Purely Organic Thermally Activated Delayed Fluorescence Materials for Organic Light‐Emitting Diodes

The design of thermally activated delayed fluorescence (TADF) materials both as emitters and as hosts is an exploding area of research. The replacement of phosphorescent metal complexes with inexpensive organic compounds in electroluminescent (EL) devices that demonstrate comparable performance metrics is paradigm shifting, as these new materials offer the possibility of developing low‐cost lighting and displays. Here, a comprehensive review of TADF materials is presented, with a focus on linking their optoelectronic behavior with the performance of the organic light‐emitting diode (OLED) and related EL devices. TADF emitters are cross‐compared within specific color ranges, with a focus on blue, green–yellow, orange–red, and white OLEDs. Organic small‐molecule, dendrimer, polymer, and exciplex emitters are all discussed within this review, as is their use as host materials. Correlations are provided between the structure of the TADF materials and their optoelectronic properties. The success of TADF materials has ushered in the next generation of OLEDs.     

Adamantyl Substitution Strategy for Realizing Solution‐Processable Thermally Stable Deep‐Blue Thermally Activated Delayed Fluorescence Materials

Highly efficient solution‐processable emitters, especially deep‐blue emitters, are greatly desired to develop low‐cost and low‐energy‐consumption organic light‐emitting diodes (OLEDs). A recently developed class of potentially metal‐free emitters, thermally activated delayed fluorescence (TADF) materials, are promising candidates, but solution‐processable TADF materials with efficient blue emissions are not well investigated. In this study, first the requirements for the design of efficient deep‐blue TADF materials are clarified, on the basis of which, adamantyl‐substituted TADF molecules are developed. The substitution not only endows high solubility and excellent thermal stability but also has a critical impact on the molecular orbitals, by pushing up the lowest unoccupied molecular orbital energy and triplet energy of the molecules. In the application to OLEDs, an external quantum efficiency (EQE) of 22.1% with blue emission having Commission Internationale de l'Eclairage (CIE) coordinates of (0.15, 0.19) is realized. A much deeper blue emission with CIE (0.15, 0.13) is also achieved, with an EQE of 11.2%. These efficiencies are the best yet among solution‐processed TADF OLEDs of CIE y < 0.20 and y < 0.15, as far as known. This work demonstrates the validity of adamantyl substitution and paves a pathway for straightforward realization of solution‐processable efficient deep‐blue TADF emitters.     

Thermally Activated Delayed Fluorescence Materials Towards the Breakthrough of Organoelectronics

The design and characterization of thermally activated delayed fluorescence (TADF) materials for optoelectronic applications represents an active area of recent research in organoelectronics. Noble metal‐free TADF molecules offer unique optical and electronic properties arising from the efficient transition and interconversion between the lowest singlet (S₁) and triplet (T₁) excited states. Their ability to harvest triplet excitons for fluorescence through facilitated reverse intersystem crossing (T₁→S₁) could directly impact their properties and performances, which is attractive for a wide variety of low‐cost optoelectronic devices. TADF‐based organic light‐emitting diodes, oxygen, and temperature sensors show significantly upgraded device performances that are comparable to the ones of traditional rare‐metal complexes. Here we present an overview of the quick development in TADF mechanisms, materials, and applications. Fundamental principles on design strategies of TADF materials and the common relationship between the molecular structures and optoelectronic properties for diverse research topics and a survey of recent progress in the development of TADF materials, with a particular emphasis on their different types of metal‐organic complexes, D‐A molecules, and fullerenes, are highlighted. The success in the breakthrough of the theoretical and technical challenges that arise in developing high‐performance TADF materials may pave the way to shape the future of organoelectronics.     

High‐Efficiency Red Organic Light‐Emitting Diodes with External Quantum Efficiency Close to 30% Based on a Novel Thermally Activated Delayed Fluorescence Emitter

Researchers have spared no effort to design new thermally activated delayed fluorescence (TADF) emitters for high‐efficiency organic light‐emitting diodes (OLEDs). However, efficient long‐wavelength TADF emitters are rarely reported. Herein, a red TADF emitter, TPA–PZCN, is reported, which possesses a high photoluminescence quantum yield (Φ_PL) of 97% and a small singlet–triplet splitting (ΔE_ST) of 0.13 eV. Based on the superior properties of TPA–PZCN, red, deep‐red, and near‐infrared (NIR) OLEDs are fabricated by utilizing different device structure strategies. The red devices obtain a remarkable maximum external quantum efficiency (EQE) of 27.4% and an electroluminescence (EL) peak at 628 nm with Commission Internationale de L'Eclairage (CIE) coordinates of (0.65, 0.35), which represents the best result with a peak wavelength longer than 600 nm among those of the reported red TADF devices. Furthermore, an exciplex‐forming cohost strategy is adopted. The devices achieve a record EQE of 28.1% and a deep‐red EL peak at 648 nm with the CIE coordinates of (0.66, 0.34). Last, nondoped devices exhibit 5.3% EQE and an NIR EL peak at 680 nm with the CIE coordinates of (0.69, 0.30).     

Triplet Harvesting with 100% Efficiency by Way of Thermally Activated Delayed Fluorescence in Charge Transfer OLED Emitters

Organic light‐emitting diodes (OLEDs) have their performance limited by the number of emissive singlet states created upon charge recombination (25%). Recently, a novel strategy has been proposed, based on thermally activated up‐conversion of triplet to singlet states, yielding delayed fluorescence (TADF), which greatly enhances electroluminescence. The energy barrier for this reverse intersystem crossing mechanism is proportional to the exchange energy (ΔE_ST) between the singlet and triplet states; therefore, materials with intramolecular charge transfer (ICT) states, where it is known that the exchange energy is small, are perfect candidates. However, here it is shown that triplet states can be harvested with 100% efficiency via TADF, even in materials with ΔE_ST of more than 20 kT (where k is the Boltzmann constant and T is the temperature) at room temperature. The key role played by lone pair electrons in achieving this high efficiency in a series of ICT molecules is elucidated. The results show the complex photophysics of efficient TADF materials and give clear guidelines for designing new emitters.     

Realizing 22.5% External Quantum Efficiency for Solution‐Processed Thermally Activated Delayed‐Fluorescence OLEDs with Red Emission at 622 nm via a Synergistic Strategy of Molecular Engineering and Host Selection

Developing high‐efficiency solution‐processable thermally activated delayed‐fluorescence (TADF) emitters, especially in longer wavelength regions, is a formidable challenge. Three red TADF emitters, namely NAI_R1, NAI_R2, and NAI_R3, are developed by phenyl encapsulation and tert‐butyl substitution on a prototypical 1,8‐naphthalimide‐acridine hybrid. This design strategy not only grants these molecules high solubility, excellent thermal stability, and good film‐forming ability, but also pulls down their charge‐transfer (CT) energy levels excited states. Furthermore, dispersing these emitters into two different host materials of mCP and mCPCN finely tailors their CT‐state energy levels. More importantly, a synergistic combination of molecular engineering and host selection can effectively manipulate the competition between the radiative and nonradiative decay rates of the CT singlet states of these emitters and the reverse intersystem crossing from their triplet to singlet states. Consequently, the optimal combination of NAI_R3 emitter and mCP host successfully results in a state‐of‐the‐art external quantum efficiency (EQE) of 22.5% for solution‐processed red TADF organic light‐emitting diodes (OLEDs) with an emission peak above 620 nm. This finding demonstrates that a synergistic strategy of molecular engineering and host selection with TADF emitters could provide a new pathway for developing efficient solution‐processable TADF systems.     

An Ultraviolet Thermally Activated Delayed Fluorescence OLED with Total External Quantum Efficiency over 9%

Owing to the difficulty in acquiring compounds with combined high energy bandgaps and lower-lying intramolecular charge-transfer excited states, the development of ultraviolet (UV) thermally activated delayed fluorescence (TADF) materials is quite challenging. Herein, through interlocking of the diphenylsulfone (PS) acceptor unit of a reported deep-blue TADF emitter (CZ-PS) by a dimethylmethylene bridge, CZ-MPS, a UV-emissive TADF compound bearing a shallower LUMO energy level and a more rigid structure than those of CZ-PS is achieved. This represents the first example of a UV-emissive TADF compound. Organic light-emitting diode (OLED) using CZ-MPS as the guest material can emit efficient UV light with emission maximum of 389 nm and maximum total external quantum efficiency (EQE_max) of 9.3%. Note that this EQE_max value is twice as high as the current record EQE_max (4.6%) for UV-OLEDs. This finding may shed light on the molecular design strategy for high-performance UV-OLED materials.