Thermally Activated Delayed Fluorescence Devices Research Articles

Highly Efficient Full-Color Thermally Activated Delayed Fluorescent Organic Light-Emitting Diodes: Extremely Low Efficiency Roll-Off Utilizing a Host with Small Singlet-Triplet Splitting.

Numerous efforts have been devoted to boost the efficiency of thermally activated delayed fluorescence (TADF) devices; however, strategies to suppress the device efficiency roll-off are still in urgent need. Here, a general and effective approach to suppress the efficiency roll-off of TADF devices is proposed, that is, utilizing TADF materials as the hosts for TADF emitters. Bearing small singlet-triplet splitting (ΔEST) with donor and acceptor units, TADF materials as the hosts possess the potential to achieve matched frontier energy levels with the adjacent transporting layers, facilitating balanced charge injection as well as bipolar charge transport mobilities beneficial to the balanced charges transportation. Furthermore, an enhanced Förster energy transfer from the host to the dopant can be anticipated, helpful to reduce the exciton concentration. Based on the principles, a new TADF material based on indeno[2,1-b]carbazole/1,3,5-triazin derivation is synthesized and used as the universal host for the full-color TADF devices. Remarkable low efficiency roll-off was achieved with above 90% of the maximum external quantum efficiencies (EQEmax's) maintained even at a brightness of 2000 cd/m2, along with EQEmax's of 23.2, 21.0, and 19.2% for orange, green, and sky-blue TADF devices, respectively. Through computational simulation, we identified the suppressed exciton annihilation rates compared with devices adopting conventional hosts. The state-of-the-art low efficiency roll-off of those TADF devices manifests the great potential of such host design strategy, paving an efficient strategy toward their practical application.

A directly coupled dual emitting core based molecular design of thermally activated delayed fluorescent emitters

New green thermally activated delayed fluorescence (TADF) materials built on a directly coupled dual emitting core based backbone structure were designed, synthesized, and applied as green dopants in TADF devices.

Dibenzothiophene Sulfone-Based Phosphine Oxide Electron Transporters with Unique Asymmetry for High-Efficiency Blue Thermally Activated Delayed Fluorescence Diodes.

Three asymmetrical electron transporters as dibenzothiophene sulfone (DBSO)-diphenylphosphine oxide (DPPO) hybrids, collectively named mnDBSODPO, were designed and prepared. All of these materials achieve the high triplet energy of ∼3.0 eV to restrain the exciton linkage from emissive layers. The dependence of inductive and steric effects for DPPO groups on the substitution position, the intermolecular interaction suppression, the encapsulations of high-polar DBSO cores, and the favorable electrical performance are successfully integrated on 36DBSODPO, which can simultaneously suppress the exciton quenching by formation of an interfacial dipole and enhancing the charge flux balance. As a result, 36DBSODPO endowed its tetralayer blue thermally activated delayed fluorescence (TADF) devices with impressive performance, including the maximum external quantum efficiency around 19%, and reduced efficiency roll-offs, which verifies the great potential of asymmetrical electron transporting materials for highly efficient TADF devices.

Alkyl effects on the optoelectronic properties of bicarbazole/cyanobenzene hybrid host materials: Double delayed fluorescent host/dopant systems in solution-processed OLEDs

Three 3,3′-bicarbazole derivatives, 4,4′-(9H,9′H-[3,3′-bicarbazole]-9,9′-diyl)bis(2-methylbenzonitrile) (pCNBCzmMe, 1), 4,4′-(9H,9′H-[3,3′-bicarbazole]-9,9′-diyl)bis(3-(trifluoromethyl)benzonitrile) (pCNBCzoCF3, 2) and 4,4′-(9H,9′H-[3,3′-bicarbazole]-9,9′-diyl)bis(2-(trifluoromethyl)benzonitrile) (pCNBCzmCF3, 3) were designed and synthesized through a simple one-step catalyst-free CN coupling reaction, by using 9H,9′H-3,3′-bicarbazole and alkyl substituted fluorocyanobenzene as starting materials. Compounds 1–3 exhibit high thermal stabilities with Td above 400 °C and Tg from 134 to 165 °C. They show thermally activated delayed fluorescence (TADF) characteristics with microsecond scale long lifetimes, similar triplet energy of ∼2.65 eV whereas different absorption and photoluminescence behavior according to the substitution of CH3 or CF3 alkyl units at different meta- or ortho- positions. Low singlet-triplet band gaps (△EST) of 0.30, 0.19 and 0.14 eV are observed for 1–3, respectively. By partially blocking the electroactive sites at the 3,3′-position of carbazole to prevent electropolymerization, these 3,3′-bicarbazole derivatives perform favorable electro-oxidative stability. From both experimental and theoretical results, the introduction of electron-withdrawing CF3 in 2 and 3 lowers both of the HOMO and LUMO levels compared to the weak electron-donating CH3-substituted 1. The hole and electron transport properties can also be tuned through different alkyl on different ortho- or meta-positions. It is interesting that the electron-donating CH3meta-structured 1 exhibit one order higher electron mobility than the strong electron-withdrawing CF3ortho-positioned 2 and meta-structured 3, while ortho-CF3 linked compound 2 with more twisted geometry showed the poorest hole-transport properties. By using the three TADF materials as hosts to conduct double host/dopant TADF systems for solution processed green TADF devices, maximum power efficiencies are achieved at 29.9, 22.7 and 30.9 lm/W for 1, 2 and 3 based devices respectively, in simple structure of ITO/PEDOT:PSS (40 nm)/1–3:4CzCNPy (40 nm)/TmPyPB (60 nm)/LiF (0.8 nm)/Al (100 nm).

Ideal Molecular Design of Blue Thermally Activated Delayed Fluorescent Emitter for High Efficiency, Small Singlet-Triplet Energy Splitting, Low Efficiency Roll-Off, and Long Lifetime.

Highly efficient thermally activated delayed fluorescent (TADF) emitters, 5-(2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5H-benzofuro[3,2-c]carbazole (oBFCzTrz), 5-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5H-benzofuro[3,2-c]carbazole (mBFCzTrz), and 5-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5H-benzofuro[3,2-c]carbazole (pBFCzTrz), were synthesized to study the effects of ortho-, meta-, and para- linkages between donor and acceptor moieties. oBFCzTrz having ortho- linked donor and acceptor moieties showed smaller singlet-triplet energy gap, shorter excited state lifetime, and higher photoluminescence quantum yield than mBFCzTrz and pBFCzTrz which are interconnected by meta- and para- positions. The TADF device using oBFCzTrz as a blue emitter exhibited high external quantum efficiency over 20%, little efficiency roll-off, and long device lifetime.

Donor Interlocked Molecular Design for Fluorescence-like Narrow Emission in Deep Blue Thermally Activated Delayed Fluorescent Emitters

Deep blue thermally activated delayed fluorescent (TADF) emitters with a narrow emission spectrum were developed by managing the molecular structure of the TADF emitters. The deep blue TADF emitters were designed to show large steric hindrance at the central core of the molecule and small singlet–triplet energy gap. The molecular engineering of the deep blue TADF emitters enabled the fabrication of the deep blue TADF device with a full width at half-maximum of only 48 nm and a quantum efficiency of 14.0%. The full width at half-maximum of the deep blue TADF device was similar to that of conventional fluorescent devices, while the quantum efficiency was more than tripled.

Correlation of doping concentration, charge transport of host, and lifetime of thermally activated delayed fluorescent devices

Origin of doping concentration dependence of lifetime of thermally activated delayed fluorescent (TADF) devices was examined using a TADF emitter doped in a hole transport type and a bipolar host material. Lifetime of the hole transport type host based TADF device was increased according to doping concentration of TADF emitter, while that of the bipolar host based TADF device was decreased according to doping concentration of TADF emitter. The doping concentration dependence of the lifetime could be correlated with recombination zone of the emitting layer. Broad recombination zone at high doping concentration in the hole transport type host and at low doping concentration in the bipolar host was proposed as the main contributor of the doping concentration dependence of the lifetime.

Decreasing the singlet–triplet gap for thermally activated delayed fluorescence molecules by structural modification on the donor fragment: First-principles study

The small energy gap between singlet excitons (S) and triplet excitons (T) of organic molecules is a dominant condition for high efficient thermally activated delayed fluorescence (TADF). In this study, influence of modification in donor groups of a series of molecules on their geometries, S–T energy gaps, and photophysical properties, is investigated based on first-principles calculations. Investigation shows that, as the electron donating ability is increased, both S–T energy gap and overlap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are decreased. This work provides strategy for designing high efficient and multi-color TADF devices.

Optimizing the Intralayer and Interlayer Compatibility for High-Efficiency Blue Thermally Activated Delayed Fluorescence Diodes.

A series of phosphine oxide hosts, 4,6-bis(diphenylphosphoryl) dibenzothiophene (DBTDPO) and 4- diphenylphosphoryldibenzothiophene (DBTSPO), and electron transporting materials (ETM), 2-(diphenylphosphoryl)dibenzothiophene sulfone (2DBSOSPO), 3-(diphenylphosphoryl)dibenzothiophene sulfone (3DBSOSPO) and 4-(diphenylphosphoryl)dibenzothiophene sulfone (4DBSOSPO) were developed to support blue thermally activated delayed fluorescence (TADF) devices with high performance through optimizing intralayer and interlayer compatibility of emissive layers. On the basis of the triplet energy of ~3.0 eV for the hosts and ETMs, excitons can be effectively confined on DMAC-DPS. Compared to DBTSPO, DBTDPO can support the excellent distribution uniformity to blue TADF dye bis[4-(9,9-dimethyl–9,10-dihydroacridine) phenyl] sulfone (DMAC-DPS), owing to their configuration similarity; while 3DBSOSPO and 4DBSOSPO are superior in compatibility with the hosts due to the similar molecular polarity or configuration. Through adjusting the molecular configuration, the electrical performance of ETMs can be feasibly tuned, including the excellent electron mobility (μe) by the order of 10−3 cm2 V−1 s−1. As the result, DBTDPO and 4DBSOSPO endowed their four-layer blue TADF devices with the maximum current efficiency of 33.5 cd A−1 and the maximum external quantum efficiency more than 17%, which are impressive among the best blue TADF devices. It is showed that intralayer compatibility determines the maximum efficiencies, while interlayer compatibility influences efficiency stability.

Correlation of Molecular Structure with Photophysical Properties and Device Performances of Thermally Activated Delayed Fluorescent Emitters

Thermally activated delayed fluorescent (TADF) emitters having bicarbazole as a donor unit based on a twin emitting core design were developed by substituting the bicarbazole donor with a diphenyltriazine acceptor. Three bicarbazole derived delayed fluorescent emitters linked via 2,3′-, 3,3′-, and 3,4′-positions of carbazole were synthesized and investigated as blue dopants of the TADF devices. A twin emitting core based TADF emitter derived from a 3,3′-bicarbazole donor exhibited a high quantum efficiency of 25.0% in the greenish blue TADF device. A 3,3′-linkage induced red shift of the emission wavelength, a small singlet–triplet energy gap, and a high quantum efficiency were revealed.

New Benzimidazole-Based Bipolar Hosts: Highly Efficient Phosphorescent and Thermally Activated Delayed Fluorescent Organic Light-Emitting Diodes Employing the Same Device Structure.

The rapid development of the thermally activated delayed fluorescence (TADF) emitters makes it necessary to produce new versatile host materials for both phosphorescent and TADF emitters. Three new bipolar host materials, 9,9'-(2'-(1H-benzimidazol-1-yl)-[1,1'-biphenyl]-3,5-diyl)bis(9H-carbazole) (o-mCPBI), 9,9'-(3'-(1H-benzimidazol-1-yl)-[1,1'-biphenyl]-3,5-diyl)bis(9H-carbazole) (m-mCPBI), and 9,9'-(4'-(1H-benzimidazol-1-yl)-[1,1'-biphenyl]-3,5-diyl)bis(9H-carbazole) (p-mCPBI), are designed and synthesized by integrating mCP with benzimidazole moiety via the ortho-, meta-, and para-positions of N-phenyl. The influence of different linking modes on the thermal, photophysical, electrochemical, and charge transport properties of the compounds is studied. By employing the same device structure except the emitting layer, the device performances of the blue, green, yellow, red, white phosphorescent and blue, green TADF organic light-emitting diodes (OLEDs) based on the three hosts are investigated. Among these three hosts, o-mCPBI exhibits the best device performance with external quantum efficiencies of over 20% for phosphorescent OLEDs and enhanced efficiencies for TADF devices. All these devices show relatively low efficiency roll-offs at high brightness. The versatility of the benzimidazole-based bipolar host o-mCPBI, such as an extremely high triplet energy level, suitable molecular orbital energy levels, improved thermal and charge transport properties, and excellent device performances for various colors, makes it a universal host material for highly efficient both phosphorescent and TADF OLEDs.

Molecular design of deep blue fluorescent emitters with 20% external quantum efficiency and narrow emission spectrum

A thermally activated delayed fluorescent (TADF) emitter, 2,7-bis(9,9-dimethylacridin-10(9H)-yl)-9,9-dimethyl-9H-thioxanthene 10,10-dioxide (DMTDAc), was developed as a deep blue TADF emitter using a rigid 9,9-dimethyl-9H-thioxanthene 10,10-dioxide (DMTD) acceptor and an acridine donor. The rigid DMTD acceptor narrowed emission spectrum of DMTDAc by interlocking two phenyl units of diphenylsulfone. A deep blue TADF device with an external quantum efficiency close to 20% with a deep blue color coordinate of (0.15,0.13) was provided using the DMTDAc TADF emitter.

Universal Host Materials for High-Efficiency Phosphorescent and Delayed-Fluorescence OLEDs.

A series of bipolar hosts, namely, 5-(2-(9H-carbazol-9-yl)-phenyl)-1,3-dipyrazolbenzene (o-CzDPz), 5-(3-(9H-carbazol-9-yl)-phenyl)-1,3-dipyrazolbenzene (m-CzDPz), 5-(9-phenyl-9H-carbazol-3-yl)-1,3-dipyrazolbenzene (3-CzDPz), and 5-(3,5-di(9H-carbazol-9-yl)-phenyl)-1,3-dipyrazolbenzene (mCPDPz), are developed for phosphorescent and thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs). They are designed by selecting pyrazole as n-type unit and carbazole as p-type one. The triplet energy (E(T)), the frontier molecular orbital level, and charge transporting abilities, are adjusted by varying the molar ratio of pyrazole to carbazole and the linking mode between them. They have high E(T) values of 2.76-3.02 eV. Their electroluminescence performance is evaluated by fabricating both phosphorescent and TADF devices with blue or green emitters. The m-CzDPz hosted blue phosphorescent OLEDs achieves high efficiency of 48.3 cd A(-1) (26.8%), the 3-CzDPz hosted green phosphorescent device exhibits 91.2 cd A(-1) (29.0%). The blue and green TADF devices with 3-CzDPz host also reach high efficiencies of 26.2 cd A(-1) (15.8%) and 41.1 cd A(-1) (13.3%), respectively. The excellent performance of all these OLEDs verifies that these pyrazole-based bipolar compounds are capable of being universal host materials for OLED application. The influence of molar ratio of n-type unit to p-type one and the molecular conformation of these hosts on their device performance is discussed and interpreted.

20% External Quantum Efficiency in Solution‐Processed Blue Thermally Activated Delayed Fluorescent Devices

Highly efficient solution‐processed blue thermally activated delayed fluorescent (TADF) devices are developed by designing soluble blue TADF emitters. The solubility and emission color could be managed by introducing F as an electron withdrawing unit instead of CN. Two soluble blue TADF emitters are synthesized and show a high external quantum efficiency of 20.0% with a color coordinate of (0.16,0.26), and it is the best quantum efficiency reported in solution‐processed TADF devices. The device performances of the solution‐processed blue TADF devices are comparable to those of vacuum‐processed blue TADF devices.

The Design of Dual Emitting Cores for Green Thermally Activated Delayed Fluorescent Materials

AbstractDual emitting cores for thermally activated delayed fluorescent (TADF) emitters were developed. Relative to the corresponding TADF emitter with a single emitting core the TADF emitter with a dual emitting core, 3,3′,5,5′‐tetra(carbazol‐9‐yl)‐[1,1′‐biphenyl]‐2,2′,6,6′‐tetracarbonitrile, showed enhanced light absorption accompanied by a high photoluminescence quantum yield. The quantum and power efficiencies of the TADF devices were enhanced by the dual emitting cores.

The Design of Dual Emitting Cores for Green Thermally Activated Delayed Fluorescent Materials

Dual emitting cores for thermally activated delayed fluorescent (TADF) emitters were developed. Relative to the corresponding TADF emitter with a single emitting core the TADF emitter with a dual emitting core, 3,3',5,5'-tetra(carbazol-9-yl)-[1,1'-biphenyl]-2,2',6,6'-tetracarbonitrile, showed enhanced light absorption accompanied by a high photoluminescence quantum yield. The quantum and power efficiencies of the TADF devices were enhanced by the dual emitting cores.

High efficiency thermally activated delayed fluorescent devices using a mixed host of carbazole and phosphine oxide derived host materials

A mixed host of a carbazole type host and phosphine oxide type host materials was developed and used as the host for green thermally activated delayed fluorescent (TADF) device to obtain high quantum efficiency and to manage the emission color of the TADF device. Two mixed hosts, 1,3-bis(N-carbazolyl) benzene (mCP):diphenylphosphine oxide-4-(triphenylsilyl) phenyl (TSPO1) and mCP:9,9-spirobifluoren-2-yl-diphenylphosphine oxide (SPPO1) were used as the mixed hosts and the device characteristics of the mixed host devices were investigated. The electron transport type of the mixed host devices could manage the quantum efficiency and emission color of the TADF devices. High quantum efficiency of 27.5% was achieved in the green TADF OLEDs using the mixed host of mCP:TSPO1 and the emission peak wavelength could be shifted by more than 10nm without sacrificing the quantum efficiency of the TADF devices.

Benzofurocarbazole and benzothienocarbazole as donors for improved quantum efficiency in blue thermally activated delayed fluorescent devices.

Benzofurocarbazole and benzothienocarbazole were used as electron donors of thermally activated delayed fluorescence (TADF) emitters and the performances of the TADF devices were examined. The benzofurocarbazole and benzothienocarbazole donor moieties were better than carbazole as the electron donors of the TADF emitters.