Stable room-temperature continuous-wave lasing in quasi-2D perovskite films.

Organic-inorganic lead halide quasi-two-dimensional (2D) perovskites are promising gain media for lasing applications because of their low cost, tunable colour, excellent stability and solution processability1-3. Optically pumped continuous-wave (CW) lasing is highly desired for practical applications in high-density integrated optoelectronics devices and constitutes a key step towards electrically pumped lasers4-6. However, CW lasing has not yet been realized at room temperature because of the 'lasing death' phenomenon (the abrupt termination of lasing under CW optical pumping), the cause of which remains unknown. Here we study lead halide-based quasi-2D perovskite films with different organic cations and observe that long-lived triplet excitons considerably impede population inversion during amplified spontaneous emission and optically pumped pulsed and CW lasing. Our results indicate that singlet-triplet exciton annihilation is a possible intrinsic mechanism causing lasing death. By using a distributed-feedback cavity with a high quality factor and applying triplet management strategies, we achieve stable green quasi-2D perovskite lasers under CW optical pumping in air at room temperature. We expect that our findings will pave the way to the realization of future current-injection perovskite lasers.

High performance from extraordinarily thick organic light-emitting diodes.

Organic light-emitting diode (OLED) technology is promising for applications in next-generation displays and lighting. However, it is difficult-especially in large-area mass production-to cover a large substrate uniformly with organic layers, and variations in thickness cause the formation of shunting paths between electrodes1,2, thereby lowering device production yield. To overcome this issue, thicker organic transport layers are desirable because they can cover particles and residue on substrates, but increasing their thickness increases the driving voltage because of the intrinsically low charge-carrier mobilities of organics. Chemical doping of organic layers increases their electrical conductivity and enables fabrication of thicker OLEDs3,4, but additional absorption bands originating from charge transfer appear5, reducing electroluminescence efficiency because of light absorption. Thick OLEDs made with organic single crystals have been demonstrated6, but are not practical for mass production. Therefore, an alternative method of fabricating thicker OLEDs is needed. Here we show that extraordinarily thick OLEDs can be fabricated by using the organic-inorganic perovskite methylammonium lead chloride, CH3NH3PbCl3 (MAPbCl3), instead of organics as the transport layers. Because MAPbCl3 films have high carrier mobilities and are transparent to visible light, we were able to increase the total thickness of MAPbCl3 transport layers to 2,000 nanometres-more than ten times the thickness of standard OLEDs-without requiring high voltage or reducing either internal electroluminescence quantum efficiency or operational durability. These findings will contribute towards a higher production yield of high-quality OLEDs, which may be used for other organic devices, such as lasers, solar cells, memory devices and sensors.

"Core-Shell" Wave Function Modulation in Organic Narrowband Emitters.

Efficient red-green-blue primary luminescence with an extraordinarily narrow band and durability is crucial for advanced display applications. Recently, the emergence of multiple-resonance (MR) from short-range atomic interactions has been shown to induce extremely narrow spectral widths in pure organic emitters. However, achieving wide-range color tuning without compromising color purity remains a persistent challenge for MR emitters. Herein, the concept of electronic donor/acceptor "core-shell" modulation is proposed within a boron/nitrogen (B/N) MR skeleton, enabling the rational utilization of intramolecular charge transfer to facilitate wavelength shift. The dense B atoms localized at the center of the molecule effectively compress the electron density and stabilize the lowest unoccupied molecular orbital wave function. This electron-withdrawing core is embedded with peripheral electron-donating atoms. Consequently, doping a single B atom into a deep-blue MR framework led to a profound bathochromic shift from 447 to 624 nm (∼0.8 eV) while maintaining a narrow spectral width of 0.10 eV in this pure-red emitter. Notably, organic light-emitting diodes assisted by thermally activated delayed fluorescence molecules achieved superb electroluminescent stability, with an LT99 (99% of the initial luminance) exceeding 400 h at an initial luminance of 1000 cd m-2, approaching commercial-level performance without the assistance of phosphors.

Dynamic Luminescence Vapochromism of Pyridinium-Based Organic Salts.

Organic vapochromic materials which undergo a drastic change in their photophysical properties upon exposure to vapors or gases are attracting growing scientific attention because of their low price and wide range of possible applications. In this work, luminescence vapochromism of carbazole-pyridinium-based organic salts with a general structure of (CzPy)X (CzPy+ = 2,3-di(9H-carbazol-9-yl)pyridinium ion; X = Cl, Br or I) is reported. It was found that (CzPy)X compounds form J-aggregates, which rearranged back to monomeric form upon exposure to methanol, ethanol, acetone, and water vapors. In contrast, acetonitrile was found to promote the J-aggregation in (CzPy)X compounds by occupying the voids in their crystal lattice and pushing cations closer together. It was further demonstrated that the efficiency of J-aggregation in (CzPy)X compounds depends on the size of the anion, which was employed to realize dynamic luminescence vapochromism, with vapochromic response times ranging from a couple of minutes in (CzPy)Cl to more than an hour in (CzPy)I. In addition, (CzPy)X compounds exhibited high melting points of about 250 °C and excellent thermal stability. (CzPy)Cl and (CzPy)Br have also shown good photoluminescence quantum yields at room temperature in a solid state.

Luminescence mechanism analysis of a TADF molecule showing peculiar thermal behavior.

In recent years, much attention has been paid to the development of thermally activated delayed fluorescence (TADF) materials with short delayed-fluorescence lifetimes to improve the device performances of OLEDs. In principle, by reducing the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) overlap, while the energy difference between S1-T1 (ΔEST) and activation energy (Ea) can be reduced, and the reverse intersystem crossing rate constant (kRISC) can be accelerated, a decrease in the radiative rate constant happens, necessitating an advanced molecular design. Furthermore, a molecule based on heptazine as a parent skeleton has recently been found to have a peculiar temperature dependence of luminescence decay, suggesting a negative gap (NG) material. In this report, we show that 9-[1,4]benzoxaborino[2,3,4-kl]phenoxaborine-7-yl-1,3,6,8-tetramethyl-9H-carbazole (TMCz-BO), a donor-acceptor linked TADF molecule with a very short delay lifetime of 750 ns, exhibits a peculiar thermal behavior similar to that of NG materials based on the temperature dependence of its luminescence decay in solution.

Molecular asymmetry and rigidification as strategies to activate and enhance thermally activated delayed fluorescence in deep-blue MR-TADF emitters.

Two novel deep-blue multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters, 1B-CzCrs and 2B-CzCrs, containing a fused carbazole unit were synthesized. The carbazole contributed to the emergence of TADF in these small molecules. Particularly, organic light-emitting diodes with 1B-CzCrs doped in the mCP host achieve a maximum external quantum efficiency of 12.8% at CIE coordinates of (0.146, 0.062).

A Rigid Multiple Resonance Thermally Activated Delayed Fluorescence Core Toward Stable Electroluminescence and Lasing.

The investigation of organic light-emitting diodes (OLEDs) and organic laser devices with thermally activated delayed fluorescence (TADF) molecules is emerging due to the potential of harnessing triplets. In this work, a boron/nitrogen multiple-resonance TADF polycyclic framework fusing carbazole units (CzBNPh) was proposed. CzBNPh exhibited a narrowband emission (<30 nm), a unity photoluminescence quantum yield, and a fast radiative rate. Consequently, CzBNPh demonstrated a low distributed feedback (DFB) lasing threshold of 0.68 µJ cm-2 . Furthermore, the stimulated emission zone of CzBNPh was effectively separated from its singlet and triplet absorption, thereby minimizing the singlet-triplet annihilation under long-pulsed excitation ranging from 20 µs to 2.5 ms. Significantly, the enhanced rigid molecular conformation, thermal stability, and photo-stability resulted in improved lasing and electroluminescence stability compared to that of 5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (DABNA)-core. These findings indicate the potential of CzBN-core as a promising framework for achieving long-pulsed wave and electrically-pumped lasing in the future.

Sequential Multiple Borylation Toward an Ultrapure Green Thermally Activated Delayed Fluorescence Material.

Multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters have emerged as an important component of organic light-emitting diodes (OLEDs) because of their narrowband emission and high exciton utilization efficiency. However, the chemical space of MR-TADF emitters remains mostly unexplored because of the lack of suitable synthetic protocols. Herein, we demonstrate a sequential multiple borylation reaction that provides new synthetically accessible chemical space. ω-DABNA, the proof-of-concept material, exhibited narrowband green TADF with a full width at half-maximum of 22 nm and a small singlet-triplet energy gap of 13 meV. The OLED employing it as an emitter exhibited electroluminescence at 512 nm, with Commission International de l'Éclairage coordinates of (0.13, 0.73) and a high external quantum efficiency (EQE) of 31.1%. Moreover, the device showed minimum efficiency roll-off, with an EQE of 29.4% at 1000 cd m-2.

Spontaneous formation of metastable orientation with well-organized permanent dipole moment in organic glassy films.

The performance of organic optoelectronic and energy-harvesting devices is largely determined by the molecular orientation and resultant permanent dipole moment, yet this property is difficult to control during film preparation. Here, we demonstrate the active control of dipole direction-that is, vector direction and magnitude-in organic glassy films by physical vapour deposition. An organic glassy film with metastable permanent dipole moment orientation can be obtained by utilizing the small surface free energy of a trifluoromethyl unit and intramolecular permanent dipole moment induced by functional groups. The proposed molecular design rule could pave a way toward the formation of spontaneously polarized organic glassy films, leading to improvement in the performance of organic molecular devices.

Organic long-persistent luminescence stimulated by visible light in p-type systems based on organic photoredox catalyst dopants.

Organic long-persistent-luminescent (OLPL) materials demonstrating hour-long photoluminescence have practical advantages in applications owing to their flexible design and easy processability. However, the energy absorbed in these materials is typically stored in an intermediate charge-separated state that is unstable when exposed to oxygen, thus preventing persistent luminescence in air unless oxygen penetration is suppressed through crystallization. Moreover, OLPL materials usually require ultraviolet excitation. Here we overcome such limitations and demonstrate amorphous OLPL systems that can be excited by radiation up to 600 nm and exhibit persistent luminescence in air. By adding cationic photoredox catalysts as electron-accepting dopants in a neutral electron-donor host, stable charge-separated states are generated by hole diffusion in these blends. Furthermore, the addition of hole-trapping molecules extends the photoluminescence lifetime. By using a p-type host less reactive to oxygen and tuning the donor-acceptor energy gap, our amorphous blends exhibit persistent luminescence stimulated by visible light even in air, expanding the applicability of OLPL materials.