Enhancing Triplet–Triplet Upconversion Efficiency and Operational Lifetime in Blue Organic Light-Emitting Diodes by Utilizing Thermally Activated Delayed Fluorescence Materials

In the process of triplet–triplet upconversion (TTU), a bright excited singlet can be generated because of the collision of two dark excited triplets. In particular, the efficiency of TTU is crucial for achieving a high exciton production yield in blue fluorescence organic light-emitting diodes (OLEDs) beyond the theoretical limit. While the theoretical upper limit of TTU contribution yield is expected to be 60%, blue OLEDs with the maximum TTU contribution are still scarce. Herein, we present a proof of concept for realizing the maximum TTU contribution yield in blue OLEDs, achieved through the doping of thermally activated delayed fluorescence (TADF) molecules in the carrier recombination zone. The bipolar carrier transport ability of TADF materials enables direct carrier recombination on the molecules, resulting in the expansion of the recombination zone. Although the external electroluminescence quantum efficiency of OLEDs is slightly lower than that of conventional TTU-OLEDs due to the low photoluminescence quantum yield of the doped layer, the TTU efficiency approaches the upper limit. Furthermore, the operational device lifetime of OLEDs employing TADF molecules increased by five times compared to the conventional ones, highlighting the expansion of the recombination zone as a crucial factor for enhancing overall OLED performance in TTU-OLEDs

Utilization of Multi-Heterodonors in Thermally Activated Delayed Fluorescence Molecules and Their High Performance Bluish-Green Organic Light-Emitting Diodes

We report a series of pentacarbazolyl-benzonitrile derivatives such as 2,4,6-tri­(9H-carbazol-9-yl)-3,5-bis­(3,6-di­(pyridin-3-yl)-9H-carbazol-9-yl)­benzonitrile (mPyBN), 3,5-bis­(3,6-bis­(4-(trifluoromethyl)­phenyl)-9H-carbazol-9-yl)-2,4,6-tri­(9H-carbazol-9-yl)­benzonitrile (pCF3BN), 2,4,6-tri­(9H-carbazol-9-yl)-3-(3,6-di­(pyridin-3-yl)-9H-carbazol-9-yl)-5-(3,6-diphenyl-9H-carbazol-9-yl)­benzonitrile (PyPhBN), 3-(3,6-bis­(4-(trifluoromethyl)­phenyl)-9H-carbazol-9-yl)-2,4,6-tri­(9H-carbazol-9-yl)-5-(3,6-di­(pyridin-3-yl)-9H-carbazol-9-yl)­benzonitrile (PyCF3BN), and 3-(3,6-bis­(4-(trifluoromethyl)­phenyl)-9H-carbazol-9-yl)-2,6-di­(9H-carbazol-9-yl)-5-(3,6-di­(pyridin-3-yl)-9H-carbazol-9-yl)-4-(9H-pyrido­[3,4-b]­indol-9-yl)­benzonitrile (CbPyCF3BN) in which some of the carbazoles are substituted with modified 3,5-diphenyl carbazoles, exhibiting thermally activated delayed fluorescence (TADF) properties. These emitters comprised two, three, and four different types of donors, capable of bluish-green emission of around 480 nm with relatively high photoluminescence quantum yields over 90% in solution. Emitters, namely, PyPhBN, PyCF3BN, and CbPyCF3BN, composed of three and four different types of donors endowed a rather short delayed lifetime (τd) of 4.25, 5.01, and 3.65 μs in their film state, respectively. Bluish-green organic light-emitting diodes based on PyPhBN, PyCF3BN, and CbPyCF3BN exhibit a high external quantum efficiency of 20.6, 19.5, and 19.6%, respectively, with unsurpassed efficiency roll-off behavior. These results indicate that the TADF properties of multidonor type molecules can be manipulated by controlling the types and number of electron donor units

Three-Dimensional Spirothienoquinoline-Based Small Molecules for Organic Photovoltaic and Organic Resistive Memory Applications

A new electron-rich spirothienoquinoline unit, tBuSAF-Th, has been developed via incorporation of a thienyl unit instead of a phenyl unit into the six-membered ring of the spiroacridine (SAF) and utilized for the first time as a building block for constructing small-molecule electron donors in organic solar cells (OSCs) and as active layers in organic resistive memory devices. The resulting three-dimensional spirothienoquinoline-containing 1–4 exhibit high-lying highest occupied molecular orbital (HOMO) energy levels. By the introduction of electron-deficient benzochalcogenodiazole linkers, with the chalcogen atoms being varied from O to S and Se, a progressively lower lowest unoccupied molecular orbital (LUMO) energy level has been achieved while keeping the HOMO energy levels similar. This strategy has allowed an enhanced light-harvesting ability without compromising open-circuit voltage (Voc) in vacuum-deposited bulk heterojunction OSCs using 1–4 as donors and C70 as the acceptor. Good photovoltaic performances with power conversion efficiencies (PCEs) of up to 3.86% and high short-circuit current densities (Jsc) of up to 10.84 mA cm–2 have been achieved. In addition, organic resistive memory devices fabricated with these donor–acceptor small molecules exhibit binary logic memory behaviors with long retention times and high on/off current ratios. This work indicates that the spirothienoquinoline moiety is a potential building block for constructing multifunctional organic electronic materials

Three-Dimensional Spirothienoquinoline-Based Small Molecules for Organic Photovoltaic and Organic Resistive Memory Applications

A new electron-rich spirothienoquinoline unit, tBuSAF-Th, has been developed via incorporation of a thienyl unit instead of a phenyl unit into the six-membered ring of the spiroacridine (SAF) and utilized for the first time as a building block for constructing small-molecule electron donors in organic solar cells (OSCs) and as active layers in organic resistive memory devices. The resulting three-dimensional spirothienoquinoline-containing 1–4 exhibit high-lying highest occupied molecular orbital (HOMO) energy levels. By the introduction of electron-deficient benzochalcogenodiazole linkers, with the chalcogen atoms being varied from O to S and Se, a progressively lower lowest unoccupied molecular orbital (LUMO) energy level has been achieved while keeping the HOMO energy levels similar. This strategy has allowed an enhanced light-harvesting ability without compromising open-circuit voltage (Voc) in vacuum-deposited bulk heterojunction OSCs using 1–4 as donors and C70 as the acceptor. Good photovoltaic performances with power conversion efficiencies (PCEs) of up to 3.86% and high short-circuit current densities (Jsc) of up to 10.84 mA cm–2 have been achieved. In addition, organic resistive memory devices fabricated with these donor–acceptor small molecules exhibit binary logic memory behaviors with long retention times and high on/off current ratios. This work indicates that the spirothienoquinoline moiety is a potential building block for constructing multifunctional organic electronic materials

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

DataSheet1_Multiple resonance type thermally activated delayed fluorescence by dibenzo [1,4] azaborine derivatives.docx

We studied the photophysical and electroluminescent (EL) characteristics of a series of azaborine derivatives having a pair of boron and nitrogen aimed at the multi-resonance (MR) effect. The computational study with the STEOM-DLPNO-CCSD method clarified that the combination of a BN ring-fusion and a terminal carbazole enhanced the MR effect and spin-orbit coupling matrix element (SOCME), simultaneously. Also, we clarified that the second triplet excited state (T2) plays an important role in efficient MR-based thermally activated delayed fluorescence (TADF). Furthermore, we obtained a blue–violet OLED with an external EL quantum efficiency (EQE) of 9.1%, implying the presence of a pronounced nonradiative decay path from the lowest triplet excited state (T1).</p

Investigation of Charge Transport Properties in a 2D Dion–Jacobson Halide Perovskite Based on Terphenyl Dications

Type II heterostructures formed by organic semiconducting ligands and inorganic layers in two-dimensional (2D) hybrid perovskites can offer separated charge transport channels for holes and electrons. In this work, we studied a new lead-based 2D Dion–Jacobson perovskite structure incorporating simple terphenyl diammonium salts as organic spacers. The investigations of the electronic and photophysical properties, combined with theoretical calculations, indicate that this 2D perovskite structure forms a type II heterostructure producing intercalated separate pathways for electrons and holes that can migrate within the inorganic and organic sublayers, respectively. The charge transport properties of this unusual type II 2D perovskite heterostructure have also been successfully investigated for the first time by the space charge limited current (SCLC) method, and maximum electron and hole mobilities based on single-crystal devices were evaluated to be 0.3 cm2 V–1 s–1 and 7.0 × 10–4 cm2 V–1 s–1, respectively. This work gives valuable insights into the charge transport mechanisms of type II heterostructures and paves the way toward optoelectronic device applications for such Dion–Jacobson-type 2D perovskites

Investigation of Charge Transport Properties in a 2D Dion–Jacobson Halide Perovskite Based on Terphenyl Dications

Type II heterostructures formed by organic semiconducting ligands and inorganic layers in two-dimensional (2D) hybrid perovskites can offer separated charge transport channels for holes and electrons. In this work, we studied a new lead-based 2D Dion–Jacobson perovskite structure incorporating simple terphenyl diammonium salts as organic spacers. The investigations of the electronic and photophysical properties, combined with theoretical calculations, indicate that this 2D perovskite structure forms a type II heterostructure producing intercalated separate pathways for electrons and holes that can migrate within the inorganic and organic sublayers, respectively. The charge transport properties of this unusual type II 2D perovskite heterostructure have also been successfully investigated for the first time by the space charge limited current (SCLC) method, and maximum electron and hole mobilities based on single-crystal devices were evaluated to be 0.3 cm2 V–1 s–1 and 7.0 × 10–4 cm2 V–1 s–1, respectively. This work gives valuable insights into the charge transport mechanisms of type II heterostructures and paves the way toward optoelectronic device applications for such Dion–Jacobson-type 2D perovskites