A Multifunctional Blue‐Emitting Material Designed via Tuning Distribution of Hybridized Excited‐State for High‐Performance Blue and Host‐Sensitized OLEDs

Actualizing full singlet exciton yield via a reverse intersystem crossing from the high‐lying triplet state to singlet state, namely, “hot exciton” mechanism, holds great potential for high‐performance fluorescent organic light‐emitting diodes (OLEDs). However, incorporating comprehensive insights into the mechanism and effective molecular design strategies still remains challenging. Herein, three blue emitters (CNNPI, 2TriPE‐CNNPI, and 2CzPh‐CNNPI) with a distinct local excited (LE) state and charge‐transfer (CT) state distributions in excited states are designed and synthesized. They show prominent hybridized local and charge‐transfer (HLCT) states and aggregation‐induced emission enhancement properties. The “hot exciton” mechanism based on these emitters reveals that a balanced LE/CT distribution can simultaneously boost photoluminescence efficiency and exciton utilization. In particular, a nearly 100% exciton utilization is achieved in the electroluminescence (EL) process of 2CzPh‐CNNPI. Moreover, employing 2CzPh‐CNNPI as the emitter, emissive dopant, and sensitizing host, respectively, the EL performances of the corresponding nondoped pure‐blue, doped deep‐blue, and HLCT‐sensitized fluorescent OLEDs are among the most efficient OLEDs with a “hot exciton” mechanism to date. These results could shed light on the design principles for “hot exciton” materials and inspire the development of next‐generation high‐performance OLEDs.     

Versatile,Benzimidazole/Amine‐Based Ambipolar Compounds for Electroluminescent Applications: Single‐Layer,Blue, Fluorescent OLEDs,Hosts for Single‐Layer,Phosphorescent OLEDs

A series of compounds containing arylamine and 1,2‐diphenyl‐1H‐benz[d]imidazole moieties are developed as ambipolar, blue‐emitting materials with tunable blue‐emitting wavelengths, tunable ambipolar carrier‐transport properties and tunable triplet energy gaps. These compounds possess several novel properties: (1) they emit in the blue region with high quantum yields; (2) they have high morphological stability and thermal stability; (3) they are capable of ambipolar carrier transport; (4) they possess tunable triplet energy gaps, suitable as hosts for yellow‐orange to green phosphors. The electron and hole mobilities of these compounds lie in the range of 0.68–144 × 10^?6 and 0.34–147 × 10^?6 cm² V^?1 s^?1, respectively. High‐performance, single‐layer, blue‐emitting, fluorescent organic light‐emitting diodes (OLEDs) are achieved with these ambipolar materials. High‐performance, single‐layer, phosphorescent OLEDs with yellow‐orange to green emission are also been demonstrated using these ambipolar materials, which have different triplet energy gaps as the host for yellow‐orange‐emitting to green‐emitting iridium complexes. When these ambipolar, blue‐emitting materials are lightly doped with a yellow‐orange‐emitting iridium complex, white organic light‐emitting diodes (WOLEDs) can be achieved, as well by the use of the incomplete energy transfer between the host and the dopant.     

Triplet Exciton Confinement in Green Organic Light‐Emitting Diodes Containing Luminescent Charge‐Transfer Cu(I) Complexes

The temperature dependence of luminescence from [Cu(dnbp)(DPEPhos)]BF₄ (dnbp = 2,9‐di‐n‐butylphenanthroline, DPEPhos = bis[2‐(diphenylphosphino)phenyl]ether) in a poly(methyl methacrylate) (PMMA) film indicates the presence of long‐life green emission arising from two thermally equilibrated charge transfer (CT) excited states and one non‐equilibrated triplet ligand center (³LC) excited state. At room temperature, the lower triplet CT state is found to be the predominantly populated excited state, and the zero‐zero energy of this state is found to be 2.72 eV from the onset of its emission at 80 K. The tunable emission maximum of [Cu(dnbp)(DPEPhos)]BF₄ in various hosts with different triplet energies is explained in terms of the multiple triplet energy levels of this complex in amorphous films. Using the high triplet energy charge transport material as a host and an exciton‐blocking layer (EBL), a [Cu(dnbp)(DPEPhos)]BF₄ based organic light‐emitting diode (OLED) achieves a high external quantum efficiency (EQE) of 15.0%, which is comparable to values for similar devices based on Ir(ppy)₃ and FIrpic. The photoluminescence (PL) and electroluminescence (EL) performance of green emissive [Cu(μI)dppb]₂ (dppb = 1,2‐bis[diphenylphosphino]benzene) in organic semiconductor films confirmed its ³CT state with a zero‐zero energy of 2.76 eV as the predominant population excited state.     

Is Poly(vinylcarbazole) a Good Host for Blue Phosphorescent Dopants in PLEDs? Dimer Formation and Their Effects on the Triplet Energy Level of Poly(N‐vinylcarbazole) and Poly(N‐Ethyl‐2‐Vinylcarbazole)

The detailed measurement and analysis of the delayed emission from poly(vinylcarbazole) (PVK) and poly(N‐ethyl‐2‐vinyl‐carbazole) (P2VK) thin films is described. PVK has rapidly become a “polymer of choice” for hosting phosphorescent dopants in PLEDs, especially blue emitters. In this respect it is important to have a full understanding of the triplet properties of this host. It is concluded that in films, the electronic 0–0 peak energy of PVK phosphorescence is found at 2.88 eV (14 K). With an increase of temperature, >44 K, increasing emission from new long lived, lower energy species, previously ascribed to “trap states” in the literature, is observed. Increasing temperature enables thermally assisted triplet exciton hopping to these trap states. Critically it is shown that some of these triplet trap species are ground state triplet dimers in origin for both PVK (2.46 eV) and P2VK (2.1 eV), and not all of them are of excimer nature as previously thought. These species can quench the emission of blue heavy metal complexes doped in PVK and drastically effect performance over lifetime if the dimer formation increases over time and at elevated operating temperature. It is therefore concluded that PVK might not be such an ideal host material for blue phosphorescent emitters.     

Efficient Near‐Infrared Emission by Adjusting the Guest–Host Interactions in Thermally Activated Delayed Fluorescence Organic Light‐Emitting Diodes

Thermally activated delayed fluorescence materials can effectively achieve high efficiency by harvesting singlet and triplet excitons in organic light‐emitting diodes (OLEDs). However, the choice of host material has a huge impact on the efficiency of the device, especially for the near‐infrared (NIR) luminescent material. In this contribution, a series of host materials are used to match the thermally activated delayed fluorescence emitter, 3,4‐bis(4‐(diphenylamino)phenyl)acenaphtho[1,2‐b]pyrazine‐8,9‐dicarbonitrile (APDC‐DTPA), for fabricating NIR OLEDs. All the host materials have the higher triplet energy than that of APDC‐DTPA. As the organometallic compound of Zn(BTZ)₂ has relatively stronger dipole moment, the electroluminescence spectral peak of doped device shows strong bathochromic shift exceeding 700 nm and changes with doping concentration. Finally, the extremely high external quantum efficiency of 7.8% (with 10 wt% of doping concentration) and 5.1% (with 20 wt% of doping concentration) are achieved with the emission peaks of 710 and 728 nm, respectively, which are superior to that of the device based on the other host materials. The approach is feasible to achieve bathochromic shift and highly efficient fluorescent OLEDs.     

Self‐Protective Room‐Temperature Phosphorescence of Fluorine and Nitrogen Codoped Carbon Dots

The unstable triplet excited state is a core problem when developing self‐protective room temperature phosphorescence (RTP) in carbon dots (CDs). Here, fluorine and nitrogen codoped carbon dots (FNCDs) with long‐lived triplet excited states, emitting pH‐stabilized blue fluorescence and pH‐responsive green self‐protective RTP, are reported for the first time. The self‐protective RTP of FNCDs arises from n–π * electron transitions for C? N/C?N bonds with a small energy gap between singlet and triplet states at room temperature. Moreover, the interdot/intradot hydrogen bonds and steric protection of C? F bonds reduce quenching of RTP by oxygen at room temperature. The RTP emission of FNCDs shows outstanding reversibility, while the blue fluorescence emission has good pH stability. Based on these FNCDs, a data encoding/reading strategy for advanced anticounterfeiting is proposed via time‐resolved luminescence imaging techniques, as well as steganography of complex patterns.     

A Twisting Donor‐Acceptor Molecule with an Intercrossed Excited State for Highly Efficient,Deep‐Blue Electroluminescence

In an organic electroluminescent (EL) device, the recombination of injected holes and electrons produces what appears to be an ion‐pair or charge‐transfer (CT) exciton, and this CT exciton decays to produce one photon directly, or relaxes to a low‐lying local exciton (LE). Thus the full utilization of both the energy of the CT exciton and the LE should be a pathway for obtaining high‐efficiency EL. Here, a twisting donor‐acceptor (D‐A) triphenylamine‐imidazol molecule, TPA‐PPI, is reported: its synthesis, photophysics, and EL performance. Prepared by a manageable, one‐pot cyclizing reaction, TPA‐PPI exhibits deep‐blue emission with high quantum yields (90%) both in solution and in the solid state. Fluorescent solvatochromic experiments for TPA‐PPI solutions show a red‐shift of 57 nm (3032 cm^?1) from low‐polarity hexane (406 nm) to high‐polarity acetonitrile (463 nm), accompanied by the gradual disappearance of the vibrational band in the spectra with increased solvent polarity. The photophysical investigation and DFT analysis suggest an intercrossed CT and LE excited state of the TPA‐PPI, originating from its twisting D‐A configuration. This is a rare instance that a CT‐state material shows highly efficient deep‐blue emission. EL characterization demonstrates that, as a deep‐blue emitter with CIE coordinates of (0.15, 0.11), the performance of a TPA‐PPI‐based device is rather excellent, displaying a maximum current efficiency of >5.0 cd A^?1, and a maximum external quantum efficiency of >5.0%, corresponding to a maximum internal quantum efficiency of >25%. The effective utilization of the excitation energy arising from materials with intercrossed‐excited‐state (LE and CT) characters is thought to be beneficial for the improved efficiency of EL devices.     

Effect of Electric Field on Coulomb‐Stabilized Excitons in Host/Guest Systems for Deep‐Blue Electrophosphorescence

Here, a study of the electric field induced quenching on the phosphorescence intensity of a deep‐blue triplet emitter dispersed in different host materials is presented. The hosts are characterized by a higher triplet excitonic level with respect to the emitter, ensuring efficient energy transfer and exciton confinement, whereas they differ in the highest occupied molecular orbital (HOMO) alignment, forming type I and type II host/guest heterostructures. While the type I structure shows negligible electric field induced quenching, a quenching up to 25% for the type II at a field of 2 MV/cm is reported. A similar quenching behaviour is also reported for thin films of the pure emitter, revealing an important luminescence loss mechanism for aggregated emitter molecules. These results are interpreted by considering Coulomb stabilized excitons in the type II heterostructure and in the pure emitter, that become very sensitive to dissociation upon application of the field. These results clarify the role of external electric field quenching on the phosphorescence of triplet emitters and provide useful insights for the design of deep‐blue electrophosphorescent devices with a reduced efficiency roll‐off.     

Highly Fluorescent and Color‐Tunable Exciplex Emission from Poly(N‐vinylcarbazole) Film Containing Nanostructured Supramolecular Acceptors

Highly fluorescent excited‐state charge‐transfer complexes (exciplexes) formed at the interfacial region between a polymeric donor matrix, here, poly(N‐vinylcarbazole), and embedded nanostructured acceptors are characterized for their photophysical properties. Exciplex‐to‐exciton emission switching is observed after solvent vapor annealing (SVA) due to the size evolution of the nanostructures beyond the exciton diffusion length. Color‐tunable exiplex emission (sky blue, green, and orange) is demonstrated for three different nanostructured acceptors with the same HOMO–LUMO gap (i.e., the same blue excitonic emission) but with different electron affinity. White‐emitting poly(N‐vinylcarbazole) film is also fabricated, simply by incorporating mixed supramolecular acceptors, which provide independent exciplex emissions. This study presents important insights into the excited‐state intermolecular interaction at the well‐defined nanoscale interface and suggests an efficient way to obtain multicolored exciplex emissions.     

Exciton–Exciton Annihilation in Thermally Activated Delayed Fluorescence Emitter

Recent studies have demonstrated that in thermally activated delayed fluorescence (TADF) materials, efficient reverse intersystem crossing occurs from nonradiative triplet exited states to radiative singlet excited states due to a small singlet–triplet energy gap. This reverse intersystem crossing significantly influences exciton annihilation processes and external quantum efficiency roll‐off in TADF based organic light‐emitting diodes (OLEDs). In this work, a comprehensive exciton quenching model is developed for a TADF system to determine singlet–singlet, singlet–triplet, and triplet–triplet annihilation rate constants. A well‐known TADF molecule, 3‐(9,9‐dimethylacridin‐10(9H)‐yl)‐9H‐xanthen‐9‐one (ACRXTN), is studied under intensity‐dependent optical and electrical pulse excitation. The model shows singlet–singlet annihilation dominates under optically excited decays, whereas singlet–triplet annihilation and triplet–triplet annihilation have strong contribution in electroluminescence decays under electrical pulse excitation. Furthermore, the efficiency roll‐off characteristics of ACRXTN OLEDs at steady state is investigated through simulation. Finally, singlet and triplet diffusion length are calculated from annihilation rate constants.     

Singlet–Triplet Splitting Energy Management via Acceptor Substitution: Complanation Molecular Design for Deep‐Blue Thermally Activated Delayed Fluorescence Emitters and Organic Light‐Emitting Diodes Application

A barely reached balance between weak intramolecular‐charge‐transfer (ICT) and small singlet–triplet splitting energy (ΔE_ST) for reverse intersystem crossing from non‐emissive triplet state to radiative singlet state impedes the realization of deep‐blue thermally activated delayed fluorescence (TADF) materials. By discarding the twisted‐ICT framework for a flattened molecular backbone and introducing a strong acceptor possessing n–π* transition character, hypsochromic color, a large radiative rate (k_F), and small ΔE_ST are achieved simultaneously. Six molecules with a 9,9‐dimethyl‐10‐phenyl‐9,10‐dihydroacridine (i‐DMAc) donor are synthesized and investigated. Coinciding with time‐dependent density functional theory, the reduced dihedral angles between donor (D) and acceptor (A) weaken ICT from dispersed charge density and enable a large k_F from increased frontier molecular orbitals overlap. Despite the separated highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) population, the intercalation of phenyl bridges between D–A increases k_F but significantly lowers the local triplet excited state, indicating small HOMO and LUMO overlap is not a sufficient, but necessary condition for reduced ΔE_ST. Integrating short conjugation length and carbonyl or triazine acceptors into the complanation molecules, deep‐blue TADF organic light‐emitting diodes demonstrate maximum external quantum efficiencies of 11.5% and 10.9% with Commission Internationale de l'Eclairage coordinates of (0.16, 0.09) and (0.15, 0.11), respectively, which is quite close to the stringent National Television System Committee blue standard.     

Achieving a Significantly Increased Efficiency in Nondoped Pure Blue Fluorescent OLED: A Quasi‐Equivalent Hybridized Excited State

Excited state characters and components play a decisive role in photoluminescence (PL) and electroluminescence (EL) properties of organic light‐emitting materials (OLEDS). Charge‐transfer (CT) state is beneficial to enhance the singlet exciton utilizations in fluorescent OLEDs by an activated reverse intersystem crossing process, due to the minimized singlet and triplet energy splitting in CT excitons. However, the dominant CT component in the emissive state significantly reduces the PL efficiency in such materials. Here, the strategy is to carry out a fine excited state modulation, aiming to reach a golden combination of the high PL efficiency locally emissive (LE) component and the high exciton utilizing CT component in one excited state. As a result, a quasi‐equivalent hybridization of LE and CT components is obtained in the emissive state upon the addition of only an extra phenyl ring in the newly synthesized material 4‐[2‐(4′‐diphenylamino‐biphenyl‐4‐yl)‐phenanthro[9,10‐d]imidazol‐1‐yl]‐benzonitrile (TBPMCN), and the nondoped OLED of TBPMCN exhibited a record‐setting performance: a pure blue emission with a Commission Internationale de L'Eclairage coordinate of (0.16, 0.16), a high external quantum efficiency of 7.8%, and a high yield of singlet exciton of 97% without delayed fluorescence phenomenon. The excited state modulation could be a practical way to design low‐cost, high‐efficiency fluorescent OLED materials.     

High‐Performance,Phosphorescent, Top‐Emitting Organic Light‐Emitting Diodes with p–i–n Homojunctions

High‐performance, green, orange, and red top‐emitting organic light‐emitting diodes (TOLEDs) with p–i–n homojunction are demonstrated. An excellent ambipolar host, 2,5‐bis(2‐(9H‐carbazol‐9‐yl)phenyl)‐1,3,4‐oxadiazole (o‐CzOXD), which has good thermal and morphological stabilities, a high triplet energy level, and equally high electron and hole mobilities, is chosen as the organic host material for the homojunction devices. By electrical doping, the carrier injection and transporting characteristics are greatly improved. The optical structure is optimized in view of light emission of different colors to enhance the color purity and improve the view characte­ristics. As a result, high efficiency p–i–n homojunction TOLEDs with saturated intrinsic emission of the emitting materials and angular independence of the emission are realized. The performances of these p–i–n homojunction TOLEDs are even higher than the multi‐layer heterojunction bottom‐emitting devices using the same emitting layers.     

Magnetic Field Effect in Organic Light‐Emitting Diodes Based on Electron Donor–Acceptor Exciplex Chromophores Doped with Fluorescent Emitters

A new type of organic light‐emitting diode (OLED) has emerged that shows enhanced operational stability and large internal quantum efficiency approaching 100%, which is based on thermally activated delayed fluorescence (TADF) compounds doped with fluorescent emitters. Magneto‐electroluminescence (MEL) in such TADF‐based OLEDs and magneto‐photoluminescence (MPL) in thin films based on donor–acceptor (D–A) exciplexes doped with fluorescent emitters with various concentrations are investigated. It has been found that both MEL and MPL responses are thermally activated with substantially lower activation energy compared to that in the pristine undoped D–A exciplex host blend. In addition, both MPL and MEL steeply decrease with the emitter's concentration. This indicates the existence of a loss mechanism, whereby the triplet charge‐transfer state in the exciplex host blend may directly decay to the lowest, nonemissive triplet state of the fluorescent emitter molecules.     

Highly Efficient TADF OLEDs: How the Emitter–Host Interaction Controls Both the Excited State Species and Electrical Properties of the Devices to Achieve Near 100% Triplet Harvesting and High Efficiency

New emitters that can harvest both singlet and triplet excited states to give 100% internal conversion of charge into light, are required to replace Ir based phosphors in organic light emitting diodes (OLEDs). Molecules that have a charge transfer (CT) excited state can potentially achieve this through the mechanism of thermally activated delayed fluorescence (TADF). Here, it is shown that a D–A charge transfer molecule in the solid state, can emit not only via an intramolecular charge transfer (ICT) excited state, but also from exciplex states, formed between the molecule and the host material. OLEDs based on a previously studied D–A–D molecule in a host TAPC achieves >14% external electroluminescence yield and shows nearly 100% efficient triplet harvesting. In these devices, it is unambiguously established that the triplet states are harvested via TADF, but more interestingly, these results are found to be independent of whether the emitter is the ICT state or the D–A–D/host exciplex.     

Rehybridization of Nitrogen Atom Induced Photoluminescence Enhancement under Pressure Stimulation

The excited state properties of organic fluorescent materials are crucial for their photoelectronic performance. Here, a study on the highly efficient electrofluorescent material 4‐(2‐(4′‐(diphenylamino)‐[1,1′‐biphenyl]‐4‐yl)‐1H‐phenanthro[9,10‐d]imidazol‐1‐yl)benzonitrile (TBPMCN) is carried out, focusing mainly on its crystal structure and photophysical properties under pressure stimulation. The special triangular‐cone (TC) configuration of triphenylamine group in TBPMCN crystal exhibits charge‐transfer (CT)‐dominated excited state property in TBPMCN, which gives rise to a blue‐shifted emission in the crystal. Theoretical calculations prove that the TC conformation is a dynamically metastable state, which is higher in energy than the three‐blade‐propeller (TBP) configuration. In a further piezochromic experiment, a unique rehybridization‐induced emission enhancement phenomenon is found in this crystal, which is essentially different from the aggregation‐induced emission enhancement (AIEE) mechanism. It can be assigned to the change of excited state property from a CT‐dominated state to a hybridized locally excited and charge‐transfer state, as a result of the rehybridization of nitrogen atom upon the increased external pressure. This work provides deep insight into the relationship between molecular structure and excited state properties in crystal by means of the pressure stimulation and further enriches the AIEE mechanism. Additionally, the large red‐shifted piezochromic phenomenon of this CT material is stressed.     

Control of Electrophosphorescence in Conjugated Dendrimer Light‐Emitting Diodes

We present a novel platinum porphyrin based phosphorescent dendrimer for use as a triplet harvesting dopant in organic light‐emitting diodes. Two types of dendritic host materials are used. Through the choice of a common branching architecture around the emissive chromophore unit of both guest and host materials, we are able to achieve excellent miscibility. The relative contribution of guest to host emission is found to depend strongly on the energy level offsets of the two blend materials, indicating strong trapping processes. Under pulsed operation, we observe a striking dependence of the emission spectrum on pulse period, independent of the host material used. This spectral modification is attributed to the quenching of triplet excitations at high excitation densities. We find excellent agreement between our measured data and a model based on bimolecular recombination.     

Improved Efficiency of Single‐Layer Polymer Light‐Emitting Devices with Poly(vinylcarbazole) Doubly Doped with Phosphorescent and Fluorescent Dyes as the Emitting Layer

We demonstrate novel organic light‐emitting diode (LED) materials that contain a green phosphorescent dye (dmbpy)Re(CO)₃Cl (dmbpy = 4,4′‐dimethyl‐2,2′‐bipyridine), and a red fluorescent dye 4‐dicyanomethylene‐6‐(p‐dimethylaminostyryl)‐2‐methyl‐4H‐pyran (DCM) as dopants and polyvinylcarbazole (PVK) as the host. The photoluminescence (PL) and electroluminescence (EL) properties of these complex materials were studied. The energy transfer efficiency from PVK host to DCM is increased by the (dmbpy)Re(CO)₃Cl co‐dopant, which has an emission energy between that of PVK and DCM. The (dmbpy)Re(CO)₃Cl, which emits a long‐lived phosphorescence, is used as an energy coupler, providing the possibility to harvest both singlet and triplet energy in the devices. The pure red emission from DCM was observed from PL and EL spectra of (dmbpy)Re(CO)₃‐Cl(> 2.0 wt.‐%):DCM(> 0.5 wt. %) doped PVK films, demonstrating an efficient energy transfer from PVK and (dmbpy)Re(CO)₃‐Cl to DCM. By optimizing the concentration of DCM and (dmbpy)Re(CO)₃Cl in PVK, a maximum EL quantum efficiency of 0.42 cd A^–1 at a current density of 9.5 mA cm^–2 was obtained. The EL quantum efficiency of the doubly doped device is significantly enhanced in comparison with both a DCM‐only doped PVK device and a DCM‐doped PVK device with the green fluorescent dye Alq₃ as co‐dopant. The improvement in the operating characteristics of the phosphorescent and fluorescent dye doubly doped device is attributed to efficient energy transfer in the system, in which both triplet and singlet excitons are used for resultant emission in the polymer device.     

All‐Organic,Temporally Pure White Afterglow in Amorphous Films Using Complementary Blue and Greenish‐Yellow Ultralong Room Temperature Phosphors

Organic molecules exhibiting afterglow emission (lifetime longer than 0.1 s) under ambient conditions have sparked tremendous attention in recent years as a sustainable energy source with potential applications in displays, lighting, and bioimaging. However, white afterglow organic materials with color purity during the entire period of delayed emission, after the cessation of excitation source, are yet to be achieved due to the different excited state lifetimes of its primary or complementary components. Herein, a remarkable, ambient “temporally pure white afterglow,” which lasts for over 7 s, by coorganizing complementary blue and greenish‐yellow organic room temperature phosphors with similar ultralong lifetimes and efficiency, in an amorphous polymer film is demonstrated. One of the most efficient blue afterglow room temperature phosphors is also reported, with an ultralong lifetime up to 2.26 s and maximum quantum efficiency of 36.8%, from purely organic triazatruxenes en route to the realization of this white afterglow. Further, broad and complementary absorption features of the coorganized phosphors in the visible region facilitates an excitation‐dependent dynamic color‐tuning of the afterglow from sky‐blue to greenish‐yellow.     

Mechanistic Study on High Efficiency Deep Blue AIE‐Based Organic Light‐Emitting Diodes by Magneto‐Electroluminescence

Aggregation‐induced emission (AIE) materials are highly attractive because of their excellent properties of high efficiency emission in nondoped organic light‐emitting diodes (OLEDs). Therefore, a deep understanding of the working mechanisms, further improving the electroluminescence (EL) efficiency of the resulting AIE‐based OLEDs, is necessary. Herein, the conversion process from higher energy triplet state (T₂) to the lowest singlet state (SS₁) is found in OLEDs based on a blue AIE material, 4′‐(4‐(diphenylamino)phenyl)‐5′‐phenyl‐[1,1′:2′,1′′‐terphenyl]‐4‐carbonitrile (TPB‐AC), obviously relating to the device efficiency, by magneto‐EL (MEL) measurements. A special line shape with rise at low field and reduction at high field is observed. The phenomenon is further clarified by theoretical calculations, temperature‐dependent MELs, and transient photoluminescence emission properties. On the basis of the T₂‐S₁ conversion process, the EL performances of the blue OLEDs based on TPB‐AC are further enhanced by introducing a phosphorescence doping emitter in the emitting layer, which effectively regulates the excitons on TPB‐AC molecules. The maximum external quantum efficiency (EQE) reaches 7.93% and the EQE keeps 7.57% at the luminance of 1000 cd m^?2. This work establishes a physical insight for designing high‐performance AIE materials and devices in the future.