In situexperimental studies have been key in uncovering the often elusive pathways of nucleation and crystal growth. In the field of material science and medicine this offers the prospect of controlling crystallization processes to fight disease or tailor materials towards specific applications. To further advance this quest there is a need for flexible techniques mapping the different stages of crystallization with maximal sensitivity. This article reviews the benefits of nonlinear optical techniques to take on this challenge. We provide a perspective on various nucleation and crystal growth studies that were carried out by nonlinear optical probing techniques. A theoretical background is established, different relevant nonlinear optical phenomena are defined, and optical setups that have been used by various authors are summarized. A primary focus is demonstrating the benefits of nonlinear optical techniques for thein situstudy of crystallization. These benefits include low detection limits, complementary information by combining second- and third-order techniques, as well as relatively simple bench-top setups. Through microscopy, high contrast imaging of concomitant formations can moreover be achieved. The discussion outlines several studies involving ionic compounds, noble metal nanoparticles, polymers, metal organic frameworks and pharmaceutical compounds. Finally, we discuss future evolutions in nonlinear optical probing that are expected to further advance the field.

Recent developments in nonlinear optical light scattering techniques have opened a window into morphological and structural characteristics for a variety of supramolecular systems. However, for the study of dynamic processes, the current way of measuring is often too slow. Here we present an alternative measurement scheme suitable for following dynamic processes. Fast acquisition times are achieved through Fourier imaging, allowing simultaneous detection at multiple scattering angles for different polarization combinations. This allows us to follow the crystal growth of the metal organic framework ZIF-8 in solution. The angle dependence of the signal provides insight into the growth mechanism by probing the evolution of size, shape and concentration, while polarization analysis yields structural information in terms of point group symmetry. Our findings highlight the potential of dynamic angle-resolved harmonic light scattering to probe crystal growth processes, assembly–disassembly of biological systems, adsorption, transport through membranes and myriad other applications.