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.

To enable applications of nanoparticle films in flexible electronics, actuators, and sensors, their mechanical properties are of critical concern. Here, we demonstrate that the elastic and viscoelastic properties of covalently cross-linked gold nanoparticles (GNPs) can be probed using AFM bulge tests. For this purpose 30−60 nm thick films consisting of 1,9-nonanedithiol (NDT) cross-linked GNPs (3.8 nm core diameter) were transferred onto substrates with ∼100 μm circular apertures. The resulting freestanding membranes were bulged by applying pressure differences of up to 10 kPa, and the deflection was measured by intermittent contact atomic force microscopy (AFM). Analyzing the pressure-deflection data using the spherical cap model, either by taking into account the peak deflection values or the measured arc profiles of the bulge, yielded 2.3 ± 0.3 and 2.7 ± 0.4 GPa for Young's modulus, respectively. When cycling the stress−strain measurements at overpressures up to 2.4 kPa, hysteresis was observed and assigned to viscoelastic effects. Creep tests performed at a pressure of 2 kPa revealed both viscoelastic retardation (time constant: 3.3 × 10 −3 s −1 ) and nonrecoverable relaxation (creep rate: 9.0 × 10 −8 s −1 ). Several membranes resisted pressures up to 10 kPa without fracturing, indicating that the ultimate biaxial tensile strength of the films was above ∼30 MPa. ■ INTRODUCTIONThin films consisting of ligand-stabilized or cross-linked gold nanoparticles (GNPs) have received considerable scientific attention during the past two decades, and various applications have been demonstrated. For example, transduction elements based on thin GNP films have enabled the fabrication of novel resistive strain gauges, 1−4 touch sensors, 5,6 and chemiresistors. 7 In these sensors the transduction mechanism is based on changes in the interparticle distances, due to either forceinduced strain or sorption-induced swelling. Because the tunneling current between neighboring nanoparticles is exponentially related to their distance, these sensors can afford extremely high sensitivities. Further, nanoparticle networks have great potential for the implementation in next-generation flexible electronics. Very recently, Kotov and co-workers 8 reported on stretchable conductors made from GNP−polyurethane composites enabling electrical tunability of mechanical properties by dynamic self-organization of the nanoparticles under stress.Obviously, the performance of sensors and flexible electronics based on nanoparticle composites critically depends on their specific mechanical properties, e.g., elasticity, viscoelasticity, and ultimate strength. To some extent, these properties have been studied by nanoindentation 9 and forcedeflection measurements employing atomic force microscopes (AFMs). 10−12 In conventional nanoindentation experiments the indenter tip is pressed into the substrate-supported specimen, and the force−distance data are analyzed to extract the material's hardness and reduced elastic modulus. 13 Recently, the micromechanical p...

Composite materials of organically stabilized or cross-linked metal nanoparticles represent a versatile material class with manifold potential applications. Numerous studies explored their tunable optical and charge transport properties. However, due to challenging experimental requirements, only a few studies addressed their mechanical properties. Here, we report the first investigation on the tunability of the elastic properties of cross-linked gold nanoparticle (GNP) composites. Thin films consisting of GNPs (diameter 3–4 nm) cross-linked with α,ω-alkanedithiols of different chain length, as well as 1,4-benzenedithiol, were fabricated by spin-coating and transferred onto circular apertures with diameters of ∼100 μm. The mechanical properties of thus-prepared freestanding membranes with thicknesses between 21 and 51 nm were probed using bulge tests with atomic force microscopy (AFM) based deflection readout. We demonstrate that, along with their optical and charge transport characteristics, the elastic modulus of these GNP composites can be adjusted in a range from ∼3.6 to ∼10 GPa by shortening the α,ω-alkanedithiol chain length from 10 to 3 methylene units. These variations in elasticity are attributed to the varying fraction of soft organic matter and to structural differences within the composites. Our results provide a basis for further experimental and theoretical studies, as well as for applications of cross-linked nanoparticle composites in future micro- and nanoelectromechanical (MEMS/NEMS) devices, their design, and modeling.

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.

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.