Yilmaz, MehmetBabur, EsraOzdemir, MehmetGieseking, Rebecca L.Dede, YavuzTamer, UgurDemirel, Gokhan2025-09-252025-09-2520171476-11221476-4660https://doi.org/10.1038/NMAT4957https://hdl.handle.net/20.500.12573/4257Yilmaz, Mehmet/0000-0003-2687-9167; Gieseking, Rebecca/0000-0002-7343-1253; Facchetti, Antonio/0000-0002-8175-7958; Dede, Yavuz/0000-0003-4854-8422; Usta, Hakan/0000-0002-0618-1979; Tamer, Ugur/0000-0001-9989-6123; Demirel, Gokhan/0000-0002-9778-917X;pi-Conjugated organic semiconductors have been explored in several optoelectronic devices, yet their use in molecular detection as surface-enhanced Raman spectroscopy (SERS)-active platforms is unknown. Herein, we demonstrate that SERS-active, superhydrophobic and ivy-like nanostructured films of a molecular semiconductor, alpha,omega-diperfluorohexylquaterthiophene (DFH-4T), can be easily fabricated by vapour deposition. DFH-4T films without any additional plasmonic layer exhibit unprecedented Raman signal enhancements up to 3.4 x 10(3) for the probe molecule methylene blue. The combination of quantum mechanical computations, comparative experiments with a fluorocarbon-free alpha,omega-dihexylquaterthiophene (DH-4T), and thin-film microstructural analysis demonstrates the fundamental roles of the pi-conjugated core fluorocarbon substitution and the unique DFH-4T film morphology governing the SERS response. Furthermore, Raman signal enhancements up to similar to 10(10) and sub-zeptomole (< 10(-21) mole) analyte detection were accomplished by coating the DFH-4T films with a thin gold layer. Our results offer important guidance for the molecular design of SERS-active organic semiconductors and easily fabricable SERS platforms for ultrasensitive trace analysis.eninfo:eu-repo/semantics/closedAccessFluorocarbonGoldAlpha,Omega-DiperfluorohexylquaterthiopheneCoated Materials, BiocompatibleFluorocarbonsGoldMembranes, ArtificialThiophenesAromatic CompoundsGold CoatingsLight TransmissionOptoelectronic DevicesOrganic PolymersQuantum TheorySemiconducting Organic CompoundsThin FilmsComparative ExperimentsConjugated Organic SemiconductorsMicrostructural AnalysisMolecular SemiconductorsNanostructured FilmsOrganic Semiconductor FilmsQuantum Mechanical ComputationsSurface Enhanced Raman SpectroscopyRaman SpectroscopyAlpha,Omega-DiperfluorohexylquaterthiopheneBiocompatible Coated MaterialFluorocarbonGoldThiophene DerivativeArtificial MembraneChemistryRaman SpectrometrySemiconductorCoated Materials, BiocompatibleFluorocarbonsGoldMembranes, ArtificialSemiconductorsSpectrum Analysis, RamanThiophenesArticle10.1038/NMAT49572-s2.0-85028464875