Disappearance of Odd–Even Effects at the Substrate Interface of <i>n</i>-Alkanes

The physical and chemical properties of organic compounds having alkyl chains are frequently influenced by the parity of the chain length, which is known as the odd-even effect. Understanding the molecular origin of this phenomenon is particularly important for designing materials used in organic thin-film devices. In this work, we focus on thin films of <i>n</i>-alkanes as the simplest model to study the odd-even effect at the substrate interface and analyze the aggregation structure using p-polarized multiple-angle incidence resolution spectrometry in combination with grazing incidence X-ray diffraction. The spectroscopic analysis shows a pronounced odd-even alternation of the molecular tilt angles in the multilayer films. In addition, high-resolution Brewster-angle transmission spectroscopy reveals that the conformation of the methyl group highly depends on whether the carbon number is even or odd. In contrast to the multilayer films, the odd-even effects do not appear in the monolayer films. We demonstrate that, in other words, the interlayer interactions of the molecules are responsible for the odd-even effects. This study also highlights the first identification of the monolayer phase of <i>n</i>-alkanes by using grazing incidence X-ray diffraction in combination with high-resolution infrared spectroscopy. These results not only reveal the molecular origin for the odd-even effect of <i>n</i>-alkanes but also provide analytical techniques for discussing the monolayer structure of various alkylated compounds on a functional group basis.