Katja Höflich

The Direct Writing of Plasmonic Gold Nanostructures by Electron‐Beam‐Induced Deposition

The rapidly growing fi eld of nano-optics requires the development of fl exible and reliable fabrication methods at the nanometer scale. For that purpose direct writing of nanostructures is ideal. [ 1 ] One direct writing method at the nanometer scale is electron-beam-induced deposition (EBID). [ 2 ] This method makes use of a precursor gas, inserted into the vacuum chamber of an electron microscope, that is cracked under the focused electron beam. For precursor gases of metal organic (MO) nature (e.g., dimethyl-gold(III)-acetylacetonate as used in the work reported here), the deposits contain the metal component in the form of metal nanoparticles embedded in an amorphous carbonaceous matrix. [ 3 ]

Plasmonic dimer antennas for surface enhanced Raman scattering

Electron beam induced deposition (EBID) has recently been developed into a method to directly write optically active three-dimensional nanostructures. For this purpose a metal-organic precursor gas (here dimethyl-gold(III)-acetylacetonate) is introduced into the vacuum chamber of a scanning electron microscope where it is cracked by the focused electron beam. Upon cracking the aforementioned precursor gas, 3D deposits are realized, consisting of gold nanocrystals embedded in a carbonaceous matrix. The carbon content in the deposits hinders direct plasmonic applications. However, it is possible to activate the deposited nanostructures for plasmonics by coating the EBID structures with a continuous silver layer of a few nanometers thickness. Within this silver layer collective motions of the free electron gas can be excited. In this way, EBID structures with their intriguing precision at the nanoscale have been arranged in arrays of free-standing dimer antenna structures with nanometer sized gaps between the antennas that face each other with an angle of 90°. These dimer antenna ensembles can constitute a reproducibly manufacturable substrate for exploiting the surface enhanced Raman effect (SERS). The achieved SERS enhancement factors are of the order of 10⁴ for the incident laser light polarized along the dimer axes. To prove the signal enhancement in a Raman experiment we used the dye methyl violet as a robust test molecule. In future applications the thickness of such a silver layer on the dimer antennas can easily be varied for tuning the plasmonic resonances of the SERS substrate to match the resonance structure of the analytes to be detected.

Near-field investigations of nanoshell cylinder dimers

Metallic nanoparticles are known to exhibit strong particle size dependent localized surface plasmon resonances due to their specific optical response described via the complex dielectric function. Using the two-dimensional finite element method, the near-field behavior of core-shell nanocylinder dimers with either a dielectric or a gold core and a silver shell was investigated. With a detailed analysis the positions of maximum field enhancement usable for highly sensitive spectroscopy were unveiled and the surface charge distributions of the different kinds of resonances were visualized. It is shown that the usual far-field spectra do not give reliable estimates of local electric field peaks. Furthermore one observes a distinct mode at the natural plasma frequency of the silver shell which is independent of the core material. This mode is identified as a volume plasmon mode.

Plasmonic gold helices for the visible range fabricated by oxygen plasma purification of electron beam induced deposits

Electron beam induced deposition (EBID) currently provides the only direct writing technique for truly three-dimensional nanostructures with geometrical features below 50 nm. Unfortunately, the depositions from metal-organic precursors suffer from a substantial carbon content. This hinders many applications, especially in plasmonics where the metallic nature of the geometric surfaces is mandatory. To overcome this problem a post-deposition treatment with oxygen plasma at room temperature was investigated for the purification of gold containing EBID structures. Upon plasma treatment, the structures experience a shrinkage in diameter of about 18 nm but entirely keep their initial shape. The proposed purification step results in a core-shell structure with the core consisting of mainly unaffected EBID material and a gold shell of about 20 nm in thickness. These purified structures are plasmonically active in the visible wavelength range as shown by dark field optical microscopy on helical nanostructures. Most notably, electromagnetic modeling of the corresponding scattering spectra verified that the thickness and quality of the resulting gold shell ensures an optical response equal to that of pure gold nanostructures.

Silver Coated Platinum Core–Shell Nanostructures on Etched Si Nanowires: Atomic Layer Deposition (ALD) Processing and Application in SERS

A new method to prepare plasmonically active noble metal nanostructures on large surface area silicon nanowires (SiNWs) mediated by atomic layer deposition (ALD) technology has successfully been demonstrated for applications of surface-enhanced Raman spectroscopy (SERS)-based sensing. As host material for the plasmonically active nanostructures we use dense single-crystalline SiNWs with diameters of less than 100 nm as obtained by a wet chemical etching method based on silver nitrate and hydrofluoric acid solutions. The SERS active metal nanoparticles/islands are made from silver (Ag) shells as deposited by autometallography on the core nanoislands made from platinum (Pt) that can easily be deposited by ALD in the form of nanoislands covering the SiNW surfaces in a controlled way. The density of the plasmonically inactive Pt islands as well as the thickness of noble metal Ag shell are two key factors determining the magnitude of the SERS signal enhancement and sensitivity of detection. The optimized Ag coated Pt islands on SiNWs exhibit great potential for ultrasensitive molecular sensing in terms of high SERS signal enhancement ability, good stability and reproducibility. The plasmonic activity of the core-shell Pt//Ag system that will be experimentally realized in this paper as an example was demonstrated in numerical finite element simulations as well as experimentally in Raman measurements of SERS activity of a highly diluted model dye molecule. The morphology and structure of the core-shell Pt//Ag nanoparticles on SiNW surfaces were investigated by scanning- and transmission electron microscopy. Optimized core-shell nanoparticle geometries for maximum Raman signal enhancement is discussed essentially based on the finite element modeling.

Unveiling the optical properties of a metamaterial synthesized by electron-beam-induced deposition

Direct writing using a focused electron beam allows for fabricating truly three-dimensional structures of sub-wavelength dimensions in the visible spectral regime. The resulting sophisticated geometries are perfectly suited for studying light-matter interaction at the nanoscale. Their overall optical response will strongly depend not only on geometry but also on the optical properties of the deposited material. In the case of the typically used metal-organic precursors, the deposits show a substructure of metallic nanocrystals embedded in a carbonaceous matrix. Since gold-containing precursor media are especially interesting for optical applications, we experimentally determine the effective permittivity of such an effective material. Our experiment is based on spectroscopic measurements of planar deposits. The retrieved permittivity shows a systematic dependence on the gold particle density and cannot be sufficiently described using the common Maxwell-Garnett approach for effective medium.

Significant performance enhancement of InGaN/GaN nanorod LEDs with multi-layer graphene transparent electrodes by alumina surface passivation

Nanotextured surfaces provide an ideal platform for efficiently capturing and emitting light. However, the increased surface area in combination with surface defects induced by nanostructuring e.g. using reactive ion etching (RIE) negatively affects the devices active region and, thus, drastically decreases device performance. In this work, the influence of structural defects and surface states on the optical and electrical performance of InGaN/GaN nanorod (NR) light emitting diodes (LEDs) fabricated by top-down RIE of c-plane GaN with InGaN quantum wells was investigated. After proper surface treatment a significantly improved device performance could be shown. Therefore, wet chemical removal of damaged material in KOH solution followed by atomic layer deposition of only 10 [Formula: see text] alumina as wide bandgap oxide for passivation were successfully applied. Raman spectroscopy revealed that the initially compressively strained InGaN/GaN LED layer stack turned into a virtually completely relaxed GaN and partially relaxed InGaN combination after RIE etching of NRs. Time-correlated single photon counting provides evidence that both treatments-chemical etching and alumina deposition-reduce the number of pathways for non-radiative recombination. Steady-state photoluminescence revealed that the luminescent performance of the NR LEDs is increased by about 50% after KOH and 80% after additional alumina passivation. Finally, complete NR LED devices with a suspended graphene contact were fabricated, for which the effectiveness of the alumina passivation was successfully demonstrated by electroluminescence measurements.

Chiroptical response of a single plasmonic nanohelix

We investigate the chiroptical response of a single plasmonic nanohelix interacting with a weakly focused circularly polarized Gaussian beam. The optical scattering at the fundamental resonance is characterized experimentally and numerically. The angularly resolved scattering of the excited nanohelix is verified experimentally and it validates the numerical results. We employ a multipole decomposition analysis to study the fundamental and first higher-order resonance of the nanohelix, explaining their chiral properties in terms of the formation of chiral dipoles.

Direct Electron Beam Writing of Silver-Based Nanostructures

Direct writing utilizing a focused electron beam constitutes an interesting alternative to resist-based techniques, as it allows for precise and flexible growth onto any conductive substrate in a single-step process. One important challenge, however, is the identification of appropriate precursors which allow for deposition of the material of choice, e.g., for envisaged applications in nano-optics. In this regard the coinage metal silver is of particular interest since it shows a relatively high plasma frequency and, thus, excellent plasmonic properties in the visible range. By utilizing the precursor compound AgO2Me2Bu, direct writing of silver-based nanostructures via local electron beam induced deposition could be realized for the first time. Interestingly, the silver deposition was strongly dependent on electron dose; at low doses of 30 nC/μm2 a dominant formation of pure silver crystals was observed, while at higher electron doses around 104 nC/μm2 large carbon contents were measured. A scheme for the enhanced silver deposition under low electron fluxes by an electronic activation of precursor dissociation below thermal CVD temperature is proposed and validated using material characterization techniques. Finally, the knowledge gained was employed to fabricate well-defined two-dimensional deposits with maximized silver content approaching 75 at. %, which was achieved by proper adjustment of the deposition parameters. The corresponding deposits consist of plasmonically active silver crystallites and demonstrate a pronounced Raman signal enhancement of the carbonaceous matrix.

Gas-assisted silver deposition with a focused electron beam

Focused electron beam induced deposition (FEBID) is a flexible direct-write method to obtain defined structures with a high lateral resolution. In order to use this technique in application fields such as plasmonics, suitable precursors which allow the deposition of desired materials have to be identified. Well known for its plasmonic properties, silver represents an interesting candidate for FEBID. For this purpose the carboxylate complex silver(I) pentafluoropropionate (AgO2CC2F5) was used for the first time in FEBID and resulted in deposits with high silver content of up to 76 atom %. As verified by TEM investigations, the deposited material is composed of pure silver crystallites in a carbon matrix. It showed good electrical properties and a strong Raman signal enhancement. Interestingly, silver crystal growth presents a strong dependency on electron dose and precursor refreshment.