Measuring the Glass Transition Temperature of Conjugated Polymer Films with Ultraviolet–Visible Spectroscopy

The glass transition temperature (<i>T</i>_g) of a conjugated polymer can be used to predict its morphological stability and mechanical properties. Despite the importance of this parameter in applications from organic solar cells to wearable electronics, it is not easy to measure. The <i>T</i>_g is often too weak to detect using conventional differential scanning calorimetry (DSC). Alternative methodse.g., variable temperature ellipsometryrequire specialized equipment. This paper describes a technique for measuring the <i>T</i>_g of thin films of semicrystalline conjugated polymers using only a hot plate and an ultraviolet–visible (UV–vis) spectrometer. UV–vis spectroscopy is used to measure changes in the absorption spectrum due to molecular-scale rearrangement of polymers when heated past <i>T</i>_g, corresponding to the onset of the formation of photophysical aggregates. A deviation metric, defined as the sum of the squared deviation in absorbance between as-cast and annealed films, is used to quantify shifts in the absorption spectra. The glass transition is observed as a change in slope in a plot of the deviation metric versus temperature. To demonstrate the usefulness of this technique, a variety of semiconducting polymers are tested: P3BT, PBTTT-C14, F8BT, PDTSTPD, PTB7, PCDTBT, TQ1, and MEH-PPV. These polymers represent a range of solid-state morphologies, from highly ordered to predominantly amorphous. A successful measurement of <i>T</i>_g depends on the ability of the polymer to form photophysical aggregates. The results obtained using this method for P3BT, PBTTT-C14, F8BT, and PDTSTPD are in agreement with values of <i>T</i>_g that have been reported in the literature. Molecular dynamics simulations are used to show how the morphology evolves upon annealing: above the <i>T</i>_g, an initially kinetically trapped morphology undergoes structural rearrangement to assume a more thermodynamically preferred structure. The temperature at which onset of this rearrangement occurs in the simulation is concomitant with the spectroscopically determined value of <i>T</i><sub>g