Enhancing the Thermoelectric Properties of Conjugated Polymers by Suppressing Dopant-Induced Disorder.

Doping is a crucial strategy to enhance the performance of various organic electronic devices. However, in many cases, the random distribution of dopants in conjugated polymers leads to the disruption of the polymer microstructure, severely constraining the achievable performance of electronic devices. Here, it is shown that by ion-exchange doping polythiophene-based P[(3HT)1-x-stat-(T)x] (x = 0 (P1), 0.12 (P2), 0.24 (P3), and 0.36 (P4)), remarkably high electrical conductivity of >400 S cm-1 and power factor of >16 µW m-1 K-2 are achieved for the random copolymer P3, ranking it among highest ever reported for unaligned P3HT-based films, significantly higher than that of P1 (<40 S cm-1, <4 µW m-1 K-2). Although both polymers exhibit comparable field-effect transistor hole mobilities of ≈0.1 cm2 V-1 s-1 in the pristine state, after doping, Hall effect measurements indicate that P3 exhibits a large Hall mobility up to 1.2 cm2 V-1 s-1, significantly outperforming that of P1 (0.06 cm2 V-1 s-1). GIWAXS measurement determines that the in-plane π-π stacking distance of doped P3 is 3.44 Å, distinctly shorter than that of doped P1 (3.68 Å). These findings contribute to resolving the long-standing dopant-induced-disorder issues in P3HT and serve as an example for achieving fast charge transport in highly doped polymers for efficient electronics.

Enhancing the Conductivity and Thermoelectric Performance of Semicrystalline Conducting Polymers through Controlled Tie Chain Incorporation.

Conjugated polymers are promising materials for thermoelectric applications, however, at present few effective and well-understood strategies exist to further advance their thermoelectric performance. Here a new model system is reported for a better understanding of the key factors governing their thermoelectric properties: aligned, ribbon-phase poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) doped by ion-exchange doping. Using a range of microstructural and spectroscopic methods, the effect of controlled incorporation of tie-chains between the crystalline domains is studied through blending of high and low molecular weight chains. The tie chains provide efficient transport pathways between crystalline domains and lead to significantly enhanced electrical conductivity of 4810 S cm-1, which is not accompanied by a reduction in Seebeck coefficient or a large increase in thermal conductivity. Respectable power factors of 173 µW m-1 K-2 are demonstrated in this model system. The approach is generally applicable to a wide range of semicrystalline conjugated polymers and could provide an effective pathway for further enhancing their thermoelectric properties and overcome traditional trade-offs in optimization of thermoelectric performance.

Multitype Electronic Interactions in Precursor Solutions of Molecular Doped P3HT Polymer.

Spin-casting of molecularly doped polymer solution mixtures is one of the commonly used methods to obtain conductive organic semiconductor films. In spin-casted films, electronic interaction between the dopant and polymer is one of the crucial factors that dictates the doping efficiency. Here, we investigate excitonic couplings using ultrafast two-dimensional electronic spectroscopy to examine the different types of electronic interactions in ion pairs of the prototype F4TCNQ-doped P3HT polymer system in a precursor solution mixture for spin-casting. Off-diagonal peaks in the 2D spectra clearly establish the excitonic coupling between P3HT+ and F4TCNQ- ions in solution. The observed excitonic coupling is the direct manifestation of a Coulombic interaction between the ion pair. The excited-state lifetime of F4TCNQ- in ion pairs shows biexponential decay at 30 and 200 fs, which hints toward the presence of a heterogeneous population with different interaction strengths. To examine the nature of these different types of interactions in solution mixtures, we study the system using molecular dynamics simulations on a fully solvated model employing the generalized Amber force field. We retrieve three dominant interaction modes of F4TCNQ anions with P3HT: side chain, π-stack, and slipped stack. To quantify these interactions, we complement our studies with electronic structure calculations, which reveal the excitonic coupling strengths of ∼ 75 cm-1 for side chain, ∼ 150 cm-1 for π-π-stack, and ∼69 cm-1 for slipped stack. These various interaction modes provide information about the key geometries of the seed structures in precursor solution mixtures, which may determine the final structures in spin-casted films. The insights gained from our study may guide new strategies to control and ultimately tune Coulomb interactions in polymer-dopant solutions.

Interplay between Side Chain Density and Polymer Alignment: Two Competing Strategies for Enhancing the Thermoelectric Performance of P3HT Analogues.

A series of polythiophenes with varying side chain density was synthesized, and their electrical and thermoelectric properties were investigated. Aligned and non-aligned thin films of the polymers were characterized in the neutral and chemically doped states. Optical and diffraction measurements revealed an overall lower order in the thin films with lower side chain density, also confirmed using polarized optical experiments on aligned thin films. However, upon doping the non-aligned films, a sixfold increase in electrical conductivity was observed for the polythiophene with the lowest side chain density compared to poly(3-hexylthiophene) (P3HT). We found that the improvement in conductivity was not due to a larger charge carrier density but an increase in charge carrier mobility after doping with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). On the other hand, doped aligned films did not show the same trend; lower side chain density instead led to a lower conductivity and Seebeck coefficient compared to those for P3HT. This was attributed to the poorer alignment of the polymer thin films with lower side chain density. The study demonstrates that optimizing side chain density is a synthetically simple and effective way to improve electrical conductivity in polythiophene films relevant to thermoelectric applications.

Effects of Processing-Induced Contamination on Organic Electronic Devices.

Organic semiconductors are a family of pi-conjugated compounds used in many applications, such as displays, bioelectronics, and thermoelectrics. However, their susceptibility to processing-induced contamination is not well understood. Here, it is shown that many organic electronic devices reported so far may have been unintentionally contaminated, thus affecting their performance, water uptake, and thin film properties. Nuclear magnetic resonance spectroscopy is used to detect and quantify contaminants originating from the glovebox atmosphere and common laboratory consumables used during device fabrication. Importantly, this in-depth understanding of the sources of contamination allows the establishment of clean fabrication protocols, and the fabrication of organic field effect transistors (OFETs) with improved performance and stability. This study highlights the role of unintentional contaminants in organic electronic devices, and demonstrates that certain stringent processing conditions need to be met to avoid scientific misinterpretation, ensure device reproducibility, and facilitate performance stability. The experimental procedures and conditions used herein are typical of those used by many groups in the field of solution-processed organic semiconductors. Therefore, the insights gained into the effects of contamination are likely to be broadly applicable to studies, not just of OFETs, but also of other devices based on these materials.

Structural and Dynamic Disorder, Not Ionic Trapping, Controls Charge Transport in Highly Doped Conducting Polymers.

Doped organic semiconductors are critical to emerging device applications, including thermoelectrics, bioelectronics, and neuromorphic computing devices. It is commonly assumed that low conductivities in these materials result primarily from charge trapping by the Coulomb potentials of the dopant counterions. Here, we present a combined experimental and theoretical study rebutting this belief. Using a newly developed doping technique based on ion exchange, we prepare highly doped films with several counterions of varying size and shape and characterize their carrier density, electrical conductivity, and paracrystalline disorder. In this uniquely large data set composed of several classes of high-mobility conjugated polymers, each doped with at least five different ions, we find electrical conductivity to be strongly correlated with paracrystalline disorder but poorly correlated with ionic size, suggesting that Coulomb traps do not limit transport. A general model for interacting electrons in highly doped polymers is proposed and carefully parametrized against atomistic calculations, enabling the calculation of electrical conductivity within the framework of transient localization theory. Theoretical calculations are in excellent agreement with experimental data, providing insights into the disorder-limited nature of charge transport and suggesting new strategies to further improve conductivities.

High-Efficiency Ion-Exchange Doping of Conducting Polymers.

Molecular doping-the use of redox-active small molecules as dopants for organic semiconductors-has seen a surge in research interest driven by emerging applications in sensing, bioelectronics, and thermoelectrics. However, molecular doping carries with it several intrinsic problems stemming directly from the redox-active character of these materials. A recent breakthrough was a doping technique based on ion-exchange, which separates the redox and charge compensation steps of the doping process. Here, the equilibrium and kinetics of ion exchange doping in a model system, poly(2,5-bis(3-alkylthiophen-2-yl)thieno(3,2-b)thiophene) (PBTTT) doped with FeCl3 and an ionic liquid, is studied, reaching conductivities in excess of 1000 S cm-1 and ion exchange efficiencies above 99%. Several factors that enable such high performance, including the choice of acetonitrile as the doping solvent, which largely eliminates electrolyte association effects and dramatically increases the doping strength of FeCl3 , are demonstrated. In this high ion exchange efficiency regime, a simple connection between electrochemical doping and ion exchange is illustrated, and it is shown that the performance and stability of highly doped PBTTT is ultimately limited by intrinsically poor stability at high redox potential.

Super-Resolution Photothermal Patterning in Conductive Polymers Enabled by Thermally Activated Solubility.

Doping-induced solubility control (DISC) patterning is a recently developed technique that uses the change in polymer solubility upon doping, along with an optical dedoping process, to achieve high-resolution optical patterning. DISC patterning can produce features smaller than predicted by the diffraction limit; however, no mechanism has been proposed to explain such high resolution. Here, we use diffraction to spatially modulate the light intensity and determine the dissolution rate, revealing a superlinear dependence on light intensity. This rate law is independent of wavelength, indicating that patterning resolution is not dominated by an optical dedoping reaction, as was previously proposed. Instead we show here that the optical patterning mechanism is primarily controlled by the thermal profile generated by the laser. To quantify this effect, the thermal profile and dissolution rate are modeled using a finite-element model and compared against patterned line cross sections as a function of wavelength, laser intensity, and dwell time. Our model reveals that although the laser-generated thermal profile is broadened considerably beyond the profile of the laser, the highly temperature dependent dissolution rate results in selective dissolution near the peak of the thermal profile. Therefore, the key factor in achieving super-resolution patterning is a strongly temperature dependent dissolution rate, a common feature of many polymers. In addition to suggesting several routes to improved resolution, our model also demonstrates that doping is not required for optical patterning of conjugated polymers, as was previously believed. Instead, we demonstrate that superlinear resolution optical patterning should be attainable in any conjugated polymer simply by tuning the solvent quality during patterning, thus extending the applicability of our method to a wide class of materials. We demonstrate the generality of photothermal patterning by writing sub-400 nm features into undoped PffBT4T-2OD.

Controlling Molecular Doping in Organic Semiconductors.

The field of organic electronics thrives on the hope of enabling low-cost, solution-processed electronic devices with mechanical, optoelectronic, and chemical properties not available from inorganic semiconductors. A key to the success of these aspirations is the ability to controllably dope organic semiconductors with high spatial resolution. Here, recent progress in molecular doping of organic semiconductors is summarized, with an emphasis on solution-processed p-type doped polymeric semiconductors. Highlighted topics include how solution-processing techniques can control the distribution, diffusion, and density of dopants within the organic semiconductor, and, in turn, affect the electronic properties of the material. Research in these areas has recently intensified, thanks to advances in chemical synthesis, improved understanding of charged states in organic materials, and a focus on relating fabrication techniques to morphology. Significant disorder in these systems, along with complex interactions between doping and film morphology, is often responsible for charge trapping and low doping efficiency. However, the strong coupling between doping, solubility, and morphology can be harnessed to control crystallinity, create doping gradients, and pattern polymers. These breakthroughs suggest a role for molecular doping not only in device function but also in fabrication-applications beyond those directly analogous to inorganic doping.

Direct-Write Optical Patterning of P3HT Films Beyond the Diffraction Limit.

Doping-induced solubility control is a patterning technique for semiconducting polymers, which utilizes the reduction in polymer solubility upon p-type doping to provide direct, optical control of film topography and doping level. In situ direct-write patterning and imaging are demonstrated, revealing sub-diffraction-limited topographic features. Photoinduced force microscopy shows that doping level can be optically modulated with similar resolution.

Optical Dedoping Mechanism for P3HT:F4TCNQ Mixtures.

Doping-induced solubility control (DISC) is a recently introduced photolithographic technique for semiconducting polymers, which utilizes reversible changes in polymer solubility upon doping to allow the polymer to function as its own photoresist. Central to this process is a wavelength sensitive optical dedoping reaction, which is poorly understood but generates subdiffraction-limited topographic features and provides optical control of the polymer doping level. Here, we examine the mechanism of optical dedoping in the semiconducting polymer poly-3-hexylthiophene (P3HT) doped by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), via a combination of ultrafast and steady-state spectroscopy, ab initio calculations, and multidimensional NMR. A simple photoinduced back electron transfer mechanism from reduced F4TCNQ to oxidized P3HT does not explain the observed photophysics. Instead, photoexcited F4TCNQ* reacts with THF solvent molecules to form a neutral, nondoping, and highly soluble F4TCNQ-THF complex. Hence, ionized F4TCNQ is removed from the P3HT indirectly by depletion of the neutral F4TCNQ. Because the reaction involves only the dopant and similar photoreactivity would expected for most other dopant molecules, we expect optical DISC patterning should be generalizable to a wide range of polymer:dopant systems.

Measurement of Small Molecular Dopant F4TCNQ and C60F36 Diffusion in Organic Bilayer Architectures.

The diffusion of molecules through and between organic layers is a serious stability concern in organic electronic devices. In this work, the temperature-dependent diffusion of molecular dopants through small molecule hole transport layers is observed. Specifically we investigate bilayer stacks of small molecules used for hole transport (MeO-TPD) and p-type dopants (F4TCNQ and C60F36) used in hole injection layers for organic light emitting diodes and hole collection electrodes for organic photovoltaics. With the use of absorbance spectroscopy, photoluminescence spectroscopy, neutron reflectometry, and near-edge X-ray absorption fine structure spectroscopy, we are able to obtain a comprehensive picture of the diffusion of fluorinated small molecules through MeO-TPD layers. F4TCNQ spontaneously diffuses into the MeO-TPD material even at room temperature, while C60F36, a much bulkier molecule, is shown to have a substantially higher morphological stability. This study highlights that the differences in size/geometry and thermal properties of small molecular dopants can have a significant impact on their diffusion in organic device architectures.

Reversible optical control of conjugated polymer solubility with sub-micrometer resolution.

Organic electronics promise to provide flexible, large-area circuitry such as photovoltaics, displays, and light emitting diodes that can be fabricated inexpensively from solutions. A major obstacle to this vision is that most conjugated organic materials are miscible, making solution-based fabrication of multilayer or micro- to nanoscale patterned films problematic. Here we demonstrate that the solubility of prototypical conductive polymer poly(3-hexylthiophene) (P3HT) can be reversibly "switched off" using high electron affinity molecular dopants, then later recovered with light or a suitable dedoping solution. Using this technique, we are able to stack mutually soluble materials and laterally pattern polymer films by evaporation or with light, achieving sub-micrometer, optically limited feature sizes. After forming these structures, the films can be dedoped without disrupting the patterned features; dedoped films have identical optical characteristics, charge carrier mobilities, and NMR spectra as as-cast P3HT films. This method greatly simplifies solution-based device fabrication, is easily adaptable to current manufacturing workflows, and is potentially generalizable to other classes of materials.