Matrix Dynamics and Their Crucial Role in Non-radiative Decay during Thermally Activated Delayed Fluorescence.

We investigated the interplay of matrix dynamics with the molecular dynamics of a thermally activated delayed fluorescence (TADF) emitter, NAI-DMAC, to identify factors that influence the photophysical processes leading to TADF. The matrix dynamics surrounding NAI-DMAC molecules were varied continuously from the liquid to the solid state by depositing toluene solutions containing poly(methyl methacrylate) (PMMA) and NAI-DMAC onto optical substrates. We monitored changes of the NAI-DMAC emission as the liquid films dried to form solid PMMA films using temperature- and time-resolved photoluminescence spectroscopy. We observed that, in low-viscosity solutions, the proportion of delayed fluorescence from NAI-DMAC was much smaller than that of prompt fluorescence, indicating that negligible TADF occurred in the low-viscosity environment. However, as the viscosity of the environment diverged at the final stages of dry-down to form solid PMMA films, the delayed fluorescence component of NAI-DMAC emission was extended to longer time scales and increased in amplitude relative to prompt emission as the temperature increased─signatures that TADF occurred in the solid state as expected. Our findings reveal the influence that matrix dynamics have on the competition between conformational motion needed to access emissive states and undergo TADF versus larger amplitude structural fluctuations that lead to non-radiative decay. Insights from these studies will inform ongoing work to understand and predict how host matrices used in organic light-emitting devices can be designed to maximize the radiative properties of TADF emitters by allowing molecular motion needed to undergo TADF while restricting larger amplitude motion leading to non-radiative decay.

Interplay of molecular dynamics and radiative decay of a TADF emitter in a glass-forming liquid.

We investigate the role of molecular dynamics in the luminescent properties of a prototypical thermally activated delayed fluorescence (TADF) emitter, NAI-DMAC, in solution using a combination of temperature dependent time-resolved photoluminescence and absorption spectroscopies. We use a glass forming liquid, 2-methylfuran, to introduce an abrupt change in the temperature dependent diffusion dynamics of the solvent and examine the influence this has on the emission intensity of NAI-DMAC molecules. Comparison of experiment with first principles molecular dynamics simulations reveals that the emission intensity of NAI-DMAC molecules follows the temperature-dependent self-diffusion dynamics of the solvent. A marked reduction of emission intensity is observed as the temperature decreases toward the glass transition because the rate at which NAI-DMAC molecules can access emissive molecular conformations is greatly reduced. Below the glass transition, the diffusion dynamics of the solvent changes more slowly with temperature, which causes the emission intensity to decrease more slowly as well. The combination of experiment and computation suggests a pathway by which TADF emitters may transiently access a distribution of conformational states and avoid the need for an average conformation that strikes a balance between lower singlet-triplet energy splittings versus higher emission probabilities.

Influence of Ligand Structure on Excited State Surface Chemistry of Lead Sulfide Quantum Dots.

The ligand-nanocrystal boundaries of colloidal quantum dots (QDs) mediate the primary energy and electron transfer processes that underpin photochemical and photocatalytic transformations at their surfaces. We use mid-infrared transient absorption spectroscopy to reveal the influence that ligand structure and bonding to nanocrystal surfaces have on the changes of the excited state surface chemistry of this boundary in PbS QDs and the corresponding impact on charge transfer processes between nanocrystals. We demonstrate that oleate ligands undergo marked changes in their bonding to surfaces in the excitonic excited states of the nanocrystals, indicating that oleate passivated PbS surfaces undergo significant structural changes following photoexcitation. These changes can impact the surface mobility of the ligands and the ability of redox shuttles to approach the nanocrystal surfaces to undergo charge transfer in photocatalytic reactions. In contrast, markedly different transient vibrational features are observed in iodide/mercaptoproprionic acid passivated PbS QD films that result from charge transfer between neighboring nanocrystals and localization of holes at the nanocrystal surfaces near MPA ligands. This ability to distinguish the influence that excitonic excited states vs charge transfer processes have on the surface chemistry of the ligand-nanocrystal boundary lays the groundwork for exploration of how this boundary can be understood and controlled for the design of nanocrystalline materials tailored for specific applications in solar energy harvesting and photocatalytic reactions.

Reproducibility of cavity-enhanced chemical reaction rates in the vibrational strong coupling regime.

One of the most exciting and debated aspects of polariton chemistry is the possibility that chemical reactions can be catalyzed by vibrational strong coupling (VSC) with confined optical modes in the absence of external illumination. Here, we report an attempt to reproduce the enhanced rate of cyanate ion hydrolysis reported by Hiura et al. [chemRxiv:7234721 (2019)] when the collective OH stretching vibrations of water (which is both the solvent and a reactant) are strongly coupled to a Fabry-Pérot cavity mode. Using a piezo-tunable microcavity, we reproduce the reported vacuum Rabi splitting but fail to observe any change in the reaction rate as the cavity thickness is tuned in and out of the strong coupling regime during a given experiment. These findings suggest that there are subtleties involved in successfully realizing VSC-catalyzed reaction kinetics and therefore motivate a broader effort within the community to validate the claims of polariton chemistry in the dark.

A General Strategy to Enhance Donor-Acceptor Molecules Using Solvent-Excluding Substituents.

While organic donor-acceptor (D-A) molecules are widely employed in multiple areas, the application of more D-A molecules could be limited because of an inherent polarity sensitivity that inhibits photochemical processes. Presented here is a facile chemical modification to attenuate solvent-dependent mechanisms of excited-state quenching through addition of a ß-carbonyl-based polar substituent. The results reveal a mechanism wherein the ß-carbonyl substituent creates a structural buffer between the donor and the surrounding solvent. Through computational and experimental analyses, it is demonstrated that the ß-carbonyl simultaneously attenuates two distinct solvent-dependent quenching mechanisms. Using the ß-carbonyl substituent, improvements in the photophysical properties of commonly used D-A fluorophores and their enhanced performance in biological imaging are shown.

Vibrational probe of the origin of singlet exciton fission in TIPS-pentacene solutions.

We use native vibrational modes of the model singlet fission chromophore 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) to examine the origins of singlet fission in solution between molecules that are not tethered by a covalent linkage. We use the C-H stretch modes of TIPS side groups of TIPS-Pn to demonstrate that singlet fission does not occur by diffusive encounter of independent molecules in solution. Instead, TIPS-Pn molecules aggregate in solution through their TIPS side groups. This aggregation breaks the symmetry of the TIPS-Pn molecules and enables the formation of triplets to be probed through the formally symmetry forbidden symmetric alkyne stretch mode of the TIPS side groups. The alkyne stretch modes of TIPS-Pn are sensitive to the electronic excited states present during the singlet fission reaction and provide unique signatures of the formation of triplets following the initial separation of triplet pair intermediates. These findings highlight the opportunity to leverage structural information from vibrational modes to better understand intermolecular interactions that lead to singlet fission.

Charged Polaron Polaritons in an Organic Semiconductor Microcavity.

We report strong coupling between light and polaron optical excitations in a doped organic semiconductor microcavity at room temperature. Codepositing MoO_{3} and the hole transport material 4, 4^{'}-cyclohexylidenebis[N, N-bis(4-methylphenyl)benzenamine] introduces a large hole density with a narrow linewidth optical transition centered at 1.8 eV and an absorption coefficient exceeding 10^{4} cm^{-1}. Coupling this transition to a Fabry-Pérot cavity mode yields upper and lower polaron polariton branches that are clearly resolved in angle-dependent reflectivity with a vacuum Rabi splitting ℏΩ_{R}>0.3 eV. This result establishes a path to electrically control polaritons in organic semiconductors and may lead to increased polariton-polariton Coulombic interactions that lower the threshold for nonlinear phenomena such as polariton condensation and lasing.

Using molecular vibrations to probe exciton delocalization in films of perylene diimides with ultrafast mid-IR spectroscopy.

Ultrafast vibrational spectroscopy in the mid-infrared was used to directly probe the delocalization of excitons in two different perylenediimide (PDI) derivatives that are predicted to preclude the formation of excimers, which can act as trap sites for excited state energy in organic semiconductors. We identified vibrational modes within the conjugated C-C stretch modes of PDI molecules whose frequencies reported the interactions of molecules within delocalized excitonic states. The vibrational linewidths of these modes, which we call intermolecular coordinate coupled (ICC) modes, provided a direct probe of the extent of exciton delocalization among the PDI molecules, which was confirmed using X-ray diffraction and electro-absorption spectroscopy. We show that a slip-stacked geometry among the PDI molecules in their crystals promotes delocalized charge-transfer (CT) excitons, while localized Frenkel excitons tend to form in crystals with helical, columnar stacking geometries. Because all molecules possess vibrational modes, the use of ultrafast mid-infrared spectroscopy to measure ICC vibrational modes offers a new approach to examine exciton delocalization in a variety of small molecule electron acceptors for optoelectronic and organic photovoltaic applications.

Dynamic Exchange During Triplet Transport in Nanocrystalline TIPS-Pentacene Films.

The multiplication of excitons in organic semiconductors via singlet fission offers the potential for photovoltaic cells that exceed the Shockley-Quiesser limit for single-junction devices. To fully utilize the potential of singlet fission sensitizers in devices, it is necessary to understand and control the diffusion of the resultant triplet excitons. In this work, a new processing method is reported to systematically tune the intermolecular order and crystalline structure in films of a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn), without the need for chemical modifications. A combination of transient absorption spectroscopy and quantitative materials characterization enabled a detailed examination of the distance- and time-dependence of triplet exciton diffusion following singlet fission in these nanocrystalline TIPS-Pn films. Triplet-triplet annihilation rate constants were found to be representative of the weighted average of crystalline and amorphous phases in TIPS-Pn films comprising a mixture of phases. Adopting a diffusion model used to describe triplet-triplet annihilation, the triplet diffusion lengths for nanocrystalline and amorphous films of TIPS-Pn were estimated to be ∼75 and ∼14 nm, respectively. Importantly, the presence of even a small fraction (<10%) of the amorphous phase in the TIPS-Pn films greatly decreased the ultimate triplet diffusion length, suggesting that pure crystalline materials may be essential to efficiently harvest multiplied triplets even when singlet fission occurs on ultrafast time scales.

Probing the electrostatics of active site microenvironments along the catalytic cycle for Escherichia coli dihydrofolate reductase.

Electrostatic interactions play an important role in enzyme catalysis by guiding ligand binding and facilitating chemical reactions. These electrostatic interactions are modulated by conformational changes occurring over the catalytic cycle. Herein, the changes in active site electrostatic microenvironments are examined for all enzyme complexes along the catalytic cycle of Escherichia coli dihydrofolate reductase (ecDHFR) by incorporation of thiocyanate probes at two site-specific locations in the active site. The electrostatics and degree of hydration of the microenvironments surrounding the probes are investigated with spectroscopic techniques and mixed quantum mechanical/molecular mechanical (QM/MM) calculations. Changes in the electrostatic microenvironments along the catalytic environment lead to different nitrile (CN) vibrational stretching frequencies and (13)C NMR chemical shifts. These environmental changes arise from protein conformational rearrangements during catalysis. The QM/MM calculations reproduce the experimentally measured vibrational frequency shifts of the thiocyanate probes across the catalyzed hydride transfer step, which spans the closed and occluded conformations of the enzyme. Analysis of the molecular dynamics trajectories provides insight into the conformational changes occurring between these two states and the resulting changes in classical electrostatics and specific hydrogen-bonding interactions. The electric fields along the CN axes of the probes are decomposed into contributions from specific residues, ligands, and solvent molecules that make up the microenvironments around the probes. Moreover, calculation of the electric field along the hydride donor-acceptor axis, along with decomposition of this field into specific contributions, indicates that the cofactor and substrate, as well as the enzyme, impose a substantial electric field that facilitates hydride transfer. Overall, experimental and theoretical data provide evidence for significant electrostatic changes in the active site microenvironments due to conformational motion occurring over the catalytic cycle of ecDHFR.

Vibrational spectroscopy of electronic processes in emerging photovoltaic materials.

Molecules affect the electronic properties of many emerging materials, ranging from organic thin film transistors and light emitting diodes for flexible displays to colloidal quantum dots (CQDs) used in solution processed photovoltaics and photodetectors. For example, the interactions of conjugated molecules not only influence morphological and charge transport properties of organic photovoltaic (OPV) materials, but they also determine the primary photophysical events leading to charge generation. Ligand-nanocrystal interactions affect the density and energetic distributions of trap states, which in turn influence minority carrier transport in CQD photovoltaics. Therefore, it is critical for scientists to understand how the underlying molecular structures and morphologies determine the electronic properties of emerging materials. Recently, chemists have used vibrational spectroscopy to study electronic processes in emerging materials, and been able to directly measure the influence molecular properties have on those processes. Time-resolved vibrational spectroscopy is uniquely positioned to examine molecular species involved in electronic processes because it combines ultrafast time resolution with measurement of the vibrational spectra of molecules. For instance, molecules at the electron donor/acceptor interfaces in OPV materials have unique vibrational features because vibrational frequencies of molecules are sensitive to their local molecular environments. Through ultrafast vibrational spectroscopy, researchers can directly examine the dynamics of charge transfer (CT) state formation and dissociation to form charge separated states specifically at donor/acceptor interfaces. Vibrational modes of ligands are also sensitive to their bonding interactions with nanocrystal surfaces, which enables chemists to directly probe the molecular nature of charge trap states in colloidal quantum dot solids. Because of the ability to connect electrical properties with the underlying molecular species, scientists can use ultrafast vibrational spectroscopy to address fundamental challenges in the development of emerging electronic materials. In this Account, we focus on two applications of vibrational spectroscopy to examine electronic processes in OPV and CQD photovoltaic materials. In the first application, we examine archetypal classes of electron acceptors in OPV materials and reveal how their molecular structures influence the dynamics and energetic barriers to CT state formation and dissociation. In the second application, we discuss the surface chemistry of ligand-nanocrystal interactions and how they impact the density and energetic distribution of charge trap states in CQD photovoltaic materials. Through direct observations of the vibrational features of ligands attached to surface trap states, we can obtain valuable insights into the nature of charge traps and begin to understand pathways for their elimination. We expect that further examination of electronic processes in materials using ultrafast vibrational spectroscopy will lead to new design rules in support of continued materials development efforts.

Reversible Ligand Detachment from CdSe Quantum Dots Following Photoexcitation.

The nanocrystal-ligand boundaries of colloidal quantum dots (QDs) mediate charge and energy transfer processes that underpin photochemical and photocatalytic transformations at their surfaces. We used time-resolved infrared spectroscopy combined with transient electronic spectroscopy to probe vibrational modes of the carboxylate anchoring groups of stearate ligands attached to cadmium selenide (CdSe) QDs that were optically excited in solid nanocrystal films. The vibrational frequencies of surface-bonded carboxylate groups revealed their interactions with surface-localized holes in the excited states of the QDs. We also observed transient and reversible photoinduced ligand detachment from CdSe nanocrystals within their excited state lifetime. By probing both surface charge distributions and ligand dynamics on QDs in their excited states, we open a pathway to explore how the nanocrystal-ligand boundary can be understood and controlled for the design of QD architectures that most effectively drive charge transfer processes in solar energy harvesting and photoredox catalysis applications.

Tuning polymer-backbone coplanarity and conformational order to achieve high-performance printed all-polymer solar cells.

All-polymer solar cells (all-PSCs) offer improved morphological and mechanical stability compared with those containing small-molecule-acceptors (SMAs). They can be processed with a broader range of conditions, making them desirable for printing techniques. In this study, we report a high-performance polymer acceptor design based on bithiazole linker (PY-BTz) that are on par with SMAs. We demonstrate that bithiazole induces a more coplanar and ordered conformation compared to bithiophene due to the synergistic effect of non-covalent backbone planarization and reduced steric encumbrances. As a result, PY-BTz shows a significantly higher efficiency of 16.4% in comparison to the polymer acceptors based on commonly used thiophene-based linkers (i.e., PY-2T, 9.8%). Detailed analyses reveal that this improvement is associated with enhanced conjugation along the backbone and closer interchain π-stacking, resulting in higher charge mobilities, suppressed charge recombination, and reduced energetic disorder. Remarkably, an efficiency of 14.7% is realized for all-PSCs that are solution-sheared in ambient conditions, which is among the highest for devices prepared under conditions relevant to scalable printing techniques. This work uncovers a strategy for promoting backbone conjugation and planarization in emerging polymer acceptors that can lead to superior all-PSCs.

Dilute Rhenium Doping and its Impact on Defects in MoS2.

Substitutionally doped 2D transition metal dichalcogenides are primed for next-generation device applications such as field effect transistors (FET), sensors, and optoelectronic circuits. In this work, we demonstrate substitutional rhenium (Re) doping of MoS2 monolayers with controllable concentrations down to 500 ppm by metal-organic chemical vapor deposition (MOCVD). Surprisingly, we discover that even trace amounts of Re lead to a reduction in sulfur site defect density by 5-10×. Ab initio models indicate the origin of the reduction is an increase in the free-energy of sulfur-vacancy formation at the MoS2 growth-front when Re is introduced. Defect photoluminescence (PL) commonly seen in undoped MOCVD MoS2 is suppressed by 6× at 0.05 atomic percent (at. %) Re and completely quenched with 1 at. % Re. Furthermore, we find that Re-MoS2 transistors exhibit a 2× increase in drain current and carrier mobility compared to undoped MoS2, indicating that sulfur vacancy reduction improves carrier transport in the Re-MoS2. This work provides important insights on how dopants affect 2D semiconductor growth dynamics, which can lead to improved crystal quality and device performance.

Colloidal-quantum-dot photovoltaics using atomic-ligand passivation.

Colloidal-quantum-dot (CQD) optoelectronics offer a compelling combination of solution processing and spectral tunability through quantum size effects. So far, CQD solar cells have relied on the use of organic ligands to passivate the surface of the semiconductor nanoparticles. Although inorganic metal chalcogenide ligands have led to record electronic transport parameters in CQD films, no photovoltaic device has been reported based on such compounds. Here we establish an atomic ligand strategy that makes use of monovalent halide anions to enhance electronic transport and successfully passivate surface defects in PbS CQD films. Both time-resolved infrared spectroscopy and transient device characterization indicate that the scheme leads to a shallower trap state distribution than the best organic ligands. Solar cells fabricated following this strategy show up to 6% solar AM1.5G power-conversion efficiency. The CQD films are deposited at room temperature and under ambient atmosphere, rendering the process amenable to low-cost, roll-by-roll fabrication.

Excited-State Dynamics of 5,14- vs 6,13-Bis(trialkylsilylethynyl)-Substituted Pentacenes: Implications for Singlet Fission.

Singlet fission is a process in conjugated organic materials that has the potential to considerably improve the performance of devices in many applications, including solar energy conversion. In any application involving singlet fission, efficient triplet harvesting is essential. At present, not much is known about molecular packing arrangements detrimental to singlet fission. In this work, we report a molecular packing arrangement in crystalline films of 5,14-bis(triisopropylsilylethynyl)-substituted pentacene, specifically a local (pairwise) packing arrangement, responsible for complete quenching of triplet pairs generated via singlet fission. We first demonstrate that the energetic condition necessary for singlet fission is satisfied in amorphous films of the 5,14-substituted pentacene derivative. However, while triplet pairs form highly efficiently in the amorphous films, only a modest yield of independent triplets is observed. In crystalline films, triplet pairs also form highly efficiently, although independent triplets are not observed because triplet pairs decay rapidly and are quenched completely. We assign the quenching to a rapid nonadiabatic transition directly to the ground state. Detrimental quenching is observed in crystalline films of two additional 5,14-bis(trialkylsilylethynyl)-substituted pentacenes with either ethyl or isobutyl substituents. Developing a better understanding of the losses identified in this work, and associated molecular packing, may benefit overcoming losses in solids of other singlet fission materials.

Vibrational solvatochromism in organic photovoltaic materials: method to distinguish molecules at donor/acceptor interfaces.

We report the observation of vibrational solvatochromism in organic photovoltaic materials. The frequency of the carbonyl (C=O) stretch of the methyl ester group of the functionalized fullerene, PCBM, is sensitive to the local phase separated morphology of polymer blends and bilayers incorporating the fullerene. In particular, PCBM molecules at interfaces with conjugated polymers exhibit higher frequency carbonyl stretch vibrations in comparison to molecules imbedded in the interiors of PCBM clusters/layers. The resulting frequency gradient was recently used to examine the dynamics of charge photogeneration in a blend of the conjugated polymer, CN-MEH-PPV, with PCBM. In this contribution, we explore the origin of the frequency shift and show that it arises from variations in the inhomogeneous solvent environments experienced by PCBM molecules as a result of phase separation in the polymer blend.

Does Dipolar Motion of Organic Cations Affect Polaron Dynamics and Bimolecular Recombination in Halide Perovskites?

The role of dipolar motion of organic cations in the A-sites of halide perovskites has been debated in an effort to understand why these materials possess such remarkable properties. Here, we show that the dipolar motion of cations such as methylammonium (MA) or formamidinium (FA) versus cesium (Cs) does not influence large polaron binding energies, delocalization lengths, formation times, or bimolecular recombination lifetimes in lead bromide perovskites containing only one type of A-site cation. We directly probe the transient absorption spectra of large polarons throughout the entire mid-infrared and resolve their dynamics on time scales from sub-100 fs to sub-µs using time-resolved mid-infrared spectroscopy. Our findings suggest that the improved optoelectronic properties reported of halide perovskites with mixed A-site cations may result from synergy among the cations and how their mixture modulates the structure and dynamics of the inorganic lattice rather than from the dipolar properties of the cations themselves.

Dynamic Ligand Surface Chemistry of Excited PbS Quantum Dots.

The ligand shell around colloidal quantum dots mediates the electron and energy transfer processes that underpin their use in optoelectronic and photocatalytic applications. Here, we show that the surface chemistry of carboxylate anchoring groups of oleate ligands passivating PbS quantum dots undergoes significant changes when the quantum dots are excited to their excitonic states. We directly probe the changes of surface chemistry using time-resolved mid-infrared spectroscopy that records the evolution of the vibrational frequencies of carboxylate groups following excitation of the electronic states. The data reveal a reduction of the Pb-O coordination of carboxylate anchoring groups to lead atoms at the quantum dot surfaces. The dynamic surface chemistry of the ligands may increase their surface mobility in the excited state and enhance the ability of molecular species to penetrate the ligand shell to undergo energy and charge transfer processes that depend sensitively on distance.

Barrierless free carrier formation in an organic photovoltaic material measured with ultrafast vibrational spectroscopy.

The dynamics of free carrier formation following photoinduced electron transfer from the conjugated polymer, CN-MEH-PPV, to the electron-accepting functionalized fullerene, PCBM, are directly measured using ultrafast vibrational spectroscopy. The vibrational frequency of the carbonyl (C horizontal lineO) stretch of PCBM is sensitive to the location of the molecules relative to the interfaces formed between PCBM clusters and CN-MEH-PPV. The correlation between the carbonyl frequency and the proximity to the interfaces provides the ability to directly measure the escape of electrons from their Coulombically bound radical pairs. The data indicate that the rate of free carrier formation is temperature independent from 200 to 350 K suggesting that excess vibrational energy resulting from the electron transfer reaction enables electrons to escape their Coulombic potentials on ultrafast time scales.