Efficient Red Electroluminescence From Phenanthro[9,10-d]imidazole-Naphtho[2,3-c][1,2,5]thiadiazole Donor-Acceptor Derivatives

Red emission is one of the three primary colors and is indispensable for full color displays. Fluorescent materials that can generate efficient red electroluminescence (EL) are limited and need to be developed. In this work, we report efficient red emitters based on phenanthro[9,10-d]imidazole-naphtho[2,3-c][1,2,5]thiadiazole donor-acceptor derivatives. The molecules, abbreviated as PINzP and PINzPCN, exhibited high photoluminescence quantum yield (PLQY) up to unity in doped films. They can also reach a relatively high PLQY of ∼30% in neat films. PINzP and PINzPCN were capable of generating efficient red EL in doped devices with a maximum external quantum efficiency (EQE) of 6.96% and 5.92%, respectively.     

Rational Design of a Near-infrared Fluorescent Material with High Solid-state Efficiency,Aggregation-induced Emission and Live Cell Imaging Property

Near-infrared(NIR) fluorescent materials with high photoluminescent quantum yields(PLQYs) have wide application prospects. Therefore, we design and synthesize a D-A type NIR organic molecule, TPATHCNE, in which triphenylamine and thiophene are utilized as the donors and fumaronitrile is applied as the acceptor. We systematically investigate its molecular structure and photophysical property. TPATHCNE shows high T_gof 110℃ and T_d of 385℃ and displays an aggregation-induced emission(AIE) property. A narrow optical bandgap of 1.65 eV is obtained. The non-doped film of TPATHCNE exhibits a high PLQY of 40.3% with an emission peak at 732 nm, which is among the best values of NIR emitters. When TPATHCNE is applied in organic light-emitting diode(OLED), the electroluminescent peak is located at 716 nm with a maximum external quantum efficiency of 0.83%. With the potential in cell imaging, the polystyrene maleic anhydride(PMSA) modified TPATHCNE nanoparticles(NPs) emit strong fluorescence when labeling HeLa cancer cells, suggesting that TPATHCNE can be used as a fluorescent carrier for specific staining or drug delivery for cellular imaging. TPATHCNE NPs fabricated by bovine serum protein(BSA) are cultivated with mononuclear yeast cells, and the intense intracellular red fluorescence indicates that it can be adopted as a specific stain for imaging.     

CsPbI3钙钛矿量子点的精细纯化及其高效发光二极管的研究

钙钛矿量子点发光二极管(QLEDs)因其色纯度高、颜色控制精准、色域广以及溶液可加工等特点,在显示和照明等领域有着极大的应用前景.针对红光钙钛矿CsPbI3量子点纯化过程中相变和表面配体损失造成的荧光退化问题,本工作发展了一种甲苯和乙酸乙酯协同的混合溶剂纯化策略,能够避免纯化过程中的相变问题,获得了纯立方相的CsPbI...     

Carbon Quantum Dots with Near-Unity Quantum Yield Bandgap Emission for Electroluminescent Light-Emitting Diodes

Carbon quantum dots (CQDs) feature bright and tunable photoluminescence, solution processability, and low toxicity, showing great potential in optoelectronics. However, the large-scale synthesis of CQDs with near-unity photoluminescence quantum yield (PLQY) has not been achieved so far. In this study, we perform radical-assisted synthesis of hexagon-shaped CQDs (H-CQDs) delivering near-unity PLQY (96 %). Experimental and theoretical analyses revealed that the large vertically oriented transition dipole moment of H-CQDs originating from high symmetry results in nearly 100 % PLQY. The H-CQDs also exhibited a high electron mobility of up to 0.07 cm² V⁻¹ s⁻¹. These properties enable the H-CQD-based light-emitting diodes with a high external quantum efficiency of 4.6 % and a record maximum brightness of over 11 000 cd m⁻². This study represents a significant advance that CQDs-based electroluminescent device can be utilized for potential display and lighting applications.     

Tailoring Extremely Narrow FWHM in Hypsochromic and Bathochromic Shift of Polycyclo-Heteraborin MR-TADF Materials for High-Performance OLEDs

Developing double boron-based emitters with extremely narrow band spectrum and high efficiency in organic light-emitting diodes (OLEDs) is crucial and challenging. Herein, we report two materials, NO-DBMR and Cz-DBMR , hinge on polycyclic heteraborin skeletons based on role-play of the highest occupied molecular orbital (HOMO) energy levels. The NO-DBMR contains an oxygen atom, whereas the Cz-DBMR has a carbazole core in the double boron-embedded ν-DABNA structure. The synthesized materials resulted in an unsymmetrical pattern for NO-DBMR and surprisingly a symmetrical pattern for Cz-DBMR . Consequently, both materials showed extremely narrow full width at half maximum (FWHM) of 14 nm in hypsochromic (pure blue) and bathochromic (Bluish green) shifted emission without losing their high color fidelity. Furthermore, both materials show high photoluminescence quantum yield (PLQY) of over 82 %, and an extremely small singlet-triplet energy gap (ΔE_ST) of 0.04 eV, resulting in high reverse intersystem crossing process (k_RISC) of 10⁵ s⁻¹. Due to the efficient thermally activated delayed fluorescence (TADF) characteristics, the fabricated OLEDs based on these heteraborins manifested maximum external quantum efficiency (EQE_max) of 33.7 and 29.8 % for NO-DBMR and Cz-DBMR , respectively. This is the first work reported with this type of strategy for achieving an extremely narrow emission spectrum in hypsochromic and bathochromic shifted emissions with a similar molecular skeleton.     

Highly Efficient Near‐Infrared Organic Light‐Emitting Diode Based on a Butterfly‐Shaped Donor–Acceptor Chromophore with Strong Solid‐State Fluorescence and a Large Proportion of Radiative Excitons

The development of near‐infrared (NIR) organic light‐emitting diodes (OLEDs) is of growing interest. Donor–acceptor (D–A) chromophores have served as an important class of NIR materials for NIR OLED applications. However, the external quantum efficiencies (EQEs) of NIR OLEDs based on conventional D–A chromophores are typically below 1 %. Reported herein is a butterfly‐shaped D–A compound, PTZ‐BZP. A PTZ‐BZP film displayed strong NIR fluorescence with an emission peak at 700 nm, and the corresponding quantum efficiency reached 16 %. Remarkably, the EQE of the NIR OLED based on PTZ‐BZP was 1.54 %, and a low efficiency roll‐off was observed, as well as a high radiative exciton ratio of 48 %, which breaks through the limit of 25 % in conventional fluorescent OLEDs. Experimental and theoretical investigations were carried out to understand the excited‐state properties of PTZ‐BZP.     

Highly stable metal halides Cs2ZnX4 (X = Cl,Br) with Sn2+ as dopants for efficient deep-red photoluminescence

The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging. In this work, we report a facile and convenient solvothermal method to synthesize metal halides Cs₂ZnX₄ (X = Cl, Br) that however is PL innert at room temperature. Upon composition engineering utilizing Sn²⁺ as the dopant, the resulting Cs₂ZnCl₄:Sn not only emits strong deep-red PL peaked at 700 nm with the highest 99.4% PLQY among the similar materials so far, but also exhibits excellent structure stability in air (PLQY remains 96% after one year exposure to the atmosphere). Detailed experimental characterizations and theoretical calculations reveal that the deep-red emission stems from self-trapped excitons induced by the Sn²⁺ dopant. Particularly, triplet emission (³P₂→¹S₀) from Sn-5s² orbitals has been observed at low temperature due to the break of parity-forbidden transition. This work provides an important guidance for the development of deep-red light-emitting materials with low price, high efficiency and excellent stability.     

A Novel Deep Blue LE-Dominated HLCT Excited State Design Strategy and Material for OLED

Deep blue luminescent materials play a crucial role in the organic light-emitting diodes (OLEDs). In this work, a novel deep blue molecule based on hybridized local and charge-transfer (HLCT) excited state was reported with the emission wavelength of 423 nm. The OLED based on this material achieved high maximum external quantum efficiency (EQE) of 4% with good color purity. The results revealed that the locally-excited (LE)-dominated HLCT excited state had obvious advantages in short wavelength and narrow spectrum emission. What is more, the experimental and theoretical combination was used to describe the excited state characteristic and to understand photophysical property.     

Linkages Make a Difference in the Photoluminescence of Covalent Organic Frameworks

Covalent organic frameworks (COFs) with structural designability and tunability of photophysical properties enable them to be a promising class of organic luminescent materials by incorporating well-designed fluorescent units directly into the periodic skeletons. The photophysical properties of COFs are mainly affected by the structural features, which determine the conjugation degree, charge delocalization ability, and exciton dynamics of COFs. To understand the relationship between COF structures and their photophysical properties, two COFs with the same pyrene chromophore units but different linkages (imine or vinylene) were designed and synthesized. Interestingly, different linkages endow COFs with huge differences in solid-state photoluminescence quantum yield (PLQY) for imine- and vinylene-linked pyrene-based COFs, which possess PLQY values of 0.34 % and 15.43 %, respectively. The femtosecond-transient absorption spectra and time-dependent density functional theory reveal the different charge-transfer pathways in imine- and vinylene-linked COFs, which influence the exciton relaxation way and fluorescence intensity. In addition, an effective white-light device was obtained by coating the vinylene-linked COF on a light-emitting diode strip.     

Synthesis of carbon dots with a tunable photoluminescence and their applications for the detection of acetone and hydrogen peroxide

Carbon dots(CDs) with multi-color emissive properties and a high photoluminescent quantum yield(PLQY) have attracted great attention recently due to their potential applications in chemical,environmental,biological and photo-electronic fields.Solvent-dependent effect in photoluminescence provides a facial and effective approach to tune the emission of CDs.In this study,green emissive nitrogen-doped carbon dots(N-CDs) are synthesized from p-hydroquinone and ethylenediamine through a simple hydrothermal method.The as-prepared N-CDs possess a robust excitation-independent green luminescence and a high PLQY of up to 15.9%.Further spectroscopic characterization indicates that the high PLQY is achieved by the balance of nitrogen doping states and the surface passivation extent in CDs.The N-CDs also exhibit solvent-dependent multi-color emissive property and distinct PLQY in different solvents(the maximum can reach up to 25.3%).Furthermore,the as-prepared N-CDs are applied as fluorescence probes to detect acetone and H2O2 in water.This method has exhibited a low detection limit of acetone(less than 0.1 %) and a quick and linear response to the H_2O_2 with the concentration from 0 to 120 μmol/L.This work broadens the knowledge of applying CDs as probes in the bio and chemical sensing fields.     

Chalcogen Effect of Atom Substitution on the Properties of Tris(2,4,6-trichlorophenyl)methyl(TTM) Radical

Luminescent open-shell organic radicals have recently been regarded as one of the most potential materials in organic light-emitting diodes(OLEDs). Herein, we have synthesized two new organic radicals, namely tris{4-[4-(tert-butyl)phenoxy]-2,6- dichlorophenyl}methane radical(TTM-O) and tris(4-{[4-(tert-butyl)- phenyl]thio}-2,6-dichlorophenyl)methane radical(TTM-S), by the substitution of chalcogen atom elements at the para position of conventional tris(2,4,6-trichlorophenyl)methyl(TTM) radical moiety. Interestingly, both TTM-O and TTM-S exhibited significantly enhanced photostability compared with the unsubstituted TTM radical parent. Moreover, the chalcogen atom also had a crucial impact on the photoluminescence quantum yield(PLQY) of the radicals, i.e., the PLQY of TTM-S was greatly enhanced compared to TTM radical while TTM-O was nearly non-emissive. Particularly, TTM-S showed intense PLQY of 37.54% and 185-fold longer photostability than that in cyclohexane solution of TTM.     

Crystal rigidifying strategy toward hybrid cadmium halide to achieve highly efficient and narrowband blue light emission

Highly efficient and narrowband blue light-emitting performance is extremely crucial for the optoelectronic applications of organic-inorganic hybrid perovskites. However, the not yet viable approach has been shown to simultaneously improve photoluminescence quantum yield (PLQY) and narrow linewidth of blue light emission. Herein, a new crystal rigidifying strategy is proposed as a viable dual-optimization avenue. Specifically, we perform a post-synthetic technique on hybrid cadmium halides and successfully convert zero-dimensional (0D) DMP-0-CdBr₄ to one-dimensional (1D) DMP-1-CdBr₃, accompanied by luminescent transformation from sky-blue (470 nm) to deep-blue (432 nm) emissions. The structural evolution from discrete block to infinite chain significantly enhances the crystal rigidity, which results in narrower emission linewidth (89 to 50 nm) and increased color purity (74.5% to 96.7%). Synchronously, the PLQY also realizes a notable enhancement from 14.0% to 52.3%. Systematical characterizations demonstrate that enhanced crystal rigidity simultaneously weakens the electron-phonon interaction and slows down nonradiative decay, which narrows the emission linewidth and boosts the PLQY. The highly efficient light-emitting performance enables them as excellent down-conversion blue phosphors to fabricate solid-state LED giving bright warm white light with high color rendering index of 95.4. This work paves a novel structural optimization way to rationally design or fine-tune high-performance blue-light emitting halides.     

Red/Near‐Infrared Thermally Activated Delayed Fluorescence OLEDs with Near 100 % Internal Quantum Efficiency

Developing red thermally activated delayed fluorescence (TADF) emitters, attainable for both high‐efficient red organic light‐emitting diodes (OLEDs) and non‐doped deep red/near‐infrared (NIR) OLEDs, is challenging. Now, two red emitters, BPPZ‐PXZ and mDPBPZ‐PXZ, with twisted donor–acceptor structures were designed and synthesized to study molecular design strategies of high‐efficiency red TADF emitters. BPPZ‐PXZ employs the strictest molecular restrictions to suppress energy loss and realizes red emission with a photoluminescence quantum yield (Φ_PL) of 100±0.8 % and external quantum efficiency (EQE) of 25.2 % in a doped OLED. Its non‐doped OLED has an EQE of 2.5 % owing to unavoidable intermolecular π–π interactions. mDPBPZ‐PXZ releases two pyridine substituents from its fused acceptor moiety. Although mDPBPZ‐PXZ realizes a lower EQE of 21.7 % in the doped OLED, its non‐doped device shows a superior EQE of 5.2 % with a deep red/NIR emission at peak of 680 nm.     

Introducing Spiro-locks into the Nitrogen/Carbonyl System towards Efficient Narrowband Deep-blue Multi-resonance TADF Emitters

The current availability of multi-resonance thermally activated delayed fluorescence (MR-TADF) materials with excellent color purity and high device efficiency in the deep-blue region is appealing. To address this issue in the emerged nitrogen/carbonyl MR-TADF system, we propose a spiro-lock strategy. By incorporating spiro functionalization into a concise molecular skeleton, a series of emitters (SFQ, SOQ, SSQ, and SSeQ) can enhance molecular rigidity, blue-shift the emission peak, narrow the emission band, increase the photoluminescence quantum yield by over 92 %, and suppress intermolecular interactions in the film state. The referent CZQ without spiro structure has a more planar skeleton, and its bluer emission in the solution state redshifts over 40 nm with serious spectrum broadening and a low PLQY in the film state. As a result, SSQ achieves an external quantum efficiency of 25.5 % with a peak at 456 nm and a small full width at half maximum of 31 nm in a simple unsensitized device, significantly outperforming CZQ. This work discloses the importance of spiro-junction in modulating deep-blue MR-TADF emitters.     

Fluorescence enhancement by symmetry breaking in a twisted triphenylene derivative

1,4,5,8,9,12-hexamethyltriphenylene (HMTP) shows a high photoluminescence quantum yield (PLQY) of 31% in the solid state, making it of interest for luminescence applications. The detailed photophysical properties of HMTP have been investigated by using time-resolved and steady-state luminescence, PLQY, and molar absorption coefficient measurements. An enhancement of the transition dipole moment for fluorescence and absorption was demonstrated compared to the case of unsubstituted triphenylene, which resulted in a 20-fold increase in the radiative decay rate. This is attributed to a breaking of triphenylene symmetry as a result of the necessarily twisted structure induced by steric crowding. In addition, it was shown that HMTP shows similar photoluminescence energies in solution, powder, and film, indicating a reduced propensity for intermolecular π-stacking compared to the case of triphenylene, as a result of this twisted structure. This work also develops a method for calculating the photoluminescence quantum yield of powders by using a calibrated photodiode in combination with an uncalibrated CCD spectrometer.     

New pyrimidine- and fluorene-containing oligo(arylene)s: synthesis, crystal structures, optoelectronic properties and a theoretical study

New pyrimidine containing oligo(arylene)s, notably the pyrimidine-fluorene hybrid systems 13-16, have been synthesised by Suzuki cross-coupling methodology. An efficient synthesis of the key reagent 9,9-dihexylfluorene-2,7-diboronic acid 10 from 2,7-dibromo-9,9-dihexylfluorene 9 is reported. Cross-coupling of 10 with two equivalents of 2-bromopyrimidine, 5-bromopyrimidine and 2,5-dibromopyrimidine gave 2,7-bis(2-pyrimidyl)-9,9-dihexylfluorene 13. 2,7-bis(5-pyrimidyl)-9,9-dihexylfluorene 14 and 2,7-bis(5-bromo-2-pyrimidyl)-9,9-dihexylfluorene 15 in 23-34% yields. A further two-fold Suzuki reaction of benzeneboronic acid with compound 15 gave 2,7-bis(5-phenyl-2-pyrimidyl)-9,9-dihexylfluorene 16 (35% yield). Ab initio calculations of the geometries and electronic structures at the Hartree Fock (HF) and density functional theory (DFT) levels of theory are reported for compounds 13, 14 and 16 (with ethyl substituents replacing hexyl) and for their dipyrazinyl and bistetraazenyl analogues, 17, 18, 20 and 21. The heterocyclic nitrogen atoms of 13 and 16 facilitate planarisation of the system, compared to 14, which is in agreement with X-ray structural data obtained for 5-bromo-2-phenylpyrimidine 6, 2,5-diphenylpyrimidine 7 and compound 15. Bistetrazenyl derivative 21 is calculated to be a fully planar system. The cyclic voltammogram (CV) of compound 16 in dichloromethane solution shows a quasi-reversible oxidation wave at E(1/2)0 = +1.36 V (vs. Ag/Ag+). Compound 13 is a poorer donor with an oxidation observed at Epa = +1.50 V which is in good agreement with the difference in the energies of their HOMO orbitals calculated at both HF and DFT levels of theory (0.11-0.12 eV). For compound 14 we were not able to measure an Eox potential which should lie at much more positive potentials. Compounds 15 and 16 are blue emitters in solution, with photoluminescence quantum yields (PLQY) of 25% and 85%, respectively. For thin films of 16 the PLQY is reduced to 21%. An OLED using compound 16 as the emissive layer has been fabricated in the configuration ITO/PEDOT/16/Ca/Al: blue-green light (lambda max 500 nm) most likely emanating primarily from excimer states is emitted at a high turn-on voltage.     

Nonbonding/Bonding Molecular Orbital Regulation of Nitrogen-Boron-Oxygen-embedded Blue/Green Multiresonant TADF Emitters with High Efficiency and Color Purity

In this study, we synthesized and characterized multiresonant thermally activated delayed fluorescent (TADF) materials embedded with nitrogen-boron-oxygen (N−B−O), exhibiting color-tunability between blue and green, namely NBO , m-DiNBO , and p-DiNBO . The three emitter materials showed a high photoluminescence quantum yield (PLQY) and a state-of-the-art narrow full width at half maximum (FWHM) of 96 %/25 nm, 87 %/17 nm, and 99 %/19 nm, respectively. For m-DiNBO and p-DiNBO , the emission color could be tuned from blue to green by regulating the nonbonding/bonding molecular orbital characters. Owing to the expanded planar molecular structure, m-DiNBO and p-DiNBO showed high horizontal dipole ratio (Θ) of 88 % and 92 %, respectively. OLEDs were prepared with NBO , m-DiNBO , and p-DiNBO , exhibiting high external quantum efficiencies of 16.8 %, 24.2 %, and 21.6 %, respectively. NBO and m-DiNBO exhibited pure-blue emission with CIE coordinates of (0.137, 0.142) and (0.126, 0.098), respectively. p-DiNBO showed pure-green emission with a CIE coordinate of (0.258, 0.665).     

A Pure-Red Doublet Emission with 90 % Quantum Yield: Stable,Colorless, Iodinated Triphenylmethane Solid

Red luminescence is found in off-white tris(iodoperchlorophenyl)methane ( 3I-PTM^H ) crystals which is characterized by a high photoluminescence quantum yield (PLQY 91 %) and color purity (CIE coordinates 0.66, 0.34). The emission originates from the doublet excited state of the neutral radical 3I-PTM^R , which is spontaneously formed and becomes embedded in the 3I-PTM^H matrix. The radical defect can also be deliberately introduced into 3I-PTM^H crystals which maintain a high PLQY with up to 4 % radical concentration. The immobilized iodinated radical demonstrates excellent photostability (estimated half-life >1 year under continuous irradiation) and intriguing luminescent lifetime (69 ns). TD-DFT calculations demonstrate that electron-donating iodine atoms accelerate the radiative transition while the rigid halogen-bonded matrix suppresses the nonradiative decay.     

Asymmetric Thermally Activated Delayed Fluorescence Materials Rendering High-performance OLEDs Through both Thermal Evaporation and Solution-processing

Exploring high-efficiency thermally activated delayed fluorescence(TADF) materials is of great importance regarding to organic light-emitting diode(OLED). Herein, we present a design strategy for developing asymmetric TADF materials based on a diphenyl sulfone-phenoxazine structure, resulting in efficient TADF emitters(CzPXZ and t-CzPXZ) with aggregation-induced emission properties, while t-CzPXZ is modified with tert-butyl groups. The two compounds exhibit high solid-state luminescence, efficient TADF, and significantly impressive device performances by both thermal evaporation and solution processing. For an instance, CzPXZ and t-CzPXZ enable the thermally-evaporated OLEDs with high external quantum efficiencies(EQEs) of over 20%. Meanwhile, t-CzPXZ allows the solution-processed device with a high EQE of 16.3% with low-efficiency roll-off, attributing to the enhanced molecular solubility and suppressed excitons quenching through tert-butyl modification on t-CzPXZ. The results reveal that the proposed asymmetric structure is a promising approach for developing high-efficiency TADF materials and OLEDs.     

Highly Emissive 9-Borafluorene Derivatives: Synthesis,Photophysical Properties and Device Fabrication

A series of 9-borafluorene derivatives, functionalised with electron-donating groups, have been prepared. Some of these 9-borafluorene compounds exhibit strong yellowish emission in solution and in the solid state with relatively high quantum yields (up to 73.6 % for FMesB-Cz as a neat film). The results suggest that the highly twisted donor groups suppress charge transfer, but the intrinsic photophysical properties of the 9-borafluorene systems remain. The new compounds showed enhanced stability towards the atmosphere, and exhibited excellent thermal stability, revealing their potential for application in materials science. Organic light-emitting diode (OLED) devices were fabricated with two of the highly emissive compounds, and they exhibited strong yellow-greenish electroluminescence, with a maximum luminance intensity of >22 000 cd m⁻². These are the first two examples of 9-borafluorene derivatives being used as light-emitting materials in OLED devices, and they have enabled us to achieve a balance between maintaining their intrinsic properties while improving their stability.