Capturing Nucleation at 4D Atomic Resolution

Nucleation plays a critical role in many physical and biological phenomena ranging from crystallization, melting and evaporation to the formation of clouds and the initiation of neurodegenerative diseases. However, nucleation is a challenging process to study in experiments especially in the early stage when several atoms/molecules start to form a new phase from its parent phase. Here, we advance atomic electron tomography to study early stage nucleation at 4D atomic resolution. Using FePt nanoparticles as a model system, we reveal that early stage nuclei are irregularly shaped, each has a core of one to few atoms with the maximum order parameter, and the order parameter gradient points from the core to the boundary of the nucleus. We capture the structure and dynamics of the same nuclei undergoing growth, fluctuation, dissolution, merging and/or division, which are regulated by the order parameter distribution and its gradient. These experimental observations differ from classical nucleation theory (CNT) and to explain them we propose the order parameter gradient (OPG) model. We show the OPG model generalizes CNT and energetically favours diffuse interfaces for small nuclei and sharp interfaces for large nuclei. We further corroborate this model using molecular dynamics simulations of heterogeneous and homogeneous nucleation in liquid-solid phase transitions of Pt. We anticipate that the OPG model is applicable to different nucleation processes and our experimental method opens the door to study the structure and dynamics of materials with 4D atomic resolution.Comment: 42 pages, 5 figures, 12 supplementary figures and one supplementary tabl

Designing Artificial Two-Dimensional Landscapes via Room-Temperature Atomic-Layer Substitution

Manipulating materials with atomic-scale precision is essential for the development of next-generation material design toolbox. Tremendous efforts have been made to advance the compositional, structural, and spatial accuracy of material deposition and patterning. The family of 2D materials provides an ideal platform to realize atomic-level material architectures. The wide and rich physics of these materials have led to fabrication of heterostructures, superlattices, and twisted structures with breakthrough discoveries and applications. Here, we report a novel atomic-scale material design tool that selectively breaks and forms chemical bonds of 2D materials at room temperature, called atomic-layer substitution (ALS), through which we can substitute the top layer chalcogen atoms within the 3-atom-thick transition-metal dichalcogenides using arbitrary patterns. Flipping the layer via transfer allows us to perform the same procedure on the other side, yielding programmable in-plane multi-heterostructures with different out-of-plane crystal symmetry and electric polarization. First-principle calculations elucidate how the ALS process is overall exothermic in energy and only has a small reaction barrier, facilitating the reaction to occur at room temperature. Optical characterizations confirm the fidelity of this design approach, while TEM shows the direct evidence of Janus structure and suggests the atomic transition at the interface of designed heterostructure. Finally, transport and Kelvin probe measurements on MoXY (X,Y=S,Se; X and Y corresponding to the bottom and top layers) lateral multi-heterostructures reveal the surface potential and dipole orientation of each region, and the barrier height between them. Our approach for designing artificial 2D landscape down to a single layer of atoms can lead to unique electronic, photonic and mechanical properties previously not found in nature

Revealing the Br{\o}nsted-Evans-Polanyi Relation in Halide-Activated Fast MoS2 Growth Towards Millimeter-Sized 2D Crystals

Achieving large-size two-dimensional (2D) crystals is key to fully exploiting their remarkable functionalities and application potentials. Chemical vapor deposition (CVD) growth of 2D semiconductors such as monolayer MoS2 has been reported to be activated by halide salts, yet clear identification of the underlying mechanism remains elusive. Here we provide unambiguous experimental evidence showing that the MoS2 growth dynamics are halogen-dependent through the Br{\o}nsted-Evans-Polanyi relation, based on which we build a growth model by considering MoS2 edge passivation by halogens, and theoretically reproduces the trend of our experimental observations. These mechanistic understandings enable us to further optimize the fast growth of MoS2 and reach record-large domain sizes that should facilitate practical applications.Comment: 18 pages, 5 figure

Towards complex and continuous manipulation : a gesture based anthropomorphic robotic hand design

Most current anthropomorphicrobotic hands can realize part of the human hand functions, particularly for object grasping. However, due to the complexity of the human hand, few current designs target at daily object manipulations, even for simple actions like rotating a pen. To tackle this problem, we introduce a gesture based framework, which adopts the widely-used 33 grasping gestures of Feix as the bases for hand design and implementation of manipulation. In the proposed framework, we first measure the motion ranges of human fingers for each gesture, and based on the results, we propose a simple yet dexterous robotic hand design with 13 degrees of actuation. Furthermore, we adopt a frame interpolation based method, in which we consider the base gestures as the key frames to represent a manipulation task, and use the simple linear interpolation strategy to accomplish the manipulation. To demonstrate the effectiveness of our framework, we define a three-level benchmark, which includes not only 62 test gestures from previous research, but also multiple complex and continuous actions. Experimental results on this benchmark validate the dexterity of the proposed design and our video is available in https://drive.google.com/file/d/1wPtkd2P0zolYSBW7_3tVMUHrZEeXLXgD/view?usp=sharing.National Research Foundation (NRF)s. This work was supported by National Research Foundation, Singapore under its International Research Centres in Singapore Funding Initiative and Institute for Media Innovation, Nanyang Technological University (IMI-NTU)

Superexchange-stabilized long-distance Cu sites in rock-salt-ordered double perovskite oxides for CO2 electromethanation

Abstract Cu-oxide-based catalysts are promising for CO2 electroreduction (CO2RR) to CH4, but suffer from inevitable reduction (to metallic Cu) and uncontrollable structural collapse. Here we report Cu-based rock-salt-ordered double perovskite oxides with superexchange-stabilized long-distance Cu sites for efficient and stable CO2-to-CH4 conversion. For the proof-of-concept catalyst of Sr2CuWO6, its corner-linked CuO6 and WO6 octahedral motifs alternate in all three crystallographic dimensions, creating sufficiently long Cu-Cu distances (at least 5.4 Å) and introducing marked superexchange interaction mainly manifested by O-anion-mediated electron transfer (from Cu to W sites). In CO2RR, the Sr2CuWO6 exhibits significant improvements (up to 14.1 folds) in activity and selectivity for CH4, together with well boosted stability, relative to a physical-mixture counterpart of CuO/WO3. Moreover, the Sr2CuWO6 is the most effective Cu-based-perovskite catalyst for CO2 methanation, achieving a remarkable selectivity of 73.1% at 400 mA cm−2 for CH4. Our experiments and theoretical calculations highlight the long Cu-Cu distances promoting *CO hydrogenation and the superexchange interaction stabilizing Cu sites as responsible for the superb performance