David Hanifi

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.

Direct Observation of Doping Sites in Temperature-Controlled, p-Doped P3HT Thin Films by Conducting Atomic Force Microscopy

The distribution of dopant sites in doped poly(3-hexylthiophene) (P3HT) thin films is characterized using optical absorption, grazing-incidence X-ray diffraction, and conducting atomic force microscopy (c-AFM). It is shown that dopant sites can be directly observed using c-AFM and that the solution temperature dramatically impacts phase separation and conductivity in spin-cast films.

Controlling the mode of operation of organic transistors through side-chain engineering

Significance Side-chain engineering is a versatile tool to modify the processability, as well as the physical, electrical, and optical properties, of conjugated polymers. This approach is used to tailor the operating mechanism of electrolyte-gated organic transistors, allowing for facile bulk doping and therefore efficient modulation of transistor channel conductance. Such transistors combine fast response with high current-to-voltage signal transduction necessary for active sensing and low-power circuit applications. Electrolyte-gated organic transistors offer low bias operation facilitated by direct contact of the transistor channel with an electrolyte. Their operation mode is generally defined by the dimensionality of charge transport, where a field-effect transistor allows for electrostatic charge accumulation at the electrolyte/semiconductor interface, whereas an organic electrochemical transistor (OECT) facilitates penetration of ions into the bulk of the channel, considered a slow process, leading to volumetric doping and electronic transport. Conducting polymer OECTs allow for fast switching and high currents through incorporation of excess, hygroscopic ionic phases, but operate in depletion mode. Here, we show that the use of glycolated side chains on a thiophene backbone can result in accumulation mode OECTs with high currents, transconductance, and sharp subthreshold switching, while maintaining fast switching speeds. Compared with alkylated analogs of the same backbone, the triethylene glycol side chains shift the mode of operation of aqueous electrolyte-gated transistors from interfacial to bulk doping/transport and show complete and reversible electrochromism and high volumetric capacitance at low operating biases. We propose that the glycol side chains facilitate hydration and ion penetration, without compromising electronic mobility, and suggest that this synthetic approach can be used to guide the design of organic mixed conductors.

Molecular Design of Semiconducting Polymers for High-Performance Organic Electrochemical Transistors

The organic electrochemical transistor (OECT), capable of transducing small ionic fluxes into electronic signals in an aqueous environment, is an ideal device to utilize in bioelectronic applications. Currently, most OECTs are fabricated with commercially available conducting poly(3,4-ethylenedioxythiophene) (PEDOT)-based suspensions and are therefore operated in depletion mode. Here, we present a series of semiconducting polymers designed to elucidate important structure–property guidelines required for accumulation mode OECT operation. We discuss key aspects relating to OECT performance such as ion and hole transport, electrochromic properties, operational voltage, and stability. The demonstration of our molecular design strategy is the fabrication of accumulation mode OECTs that clearly outperform state-of-the-art PEDOT-based devices, and show stability under aqueous operation without the need for formulation additives and cross-linkers.

PbS Nanoparticles Capped with Tetrathiafulvalenetetracarboxylate: Utilizing Energy Level Alignment for Efficient Carrier Transport

We fabricate a field-effect transistor by covalently functionalizing PbS nanoparticles with tetrathiafulvalenetetracarboxylate. Following experimental results from cyclic voltammetry and ambient-pressure X-ray photoelectron spectroscopy, we postulate a near-resonant alignment of the PbS 1Sh state and the organic HOMO, which is confirmed by atomistic calculations. Considering the large width of interparticle spacing, we observe an abnormally high field-effect hole mobility, which we attribute to the postulated resonance. In contrast to nanoparticle devices coupled through common short-chained ligands, our system maintains a large degree of macroscopic order as revealed by X-ray scattering. This provides a different approach to the design of hybrid organic-inorganic nanomaterials, circumvents the problem of phase segregation, and holds for versatile ways to design ordered, coupled nanoparticle thin films.

N-type organic electrochemical transistors with stability in water.

Organic electrochemical transistors (OECTs) are receiving significant attention due to their ability to efficiently transduce biological signals. A major limitation of this technology is that only p-type materials have been reported, which precludes the development of complementary circuits, and limits sensor technologies. Here, we report the first ever n-type OECT, with relatively balanced ambipolar charge transport characteristics based on a polymer that supports both hole and electron transport along its backbone when doped through an aqueous electrolyte and in the presence of oxygen. This new semiconducting polymer is designed specifically to facilitate ion transport and promote electrochemical doping. Stability measurements in water show no degradation when tested for 2 h under continuous cycling. This demonstration opens the possibility to develop complementary circuits based on OECTs and to improve the sophistication of bioelectronic devices.

The Effect of Processing Additives on Energetic Disorder in Highly Efficient Organic Photovoltaics: A Case Study on PBDTTT-C-T:PC71BM

Energetic disorder, an important parameter affecting the performance of organic photovoltaics, is significantly decreased upon the addition of processing additives in a highly efficient benzodithiophene-based copolymer blend (PBDTTT-C-T:PC71 BM). Wide-angle and small-angle X-ray scattering measurements suggest that the origin of this reduced energetic disorder is due to increased aggregation and a larger average fullerene domain size together with purer phases.

Naphthalenediimide Polymers with Finely Tuned In-Chain π-Conjugation: Electronic Structure, Film Microstructure, and Charge Transport Properties

Naphthalenediimide-based random copolymers (PNDI-TVTx) with different π-conjugated dithienylvinylene (TVT) versus π-nonconjugated dithienylethane (TET) unit ratios (x = 100→0%) are investigated. The PNDI-TVTx-transistor electron/hole mobilities are affected differently, a result rationalized by molecular orbital topologies and energies, with hole mobility vanishing but electron mobility decreasing only by ≈2.5 times when going from x = 100% to 40%.

Fused electron deficient semiconducting polymers for air stable electron transport

Conventional semiconducting polymer synthesis typically involves transition metal-mediated coupling reactions that link aromatic units with single bonds along the backbone. Rotation around these bonds contributes to conformational and energetic disorder and therefore potentially limits charge delocalisation, whereas the use of transition metals presents difficulties for sustainability and application in biological environments. Here we show that a simple aldol condensation reaction can prepare polymers where double bonds lock-in a rigid backbone conformation, thus eliminating free rotation along the conjugated backbone. This polymerisation route requires neither organometallic monomers nor transition metal catalysts and offers a reliable design strategy to facilitate delocalisation of frontier molecular orbitals, elimination of energetic disorder arising from rotational torsion and allowing closer interchain electronic coupling. These characteristics are desirable for high charge carrier mobilities. Our polymers with a high electron affinity display long wavelength NIR absorption with air stable electron transport in solution processed organic thin film transistors.Semiconducting polymers are usually prepared by transition metal mediated coupling reactions that cause problems for sustainability and biological applications. Here the authors synthesise fused electron deficient polymers that are air stable and have high electron affinities, via metal free aldol polymerisation reactions.

The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.