Role of Intermolecular Coupling in the Photophysics of Disordered Organic Semiconductors: Aggregate Emission in Regioregular Polythiophene
TL;DR: The role of excitonic coupling on the nature of photoexcitations in the conjugated polymer regioregular poly(3-hexylthiophene) is addressed by means of temperature-dependent absorption and photoluminescence spectroscopy.
Abstract: We address the role of excitonic coupling on the nature of photoexcitations in the conjugated polymer regioregular poly(3-hexylthiophene). By means of temperature-dependent absorption and photoluminescence spectroscopy, we show that optical emission is overwhelmingly dominated by weakly coupled H aggregates. The relative absorbance of the 0-0 and 0-1 vibronic peaks provides a powerfully simple means to extract the magnitude of the intermolecular coupling energy, of approximately 5 and 30 meV for films spun from isodurene and chloroform solutions, respectively.
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TL;DR: In this article, a unified model of how charge carriers travel in conjugated polymer films is proposed, and it is shown that in high-molecular-weight polymers, efficient charge transport is allowed due to a network of interconnected aggregates that are characterized by short-range order.
Abstract: 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. The recent demonstration that highly disordered polymer films can transport charges as effectively as polycrystalline semiconductors has called into question the relationship between structural order and mobility in organic materials. It is now shown that, in high-molecular-weight polymers, efficient charge transport is allowed due to a network of interconnected aggregates that are characterized by short-range order.
1,662 citations
TL;DR: This Account shows that the aggregation-induced deviations from the Poissonian distribution of vibronic peak intensities take on two extremes identified with ideal H- and J-aggregates, and reveals several more distinguishing traits between the two aggregate types.
Abstract: Electronic excitations in small aggregates, thin films, and crystals of conjugated organic molecules play a fundamental role in the operation of a wide array of organic-based devices including solar cells, transistors, and light-emitting diodes. Such excitations, or excitons, are generally spread out over several molecules: a balance between the delocalizing influence of resonant intermolecular coupling and the localizing influence of static and dynamic disorder determines the coherence range of the exciton. Because of the "soft" nature of organic materials, significant nuclear relaxation in the participating molecules also accompanies the electronic excitations. To properly understand energy or charge transport, one must treat intermolecular (excitonic) coupling, electron-vibrational coupling, and disorder on equal footing. In this Account, we review the key elements of a theoretical approach based on a multiparticle representation that describes electronic excitations in organic materials as vibronic excitations surrounded by a field of vibrational excitations. Such composite excitations are appropriately called Frenkel excitonic polarons. For many conjugated molecules, the bulk of the nuclear reorganization energy following electronic excitation arises from the elongation of a symmetric vinyl stretching mode with energy approximately 1400 cm(-1). To appreciate the impact of aggregation, we study how the vibronic progression of this mode, which dominates the isolated (solvated) molecule absorption and emission spectra, is distorted when molecules are close enough to interact with each other. As we demonstrate in this Account, the nature of the distortion provides a wealth of information about how the molecules are packed, the strength of the excitonic interactions between molecules, the number of molecules that are coherently coupled, and the nature of the disorder. We show that the aggregation-induced deviations from the Poissonian distribution of vibronic peak intensities take on two extremes identified with ideal H- and J-aggregates. The sign of the nearest neighbor electronic coupling, positive for H and negative for J, distinguishes the two basic aggregate forms. For several decades, researchers have known that H-aggregates exhibit blue-shifted absorption spectra and are subradiant while J-aggregates exhibit the opposite behavior (red-shifted absorption and superradiance). However, the exact inclusion of exciton-vibrational coupling reveals several more distinguishing traits between the two aggregate types: in H(J)-aggregates the ratio of the first two vibronic peak intensities in the absorption spectrum decreases (increases) with increasing excitonic coupling, while the ratio of the 0-0 to 0-1 emission intensities increases (decreases) with disorder and increases (decreases) with increasing temperature. These two extreme behaviors provide the framework for understanding absorption and emission in more complex morphologies, such as herringbone packing in oligo(phenylene vinylene)s, oligothiophenes and polyacene crystals, as well as the polymorphic packing arrangements observed in carotenoids.
1,307 citations
TL;DR: This review article takes a retrospective look at the research and development of OPV, and focuses on recent advances of solution-processed materials and devices during the last decade, particular the polymer version of the materials and Devices.
Abstract: Organic photovoltaic (OPV) technology has been developed and improved from a fancy concept with less than 1% power conversion efficiency (PCE) to over 10% PCE, particularly through the efforts in the last decade. The significant progress is the result of multidisciplinary research ranging from chemistry, material science, physics, and engineering. These efforts include the design and synthesis of novel compounds, understanding and controlling the film morphology, elucidating the device mechanisms, developing new device architectures, and improving large-scale manufacture. All of these achievements catalyzed the rapid growth of the OPV technology. This review article takes a retrospective look at the research and development of OPV, and focuses on recent advances of solution-processed materials and devices during the last decade, particular the polymer version of the materials and devices. The work in this field is exciting and OPV technology is a promising candidate for future thin film solar cells.
1,073 citations
TL;DR: The authors would like to thank M. Chabinyc, H. Ade, B. Noriega, K. Vandewal, and D. Duong for fruitful discussions in the preparation of this review and the Center for Advanced Molecular Photovoltaics for funding.
Abstract: The authors would like to thank M. Chabinyc, H. Ade, B. Collins, R. Noriega, K. Vandewal, and D. Duong for fruitful discussions in the preparation of this review. Stanford Synchrotron Radiation Lightsource (SSRL) is a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. This publication was partially supported by the Center for Advanced Molecular Photovoltaics (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST).
1,072 citations
TL;DR: This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated.
Abstract: The electronic excited states of molecular aggregates and their photophysical signatures have long fascinated spectroscopists and theoreticians alike since the advent of Frenkel exciton theory almost 90 years ago. The influence of molecular packing on basic optical probes like absorption and photoluminescence was originally worked out by Kasha for aggregates dominated by Coulombic intermolecular interactions, eventually leading to the classification of J- and H-aggregates. This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated. An assortment of packing geometries is considered from the humble molecular dimer to more exotic structures including linear and bent aggregates, two-dimensional herringbone and “HJ” aggregates, and chiral aggregates. The interplay between long-range Coulomb coupling and short-range charge-transfer-mediated coupling strongly depends on the aggregate ...
865 citations
References
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TL;DR: In this article, the authors used thin-film, field effect transistor structures to probe the transport properties of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT.
Abstract: Self-organization in many solution-processed, semiconducting conjugated polymers results in complex microstructures, in which ordered microcrystalline domains are embedded in an amorphous matrix1. This has important consequences for electrical properties of these materials: charge transport is usually limited by the most difficult hopping processes and is therefore dominated by the disordered matrix, resulting in low charge-carrier mobilities2 (⩽10-5 cm2 V-1 s-1). Here we use thin-film, field-effect transistor structures to probe the transport properties of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT. Self-organization in P3HT results in a lamella structure with two-dimensional conjugated sheets formed by interchain stacking. We find that, depending on processing conditions, the lamellae can adopt two different orientations—parallel and normal to the substrate—the mobilities of which differ by more than a factor of 100, and can reach values as high as 0.1 cm2 V-1 s-1 (refs 3, 4). Optical spectroscopy of the field-induced charge, combined with the mobility anisotropy, reveals the two-dimensional interchain character of the polaronic charge carriers, which exhibit lower relaxation energies than the corresponding radical cations on isolated one-dimensional chains. The possibility of achieving high mobilities via two-dimensional transport in self-organized conjugated lamellae is important for applications of polymer transistors in logic circuits5 and active-matrix displays4,6.
4,306 citations
TL;DR: An all-polymer semiconductor integrated device is demonstrated with a high-mobility conjugated polymer field-effect transistor driving a polymer light-emitting diode (LED) of similar size, which represents a step toward all- polymer optoelectronic integrated circuits such as active-matrix polymer LED displays.
Abstract: An all-polymer semiconductor integrated device is demonstrated with a high-mobility conjugated polymer field-effect transistor (FET) driving a polymer light-emitting diode (LED) of similar size. The FET uses regioregular poly(hexylthiophene). Its performance approaches that of inorganic amorphous silicon FETs, with field-effect mobilities of 0.05 to 0.1 square centimeters per volt second and ON-OFF current ratios of >10 6 . The high mobility is attributed to the formation of extended polaron states as a result of local self-organization, in contrast to the variable-range hopping of self-localized polarons found in more disordered polymers. The FET-LED device represents a step toward all-polymer optoelectronic integrated circuits such as active-matrix polymer LED displays.
2,657 citations
TL;DR: In this article, it was shown that the lowest energy feature in the region of the absorption spectrum is associated with an interchain absorption, the intensity of which is correlated with the degree of order in the polymer.
Abstract: The absorption spectrum of polythiophene and its derivative poly(3-hexylthiophene) (P3HT) is usually described in terms of an intrachain exciton coupled to a single phonon mode. We show that this model is too simplistic for highly ordered, regioregular P3HT and that, analogous to the case of charged polarons in this material, interchain interactions must be taken into account to correctly describe the absorption spectrum. We show that the lowest energy feature in the $\ensuremath{\pi}\ensuremath{-}{\ensuremath{\pi}}^{*}$ region of the absorption spectrum is associated with an interchain absorption, the intensity of which is correlated with the degree of order in the polymer. Correspondingly, we show that the emission from P3HT also exhibits contributions from both interchain and intrachain states, in a manner similar to that recently shown for poly(phenylenevinylene). Having reinterpreted the physical origin of the features in the absorption and emission spectra of P3HT, we then model these spectra and show how they evolve as the degree of order in the polymer is changed by varying several physical parameters including temperature and regioregularity of the polymer.
908 citations
TL;DR: Evidence that interchain electronic species do form in conjugated polymer films is reviewed and their number and chemical nature depend on processing conditions; the chain conformation, degree of interchain contact, and rate of energy transfer can be controlled by factors such as choice of solvent, polymer concentration, thermal annealing, presence of electrically charged side groups, and encapsulation of the polymer chains in mesoporous silica.
Abstract: The electronic structure of conjugated polymers is of current interest because of the wide range of potential applications for such materials in optoelectronic devices. It is increasingly clear that the electronic properties of conjugated polymers depend sensitively on the physical conformation of the polymer chains and the way the chains pack together in films. This article reviews the evidence that interchain electronic species do form in conjugated polymer films, and that their number and chemical nature depend on processing conditions; the chain conformation, degree of interchain contact, and rate of energy transfer can be controlled by factors such as choice of solvent, polymer concentration, thermal annealing, presence of electrically charged side groups, and encapsulation of the polymer chains in mesoporous silica. Taken together, the results reconcile many contradictions in the literature and provide a prescription for the optimization of conjugated polymer film morphology for device applications.
899 citations
TL;DR: In this paper, it was shown that head to tail poly(3-alkylthiophene)s (PATs) undergo solid-state macromolecular self-assembly and give self-oriented structures, as determined by X-ray diffraction studies.
Abstract: It is found that head to tail poly(3-alkylthiophene)s (PAT) undergo solid-state macromolecular self-assembly and give self-oriented structures, as determined by X-ray diffraction studies. In addition, it is found that PATs with longer alkyl side chains (e.g. C 12 H 25 ) produce the structures with the most desirable electronic, electrochemical and optical properties and induce the formation of planar main-chain structures
662 citations