Widely Varying Kondo and Magnetic Interactions in Molecule Gold Nanostructured Materials by Changing the Gold Nanoarchitecture.

Delocalized-localized electron interactions are central to strongly correlated electron phenomena. Here, we study the Kondo effect, a prototypical strongly correlated phenomena, in a tunable fashion using gold nanostructures (nanoparticle, NP, and nanoshell, NS) + molecule cross-linkers (butanedithiol, BDT). NP films exhibit hallmark signatures of the Kondo effect, including (1) a log temperature resistance upturn as temperature decreases in a metallic regime, and (2) zero-bias conductance peaks (ZBCPs) that are well fit by a Frota function near a percolation insulator transition, previously used to model Kondo peaks observed using tunnel junctions. Remarkably, NP + NS films exhibit ZBCPs that persist to >220 K, i.e., >10-fold higher than that in NP films. Magnetic measurements reveal that moments in NP powders align, and in NS powders, they antialign at low temperatures. Based on these observations, we propose a mechanism in which varying such material nanobuilding blocks can modify electron-electron interactions to such a large degree.

Large emergent optoelectronic enhancement in molecularly cross-linked gold nanoparticle nanosheets.

A central goal in molecular electronics and optoelectronics is to translate tailorable molecular properties to larger materials and to the device level. Here, we present a method to fabricate molecularly cross-linked, self-assembled 2D nanoparticle sheets (X-NS). Our method extends a Langmuir approach of self-assembling gold nanoparticle (NP) arrays at an air-water interface by replacing the liquid sub-phase to an organic solvent to enable cross-linking with organic molecules, and then draining the sub-phase to deposit films. Remarkably, X-NS comprising conjugated oligophenylene dithiol cross-linkers (HS-(C6H4)n-SH, 1 ≤ n ≤ 3) exhibit increasing conductance with molecule length, ~6 orders of magnitude enhancement in UV-Vis extinction coefficients, and photoconductivity with molecule vs. NP contributions varying depending on the excitation wavelength. Finite difference time domain (FDTD) analyses and control measurements indicate that these effects can be modeled provided the local complex dielectric constant is strongly modified upon cross-linking. This suggests quantum hybridization at a molecule-band (q-MB) level. Given the vast number of molecules and nano-building blocks available, X-NS have potential to significantly increase the range of available 2D nanosheets and associated quantum properties.

Large Kondo effect in assemblies of Au nanoparticles linked with alkanedithiol electron bridges.

Using a prototypical nanoparticle-molecule assembly, namely alkanedithiol-linked gold nanoparticle films, we observe hallmark signatures of the Kondo effect in conductance vs. voltage as well as temperature measurements. Its contribution to temperature dependence of conductance is much larger than those from all other temperature-dependant effects up to 300 K by >20-fold - much larger than previous reports of the Kondo effect using other platforms. We find that previous models of the Kondo effect describe our data even in this regime. Given the synthetic control available over nanoparticle properties such as surface area, shape, and chemical composition, our work points to combining flexibility afforded by molecule + nanoparticle assemblies as a powerful way to generate materials exhibiting strong spin-electron interactions.

Magnetic and Structural Studies of G-Phase Compound Mn6Ni16Si7.

Transition metal compounds with complex crystal structures tend to demonstrate interesting magnetic coupling resulting in unusual magnetic properties. In this work, the structural and magnetic characterization of a single crystal of the Ni-Mn-Si based G-phase compound, Mn6Ni16Si7, grown by the Czochralski method, is reported. In this structure, isolated octahedral Mn6 clusters form an fcc lattice. As each octahedron consists of eight edge-sharing equilateral triangles, the possibility for geometric frustration exists. Magnetization and specific heat measurements showed two magnetic phase transitions at 197 and 50 K, respectively. At 100 K neutron diffraction on powder samples shows a magnetic structure with k = (001) in which only four of the six Mn spins per cluster order along ⟨100⟩ directions giving a two-dimensional magnetic structure consistent with intracluster frustration. Below the 50 K phase transition, the Mn spin-cants away from ⟨100⟩ directions, and a weak moment develops on the two remaining Mn octahedral sites.

Single atomic layer detection of Ca and defect characterization of Bi-2212 with EELS in HA-ADF STEM.

By forming a small electron probe in a scanning transmission electron microscope equipped with a high-angle annular dark-field (HA-ADF) detector, the Bi-O atomic planes in Bi2Sr2CaCu2O(8+delta) (Bi-2212) can be directly observed with the incoherent Z-contrast imaging technique. Using a combination of electron energy loss spectroscopy (EELS) and HA-ADF imaging, we were able to detect the Ca signals from individual Ca atomic planes in this structure, so that the Ca distribution could be probed within individual unit cells. This high-spatial-resolution EELS technique has been successfully applied to characterize planar defects such as the half-unit cell intergrowth of Bi-2201 on the nanometer scale. Present results show that EELS, in conjunction with high-resolution HA-ADF imaging, provides a powerful tool to study chemical and structural nature of this material on the atomic scale.