Nanoparticle‐Enhanced Silver‐Nanowire Plasmonic Electrodes for High‐Performance Organic Optoelectronic Devices

Improved performance in plasmonic organic solar cells (OSCs) and organic light‐emitting diodes (OLEDs) via strong plasmon‐coupling effects generated by aligned silver nanowire (AgNW) transparent electrodes decorated with core–shell silver–silica nanoparticles (Ag@SiO₂NPs) is demonstrated. NP‐enhanced plasmonic AgNW (Ag@SiO₂NP–AgNW) electrodes enable substantially enhanced radiative emission and light absorption efficiency due to strong hybridized plasmon coupling between localized surface plasmons (LSPs) and propagating surface plasmon polaritons (SPPs) modes, which leads to improved device performance in organic optoelectronic devices (OODs). The discrete dipole approximation (DDA) calculation of the electric field verifies a strongly enhanced plasmon‐coupling effect caused by decorating core–shell Ag@SiO₂NPs onto the AgNWs. Notably, an electroluminescence efficiency of 25.33 cd A^?1 (at 3.2 V) and a power efficiency of 25.14 lm W^?1 (3.0 V) in OLEDs, as well as a power conversion efficiency (PCE) value of 9.19% in OSCs are achieved using hybrid Ag@SiO₂NP–AgNW films. These are the highest values reported to date for optoelectronic devices based on AgNW electrodes. This work provides a new design platform to fabricate high‐performance OODs, which can be further explored in various plasmonic and optoelectronic devices.     

Junction‐Free Electrospun Ag Fiber Electrodes for Flexible Organic Light‐Emitting Diodes

Fabrication of junction‐free Ag fiber electrodes for flexible organic light‐emitting diodes (OLEDs) is demonstrated. The junction‐free Ag fiber electrodes are fabricated by electrospun polymer fibers used as an etch mask and wet etching of Ag thin film. This process facilitates surface roughness control, which is important in transparent electrodes based on metal wires to prevent electrical instability of the OLEDs. The transmittance and resistance of Ag fiber electrodes can be independently adjusted by controlling spinning time and Ag deposition thickness. The Ag fiber electrode shows a transmittance of 91.8% (at 550 nm) at a sheet resistance of 22.3 Ω □^?1, leading to the highest OLED efficiency. In addition, Ag fiber electrodes exhibit excellent mechanical durability, as shown by measuring the change in resistance under repeatable mechanical bending and various bending radii. The OLEDs with Ag fiber electrodes on a flexible substrate are successfully fabricated, and the OLEDs show an enhancement of EQE (≈19%) compared to commercial indium tin oxide electrodes.     

Effect of Shell Coating Techniques on Dynamic Response of Photoconductive Core/Shell Nanorod Arrays

Efficient carrier collection in the core/shell nanowire (nanorod) arrays requires a high quality interface between core and shell materials. A highly conformal shell layer around nanorods can lead to fast dynamic response in photoconductive devices by a radial charge flow. Therefore, choice of the deposition technique for the conformal shell layer becomes crucial. In this study, the dynamic response of indium sulfide (In₂S₃) nanorods/silver (Ag) core/shell devices is compared in which Ag shell layers are deposited by different physical vapor deposition (PVD) techniques. In₂S₃ nanorods are fabricated by glancing angle deposition. The core/shell devices with Ag shell sputtered at a relatively high working gas pressure (≈3 × 10⁻² mbar) produce the highest photocurrent compared to other devices in which more directional incident flux (with working gas pressure of ≈3 × 10⁻³ mbar) is utilized for Ag shell layer. The reduced transit times indicate a conformal shell achieved by the high pressure sputtering technique that has a wide angular distribution flux. In addition, a more directional flux yet with a small angle (≈30°) incidence with respect to the substrate surface normal also helps increase the photocurrent. Such simple and scalable PVD techniques are shown to offer alternative fabrication approaches in producing high quality core/shell nanostructures.     

Efficient top-emitting organic light-emitting diodes with Sm/Ag bilayer cathode

A bilayer is used as a semitransparent cathode for top-emitting organic light emitting devices (top-emitting OLEDs). The bilayer cathode consists of samarium (Sm) and silver (Ag). Top-emitting OLEDs with the bilayer cathode showed enhanced current injection and high electroluminescence efficiency as compared with a Sm cathode. The maximum current efficiency of the top-emitting OLEDs with a Sm/Ag cathode is 9.9 cd/A, much greater than 4.9 cd/A obtained from the top-emitting OLEDs with a Sm cathode. The improved performance can be attributed to the balance between optical transparency and electrical conductivity of the Sm/Ag cathode.     

Blocking Energy‐Loss Pathways for Ideal Fluorescent Organic Light‐Emitting Diodes with Thermally Activated Delayed Fluorescent Sensitizers

Organic light‐emitting diodes (OLEDs) based on thermally activated delayed fluorescence‐sensitized fluorescence (TSF) offer the possibility of attaining an ultimate high efficiency with low roll‐off utilizing noble‐metal free, easy‐to‐synthesize, pure organic fluorescent emitters. However, the performances of TSF‐OLEDs are still unsatisfactory. Here, TSF‐OLEDs with breakthrough efficiencies even at high brightnesses by suppressing the competitive deactivation processes, including direct charge recombination on conventional fluorescent dopants (CFDs) and Dexter energy transfer from the host to the CFDs, are demonstrated. On the one hand, electronically inert terminal‐substituents are introduced to protect the electronically active core of the CFDs; on the other hand, delicate device structures are designed to provide multiple energy‐funneling paths. As a result, unprecedentedly high maximum external quantum efficiency/power efficiency of 24%/71.4 lm W^?1 in a green TSF‐OLED are demonstrated, which remain at 22.6%/52.3 lm W^?1 even at a high luminance of 5000 cd m^?2. The work unlocks the potential of TSF‐OLEDs, paving the way toward practical applications.     

Chiral Octahydro‐Binaphthol Compound‐Based Thermally Activated Delayed Fluorescence Materials for Circularly Polarized Electroluminescence with Superior EQE of 32.6% and Extremely Low Efficiency Roll‐Off

Circularly polarized organic light‐emitting diodes (CP‐OLEDs) are particularly favorable for the direct generation of CP light, and they demonstrate a promising application in 3D display. However, up to now, such CP devices have suffered from low brightness, insufficient efficiency, and serious efficiency roll‐off. In this study, a pair of octahydro‐binaphthol ( OBN )‐based chiral emitting enantiomers, (R/S)‐OBN‐Cz , are developed by ingeniously merging a chiral source and a luminophore skeleton. These chirality–acceptor–donor (C–A–D)‐type and rod‐like compounds concurrently generate thermally activated delayed fluorescence with a small ΔE_ST of 0.037 eV, as well as a high photoluminescence quantum yield of 92% and intense circularly polarized photoluminescence with dissymmetry factors (|g_PL|) of ≈2.0 × 10^?3 in thin films. The CP‐OLEDs based on (R/S)‐OBN‐Cz enantiomers not only display obvious circularly polarized electroluminescence signals with a |g_EL| of ≈2.0 × 10^?3, but also exhibit superior efficiencies with maximum external quantum efficiency (EQE_max) up to 32.6% and extremely low efficiency roll‐off with an EQE of 30.6% at 5000 cd m^?2, which are the best performances among the reported CP devices to date.     

Core/Shell ZnO/ZnS Nanoparticle Electron Transport Layers Enable Efficient All-Solution-Processed Perovskite Light-Emitting Diodes

Solution-processed perovskite-based light-emitting diodes (PeLEDs) are promising candidates for low-cost, large-area displays, while severe deterioration of the perovskite light-emitting layer occurs during deposition of electron transport layers from solution in an issue. Herein, core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer in PeLED based on quasi-2D PEA₂Cs_n−1Pb_nBr_3n+1 (PEA = phenylethylammonium) perovskite are employed. The deposition of ZnS shell mitigates trap states on ZnO core by anchoring sulfur to oxygen vacancies, and at the same time removes residual hydroxyl groups, which helps to suppress the interfacial trap-assisted non-radiative recombination and the deprotonation reaction between the perovskite layer and ZnO. The core/shell ZnO/ZnS nanoparticles show comparably high electron mobility to pristine ZnO nanoparticles, combined with the reduced energy barrier between the electron transport layer and the perovskite layer, improving the charge injection balance in PeLEDs. As a result, the optimized PeLEDs employing core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer exhibit high peak luminance reaching 32 400 cd m⁻², external quantum efficiency of 10.3%, and 20-fold extended longevity as compared to the devices utilizing ZnO nanoparticles, which represents one of the highest overall performances for solution-processed PeLEDs.     

Understanding and Manipulating the Interplay of Wide‐Energy‐Gap Host and TADF Sensitizer in High‐Performance Fluorescence OLEDs

Comprising an emitting layer (EML) constituting a wide‐energy‐gap host, a thermally activated delayed fluorescence (TADF) sensitizer and a conventional fluorescent dopant, TADF‐sensitizing‐fluorescence organic light‐emitting diodes (TSF‐OLEDs) highly depend on component interplay to maximize their performance, which, however, is still under‐researched. Taking the host type (TADF or non‐TADF) and the recombination position (on the host or on the TADF sensitizer) into consideration, the interplay of host and TADF sensitizer is comprehensively studied and manipulated. A wide‐energy‐gap host with TADF and recombination of charges on it are both required to maximize device performances by triggering multiple sensitizing processes to eliminate exciton losses. Based on those findings, a maximum external quantum efficiency (EQE)/power efficiency (PE) of 23.2%/76.9 lm W^?1 is realized with a newly developed TADF host, significantly outperforming the reference devices. Further device optimization leads to unprecedently high EQE/PE of 24.2%/89.5 lm W^?1 and a half‐lifetime of over 400 h at an initial luminance of 2000 cd m^?2, with the peak PE being the highest value among the reported TSF‐OLEDs. This work reveals the importance of manipulating the component interplay in EMLs, opening a new avenue toward highly efficient TSF‐OLEDs.     

OLEDs: Degradation Mechanisms in Small‐Molecule and Polymer Organic Light‐Emitting Diodes (Adv. Mater. 34/2010)

Degradation in organic light‐emitting diodes (OLEDs) is a complex problem. Depending upon the materials and the device architectures used, the degradation mechanism can be very different. In this Progress Report, using examples in both small molecule and polymer OLEDs, the different degradation mechanisms in two types of devices are examined. Some of the extrinsic and intrinsic degradation mechanisms in OLEDs are reviewed, and recent work on degradation studies of both small‐molecule and polymer OLEDs is presented. For small‐molecule OLEDs, the operational degradation of exemplary fluorescent devices is dominated by chemical transformations in the vicinity of the recombination zone. The accumulation of degradation products results in coupled phenomena of luminance‐efficiency loss and operating‐voltage rise. For polymer OLEDs, it is shown how the charge‐transport and injection properties affect the device lifetime. Further, it is shown how the charge balance is controlled by interlayers at the anode contact, and their effects on the device lifetime are discussed.     

Continuous and Controllable Liquid Transfer Guided by a Fibrous Liquid Bridge: Toward High‐Performance QLEDs

Solution processing is widely used for preparing quantum dot (QD) films for fabricating QD light‐emitting diode display (QLED) devices. However, current approaches suffer from either the coffee‐ring effect or a large amount of wasted solution, leading to low performance and high cost. Here, a facile approach guided by a fibrous liquid bridge is developed for the continuous and controllable transfer of QD solution into ultrasmooth films by using a taut fiber with its two ends placed into capillary tubes. Guided along the fiber, a liquid bridge is formed between the horizontal fiber and the substrate, with a large mass of liquid steadily being held within the vertically placed tubes. Directionally moving the liquid bridge generates a high‐quality QD film on the substrate. Particularly, the liquid consumption is quantitative, namely, in proportion to the area of the as‐prepared film. Moreover, multilayered ultrasmooth red/green/blue QD films are prepared by multiple transfers of liquid onto the same targeted area in sequence. The as‐prepared white QLEDs show a rather high performance with a maximum luminance of 57 190 cd m^?2 and a maximum current efficiency of 15.868 cd A^?1. It is envisioned that this strategy offers new perspectives for the low‐cost fabrication of high‐performance QLED devices.     

Air‐Stable and High‐Performance Solution‐Processed Organic Light‐Emitting Devices Based on Hydrophobic Polymeric Ionic Liquid Carrier‐Injection Layers

A lot of research, mostly using electron‐injection layers (EILs) composed of alkali‐metal compounds has been reported with a view to increase the efficiency of solution‐processed organic light‐emitting devices (OLEDs). However, these materials have intractable properties, such as a strong affinity for moisture, which cause the degradation of OLEDs. Consequently, optimal EIL materials should exhibit high electron‐injection efficiency as well as be stable in air. In this study, polymer light‐emitting devices (PLEDs) based on the commonly used yellow‐fluorescence‐emitting polymer F8BT, which utilize poly(diallyldimethylammonium)‐based polymeric ionic liquids, are experimentally and analytically investigated. As a result, the optimized PLED employing an EIL comprising poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (poly(DDA)TFSI), which is expected to display good moisture resistance because of water repellency of fluorocarbon groups, exhibits excellent storage stability in air and electroluminescence performance with a low turn‐on voltage of 2.01 V, maximum external quantum efficiency of 9.00%, current efficiency of 30.1 cd A^?1, and power efficiency of 32.4 lm W^?1. The devices with poly(DDA)TFSI show one of the highest efficiencies as compared to the reported standard PLEDs. Moreover, poly(DDA)TFSI is applied as a hole‐injection layer (HIL). The optimized PLED using poly(DDA)TFSI as the HIL exhibits performances comparable to those of a device that uses a conventional poly(3,4‐ethylenedioxy‐thiophene):poly(4‐styrenesulfonate) HIL.     

High efficiency in blue organic light-emitting diodes using an anthracene-based emitting material

A highly efficient deep blue emitting material based on anthracene core structure, 9,10-bis-[4-(2-(4-naphthalene-1-yl-phenyl)-vinyl)-phenyl]anthracene (NSA), was synthesized and the device performances of blue organic light-emitting diodes (OLEDs) with NSA as an emitting material were investigated. High efficiency value of 7.75 Candela (cd)/A was obtained in NSA blue devices compared with 3.6 cd/A of 9,10-bis(4-(2,2-diphenylvinyl)phenyl anthracene devices. The introduction of a phenylanthracene core and a rigid naphthylphenyl side group gave high thermal stability due to non-coplanar structure and limited intermolecular interactions, resulting in high efficiency in blue OLEDs.     

High‐Performance Fluorescent Organic Light‐Emitting Diodes Utilizing an Asymmetric Anthracene Derivative as an Electron‐Transporting Material

Fluorescent organic light‐emitting diodes with thermally activated delayed fluorescent sensitizers (TSF‐OLEDs) have aroused wide attention, the power efficiencies of which, however, are limited by the mutual exclusion of high electron‐transport mobility and large triplet energy of electron‐transporting materials (ETMs). Here, an asymmetric anthracene derivative with electronic properties manipulated by different side groups is developed as an ETM to promote TSF‐OLED performances. Multiple intermolecular interactions are observed, leading to a kind of “cable‐like packing” in the crystal and favoring the simultaneous realization of high electron‐transporting mobility and good exciton‐confinement ability, albeit the low triplet energy of the ETM. The optimized TSF‐OLEDs exhibit a record‐high maximum external quantum efficiency/power efficiency of 24.6%/76.0 lm W^?1, which remain 23.8%/69.0 lm W^?1 at a high luminance of even 5000 cd m^?2 with an extremely low operation voltage of 3.14 V. This work opens a new paradigm for designing ETMs and also paves the way toward practical application of TSF‐OLEDs.     

Enhanced Electroluminescence from Organic Light‐Emitting Diodes with an Organic–Inorganic Perovskite Host Layer

The development of host materials with high performance is essential for fabrication of efficient and stable organic light‐emitting diodes (OLEDs). Although host materials used in OLEDs are typically organics, in this study, it is shown that the organic–inorganic perovskite CH₃NH₃PbCl₃ (MAPbCl₃) can be used as a host layer for OLEDs. Vacuum‐evaporated MAPbCl₃ films have a wide band gap of about 3 eV and very high and relatively balanced hole and electron mobilities, which are suitable for the host material. Photoluminescence and electroluminescence take place through energy transfer from MAPbCl₃ to an organic emitter in films. Incorporation of an MAPbCl₃ host layer into OLEDs leads to a reduction of driving voltage and enhancement of external quantum efficiency as compared to devices with a conventional organic host layer. Additionally, OLEDs with an MAPbCl₃ host layer demonstrate very good operational stability under continuous current operation. These results can be extensively applied to organic‐ and perovskite‐based optoelectronics.     

“Quasi‐freestanding” Graphene‐on‐Single Walled Carbon Nanotube Electrode for Applications in Organic Light‐emitting Diode

An air‐stable transparent conductive film with “quasi‐freestanding” graphene supported on horizontal single walled carbon nanotubes (SWCNTs) arrays is fabricated. The sheet resistance of graphene films stacked via layer‐by‐layer transfer (LBL) on quartz, and modified by 1‐Pyrenebutyric acid N‐hydroxysuccinimide ester (PBASE), is reduced from 273 Ω/sq to about 76 Ω/sq. The electrical properties are stable to heat treatment (up to 200 ºC) and ambient exposure. Organic light‐emitting diodes (OLEDs) constructed of this carbon anode (T ≈ 89.13% at 550 nm) exhibit ≈88% power efficiency of OLEDs fabricated on an ITO anode (low turn on voltage ≈3.1 eV, high luminance up to ≈29 490 cd/m², current efficiency ≈14.7 cd/A). Most importantly, the entire graphene‐on‐SWCNT hybrid electrodes can be transferred onto plastic (PET) forming a highly‐flexible OLED device, which continues to function without degradation in performance at bending angles >60°.     

3D/2D Core/Shell Perovskite Nanocrystals for High-Performance Solar Cells

All-inorganic lead halide perovskite nanocrystals (NCs) emerge as a rising star in photovoltaic fields on account of their excellent optoelectronic properties. However, it still remains challenging to further promote photovoltaic efficiency due to the susceptible surface and inevitable vacancies. Here, this work reports a 3D/2D core/shell perovskite heterojunction based on CsPbI₃ NCs and its performance in solar cells. The guanidinium (GA⁺) rich 2D nanoshells can significantly passivate surface trap states and lower the capping ligand density, resulting in improved photoelectric properties and carrier transport and diminished nonradiative recombination centers via the hydrogen bonds from amino groups in GA⁺ ions. Consequently, an outstanding power conversion efficiency (PCE) of up to 15.53% is realized, substantially higher than the control device (13.77%). This work highlights the importance of surface chemistry and offers a feasible avenue to achieve high-performance perovskite NCs-based optoelectronic devices.     

Blue fluorescent organic light emitting diodes with multilayered graphene anode

As an innovative anode for organic light emitting devices (OLEDs), we have investigated graphene films. Graphene has importance due to its huge potential in flexible OLED applications. In this work, graphene films have been catalytically grown and transferred to the glass substrate for OLED fabrications. We have successfully fabricated 2 mm × 2 mm device area blue fluorescent OLEDs with graphene anodes which showed 2.1% of external quantum efficiency at 1000 cd/m². This is the highest value reported among fluorescent OLEDs using graphene anodes. Oxygen plasma treatment on graphene has been found to improve hole injections in low voltage regime, which has been interpreted as oxygen plasma induced work function modification. However, plasma treatment also increases the sheet resistance of graphene, limiting the maximum luminance. In summary, our works demonstrate the practical possibility of graphene as an anode material for OLEDs and suggest a processing route which can be applied to various graphene related devices.     

Rare‐Earth‐Element‐Ytterbium‐Substituted Lead‐Free Inorganic Perovskite Nanocrystals for Optoelectronic Applications

Lead‐(Pb‐) halide perovskite nanocrystals (NCs) are interesting nanomaterials due to their excellent optical properties, such as narrow‐band emission, high photoluminescence (PL) efficiency, and wide color gamut. However, these NCs have several critical problems, such as the high toxicity of Pb, its tendency to accumulate in the human body, and phase instability. Although Pb‐free metal (Bi, Sn, etc.) halide perovskite NCs have recently been reported as possible alternatives, they exhibit poor optical and electrical properties as well as abundant intrinsic defect sites. For the first time, the synthesis and optical characterization of cesium ytterbium triiodide (CsYbI₃) cubic perovskite NCs with highly uniform size distribution and high crystallinity using a simple hot‐injection method are reported. Strong excitation‐independent emission and high quantum yields for the prepared NCs are verified using photoluminescence measurements. Furthermore, these CsYbI₃ NCs exhibit potential for use in organic–inorganic hybrid photodetectors as a photoactive layer. The as‐prepared samples exhibit clear on–off switching behavior as well as high photoresponsivity (2.4 × 10³ A W^?1) and external quantum efficiency (EQE, 5.8 × 10⁵%) due to effective exciton dissociation and charge transport. These results suggest that CsYbI₃ NCs offer tremendous opportunities in electronic and optoelectronic applications, such as chemical sensors, light emitting diodes (LEDs), and energy conversion and storage devices.     

Degradation Mechanisms in Small‐Molecule and Polymer Organic Light‐Emitting Diodes

Degradation in organic light‐emitting diodes (OLEDs) is a complex problem. Depending upon the materials and the device architectures used, the degradation mechanism can be very different. In this Progress Report, using examples in both small molecule and polymer OLEDs, the different degradation mechanisms in two types of devices are examined. Some of the extrinsic and intrinsic degradation mechanisms in OLEDs are reviewed, and recent work on degradation studies of both small‐molecule and polymer OLEDs is presented. For small‐molecule OLEDs, the operational degradation of exemplary fluorescent devices is dominated by chemical transformations in the vicinity of the recombination zone. The accumulation of degradation products results in coupled phenomena of luminance‐efficiency loss and operating‐voltage rise. For polymer OLEDs, it is shown how the charge‐transport and injection properties affect the device lifetime. Further, it is shown how the charge balance is controlled by interlayers at the anode contact, and their effects on the device lifetime are discussed.     

CdS@SiO2 Core–Shell Electroluminescent Nanorod Arrays Based on a Metal–Insulator–Semiconductor Structure

Enormous advancement has been achieved in the field of one‐dimensional (1D) semiconductor light‐emitting devices (LEDs), however, LEDs based on 1D CdS nanostructures have been rarely reported. The fabrication of CdS@SiO₂ core–shell nanorod array LEDs based on a Au–SiO₂–CdS metal–insulator–semiconductor (MIS) structure is presented. The MIS LEDs exhibit strong yellow emission with a low threshold voltage of 2.7 V. Electroluminescence with a broad emission ranging from 450 nm to 800 nm and a shoulder peak at 700 nm is observed, which is related to the defects and surface states of the CdS nanorods. The influence of the SiO₂ shell thickness on the electroluminescence intensity is systematically investigated. The devices have a high light‐emitting spatial resolution of 1.5 μm and maintain an excellent emission property even after shelving at room temperature for at least three months. Moreover, the fabrication process is simple and cost effective and the MIS device could be fabricated on a flexible substrate, which holds great potential for application as a flexible light source. This prototype is expected to open up a new route towards the development of large‐scale light‐emitting devices with excellent attributes, such as high resolution, low cost, and good stability.