All Publications

  • Anomalous pressure-dependence in surface-modified silicon-derived nanoparticles NANO RESEARCH Li, Q., Parakh, A., Jin, R., Gu, X. 2021
  • Effect of crystal structure and grain size on corrosion properties of AlCoCrFeNi high entropy alloy JOURNAL OF ALLOYS AND COMPOUNDS Parakh, A., Vaidya, M., Kumar, N., Chetty, R., Murty, B. S. 2021; 863
  • Ductile Metallic Glass Nanoparticles via Colloidal Synthesis. Nano letters Kiani, M. T., Barr, C. M., Xu, S., Doan, D., Wang, Z., Parakh, A., Hattar, K., Gu, X. W. 2020


    The design of ductile metallic glasses has been a longstanding challenge. Here, we use colloidal synthesis to fabricate nickel-boron metallic glass nanoparticles that exhibit homogeneous deformation at room temperature and moderate strain rates. In situ compression testing is used to characterize the mechanical behavior of 90-260 nm diameter nanoparticles. The force-displacement curves consist of two regimes separated by a slowly propagating shear band in small, 90 nm particles. The propensity for shear banding decreases with increasing particle size, such that large particles are more likely to deform homogeneously through gradual shape change. We relate this behavior to differences in composition and atomic bonding between particles of different size using mass spectroscopy and XPS. We propose that the ductility of the nanoparticles is related to their internal structure, which consists of atomic clusters made of a metalloid core and a metallic shell that are connected to neighboring clusters by metal-metal bonds.

    View details for DOI 10.1021/acs.nanolett.0c02177

    View details for PubMedID 32786936

  • Stress-Induced Structural Transformations in Au Nanocrystals. Nano letters Parakh, A. n., Lee, S. n., Kiani, M. T., Doan, D. n., Kunz, M. n., Doran, A. n., Ryu, S. n., Gu, X. W. 2020


    Nanocrystals can exist in multiply twinned structures like icosahedron or single crystalline structures like cuboctahedron. Transformations between these structures can proceed through diffusion or displacive motion. Experimental studies on nanocrystal structural transformations have focused on high-temperature diffusion-mediated processes. Limited experimental evidence of displacive motion exists. We report structural transformation of 6 nm Au nanocrystals under nonhydrostatic pressure of 7.7 GPa in a diamond anvil cell that is driven by displacive motion. X-ray diffraction and transmission electron microscopy were used to detect the structural transformation from multiply twinned to single crystalline. Single crystalline nanocrystals were recovered after unloading, then quickly reverted to the multiply twinned state after dispersion in toluene. The dynamics of recovery was captured using TEM which showed surface recrystallization and rapid twin boundary motion. Molecular dynamics simulations showed that twin boundaries are unstable due to defects nucleated from the interior of the nanocrystal.

    View details for DOI 10.1021/acs.nanolett.0c03371

    View details for PubMedID 33016704

  • Nucleation of Dislocations in 3.9 nm Nanocrystals at High Pressure. Physical review letters Parakh, A. n., Lee, S. n., Harkins, K. A., Kiani, M. T., Doan, D. n., Kunz, M. n., Doran, A. n., Hanson, L. A., Ryu, S. n., Gu, X. W. 2020; 124 (10): 106104


    As circuitry approaches single nanometer length scales, it has become important to predict the stability of single nanometer-sized metals. The behavior of metals at larger scales can be predicted based on the behavior of dislocations, but it is unclear if dislocations can form and be sustained at single nanometer dimensions. Here, we report the formation of dislocations within individual 3.9 nm Au nanocrystals under nonhydrostatic pressure in a diamond anvil cell. We used a combination of x-ray diffraction, optical absorbance spectroscopy, and molecular dynamics simulation to characterize the defects that are formed, which were found to be surface-nucleated partial dislocations. These results indicate that dislocations are still active at single nanometer length scales and can lead to permanent plasticity.

    View details for DOI 10.1103/PhysRevLett.124.106104

    View details for PubMedID 32216385

  • Pressure-Induced Optical Transitions in Metal Nanoclusters. ACS nano Li, Q. n., Mosquera, M. A., Jones, L. O., Parakh, A. n., Chai, J. n., Jin, R. n., Schatz, G. C., Gu, X. W. 2020


    Currently, a comprehensive understanding of the relationship between atomic structures and optical properties of ultrasmall metal nanoclusters with diameters between 1 and 3 nm is lacking. To address this challenge, it is necessary to develop tools for perturbing the atomic structure and modulating the optical properties of metal nanoclusters beyond what can be achieved using synthetic chemistry. Here, we present a systematic high-pressure study on a series of atomically precise ligand-protected metal nanoclusters. A diamond anvil cell is used as a high-pressure chamber to gradually compress the metal nanoclusters, while their optical properties are monitored in situ. Our experimental results show that the photoluminescence (PL) of these nanoclusters is enhanced by up to 2 orders of magnitude at pressures up to 7 GPa. The absorption onset red-shifts with increasing pressure up to ∼12 GPa. Density functional theory calculations reveal that the red-shift arises because of narrowing of the spacing between discrete energy levels of the cluster due to delocalization of the core electrons to the carbon ligands. The pressure-induced PL enhancement is ascribed to (i) the enhancement of the near-band-edge transition strength, (ii) suppression of the nonradiative vibrations, and (iii) hindrance of the excited-state structural distortions. Overall, our results demonstrate that high pressure is an effective tool for modulating the optical properties and improving the luminescence brightness of metal nanoclusters. The insights into structure-property relations obtained here also contribute to the rational design of metal nanoclusters for various optical applications.

    View details for DOI 10.1021/acsnano.0c04813

    View details for PubMedID 32790326