaneous enhancement of the electron mobility and the Seebeck coefficient, which produced an improved thermoelectric power factor. Most notably, the mechanical durability of the PEDOT:PSS film was greatly improved tolerating up to a 60% static strain and over several hundred cycles of 50% strain. The demonstrated concomitant enhancement of the mechanical stretchability and thermoelectric performance inspires a promising approach for improving shape-adjustable self-powering devices.     

Thermoelectric Performance Enhancement of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) Composite Films by Addition of Dimethyl Sulfoxide and Urea

Significant enhancement of thermoelectric (TE) performance was observed for free-standing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) composite films obtained from a PEDOT:PSS aqueous solution by simultaneous addition of dimethyl sulfoxide (DMSO) and different concentrations of urea. The electrical conductivity was enhanced from 8.16?S?cm^?1 to over 400?S?cm^?1, and the maximum Seebeck coefficient reached a value of 18.81???V?K^?1 at room temperature. The power factor of the PEDOT:PSS composite films reached 8.81???W?m^?1?K^?2. The highest thermoelectric figure of merit (ZT) in this study was 0.024 at room temperature, which is at least one order of magnitude higher than most polymers and bulk Si. These results indicate that the obtained composite films are a promising thermoelectric material for applications in thermoelectric refrigeration and thermoelectric microgeneration.     

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.     

Highly improved thermoelectric performances of PEDOT:PSS/SWCNT composites by solvent treatment

Composites of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) and single-wall carbon nanotube (SWCNT) were prepared by mixing aqueous dispersions of PEDOT:PSS and SWCNT at different weight ratios. By being soaked with DMSO for 2 min at room temperature, the PEDOT:PSS/SWCNT composite with an optimized SWCNT weight ratio of 74 wt% exhibited a high electric conductivity of 3800 S cm⁻¹ and a reasonable Seebeck coefficient of 28 μV K⁻¹, leading to a promising power factor of 300 μW m⁻¹ K⁻² and a hopeful ZT value of 0.13. Possible reasons for the highly improved properties are carefully discussed.     

Explaining the effects of processing on the electrical properties of PEDOT:PSS

By simultaneously measuring the Seebeck coefficient and the conductivity in differently processed PEDOT:PSS films, fundamental understanding is gained on how commonly used processing methods improve the conductivity of PEDOT:PSS. Use of a high boiling solvent (HBS) enhances the conductivity by 3 orders of magnitude, as is well-known. Simultaneously, the Seebeck coefficient S remains largely unaffected, which is shown to imply that the conductivity is improved by enhanced connectivity between PEDOT-rich filaments within the film, rather than by improved conductivity of the separate PEDOT filaments. Post-treatment of PEDOT:PSS films by washing with H₂SO₄ leads to a similarly enhanced conductivity and a significant reduction in the layer thickness. This reduction strikingly corresponds to the initial PSS ratio in the PEDOT:PSS films, which suggests removal and replacement of PSS in PEDOT:PSS by HSO₄⁻ or SO₄²⁻ after washing. Like for the HBS treatment, this improves the connectivity between PEDOT filaments. Depending on whether the H₂SO₄ treatment is or is not preceded by an HBS treatment also the intra-filament transport is affected. We show that by characterization of S and σ it is possible to obtain more fundamental understanding of the effects of processing on the (thermo)electrical characteristics of PEDOT:PSS.     

Plasmonic Au nanoparticles for enhanced broadband light absorption in inverted organic photovoltaic devices by plasma assisted physical vapour deposition

We use a low vacuum plasma assisted physical vapour deposition (PAPVD) method to deposit a Au nanoparticles (NPs) thin film onto the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer in inverted poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methylester (P3HT:PCBM) organic photovoltaic (OPV) devices. The Au NPs that incorporated into the PEDOT:PSS layer and reached to the active P3HT:PCBM layer can provide significant plasmonic broadband light absorption enhancement to the active layer. An approximately 50–90% improvement in short-circuit current density and in power convention efficiency has been achieved compared with those OPV devices without the plasmonic light absorption enhancement. This technique can be adopted and easily fit into most OPV device fabrication processes without changing other layers’ processing methods, morphologies, and properties.     

Improvement of electrical conductivity of PEDOT:PSS films by 2-Methylimidazole post treatment

The electrical conductivity of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films was significantly improved without losing the optical transparency by treating the films with solution of 2-Methylimidazole in ethanol. The maximum electrical conductivity of such a thin film reached 930 S cm⁻¹, more than 1150 order of magnitude higher than that of pure PEDOT:PSS film. The mechanism of conductivity enhancement of treated thin PEDOT:PSS films was explored by atomic force microscopy (AFM) and UV/VIS spectrophotometer. The AFM scans show that the surface of the 2-Methylimidazole treated PEDOT:PSS layer is smoother than that of the pristine PEDOT:PSS thin film. Improvement in the morphology, electrical and optical properties of PEDOT:PSS films makes them highly suitable for numerous applications in optoelectronic devices.     

Conductive PEDOT:PSS on surface-functionalized chitosan biopolymers for stretchable skin-like electronics

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a promising alternative transparent electrode to replace conventional indium tix oxide (ITO) for flexible and stretchable electronics. For their applications in optoelectronic devices, realizing both high conductivity and transmittance for the films is of great necessity as a suitable high performance transparent electrode. Here, we demonstrate simultaneously enhanced electrical and optical properties of PEDOT:PSS films prepared on chitosan bio-substrates by using an organic surface modifier, 11-aminoundecanoic acid (11-AA). The sheet resistance of PEDOT:PSS films decreases from 1120.8 to 292.8 Ω/sq with an increase in a transmittance from 75.9 to 80.4% by 11-AA treatment on the chitosan films. The functional groups of 11-AA effectively enhance the adhesion property at the interface between the chitosan substrate and PEDOT:PSS by forming strong interfacial bondings and decrease insulating PSS from PEDOT:PSS films. The wearable heater devices and on-skin sensors based on the 11-AA-treated PEDOT:PSS on the chitosan bio-substrates are successfully fabricated, showing the excellent thermal and sensing performances. The 11-AA surface-modification approach for highly conductive PEDOT:PSS on chitosan bio-substrates presents a great potential for applications toward transparent, flexible and stretchable electronics.     

Toward Stretchable Self‐Powered Sensors Based on the Thermoelectric Response of PEDOT:PSS/Polyurethane Blends

The development of new flexible and stretchable sensors addresses the demands of upcoming application fields like internet‐of‐things, soft robotics, and health/structure monitoring. However, finding a reliable and robust power source to operate these devices, particularly in off‐the‐grid, maintenance‐free applications, still poses a great challenge. The exploitation of ubiquitous temperature gradients, as the source of energy, can become a practical solution, since the recent discovery of the outstanding thermoelectric properties of a conductive polymer, poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS). Unfortunately the use of PEDOT:PSS is currently constrained by its brittleness and limited processability. Herein, PEDOT:PSS is blended with a commercial elastomeric polyurethane (Lycra), to obtain tough and processable self‐standing films. A remarkable strain‐at‐break of ≈700% is achieved for blends with 90 wt% Lycra, after ethylene glycol treatment, without affecting the Seebeck voltage. For the first time the viability of these novel blends as stretchable self‐powered sensors is demonstrated.     

Thermoelectric Properties and Thermal Stability of PEDOT:PSS Films on a Polyimide Substrate and Application in Flexible Energy Conversion Devices

In this study, we investigated the flexibility and thermal stability of films consisting of a complex of poly(3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS) cast onto a polyimide substrate. We also prepared a PEDOT:PSS-based flexible device for thermoelectric energy conversion. The thermal stability of a PEDOT:PSS film was evaluated by measuring the Seebeck coefficient (S) and electrical conductivity (σ) for 30 heating and cooling cycles at 330 K to 380 K. Furthermore, the durability of the PEDOT:PSS film was examined by heating at 353 K in air for 4000 h. The approximate values of S and σ were 14 μV K^?1 and 600 S cm^?1, respectively. These values were almost the same before and after repeated bending treatments (10,000 times, radius of curvature 10 mm). In addition, the S and σ values for the PEDOT:PSS film were nearly constant during the heating cycle treatments. In the durability test, σ gradually decreased with increasing heating time (7% at 300 h, 17% at 3600 h). Thus, it was found that PEDOT:PSS films have both flexibility and mechanical toughness as well as relatively good thermal stability in air up to 3600 h. The maximum electric power for the PEDOT:PSS-based flexible device was 0.334 μW at ΔT = 100 K. These results for the power-generating properties of the flexible device are consistent with values calculated from the properties of the constituent materials.     

Graphene‐Conducting Polymer Hybrid Transparent Electrodes for Efficient Organic Optoelectronic Devices

To achieve the broad utilization of the full functionality of graphene (GR) in devices, a transfer method should be developed that can simplify the process without leaving residue of the insulating supporting layer on the surface of GR. Furthermore, stable GR doping without the use of an insulating polymer is required. Here, a new GR transfer method that uses a popular conducting polymer, poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), is reported as a new supporting layer for the transfer of GR films that are synthesized by chemical vapor deposition. The GR/PEDOT:PSS bilayer can be directly utilized without the removal process. Therefore, this transfer method simplifies the transfer process and solves the residue problem of conventional transfer methods. The stable doping of GR films is simultaneously achieved by using the PEDOT:PSS layer. The new GR/PEDOT:PSS hybrid electrodes are fully functional in polymer solar cells and polymer light‐emitting diodes, outperforming the conventionally transferred GR electrodes and indium tin oxide electrodes.     

Efficient ITO-free organic light-emitting diodes comprising PEDOT:PSS transparent electrodes optimized with 2-ethoxyethanol and post treatment

We demonstrate highly conductive poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) films introduced with a newly investigated solvent 2-ethoxyethanol. The films are optimized by simple solvent post treatment and show enhanced conductivities and reduced sheet resistances. Solvent post treatment for 2-ethoxyethanol added PEDOT:PSS films reduces insulating PSS and forms conductive PEDOT networks in conductive films, resulting in improved electrical properties. ITO-free white OLEDs are fabricated with post-treated PEDOT:PSS electrodes and show almost equal performance to ITO-based OLEDs. Our work demonstrate that the conductive PEDOT:PSS electrode optimized by 2-ethoxyethanol and post treatment promises its potential as alternative transparent electrode in flexible, low-cost, high-performance ITO-free OLEDs.