Franz Schmidt

Morphing a Plasmonic Nanodisk into a Nanotriangle

We morph a silver nanodisk into a nanotriangle by producing a series of nanoparticles with electron beam lithography. Using electron energy loss spectroscopy (EELS), we map out the plasmonic eigenmodes and trace the evolution of edge and film modes during morphing. Our results suggest that disk modes, characterized by angular order, can serve as a suitable basis for other nanoparticle geometries and are subject to resonance energy shifts and splittings, as well as to hybridization upon morphing. Similar to the linear combination of atomic orbitals (LCAO) in quantum chemistry, we introduce a linear combination of plasmonic eigenmodes to describe plasmon modes in different geometries, hereby extending the successful hybridization model of plasmonics.

Correlated 3D Nanoscale Mapping and Simulation of Coupled Plasmonic Nanoparticles.

Electron tomography in combination with electron energy-loss spectroscopy (EELS) experiments and simulations was used to unravel the interplay between structure and plasmonic properties of a silver nanocuboid dimer. The precise 3D geometry of the particles fabricated by means of electron beam lithography was reconstructed through electron tomography, and the full three-dimensional information was used as an input for simulations of energy-loss spectra and plasmon resonance maps. Excellent agreement between experiment and theory was found throughout, bringing the comparison between EELS imaging and simulations to a quantitative and correlative level. In addition, interface mode patterns, normally masked by the projection nature of a transmission microscopy investigation, could be unambiguously identified through tomographic reconstruction. This work overcomes the need for geometrical assumptions or symmetry restrictions of the sample in simulations and paves the way for detailed investigations of realistic and complex plasmonic nanostructures.

Synthesis and morphology of iron-iron oxide core-shell nanoparticles produced by high pressure gas condensation

Core-shell structured Fe nanoparticles (NPs) produced by high pressure magnetron sputtering gas condensation were studied using transmission electron microscopy (TEM) techniques, electron diffraction, electron energy-loss spectroscopy (EELS), tomographic reconstruction, and Wulff shape construction analysis. The core-shell structure, which is composed of an Fe core surrounded by a maghemite (γ-Fe2O3) and/or magnetite (Fe3O4) shell, was confirmed by fast Fourier transform (FFT) analysis combined with EELS. It was found that the particle size and shape strongly depend on the gas environment. Moreover, extensive analysis showed that NPs with a size between 10-20 nm possess a truncated cubic morphology, which is confined by the 6 {100} planes that are truncated by the 12 {110} planes at different degrees. For NPs larger than 20 nm, the rhombic dodecahedron defined by the 12 {110} planes is the predominant crystal shape, while truncated rhombic dodecahedrons, as well as non-truncated and truncated cubic NPs, were also observed. The NPs without truncation showed a characteristic inward relaxation indicating that besides thermodynamics kinetics also plays a crucial role during particle growth.

In situ Determination and Imaging of Physical Properties of Soft Organic Materials by Analytical Transmission Electron Microscopy

Analytical transmission electron microscopy (ATEM) offers great flexibility in identification of the structural-chemical organization of soft materials at the level of individual macromolecules. However, the determination of mechanical characteristics such as hardness/elasticity of the amorphous and polycrystalline organic substances by ATEM has been problematic so far. Here, we show that energy filtered TEM (EFTEM) measurements enable direct identification and study of mechanical properties in complex (bio-)polymer systems of relevance for different industrial and (bio-)medical applications. We experimentally demonstrate strong correlations between hardness/elasticity of different polymers (polycaprolactone, polylactid, polyethelene, etc.) and their volume plasmon energy. Thickness and anisotropy effects, which substantially mask the material contrast in EFTEM bulk plasmon images, can be adequately removed by normalizing the latter by carbon elemental map. EFTEM data has been validated using atomic force microscopy phase images, where phase shift related to the hardness and elastic modulus of the materials.

How Dark Are Radial Breathing Modes in Plasmonic Nanodisks

Due to a vanishing dipole moment, radial breathing modes in small flat plasmonic nanoparticles do not couple to light and have to be probed with a near-field source, as in electron energy loss spectroscopy (EELS). With increasing particle size, retardation gives rise to light coupling, enabling probing breathing modes optically or by cathodoluminescence (CL). Here, we investigate single silver nanodisks with diameters of 150–500 nm by EELS and CL in an electron microscope and quantify the EELS/CL ratio, which corresponds to the ratio of full to radiative damping of the breathing mode. For the investigated diameter range, we find the CL signal to increase by about 1 order of magnitude, in agreement with numerical simulations. Due to reciprocity, our findings corroborate former optical experiments and enable a quantitative understanding of the light coupling of dark plasmonic modes.

Analytical Electron Tomography: Methods and Applications

Electron tomography is a powerful technique for 3D characterization at the nanoscale. Recent developments focus on extracting a wide range of information about a sample in 3D [1]. Of special interest is the combination of electron tomography with spectroscopic techniques EFTEM, EELS and EDS to recover the information present in spectroscopic signals in three dimensions. Analytical electron tomography allows mapping of chemical variations and gradients, approaching the goal of full 3D elemental quantification [2]. Additionally, EELS tomography can be used to extract information about materials properties or chemical bonding [3,4]. In this presentation we will discuss the steps necessary to successfully combine spectroscopy and tomography and show respective applications.