Fluoropolymer-assisted graphene electrode for organic light-emitting diodes

Organic light-emitting diodes (OLEDs) were fabricated on a graphene electrode, with synthesized graphene being transferred and simultaneously doped with supporting polymers. Poly[methyl methacrylate] (PMMA) and fluoropolymer (CYTOP) layers were used as the supporting polymers. The sheet resistance of CYTOP-assisted graphene (CYTOP-G) with 4 layers of graphene is 200 Ω/sq., which is lower than that of PMMA-assisted graphene (PMMA-G, 330 Ω/sq.) The transmittance value of PMMA-G and CYTOP-G with 4 graphene layers is higher than 85%. CYTOP-G is shown to exhibit a higher tolerance to UV–O₃ treatment and thermal annealing than PMMA-G. Work function of CYTOP-G is 4.7 eV, which is higher than that of PMMA-G (4.3 eV). X-ray photoemission and Raman spectroscopy data indicate that CYTOP-G has numerous C-F bonds on the surface exhibiting p-type semiconductor properties, owing to the high electronegativity of fluorine. The turn-on voltage of an OLED based on CYTOP-G with 4 graphene layers is 4.2 V, which is lower than that of indium tin oxide (ITO)-based one (4.5 eV). Furthermore, the luminance ratio of graphene-based OLEDs to ITO-based OLEDs was calculated to be 104% for CYTOP-G, and 97% for PMMA-G. According to the ultraviolet photoemission spectra, the hole injection barrier in CYTOP-G is lower by about 0.5 eV than the hole injection barrier in PMMA-G. These results are very encouraging to the prospect of replacing ITO electrodes with graphene ones in OLED applications.     

Soft fabric-based flexible organic light-emitting diodes

We reported the first organic light-emitting diodes (OLEDs) on actual soft fabrics that can be used for a wearable display. Polyurethane (PU) and poly(vinyl alcohol) (PVA) layers, which only degrade slightly the flex stiffness of bare fabrics due to their ductile characteristics, were used as planarization layers via a simple fabrication process involving lamination and spin-coating. Therefore, many of the mechanical characteristics of the bare fabric substrates were retained in the planarized fabric substrates. Non-inverted top-emitting OLEDs, designed by considering the optical microcavity effects, were fabricated on a planarized surface by thermal evaporation. The fabricated OLEDs on soft fabrics showed a high current efficiency of around 8 cd/A, reliability during a 1000 cycle bending test with a bending radius of 5 mm, and clear green emission up to an emission angle of 70°. Consequently, we developed high-performance OLEDs on very similar to real fabric via a simple universalized fabrication method.     

Heat evolution and dissipation in organic light-emitting diodes on flexible polymer substrates

We investigated the effect of the heat generated in organic light-emitting diodes (OLEDs) on their performance with a focus on the thermo-physical properties of the substrates. OLEDs were fabricated on polyethylene terephthalate (PET), polyimide (PI), and glass substrates, and the instantaneous and time-resolved performances of the OLEDs were compared. The device operation temperature (T) was predicted via heat transfer analysis using the finite element method (FEM). The value of T during operation was experimentally measured using an infrared (IR) camera, and the results were compared with the numerically calculated values. The effects of T on the time-resolved electroluminescence (EL) spectra of the OLEDs on the different substrates were also investigated. The experimental results of this study agreed well with the numerical predictions that the T of the OLEDs on the polymers are higher than the T of the OLEDs on glass during operation due to the relatively low thermal diffusivity (α) of the polymer substrates used in this study. The results also showed that the performance and reliability of the flexible OLEDs (f-OLED) are highly dependent on the heat extraction capabilities of the substrates; thus, the current density (J), luminescence (L), voltage (V) characteristics, and efficiencies (η) over time of the OLEDs on PET and PI are inferior to the OLEDs on the glass substrate.     

Fabrication of flexible conductive graphene/Ag/Al-doped zinc oxide multilayer films for application in flexible organic light-emitting diodes

Graphene/Ag/Al-doped zinc oxide (AZO) multilayer films were fabricated by using chemical vapor deposition and magnetron sputtering methods. The electrical and optical properties of the transparent conductive graphene/Ag/AZO films were investigated. The graphene/Ag/AZO film can maintain high conductivity and transmittance without obvious degradation during bending test. A green flexible organic light emitting diode with a structure of graphene/Ag/AZO/N,N-diphenyl-N,N-bis(1-napthyl)-1,1-biphenyl-4,4-diamine/tris(8-hydroxyquinoline) aluminum(III)/lithium fluoride/Al exhibited a stable green emission and light-emitting efficiency during the cycle bending test. The multilayer films hold promise for application in flexible optoelectronic devices.     

Efficient,color-stable flexible white top-emitting organic light-emitting diodes

Flexible white top-emitting organic light-emitting diodes (WTEOLEDs) with red and blue phosphorescent dual-emitting layers were fabricated onto polyethylene terephthalate (PET) substrates. By inserting a 2-nm thin tris(phenypyrazole)iridium between the red and the blue emitters as an electron/exciton blocking layer, significant improvements on luminous efficiency and color stability were observed, reaching 9.9 cd/A (3.74 lm/W) and a small chromaticity change of (0.019, 0.011) in a wide luminance range of 80–5160 cd/m². The origin on color stability was explored by analyzing the electroluminescent spectra, the time-resolved transient photoluminescence decay lifetimes of phosphors, and the tunneling phenomenon. In addition, mechanical bending lifetimes in WTEOLEDs with spin-coated     

基于纳米压印PET基底的高效柔性有机电致发光器件

为了克服现有的以玻璃为基底、ITO为电极的有机电致发光器件（OLED）的韧性差、对裂纹缺陷敏感等固有缺点,对现有的OLED器件结构进行优化。本文提出了以PET为基底,旋涂高导PEDOT：PSS作为阳极的高效柔性OLED器件结构。并在此基础上,通过纳米压印蛾眼模板将光耦合结构引入器件,提高器件的光取出效率。此绿光FOLED器件在亮度为1 000 cd·m^-2时,功率效率为36.10 lm·W^-1。在此基础上,通过纳米压印引入光耦合结构的柔性OLED器件表现出良好的光电性质,在亮度为1 000 cd·m^-2时,功率效率可达到80.46 lm·W^-1。并且这种绿光柔性OLED器件在以器件半边长为曲率半径180°弯折200次后亮度衰减很少。此种高导PEDOT：PSS电极和柔性PET基底可以成为较好的ITO透明电极和刚性玻璃基底的替代物,为生产可穿戴式设备提供了可能。     

基于石墨烯的柔性黄光有机发光二极管制备与性能

采用喷涂技术制备了石墨烯/PEDOT:PSS复合透明导电薄膜,并在此基础上制备了柔性黄光OLED器件。通过设计DPVBi/Rubrene/DPVBi势阱结构,可以实现电荷的有效陷获,获得稳定明亮的黄光发射。实验结果表明,适当增加发光区的厚度,可以提升器件的发光效率和稳定性,在12 V时器件的效率为0.9 cd/A。该柔性黄光OLED器件在反复弯曲测试中表现出了良好的发光稳定性,发光效率没有产生明显变化。     

Research on flexible silver nanowire electrode for organic light-emitting devices

By spin-coating silver nanowires(AgNWs) and polymethyl methacrylate(PMMA), applying pressure imprint and plasma treatment, we obtained flat Ag NW thin film with a sheet resistance of 20 Ω/sq and a transmittance of 78% at 550 nm with low surface roughness. No significant change in sheet resistance was observed after cyclic bending(bending radius is 5 mm) test and tape test. After 1 000 bending tests, the change rate of sheet resistance was only 8.3%. The organic light-emitting devices(OLEDs) were prepared by using such Ag NW electrodes and a maximum brightness of 5 090 cd/m² was obtained. Compared with the Ag NWs electrode without any treatment, the present Ag NW electrodes have lower sheet resistance and better hole injection. Our results show spin-coated with flat layers, embossed and plasma-treated Ag NW electrodes are suitable for manufacturing flexible organic optoelectronic devices.     

Inverted top-emitting organic light-emitting diodes by whole device transfer

We present a method for improving the efficiency of charge carrier injection at both cathode and anode of inverted top-emitting organic light-emitting diode (TOLED). In this method, a bottom-emitting OLED (BOLED) is first fabricated on a flexible substrate, which is then transferred as a whole to a glass substrate for the fabrication of the inverted TOLED (ITOLED). The electrode engineering that is responsible for the improvement, which is not possible in the traditional fabrication of ITOLED, is made realizable by the whole device transfer.     

Ultrasmooth,highly conductive and transparent PEDOT:PSS/silver nanowire composite electrode for flexible organic light-emitting devices

The next generation of optoelectronic devices requires transparent conductive electrodes to be flexible, inexpensive and compatible with large scale manufacturing processes. We report an ultrasmooth, highly conductive and transparent composite electrode on a flexible photopolymer substrate by employing a template stripping method. A random silver nanowire (AgNW) network buried in poly(3,4ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film constituted the composite electrode. Besides the effectively decreased surface roughness, its sheet resistance and transmittance are comparable to those of conventional PEDOT:PSS electrode. As a result, the efficiency of the OLEDs based on the composite electrode exhibited 25% enhancement compared to the OLEDs with conventional PEDOT:PSS electrode. Moreover, the performance of the flexible OLEDs remains stable after over one hundred bending cycles.     

Hole injection polymer effect on degradation of organic light-emitting diodes

Polythienothiophene:poly(perfluoroethylene-perfluoroethersulfonic acid) (PTT:PFFSA) has been used to enhance hole injection into small molecule OLEDs. Compared to devices with polyethylene dioxythiophene polystyrene sulfonate (PEDOT:PSS) as the hole injection layer (HIL), the OLED using PTT:PFFSA as a HIL gives enhanced efficiency and a slower luminance decay as well as a slower rise in operating voltage. Further studies of capacitance–voltage characteristics reveal that positive trapped charges accumulate in the hole transporting layer during operation. These results thus highlight the significance of hole injection layer to OLED operational stability.     

CMOS-compatible organic light-emitting diodes

We report a new method for the integration of light-emitting devices on a silicon substrate. As an active layer, we use unsubstituted PPV or PPV-based organic macromolecules with a p⁺-silicon anode and a cathode made from aluminum or titanium. The polymer is deposited by spin-coating the precursor, followed by a thermal conversion step to form the macromolecules. All process steps, including the possibility of dry etching of the active layer and the upper electrode, are typical for MOS technology. Spectrum analysis, current-voltage, and intensity measurements have been carried out for device characterization. These organic light-emitting diodes allow the monolithic integration of microelectronic circuits and light-emitting devices on one silicon chip applying only typical MOS process steps     

Enhanced outcoupling in flexible organic light-emitting diodes on scattering polyimide substrates

We demonstrate an upscalable approach to increase outcoupling in organic light-emitting diodes (OLEDs) fabricated on flexible substrates. The outcoupling enhancement is enabled by introducing a thin film of microporous polyimide on the backside of silver nanowire (AgNW) electrodes embedded in neat colorless polyimide. This porous polyimide film, prepared by immersion precipitation, utilizes a large index contrast between the polyimide host and randomly distributed air voids, resulting in broadband haze (>75%). In addition, the composite polyimide/AgNW scattering substrate inherits the high thermal (>360 °C), chemical, and mechanical stability of polyimides. The outcoupling efficiency of the composite scattering substrate is studied via optical characterization of the composite substrate and electron microscopy of the scattering film. The flexible scattering substrates compared to glass/indium tin oxide (ITO) allows for a 74% enhancement in external quantum efficiency (EQE) for a phosphorescent green OLED, and 68% EQE enhancement for a phosphorescent white OLED. The outcoupling enhancement remains unharmed after 5000 bending cycles at a 2 mm bending radius. Moreover, the color uniformity over viewing angles is improved, an important feature for lighting applications.     

Low resistive transparent and flexible ZnO/Ag/ZnO/Ag/WO3 electrode for organic light-emitting diodes

Transparent electrodes cannot easily be created with high transmittance and low sheet resistance simultaneously, although some optoelectronic devices, such as large organic light-emitting diode (OLED) displays and lightings, require very low resistive transparent electrodes. Here, we propose a very low resistive transparent electrode (～1.6 Ω/sq) with a high transmittance (～75%) for OLED devices, the transmittance level of which represents the highest reported value to date given such a low sheet resistance level. It consists of a stacked silver (Ag)/zinc oxide (ZnO)/Ag multilayer covered by high refractive index dielectric layers. The proposed multilayer electrode with optimal layer thicknesses has a high and wide spectral transmittance peak due to interference. The low sheet resistance is a result of two Ag layers connected via the sandwiched ZnO layer. In addition to its low sheet resistance coupled with high transmittance, the proposed multilayer electrode has good flexibility. An OLED with an anode of the stacked Ag/ZnO/Ag multilayer shows performance comparable to that of an anode of indium tin oxide.     

Enhancement of red organic light-emitting diodes via cascade energy transfer

We have demonstrated that efficient red electroluminescence is obtained via cascade energy transfer from Alq to fluorescent dye Coumarin(C545) and then from C545 to 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB). The cell structure was indium tin oxide (ITO)/ N,N′-bis-(1-naphenyl)-N,N′-biphenyl-1,1′-bipheny1-4-4′-diamine (NPB)/ tris (8-hydroxyquinoline) aluminum (Alq): C545: DCJTB/Alq/LiF/Al. An additional dopant, C545, was used to assist the energy transfer from Alq to the red dopant. Compared with the devices where the emitting layer is only composed of Alq and DCJTB, the emission efficiency and color purity were improved. We attribute these improvements to the assistant dopant C545 which leads to the more efficient energy transfer from Alq to DCJTB. The co-doping system is a promising method for red organic light-emitting diodes.     

Stability of polymer light-emitting diodes

In this paper, we report on the lifetime of polymer LEDs fabricated at Philips Research. For single-layer LEDS, we find that the operational lifetime in nitrogen gas is limited by the stability of the indium-tin-oxide (ITO) anode. By using a polymeric capping layer for the ITO, we obtain more stable devices. In air, the lifetime is limited by black spot formation. Small pinholes in the cathode layer are the origins of the black spots. Water or oxygen may diffuse through these pinholes and react with the cathode, causing degradation. By encapsulating the devices we can prevent black spot formation. Our present 8 cm² devices have lifetimes of many thousands of hours at daylight visibility under ambient conditions.     

Phthalonitrile based charge transfer type host for yellow phosphorescent organic light-emitting diodes

An phthalonitrile based 3,3''-di(9H-carbazol-9-yl)-[1,1':2′,1''-terphenyl]-4′,5′-dicarbonitrile (IPNCz) was explored as a charge transfer type host of a yellow emitting bis(4-phenyl-thieno[3,2-c]pyridinato-C2,N)(acetylacetonato)iridium(III) (PO-01) dopant. The phthalonitrile unit was an electron deficient unit and 9-phenylcarbazole was an electron rich unit of the IPNCz host. The phthalonitrile unit combined with the phenylcarbazole unit allowed strong charge transfer character by the donor-acceptor structure, delivering good thermal stability, bipolar carrier transport and proper triplet energy. Therefore, the IPNCz host assisted low driving voltage and high quantum efficiency close to 25% in the yellow phosphorescent device.     

Features of the current-voltage characteristics in thin conductive layers of organic light-emitting diodes

The current-voltage characteristic of a thin organic layer located between conductive electrodes is analytically modeled. To this end, a theoretical model is developed which considers not only the interaction of an injected carrier with its mirror charge “reflected” in the nearest electrode, but also the effect of multiple reflections and the injection current from the opposite electrode. The current-voltage characteristics at various temperatures and barrier heights are compared to the model previously developed by Arkhipov et al. The limits of applicability of this model are determined. At low temperatures and voltages, the effect of multiple reflections becomes significant, which cause an increase in the current. These results should be considered when testing individual thin layers constituting multilayer organic light-emitting diodes.     

High efficiency ITO-free flexible white organic light-emitting diodes based on multi-cavity technology

The technology of white organic light-emitting diodes (WOLEDs) is attracting growing interest due to their potential application in indoor lighting. Nevertheless the simultaneous achievement of high luminous efficacy (LE), high color rendering index (CRI), very low manufacturing costs and compatibility with flexible thin substrates is still a great challenge. Indeed, very high efficiency devices show usually low values of CRI, not suitable for lighting applications, and use expensive indium tin oxide (ITO) electrodes which are not compatible with low cost and/or flexible products. Here we show a novel low cost ITO-free WOLED structure based on a multi-cavity architecture with increased photonic mode density and still broad white emission spectrum, which allows for simultaneous optimization of all device characteristics. Without using out-coupling optics or high refractive index substrates, CRI of 85 and LE as high as 33 lm W⁻¹ and 14 lm W⁻¹ have been demonstrated on ITO-free glass and flexible substrates, respectively.     

Highly efficient ITO-free organic light-emitting diodes employing a roughened ultra-thin silver electrode

We investigated an efficient organic light-emitting diodes (OLEDs) using an ultra-thin silver (Ag) anode, whereas Ag was deposited on a roughened glass substrate by laser patterning method. The thin-film property of this roughened silver anode exhibited an optical transmittance of more than 65% in visible light at 532 nm and a low electrical sheet resistance of 3.2 Ω/sq, which is superior to standard indium-tin-oxide (ITO) glass. Therefore, we report an ITO-free, exciplex-forming phosphorescent OLED showing Lambertian emission with a luminance of 128,000 cd/m² at 8 V, and maximum current efficiency of 92.3 cd/A (external quantum efficiency of ∼24.5%) at 100 cd/m². We also observed the improvement in hole-injection efficiency at the interface of the Ag anode/di-[4-(N,N-ditolyl-amino)-phenyl]cyclohexane due to the modification in the worfunction of roughened Ag anode from 4.6 to 5.4 eV.