Influence of host matrix on thermally-activated delayed fluorescence: Effects on emission lifetime,photoluminescence quantum yield,and device performance

The influence of the host molecules on the photoluminescent (PL) and electroluminescent (EL) properties of organic light-emitting diode (OLED) emitters showing efficient thermally-activated delayed fluorescence (TADF) has yet to be investigated in detail. Here we demonstrate that the choice of host can cause large variations in the PL quantum yield (Φ_PL ∼15–70%) and delayed PL transient decay (τ_del ∼2–70 ms) of a spiro-acridine-based TADF guest. We show that the effect of exciplex formation on Φ_PL must be considered even at low concentrations of the TADF guest. Using the same TADF guest but changing the host layer, we are able to greatly vary the PL transient decay time from ∼4 to ∼70 ms while maintaining a high Φ_PL ∼70%, which can lead to new applications. Detailed spectral characterization during PL decay reveals a gradually increasing singlet–triplet energy gap (ΔE_ST) as the origin of these observations. The time-varying ΔE_ST is explained based on dipole interactions between the host and guest molecules. Finally, PL and electrical considerations for host selection are discussed based on the performance of OLED devices.     

Molecular engineering of “A-D-D-A” dual-emitting-cores emitters with thermally activated delayed fluorescence and aggregation-induced emission characteristics

Endowing thermally activated delayed fluorescence (TADF) emitter with aggregation-induced emission (AIE) peculiarity is of great significance for realizing more promising commercial applications. Herein, two new dual-emitting-cores emitters with a structure of acceptor-donor-donor-acceptor (A-D-D-A), namely 2DBT-BZ-2Cz and 2DFT-BZ-2Cz, were designed and synthesized to explore their luminescence trait. The emitters, adopting dual carbazole as donor segments and dual phenyl ketone in peripheral skeleton as electron acceptor units, were featured with small singlet (S₁)–triplet (T₁) splitting energy (ΔE_ST) of 0.02 eV and 0.01 eV. The efficient thermally activated delayed fluorescence (TADF) characteristics and aggregation-induced emission property make them suitable for nondoped OLED devices. The solution-processed green OLEDs based on 2DBT-BZ-2Cz demonstrated greater device performance with current efficiency of 20.7 cd A⁻¹ and maximum luminescence of 10,000 cd m⁻². This work thus provides the direction to explore luminogens of dual-emitting-cores with TADF and AIE features as promising candidates in solid state lighting.     

The effect of the electron-donor ability on the OLED efficiency of twisted donor-acceptor type emitters

Two twisted donor-acceptor (D-A) chemical structures, CCDMB and PCDMB, were developed as a new class of thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs). Two emitters consist of 3-substituted carbazole as a first donor and trivalent boron as an electron acceptor in common, and carbazole and phenoxazine as second donors with different electron donor ability. While PCDMB with a strong phenoxazine donor decreased the lowest singlet excited state (S₁) level and thus showed a small singlet-triplet energy difference (ΔE_ST) value of 0.13 eV, resulting in effective reverse intersystem crossing (RISC), however, CCDMB with a weak donor showed a large ΔE_ST value of 0.21 eV. Efficient triplet harvesting of PCDMB was confirmed by a delayed component in transient PL decay curves of 25 wt% PCDMB-doped bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO) films. OLED devices with a CCDMB emitter showed deep-blue emission with Commission Internationale de l’Éclairage (CIE) of (0.16, 0.12) but a low maximum EQE of 5.5%, indicative of insufficient triplet harvesting. PCDMB-based devices showed green emission with CIE of (0.21, 0.45) and a high maximum EQE of 22.3%. Our study revealed the effect of the electron donor ability of structurally similar emitters on ΔE_ST values, triplet harvesting, and device efficiency.     

Highly efficient near-infrared thermally activated delayed fluorescence material based on a spirobifluorene decorated donor

The development of red/near-infrared (NIR) thermally activated delayed fluorescence (TADF) emitters are relatively lagging due to the spin statistics and energy gap law. Herein, we designed and synthesized a new NIR TADF emitter, 3-(4-(9,9′-spirobi[fluorene]-3-yl(phenyl)amino)phenyl)acenaphtho[1,2-b]pyrazine-8,9-dicarboni-trile (SDPA-APDC), by incorporating a spiro-type electron-donating moiety N,N-diphenyl-9,9′-spirobi[fluorene]-2-amine (SDPA) to an electron-withdrawing unit acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile (APDC). The photophysical, electrochemical and thermal properties of SDPA-APDC have been systematically explored. Consequently, the emitter was found high photoluminescence quantum yield (PLQY), narrow bandgap, small singlet-triplet energy gap (ΔE_ST) and excellent thermal stability. Furthermore, SDPA-APDC was developed for electroluminescence devices. The doped devices of SDPA-APDC achieved a red emission peak at 696 nm with a maximum external quantum efficiency (EQE) of 10.75%. And the non-doped device exhibited a NIR emission peak at 782 nm with a maximum EQE of 2.55%     

Triptycene-derived TADF enantiomers displaying circularly polarized luminescence and high-efficiency electroluminescence

A pair of novel circularly polarized thermally activated delayed fluorescence (CP-TADF) enantiomers (+)-(S,S)-CTRI-Cz and (−)-(R,R)-CTRI-Cz based on chiral triptycene scaffold were designed and synthesized. The obtained triptycene-derived enantiomers displayed obvious TADF activities with small singlet-triplet energy gap value (ΔE_ST) of 0.20 eV and characteristic microsecond delayed lifetime of 15.4 μs. Moreover, the TADF enantiomers showed mirror-image circular dichroism (CD) and circularly polarized luminescence (CPL) activities, and their luminescence dissymmetry factors (g_lum) were about ±0.9 × 10⁻³. Finally, by using the TADF enantiomers as emitters, the optimized organic light-emitting diodes (OLEDs) achieved maximum external quantum efficiency (EQE_max), current efficiency (CE_max) and power efficiency (PE_max) of 15.0%, 48.8 cd/A and 46.9 lm/W, respectively.     

Novel D-σ-A type thermally activated delayed fluorescence emitters with C–S σ bond for the orange-red OLEDs

Three D-σ-A type thermally activated delayed fluorescent materials (TADF), AQ-S-Cz, AQ-S-DPA and AQ-S-DMAC, with sulfur atom connect donors and acceptor, were designed and synthesized. All of the emitters exhibit small ΔE_ST (<0.2 eV) and the limited overlap of the molecular frontier orbitals because of the C–S σ bond and the distorted molecular structure. AQ-S-Cz and AQ-S-DMAC with rigid donor obtained higher photoluminescence quantum yields than AQ-S-DPA. The three emitters have excellent TADF performance and short delayed fluorescence lifetimes (0.32 μs for AQ-S-Cz, 0.15 μs for AQ-S-DPA, 0.28 μs for AQ-S-DMAC). The experiment results show that the three emitters have intra-molecular charge transition (intra-CT), especially inter-molecular charge transition (inter-CT) effect. The luminescence of these emitters can be efficiently regulated by intra-CT, especially inter-CT and realize prominent red shift from yellow (556 nm) to red emission (657 nm). Compared with that of AQ-S-Cz and AQ-S-DPA, the device based on AQ-S-DMAC obtained maximum external quantum efficiencies of 7.17% with turn-on voltage of 3.5 V. This work enriches the D-σ-A type orange-red TADF materials and provides a perspective approach of developing long wavelength TADF emitters.     

Aromatic-imide-based TADF material as emitter for efficient yellow and white organic light-emitting diodes

An aromatic-imide based TADF emitter (AI-4Cz) was designed and synthesized. The TADF emitter showed high thermal stability, good electrochemical properties, obvious AIE activity, small ΔE_ST value of 0.02 eV, and intense yellow emissions with PLQY of 76%. AI-4Cz also exhibited obvious microsecond-scale delayed fluorescence lifetime. Yellow OLED based on AI-4Cz was further fabricated, which achieved EQE_max of 16.7%. Moreover, a white OLED was fabricated through the dual emission layer strategy by using AI-4Cz and DMAC-DPS as emitting dopants, and the device obtained CIE coordinates of (0.30, 0.40), CRI value of 66, and an EQE_max of 13.6%.     

Conjugation‐Induced Thermally Activated Delayed Fluorescence (TADF): From Conventional Non‐TADF Units to TADF‐Active Polymers

Thermally activated delayed fluorescence (TADF)‐type compounds have great potential as emitter molecules in organic light‐emitting diodes, allowing for electrofluorescence with 100% internal quantum efficiency. In small molecules, TADF is achieved through the formation of intramolecular charge‐transfer states. The only design limitation is the requirement that donor and acceptor entities spatially decouple the highest occupied and lowest unoccupied molecular orbitals, respectively, to minimize exchange splitting. The development of polymeric TADF emitters, on the contrary, has seen comparably small progress and those are typically built up from monomeric units that show promising TADF properties in small molecule studies beforehand. By contrast, herein, a way to achieve TADF properties in cyclic oligomers and polymers composed of non‐TADF building blocks is shown. Due to a strongly decreased energy splitting of the polymer with respect to the individual repeating unit between the lowest singlet and triplet excited state (ΔE_ST) and a sufficiently high radiative decay rate k^S_r, a highly efficient TADF polymer with up to 71% photoluminescence quantum yield is obtained. For the first time, an encouraging method is provided for producing highly efficient TADF oligomers and polymers from solely non‐TADF units via induced conjugation, opening a new design strategy exclusive for polymers.     

High-performance red organic light-emitting devices based on an exciplex system with thermally activated delayed fluorescence characteristic

To realize high-performance red organic light-emitting diodes (OLEDs), a novel exciplex system Tris-PCz:B4PyPPM with thermally activated delayed fluorescence (TADF) characteristic was developed as the host of both red fluorescent and phosphorescent emitters. Due to the blue-green PL spectrum and suitable triplet energy level of 2.53 eV, the exciplex system matches the requirements of both red fluorescent and phosphorescent dopants. With an optimized mixing molar ratio of 5:5, Tris-PCz:B4PyPPM exciplex system shows outstanding host performance in both the red fluorescent and phosphorescent devices. The red fluorescent device based on DCJTB exhibits a low turn-on voltage of 2.3 V and an extremely high maximum external quantum efficiency (EQE) of 9.3%. And the red phosphorescent device with the Ir(MDQ)₂acac as the emitter realizes a maximum EQE of 20.3%. These remarkable results prove the feasibility of TADF exciplex systems simultaneously as the hosts of both high-performance fluorescent and phosphorescent red devices.     

Malononitrile based ternary AIE-ML materials: Experimental proof for emission switch from non-TADF to TADF

Three malononitrile based D-A-D compounds with TPA, PhCz and DMAC donor (DPMM-2TPA, DPMM-2PhCz and DPMM-2DMAC) at the para-position of phenyl group on the DPMM unit are synthesized and their photophysical properties are systematically investigated. All compounds display positive solvatochromic behaviour, good thermal and electrochemical stability. Moreover, pronounced aggregation-induced emission and mechanochromic luminescence are observed in their solid states. DPMM-2TPA and DPMM-2DMAC realized red fluorescence, extremely small ΔE_ST of 0.06 and 0.01 eV and significant thermally activated delayed fluorescence character, due to the operative RISC process via spin orbit coupling from ³LE to ¹CT and hyperfine coupling between ³CT and ¹CT, respectively. Nevertheless, TADF cannot be detected for DPMM-2PhCz because of its large ¹CT and ³CT gap (0.34 eV) and inaccessible endothermic energy transfer. These results suggest that the energy level of ¹CT, ³LE and ³CT is adjustable by carefully designing the molecular configuration and thus enable the emission switch from non-TADF to TADF. Multilayer OLEDs based on DPMM-2TPA and DPMM-2DMAC exhibit a maximum EQE of 16.5% and 12.7%, respectively, which is 3–4 times higher than DPMM-2PhCz based non-TADF OLEDs (EQE = 4.4%).     

High-Performance Solution-Processed Nondoped Circularly Polarized OLEDs with Chiral Triptycene Scaffold-Based TADF Emitters Realizing Over 20% External Quantum Efficiency

Recently, circularly polarized organic light-emitting diodes (CP-OLEDs) fabricated with thermally activated delayed fluorescence (TADF) emitters are developed rapidly. However, most devices are fabricated by vacuum deposition technology, and developing efficient solution-processed CP-OLEDs, especially nondoped devices, is still a challenge. Herein, a pair of triptycene-based enantiomers, (S,S)-/(R,R)-TpAc-TRZ, are synthesized. The novel chiral triptycene scaffold of enantiomers avoids their intermolecular π–π stacking, which is conducive to their aggregation-induced emission characteristics and high photoluminescence quantum yield of 85% in the solid state. Moreover, the triptycene-based enantiomers exhibit efficient TADF activities with a small singlet-triplet energy gap (ΔE_ST) of 0.03 eV and delayed fluorescence lifetime of 1.1 µs, as well as intense circularly polarized luminescence with dissymmetry factors (|g_PL|) of about 1.9 × 10⁻³. The solution-processed nondoped CP-OLEDs based on (S,S)-/(R,R)-TpAc-TRZ not only display obvious circularly polarized electroluminescence signals with g_EL values of +1.5 × 10⁻³ and −2.0 × 10⁻³, respectively, but also achieve high efficiencies with external quantum, current, and power efficiency up to 25.5%, 88.6 cd A⁻¹, and 95.9 lm W⁻¹, respectively.     

1,8-Naphthalimide-based hybrids for efficient red thermally activated delayed fluorescence organic light-emitting diodes

The connection of an electron deficient 1,8-naphthalimide acceptor moiety with a phenoxazine or phenothiazine donor moiety afforded 6-(10H-phenoxazin-10-yl)-2-phenyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (PXZ-NAI) and 6-(10H-phenothiazin-10-yl)-2-phenyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (PTZ-NAI) as two novel red thermally activated delayed fluorescence (TADF) emitters. The two emitters exhibited distinct TADF characteristics with small energy gaps between the lowest singlet and triplet excited states, which originated from the well-separated highest occupied molecular orbital and lowest unoccupied molecular orbital distributions. The optimized TADF organic light-emitting diodes based on PXZ-NAI and PTZ-NAI offered maximum external quantum efficiencies (EQEs) of 13.0% and 11.4% with maximum power efficiencies of 14.8 and 9.8 lm/W, respectively. Both devices emitted red electroluminescence spectra with peaks at 624 and 632 nm, and Commission Internationale de L'Eclairage coordinates of (0.610, 0.388) and (0.630, 0.368), respectively. These findings demonstrate that the combination of 1,8-naphthalimide with phenoxazine or phenothiazine could be an effective pathway for developing red TADF emitters.     

High‐Performance Dibenzoheteraborin‐Based Thermally Activated Delayed Fluorescence Emitters: Molecular Architectonics for Concurrently Achieving Narrowband Emission and Efficient Triplet–Singlet Spin Conversion

Thermally activated delayed fluorescence (TADF) materials, which enable the full harvesting of singlet and triplet excited states for light emission, are expected as the third‐generation emitters for organic light‐emitting diodes (OLEDs), superseding the conventional fluorescence and phosphorescence materials. High photoluminescence quantum yield (Φ_PL), narrow‐band emission (or high color purity), and short delayed fluorescence lifetime are all strongly desired for practical applications. However, to date, no rational design strategy of TADF emitters is established to fulfill these requirements. Here, an epoch‐making design strategy is proposed for producing high‐performance TADF emitters that concurrently exhibiting high Φ_PL values close to 100%, narrow emission bandwidths, and short emission lifetimes of ≈1 µs, with a fast reverse intersystem crossing rate of over 10⁶ s^?1. A new family of TADF emitters based on dibenzoheteraborins is introduced, which enable both doped and non‐doped TADF‐OLEDs to achieve markedly high external electroluminescence quantum efficiencies, exceeding 20%, and negligible efficiency roll‐offs at a practical high luminance. Systematic photophysical and theoretical investigations and device evaluations for these dibenzoheteraborin‐based TADF emitters are reported here.     

Multiresonant Thermally Activated Delayed Fluorescence Emitters Based on Heteroatom‐Doped Nanographenes: Recent Advances and Prospects for Organic Light‐Emitting Diodes

Since the first report in 2015, multiresonant thermally activated delayed fluorescent (MR‐TADF) compounds, a subclass of TADF emitters based on a heteroatom‐doped nanographene material, have come to the fore as attractive hosts as well as emitters for organic light‐emitting diodes (OLEDs). MR‐TADF compounds typically show very narrow‐band emission, high photoluminescence quantum yields, and small ΔE_ST values, typically around 200 meV, coupled with high chemical and thermal stabilities. These materials properties have translated into some of the best reported deep‐blue TADF OLEDs. Here, a detailed review of MR‐TADF compounds and their derivatives reported so far is presented. This review comprehensively documents all MR‐TADF compounds, with a focus on the synthesis, optoelectronic behavior, and OLED performance. In addition, computational approaches are surveyed to accurately model the excited state properties of these compounds.     

Aggregation induced intermolecular charge transfer in simple nonconjugated donor–acceptor system

The exploration of exciplex for organic light-emitting diodes (OLEDs) has been fleetly developed. However, many of them confront with the problems like phase separation and poor solubility, hampering their utilization in solution process. Hence, a series of soluble exciplex luminophores with the simple architecture of D-spacer-A (mCP-6C-TRZ, phCz-6C-TRZ and 2phCz-6C-TRZ) are synthesized and characterized, in which, the alkyl chain as ample spacer breaks the molecular backbone conjugation, induces intermolecular charge transfer process instead of intramolecular charge transfer in solid state. These materials are endowed with narrowed singlet−triplet splitting energy (ΔE_ST), efficient reverse intersystem crossing (RISC) process, and distinct thermally activated delayed fluorescence (TADF) characteristics. In view of their high triplet energy level (E_T) and bipolar carrier transport ability, where efficient exciplexes are applied as the host, the solution-processed phosphorescence devices realize a low efficiency roll-off of 7.0% at 1000 cd m⁻², high luminance, current efficiency (CE) and external quantum efficiency (EQE) of 25,990 cd m⁻², 20.0 cd A⁻¹ and 6.7%, respectively. These results offer a promising tactic to the establishment of exciplex with TADF feature as host for fabricating efficient solution processed OLEDs.     

An Effective Approach toward Yellow-to-Orange Multi-Resonance TADF Emitters by Integrating Strong Electron Donor into B/N-Based Polycyclic Architecture: High Performance OLEDs with Nearly 40% EQE

B/N-based multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters and the corresponding narrow band emissive organic light-emitting diodes (OLEDs) exhibit great potential for next-generation high-resolution displays. Nonetheless, designing MR-TADF emitters with emission wavelength over 550 nm remains challenging. Herein, an effective approach toward yellow-to-orange MR-TADF emitters by integrating a strong electron-donating indolophenazine building block into the B/N-doped polycyclic aromatic hydrocarbons is proposed. The investigation of photophysical properties reveals that the electron-donating difference between the donor segments of MR framework has a dramatic influence on the luminescent features, including the emission wavelength and full-width at half-maximum (FWHM). These TADF emitters display excellent photophysical characteristics such as near-unity photoluminescence quantum yields and almost 100% horizontal dipole ratio. As a result, yellow and orange OLEDs employing these emitters achieve state-of-the-art device performances with an ultrahigh external quantum efficiency of up to nearly 40%, power efficiency of 163 lm W⁻¹, and luminance close to 120 000 cd m⁻², which set a record among MR-TADF based OLEDs with emission peaks over 550 nm. More impressively, the fabricated device presents outstanding operational stability of LT₉₉ over 110 h at the initial brightness of 3000 cd m⁻².     

Improving the Efficiency of Red Thermally Activated Delayed Fluorescence Organic Light‐Emitting Diode by Rational Isomer Engineering

The development of efficient red thermally activated delayed fluorescence (TADF) emitters with an emission wavelength beyond 600 nm remains a great challenge for organic light‐emitting diodes (OLEDs). Herein, two pairs of isomers are designed and synthesized by attaching electron‐donor 9,9‐diphenyl‐9,10‐dihydroacridine (DPAC) moiety to the different positions of two kinds of highly rigid planar acceptor cores (PDCN and PPDCN). Their TADF efficiencies and emission maxima (599–726 nm) are regulated by molecular isomer manipulation. Interestingly, the photoluminescence quantum yields (Φ_PLs) of trans‐isomers T‐DA‐1 and T‐DA‐2 (78% and 89%) are remarkably higher than those of their corresponding cis‐isomers C‐DA‐1 and C‐DA‐2 (12% and 14%). Significantly increased Φ_PL values can be explained by single crystal structures and theoretical simulation. As a result, a deep red TADF‐OLED based on T‐DA‐2 displays a maximum external quantum efficiency (EQE) of 26.26% at 640 nm. Notably, at a brightness of 100 cd m^?2, the EQE value of T‐DA‐2‐based device still remains at an extremely high level of 23.95%, representing the highest value for reported red TADF‐OLEDs at the same brightness. These results provide a reasonable pathway to optimize optoelectronic properties and thereby construct efficient red TADF emitters through rational isomer engineering.     

Color stable and highly efficient hybrid white organic light-emitting devices using heavily doped thermally activated delayed fluorescence and ultrathin non-doped phosphorescence layers

Blue/orange complementary fluorescence/phosphorescence hybrid white organic light-emitting devices with excellent color stability and high efficiency have been fabricated, which are based on an easily fabricated multiple emissive layer (EML) configuration with an ultrathin non-doped orange phosphorescence EML selectively inserted between heavily doped blue thermally activated delayed fluorescence (TADF) EMLs. Through systematic investigation and improvement on luminance-dependent color shift and efficiency deterioration, a slight Commission Internationale de 1′Eclairage coordinates shift of (0.008, 0.003) at a practical luminance range from 1000 to 10000 cd/m², a maximum power efficiency of 45.8 lm/W, a maximum external quantum efficiency (EQE) of 15.7% and an EQE above 12% at 1000 cd/m² have been achieved. The heavily doped blue TADF emitters which act as the main charge transport channels and recombination sites in the host with high-lying lowest triplet excited state, take advantage of the bipolar transport ability to broaden the major charge recombination region, which alleviates triplet energy loss. The selectively inserted ultrathin non-doped orange EML makes its emission mechanism dominated by Förster energy transfer, which is effective to keep color stable under different drive voltages.     

Efficient and Tunable Thermally Activated Delayed Fluorescence Emitters Having Orientation‐Adjustable CN‐Substituted Pyridine and Pyrimidine Acceptor Units

A series of twisted D–π–A type emitters based on the acridine donor unit and CN‐substituted pyridine, pyrimidine, and benzene acceptor units are studied. They not only allow one to systematically probe the influence of different acceptor strengths, but also permit one to intriguingly probe the influence of tunable conformations (twist angles) within the acceptor moieties through controlling the orientation of asymmetric heteroaromatic ring relative to the donor component. Intramolecular charge‐transfer transitions are observed in all these compounds and emission wavelengths are widely tunable from deep blue to yellow not only by the general acceptor strength due to the characters of heteroarene and CN‐substitution pattern but also by the subtle control of in‐acceptor conformation (twist angles). Small triplet‐to‐singlet energy gaps (ΔE_ST) and significant thermally activated delayed fluorescence (TADF) characteristics are obtained in a series of D–π–A compounds with sufficient acceptor strengths and tunable in‐acceptor conformation, yielding a series of efficient blue‐green to yellow TADF emitters with promisingly high photoluminescence quantum yields of 90%–100%. Highly efficient blue‐green to yellow TADF organic light‐emitting diodes (OLEDs) having external quantum efficiencies of up to 23.1%–31.3% are achieved using these efficient TADF emitters, which are among the most efficient TADF OLEDs ever reported.     

Acceptor-Donor-Acceptor-Configured Delayed Fluorescence Emitters for Efficient Orange-Red and White Devices with Low Roll-off

Organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) materials are promising for the realization of highly efficient emitters. However, severe efficiency roll-off at high brightness still remains as a huge challenge for TADF-based OLEDs. Herein, rod-like orange-red TADF emitters of 2BNCz-PZ and 2BNtCz-PZ with acceptor-donor-acceptor (A-D-A) configuration are developed by bearing dihydrophenazine donor and discoidal rigid boron, nitrogen-contained polycyclic aromatic hydrocarbons acceptors. Both emitters exhibit hybrid long-range/short-range charge-transfer excitation for small singlet-triplet energy splitting, short delayed lifetime, and high photoluminescence quantum yield, leading to fast singlet radiation rate over 10⁷ s⁻¹ and fast reverse intersystem crossing rate over 10⁶ s⁻¹. Furthermore, a horizontal emitting dipole orientation factor over 90% is realized. The optimized orange-red OLED based on 2BNtCz-PZ presents a maximum external quantum efficiency (EQE) of 31.0% and a slight EQE roll-off to 22.2% at 1 000 cd m⁻² with emission peak over 600 nm. In addition, the single-emitting layer white OLEDs achieve a maximum EQE of 30.6% due to the use of these orange-red dopants with intense charge-transfer absorption band. This work reveals the potential of the rod-like A-D-A configuration for constructing highly efficient orange-red TADF emitters with low-efficiency roll-off.