Sky-blue Emission Research Articles

A QM/MM study on through space charge transfer-based thermally activated delayed fluorescence molecules in the solid state

A QM/MM study on through space charge transfer (TSCT)-based thermally activated delayed fluorescence (TADF) molecules with sky-blue emission.

Asymmetric sky-blue thermally-activated delayed fluorescence emitters bearing tris(triazolo)triazine moiety for solution-processable organic light-emitting diodes

Two sky-blue TADF emitters bearing the tris(triazolo)triazine acceptor moiety were designed and synthesized. The solution-processed OLEDs based on these two emitters achieved a maximum EQE of 10.01% at 474 nm.

Acceptor modulation for blue and yellow TADF materials and fabrication of all-TADF white OLED

4,4′-(4-Phenylpyridine-2,6-diyl)dibenzonitrile is designed as an acceptor to develop a sky-blue TADF emitter that exhibits a fluorescence rate constant of 107 s−1 and high EQEs of 25.6% and 18.5% in sky-blue and all-TADF white organic light-emitting diodes.

Unipolar 1-phenylimidazo[1,5-a]pyridine: a new class of ultra-bright sky-blue emitters for solution-processed organic light emitting diodes

Sky-blue emitters based on unipolar imidazo[1,5-a]pyridine (ImPy) materials were explored for OLED applications.

Achieving highly efficient narrowband sky-blue electroluminescence with alleviated efficiency roll-off by molecular-structure regulation and device-configuration optimization

B–N-containing emitter based MR-TADF OLEDs exhibiting a narrowband sky-blue emission with the FWHM of 29 nm, the maximum EQE of 31.0% and low efficiency roll-off were achieved by molecular regulation and device optimization.

Synthesis, optical properties and self-organization of blue-emitting butterfly-shaped dithienobenzosiloles

Ten novel butterfly-shaped dithienobenzosilole-based luminogens, which are peripherally installed with a variety of substituents including hydrogen, phenyl and substituted phenyl groups, have been readily prepared via an iodine-induced intramolecular electrophilic double-cyclisation reaction and subsequent deiodination or coupling reactions. The optical and electrochemical properties of these compounds were systematically investigated to clarify the relationships between their structures and properties, supported by theoretical calculations. These compounds exhibit deep-blue to sky-blue emissions and high photoluminescence quantum yields up to 0.84 in solution and solid states which are regulated by the functional blades and their steric hindrance on the α– and β–positions of thiophene rings. Their high thermal- and photo- stabilities have been revealed and mainly attributed to the dithienobenzosilole core.

Acridin-9(10H)-one-based blue thermally activated delayed fluorescence materials: improvement of color purity and efficiency stability

A series of donor-acceptor-donor (D-A-D) type blue thermally activated delayed fluorescence (TADF) emitters, namely, 2,7-DtBuCz-AD, 3,6-DtBuCz-AD, 3,6-DMAC-AD, and 3,6-DMAC-AD-CF3, were developed with highly rigid acridin-9(10H)-one (i.e. acridone [AD]) as acceptor. The regioisomeric effect study revealed that the attachment of donors at 3,6-sites of AD ring dramatically enhanced TADF ratio in comparison with the 2,7-site isomer. On the one hand, by varying donors from dimethylacridine (DMAC) to tert-butylcarbazole (tBuCz) at 3,6-sites of AD ring, the emission color purity of blue TADF emitters was improved from sky blue to deep blue. On the other hand, by introducing trifluoromethyl (CF3) onto 9-site phenyl ring of 3,6-DtBuCz-AD, the efficiency stability of the sky blue emission for 3,6-DMAC-AD-CF3 was remarkably improved. The deep blue organic light-emitting diode (OLED) of 3,6-DtBuCz-AD exhibited a maximum external quantum efficiency (EQEmax) of 17.88% with CIE coordinates of (0.15, 0.08), which is among the best performances ever reported for deep blue TADF-OLEDs. The sky-blue OLED of 3,6-DMAC-AD realized an EQEmax of 23.16%. And with the incorporation of CF3, the sky blue device of 3,6-DMAC-AD-CF3 exhibited extremely low efficiency loss of only 5.1% at the high brightness of 1,000 cd/m2.

Suppressing exciton deconfinement and dissociation for efficient thermally activated delayed fluorescence OLEDs

The efficiency of organic light-emitting diodes that utilize the principle of thermally activated delayed fluorescence (TADF) depends sensitively on the host material in which the TADF emitter molecules (guests) are embedded. Potential loss processes are “deconfinement,” the transfer of excitons from the guest to the host, and “dissociation,” the formation of intermolecular charge-transfer states. We investigate how both processes can be suppressed by studying the photoluminescence efficiency, emission spectrum, and time-resolved emission intensity of eight thin-film systems in which 5 mol. % of the sky-blue TADF emitter 4-carbazolyl-methylphthalimide (abbreviated here as CzPIMe) is embedded in various host materials. Deconfinement is found to be entirely suppressed if the triplet energy of the host is 0.25 eV or more above that of the guest. For systems allowing for deconfinement, the dependence on the energy difference is consistent with a recent theoretical analysis [C. Hauenstein et al., J. Appl. Phys. 128, 075501 (2020)]. Dissociation, due to hole transfer to a host molecule, is found to be suppressed if the host’s highest occupied molecular orbital energy is not more than about 0.2 eV higher than that of the guest. Otherwise, we observe an efficiency loss, a spectral redshift, and the disappearance of distinct prompt and delayed emission regimes. A comprehensive rate-equation model is developed from which we study the sensitivity of these observations to the energy level structure, the intermolecular interaction rates, and the photophysical rates that follow from a fit to the experimental data for the CzPIMe:TCTA[tris(4-carbazoyl-9-ylphenyl)amine] system.

Molecular engineering by σ-linkers enables delayed fluorescence emitters for high-efficiency sky-blue solution-processed OLEDs

Two novel thermally activated delayed fluorescence (TADF) emitters, namely Me2AcBO and F2AcBO, based on the 9,9-dimethrylacridine donor and a rigid oxygen-bridged cyclized boron acceptor, were designed and synthesized for highly efficient blue solution-processed organic light-emitting diodes (OLEDs). Me2AcBO and F2AcBO feature a twin structure derived by coupling two individual TADF monomers through non-conjugated linkers. The two new emitters exhibit 3D molecular structures, excellent thermal/morphological properties, high photoluminescence quantum yields over 97%, and high reverse intersystem crossing rates on the order of 106 s−1, which greatly benefit the high device efficiency. Solution-processed sky-blue TADF OLEDs based on Me2AcBO and F2AcBO achieved the maximum external quantum efficiency of 11.0% and 10.9%, respectively, with Commission Internationale de L’Eclairage (CIE) coordinates of (0.14, 0.25). Interestingly, relatively low efficiency roll-offs of 33% and 34% at the luminance of 1000 cd/m2 were demonstrated for Me2AcBO and F2AcBO based devices, respectively. This study presents a novel strategy to realize highly efficient sky-blue TADF emitters for solution-processed OLEDs.

Fused-Nonacyclic Multi-Resonance Delayed Fluorescence Emitter Based on Ladder-Thiaborin Exhibiting Narrowband Sky-Blue Emission with Accelerated Reverse Intersystem Crossing.

Developing organic luminophores with unique capability of strong narrowband emission is both crucial and challenging for the further advancement of organic light-emitting diodes (OLEDs). Herein, a nanographitic fused-nonacyclic π-system (BSBS-N1), which was strategically embedded with multiple boron, nitrogen, and sulfur atoms, was developed as a new multi-resonance thermally activated delayed fluorescence (MR-TADF) emitter. Narrowband sky-blue emission with a peak at 478 nm, full width at half maximum of 24 nm, and photoluminescence quantum yield of 89 % was obtained with BSBS-N1. Additionally, the spin-orbit coupling was enhanced by incorporating two sulfur atoms, thereby facilitating the spin-flipping process between the excited triplet and singlet states. OLEDs based on BSBS-N1 as a sky-blue MR-TADF emitter achieved a high maximum external electroluminescence quantum efficiency of 21.0 %, with improved efficiency roll-off.

Chameleonic Photo- and Mechanoluminescence in Pyrazolate-Bridged NHC Cyclometalated Platinum Complexes.

DFT investigations on the ground (GS) and the first triplet (T1) excited state potential energy surfaces (PES) were performed on a new series of platinum-butterfly complexes, [{Pt(C∧C*)(μ-Rpz)}2] (Rpz: pz, 1; 4-Mepz, 2; 3,5-dmpz, 3; 3,5-dppz, 4), containing a cyclometalated NHC in their wings. The geometries of two close-lying local minima corresponding to butterfly spread conformers, 1s–4s, and butterfly folded ones, 1f–4f, with long and short Pt–Pt separations, respectively, were optimized in the GS and T1 PES. A comparison of the GS and T1 energy profiles revealed that an opposite trend is obtained in the relative stability of folded and spread conformers, the latter being more stabilized in their GS. Small ΔG (s/f) along with small-energy barriers in the GS support the coexistence of both kinds of conformers, which influence the photo- and mechanoluminescence of these complexes. In 5 wt % doped PMMA films in the air, these complexes exhibit intense sky-blue emissions (PLQY: 72.0–85.9%) upon excitation at λ ≤ 380 nm arising from 3IL/MLCT excited states, corresponding to the predominant 1s–4s conformers. Upon excitation at longer wavelengths (up to 450 nm), the minor 1f–4f conformers afford a blue emission as well, with PLQY still significant (40%–60%). In the solid state, the as-prepared powder of 4 exhibits a greenish-blue emission with QY ∼ 29%, mainly due to 3IL/3MLCT excited states of butterfly spread molecules, 4s. Mechanical grinding resulted in an enhanced and yellowish-green emission (QY ∼ 51%) due to the 3MMLCT excited states of butterfly folded molecules, 4f, in such a way that the mechanoluminescence has been associated with an intramolecular structural change induced by mechanical grinding.

Multichromophore Molecular Design for Thermally Activated Delayed-Fluorescence Emitters with Near-Unity Photoluminescence Quantum Yields.

Three multichromophore thermally activated delayed fluorescence (TADF) molecules, p-di2CzPN, m-di2CzPN, and 1,3,5-tri2CzPN, were synthesized and characterized. These molecules were designed by connecting the TADF moiety 4,5-di(9H-carbazol-9-yl)phthalonitrile (2CzPN) to different positions of a central benzene ring scaffold. Three highly soluble emitters all exhibited near-quantitative photoluminescence quantum yields (ΦPL) in toluene. High ΦPLs were also achieved in doped films, 59 and 70% for p-di2CzPN and m-di2CzPN in 10 wt % DPEPO doped film, respectively, and 54% for 1,3,5-tri2CzPN in 20 wt % doped CBP films. The rate constant of reverse intersystem crossing (kRISC) for p-di2CzPN and m-di2CzPN in DPEPO films reached 1.1 × 105 and 0.7 × 105 s-1, respectively, and kRISC for 1,3,5-tri2CzPN in the CBP film reached 1.7 × 105 s-1. A solution-processed organic light-emitting diode based on 1,3,5-tri2CzPN exhibited a sky-blue emission with CIE coordinates of (0.22, 0.44) and achieved a maximum external quantum efficiency of 7.1%.

Highly Luminescent Zero-Dimensional Organic Copper Halides for X-ray Scintillation

The present work reports highly efficient flexible and reabsorption-free scintillators based on two zero-dimensional (0D) organic copper halides (TBA)CuX2 (TBA = tetrabutylammonium cation; X = Cl, Br). The (TBA)CuX2 exhibit highly luminescent green and sky-blue emissions peaked at 510 and 498 nm, with large Stokes shifts of 224 and 209 nm and high photoluminescence quantum yields (PLQYs) of 92.8% and 80.5% at room temperature for (TBA)CuCl2 and (TBA)CuBr2 single crystals (SCs), respectively. Interestingly, above room temperature, their PLQYs increase with temperature and reach near unity at 320 and 345 K for (TBA)CuCl2 and (TBA)CuBr2, respectively. The excellent properties originate from self-trapped excitons (STEs) in individual [CuX2]- quantum rods, which is demonstrated by the temperature-dependent PL, ultrafast transient absorption (TA) combined with density functional theory (DFT) calculations. The (TBA)CuX2 scintillators show bright radioluminescence (RL), impressive linear response to dose rate in a broad range, and high light yields. Their potential application in X-ray imaging is demonstrated by using (TBA)CuX2 composite scintillation screens. Importantly, flexible scintillators are demonstrated to be superior than flat ones for imaging nonplanar objects by conformally coating, which produce accurate images with negligible distortion.

Synthesis of luminescent phosphine-containing rigid-rod dinuclear alkynylgold(I) complexes and their X-Ray structural, photophysical, self-assembly and electroluminescence studies

A series of rigid-rod dinuclear alkynylgold(I) complexes bearing triethylene glycol monomethyl ether or dibutoxy-substituted oligo(p-phenylene ethynylene)s moieties as the backbone, and phosphine ligands that are charge-neutral or bear a positive or negative charge, has been designed and synthesized. The alkynylgold(I) complexes with charge-neutral phosphines are found to show polymeric zig-zag chain structure with short gold‧‧‧gold distances in their X-ray crystal structures, while those with negatively charged phosphine ligands demonstrate spherical aggregates in dimethyl sulfoxide (DMSO)-water dispersions. The aggregation behaviour of the complex with positively charged phosphine ligand is found to follow an isodesmic mechanism upon increasing the water content in DMSO. Representative complexes have been applied as the emitting material in solution-processed organic light-emitting devices, exhibiting sky-blue emission with emission maxima at 432 nm. This work has provided further insights into the aggregation behaviour of this class of alkynylgold(I) complexes, as well as the understanding of their molecular packing and alignment for the future design of structurally-related rigid-rod organometallic materials.

Asymmetric Spirobiacridine-based Delayed Fluorescence Emitters for High-performance Organic Light-Emitting Devices.

Recently, researchers have focused on thermally activated delayed fluorescence (TADF) for efficient future lighting and displays. Among TADF emitters, a combination of triazine and acridine is a promising candidate for realizing high-efficiency organic light-emitting devices (OLEDs). However, simultaneous development of perfect horizontal orientation (Θ=100 %) and an external quantum efficiency (EQE) of over 40 % is still challenging. Here, to obtain insights for further improvements of a triazine/acridine combination, various asymmetric spirobiacridine (SBA)-based TADF emitters with a unity photoluminescence quantum yield and high Θ ratio of over 80 % were developed. Furthermore, the substitution effects of the triazine acceptor unit on the photophysical properties were studied, including molecular orientations and OLED performance. The corresponding OLED exhibited sky-blue emission with a high EQE of over 30 %.

Planar and Rigid Pyrazine‐Based TADF Emitter for Deep Blue Bright Organic Light‐Emitting Diodes

AbstractTwo blue thermally activated delayed fluorescence (TADF) emitters bearing di‐tert‐butyl carbazoles as the electron donor groups and pyrazine (DTCz‐Pz) or dipyrazine (DTCz‐Pz) as the electron acceptor are presented. The DFT calculations predict DTCz‐Pz and DTCz‐DPz to possess high S1 energies (3.19 eV and 3.08 eV, respectively), and relatively large ΔEST values (0.52 eV and 0.56 eV, respectively). The closely layered intermediate triplet states between S1 and T1, predicted by DFT calculations, are expected to facilitate the reverse intersystem crossing (RISC) and improve spin‐vibronic coupling efficiency between the excited states, even the relatively larger ΔESTs. The ΔESTs for DTCz‐Pz and DTCz‐DPz are 0.27 eV and 0.38 eV, and both molecules show high photoluminescence quantum yields (65 %, and 70 %, respectively). The decay lifetimes show temperature dependence in a PPT host, which is consistent with the fact that both molecules are TADF emitters in PPT. The OLEDs based on DTCz‐Pz exhibit deep blue emission with λEL of 460 nm and CIE of (0.15, 0.16). The maximum external quantum efficiency (EQEmax) reaches 11.6 %, with a maximum luminance (Lmax) of up to 6892 cd m−2, while the device based on DTCz‐DPz exhibits sky blue emission with λEL of 484 nm and CIE of (0.15, 0.30), an EQEmax of 7.2 %, and Lmax of 8802 cd m−2.

Modulating low-dimensional domains of self-assembling quasi-2D perovskites for efficient and spectra-stable blue light-emitting diodes

Abstract Perovskite light-emitting diodes (PeLEDs) with green and red emissions have made tremendous progress in recent years. However, the realization of efficient and spectra-stable blue-emission PeLEDs remains challenging, which greatly limits their future commercialization. Here, a self-assembling strategy is proposed to achieve efficient blue PeLEDs with stable emission by modulating low-dimensional domains of pure-bromide perovskites to Bohr’s radii. A spacer of butylamine with polyamine is used as a modifier to facilitate the formation of homogeneous perovskite films with precious tailoring of the numbers (N) of metal halide octahedron PbBr64− layers. The cubic-phase quasi-2D perovskite films featuring the improved domain distributions and the enhanced luminance are realized, and their emissions can be modulated from violet (~436 nm) to greenish region (~500 nm), corresponding to the emission from N = 2 to N > 3 layered perovskites. The PeLEDs with deep-blue, pure-blue, and sky-blue emissions are obtained with the colour coordinates of (0.13, 0.06), (0.11, 0.13), and (0.08, 0.25), respectively, yielding the maximum external quantum efficiencies of 1.74%, 2.44%, and 5.71%. The approach demonstrated in this work paves the way for constructing efficient, endurable, spectra-stable perovskite emitters for the next-generation display and lighting technologies.

Thermally activated delayed fluorescence materials based on 3, 3′-position substituted bis(phenylsulfonyl)benzene

Two highly efficient thermally activated delayed fluorescent (TADF) materials with twisted donor-acceptor-donor (D-A-D) structure, DMACBB and PXZBB, have been designed and synthesized based on bis(phenylsulfonyl)benzene as the acceptor (A) and 9,9-dimethyl-9,10-dihydroacridine (DMAC) or phenoxazine (PXZ) as the donor (D). Attaching the donor to the 3, 3′-positions of bis(phenylsulfonyl)benzene obtains larger torsion angle between donor and acceptor as well as suitable ICT effects, which results in almost complete separation of their FMOs and limited overlap. Both emitters successfully achieve small ΔEST (≤0.2 eV), simultaneously exhibit high photoluminescence quantum yields (≥80%). Both of them possess distinct TADF features. The DMACBB-based device exhibits sky blue emission with the peak at 472 nm, while the PXZBB-based device shows slightly red-shifted and emits green light with the peak at 507 nm because of the stronger electron-donating ability of PXZ than that of DMAC. The TADF-OLED based on DMACBB achieves higher the maximum external quantum efficiency (EQEmax of 10.1%) than the TADF-OLED based on PXZBB (EQEmax of 8.2%) with the turn-on voltage of 3.5 V.

Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation.

The trifluoromethyl group has been previously explored as a non-conjugated electron-withdrawing group in donor–acceptor thermally activated delayed fluorescence (TADF) emitters. In the present study, we investigate computationally the potential of other fluorine-containing acceptors, trifluoromethoxy (OCF3), trifluoromethylthio (SCF3), and pentafluorosulfanyl (SF5), within two families of donor–acceptor TADF emitters. Time-dependent density functional theory calculations indicate that when only two ortho-disposed carbazole donors are used (Type I molecules), the lowest-lying triplet state possesses locally excited (LE) character while the lowest-lying singlet state possesses charge-transfer character. When five carbazole donors are present in the emitter design (Type II molecules), now both S1 and T1 states possess CT character. For molecules 2CzOCF3 and 5CzOCF3, the singlet energies are predicted to be 3.92 eV and 3.45 eV; however, the singlet-triplet energy gaps, ΔESTs, are predicted to be large at 0.46 eV and 0.37 eV, respectively. The compounds 2CzCF3, 2CzSCF3, and 2CzSF5, from Type I molecules, show significant promise as deep blue TADF emitters, possessing high calculated singlet energies in the gas phase (3.62 eV, 3.66 eV, and 3.51 eV, respectively) and small, ΔESTs, of 0.17 eV, 0.22 eV, and 0.07 eV, respectively. For compounds 5CzSCF3 and 5CzSF5, from Type II molecules, the singlet energies are stabilized to 3.24 eV and 3.00 eV, respectively, while ΔESTs are 0.27 eV and 0.12 eV, respectively, thus both show promise as blue or sky-blue TADF emitters. All these six molecules possess a dense number of intermediate excited states between S1 and T1, thus likely leading to a very efficient reverse intersystem crossing in these compounds.

Benzofurodibenzofuran as a universal chemical platform of highly efficient sky-blue thermally activated delayed fluorescence emitters and hosts

A benzofuran based chemical platform, benzofurodibenzofuran, was designed and synthesized as a core structure to develop hosts for phosphorescent organic light-emitting diodes and thermally activated delayed fluorescence (TADF) emitters. The high triplet energy and rigid molecular structure of the benzofurodibenzofuran unit enabled the universal application of it as the building unit of the sky-blue hosts and emitters. The sky-blue TADF emitters built on the benzofurodibenzofuran platform showed high external quantum efficiency, narrow emission spectrum and blue-shifted emission color compared with the conventional phenyl based emitters. Moreover, the high triplet energy hosts obtained from benzofurodibenzofuran efficiently harvested the triplet excitons of the sky-blue phosphors and TADF emitters. Therefore, the benzofurodibenzofuran can work as the basic platform of designing host and emitters for high efficiency sky-blue organic light-emitting diodes.