Achieving High‐Performance Nondoped OLEDs with Extremely Small Efficiency Roll‐Off by Combining Aggregation‐Induced Emission and Thermally Activated Delayed Fluorescence

Luminescent materials with thermally activated delayed fluorescence (TADF) can harvest singlet and triplet excitons to afford high electroluminescence (EL) efficiencies for organic light‐emitting diodes (OLEDs). However, TADF emitters generally have to be dispersed into host matrices to suppress emission quenching and/or exciton annihilation, and most doped OLEDs of TADF emitters encounter a thorny problem of swift efficiency roll‐off as luminance increases. To address this issue, in this study, a new tailor‐made luminogen (dibenzothiophene‐benzoyl‐9,9‐dimethyl‐9,10‐dihydroacridine, DBT‐BZ‐DMAC) with an unsymmetrical structure is synthesized and investigated by crystallography, theoretical calculation, spectroscopies, etc. It shows aggregation‐induced emission, prominent TADF, and interesting mechanoluminescence property. Doped OLEDs of DBT‐BZ‐DMAC show high peak current and external quantum efficiencies of up to 51.7 cd A^?1 and 17.9%, respectively, but the efficiency roll‐off is large at high luminance. High‐performance nondoped OLED is also achieved with neat film of DBT‐BZ‐DMAC, providing excellent maxima EL efficiencies of 43.3 cd A^?1 and 14.2%, negligible current efficiency roll‐off of 0.46%, and external quantum efficiency roll‐off approaching null from peak values to those at 1000 cd m^?2. To the best of the authors' knowledge, this is one of the most efficient nondoped TADF OLEDs with small efficiency roll‐off reported so far.     

Multiferroic Clusters: A New Perspective for Relaxor‐Type Room‐Temperature Multiferroics

Multiferroics are promising for sensor and memory applications, but despite all efforts invested in their research no single‐phase material displaying both ferroelectricity and large magnetization at room‐temperature has hitherto been reported. This situation has substantially been improved in the novel relaxor ferroelectric single‐phase (BiFe_0.9Co_0.1O₃)_0.4–(Bi_1/2K_1/2TiO₃)_0.6, where polar nanoregions (PNR) transform into static‐PNR as evidenced by piezoresponse force microscopy (PFM) and simultaneously enable congruent multiferroic clusters (MFC) to emerge from inherent strongly magnetic Bi(Fe,Co)O₃ rich regions as verified by magnetic force microscopy (MFM) and secondary ion mass spectrometry. The material's exceptionally large Néel temperature T_N = 670 ± 10 K, as found by neutron diffraction, is proposed to be a consequence of ferrimagnetic order in MFC. On these MFC, exceptionally large direct and converse magnetoelectric (ME) coupling coefficients, α ≈ 1.0 × 10^?5 s m^?1 at room‐temperature, are measured by PFM and MFM, respectively. It is expected that the non‐ergodic relaxor properties which are governed by the Bi_1/2K_1/2TiO₃ component to play a vital role in the strong ME coupling, by providing an electrically and mechanically flexible environment to MFC. This new class of non‐ergodic relaxor multiferroics bears great potential for applications. Especially the prospect of a ME nanodot storage device seems appealing.     

High Performance p‐ and n‐Type Light‐Emitting Field‐Effect Transistors Employing Thermally Activated Delayed Fluorescence

Light‐emitting field‐effect transistors (LEFETs) are an emerging type of devices that combine light‐emitting properties with logical switching function. One of the factors limiting their efficiency stems from the spin statistics of electrically generated excitons. Only 25% of them, short lived singlet states, are capable of light emission, with the other 75% being long lived triplet states that are wasted as heat due to spin‐forbidden processes. Traditionally, the way to overcome this limitation is to use phosphorescent materials as additional emission channel harnessing the triplet excitons. Here, an alternative strategy for triplet usage in LEFETs in the form of thermally activated delayed fluorescence (TADF) is presented. Devices employing a TADF capable material, 4CzIPN (2,4,5,6‐tetra[9H‐carbazol‐9‐yl]isophthalonitrile), in both n‐type and p‐type configurations are shown. They manifest excellent electrical characteristics, consistent brightness in the range of 100–1,000 cd m^‐2 and external quantum efficiency (EQE) of up to 0.1%, which is comparable to the equivalent organic light‐emitting diode (OLED) based on the same materials. Simulation identifies the poor light out‐coupling as the main reason for lower than expected EQEs. Transmission measurements show it can be partially alleviated using a more transparent top contact, however more structural optimization is needed to tap the full potential of the device.     

Low‐Symmetry Monoclinic Phases and Polarization Rotation Path Mediated by Epitaxial Strain in Multiferroic BiFeO3 Thin Films

A morphotropic phase boundary driven by epitaxial strain has been observed in lead‐free multiferroic BiFeO₃ thin films and the strain‐driven phase transitions have been widely reported as iso‐symmetric Cc‐Cc by recent works. In this paper, it is suggested that the tetragonal‐like BiFeO₃ phase identified in epitaxial films on (001) LaAlO₃ single crystal substrates is monoclinic M_C. This M_C phase is different from the M_A type monoclinic phase reported in BiFeO₃ films grown on low mismatch substrates, such as SrTiO₃. This is confirmed not only by synchrotron X‐ray studies but also by piezoresponse force microscopy measurements. The polarization vectors of the tetragonal‐like phase lie in the (100) plane, not the (11 0) plane as previously reported. A phenomenological analysis is proposed to explain the formation of M_C Phase. Such a low‐symmetry M_C phase, with its linkage to M_A phase and the multiphase coexistence open an avenue for large piezoelectric response in BiFeO₃ films and shed light on a complete understanding of possible polarization rotation paths and enhanced multiferroicity in BiFeO₃ films mediated by epitaxial strain. This work may also aid the understanding of developing new lead‐free strain‐driven morphotropic phase boundary in other ferroic systems.     

液体激光系统流场特性对热畸变的影响

液体介质的循环流动为消除激光系统的热效应提供了有效途径,对改善激光系统的光束质量具有重要意义.根据液体介质的流场特性,结合Fluent6.53软件模拟计算,分析了抽运区介质流速、湍流强度与附面层厚度、温度扰动的关系及时激光热畸变的影响.增大抽运区介质流速能有效减小热畸变和附面层厚度;在给定抽运条件下,采用光阑限孔的方法进一步减小热畸变,流速为20 m/s时的光程差(OPD)最人差值由 10个波长下降到5个波长.     

外延用300mm重掺B Si衬底中热致微缺陷研究

研究了重掺B对300 mm直拉Si衬底中热致微缺陷的影响.通过800℃/4～16 h+1 100℃/16 h的低-高两步退火处理发现,与普通(CZ)Si片相比,重掺B(HBCZ)Si片体内生成了高密度的热致微缺陷--体微缺陷(BMDs);B浓度的不同对BMDs的形态也有重要影响,重掺B Si片中出现杆状层错,随着B浓度的增加,层错密度增加,尺寸减小.研究表明,重掺B对BMDs的促进作用主要归功于B原子促进了氧沉淀的异质形核并由于原子半径效应使得这些核心较容易长大,而晶体中初始氧含量不是重掺B促进氧沉淀的主要因素.     

Interlayer‐Sensitized Linear and Nonlinear Photoluminescence of Quasi‐2D Hybrid Perovskites Using Aggregation‐Induced Enhanced Emission Active Organic Cation Layers

A concept of interlayer‐sensitized photoluminescence (PL) of quasi‐2D hybrid perovskite (PVK) with a π‐conjugated optically interacting organic cation layer is introduced and demonstrated. A rod‐shaped aggregation‐induced enhanced emission (AIEE) organic cation (BPCSA+), well fitted into the lattice size of 2D PVK layers, is designed and synthesized to prolong the exciton lifetime in a condensed layer assembly in the PVK. The BPCSA+ promotes the PL of this hybrid PVK up to 10‐folds from that of a non‐π‐conjugated organic cation (OA) 2D PVK. Notably, different from PL of OA 2D PVK, the increased PL intensity of BPCSA 2D PVKs with an increase of the BPCSA ratio in the PVK indicates a critical photon‐harvesting contribution of BPCSA. The films of BPCSA 2D PVKs are incredibly stable in ambient environments for more than 4 months and even upon direct contact with water. Additionally, due to the strong two‐photon absorption property of BPCSA, the BPCSA 2D PVK displays superior emission properties upon two‐photon excitation with a short wavelength IR laser. Thus, the AIEE sensitization system for quasi‐2D PVK hybrid system can make a drastic improvement in performance as well as in the stability of the PVK emitter and PVK based nonlinear optical devices.     

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.     

Flexible Near‐Infrared Plastic Phototransistors with Conjugated Polymer Gate‐Sensing Layers

Flexible near‐infrared (NIR) light‐sensing detectors are strongly required in the fast‐growing flexible electronics era, because they can serve as a vision system like eyes in various innovative applications including humanoid robots. Recently, keen interest has been paid to organic phototransistors due to their unique signal amplification and active matrix driving features over organic photodiodes. However, conventional NIR‐sensing organic phototransistors suffer from the limited use of organic materials because the channel layers play a dual role in both charge transport and sensing so that organic semiconducting materials with reasonably high charge mobility can be applied only. Here, it is demonstrated that a conjugated polymer, poly[{2,5‐bis‐(2‐ethylhexyl)‐3,6‐bis‐(thien‐2‐yl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐diyl}‐co‐{2,2′‐(2,1,3‐benzothiadiazole)]‐5,5′‐diyl}] (PEHTPPD‐BT), which exhibits no transistor performance as a channel layer, can stably detect a NIR light (up to 1000 nm) as a gate‐sensing layer (GSL) when it is placed between gate‐insulating layers and gate electrodes. The flexible array (10 × 10) detectors with the PEHTPPD‐BT GSLs could effectively sense NIR light without visible light interference by applying visible light cut films.     

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.     

Scalable Oxygen‐Ion Transport Kinetics in Metal‐Oxide Films: Impact of Thermally Induced Lattice Compaction in Acceptor Doped Ceria Films

In this paper, we focus on the effect of processing‐dependent lattice strain on oxygen ion conductivity in ceria based solid electrolyte thin films. This is of importance for technological applications, such as micro‐SOFCs, microbatteries, and resistive RAM memories. The oxygen ion conductivity can be significantly modified by control of lattice strain, to an extent comparable to the effect of doping bulk ceria with cations of different diameters. The interplay of dopant radii, lattice strain, microstrain, anion‐cation near order and oxygen ion transport is analyzed experimentally and interpreted with computational results. Key findings include that films annealed at 600 °C exhibit lattice parameters close to those of their bulk counterparts. With increasing anneal temperature, however, the films exhibited substantial compaction with lattice parameters decreasing by as much as nearly 2% (viz, Δd_{600–1100 °C}: –1.7% (Sc⁺³) > –1.5% (Gd⁺³) > –1.2% (La⁺³)) for the annealing temperature range of 600–1100 °C. Remarkably 2/3^rd of the lattice parameter change obtained in bulk ceria upon changing the acceptor diameter from the smaller Sc to larger La, can be reproduced by post annealing a film with fixed dopant diameter. While the impact of lattice compaction on defect association/ordering cannot be entirely excluded, DFT computation revealed that the main effect appears to result in an increase in migration energy and consequent drop in ionic conductivity. As a consequence, it is clear that annealing procedures should be held to a minimum to maintain the optimum level of oxygen ion conductivity for energy‐related applications. Results reveal also the importance to understand the role of electro‐chemo‐mechanical coupling that is active in thin film materials.     

高功率半导体激光器端面泵浦Nd：YVO4固体激光器热致损耗的研究

本文提出了一种测量端面泵浦固体激光器热致损耗的方法。研究了Ｎｄ＾３＋浓度分别为０．５％和２％两种Ｎｄ：ＹＶＯ４晶体,基模半径与泵浦光斑半径之比Ｗ１／Ｗｐ分别为０．５和１情形下热致损耗随泵浦功率的变化,结果表明,热致损耗随泵浦功率的增加而增大,且强烈依赖于Ｗ１／Ｗｐ,大的基模半径会导致严重的热损耗,Ｎｄ：ＹＶＯ４晶体的Ｎｄ＾３＋浓度对热致损耗也有很大影响,在大模半径情形,高浓度晶体的热致损耗远大于低     

Over 10% EQE Near‐Infrared Electroluminescence Based on a Thermally Activated Delayed Fluorescence Emitter

Significant effort has been made to develop novel material systems to improve the efficiency of near‐infrared organic light‐emitting diodes (NIR OLEDs). Of those, fluorescent chromophores are mostly studied because of their advantages in cost and tunability. However, it is still rare for fluorescent NIR emitters to present good color purities in the NIR range and to have high external quantum efficiency (EQE). Here, a wedge‐shaped D‐π‐A‐π‐D emitter APDC‐DTPA with thermally activated delayed fluorescence property and a small single‐triplet splitting (ΔE_st) of 0.14 eV is presented. The non‐doped NIR device exhibits excellent performance with a maximum EQE of 2.19% and a peak wavelength of 777 nm. Remarkably, when 10 wt% of APDC‐DTPA is doped in 1,3,5‐tris(1‐phenyl‐1H‐benzimidazol‐2‐yl)benzene host, an extremely high EQE of 10.19% with an emission peak of 693 nm is achieved. All these values represent the best result for NIR OLEDs based on a pure organic fluorescent emitter with similar device structure and color gamut.     

The Role of Transition Metal Oxides in Charge‐Generation Layers for Stacked Organic Light‐Emitting Diodes

The mechanism of charge generation in transition metal oxide (TMO)‐based charge‐generation layers (CGL) used in stacked organic light‐emitting diodes (OLEDs) is reported upon. An interconnecting unit between two vertically stacked OLEDs, consisting of an abrupt heterointerface between a Cs₂CO₃‐doped 4,7‐diphenyl‐1,10‐phenanthroline layer and a WO₃ film is investigated. Minimum thicknesses are determined for these layers to allow for simultaneous operation of both sub‐OLEDs in the stacked device. Luminance–current density–voltage measurements, angular dependent spectral emission characteristics, and optical device simulations lead to minimum thicknesses of the n‐type doped layer and the TMO layer of 5 and 2.5 nm, respectively. Using data on interface energetic determined by ultraviolet photoelectron and inverse photoemission spectroscopy, it is shown that the actual charge generation occurs between the WO₃ layer and its neighboring hole‐transport material, 4,4',4”‐tris(N‐carbazolyl)‐triphenyl amine. The role of the adjacent n‐type doped electron transport layer is only to facilitate electron injection from the TMO into the adjacent sub‐OLED.     

Low‐Work‐Function Surface Formed by Solution‐Processed and Thermally Deposited Nanoscale Layers of Cesium Carbonate

Nanostructured layers of Cs₂CO₃ are shown to function very effectively as cathodes in organic electronic devices because of their good electron‐injection capabilities. Here, we report a comprehensive study of the origin of the low work function of nanostructured layers of Cs₂CO₃ prepared by solution deposition and thermal evaporation. The nanoscale Cs₂CO₃ layers are probed by various characterization methods including current–voltage (I–V) measurements, photovoltaic studies, X‐ray photoelectron spectroscopy (XPS), UV photoelectron spectroscopy (UPS), and impedance spectroscopy. It is found that thermally evaporated Cs₂CO₃ decomposes into CsO₂ and cesium suboxides. The cesium suboxides dope CsO₂, yielding a heavily doped n‐type semiconductor with an intrinsically low work function. As a result, devices fabricated using thermally evaporated Cs₂CO₃ are relatively insensitive to the choice of the cathode metal. The reaction of thermally evaporated Cs₂CO₃ with Al can further reduce the work function to 2.1 eV by forming an Al–O–Cs complex. Solution‐processed Cs₂CO₃ also reduces the work function of Au substrates from 5.1 to 3.5 eV. However, devices prepared using solution‐processed Cs₂CO₃ exhibit high efficiency only if a reactive metal such as Al or Ca is used as the cathode metal. A strong chemical reaction occurs between spin‐coated Cs₂CO₃ and thermally evaporated Al. An Al–O—Cs complex is formed as a result of this chemical reaction at the interface, and this layer significantly reduces the work function of the cathode. Finally, impedance spectroscopy results prove that this layer is highly conductive.     

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.     

Performances of Liquid‐Exfoliated Transition Metal Dichalcogenides as Hole Injection Layers in Organic Light‐Emitting Diodes

2D transition metal dichalcogenide (TMD) nanosheets, including MoS₂, WS₂, and TaS₂, are used as hole injection layers (HILs) in organic light‐emitting diodes (OLEDs). MoS₂, WS₂, and TaS₂ nanosheets are prepared using an exfoliation by ultrasonication method. The thicknesses and sizes of the TMD nanosheets are measured to be 3.1–4.3 nm and more than 100 nm, respectively. The work functions of the TMD nanosheets increase from 4.4–4.9 to 4.9–5.1 eV following ultraviolet/ozone (UVO) treatment. The turn‐on voltages at 10 cd m^?2 for UVO‐treated TMD‐based devices decrease from 7.3–12.8 to 4.3–4.4 V and maximum luminance efficiencies increase from 5.74–9.04 to 12.01–12.66 cd A^?1. In addition, this study confirms that the stabilities of the devices in air can be prolonged by using UVO‐treated TMDs as HILs in OLEDs. These results demonstrate the great potential of liquid‐exfoliated TMD nanosheets for use as HILs in OLEDs.