Investigation of Intrachain Exciton Diffusion of MEH-PPV in Solution with Different Polarity

Femtosecond time-resolved transient grating technique was adopted to insight into the intra-chain exciton diffusion of MEH-PPV in solution with different polarity. Broadband white-light continuum was introduced as the probe to observe the transient absorption and the femtosecond time-resolved transient grating information simultaneously. The vibrational dephasing behaviors, single exciton relaxation, and population relaxation dynamics of MEH-PPV were systematically investigated. The result shows that the relaxation processes of the sample solution will be accelerated in the solvent with larger polarity.

Controllable Exciton Diffusion Length and Ultrafast Charge Generation in Ternary Organic Solar Cells

Charge generation,a critical process in the operation of organic solar cell(OSC),requires thorough investigation in an ultrafast perspective.This work demonstrates that the utilization of alloy model for the non-fullerene acceptor(NFA)component can regulate the crystallization properties of active layer films,which in turn affects exciton diffusion and hole transfer(HT),ultimately influencing the charge generation process.By incorporating BTP-eC7 as a third component,without expanding absorption range or changing molecular energy levels but regulating the ultrafast exciton diffusion and HT processes,the power conversion efficiency(PCE)of the optimized PM6:BTP-eC9:BTP-eC7 based ternary OSC is improved from 17.30%to 17.83%,primarily due to the enhancement of short-circuit current density(JSC).Additionally,the introduction of BTP-eC7 also reduces the trap state density in the photoactive layer which helps to reduce the loss of JSC.This study introduces a novel approach for employing ternary alloy models by incorporating dual acceptors with similar structures,and elucidates the underlying mechanism of charge generation and JSC in ternary OSCs.

Hot-exciton effects on exciton diffusion and circular polarization dynamics in a single PbI_(2)nanoflake

As one of the emerging two-dimensional lead halide materials,lead iodide(PbI_(2))nanosheets have proven to possess strong application potential in the fields of high-energy radiation detection and highly efficient perovskite solar cells.However,the underlying photophysical properties such as hot-exciton-related carrier dynamics remain unclear for PbI_(2)nanosheets.Here,we report the exciton dynamics of a single PbI_(2)nanoflake prepared by an aqueous solution method.Through a three-dimensional(3D)diffusion model,we obtain the exciton annihilation radius and diffusion coefficient of a single PbI_(2)nanoflake under nonresonant and resonant excitation conditions of band-edge exciton state.As initial exciton densities increase,we find the carrier recombination mechanism for a single PbI_(2)nanoflake gradually changes from exciton-exciton annihilation to free-carrier recombination.Finally,we reveal the room-temperature circular polarization of a single PbI_(2)nanoflake is due to free-carrier recombination with a band-edge exciton dissociation time of~120 fs under the resonant excitation condition.

Simultaneously optimizing exciton diffusion length and nonradiative energy loss in organic solar cells via ternary strategy

Significant nonradiative energy loss and short exciton diffusion length in organic solar cells(OSCs)are two major obstacles to achieving state-of-the-art efficiencies.It is crucial to conduct a study on the intensive mechanism and improvement strategies for future breakthroughs in the efficiency of OSCs.In this work,nonradiative energy loss and exciton diffusion length are optimized simultaneously by incorporating a guest acceptor(LA15)to construct ternary OSC(D18:L8-BO:LA15).Firstly,LA15 exhibits excellent compatibility with the host acceptor L8-BO,and effectively improves the fluorescence quantum efficiency(FLQY),resulting in suppressed non-radiative energy loss.Moreover,LA15 effectively prolongs the fluorescent lifetime of the acceptor phase from 0.85 to 1.12 ns,leading to larger exciton diffusion length,which is beneficial for reducing geminate recombination.Besides,the addition of LA15 optimizes the crystallinity of the active layer with amplified charge transport capacity.As a result,the optimized D18:L8-BO:LA15 device achieves ultralow nonradiative energy loss of 0.18 e V and improved fill factor(FF)with high efficiency up to 19.13%.These results highlight the crucial roles of regulating FLQYand exciton lifetime in achieving highefficiency OSCs.

Exciton diffusion and dissociation in organic and quantum-dot solar cells

For the process of photovoltaic conversion in organic solar cells(OSCs)and quantum-dot solar cells(QDSCs),three of four steps are determined by exciton behavior,namely,exciton generation,exciton diffusion,and exciton dissociation.Therefore,it is of great importance to regulate exciton behavior in OSCs and QDSCs for achieving high power conversion efficiency.Due to the rapid development in materials and device fabrication,great progress has been made to manage the exciton behavior to achieve prolonged exciton diffusion length and improved exciton dissociation in recent years.In this review,we first introduce the parameters that affect exciton behavior,followed by the methods to measure exciton diffusion length.Then,we provide an overview of the recent advances with regard to exciton behavior investigation in OSCs and QDSCs,including exciton lifetime,exciton diffusion coefficient,and exciton dissociation.Finally,we propose future directions in deepening the understanding of exciton behavior and boosting the performance of OSCs and QDSCs.

Enhanced exciton diffusion from interlayer charge-transfer transitions in PtSe2/MoSe_(2) van der Waals heterojunction

Artificial van der Waals(vdWs)heterostructures offer unprecedented opportunities to explore and reveal novel synergistic electronic and optical phenomena,which are beneficial for the development of novel optoelectronic devices at atomic limits.However,due to the damage caused by the device fabrication process,their inherent properties such as carrier mobility are obscured,which hinders the improvement of device performance and the incorporation of vdWs materials into next-generation integrated circuits.Herein,combining pump-probe spectroscopic and scanning probe microscopic techniques,the intrinsic optoelectronic properties of PtSe_(2)/MoSe_(2)heterojunction were nondestructively and systematically investigated.The heterojunction exhibits a broad-spectrum optical response and maintains ultrafast carrier dynamics(interfacial charge transfer~0.8 ps and carrier lifetime~38.2 ps)simultaneously.The in-plane exciton diffusion coefficient of the heterojunction was extracted(19.4±7.6 cm^(2)∙s^(−1)),and its exciton mobility as high as 756.8 cm^(2)∙V−1∙s^(−1)was deduced,exceeding the value of its components.This enhancement was attributed to the formation of an n-type Schottky junction between PtSe_(2)and MoSe_(2),and its built-in electric field assisted the ultrafast transfer of photogenerated carriers from MoSe_(2)to PtSe_(2),enhancing the in-plane exciton diffusion of the heterojunction.Our results demonstrate that PtSe_(2)/MoSe_(2)is suitable for the development of broadspectrum and sensitive optoelectronic devices.Meanwhile,the results contribute to a fundamental understanding of the performance of various optoelectronic devices based on such PtSe_(2)two-dimensional(2D)heterostructures.

Highly Fluorescent Semiconducting Two-Dimensional Conjugated Polymer Films Achieved by Side-Chain Engineering Showing Large Exciton Diffusion Length

Semiconducting two-dimensional conjugated polymers(2DCPs)with strong fluorescence emission have great potential for various optoelectronic applications.However,it is enormously challenging to achieve this goal due to the significant compact interlayerπ-πstacking-induced quenching effect in these systems.In this work,we found that highly fluorescent semiconducting 2DCPs can be prepared through an effective side-chain engineering approach in which interlayer spacers are introduced to reduce the fluorescence quenching effect.The obtained two truxene-based 2DCP films that,along with-C6H13 and-C_(12)H_(25)alkyl side chains as interlayer spacers both demonstrate superior fluorescence properties with a high photoluminescence quantum yield of 5.6%and 14.6%,respectively.These are among the highest values currently reported for 2DCP films.Moreover,an ultralong isotropic quasi-twodimensional exciton diffusion length constrained in the plane with its highest value approaching 110 nm was revealed by the transient photoluminescence microscopy technique,suggesting that theπ-conjugated structure in these truxene-based 2DCP films has effectively been extended.This work can enable a broad exploration of highly fluorescent semiconducting 2DCP films for more deeply fundamental properties and optoelectronic device applications.

Secondary Aggregation Induced by Volatile Additive for Improved Exciton Diffusion and Charge Separation in High Efficiency Organic Photovoltaic Devices

Comprehensive Summary The morphology of the active layer plays a crucial role in the performance of organic photovoltaics.Although volatile additives are commonly used to manipulate the morphology,their mechanism of action remains poorly understood.In this study,we conducted a systematic exploration of the mechanism of the traditional volatile additive 1-CN in film formation kinetics of typical PM6:Y6 system.We found that 1-CN induces a secondary aggregation effect,improving film morphology and promoting face-on crystalline orientation.Through elucidating its impact on exciton dynamics,we established a link between morphology optimization and increased exciton diffusion length and accelerated charge separation.Our findings unveil the unique mechanism of action of volatile additive,providing a new perspective for improving the morphology and enhancing the performance of organic photovoltaic devices.

Universal,predominant exciton transfer in perovskite nanocrystal solids

Perovskite nanocrystal(PNC)solids are promising materials for optoelectronic applications.Recent studies have shown that exciton diffusion in PNC solids occurs via alternate exciton hopping(EH)and photon recycling(PR).The energy disorder induced by the size distribution is a common factor in PNC solids,and the impact of this energy disorder on the exciton diffusion remains unclear.Here,we investigated the exciton diffusion in CsPbBr3 NC solids with a Gaussian size distribution of 11.2±6.8 nm via steady and time-resolved photoluminescence(PL)spectroscopy with multiple detection bands in transmission mode.Our results indicated that exciton diffusion was controlled by a downhill transfer among the different energy sites through the disordered energy landscape,as confirmed by the accompanying low-temperature PL analysis.A detailed examination revealed that the acceptor distribution in tandem with the reabsorption coefficient determined the contribution of EH and PR to exciton transfer between different energy sites.Consequently,the exciton diffusion mechanism varied in PNC solids of different thicknesses:in a thin solid with a thickness of several hundred nanometers,the exciton transfer was dominated by efficient EH and PR from the high-energy sites to the lower-energy sites;in a few-micrometer-thick solid,transfer from the medium-energy sites toward the lower-energy sites also became prominent and occurred mainly through PR.These findings enhance the understanding of the vital role that the acceptor distribution plays in the exciton diffusion process in PNC solids,providing important insights for optoelectronic applications based on PNC solids.Our work also exploits the use of commonly available tools for in-depth exciton diffusion studies,which reveals the interior diffusion information that is usually hidden in surface sensitive PL imaging methods.

Defect-induced distinct exciton-exciton interactions in WS2 monolayers

The optoelectronic properties of atomically thin transition metal dichalcogenides(TMDs)are largely influenced by defect populations(DPs).In this work,we fabricate WSmonolayers with different DPs by varying the fabrication methods and further reveal their distinct exciton-exciton interactions.Steady-state photoluminescence(PL)experiments show that the monolayer with the lowest DP shows optimal PL intensity at low excitation power;however,it is overtaken and significantly surpassed by monolayers with higher DPs at high excitation powers.Excitation-power-dependent experiments demonstrate that these monolayers exhibit distinct PL saturation behaviors with the threshold power differing by four orders of magnitude.Combined with in situ PL imaging and time-resolved PL experiments,we attribute such PL evolution discrepancies to the different DPs within these monolayers,which largely influence the exciton diffusion behavior and subsequently bring about distinct nonradiative exciton-exciton annihilations(EEAs).Valley polarization experiments are further employed to re-examine the DPs of these monolayers.This work reveals the distinct PL behaviors and underlying exciton dynamics in TMD monolayers with different DPs,which can largely facilitate the engineering of relevant high-performance devices for practical applications.

Phonon scattering and exciton localization: molding exciton flux in two dimensional disorder energy landscape

Two dimensional excitonic devices are of great potential to overcome the dilemma of response time and integration in current generation of electron or/and photon based systems.The ultrashort diffusion length of exciton arising from ultrafast relaxation and low carrier mobility greatly discounts the performance of excitonic devices.Phonon scattering and exciton localization are crucial to understand the modulation of exciton flux in two dimensional disorder energy landscape,which still remain elusive.Here,we report an optimized scheme for exciton diffusion and relaxation dominated by phonon scattering and disorder potentials in WSe2 monolayers.The effective diffusion coefficient is enhanced by>200%at 280 K.The excitons tend to be localized by disorder potentials accompanied by the steadily weakening of phonon scattering when temperature drops to 260 K,and the onset of exciton localization brings forward as decreasing temperature.These findings identify that phonon scattering and disorder potentials are of great importance for long-range exciton diffusion and thermal management in exciton based systems,and lay a firm foundation for the development of functional excitonic devices.

From electronic excited state theory to the property predictions of organic optoelectronic materials

We introduce here a work package for a National Natural Science Foundation of China Major Project. We propose to develop computational methodology starting from the theory of electronic excitation processes to predicting the opto-electronic property for organic materials, in close collaborations with experiments. Through developing methods for the electron dynamics, considering superexchange electronic couplings, spin-orbit coupling elements between excited states, electron-phonon relaxation, intermolecular Coulomb and exchange terms we combine the statistical physics approaches including dynamic Monte Carlo, Boltzmann transport equation and Boltzmann statistics to predict the macroscopic properties of opto-electronic materials such as light-emitting efficiency, charge mobility, and exciton diffusion length. Experimental synthesis and characterization of D-A type ambipolar transport material as well as novel carbon based material will provide a test ground for the verification of theory.

Theoretical study of the low-lying electronic excited states for molecular aggregates

We present here a brief summary of a National Natural Science Foundation Major Project entitled "Theoretical study of the low-lying electronic excited state for molecular aggregates". The project focuses on theoretical investigation of the electronic structures and dynamic processes upon photo-and electric-excitation for molecules and aggregates. We aim to develop reliable methodology to predict the optoelectronic properties of molecular materials related to the electronic excitations and to apply in the experiments. We identify two essential scientific challenges: (i) nature of intramolecular and intermolecular electronic excited states; (ii) theoretical description of the dynamic processes of the coupled motion of electronic excitations and nucleus. We propose the following four subjects of research: (i) linear scaling time-dependent density-functional theory and its application to open shell system; (ii) computational method development of electronic excited state for molecular aggregates; (iii) theoretical investigation of the time evolution of the excited state dynamics; (iv) methods to predict the optoelectronic properties starting from electronic excited state investigation for organic materials and experimental verifications.

Charge generation in organic solar cells: Journey toward 20% power conversion efficiency

The power conversion efficiencies of organic solar cells(OSCs)have routinely lagged far behind those of their inorganic counterparts.However,owing to the enor-mous contributions of many researchers,the power conversion efficiencies of OSCs have rapidly improved and now exceed 19%.The charge generation mechanisms in OSCs have been heavily debated during this period while acquiring valuable knowl-edge.This review highlights fundamental and cutting-edge research that rationalizes why OSCs can generate photocurrent so efficiently.In particular,a photophysi-cist’s views on exciton diffusion to donor:acceptor interfaces,charge transfer at the donor:acceptor interface,and long-range spatial dissociation of charge transfer states are discussed.Although a general consensus in this area has not been reached yet,recent time-resolved spectroscopic measurements provide important photophys-ical insights that can help achieving a better understanding of the charge generation mechanism in OSCs.Based on these observations,future research directions for realizing further improvements in OSC performance are discussed.