Joshua H. Carpenter

Highly Efficient Organic Solar Cells with Improved Vertical Donor-Acceptor Compositional Gradient Via an Inverted Off-Center Spinning Method.

A novel, yet simple solution fabrication technique to address the trade-off between photocurrent and fill factor in thick bulk heterojunction organic solar cells is described. The inverted off-center spinning technique promotes a vertical gradient of the donor-acceptor phase-separated morphology, enabling devices with near 100% internal quantum efficiency and a high power conversion efficiency of 10.95%.

Rigidifying Nonplanar Perylene Diimides by Ring Fusion Toward Geometry-Tunable Acceptors for High-Performance Fullerene-Free Solar Cells.

Rigid fused perylene diimide (PDI) dimers bridged with heterocycles exhibit superior photovoltaic performance compared to their unfused semiflexible analogues. Changing the chalcogen atoms in the aromatic bridges gradually increases the twist angles between the two PDI planes, leading to a varied morphology in which the one bridged by thiophene achieves a balance and shows the best efficiency of 6.72%.

Influence of Regio- and Chemoselectivity on the Properties of Fluoro-Substituted Thienothiophene and Benzodithiophene Copolymers

By studying the regio- and chemoselectivity of fluoro-substituted thienothiophene and benzodithiophene copolymers, we found polymers made from conventional one-pot polycondensation reaction consist of two distinctly different segments with a ratio of 0.36/0.64. Through further comparative studies of neat regioregular polymers based on each individual segment, we have identified the specific segment that contributes to the superior absorption, packing order, and charge mobility in the corresponding polymers. The unique structure-property relationships are the result of cooperative molecular arrangements of the key segment and noncovalent interaction between the fluoro group and the aromatic proton on the thiophene side-chain of the polymers.

Quantitative relations between interaction parameter, miscibility and function in organic solar cells

Although it is known that molecular interactions govern morphology formation and purity of mixed domains of conjugated polymer donors and small-molecule acceptors, and thus largely control the achievable performance of organic solar cells, quantifying interaction–function relations has remained elusive. Here, we first determine the temperature-dependent effective amorphous–amorphous interaction parameter, χaa(T), by mapping out the phase diagram of a model amorphous polymer:fullerene material system. We then establish a quantitative ‘constant-kink-saturation’ relation between χaa and the fill factor in organic solar cells that is verified in detail in a model system and delineated across numerous high- and low-performing materials systems, including fullerene and non-fullerene acceptors. Our experimental and computational data reveal that a high fill factor is obtained only when χaa is large enough to lead to strong phase separation. Our work outlines a basis for using various miscibility tests and future simulation methods that will significantly reduce or eliminate trial-and-error approaches to material synthesis and device fabrication of functional semiconducting blends and organic blends in general.This work reports a quantitative investigation of the interaction parameter and miscibility of donor and acceptor organic molecules and their relationship with the fill factor and photovoltaic performance of bulk-heterojunction organic solar cells.

Fluctuation modes of nanoconfined DNA.

We report an experimental investigation of the magnitude of length and density fluctuations in DNA that has been stretched in nanofluidic channels. We find that the experimental data can be described using a one-dimensional overdamped oscillator chain with nonzero equilibrium spring length and that a chain of discrete oscillators yields a better description than a continuous chain. We speculate that the scale of these discrete oscillators coincides with the scale at which the finite extensibility of the polymer manifests itself. We discuss how the measurement process influences the apparent measured dynamic properties, and outline requirements for the recovery of true physical quantities.

Density fluctuations dispersion relationship for a polymer confined to a nanotube

DNA confined to rigid nanotubes shows density fluctuations around its stretched equilibrium conformation. We report an experimental investigation of the length-scale dependent dynamics of these density fluctuations. We find that for highly elongated molecules a Rouse description is consistent with observations at sufficiently large length scales. We further find that for strongly fluctuating molecules, or short length scales, such Rouse modes cannot be detected due to strong mixing of fluctuation modes.

A regioregular conjugated polymer for high performance thick-film organic solar cells without processing additive

To address the challenges of reliability and facile processability of a benchmark polymer PTB7-Th, one of the most prevailing donor materials utilized in organic solar cells, we have systematically investigated the correlations among chemical structure, processing, morphology and device performance. Our study reveals that the regioregularity of PTB7-Th plays a crucial role in polymer properties as well as the fabrication process of devices. The regioregular polymer entirely consisting of favourable repeat units is capable of realizing high power conversion efficiency (>10%) in organic solar cells without using any solvent additive and tedious processing treatments. More importantly, the device efficiency based on this regioregular polymer is insensitive over a broad range of film thickness (from 100 nm to >400 nm). This will be very advantageous for manufacturing highly efficient and stable polymer solar cells by high throughput fabrication processes.

Integrated circuits based on conjugated polymer monolayer

It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm2 V−1 s−1. The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Real logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.Polymer monolayer field-effect transistors hold promise for faster circuits, but their performance is currently limited by the polymer packing disorder. Li et al. pre-aggregate polymers in a solution to achieve high carrier mobility of 3 cm2 V−1s−1 in monolayers and utilize them in integrated circuits.

The Role of FRET in Non-Fullerene Organic Solar Cells: Implications for Molecular Design

Non-fullerene acceptors (NFAs) have been demonstrated to be promising candidates for highly efficient organic photovoltaic (OPV) devices. The tunability of absorption characteristics of NFAs can be used to make OPVs with complementary donor-acceptor absorption to cover a broad range of the solar spectrum. However, both charge transfer from donor to acceptor moieties and energy (energy) transfer from high-bandgap to low-bandgap materials are possible in such structures. Here, we show that when charge transfer and exciton transfer processes are both present, the coexistence of excitons in both domains can cause a loss mechanism. Charge separation of excitons in a low-bandgap material is hindered due to exciton population in the larger bandgap acceptor domains. Our results further show that excitons in low-bandgap material should have a relatively long lifetime compared to the transfer time of excitons from higher bandgap material in order to contribute to the charge separation. These observations provide significant guidance for design and development of new materials in OPV applications.