Light Emission and Conductance Fluctuations in Electrically Driven and Plasmonically Enhanced Molecular Junctions.

Electrically connected and plasmonically enhanced molecular junctions combine the optical functionalities of high field confinement and enhancement (cavity function), and of high radiative efficiency (antenna function) with the electrical functionalities of molecular transport. Such combined optical and electrical probes have proven useful for the fundamental understanding of metal-molecule contacts and contribute to the development of nanoscale optoelectronic devices including ultrafast electronics and nanosensors. Here, we employ a self-assembled metal-molecule-metal junction with a nanoparticle bridge to investigate correlated fluctuations in conductance and tunneling-induced light emission at room temperature. Despite the presence of hundreds of molecules in the junction, the electrical conductance and light emission are both highly sensitive to atomic-scale fluctuations-a phenomenology reminiscent of picocavities observed in Raman scattering and of luminescence blinking from photoexcited plasmonic junctions. Discrete steps in conductance associated with fluctuating emission intensities through the multiple plasmonic modes of the junction are consistent with a finite number of randomly localized, point-like sources dominating the optoelectronic response. Contrasting with these microscopic fluctuations, the overall plasmonic and electronic functionalities of our devices feature long-term survival at room temperature and under an electrical bias of a few volts, allowing for measurements over several months.

Complex chemical reaction networks for future information processing.

Tackling the increasing energy demand of our society is one of the key challenges today. With the rise of artificial intelligence, information and communication technologies started to substantially contribute to this alarming trend and therefore necessitate more sustainable approaches for the future. Brain-inspired computing paradigms represent a radically new and potentially more energy-efficient approach for computing that may complement or even replace CMOS in the long term. In this perspective, we elaborate on the concepts and properties of complex chemical reaction networks (CRNs) that may serve as information-processing units based on chemical reactions. The computational capabilities of simpler, oscillatory chemical reactions have already been demonstrated in scenarios ranging from the emulation of Boolean gates to image-processing tasks. CRNs offer higher complexity and larger non-linearity, potentially at lower energy consumption. Key challenges for the successful development of CRN-based computers are associated with their specific physical implementations, operability, and readout modalities. CRNs are sensible to various reaction triggers, and provide multiple and interlinked reaction pathways and a diverse compound space. This bears a high potential to build radically new hardware and software concepts for energy-efficient computing based on neuromorphic architectures-with computing capabilities in real-world applications yet to be demonstrated.

Microfluidic Giant Polymer Vesicles Equipped with Biopores for High-Throughput Screening of Bacteria.

Understanding the mechanisms of antibiotic resistance is critical for the development of new therapeutics. Traditional methods for testing bacteria are often limited in their efficiency and reusability. Single bacterial cells can be studied at high throughput using double emulsions, although the lack of control over the oil shell permeability and limited access to the droplet interior present serious drawbacks. Here, a straightforward strategy for studying bacteria-encapsulating double emulsion-templated giant unilamellar vesicles (GUVs) is introduced. This microfluidic approach serves to simultaneously load bacteria inside synthetic GUVs and to permeabilize their membrane with the pore-forming peptide melittin. This enables antibiotic delivery or the influx of fresh medium into the GUV lumen for highly parallel cultivation and antimicrobial efficacy testing. Polymer-based GUVs proved to be efficient culture and analysis microvessels, as microfluidics allow easy selection and encapsulation of bacteria and rapid modification of culture conditions for antibiotic development. Further, a method for in situ profiling of biofilms within GUVs for high-throughput screening is demonstrated. Conceivably, synthetic GUVs equipped with biopores can serve as a foundation for the high-throughput screening of bacterial colony interactions during biofilm formation and for investigating the effect of antibiotics on biofilms.

Silicon-Based 3D Microfluidics for Parallelization of Droplet Generation.

Both the diversity and complexity of microfluidic systems have experienced a tremendous progress over the last decades, enabled by new materials, novel device concepts and innovative fabrication routes. In particular the subfield of high-throughput screening, used for biochemical, genetic and pharmacological samples, has extensively emerged from developments in droplet microfluidics. More recently, new 3D device architectures enabled either by stacking layers of PDMS or by direct 3D-printing have gained enormous attention for applications in chemical synthesis or biomedical assays. While the first microfluidic devices were based on silicon and glass structures, those materials have not yet been significantly expanded towards 3D despite their high chemical compatibility, mechanical strength or mass-production potential. In our work, we present a generic fabrication route based on the implementation of vertical vias and a redistribution layer to create glass-silicon-glass 3D microfluidic structures. It is used to build different droplet-generating devices with several flow-focusing junctions in parallel, all fed from a single source. We study the effect of having several of these junctions in parallel by varying the flow conditions of both the continuous and the dispersed phases. We demonstrate that the generic concept enables an upscaling in the production rate by increasing the number of droplet generators per device without sacrificing the monodispersity of the droplets.

Quantitative laser-matter interaction: a 3D study of UV-fs-laser ablation on single crystalline Ru(0001).

Laser ablation is nowadays an extensively applied technology to probe the chemical composition of solid materials. It allows for precise targeting of micrometer objects on and in samples, and enables chemical depth profiling with nanometer resolution. An in-depth understanding of the 3D geometry of the ablation craters is crucial for precise calibration of the depth scale in chemical depth profiles. Herein we present a comprehensive study on laser ablation processes using a Gaussian-shaped UV-femtosecond irradiation source and present how the combination of three different imaging methods (scanning electron microscopy, interferometric microscopy, and X-ray computed tomography) can provide accurate information on the crater's shapes. Crater analysis by applying X-ray computed tomography is of considerable interest because it allows the imaging of an array of craters in one step with sub-µm accuracy and is not limited to the aspect ratio of the crater. X-ray computed tomography thereby complements the analysis of laser ablation craters. The study investigates the effect of laser pulse energy and laser burst count on a single crystal Ru(0001) sample. Single crystals ensure that there is no dependence on the grain orientations during the laser ablation process. An array of 156 craters of different dimensions ranging from <20 nm to ∼40 µm in depth were created. For each individually applied laser pulse, we measured the number of ions generated in the ablation plume with our laser ablation ionization mass spectrometer. We show to which extent the combination of these four techniques reveals valuable information on the ablation threshold, the ablation rate, and the limiting ablation depth. The latter is expected to be a consequence of decreasing irradiance upon increasing crater surface area. The ion signal generated was found to be proportional to the volume ablated up to the certain depth, which enables in-situ depth calibration during the measurement.

Direct electrification of silicon microfluidics for electric field applications.

Microfluidic systems are widely used in fundamental research and industrial applications due to their unique behavior, enhanced control, and manipulation opportunities of liquids in constrained geometries. In micrometer-sized channels, electric fields are efficient mechanisms for manipulating liquids, leading to deflection, injection, poration or electrochemical modification of cells and droplets. While PDMS-based microfluidic devices are used due to their inexpensive fabrication, they are limited in terms of electrode integration. Using silicon as the channel material, microfabrication techniques can be used to create nearby electrodes. Despite the advantages that silicon provides, its opacity has prevented its usage in most important microfluidic applications that need optical access. To overcome this barrier, silicon-on-insulator technology in microfluidics is introduced to create optical viewports and channel-interfacing electrodes. More specifically, the microfluidic channel walls are directly electrified via selective, nanoscale etching to introduce insulation segments inside the silicon device layer, thereby achieving the most homogeneous electric field distributions and lowest operation voltages feasible across microfluidic channels. These ideal electrostatic conditions enable a drastic energy reduction, as effectively shown via picoinjection and fluorescence-activated droplet sorting applications at voltages below 6 and 15 V, respectively, facilitating low-voltage electric field applications in next-generation microfluidics.

Automated, 3-D and Sub-Micron Accurate Ablation-Volume Determination by Inverse Molding and X-Ray Computed Tomography.

Ablation of materials in combination with element-specific analysis of the matter released is a widely used method to accurately determine a material's chemical composition. Among other methods, repetitive ablation using femto-second pulsed laser systems provides excellent spatial resolution through its incremental removal of nanometer thick layers. The method can be combined with high-resolution mass spectrometry, for example, laser ablation ionization mass spectrometry, to simultaneously analyze chemically the material released. With increasing depth of the volume ablated, however, secondary effects start to play an important role and the ablation geometry deviates substantially from the desired cylindrical shape. Consequently, primarily conical but sometimes even more complex, rather than cylindrical, craters are created. Their dimensions need to be analyzed to enable a direct correlation with the element-specific analytical signals. Here, a post-ablation analysis method is presented that combines generic polydimethylsiloxane-based molding of craters with the volumetric reconstruction of the crater's inverse using X-ray computed tomography. Automated analysis yields the full, sub-micron accurate anatomy of the craters, thereby a scalable and generic method to better understand the fundamentals underlying ablation processes applicable to a wide range of materials. Furthermore, it may serve toward a more accurate determination of heterogeneous material's composition for a variety of applications without requiring time- and labor-intensive analyses of individual craters.

Thermal Simulation and Experimental Analysis of Optically Pumped InP-on-Si Micro- and Nanocavity Lasers.

There is a general trend of downscaling laser cavities, but with high integration and energy densities of nanocavity lasers, significant thermal issues affect their operation. The complexity of geometrical parameters and the various materials involved hinder the extraction of clear design guidelines and operation strategies. Here, we present a systematic thermal analysis of InP-on-Si micro- and nanocavity lasers based on steady-state and transient thermal simulations and experimental analysis. In particular, we investigate the use of metal cavities for improving the thermal properties of InP-on-Si micro- and nanocavity lasers. Heating of lasers is studied by using Raman thermometry and the results agree well with simulation results, both revealing a temperature reduction of hundreds of kelvins for the metal-clad cavity. Transient simulations are carried out to improve our understanding of the dynamic temperature variation under pulsed and continuous wave pumping conditions. The results show that the presence of a metal cladding not only increases the overall efficiency in heat dissipation but also causes a much faster temperature response. Together with optical experimental results under pulsed pumping, we conclude that a pulse width of 10 ns and a repetition rate of 100 kHz is the optimal pumping condition for a 2 µm wide square cavity.

Freestanding and Permeable Nanoporous Gold Membranes for Surface-Enhanced Raman Scattering.

Surface-enhanced Raman spectroscopy (SERS) demands reliable, high-enhancement substrates in order to be used in different fields of application. Here we introduce freestanding porous gold membranes (PAuM) as easy-to-produce, scalable, mechanically stable, and effective SERS substrates. We fabricate large-scale sub-30 nm thick PAuM that form freestanding membranes with varying morphologies depending on the nominal gold thickness. These PAuM are mechanically stable for pressures up to more than 3 bar and exhibit surface-enhanced Raman scattering with local enhancement factors from 104 to 105, which we demonstrate by wavelength-dependent and spatially resolved Raman measurements using graphene as a local Raman probe. Numerical simulations reveal that the enhancement arises from individual, nanoscale pores in the membrane acting as optical slot antennas. Our PAuM are mechanically stable, provide robust SERS enhancement for excitation power densities up to 106 W cm-2, and may find use as a building block in SERS-based sensing applications.

Monitoring Solid-Phase Reactions in Self-Assembled Monolayers by Surface-Enhanced Raman Spectroscopy.

Nanopatterned surfaces enhance incident electromagnetic radiation and thereby enable the detection and characterization of self-assembled monolayers (SAMs), for instance in surface-enhanced Raman spectroscopy (SERS). Herein, Au nanohole arrays, developed and characterized as SERS substrates, are exemplarily used for monitoring a solid-phase deprotection and a subsequent copper(I)-catalyzed azide-alkyne cycloaddition "click" reaction, performed directly on the corresponding SAMs. The SERS substrate was found to be highly reliable in terms of signal reproducibility and chemical stability. Furthermore, the intermediates and the product of the solid-phase synthesis were identified by SERS. The spectra of the immobilized compounds showed minor differences compared to spectra of the microcrystalline solids. With its uniform SERS signals and the high chemical stability, the platform paves the way for monitoring molecular manipulations in surface functionalization applications.

Combinatorial Strategy for Studying Biochemical Pathways in Double Emulsion Templated Cell-Sized Compartments.

Cells rely upon producing enzymes at precise rates and stoichiometry for maximizing functionalities. The reasons for this optimal control are unknown, primarily because of the interconnectivity of the enzymatic cascade effects within multi-step pathways. Here, an elegant strategy for studying such behavior, by controlling segregation/combination of enzymes/metabolites in synthetic cell-sized compartments, while preserving vital cellular elements is presented. Therefore, compartments shaped into polymer GUVs are developed, producing via high-precision double-emulsion microfluidics that enable: i) tight control over the absolute and relative enzymatic contents inside the GUVs, reaching nearly 100% encapsulation and co-encapsulation efficiencies, and ii) functional reconstitution of biopores and membrane proteins in the GUVs polymeric membrane, thus supporting in situ reactions. GUVs equipped with biopores/membrane proteins and loaded with one or more enzymes are arranged in a variety of combinations that allow the study of a three-step cascade in multiple topologies. Due to the spatiotemporal control provided, optimum conditions for decreasing the accumulation of inhibitors are unveiled, and benefited from reactive intermediates to maximize the overall cascade efficiency in compartments. The non-system-specific feature of the novel strategy makes this system an ideal candidate for the development of new synthetic routes as well as for screening natural and more complex pathways.

Resonant Optical Antennas with Atomic-Sized Tips and Tunable Gaps Achieved by Mechanical Actuation and Electrical Control.

Enhanced electromagnetic fields in nanometer gaps of plasmonic structures increase the optical interaction with matter, including Raman scattering and optical absorption. Quantum electron tunneling across sub-1 nm gaps, however, lowers these effects again. Understanding these phenomena requires controlled variation of gap sizes. Mechanically actuated plasmonic antennas enable repeatable tuning of gap sizes from the weak-coupling over the quantum-electron-tunneling to the direct-electrical-contact regime. Gap sizes are controlled electrically via leads that only weakly disturb plasmonic modes. Conductance signals show a near-continuous transition from electron tunneling to metallic contact. As the antenna's absorption cross-section is reduced, thermal expansion effects are negligible, in contrast to conventional break-junctions. Optical scattering spectra reveal first continuous red shifts for decreasing gap sizes and then blue shifts below gaps of 0.3 nm. The approach provides pathways to study opto- and electromolecular processes at the limit of plasmonic sensing.

Metallic nanoparticle contacts for high-yield, ambient-stable molecular-monolayer devices.

Accessing the intrinsic functionality of molecules for electronic applications1-3, light emission4 or sensing5 requires reliable electrical contacts to those molecules. A self-assembled monolayer (SAM) sandwich architecture6 is advantageous for technological applications, but requires a non-destructive, top-contact fabrication method. Various approaches ranging from direct metal evaporation6 over poly(3,4-ethylenedioxythiophene) polystyrene sulfonate7 (PEDOT:PSS) or graphene8 interlayers to metal transfer printing9 have been proposed. Nevertheless, it has not yet been possible to fabricate SAM-based devices without compromising film integrity, intrinsic functionality or mass-fabrication compatibility. Here we develop a top-contact approach to SAM-based devices that simultaneously addresses all these issues, by exploiting the fact that a metallic nanoparticle can provide a reliable electrical contact to individual molecules10. Our fabrication route involves first the conformal and non-destructive deposition of a layer of metallic nanoparticles directly onto the SAM (itself laterally constrained within circular pores in a dielectric matrix, with diameters ranging from 60 nanometres to 70 micrometres), and then the reinforcement of this top contact by direct metal evaporation. This approach enables the fabrication of thousands of identical, ambient-stable metal-molecule-metal devices. Systematic variation of the composition of the SAM demonstrates that the intrinsic molecular properties are not affected by the nanoparticle layer and subsequent top metallization. Our concept is generic to densely packed layers of molecules equipped with two anchor groups, and provides a route to the large-scale integration of molecular compounds into solid-state devices that can be scaled down to the single-molecule level.

Insights into Laser Ablation Processes of Heterogeneous Samples: Toward Analysis of Through-Silicon-Vias.

State-of-the-art three-dimensional very large-scale integration (3D-VLSI) relies, among other factors, on the purity of high-aspect-ratio Cu interconnects such as through-silicon-vias (TSVs). Accurate spatial chemical analysis of electroplated TSV structures has been proven to be challenging due to their large aspect ratios and their multimaterial composition (Cu and Si) with distinct physical properties. Here, we demonstrate that these structures can be accurately analyzed by femtosecond (fs) laser beam ablation techniques in combination with ionization mass spectrometry (LIMS). We specifically report on novel preparation approaches for the postablation analysis of craters formed upon TSV depth profiling. The novel TSV sample preparation is based on deep and material-selective reactive-ion etching of the Si matrix surrounding the Cu interconnects thus facilitating systematic focused-ion-beam (FIB) investigations of the high-aspect-ratio TSV structures upon ablation. The particular structure of the TSV analyte combined with the ⌀beam > ⌀Cu-TSV condition allowed for an in-depth investigation of fundamental laser ablation processes, particularly focusing on the redeposition of ablated material at the inner side-walls of the LIMS craters. This phenomenon is of imminent importance for the ultimate quantification in any laser ablation-based depth profiling. In addition, we have developed a new method which allows the unambiguous determination of the crossing-point of the Si/Cu||bare Si interface upon Cu-TSV depth profiling which is based on pronounced, depth-dependent changes in the mass-spectrometric detection of those Si xy+ species formed upon the LIMS depth erosion.

Depth Profiling and Cross-Sectional Laser Ablation Ionization Mass Spectrometry Studies of Through-Silicon-Vias.

Through-silicon-via (TSV) technology enables 3D integration of multiple 2D components in advanced microchip architectures. Key in the TSV fabrication is an additive-assisted Cu electroplating process in which the additives employed may get embedded in the TSV body. This incorporation negatively influences the reliability and durability of the Cu interconnects. Here, we present a novel approach toward the chemical analysis of TSVs which is based on femtosecond laser ablation ionization mass spectrometry (fs-LIMS). The conditions for LIMS depth profiling were identified by a systematic variation of the laser pulse energy and the number of laser shots applied. In this contribution, new aspects are addressed related to the analysis of highly heterogeneous specimens having dimensions in the range of the probing beam itself. Particularly challenging were the different chemical and physical properties of which the target specimens were composed. Depth profiling of the TSVs along their main axis (approach 1) revealed a gradient in the carbon (C) content. These differences in the C concentration inside the TSVs could be confirmed and quantified by LIMS analyses of cross-sectionally sliced TSVs (approach 2). Our quantitative analysis revealed a C content that is ∼1.5 times higher at the TSV top surface compared to its bottom. Complementary Scanning Auger Microscopy (SAM) data confirmed a preferential embedment of suppressor additives at the side walls of the TSV. These results demonstrate that the TSV filling concept significantly deviates from common Damascene electroplating processes and will therefore contribute to a more comprehensive, mechanistic understanding of the underlying mechanisms.

Combining Anisotropic Etching and PDMS Casting for Three-Dimensional Analysis of Laser Ablation Processes.

State-of-the-art laser ablation (LA) depth-profiling techniques (e.g. LA-ICP-MS, LIBS, and LIMS) allow for chemical composition analysis of solid materials with high spatial resolution at micro- and nanometer levels. Accurate determination of LA-volume is essential to correlate the recorded chemical information to the specific location inside the sample. In this contribution, we demonstrate two novel approaches towards a better quantitative analysis of LA craters with dimensions at micrometer level formed by femtosecond-LA processes on single-crystalline Si(100) and polycrystalline Cu model substrates. For our parametric crater evolution studies, both the number of applied laser shots and the pulse energy were systematically varied, thus yielding 2D matrices of LA craters which vary in depth, diameter, and crater volume. To access the 3D structure of LA craters formed on Si(100), we applied a combination of standard lithographic and deep reactive-ion etching (DRIE) techniques followed by a HR-SEM inspection of the previously formed crater cross sections. As DRIE is not applicable for other material classes such as metals, an alternative and more versatile preparation technique was developed and applied to the LA craters formed on the Cu substrate. After the initial LA treatment, the Cu surface was subjected to a polydimethylsiloxane (PDMS) casting process yielding a mold being a full 3D replica of the LA craters, which was then analyzed by HR-SEM. Both approaches revealed cone-like shaped craters with depths ranging between 1 and 70 µm and showed a larger ablation depth of Cu that exceed the one of Si by a factor of about 3.

Charge Transport and Conductance Switching of Redox-Active Azulene Derivatives.

Azulene (Az) is a non-alternating, aromatic hydrocarbon composed of a five-membered, electron-rich and a seven-membered, electron-poor ring; an electron distribution that provides intrinsic redox activity. By varying the attachment points of the two electrode-bridging substituents to the Az center, the influence of the redox functionality on charge transport is evaluated. The conductance of the 1,3 Az derivative is at least one order of magnitude lower than those of the 2,6 Az and 4,7 Az derivatives, in agreement with density functional theory (DFT) calculations. In addition, only 1,3 Az exhibits pronounced nonlinear current-voltage characteristics with hysteresis, indicating a bias-dependent conductance switching. DFT identifies the LUMO to be nearest to the Fermi energy of the electrodes, but to be an active transport channel only in the case of the 2,6 and the 4,7 Az derivatives, whereas the 1,3 Az derivative uses the HOMO at low and the LUMO+1 at high bias. In return, the localized, weakly coupled LUMO of 1,3 Az creates a slow electron-hopping channel responsible for the voltage-induced switching due to the occupation of a single molecular orbital (MO).

Functional Nanopores: A Solid-state Concept for Artificial Reaction Compartments and Molecular Factories.

On the road towards the long-term goal of the NCCR Molecular Systems Engineering to create artificial molecular factories, we aim at introducing a compartmentalization strategy based on solid-state silicon technology targeting zeptoliter reaction volumes and simultaneous electrical contact to ensembles of well-oriented molecules. This approach allows the probing of molecular building blocks under a controlled environment prior to their use in a complex molecular factory. Furthermore, these ultra-sensitive electrical conductance measurements allow molecular responses to a variety of external triggers to be used as sensing and feedback mechanisms. So far, we demonstrate the proof-of-concept by electrically contacting self-assembled mono-layers of alkane-dithiols as an established test system. Here, the molecular films are laterally constrained by a circular dielectric confinement, forming a so-called 'nanopore'. Device yields above 85% are consistently achieved down to sub-50 nm nanopore diameters. This generic platform will be extended to create distributed, cascaded reactors with individually addressable reaction sites, including interconnecting micro-fluidic channels for electrochemical communication among nanopores and sensing sites for reaction control and feedback. In this scientific outlook, we will sketch how such a solid-state nanopore concept can be used to study various aspects of molecular compounds tailored for operation in a molecular factory.

Coherent commensurate electronic states at the interface between misoriented graphene layers.

Graphene and layered materials in general exhibit rich physics and application potential owing to their exceptional electronic properties, which arise from the intricate π-orbital coupling and the symmetry breaking in twisted bilayer systems. Here, we report room-temperature experiments to study electrical transport across a bilayer graphene interface with a well-defined rotation angle between the layers that is controllable in situ. This twisted interface is artificially created in mesoscopic pillars made of highly oriented pyrolytic graphite by mechanical actuation. The overall measured angular dependence of the conductivity is consistent with a phonon-assisted transport mechanism that preserves the electron momentum of conduction electrons passing the interface. The most intriguing observations are sharp conductivity peaks at interlayer rotation angles of 21.8° and 38.2°. These angles correspond to a commensurate crystalline superstructure leading to a coherent two-dimensional (2D) electronic interface state. Such states, predicted by theory, form the basis for a new class of 2D weakly coupled bilayer systems with hitherto unexplored properties and applications.

Field-induced conductance switching by charge-state alternation in organometallic single-molecule junctions.

Charge transport through single molecules can be influenced by the charge and spin states of redox-active metal centres placed in the transport pathway. These intrinsic properties are usually manipulated by varying the molecule's electrochemical and magnetic environment, a procedure that requires complex setups with multiple terminals. Here we show that oxidation and reduction of organometallic compounds containing either Fe, Ru or Mo centres can solely be triggered by the electric field applied to a two-terminal molecular junction. Whereas all compounds exhibit bias-dependent hysteresis, the Mo-containing compound additionally shows an abrupt voltage-induced conductance switching, yielding high-to-low current ratios exceeding 1,000 at bias voltages of less than 1.0 V. Density functional theory calculations identify a localized, redox-active molecular orbital that is weakly coupled to the electrodes and closely aligned with the Fermi energy of the leads because of the spin-polarized ground state unique to the Mo centre. This situation provides an additional slow and incoherent hopping channel for transport, triggering a transient charging effect in the entire molecule with a strong hysteresis and large high-to-low current ratios.