Signe Damm

Photoreduction of SERS-Active Metallic Nanostructures on Chemically Patterned Ferroelectric Crystals

Photodeposition of metallic nanostructures onto ferroelectric surfaces is typically based on patterning local surface reactivity via electric field poling. Here, we demonstrate metal deposition onto substrates which have been chemically patterned via proton exchange (i.e., without polarization reversal). The chemical patterning provides the ability to tailor the electrostatic fields near the surface of lithium niobate crystals, and these engineered fields are used to fabricate metallic nanostructures. The effect of the proton exchange process on the piezoelectric and electrostatic properties of the surface is characterized using voltage-modulated atomic force microscopy techniques, which, combined with modeling of the electric fields at the surface of the crystal, reveal that the deposition occurs preferentially along the boundary between ferroelectric and proton-exchanged regions. The metallic nanostructures have been further functionalized with a target probe molecule, 4-aminothiophenol, from which surface-enhanced Raman scattering (SERS) signal is detected, demonstrating the suitability of chemically patterned ferroelectrics as SERS-active templates.

Surface enhanced luminescence and Raman scattering from ferroelectrically defined Ag nanopatterned arrays

Ag nanopatterned arrays prepared using periodically proton exchanged templates have been demonstrated to support surface enhanced luminescence. Fluorescence lifetime imaging reveals that luminescence intensity is greatest on Ag and that the lifetime of the molecular probe is reduced, in line with a surface enhanced luminescence mechanism. Studies establish that the substrate simultaneously supports surface enhanced luminescence and Raman scattering. Spatial dependence along the nanopatterned arrays shows <7% variation in Raman scattering signal intensity, offering high reproducibility for practical applications. Fluorophores emitting near the plasmon absorption maxima are enhanced 4-fold.

Application of AAO Matrix in Aligned Gold Nanorod Array Substrates for Surface-Enhanced Fluorescence and Raman Scattering

In this paper, we probed surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) from probe molecule Rhodamine 6G (R6G) on self-standing Au nanorod array substrates made using a combination of anodization and potentiostatic electrodeposition. The initial substrates were embedded within a porous alumina template (AAO). By controlling the thickness of the AAO matrix, SEF and SERS were observed exhibiting an inverse relationship. SERS and SEF showed a non-linear response to the removal of AAO matrix due to an inhomogeneous plasmon activity across the nanorod which was supported by FDTD calculations. We showed that by optimizing the level of AAO thickness, we could obtain either maximized SERS, SEF or simultaneously observe both SERS and SEF together.

The Effect of Ag Nanoparticles on Surface-Enhanced Luminescence from Au Nanovoid Arrays

Studies comparing the effect of adding two different nanoparticle compositions on the plasmonic properties of Au nanovoid arrays were undertaken. Surface-enhanced resonance luminescence and surface-enhanced resonance Raman studies comparing dispersed Ag nanoparticles and Ag nanoparticle aggregates on gold nanovoid arrays were undertaken. These studies showed that using Ag nanoparticle aggregates increased both luminescence and Raman efficiency relative to when dispersed nanoparticles were used; in addition, these studies also showed that adding dispersed Ag nanoparticles supported a more reproducible enhancement in luminescence and Raman across the substrate compared to using Ag nanoparticle aggregates. Finite element analysis simulations indicated that surface plasmon polariton distribution in the sample was affected by the presence of the Ag nanoparticles on the Au nanovoid array.

Plasmon enhanced fluorescence studies from aligned gold nanorod arrays modified with SiO2 spacer layers

Here, we demonstrate that quasi self-standing Au nanorod arrays prepared with plasma polymerisation deposited SiO2 dielectric spacers support surface enhanced fluorescence (SEF) while maintaining high signal reproducibility. We show that it is possible to find a balance between enhanced radiative and non-radiative decay rates at which the fluorescent intensity is maximized. The SEF signal optimised with a 30 nm spacer layer thickness showed a 3.5-fold enhancement with a signal variance of <15% thereby keeping the integrity of the nanorod array. We also demonstrate the decreased importance of obtaining resonance conditions when localized surface plasmon resonance is positioned within the spectral region of Au interband transitions. Procedures for further increasing the SEF enhancement factor are also discussed.

Protein assemblies on ferroelectrically patterned microarrays of Ag nanoparticles

ABSTRACT Nano-bio interfaces play a significant role in assay device design and performance, here we study the use of a combined plasmonic and ferroelectric active substrate design for protein assemblies on a plasmon active array. We demonstrate that biotinylation and protein assemblies can be made on metal nanoparticles patterned on ferroelectric substrates. These results in turn demonstrate that ferroelectric substrates combined with active plasmonics is potentially applicable as substrates for biological assays.

Control over plasmon enhanced Raman and fluorescence from quasi free-standing Au nanorod arrays

Nanoscale structures made from coinage metals such as gold or silver possess localized surface plasmon-polariton (LSP) excitations when the material interacts with light of the correct frequency and polarization. LSPs generated from freestanding 2D nanorod arrays have been applied to enable surface-enhanced Raman scattering (SERS) and surface enhanced fluorescence (SEF) spectra from Rhodamine 6G molecules adsorbed on the surface of the arrays. We study the conditions that optimize SERS and SEF from self-standing Au nanorod arrays by studying the effect of changing the surrounding environment using Al2O3 as a dielectric spacer layer.

Effect of matrix on Raman scattering and luminescence in 2D gold nanorod arrays

In this paper we probe the surface enhanced fluorescence (SEF) and Raman scattering (SERS) from arrays of selfstanding Au nanorod arrays embedded within a porous alumina template (AAO). By controlling the thickness of the AAO matrix both SEF and SERS are observed exhibiting an inverse relationship. SERS and SEF show a nonlinear response to the removal of AAO matrix due to an inhomogeneous plasmon activity across the nanorod. Optimization of the level of alumina matrix thickness optimizes conditions for obtaining either maximized SERS, SEF or for simultaneously observing both SERS and SEF together.

Formation of ferroelectrically defined Ag nanoarray patterns

In order to produce the most effective Ag nanoarrays for plasmon enhanced fluorescence and Raman scattering made using ferroelectric substrates, the optimum conditions for the creation of arrays must be identified. We study here Ag nanopattern arrays formed using ferroelectric lithography based on periodically proton exchanged (PPE) template methods. We examine different conditions in regard to deposition of Ag nanoparticles and analyze the plasmon enhanced signal from the resulting nanoarray. We apply FLIM (fluorescence lifetime imaging) to assess different Ag nanoarray preparation conditions on fluorescence emission from selected fluorphores. In addition, we apply Raman and luminescence spectroscopy with AFM (atomic force microscopy) to study the plasmon enhancement of luminescence and Raman from the Ag nanoarrays.

SERS from Ag and Au nanoarrays made using photochemical patterning

Photochemical patterning on LiNbO3 is used to create location specific photo deposition of metallic nanoparticles, by inducing disruption to the LiNbO3 surface. This method achieves structures on the nanoto microscale as well as high reproducibility. The LiNbO3 substrates are photochemically patterned by proton exchange of Li+ ions with H+ ions from an acid solution, and a Ti mask determines the pattern available for photodeposition of metal nanoparticles. In this paper a periodic TI mask is used, creating periodic proton exchange (PPE) gold and silver nanoarrays. We demonstrate that such nanoarrays are plasmon active. Raman spectroscopy was applied to study a molecular probe [Ru(bpy)2(Qbpy)]2+ absorbed onto a silver and gold nanostructured array.