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Adlayers are often placed at metal-on-organic interfaces as a common strategy to alleviate damage during metal deposition by thermal evaporation. Methods of chemically installing adlayers have been recently demonstrated on organic semiconductors that address these interfacial issues while providing many secondary benefits. Chemical installation has yet to be attempted at the cathode-electron transport layer (ETL) interface within organic light-emitting devices (OLEDs), offering a powerful option to optimize electron injection, improve surface wetting, and reduce metal penetration. Here, a reaction between TPBi (2,2′,2′’-(1,2,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) and propylene oxide results in a controllable 1–3 nm thick layer of propylene oxide as shown by high-resolution X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX). The reactive addition of the adlayer at temperatures below 40℃ does not affect the morphology of the thin film and reaches a high degree of coverage within 3 h. Integration of this layer into a phosphorescent OLED does not introduce any significant negative impact on device function. This result opens up the possibility of introducing further specific functionality into the adlayer to engineer OLED performance. 

Pentacene thin-films OFETs show increased conductance and mobility after exposure to maleic anhydride which shifts the mean energy in the grain boundaryviaan applied dipole. 

Morphology plays a critical role in determining the properties of solid-state molecular materials, yet fluctuates wildly as these materials undergo reaction. A prototypical system, a vapor–solid Diels–Alder reaction of tetracene and pentacene thin-films, is used to observe the evolution of morphology features as the reaction transitions from surface to bulk. The initial stages of reaction display little topographical change as measured by atomic force microscopy (AFM) and scanning electron microscopy (SEM), and substrates are coated with a uniform layer of product 1–2 molecules thick, as determined by energy-dispersive X-ray (EDX) spectroscopy. The highly textured surfaces of late stage reactions are a result of aggregated products, as identified via EDX spectroscopy and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS); areas of the surface in between product aggregates resemble the initial stages. The mechanism by which products aggregate into surface asperities requires the assistance of a facilitating media – in this case condensed vapor; simple thermally assisted surface diffusion was unable to generate these morphology changes. The combined data indicate that reactions of molecular solids, could be confined to the surface in the absence of condensate of the vapor phase reactant. 

Anhydride terminated acene thin films were chemically transformed to thiol or carboxylic acid functionalities, groups heretofore incompatible with monolayer reactions. The molecular surface imparts large rate acceleration when imides are formed, while disfavored disulfides can be formed from the thiols. The modified surface imparts improved adhesion to top metal contacts in flexible/bendable applications. 

Reactivity trends for molecular solids cannot be explained exclusively through the topochemical phenomenon ( i.e. diffusivity, reaction cavities) or electronic structure of the molecules. As an example of this class, Diels–Alder reactions of small molecules with pentacene thin films are examined to elucidate the importance of surface phenomena to reactivity. Polarization modulation-infrared reflection–absorption spectroscopy (PM-IRRAS) has revealed that vapors from the small molecules condense on the surface, in a non-covalent manner, to form a coating 2–3 molecules thick. The phase of this layer can provide increased surface diffusion (both reactant and product) which rapidly accelerates the reaction rate. Kinetic studies of pentacene thin film reactions demonstrate the importance of this condensed state to trends in reactivity, with layers in a quasi-liquid state showing a rate acceleration of 13–30 times compared to those in a quasi-solid state. Scanning electron microscopy provides further evidence of this phase behavior, while solid-state UV-vis confirms the kinetic results.