Yiliang Liao

Chemical mapping of a single molecule by plasmon-enhanced Raman scattering

Visualizing individual molecules with chemical recognition is a longstanding target in catalysis, molecular nanotechnology and biotechnology. Molecular vibrations provide a valuable ‘fingerprint’ for such identification. Vibrational spectroscopy based on tip-enhanced Raman scattering allows us to access the spectral signals of molecular species very efficiently via the strong localized plasmonic fields produced at the tip apex. However, the best spatial resolution of the tip-enhanced Raman scattering imaging is still limited to 3−15 nanometres, which is not adequate for resolving a single molecule chemically. Here we demonstrate Raman spectral imaging with spatial resolution below one nanometre, resolving the inner structure and surface configuration of a single molecule. This is achieved by spectrally matching the resonance of the nanocavity plasmon to the molecular vibronic transitions, particularly the downward transition responsible for the emission of Raman photons. This matching is made possible by the extremely precise tuning capability provided by scanning tunnelling microscopy. Experimental evidence suggests that the highly confined and broadband nature of the nanocavity plasmon field in the tunnelling gap is essential for ultrahigh-resolution imaging through the generation of an efficient double-resonance enhancement for both Raman excitation and Raman emission. Our technique not only allows for chemical imaging at the single-molecule level, but also offers a new way to study the optical processes and photochemistry of a single molecule.

Aligned electrospun ZnO nanofibers for simple and sensitive ultraviolet nanosensors.

The current of uni-axially aligned electrospun ZnO nanofibers is modulated reversibly under UV irradiation, with the sensitivity of the UV nanosensors depending on the surface coating of the nanofibers, due to the effect on the photo-generated current.

Nucleation of Highly Dense Nanoscale Precipitates Based on Warm Laser Shock Peening

Warm laser shock peening (WLSP) is an innovative thermomechanical processing technique, which combines the advantages of laser shock peening (LSP) and dynamic aging (DA). It has been found that a unique microstructure with highly dense nanoscale precipitates surrounded by dense dislocation structures is generated by WLSP. In order to understand the nucleation mechanism of the highly dense precipitates during WLSP, aluminum alloy 6061 (AA6061) has been used by investigating the WLSP process with experiments and analytical modeling. An analytical model has been proposed to estimate the nucleation rate in metallic materials after WLSP. The effects of the processing temperature and high strain rate deformation on the activation energy of nucleation have been considered in this model. This model is based on the assumption that DA during WLSP can be assisted by the dense dislocation structures and warm temperature. The effects of the working temperature and dislocation density on the activation energy of precipitation have been investigated. This model is validated by a series of experiments and characterizations after WLSP. The relationships between the processing conditions, the nucleation density of precipitates and the defect density have been investigated.

Deformation induced martensite in NiTi and its shape memory effects generated by low temperature laser shock peening

In this study, laser shock peening (LSP) was utilized to generate localized deformation induced martensite (DIM) in NiTi shape memory alloy. The DIM was investigated by x-ray diffraction and transmission electron microscopy. The effects of temperature and laser intensity on DIM transformation were investigated. It has been found that higher laser intensity and lower processing temperature leads to higher volume fraction of DIM. This is attributed to the increase of the chemical driving force and the increase in the density of potential martensite variant for martensite nucleation at low temperatures. The localized shape memory effect in micrometer scale after low temperature LSP has been evaluated.

Microstructure and mechanical properties of copper subjected to cryogenic laser shock peening

In this study, an innovative materials processing technique, cryogenic laser shock peening (CLSP), is investigated. Copper is processed by laser shock peening (LSP) at the cryogenic temperature and compared with LSP at room temperature (RT-LSP). The microstructure of copper after processing is characterized by transmission electron microscopy (TEM). Nanotwins were observed in copper after CLSP due to the effect of cryogenic temperature. In addition, more energy is stored in the material as defects (dislocations) by CLSP compared to RT-LSP. Because of these unique microstructure changes, it is found that high material strength with good thermal stability is achieved after CLSP. The mechanical properties after CLSP, RT-LSP, and as-received are compared.

Mechanism of Fatigue Performance Enhancement in a Laser Sintered Superhard Nanoparticles Reinforced Nanocomposite Followed by Laser Shock Peening

This study investigates the fundamental mechanism of fatigue performance enhancement during a novel hybrid manufacturing process, which combines laser sintering of superhard nanoparticles integrated nanocomposites and laser shock peening (LSP). Through laser sintering, TiN nanoparticles are integrated uniformly into iron matrix to form a nanocomposite layer near the surface of AISI4140 steel. LSP is then performed on the nanocomposite layer to generate interaction between nanoparticles and shock waves. The fundamental mechanism of fatigue performance enhancement is discussed in this paper. During laser shock interaction with the nanocomposites, the existence of nanoparticles increases the dislocation density and also helps to pin the dislocation movement. As a result, both dislocation density and residual stress are stabilized, which is beneficial for fatigue performance.

Cryogenic ultrahigh strain rate deformation induced hybrid nanotwinned microstructure for high strength and high ductility

Nanocrystalline metallic materials prepared by severe plastic deformation often possess high strength but low ductility due to the low dislocation accumulation capacity of the nanograins. Here, we report a unique process, namely, cryogenic laser shock peening (CLSP), to generate gradient nanotwinned microstructure that leads to high strength while preserving the ductility. It was observed that gradient structure was generated in copper. Near the top surface, nanocrystalline with high dense nanotwins have been observed; with the depth increasing, the fraction of the twin boundaries reduces and more heavily dislocated subgrains are observed. It has been demonstrated that CLSP can significantly improve material strength while preserving the ductility. The mechanism of the formation of gradient microstructure and high dense nanotwins near the surface was discussed. The reason behind the improvement in strength and ductility was investigated.

Dislocation Pinning Effects Induced by Nano-precipitates During Warm Laser Shock Peening: Dislocation Dynamic Simulation and Experiments

Warm laser shock peening (WLSP) is a new high strain rate surface strengthening process that has been demonstrated to significantly improve the fatigue performance of metallic components. This improvement is mainly due to the interaction of dislocations with highly dense nanoscale precipitates, which are generated by dynamic precipitation during the WLSP process. In this paper, the dislocation pinning effects induced by the nanoscale precipitates during WLSP are systematically studied. Aluminum alloy 6061 and AISI 4140 steel are selected as the materials with which to conduct WLSP experiments. Multiscale discrete dislocation dynamics (MDDD) simulation is conducted in order to investigate the interaction of dislocations and precipitates during the shock wave propagation. The evolution of dislocation structures during the shock wave propagation is studied. The dislocation structures after WLSP are characterized via transmission electron microscopy and are compared with the results of the MDDD simulation. The results show that nano-precipitates facilitate the generation of highly dense and uniformly distributed dislocation structures. The dislocation pinning effect is strongly affected by the density, size, and space distribution of nano-precipitates.

Tip-plasmon mediated molecular electroluminescence on the highly oriented pyrolytic graphite substrate

Well-defined molecular fluorescence is realized by tunneling electron excitations from porphyrins on highly oriented pyrolytic graphite that is non-plasmonic in the visible spectral range. The occurrence of molecular electroluminescence is found to rely critically on the plasmonic emitting state of scanning tunneling microscope tip that is pre-examined on silver. These observations, together with the selective enhancement of molecular emission bands by energy-matching tip plasmons, suggest that the plasmonic field is indispensable for the generation of molecular electroluminescence, and the tip plasmon alone is sufficient in achieving this. Excitation of molecules directly by electrons is inefficient to produce light.

Enhancement and suppression effect of molecules on nanocavity plasmon emissions excited by tunneling electrons

We use tunneling electron induced luminescence techniques to investigate the role of adsorbed molecules in nanocavity plasmon (NCP) mediated emissions. Porphyrin molecules directly adsorbed on metals are found to suppress NCP emissions, while molecules on top of an inserted ultrathin oxide layer on the metal substrate yield enhanced NCP emissions. We attribute such difference in enhancement versus suppression to a competing mechanism of two major roles of molecules on the local field enhancement: geometrical spacer and dynamic dipole oscillator. The latter could become dominant when molecules are sufficiently decoupled from the substrate, leading to the overall enhancement of NCP emissions.