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A low lasing threshold of up to 0.27 μJ cm−1 was achieved by using TADF materials. Advanced light amplification architectures composed of dual DABNA derivatives were also demonstrated.

Bond lengths analysis highlights their closed-shell structures and gives insight on the bond lengths of diindenoacene diradicaloids. They are low band gap molecules with high electron affinity and exhibit ambipolar behavior in OFETs.

Solution-processed hyperfluorescent red organic light-emitting diodes with external quantum efficiencies of 15.3% was achieved by using cibalackrot as the fluorescent emitter, where attaching tert-butyl groups to the assistant host significantly contributes to device performance.

A tetracene dimer, 5,5′-bitetracene (55BT), has successfully been synthesized for the first time and its structure was confirmed by X-ray single crystal analysis. The electrochemical and optical pr...

Near-IR organic light-emitting diodes (NIR-OLEDs) are potential light-sources for various sensing applications as OLEDs have unique features such as ultra-flexibility and low-cost fabrication. However, the low external electroluminescence (EL) quantum efficiency (EQE) of NIR-OLEDs is a critical obstacle for potential applications. Here, we demonstrate a highly efficient NIR emitter with thermally activated delayed fluorescence (TADF) and its application to NIR-OLEDs. The NIR-TADF emitter, TPA-PZTCN, has a high photoluminescence quantum yield of over 40 % with a peak wavelength at 729 nm even in a highly doped co-deposited film. The EL peak wavelength of the NIR-OLED is 734 nm with an EQE of 13.4 %, unprecedented among rare-metal-free NIR-OLEDs in this spectral range. TPA-PZTCN can sensitize a deeper NIR fluorophore to achieve a peak wavelength of approximately 900 nm, resulting in an EQE of over 1 % in a TADF-sensitized NIR-OLED with high operational device durability (LT95 >600 h.).

This work reports a new acceptor for constructing donor-acceptor type (D-A type) blue thermally activated delayed fluorescence (TADF) emitters with narrowed charge-transfer (CT) emissions. A new acceptor core, carbazole-2-carbonitrile (CCN), is formed by the fusion of carbazole and benzonitrile. Three D-A type TADF emitters based on the CCN acceptor, namely 3CzCCN, 3MeCzCCN, and 3PhCzCCN, have been successfully synthesized and characterized. These emitters show deep-blue emissions from 439 to 457 nm with high photoluminescence quantum yields of up to 85% in degassed toluene solutions. Interestingly, all CCN-based deep-blue TADF emitters result in narrow CT emissions with full-width at half-maximums (FWHMs) of less than 50 nm in toluene solutions, which are pretty narrower compared with those of typical D-A type TADF emitters. Devices based on these emitters show high maximum external quantum efficiencies of up to 17.5%.

Organic laser dyes exhibiting very low amplified spontaneous emission (ASE) thresholds in green and yellow regions were developed based on a stilbene structure which is often used for the blue laser molecules. Although the thresholds are generally increased with decreasing energy levels of molecules, the introduction of a naphthalene unit can shift the emission colors without sacrificing optical properties. In particular, the suppression of concentration quenching by naphthalene moieties resulted in high radiative decay rate constants and low ASE thresholds in the neat films. In addition, the photo- and thermal-stabilities of the naphthalene derivatives were improved compared to those of the corresponding phenylene derivatives. This study demonstrates a simple and effective molecular design for developing green and yellow laser dyes by a small modification from the standard blue emitters.

For an improved understanding of molecular design for efficient laser materials, we report structure–property relationships in a series of oligo(p-phenylenevinylene) derivatives. The π-extended phenylenevinylene systems have been studied less frequently than the well-known 1,4-distyrylbenzene framework, despite easy syntheses and great prospects for optoelectronic devices. Here, light amplification behaviours, with amplified spontaneous emission thresholds as low as 7.2 μJ cm−2, were characterized for oligo(p-phenylenevinylene) crystals. Substitution with cyano groups significantly changes the crystal packing and emission properties, while also improves the lasing behaviour.

peri-Acenes have shown great potential for use as functional materials because of their open-shell singlet biradical character. However, only a limited number of peri-acene derivatives larger than peri-tetracene have been synthesized to date, presumably owing to the low stability of the target compounds in addition to the complicated synthesis scheme. Here, a very simple synthesis route for the tetrabenzo[a,f,j,o]perylene (TBP) structure enables the development of highly stable peri-tetracene analogues. Despite a high degree of singlet biradical character, the compounds with four substituents at the zigzag edge show a remarkable stability in solution under ambient conditions, which is better than that of acene derivatives with a closed-shell electronic configuration. The crystal structures of the TBP derivatives were obtained for the first time; these are valuable to understand the relationship between the structure and biradical character of peri-acenes. The application of peri-acenes in electronic devices should also be investigated. Therefore, the semiconducting properties of the TBP derivative were investigated by fabricating the field-effect transistors., Highly stable peri-tetracene analogues with a high degree of singlet biradical character were synthesized in a very simple route, and their crystal structures and semiconducting properties were investigated.

A simple way to control only the surface properties of polymer materials, without changing the bulk properties, has long been desired. The segregation behavior when a component with a tiny amount fed into the matrix is thermodynamically enriched at the surface is one of the candidate methods. This capability was examined herein by focusing on a star-shaped polyhedral oligomeric silsesquioxane (s-POSS), where the central POSS unit is tethered to eight isobutyl-substituted POSS cages as a surface modifier. X-ray photoelectron spectroscopy revealed that the surface of a film of poly(methyl methacrylate) (PMMA) was almost completely covered with POSS units by adding just 5 wt % s-POSS to it. The segregated POSS dramatically altered the physical properties such as molecular motion and the mechanical and dielectric responses at the surface of the PMMA film. These findings make it clear that s-POSS is an excellent surface modifier for glassy polymers.

We describe the photophysical processes that give rise to thermally activated delayed fluorescence in the excited state intramolecular proton transfer (ESIPT) molecule, triquinolonobenzene (TQB). Using transient absorption and time-resolved photoluminescence spectroscopy, we fully characterize prompt and delayed emission, phosphorescence, and oxygen quenching to reveal the reverse intersystem crossing mechanism (rISC). After photoexcitation and rapid ESIPT to the TQB-TB tautomer, emission from S1 is found to compete with thermally activated ISC to an upper triplet state, T2, very close in energy to S1 and limiting photoluminescence quantum yield. T2 slowly decays to the lowest triplet state, T1, via internal conversion. In the presence of oxygen, T2 is quenched to the ground state of the double proton transferred TQB-TC tautomer. Our measurements demonstrate that rISC in TQB occurs from T2 to S1 driven by thermally activated reverse internal conversion from T1 to T2 and support recent calculations by Cao et al. (Cao, Y.; Eng, J.; Penfold, T. J. Excited State Intramolecular Proton Transfer Dynamics for Triplet Harvesting in Organic Molecules.

Hyperfluorescent organic light-emitting diodes (HF-OLEDs) enable a cascading Förster resonance energy transfer (FRET) from a suitable thermally activated delayed fluorescent (TADF) assistant host to a fluorescent end-emitter to give efficient OLEDs with relatively narrowed electroluminescence compared to TADF-OLEDs. Efficient HF-OLEDs require optimal FRET with minimum triplet diffusion via Dexter-type energy transfer (DET) from the TADF assistant host to the fluorescent end-emitter. To hinder DET, steric protection of the end-emitters has been proposed to disrupt triplet energy transfer. In this work, the first HF-OLEDs based on structurally well-defined macromolecules, dendrimers is reported. The dendrimers contain new highly twisted dendrons attached to a Cibalackrot core, resulting in high solubility in organic solvents. HF-OLEDs based on dendrimer blend films are fabricated to show external quantum efficiencies of10% at 100 cd m

The limitation of lasing duration less than nanosecond order has been a major problem for realizing organic solid-state continues-wave (CW) lasers and organic semiconductor laser diodes. Triplets accumulation under CW excitation has been well recognized as a critical inhibiting factor. To overcome this issue, the utilization of thermally activated delayed fluorescence (TADF) emitters is a promising mechanism because of efficient reverse intersystem crossing. Herein, we model the triplet accumulation processes under lasing and propose the active utilization of TADF for lasing based on our simulation analysis. We used the rate constants experimentally determined from the optical properties of a boron difluoride curcuminoid fluorophore showing both TADF and lasing. We demonstrate that the intersystem crossing efficiency is gradually increased after the convergence of relaxation oscillation, i.e., terminating laser oscillation. In addition, we found that when the reverse intersystem crossing rate is close to the intersystem crossing rate, CW lasing becomes dominant.

A new molecular design for organic semiconductor laser dyes showing excellent optical properties and high robustness is disclosed in this work. The suitability of a furan moiety for increasing the ...

There has been increasing interest in blue organic light-emitting diodes based on thermally activated delayed fluorescence (TADF). The construction of a fully optimized device architecture is crucial in accordance with developing high-performance materials because highly efficient electroluminescence cannot be realized without balancing both carrier injection and transport with decreasing several exciton loss processes. Thus, the detailed mechanism of carrier injection, transport, and recombination in emitting layers has to be clarified. In this study, various device architectures for a recently emerged blue TADF molecular system based on multiple donors and acceptors were systematically investigated, especially by focusing on the interlayers. This work also aims to offer guidelines for improving device stabilities. Our findings clarify the role of each layer, providing in-depth insight into device design and the selection of proper materials for each constituted layer.

Recently, there has been increasing interest in a class of polycyclic aromatic hydrocarbons (PAHs) with peri-extension of acenes. These peri-fused systems, referred to as peri-acenes and acenoacenes, are considered to be nanographenes.[1–3] Thus, the compounds based on tetracene and larger acenes show singlet biradical nature at the zigzag edge, offering unique and interesting properties. However, the synthesis schemes for these compounds are generally complicated, which hinder the extensive development of these derivatives and application to organic optoelectronics such as organic field-effect transistors (OFETs) and organic light-emitting diodes (OLEDs). A pentacene derivative with two triisopropylsilylethynyl groups at the central ring (TIPS-PEN) was developed in 2001. It shows good solubility, stability, and semiconducting property, resulting in being one of the most studied organic semiconductors. In contrast, the peri-extended compound of TIPS-PEN has not been developed because of the difficulty in synthesis using the same method as TIPS-PEN.[4] Here, we found the synthetic conditions to avoid the competition between 1,2- and 1,4-addition of lithium acetylide on large aromatic dione and succeeded in synthesizing TIPS-ethynyl-substituted peri-pentacenopentacene (TIPS-PPP).[5] The stability of TIPS-PPP was 16 times superior to that of TIPS-PEN, which is attributed to higher aromaticity as shown in an electronic structure of two-fused anthracene. TIPS-PPP shows the crystal packing of the 2D-brickwall motif like TIPS-PEN. The high mobility of up to 1 cm2 V−1 s−1 was obtained in OFET fabricated by wet process owing to large transfer integrals and low reorganization energies. In addition, TIPS-PPP showed high quantum yield in near-infrared (NIR) region. Thus, it was used as an emitter for NIR-OLED devices, resulting in high external quantum efficiency at 800 nm. These results suggest that acene-like materials are very promising for developing NIR emitters. References [1] M. Mamada, R. Nakamura, C. Adachi, Chem. Sci. 2021, 12, 552. DOI: 10.1039/D0SC04699J [2] T. Jousselin-Oba, M. Mamada, J. Marrot, A. Maignan, C. Adachi, A. Yassar, M. Frigoli, J. Am. Chem. Soc. 2019, 141, 9373. DOI: 10.1021/jacs.9b03488 [3] Y. Gu, Y. G. Tullimilli, J. Feng, H. Phan, W. Zeng, J. Wu, Chem. Commun. 2019, 55, 5567. DOI: 10.1039/c9cc01986c [4] X. Zhang, J. Li, H. Qu, C. Chi, J. Wu, Org. Lett. 2010, 12, 3946. DOI: 10.1021/ol101720e [5] T. Jousselin-Oba, M. Mamada, K. Wright, J. Marrot, C. Adachi, A. Yassar, M. Frigoli, Angew. Chem. Int. Ed. 2021, DOI: 10.1002/anie.202112794.

A bright near-infrared (NIR) fluorescent molecule was developed based on the donor-acceptor-donor (D-A-D) approach using an aza-BODIPY analog called pyrrolopyrrole aza-BODIPY (PPAB) as an electron-accepting chromophore. Directly introducing electron-donating triphenylamine (TPA) to develop a D-A-D structure caused redshifts of absorption and emission of PPAB into the NIR region with an enhanced fluorescence brightness of up to 5.2×104 m-1 cm-1 , whereas inserting a phenylene linker between the TPA donor and the PPAB acceptor induced solvatochromic behavior in emission. Transient absorption spectra and theoretical calculations revealed the presence of a highly emissive hybridized locally excited and charge-transfer state in the former case and the contribution of the dark charge-separated state to the excited state in the latter case. The bright D-A-D PPAB as a novel emitter resulted in a NIR electroluminescence with a high external quantum efficiency of 3.7 % and a low amplified spontaneous emission threshold of ca. 80 μJ cm-2 , indicating the high potential for NIR optoelectronic applications.

International audience; We report the synthesis and optoelectronic properties of TIPS-peri-pentacenopentacene (TIPS-PPP), a vertical extension of TIPS-pentacene (TIPS-PEN) and a low-band-gap material with remarkable stability. We found the synthetic conditions to avoid the competition between 1,2- and 1,4-addition of lithium acetylide on the large aromatic dione. The high stability of TIPS-PPP is due to the peri-fusion which increases the aromaticity by generating two localized aromatic sextets that are flanked with 2 diene fragments, similar to two fused-anthracenes. Like TIPS-PEN, TIPS-PPP shows the archetypal 2D brickwall motif in crystals with a larger transfer integral and smaller reorganization energy. The high mobility of up to 1 cm2 V−1 s−1 was obtained in an organic field-effect transistor fabricated by a wet process. Also, TIPS-PPP was used as a near-infrared (NIR) emitter for NIR organic-light-emitting-diode devices resulting in a high external quantum efficiency at 800 nm.

International audience; Five new N-phenyl-carbazole benzopyrans bearing different substitutions on one of the phenyl rings at the sp3 carbon have been synthesized. Their molecular structures were investigated by X-ray and NMR analyses and through quantum chemical calculations. The photochromic mechanism under UV irradiation in toluene, consisting of the consecutive formation of transoid-cis (TC) and transoid-trans (TT) isomers, was studied by UV-vis spectral and kinetic analyses. These molecules have been specifically designed to ascertain the possibility of favouring the formation of the less thermodynamically stable TT at the photostationary state, upon exploiting steric hindrance effects on the diene part of the molecule. The spectrokinetic study allowed the estimation of most of the spectrokinetic parameters, such as molar extinction coefficients, quantum yields of UV colouration and visible photobleaching, and the rate constants of the fast and slow thermal bleaching processes. Peculiar effects of substituents with different donor strengths on one phenyl ring located at the 3-position were observed on the spectrokinetic propertie

The yellow-green emissive poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) polymer is widely used because of its suitability for a variety of applications. However, we have found that F8BT sho...

External quantum efficiency (EQE) roll-off under high current injection has been one of the major limiting factors toward the development of organic semiconductor laser diodes (OSLDs). While significant progress in this regard has been made on organic semiconductors (OSCs) emitting in the blue-green region of the visible spectrum, OSCs with longer wavelength emission (600 nm) have fallen behind in both material development and the advancement in device architectures suitable for the realization of OSLDs. Therefore, to make simultaneous incremental advancements, a host-guest system comprising of a high performing poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) polymer and an efficient small molecule laser dye, dithiophenyl diketopyrrolopyrrole (DT-DPP), is used. This combination provides an extremely low amplified spontaneous emission threshold of 4.2 µJ cm

The inclusion of a tetraphenylbenzene (4Ph) unit in thermally activated delayed fluorescence emitters is demonstrated as a novel strategy for greatly enhancing the horizontally oriented alignment of the emitters without shifting the emission spectrum to longer wavelengths. Doping of blue-emitting 4PhOXDDMAC or greenish-blue-emitting 4PhOXDPXZ into o-DiCbzBz host layers yielded much higher degrees of horizontally oriented alignment for the emitter (up to 92%) compared to those when the 4Ph unit was excluded (69 and 75%, respectively). The enhanced alignment results in high outcoupling efficiencies of 24 and 35% in organic light-emitting diodes based on 4PhOXDDMAC and 4PhOXDPXZ, respectively, and boosts the external quantum efficiencies to values (8.8 and 29.2%, respectively) that are higher than what would be expected for randomly oriented emitters (outcoupling efficiency of 20%). These enhancements are achieved while avoiding the redshift that often occurs using the common strategy of increasing molecular length and, thereby, conjugation, to increase orientation.

The search for new classes of efficient electroluminescent organic laser dyes with low amplified spontaneous emission (ASE) threshold (Eth) and low optical losses is crucial toward the realization of organic injection lasers. In this work, we report in-depth studies of an organic semiconducting laser dye, benzo[d]thiazol-2-yl)-5-(9H-carbazol-9-yl)phenol (HBT-Cz), and compare the photophysical study with its parent HBT dye. While HBT is not laser-active in solution, the carbazole derivatized dye (i.e., HBT-Cz) showed a low solution ASE threshold of 21 mJ/cm2, which is comparable to a common high-performing commercial laser dye, Rhodamine 6G (Rh-6G). HBT-Cz also exhibited a low film ASE threshold of 2.4 μJ/cm2 with a low optical loss coefficient of 1.5 cm–1, which is the lowest waveguide loss coefficient reported for solution-processed organic semiconductors. Organic light-emitting diodes based on this material showed a high maximum EQE of 1.9%, which is close to the theoretical EQE limit of the emitter, an...

Understanding excited-state dynamics is critical for improving the photoluminescence (PL) efficiency of exciplexes. A series of exciplexes based on conventional hole-transporting materials as donor and newly developed phenylpyridinato boron derivatives as acceptor were investigated. High PL efficiencies were achieved in only some combinations, and a large difference in performance among combinations provided insight into nonradiative processes in exciplex systems. Furthermore, the triplet local excited states (3 LE) of each donor and acceptor were found play an important role in triplet exciplex harvesting. Significant contributions from triplets were clearly observed when the charge-transfer excited states (1 CT and 3 CT) and 3 LE were ideally aligned. We also demonstrated fine control of relative energy alignment via the concentration to improve the PL efficiency.

Thermally activated delayed fluorescence (TADF) materials have shown great potential for highly efficient organic light-emitting diodes (OLEDs). While the current molecular design of TADF materials primarily focuses on combining donor and acceptor units, we present a novel system based on the use of excited-state intramolecular proton transfer (ESIPT) to achieve efficient TADF without relying on the well-established donor–acceptor scheme. In an appropriately designed acridone-based compound with intramolecular hydrogen bonding, ESIPT leads to separation of the highest occupied and lowest unoccupied molecular orbitals, resulting in TADF emission with a photoluminescence quantum yield of nearly 60%. High external electroluminescence quantum efficiencies of up to 14% in OLEDs using this emitter prove that efficient triplet harvesting is possible with ESIPT-based TADF materials. This work will expand and accelerate the development of a wide variety of TADF materials for high performance OLEDs., Excited-state intramolecular proton transfer opens a new route for efficient organic light-emitting diodes emitters based on thermally activated delayed fluorescence without relying on a donor−acceptor scheme.

Anthra[2,3-b]thieno[2,3-d]thiophene (ATT), which is readily accessed from thieno[3,2-b]thiophene and 2,3-naphthalenedicarboxylic anhydride, allows for selective substitution at the terminal thiophene ring, thereby providing asymmetric monoalkyl and monoalkylthienyl thienoacenes. Alkyl-substituted ATT (CnATT, n = 6, 8, 10, 12) has characteristics of a p-type field-effect transistor (FET), with mobility on the order of 0.01 cm2 V–1 s–1, which is the same as ATT. Conversely, alkylthienyl-substituted ATT (CnTATT, n = 6, 8, 10, 12) exhibits FET mobility of 0.15–1.9 cm2 V–1 s–1, which is up to 2 orders of magnitude greater than that of ATT and CnATT. Moreover, CnTATT forms crystalline thin films both by spin coating and drop casting, and C8TATT in particular exhibits a mobility of up to 1.6 cm2 V–1 s–1 in the drop-cast film. X-ray diffraction patterns of CnTATT thin films indicate that the molecules become oriented edge-on at the substrate surface with a highly ordered structure in the in-plane direction. Accor...

Two novel bent-shaped thienoacenes, naphtho[2,3-b]naphtho[2′,3′:4,5]thieno[3,2-d]thiophene (bent-DNTT) and anthra[2,3-b]anthra[2′,3′:4,5]thieno[3,2-d]thiophene (bent-DATT) were synthesized from thieno[2,3-b]thiophene and their corresponding aromatic anhydrides by three steps: Friedel–Crafts acylation, acid-promoted cyclization, and reductive aromatization. The structural curvature improved the solubility of these thienoacenes in organic solvents. The bent-DNTT based FET device was fabricated by the spin-coating method. The device exhibited p-type characteristics with a mobility of 5.1 × 10−5 cm2 V−1 s−1. Its thin-film structure was fully characterized as an edge-on orientation with large intermolecular orbital coupling.

International audience; Designing stable open-shell organic materials through the modifications of the π-topology of molecular organic semiconductors have attracted recently considerable attention. However, their uses as an active layer in organic field-effect transistors (OFETs) are very limited and the obtained hole and electron charge mobilities are around 10 −3 cm 2 V −1 s −1. Herein, we disclosed the synthesis of two materials so-called tetraceno-tetracene (TT) and pentacenopentacene (PP) which have low band gap of 1.79 and 1.42 eV, respectively. Their ground state natures have been investigated by different experiments including steady state absorption, electron spin resonance, superconducting quantum interfering device (SQUID) and variable temperature NMR along with DFT calculations. TT and PP have closed-shell and singlet open-shell structures in their ground state, respectively , and possess high stability. Their biradical characteristics were found to be 0.50 and 0.64. The origin of the open-shell character of PP is related to the concomitant opening of two tetracenes with the recovering of two extra aromatic sextets and a small HOMO-LUMO energy gap (gap < 1.5 eV). Thanks to the high stability, thin film OFET devices could be fabricated. In TG-BC configuration PP shows remarkably high hole mobility of 1.4 cm 2 V −1 s −1 while TT exhibits a hole mobility of 0.77 cm 2 V −1 s −1. In configuration of BG-TC, ambipolar behaviors for both were obtained with hole and electron mobilities of 0.21 and 0.01 cm 2 V −1 s −1 for PP and 0.14 and 0.006 cm 2 V −1 s −1 for TT.

Organic light‐emitting diodes (OLEDs) exhibiting thermally activated delayed fluorescence (TADF) have attracted great interest because of their excellent exciton harvesting ability in electroluminescence (EL). While TADF‐OLEDs show a high EL efficiency, the device operational stability is not necessarily satisfactory for commercial applications. Herein, the isotope effect of the host material on the device operational stability in TADF‐OLEDs is investigated. It is unveiled that the deuterated host, i.e., PYD2Cz‐d16, forms a denser film than that of the nondeuterated host, PYD2Cz, demonstrating enhanced stable amorphous nature and balanced carrier transport properties. In green TADF‐OLEDs, the PYD2Cz‐d16‐based OLED considerably lengthens the device operational stability of LT95 (95% of the initial luminance) to ≈140 h at an initial luminance of 1000 cd m−2, which is 1.7 times longer than that of PYD2Cz. Device stabilities of blue TADF‐OLEDs with PYD2Cz‐d16 as a host are also demonstrated with an enhancement of 2 times in LT50 at an initial luminance of 1000 cd m−2. It is suggested that the deuterated materials have a positive effect on the device stability in not only TADF‐OLEDs, but also all other OLEDs having fluorescence and phosphorescence emitters.

Mellitic triimide derivatives with N-benzyl groups form conformations with concave cavities, that are capable of including aromatic molecules such as benzene, nitrobenzene, etc. In addition, they act as supramolecular gelators, which enable the detection of aromatic molecules as a gel-sol phase transition.