This study is focused on the Y6 electron acceptor to assess the impact of elongating the inner side chain from 8 to 12 carbon atoms by combining DFT calculations, UV-visible spectroscopy, atomic force microscopy analysis and device characterization.
Presently, metallic nanowires (NWs) are the most promising materials to fabricate flexible transparent electrodes as an alternative to indium tin oxide. Here, the high performance of transparent conductive electrodes (TCEs) based on silver nanowires (AgNWs) percolation networks is reported. With optimized experimental conditions for the deposition, the AgNWs result in low sheet resistance of 10 Ω sq −1 combined with a high optical transmittance of 92.6% at λ = 550 nm. This leads to a valuable figure of merit as compared to other TCEs. In this study, the nanoscale electrical properties of the AgNWs are measured via conductive atomic force microscopy to characterize the percolation network. The electrical resistivity value calculated for a single AgNW is found to be about 12.35 µΩ cm, while a nanoscale conductivity map over an AgNW network bridging two electrodes has revealed high levels of current within the network over a distance of more than 1000 µm. The favorable determined conductivity results along with the high optical properties of the AgNWs network strongly suggest that thin‐film electrodes based on AgNWs will be a potential approach for future flexible electronic devices.
Spiro compounds are widely used as host matrices in organic light‐emitting diodes (OLEDs). Here, inspired by the recent developments in thermally activated delayed fluorescence (TADF) materials, the potential as a light emitter of two spiro‐configured organic semi‐conductors is investigated, constructed by the association of quinolinophenothiazine (QPTZ) or indoloacridine (IA) as the electron‐rich fragment and diphenylphosphine oxide fluorene as the electron‐poor fragment. By comparison with structural analogues lacking phosphine oxides, the crucial role played by these electron‐accepting substituents not only on the photo‐physical properties but also on the device performances is evidenced. Despite a very low quantum yield in solution, these two compounds unexpectedly display good emission properties when incorporated as a pure layer in OLEDs, thus highlighting the role of intermolecular effects.
Aiming to develop efficient blue-emitting thermally activated delayed fluorescence (TADF) compounds, we have designed and synthesized derivatives of the well-known sky-blue emitter 2CzPN that contain electron-accepting phosphine chalcogenide groups to stabilize the HOMO level relative to the pristine compound, thus increasing the HOMO-LUMO gap and blue-shifting the emission wavelength. By cyclic voltammetry, photophysical data and quantum-chemical calculations, it was found that polar solvents and matrices validated the proposed concept, but these trends were not recovered in non-polar media. The suitability of these 2CzPN derivatives in polar matrices for optoelectronic applications was explored with electrochemiluminescence (ECL) by measuring emission delays, radical stability, emission stabilities, emission efficiencies and emission spectra. Some of the 2CzPN derivatives showed an unprecedented delayed onset of the ECL, and delayed rising time to the ECL maximum, as well as long ECL emission decay. All of these mentioned delay times suggest that these luminophores primarily emit via organic long-persistent electrochemiluminescence (OLECL) mechanisms. The derivatization of the donor groups of the emitters affected both the radical stability and the predominant emission mechanism, providing important insight into their potential as emitters in solid-state electroluminescent devices.
We have investigated the potential as an OLED emitter of a spiro compound with phosphine substituents initially designed as a host layer for triplet emitters. This is motivated by the fact that the spiro architecture is expected to reduce the detrimental impact of intermolecular interactions, thus allowing for the use of a single-component layer. Moreover, theoretical calculations suggest that this compound displays all features required for a thermally-assisted delayed fluorescence (TADF) behavior. The photophysical properties of the compound in solution are extremely unusual, as illustrated in particular by a dual emission band with relative intensities strongly depending on the experimental conditions. Although no TADF behavior is evidenced in OLED devices, the compound unexpectedly generates a white light signal, which is interpreted as the result of the formation of both intramolecular and intermolecular (exciplex) charge-transfer states.
Patterned and layered hydrophilic/phobic coatings were deposited on multiple surfaces using nonfluorinated precursors (AA, acrylic acid; PMA, propargyl methacrylate) with an atmospheric pressure dielectric barrier discharge operating in open air. Water contact angles of the resulting films could be tuned from <5° (superhydrophilic) to >135° (very hydrophobic) by adjusting the AA/PMA feed ratio and/or via postdeposition exposure of films to an Ar/O2 plasma treatment. Coatings could be applied to any surface and were seen to be water stable, due in large part to cross-linking induced from the reactivity of the PMA pendant groups. Hybrid hydrophilic/phobic patterns at submillimeter length scales, and philic/phobic/philic laminates were produced using a shadow mask and sequential deposition, respectively. Chemical heterogeneity of films was assessed using XPS, SIMS, and micro-IR imaging and suggest that localization of COOH and OH groups are primarily responsible for hydrophilicity. Overall, this work demonstrates that atmospheric pressure plasma polymerization is a simple and scalable method for robust and tunable control of wettability of surfaces of all kinds.
To succeed in commercial applications, donor materials for organic solar cells should combine high stability and simple synthesis with high performance in devices. Here, we present a new small pi-conjugated molecule, TPA-T-DCV-Ph, which meets those requirements. Simple and efficient three-step synthesis produces a push-pull molecule with triphenylamine donor and phenyldicyanovinyl acceptor groups, which is suitable for both solution processing and vacuum deposition. The unique property of TPA-T-DCV-Ph is an unusually long exciton diffusion length of > 25 nm due to the combined effect of long exciton lifetime and surprisingly low energy disorder. This, together with a device engineering, resulted in > 5% efficiency for TPA-T-DCV-Ph:C-70 vacuum-processed solar cells. The results obtained are envisioned to be further improved by optimizing the absorption of the molecule and light management in the device which can push the efficiency even further.
The synthesis and texturization processes of fluorinated surfaces by means of atmospheric plasma are investigated and presented through an integrated study of both the plasma phase and the resulting material surface. Three methods enhancing the surface hydrophobicity up to the production of super-hydrophobic surfaces are evaluated: (i) the modification of a polytetrafluoroethylene (PTFE) surface, (ii) the plasma deposition of fluorinated coatings and (iii) the incorporation of nanoparticles into those fluorinated films. In all the approaches, the nature of the plasma gas appears to be a crucial parameter for the desired property. Although a higher etching of the PTFE surface can be obtained with a pure helium plasma, the texturization can only be created if O_2 is added to the plasma, which simultaneously decreases the total etching. The deposition of C_xF_y films by a dielectric barrier discharge leads to hydrophobic coatings with water contact angles (WCAs) of 115°, but only the filamentary argon discharge induces higher WCAs. Finally, nanoparticles were deposited under the fluorinated layer to increase the surface roughness and therefore produce super-hydrophobic hybrid coatings characterized by the nonadherence of the water droplet at the surface.
The atmospheric pressure PECVD deposition and texturization of hydrophobic coatings using liquid fluorinated C 6 F 12 and C 6 F 14 precursors are investigated. The effect of the carrier gas (argon and helium) is discussed in terms of the behavior of the gas phase and of the characteristics of the deposited film. Mass spectrometry measurements indicate that the fragmentation is higher with argon while helium reacts very easily with oxygen impurities leading to the formation of C x F y O z compounds. These observations are consistent with the chemical composition of the films determined by XPS and the variation in the deposition rate. Moreover, the streamers present in the argon discharge affect the morphology of the surface by increasing the roughness, which leads to the increase in the hydrophobicity of the coatings.
The reactivity of water vapor introduced in an atmospheric dielectric barrier discharge supplied in argon is investigated through optical emission spectroscopy measurements. This discharge is also used for the treatment of LDPE surfaces. Water contact angles measurements, XPS and AFM techniques are used to study the grafting of oxygen functions on the LDPE surface and increase its hydrophilicity.
Plasma polymer films are more and more used in numerous applications such as the day-today packaging, which requires a good mechanical resistance of the coating. Since mechanical properties are function of the cross-linking degree of the thin films, it is important to understand the relationship between the two. In this work, plasma polymer films were studied in terms of cross-linking degree and mechanical properties, measured by means of ToF-SIMS coupled to PCA and depth-sensing nanoindentation, respectively. The data reveal that when the power increases, the films are more cross-linked and show higher hardness, higher elastic recovery, lower creep strain and an increased ability for self-healing. As the plasma polymer films are more cross-linked, the plasticity drops and the viscoelasticity and hardness increase.
Among various surface modification techniques, plasma can be used as a source for tailoring the surface properties of diverse materials. HDPE and fluoropolymer surfaces have been treated by the post-discharge of an atmospheric RF-plasma torch supplied with helium and oxygen gases. The plasma-treated surfaces were characterized by measurements of mass losses, water contact angles, x-ray photoelectron spectroscopy and atomic force microscopy. This experimental approach correlated with an optical characterization of the plasma phase allowed us to propose etching mechanisms occurring at the post-discharge/polymer interface. We discuss how competitive and synergistic effects can result from the oxidation and/or the roughening of the surface but also from the excimer VUV radiation, the He metastable species and the O radicals reaching the plasma-polymer interface.
Part of the light rays generated within a luminescent medium with a higher refractive index than that of the exit medium, typically air, undergo total internal reflection phenomenon (TIR); these rays will be trapped and guided into the emissive material and will not be extracted out of an OLED device for instance. Trapped light is reabsorbed and eventually converted into heat that will be detrimental to the device performance and lifetime. The amount of trapped energy is highly dependent on the values of the refractive indices involved in the multilayer stack constituting the light emitting device. The amount of trapped energy can be extensive and can even reach as much as 75% in certain cases. Solutions to improve the outcoupling efficiency are therefore attractive. In this paper we propose to use laser speckle to produce a random surface with controlled parameters to enhance the OLED outcoupling. A laser speckle pattern is transferred onto a photoresist which will be subsequently converted into a surface relief profile. The optical setup parameters drive the properties of such surface and thus the outcoupling properties. The resulting surface has a quasi-random shape which could be assimilated to a corrugated surface. We will show that these typical surfaces exhibit light extraction enhancement properties. The generated pattern is then transferred onto the exit interfaces of the emitting device. An extraction improvement close to a factor 3 is measured. We finally discuss a practical case for which the laser speckle shape is applied to texture the surface of encapsulating cover glasses in a top-emitting OLED on steel substrates.