Implementing the modern technologies of light-emitting devices, light harvesting, and quantum information processing requires the understanding of the structure–function relations at spatial scales below the optical diffraction limit and time scales of energy and information flows. Here, we distinctively combine cathodoluminescence (CL) with ultrafast electron microscopy (UEM), termed CL-UEM, because CL and UEM synergetically afford the required spectral and spatiotemporal sensitivities, respectively. For color centers in nanodiamonds, we demonstrate the measurement of CL lifetime with a local sensitivity of 50 nm and a time resolution of 100 ps. It is revealed that the emitting states of the color centers can be populated through charge transfer among the color centers across diamond lattices upon high-energy electron beam excitation. The technical advance achieved in this study will facilitate the specific control over energy conversion at nanoscales, relevant to quantum dots and single-photon sources.

The shaping of matter into desired nanometric structures with on-demand functionalities can enhance the miniaturization of devices in nanotechnology. Herein, strong light–matter interaction was used as an optical lithographic tool to tailor two-dimensional (2D) matter into nanoscale architectures. We transformed 2D black phosphorus (BP) into ultrafine, well-defined, beyond-diffraction-limit nanostructures of ten times smaller size and a hundred times smaller spacing than the incident, femtosecond-pulsed light wavelength. Consequently, nanoribbons and nanocubes/cuboids scaling tens of nanometers were formed by the structured ablation along the extremely confined periodic light fields originating from modulation instability, the tailoring process of which was visualized in real time via light-coupled in situ transmission electron microscopy. The current findings on the controllable nanoscale shaping of BP will enable exotic physical phenomena and further advance the optical lithographic techniques for 2D materials.

Using an energy filter in transmission electron microscopy has enabled elemental mapping at the atomic scale and improved the precision of structural determination by gating inelastic and elastic imaging electrons, respectively. Here, we use an energy filter in ultrafast electron microscopy to enhance the temporal resolution toward the domain of atomic motion. Visualizing transient structures with femtosecond temporal precision was achieved by selecting imaging electrons in a narrow energy distribution from dense chirped photoelectron packets with broad longitudinal momentum distributions and thus typically exhibiting picosecond durations. In this study, the heterogeneous ultrafast phase transitions of vanadium dioxide (VO 2 ) nanoparticles, a representative strongly correlated system, were filmed and attributed to the emergence of a transient, low-symmetry metallic phase caused by different local strains. Our approach enables electron microscopy to access the time scale of elementary nuclear motion to visualize the onset of the structural dynamics of matter at the nanoscale.