New Avenues for Organic Solar Cells Using Intrinsically Charge-Generating Materials.

The molecular electron acceptor material Y6 has been a key part of the most recent surge in organic solar cell sunlight-to-electricity power conversion efficiency, which is now approaching 20%. Numerous studies have sought to understand the fundamental photophysical reasons for the exceptional performance of Y6 and its growing family of structural derivatives. Though significant uncertainty about several details remains, many have concluded that initially photogenerated excited states rapidly convert into electron-hole charge pairs in the neat material. These charge pairs are characterized by location of the electron and hole on different Y6 molecules, in contrast to the Frenkel excitons that dominate the behavior of most organic semiconductor materials. Here, we summarize the current state of knowledge regarding Y6 photophysics and the key observations that have led to it. We then link this understanding to other advances, such as the role of quadrupolar fields in donor-acceptor blends, and the importance of molecular interactions and organization in providing the structural basis for Y6's properties. Finally, we turn our attention to ways of making use of the new photophysics of Y6, and suggest molecular doping, crystal structure tuning, and electric field engineering as promising avenues for future exploration.

Tuneable emission in single molecule dyads mediated by a charge transfer state.

The demand for fluorescent organic dyes across a broad range of applications has led to investigation into tuneable emission dyes. The tuneable nature of these dyes makes them desirable for applications in a variety of fields, including organic light-emitting diodes (OLEDs), optical sensing devices, and fluorescence imaging. In recent investigations, there have only been a handful of mechanisms used to tune emission. Herein, we present four novel perylene-acene dyads that undergo solvent tuneable emission, and propose a novel mechanism for this tuneability based on the presence of a charge transfer state. These dyes were shown to reach photoluminescence quantum efficiencies (PLQEs) as high as 45%, depending on the solvent, showing the ability for this mechanism to be used to access higher PLQE tuneable emission.

Exciton diffusion in amorphous organic semiconductors: Reducing simulation overheads with machine learning.

Simulations of exciton and charge hopping in amorphous organic materials involve numerous physical parameters. Each of these parameters must be computed from costly ab initio calculations before the simulation can commence, resulting in a significant computational overhead for studying exciton diffusion, especially in large and complex material datasets. While the idea of using machine learning to quickly predict these parameters has been explored previously, typical machine learning models require long training times, which ultimately contribute to simulation overheads. In this paper, we present a new machine learning architecture for building predictive models for intermolecular exciton coupling parameters. Our architecture is designed in such a way that the total training time is reduced compared to ordinary Gaussian process regression or kernel ridge regression models. Based on this architecture, we build a predictive model and use it to estimate the coupling parameters which enter into an exciton hopping simulation in amorphous pentacene. We show that this hopping simulation is able to achieve excellent predictions for exciton diffusion tensor elements and other properties as compared to a simulation using coupling parameters computed entirely from density functional theory. This result, along with the short training times afforded by our architecture, shows how machine learning can be used to reduce the high computational overheads associated with exciton and charge diffusion simulations in amorphous organic materials.

How Saliva Interferes with Colorimetric Gold Nanoparticle Aptasensors: Understanding and Mitigating Surface Interactions.

Colorimetric gold-nanoparticle-based biosensors are an attractive platform for the detection of small-molecule analytes. Taking advantage of the adsorption of DNA aptamer probes on AuNPs, these sensors can be simple, rapid, sensitive, selective, and cost-effective. These properties are important for rapid detection of drugs like methamphetamine in biological matrices. Saliva is a highly desirable matrix for development of diagnostic tests because saliva sampling is minimally invasive and drug levels relate to recent use rather than accumulation from historical use. However, saliva is a complex fluid that presents a multitude of challenges when applying colorimetric aggregation assays. Here, we show that the contents of saliva interfere with the sensor in two main ways: (i) suppressing color change signals due to proteins nonspecifically adsorbing to nanoparticles and (ii) blocking aggregation and generating false signals due to specific electrolytes that induce aggregation. With this knowledge, we examine strategies to mitigate these effects, including sample collection and pretreatment procedures. These measures ultimately result in a sensor that can detect methamphetamine spiked into saliva samples and suggest immense promise for the feasibility of these platforms for on-site diagnostic applications.

Triplets with a Twist: Ultrafast Intersystem Crossing in a Series of Electron Acceptor Materials Driven by Conformational Disorder.

Control over the populations of singlet and triplet excitons is key to organic semiconductor technologies. In different contexts, triplets can represent an energy loss pathway that must be managed (i.e., solar cells, light-emitting diodes, and lasers) or provide avenues to improve energy conversion (i.e., photon upconversion and multiplication systems). A key consideration in the interplay of singlet and triplet exciton populations in these systems is the rate of intersystem crossing (ISC). In this work, we design, measure, and model a series of new electron acceptor molecules and analyze them using a combination of ultrafast transient absorption and ultrafast broadband photoluminescence spectroscopies. We demonstrate that intramolecular triplet formation occurs within several hundred picoseconds in solution and is accelerated considerably in the solid state. Importantly, ISC occurs with sufficient rapidity to compete with charge formation in modern organic solar cells, implicating triplets in intrinsic exciton loss channels in addition to charge recombination. Density functional theory calculations reveal that ISC occurs in triplet excited states characterized by local deviations from orbital π-symmetry associated with rotationally flexible thiophene rings. In disordered films, structural distortions, therefore, result in significant increases in spin-orbit coupling, enabling rapid ISC. We demonstrate the generality of this proposal in an oligothiophene model system where ISC is symmetry-forbidden and show that conformational disorder introduced by the formation of a solvent glass accelerates ISC, outweighing the lower temperature and increased viscosity. This proposal sheds light on the factors responsible for facile ISC and provides a simple framework for molecular control over spin states.

The photoprotection mechanism in the black-brown pigment eumelanin.

The natural black-brown pigment eumelanin protects humans from high-energy UV photons by absorbing and rapidly dissipating their energy before proteins and DNA are damaged. The extremely weak fluorescence of eumelanin points toward nonradiative relaxation on the timescale of picoseconds or shorter. However, the extreme chemical and physical complexity of eumelanin masks its photoprotection mechanism. We sought to determine the electronic and structural relaxation pathways in eumelanin using three complementary ultrafast optical spectroscopy methods: fluorescence, transient absorption, and stimulated Raman spectroscopies. We show that photoexcitation of chromophores across the UV-visible spectrum rapidly generates a distribution of visible excitation energies via ultrafast internal conversion among neighboring coupled chromophores, and then all these excitations relax on a timescale of ∼4 ps without transferring their energy to other chromophores. Moreover, these picosecond dynamics are shared by the monomeric building block, 5,6-dihydroxyindole-2-carboxylic acid. Through a series of solvent and pH-dependent measurements complemented by quantum chemical modeling, we show that these ultrafast dynamics are consistent with the partial excited-state proton transfer from the catechol hydroxy groups to the solvent. The use of this multispectroscopic approach allows the minimal functional unit in eumelanin and the role of exciton coupling and excited-state proton transfer to be determined, and ultimately reveals the mechanism of photoprotection in eumelanin. This knowledge has potential for use in the design of new soft optical components and organic sunscreens.

Quasi-Homojunction Organic Nonfullerene Photovoltaics Featuring Fundamentals Distinct from Bulk Heterojunctions.

In contrast to classical bulk heterojunction (BHJ) in organic solar cells (OSCs), the quasi-homojunction (QHJ) with extremely low donor content (≤10 wt.%) is unusual and generally yields much lower device efficiency. Here, representative polymer donors and nonfullerene acceptors are selected to fabricate QHJ OSCs, and a complete picture for the operation mechanisms of high-efficiency QHJ devices is illustrated. PTB7-Th:Y6 QHJ devices at donor:acceptor (D:A) ratios of 1:8 or 1:20 can achieve 95% or 64% of the efficiency obtained from its BHJ counterpart at the optimal D:A ratio of 1:1.2, respectively, whereas QHJ devices with other donors or acceptors suffer from rapid roll-off of efficiency when the donors are diluted. Through device physics and photophysics analyses, it is observed that a large portion of free charges can be intrinsically generated in the neat Y6 domains rather than at the D/A interface. Y6 also serves as an ambipolar transport channel, so that hole transport as also mainly through Y6 phase. The key role of PTB7-Th is primarily to reduce charge recombination, likely assisted by enhancing quadrupolar fields within Y6 itself, rather than the previously thought principal roles of light absorption, exciton splitting, and hole transport.

Simultaneously Enhancing Exciton/Charge Transport in Organic Solar Cells by an Organoboron Additive.

Efficient exciton diffusion and charge transport play a vital role in advancing the power conversion efficiency (PCE) of organic solar cells (OSCs). Here, a facile strategy is presented to simultaneously enhance exciton/charge transport of the widely studied PM6:Y6-based OSCs by employing highly emissive trans-bis(dimesitylboron)stilbene (BBS) as a solid additive. BBS transforms the emissive sites from a more H-type aggregate into a more J-type aggregate, which benefits the resonance energy transfer for PM6 exciton diffusion and energy transfer from PM6 to Y6. Transient gated photoluminescence spectroscopy measurements indicate that addition of BBS improves the exciton diffusion coefficient of PM6 and the dissociation of PM6 excitons in the PM6:Y6:BBS film. Transient absorption spectroscopy measurements confirm faster charge generation in PM6:Y6:BBS. Moreover, BBS helps improve Y6 crystallization, and current-sensing atomic force microscopy characterization reveals an improved charge-carrier diffusion length in PM6:Y6:BBS. Owing to the enhanced exciton diffusion, exciton dissociation, charge generation, and charge transport, as well as reduced charge recombination and energy loss, a higher PCE of 17.6% with simultaneously improved open-circuit voltage, short-circuit current density, and fill factor is achieved for the PM6:Y6:BBS devices compared to the devices without BBS (16.2%).

Accounting for Interaction Kinetics between Gold Nanoparticles and Aptamers Enables High-Performance Colorimetric Sensors.

DNA aptamers have emerged as promising probes for challenging analytes that cannot be easily detected by conventional probes, including small-molecule targets. Among the different signal transduction approaches, gold nanoparticle (AuNP) aggregation assays have been widely used to generate a colorimetric response from aptamer-target interactions. This sensor design relies on the competition between the aptamer adsorbing to the AuNP surface versus interacting with the target, whereby target binding reduces the number of adsorbed aptamers that destabilizes AuNPs toward salt-induced aggregation, thereby inducing a color change. However, this thermodynamic framework overlooks the potential influence of interaction kinetics of different aptamer conformations with AuNP surfaces and with targets in solution or near surfaces. Here, we show that aptamers become more strongly adsorbed on AuNPs over time, and these trapped aptamers are less responsive toward the target analyte. By varying the sequence of addition in sensing assays, we demonstrate that these interaction kinetics have a significant effect on the sensor response and thereby produce an effective sensor for methamphetamine (meth) at biologically relevant levels in oral fluids. Along with underpinning new tools for assay development, this new knowledge also highlights the need for aptamer selection strategies that evolve aptamer sequences based on the functionality that they need to exhibit in an actual sensor.

Free charge photogeneration in a single component high photovoltaic efficiency organic semiconductor.

Organic photovoltaics (OPVs) promise cheap and flexible solar energy. Whereas light generates free charges in silicon photovoltaics, excitons are normally formed in organic semiconductors due to their low dielectric constants, and require molecular heterojunctions to split into charges. Recent record efficiency OPVs utilise the small molecule, Y6, and its analogues, which - unlike previous organic semiconductors - have low band-gaps and high dielectric constants. We show that, in Y6 films, these factors lead to intrinsic free charge generation without a heterojunction. Intensity-dependent spectroscopy reveals that 60-90% of excitons form free charges at AM1.5 light intensity. Bimolecular recombination, and hole traps constrain single component Y6 photovoltaics to low efficiencies, but recombination is reduced by small quantities of donor. Quantum-chemical calculations reveal strong coupling between exciton and CT states, and an intermolecular polarisation pattern that drives exciton dissociation. Our results challenge how current OPVs operate, and renew the possibility of efficient single-component OPVs.

Unraveling the binding mode of a methamphetamine aptamer: A spectroscopic and calorimetric study.

Nucleic-acid aptamers are bio-molecular recognition agents that bind to their targets with high specificity and affinity and hold promise in a range of biosensor and therapeutic applications. In the case of small-molecule targets, their small size and limited number of functional groups constitute challenges for their detection by aptamer-based biosensors because bio-recognition events may both be weak and produce poorly transduced signals. The binding affinity is principally used to characterize aptamer-ligand interactions; however, a structural understanding of bio-recognition is arguably more valuable in order to design a strong response in biosensor applications. Using a combination of nuclear magnetic resonance, circular dichroism, and isothermal titration calorimetry, we propose a binding model for a new methamphetamine aptamer and determine the main interactions driving complex formation. These measurements reveal only modest structural changes to the aptamer upon binding and are consistent with a conformational-selection binding model. The aptamer-methamphetamine complex formation was observed to be entropically driven, apparently involving hydrophobic and electrostatic interactions. Taken together, our results exemplify a means of elucidating small molecule-aptamer binding interactions, which may be decisive in the development of aptasensors and therapeutics and may contribute to a deeper understanding of interactions driving aptamer selection.

Extracting quantitative dielectric properties from pump-probe spectroscopy.

Optical pump-probe spectroscopy is a powerful tool for the study of non-equilibrium electronic dynamics and finds wide applications across a range of fields, from physics and chemistry to material science and biology. However, a shortcoming of conventional pump-probe spectroscopy is that photoinduced changes in transmission, reflection and scattering can simultaneously contribute to the measured differential spectra, leading to ambiguities in assigning the origin of spectral signatures and ruling out quantitative interpretation of the spectra. Ideally, these methods would measure the underlying dielectric function (or the complex refractive index) which would then directly provide quantitative information on the transient excited state dynamics free of these ambiguities. Here we present and test a model independent route to transform differential transmission or reflection spectra, measured via conventional optical pump-probe spectroscopy, to changes in the quantitative transient dielectric function. We benchmark this method against changes in the real refractive index measured using time-resolved Frequency Domain Interferometry in prototypical inorganic and organic semiconductor films. Our methodology can be applied to existing and future pump-probe data sets, allowing for an unambiguous and quantitative characterisation of the transient photoexcited spectra of materials. This in turn will accelerate the adoption of pump-probe spectroscopy as a facile and robust materials characterisation and screening tool.

Broadband Optical Phase Modulation by Colloidal CdSe Quantum Wells.

Two-dimensional (2D) semiconductors are primed to realize a variety of photonic devices that rely on the transient properties of photogenerated charges, yet little is known on the change of the refractive index. The associated optical phase changes can be beneficial or undesired depending on the application, but require proper quantification. Measuring optical phase modulation of dilute 2D materials is, however, not trivial with common methods. Here, we demonstrate that 2D colloidal CdSe quantum wells, a useful model system, can modulate the phase of light across a broad spectrum using a femtosecond interferometry method. Next, we develop a toolbox to calculate the time-dependent refractive index of colloidal 2D materials from widely available transient absorption experiments using a modified effective medium algorithm. Our results show that the excitonic features of 2D materials result in broadband, ultrafast, and sizable phase modulation, even extending to the near infrared because of intraband transitions.

Stimulated Emission through an Electron-Hole Plasma in Colloidal CdSe Quantum Rings.

Colloidal CdSe quantum rings (QRs) are a recently developed class of nanomaterials with a unique topology. In nanocrystals with more common shapes, such as dots and platelets, the photophysics is consistently dominated by strongly bound electron-hole pairs, so-called excitons, regardless of the charge carrier density. Here, we show that charge carriers in QRs condense into a hot uncorrelated plasma state at high density. Through strong band gap renormalization, this plasma state is able to produce broadband and sizable optical gain. The gain is limited by a second-order, yet radiative, recombination process, and the buildup is counteracted by a charge-cooling bottleneck. Our results show that weakly confined QRs offer a unique system to study uncorrelated electron-hole dynamics in nanoscale materials.

Efficient energy transport in an organic semiconductor mediated by transient exciton delocalization.

Efficient energy transport is desirable in organic semiconductor (OSC) devices. However, photogenerated excitons in OSC films mostly occupy highly localized states, limiting exciton diffusion coefficients to below ~10-2 cm2/s and diffusion lengths below ~50 nm. We use ultrafast optical microscopy and nonadiabatic molecular dynamics simulations to study well-ordered poly(3-hexylthiophene) nanofiber films prepared using living crystallization-driven self-assembly, and reveal a highly efficient energy transport regime: transient exciton delocalization, where energy exchange with vibrational modes allows excitons to temporarily re-access spatially extended states under equilibrium conditions. We show that this enables exciton diffusion constants up to 1.1 ± 0.1 cm2/s and diffusion lengths of 300 ± 50 nm. Our results reveal the dynamic interplay between localized and delocalized exciton configurations at equilibrium conditions, calling for a re-evaluation of exciton dynamics and suggesting design rules to engineer efficient energy transport in OSC device architectures not based on restrictive bulk heterojunctions.

Bandgap control in two-dimensional semiconductors via coherent doping of plasmonic hot electrons.

Bandgap control is of central importance for semiconductor technologies. The traditional means of control is to dope the lattice chemically, electrically or optically with charge carriers. Here, we demonstrate a widely tunable bandgap (renormalisation up to 550 meV at room-temperature) in two-dimensional (2D) semiconductors by coherently doping the lattice with plasmonic hot electrons. In particular, we integrate tungsten-disulfide (WS2) monolayers into a self-assembled plasmonic crystal, which enables coherent coupling between semiconductor excitons and plasmon resonances. Accompanying this process, the plasmon-induced hot electrons can repeatedly fill the WS2 conduction band, leading to population inversion and a significant reconstruction in band structures and exciton relaxations. Our findings provide an effective measure to engineer optical responses of 2D semiconductors, allowing flexibilities in design and optimisation of photonic and optoelectronic devices.

Single 3.3 fs multiple plate compression light source in ultrafast transient absorption spectroscopy.

Ultrafast transient absorption spectroscopy is a powerful tool to reveal excited state dynamics in various materials. Conventionally, probe pulses are generated via bulk supercontinuum generation or (noncollinear) optical parametric amplifiers whilst pump pulses are generated separately using (noncollinear) optical parametric amplifiers. These systems are limited by either their spectral density, stability, spectral range, and/or temporal compressibility. Recently, a new intense broadband light source is being developed, the multi-plate compression, which promises to overcome these limitations. In this paper, we analyze the supercontinuum generated by a single Multiple Plate Compression system to set a benchmark for its use in the field of ultrafast pump-probe spectroscopy. We have compressed the supercontinuum to 3.3 fs using chirp mirrors alone, making it an excellent candidate for pump-probe experiments requiring high temporal resolution. Furthermore, the single light source can be used to generate both probe and pump pulses due to its high spectral density (>14.5 nJ/nm) between 490 and 890 nm. The intensity has an average shot-to-shot relative standard deviation of 4.6 % over 490 to 890 nm, calculated over 2,000 sequential shots. By using only 1,000 shot pairs, a [Formula: see text] noise level of [Formula: see text] RMS is achieved. Finally, as a proof of concept, the transient absorption spectrum of a methylammonium lead iodide perovskite film is taken, showing great signal to noise with only 1,000 shot pairs. These results show great potential for the employment of this technique in other spectroscopic techniques such as coherent multidimensional spectroscopy.

Unraveling the influence of non-fullerene acceptor molecular packing on photovoltaic performance of organic solar cells.

In non-fullerene organic solar cells, the long-range structure ordering induced by end-group π-π stacking of fused-ring non-fullerene acceptors is considered as the critical factor in realizing efficient charge transport and high power conversion efficiency. Here, we demonstrate that side-chain engineering of non-fullerene acceptors could drive the fused-ring backbone assembly from a π-π stacking mode to an intermixed packing mode, and to a non-stacking mode to refine its solid-state properties. Different from the above-mentioned understanding, we find that close atom contacts in a non-stacking mode can form efficient charge transport pathway through close side atom interactions. The intermixed solid-state packing motif in active layers could enable organic solar cells with superior efficiency and reduced non-radiative recombination loss compared with devices based on molecules with the classic end-group π-π stacking mode. Our observations open a new avenue in material design that endows better photovoltaic performance.

An Optimized Fibril Network Morphology Enables High-Efficiency and Ambient-Stable Polymer Solar Cells.

Morphological stability is crucially important for the long-term stability of polymer solar cells (PSCs). Many high-efficiency PSCs suffer from metastable morphology, resulting in severe device degradation. Here, a series of copolymers is developed by manipulating the content of chlorinated benzodithiophene-4,8-dione (T1-Cl) via a random copolymerization approach. It is found that all the copolymers can self-assemble into a fibril nanostructure in films. By altering the T1-Cl content, the polymer crystallinity and fibril width can be effectively controlled. When blended with several nonfullerene acceptors, such as TTPTT-4F, O-INIC3, EH-INIC3, and Y6, the optimized fibril interpenetrating morphology can not only favor charge transport, but also inhibit the unfavorable molecular diffusion and aggregation in active layers, leading to excellent morphological stability. The work demonstrates the importance of optimization of fibril network morphology in realizing high-efficiency and ambient-stable PSCs, and also provides new insights into the effect of chemical structure on the fibril network morphology and photovoltaic performance of PSCs.