Computationally predicting reverse intersystem crossing (RISC) rates is important for designing new thermally activated delayed fluorescence (TADF) materials. We report a method that can quantitatively predict RISC rates by explicitly considering the spin–vibronic coupling mechanism. The coupling element of the spin–vibronic Hamiltonian is obtained by expanding the spin–orbit and the non-Born–Oppenheimer terms to second order and is then brought into the Golden Rule rate under the Condon approximation. The rate equation is solved directly in the time domain using a correlation function approach. The contributions of the first-order direct spin–orbit coupling and the second-order spin–vibronic coupling to an RISC rate can be quantitatively analyzed in a separate manner. We demonstrate the utility of the method by applying it to a representative TADF system, where we observe that the spin–vibronic portion is substantial but not dominant especially with a relatively small triplet–singlet energy gap. Likewise, our method may elucidate the physical background of efficient nonradiative transitions from the lowest triplet to a higher lying singlet in other purely organic TADF systems, and it will be of great utility toward designing new such molecules.
Materials showing reversible resistance switching between high-resistance state and low-resistance state at room temperature are attractive for today’s semiconductor technology. In this letter, the reproducible hysteresis and resistive switching characteristics of metal-CuxO-metal (M-CuxO-M) heterostructures driven by low voltages are demonstrated. The fabrication of the M-CuxO-M heterostructures is fully compatible with the standard complementary metal-oxide semiconductor process. The hysteresis and resistive switching behavior are discussed. The good retention characteristics are exhibited in the M-CuxO-M heterostructures by the accurate controlling of the preparation parameters.
Several methods of harvesting singlet excitons via delayed fl uorescence have been introduced in OLED so far. These methods include up-conversion to singlet excitons by triplet-triplet annihilation (TTA) [ 3,4 ] or triplet fusion in materials that show a strong singlet fi ssion. [ 5 ] A different approach for enhancing the singlet emission that involves triplet excitons was introduced recently, whereby the triplet excitons may undergo reverse intersystem crossing (RISC) to singlet excitons and consequently give rise to thermally activated delayed fl uorescence (TADF). [6][7][8][9][10][11][12] This occurs in compounds with small electron exchange energy, and thus small singlet-triplet energy splitting, Δ E ST that enables triplet excitons to undergo thermally activated RISC to the singlet manifold. [ 13 ] A fi rm indication for TADFrelated emission in compounds that possess RISC is that the EL in these OLED is thermally activated, with activation energy E act ≈ Δ E ST Ͻ Ͻ 0.7 eV (which is Δ E ST in traditional organic semiconductors). During the last few years there has been a large interest in magnetic fi eld effect (MFE) in conjugated organic compounds, mainly because of the possibility to enhance the electroluminescence effi ciency, which was dubbed magneto-EL (MEL). [ 11,[14][15][16][17][18][19][20][21] In this effect, the magnetic fi eld changes the exchange rate between PP singlet (PP S ) and triplet (PP T ), which can be detected through the induced change in the EL emission intensity (MEL) or the current density (MC) in the device. This occurs if the PP S and PP T recombination rates ( R S , R T ) and/or dissociation rates ( d S , d T ) differ from each other. [ 17,22 ] So far the MEL maximum value, MEL max at room temperature (RT) has been less than ≈20% in OLEDs.In conventional OLEDs, spin mixing occurs within the PP states rather than at the exciton levels because the electron-hole orbitals strongly overlap in the latter species leading to large exchange energy, J , that consequently causes large energy gap, Δ E ST (=2 J ) between singlet and triplet states. In contrast, materials showing RISC may allow spin-mixing among the PP spin levels and in the exciton levels because Δ E ST is small. [ 23 ] In this case, possible spin-mixing mechanism may be the hyperfi ne interaction [ 24,25 ] and/or the Δ g mechanism, [ 26 ] where the difference, Δ g in the g -values of positive and negative carrier in the pair may promote intersystem crossing. The obtained full width Reverse intersystem crossing (RISC) from triplet to singlet states has been recently introduced to photophysics of organic chromophores. One type of RISC occurs in donor (D)-acceptor (A) composites that form an exciplex manifold in which the energy difference, Δ E ST between the lowest singlet (S 1 ) and triplet (T 1 ) levels of the exciplex is small (<100 meV) thus allowing RISC at room temperature. This adds a delayed component to the photoluminescence emission that is widely known as thermally activated delayed fl uorescence. Here, it is found t...
Finding narrow-band, ultrapure blue thermally activated delayed fluorescence (TADF) materials is extremely important for developing highly efficient organic light-emitting diodes (OLEDs). Here, spin-vibronic coupling (SVC)-assisted ultrapure blue emitters obtained by joining two carbazole-derived moieties at a para position of a phenyl unit and performing substitutions using several blocking groups are presented. Despite a relatively large singlet-triplet gap (∆E ST ) of >0.2 eV, efficient triplet-to-singlet crossover can be realized, with assistance from resonant SVC. To enhance the spin crossover, electronic energy levels are fine-tuned, thereby causing ∆E ST to be in resonance with a triplet-triplet gap (∆E TT ). A sizable population transfer between spin multiplicities (>10 3 s −1 ) is achieved, and this result agrees well with theoretical predictions. An OLED fabricated using a multiple-resonance-type SVC-TADF emitter with CIE color coordinates of (0.15, 0.05) exhibits ultrapure blue emissions, with a narrow full-width-at-half-maximum of 21 nm and a high external quantum efficiency of 23.1%.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.