Gold Substrate Research Articles

Active Broadband Absorber Based on Phase-Change Materials Optimized via Evolutionary Algorithm

This article proposes a temperature-controlled absorber based on VO2, which consists of five layers: a disk-shaped VO2 layer array, a dielectric layer, a circular hole VO2 array, a SiO2 layer, and a gold substrate from top to bottom. We optimized the thickness of the other four layers of the absorber, except for the gold layer, using PSO. After ten iterations, we determined that the optimal parameters for the top-to-bottom four-layer thicknesses were 0.183 μm, 0.452 μm, 0.557 μm and 1.994 μm. At this point, our absorber reached the optimal absorption parameters, and we plotted the absorption spectrum under these conditions. We found that the absorption rate at 29.1–47.2 THz was higher than 90%, and the absorption bandwidth was as high as 18.1 THZ. This frequency band covers most of the atmospheric window area (23–37.5 THz), so it will have good practicality. At 30.8 THz and 43.12 THz, there were perfect absorption peaks with absorption rates of 99.99% and 99.99%, respectively. We explained the cause of absorption from the perspective of electric field, and then we studied the change in the absorption curve of the absorber when the temperature of VO2 changed, and we can directly observe the changes in the electric field to explain this. Finally, we can tune the bandwidth and absorption rate of the absorber by changing the structure of the VO2 pattern. After comparing with other absorbers developed in recent years, our absorber still has good competitiveness, and we believe that our solution is expected to have outstanding performance in fields such as photothermal conversion and thermal stealth in the future.

Surface Acoustic Wave Immunosensor for Detection of Botulinum Neurotoxin.

A Love-type acoustic wave sensor (AT-cut quartz substrate, SiO2 guiding layer) with a center frequency of approximately 120 MHz was used to detect a simulant of pathogenic botulinum neurotoxin type A-recombinant of BoNT-A light chain-in liquid samples. The sensor was prepared by immobilizing monoclonal antibodies specific for botulinum neurotoxin via a thiol monolayer deposited on a gold substrate. Studies have shown that the sensor enables selective analyte detection within a few minutes. In addition, the sensor can be used several times (regeneration of the sensor is possible using a low pH buffer). Nevertheless, the detectability of the analyte is relatively low compared to other analytical techniques that can be used for rapid detection of botulinum neurotoxin. The obtained results confirm the operation of the proposed sensor and give hope for further development of this label-free technique for detecting botulinum neurotoxin.

Stability of N-Heterocyclic Carbene Monolayers Under Continuous Voltammetric Cycling

N-heterocyclic carbenes (NHCs) are promising monolayer-forming chemistries that can overcome limitations of thiol-based monolayers in terms of stability, surface functionality and reactivity across a variety of transition metal surfaces. Recent publications have reported the ability of NHCs to support biomolecular receptors on gold substrates for sensing applications, and improved tolerance to prolonged biofluid exposure relative to thiol chemistries. However, important questions remain regarding the stability of these monolayers when subjected to voltage perturbations, which is needed for technology application in electrochemical platforms. In response, we investigated the ability of two NHC chemistries, 1,3-diisopropylbenzimidazole and 5-(ethoxycarbonyl)-1,3-diisopropylbenzimidazole, to form monolayers via self-assembly from methanolic solutions of their trifluoromethanesulfonate salts. We compared the electrochemical behavior of the resulting monolayers relative to that of benchmark mercaptohexanol monolayers in phosphate-buffered saline. In this presentation I will discuss the results of this study and how they can affect future use of NHCs in electrochemical biosensors.

Spin-Crossover and Fragmentation of Fe(neoim)2 on Silver and Gold.

The neutral spin crossover complex Fe(neoim)2, neoim being the deprotonated form of the ionogenic ligand 2-(1H-imidazol-2-yl)-9-methyl-1,10-phenanthroline (neoimH), is investigated on the (111) surfaces of Au and Ag using scanning tunneling microscopy and density functional theory calculations. The complex sublimates and adsorbs intact on Ag(111), where it exhibits an electron-induced spin crossover. However, it fragments on Au. According to density functional theory calculations, the adsorbed complex is drastically distorted by the interactions with the substrates, in particular by van der Waals forces. Dispersion interaction is also decisive for the relative stabilities of the low- and high-spin states of the adsorbed complex. The unexpected instability of the complex on the gold substrate is attributed to enhanced covalent bonding of the fragments to the substrate.

Nanostructured Ir-based electrocatalysts for oxygen evolution prepared by galvanic displacement of Co and Ni

Proton exchange membrane (PEM) electrolysers are promising devices to produce hydrogen as a green fuel. Currently, this technology is limited by the sluggish kinetics of the oxygen evolution reaction (OER). In this work, we describe an environmentally safe method for the preparation of Ir oxide thin films (IrO2) for OER. Electrodeposition of Co and Ni was performed in the non-toxic choline chloride:urea deep eutectic solvent (ChCl:urea DES), followed by galvanic displacement reaction (GDR) of Co and Ni by Ir(IV). We evaluated how the GDR conditions, such as the metal replaced (Co or Ni), time and temperature affect both the activity and stability of the deposited IrO2 films on gold substrates. We observed that GDR of Ni at 90 °C induces morphological changes on the IrO2 nanostructures which resulted in higher activity and stability towards OER. We highlight that not only reducing mass loadings of Ir but also tuning the surface morphology and structure controlling the synthesis preparation, as well as investigating the role of the substrate, are key to design more active and stable OER electrocatalysts.

Impact of Surface Functionalization and Deposition Method on Cu-BDC surMOF Formation, Morphology, Crystallinity, and Stability.

For direct integration into device architectures, surface-anchored metal-organic framework (surMOF) thin films are attractive systems for a wide variety of electronic, photonic, sensing, and gas storage applications. This research systematically investigates the effect of deposition method and surface functionalization on the film formation of a copper paddle-wheel-based surMOF. Solution-phase layer-by-layer (LBL) immersion and LBL spray deposition methods are employed to deposit copper benzene-1,4-dicarboxylate (Cu-BDC) on gold substrates functionalized with carboxyl- and hydroxyl-terminated alkanethiol self-assembled monolayers (SAMs). A difference in crystal orientation is observed by atomic force microscopy and X-ray diffractometry based on surface functionalization for films deposited by the LBL immersion method but not for spray-deposited films. Cu-BDC crystallites with a strong preferred orientation perpendicular to the substrate were observed for the films deposited by the LBL immersion method on carboxyl-terminated SAMs. These crystals could be removed upon testing adhesive properties, whereas all other Cu-BDC surMOF film structures demonstrated excellent adhesive properties. Additionally, film stability upon exposure to water or heat was investigated. Ellipsometric data provide insight into film formation elucidating 7 and 14 Å average thicknesses per deposition cycle for films deposited by the immersion method on 11-mercapto-1-undecanol (MUD) and 16-mercaptohexadecanoic acid (MHDA), respectively. In contrast, the films deposited by the spray method are thicker with the same average thickness per deposition cycle (21 Å) for both SAMs. While the spray method takes less time to grow thicker films, it produces similar crystallite structures, regardless of the surface functionalization. This research is fundamental to understanding the impact of deposition method and surface functionalization on surMOF film growth and to provide strategies for the preparation of high-quality surMOFs.

Amplified hybrid surface plasmon polaritons in partially reduced graphene oxide supported on gold

We experimentally investigated the surface plasmon polaritons' (SPPs) localisation, resonance, and propagation in three plasmonic waveguides: graphene oxide (GO), partially reduced graphene oxide (PRGO), and reduced graphene oxide (RGO) in two configurations; as stand-alone structures and when deposited on gold films. Our experiments measuring the nonlinear absorption/refraction and leakage radiation microscopy (LRM) reveal that the intense Lorenz/Fano resonance of surface plasmon polaritons can occur in the PRGO-based waveguide. We also observe an increasing surface plasmon polaritons generation rate in PRGO-supported Au waveguide, a procedure similar to the spaser (surface plasmon nanolaser) mechanism. This, in turn, leads to increasing the propagation length. Furthermore, our analytical simulation results also suggest the suitability of PRGO as a superior optical material for spaser application. Our density functional calculations confirm that oxidised graphene has a more robust absorption spectrum in infrared wavelengths than pure graphene. Additionally, through van der Waals interaction, PRGO forms a more consistent and uniform bond with gold substrate than pristine graphene, reinforcing the suitability of PRGO as plasmonic waveguides.

Tunable optical properties of bipyridine dithiol molecules self-assembled on gold substrate

Using density functional theory calculations, we study the effect of intermolecular cross-linking and metal ion inclusion on the electronic and optical properties of 5,5’-bis(mercaptomethyl)-2,2’-bipyridine (BPD) molecules self-assembled on gold substrate. The contribution of the molecules to the density of states of the system near the Fermi level becomes more pronounced after cross-linking due to the delocalization of the electronic states towards the molecules. Consequently, the absorption intensity in the infrared and visible ranges of the spectrum enhances after the cross-linking. The other optical parameters of the system (such as refractive index and reflectivity) is also affected by the cross-linking induced structural changes. Optical properties of self-assembled BPD molecules can further be improved by intercalating metal ions which get encapsulated between the pyridinic units of the molecules and create new absorption sites in the visible and UV ranges of the spectrum. These findings can be useful in tuning optical properties of different materials using molecular self-assembly approach.

Stability of N-Heterocyclic Carbene Monolayers under Continuous Voltammetric Interrogation.

N-Heterocyclic carbenes (NHCs) are promising monolayer-forming ligands that can overcome limitations of thiol-based monolayers in terms of stability, surface functionality, and reactivity across a variety of transition-metal surfaces. Recent publications have reported the ability of NHCs to support biomolecular receptors on gold substrates for sensing applications and improved tolerance to prolonged biofluid exposure relative to thiols. However, important questions remain regarding the stability of these monolayers when subjected to voltage perturbations, which is needed for applications with electrochemical platforms. Here, we investigate the ability of two NHCs, 1,3-diisopropylbenzimidazole and 5-(ethoxycarbonyl)-1,3-diisopropylbenzimidazole, to form monolayers via self-assembly from methanolic solutions of their trifluoromethanesulfonate salts. We compare the electrochemical behavior of the resulting monolayers relative to that of benchmark mercaptohexanol monolayers in phosphate-buffered saline. Within the -0.15 to 0.25 V vs Ag|AgCl voltage window, NHC monolayers are stable on gold surfaces, wherein they electrochemically perform like thiol-based monolayers and undergo similar reorganization kinetics, displaying long-term stability under incubation in buffered media and under continuous voltammetric interrogation. At negative voltages, NHC monolayers cathodically desorb from the electrode surface at lower bias (-0.1 V) than thiol-based monolayers (-0.5 V). At voltages more positive than 0.25 V, NHC monolayers anodically desorb from electrode surfaces at similar voltages to thiol-based monolayers. These results highlight new limitations to NHC monolayer stability imposed by electrochemical interrogation of the underlying gold electrodes. Our results serve as a framework for future optimization of NHC monolayers on gold for electrochemical applications, as well as structure-functionality studies of NHCs on gold.

Anisotropic Plasmonic Metasurfaces with Linear Polarization‐Dependent Focusings

AbstractAs a burgeoning approach to modulate electromagnetic waves, metasurfaces fascinate many researchers. However, it is a persistent problem to realize independent wavefront tailoring in different polarization states. In this work, anisotropic plasmonic metasurfaces are presented with linear polarization‐dependent focusings. The designed plasmonic meta‐atoms consist of cross‐shaped gold, silica spacer, and gold substrate. Phase modulation in different polarization channels is independently achieved by adjusting the dimensions of cross‐shaped gold in x‐ and y‐directions. Three metasurfaces are presented to verify linear polarization‐dependent focusings at 200 THz. First, a focusing metasurface is designed with focal lengths of 5.2 µm under x‐polarized incidence and 6.5 µm under y‐polarized incidence. Second, by applying convolution operation, the second metasurface exhibits different focusings with different deflection angles at opposite directions under orthogonally polarized incidences. Finally, a multi‐focal metasurface is demonstrated, which switches between dual‐ and quad‐focal points depending on polarization state. The work may provide a novel platform for near‐infrared integrated photonics.

Broadband all-metal reflective-mode geometric metasurfaces for visible multi‐functional wavefront manipulation

Visible light manipulation has become a well-explored subject over recent years owing to its fascinating prospect in the optical communication field. Nevertheless, the limitations imposed by materials inherent in natural hamper the progress of the optical devices. Here, a broadband reflective-mode all-metal geometric metasurface (GMS) capable of high-efficient circular polarization (CP) conversion and applicable for multi-functional wavefront manipulation was proposed and investigated numerically in visible region. The proposed all-metal GMS is comprised of the periodically arranged gold dumbbell-shaped (DBS) nanostructure with symmetrical square notch adhered on the gold substrate. Simulation results demonstrate that the cross-polarized reflection amplitude of the all-metal GMS for normal incident CP light is practically higher than 85% from 310 THz to 500 THz, and the full 2π phase shift in this frequency range can be acquired by varying oriented angle of the DBS nanostructure. As proofs of multi-functional wavefront manipulation devices, beam deflectors, reflective planar focusing metalens and vortex beam generators were constructed and demonstrated numerically with the all-metal DBS nanostructure based on geometric phase principle. Overall, the proposed GMS carries with it considerable advantages of compaction and high efficiency, thus possessing infinite potential in optical devices.

Impact of Plasmonic and Dielectric Substrates on the Whispering-Gallery Modes in Self-Assembled Fluorescent Semiconductor Polymer Microspheres.

In this work, the impact of metallic and dielectric conducting substrates, gold and indium tin oxide (ITO)-coated glass, on the whispering gallery modes (WGMs) of semiconductor π-conjugated polymer microspheres is investigated. Hyperspectral mapping was performed to obtain the excitation-position-dependent emission spectra of the microspheres. Substrate-dependent quenching of WGMs sensitive to mode polarization was observed and explained. On a glass substrate, both transverse-electric (TE) and transverse-magnetic (TM) WGMs are quenched due to frustrated total internal reflection. On a gold substrate, however, only the TM WGMs are allowed in symmetry to leak into surface plasmons. An atomically flat gold substrate with subwavelength slits was used to experimentally verify the leakage of WGMs into the surface plasmon polaritons (SPPs). This work provides insight into the damping mechanisms of WGMs in microspheres on metallic and dielectric substrates.

Character of Electronic States in the Transport Gap of Molecules on Surfaces.

We report on scanning tunneling microscopy (STM) topographs of individual metal phthalocyanines (MPc) on a thin salt (NaCl) film adsorbed on a gold substrate, at tunneling energies within the molecule's electronic transport gap. Theoretical models of increasing complexity are discussed. The calculations for MPcs adsorbed on a thin NaCl layer on Au(111) demonstrate that the STM pattern rotates with the molecule's orientations─in excellent agreement with the experimental data. Thus, even the STM topography obtained for energies in the transport gap represent the structure of a one atom thick molecule. It is shown that the electronic states inside the transport gap can be rather accurately approximated by linear combinations of bound molecular orbitals (MOs). The gap states include not only the frontier orbitals but also surprisingly large contributions from energetically much lower MOs. These results will be essential for understanding processes, such as exciton creation, which can be induced by electrons tunneling through the transport gap of a molecule.

A universal stimuli-responsive biosensor for disease biomarkers through their cysteine residues: A proof of concept on carcinoembryonic antigen (CEA) biomarker

Carcinoembryonic antigen (CEA) is the gold standard biomarker for the clinical diagnosis of cancers diseases. Accurate, fast, and sensitive screening of CEA plays an important role in cancer disease detection and prognosis. This work reports the development of a new stimuli-responsive biosensor that determines the CEA blood plasma concentration within 10 min. Tert-butyl carbonate Naphthalene-flanked diketopyrroloprrole (mono-TBC-DPPN) fluorescent agent was synthesised, characterised and immobilised gold nanoparticles to develop the stimuli-responsive sensor. The target protein was purified from spiked plasma (from human blood), using an antibody-coated gold substrate. The purified CEA was then chemically modified to provide thiol groups (SH) that interact with the mono-TBC-DPPN on the surface of the stimuli-responsive biosensor to spontaneously displace it, thus leading to its fluorescence emission at 532 nm to a turn on. The new method and sensor was implemented to quantify CEA in spiked blood plasma down to 10 pg.mL−1 within 45 min (35 min for the protein purification and modification and 10 min for its quantification using the sensor)

Solution-Processed Formation of DNA-Origami-Supported Polyoxometalate Multi-Level Switches with Countercation-Controlled Conductance Tunability

We report a chemically programmed design and the switching characteristics of a functional metal–DNA-origami–polyoxometalate (POM) material obtained from the solution-processed assembling of biocompatible molecular precursors. The DNA origami is immobilized on the gold surface via thiolate groups and acts as a carrier (ad-layer) structure, ensuring the spatially controlled hybridization of the pre-defined six-helix bundle (6HB) positions with DNA-augmented, tris(alkoxo)-ligated Lindqvist-type polyoxovanadate (POV6) units. The DNA-confined POV6 units accept electrons in a stepwise fashion, allowing for a multi-logic function, which we directly probe using scanning tunneling electron microscopy and spectroscopy. Electron acceptance and injection into the originally non-conducting DNA structure and the subsequent release to the gold substrate depend upon the potential at the nanoscale tip and the oxidation state of POV6, as well as on the mechanism of action of POV6 countercations. By combining experiment and theory, we show that the bio-hybrid heterojunction has far-reaching potential to create a chemically controlled POM-based nano-environment with synaptic behavior.

Terahertz broadband tunable chiral metamirror based on VO2-metal hybrid structure.

Aiming at the problems of narrow working bandwidth, low efficiency, and complex structure of existing terahertz chiral absorption, we propose a chiral metamirror composed of C-shaped metal split ring and L-shaped vanadium dioxide (VO2). This chiral metamirror is composed of three layers of structure, a gold substrate at the bottom, the first polyethylene cyclic olefin copolymer (Topas) dielectric layer and VO2-metal hybrid structure as the top. Our theoretical results led us to show that this chiral metamirror has a circular dichroism (CD) value greater than 0.9 at 5.70 to 8.55 THz and has a maximum value of 0.942 at f = 7.18 THz. In addition, by adjusting the conductivity of VO2, the CD value can be continuously adjustable from 0 to 0.942, which means that the proposed chiral metamirror supports the free switching of the CD response between the on and off states, and the CD modulation depth exceeds 0.99 in the range of 3 to 10 THz. Moreover, we discuss the influence of structural parameters and the change of incident angle on the performance of the metamirror. Finally, we believe that the proposed chiral metamirror has important reference value in the terahertz range for constructing chiral light detectors, CD metamirrors, switchable chiral absorbers and spin-related systems. This work will provide a new idea for improving the terahertz chiral metamirror operating bandwidth and promote the development of terahertz broadband tunable chiral optical devices.

Surface‐enhanced Raman imaging of intact cancer cell membrane on a rough aluminum substrate

AbstractThe plasma membrane of cancer cells displays differences in lipid and protein composition which distinguish them from healthy cells. Certain molecules have such prominent vibrational characteristics that they can be considered cancer biomarkers. Although Raman spectroscopy is a label‐free non‐invasive method of chemical analysis, it, however, has been limited by weak signals from the membrane compared to the bulk interior of cells. Surface‐enhanced Raman scattering (SERS) on plasmonic gold and silver substrates has previously been used to overcome this limitation. However, the high cost, poor repeatability, and toxicity of these noble metals hinder their practical applications. These challenges may be solved by using different materials and nanostructures. Here, we performed SERS imaging of ovarian cancer cells on rough aluminum substrates and extracted the Raman signals of intact cell membranes by comparing these with the corresponding measurements on Si substrates. We used atomic force microscopy (AFM) for Raman signal calibration. The comparison of cancer and normal cell membranes revealed the different lipid/protein peak ratios in cytoplasm and nucleus‐proximal areas. These Raman signatures of the ovarian cancer can be used as new biomarkers. This method may be extended to other types of cancer biosensing based on aluminum plasmonics.

Mode-Coupling Generation Using ITO Nanodisk Arrays with Au Substrate Enabling Narrow-Band Biosensing.

Plasmonic metal nanostructures have promising applications in biosensing due to their ability to facilitate light-matter interaction. However, the damping of noble metal leads to a wide full width at half maximum (FWHM) spectrum which restricts sensing capabilities. Herein, we present a novel non-full-metal nanostructure sensor, namely indium tin oxide (ITO)-Au nanodisk arrays consisting of periodic arrays of ITO nanodisk arrays and a continuous gold substrate. A narrow-band spectral feature under normal incidence emerges in the visible region, corresponding to the mode-coupling of surface plasmon modes, which are excited by lattice resonance at metal interfaces with magnetic resonance mode. The FWHM of our proposed nanostructure is barely 14 nm, which is one fifth of that of full-metal nanodisk arrays, and effectively improves the sensing performance. Furthermore, the thickness variation of nanodisks hardly affects the sensing performance of this ITO-based nanostructure, ensuring excellent tolerance during preparation. We fabricate the sensor ship using template transfer and vacuum deposition techniques to achieve large-area and low-cost nanostructure preparation. The sensing performance is used to detect immunoglobulin G (IgG) protein molecules, promoting the widespread application of plasmonic nanostructures in label-free biomedical studies and point-of-care diagnostics. The introduction of dielectric materials effectively reduces FWHM, but sacrifices sensitivity. Therefore, utilizing structural configurations or introducing other materials to generate mode-coupling and hybridization is an effective way to provide local field enhancement and effective regulation.

Conformational Changes in Surface-Immobilized Proteins Measured Using Combined Atomic Force and Fluorescence Microscopy.

Biological organisms rely on proteins to perform the majority of their functions. Most protein functions are based on their physical motions (conformational changes), which can be described as transitions between different conformational states in a multidimensional free-energy landscape. A comprehensive understanding of this free-energy landscape is therefore of paramount importance for understanding the biological functions of proteins. Protein dynamics includes both equilibrium and nonequilibrium motions, which typically exhibit a wide range of characteristic length and time scales. The relative probabilities of various conformational states in the energy landscape, the energy barriers between them, their dependence on external parameters such as force and temperature, and their connection to the protein function remain largely unknown for most proteins. In this paper, we present a multimolecule approach in which the proteins are immobilized at well-defined locations on Au substrates using an atomic force microscope (AFM)-based patterning method called nanografting. This method enables precise control over the protein location and orientation on the substrate, as well as the creation of biologically active protein ensembles that self-assemble into well-defined nanoscale regions (protein patches) on the gold substrate. We performed AFM-force compression and fluorescence experiments on these protein patches and measured the fundamental dynamical parameters such as protein stiffness, elastic modulus, and transition energies between distinct conformational states. Our results provide new insights into the processes that govern protein dynamics and its connection to protein function.

Label-free detection and identification of single bacteria via terahertz near-field imaging.

In recent years, terahertz (THz) imaging has attracted much attention because of its ability to obtain physical and chemical information in a label-free, noninvasive and nonionizing manner. However, the low spatial resolution of traditional THz imaging systems and the weak dielectric response of biological samples hinder the application of this technology in the biomedical field. In this paper, we report a new THz near-field imaging method for a single bacteria, through the coupling effect of nanoscale radius of probe and platinum gold substrate, which greatly enhances THz near-field signal of biological samples. A THz super-resolution image of bacteria has been successfully obtained by strictly controlling the relevant test parameters such as tip parameters and driving amplitude. By analyzing and processing the THz spectral image, the morphology and inner structure of bacteria have been observed. The method has been used to detect and identify Escherichia coli represented by Gram-negative bacteria and Staphylococcus aureus represented by Gram-positive bacteria. This application provides a new label-free, noninvasive and nonionizing testing protocol for the detection of single bacteria.