Time-of-flight secondary ion tandem mass spectrometry depth profiling of organic light-emitting diode devices for elucidating the degradation process.

RATIONALE: Organic light-emitting diode (OLED) products based on display applications have become popular in the past 10 years, and new products are being commercialized with rapid frequency. Despite the many advantages of OLEDs, these devices still have a problem concerning lifetime. To gain an understanding of the degradation process, the authors have investigated the molecular information for deteriorated OLED devices using time-of-flight secondary ion mass spectrometry (TOF-SIMS). METHODS: TOF-SIMS depth profiling is an indispensable method for evaluating OLED devices. However, the depth profiles of OLEDs are generally difficult due to the mass interference among organic compounds, including degradation products. In this study, the tandem mass spectrometry (MS/MS) depth profiling method was used to characterize OLED devices. RESULTS: After degradation, defects comprised of small hydrocarbons were observed. Within the defect area, the diffusion of all OLED compounds was also observed. It is supposed that the source of the small hydrocarbons derives from decomposition of the OLED compounds and/or contaminants at the ITO interface. CONCLUSIONS: The true compound distributions have been determined using MS/MS depth profiling methods. The results suggest that luminance decay is mainly due to the decomposition and diffusion of OLED compounds, and that OLED decomposition may be accelerated by adventitious hydrocarbons present at the ITO surface.

Interfacial Engineering in Solution Processing of Silicon-Based Hybrid Multilayer for High Performance Thin Film Encapsulation.

Solution processing of thin film encapsulation (TFE) has been a long anticipated technology to bridge the big idea of flexible organic electronics to become real world values, since only small-sized flexible devices are currently achieved with expensive multilayered TFE by complex vacuum processing. Highly demanding conditions are to carry out the process under inert gas, at a low temperature, and without aggressive chemicals to avoid damages to the organic materials. Here we show for the first time a solution-processed TFE to totally equal the level of conventional glass-cap encapsulation to achieve a "ready-to-be-used" stability of an organic light emitting diode (OLED). A seamless organic/inorganic multilayer in a structure such as polydimethylsiloxane (PDMS)/SiOx/SiNy/SiOxNy with a built-in compositional gradient, as we named "PONT", was achieved by a combination of two Si-based polymer coatings, UV-curable PDMS, perhydropolysilazane (PHPS), and their photochemical conversion under irradiation of vacuum ultraviolet (VUV) light (λ = 172 nm) in an N2-filled glovebox at room temperature. PDMS precursors diluted with decamethylcyclopentasiloxane were directly coated to OLED to form a protective layer. The presence of soft, elastic PDMS and its surface conversion to SiOx to improve wetting resulted in strong adhesion at the interfaces and relaxed strain to avoid cracks in ultrathin and high density SiOxNy to serve as a perfect barrier. A remarkably low water vapor transmission rate <10-4 g/m2/day was confirmed for a single PONT as thin as 280 nm. Standardized OLED devices with PONT TFEs have proven 3,864 and 528 h stability under atmospheric (25 °C, 50% relative humidity (RH)) and accelerated (60 °C, 90%RH) degradation tests, respectively, without formation of nonemissive dark spots in OLEDs. The fast processing of PONT TFE can be applied to roll-to-roll fabrication of various organic devices at low cost and in large areas, since direct solution coating as well as VUV irradiation do not cause any noticeable damages to sensitive organic materials.

Concerted Photoluminescence of Electrochemically Self-Assembled CuSCN/Stilbazolium Dye Hybrid Thin Films.

Hybrid thin films of crystalline CuSCN and 4-(N,N-dimethylamino)-4'-(N'-methyl)stilbazolium (DAS) in three distinctively different nanostructures were obtained by electrochemical self-assembly from a single pot containing all the chemical ingredients. Their optical properties for UV-vis-NIR absorption, photoluminescence (PL), and PL excitation spectra were examined between 77 and 298 K, in comparison with solution and solid powder of DAS tosylate (DAST). Unlike all other dyes we tested before, PL of DAS was not quenched but rather enhanced when hybridized with CuSCN. DAST exhibited a strong exciton-phonon coupling to weaken, broaden, and red shift PL at room temperature, so that it inversely is strongly enhanced, sharpened, and blue-shifted at 77 K. The PL of the same dye in the hybrid thin film, however, shows a slight red shift and only a moderate enhancement at reduced temperatures due to strong exciton stabilization in dielectric environment of CuSCN and concerted PL by energy transfer from CuSCN to DAS luminophore, making it a unique nearly temperature-independent luminescent material.

Solution-processed multilayer small-molecule light-emitting devices with high-efficiency white-light emission.

Recent developments in the field of π-conjugated polymers have led to considerable improvements in the performance of solution-processed organic light-emitting devices (OLEDs). However, further improving efficiency is still required to compete with other traditional light sources. Here we demonstrate efficient solution-processed multilayer OLEDs using small molecules. On the basis of estimates from a solvent resistance test of small host molecules, we demonstrate that covalent dimerization or trimerization instead of polymerization can afford conventional small host molecules sufficient resistance to alcohols used for processing upper layers. This allows us to construct multilayer OLEDs through subsequent solution-processing steps, achieving record-high power efficiencies of 36, 52 and 34 lm W(-1) at 100 cd m(-2) for solution-processed blue, green and white OLEDs, respectively, with stable electroluminescence spectra under varying current density. We also show that the composition at the resulting interface of solution-processed layers is a critical factor in determining device performance.

Hydrogen evolution coupled with the photochemical oxygenation of cyclohexene with water sensitized by tin(IV) porphyrins by visible light.

Hydrogen evolution coupled with the photochemical oxygenation of cyclohexene with water was observed in the system sensitized by Sn(IV)-porphyrin adsorbed on Pt loaded TiO2 nano-particles in aqueous acetonitrile solution upon visible light irradiation.

Phosphorescent cyclometalated complexes for efficient blue organic light-emitting diodes.

Phosphorescent emitters are extremely important for efficient organic light-emitting diodes (OLEDs), which attract significant attention. Phosphorescent emitters, which have a high phosphorescence quantum yield at room temperature, typically contain a heavy metal such as iridium and have been reported to emit blue, green and red light. In particular, the blue cyclometalated complexes with high efficiency and high stability are being developed. In this review, we focus on blue cyclometalated complexes. Recent progress of computational analysis necessary to design a cyclometalated complex is introduced. The prediction of the radiative transition is indispensable to get an emissive cyclometalated complex. We summarize four methods to control phosphorescence peak of the cyclometalated complex: (i) substituent effect on ligands, (ii) effects of ancillary ligands on heteroleptic complexes, (iii) design of the ligand skeleton, and (iv) selection of the central metal. It is considered that novel ligand skeletons would be important to achieve both a high efficiency and long lifetime in the blue OLEDs. Moreover, the combination of an emitter and a host is important as well as the emitter itself. According to the dependences on the combination of an emitter and a host, the control of exciton density of the triplet is necessary to achieve both a high efficiency and a long lifetime, because the annihilations of the triplet state cause exciton quenching and material deterioration.