Project description:By means of scanning tunnelling microscopy (STM), complementary density functional theory (DFT) and X-ray photoelectron spectroscopy (XPS) we investigate the binding and self-assembly of a saturated molecular layer of model N-heterocyclic carbene (NHC) on Cu(111), Ag(111) and Au(111) surfaces under ultra-high vacuum (UHV) conditions. XPS reveals that at room temperature, coverages up to a monolayer exist, with the molecules engaged in metal carbene bonds. On all three surfaces, we resolve similar arrangements, which can be interpreted only in terms of mononuclear M(NHC)2 (M = Cu, Ag, Au) complexes, reminiscent of the paired bonding of thiols to surface gold adatoms. Theoretical investigations for the case of Au unravel the charge distribution of a Au(111) surface covered by Au(NHC)2 and reveal that this is the energetically preferential adsorption configuration.
Project description:A water-immersion laser-scanning annealing (WILSA) method was developed for the heat treatment of a deposited polycrystalline Au film on a glass. The material characterization using X-ray diffraction, field-emission scanning electron microscopy, and electron backscatter diffraction shows improved crystallinity with a more uniform crystallographic orientation of (111) and the grain growth of the annealed Au film. Additionally, the optical constants of the Au film before and after annealing were characterized by spectroscopic ellipsometry in the visible to near-infrared (NIR) regime, and the corresponding optical densities (ODs) were measured by transmittance spectroscopy. Our results show that the extinction coefficient and the OD of the annealed film are significantly reduced, particularly in the NIR regime. This is because the grain growth caused by the annealing reduces the density of grain boundaries, leading to the decrease of the loss of free electrons' scattering at grain boundaries. Hence, the damping effect of the surface plasmon is reduced. Additionally, the integrity of the WILSA-treated thin film is kept intact without pinholes, usually produced by the conventional thermal annealing. Based on the improved optical property of the WILSA-treated Au film, two performances of an insulator-metal-insulator (IMI) layered structure of biosensors are theoretically analyzed. Numerical results show that the propagation length of a long-range surface plasmon polariton along an IMI structure with an annealed Au film is significantly increased, compared to an unannealed film, particular in the NIR region. For the other application of using an IMI sensor to detect the shift of the surface-plasmon-resonance dip in the total internal reflection spectrum for the measurement of a change of the medium's refractive index, the sensitivity is also profoundly improved by the WILSA method. It is worth mentioning that the optimal heating conditions (laser wavelength, fluence, exposure time, and scanning step) depend on the thickness of the Au film. Our study provides a postprocess of WILSA to improve the optical properties of a deposited polycrystalline Au film for raising the sensitivity of the related biosensors.
Project description:As technology development drives the thickness of thin film depositions down into the nano regime, understanding and controlling the dewetting of thin films has become essential for many applications. The dewetting of ultra-thin Ag (9 nm) films with Ti (0.5 nm) adhesion and capping layers on glass substrates was investigated in this work. Various thin film stacks were created using magnetron sputtering and were analyzed using scanning electron microscopy/energy dispersive X-rays, Vis/IR spectrometry, and four four-point probe resistivity measurements. Upon annealing for 5 h in air at 250 °C, the addition of a 0.5 nm thick Ti capping layer reduced the dewet area by an order of magnitude. This is reflected in film resistivity, which remained 2 orders of magnitude lower than uncapped variants. This Ti/Ag/Ti structure was then deployed in a typical low-emissivity window coating structure with additional antireflective layers of AZO, resulting in a superior performance upon annealing. These results demonstrate an easy, manufacturable process that improves the longevity of devices and products containing thin Ag films.
Project description:Herein, we combine titania layers with gold species in a laser-supported process and report a substantial change of properties of the resulting heterostructures depending on the major processing parameters. Electrodes were fabricated via an anodisation process complemented with calcination to ensure a crystalline phase, and followed by magnetron sputtering of metallic films. The obtained TiO2 nanotubes with deposited thin (5, 10 nm) Au films were treated with a UV laser (355 nm) to form Au nanoparticles on top of the nanotubes. It was proven that selected laser working parameters ensure not only the formation of Au nanoparticles, but also simultaneously provide preservation of the initial tubular architecture, while above-threshold laser fluences result in partial destruction (melting) of the top layer of the nanotubes. For almost all of the samples, the crystalline phase of the nanotubes observed in Raman spectra was maintained independently of the laser processing parameters. Enhanced photoresponse up to ca 6 mA/cm2 was demonstrated by photoelectrochemical measurements on samples obtained by laser annealing of the 10 nm Au coating on a titania support. Moreover, a Mott-Schottky analysis indicated the dramatically increased (two orders of magnitude) concentration of donor density in the case of a laser-treated Au-TiO2 heterojunction compared to reference electrodes.
Project description:Thin polymer films on hydrophobic substrates are susceptible to rupture and hole formation. This, in turn, initiates a complex dewetting process, which ultimately leads to characteristic droplet patterns. Experimental and theoretical studies suggest that the type of droplet pattern depends on the specific interfacial condition between the polymer and the substrate. Predicting the morphological evolution over long timescales and on the different length scales involved is a major computational challenge. In this study, a highly adaptive numerical scheme is presented, which allows for following the dewetting process deep into the nonlinear regime of the model equations and captures the complex dynamics, including the shedding of droplets. In addition, our numerical results predict the previously unknown shedding of satellite droplets during the destabilization of liquid ridges that form during the late stages of the dewetting process. While the formation of satellite droplets is well known in the context of elongating fluid filaments and jets, we show here that, for dewetting liquid ridges, this property can be dramatically altered by the interfacial condition between polymer and substrate, namely slip. This work shows how dissipative processes can be used to systematically tune the formation of patterns.
Project description:Responsive polymer-based sensors have attracted considerable attention due to their ability to detect the presence of analytes and convert the detected signal into a physical and/or chemical change. High responsiveness, fast response speed, good linearity, strong stability, and small hysteresis are ideal, but to gain these properties at the same time remains challenging. This paper presents a facile and efficient method to improve the photonic sensing properties of polymeric gels by using non-close-packed monolayer colloidal crystals (ncp MCCs) as the template. Poly-(2-vinyl pyridine) (P2VP), a weak electrolyte, was selected to form the pH-responsive gel material, which was deposited onto ncp MCCs obtained by controlled O₂ plasma etching of close-packed (cp) MCCs. The resultant ultrathin photonic polymer gel film (UPPGF) exhibited significant improvement in responsiveness and linearity towards pH sensing compared to those prepared using cp MCCs template, achieving fast visualized monitoring of pH changes with excellent cyclic stability and small hysteresis loop. The responsiveness and linearity were found to depend on the volume and filling fraction of the polymer gel. Based on a simple geometric model, we established that the volume increased first and then decreased with the decrease of template size, but the filling fraction increased all the time, which was verified by microscopy observations. Therefore, the responsiveness and linearity of UPPGF to pH can be improved by simply adjusting the etching time of oxygen plasma. The well-designed UPPGF is reliable for visualized monitoring of analytes and their concentrations, and can easily be combined in sensor arrays for more accurate detection.
Project description:The stability of the film poly(n-butyl methacrylate) (PnBMA) with different tacticities, prepared on silicon oxide and exposed to aqueous phosphate-buffered saline with different concentrations of bovine serum albumin (CBSA between 0 and 4.5 mg/mL), was examined at temperatures close to the physiological limit (between 4 and 37 °C) with optical microscopy, contact angle measurements, atomic force microscopy, and time-of-flight secondary ion mass spectrometry. For PBS solutions with CBSA = 0, the stability of atactic PnBMA and dewetting of isotactic PnBMA was observed, caused by the interplay between the stabilizing long-range dispersion forces and the destabilizing short-range polar interactions. Analogous considerations of excess free energy cannot explain the retardation of dewetting observed for isotactic PnBMA in PBS solutions with higher CBSA. Instead, formation of a BSA overlayer, adsorbed preferentially but not exclusively to uncovered SiOx regions, is evidenced and postulated to hinder polymer dewetting. Polymer dewetting and protein patterning are obtained in one step, suggesting a simple approach to fabricate biomaterials with micropatterned proteins.
Project description:Understanding dewetting of solvent molecules confined to layered material (LM) interfaces is crucial to the synthesis of two-dimensional materials by liquid-phase exfoliation. Here, we examine dewetting behavior of water and isopropanol/water (IPA/H2O) mixtures between molybdenum disulfide (MoS2) membranes using molecular dynamics (MD) simulations. We find that a monolayer of water spontaneously ruptures into nanodroplets surrounded by dry regions. The average speed of receding dry patches is close to the speed of sound in air. In contrast, monolayer mixtures of IPA/H2O between MoS2 membranes slowly transform into percolating networks of nanoislands and nanochannels in which water molecules diffuse inside and IPA molecules stay at the periphery of islands and channels. These contrasting behaviors may explain why IPA/H2O mixtures are much more effective than H2O alone in weakening interlayer coupling and exfoliating MoS2 into atomically thin sheets.
Project description:Molybdenum disulphide (MoS2) is a promising material for heterogeneous catalysis and novel two-dimensional (2D) optoelectronic devices. In this work, we synthesized single-layer (SL) MoS2 structures on Au(111) by pulsed laser deposition (PLD) under ultra-high vacuum (UHV) conditions. By controlling the PLD process, we were able to tune the sample morphology from low-coverage SL nanocrystals to large-area SL films uniformly wetting the whole substrate surface. We investigated the obtained MoS2 structures at the nanometer and atomic scales by means of in situ scanning tunneling microscopy/spectroscopy (STM/STS) measurements, to study the interaction between SL MoS2 and Au(111)-which for example influences MoS2 lattice orientation-the structure of point defects and the formation of in-plane MoS2/Au heterojunctions. Raman spectroscopy, performed ex situ on large-area SL MoS2, revealed significant modifications of the in-plane E12g and out-of-plane A1g vibrational modes, possibly related to strain and doping effects. Charge transfer between SL MoS2 and Au is also likely responsible for the total suppression of excitonic emission, observed by photoluminescence (PL) spectroscopy.
Project description:Dewetting is a ubiquitous phenomenon in nature; many different thin films of organic and inorganic substances (such as liquids, polymers, metals, and semiconductors) share this shape instability driven by surface tension and mass transport. Via templated solid-state dewetting, we frame complex nanoarchitectures of monocrystalline silicon on insulator with unprecedented precision and reproducibility over large scales. Phase-field simulations reveal the dominant role of surface diffusion as a driving force for dewetting and provide a predictive tool to further engineer this hybrid top-down/bottom-up self-assembly method. Our results demonstrate that patches of thin monocrystalline films of metals and semiconductors share the same dewetting dynamics. We also prove the potential of our method by fabricating nanotransfer molding of metal oxide xerogels on silicon and glass substrates. This method allows the novel possibility of transferring these Si-based patterns on different materials, which do not usually undergo dewetting, offering great potential also for microfluidic or sensing applications.