Quantifying local thickness and composition in thin films of organic photovoltaic blends by Raman scatteringElectronic supplementary information (ESI) available: Further details about the application of the methodology in different Raman setups; the multi-wavelength fitting approach in P3HT films; the sensitivity of the methodology in thin film architectures with a high refractive index contrast; and the effect of photodegradation on the Raman intensity in some polymer:fullerene blends. See DOI:

• Main Authors: Rodríguez-Martínez, Xabier, Vezie, Michelle S, Shi, Xingyuan, McCulloch, Iain, Nelson, Jenny, Goñi, Alejandro R, Campoy-Quiles, Mariano
• Format: Journal Article
• Language: English
• Published: 27.07.2017
• ISSN: 2050-7526; 2050-7534
• DOI: 10.1039/c7tc01472d

We report a methodology based on Raman spectroscopy that enables the non-invasive and fast quantitative determination of local thickness and composition in thin films (from a few monolayers to hundreds of nm) of one or more components. We apply our methodology to blends of organic conjugated materials relevant in the field of organic photovoltaics. As a first step, we exploit the transfer-matrix formalism to describe the Raman process in thin films including reabsorption and interference effects of the incoming and scattered electric fields. This allows determining the effective solid-state Raman cross-section of each material by studying the dependence of the Raman intensity on film thickness. These effective cross sections are then used to estimate the local thickness and composition in a series of polymer:fullerene blends. We find that the model is accurate within ±10 nm in thickness and ±5 vol% in composition provided that (i) the film thickness is kept below the thickness corresponding to the first maximum of the calculated Raman intensity oscillation; (ii) the materials making up the blend show close enough effective Raman cross-sections; and (iii) the degree of order attained by the conjugated polymer in the blend is similar to that achieved when cast alone. Our methodology opens the possibility of making quantitative maps of composition and thickness over large areas (from microns to centimetres squared) with diffraction-limited resolution and in any multi-component system based thin film technology. Optical modeling of the Raman-scattered light enables the simultaneous quantification of thickness ( d ) and volumetric composition (vol%) in multi-component thin films.