Nanoscale visualization of metallic electrodeposition in a well-controlled chemical environment.

Liquid phase transmission electron microscopy (TEM) provides a useful means to study a wide range of dynamics in solution with near-atomic spatial resolution and sub-microsecond temporal resolution. However, it is still a challenge to control the chemical environment (such as the flow of liquid, flow rate, and the liquid composition) in a liquid cell, and evaluate its effect on the various dynamic phenomena. In this work, we have systematically demonstrated the flow performance of anin situliquid TEM system, which is based on 'on-chip flow' driven by external pressure pumps. We studied the effects of different chemical environments in the liquid cell as well as the electrochemical potential on the deposition and dissolution behavior of Cu crystals. The results show that uniform Cu deposition can be obtained at a higher liquid flow rate (1.38µl min-1), while at a lower liquid flow rate (0.1µl min-1), the growth of Cu dendrites was observed. Dendrite formation could be further promoted byin situaddition of foreign ions, such as phosphates. The generality of this technique was confirmed by studying Zn electrodeposition. Our direct observations not only provide new insights into understanding the nucleation and growth but also give guidelines for the design and synthesis of desired nanostructures for specific applications. Finally, the capability of controlling the chemical environment adds another dimension to the existing liquid phase TEM technique, extending the possibilities to study a wide range of dynamic phenomena in liquid media.

In situ electrochemistry inside a TEM with controlled mass transport.

The field of electrochemistry promises solutions for the future energy crisis and environmental deterioration by developing optimized batteries, fuel-cells and catalysts. Combined with in situ transmission electron microscopy (TEM), it can reveal functional and structural changes. A drawback of this relatively young field is lack of reproducibility in controlling the liquid environment while retaining the imaging and analytical capabilities. Here, a platform for in situ electrochemical studies inside a TEM with a pressure-driven flow is presented, with the capability to control the flow direction and to ensure the liquid will always pass through the region of interest. As a result, the system offers the opportunity to define the mass transport and control the electric potential, giving access to the full kinetics of the redox reaction. In order to show the benefits of the system, copper dendrites are electrodeposited and show reliable electric potential control. Next, their morphology is changed by tuning the mass transport conditions. Finally, at a liquid thickness of approximately 100 nm, the diffraction pattern revealed the 1,1,1 planes of the copper crystals, indicating an atomic resolution down to 2.15 Å. Such control of the liquid thickness enabled elemental mapping, allowing us to distinguish the spatial distribution of different elements in liquid.