High‐Throughput Combinatorial Optimizations of Perovskite Light‐Emitting Diodes Based on All‐Vacuum Deposition

Light‐emitting diodes (LEDs) based on lead halide perovskites demonstrate outstanding optoelectronic properties and are strong competitors for display and lighting applications. While previous halide perovskite LEDs are mainly produced via solution processing, here an all‐vacuum processing method is employed to construct CsPbBr₃ LEDs because vacuum processing exhibits high reliability and easy integration with existing OLED facilities for mass production. The high‐throughput combinatorial strategies are further adopted to study perovskite composition, annealing temperature, and functional layer thickness, thus significantly speeding up the optimization process. The best rigid device shows a current efficiency (CE) of 4.8 cd A^?1 (EQE of 1.45%) at 2358 cd m^?2, and best flexible device shows a CE of 4.16 cd A^?1 (EQE of 1.37%) at 2012 cd m^?2 with good bending tolerance. Moreover, by choosing NiO_x as the hole‐injection layer, the CE is improved to 10.15 cd A^?1 and EQE is improved to a record of 3.26% for perovskite LEDs produced by vacuum deposition. The time efficient combinatorial approaches can also be applied to optimize other perovskite LEDs.     

Merging Biology and Solid‐State Lighting: Recent Advances in Light‐Emitting Diodes Based on Biological Materials

Solid‐state lighting (SSL) is one of the biggest achievements of the 20^th century. It has completely changed our modern life with respect to general illumination (light‐emitting diodes), flat devices and displays (organic light‐emitting diodes), and small labeling systems (light‐emitting electrochemical cells). Nowadays, it is however mandatory to make a transition toward green, sustainable, and equally performing lighting systems. In this regard, several groups have realized that the actual SSL technologies can easily and efficiently be improved by getting inspiration from how natural systems that manipulate light have been optimized over millennia. In addition, various natural and biocompatible materials with suitable properties for lighting applications have been used to replace expensive and unsustainable components of current lighting devices. Finally, SSL has also started to revolutionize the biomedical field with the achievement of efficient implantable lighting systems. Herein, the‐state‐of‐art of (i) biological materials for lighting devices, (ii) bioinspired concepts for device designs, and (iii) implantable SSL technologies is summarized, highlighting the perspectives of these emerging fields.     

Beryllium‐Assisted p‐Type Doping for ZnO Homojunction Light‐Emitting Devices

A key step in realization of a ZnO homojunction light‐emitting diode is the effective p‐type doping in ZnO:N. In this article, a feasible route is demonstrated to enhance hole doping in ZnO:N films by the assistance of Beryllium. The newly synthesized p‐type ZnO is applied in light‐emitting devices. The corresponding p–i–n junction exhibits excellent diode characteristics, and strong near band edge ultraviolet emissions is also observed even at temperatures as high as 400 K under the injection of continuous current. The results represent a critical advance toward the development of high‐efficiency and stabilized p‐type ZnO, which is also a desirable key step for future ZnO‐based optoelectronic applications.     

Starburst DCM‐Type Red‐Light‐Emitting Materials for Electroluminescence Applications

Three new starburst DCM (4‐(dicyanomethylene)‐2‐methyl‐6‐[4‐(dimethylaminostyryl)‐4H‐pyran]) derivatives, 4,4′,4′′‐tris[2‐(4‐dicyanomethylene‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (TDCM), 4,4′,′′‐tris[2‐(4‐(1′,3′‐indandione)‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (TIN), and 4‐methoxy‐4′,4′′‐bis[2‐(4‐(1′,3′‐indandione)‐6‐t‐butyl‐4H‐pyran‐2‐yl)‐ethylene]triphenylamine (MBIN), have been designed and synthesized for application as red‐light emitters in organic light‐emitting diodes (OLEDs). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) reveal their extremely high glass‐transition temperatures and decomposition temperatures, as well as their low tendency to crystallize. Photoluminescence and electroluminescence measurements show that they exhibit a greatly restricted concentration‐quenching effect compared to DCM1 (4‐(dicyanomethylene)‐2‐methyl‐6‐[p‐(N,N‐dimethylamino)‐styryl]‐4H‐pyran), a simple but typical DCM‐type dye, as a result of their non‐planar, three‐dimensional structures that result from their unique propeller‐like triphenylamine electron‐donating cores. The peripheral electron‐withdrawing moieties also play a key role in the restriction of concentration quenching. That is, TIN and MBIN, bearing 1,3‐indandione acceptors, emit more efficiently than TDCM and DCM1, which have dicyanomethylene as acceptors at a high doping concentration of 10 wt.‐% in poly(9‐vinylcarbazole) (PVK) film, irrespective of whether they are photoexcited or electroexcited, though their fluorescence quantum yields in dilute solutions are much lower than that of DCM1. By way of the co‐doping approach, the electroluminescence device with the configuration indium tin oxide (ITO)/PVK:MBIN(10 wt.‐%):tris(4‐(2‐phenylethynyl)‐phenyl)amine (TPA; 30 wt.‐%) (70 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 20 nm)/tris(8‐quinolinolato) aluminum (Alq₃;15 nm)/LiF (0.3 nm)/Al (150 nm) exhibits a turn‐on voltage of 5.1 V, a maximum luminance of 6971 cd m^–2, a maximum efficiency of 6.14 cd A^–1 (405 cd m^–2), and chromaticity coordinates of (0.66,0.33). The encouraging electroluminescence performance suggests potential applications of the starburst DCM red‐light emitters in OLEDs.     

Discovery of New Green Phosphors and Minimization of Experimental Inconsistency Using a Multi‐Objective Genetic Algorithm‐Assisted Combinatorial Method

A multi‐objective genetic algorithm‐assisted combinatorial materials search (MOGACMS) strategy was employed to develop a new green phosphor for use in a cold cathode fluorescent lamp (CCFL) for a back light unit (BLU) in liquid crystal display (LCD) applications. MOGACMS is a method for the systematic control of experimental inconsistency, which is one of the most troublesome and difficult problems in high‐throughput combinatorial experiments. Experimental inconsistency is a very serious problem faced by all scientists in the field of combinatorial materials science. For this study, experimental inconsistency and material property were selected as dual objective functions that were simultaneously optimized. Specifically, in an attempt to search for promising phosphors with high reproducibility, luminance was maximized and experimental inconsistency was minimized using the MOGACMS strategy. A divalent manganese‐doped alkali alkaline germanium oxide system was screened using MOGACMS. As a result of MOGA reiteration, we identified a phosphor, Na₂MgGeO₄:Mn²⁺, with improved luminance and reliable reproducibility.     

Blue Single‐Layer Organic Light‐Emitting Diodes Using Fluorescent Materials: A Molecular Design View Point

Since the beginning of organic light‐emitting diodes (OLEDs), blue emission has attracted the most attention and many research groups worldwide have worked on the design of materials for stable and highly efficient blue OLEDs. However, almost all the high‐efficiency blue OLEDs using fluorescent materials are multilayer devices, which are constituted of a stack of organic layers to improve the injection, transport, and recombination of charges within the emissive layer. Although the technology has been mastered, it suffers from real complexity and high cost and is time‐consuming. Simplifying the multilayer structure with a single‐layer one, the simplest devices made only of electrodes and the emissive layer have appeared as an appealing strategy for this technology. However, removing the functional organic layers of an OLED stack leads to a dramatic decrease of the performance and achieving high‐efficiency blue single‐layer OLEDs requires intense research especially in terms of materials design. Herein, an exhaustive review of blue emitting fluorophores that have been incorporated in single‐layer OLEDs is reported, and the links between their electronic properties and the device performance are discussed. Thus, a structure/properties/device performance relationship map is drawn, which is of interest for the future design of organic materials.     

Synthesis and Characterization of n‐Type Materials for Non‐Doped Organic Red‐Light‐Emitting Diodes

Two compounds, 2,3‐dicyano‐5,6‐di(4′‐diphenylamino‐biphenyl‐4‐yl)pyrazine (CAPP) and 6,7‐dicyano‐2,3‐di(4′‐diphenylamino‐biphenyl‐4‐yl)quinoxaline (CAPQ), capable of intramolecular charge transfer, have been designed and synthesized in high yield by a convenient procedure. The compounds have been fully characterized spectroscopically. They have a high thermal stability and show bright light emission both in non‐polar solvents and in the solid state. Moreover, they exhibit excellent reversible oxidation and reduction waves. The higher energy level of the highest occupied molecular orbital (–5.3 eV) and the triphenylamine group are advantageous for hole‐injection/transport. In addition, the high electron affinities of 3.4 eV and the observed reversible reductive process suggest that these compounds enhance electron injection and have potential for use in electron transport. Three types of non‐doped red‐light‐emitting diodes have been studied using CAPP and CAPQ as the electron‐transporting and host‐light‐emitting layers, respectively. The devices exhibit red electroluminescence (EL), and constant Commission Internationale de l'Eclairage coordinates have been observed on increasing the current density. Pure red EL of CAPP, with a maximum brightness of 536 cd m^–2 and an external quantum efficiency of 0.7 % in ambient air, was achieved.     

Multifunctional Triphenylamine/Oxadiazole Hybrid as Host and Exciton‐Blocking Material: High Efficiency Green Phosphorescent OLEDs Using Easily Available and Common Materials

A new triphenylamine/oxadiazole hybrid, namely m‐TPA‐o‐OXD, formed by connecting the meta‐position of a phenyl ring in triphenylamine with the ortho‐position of 2,5‐biphenyl‐1,3,4‐oxadiazole, is designed and synthesized. The new bipolar compound is applicable in the phosphorescent organic light‐emitting diodes (PHOLEDs) as both host and exciton‐blocking material. By using the new material and the optimization of the device structures, very high efficiency green and yellow electrophosphorescence are achieved. For example, by introducing 1,3,5‐tris(N‐phenylbenzimidazol‐2‐yl)benzene (TPBI) to replace 2, 9‐dimethyl‐4,7‐diphenyl‐1, 10‐phenanthroline (BCP)/tris(8‐hydroxyquinoline)aluminium (Alq₃) as hole blocking/electron transporting layer, followed by tuning the thicknesses of hole‐transport 1, 4‐bis[(1‐naphthylphenyl)amino]biphenyl (NPB) layer to manipulate the charge balance, a maximum external quantum efficiency (η_EQE,max) of 23.0% and a maximum power efficiency (η_p,max) of 94.3 lm W⁻¹ are attained for (ppy)₂Ir(acac) based green electrophosphorescence. Subsequently, by inserting a thin layer of m‐TPA‐o‐OXD as self triplet exciton block layer between hole‐transport and emissive layer to confine triplet excitons, a η_EQE,max of 23.7% and η_p,max of 105 lm W⁻¹ are achieved. This is the highest efficiency ever reported for (ppy)₂Ir(acac) based green PHOLEDs. Furthermore, the new host m‐TPA‐o‐OXD is also applicable for other phosphorescent emitters, such as green‐emissive Ir(ppy)₃ and yellow‐emissive (fbi)₂Ir(acac). A yellow electrophosphorescent device with η_EQE,max of 20.6%, η_c,max of 62.1 cd A⁻¹, and η_p,max of 61.7 lm W⁻¹, is fabricated. To the author’s knowledge, this is also the highest efficiency ever reported for yellow PHOLEDs.     

Microwave‐Assisted Preparation of White Fluorescent Graphene Quantum Dots as a Novel Phosphor for Enhanced White‐Light‐Emitting Diodes

Graphene quantum dots (GQDs) with white fluorescence are synthesized by a microwave‐assisted hydrothermal method using graphite as the precursor. A solution‐processed white‐light‐emitting diode (WLED) is fabricated using the as‐prepared white fluorescent GQDs (white‐light‐emitting graphene quantum dots, WGQDs) doped 4,4‐bis(carbazol‐9‐yl)biphenyl as the emissive layer. White‐light emission is obtained from the WLED with 10 wt% doping concentration of WGQDs, which shows a luminance of 200 cd m^?2 at the applied voltage of 11–14 V. Importantly, an external quantum efficiency of 0.2% is achieved, which is the highest among all the reported WLED based on GQDs or carbon dots. The results demonstrate that WGQDs as a novel phosphor may open up a new avenue to develop the environmentally friendly WLEDs for practical application in solid‐state lighting.     

Electron‐Rich Alcohol‐Soluble Neutral Conjugated Polymers as Highly Efficient Electron‐Injecting Materials for Polymer Light‐Emitting Diodes

We report the design and synthesis of three alcohol‐soluble neutral conjugated polymers, poly[9,9‐bis(2‐(2‐(2‐diethanolaminoethoxy) ethoxy)ethyl)fluorene] (PF‐OH), poly[9,9‐bis(2‐(2‐(2‐diethanol‐aminoethoxy)ethoxy)ethyl)fluorene‐alt‐4,4′‐phenylether] (PFPE‐OH) and poly[9,9‐bis(2‐(2‐(2‐diethanolaminoethoxy) ethoxy)ethyl)fluorene‐alt‐benzothiadizole] (PFBT‐OH) with different conjugation length and electron affinity as highly efficient electron injecting and transporting materials for polymer light‐emitting diodes (PLEDs). The unique solubility of these polymers in polar solvents renders them as good candidates for multilayer solution processed PLEDs. Both the fluorescent and phosphorescent PLEDs based on these polymers as electron injecting/transporting layer (ETL) were fabricated. It is interesting to find that electron‐deficient polymer (PFBT‐OH) shows very poor electron‐injecting ability compared to polymers with electron‐rich main chain (PF‐OH and PFPE‐OH). This phenomenon is quite different from that obtained from conventional electron‐injecting materials. Moreover, when these polymers were used in the phosphorescent PLEDs, the performance of the devices is highly dependent on the processing conditions of these polymers. The devices with ETL processed from water/methanol mixed solvent showed much better device performance than the devices processed with methanol as solvent. It was found that the erosion of the phosphorescent emission layer could be greatly suppressed by using water/methanol mixed solvent for processing the polymer ETL. The electronic properties of the ETL could also be influenced by the processing conditions. This offers a new avenue to improve the performance of phosphorescent PLEDs through manipulating the processing conditions of these conjugated polymer ETLs.     

Creation of Bifunctional Materials: Improve Electron‐Transporting Ability of Light Emitters Based on AIE‐Active 2,3,4,5‐Tetraphenylsiloles

2,3,4,5‐Tetraphenylsiloles are excellent solid‐state light emitters featured aggregation‐induced emission (AIE) characteristics, but those that can efficiently function as both light‐emitting and electron‐transporting layers in one organic light‐emitting diode (OLED) are much rare. To address this issue, herein, three tailored n‐type light emitters comprised of 2,3,4,5‐tetraphenylsilole and dimesitylboryl functional groups are designed and synthesized. The new siloles are fully characterized by standard spectroscopic and crystallographic methods with satisfactory results. Their thermal stabilities, electronic structures, photophysical properties, electrochemical behaviors and applications in OLEDs are investigated. These new siloles exhibit AIE characteristics with high emission efficiencies in solid films, and possess lower LUMO energy levels than their parents, 2,3,4,5‐tetraphenylsiloles. The double‐layer OLEDs [ITO/NPB (60 nm)/silole (60 nm)/LiF (1 nm)/Al (100 nm)] fabricated by adopting the new siloles as both light emitter and electron transporter afford excellent performances, with high electroluminescence efficiencies up to 13.9 cd A^–1, 4.35% and 11.6 lm W^–1, which are increased greatly relative to those attained from the triple‐layer devices with an additional electron‐transporting layer. These results demonstrate effective access to n‐type solid‐state emissive materials with practical utility.     

Recent Progress in High‐Efficiency Blue‐Light‐Emitting Materials for Organic Light‐Emitting Diodes

Organic light‐emitting diodes (OLEDs) are increasingly used in displays replacing traditional flat panel displays; e.g., liquid crystal displays. Especially, the paradigm shifts in displays from rigid to flexible types accelerated the market change from liquid crystal displays to OLEDs. However, some critical issues must be resolved for expansion of OLED use, of which blue device performance is one of the most important. Therefore, recent OLED material development has focused on the design, synthesis and application of high‐efficiency and long‐life blue emitters. Well‐known blue fluorescent emitters have been modified to improve their efficiency and lifetime, and blue phosphorescent emitters are being investigated to overcome the lifetime issue. Recently, thermally activated delayed fluorescent emitters have received attention due to the potential of high‐efficiency and long‐living emitters. Therefore, it is timely to review the recent progress and future prospects of high‐efficiency blue emitters. In this feature article, we summarize recent developments in blue fluorescent, phosphorescent and thermally activated delayed fluorescent emitters, and suggest key issues for each emitter and future development strategies.     

New Insights into Tunable Volatility of Ionic Materials through Counter‐Ion Control

Recent development in the field of small molecular materials has led to great advances in the performance of vacuum‐evaporated organic light‐emitting diodes. However, as a significant class of phosphorescent emitters, ionic transition metal complexes are seldom sublimable due to the inherent ionic nature and low vapor pressure, restricting their applications in state‐of‐the‐art devices fabricated by vacuum evaporation deposition. Here a facile, feasible and versatile strategy is shown to tune the volatility of ionic transition metal complexes through counter‐ion control. By introducing counter‐ions with large steric hindrance and well‐dispersed charges, a series of evaporable ionic iridium complexes are developed, and efficient vapor‐processed devices with a high brightness, small efficiency roll‐off, and polychromic emission ranging from deep‐blue to red‐orange are achieved. Our findings unlock the utilization of ionic functional materials in vacuum‐evaporated devices, and may open new doors for modern electronic materials technology.     

Rapid Combinatorial Synthesis and Chromatography Based Screening of Phosphorescent Iridium Complexes for Solution Processing

This work reports the combinatorial synthesis and screening of phosphorescent iridium complexes as solution processable emitters for OLEDs. The approach taken here allows for the rapid synthesis, isolation, spectroscopic characterization and identification of the libraries based on chromatographic methods. Subsequent analysis of the irradiation induced degradation provides insight on the stability of the complexes under continuous excitation. The method is versatile and can easily be applied to other metal complexes or organic dyes for various applications, e.g., in electroluminescence, photovoltaics and sensing.     

Boosting the Efficiency of Near‐Infrared Fluorescent OLEDs with an Electroluminescent Peak of Nearly 800 nm by Sensitizer‐Based Cascade Energy Transfer

A sensitization‐based cascade energy transfer channel is proposed to boost the electroluminescent performances of the solution‐processed near‐infrared organic light‐emitting devices (OLEDs) featuring an electroluminescent peak of 786 nm from a new fluorescent emitter of N⁴,N⁴,N⁹,N⁹‐tetra‐p‐tolylnaphtho[2,3‐c][1,2,5]thiadiazole‐4,9‐diamine (NZ2mDPA) with unique aggregation‐induced emission (AIE) property. The optimized device is composed of 4,4′‐N,N‐dicarbazole‐biphenyl (CBP) as the host, bis(2‐phenyl‐1,3‐benzothiozolato‐N,C^2′)iridium (Ir(bt)₂(acac)) as the sensitizer, and NZ2mDPA as the emitter, where the cascade energy transfer can occur via two steps realizing unexpected triplet–singlet energy transfer by the Förster mechanism. The first step features efficient triplet harvesting from CBP to Ir(bt)₂(acac), and then the second step involves in resonant energy transfer from the phosphorescent sensitizer to the near‐infrared AIE emitter of NZ2mDPA, which finally endows two channels of harvesting singlet and triplet excitons. The unique scheme achieves not only more efficient Förster energy transfer but also the higher utilization efficiency of triplet excitons. As a result, the near‐infrared OLEDs can realize a factor of 2.7 enhancement of external quantum efficiency by employing the phosphor‐sensitized AIE lumogen compared with the commonly used binary host–guest system.     

New Solution‐Processable Electron Transport Materials for Highly Efficient Blue Phosphorescent OLEDs

Several new solution‐processable organic semiconductors based on dendritic oligoquinolines were synthesized and were used as electron‐transport and hole‐blocking materials to realize highly efficient blue phosphorescent organic light‐emitting diodes (PhOLEDs). Various substitutions on the quinoline rings while keeping the central meta‐linked tris(quinolin‐2‐yl)benzene gave electron transport materials that combined wide energy gap (>3.3 eV), moderate electron affinity (2.55‐2.8 eV), and deep HOMO energy level (<‐6.08 eV) with electron mobility as high as 3.3 × 10^?3 cm² V^?1 s^?1. Polymer‐based PhOLEDs with iridium (III) bis(4,6‐(di‐fluorophenyl)pyridinato‐N,C^2′)picolinate (FIrpic) blue triplet emitter and solution‐processed oligoquinolines as the electron‐transport layers (ETLs) gave luminous efficiency of 30.5 cd A^?1 at a brightness of 4130 cd m^?2 with an external quantum efficiency (EQE) of 16.0%. Blue PhOLEDs incorporating solution‐deposited ETLs were over two‐fold more efficient than those containing vacuum‐deposited ETLs. Atomic force microscopy imaging shows that the solution‐deposited oligoquinoline ETLs formed vertically oriented nanopillars and rough surfaces that enable good ETL/cathode contacts, eliminating the need for cathode interfacial materials (LiF, CsF). These solution‐processed blue PhOLEDs have the highest performance observed to date in polymer‐based blue PhOLEDs.     

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.     

Harnessing “Click”‐Type Chemistry for the Preparation of Novel Electronic Materials

Sequence‐independent or “click”‐type chemistry is applied for the preparation of novel π‐conjugated oligomers. A variety of bi‐functional monomers for Wittig–Horner olefination are developed and applied in a sequential protection–deprotection process for the preparation of structurally similar π‐conjugated oligomers. Selected oligomers are incorporated as the organic semiconductors in light‐emitting diodes and a field‐effect transistor, demonstrating the potential of the approach.     

Graphene‐Assisted Epitaxy of Nitrogen Lattice Polarity GaN Films on Non‐Polar Sapphire Substrates for Green Light Emitting Diodes

Lattice polarity is a key point for hexagonal semiconductors such as GaN. Unfortunately, only Ga‐polarity GaN have been achieved on graphene till now. Here, the epitaxy of high quality nitrogen‐polarity GaN films on transferred graphene on non‐polar sapphire substrates by molecular beam epitaxy is reported. This success is achieved through atomic nitrogen irradiation, where C? N bonds are formed in graphene and provide nucleation sites for GaN and leading to N‐polarity GaN epitaxy. The N‐polarity characteristics are confirmed by chemical etching and transmission electron microscopy measurement. Due to the higher growth temperature of InGaN at N‐polarity than that at Ga‐polarity, green light emitting diodes are fabricated on the graphene‐assisted substrate, where a large redshift of emission wavelength is observed. These results open a new avenue for the polarity modulation of III‐nitride films based on 2D materials, and also pave the way for potential application in longer wavelength light emitting devices.     

Self‐Doping Cathode Interfacial Material Simultaneously Enabling High Electron Mobility and Powerful Work Function Tunability for High‐Efficiency All‐Solution‐Processed Polymer Light‐Emitting Diodes

A variety of N ‐hydrogenated/N ‐methylated pyridinium salts are elaborately designed and synthesized. Thermogravimetric and X‐ray photoelectron spectra analysis indicate the intensities of the N? H covalent bonds are strengthened step‐by‐step from 3,3′‐(5′‐(3‐(pyridin‐3‐yl)phenyl)‐[1,1′:3′,1″‐terphenyl]‐3,3″‐diyl)dipyridine (Tm)‐HCl to Tm‐HBr and then Tm‐TfOH, which results in gradually improved cathode interfacial modification abilities. The larger dipole moments of N⁺? H containing moieties compared to those of the N⁺? CH₃ endow them with more preferable interfacial modification abilities. Electron paramagnetic resonance signals reveal the existence of radical anions in the solid state of Tm‐TfOH, which enables its self‐doping property and high electron mobility up to 1.67 × 10^?3 cm² V^?1 s^?1. Using the Tm‐TfOH as the cathode interfacial layers (CILs), the phenyl‐substituted poly(para ‐phenylene vinylene)‐based all‐solution‐processed polymer light‐emitting diodes (PLEDs) achieve more preferable device performances than the poly[(9,9‐bis(3′‐(N ,N ‐dimethylamino)propyl)‐2,7‐fluorene)‐alt ‐2,7‐(9,9‐dioctylfluorene)]‐based ones, i.e., high current density of nearly 300 mA cm^?2, very high luminance over 15 000 cd m^?2 at a low bias of 5 V. Remarkably, the thickness of the CILs has little impact on the device performance and high efficiencies are maintained even at thicknesses up to 85 nm, which is barely realized in PLEDs with small‐molecule‐based electron transporting layers.