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Understanding the mechanism of refractive index modulation in materials undergoing photo-Fries rearrangement
Affiliation:1. INAF – Osservatorio Astronomico di Brera, via Bianchi 46, 23807 Merate (LC), Italy;2. Dipartimento di Chimica, Materiali ed Ingegneria Chimica, Politecnico di Milano, piazza L. da Vinci 32, 20133 Milano, Italy;3. Center for Nano Science and Technology (CNST) of IIT@PoliMi, via Pascoli 70/3, 20133 Milano, Italy;1. Key Laboratory of Photo-electronic Materials, Ningbo University, Ningbo, Zhejiang 315211, China;2. Department of Physics, Dalian Maritime University, Dalian, Liaoning Province 116026, China;3. Ningbo Institute of Materials Technology and Engineering, The Chinese Academy of Sciences, Ningbo, Zhejiang 315211, China;1. A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 664033 Irkutsk, Russian Federation;2. N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russian Federation;1. Laboratoire de Chimie des Polymères Organiques—Ecole Nationale Supérieure de Chimie, de Biologie et de Physique, UMR CNRS 5629, Université de Bordeaux, 16 avenue Pey-Berland, F-33607 Pessac Cedex, France;2. University of Waterloo, Department of Chemical Engineering, 200 University Av. W, Waterloo, ON N2L 3G1, Canada;3. University of Waterloo, Department of Chemistry, 200 University Av W., Waterloo, ON N2L 3G1, Canada
Abstract:Molecules and polymers that undergo a photo-Fries rearrangement are studied by using DFT calculation in order to predict the refractive index modulation which accompanies this light induced process. In particular, monomeric units of polystyrene derivatives (such as poly(p-formyloxystyrene) and poly(4-acetoxystyrene)) are considered and the refractive index calculated starting from the molecular polarizability and following the Lorentz–Lorenz approach. The results demonstrate that the conversion of ester groups to ketone/alcohol provides just a small modulation of the refractive index that does not fit the experimental results reported in the literature. A change in material density is therefore considered as main source of the modulation of the refractive index. Theoretical and experimental evidences are reported to support the picture.
Keywords:Refractive index  Photo-Fries  DFT  Lithography  Polymers  Polarizability
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