A Journey Through the Landscapes of Small Particles in Binary Colloidal Assemblies: Unveiling Structural Transitions from Isolated Particles to Clusters upon Variation in Composition

Two-dimensional (2D) amorphous binary colloidal assemblies composed of particles of two different sizes are characterized by the loss of hexagonal close-packing for larger particles, occurring when the size ratio between small (S) and large (L) particles [Formula: see text] exceeds a certain threshold value. For moderately low particle number ratios [Formula: see text] large particles still retain a denser arrangement with transitions from hexagonal symmetry to the coexistence of different types of symmetries as [Formula: see text] progressively departs from 0 to higher values. On the other hand, small particles reveal sparser arrangements: shape identification and quantification of structural transitions in small particle arrangements appear particularly challenging. In this article, we investigate their shapes and transitions for amorphous binary colloidal particles assembled at the air/water interface. For the quantitative characterization of the evolution in particle arrangements for [Formula: see text] variable between 0.5 and 2, we develop an innovative procedure for morphological analysis, combining Minkowski functionals, Voronoi diagrams and ad hoc techniques to recognize and classify specific features. Such a powerful approach has revealed a wide variety of landscapes featuring isolated particles, dimers, chains, small clusters evolving with the colloidal suspension composition. Our method can be applied to the analysis of spatial configurations of sparse colloidal patterns obtained in different conditions.