Martin Drost

Region‐Selective Deposition of Core–Shell Nanoparticles for 3 D 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.

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

Summary 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.

On the magnetic properties of iron nanostructures fabricated via focused electron beam induced deposition and autocatalytic growth processes

We employ Electron beam induced deposition (EBID) in combination with autocatalytic growth (AG) processes to fabricate magnetic nanostructures with controllable shapes and thicknesses. Following this route, different Fe deposits were prepared on silicon nitride membranes under ultra-high vacuum conditions and studied by scanning electron microscopy (SEM) and scanning transmission x-ray microspectroscopy (STXM). The originally deposited Fe nanostructures are composed of pure iron, especially when fabricated via autocatalytic growth processes. Quantitative near-edge x-ray absorption fine structure (NEXAFS) spectroscopy was employed to derive information on the thickness dependent composition. X-ray magnetic circular dichroism (XMCD) in STXM was used to derive the magnetic properties of the EBID prepared structures. STXM and XMCD analysis evinces the existence of a thin iron oxide layer at the deposit-vacuum interface, which is formed during exposure to ambient conditions. We were able to extract magnetic hysteresis loops for individual deposits from XMCD micrographs with varying external magnetic field. Within the investigated thickness range (2-16 nm), the magnetic coercivity, as evaluated from the width of the hysteresis loops, increases with deposit thickness and reaches a maximum value of ∼160 Oe at around 10 nm. In summary, we present a viable technique to fabricate ferromagnetic nanostructures in a controllable way and gain detailed insight into their chemical and magnetic properties.

Additive fabrication of nanostructures with focused soft X-rays

We report on a novel technique for the fabrication of metallic nanostructures via soft X-ray irradiation of precursor molecules supplied from the gas phase. With this technique we were able to produce localized Co nanostructures with a growth rate and purity competitive with electron beam induced deposition. We demonstrate that our approach exhibits significant selectivity with respect to incident photon energy leading to enhanced growth for resonant absorption energy of the precursor molecule. Based on this finding we propose a unique new pathway of selective deposition from precursor mixtures. Furthermore, we investigated the growth rate with respect to precursor pressure and growth time and discuss the potential resolution limits of this new technique.

Exploring the fabrication of Co and Mn nanostructures with focused soft x-ray beam induced deposition

Focused soft X-ray beam induced deposition of metallic deposits from metal organic precursors is a promising novel technique for additive nanostructure fabrication. In the present work, the authors present a comparative study for deposition and in situ characterization of Co and Mn nanostructures in a scanning transmission x-ray microscope. The authors detect a significant selectivity of the deposition process with respect to the incident photon energy that arises from the enhanced x-ray absorption cross section of the precursor molecules for near-threshold excitation. This effect has been investigated for the L2,3-edges of the respective metal centers of two different precursor molecules as well as the N and O K-edges of the respective ligands. The authors find a photon-limited growth mode for deposition from cobalt tricarbonyl nitrosyl [Co(CO)3NO], while the process is precursor-limited for methylcyclopentadienyl manganese tricarbonyl [MeCpMn(CO)3] possibly due to a comparably low vapor pressure of the ...

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.