Solution-processed organic photovoltaics (OPV) offer the attractive prospect of low-cost, light-weight and environmentally benign solar energy production. The highest efficiency OPV at present use low-bandgap donor polymers, many of which suffer from problems with stability and synthetic scalability. They also rely on fullerene-based acceptors, which themselves have issues with cost, stability and limited spectral absorption. Here we present a new non-fullerene acceptor that has been specifically designed to give improved performance alongside the wide bandgap donor poly(3-hexylthiophene), a polymer with significantly better prospects for commercial OPV due to its relative scalability and stability. Thanks to the well-matched optoelectronic and morphological properties of these materials, efficiencies of 6.4% are achieved which is the highest reported for fullerene-free P3HT devices. In addition, dramatically improved air stability is demonstrated relative to other high-efficiency OPV, showing the excellent potential of this new material combination for future technological applications.

Technological deployment of organic photovoltaic modules requires improvements in device light-conversion efficiency and stability while keeping material costs low. Here we demonstrate highly efficient and stable solar cells using a ternary approach, wherein two non-fullerene acceptors are combined with both a scalable and affordable donor polymer, poly(3-hexylthiophene) (P3HT), and a high efficiency, low band-gap polymer in a single-layer bulk-heterojunction devices. The addition of a strongly absorbing small molecule acceptor into a P3HT-based non-fullerene blend increases the device efficiency up to 7.7 ± 0.1% without any solvent additives. The improvement is assigned to changes in microstructure that reduces charge recombination and increases the photovoltage, and to improved light harvesting across the visible region. The stability of P3HT-based devices in ambient conditions is also significantly improved relative to polymer:fullerene devices. Combined with a low band gap donor polymer (PBDTTT-EFT, also known as PCE10), the two mixed acceptors also lead to solar cells with 11.0 ± 0.4% efficiency and a high open-circuit voltage of 1.03 ± 0.01V.Currently, the materials used in organic photovoltaics (OPV) are dominated by fullerene acceptors in combination with low band gap donor polymers which typically require complex and multi-step syntheses. [1][2][3][4][5] However, the commercialization of OPV requires the availability of inexpensive materials in large quantities such as poly(3-hexylthiophene) (P3HT). P3HT is readily scalable via flow or micro-reactor synthesis, even using 'green' solvents, whilst retaining a high degree of control over molecular weight and regioregularity. 6 The P3HT:60PCBM blend exhibits one of the most robust microstructures within OPV. [7][8][9] However, it has a limited open-circuit voltage (Voc) and short-circuit current (Jsc) in photovoltaic devices. 10 We have recently shown that solar cells using an alternative small molecule non-fullerene acceptor (NFA), IDTBR, when mixed with P3HT, can achieve power conversion efficiencies of up to 6.4%. 11 These results have revived interest in the use of P3HT for high performing devices and non-fullerene acceptors. [12][13][14][15][16][17][18] The combination of stability, cost and performance for P3HT:NFA devices, make them a compelling choice for commercialization of OPV compared to devices using fullerenes, for which the high costs and energy involved are prohibitive for large scale production.Recently, multi-component heterojunctions (ternary or more) have emerged as a promising strategy to overcome the power conversion efficiency (PCE) bottleneck associated with binary bulk-heterojunction (BHJ) solar cells. 3,4,[19][20][21][22][23]24 However, simultaneous increase in the Voc, Jsc and FF is a challenge in the ternary approach because of the trade-off between photocurrent and voltage. 23,25,26 Reports show ternary blends using fullerene acceptors, where the Voc is increased using a second acceptor (A2) with a higher electron affin...

ConspectusThe active layer in a solution processed organic photovoltaic device comprises a light absorbing electron donor semiconductor, typically a polymer, and an electron accepting fullerene acceptor. Although there has been huge effort targeted to optimize the absorbing, energetic, and transport properties of the donor material, fullerenes remain as the exclusive electron acceptor in all high performance devices. Very recently, some new non-fullerene acceptors have been demonstrated to outperform fullerenes in comparative devices. This Account describes this progress, discussing molecular design considerations and the structure–property relationships that are emerging.The motivation to replace fullerene acceptors stems from their synthetic inflexibility, leading to constraints in manipulating frontier energy levels, as well as poor absorption in the solar spectrum range, and an inherent tendency to undergo postfabrication crystallization, resulting in device instability. New acceptors have to address these limitations, providing tunable absorption with high extinction coefficients, thus contributing to device photocurrent. The ability to vary and optimize the lowest unoccupied molecular orbital (LUMO) energy level for a specific donor polymer is also an important requirement, ensuring minimal energy loss on electron transfer and as high an internal voltage as possible. Initially perylene diimide acceptors were evaluated as promising acceptor materials. These electron deficient aromatic molecules can exhibit good electron transport, facilitated by close packed herringbone crystal motifs, and their energy levels can be synthetically tuned. The principal drawback of this class of materials, their tendency to crystallize on too large a length scale for an optimal heterojunction nanostructure, has been shown to be overcome through introduction of conformation twisting through steric effects. This has been primarily achieved by coupling two units together, forming dimers with a large intramolecular twist, which suppresses both nucleation and crystal growth. The generic design concept of rotationally symmetrical aromatic small molecules with extended π orbital delocalization, including polyaromatic hydrocarbons, phthalocyanines, etc., has also provided some excellent small molecule acceptors. In most cases, additional electron withdrawing functionality, such as imide or ester groups, can be incorporated to stabilize the LUMO and improve properties. New calamitic acceptors have been developed, where molecular orbital hybridization of electron rich and poor segments can be judiciously employed to precisely control energy levels. Conformation and intermolecular associations can be controlled by peripheral functionalization leading to optimization of crystallization length scales. In particular, the use of rhodanine end groups, coupled electronically through short bridged aromatic chains, has been a successful strategy, with promising device efficiencies attributed to high lying LUMO energy levels and subsequently large...

Non-fullerene acceptors with optimized energy levels enable 10% efficient solar cells with reduced voltage losses <0.6 V.

In this review, we describe and discuss recent advances in the performance of polymeric semiconductors in organic field effect transistors (OFETs). Design concepts such as short intermolecular contacts, low conformational disorder, side chain optimization, and noncovalent interactions have all been successfully employed to improve the charge carrier mobility of polymer thin films. The relationship between the molecular design, thin film microstructure, and electrical performance has been exemplified by a range of thiophene, bridged and fused ring, diketopyrrolopyrrole (DPP), and isoindigo containing polymers which are reviewed and discussed.