Singlet-triplet Energy Splitting Research Articles

Endo-Encapsulated Multi-Resonance Dendrimers with Through-Space Interactions for Efficient Narrowband Blue-Emitting Solution-Processed OLEDs.

Different from conventional luminescent dendrimers with fluorophore tethered outside to dendron, here we first developed endo-encapsulated luminescent dendrimers with multi-resonance (MR) fluorophore embedded inside of carbazole dendrons by growing dendrons through 1,8-positions of central carbazole moiety to create a cavity for accommodating the fluorophore. This endo-encapsulated structure not only shields the fluorophore to fully resist aggregation-caused spectral broadening, but also induce through-space interactions between dendron and fluorophore via intramolecular π-stacking, giving lowered singlet state energy and reduced singlet-triplet energy splitting to accelerate reverse intersystem crossing (RISC) from triplet to singlet states. The resultant dendrimer containing 1,8-linked second-generation carbazole dendrons and boron, sulfur-doped polycyclic MR fluorophore exhibits narrowband blue emission at 471 nm with FWHM kept at 34 nm even in neat film, together with ~4 times enhancement of RISC rate constant compared to its exo-tethered counterpart. Solution-processed OLEDs based on the endo-encapsulated dendrimer reveal efficient narrowband blue emissions with maximum external quantum efficiency of 22.6%, representing the best device efficiency for blue-emitting multi-resonance dendrimers so far.

Sulfur-doped carbon dots and g-C3N4 composite with thermally activated delayed fluorescence for white-light illumination and anticounterfeiting

Long-lived afterglow materials have attracted considerable interest in the fields of information security and illumination. Herein, a novel carbon dot (CD)-based thermally activated delayed fluorescence (TADF) material was synthesized by embedding sulfur-doped CDs (SCDs) into a graphitic carbon nitride matrix. The formation of covalent bonds between the matrix and SCDs enhances the stabilization of the triplet state in the composite, effectively suppressing nonradiative transitions. This stabilization, coupled with the effects of sulfur doping and covalent bonding, reduces the singlet–triplet splitting energy in the composite, thereby facilitating reverse intersystem crossing and resulting in TADF emission. This composite material has been successfully employed in the development of three types of CD-based white light–emitting diodes (WLEDs) excited by blue light. These WLEDs exhibit color temperatures of 7641, 5590, and 3215 K, with CIE coordinates of (0.30, 0.29), (0.33, 0.30), and (0.42, 0.40), respectively. The corresponding values of the color rendering index are recorded as 81.86, 90.13, and 75.07. In addition, this research provides a brief demonstration of the potential of the composite in information encryption and visible-light encryption applications. Furthermore, this study contributes to the advancement of CD utilization in the WLED field, promoting the development of next-generation CD-based WLEDs with exceptional properties.

Cyanonaphthalene and cyanonaphthyl radicals: Vibrational structures via computed negative ion photoelectron spectra and thermochemistry of 1- and 2-cyanonaphthalene.

A double harmonic oscillator model is applied to compute the negative ion photoelectron spectra (NIPES) of the 1- and 2-cyanonaphthalene (CNN) radical anions. The computed Franck-Condon factors utilize optimized structures and harmonic vibrational frequencies obtained using density functional theory with the B3LYP 6-311++G (2d,2p) basis set while considering the mode-mixing Duschinsky effects. To test the accuracy of our model, the NIPES of α and β naphthyl radical anions were computed, and a strong agreement between the slow electron velocity-map ion imaging spectra and the predicted spectra was found. The adiabatic electron affinities (EAs) of the ground singlet states (S0) in 1-CNN and 2-CNN are 0.856 and 0.798eV, respectively. The origin of the lowest-lying triplet (T1) states in 1-CNN and 2-CNN is found to be 3.226 and 3.266eV, resulting in singlet-triplet energy splittings (ΔEST) of 2.370 and 2.468eV, respectively. Both the NIPES for electron detachment to the S0 and T1 states exhibit well-resolved vibrational features, allowing for the assignment of several vibrational fundamental frequencies. Following deprotonation, several isomers are formed, with the most stable deprotonated radical anions in 1-CNN and 2-CNN, corresponding to the removal of the most acidic proton, with EAs of 2.062 and 2.16eV. The rich spectroscopic and thermochemical data obtained in the current study make the CNN radical anions and their deprotonated species interesting systems for investigation in gas-phase, negative-ion experiments.

High-performance fully solution-processed OLEDs based on carbazole-benzonitrile TADF emitter with long alkyl chains

The introduction of alkyl chains into the luminescent molecules will increase solubility and film-forming performance for fabricating solution-processed organic semiconductor devices. In this work, 5CzBN-9CSP and 5CzBN-12CSP with long alkyl chains were synthesized based on the typical thermally activated delayed fluorescence (TADF) molecule 5CzBN as core, and bipolar 9,9′-spirobi[fluorene] (SP) groups as peripheral dendrons. Not only the excellent solution processability is invested, but also the uniform photophysical property is sustained, including small singlet-triplet splitting energy (ΔEST) and high reverse intersystem crossing (RISC) rate. However, excessive length of alkyl chains degrading thermodynamic stability and carrier transport and balance, results in a maximum external quantum efficiency (EQEmax) of 17.6% for 5CzBN-12CSP-based fully solution-processed non-doped device, which is lower than that for 5CzBN-9CSP counterpart. Furthermore, TADF sensitized (TSF) solution-processed device obtains a high EQEmax of 25.9% within 5CzBN-12CSP host and multiple-resonance (MR) final emitter thanks to an efficient energy transfer.

Derivatives of Phenyl Pyrimidine and of the Different Donor Moieties as Emitters for OLEDs.

Two derivatives of phenyl pyrimidine as acceptor unit and triphenylamino or 4,4'-dimethoxytriphenylamino donor groups were designed and synthesized as emitters for organic light-emitting diodes (OLEDs) aiming to utilize triplet excitons in the electroluminescence. Thermogravimetric analysis revealed high thermal stability of the compounds with 5% weight loss temperatures of 397 and 438 °C. The theoretical estimations and photophysical data show the contributions of local excited and charge transfer states into emission. The addition of the methoxy groups led to the significant improvement of hole-transporting properties and the bathochromic shift of the emission from blue to green-blue spectral diapason. It is shown that mixing of the compounds with the organic host results in facilitation of the delayed emission. The singlet-triplet energy splitting was found to be too big for the thermally activated delayed fluorescence. No thermal activation of the long-lived emission was detected. No experimental evidence for triplet-triplet annihilation and room temperature phosphorescence were detected making the hot exciton mechanism the most probable one. The OLEDs based on the compounds reached the maximum external quantum efficiency of up to 10.6%.

Rational molecular design of efficient yellow-red dendrimer TADF for solution-processed OLEDs: a combined effect of substitution position and strength of the donors

AbstractThe development of high-performance solution-processed red organic light-emitting diodes (OLEDs) remains a challenge, particularly in terms of maintaining efficiency at high luminance. Here, we designed and synthesized four novel orange-red thermally activated delayed fluorescence (TADF) dendrimers that are solution-processable: 2GCzBP, 2DPACzBP, 2FBP2GCz and 2FBP2DPACz. We systematically investigated the effect of substitution position and strength of donors on the optoelectronic properties. The reverse intersystem crossing rate constant (kRISC) of the emitters having donors substituted at positions 11 and 12 of the dibenzo[a,c]phenazine (BP) is more than 10-times faster than that of compounds substituted having donors substituted at positions 3 and 6. Compound 2DPACzBP, containing stronger donors than 2GCzBP, exhibits a red-shifted emission and smaller singlet-triplet energy splitting, ΔEST, of 0.01 eV. The solution-processed OLED with 10 wt% 2DPACzBP doped in mCP emitted at 640 nm and showed a maximum external quantum efficiency (EQEmax) of 7.8%, which was effectively maintained out to a luminance of 1,000 cd m−2. Such a device∙s performance at relevant display luminance is among the highest for solution-processed red TADF OLEDs. The efficiency of the devices was improved significantly by using 4CzIPN as an assistant dopant in a hyperfluorescence (HF) configuration, where the 2DPACzBP HF device shows an EQEmax of 20.0% at λEL of 605 nm and remains high at 11.8% at a luminance of 1,000 cd m−2, which makes this device one of the highest efficiency orange-to-red HF SP-OLEDs to date.

Achieving Visible-Light-Excitable Blue TADF-Type Afterglow via Delicate Control of Excited States in Difluoroboron β-Diketonate Systems.

Blue afterglow constitutes of one of the primary afterglow colors and can convert into other afterglow colors through energy transfer. The reported studies show the fabrication of blue afterglow emitters, but most of them are formed by room-temperature phosphorescence mechanism and require UVB lights as excitation source (these high-energy lights may damage organic systems). Here we report visible-light-excitable blue thermally activated delayed fluorescence type (TADF-type) afterglow materials via delicate control of excited states in difluoroboron β-diketonate (BF2bdk) systems. Tiny change of the substituents in BF2bdk system has been found to pose significant influence on excited state energy levels and consequently narrow the singlet-triplet splitting energy of the system. As a result, both forward and reverse intersystem crossing have been accelerated, leading to the emergence of BF2bdk's TADF-type organic afterglow in rigid crystalline matrices. The resultant TADF-type afterglow materials exhibit emission lifetimes of several hundred milliseconds, photoluminescence quantum yield (PLQY) of 24.7 % and display temperature responsive property.

A database of thermally activated delayed fluorescent molecules auto-generated from scientific literature with ChemDataExtractor

A database of thermally activated delayed fluorescent (TADF) molecules was automatically generated from the scientific literature. It consists of 25,482 data records with an overall precision of 82%. Among these, 5,349 records have chemical names in the form of SMILES strings which are represented with 91% accuracy; these are grouped in a subsidiary database. Each data record contains one of the following four properties: maximum emission wavelength (λEM), photoluminescence quantum yield (PLQY), singlet-triplet energy splitting (ΔEST), and delayed lifetime (τD). The databases were created through text mining using ChemDataExtractor, a chemistry-aware natural-language-processing toolkit, which has been adapted for TADF research. The text-mined corpus consisted of 2,733 papers from the Royal Society of Chemistry and Elsevier. To the best of our knowledge, these databases are the first databases that have been auto-generated for TADF molecules from existing publications. The databases have been publicly released for experimental and computational applications in the TADF research field.

Molecular Engineering Modulating the Singlet-Triplet Energy Splitting of Indolocarbazole-Based TADF Emitters Exhibiting AIE Properties for Nondoped Blue OLEDs with EQE of Nearly 20.

The development of efficient blue thermally activated delayed fluorescence (TADF) emitters with an aggregation-induced emission (AIE) nature, for the construction of organic light-emitting diodes (OLEDs), is still insufficient. This can be attributed to the challenges encountered in molecular design, including the inherent trade-off between radiative decay and reverse intersystem crossing (RISC), as well as small singlet-triplet energy splitting (ΔEST) and the requirement for high photoluminescence quantum yields (ΦPL). Herein, we present the design of three highly efficient blue TADF molecules with AIE characteristics by combining π-extended donors with different acceptors to modulate the differences in the electron-donating and electron-withdrawing abilities. This approach not only ensures high emission efficiency by suppressing close π-π stacking, weakening nonradiative relaxation, and enhancing radiative transition but also maintains the equilibrium ratio between the triplet and singlet excitons by facilitating the process of RISC. These emitters exhibit AIE and TADF properties, featuring quick radiative rates and low nonradiative rates. The ΦPL of these emitters reached an impressive 88%. Based on their excellent comprehensive performance, nondoped PICzPMO and PICzPMO OLEDs achieved excellent electroluminescence performance, exhibiting maximum external quantum efficiency (EQEmax) of up to 19.5%, while the doped device achieved a higher EQEmax of 20.8%. This work demonstrated that by fusing π-extended large rigid donors with different acceptors, it is possible to regulate the difference in electron-donating and electron-withdrawing abilities, resulting in a small ΔEST, high ΦPL, and fast RISC process, which is a highly feasible strategy for designing efficient TADF molecules.

Transformation of organic afterglow mechanism from room-temperature phosphorescence to thermally-activated delayed fluorescence in intramolecular charge transfer systems

Organic afterglow materials have emerged as an important class of luminescent materials. These afterglow systems feature small rate constants of key photophysical processes, such as phosphorescence decay and nonradiative decay of triplet excited states. When coupled to other photophysical processes, these afterglow systems would give rise to intriguing photophysical behaviors. Here we report the transformation of afterglow mechanism from room-temperature phosphorescence (RTP) to thermally-activated delayed fluorescence (TADF) in intramolecular charge transfer (ICT) systems. Detailed studies reveal that the increase of the acceptor strength of ICT molecules can reduce singlet-triplet splitting energy and consequently open reverse intersystem crossing (RISC) pathway with moderate kRISC of 1–10 s−1 to harvest triplet energies, leading to the RTP-to-TADF afterglow transformation. Such observations provide deep understanding on the behaviors of organic triplets with small photophysical rate constants. Besides, these organic ICT molecules have been incorporated into aqueous emulsion systems to exhibit promising applications.

Tuning photophysical properties of bicarbazole-based blue TADF emitters with AIE feature: Trade-off between small singlet-triplet energy splitting and high photoluminescence quantum yield

Three aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) blue light-emitting materials were successfully synthesized using bicarbazole and phenylsulfonyl/benzophenone moieties as electron donors and acceptors, respectively, via Buchwald-Hartwig reaction. Density functional theory calculations showed that the three emitters have a moderate dihedral angle between the two carbazole planes and between the donor and acceptor, resulting in a good conjugated structure and a trade-off between the small ΔEST and high photoluminescence quantum yield of the BCzDPM molecule. The cyclic voltammetry, thermogravimetric analysis and differential scanning calorimetry tests demonstrated that the three materials had high electrochemical and thermal stability. The three emitters exhibited obvious intramolecular charge transfer characteristics in solution and film. According to the fluorescence and low-temperature phosphorescence spectra, the lowest singlet and triplet excited state energy levels of BCzDPM were 2.96 eV and 2.78 eV, respectively, with a ΔEST of 0.18 eV. Using these emitters as non-doped emissive layers, efficient blue electroluminescent devices were fabricated. The maximum current efficiency and external quantum efficiency reached 15.4 cd/A and 7.05% for the BCzDPM device, respectively, and the efficiency roll-off of BCzDPM was smaller than that of PSOBCz and PBCzPM, under high current density.

Space-confined through-space charge-transfer emitters based on CN-substituted fluorene acceptors: Design, synthesis, and thermally-activated delayed fluorescence

Space-confined through-space charge-transfer (TSCT) emitters have been extensively explored for developing thermally-activated delayed fluorescence (TADF), but their donor/acceptor units need to be expanded for tuning the emission properties. Herein we report TSCT-TADF emitters 1–3 by chemically fixing cyano-substituted fluorenes as the acceptors. For 1 and 2, 9H-fluorene-2,5-dicarbonitrile (2,5-CN-FL) and 9H-fluorene-2,7-dicarbonitrile (2,7-CN-FL) are used as the acceptors, respectively, and 1,3,6,8-tetramethyl-9H-carbazole is used as the donor. For emitter 3, 2,7-CN-FL and benzo[5,6][1,4]oxazino[2,3,4-kl]phenoxazine are used as the acceptor and the donor, respectively. Single-crystal structures and theoretical calculations reveal close, cofacial donor/acceptor alignments and thus effective TSCT in 1–3. In doped 2,8-bis(diphenylphosphoryl) dibenzo[b,d]furan films, emitters 1 and 2 show similar blue-green emission centered at around 510 nm, and emitter 3 shows yellow emission centered at 562 nm, with photoluminescent efficiencies at 0.66−0.76. Compared to emitters 1 and 2, emitter 3 shows much faster reverse intersystem crossing due to its much smaller singlet-triplet energy splitting. Organic light-emitting diodes (OLEDs) using 1–3 as the emitters afford blue-green or yellow electroluminescence with high external quantum efficiencies up to 14.9%. The work demonstrates that cyano-substituted fluorenes with a planar and rigid geometry are promising acceptors for developing TSCT-TADF emitters for OLED applications.

High‐Performance Narrowband OLED with Low Efficiency Roll‐Off Based on Sulfur‐Incorporated Organoboron Emitter

AbstractMulti‐resonance (MR) based organoboron emitters exhibiting high‐efficiency narrowband thermally activated delayed fluorescence (TADF) have become a critical material component for constructing high‐performance organic light‐emitting diodes (OLEDs) with high color purity and high color gamut. However, most of the MR‐TADF devices suffer from severe efficiency roll‐off at high current density due to the relatively large singlet–triplet splitting energy, long excited state lifetime, and slow reverse intersystem crossing rate (k RISC). Herein, by utilizing a sulfur atom‐fused donor unit, 7H‐benzo[4,5]thieno[2,3‐b]carbazole, an organic boron emitter (BTC‐BNCz) capable of high efficiency and low efficiency roll‐off narrowband TADF emission is developed. Benefitting from the heavy atom effect of the sulfur atom, kRISC up to 1.6 × 105 s−1 is achieved, which could greatly reduce the undesired quenching effect. Consequently, the OLED using BTC‐BNCz as dopant exhibits high external quantum efficiency (EQE) of 27.0% with full width at half maximum (FWHM) of 35 nm. Moreover, by utilizing a TADF material with a high horizontal dipole ratio as assistant host, outstanding device performance is achieved with a maximum EQE of 35.2% and FWHM of 37 nm, featuring slow efficiency roll‐off.

Highly rigid polycyclic acceptors by incorporating quinoxaline and naphthalimideacridine towards red TADF emitters

The development of red thermally activated delayed fluorescence (TADF) emitters with the emission peak above 600 nm remains far behind blue and green emitters. Herein, the highly rigid polycyclic acceptors with strong electron-withdrawing ability, integrated by quinoxaline and 1,8-naphthalimideacridine units, were utilized to construct two new red emitters with emission peak at 640 nm. Both target molecules display the twisted configuration to decrease singlet-triplet splitting energy (ΔEST) for the TADF property. Red organic light-emitting diodes (OLEDs) employing the emitters achieve the maximum external quantum efficiencies of 5.2% with electroluminescence peaks over 600 nm. This work provides a feasible strategy of the new polycyclic acceptors for developing efficient red TADF emitters.

Purely Organic Fluorescence Afterglow: Visible-Light-Excitation, Inherent Mechanism, Tunable Color, and Practical Applications with Very Low Cost.

Purely organic materials with visible light excitable fluorescence afterglow are promising for applications. Herein, fluorescence afterglow with various intensity and duration was observed on fluorescent dyes once being dispersed in polymer matrix, thanks to the slow reverse intersystem crossing rate (kRISC ) and long delayed fluorescence lifetime (τDF ) derived from the coplanar and rigid chemical structure of the dyes. To verify the mechanism, different polymers were used to tune singlet-triplet splitting energy based on solvent effect. And commercial acriflavine (Acf) film showed blue shifted fluorescence compared to purified one, with slower kRISC (≈100 s-1 ) and longer τDF (0.6 s). Via energy transfer from Acf to rhodamine B, the afterglow color was further regulated, with the largest fluorescence quantum yield of 42.4 %. It was demonstrated that the materials worked on color tunable light sources, and low-cost ($2 for 50 000 labels) anti-counterfeit labels recognized by white light.

Synthesis and Properties of Short-Lifetime Thermally Activated Delayed Fluorescence Materials.

Compounds MBZ-mPXZ, MBZ-2PXZ, MBZ-oPXZ, EBZ-PXZ, and TBZ-PXZ were conveniently synthesized, and they were found to exhibit TADF properties with lifetimes of 857, 575, 561, 768, and 600 ns, respectively. These short lifetimes of the compounds might be due to the combination of small singlet-triplet splitting energy (ΔEST) and benzoate group, which could be an efficient strategy for the further design of short-lifetime TADF materials.

Temperature dependent triplet-exciton relay from thermally activated delayed fluorescence (TADF) to self-sensitized triplet–triplet annihilation (TTA) of asymmetrical diphenylsulfone-based blue emitter

The utilization of triplet excitons is greatly concerned in organic luminophores. For thermally activated delayed fluorescence (TADF) emitters, the reverse intersystem crossing (RISC) which activates the triplet excitons at low temperature remains challenging without thermal stimulation. Herein, a temperature-dependent promotion relay of the triplet excitons from TADF to self-sensitized triplet − triplet annihilation up-conversion (TTA-UC) was demonstrated in an asymmetrical TADF luminophore based on 9,9-dimethyl-9,10-dihydroacridine (DMAC) donor and diphenylfonyl (DPS) acceptor. Single-crystal structure analysis combined with theoretical calculations revealed that the alternate strong-and-weak contact of the molecules reduced the singlet–triplet splitting energy (ΔEST), amplified the singlet–triplet coupling (SOC) strength and exciton coupling (EC), leading to highly efficient RISC process over a wide range of temperatures. Moreover, benefiting from the extreme small ΔEST value and large SOC strength, highly efficient blue OLEDs were achieved with the highest CEmax, PEmax and EQEmax of 32.0 cd A-1, 33.5 lm W−1 and 14.7%, and low efficiency roll-off. This work provides a design guidance for high utilization of the triplet excitons through RISC to improve the luminescence efficiency and reduce the device efficiency roll-off.

Steric modulation of thermally activated delayed fluorescence-type host for high quantum efficiency in blue phosphorescent organic light-emitting diodes

In organic light-emitting diodes (OLEDs), host engineering is important in improving the device performance. however, it remains as a big challenge in blue phosphorescent OLEDs because of the high triplet energy of blue phosphors. In this work, we develop a sterically modulated thermally activated delayed fluorescence-type host based on an ortho-linked carbazole–triazine backbone structure. An additional π-spacer spatially twisting the two moieties delivers a short delayed decay time of 5.0 μs without any loss of the photoluminescence quantum yield while realizing high triplet and small singlet-triplet energy splitting. The photophysical modulation enables a more efficient utilization of the triplet excitons of the two blue phosphorescent emitters in OLEDs. The fabricated blue phosphorescent OLEDs exhibit a significantly improved device performance in all efficiency parameters compared to reference devices with a maximum external quantum efficiency of 23.6%. This work demonstrates a simple and powerful thermally activated delayed fluorescence host design strategy to realize high efficiency blue-phosphorescence OLEDs.

Multiphoton excited singlet/triplet mixed self-trapped exciton emission

Multiphoton excited luminescence is of paramount importance in the field of optical detection and biological photonics. Self-trapped exciton (STE) emission with self-absorption-free advantages provide a choice for multiphoton excited luminescence. Herein, multiphoton excited singlet/triplet mixed STE emission with a large full width at half-maximum (617 meV) and Stokes shift (1.29 eV) has been demonstrated in single-crystalline ZnO nanocrystals. Temperature dependent steady state, transient state and time-resolved electron spin resonance spectra demonstrate a mixture of singlet (63%) and triplet (37%) mixed STE emission, which contributes to a high photoluminescence quantum yield (60.5%). First-principles calculations suggest 48.34 meV energy per exciton stored by phonons in the distorted lattice of excited states, and 58 meV singlet-triplet splitting energy for the nanocrystals being consistent with the experimental measurements. The model clarifies long and controversial debates on ZnO emission in visible region, and the multiphoton excited singlet/triplet mixed STE emission is also observed.

Enhanced Efficiency of Exciplex Emission from a 9-Phenylfluorene Derivative.

The exciplex-thermally activated delayed fluorescence (exciplex-TADF) system is an excellent candidate for the fabrication of high-efficiency organic light-emitting diodes (OLEDs) because of its more easily achieved small singlet-triplet energy splitting (ΔEST) and doping control. However, exciplex-TADF is still faced with the problems of low external quantum efficiency (ηext) and unclear effect of structure modification in electron acceptors. Herein, we provide a steric hindrance increase strategy to obtain high-efficiency exciplex emissions. Through introducing a 9-phenylfluorene group into N-ethylcarbazole of the dicyano-substituted 9-phenylfluorene, an electron acceptor material with increased steric hindrance is obtained, which helps the exciplex harvest a larger driving force and higher emission efficiencies. Encouragingly, the obtained OLED displays a maximum ηext of 25.8%, which is one of the best efficiency values among reported exciplex-OLEDs, simultaneously possessing excellent current efficiency of 83.6 cd A-1 and power efficiency of 93.7 lm W-1. It is expected that this work will offer a new avenue for designing electron acceptors for highly efficient exciplex emissions.