A Quadruple-Borylated Multiple-Resonance Emitter with para/meta Heteroatomic Patterns for Narrowband Orange-Red Emission

Hindered by spectral broadening issues with redshifted emission, long-wavelength (e.g., maxima beyond 570 nm) multiple resonance (MR) emitters with full width at half maxima (FWHMs) below 20 nm remain absent. Herein, by strategically embedding diverse boron (B)/nitrogen (N) atomic pairs into a polycyclic aromatic hydrocarbon (PAH) skeleton, we propose a hybrid pattern for the construction of a long-wavelength narrowband MR emitter. The proof-of-concept emitter B4N6-Me realized orange-red emission with an extremely small FWHM of 19 nm (energy unit: 70 meV), representing the narrowest FWHM among all reported long-wavelength MR emitters. Theoretical calculations revealed that the cooperation of the applied para B-π-N and para B-π-B/N-π-N patterns is complementary, which gives rise to both narrowband and redshift characteristics. The corresponding organic light-emitting diode (OLED) employing B4N6-Me achieved state-of-the-art performance, e.g., a narrowband orange-red emission with an FWHM of 27 nm (energy unit: 99 meV), an excellent maximum external quantum efficiency (EQE) of 35.8 %, and ultralow efficiency roll-off (EQE of 28.4 % at 1000 cd m⁻²). This work provides new insights into the further molecular design and synthesis of long-wavelength MR emitters.     

Boron-Dipyrromethene-Based Fluorescent Emitters Enable High-Performance Narrowband Red Organic Light-Emitting Diodes

Narrowband organic light-emitting diodes (OLEDs) are receiving significant attention and have demonstrated impressive performance in blue and green OLEDs. However, developing high-performance narrowband red OLEDs remains a highly desired yet challenging task. Herein, we have developed narrowband red fluorescent emitters by utilizing a boron-dipyrromethene (BODIPY) skeleton in combination with a methyl-shield strategy. These emitters exhibit small full-width at half-maxima (FWHM) ranging from 21 nm (0.068 eV) to 25 nm (0.081 eV) and high photoluminescence quantum yields (Φ_PL) ranging from 88.5 % to 99.0 % in toluene solution. Using BODIPY-based luminescent materials as emitters, high-performance narrowband red OLEDs have been assembled with external quantum efficiency as high as 18.3 % at 623 nm and 21.1 % at 604 nm. This work represents, to our knowledge, the first successful case of achieving NTSC pure-red OLEDs with the Commission Internationale de l’Éclairage (CIE) coordinates of [0.67, 0.33] based on conventional fluorescent emitters.     

[C6H14N]PbBr3: An ABX3‐Type Semiconducting Perovskite Hybrid with Above‐Room‐Temperature Phase Transition

Organic–inorganic hybrid perovskites, with the formula ABX₃ (A=organic cation, B=metal cation, and X=halide; for example, CH₃NH₃PbI₃), have diverse and intriguing physical properties, such as semiconduction, phase transitions, and optical properties. Herein, a new ABX₃‐type semiconducting perovskite‐like hybrid, (hexamethyleneimine)PbBr₃ ( 1 ), consisting of one‐dimensional inorganic frameworks and cyclic organic cations, is reported. Notably, the inorganic moiety of 1 adopts a perovskite‐like architecture and forms infinite columns composed of face‐sharing PbBr₆ octahedra. Strikingly, the organic cation exhibits a highly flexible molecular configuration, which triggers an above‐room‐temperature phase transition, at T_c=338.8 K; this is confirmed by differential scanning calorimetry (DSC), specific heat capacity (C_p), and dielectric measurements. Further structural analysis reveals that the phase transition originates from the molecular configurational distortion of the organic cations coupled with small‐angle reorientation of the PbBr₆ octahedra inside the inorganic components. Moreover, temperature‐dependent conductivity and UV/Vis absorption measurements reveal that 1 also displays semiconducting behavior below T_c. It is believed that this work will pave a potential way to design multifeatured perovskite hybrids by utilizing cyclic organic amines.     

[(18‐Crown‐6)K][Fe(1)Cl(1)4]0.5[Fe(2)Cl(2)4]0.5: A Multifunctional Molecular Switch of Dielectric,Conductivity and Magnetic Properties

Multifunctional materials that exhibit different physical properties in a single phase have potential for use in multifunctional devices. Herein, we reported an organic–inorganic hybrid compound [(18‐crown‐6)K][Fe(1)Cl(1)₄]_0.5[Fe(2)Cl(2)₄]_0.5 ( 1 ) by incorporating KCl and FeCl₃ into a 18‐crown‐6 molecule, which acts as a host of the six O atoms providing a lone pair of electrons to anchor the guest potassium cation, and [FeCl₄]^? as a counterion for charge balance to construct a complex salt. This salt exhibited a one‐step reversible structural transformation giving two separate high and low temperature phases at 373 K, which was confirmed by systematic characterizations including differential scanning calorimetry (DSC) measurements, variable‐temperature structural analyses, and dielectric, impedance, variable‐temperature magnetic susceptibility measurements. Interestingly, the structural transformation was coupled to both hysteretic dielectric phase transition, conductivity switch and magnetic‐phase transition at 373 K. This result gives an idea for designing a new type of phase‐transition materials harboring technologically important magnetic, conductivity and dielectric properties.     

Semi-conductive,Switchable Dielectric and Photoluminescent Properties of Two High-Temperature Phase Transition Hybrids

Bistable switches (electrical switching between “ON” and “OFF” bistable states) have gradually developed into an ideal category of highly intelligent materials, due to their significant applications in optical technology, signal processors, data storage and other switchable media applications in the field of electrical devices. Here, we successfully designed and synthesized [(FC₆H₄C₂H₄NH₃)₂MCl₄]_n(FC₆H₄C₂H₄NH₃⁺)=deprotonated 4-fluoro- phenethylamine; M=Cd ( 1 ), Mn ( 2 )), which realized the coupling of thermo-dielectric switching characteristics, semi-conductor characteristics and photo-luminescent properties. DSC (differential scanning calorimetry) and dielectric measurements show that 1 is a sensitive dielectric bistable switch between the high dielectric (ON) and low dielectric (OFF) states. The temperature-variable single crystal structure shows that the both 1 and 2 undergo a high-temperature reversible phase transition around 383 K/380 K, which is caused by the order-disordered transformation of organic cations and the slight distortion of the inorganic framework. In particular, 1 shows outstanding switchable dielectric behavior and semiconducting properties. Further, 1 and 2 emit strong green and yellow luminescence at 527 and 595 nm, respectively.     

Solution-processed multi-resonance organic light-emitting diodes with high efficiency and narrowband emission

With excellent color purity(full-width half maximum(FWHM) 40 nm) and high quantum yield,multiresonance(MR) molecules can harvest both singlet and triplet excitons for highly efficient narrowband organic light-emitting diodes(OLEDs) owing to their thermally activated delayed fluorescence(TADF)nature.However,the highly rigid molecular skeleton with the oppositely positioned bo ron and nitrogen in generating MR effects results in the intrinsic difficulties in the solution-processing of MR-OLEDs.Here,we demonstrate a facile strategy to increase the solubility,enhance the efficiencies and modulate emission color of MR-TADF molecules by extending aromatic rings and introducing tert-butyls into the MR backbone.Two MR-TADF emitters with smaller singlet-triplet splitting energies(ΔE~(ST))and larger oscillator strengths were prepared conveniently,and the solution-processed MR-OLEDs were fabricated for the first time,exhibiting efficient bluish-green electroluminescence with narrow FWHM of 32 nm and external quantum efficiency of 16.3%,which are even comparable to the state-of-the-art performances of the vacuum-evaporated devices.These results prove the feasibility of designing efficient solutionprocessible MR molecules,offering important clues in developing high-performance solution-processed MR-OLEDs with high efficiency and color purity.     

Two-Step Dielectric Responsive Organic-Inorganic Hybrid Material with Mid-Band Light Emission

Hybrid organic-inorganic perovskite (HOIP) have received tremendous scientific attention because of the phase transition and photovoltaic properties. However, achieving the special perovskite structure with both two-step dielectric response and luminescence characteristics is rarely reported. Herein, we report an organic-inorganic hybrid perovskite, [(BA)₂ ⋅ PbI₄] (Compound 1, BA=n-butylamine) by introducing flexible organic cations (HBA⁺), with direct mid-band gap as 2.28 eV. Interestingly, this material exhibits two-step reversible dielectric response at 350 K and 460 K (in heating process), respectively. Besides, the photoluminescence was found: it emits charming green light under 365 nm lamp (Photoluminescence quantum yield is 9.52 %). The outstanding two-step dielectric response and luminescence characteristics of this compound might pave the way for the application of dielectric and ferroelectric functional materials in temperature sensors and mechanical switches.     

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.     

Molecular Engineering of Push-Pull Diphenylsulfone Derivatives towards Aggregation-Induced Narrowband Deep Blue Thermally Activated Delayed Fluorescence (TADF) Emitters

Narrowband deep blue thermally activated delayed fluorescent (TADF) materials have attracted significant attention. Herein, four asymmetrical structured TADF emitters based on diphenylsulfone (DPS) acceptor and 9,9-dimethyl-9,10-dihydroacridine (DMAC) donor with progressive performances were developed. The tert-butyloxy auxiliary electron-donor was adopted to restrict the intramolecular rotations and provide efficient steric hindrance. Regioisomerization by altering the substitution position of DMAC on DPS unit further enhanced the intra- and inter-molecular interactions. The accompanying effects yielded increased energy level, minimized reorganization energy, and inhibited non-radiative transitions in the crystals of t BuO-SOmAD , which achieved narrowband deep-blue emission peaking at 424 nm (FWHM=64 nm, Φ_F=33.6 %) through aggregation-induced, blue-shifted emission (AIBSE). In addition, deep-blue organic light emitting diodes (OLEDs) based on t BuO-SOmAD realized the electroluminescence (EL) spectrum peaking located at 435 nm and CIE coordination of (0.12, 0.09).     

Combining Carbazole Building Blocks and ν-DABNA Heteroatom Alignment for a Double Boron-Embedded MR-TADF Emitter with Improved Performance

Building blocks and heteroatom alignments are two determining factors in designing multiple resonance (MR)-type thermally activated delayed fluorescence (TADF) emitters. Carbazole-fused MR emitters, represented by CzBN derivatives, and the heteroatom alignments of ν-DABNA are two star series of MR-TADF emitters that show impressive performances from the aspects of building blocks and heteroatom alignments, respectively. Herein, a novel CzBN analog, Π-CzBN, featuring ν-DABNA heteroatom alignment is developed via facile one-shot lithium-free borylation. Π-CzBN exhibits superior photophysical properties with a photoluminescence quantum yield close to 100 % and narrowband sky blue emission with a full width at half maximum (FWHM) of 16 nm/85 meV. It also gives efficient TADF properties with a small singlet-triplet energy offset of 40 meV and a fast reverse intersystem crossing rate of 2.9×10⁵ s⁻¹. The optimized OLED using Π-CzBN as the emitter achieves an exceptional external quantum efficiency of 39.3 % with a low efficiency roll-off of 20 % at 1000 cd m⁻² and a narrowband emission at 495 nm with FWHM of 21 nm/106 meV, making it one of the best reported devices based on MR emitters with comprehensive performance.     

Triptycene-Fused Sterically Shielded Multi-Resonance TADF Emitter Enables High-Efficiency Deep Blue OLEDs with Reduced Dexter Energy Transfer

Designing multi-resonance (MR) emitters that can simultaneously achieve narrowband emission and suppressed intermolecular interactions is challenging for realizing high color purity and stable blue organic light-emitting diodes (OLEDs). Herein, a sterically shielded yet extremely rigid emitter based on a triptycene-fused B,N core (Tp-DABNA) is proposed to address the issue. Tp-DABNA exhibits intense deep blue emissions with a narrow full width at half maximum (FWHM) and a high horizontal transition dipole ratio, superior to the well-known bulky emitter, t-DABNA. The rigid MR skeleton of Tp-DABNA suppresses structural relaxation in the excited state, with reduced contributions from the medium- and high-frequency vibrational modes to spectral broadening. The hyperfluorescence (HF) film composed of a sensitizer and Tp-DABNA shows reduced Dexter energy transfer compared to those of t-DABNA and DABNA-1. Notably, deep blue TADF-OLEDs with the Tp-DABNA emitter display higher external quantum efficiencies (EQE_max=24.8 %) and narrower FWHMs (≤26 nm) than t-DABNA-based OLEDs (EQE_max=19.8 %). The HF-OLEDs based on the Tp-DABNA emitter further demonstrate improved performance with an EQE_max of 28.7 % and mitigated efficiency roll-offs.     

PREPARATION OF POLYIMIDE-BaTiO3 HYBRID FILMS BY A DISPERSION PROCESS AND THEIR MICROSTRUCTURE*

 Barium titanate (BaTiO₃) powders with particle sizes of 30～50 nm were prepared from barium stearate, titanium alkoxides and stearic acid by stearic acid-gel method. Dispersing the agglomerate of BaTiO₃ nanoparticles into poly(amic acid) solution followed by curing led to the formation of polyimide hybrid films. The hybrid films were transparent and well distributed with BaTiO3 nanoparticles when the BaTiO₃ content was less than 1 wt%. Highly loaded hybrid film containing 30 wt % BaTiO₃ was tough, had a smooth surface and possessed much higher dielectric and piezoelectric constants than the parent polyimide.     

Synthesis and electrophoretic deposition of high-dielectric-constant SrTiO3 nanoparticles

We have investigated on the synthesis of SrTiO₃ nanoparticles whose bulk exhibits dielectric constant of 300, and their colloidal dispersion. As a result, we successfully synthesized SrTiO₃ nanoparticles with an average diameter of 134–485 nm measured by a scanning electron microscopic observation. The SrTiO₃ nanoparticles with a negative charge (ζ = −25 to −31 mV) can be dispersed as colloidal nanoparticles in water, and the average diameter in the dispersion were 138–356 nm measured by a dynamic light scattering technique. The colloidal dispersion of SrTiO₃ nanoparticles is promising for fabrication of low-voltage organic field-effect transistors (FETs) by a wet-processing fabrication. We have also successfully prepared SrTiO₃ films with a thickness of 1–10 μm on n-doped silicon substrates by an electrophoretic deposition technique. The SrTiO₃ films on the silicon substrates are likely used as dielectric gate insulator to low-voltage organic FETs after a sintering treatment.     

A Deep-Blue-Emitting Heteroatom-Doped MR-TADF Nonacene for High-Performance Organic Light-Emitting Diodes**

We present a p- and n-doped nonacene compound, NOBNacene, that represents a rare example of a linearly extended ladder-type multiresonant thermally activated delayed fluorescence (MR-TADF) emitter. This compound shows efficient narrow deep blue emission, with a λ_PL of 410 nm, full width at half maximum, FWHM, of 38 nm, photoluminescence quantum yield, Φ_PL of 71 %, and a delayed lifetime, τ_d of 1.18 ms in 1.5 wt % TSPO1 thin film. The organic light-emitting diode (OLED) using this compound as the emitter shows a comparable electroluminescence spectrum peaked at 409 nm (FWHM=37 nm) and a maximum external quantum efficiency (EQE_max) of 8.5 % at Commission Internationale de l’Éclairage (CIE) coordinates of (0.173, 0.055). The EQE_max values were increased to 11.2 % at 3 wt % doping of the emitter within the emissive layer of the device. At this concentration, the electroluminescence spectrum broadened slightly, leading to CIE coordinates of (0.176, 0.068).     

Fabrication and room-temperature exciton photoluminescence stability studies of inorganic–organic hybrid (C12H25NH3)2SnI4 thin films

A new methodology has been developed to fabricate the thin films of Tin (II) iodide based inorganic–organic (IO) hybrid, (C₁₂H₂₅NH₃)₂SnI₄, from direct and cost-effective three-step processing. The fabrication is based on room-temperature electrochemical deposition followed by simple solution processing. These IO hybrid films show room-temperature exciton related photoluminescence at 616 nm due to quantum and dielectric confinement effects. Systematic X-ray diffraction and optical studies are performed to understand the structural modification due to oxidation and consequent emission degradation. Post-processing methods to avoid emission degradation are also been demonstrated. The simple solution processing methodology and unique highly red-emitting IO hybrids, would be of interest for many multi-functional optoelectronic applications.     

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2O Vapor Sorption

In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure-directing agents and counter-cations. Reaction of the [2.2.2] cryptand (DHS) linker with Pb^II in acidic media gave rise to the first porous and water-stable 2D metal halide semiconductor (DHS)₂Pb₅Br₁₄. The corresponding material is stable in water for a year, while gas and vapor-sorption studies revealed that it can selectively and reversibly adsorb H₂O and D₂O at room temperature (RT). Solid-state NMR measurements and DFT calculations verified the incorporation of H₂O and D₂O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half-maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid-state batteries) for this class of hybrid semiconductors.     

Tunable phase transition,band gap and SHG properties by halogen replacement of hybrid perovskites [(thiomorpholinium)PbX3, X = Cl,Br, I]

By the replacement of halogen anion, three new multifunctional organic-inorganic hybrid perovskites (thiomorpholinium)PbX₃ (X = Cl, Br, I) were successfully synthesized and underwent reversible structural transformation above room temperature, accompanied by the anomalous change of dielectric constant. With the adjustment of the halogen anion from Cl to I in the inorganic skeleton, the space group is transformed from centrosymmetric space group P2₁/c ((thiomorpholinium)PbCl₃) to chiral one P2₁2₁2₁ ((thiomorpholinium)PbBr₃, (thiomorpholinium)PbI₃) at room temperature. The ordered-disordered transition of organic cations and the change of hydrogen bonds with the increase of temperature lead to above-room-temperature phase transitions. Ultraviolet absorption and second-harmonic generation (SHG) measurements confirmed that both the band gap and SHG activity of (thiomorpholinium)PbX₃ (X = Cl, Br, I) crystals were tunable. The band gaps reveal a broadening trend with 3.532 eV, 3.410 eV and 3.175 eV along the Cl → Br → I series. This work provides an effective molecular design for multifunctional organic-inorganic perovskites.     

PMMA-SiO<Subscript>2</Subscript> organic–inorganic hybrid films: determination of dielectric characteristics

Organic–inorganic hybrid thin films have been prepared by a modified sol–gel route using tetraethyl orthosilicate as the inorganic (silica) source, methyl methacrylate (MMA) as the organic source, and 3-trimetoxysilylpropyl methacrylate as the coupling agent. The films were prepared by spin coating on Si (100) p-type substrates and subsequently heat-treated at 90 °C. Fourier transform infrared results reveal a set of absorption bands associated with the formation of both PMMA and SiO₂ phases in the hybrid films. Capacitance–voltage (C–V) characterization was carried out on metal-insulator-metal (MIM) and metal-insulator-semiconductor (MIS) structures, with the hybrid films as the insulator layer to evaluate the electrical properties. We present a detailed comparative analysis of the dielectric constant obtained from C–V characterization in the frequency range of 1 kHz–1 MHz. For the PMMA-SiO₂ hybrid material the dielectric constant values obtained were around 9.5 at 1 MHz which is superior to the values reported for thermally grown SiO₂ and pure PMMA materials. The interface state density for PMMA-SiO₂ on Si was approximately 10¹⁰ cm⁻², which is comparable to the standard SiO₂/Si structures. Due to the electrical behavior and low processing temperatures this hybrid dielectric is a very promising candidate for flexible electronic devices and its subsequent implementation does not require complex equipment.     

镉基杂化晶体的介电相变和蓝白光致发光双重特性

通过采用容易无序的胺,我们合成了2种有机无机杂化晶体,分别为基于bempy （bempy=1-甲基-1-溴乙基吡咯烷阳离子）的溴盐化合物（bempy） Br （1）和镉基溴化物（bempy）₂CdBr₄（2）,并对其结构相变、介电相变和蓝白荧光进行了详细的表征分析。化合物1在测试温度范围内未观察到可逆相变,化合物2为高温介电相变,介电和差示扫描量热法测试表征其相变温度为357 K。同时,化合物1和2均具备蓝白光致发光特性,荧光测试表明,化合物1和2分别在538 nm和547、750 nm处存在发射峰。化合物2具备介电相变和蓝白光致发光的双重特性。     

Structure‐Triggered High Quantum Yield Luminescence and Switchable Dielectric Properties in Manganese(II) Based Hybrid Compounds

Two new manganese(II) based organic–inorganic hybrid compounds, C₁₁H₂₁Cl₃MnN₂ ( 1 ) and C₁₁H₂₂Cl₄MnN₂ ( 2 ), with prominent photoluminescence and dielectric properties were synthesized by solvent modulation. Compound 1 with novel trigonal bipyramidal geometry exhibits bright red luminescence with a lifetime of 2.47 ms and high quantum yield of 35.8 %. Compound 2 with tetrahedral geometry displays intense long‐lived (1.54 ms) green light emission with higher quantum yield of 92.3 %, accompanied by reversible solid‐state phase transition at 170 K and a distinct switchable dielectric property. The better performance of 2 results from the structure, including a discrete organic cation moiety and inorganic metal anion framework, which gives the cations large freedom of motion.