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Bay-Linked Perylenediimides are Two Molecules in One: Insights from Ultrafast Spectroscopy, Temperature Dependence, and Time-Dependent Density Functional Theory Calculations
摘要： Bay-linked di-perylenediimide (di-PDI) molecules are finding increasing use in organic electronics due to their steric hindrance that 'twists' the two monomer units relative to one another, decreasing molecular aggregation. In this paper we explore the electronic spectroscopy and ultrafast dynamics of the singly-linked β-β-S-di-PDI (2,9'-di(undecan-5-yl)-2',9-di(undecan-6-yl)-[5,5'-bianthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin]-1,1',3,3',8,8',10,10'(2H,2'H,9H,9'H)-octaone). Excitation-emission spectroscopy reveals two distinct emitting species, which are further characterized by time-dependent density functional theory (TD-DFT), demonstrating that the bay-linked PDI dimers exist in two geometrical conformations. These conformations are an 'open' geometry, where the two monomer sub-units are oriented nearly at right angles, giving them more J-like coupling, and a 'closed' geometry, in which the two monomer sub-units are nearly π-stacked, resulting in more H-like coupling. Given the extent of through-space and through-bond coupling, however, neither di-PDI conformer can be well-described simply in terms of independently-coupled monomers; instead, a full quantum chemistry description is required to understand the electronic structure of this molecule. Temperature-dependent experiments and the TD-DFT calculations indicate that the 'closed' conformer is ～70 meV more stable than the 'open' conformer, so that both conformers are important to the behavior of the molecule at room temperature and above. We use a combination of steady-state and femtosecond transient absorption and emission spectroscopies to globally fit the multiple electronic transitions underlying the spectra of both the 'closed' and 'open' conformers, which agree well with the TD-DFT calculations. The fact that di-PDI molecules are molecular species that adopt two distinct quasi-independent chemical identities has important ramifications for charge trapping and mobility in the organic electronic devices employing these materials.
关键词： TD-DFT calculations,ultrafast spectroscopy,conformational isomers,organic electronics,Bay-linked perylenediimides
更新于2025-09-23 15:22:29
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Highly Conjugated, Fused-Ring, Quadrupolar Organic Chromophores with Large Two-Photon Absorption Cross-Sections in the Near-Infrared
摘要： The two-photon absorption (2PA) properties are investigated for two series of organic, π-conjugated, fused-ring, quadrupolar A-π-D-π-A chromophores of the type originally developed as non-fullerene acceptors for organic photovoltaics. These molecules are found to exhibit large nondegenerate two-photon absorption (ND2PA) cross-sections (ca. 6-27 × 103 GM) in the near infrared (NIR). In the first series, involving molecules of varying core size, ND2PA spectra and cross-sections characterized by femtosecond ND2PA spectroscopy in chloroform solutions reveal that increases in core size, and thus conjugation length, leads to substantially red-shifted and enhanced 2PA. In a second series, variation of the strength of the terminal acceptor (A) with constant core size (7 rings, indacene-based) led to less dramatic variation in the 2PA properties. Among the two core types studied, compounds in which the donor has a thieno[3,2-b]thiophene center demonstrate larger 2PA cross-sections than their indacene-centered counterparts, due to the greater electron-richness of their cores amplifying intramolecular charge transfer. Excited-state absorption (ESA) contributions to nonlinear absorption measured by open-aperture Z-scans are deduced for some of the compounds by analyzing the spectral overlap between 2PA bands and NIR ESA transitions obtained by ND2PA and transient absorption measurements, respectively. ESA cross-sections extracted from transient absorption and irradiance-dependent open-aperture Z-scans are in reasonable agreement and their moderate magnitudes (ca. 10-21 m2) suggest that, although ESA contributions are non-negligible, the effective response is predominantly instantaneous 2PA.
关键词： pump-probe spectroscopy,Nonlinear optics,Z-scan,organic optoelectronics,ultrafast spectroscopy,two-photon absorption
更新于2025-09-23 15:21:01
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Hidden Isolated OH at the Charged Hydrophobic Interface Revealed by Two-Dimensional Heterodyne-Detected VSFG Spectroscopy
摘要： Water around hydrophobic groups mediates hydrophobic interactions that play key roles in many chemical and biological processes. Thus, the molecular-level elucidation of the properties of water in the vicinity of hydrophobic groups is important. We report on the structure and dynamics of water at two oppositely charged hydrophobic ion/water interfaces, the tetraphenylborate-ion (TPB?)/water and tetraphenylarsonium-ion (TPA+)/water interfaces, which are clarified by two-dimensional heterodyne-detected vibrational sum-frequency generation (2D HD-VSFG) spectroscopy. The obtained 2D HD-VSFG spectra of the anionic TPB? interface reveal the existence of distinct π-hydrogen bonded OH groups in addition to the usual hydrogen-bonded OH groups, which are hidden in the steady-state spectrum. In contrast, 2D HD-VSFG spectra of the cationic TPA+ interface only show the presence of usual hydrogen-bonded OH groups. The present study demonstrates that the sign of the interfacial charge governs the structure and dynamics of water molecules that face the hydrophobic region.
关键词： hydrophobic interfaces,sum-frequency generation,ultrafast spectroscopy,interfacial water,vibrational dynamics
更新于2025-09-23 15:21:01
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Spectroscopic Studies of Charge-Transfer Character and Photoresponses of F <sub/>4</sub> TCNQ-Based Donora??Acceptor Complexes
摘要： F4TCNQ (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 F4TCNQ?? 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 F4TCNQ 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 F4TCNQ??:MPDA+ CTCs, due to a ～150 mV difference in MPDA+/MPDA and F4TCNQ/F4TCNQ?? reduction potentials. Ultrafast spectroscopic studies of the CTC as well as electrochemically generated F4TCNQ?? 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 D1 excited state, followed by slower (～10 ps) vibrational cooling in the anion D0 state. Excitation to the higher-lying D2 state results in a rapid relaxation to the D1 state, in contrast to direct D2 → D0 relaxation previously observed for F4TCNQ?? in the 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 F4TCNQ??. 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 F4TCNQ, 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.
关键词： photoresponses,ultrafast spectroscopy,charge-transfer complexes,F4TCNQ,organic semiconducting materials
更新于2025-09-23 15:19:57
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Thienyl Sidechain Substitution and Backbone Fluorination of Benzodithiophene-Based Donor Polymers Concertedly Minimize Carrier Losses in ITIC-Based Organic Solar Cells
摘要： Non-fullerene acceptor (NFA) based organic solar cells have outperformed fullerene-based devices, yet their photophysics is less well understood. Herein, changes in the donor polymer backbone side-chain substitution and backbone fluorination in benzodithiophene (BDT)-thiophene copolymers are linked to the photophysical processes and performance of bulk heterojunction (BHJ) solar cells, using ITIC as NFA. Increased geminate recombination is observed when the donor polymer is alkoxy-substituted in conjunction with faster non-geminate recombination of free charges, limiting both the short circuit current and device fill factor. In contrast, thienyl-substitution reduces geminate recombination, albeit non-geminate recombination remains significant, leading to improved short circuit current density, yet not fill factor. Only the combination of thienyl-substitution and polymer backbone fluorination yields both efficient charge separation and significantly reduced non-geminate recombination, resulting in fill factors (FFs) in excess of 60 %. Time-delayed collection field measurements ascertain that charge generation is field-independent in the thienyl-substituted donor polymer:ITIC systems, while weakly field dependent in the alkoxy-substitued polymer:ITIC blend, indicating the low FFs are primarily caused by non-geminate recombination. This work provides insight into the interplay of donor polymer structure, BHJ photophysics, and device performance for a prototypical NFA, namely ITIC. More specifically, it links the donor polymer chemical structure to quantifiable changes of kinetic parameters and the yield of individual processes in ITIC-based BHJ blends.
关键词： non-fullerene acceptor,ultrafast spectroscopy,bulk heterojunction,charge generation,organic photovoltaics
更新于2025-09-23 15:19:57
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Hidden isolated OH at the charged hydrophobic interface revealed by two-dimensional heterodyne-detected VSFG spectroscopy
摘要： Water around the hydrophobic groups mediates hydrophobic interaction that plays key roles in many chemical and biological processes. Thus, molecular-level elucidation of the properties of the water in the vicinity of the hydrophobic group is important. We report on the structure and dynamics of water at two oppositely charged hydrophobic interfaces, i.e., the tetraphenylborate ion (TPB-)/water and tetraphenylarsonium ion (TPA+)/water interfaces, which are clarified by two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) spectroscopy. The obtained 2D HD-VSFG spectra of anionic TPB- interface reveal the existence of distinct π-hydrogen bonded OH groups in addition to the usual hydrogen bonded OH groups, which is hidden in the steady-state spectrum. In contrast, 2D HD-VSFG spectra of cationic TPA+ interface only show the presence of usual hydrogen bonded OH groups. The present study demonstrates that the sign of the interfacial charge governs the structure and dynamics of water molecules that face the hydrophobic region.
关键词： sum-frequency generation,ultrafast spectroscopy,hydrophobic interfaces,interfacial water,vibrational dynamics
更新于2025-09-23 15:19:57
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Ultrafast spectroscopic investigation of the effect of solvent additives on charge photogeneration and recombination dynamics in non-fullerene organic photovoltaic blends
摘要： The PBDB-TF:IT-4F blend is a kind of state-of-the-art non-fullerene photovoltaic blend. Herein, the effects of 1,8-diiodooctane (DIO) and 1-chloronaphthalene (CN) additives on the neat and blend film morphologies and the related ultrafast photophysical processes are studied. It is found that both DIO and CN can lead to an enhanced structural order in the in-plane direction and increased average lifetime of excitons in neat PBDB-TF films. The face-on orientation of PBDB-TF still exists in the DIO-processed PBDB-TF:IT-4F blend film, while in the case of the CN-processed blend film, molecular packing orientation is similar to that of the pristine blend film. The blend samples prepared with the two additives show increased initial exciton yields. Interestingly, in the blend samples prepared with the DIO additive, the recombination loss via the formation of polymer triplet excitons can be effectively suppressed, in comparison to the pristine and CN-processed samples. Both the DIO- and CN-processed devices show increased short-circuit current densities. The DIO-processed device is also found to have a superior fill factor due to suppressed recombination loss. The work provides a comprehensive insight into the ultrafast photophysical processes in varied blend morphologies induced by additives and their effect on the photovoltaic parameters of the devices.
关键词： charge photogeneration,ultrafast spectroscopy,recombination dynamics,solvent additives,non-fullerene photovoltaic blend
更新于2025-09-23 15:19:57
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Biexciton Auger recombination in mono-dispersed, quantum-confined CsPbBr3 perovskite nanocrystals obeys universal volume-scaling
摘要： Auger recombination has been a long-standing obstacle to many prospective applications of colloidal quantum dots (QDs) ranging from lasing, light-emitting diodes to bio-labeling. As such, understanding the physical underpinnings and scaling laws for Auger recombination is essential to these applications. Previous studies of biexciton Auger recombination in various QDs established a universal scaling of biexciton lifetime (τXX) with QD volume (V ): τXX = γV. However, recent measurements on perovskite nanocrystals (NCs), an emerging class of enablers for light harvesting and emitting applications, showed significant deviations from this universal scaling law, likely because the measured NCs are weakly-confined and also have relatively broad size-distributions. Here we study biexciton Auger recombination in mono-dispersed (size distributions within 1.7%–9.0%), quantum-confined CsPbBr3 NCs (with confinement energy up to 410 meV) synthesized using a latest approach based on thermodynamic equilibrium control. Our measurements clearly reproduce the volume-scaling of τXX in confined CsPbBr3 QDs. However, the scaling factor γ (0.085 ± 0.001 ps/nm3) is one order of magnitude lower than that reported for CdSe and PbSe QDs (1.00 ± 0.05 ps/nm3), suggesting unique mechanisms enhancing Auger recombination rate in perovskite NCs.
关键词： biexciton,Auger recombination,perovskite nanocrystals,ultrafast spectroscopy,volume-scaling
更新于2025-09-23 15:19:57
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Lighting Up Invisible Twisted Intramolecular Charge Transfer State by High Pressure
摘要： The twisted intramolecular charge transfer (TICT) state plays an important role in determining the performance of optoelectronic devices. However, for some non-fluorescent TICT molecules, 'invisible' TICT state could only be visualized by modifying the molecular structure. Here, we introduce a new facile pressure-induced approach to light up the TICT state through the use of the pressure related liquid–solid phase transition of the surrounding solvent. Combining ultrafast spectroscopy and quantum chemical calculations, it reveals that the 'invisible' TICT state can emit fluorescence when the rotation of a donor group is restricted by the frozen acetonitrile solution. Furthermore, the TICT process can even be effectively regulated by the external pressure. Our study offers a unique strategy to achieve dual fluorescence behavior in charge transfer molecules and is of significance for optoelectronic and biomedical applications.
关键词： Dual fluorescence,Twisted intramolecular charge transfer,High pressure,Ultrafast spectroscopy
更新于2025-09-19 17:15:36
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Ultrafast Hole Transfer and Carrier Transport Controlled by Nanoscale-Phase Morphology in Nonfullerene Organic Solar Cells
摘要： Nonfullerene acceptors (NFAs) have attracted great attention in high-efficiency organic solar cells (OSCs). While the effect of molecular properties including structures and energetics on charge transfer have been extensively investigated, the effect of macroscopic phase properties is yet to be revealed. Here we have performed a correlation study of the nanoscale phase morphology on photoexcited hole transfer (HT) process and photovoltaic performance, by combing ultrafast spectroscopy with high temporal resolution and photo-induced force microscopy (PiFM) with high spatial and chemical resolution. In PM6/IT-4F, we observe a biphasic HT behavior with a minor ultrafast (< 100 fs) interfacial process and a major diffusion mediated HT process till ~ 100 ps, which depends on phase segregation strongly. Because of the interplay between charge transfer and transport, a compromised domain size of 20 ~ 30 nm for NFAs shows best performance. This study highlights the critical role of phase morphology in high-efficiency OSCs.
关键词： photo-induced force microscopy,phase morphology,ultrafast spectroscopy,organic solar cells,hole transfer,Nonfullerene acceptors
更新于2025-09-19 17:13:59