- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Enhancing Reverse Intersystem Crossing via Secondary Acceptors: towards Sky-Blue Fluorescent Diodes with Tenfold-Improved Exter-nal Quantum Efficiency
摘要： How to simply but effectively facilitate reverse intersystem crossing (RISC) transition is always the key issue for developing high-performance thermally activated delayed fluorescence (TADF) dyes. In this work, as a proof of concept, a feasible strategy named 'acceptor enhancement' is demonstrated with a series of ternary blue emitters (xCzmPOnTPTZ) using diphenylphosphine oxide (PO) as secondary acceptors. Compared with its PO-free binary analogue, such simple introduction of PO groups in pCzPO2TPTZ dramatically enhances its RISC rate constant (kRISC) by 10 times to the level of ~105 s-1, accompanied by RISC efficiency (ηRISC) of 92%, which further improves the triplet-to-singlet upconversion for effective triplet harvesting in its devices. As the result, on the basis of a trilayer device structure, pCzPO2TPTZ realized a state-of-the-art external quantum efficiency (EQE) beyond 20% with tenfold improvement.
关键词： Organic Light-Emitting Diode,Thermally Activated Delayed Fluorescence,Excited State Transition,Blue Emission,Reverse Intersystem Crossing,Phosphine Oxide Acceptor
更新于2025-09-23 15:23:52
-
Ultrafast spectroscopy of the primary charge transfer and ISC processes in 9-anthraldehyde
摘要： The ultrafast charge transfer (CT) and the following intersystem crossing (ISC) processes of 9-anthraldehyde were investigated in ethanol and hexane using femtosecond transient absorption spectroscopy combined with quantum chemical calculations. The CT was observed within 0.11 ps in ethanol and 0.23 ps in hexane. Due to the stronger polarity in ethanol, the CT is faster than in hexane. The following ISC is determined to be 22.3 ps and 21.4 ps in two solvents, respectively. However, the timescales of ISC are similar in both solvents since the excited energies of the S1 and triplet states are close.
关键词： Time-resolved transient absorption spectroscopy,intramolecular charge transfer,radiationless intersystem crossing
更新于2025-09-23 15:23:52
-
Efficient and Stable Deep-Blue Fluorescent Organic Light-Emitting Diodes Employing a Sensitizer with Fast Triplet Upconversion
摘要： Multiple donor–acceptor-type carbazole–benzonitrile derivatives that exhibit thermally activated delayed fluorescence (TADF) are the state of the art in efficiency and stability in sky-blue organic light-emitting diodes. However, such a motif still suffers from low reverse intersystem crossing rates (kRISC) with emission peaks <470 nm. Here, a weak acceptor of cyanophenyl is adopted to replace the stronger cyano one to construct blue emitters with multiple donors and acceptors. Both linear donor–π–donor and acceptor–π–acceptor structures are observed to facilitate delocalized excited states for enhanced mixing between charge-transfer and locally excited states. Consequently, a high kRISC of 2.36 × 106 s?1 with an emission peak of 456 nm and a maximum external quantum efficiency of 22.8% is achieved. When utilizing this material to sensitize a blue multiple-resonance TADF emitter, the corresponding device simultaneously realizes a maximum external quantum efficiency of 32.5%, CIEy ≈ 0.12, a full width at half maximum of 29 nm, and a T80 (time to 80% of the initial luminance) of > 60 h at an initial luminance of 1000 cd m?2.
关键词： stable deep-blue devices,sensitized emission,high reverse intersystem crossing,thermally activated delayed fluorescence,multiple donors and acceptors
更新于2025-09-23 15:21:01
-
Photorelaxation Pathways of 4-(N,N-Dimethylamino)-4a?2-nitrostilbene Upon S1 Excitation Revealed by Conical Intersection and Intersystem Crossing Networks
摘要： Multi-state n-electron valence state second order perturbation theory (MS-NEVPT2) was utilized to reveal the photorelaxation pathways of 4-(N,N-dimethylamino)-4'-nitrostilbene (DANS) upon S1 excitation. Within the interwoven networks of five S1/S0 and three T2/T1 conical intersections (CIs), and three S1/T1 intersystem crossings (ISCs), those competing nonadiabatic decay pathways play different roles in trans-to-cis and cis-to-trans processes, respectively. After being excited to the Franck–Condon (FC) region of the S1 state, trans-S1-FC firstly encounters an ultrafast conversion to quinoid form. Subsequently, the relaxation mainly proceeds along the triplet pathway, trans-S1-FC → ISC-S1/T1-twist → trans- or cis-S0. The singlet relaxation pathway mediated by CI-S1/S0-twist-c is hindered by the prominent energy barrier on S1 surface and by the reason that CI-S1/S0-twist-t are both not energetically accessible upon S1 excitation. On the other hand, the cis-S1-FC lies at the top of steeply decreasing potential energy surfaces (PESs) towards the CI-S1/S0-DHP regions; therefore, the initial twisting directions of DN and DAP moieties determine the branching ratio between αC=C twisting (cis-S1-FC → CI-S1/S0-twist-c → trans- or cis-S0) and DHP formation relaxation pathways (cis-S1-FC → CI-S1/S0-DHP → DHP-S0) on the S1 surface. Moreover, the DHP formation could also take place via the triplet relaxation pathway, cis-S1-FC → ISC-S1/T1-cis → DHP-T1 → DHP-S0, however, which may be hindered by insufficient spin-orbit coupling (SOC) strength. The other triplet pathways for cis-S1-FC mediated by ISC-S1/T2-cis are negligible due to the energy or geometry incompatibility of possible consecutive stepwise S1 → T2 → T1 or S1 → T2 → S1 processes. The present study reveals photoisomerization dynamic pathways via conical intersection and intersystem crossing networks and provides nice physical insight into experimental investigation of DANS.
关键词： MS-NEVPT2,intersystem crossing,photorelaxation,conical intersection
更新于2025-09-23 15:21:01
-
Unveiling the photophysics of thiourea from CASPT2/CASSCF potential energy surfaces and singlet/triplet excited state molecular dynamics simulations
摘要： This work describes the decay mechanism of photoexcited thiourea, both in gas phase and in solution, from the information inferred from the topography of the excited and ground state potential energy surfaces and mixed singlet/triplet quantum classical molecular dynamics simulations. Our gas phase results reveal T1/S0 intersystem crossing as the dominant (49%) intrinsic decay channel to the ground state, which reaches a population of 0.28 at the final time of our simulations (10 ps). Population of the T1, would occur after internal conversion to the S1 from the spectroscopic S2 electronic state, followed by S1->T2 intersystem crossing and T2->T1 internal conversion processes. Minor decay channels occurring exclusively along the singlet manifold, i.e. S2->S0 (33%) and S1->S0 (18%), were also observed to play a role in the relaxation of photoexcited thiourea in the gas phase. The explicit incorporation of water-thiourea interactions in our simulations was found to provoke a very significant delay in the decay to the ground state of the system, with no transitions to the S0 being registered during the first 10 ps of our simulations. Intermolecular vibrational energy redistribution and explicit hydrogen bond interaction established between water molecules and the NH2 group of thiourea were found to structurally or energetically hamper the access to the intersystem crossing or internal conversion funnels with the S0.
关键词： intersystem crossing,internal conversion,CASPT2 calculations,thiourea,molecular dynamics simulations
更新于2025-09-19 17:15:36
-
Plasmonic Silver Nanoprism-Induced Emissive Mode Control between Fluorescence and Phosphorescence of a Phosphorescent Palladium Porphyrin Derivative
摘要： We have succeeded in significantly enhancing fluorescence from intrinsically phosphorescent palladium octaethylporphyrin (Pd-porphyrin) that has an intersystem crossing efficiency of ~1 by using silver nanoprisms (AgPRs). This was achieved by controlling the wavelength of localized surface plasmon (LSP) resonance of AgPRs and the distance between the Pd-porphyrin molecules and the AgPR surfaces. In addition to enhancing phosphorescence by spectrally overlapping the phosphorescence band with the LSP resonance band, tuning the LSP wavelength to approximately 520 nm led to the appearance of a new emission band around the wavelength corresponding to the fluorescent radiation. The appearance of fluorescence suggests that the nonradiative energy transfer from the singlet excited state of Pd-porphyrin to the LSP of AgPRs overcame the ultrafast intramolecular intersystem crossing to the triplet excited state, manifesting the spectral properties of the singlet excited state of Pd-porphyrin. The fluorescence nature of this radiation was strongly supported by lifetime measurements of the hybrids of Pd-porphyrin and AgPRs. Furthermore, the dependence of the emissive intensities on the distance between the Pd-porphyrin molecules and the AgPR surfaces showed interesting opposite trends. The fluorescence intensity was increased as the distance between the molecules and the AgPRs was decreased from 10.5 nm to 1 nm, while the phosphorescence intensity was decreased, which indicates that the LSP-induced fluorescence radiation process from Pd-porphyrin near the AgPRs outweighed the quenching by the AgPRs, even though the phosphorescence significantly suffered quenching.
关键词： silver nanoprisms,localized surface plasmon resonance,palladium porphyrin,phosphorescence,metal-enhanced fluorescence,fluorescence,intersystem crossing
更新于2025-09-19 17:13:59
-
Recent advances in thermally activated delayed fluorescence for white OLEDs applications
摘要： Thermally activated delayed fluorescence (TADF) materials, which can harvest all excitons without utilizing any noble metals to emit light, are becoming the key cornerstone for developing the next generation of organic light-emitting diode (OLED) devices. In recent years, TADF materials are attracting numerous attentions as a new surge of research focuses on both science and industry owing to their high efficiency, low power consumption, and low production cost attributes when applied to white OLEDs. The design and application of TADF in WOLED devices have also experienced the rapid development in fundamental science and industrial technology perspectives. In the present review, the specific reverse intersystem crossing mechanism and evolution of TADF is outlined firstly, and then the latest research progress of TADF-WOLEDs is summarized and discussed. TADF/conventional fluorescence, TADF/phosphorescence, all TADF and TADF exciplex-based WOLEDs are categorized and elaborated in terms of the device structure, working mechanism, efficiency, color-rendering index, etc. Finally, we conclude with the future challenges and opportunities in high-quality TADF devices and application area.
关键词： Thermally activated delayed fluorescence,exciplex,OLED,TADF,RISC,white OLEDs,organic light-emitting diode,reverse intersystem crossing
更新于2025-09-19 17:13:59
-
Enhanced triplet state generation through radical pair intermediates in BODIPY-quantum dot complexes
摘要： Generation of triplet excited states through radical pair intermediates has been extensively studied in molecular complexes. Similar schemes remain rare in hybrid structures of quantum dot-organic molecules, despite intense recent interest of quantum dot sensitized triplet excited state generation. Herein, we demonstrate that the efficiency of the intersystem crossing from the singlet to the triplet state in boron dipyrromethene (BODIPY) can be enhanced in CdSe quantum dot-BODIPY complexes through a radical pair intermediate state consisting of an unpaired electron in the quantum dot conduction band and that in oxidized BODIPY. By transient absorption spectroscopy, we show that the excitation of BODIPY with 650 nm light leads to the formation of a charge separated state by electron transfer from BODIPY to CdSe (with a time constant of 6.33 ± 1.13 ns), competing with internal conversion to the ground state within BODIPY, and the radical pair state decays subsequently by back charge recombination to generate a triplet excited state (with a time constant of 158 ± 28 ns) or the ground state of BODIPY. The overall quantum efficiency of BODIPY triplet excited state generation was determined to be (27.2 ± 3.0)%. The findings of efficient triplet state formation and intermediate radical pair states in this hybrid system suggest that quantum dot-molecule complexes may be a promising platform for spintronics applications.
关键词： CdSe quantum dot,radical pair intermediates,transient absorption spectroscopy,intersystem crossing,spintronics,triplet excited states,BODIPY,quantum dot-organic molecules
更新于2025-09-12 10:27:22
-
Aggregation-Induced Delayed Fluorescence Luminogens with Accelerated Reverse Intersystem Crossing for High-Performance OLEDs
摘要： A fast reverse intersystem crossing (RISC) is of high importance for delayed fluorescence emitters in terms of increasing exciton utilization and suppressing efficiency roll-off. Herein, new robust luminogens comprised of carbonyl, phenoxazine and chlorine-substituted carbazole derivatives are synthesized and characterized. They own distinct aggregation-induced delayed fluorescence (AIDF) feature, and exhibit high photoluminescence efficiencies and short delayed fluorescence lifetimes in neat films. The RISC is conspicuously accelerated owing to their tiny singlet-triplet energy splitting and greatly enhanced spin-orbit coupling by heavy atom effect in neat films. They can function efficiently as light-emitting layers in nondoped OLEDs, providing excellent maximum electroluminescence (EL) efficiencies of 20.4–21.7%, and can also perform outstandingly in doped OLEDs in a wide doping concentration range (5–90 wt%), affording impressive EL efficiencies of up to 100.1 cd A–1, 104.8 lm W–1 and 29.1%, with small efficiency roll-off. These findings demonstrate the AIDF luminogens with fast RISC are promising candidates to fulfill various demands of production and application of OLEDs.
关键词： OLEDs,Reverse Intersystem Crossing,Luminogens,Aggregation-Induced Delayed Fluorescence,High-Performance
更新于2025-09-11 14:15:04
-
Highly efficient thermally activated delayed fluorescence with slow reverse intersystem crossing
摘要： We report an efficient luminescent molecule exhibiting thermally activated delayed fluorescence with a long-delayed fluorescence lifetime of 0.8 ms. Although the reverse intersystem crossing rate constant is small at 2.1 × 103 s?1, the molecule shows a high photoluminescence quantum yield of 89±2%, indicating the suppression of nonradiative decay from the triplet state.
关键词： Long triplet lifetime,Thermally activated delayed fluorescence (TADF),Reverse intersystem crossing (RISC)
更新于2025-09-10 09:29:36