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.     

Deep‐Red/Near‐Infrared Electroluminescence from Single‐Component Charge‐Transfer Complex via Thermally Activated Delayed Fluorescence Channel

Formation of a single‐component charge‐transfer complex (SCCTC) is unveiled in solid state of an intermolecular charge‐transfer molecule 2‐(4‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)phenyl)anthracene‐9,10‐dione (PIPAQ). Intermolecular donor–acceptor interactions between two PIPAQ molecules is the primary driving force for self‐association and contributes to intermolecular charge transfer. The SCCTC character is fully verified by crystallographic, photophysical, electron spin resonance, and vibrational characterizations. The PIPAQ‐based SCCTC is first applied in light‐emitting devices as an emissive layer to realize efficient deep‐red/near‐infrared electroluminescence. This work provides new insights into SCCTC and represents an important step toward their applications in optoelectronic devices.     

Solution‐Processed,Alkali Metal‐Salt‐Doped,Electron‐Transport Layers for High‐Performance Phosphorescent Organic Light‐Emitting Diodes

High‐performance, blue, phosphorescent organic light‐emitting diodes (PhOLEDs) are achieved by orthogonal solution‐processing of small‐molecule electron‐transport material doped with an alkali metal salt, including cesium carbonate (Cs₂CO₃) or lithium carbonate (Li₂CO₃). Blue PhOLEDs with solution‐processed 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) electron‐transport layer (ETL) doped with Cs₂CO₃ show a luminous efficiency (LE) of 35.1 cd A^?1 with an external quantum efficiency (EQE) of 17.9%, which are two‐fold higher efficiency than a BPhen ETL without a dopant. These solution‐processed blue PhOLEDs are much superior compared to devices with vacuum‐deposited BPhen ETL/alkali metal salt cathode interfacial layer. Blue PhOLEDs with solution‐processed 1,3,5‐tris(m‐pyrid‐3‐yl‐phenyl)benzene (TmPyPB) ETL doped with Cs₂CO₃ have a luminous efficiency of 37.7 cd A^?1 with an EQE of 19.0%, which is the best performance observed to date in all‐solution‐processed blue PhOLEDs. The results show that a small‐molecule ETL doped with alkali metal salt can be realized by solution‐processing to enhance overall device performance. The solution‐processed metal salt‐doped ETLs exhibit a unique rough surface morphology that facilitates enhanced charge‐injection and transport in the devices. These results demonstrate that orthogonal solution‐processing of metal salt‐doped electron‐transport materials is a promising strategy for applications in various solution‐processed multilayered organic electronic devices.     

m‐Indolocarbazole Derivative as a Universal Host Material for RGB and White Phosphorescent OLEDs

The host materials designed for highly efficient white phosphorescent organic light‐emitting diodes (PhOLEDs) with power efficiency (PE) >50 lm W^‐1 and low efficiency roll‐off are very rare. In this work, three new indolocarbazole‐based materials (ICDP, 4ICPPy, and 4ICDPy) are presented composed of 6,7‐dimethylindolo[3,2‐a]carbazole and phenyl or 4‐pyridyl group for hosting blue, green, and red phosphors. Among this three host materials, 4ICDPy‐based devices reveal the best electroluminescent performance with maximum external quantum efficiencies (EQEs) of 22.1%, 27.0%, and 25.3% for blue (FIrpic), green (fac‐Ir(ppy)₃), and red ((piq)₂Ir(acac)) PhOLEDs. A two‐color and single‐emitting‐layer white organic light‐emitting diode hosted by 4ICDPy with FIrpic and Ir(pq)₃ as dopants achieves high EQE of 20.3% and PE of 50.9 lm W^?1 with good color stability; this performance is among the best for a single‐emitting‐layer white PhOLEDs. All 4ICDPy‐based devices show low efficiency roll‐off probably due to the excellent balanced carrier transport arisen from the bipolar character of 4ICDPy.     

Molecular Engineering of Blue Fluorescent Molecules Based on Silicon End‐Capped Diphenylaminofluorene Derivatives for Efficient Organic Light‐Emitting Materials

Blue fluorescent materials based on silicone end‐capped 2‐diphenylaminofluorene derivatives are synthesized and characterized. These materials are doped into a 2‐methyl‐9,10‐di‐[2‐naphthyl]anthracene host as blue dopant materials in the emitting layer of organic light‐emitting diode devices bearing a structure of ITO/DNTPD (60 nm)/NPB (30 nm)/emitting layer (30 nm)/Alq₃ (20 nm)/LiF (1.0 nm)/Al (200 nm). All devices exhibit highly efficient blue electroluminescence with high external quantum efficiencies (3.47%–7.34% at 20 mA cm^?2). The best luminous efficiency of 11.2 cd A^?1 and highest quantum efficiency of 7.34% at 20 mA cm^?2 are obtained in a device with CIE coordinates (0.15, 0.25). A deep‐blue OLED with CIE coordinates (0.15, 0.14) exhibits a luminous efficiency of 3.70 cd A^?1 and quantum efficiency of 3.47% at 20 mA cm^?2.     

Achieving Highly Efficient Fluorescent Blue Organic Light‐Emitting Diodes Through Optimizing Molecular Structures and Device Configuration

Based on the results of first‐principles calculations of the electronic properties of blue light‐emitting materials, the molecular structures of oligofluorenes are optimized by incorporating electron‐withdrawing groups into the molecules to balance hole and electron injection and transport for organic light‐emitting diodes (OLEDs). The result is a remarkable improvement in the maximum external quantum efficiency (EQE) of the undoped device from 2.0% to 4.99%. Further optimization of the device configurations and processing procedures, e.g., by changing the thickness of the emitting layer and through thermal annealing treatments, leads to a very high maximum EQE of 7.40% for the undoped sky‐blue device. Finally, by doping the emitter in a suitable host material, 4,4’‐bis(carbazol‐9‐yl)biphenyl (CBP), at the optimal concentration of 6%, pure blue emission with extremely high maximum EQE of 9.40% and Commission Internationale de l’Eclairage (CIE) coordinates of (0.147, 0.139) is achieved.     

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.     

Crosslinkable TAPC‐Based Hole‐Transport Materials for Solution‐Processed Organic Light‐Emitting Diodes with Reduced Efficiency Roll‐Off

1‐Bis[4‐[N,N‐di(4‐tolyl)amino]phenyl]‐cyclohexane (TAPC) has been widely used in xerography and organic light‐emitting diodes (OLEDs), but derivatives are little known. Here, a new series of solution‐processable, crosslinkable hole conductors based on TAPC with varying highest occupied molecular orbital (HOMO) energies from ?5.23 eV to ?5.69 eV is implemented in blue phosphorescent OLEDs. Their superior perfomance compared with the well‐known N4,N4,N4′,N4′‐tetraphenylbiphenyl‐4,4′‐diamine (TPDs) analogues regarding hole‐injection and mobility, electron and exciton blocking capabilities, efficiency, and efficiency roll‐off is demonstrated. Overall, the TAPC‐based devices feature higher luminous and power efficiency over a broader range of brightness levels and reduced efficiency roll off. A systematic broadening of the emission zone is observed as the hole‐injection barrier between the anode and the hole‐transporting layer increased.     

Multifunctional Deep‐Blue Emitter Comprising an Anthracene Core and Terminal Triphenylphosphine Oxide Groups

A highly efficient blue‐light emitter, 2‐tert‐butyl‐9,10‐bis[4′‐(diphenyl‐phosphoryl)phenyl]anthracene (POAn) is synthesized, and comprises electron‐deficient triphenylphosphine oxide side groups appended to the 9‐ and 10‐positions of a 2‐tert‐butylanthracene core. This sophisticated anthracene compound possesses a non‐coplanar configuration that results in a decreased tendency to crystallize and weaker intermolecular interactions in the solid state, leading to its pronounced morphological stability and high quantum efficiency. In addition to serving as an electron‐transporting blue‐light‐emitting material, POAn also facilitates electron injection from the Al cathode to itself. Consequently, simple double‐layer devices incorporating POAn as the emitting, electron‐transporting, and ‐injecting material produce bright deep‐blue lights having Commission Internationale de L'Eclairage coordinates of (0.15,0.07). The peak electroluminescence performance was 4.3% (2.9 cd A^?1). For a device lacking an electron‐transport layer or alkali fluoride, this device displays the best performance of any such the deep‐blue organic light‐emitting diodes reported to date.     

Dibenzothiophene/Oxide and Quinoxaline/Pyrazine Derivatives Serving as Electron‐Transport Materials

A series of 2,8‐disubstituted dibenzothiophene and 2,8‐disubstituted dibenzothiophene‐S,S‐dioxide derivatives containing quinoxaline and pyrazine moieties are synthesized via three key steps: i) palladium‐catalyzed Sonogashira coupling reaction to form dialkynes; ii) conversion of the dialkynes to diones; and iii) condensation of the diones with diamines. Single‐crystal characterization of 2,8‐di(6,7‐dimethyl‐3‐phenyl‐2‐quinoxalinyl)‐5H‐5λ⁶‐dibenzo[b,d]thiophene‐5,5‐dione indicates a triclinic crystal structure with space group P1 and a non‐coplanar structure. These new materials are amorphous, with glass‐transition temperatures ranging from 132 to 194 °C. The compounds (Cpd) exhibit high electron mobilities and serve as effective electron‐transport materials for organic light‐emitting devices. Double‐layer devices are fabricated with the structure indium tin oxide (ITO)/Qn/Cpd/LiF/Al, where yellow‐emitting 2,3‐bis[4‐(N‐phenyl‐9‐ethyl‐3‐carbazolylamino)phenyl]quinoxaline (Qn) serves as the emitting layer. An external quantum efficiency of 1.41 %, a power efficiency of 4.94 lm W^–1, and a current efficiency of 1.62 cd A^–1 are achieved at a current density of 100 mA cm^–2.     

High‐Efficiency and Color Stable Blue‐Light‐Emitting Polymers and Devices

Novel fluorene‐based blue‐light‐emitting copolymers with an ultraviolet‐blue‐light (UV‐blue‐light) emitting host and a blue‐light emitting component, 4‐N,N‐diphenylaminostilbene (DPS) have been designed and synthesized by using the palladium‐ catalyzed Suzuki coupling reaction. It was found that both copolymers poly [2,7‐(9,9‐dioctylfluorene)‐alt‐1,3‐(5‐carbazolphenylene)] (PFCz) DPS1 and PFCz‐DPS1‐OXD show pure blue‐light emission even with only 1 % DPS units because of the efficient energy transfer from the UV‐blue‐light emitting PFCz segments to the blue‐light‐emitting DPS units. Moreover, because of the efficient energy transfer/charge trapping in these copolymers, PFCz‐DPS1 and PFCz‐DPS1‐OXD show excellent device performance with a very stable pure blue‐light emission. By using a neutral surfactant poly[9,9‐bis(6'‐(diethanolamino)hexyl)‐fluorene] (PFN‐OH) as the electron injection layer, the device based on PFCz‐DPS1‐OXD5 with the configuration of ITO/PEDOT:PSS/PVK/polymer/PFN‐OH/Al showed a maximum quantum efficiency of 2.83 % and a maximum luminous efficiency of 2.50 cd A^–1. Its CIE 1931 chromaticity coordinates of (0.156, 0.080) match very well with the NTSC standard blue pixel coordinates of (0.14, 0.08). These results indicate that this kind of dopant/host copolymer could be a promising candidate for blue‐light‐emitting polymers with high efficiency, good color purity, and excellent color stability.     

Nanodot‐Enhanced High‐Efficiency Pure‐White Organic Light‐Emitting Diodes with Mixed‐Host Structures

A relatively high‐efficiency, fluorescent pure‐white organic light‐emitting diode was fabricated using a polysilicic acid (PSA) nanodot‐embedded polymeric hole‐transporting layer (HTL). The diode employed a mixed host in the single emissive layer, which comprised 0.5 wt % yellow 5,6,11,12‐tetra‐phenylnaphthacene doped in the mixed host of 50 % 2‐(N,N‐diphenyl‐amino)‐6‐[4‐(N,N‐diphenylamino)styryl]naphthalene and 50 % N,N′‐bis‐(1‐naphthyl)‐N,N′‐diphenyl‐1,10‐biphenyl‐4‐4′‐diamine. By incorporating 7 wt % 3 nm PSA nanodot into the HTL of poly(3,4‐ethylene‐dioxythiophene)‐poly‐(styrenesulfonate), the efficiency at 100 cd m^–2 was increased from 13.5 lm W^–1 (14.7 cd A^–1; EQE: 7.2 %) to 17.1 lm W^–1 (17.6 cd A^–1; EQE: 8.3 %). The marked efficiency improvement may be attributed to the introduction of the PSA nanodot, leading to a better carrier‐injection‐balance.     

A Blue‐Light‐Emitting Polymer with a Rigid Backbone for Enhanced Color Stability

Despite the promising expectations of poly(fluorene) (PF)‐type materials as efficient blue‐light‐emitting polymers, the devices based on these materials are not yet fully utilized. Under prolonged operation of the devices, the PF‐type materials undergo degradation with the appearance of a long‐range emission around 2.2–2.3 eV. As a consequence, the emissive color changes from blue to green with a decrease in the device efficiency. Here, an innovative approach that leads to a new blue‐emitting polymer with remarkable color stability is reported. By modifying the chemical structure of PF to inhibit the formation of keto defects, it is demonstrated that the devices exhibit excellent color stability. This new blue‐emitting polymer, poly(2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta‐[def]phenanthrene)) (PCPP), emits a stabilized, efficient blue electroluminescence without exhibiting any peak in the long‐wavelength region even after prolonged operation of the devices in air.     

Solution‐Processible Phosphorescent Blue Dendrimers Based on Biphenyl‐Dendrons and Fac‐tris(phenyltriazolyl)iridium(III) Cores

Solution‐processible saturated blue phosphorescence is an important goal for organic light‐emitting diodes (OLEDs). Fac‐tris(5‐aryltriazolyl)iridium(III) complexes can emit blue phosphorescence at room temperature. Mono‐ and doubly dendronized fac‐tris(1‐methyl‐5‐phenyl‐3‐n‐propyl‐1H‐[1,2,4]triazolyl)iridium(III) 1 and fac‐tris{1‐methyl‐5‐(4‐fluorophenyl)‐3‐n‐propyl‐1H‐[1,2,4]triazolyl}iridium(III) 4 with first generation biphenyl‐based dendrons were prepared. The dendrimers emitted blue light at room temperature and could be solution processed to form thin films. The doubly dendronized 3 had a film photoluminescence quantum yield of 67% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.17, 0.33). OLEDs comprised of a neat film of dendrimer 3 and an electron transport layer achieved a brightness of 142 cd m^?2 at 3.8 V with an external quantum efficiency of 7.9%, and CIE coordinates of (0.18, 0.35). Attachment of the fluorine atom to the emissive core had the effect of moving the luminescence to shorter wavelengths but also quenched the luminescence of the mono‐ and doubly dendronized dendrimers.     

2D Ruddlesden–Popper Perovskite Nanoplate Based Deep‐Blue Light‐Emitting Diodes for Light Communication

Ruddlesden–Popper perovskite, (PEA)₂PbBr₄ (PEA = C₈H₉NH₃), is a steady and inexpensive material with a broad bandgap and a narrow‐band emission. These features make it a potential candidate for deep‐blue light‐emitting diodes (LEDs). However, due to the weak exciton binding energy, LEDs based on the perovskite thin films usually possess a very low external quantum efficiency (EQE) of <0.03%. Here, for the first time, the construction of high‐performance deep‐blue LEDs based on 2D (PEA)₂PbBr₄ nanoplates (NPs) is demonstrated. The as‐fabricated (PEA)₂PbBr₄ NPs film shows a deep‐blue emission at 410 nm with excellent stability under ambient conditions. Impressively, LEDs based on the (PEA)₂PbBr₄ NPs film deliver a bright deep‐blue emission with a maximum luminance of 147.6 cd m^?2 and a high EQE up to 0.31%, which represents the most efficient and brightest perovskite LEDs operating at deep‐blue wavelengths. Furthermore, the LEDs retain over 80% of their efficiencies for over 1350 min under ≈60% relative humidity. The steady and bright deep‐blue LEDs can be used as an excitation light source to realize white light emission, which shows the potential for light communication. The work provides scope for developing perovskite into efficient and deep‐blue LEDs for low‐cost light source and light communication.     

n‐Doping of a Low‐Electron‐Affinity Polymer Used as an Electron‐Transport Layer in Organic Light‐Emitting Diodes

n‐Doping electron‐transport layers (ETLs) increases their conductivity and improves electron injection into organic light‐emitting diodes (OLEDs). Because of the low electron affinity and large bandgaps of ETLs used in green and blue OLEDs, n‐doping has been notoriously more difficult for these materials. In this work, n‐doping of the polymer poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)] (F8BT) is demonstrated via solution processing, using the air‐stable n‐dopant (pentamethylcyclopentadienyl)(1,3,5‐trimethylbenzene)ruthenium dimer [RuCp*Mes]₂. Undoped and doped F8BT films are characterized using ultraviolet and inverse photoelectron spectroscopy. The ionization energy and electron affinity of the undoped F8BT are found to be 5.8 and 2.8 eV, respectively. Upon doping F8BT with [RuCp*Mes]₂, the Fermi level shifts to within 0.25 eV of the F8BT lowest unoccupied molecular orbital, which is indicative of n‐doping. Conductivity measurements reveal a four orders of magnitude increase in the conductivity upon doping and irradiation with ultraviolet light. The [RuCp*Mes]₂‐doped F8BT films are incorporated as an ETL into phosphorescent green OLEDs, and the luminance is improved by three orders of magnitude when compared to identical devices with an undoped F8BT ETL.     

Rational Design of Charge‐Neutral,Near‐Infrared‐Emitting Osmium(II) Complexes and OLED Fabrication

A new series of charge neutral Os(II) isoquinolyl triazolate complexes ( 1 – 4 ) with both trans and cis arrangement of phosphine donors are synthesized, and their structural, electrochemical and photophysical properties are established. In sharp contrast to the cis‐arranged complexes 2 – 4 , the trans derivative 1 , which shows a planar arrangement of chromophoric N‐substituted chelates, offers the most effective extended π‐delocalization and hence the lowest excited state energy gap. These complexes exhibit phosphorescence with peak wavelengths ranging from 692–805 nm in degassed CH₂Cl₂ at room temperature. Near‐infrared (NIR)‐emitting electroluminescent devices employing 6 wt % of 1 (or 4 ) doped in Alq₃ host material are successfully fabricated. The devices incorporating 1 as NIR phosphor exhibit fairly intense emission with a peak wavelength at 814 nm. Forward radiant emittance reaches as high as 65.02 µW cm^?2, and a peak EQE of ～1.5% with devices employing Alq₃, TPBi and/or TAZ as electron‐transporting/exciton‐blocking layers. Upon switching to phosphor 4 , the electroluminescence blue shifts to 718 nm, while the maximum EQE and radiance increase to 2.7% and 93.26 (μW cm^?2) respectively. Their performances are optimized upon using TAZ as the electron transporting and exciton‐blocking material. The OLEDs characterized represent the only NIR‐emitting devices fabricated using charge‐neutral and volatile Os(II) phosphors via thermal vacuum deposition.     

Solution‐Processed Organic Light‐Emitting Transistors Incorporating Conjugated Polyelectrolytes

Improved performance of p‐type organic light‐emitting transistors (OLETs) is demonstrated by introducing a conjugated polyelectrolyte (CPE) layer and symmetric high work function (WF) source and drain metal electrodes. The OLET comprises a tri‐layer film consisting of a hole transporting layer, an emissive layer, and a CPE layer as an electron injection layer. The thickness of the CPE layer is critical for achieving good performance and provides an important structural handle for consideration in future optimization studies. We also demonstrate for the first time, good performance solution‐processed blue‐emitting OLETs. These results further demonstrate the simplification of device fabrication and improved performance afforded by integrating CPE interlayers into organic optoelectronic devices.     

Solution‐Processed Zinc Oxide as High‐Performance Air‐Stable Electron Injector in Organic Ambipolar Light‐Emitting Field‐Effect Transistors

Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.     

Controlling the Recombination Zone of White Organic Light‐Emitting Diodes with Extremely Long Lifetimes

The lifetime of the organic devices remains a major challenge that must be overcome before the wide application of white organic light‐emitting diodes (WOLEDs) technology. In this work, we present a new strategy to achieve WOLEDs with an extremely long lifetime by wisely control of the recombination zone. A blue emitting layer of 6,6′‐(1,2‐ethenediyl)bis(N‐2‐naphthalenyl‐N‐phenyl‐2‐naphthalenamine doped 9‐(1‐naphthyl)‐10‐(2‐naphthyl)‐anthracene was deposited on top of the mixed host blue emitting layer to prevent hole penetration into the electron transporting layer and to attain better confinement of carrier recombination. In this way, we obtained a WOLED with a record high lifetime of over 150 000 hours at an initial brightness of 1000 cd m^?2, 40 times longer than the conventional bilayer WOLED. The electroluminescent spectra of the long‐lived WOLED showed almost no color‐shifting after accelerated aging. It is anticipated that these results might be a starting point for further research towards ultrastable OLED displays and lightings.