@article{discovery10186503, note = {{\copyright} 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0.}, pages = {1420--1427}, journal = {The Journal of Physical Chemistry Letters}, volume = {15}, title = {Beyond the Meso/Macroporous Boundary: Extending Capillary Condensation-Based Pore Size Characterization in Thin Films Through Tailored Adsorptives}, publisher = {American Chemical Society (ACS)}, month = {January}, year = {2024}, issn = {1948-7185}, author = {F{\"u}redi, M{\'a}t{\'e} and Manzano, Cristina V and Marton, Andr{\'a}s and Fodor, B{\'a}lint and Alvarez-Fernandez, Alberto and Guldin, Stefan}, abstract = {The characterization of thin films containing nanopores with diameters exceeding 50 nm poses significant challenges, especially when deploying sorption-based techniques. Conventional volumetric physisorption or mercury intrusion methods have limited applicability in thin films due to constraints in sample preparation and nondestructive testing. In this context, ellipsometric porosimetry represents a viable alternative, leveraging its optical sensitivity to thin films. With existing setups relying on the capillary condensation of volatile compounds such as water, applicability is typically restricted to pore dimensions {\ensuremath{<}}50 nm. In this study, we introduce two high-molar-mass hydrocarbon adsorptives, namely ethylbenzene and n-nonane. These adsorptives exhibit substantial potential in improving the accuracy of physisorption measurements beyond mesoporosity (i.e., {\ensuremath{>}}50 nm). Specifically, with n-nonane, applicability is extended up to 80 nm pores. Our measurement guidelines propose a nondestructive, expeditious ({\ensuremath{<}}60 min), low-pressure ({\ensuremath{<}}0.03 bar) approach to investigate nanoporous thin films with potential adaptability to diverse structural architectures.}, url = {http://dx.doi.org/10.1021/acs.jpclett.3c03442} }