High-efficiency phosphorescent polymer light-emitting devices

In this paper, we describe the performance of polymer light-emitting devices (PLEDs) that are based on phosphorescent polymers involving a carbazole unit and an iridium-complex unit. The PLEDs exhibit red, green or blue emission, depending on the phosphorescent polymer used in the emissive layer. We achieved highly external quantum efficiencies of 5.5%, 9% and 3.5% in respective red, green and blue PLEDs by selecting the electron transport material for the emissive layer and optimizing the content of the iridium-complex unit in the phosphorescent polymer chain. Furthermore, we demonstrated white emission in PLEDs by using blue-phosphorescent and red-phosphorescent polymers. An external quantum efficiency of 4.5% was obtained for this emission.     

Bright Blue Solution Processed Triple‐Layer Polymer Light‐Emitting Diodes Realized by Thermal Layer Stabilization and Orthogonal Solvents

The realization of fully solution processed multilayer polymer light‐emitting diodes (PLEDs) constitutes the pivotal point to push PLED technology to its full potential. Herein, a fully solution processed triple‐layer PLED realized by combining two different deposition strategies is presented. The approach allows a successive deposition of more than two polymeric layers without extensively redissolving already present layers. For that purpose, a poly(9,9‐dioctyl‐fluorene‐co‐N‐(4‐butylphenyl)‐diphenylamine) (TFB) layer is stabilized by a hard‐bake process as hole transport layer on top of poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). As emitting layer, a deep blue emitting pyrene‐triphenylamine copolymer is deposited from toluene solution. To complete the device assembly 9,9‐bis(3‐(5′,6′‐bis(4‐(polyethylene glycol)phenyl)‐[1,1′:4′,1″‐terphenyl]‐2′‐yl)propyl)‐9′,9′‐dioctyl‐2,7‐polyfluorene (PEGPF), a novel polyfluorene‐type polymer with polar sidechains, which acts as the electron transport layer, is deposited from methanol in an orthogonal solvent approach. Atomic force microscopy verifies that all deposited layers stay perfectly intact with respect to morphology and layer thickness upon multiple solvent treatments. Photoelectron spectroscopy reveals that the offsets of the respective frontier energy levels at the individual polymer interfaces lead to a charge carrier confinement in the emitting layer, thus enhancing the exciton formation probability in the device stack. The solution processed PLED‐stack exhibits bright blue light emission with a maximum luminance of 16 540 cd m^?2 and a maximum device efficiency of 1.42 cd A^?1, which denotes a five‐fold increase compared to corresponding single‐layer devices and demonstrates the potential of the presented concept.     

Langevin and Trap‐Assisted Recombination in Phosphorescent Organic Light Emitting Diodes

Bimolecular and trap‐assisted recombination mechanisms are investigated in small molecule‐based phosphorescent organic light emitting diodes (PhOLEDs) using the current?voltage?luminance characteristics in the diffusion current region, along with transient electroluminescence and capacitance measurements. Two different PhOLEDs, one with a single host, 4,4′‐Bis(carbazol‐9‐yl)biphenyl, and the other with an exciplex‐forming co‐host, are studied. Trap‐assisted recombination with a large number of trapped charges is dominant in the PhOLED with the single host because of the large energy gap between the host and the dopant state. In contrast, bimolecular Langevin recombination is dominant in the PhOLED with the exciplex forming co‐host, where a phosphorescent dye is doped in the co‐host. As a result, the accumulated charge density is lower in the co‐host system than in the single host emission layer, leading to high efficiency that approaches the theoretical limit, with an extremely low efficiency roll‐off.     

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.     

Dye Encapsulated Metal‐Organic Framework for Warm‐White LED with High Color‐Rendering Index

A strategy by encapsulating organic dyes into the pores of a luminescent metal‐organic framework (MOF) is developed to achieve white‐light‐emitting phosphor. Both the red‐light emitting dye 4‐(p‐dimethylaminostyryl)‐1‐methylpyridinium ( DSM ) and the green‐light emitting dye acriflavine ( AF ) are encapsulated into a blue‐emitting anionic MOF ZJU‐28 through an ion‐exchange process to yield the MOF?dye composite ZJU‐28?DSM/AF . The emission color of the obtained composite can be easily modulated by simply adjusting the amount and component of dyes. With careful adjustment of the relative concentration of the dyes DSM and AF , the resulting ZJU‐28?DSM/AF (0.02 wt% DSM , 0.06 wt% AF ) exhibits a broadband white emission with ideal CIE coordinates of (0.34, 0.32), high color‐rendering index value of 91, and moderate correlated color temperature value of 5327 K. Such a strategy can be easily expanded to other luminescent MOFs and dyes, thus opening a new perspective for the development of white light emitting materials.     

Efficient Charge Carrier Injection and Balance Achieved by Low Electrochemical Doping in Solution‐Processed Polymer Light‐Emitting Diodes

Charge carrier injection and transport in polymer light‐emitting diodes (PLEDs) is strongly limited by the energy level offset at organic/(in)organic interfaces and the mismatch in electron and hole mobilities. Herein, these limitations are overcome via electrochemical doping of a light‐emitting polymer. Less than 1 wt% of doping agent is enough to effectively tune charge injection and balance and hence significantly improve PLED performance. For thick single‐layer (1.2 µm) PLEDs, dramatic reductions in current and luminance turn‐on voltages (V_J = 11.6 V from 20.0 V and V_L = 12.7 V from 19.8 V with/without doping) accompanied by reduced efficiency roll‐off are observed. For thinner (<100 nm) PLEDs, electrochemical doping removes a thickness dependence on V_J and V_L, enabling homogeneous electroluminescence emission in large‐area doped devices. Such efficient charge injection and balance properties achieved in doped PLEDs are attributed to a strong electrochemical interaction between the polymer and the doping agents, which is probed by in situ electric‐field‐dependent Raman spectroscopy combined with further electrical and energetic analysis. This approach to control charge injection and balance in solution‐processed PLEDs by low electrochemical doping provides a simple yet feasible strategy for developing high‐quality and efficient lighting applications that are fully compatible with printing technologies.     

The Fabrication and Characterization of Single‐Component Polymeric White‐Light‐Emitting Diodes

By using Ni⁰‐mediated polymerization, we have systematically synthesized a series of fluorene‐based copolymers composed of blue‐, green‐, and red‐light‐emitting comonomers with a view to producing polymers with white‐light emission. 2,7‐Dibromo‐9,9‐dihexylfluorene, {4‐(2‐[2,5‐dibromo‐4‐{2‐(4‐diphenylamino‐phenyl)‐vinyl}‐phenyl]‐vinyl)‐phenyl}‐diphenylamine (DTPA), and 2‐{2‐(2‐[4‐{bis(4‐bromo‐phenyl)amino}‐phenyl]‐vinyl)‐6‐tert‐butyl‐pyran‐4‐ylidene}‐malononitrile (TPDCM) were used as the blue‐, green‐, and red‐light‐emitting comonomers, respectively. It was found that the emission spectra of the resulting copolymers could easily be tuned by varying their DTPA and TPDCM content. Thus with the appropriate red/green/blue (RGB) unit ratio, we were able to obtain white‐light emission from these copolymers. A white‐light‐emitting diode using the polyfluorene copolymer containing 3 % green‐emitting DTPA and 2 % red‐emitting TPDCM (PG3R2) with a structure of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonic acid)/PG3R2/Ca/Al was found to exhibit a maximum brightness of 820 cd m^–2 at 11 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.33,0.35), which are close to the standard CIE coordinates for white‐light emission (0.33,0.33).     

Toward Highly Efficient Solid‐State White Light‐Emitting Electrochemical Cells: Blue‐Green to Red Emitting Cationic Iridium Complexes with Imidazole‐Type Ancillary Ligands

Using imidazole‐type ancillary ligands, a new class of cationic iridium complexes ( 1 – 6 ) is prepared, and photophysical and electrochemical studies and theoretical calculations are performed. Compared with the widely used bpy (2,2′‐bipyridine)‐type ancillary ligands, imidazole‐type ancillary ligands can be prepared and modified with ease, and are capable of blueshifting the emission spectra of cationic iridium complexes. By tuning the conjugation length of the ancillary ligands, blue‐green to red emitting cationic iridium complexes are obtained. Single‐layer light‐emitting electrochemical cells (LECs) based on cationic iridium complexes show blue‐green to red electroluminescence. High efficiencies of 8.4, 18.6, and 13.2 cd A^?1 are achieved for the blue‐green‐emitting, yellow‐emitting, and orange‐emitting devices, respectively. By doping the red‐emitting complex into the blue‐green LEC, white LECs are realized, which give warm‐white light with Commission Internationale de L'Eclairage (CIE) coordinates of (0.42, 0.44) and color‐rendering indexes (CRI) of up to 81. The peak external quantum efficiency, current efficiency, and power efficiency of the white LECs reach 5.2%, 11.2 cd A^?1, and 10 lm W^?1, respectively, which are the highest for white LECs reported so far, and indicate the great potential for the use of these cationic iridium complexes in white LECs.     

Remote Biosensing with Polychromatic Optical Waveguide Using Blue Light‐Emitting Organic Nanowires Hybridized with Quantum Dots

Nanometer‐scale optical waveguides are attractive due to their potential applicability in photonic integration, optoelectronic communication, and optical sensors. Nanoscale white light‐emitting and/or polychromatic optical waveguides are desired for miniature white‐light generators in microphotonic circuits. Here, polychromatic (i.e., blue, green, and red) optical waveguiding characteristics are presented using a novel hybrid composite of highly crystalline blue light‐emitting organic nanowires (NWs) combined with blue, green, and red CdSe/ZnS quantum dots (QDs). Near white‐color waveguiding is achieved for organic NWs hybridized with green and red QDs. Light, emitted from QDs, can be transferred to the organic NW and then optically waveguided through highly packed π‐conjugated organic molecules in the NW with different decay characteristics. Remote biosensing using dye‐attached biomaterials is presented by adapting the transportation of QD‐emitted light through the organic NW.     

Alternating‐Current MXene Polymer Light‐Emitting Diodes

MXenes (Ti₃C₂) are 2D transition‐metal carbides and carbonitrides with high conductivity and optical transparency. However, transparent MXene electrodes suitable for polymer light‐emitting diodes (PLEDs) have rarely been demonstrated. With the discovery of the excellent electrical stability of MXene under an alternating current (AC), herein, PLEDs that employ MXene electrodes and exhibit high performance under AC operation (AC MXene PLEDs) are presented. The PLED exhibits a turn‐on voltage, current efficiency, and brightness of 2.1 V, 7 cd A^?1, and 12 547 cd m^?2, respectively, when operated under AC with a frequency of 1 kHz. The results indicate that the undesirable electric breakdown associated with heat arising from the poor interface of the MXene with a hole transport layer in the direct‐current mode is efficiently suppressed by the transient injection of carriers accompanied by the alternating change of the electric polarity under the AC, giving rise to reliable light emission with a high efficiency. The solution‐processable MXene electrode can be readily fabricated on a flexible polymer substrate, allowing for the development of a mechanically flexible AC MXene PLED with a higher performance than flexible PLEDs employing solution‐processed nanomaterial‐based electrodes such as carbon nanotubes, reduced graphene oxide, and Ag nanowires.     

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.     

Luminescent Poly(p‐phenylenevinylene) Hole‐Transport Layers with Adjustable Solubility

The active part of present polymer light‐emitting diodes (PLEDs) consists of only a single layer. Multilayer devices have the advantage that the electron and hole transport can be balanced and that the recombination can be removed from the metallic cathode, leading to higher efficiencies. A major problem for polymer‐based multilayer devices is the solubility of the materials used; a multilayer can not be fabricated when a spin‐cast layer dissolves in the solvent of the subsequent layer. We demonstrate the development of high‐mobility poly(p‐phenylenevinylene) (PPV)‐based hole‐transport layers with tunable solubility by chemical modification. Enhanced charge‐transport properties are achieved by using symmetrically substituted PPVs; copolymers of long and short side chains enable us to tune the solubility without loss of the enhanced charge transport. Dual‐layer PLEDs, in which the holes are efficiently transported via this copolymer towards the luminescent layer, exhibit an enhanced efficiency at high voltages (> 10 V) and a strongly improved robustness against electrical breakdown.     

Tuning the Emitting Color of Organic Light‐Emitting Diodes Through Photochemically Induced Transformations: Towards Single‐Layer,Patterned, Full‐Color Displays and White‐Lighting Applications

Photochemically induced emission tuning for the definition of pixels emitting the three primary colors, red, green, blue (RGB), in a single conducting polymeric layer is investigated. The approach proposed is based on an acid‐induced emission shift of the (1‐[4‐(dimethylamino)phenyl]‐6‐phenylhexatriene) (DMA‐DPH) green emitter and acid‐induced quenching of the red fluorescent emitter (4‐dimethylamino‐4′‐nitrostilbene) (DANS). The two emitters are dispersed in the wide bandgap conducting polymer poly(9‐vinylcarbazole) (PVK), along with a photoacid generator (PAG). In the unexposed film areas, red emission is observed because of efficient energy transfer from PVK and DMA‐DPH to DANS. Exposure of selected areas of the film at different doses results in quenching of the red emitter's fluorescence and the formation of green, blue, or even other color‐emitting pixels, depending on the exposure dose and the relative concentrations of the different compounds in the film. Organic light‐emitting diodes having the PVK polymer containing the appropriate amounts of DMA‐DPH, DANS, and PAG as the emitting layer are fabricated and electroluminescence spectra are recorded. The time stability of induced emission spectrum changes and the color stability during device operation are also examined, and the first encouraging results are obtained.     

The Effect of Ketone Defects on the Charge Transport and Charge Recombination in Polyfluorenes

The effect of on‐chain ketone defects on the charge transport of the polyfluorene derivative poly(9,9‐dioctylfluorene) (PFO) is investigated. Using MoO₃ as ohmic hole contact, the hole transport in a pristine PFO diode is observed to be limited by space‐charge, whereas fluorenone contaminated PFO (PFO‐F) is shown to be trap limited by the occurrence of an exponential trap distribution with a trap depth of 0.18 eV. The electron transport in PFO is also observed to be trap limited, but in order to describe the electron transport of PFO‐F, an additional trap level with a depth of 0.46 eV must be introduced. The obtained energy levels of the fluorenone trapping sites are in close agreement with cyclic voltammetry (CV) measurements reported in literature. As a result, the fluorenone defects are shown to simultaneously act as hole‐ and electron trap. Moreover, through ideality factor measurements, the green emission associated with these defects is observed to originate from trap‐assisted recombination.     

Cover Picture: White Electroluminescence from a Single‐Polymer System with Simultaneous Two‐Color Emission: Polyfluorene as the Blue Host and a 2,1,3‐Benzothiadiazole Derivative as the Orange Dopant (Adv. Funct. Mater. 7/2006)

New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized by Wang and co‐workers on p. 957. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue and orange emission from the corresponding emitting species. A single‐layer device has been fabricated that has performance characteristics roughly comparable to those of organic white‐light‐emitting diodes with multilayer device structures. New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue (λ_max = 421 nm/445 nm) and orange emission (λ_max = 564 nm) from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light‐emitting diodes (PLEDs) based on the single‐polymer systems has been investigated. The introduction of the highly efficient 4,7‐bis(4‐(N‐phenyl‐N‐(4‐methylphenyl)amino)phenyl)‐2,1,3‐benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single‐layer device fabricated in air (indium tin oxide/poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure‐white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m^–2, luminance efficiency of 7.30 cd A^–1, and power efficiency of 3.34 lm W^–1 can be obtained. This device is approximately two times more efficient than that utilizing a single polyfluorene containing 1,8‐naphthalimide moieties, and shows remarkable improvement over the corresponding blend systems in terms of efficiency and color stability. Thermal treatment of the single‐layer device before cathode deposition leads to the further improvement of the device performance, with CIE coordinates of (0.35,0.34), turn‐on voltage of 3.5 V, luminance efficiency of 8.99 cd A^–1, power efficiency of 5.75 lm W^–1, external quantum efficiency of 3.8 %, and maximum brightness of 12 680 cd m^–2. This performance is roughly comparable to that of white organic light‐emitting diodes (WOLEDs) with multilayer device structures and complicated fabrication processes.     

Fabrication of high efficiency and color stable white organic light-emitting diodes by an alignment free mask patterning

Small molecule based white organic light-emitting diodes were fabricated by using an alignment free mask patterning method. A phosphorescent red/green emitting layer was patterned by a metal mask without any alignment and a blue phosphorescent emitting layer was commonly deposited on the patterned red/green emitting layer. A white emission could be obtained due to separate emission of red/green and blue emitting layers. A maximum current efficiency of 30.7 cd/A and a current efficiency of 26.0 cd/A at 1000 cd/m² were obtained with a color coordinate of (0.39, 0.45). In addition, there was little change of emission spectrum according to luminance because of balanced red/green and blue emissions.     

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.     

Cyanocarbazole Derivatives for High‐Performance Electroluminescent Devices

3‐Cyano‐9‐diarylamino carbazoles have been synthesized. These new compounds emit in the blue to green region. Double‐layer electroluminescent devices using these compounds as the hole‐transport/emitting materials are highly efficient. Two of the compounds can be fabricated into single‐layer devices with good performance. Green‐ and blue‐emitting devices with good performance were also fabricated using one of the compounds as the hole‐injection layer.     

The role of exciplex states in phosphorescent OLEDs with poly(vinylcarbazole) (PVK) host

Polymer light emitting diodes (PLEDs) may revolutionize lighting and display industries. PLEDs would enable printing of display or lighting panels on large area substrates that could substantially reduce fabrication costs by avoiding expensive vacuum processes presently used in OLED technologies. PVK is one of the most popular hosts for blue PLEDs. However, PVK has very poor electron transport properties and oxadiazole based electron dopants, e.g. PBD or OXD-7, are used to improve charge transport. This is generally ascribed to capture and transport of electrons on the PBD or OXD-7. Here we show that this is not necessarily the only reason for improved efficiency upon PVK doping. We demonstrate that devices with PVK doped with PBD or OXD-7 have emission lasting up to 1 ms which in some cases may be greater than prompt emission from excitons formed initially on the dopant. This long-lived emission is arising mainly due to formation of an exciplex between the PVK and PBD/OXD-7. This exciplex state then repopulates dopant iridium complexes over a long period of time giving very long-lived emission. We also note that this exciplex-fed long-lived emission from heavy metal complexes is observed in several PLEDs with PBD and PVK (and also OXD-7) doped with blue or green iridium phosphors indicating this to be a general phenomenon.     

Precisely voltage tunable polymeric light emitting diodes by controlling polymer chemical oxidation and adding inorganic semiconducting nanoparticles. From blue to red stopping at white in the same device

We present a detailed study and experimental recipes to tune the outcoming light of single layer polymeric diodes fabricated with commercially available polyfluorene. The standard blue emission peaking at 440 nm can be tuned to obtain even white emission by controlling the deliberate oxidation of the material. Furthermore, with the addition of inorganic quantum dots was not only possible to redshift the emission as a function of the blend composition but also a fine tuning of the emitted light as a function of the external applied voltage. Merging these two effects we fabricated PFO and PFO:QD light emitting diodes that practically cover the entire visible spectrum. The same device exhibits emission from blue to red depending on the applied bias, from blue to green depending on the oxidation degree of the polymer and from white to blue and/or red combining both. The door is already open to cover the whole color gamut with solely one device.