Crystal phase switching between the zincblende and wurtzite structures in III-V nanowires is crucial from the fundamental viewpoint as well as for electronic and photonic applications of crystal phase heterostructures. Here, the results of in situ monitoring of self-catalyzed vapor-liquid-solid growth of GaAs nanowires by molecular beam epitaxy inside a transmission electron microscope is presented. It is demonstrated that the occurrence of the zincblende or wurtzite phase in self-catalyzed nanowires is determined by the sole parameter, the droplet contact angle, which can be finely tuned
Galvanic replacement (GR) is a simple and widely used approach to synthesize hollow nanostructures for applications in catalysis, plasmonics, and biomedical research. The reaction is driven by the difference in electrochemical potential between two metals in a solution. However, transient stages of this reaction are not fully understood. Here, we show using liquid cell transmission electron microscopy that silver (Ag) nanocubes become hollow via the nucleation, growth, and coalescence of voids inside the nanocubes, as they undergo GR with gold (Au) ions at different temperatures. These direct in situ observations indicate that void formation due to the nanoscale Kirkendall effect occurs in conjunction with GR. Although this mechanism has been suggested before, it has not been verified experimentally until now. These experiments can inform future strategies for deriving such nanostructures by providing insights into the structural transformations as a function of Au ion concentration, oxidation state of Au, and temperature.
Nanoparticles (NPs) confined in thin layers of liquid within liquid cells used for in situ transmission electron microscopy (TEM) move very slowly, in contrast to free particles in bulk liquid. The reason is still poorly understood. Here, we tracked gold NPs moving in water at the liquid−solid interface with in situ TEM at rates of 100 frames per second. The recorded motion exhibited three key features: (1) it was made up of sustained sequences of "sticky" motion where NPs only moved a few nanometers each time; (2) sporadic long "flights" where the NPs traveled tens to hundreds of nanometers between frames; and (3) "flights" are accompanied by intermittent, fast pivoted rotations. Trajectory analysis shows that the displacements follow a truncated Levy distribution, pointing to desorptionmediated motion of NPs at the liquid−solid interface. We further associate pivoted rotations with a transient "weakly adsorbed" state between desorption and adsorption of NPs. The frequency of desorption was also controlled by electron flux and solution chemistry. We propose that the pattern of motion is the result of an inhomogeneous distribution of surface charges on silicon nitride (SiN x ). Such insight into the interactions between NPs and solid surfaces in liquids is useful for understanding dynamics at liquid−solid interfaces and has general implications for microfluidics, nanotribology, sensing, and self-assembly.
The catalytic performance of bimetallic nanoparticles (NPs) strongly depends on their structural and compositional changes under reaction conditions. At the fundamental level, these changes are driven by redox reactions that occur on the surface of the NPs. The degree of complexity in the redox reactions is further amplified in bimetallic NPs because both metals can have their own reactions with the reactant molecules, in addition to any synergistic effects between the metal nanocatalysts and their reducible oxides. Here, the gas phase oxidation and reduction reactions, and the oxidation of carbon monoxide (CO) over Pt–Ni rhombic dodecahedron NPs with segregated Pt frames and Pt–Ni alloy NPs are investigated using in situ gas cell transmission electron microscopy. The real‐time observations show that NiO shell formation and Pt segregation are two important features during the oxidation and reduction of Pt–Ni NPs, respectively. Moreover, the two types of NPs evolved in different ways. By combining high‐resolution imaging, mass spectroscopy, and modeling, it is shown that the evolution of NP morphology and composition during redox reactions plays an important role in controlling the catalytic activity of the NPs.
Both chemical and electrochemical etching are effective methods for tailoring the surface composition of Pt-based catalytic bimetallic nanoparticles (NPs). However, the detailed nanoscale etching mechanisms, which are needed for achieving fine control over the etch processes, are still not understood. Here, we study selective chemical and electrochemical Ni etching of Pt−Ni rhombic dodecahedron NPs using in situ liquid-phase transmission electron microscopy. Our real-time observations show that the intermediate NP structures evolve differently in the two cases. Chemical etching of Ni starts from localized pits on the NP surface, in contrast to the uniform dissolution of Ni during the electrochemical etching. Our study reveals how oxidative etching participates in the removal of a non-noble metal and the subsequent formation of noblemetal-rich NPs. The mechanistic insights reported here highlight the role of a native surface oxide layer on the etching behavior, which is important for the design of NPs with specific surface composition for applications in electrocatalysis.
At elevated temperatures, bimetallic nanomaterials change their morphologies because of the interdiffusion of atomic species, which also alters their properties. The Kirkendall effect (KE) is a well-known phenomenon associated with such interdiffusion. Here, we show how KE can manifest in bimetallic nanoparticles (NPs) by following core–shell NPs of Au and Pd during heat treatment with in situ transmission electron microscopy. Unlike monometallic NPs, these core–shell NPs did not evolve into hollow core NPs. Instead, nanoscale voids formed at the bimetallic interface and then, migrated to the NP surface. Our results show that: (1) the direction of vacancy flow during interdiffusion reverses due to the higher vacancy formation energy of Pd compared to Au, and (2) nanoscale voids migrate during heating, contrary to conventional assumptions of immobile voids and void shrinkage through vacancy emission. Our results illustrate how void behavior in bimetallic NPs can differ from an idealized picture based on atomic fluxes and have important implications for the design of these materials for high-temperature applications.
Dense arrays of high-aspect-ratio (HAR) vertical nanostructures are essential elements of microelectronic components, photovoltaics, nanoelectromechanical, and energy storage devices. One of the critical challenges in manufacturing the HAR nanostructures is to prevent their capillary-induced aggregation during solution-based nanofabrication processes. Despite the importance of controlling capillary effects, the detailed mechanisms of how a solution interacts with nanostructures are not well understood. Using in situ liquid cell transmission electron microscopy (TEM), we track the dynamics of nanoscale drying process of HAR silicon (Si) nanopillars in real-time and identify a new mechanism responsible for pattern collapse and nanostructure aggregation. During drying, deflection and aggregation of nanopillars are driven by thin-liquid-film instability, which results in much stronger capillary interactions between the nanopillars than the commonly proposed lateral meniscus interaction forces. The importance of thin-film instability in dewetting has been overlooked in prevalent theories on elastocapillary aggregation. The new dynamic mechanism revealed by in situ visualization is essential for the development of robust nanofabrication processes.
Nanoparticles (NPs) can self-assemble into complex, organized superstructures on patterned surfaces through fluid-mediated interactions. However, the detailed mechanisms for such NP assemblies are largely unknown. Here, using in situ transmission electron microscopy, the stepwise self-assembly dynamics of hydrophobic gold NPs into long filaments formed on the surfaces of water-filled patterned nanochannel templates is observed. First, the formation of a meniscus between the nanochannel walls, during the slow drying of water, causes accumulation of the NPs in the middle of the nanochannels. Second, owing to the strong van der Waals attraction between the NP ligands, the NPs condense into filaments along the centers of the nanochannels. Filaments with highly fluctuating longitudinal NP densities are also observed to fragment into separated structures. Understanding the intermediate stages of fluid-mediated NP self-assembly on patterned surfaces will have important implications for the controlled formation of templated NP assemblies with numerous applications.
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