The effects of ionisation density on the structure of the glow curve of LiF:Mg,Ti (TLD-100) are briefly reviewed and discussed within the framework of the spatially correlated TC/LC model and localised recombination. The effects of ‘slow-cooling’ on the structure of composite peak 5 following low-ionisation density beta/gamma irradiation are described and analysed in both ‘slow-cooled’ and ‘normally cooled’ samples. It is demonstrated that ‘slow-cooling’ using a cooling rate of 30°C h⁻¹ increases the relative intensity of glow peak 5a to composite glow peak 5 from ∼0.1 to ∼2, thereby greatly improving the precision of measurement of the ratio 5a/5. The improved precision removes a hurdle impeding the development of the ionisation density discrimination properties of the peak 5a/5 nanodosimeter.