Scanning transmission electron microscopy (STEM) allows atomic scale characterization of solid–solid interfaces, but has seen limited applications to solid–liquid interfaces due to the volatility of liquids in the microscope vacuum. Although cryo-electron microscopy is routinely used to characterize hydrated samples stabilized by rapid freezing, sample thinning is required to access the internal interfaces of thicker specimens. Here, we adapt cryo-focused ion beam (FIB) “lift-out,” a technique recently developed for biological specimens, to prepare intact internal solid–liquid interfaces for high-resolution structural and chemical analysis by cryo-STEM. To guide the milling process we introduce a label-free in situ method of localizing subsurface structures in suitable materials by energy dispersive X-ray spectroscopy (EDX). Monte Carlo simulations are performed to evaluate the depth-probing capability of the technique, and show good qualitative agreement with experiment. We also detail procedures to produce homogeneously thin lamellae, which enable nanoscale structural, elemental, and chemical analysis of intact solid–liquid interfaces by analytical cryo-STEM. This work demonstrates the potential of cryo-FIB lift-out and cryo-STEM for understanding physical and chemical processes at solid–liquid interfaces.

Materials phenomena ranging from the melting or freezing of ice to biomineralization in living organisms, to lubrication and the commercial casting of superalloys, are known to be critically influenced by molecular-scale structure and processes occurring at the interfaces between the crystalline solid and liquid phases. The properties of solid–liquid interfaces have long been a topic of intense interest in materials science, primarily because of their role in governing nucleation, growth, and morphological evolution in crystal growth from the melt or solutions.This issue of the MRS Bulletin provides an overview, highlighting new developments in experiment, theory, and modeling techniques that have led to substantial recent progress in the characterization of the molecular-level structural and thermodynamic properties of solid–liquid interfaces and their consequences for a variety of crystallization phenomena.

In situ transmission electron microscopy (TEM) studies allow one to determine the structure, chemistry, and kinetic behavior of solid–liquid (S–L) interfaces with subnanometer spatial resolution. This article illustrates some important contributions of in situ TEM to our understanding of S–L interfaces in Al-Si alloys and liquid In particles in Al and Fe matrices.Four main areas are discussed:ordering in the liquid at a S–L interface, compositional changes across the interface, the kinetics and mechanisms of interface migration, and the contact angles and equilibrium melting temperature of small particles.Results from these studies reveal that (1)partially ordered layers form in the liquid at a Si{111} S–L interface in an Al–Si alloy, (2)the crystalline and compositional changes occur simultaneously across an Al S–L interface, (3)the Al interface is diffuse and its growth can be followed at velocities of a fewnm/s at extremely low undercoolings, and (4)the melting temperature of In particles less than ~ 10 nm in diameter can be raised or lowered in Al or Fe, depending on the contact angle that the S–L interface makes at the three-phase junction. These results illustrate the benefits of in situ TEM for providing fundamental insight into the mechanisms that control the behavior of S–L interfaces in materials.