Bob C. Schroeder

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.

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.

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.

Chalcogenophene comonomer comparison in small band gap diketopyrrolopyrrole-based conjugated polymers for high-performing field-effect transistors and organic solar cells.

The design, synthesis, and characterization of a series of diketopyrrolopyrrole-based copolymers with different chalcogenophene comonomers (thiophene, selenophene, and tellurophene) for use in field-effect transistors and organic photovoltaic devices are reported. The effect of the heteroatom substitution on the optical, electrochemical, and photovoltaic properties and charge carrier mobilities of these polymers is discussed. The results indicate that by increasing the size of the chalcogen atom (S < Se < Te), polymer band gaps are narrowed mainly due to LUMO energy level stabilization. In addition, the larger heteroatomic size also increases intermolecular heteroatom-heteroatom interactions facilitating the formation of polymer aggregates leading to enhanced field-effect mobilities of 1.6 cm(2)/(V s). Bulk heterojunction solar cells based on the chalcogenophene polymer series blended with fullerene derivatives show good photovoltaic properties, with power conversion efficiencies ranging from 7.1-8.8%. A high photoresponse in the near-infrared (NIR) region with excellent photocurrents above 20 mA cm(-2) was achieved for all polymers, making these highly efficient low band gap polymers promising candidates for use in tandem solar cells.

Design of Semiconducting Indacenodithiophene Polymers for High Performance Transistors and Solar Cells

The prospect of using low cost, high throughput material deposition processes to fabricate organic circuitry and solar cells continues to drive research towards improving the performance of the semiconducting materials utilized in these devices. Conjugated aromatic polymers have emerged as a leading candidate semiconductor material class, due to their combination of their amenability to processing and reasonable electrical and optical performance. Challenges remain, however, to further improve the charge carrier mobility of the polymers for transistor applications and the power conversion efficiency for solar cells. This optimization requires a clear understanding of the relationship between molecular structure and both electronic properties and thin film morphology. In this Account, we describe an optimization process for a series of semiconducting polymers based on an electron rich indacenodithiophene aromatic backbone skeleton. We demonstrate the effect of bridging atoms, alkyl chain functionalization, and co-repeating units on the morphology, molecular orbital energy levels, charge carrier mobility, and solar cell efficiencies. This conjugated unit is extremely versatile with a coplanar aromatic ring structure, and the electron density can be manipulated by the choice of bridging group between the rings. The functionality of the bridging group also plays an important role in the polymer solubility, and out of plane aliphatic chains present in both the carbon and silicon bridge promote solubility. This particular polymer conformation, however, typically suppresses long range organization and crystallinity, which had been shown to strongly influence charge transport. In many cases, polymers exhibited both high solubility and excellent charge transport properties, even where there was no observable evidence of polymer crystallinity. The optical bandgap of the polymers can be tuned by the combination of the donating power of the bridging unit and the electron withdrawing nature of co-repeat units, alternating along the polymer backbone. Using strong donors and acceptors, we could shift the absorption into the near infrared.

Intrinsically stretchable and healable semiconducting polymer for organic transistors

Thin-film field-effect transistors are essential elements of stretchable electronic devices for wearable electronics. All of the materials and components of such transistors need to be stretchable and mechanically robust. Although there has been recent progress towards stretchable conductors, the realization of stretchable semiconductors has focused mainly on strain-accommodating engineering of materials, or blending of nanofibres or nanowires into elastomers. An alternative approach relies on using semiconductors that are intrinsically stretchable, so that they can be fabricated using standard processing methods. Molecular stretchability can be enhanced when conjugated polymers, containing modified side-chains and segmented backbones, are infused with more flexible molecular building blocks. Here we present a design concept for stretchable semiconducting polymers, which involves introducing chemical moieties to promote dynamic non-covalent crosslinking of the conjugated polymers. These non-covalent crosslinking moieties are able to undergo an energy dissipation mechanism through breakage of bonds when strain is applied, while retaining high charge transport abilities. As a result, our polymer is able to recover its high field-effect mobility performance (more than 1 square centimetre per volt per second) even after a hundred cycles at 100 per cent applied strain. Organic thin-film field-effect transistors fabricated from these materials exhibited mobility as high as 1.3 square centimetres per volt per second and a high on/off current ratio exceeding a million. The field-effect mobility remained as high as 1.12 square centimetres per volt per second at 100 per cent strain along the direction perpendicular to the strain. The field-effect mobility of damaged devices can be almost fully recovered after a solvent and thermal healing treatment. Finally, we successfully fabricated a skin-inspired stretchable organic transistor operating under deformations that might be expected in a wearable device.

On the Energetic Dependence of Charge Separation in Low-Band-Gap Polymer/Fullerene Blends

The energetic driving force required to drive charge separation across donor/acceptor heterojunctions is a key consideration for organic optoelectronic devices. Herein we report a series of transient absorption and photocurrent experiments as a function of excitation wavelength and temperature for two low-band-gap polymer/fullerene blends to study the mechanism of charge separation at the donor/acceptor interface. For the blend that exhibits the smallest donor/acceptor LUMO energy level offset, the photocurrent quantum yield falls as the photon excitation energy is reduced toward the band gap, but the yield of bound, interfacial charge transfer states rises. This interplay between bound and free charge generation as a function of initial exciton energy provides key evidence for the role of excess energy in driving charge separation of direct relevance to the development of low-band-gap polymers for enhanced solar light harvesting.

Highly stretchable polymer semiconductor films through the nanoconfinement effect

Trapping polymers to improve flexibility Polymer molecules at a free surface or trapped in thin layers or tubes will show different properties from those of the bulk. Confinement can prevent crystallization and oddly can sometimes give the chains more scope for motion. Xu et al. found that a conducting polymer confined inside an elastomer—a highly stretchable, rubber-like polymer—retained its conductive properties even when subjected to large deformations (see the Perspective by Napolitano). Science, this issue p. 59; see also p. 24 A high-performance conjugated polymer is combined with an elastomer to produce a fully stretchable transistor. Soft and conformable wearable electronics require stretchable semiconductors, but existing ones typically sacrifice charge transport mobility to achieve stretchability. We explore a concept based on the nanoconfinement of polymers to substantially improve the stretchability of polymer semiconductors, without affecting charge transport mobility. The increased polymer chain dynamics under nanoconfinement significantly reduces the modulus of the conjugated polymer and largely delays the onset of crack formation under strain. As a result, our fabricated semiconducting film can be stretched up to 100% strain without affecting mobility, retaining values comparable to that of amorphous silicon. The fully stretchable transistors exhibit high biaxial stretchability with minimal change in on current even when poked with a sharp object. We demonstrate a skinlike finger-wearable driver for a light-emitting diode.

Random benzotrithiophene-based donor-acceptor copolymers for efficient organic photovoltaic devices

A series of benzotrithiophene-containing random terpolymers for polymer solar cells is reported. Through variations of the two other components in the terpolymers, the absorption profile and the frontier energy levels are optimized and maximum power conversion efficiencies are nearly doubled (5.14%) relative to the parent alternating copolymer.

Recent advances in high mobility donor–acceptor semiconducting polymers

A combination of improved understanding of molecular design criteria and polymer purification techniques, as well as optimised fabrication techniques and device surface treatments, have driven recent advances in the performance of semiconducting polymers for transistor applications. This development has allowed polymer-based devices to reach parity with the best values obtained for small molecule evaporated devices. Herein, we present the most recent work on solution processable high mobility donor–acceptor type polymers. We discuss the approaches that have been taken to improve both hole (and electron) mobility further. We will not only focus on chemical design criteria, but also describe certain processing approaches which have led to impressive hole mobilities of up to 5.5 cm2 V−1 s−1.