Imidazo[1,2-a]pyridine as an Electron Acceptor to Construct High-Performance Deep-Blue Organic Light-Emitting Diodes with Negligible Efficiency Roll-Off.

Two novel bipolar deep-blue fluorescent emitters, IP-PPI and IP-DPPI, featuring different lengths of the phenyl bridge, were designed and synthesized, in which imidazo[1,2-a]pyridine (IP) and phenanthroimidazole (PI) were proposed as an electron acceptor and an electron donor, respectively. Both of them exhibit outstanding thermal stability and high emission quantum yields. All the devices based on these two materials showed negligible efficiency roll-off with increasing current density. Impressively, non-doped organic light-emitting diodes (OLEDs) based on IP-PPI and IP-DPPI exhibited external quantum efficiencies (EQEs) of 4.85 % and 4.74 % with CIE coordinates of (0.153, 0.097) and (0.154, 0.114) at 10000 cd m-2 , respectively. In addition, the 40 wt % IP-PPI doped device maintained a high EQE of 5.23 % with CIE coordinates of (0.154, 0.077) at 10000 cd m-2 . The doped device based on 20 wt % IP-DPPI exhibited a higher deep-blue electroluminescence (EL) performance with a maximum EQE of up to 6.13 % at CIE of (0.153, 0.078) and maintained an EQE of 5.07 % at 10000 cd m-2 . To the best of our knowledge, these performances are among the state-of-the art devices with CIEy ≤0.08 at a high brightness of 10000 cd m-2 . Furthermore, by doping a red phosphorescent dye Ir(MDQ)2 (MDQ=2-methyldibenzo[f,h]quinoxaline) into the IP-PPI and IP-DPPI hosts, high-performance red phosphorescent OLEDs with EQEs of 20.8 % and 19.1 % were achieved, respectively. This work may provide a new approach for designing highly efficient deep-blue emitters with negligible roll-off for OLED applications.

Ternary Acceptor-Donor-Acceptor Asymmetrical Phenanthroimidazole Molecule for Highly Efficient Near-Ultraviolet Electroluminescence with External Quantum Efficiency (EQE) >4 .

A new ternary acceptor (A)-donor (D)-acceptor (A) asymmetrically twisted deep-blue emitting molecule, PPI-2BI, was synthesized by attaching two electrophilic benzimidazole (BI) units to the C2 and N1 positions of a phenanthroimidazole (PI) donor unit. Profiting from the enhanced D-A electronic coupling, the electron injecting and transporting abilities of the new triangle-shaped A-D-A molecule are considerably improved and the molecule shows high photoluminescence (PL) and electroluminescence (EL) efficiencies. By using PPI-2BI as a non-doped emitting layer (EML), the resulting organic light-emitting device exhibits emission with color coordinates of (0.158, 0.124) and a maximum external quantum efficiency (EQE), current efficiency (CE), and power efficiency (PE) of 4.63 %, 4.98 cd A-1 , and 4.82 lm W-1 , respectively. Additionally, a simple bilayer device using PPI-2BI as both the EML and the electron-transporting layer (ETL) also shows an EQE of 3.81 % with little changes to the color purity. Remarkably, a PPI-2BI-based doped device emits efficient near-ultraviolet EL with color coordinates of (0.154, 0.047) and an EQE of 4.12 %, which is comparable to that of the best reported near-UV emitting devices.

Intermolecular Charge-Transfer Transition Emitter Showing Thermally Activated Delayed Fluorescence for Efficient Non-Doped OLEDs.

A novel molecular model of connecting electron-donating (D) and electron-withdrawing (A) moieties via a space-enough and conjugation-forbidden linkage (D-Spacer-A) is proposed to develop efficient non-doped thermally activated delayed fluorescence (TADF) emitters. 10-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl) phenoxy) phenyl)-9,9-dimethyl-9,10-dihydroacridine (DMAC-o-TRZ) was designed and synthesized accordingly. As expected, it exhibits local excited properties in single-molecule state as D-Spacer-A molecular backbone strongly suppress the intramolecular charge-transfer (CT) transition. And intermolecular CT transition acted as the vital radiation channel for neat DMAC-o-TRZ film. As in return, the non-doped device exhibits a remarkable maximum external quantum efficiency (EQE) of 14.7 %. These results prove the feasibility of D-Spacer-A molecules to develop intermolecular CT transition TADF emitters for efficient non-doped OLEDs.

Unraveling non-radiative decay channels of exciplexes to construct efficient red emitters for organic light-emitting diodes.

Exciplex emitters naturally have thermally activated delayed fluorescence characteristics due to their spatially separated molecular orbitals. However, the intermolecular charge transfer potentially induces diverse non-radiative decay channels, severely hindering the construction of efficient red exciplexes. Thus, a thorough comprehension of this energy loss is of paramount importance. Herein, different factors, including molecular rigidity, donor-acceptor interactions and donor-donor/acceptor-acceptor interactions, that impact the non-radiative decay were systematically investigated using contrasting exciplex emitters. The exciplex with rigid components and intermolecular hydrogen bonds showed a photoluminescence quantum yield of 84.1% and a singlet non-radiative decay rate of 1.98 × 106 s-1 at an optimized mixing ratio, respectively, achieving a 3.3-fold increase and a 70% decrease compared to the comparison group. In the electroluminescent device, a maximum external quantum efficiency of 23.8% was achieved with an emission peak of 608 nm, which represents the state-of-the-art organic light-emitting diodes using exciplex emitters. Accordingly, a new strategy is finally proposed, exploiting system rigidification to construct efficient red exciplex emitters that suppress non-radiative decay.

A novel orange-red thermally activated delayed fluorescence emitter with high molecular rigidity and planarity realizing 32.5% external quantum efficiency in organic light-emitting diodes.

Simultaneous optimization of photoluminescence quantum yield (ΦPL) and horizontally oriented dipoles (Θ‖) is considerably challenging for orange and red thermally activated delayed fluorescence (TADF) emitters, due to the conflicts between enhancing molecular rigidity and improving molecular planarity. Herein, a novel orange-red TADF emitter 10-(dipyrido[3,2-a:2',3'-c]phenazin-11-yl)-10H-spiro[acridine-9,9'-fluorene] (SAF-2NP) was constructed with a donor-acceptor structure. The highly rigid donor and acceptor segments ensure the overall rigidity of the emitter. More importantly, the quasi-coplanar structure between the acceptor and the fluorene moiety in the donor unit enlarges the molecular plane without weakening rigidity. Consequently, SAF-2NP exhibited extremely high ΦPL and Θ‖ of 99% and 85%, respectively. The optimal organic light-emitting diode using SAF-2NP as the emitter and 4,4'-di(9H-carbazol-9-yl)-1,1'-biphenyl (CBP) as the host demonstrated an unparalleled external quantum efficiency of 32.5% and a power efficiency of 85.2 lm W-1 without any extra light extraction structure. This work provides a feasible strategy to establish efficient orange and red TADF emitters with both high rigidity and planarity.

Thermally activated delayed fluorescence exciplex emitters for high-performance organic light-emitting diodes.

Owing to their natural thermally activated delayed fluorescence (TADF) characteristics, the development of exciplex emitters for organic light-emitting diodes (OLEDs) has witnessed booming progress in recent years. Formed between electron-donating and electron-accepting molecules, exciplexes with intermolecular charge transfer processes have unique advantages compared with unimolecular TADF materials, offering a new way to develop high-performance TADF emitters. In this review, a comprehensive overview of TADF exciplex emitters is presented with a focus on the relationship between the constituents of exciplexes and their electroluminescence performance. We summarize and discuss the latest and most significant developments of TADF exciplex emitters. Notably, the design principles of efficient TADF exciplex emitters are systematically categorized into three systems within this review. These progressive achievements of TADF exciplex emitters point out future challenges to trigger more research endeavors in this growing field.

Highly Efficient Thermally Activated Delayed Fluorescence Emitter Developed by Replacing Carbazole With 1,3,6,8-Tetramethyl-Carbazole.

Carbazole (Cz) is the one of the most popular electron donors to develop thermally activated delayed fluorescence (TADF) emitters, but additional groups are generally required in the molecules to enhance the steric hindrance between Cz and electron acceptor segments. To address this issue, we replaced Cz with its derivative 1,3,6,8-tetramethyl-carbazole (tMCz) to develop TADF emitters. Two novel compounds, 6-(4-(carbazol-9-yl)phenyl)-2,4-diphenylnicotinonitrile (CzPN) and 2,4-diphenyl-6-(4- (1,3,6,8-tetramethyl-carbazol-9-yl)phenyl) nicotinonitrile (tMCzPN) were designed and synthesized accordingly. With the same and simple molecular framework, tMCzPN successfully exhibits TADF behavior, while CzPN is a non-TADF fluorophor, as the additional steric hindrance of methyl groups leads to a more twisted structure of tMCzPN. In the organic light-emitting diodes (OLEDs), tMCzPN exhibits extremely high forward-viewing maximum external quantum efficiency of 26.0%, without any light out-coupling enhancement, which is significantly higher than that of 5.3% for CzPN. These results indicate that tMCzPN is an excellent TADF emitter and proves that tMCz is a more appropriate candidate than Cz to develop TADF emitters.

Development of Red Exciplex for Efficient OLEDs by Employing a Phosphor as a Component.

Exciplexes are ideal candidates as effective thermally activated delayed fluorescence (TADF) emitters. However, efficient orange and red TADF exciplexes have been reported seldomly, because their significant non-radiative (NR) decay of excited states lead to unavoidable energy loss. Herein, we propose a novel strategy to construct efficient red TADF exciplexes by introducing phosphor as one component. Due to the strong spin-orbit coupling of heavy metal (e.g., Ir, Pt, et al.) ion cores, the NR decays will be evidently decreased for both singlet and triplet excitons, reducing the undesired exciton waste. Moreover, compared with the conventional exciplexes, phosphorescence plays an important role for such novel exciplexes, further improving the exciton utilization. Based on this strategy, we fabricated a red exciplex containing 1,3,5-triazine-2,4,6-triyl)tris(benzene-3,1-diyl)tris(diphenylphosphine oxide) (PO-T2T) and tris(2-phenylpyridine) iridium(III) (Ir(ppy)3) as components and realize a red emission with a peak at 604 nm, a CIE coordinate of (0.55, 0.44), and a high maximum external quantum efficiency of 5% in organic light-emitting device. This efficiency is 2.6 times higher than that of the device based on the conventional red exciplex emitter, proving the superiority of our novel strategy to construct TADF exciplexes with phosphors.

Tricomponent Exciplex Emitter Realizing over 20% External Quantum Efficiency in Organic Light-Emitting Diode with Multiple Reverse Intersystem Crossing Channels.

With the naturally separated frontier molecular orbitals, exciplexes are capable of thermally activated delayed fluorescence emitters for organic light-emitting diodes (OLEDs). And, the current key issue for exciplex emitters is improving their exciton utilization. In this work, a strategy of building exciplex emitters with three components is proposed to realize multiple reverse intersystem crossing (RISC) channels, improving their exciton utilization by enhancing upconversion of nonradiative triplet excitons. Accordingly, a tricomponent exciplex DBT-SADF:PO-T2T:CDBP is constructed with three RISC channels respectively on DBT-SADF, DBT-SADF:PO-T2T, and CDBP:PO-T2T. Furthermore, its photoluminescence quantum yield and rate constant of the RISC process are successfully improved. In the OLED, DBT-SADF:PO-T2T:CDBP exhibits a remarkably high maximum external quantum efficiency (EQE) of 20.5%, which is the first report with an EQE over 20% for the OLEDs based on exciplex emitters to the best of our knowledge. This work not only demonstrates that introducing multiple RISC channels can effectively improve the exciton utilization of exciplex emitters, but also proves the superiority of the tricomponent exciplex strategy for further development of exciplex emitters.

Control of Dual Conformations: Developing Thermally Activated Delayed Fluorescence Emitters for Highly Efficient Single-Emitter White Organic Light-Emitting Diodes.

In this work, we propose a novel concept to develop two fluorophores 2-(10 H-phenothiazin-10-yl)thianthrene 5,5,10,10-tetraoxide (PTZ-TTR) and 2-(4-(10 H-phenothiazin-10-yl)phenyl)thianthrene 5,5,10,10-tetraoxide (PTZ-Ph-TTR) showing dual conformations for highly efficient single-emitter white organic light-emitting diodes (WOLEDs). Both molecules exist in two stable conformations. Their nearly orthogonal forms own lower energy levels and show thermally activated delayed fluorescence (TADF) characteristics, whereas their nearly planar conformers possess higher energy levels and show only prompt fluorescence. These dual conformers were exploited for fabricating WOLEDs with complementary emission colors contributed by the two conformations. Moreover, the originally wasted triplet energy on the nearly planar conformation can be transferred to the nearly orthogonal one and then harvested via the TADF channel, realizing full exciton utilization. A PTZ-TTR-based single-emitter device exhibits standard white emission with a CIE coordinate of (0.33, 0.33) and a high color rendering index value of 92. On the other hand, the PTZ-Ph-TTR-based single-emitter device realizes an emission approaching warm white light and a high maximum external quantum efficiency of 16.34%. These results demonstrate an alternative approach for designing high-performance WOLEDs based on single TADF emitters.

Red Organic Light-Emitting Diode with External Quantum Efficiency beyond 20% Based on a Novel Thermally Activated Delayed Fluorescence Emitter.

A novel thermally activated delayed fluorescence (TADF) emitter 12,15-di(10H-phenoxazin-10-yl)dibenzo[a,c]dipyrido[3,2-h:2',3'-j]phenazine (DPXZ-BPPZ) is developed for a highly efficient red organic light-emitting diode (OLED). With rigid and planar constituent groups and evident steric hindrance between electron-donor (D) and electron-acceptor (A) segments, DPXZ-BPPZ realizes extremely high rigidity to suppress the internal conversion process. Meanwhile, the highly twisted structure between D and A segments will also lead to an extremely small singlet-triplet energy split to DPXZ-BPPZ. Therefore, DPXZ-BPPZ successfully realizes an efficient fluorescent radiation transition and reverse intersystem crossing process, and possesses an extremely high photoluminescence quantum efficiency of 97.1 ± 1.1% under oxygen-free conditions. The OLED based on DPXZ-BPPZ shows red emission with a peak at 612 nm and a Commission Internationale de L'Eclairage (CIE) coordinate of (0.60, 0.40), and it achieves high maximum forward-viewing efficiencies of 20.1 ± 0.2% (external quantum efficiency), 30.2 ± 0.6 cd A-1 (current efficiency), and 30.9 ± 1.3 lm W-1 (power efficiency). The prepared OLED has the best performance among the reported red TADF OLEDs. These results prove that DPXZ-BPPZ is an ideal candidate for red TADF emitters, and the designing approach is valuable for highly efficient red TADF emitters.

Fluorescence turn on of coumarin derivatives by metal cations: a new signaling mechanism based on C=N isomerization.

[reaction: see text] A new sensing mechanism based on C=N isomerization, which shows a very significant fluorescence enhancement to the metal cations in a simple and efficient way, is demonstrated. A coumarin derivative (L) containing a C=N group was designed as an example for illustration. The free ligand L is almost nonfluorescent due to the isomerization of C=N double bond in the excited state. However, the solution of ligand shows about a 200-fold increase of fluorescence quantum yield (about 30%) upon addition of Zn(ClO4)2.

Ternary Organic Solar Cells with Coumarin7 as the Donor Exhibiting Greater Than 10% Power Conversion Efficiency and a High Fill Factor of 75.

Ternary bulk heterojunction (BHJ) is a brilliant photovoltaic technology for improving the performance of organic solar cells (OSCs), because the light absorption range can be significantly extended by using multiple donors or acceptor materials. In this paper, coumarin7 (C7), a small organic molecule typical led used in organic light-emitting diodes, was initially exploited as second electron-donor component in ternary bulk heterojunction OSCs along with conventional blend system spolythieno[3,4-b]-thiophene/benzodithiophene(PTB7) and [6,6]-phenyl-C71 -butyric acid methyl(PC71 BM). A champion PCE value of 10.28% was realized in the ternary OSCs when incorporated with 10 wt % C7 doping ratio in the donors, corresponding to about 35% enhancement compared with the PTB7:PC71BM-based OSCs, a high fill factor (FF) of 75.03%, a short-circuit currentdensity (Jsc) of 18.72 mA cm-2 and an open-circuit voltage (Voc) of 0.73 V. The enhanced performance of the ternary OSCs can be attributed to the simultaneous improvement of the FF and the Jsc. In addition to extended light absorption, a perfect nanofiber filament active layer morphology is obtained due to the good compatibility between C7 and PTB7, which facilitates the balance of charge transportation and the suppression of charge recombination. This investigation suggests that coumarin derivatives, which have completely different structure with polymer donors, can also be used to fabricate ternary solar cells and have the potential applications to obtain amazing performance after further device engineering and optimization.

Avoiding Energy Loss on TADF Emitters: Controlling the Dual Conformations of D-A Structure Molecules Based on the Pseudoplanar Segments.

The recent introduction of thermally activated delayed fluorescence (TADF) emitters is regarded as an important breakthrough for the development of high efficiency organic light-emitting devices (OLEDs). The planar D and A groups are generally used to construct TADF emitters for their rigid structure and large steric hindrance. In this work, it is shown that many frequently used nonaromatic (noncontinuous conjugation or without satisfying Hückel's rule) planar segments, such as 9,9-dimethyl-9,10-dihydroacridine, are actually pseudoplanar segments and have two possible conformations-a planar form and a crooked form. Molecules constructed from pseudoplanar segments can thus have two corresponding conformations. Their existence can have significant impact on the performance of many TADF emitters. Two design strategies are presented for addressing the problem by either (1) increasing the rigidity of these groups to suppress its crooked form or (2) increasing the steric hindrance of the linked group to minimize energy of the emitters with the highly twisted form. Following these strategies, two new emitters are synthesized accordingly and successfully applied in OLEDs demonstrating high external quantum efficiencies (20.2% and 18.3%).

Isomeric Thermally Activated Delayed Fluorescence Emitters for Color Purity-Improved Emission in Organic Light-Emitting Devices.

To improve the color purity of thermally activated delayed fluorescence (TADF) emitters, two isomeric compounds, oPTC (5'-(phenoxazin-10-yl)-[1,1':3',1″-terphenyl]-2'-carbonitrile) and mPTC (2'-(phenoxazin-10-yl)-[1,1':3',1″-terphenyl]-5'-carbonitrile), were designed and synthesized with same skeleton but different molecular restrictions. Both compounds exhibit similar highest occupied molecular orbital and lowest unoccupied molecular orbital distributions and energy levels, photophysical properties in nonpolar cyclohexane solution, and high external quantum efficiencies (19.9% for oPTC and 17.4% for mPTC) in the devices. With the increased molecular space restriction induced by the additional phenyl substitutions at meta-position of the cyano group from mPTC to oPTC, much weaker positive solvatochromic effect is observed for mPTC. And the color purity of emission from mPTC (full width at half-maximum (fwhm) of 86 nm) is also improved contrasted with that of oPTC (fwhm of 97 nm) in the devices. These results prove that increased restriction of the molecular structure is a simple and effective method to improve the color purity of the TADF emitters.

High Performance All Fluorescence White Organic Light Emitting Devices with a Highly Simplified Structure Based on Thermally Activated Delayed Fluorescence Dopants and Host.

Thermally activated delayed fluorescence (TADF) emitters of different colors commonly need different hosts, which cause the complexed device structure and low efficiency of all fluorescence white organic light-emitting devices (F-WOLEDs). To solve this, novel concept of employing TADF exciplex as universal host of TADF emitters with different colors was proposed. All blue, green, and orange devices based on the TADF exciplex host show much lower turn-on voltages, and comparable and even higher efficiencies than corresponding devices based on conventional hosts. The two color F-WOLED with extremely simplified device structure was finally fabricated, achieving a white emission with the maximum current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE) respectively of 50.1 cd A-1, 63.0 lm W-1, and 19.0% in the forward-viewing direction without any light out-coupling technology, which is the best performance among reported F-WOLEDs, demonstrating the superiority of the novel concept.