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We have found that the polarization dependence of Raman scattering in organic crystals at finite temperatures can only be described by a fourth-rank tensor formalism. This generalization of the second-rank Raman tensor stems from the effect of off diagonal components in the crystal self-energy on the light scattering mechanism. We thus establish a novel manifestation of phonon-phonon interaction in inelastic light scattering, markedly separate from the better-known phonon lifetime., Funding Agencies|European Research Counsel [850041]; Swedish Research Council (VR) [2020-04630]; Belgian National Fund for Scientific Research (FNRS) [T.0072.18, T.0094.22, U.G001.19, O.005018F, O.00322]; French Community of Belgian (ARC) [20061]

Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices., SCOPUS: ar.j, info:eu-repo/semantics/published

We combine temperature-dependent low-frequency Raman measurements and first-principles calculations to obtain a mechanistic understanding of the order–disorder phase transition of 2,7-di-tert-butylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (ditBu-BTBT) and 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) semiconducting amphidynamic crystals. We identify the lattice normal modes associated with the phase transition by following the position and width of the Raman peaks with temperature and identifying peaks that exhibit nonlinear dependence toward the phase transition temperature. Our findings are interpreted according to the “hardcore mode” model previously used to describe order–disorder phase transitions in inorganic and hybrid crystals with a Brownian sublattice. Within the framework of this model, ditBu-BTBT exhibits an ideal behavior where only one lattice mode is associated with the phase transition. TIPS-pentacene deviates strongly from the model due to strong interactions between lattice modes. We discuss the origin of the different behaviors and suggest side-chain engineering as a tool to control polymorphism in amphidynamic crystals., SCOPUS: ar.j, info:eu-repo/semantics/published

info:eu-repo/semantics/published

The lack of long-term stability in thin films of organic semiconductors can often be caused by the low structural stability of metastable phases that are frequently formed upon deposition on a substrate surface. Here, thin films of 2,7-dioctyloxy[1]benzothieno[3,2-b]benzothiophene (C8O-BTBT-OC8) and blends of this material with polystyrene by solution shearing are fabricated. Both types of films exhibit the metastable surface-induced herringbone phase (SIP) in all the tested coating conditions. The blended films reveal a higher device performance with a field-effect mobility close to 1 cm2 V−1 s−1, a threshold voltage close to 0 V, and an on/off current ratio above 107. In situ lattice phonon Raman microscopy is used to study the stability of the SIP polymorph. It is found that films based on only C8O-BTBT-OC8 slowly evolve to the Bulk cofacial phase, significantly impacting device electrical performance. In contrast, the blended films stabilize the SIP phase, leading to devices that maintain a high performance over 1.5 years. This work demonstrates that blending small-molecule organic semiconductors with insulating binding polymers can trap metastable polymorphs, which can lead to devices with both improved performance and long-term stability., SCOPUS: ar.j, info:eu-repo/semantics/published

The field of organic electronics has been prolific in the last couple of years, leading to the design and synthesis of several molecular semiconductors presenting a mobility in excess of 10 cm2 V-1 s-1. However, it also started to recently falter, as a result of doubtful mobility extractions and reduced industrial interest. This critical review addresses the community of chemists and materials scientists to share with it a critical analysis of the best performing molecular semiconductors and of the inherent charge transport physics that takes place in them. The goal is to inspire chemists and materials scientists and to give them hope that the field of molecular semiconductors for logic operations has not engaged into a dead end. To the contrary, it offers plenty of research opportunities in materials chemistry., SCOPUS: re.j, info:eu-repo/semantics/published