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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Influence of substituents on the vectorial difference static dipole upon excitation in synthetic bacteriochlorins

Organic dye aggregates have been shown to exhibit exciton delocalization in natural and synthetic systems. Such dye aggregates show promise in the emerging area of quantum information science (QIS). We believe that the difference static dipole (Δd) is an essential dye parameter in the development of molecular QIS systems. However, a foundational understanding of the structural factors influencing Δd remains elusive. Bacteriochlorins play a vital role in photosynthesis due to their exceptional photophysical properties. Therefore, bacteriochlorins are particularly suitable dyes for the construction of aggregate systems for QIS. Synthetic bacteriochlorins further offer stability and tunability via chemical modifications. Here, the influence of substituents on the Δd of monomeric (non-aggregated) dyes was investigated via density functional theory (DFT) and time-dependent (TD-)DFT in a set of 5-methoxybacteriochlorins progressively substituted with ethynyl, phenyl, and phenylethynyl substituents at the 3,13- and 3,13,15-positions of the macrocycle. Symmetrically substituted 5-methoxybacteriochlorins were shown to have the largest Δd. The increase in Δd in the series of dyes was largely due to changes in orientation of the static dipole upon excitation rather than large changes in magnitude. In addition, the transition dipole (μ) and the angle between Δd and μ (ζ) were calculated. Three 5-methoxybacteriochlorins with high predicted Δd and μ were synthesized and characterized spectroscopically. The trend in Δd values empirically determined using the solvatochromic Stokes shift method was comparable with the DFT calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Roadmap for Molecular Benchmarks in Nonadiabatic Dynamics

Simulating the coupled electronic and nuclear response of a molecule to light excitation requires the application of nonadiabatic molecular dynamics. However, when faced with a specific photophysical or photochemical problem, selecting the most suitable theoretical approach from the wide array of available techniques is not a trivial task. The challenge is further complicated by the lack of systematic method comparisons and rigorous testing on realistic molecular systems. This absence of comprehensive molecular benchmarks remains a major obstacle to advances within the field of nonadiabatic molecular dynamics. A CECAM workshop, Standardizing Nonadiabatic Dynamics: Towards Common Benchmarks, was held in May 2024 to address this issue. This Perspective highlights the key challenges identified during the workshop in defining molecular benchmarks for nonadiabatic dynamics. Specifically, this work outlines some preliminary observations on essential components needed for simulations and proposes a roadmap aiming to establish, as an ultimate goal, a community-driven, standardized molecular benchmark set.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Reconciling the Different Apparent Decay Pathways for Iron(III) Tetraphenylporphyrin Chloride: Evidence for Excited State Branching

Detailed understanding of the photophysical properties of metalloporphyrins is key to rationally exploiting them in a variety of applications ranging from photocatalysis to opto-magnetics. Previous studies of the ferric-tetraphenylporphyrin chloride have provided contradictory descriptions of the excited state evolution. Optical transient-absorption suggested initial formation of a ππ* excited state, followed by ligand-to-metal charge-transfer (LMCT) from the porphyrin ring and then decay on the ∼2 ps time scale to a metal-centered excited state that had a lifetime of ∼15 ps. In contrast, femtosecond extreme ultraviolet transient-absorption at the Fe M 2,3 -edge, while agreeing on the initial formation of an LMCT state, found evidence that this decayed in ∼2 ps to the ground state. Here, we have used K-edge transient X-ray absorption and X-ray emission, together with time-resolved X-ray solution scattering to explore this system. Based on these data, we propose a new model, consistent with both the earlier and the current data, in which photoexcited FeTPPCl evolves through three different states on the LMCT manifold, with the ∼2 ps decay now seen to involve a branching between return to the ground state (∼70%) and formation of a long-lived LMCT state (∼30%).

Excited states↗
DOE OSTI2026

Simplifying the Chemical Design of Nonfused-Ring Electron Acceptors─Lessons Learned from Thienothiophene and Benzodithiophene Cores

Nonfused-ring electron acceptors (NFREA)s have been proposed as alternatives to fused-ring acceptors in organic photovoltaics (OPV)s. The simpler molecular design of NFREAs results in a reduced synthetic complexity, potentially lowering manufacturing costs, and easier access to desired optoelectronic properties by structural modifications. However, they have not seen the same rise in popularity as fused nonfullerene acceptors (NFA)s due to their lower performances in devices. In this work, we explore structure–property relationships of three NFREA molecules based on thieno[3,2-b]thiophene (TT) and benzo[1,2-b:4,5-b′]dithiophene (BDT) cores and malononitrile functionalized-isatin end group acceptors. We describe their synthetic routes, computational analysis, and photophysical and electronic properties. Here, we investigated the effect of changing the core from TT to BDT on electronic properties of the molecules─a result of raising/lowering of the frontier molecular orbital (FMO) levels. We also explored the effect of branched vs nonbranched alkyl groups on the morphological and blend-capabilities in bulk heterojunction (BHJ) OPV devices. These effects were then reflected in the overall device performances, primarily due to favorable FMO energy alignment between the NFREA and polymer. To investigate the behavior of the excited states of the NFREAs within the active layer of the devices, we performed time-resolved microwave conductivity and transient absorption experiments, which confirmed that the TT molecules exhibited very low conductance while the BDT molecule showed moderate photoconductance. Our combined theoretical, synthetic, device, and charge carrier dynamics studies of these materials reveal the central role that structure–property relationships play in future molecular designs of NFREAs that can perform as well as their fused counterparts.

14 SOLAR ENERGY↗
DOE OSTI2026

Exploring Excited State Proton Transfer Dynamics upon Ultraviolet Excitation

Excited state intramolecular proton transfer (ESIPT) has been investigated in two prototypical systems─salicylaldehyde azine (SAA) and 1,5-dihydroxyanthraquinone (DHAQ)─using transient absorption spectroscopy upon ultraviolet excitation into the less studied higher excited (S n ) manifold. Excitation with sub-30 fs pulses and broadband visible probing has allowed for direct measurement of the ESIPT rate. In conjunction with steady-state measurements and TD-DFT calculations, a complete delineation of the ultrafast photophysics has been carried out. In SAA, ESIPT remains ultrafast (∼30 fs), consistent with previous S 1 excitation studies. Coherent vibrational beats maps reveal significant wavelength dependence, however. Theoretical analysis suggests that the observed modes and their intensities in coherent vibrational spectra are modulated by the nature of the electronically excited state. In DHAQ, the first direct observation of ESIPT presents a time-constant of ∼85 fs, and a slower component of 9 ps, akin to previous reports on double-proton transfer systems. Collectively, the results suggest that while the ultrafast ESIPT rate remains largely invariant vis-à-vis the excitation energy, the product yield, as well as accompanying coherent oscillations, may be substantively altered, owing to the existence of alternative decay pathways.

excited states↗
DOE OSTI2020

Ultrafast Relaxations in Ruthenium Polypyridyl Chromophores Determined by Stochastic Kinetics Simulations

Maximizing the efficiency of solar energy conversion using dye assemblies rests on understanding where the energy goes following absorption. Transient spectroscopies in solution are useful for this purpose, and the time-resolved data are usually analyzed with a sum of exponentials. This treatment assumes that dynamic events are well separated in time, and that the resulting exponential prefactors and phenomenological lifetimes are related directly to primary physical values. Such assumptions break down for coincident absorption, emission, and excited state relaxation that occur in transient absorption and photoluminescence of tris(2,2'-bipyridine)ruthenium(2+) derivatives, confounding the physical meaning of the reported lifetimes. Here, we use inductive modeling and stochastic chemical kinetics to develop a detailed description of the primary ultrafast photophysics in transient spectroscopies of a series of Ru dyes, as an alternative to sums of exponential analysis. Commonly invoked three-level schemes involving absorption, intersystem crossing (ISC), and slow nonradiative relaxation and incoherent emission to the ground state cannot reproduce the experimentally measured spectra. The kinetics simulations reveal that ultrafast decay from the singlet excited state manifold to the ground state competes with ISC to the triplet excited state, whose efficiency was determined to be less than unity. The populations predicted by the simulations are used to estimate the magnitudes of transition dipoles for excited state excitations and evaluate the influence of specific ligands. The mechanistic framework and methodology presented here are entirely general, applicable to other dye classes, and can be extended to include charge injection by molecules bound to semiconductor surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Exciton Delocalization in Indolenine Squaraine Aggregates Templated by DNA Holliday Junction Scaffolds

Exciton delocalization plays a prominent role in the photophysics of molecular aggregates, ultimately governing their particular function or application. DNA is a compelling scaffold in which to template molecular aggregates and promote exciton delocalization. As individual dye molecules are the basis of exciton delocalization in molecular aggregates, their judicious selection is important. Motivated by their excellent photostability and spectral properties, here we examine the ability of squaraine dyes to undergo exciton delocalization when aggregated via a DNA Holliday junction (HJ) template. A commercially available indolenine squaraine dye was chosen for the study given its strong structural resemblance to Cy5, a commercially available cyanine dye previously shown to undergo exciton delocalization in DNA HJs. Three types of DNA-dye aggregate configurations—transverse dimer, adjacent dimer, and tetramer—were investigated. Signatures of exciton delocalization were observed in all squaraine-DNA aggregates. Specifically, strong blue shift and Davydov splitting were observed in steady-state absorption spectroscopy and exciton-induced features were evident in circular dichroism spectroscopy. Strongly suppressed fluorescence emission provided additional, indirect evidence for exciton delocalization in the DNA-templated squaraine dye aggregates. To quantitatively evaluate and directly compare the excitonic Coulombic coupling responsible for exciton delocalization, the strength of excitonic hopping interactions between the dyes were obtained by simultaneous fitting the experimental steady-state absorption and CD spectra via a Holstein-like Hamiltonian in which, following the theoretical approach of Kühn, Renger, and May, the dominant vibrational mode is explicitly considered. The excitonic hopping strength within indolenine squaraines was found to be comparable to that of the analogous Cy5 DNA-templated aggregate. The squaraine aggregates adopted primarily an H-type (dyes oriented parallel to each other) spatial arrangement. Extracted geometric details of dye mutual orientation in the aggregates enabled close comparison of aggregate configurations and the elucidation of the influence of dye angular relationship on excitonic hopping interactions in squaraine aggregates. Furthermore, these results encourage the application of squaraine-based aggregates in next generation systems driven by molecular excitons.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Spectroscopic Studies of Charge-Transfer Character and Photoresponses of F 4 TCNQ-Based Donor–Acceptor Complexes

F 4 TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) is used widely as a hole-doping agent in photoresponsive organic semiconducting materials, yet relatively little is known about the photoresponses of the F 4 TCNQ· - anion generated via doping. Furthermore, there is still relatively little systematic exploration of how the properties of the local material or chemical environment impacts the driving force for generating these charge-transfer complexes. Here we present spectroscopic and photophysical studies of F 4 TCNQ in charge-transfer complexes (CTCs) with the electron donor N,N’-Diphenyl-N-N’-di-p-tolylbenzene-1,4-diamine (MPDA) both in dichloroethane solution and polystyrene matrices. Integer charge transfer (ICT) between donor and acceptor occurs readily in dichloroethane solvent to form F 4 TCNQ· - :MPDA + CTCs, due to a ~150 mV difference in MPDA + /MPDA and F 4 TCNQ/F 4 TCNQ· - reduction potentials. Ultrafast spectroscopic studies of the CTC as well as electrochemically generated F 4 TCNQ· - and MDPA + reveal that the photoresponses of these CTCs are dominated by that of the dopant anion, including rapid deactivation (800 fs) after excitation to the anion D 1 excited state, followed by slower (~10 ps) vibrational cooling in the anion D 0 state. Excitation to the higher-lying D 2 state results in a rapid relaxation to the D 1 state, in contrast to direct D 2 -D 0 relaxation previously observed for F 4 TCNQ· - in gas phase. CTCs embedded in polystyrene (PS) matrices are observed to lose their integer charge-transfer character upon evaporation of solvent, as evidenced by changes to electronic and vibrational absorption features associated with F 4 TCNQ· - . This change is attributed to the loss of solvent stabilization of the ion pair formed through the charge-transfer reaction. Ultrafast spectral measurements reveal that the photoresponses of the partial charge-transfer (PCT) species embedded in PS are still highly similar to those of the ICT species and unlike that of neutral F 4 TCNQ, implying the electronic properties of the PCT state are likewise dominated by properties of the reduced acceptor molecule. We conclude that excitation of ICT or PCT states introduces optical losses for photoresponses of doped organic semiconductor materials due to the large anion absorption cross section and its rapid, dissipative deactivation dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The Bright Side and Dark Side of Hybrid Organic–Inorganic Perovskites

The previously developed bistable amphoteric native defect (BAND) model is used for a comprehensive explanation of the unique photophysical properties and for understanding the remarkable performance of perovskites as photovoltaic materials. It is shown that the amphoteric defects in the donor (acceptor) configuration capture a fraction of photoexcited electrons (holes) dividing them into two groups: higher-energy bright and lower-energy dark electrons (holes). The spatial separation of the dark electrons and dark holes and the k-space separation of the bright and dark charge carriers reduce electron-hole recombination rates, emulating the properties of an ideal photovoltaic material with a balanced, spatially separated transport of electrons and holes. The BAND model also offers a straightforward explanation for the exceptional insensitivity of the photovoltaic performance of polycrystalline perovskite films to structural and optical inhomogeneities. The blue-shifted radiative recombination of bright electrons and holes results in a large anti-Stokes effect that provides a quantitative explanation for the spectral dependence of the laser cooling effect measured in perovskite platelets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Determining the Structure-Property Relationships of Quasi-Two-Dimensional Semiconductor Nanoplatelets.

We report a theoretical study of CdSe nanoplatelets aimed at identifying the main factors determining their photophysical properties. Using atomic configurations optimized with density functional theory calculations, we computed quasiparticle and exciton binding energies of nanoplatelets with two to seven monolayers. We employed many body perturbation theory at the GW level and solved the Bethe-Salpeter equation to obtain absorption spectra and excitonic properties. Our results, which agree well with recent experiments, were then used to design a model that allows us to disentangle the effects of quantum confinement, strain induced by passivating ligands, and dielectric environment on the electronic properties of nanoplatelets. We found that, for the model to accurately reproduce our first principle results, it is critical to account for surface stress and consider a finite potential barrier and energy-dependent effective masses when describing quantum confinement. Our findings call into question previous assumptions on the validity of an infinite barrier to describe carrier confinement in nanoplatelets, suggesting that it may be possible to optimize interfacial charge transfer and extraction by appropriately choosing passivating ligands. The model developed here is generalizable to core-shell platelets and enables the description of system sizes not yet directly treatable by first-principles calculations.

Greenwood, Arin R.↗
DOE OSTI2021

Ultrafast Charge Transfer Dynamics at the Origin of Photoconductivity in Doped Organic Solids

In spite of their growing importance for optoelectronic devices, the fundamental properties and photophysics of molecularly doped organic solids remain poorly understood. Such doping typically leads to a small fraction of free conductive charges, with most electronic carriers remaining Coulombically bound to the ionized dopant. Recently, we have reported photocurrent for devices containing vacuum-deposited TAPC (1,1-bis(4-bis(4- methylphenyl)aminophenyl)cyclohexane) doped with MoO 3 , showing that photoexcitation of charged TAPC molecules increases the concentration of free holes that contribute to conduction. Here, we elucidate the excited-state dynamics of such doped TAPC films to unravel the key mechanisms responsible for this effect. We demonstrate that excitation of different electronic transitions in charged and neutral TAPC molecules allows bound holes to overcome the Coulombic attraction to their MoO 3 counterions, resulting in an enhanced yield of long-lived free carriers. This is caused by ultrafast back-and-forth shuffling of charges and excitation energy between adjacent cations and neutral molecules, competing with relatively slow nonradiative decay from higher excited states of TAPC •+ . The light-induced generation of conductive carriers requires the coexistence of cationic and neutral TAPC, a favorable energy level alignment, and intermolecular interactions in the solid state.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Assigning Optical Absorption Transitions with Light-Induced Crystal Structures: Case Study of a Single-Crystal Nanooptomechanical Transducer

UV/vis absorption spectroscopy affords indirect structural information about the photochemistry and photophysics of molecules by inferring types of electronic transitions from spectral features. Direct structural information would become available, though, if light-induced crystal structures could be mapped against changes in optical absorption spectra as a photochemical process evolves. We present a series of light-induced crystal structures that track real-time changes in solid-state optical absorption spectra of a crystalline nanooptomechanical transducer, while the transduction process unfolds within its crystal lattice at 100 K. Results afford a combined structural and spectral mapping of its solid-state optical absorption, from which the operational mechanism of nanooptomechanical transduction is revealed. Metal-to-ligand and metal-centered charge-transfer bands are assigned to optical absorption peaks directly from their 3-D light-induced crystal structures. This approach could be used to characterize many solid-state optoelectronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Single-Crystal Optical Actuation Generated by 100% SO 2 Linkage Photoisomerization in a Ruthenium-Based Coordination Complex

Single-crystal optical actuators are emerging as a new field of materials chemistry because of their wide-ranging potential applications, from light-induced molecular motors to photosensing technologies. Ruthenium-based coordination complexes that contain sulfur dioxide linkage photoisomers have shown particular promise as optical actuators, given that they may exhibit either optical switching or nano-optomechanical transduction in their single-crystal form. The type of single-crystal optical actuation observed in a specific compound within this family of complexes depends upon the nature of the ligand that lies trans to this SO 2 linkage photoisomer, since this governs the type and extent of photoisomer (η 2 -(OS)O or η 1 -OSO) that will form upon the application of light. We report the discovery of a new complex, trans-[Ru(SO 2 )(NH 3 ) 4 (3-iodopyridine)]tosylate 2 (1), which forms an η 1 -OSO photoisomer with 100% photoconversion upon the application of 505 nm light. The photoisomerization process in the ruthenium-based cation of 1 stimulates rotation and translation of the toluenic constituent of its neighboring anion, thereby affording nano-optomechnical transduction. We show that this η 1 -OSO photoisomer transitions to its more thermally stable η 2 -(OS)O photoisomer with an activation energy, E a , of 11(2) kJ/mol using thermally activated single-crystal optical absorption spectroscopy. The application of external light with different wavelengths to 1 is also shown to cause a variation in its optical absorption spectral characteristics. Here, this suggests that the photophysical properties of 1 may be tunable with light.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Competing Singlet Fission and Excimer Formation in Solid Fluorinated 1,3-Diphenylisobenzofurans

Singlet fission (kSF) and excimer formation (kEXC) rate constants along with other photophysical properties of thin solid layers of 1,3-diphenylisobenzofuran and 11 of its fluorinated derivatives have been determined. The molecular properties of these compounds are similar, but their crystal packing varies widely. Most of them undergo singlet fission whereas excitation in others is trapped in excimers. The trend in rate constants kSF agrees qualitatively with results of calculations by a simplified version of the frontier orbital model for a molecular pair. The main shortcoming of the model is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Lattice Dynamics and Optoelectronic Properties of Vacancy-Ordered Double Perovskite Cs 2 TeX 6 (X = Cl – , Br – , I – ) Single Crystals

The soft, dynamic lattice of inorganic lead halide perovskite CsPbX 3 (X = Cl ⁻ , Br ⁻ , I ⁻ ) leads to the emergence of many interesting photophysical and optoelectronic phenomena. However, probing their lattice dynamics with vibrational spectroscopy remains challenging. The influence of the fundamental octahedral building block in the perovskite lattice can be better resolved in zero-dimensional (0D) vacancy-ordered double perovskites of form A 2 BX 6 . Here we study Cs 2 TeX 6 (X = Cl ⁻ , Br ⁻ , I ⁻ ) single crystals to yield detailed insight into the fundamental octahedral building block and to explore the effect that its isolation in the crystal structure has on structural and electronic properties. The isolated [TeX 6 ] 2- octahedral units serve as the vibrational, absorbing, and emitting centers within the crystal. Serving as the vibrational centers, the isolated octahedra inform the likelihood of a random distribution of 10 octahedral symmetries within the mixed-halide spaces, as well as the presence of strong exciton-phonon coupling and anharmonic lattice dynamics. Serving as the absorbing and emitting centers, the isolated octahedra exhibit compositionally tunable absorption (1.50-3.15 eV) and emission (1.31-2.11 eV) energies. Due to greater molecular orbital overlap between neighboring octahedra with increasing halide anion size, there is a transition from a more molecule-like electronic structure in Cs 2 TeCl 6 and Cs 2 TeBr 6 -as expected from the effective 0D nature of these single crystals-to a dispersive electronic structure in Cs 2 TeI 6 , typical of three-dimensional (3D) bulk single crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Long-Lived Excited State in a Solubilized Graphene Nanoribbon

Graphene nanoribbons have excellent light-absorbing properties, but often exhibit short excited-state lifetimes that prevent their applications in photocatalysis. Here, we report a long-lived charge-transfer triplet excited state in a well solubilized, chlorinated graphene nanoribbon (Cl-GNR) with edges modified by bipyrimidine (bpm) moieties. The photophysical behavior of Cl-GNR was observed and characterized by steady-state UV-vis absorption and emission spectroscopy, transient absorption spectroscopy on the ps-ms timescale, and density functional theory (DFT) calculations. In this work, both the Cl-GNR and its monomeric subunit, chlorinated graphene quantum dot (Cl-GQD), were synthesized using bottom-up techniques to produce the H- analogs of the compounds followed by edge-chlorination to achieve soluble products. The absorption spectra of Cl-GQD and Cl-GNR appear in the UV-vis range with lowest-energy peaks at 375 and 600 nm, respectively. The excitons in Cl-GNR were found to exhibit charge-transfer character with the bpm edges serving as electron acceptors. DFT calculations indicate that the excitons are relatively localized, spreading over at most two monomeric units of the GNR. Transient absorption spectroscopy shows that singlet excited states of Cl-GQD and Cl-GNR undergo intersystem crossing with ~300 ps lifetime to form triplet states that last for 15.7 μs (Cl-GQD) and 106 μs (Cl-GNR). These properties, combined with the ability of the bpm sites to coordinate transition metals, make Cl-GNRs promising light-harvesting motifs for photocatalytic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Visible Light Absorption and Hot Carrier Trapping in Anatase TiO 2 : The Role of Surface Oxygen Vacancies

Anatase TiO 2 is an efficient water splitting photocatalyst using UV light, but solar energy harvesting requires the presence of midgap states to increase visible light absorption. Despite numerous studies, important questions remain regarding the photophysics in O vacancy doped TiO 2 . Here, by employing extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy at the Ti M2,3-edge, spectral signatures of both large and small polaron states are identified, allowing ultrafast electron and hole dynamics in these states to be independently resolved. Results show that visible light absorption occurs via promotion of an electron from the small polaron state to the TiO 2 conduction band. In contrast, absorption of UV light results in direct band gap excitation followed by carrier relaxation during which hot holes trap as small polarons in 45 ± 42 fs, and hot electrons couple to polar optical phonons leading to vibrational coherence and large polaron formation in 945 ± 92 fs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Annealing Controls Ultrafast Dynamics of Carrier Production in Organic Photovoltaics Incorporating a Nonfullerene Acceptor

Nonfullerene acceptors have emerged as leading candidates in organic photovoltaics pushing past some of the limitations of their fullerene counterparts with absorption extending in the visible and NIR, decreased air-sensitivity, and tunable energy levels. Significant progress has been made in demonstrating the potential of nonfullerene acceptor-based devices to reach high efficiencies; however, a photophysical and mechanistic understanding of charge generation in these nonfullerene acceptors lags behind. In particular, the effects of annealing on carrier production have not been previously examined. Here, we use transient absorption spectroscopy and atomic force microscopy to examine the effect of solvent vapor annealing on a perylene diimide-based nonfullerene acceptor, PDI-DPP-PDI. We find that when mixed with the donor PTB7-Th, the effect of solvent vapor annealing on PDI-DPP-PDI is to reduce geminate recombination, leading to balanced exciton generation and charge separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗