Iain McCulloch

Materials and Applications for Large Area Electronics: Solution-Based Approaches

2.3. Medical Devices and Sensors 9 2.4. Radio Frequency Applications 10 3. Materials 12 3.1. Organic Electronics Materials 12 3.2. Semiconducting Polymer Design 13 3.3. Poly(3-alkylthiophenes) 14 3.4. Poly(thieno(3,2-b)thiophenes 15 3.5. Benchmark Polymer Semiconductors 15 3.6. High Performance Polymer Semiconductors 15 4. Device Stability 16 4.1. Bias Stress in Organic Transistors 17 4.1.1. Bias Stress Characterization 17 4.1.2. Bias Stress Mechanism 18 4.2. Short Channel Effects in Organic Transistors 19 5. Materials Patterning and Integration 20 6. Conclusions 22 7. Acknowledgments 22 8. References 22

Non-fullerene electron acceptors for use in organic solar cells.

Conspectus The 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 open circuit voltages.

Recent Advances in the Development of Semiconducting DPP‐Containing Polymers for Transistor Applications

This progress report summarizes the numerous DPP-containing polymers recently developed for field-effect transistor applications including diphenyl-DPP and dithienyl-DPP-based polymers as the most commonly reported materials, but also difuranyl-DPP, diselenophenyl-DPP and dithienothienyl-DPP-containing polymers. We discuss the hole and electron mobilities that were reported in relation to structural properties such as alkyl substitution patterns, polymer molecular weights and solid state packing, as well as electronic properties including HOMO and LUMO energy levels. We moreover consider important aspects of ambipolar charge transport and highlight fundamental structure-property relations such as the relationships between the thin film morphologies and the charge carrier mobilities observed for DPP-containing polymers.

High-performance ambipolar diketopyrrolopyrrole-thieno[3,2-b]thiophene copolymer field-effect transistors with balanced hole and electron mobilities.

Ambipolar OFETs with balanced hole and electron field-effect mobilities both exceeding 1 cm(2) V(-1) s(-1) are achieved based on a single-solution-processed conjugated polymer, DPPT-TT, upon careful optimization of the device architecture, charge injection, and polymer processing. Such high-performance OFETs are promising for applications in ambipolar devices and integrated circuits, as well as model systems for fundamental studies.

High-efficiency and air-stable P3HT-based polymer solar cells with a new non-fullerene acceptor

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.

Molecular Packing of High-Mobility Diketo Pyrrolo-Pyrrole Polymer Semiconductors with Branched Alkyl Side Chains

We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm(2) V(-1) s(-1), with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packing and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.

Reducing the efficiency-stability-cost gap of organic photovoltaics with highly efficient and stable small molecule acceptor ternary solar cells

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-bandgap polymer in a single-layer bulk-heterojunction device. 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 reduce charge recombination and increase 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-bandgap 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 ± 0.01 V.

Recombination Dynamics as a Key Determinant of Open Circuit Voltage in Organic Bulk Heterojunction Solar Cells: A Comparison of Four Different Donor Polymers

[*] Prof. J. R. Durrant, Mr. A. Maurano, Dr. R. Hamilton, Dr. C. G. Shuttle, Dr. B. O’Regan, Dr. W. Zhang, Prof. I. McCulloch Departments of Chemistry, Imperial College London South Kensington SW7 2AZ (United Kingdom) E-mail: j.durrant@imperial.ac.uk Dr. A. M. Ballantyne, Prof. J. Nelson Departments of Physics, Imperial College London South Kensington SW7 2AZ (United Kingdom) Dr. H. Azimi, Dr. M. Morana, Prof. C. J. Brabec Konarka Austria, Altenbergerstrasse 69 A-4040 Linz (Austria) Dr. H. Azimi Christian Doppler Laboratory for Surface Optics Johannes Kepler University Linz (Austria)

A Rhodanine Flanked Nonfullerene Acceptor for Solution-Processed Organic Photovoltaics

A novel small molecule, FBR, bearing 3-ethylrhodanine flanking groups was synthesized as a nonfullerene electron acceptor for solution-processed bulk heterojunction organic photovoltaics (OPV). A straightforward synthesis route was employed, offering the potential for large scale preparation of this material. Inverted OPV devices employing poly(3-hexylthiophene) (P3HT) as the donor polymer and FBR as the acceptor gave power conversion efficiencies (PCE) up to 4.1%. Transient and steady state optical spectroscopies indicated efficient, ultrafast charge generation and efficient photocurrent generation from both donor and acceptor. Ultrafast transient absorption spectroscopy was used to investigate polaron generation efficiency as well as recombination dynamics. It was determined that the P3HT:FBR blend is highly intermixed, leading to increased charge generation relative to comparative devices with P3HT:PC60BM, but also faster recombination due to a nonideal morphology in which, in contrast to P3HT:PC60BM devices, the acceptor does not aggregate enough to create appropriate percolation pathways that prevent fast nongeminate recombination. Despite this nonoptimal morphology the P3HT:FBR devices exhibit better performance than P3HT:PC60BM devices, used as control, demonstrating that this acceptor shows great promise for further optimization.

Photocurrent enhancement from diketopyrrolopyrrole polymer solar cells through alkyl-chain branching point manipulation.

Systematically moving the alkyl-chain branching position away from the polymer backbone afforded two new thieno[3,2-b]thiophene-diketopyrrolopyrrole (DPPTT-T) polymers. When used as donor materials in polymer:fullerene solar cells, efficiencies exceeding 7% were achieved without the use of processing additives. The effect of the position of the alkyl-chain branching point on the thin-film morphology was investigated using X-ray scattering techniques and the effects on the photovoltaic and charge-transport properties were also studied. For both solar cell and transistor devices, moving the branching point further from the backbone was beneficial. This is the first time that this effect has been shown to improve solar cell performance. Strong evidence is presented for changes in microstructure across the series, which is most likely the cause for the photocurrent enhancement.