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.

Controlling Molecular Doping in Organic Semiconductors

The electrical performance of doped semiconducting polymers is strongly governed by processing methods and underlying thin-film microstructure. We report on the influence of different doping methods (solution versus vapor) on the thermoelectric power factor (PF) of PBTTT molecularly p-doped with F n TCNQ (n = 2 or 4). The vapor-doped films have more than two orders of magnitude higher electronic conductivity (σ) relative to solution-doped films. On the basis of resonant soft x-ray scattering, vapor-doped samples are shown to have a large orientational correlation length (OCL) (that is, length scale of aligned backbones) that correlates to a high apparent charge carrier mobility (μ). The Seebeck coefficient (α) is largely independent of OCL. This reveals that, unlike σ, leveraging strategies to improve μ have a smaller impact on α. Our best-performing sample with the largest OCL, vapor-doped PBTTT:F4TCNQ thin film, has a σ of 670 S/cm and an α of 42 μV/K, which translates to a large PF of 120 μW m-1 K-2. In addition, despite the unfavorable offset for charge transfer, doping by F2TCNQ also leads to a large PF of 70 μW m-1 K-2, which reveals the potential utility of weak molecular dopants. Overall, our work introduces important general processing guidelines for the continued development of doped semiconducting polymers for thermoelectrics.

/pdf/morphology-controls-the-thermoelectric-power-factor-of-a-1fw026wz6m.pdf

Morphology controls the thermoelectric power factor of a doped semiconducting polymer

Doping polymeric semiconductors often drastically reduces the solubility of the polymer, leading to difficulties in processing doped films. Here, we compare optical, electrical, and morphological properties of P3HT films doped with F4TCNQ, both from mixed solutions and using sequential solution processing with orthogonal solvents. We demonstrate that sequential doping occurs rapidly (<1 s), and that the film doping level can be precisely controlled by varying the concentration of the doping solution. Furthermore, the choice of sequential doping solvent controls whether dopant anions are included or excluded from polymer crystallites. Atomic force microscopy (AFM) reveals that sequential doping produces significantly more uniform films on the nanoscale than the mixed-solution method. In addition, we show that mixed-solution doping induces the formation of aggregates even at low doping levels, resulting in drastic changes to film morphology. Sequentially coated films show 3–15 times higher conductivities at a given doping level than solution-doped films, with sequentially doped films processed to exclude dopant anions from polymer crystallites showing the highest conductivities. We propose a mechanism for doping induced aggregation in which the shift of the polymer HOMO level upon aggregation couples ionization and solvation energies. To show that the methodology is widely applicable, we demonstrate that several different polymer:dopant systems can be prepared by sequential doping.

/pdf/comparison-of-solution-mixed-and-sequentially-processed-p3ht-tjynnvhy5x.pdf

Comparison of solution-mixed and sequentially processed P3HT:F4TCNQ films: effect of doping-induced aggregation on film morphology

Photocrosslinkable bromine-functionalized poly(3-hexylthiophene) (P3HT-Br) copolymers designed for application in solution-processed organic photovoltaics are prepared by copolymerization of 2-bromo-3-(6-bromohexyl) thiophene and 2-bromo-3-hexylthiophene. The monomer ratio is carefully controlled to achieve a UV photocrosslinkable layer while retaining the π–π stacking feature of the conjugated polymers. The new materials are used as electron donors in both bulk heterojunction (BHJ) and bilayer type photovoltaic devices. Unlike devices prepared from either P3HT:PCBM blend or P3HT-Br:PCBM blend without UV treatment, photocrosslinked P3HT-Br:PCBM devices are stable even when annealed for two days at the elevated temperature of 150 °C as the nanophase separated morphology of the bulk heterojunction is stabilized as confirmed by optical microscopy and grazing incidence wide angle X-ray scattering (GIWAXS). When applied to solution-processed bilayer devices, the photocrosslinkable materials show high power conversion efficiencies (∼2%) and excellent thermal stability (3 days at 150 °C). Such performance, one of the highest obtained for a bilayer device fabricated by solution processing, is achieved as crosslinking does not disturb the π–π stacking of the polymer as confirmed by GIWAXS measurements. These novel photocrosslinkable materials provide ready access to efficient bilayer devices thus enabling the fundamental study of photophysical characteristics, charge generation, and transport across a well-defined interface.

http://absimage.aps.org/image/MAR09/MWS_MAR09-2008-000095.pdf

Photo-crosslinkable Polythiophenes for Efficient Thermally Stable Organic Photovoltaics

Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design. We propose a unified model of how charge carriers travel in conjugated polymer films. We show that in high-molecular-weight semiconducting polymers the limiting charge transport step is trapping caused by lattice disorder, and that short-range intermolecular aggregation is sufficient for efficient long-range charge transport. This generalization explains the seemingly contradicting high performance of recently reported, poorly ordered polymers and suggests molecular design strategies to further improve the performance of future generations of organic electronic materials.

http://absimage.aps.org/image/MAR14/MWS_MAR14-2013-020288.pdf

A general relationship between disorder, aggregation and charge transport in conjugated polymers

https://escholarship.org/content/qt1qf0695g/qt1qf0695g.pdf?t=o94sbe

The effect of thermal annealing on dopant site choice in conjugated polymers

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.

Erik W. Aasen

Papers

Comparison of solution-mixed and sequentially processed P3HT:F4TCNQ films: effect of doping-induced aggregation on film morphology

The effect of thermal annealing on dopant site choice in conjugated polymers

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