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This work reports the first observation of circularly polarized electroluminescence (CPEL) in thin films of self‐organized oligothiophenes. Four new 1,4‐phenylene and 9H‐carbazole‐based oligothiophenes were ad hoc designed to ensure efficient spontaneous formation of chiral supramolecular order. They were easily synthesized and their chiroptical properties in thin films were measured. Circularly polarized luminescence (CPL) spectra revealed glum in the order of 10−2 on a wide wavelengths range, originating from their self‐organized chiral supramolecular organization. These molecules have reasonable properties as organic semiconductors and for this reason they can constitute the active layer of circularly‐polarized organic light‐emitting diodes (CP‐OLEDs). Thus, we could investigate directly their electroluminescence (EL) and CPEL, without resorting to blends, but rather in a simple multilayer device with basic architecture. This is the first example of a CP‐OLED with active layer made only of a small organic compound. [ABSTRACT FROM AUTHOR]

We present a joint experimental and computational study of the role of the substrate thermal conductivity on scanning thermochemical lithography (SThL) of thin organic films. We aim this study at lithography of the luminescent conjugated polymer poly(p-phenylene vinylene) (PPV) from its soluble precursor poly(p-xylene tetrahydrothiophenium chloride) (PXT), but our results provide relevant insights into the SThL of thermosensitive polymers in general, and into a wide range of nanoscale thermal and thermochemical processes in thin films. As high thermal conductivity substrates we used gold films on silicon, and indium-tin oxide (ITO) films on glass, successfully patterning PPV on both substrates. We find that a higher probe temperature (>300 °C instead of ≈250 °C) is necessary for lithography of PXT films on ITO compared to those on fused silica (for the same scanning speed and comparable precursor thickness). Surprisingly, however, our experiments show that minimum feature sizes are nearly independent of the underlying substrate. While a lateral resolution (full width at half maximum, FWHM) of 37 nm was achieved previously on fused silica for a 40 nm thick PXT film, we obtain here a FWHM of 36 nm for a 35 nm thick PXT layer on ITO. We compare our experiments with finite element simulations and gain further insight into the possibilities of thermochemical lithography, the necessary minimum probe temperature and the highest attainable resolutions. The model shows that for high thermal conductivity substrates there should be a region of unconverted polymer near the polymer-substrate interface. Our experiments demonstrate that patterned features are able to adhere to the substrate despite this unconverted layer, thus allowing SThL to work on very high thermal conductivity substrates such as gold. Our model builds on this experimental finding and accounts for the experimental lack of dependence of lateral size with substrate conductivity, i.e. it predicts that the minimum feature size increases only slightly for increasing thermal conductivities of the substrates. [ABSTRACT FROM AUTHOR]

The photophysics and electroluminescence (EL) of thin films of unthreaded and cyclodextrin-encapsulated poly(4,4′-diphenylenevinylene) (PDV) with potassium countercations, blended with poly(ethylene oxide) (PEO) are investigated as a function of the PEO concentration. We show that three main factors contribute to increasing the photoluminescence (PL) quantum efficiency as a result of suppressed intermolecular interactions, namely: the high degree of encapsulation of the polyrotaxanes, the relatively large countercation (e.g., compared to lithium), and the complexation of the rotaxanes with PEO. By facilitating cationic transport to the negative electrodes, PEO also leads to devices with enhanced electron injection and improved charge balance, whose operation therefore resembles that of “virtually unipolar” light-emitting electrochemical cells. This effect, together with the enhanced PL efficiency, leads to higher EL efficiency for both polyrotaxanes and unthreaded polymers, upon addition of the PEO. We show that the concurrent exploitation of the various strategies above lead to an overall EL efficiency that is approximately twice the value previously reported for Li-based PDV. A blueshift of the EL spectrum during the devices turn-on is also reported and analyzed in terms of interference and doping effects. [ABSTRACT FROM AUTHOR]

Oxygen-plasma treatment of indium-tin oxide (ITO) anodes is now widely used as one of the most effective ways to improve the device performance of organic light-emitting diodes (LEDs). However, the role of oxygen-plasma treatment has not been clearly understood. We have performed detailed studies of the surface and bulk of the ITO thin films exposed to oxygen-plasma. We employed a multitude of experimental techniques, including X-ray and ultraviolet photoelectron spectroscopies, atomic force microscopy, dynamic contact angle measurement, four-point probe and Hall measurements to investigate the changes induced by the plasma. We have also analyzed the device characteristics of polymer LEDs fabricated with these anodes. We found significant modifications of the physico-chemical, morphological, transport and optical properties of the oxygen-plasma treated ITO. Although oxygen-plasma does not show any measurable etching effect, it induces considerable changes leading to an increase in work function, electron carrier concentration and conductivity. It also increases the surface energy and polarity. We relate these modifications to enhancement of the device performance, such as electroluminescence efficiency and lifetime, through their effects on hole injection, and interface structure and stability. Finally, we show that even in the presence of a hole-transport layer such as a poly(styrene sulphonate)-doped poly(3,4-ethylene dioxythiophene) (PEDOT:PSS) inserted between the anode and the emissive polymer layer, oxygen-plasma treatment of the ITO anodes is still beneficial for the devices. [Copyright &y& Elsevier]

We present the synthesis and characterization of a series of encapsulated diketopyrrolopyrrole red-emitting conjugated polymers. The novel materials display extremely high fluorescence quantum yields in both solution (>70%) and thin film (>20%). Both the absorption and emission spectra show clearer, more defined features compared to their naked counterparts demonstrating the suppression of inter and intramolecular aggregation. We find that the encapsulation results in decreased energetic disorder and a dramatic increase in backbone colinearity as evidenced by scanning tunnelling microscopy. This study paves the way for diketopyrrolopyrrole to be used in emissive solid state applications and demonstrates a novel method to reduce structural disorder in conjugated polymers. [ABSTRACT FROM AUTHOR]

Abstract: For efficient hole-extraction in solution processed organic solar cells the transparent indium-tin oxide (ITO) electrode is invariably pre-coated with a thin layer of the high work function conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate). Herein we show that thin films of partially oxidised multi-wall and single-wall carbon nanotubes are equally effective at facilitating hole-extraction in efficient (∼2.7%) bulk-heterojunction organic solar cells based on poly(3-hexylthiophene) (P3HT): [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) blends. Crucially, in contrast to PEDOT:PSS, deposition is from aqueous solutions of low acidity (pH 6–7) ensuring compatibility with ITO and other emerging conducting oxides. Furthermore, thin oxidised carbon nanotube films offer greater transparency in the near-infrared as compared to PEDOT:PSS films of comparable thickness. The functionality of these nano-structured films is demonstrated in relatively large area devices (∼0.35 cm2) and the performance rationalised based on measurements of the electronic structure and morphology. [Copyright &y& Elsevier]

• A covalent composite of diketopyrrolopyrrole and few layers graphene is synthesized. • The material shows excellent film-forming ability and is conductive. • The system undergoes total energy transfer after photo-excitation and is photo-stable. • The composite is proposed as a perspective material for photo-protective anti-static coating. A dianiline derivative of a symmetric donor-acceptor-donor diketopyrrolopyrrole-based dye is employed for the two-sided covalent functionalization of liquid exfoliated few layers graphene flakes, through a direct arylation reaction. The resulting nanohybrid features the properties of a polymeric species, being solution-processed into homogeneous thin films, featuring a pronounced red-shift of the main absorption band with respect to the model dye unit and energy levels comparable to those of common diketopyrrolopyrrole-based polymers. A good electrical conductivity and the absence of radical signals generated after intense white light illumination, as probed through electron paramagnetic resonance, suggest a possible future application of this composite material in the field of photoprotective, antistatic layers with tunable colors. [ABSTRACT FROM AUTHOR]