Selected Area Manipulation of MoS2 via Focused Electron Beam-Induced Etching for Nanoscale Device Editing.

We demonstrate direct-write patterning of single and multilayer MoS2 via a focused electron beam-induced etching (FEBIE) process mediated with the XeF2 precursor. MoS2 etching is performed at various currents, areal doses, on different substrates, and characterized using scanning electron and atomic force microscopies as well as Raman and photoluminescence spectroscopies. Scanning transmission electron microscopy reveals a sub-40 nm etching resolution and the progression of point defects and lateral etching of the consequent unsaturated bonds. The results confirm that the electron beam-induced etching process is minimally invasive to the underlying material in comparison to ion beam techniques, which damage the subsurface material. Single-layer MoS2 field-effect transistors are fabricated, and device characteristics are compared for channels that are edited via the selected area etching process. The source-drain current at constant gate and source-drain voltage scale linearly with the edited channel width. Moreover, the mobility of the narrowest channel width decreases, suggesting that backscattered and secondary electrons collaterally affect the periphery of the removed area. Focused electron beam doses on single-layer transistors below the etching threshold were also explored as a means to modify/thin the channel layer. The FEBIE exposures showed demonstrative effects via the transistor transfer characteristics, photoluminescence spectroscopy, and Raman spectroscopy. While strategies to minimize backscattered and secondary electron interactions outside of the scanned regions require further investigation, here, we show that FEBIE is a viable approach for selective nanoscale editing of MoS2 devices.

Selected Area Deposition of High Purity Gold for Functional 3D Architectures.

Selected area deposition of high purity gold films onto nanoscale 3D architectures is highly desirable as gold is conductive, inert, plasmonically active, and can be functionalized with thiol chemistries, which are useful in many biological applications. Here, we show that high-purity gold coatings can be selectively grown with the Me2Au (acac) precursor onto nanoscale 3D architectures via a pulsed laser pyrolytic chemical vapor deposition process. The selected area of deposition is achieved due to the high thermal resistance of the nanoscale geometries. Focused electron beam induced deposits (FEBID) and carbon nanofibers are functionalized with gold coatings, and we demonstrate the effects that laser irradiance, pulse width, and precursor pressure have on the growth rate. Furthermore, we demonstrate selected area deposition with a feature-targeting resolutions of ~100 and 5 µm, using diode lasers coupled to a multimode (915 nm) and single mode (785 nm) fiber optic, respectively. The experimental results are rationalized via finite element thermal modeling.

Thermal and Photophysical Properties of Highly Quadrupolar Liquid-Crystalline Derivatives of the [closo-B12 H12 ]2- Anion.

Two series of 1,12-bis-zwitterionic derivatives of the [closo-B12 H12 ]2- anion (B), containing either two 4-alkoxypyridinium groups (1B[n]-p) or one 4-alkoxypyridinium and one 4-pentylthianium groups (2B[n]-p), were prepared and their structural (XRD, DFT), thermal, and photophysical properties were compared with those of the analogous derivatives of the [closo-B10 H10 ]2- anion (1A[n]-p and 2A[n]-p). Some 1,7-derivatives of B were isolated and investigated. Both series 1[n] and 2[n] exhibit nematic and crystalline polymorphism; the 12-vertex derivatives (B) have higher transition temperatures than those of the 10-vertex analogues (A). All compounds fluoresce with quantum yields higher for 1B (ΦF =0.37 for 1B[7]-p and ΦF =0.27 for 2B[7]-p) than those for the 10-vertex analogues (ΦF =0.04 for 2A[5]-p). DFT calculations demonstrate an order of magnitude lower first hyperpolarizability, ß(-ω,ω,0) , for 2B[7]-p than that for the 10-vertex analogue 2A[7]-p (1.7×10-30 vs. 18.9×10-30  esu at ω=0).

Nonequilibrium Synthesis of TiO2 Nanoparticle "Building Blocks" for Crystal Growth by Sequential Attachment in Pulsed Laser Deposition.

Nonequilibrium growth pathways for crystalline nanostructures with metastable phases are demonstrated through the gas-phase formation, attachment, and crystallization of ultrasmall amorphous nanoparticles as building blocks in pulsed laser deposition (PLD). Temporally and spatially resolved gated-intensified charge couple device (ICCD) imaging and ion probe measurements are employed as in situ diagnostics to understand and control the plume expansion conditions for the synthesis of nearly pure fluxes of ultrasmall (∼3 nm) amorphous TiO2 nanoparticles in background gases and their selective delivery to substrates. These amorphous nanoparticles assemble into loose, mesoporous assemblies on substrates at room temperature but dynamically crystallize by sequential particle attachment at higher substrate temperatures to grow nanostructures with different phases and morphologies. Molecular dynamics calculations are used to simulate and understand the crystallization dynamics. This work demonstrates that nonequilibrium crystallization by particle attachment of metastable ultrasmall nanoscale "building blocks" provides a versatile approach for exploring and controlling the growth of nanoarchitectures with desirable crystalline phases and morphologies.