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.

Solution processed polymer/fullerene blend films are receiving extensive attention as the photoactive layer of organic solar cells. In this paper we report a range of photophysical, electrochemical, physicochemical and structural data which provide evidence that formation of a relatively pure, molecularly ordered phase of the fullerene component, phenyl-C 61 -butyric acid methyl ester (PCBM), may be the key factor driving the spatial separation of photogenerated electrons and holes in many of these devices. PCBM crystallisation is shown to result in an increase in its electron affinity, providing an energetic driving force for spatial separation of electrons and holes. Based upon our observations, we propose a functional model applicable to many organic bulk heterojunction devices based upon charge generation in a finely intermixed polymer/fullerene phase followed by spatial separation of electrons and holes at the interface of this mixed phase with crystalline PCBM domains. This model has significant implications for the design of alternative acceptor materials to PCBM for organic solar cells.

The most promising device structure for organic photovoltaic devices presented to date is the ''bulk-heterojunction'' whereby a hole-conducting (electron-donating) conjugated polymer, such as poly(3-hexylthiophene) (P3HT), is blended with an electron-conducting (electron-accepting) smallmolecular compound, such as a fullerene derivative. The reported strong composition-and thermal-treatment dependence of the power conversion efficiency of such binaries suggests that phase behavior, processing conditions and the resulting microstructure play a dominant role in the performance of devices based on these systems. Here, we propose a simple rationale for selecting the optimum composition of such crystalline/crystalline polymer/small molecule blends. We find that these binary systems feature simple eutectic phase behavior, and that the optimum composition for device performance is slightly hypoeutectic when expressed in terms of the polymer component. In accord with classical understanding of eutectic solidification, these blends feature a finely phase-separated matrix surrounding primary crystals of the small-molecular species. The combination of large interfacial area and component connectivity yield a desired microstructure for use in bulk-heterojunctions.While significant advances have been made in recent years, [1][2][3][4] power conversion efficiencies of organic photovoltaic devices still lag behind those of conventional inorganic solar cells. These lower values are primarily due to reduced photocurrents, resulting not only from poor optical absorption in the red but also, in many cases, from a failure to convert absorbed photons into current with high efficiency. In devices comprising bulk-heterojunction binaries, deposited from solution as a single composite film, a major obstacle to enhanced performance is the laborious optimization of the ratio of components [5][6][7][8][9][10][11] and processing protocols [7][8][9][10][11][12][13][14][15][16] in order to achieve a blend microstructure that simultaneously maximizes exciton generation, exciton dissociation, and charge transport to electrodes. From the perspective of a binary blend of non-interacting donor and acceptor components, optimum photocurrent generation should result for the optimum compromise between (i) high light absorption, achieved by maximizing the volume fraction of the component with the stronger absorption in the visible (usually the polymer in a polymer/small molecule bulk-heterojunction device), (ii) efficient charge separation, realized by maximizing the donor-acceptor interface area, and (iii) balanced charge transport, accomplished by compensating any imbalance in mobility by the volume available for charge conduction, provided that both components form percolating structures. [17,18] However, this view does not allow for the effects of compositional changes on molecular order and microstructure, and hence on the optoelectronic material properties. In practice, photocurrent is maximized in many donor-acceptor systems at compositions quite...

Analogous to conventional inorganic semiconductors, the performance of organic semiconductors is directly related to their molecular packing, crystallinity, growth mode, and purity. In order to achieve the best possible performance, it is critical to understand how organic semiconductors nucleate and grow. Clever use of surface and dielectric modification chemistry can allow one to control the growth and morphology, which greatly influence the electrical properties of the organic transistor. In this Review, the nucleation and growth of organic semiconductors on dielectric surfaces is addressed. The first part of the Review concentrates on small-molecule organic semiconductors. The role of deposition conditions on film formation is described. The modification of the dielectric interface using polymers or self-assembled mono-layers and their effect on organic-semiconductor growth and performance is also discussed. The goal of this Review is primarily to discuss the thin-film formation of organic semiconducting species. The patterning of single crystals is discussed, while their nucleation and growth has been described elsewhere (see the Review by Liu et. al).([¹]) The second part of the Review focuses on polymeric semiconductors. The dependence of physico-chemical properties, such as chain length (i.e., molecular weight) of the constituting macromolecule, and the influence of small molecular species on, e.g., melting temperature, as well as routes to induce order in such macromolecules, are described.

The optoelectronic properties of macromolecular semiconductors depend fundamentally on their solid-state microstructure and phase morphology. Hence, it is of central importance to manipulate -from the outset -the molecular arrangement and packing of this special class of polymers from the nano-to the micrometer scale when they are integrated in thin film devices such as photovoltaic cells, transistors or light-emitting diodes, for example. One effective strategy for this purpose is to vary their molecular weight. The reason for this is that materials of different weight-average molecular weight (Mw) lead to different microstructures. Polymers of low Mw form unconnected, extended-chain crystals because of their non-entangled nature. As a result, a polycrystalline, one-phase morphology is obtained. In contrast, high-Mw materials, in which average chain lengths are longer than the length between entanglements, form two-phase morphologies comprised of crystalline moieties embedded in largely un-ordered (amorphous) regions. Here, we discuss how changes in these structural features affect exciton dissociation processes. We utilise neat regioregular poly(3-hexylthiophene) (P3HT) of varying Mw as a model system and apply time-resolved photoluminescence (PL) spectroscopy to probe the electronic landscape in a range of P3HT thin-film architectures. We find that at 10 K, PL originating from recombination of long-lived charge pairs decays over microsecond timescales. Tellingly, both the amplitude and decay-rate distribution depend strongly on Mw. In films with dominant one-phase, chain-extended microstructures, the delayed PL is suppressed as a result of a diminished yield of photoinduced charges. Its decay is significantly slower than in two-phase microstructures. We therefore conclude that excitons in disordered regions between crystalline and amorphous phases dissociate extrinsically with yield and spatial distribution that depend intimately upon microstructure, in agreement with previous work [Paquin et al. Phys. Rev. Lett., 2011, 106, 197401]. We note, however, that independent of Mw, the delayed-PL lineshape due to charge recombination is representative of that in low-Mw microstructures. We thus hypothesize that charge recombination at these low temperatures -and likely also charge generation -occur in torsionally disordered chains forming more strongly coupled photophysical aggregates than those in the steady-state ensemble, producing a delayed PL lineshape reminiscent of that in paraffinic morphologies at steady state. 2

Blends and other multicomponent systems are used in various polymer applications to meet multiple requirements that cannot be fulfilled by a single material. In polymer optoelectronic devices it is often desirable to combine the semiconducting properties of the conjugated species with the excellent mechanical properties of certain commodity polymers. Here we investigate bicomponent blends comprising semicrystalline regioregular poly(3-hexylthiophene) and selected semicrystalline commodity polymers, and show that, owing to a highly favourable, crystallization-induced phase segregation of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor can be reduced to values as low as 3 wt% without any degradation in device performance. This is in stark contrast to blends containing an amorphous insulating polymer, for which significant reduction in electrical performance was reported. Crystalline-crystalline/semiconducting-insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer itself.

Semiconducting diblock copolymers of polyethylene (PE) and regioregular poly(3‐hexylthiophene) (P3HT) are demonstrated to exhibit a rich phase behaviour, judicious use of which permitted us to fabricate field‐effect transistors that show saturated charge carrier mobilities, μFET, as high as 2 × 10–2 cm2 V–1 s–1 and ON‐OFF ratios, Ion/Ioff ∼ 105 at contents of the insulating PE moiety as high as 90 wt %. In addition, the diblock copolymers display outstanding flexibility and toughness with elongations at break exceeding 600 % and true tensile strengths around 70 MPa, opening the path towards robust and truly flexible electronic components.

We probe charge photogeneration and subsequent recombination dynamics in neat regioregular poly(3-hexylthiophene) films over six decades in time by means of time-resolved photoluminescence spectroscopy. Exciton dissociation at 10K occurs extrinsically at interfaces between molecularly ordered and disordered domains. Polaron pairs thus produced recombine by tunnelling with distributed rates governed by the distribution of electron-hole radii. Quantum-chemical calculations suggest that hot-exciton dissociation at such interfaces results from a high charge-transfer character.