Lars O. Herrmann

DNA origami based assembly of gold nanoparticle dimers for surface-enhanced Raman scattering

Plasmonic sensors are extremely promising candidates for label-free single-molecule analysis but require exquisite control over the physical arrangement of metallic nanostructures. Here we employ self-assembly based on the DNA origami technique for accurate positioning of individual gold nanoparticles. Our innovative design leads to strong plasmonic coupling between two 40 nm gold nanoparticles reproducibly held with gaps of 3.3 ± 1 nm. This is confirmed through far field scattering measurements on individual dimers which reveal a significant red shift in the plasmonic resonance peaks, consistent with the high dielectric environment due to the surrounding DNA. We use surface-enhanced Raman scattering (SERS) to demonstrate local field enhancements of several orders of magnitude through detection of a small number of dye molecules as well as short single-stranded DNA oligonucleotides. This demonstrates that DNA origami is a powerful tool for the high-yield creation of SERS-active nanoparticle assemblies with reliable sub-5 nm gap sizes.

Nanooptics of molecular-shunted plasmonic nanojunctions

Gold nanoparticles are separated above a planar gold film by 1.1 nm thick self-assembled molecular monolayers of different conductivities. Incremental replacement of the nonconductive molecules with a chemically equivalent conductive version differing by only one atom produces a strong 50 nm blue-shift of the coupled plasmon. With modeling this gives a conductance of 0.17G0 per biphenyl-4,4′-dithiol molecule and a total conductance across the plasmonic junction of 30G0. Our approach provides a reliable tool quantifying the number of molecules in each plasmonic hotspot, here <200.

Monitoring Morphological Changes in 2D Monolayer Semiconductors Using Atom-Thick Plasmonic Nanocavities

Nanometer-sized gaps between plasmonically coupled adjacent metal nanoparticles enclose extremely localized optical fields, which are strongly enhanced. This enables the dynamic investigation of nanoscopic amounts of material in the gap using optical interrogation. Here we use impinging light to directly tune the optical resonances inside the plasmonic nanocavity formed between single gold nanoparticles and a gold surface, filled with only yoctograms of semiconductor. The gold faces are separated by either monolayers of molybdenum disulfide (MoS2) or two-unit-cell thick cadmium selenide (CdSe) nanoplatelets. This extreme confinement produces modes with 100-fold compressed wavelength, which are exquisitely sensitive to morphology. Infrared scattering spectroscopy reveals how such nanoparticle-on-mirror modes directly trace atomic-scale changes in real time. Instabilities observed in the facets are crucial for applications such as heat-assisted magnetic recording that demand long-lifetime nanoscale plasmonic structures, but the spectral sensitivity also allows directly tracking photochemical reactions in these 2-dimensional solids.

Nanoimprint Lithography of Al Nanovoids for Deep-UV SERS

Deep-ultraviolet surface-enhanced Raman scattering (UV-SERS) is a promising technique for bioimaging and detection because many biological molecules possess UV absorption lines leading to strongly resonant Raman scattering. Here, Al nanovoid substrates are developed by combining nanoimprint lithography of etched polymer/silica opal films with electron beam evaporation, to give a high-performance sensing platform for UV-SERS. Enhancement by more than 3 orders of magnitude in the UV-SERS performance was obtained from the DNA base adenine, matching well the UV plasmonic optical signatures and simulations, demonstrating its suitability for biodetection.

Quantitative multiplexing with nano-self-assemblies in SERS

Multiplexed or simultaneous detection of multiple analytes is a valuable tool in many analytical applications. However, complications caused by the presence of interfering compounds in a sample form a major drawback in existing molecular sensor technologies, particularly in multi-analyte systems. Although separating analytes through extraction or chromatography can partially address the problem of interferents, there remains a need for developing direct observational tools capable of multiplexing that can be applied in situ. Surface-enhanced Raman Spectroscopy (SERS) is an optical molecular finger-printing technique that has the ability to resolve analytes from within mixtures. SERS has attracted much attention for its potential in multiplexed sensing but it has been limited in its quantitative abilities. Here, we report a facile supramolecular SERS-based method for quantitative multiplex analysis of small organic molecules in aqueous environments such as human urine.

Large-scale ordering of nanoparticles using viscoelastic shear processing

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles.

Observing Single Molecules Complexing with Cucurbit[7]uril through Nanogap Surface-Enhanced Raman Spectroscopy

In recent years, single-molecule sensitivity achievable by surface-enhanced Raman spectroscopy (SERS) has been widely reported. We use this to investigate supramolecular host-guest chemistry with the macrocyclic host cucurbit[7]uril, on a few-to-single-molecule level. A nanogap geometry, comprising individual gold nanoparticles on a planar gold surface spaced by a single layer of molecules, gives intense SERS signals. Plasmonic coupling between the particle and the surface leads to strongly enhanced optical fields in the gap between them, with single-molecule sensitivity established using a modification of the well-known bianalyte method. Changes in the Raman modes of the host molecule are observed when single guests included inside its cavity internally stretch it. Anisotropic intermolecular interactions with the guest are found which show additional distinct features in the Raman modes of the host molecule.

Size Dependent Plasmonic Effect on BiVO4 Photoanodes for Solar Water Splitting.

Plasmonic nanostructures show great promise in enhancing the solar water splitting efficiency due to their ability to confine light to extremely small volumes inside semiconductors. While size plays a critical role in the plasmonic performance of Au nanoparticles (AuNPs), its influence on plasmon-assisted water splitting is still not fully understood. This holds especially true for low band gap semiconductors, for which interband excitations occur in wavelength regions that overlap with plasmonic resonances. Here, BiVO4 films are modified with AuNPs of diameters varying from 10 to 80 nm to study the size dependence of the plasmonic effect. Plasmon resonance energy transfer (PRET) is found to be the dominant effect in enhancing the water splitting efficiency of BiVO4. “Hot electron” injection effect is weak in the case of BiVO4/AuNP. This is attributed to the interband excitation of BiVO4, which is unfavourable for the hot electrons accumulation in BiVO4 conduction band. The resonant scattering effect also contributes to the enhanced water splitting efficiency for the larger diameter AuNPs. It is also for the first time found that higher PRET effect can be achieved at larger off-normal irradiation angle.

Watching Single Nanoparticles Grow in Real Time through Supercontinuum Spectroscopy

A fast dark-field scattering technique capturing full broadband spectra with millisecond time-resolution enables us to monitor the growth or assembly of single nano-objects in situ and in real time. Applying this technique to study the growth of single gold nanorods, together with scanning electron microscopy and finite-difference time-domain simulations, reveals precise quantitative information about gold nanorod growth kinetics.

Self‐Aligned Colloidal Lithography for Controllable and Tuneable Plasmonic Nanogaps

Au nanoparticles (NPs) deposited on a substrate function as ring shaped colloidal shadow masks. Using e-beam evaporation of gold, nanometer sized gaps are formed as a result. The size of these gaps can be accurately tuned by controlling the thickness of the gold deposition, thereby tuning the plasmonic coupling of the NPs with the substrate. The clean cavity produced between the Au NPs and the Au film provides an excellent SERS platform for trace molecule detection.