Gold Nanoparticles with N-Heterocyclic Carbene/Triphenylamine Surface Ligands: Stable and Electrochromically Active Hybrid Materials for Optoelectronics.

Organic-hybrid particle-based materials are increasingly important in (opto)electronics, sensing, and catalysis due to their printability and stretchability as well as their potential for unique synergistic functional effects. However, these functional properties are often limited due to poor electronic coupling between the organic shell and the nanoparticle. N-heterocyclic carbenes (NHCs) belong to the most promising anchors to achieve electronic delocalization across the interface, as they form robust and highly conductive bonds with metals and offer a plethora of functionalization possibilities. Despite the outstanding potential of the conductive NHC-metal bond, synthetic challenges have so far limited its application to the improvement of colloidal stabilities, disregarding the potential of the conductive anchor. Here, NHC anchors are used to modify redox-active gold nanoparticles (AuNPs) with conjugated triphenylamines (TPA). The resulting AuNPs exhibit excellent thermal and redox stability benefiting from the robust NHC-gold bond. As electrochromic materials, the hybrid materials show pronounced color changes from red to dark green, a highly stable cycling stability (1000 cycles), and a fast response speed (5.6 s/2.1 s). Furthermore, TPA-NHC@AuNP exhibits an ionization potential of 5.3 eV and a distinct out-of-plane conductivity, making them a promising candidate for application as hole transport layers in optoelectronic devices.

Fabrication of Eco-Friendly Wearable Strain Sensor Arrays via Facile Contact Printing for Healthcare Applications.

Wearable flexible strain sensors with spatial resolution enable the acquisition and analysis of complex actions for noninvasive personalized healthcare applications. To provide secure contact with skin and to avoid environmental pollution after usage, sensors with biocompatibility and biodegradability are highly desirable. Herein, wearable flexible strain sensors composed of crosslinked gold nanoparticle (GNP) thin films as the active conductive layer and transparent biodegradable polyurethane (PU) films as the flexible substrate are developed. The patterned GNP films (micrometer- to millimeter-scale square and rectangle geometry, alphabetic characters, and wave and array patterns) are transferred onto the biodegradable PU film via a facile, clean, rapid and high-precision contact printing method, without the need of a sacrificial polymer carrier or organic solvents. The GNP-PU strain sensor with low Young's modulus (≈17.8 MPa) and high stretchability showed good stability and durability (10 000 cycles) as well as degradability (42% weight loss after 17 days at 74 °C in water). The GNP-PU strain sensor arrays with spatiotemporal strain resolution are applied as wearable eco-friendly electronics for monitoring subtle physiological signals (e.g., mapping of arterial lines and sensing pulse waveforms) and large-strain actions (e.g., finger bending).

Transfer Printing of Freestanding Nanoassemblies: A Route to Membrane Resonators with Adjustable Prestress.

Freestanding nanoassemblies represent a new class of functional materials with highly responsive optical, electrical, and mechanical properties. Hence, they are well-suited for applications in advanced sensor devices. Here, it is shown that transfer printing enables the well-controlled fabrication of freestanding membranes from layered nanoassemblies: Using a polydimethylsiloxane (PDMS) stamp, thin films (thickness: ∼45 to ∼51 nm) of 1,6-hexanedithiol cross-linked gold nanoparticles (diameter: ∼3.9 ± 0.8 nm) were transferred onto surface-oxidized silicon substrates featuring square microcavities with edge lengths of ∼78 µm. After adjusting the contact pressure to 1.8 bar, intact membranes were printed in yields of ∼70%. The prestress of printed membranes was determined by measuring their resonance frequencies under electrostatic actuation. In general, the prestress values were in the ∼10 MPa range with standard deviations below 10% for parallel printed resonators. The deviations in average prestress between resonators printed onto different substrates were 21% or less. By increasing the temperature during the final transfer step from 5 to 48 °C, it was possible to tune the average prestress from ∼14 to ∼28 MPa. This effect was attributed to the pronounced thermal expansion of the PDMS stamp. Finally, by transfer printing layered films of graphene oxide/silk fibroin (GO/SF), it is shown that the approach can be adapted for the fabrication of freestanding membranes from very different nanomaterials.

Elasticity of Cross-Linked Titania Nanocrystal Assemblies Probed by AFM-Bulge Tests.

In order to enable advanced technological applications of nanocrystal composites, e.g., as functional coatings and layers in flexible optics and electronics, it is necessary to understand and control their mechanical properties. The objective of this study was to show how the elasticity of such composites depends on the nanocrystals' dimensionality. To this end, thin films of titania nanodots (TNDs; diameter: ~3-7 nm), nanorods (TNRs; diameter: ~3.4 nm; length: ~29 nm), and nanoplates (TNPs; thickness: ~6 nm; edge length: ~34 nm) were assembled via layer-by-layer spin-coating. 1,12-dodecanedioic acid (12DAC) was added to cross-link the nanocrystals and to enable regular film deposition. The optical attenuation coefficients of the films were determined by ultraviolet/visible (UV/vis) absorbance measurements, revealing much lower values than those known for titania films prepared via chemical vapor deposition (CVD). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed a homogeneous coverage of the substrates on the µm-scale but a highly disordered arrangement of nanocrystals on the nm-scale. X-ray photoelectron spectroscopy (XPS) analyses confirmed the presence of the 12DAC cross-linker after film fabrication. After transferring the films onto silicon substrates featuring circular apertures (diameter: 32-111 µm), freestanding membranes (thickness: 20-42 nm) were obtained and subjected to atomic force microscopy bulge tests (AFM-bulge tests). These measurements revealed increasing elastic moduli with increasing dimensionality of the nanocrystals, i.e., 2.57 ± 0.18 GPa for the TND films, 5.22 ± 0.39 GPa for the TNR films, and 7.21 ± 1.04 GPa for the TNP films.

Fabrication of Strain Gauges via Contact Printing: A Simple Route to Healthcare Sensors Based on Cross-Linked Gold Nanoparticles.

In this study, we developed a novel and efficient process for the fabrication of resistive strain gauges for healthcare-related applications. First, 1,9-nonanedithiol cross-linked gold nanoparticle (GNP) films were prepared via layer-by-layer (LbL) spin-coating and subsequently transferred onto flexible polyimide foil by contact printing. Four-point bending tests revealed linear response characteristics with gauge factors of ∼14 for 4 nm GNPs and ∼26 for 7 nm GNPs. This dependency of strain sensitivity is attributed to the perturbation of charge carrier tunneling between neighboring GNPs, which becomes more efficient with increasing particle size. Fatigue tests revealed that the strain-resistance performance remained nearly the same after 10.000 strain/relaxation cycles. We demonstrate that these sensors are well suited to monitor muscle movements. Furthermore, we fabricated all-printed strain sensors by directly transferring cross-linked GNP films onto soft PDMS sheets equipped with interdigitated electrodes. Due to the low elastic modulus of poly(dimethylsiloxane) (PDMS), these sensors are easily deformed and, therefore, they respond sensitively to faint forces. When taped onto the skin above the radial artery, they enable the well-resolved and robust recording of pulse waves with diagnostically relevant details.

Cross-Linked Gold-Nanoparticle Membrane Resonators as Microelectromechanical Vapor Sensors.

We report a novel approach for the detection of volatile compounds employing electrostatically driven drumhead resonators as sensing elements. The resonators are based on freestanding membranes of alkanedithiol cross-linked gold nanoparticles (GNPs), which are able to sorb analytes from the gas phase. Under reduced pressure, the fundamental resonance frequency of a resonator is continuously monitored while the device is exposed to varying partial pressures of toluene, 4-methylpentan-2-one, 1-propanol, and water. The measurements reveal a strong, reversible frequency shift of up to ∼10 kHz, i.e., ∼5% of the fundamental resonance frequency, when exposing the sensor to toluene vapor with a partial pressure of ∼20 Pa. As this strong shift cannot be explained exclusively by the mass uptake in the membrane, our results suggest a significant impact of analyte sorption on the pre-stress of the freestanding GNP membrane. Thus, our findings point to the possibility of designing highly sensitive resonators, which utilize sorption induced changes in the membrane's pre-stress as primary transduction mechanism.

Electrostatically driven drumhead resonators based on freestanding membranes of cross-linked gold nanoparticles.

Freestanding, nanometer-thin membranes of alkanedithiol cross-linked gold nanoparticles represent elastic, mechanically robust and electrically conductive materials, which are interesting for the fabrication of novel nano- and microelectromechanical devices. In this work we present the first electrostatically driven drumhead resonators based on such nanoparticle membranes. These circular membranes have a thickness of 33 to 52 nm, a diameter of either 50 µm or 100 µm, and are equally spaced from their back electrode by ∼10 µm. Using an interferometric nanovibration analyzer various vibrational modes with resonance amplitudes of up to several 100 nm could be detected when the membranes are excited by applying AC voltages (<30 V) with drive frequencies of up to 2 MHz. Further, spatial amplitude distributions of different vibrational modes could be imaged. The devices showed fundamental resonance frequencies in the high kHz range and quality factors Q up to ∼2000. Finally, vibrational spectra and observed mode patterns could be well interpreted using the theory for a clamped circular membrane with negligible bending stiffness. Our findings mark an important step towards the integration of freestanding gold nanoparticle composite membranes into electromechanical devices with various applications, such as novel types of pressure or mass sensors.

Resistive pressure sensors based on freestanding membranes of gold nanoparticles.

In this communication the application of gold nanoparticle membranes as ambient pressure sensors with electromechanical signal transduction is demonstrated. The devices were fabricated by sealing microstructured cavities with membranes of 1,6-hexanedithiol cross-linked gold nanoparticles, which were electrically contacted by metal electrodes deposited on both sides of the cavities. Variations of the external pressure resulted in a deflection of the membranes and, thus, increased the average interparticle distances. Therefore, the pressure change could easily be detected by simply monitoring the resistance of the membranes.

Freestanding membranes of cross-linked gold nanoparticles: novel functional materials for electrostatic actuators.

Their tunable electrical, optical, and mechanical properties make freestanding membranes of organically cross-linked gold nanoparticles (GNPs) interesting materials for applications in micro- and nanoelectromechanical systems. Here, we demonstrate the application of α,ω-alkanedithiol-cross-linked GNP membranes as electrostatically driven actuators. The devices were fabricated by depositing these membranes (thickness 29-45 nm) onto cylindrical cavities (diameter ∼200 µm; depth ∼8-15 µm), which were lithographically patterned in a SU-8 resist. Applying voltages of up to ±40 V across the membrane and the silicon substrate deflected the membranes by several hundreds of nanometers, as measured by atomic force microscopy, confocal microscopy, and interferometry. A simple electrostatic model, which takes into account the membranes' mechanical properties, was used to interpret the experimental data.

Controlling molecular conductance: switching off π sites through protonation.

Conductance switching through chemical modification of a molecular bridge is a major goal in molecular electronics, with the potential to lead to molecule-based functional devices. In terms of switching speed, mechanisms that rely on only minor rearrangements of molecular structures are particularly promising. We demonstrate, based on density functional theory calculations combined with a coherent tunneling approach, how protonation and deprotonation of amine-substituted or amine-bridged model molecular wires can switch off and on π-sites and thus: a) remove or introduce interference features in the electron transmission, and b) decrease or increase coupling along a chain. This mechanism may also be relevant for interactions between molecular bridges and metal cations, for example, in sensor applications.

Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating.

A new, extremely efficient method for the fabrication of films comprised of gold nanoparticles (GNPs) crosslinked by organic dithiols is presented in this paper. The method is based on layer-by-layer spin-coating of both components, GNPs and crosslinker, and enables the deposition of films several tens of nanometers in thickness within a few minutes. X-ray diffraction and conductance measurements reveal the proper adjustment concentration of the crosslinker solution of the critical is in order to prevent the destabilization and coalescence of particles. UV/vis spectroscopy, atomic force microscopy, and conductivity measurements indicate that films prepared via layer-by-layer spin-coating are of comparable quality to coatings prepared via laborious layer-by-layer self-assembly using immersion baths. Because spin-coated films are not bound chemically to the substrate, they can be lifted-off by alkaline underetching and transferred onto 3d-electrodes to produce electrically addressable, freely suspended films. Comparative measurements of the sheet resistances indicate that the transfer process does not compromise the film quality.