Region-Selective Deposition of Core-Shell Nanoparticles for 3D Hierarchical Assemblies by the Huisgen 1,3-Dipolar Cycloaddition.

A method for the region-selective deposition of nanoparticles (NPs) by the Huisgen 1,3-dipolar cycloaddition is presented. The approach enables defined stacking of various oxide NPs in any order with control over layer thickness. Thereby the reaction is performed between a substrate, functionalized with a self-assembled monolayer of an azide-bearing phosphonic acid (PA) and aluminum oxide (AlO(x)) NPs functionalized with an alkyne bearing PA. The layer of alkyne functionalized AlO(x) NPs is then used as substrate for the deposition of azide-functionalized indium tin oxide (ITO) NPs to provide a binary stack. This progression is then conducted with alkyne-functionalized CeO2 NPs, yielding a ternary stack of NPs with three different NP cores. The stacks are characterized by AFM and SEM, defining the region-selectivity of the deposition technique. Finally, these assemblies have been tested in devices as a dielectric to form a capacitor resulting in a dramatic increase in the measured capacitance.

Coverage dependent disorder-order transition of 2H-tetraphenylporphyrin on Cu(111).

In this study, we investigate the peculiar coverage dependent supramolecular arrangement of 2H-tetraphenylporhpyrin (2HTPP) on Cu(111) with scanning tunneling microscopy at room-temperature. At low coverage, "slow" diffusion of individual 2HTPP molecules along the close-packed atomic rows of the substrate is observed, and no supramolecular ordering occurs. However, at higher coverage, the formation of ordered, checkerboard-like domains is found, with two molecules per unit cell at different distances from the surface. This behavior is attributed to a complex interplay of site specific molecule-substrate interaction, mainly the strong interaction between the iminic N atoms and Cu substrate atoms, with intermolecular T-type and π-π interactions.

Surface-Anchored Metal-Organic Frameworks as Versatile Resists for Gas-Assisted E-Beam Lithography: Fabrication of Sub-10 Nanometer Structures.

We demonstrate that surface-anchored metal-organic frameworks (SURMOFs) are extraordinary well-suited as resists for high-resolution focused electron beam induced processing (FEBIP) techniques. The combination of such powerful lithographic protocols with the huge versatility of MOF materials are investigated in respect to their potential in nanostructures fabrication. The applied FEBIP methods rely on the local decomposition of Fe(CO)5 and Co(CO)3NO as precursors, either by the direct impact of the focused electron beam (electron beam induced deposition, EBID) or through the interaction of the precursor molecules with preirradiated/activated SURMOF areas (electron beam induced surface activation, EBISA). We demonstrate the huge potential of the approach for two different types of MOFs (HKUST-1 and Zn-DPDCPP). Our "surface science" approach to FEBIP, yields well-defined deposits with each investigated precursor/SURMOF combination. Local Auger electron spectroscopy reveals clean iron deposits from Fe(CO)5; deposits from Co(CO)3NO contain cobalt, nitrogen, and oxygen. EBISA experiments were successful with Fe(CO)5. Remarkably EBISA with Co(CO)3NO does not result in deposit formation on both resists, making the process chemically selective. Most importantly we demonstrate the fabrication of "nested-L" test structures with Fe(CO)5 on HKUST-1 with extremely narrow line widths of partially less than 8 nm, due to reduced electron proximity effects within the MOF-based resists. Considering that the actual diameter of the electron beam was larger than 6 nm, we see a huge potential for significant reduction of the structure sizes. In addition, the role and high potential of loading and transport of the precursor molecules within the porous SURMOF materials is discussed.

Localized growth of carbon nanotubes via lithographic fabrication of metallic deposits.

We report on the fabrication of carbon nanotubes (CNTs) at predefined positions and controlled morphology, for example, as individual nanotubes or as CNT forests. Electron beam induced deposition (EBID) with subsequent autocatalytic growth (AG) was applied to lithographically produce catalytically active seeds for the localized growth of CNTs via chemical vapor deposition (CVD). With the precursor Fe(CO)5 we were able to fabricate clean iron deposits via EBID and AG. After the proof-of-principle that these Fe deposits indeed act as seeds for the growth of CNTs, the influence of significant EBID/AG parameters on the deposit shape and finally the yield and morphology of the grown CNTs was investigated in detail. Based on these results, the parameters could be optimized such that EBID point matrixes (6 × 6) were fabricated on a silica surface whereby at each predefined site only one CNT was produced. Furthermore, the localized fabrication of CNT forests was targeted and successfully achieved on an Al2O3 layer on a silicon sample. A peculiar lift-up of the Fe seed structures as "flakes" was observed and the mechanism was discussed. Finally, a proof-of-principle was presented showing that EBID deposits from the precursor Co(CO)3NO are also very effective catalysts for the CNT growth. Even though the metal content (Co) of the latter is reduced in comparison to the Fe deposits, effective CNT growth was observed for the Co-containing deposits at lower CVD temperatures than for the corresponding Fe deposits.

Electron-beam induced deposition and autocatalytic decomposition of Co(CO)3NO.

The autocatalytic growth of arbitrarily shaped nanostructures fabricated by electron beam-induced deposition (EBID) and electron beam-induced surface activation (EBISA) is studied for two precursors: iron pentacarbonyl, Fe(CO)5, and cobalt tricarbonyl nitrosyl, Co(CO)3NO. Different deposits are prepared on silicon nitride membranes and silicon wafers under ultrahigh vacuum conditions, and are studied by scanning electron microscopy (SEM) and scanning transmission X-ray microscopy (STXM), including near edge X-ray absorption fine structure (NEXAFS) spectroscopy. It has previously been shown that Fe(CO)5 decomposes autocatalytically on Fe seed layers (EBID) and on certain electron beam-activated surfaces, yielding high purity, polycrystalline Fe nanostructures. In this contribution, we investigate the growth of structures from Co(CO)3NO and compare it to results obtained from Fe(CO)5. Co(CO)3NO exhibits autocatalytic growth on Co-containing seed layers prepared by EBID using the same precursor. The growth yields granular, oxygen-, carbon- and nitrogen-containing deposits. In contrast to Fe(CO)5 no decomposition on electron beam-activated surfaces is observed. In addition, we show that the autocatalytic growth of nanostructures from Co(CO)3NO can also be initiated by an Fe seed layer, which presents a novel approach to the fabrication of layered nanostructures.