Gold Flakes Research Articles

Gold Flake-Enabled Miniature Capacitive Picobalances.

Measurement of masses of microscale objects or weak force with ultrahigh sensitivity (down to nanogram/piconewton level) and compact configuration is highly desired for fundamental research and applications in various disciplines. Here, by using freestanding gold flakes with high reflectivity (≈98% at 980nm) as the sample tray and silica microfibers with extremely low spring constant (≈0.05 mNm-1) as the cantilever beams, miniature capacitive balances are reported with piconewton-level detection limit (picobalances) and reliable radiation force-based calibration. In the design, the gold flake is suspended by two silica microfibers, which also functions as an electrode to form a capacitor with an underneath gold electrode. Benefitting from the high reflectivity of the gold flake, the performance of picobalances can be precisely calibrated by exerting piconewton-level radiation pressure on the gold flake (working as a mirror) with a laser, showing a detection limit as low as 6.9 pN. Finally, using a fiber taper-assisted micromanipulation technique, masses of various types of pollens (with weights ranging from 4.6 to 96.3ng) are readily measured by a picobalance at single-particle level. The miniature picobalances should find applications in precise measurement of masses of micro or nanoscale objects and various types of weak forces.

Quantum-mechanical effects in photoluminescence from thin crystalline gold films.

Luminescence constitutes a unique source of insight into hot carrier processes in metals, including those in plasmonic nanostructures used for sensing and energy applications. However, being weak in nature, metal luminescence remains poorly understood, its microscopic origin strongly debated, and its potential for unraveling nanoscale carrier dynamics largely unexploited. Here, we reveal quantum-mechanical effects in the luminescence emanating from thin monocrystalline gold flakes. Specifically, we present experimental evidence, supported by first-principles simulations, to demonstrate its photoluminescence origin (i.e., radiative emission from electron/hole recombination) when exciting in the interband regime. Our model allows us to identify changes to the measured gold luminescence due to quantum-mechanical effects as the gold film thickness is reduced. Excitingly, such effects are observable in the luminescence signal from flakes up to 40 nm in thickness, associated with the out-of-plane discreteness of the electronic band structure near the Fermi level. We qualitatively reproduce the observations with first-principles modeling, thus establishing a unified description of luminescence in gold monocrystalline flakes and enabling its widespread application as a probe of carrier dynamics and light-matter interactions in this material. Our study paves the way for future explorations of hot carriers and charge-transfer dynamics in a multitude of material systems.

High-sensitivity fiber-tip acoustic sensor with ultrathin gold diaphragm

Miniature acoustic sensors with high sensitivity are highly desired for applications in medical photoacoustic imaging, acoustic communications and industrial nondestructive testing. However, conventional acoustic sensors based on piezoelectric, piezoresistive and capacitive detectors usually require a large element size on a millimeter to centimeter scale to achieve a high sensitivity, greatly limiting their spatial resolution and the application in space-confined sensing scenarios. Herein, by using single-crystal two-dimensional gold flakes (2DGFs) as the sensing diaphragm of an extrinsic Fabry-Perot interferometer on a fiber tip, we demonstrate a miniature optical acoustic sensor with high sensitivity. Benefiting from the ultrathin thickness (∼8 nm) and high reflectivity of the 2DGF, the fiber-tip acoustic sensor gives an acoustic pressure sensitivity of ∼300 mV/Pa in the frequency range from 100 Hz to 20 kHz. The noise-equivalent pressure of the fiber-tip acoustic sensor at the frequency of 13 kHz is as low as 62.8 µPa/Hz1/2, which is one or two orders of magnitude lower than that of reported optical acoustic sensors with the same size.

Large area single crystal gold of single nanometer thickness for nanophotonics

Two-dimensional single crystal metals, in which the behavior of highly confined optical modes is intertwined with quantum phenomena, are highly sought after for next-generation technologies. Here, we report large area (>104 μm2), single crystal two-dimensional gold flakes (2DGFs) with thicknesses down to a single nanometer level, employing an atomic-level precision chemical etching approach. The decrease of the thickness down to such scales leads to the quantization of the electronic states, endowing 2DGFs with quantum-confinement-augmented optical nonlinearity, particularly leading to more than two orders of magnitude enhancement in harmonic generation compared with their thick polycrystalline counterparts. The nanometer-scale thickness and single crystal quality makes 2DGFs a promising platform for realizing plasmonic nanostructures with nanoscale optical confinement. This is demonstrated by patterning 2DGFs into nanoribbon arrays, exhibiting strongly confined near infrared plasmonic resonances with high quality factors. The developed 2DGFs provide an emerging platform for nanophotonic research and open up opportunities for applications in ultrathin plasmonic, optoelectronic and quantum devices.

Evolutionary Optimized, Monocrystalline Gold Double Wire Gratings as a Novel SERS Sensing Platform.

Achieving reliable and quantifiable performance in large-area surface-enhanced Raman spectroscopy (SERS) substrates poses a formidable challenge, demanding signal enhancement while ensuring response uniformity and reproducibility. Conventional SERS substrates often made of inhomogeneous materials with random resonator geometries, resulting in multiple or broadened plasmonic resonances, undesired absorptive losses, and uneven field enhancement. These limitations hamper reproducibility, making it difficult to conduct comparative studies with high sensitivity. This study introduces an innovative approach that addresses these challenges by utilizing monocrystalline gold flakes to fabricate well-defined plasmonic double-wire resonators through focused ion-beam lithography. Inspired by biological strategy, the double-wire grating substrate (DWGS) geometry is evolutionarily optimized to maximize the SERS signal by enhancing both excitation and emission processes. The use of monocrystalline material minimizes absorption losses and ensures shape fidelity during nanofabrication. DWGS demonstrates notable reproducibility (RSD=6.6%), repeatability (RSD=5.6%), and large-area homogeneity >104µm2. It provides a SERS enhancement for sub-monolayer coverage detection of 4-Aminothiophenol analyte. Furthermore, DWGS demonstrates reusability, long-term stability on the shelf, and sustained analyte signal stability over time. Validation with diverse analytes, across different states of matter, including biological macromolecules, confirms the sensitive and reproducible nature of DWGSs, thereby establishing them as a promising platform for future sensing applications.

Contrasting evolution of beach gold on two sides of an active orogen, Southern Alps, New Zealand

ABSTRACT Placer gold on beaches on either side of a major active mountain belt has strongly contrasting compositions and morphologies. Pleistocene-Holocene beach gold placers have formed along the West Coast where silver (Ag)-bearing gold has been eroded from mountains via steep rivers and glaciers, followed by rapid burial in the abundant associated coastal sediments. Deformation along transport pathways has produced flattened gold flakes, but some primary crystalline shapes are preserved. Internal deformation of particles has caused recrystallisation to fine-grained (µm scale) grain structures including mylonitic banding. However, only minor localised (µm scale) Ag leaching has occurred on some particle margins. In contrast, Pleistocene beach placers formed on the southern side of the mountains contain flattened gold particles with a complex transport history involving long-distance (hundreds of km) fluvial transport since Cretaceous. Most primary Ag has been leached from this gold during transport-related recrystallisation to fine (5–20 µm) internal grains. Sand-blasting on the southern beaches with low sediment supply has resulted in further deformation and leaching of Ag to form toroidal shapes with Ag-free delicate extremities. Placer gold which has undergone rapid transport and deposition is useful as a prospecting tool for bedrock deposits in glaciated terranes around the world.

Determination and Characterization of Gold Nanoparticles in Liquor Using Asymmetric Flow Field-Flow Fractionation Hyphenated with Inductively Coupled Plasma Mass Spectrometry.

The EU has approved the usage of gold as a food additive (E175) and it has been applied in numerous foods for coloring and decoration purposes. Different from the general assumption that edible gold is mainly present in the form of flakes or external coating in foods, this work demonstrated that gold nanoparticles (Au NPs) can be released from gold flakes and extracted under optimized conditions. To support future risk assessment associated with the exposure of Au NPs to human health, an effective approach was established in this study for both size characterization and mass determination of Au NPs released in a commercial gold-containing liquor using Asymmetric Flow Field-flow Fractionation (AF4) hyphenated with Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Our results showed that no Au NPs were detected in the original liquor product and only after ultrasonication for several minutes did Au NPs occur in the ultrasound-treated liquor. Particularly, Au NPs released in the liquor can be well extracted after 100-fold enrichment of gold flakes and the subsequent ultrasonication for 25 min. Size characterization of Au NPs was conducted by AF4-ICP-MS under calibration with Au NP standards. The gold particle sizes detected ranged from 8.3-398.0 nm and the dominant size of the released Au NPs was around 123.7 nm in the processed liquor. The mass concentration of gold particles determined in the liquor sample with gold flakes concentrated and subsequently sonicated was 48.1 μg L-1 by pre-channel calibration and the overall detection recoveries ranged over 82-95%. For the comparison control samples without ultrasonication, there was no detection of Au NPs. The established method was demonstrated to be useful for monitoring Au NPs in liquor and is possibly applied to other similar foodstuffs.

Morphology and structural evolution of fine beach gold in comparison to detrital platinum, southern New Zealand

AbstractBeach placer gold has been mined around the world historically, but extraction of fine (~ 100 µm) gold particles is notoriously difficult. This study illustrates morphological and mineralogical changes that transform fine gold during aeolian processes on windy beaches and contribute to mine concentration inefficiencies. Sandblasting on exposed beaches in southern New Zealand has caused extreme attenuation of edges of gold flakes that were previously transported in rivers for > 200 km. Flakes have been transformed into complex but compact toroids and spheroids with thin (~ 20 µm) internal and external strands of attenuated gold. Most of the gold within the attenuated strands has recrystallised to fine (micron-scale) undeformed grains with little or no Ag (< 1 wt%). Some coarse (> 40 µm) gold grains remain from the precursor fluvial particles, and these retain original Ag contents (1–10 wt%). These coarse grains show substantial internal crystallographic deformation and sub-grain formation, although some of these strain effects may have been inherited from fluvial transport. Co-existing detrital platinum minerals are much less malleable than gold during sandblasting and have only minor (10-µm scale) toroidal deformation on edges of fluvial flakes. The complex frameworks of the fine toroidal and spheroidal gold particles can include air, water, and clay, which lowers their average density and so they commonly float on water and are readily entrained with other heavy minerals. The fine particle size, compact shapes, and clay coatings also resist mercury amalgamation.

On the likely origin of the Gold Dust Defect in the production line of industrial ferritic stainless steel

The “Gold Dust Defect” that sometimes appears on the surface of the AISI 430 ferritic stainless steel has been related to an improper recrystallization of the material. Hot-rolling, a decisive step in the production process, seems the step where this defect is induced and temperature during this treatment plays a key role. To trace back the origin of this defect, the microstructural evolution of a sample of an AISI 430 was monitored at the different stages in the production process of the steel. In particular, a detailed study combining electron backscatter diffraction with other techniques, such as optical microscopy and scanning electron microscopy has been performed. The whole set of results evidences that after hot-rolling and subsequent annealing, the material contains a large amount of martensite in the center of the cross-section due to a fast cooling of the austenite originated during rolling. In addition, the surface shows a top-layer made up by unrecrystallized subgrains separated from the matrix by an accumulation of chromium carbides. After pickling, the top-layer of subgrains semi-detaches from the surface forming flakes which cannot recrystallize. Most of these flakes do not peel off during the subsequent stages but survive until the end of the production process, forming Gold Dust Defect flakes.

Nonlinear Photoluminescence in Gold Thin Films

Promising applications in photonics are driven by the ability to fabricate crystal-quality metal thin films of controlled thickness down to a few nanometers. In particular, these materials exhibit a highly nonlinear response to optical fields owing to the induced ultrafast electron dynamics, which is however poorly understood on such mesoscopic length scales. Here, we reveal a new mechanism that controls the nonlinear optical response of thin metallic films, dominated by ultrafast electronic heat transport when the thickness is sufficiently small. By experimentally and theoretically studying electronic transport in such materials, we explain the observed temporal evolution of photoluminescence in two-pulse correlation measurements that we report for crystalline gold flakes. Incorporating a first-principles description of the electronic band structure, we model electronic transport and find that ultrafast thermal dynamics plays a pivotal role in determining the strength and time-dependent characteristics of the nonlinear photoluminescence signal, which is largely influenced by the distribution of hot electrons and holes, subject to diffusion across the film as well as relaxation to lattice modes. Our findings introduce conceptually novel elements ruling the nonlinear optical response of nanoscale materials, while suggesting additional ways to control and leverage hot carrier distributions in metallic films.

Wrinkle Clamp Down on Structure Crack Strain Sensor Based on High Poisson's Ratio Material for Home Health Monitoring and Human-Machine Interaction.

Flexible wearable crack strain sensors are currently receiving significant attention because they can be used in a wide range of physiological signal monitoring and human-machine interaction applications. However, sensors with high sensitivity, great repeatability, and wide sensing range remain challenging. Herein, a tunable wrinkle clamp down structure (WCDS) crack strain sensor based on high Poisson's ratio material with high sensitivity, high stability, and wide strain range is proposed. Based on the high Poisson's ratio of the acrylic acid film, the WCDS was prepared by a prestretching process. The wrinkle structures can clamp down the crack to improve the cyclic stability of the crack strain sensor while maintaining its high sensitivity. Moreover, the tensile properties of the crack strain sensor are improved by introducing wrinkles in the bridge-like gold stripes connecting each separated gold flake. Owing to this structure, the sensitivity of the sensor can reach 3627, stable operation over 10 000 cycles is achieved, and the strain range can reach about 9%. In addition, the sensor exhibits low dynamic response and good frequency characteristics. Because of its demonstrated excellent performance, the strain sensor can be used in pulse wave and heart rate monitoring, as well as posture recognition and game control.

Tunable critical Casimir forces counteract Casimir–Lifshitz attraction

In developing micro- and nanodevices, stiction between their parts, that is, static friction preventing surfaces in contact from moving, is a well-known problem. It is caused by the finite-temperature analogue of the quantum electrodynamical Casimir–Lifshitz forces, which are normally attractive. Repulsive Casimir–Lifshitz forces have been realized experimentally, but their reliance on specialized materials severely limits their applicability and prevents their dynamic control. Here we demonstrate that repulsive critical Casimir forces, which emerge in a critical binary liquid mixture upon approaching the critical temperature, can be used to counteract stiction due to Casimir–Lifshitz forces and actively control microscopic and nanoscopic objects with nanometre precision. Our experiment is conducted on a microscopic gold flake suspended above a flat gold-coated substrate immersed in a critical binary liquid mixture. This may stimulate the development of micro- and nanodevices by preventing stiction as well as by providing active control and precise tunability of the forces acting between their constituent parts.

Low‐Loss Anisotropic Image Polaritons in van der Waals Crystal α‐MoO3 (Advanced Optical Materials 21/2022)

Monocrystalline gold flakes serve as an atomically-flat low-loss substrate for the highly confined mid-infrared “image polaritons” stemming from hybridization of polaritons with their mirror image in the metal. By leveraging the physical properties of the gold flakes, the strongly anisotropic image phonon polaritons are rigorously studied in a biaxial van der Waals crystal α-MoO3 (see article number 2201492 by Min Seok Jang and co-workers). Notably, the image phonon polaritons provide approximately twice stronger field confinement yet longer lifetime compared to the phonon polaritons on a dielectric substrate.

Low‐Loss Anisotropic Image Polaritons in van der Waals Crystal α‐MoO3

AbstractOrthorhombic molybdenum trioxide (α‐MoO3), a newly discovered polaritonic van der Waals crystal, is attracting significant attention due to its strongly anisotropic mid‐infrared phonon‐polaritons. At the same time, coupling of polariton with its mirror image in an adjacent metal gives rise to a significantly more confined image mode. Here, monocrystalline gold flakes—an atomically flat low‐loss substrate for mid‐infrared image polaritons—are employed to measure the full complex‐valued propagation constant of the hyperbolic image phonon‐polaritons in α‐MoO3 by near‐field probing. The anisotropic dispersion is mapped and the damping of the polaritons propagating at different angles to the crystallographic directions of α‐MoO3 is analyzed. These experiments demonstrate the strongly confined image phonon‐polaritons in α‐MoO3 exhibiting intrinsic limiting lifetime of 4.2 ps and a propagation length of 4.5 times the polariton wavelength, owing to the negligible substrate‐mediated loss. Furthermore, it is shown that the image modes with positive group velocity have simultaneously larger momentum and lifetime compared to their counterparts on a dielectric substrate, while the image modes with negative group velocity possess a smaller momentum. These results spotlight the hyperbolic image phonon‐polaritons as a superior platform for unconventional light manipulation at the nanoscale.

Near-field probing of image phonon-polaritons in hexagonal boron nitride on gold crystals.

Near-field mapping has been widely used to study hyperbolic phonon-polaritons in van der Waals crystals. However, an accurate measurement of the polaritonic loss remains challenging because of the inherent complexity of the near-field signal and the substrate-mediated loss. Here we demonstrate that large-area monocrystalline gold flakes, an atomically flat low-loss substrate for image polaritons, provide a platform for precise near-field measurement of the complex propagation constant of polaritons in van der Waals crystals. As a topical example, we measure propagation loss of the image phonon-polaritons in hexagonal boron nitride, revealing that their normalized propagation length exhibits a parabolic spectral dependency. Furthermore, we show that image phonon-polaritons exhibit up to a twice longer normalized propagation length, while being 2.4 times more compressed compared to the case of the dielectric substrate. We conclude that the monocrystalline gold flakes provide a unique nanophotonic platform for probing and exploitation of the image modes in low-dimensional materials.

Extremely confined gap plasmon modes: when nonlocality matters

Historically, the field of plasmonics has been relying on the framework of classical electrodynamics, with the local-response approximation of material response being applied even when dealing with nanoscale metallic structures. However, when the confinement of electromagnetic radiation approaches atomic scales, mesoscopic effects are anticipated to become observable, e.g., those associated with the nonlocal electrodynamic surface response of the electron gas. Here, we investigate nonlocal effects in propagating gap surface plasmon modes in ultrathin metal–dielectric–metal planar waveguides, exploiting monocrystalline gold flakes separated by atomic-layer-deposited aluminum oxide. We use scanning near-field optical microscopy to directly access the near-field of such confined gap plasmon modes and measure their dispersion relation via their complex-valued propagation constants. We compare our experimental findings with the predictions of the generalized nonlocal optical response theory to unveil signatures of nonlocal damping, which becomes appreciable for few-nanometer-sized dielectric gaps.

Coherent two-beam steering of delocalized nonlinear photoluminescence in a plasmon cavity.

We aim at controlling the spatial distribution of nonlinear photoluminescence in a shaped micrometer-size crystalline gold flake. Interestingly, the underlying surface plasmon modal landscape sustained by this mesoscopic structure can be advantageously used to generate nonlinear photoluminescence (nPL) in remote locations away from the excitation spot. By controlling the modal pattern, we show that the delocalized nonlinear photoluminescence intensity can be redistributed spatially. This is first accomplished by changing the polarization orientation of the pulsed laser excitation in order to select a subset of available surface plasmon modes within a continuum. We then propose a second approach to redistribute the nPL within the structure by implementing a phase control of the plasmon interference pattern arising from a coherent two-beam excitation. Control and engineering of the nonlinear photoluminescence spatial extension is a prerequisite for deploying the next generation of plasmonic-enabled integrated devices relying on hot carriers.

Anisotropic second-harmonic generation from monocrystalline gold flakes.

Noble metals with well-defined crystallographic orientation constitute an appealing class of materials for controlling light-matter interactions on the nanoscale. Nonlinear optical processes, being particularly sensitive to anisotropy, are a natural and versatile probe of crystallinity in nano-optical devices. Here we study the nonlinear optical response of monocrystalline gold flakes, revealing a polarization dependence in second-harmonic generation from the {111} surface that is markedly absent in polycrystalline films. Our findings confirm that second-harmonic microscopy is a robust and non-destructive method for probing the crystallographic orientation of gold, and can serve as a guideline for enhancing nonlinear response in plasmonic systems.

Разработка технологии кучного выщелачивания руд с плавучим золотом

The features of the technology of heap leaching with floating gold are disclosed. It was found that significant technological losses of gold in the processes of enrichment of gold-bearing ores, as a rule, are associated with its natural fine mineralization or technogenic transformation to such a state. It has been shown that flat gold flakes (even with a gold grain size of more than 1 mm) are quite well retained on the surface of technological solutions, i.e., have a certain buoyancy. The wettability of gold particles is explained by the manifestation of the surface tension forces of aqueous solutions, the mechanisms of which are determined by the van der Waals interaction. In addition, the wettability of gold grains is affected by their electric charge, which, accumulating on a convex surface, creates a negative charge that prevents the formation of a double electric field around the gold particle, which is an additional reason for the non-wettability of gold. The mechanism of the formation of gold films, which are formed at a high value of surface tension, with the formation of floating "islands" covered with a hydrophilic shell, is explained. It was revealed that the energy of interaction of a gold nanoparticle with water can serve as a quantitative indicator of the buoyancy of gold grains and "islands" of nanogold, at a value of which of 0.05427 eV, clearly pronounced hydrophilic properties appear. The theoretical substantiation of the buoyancy of gold grains and "islands" of nanogold is the van der Waals interaction. On this basis, heap leaching technology was developed, with the targeted deposition of floating gold in the most suitable places. As a result of a decrease in the surface tension of leaching solutions, nanogold loses their initial buoyancy and sink from them to the bottom, where they will be subjected to the processes of their disembarkation (collection and extraction).

Gold Spherical and Flake Assemblies Fabrication Through Calcination of Gold Nanoparticles Incorporated Poly(acrylonitrile) Nanofibers

This work reports on the outcome of the calcination of gold nanoparticles incorporated polyacrylonitrile nanofibers in air which results in the formation of gold spherical and flake cluster assemblies. The architecture and morphology of gold nanostructures play a role in determining their different applications. The results of this research showed that calcination at 650 °C for 5 h led to almost complete disintegration and disappearance of the poly(acrylonitrile) matrix and polyhedral nanostructures were formed. FTIR analysis showed the complete disappearance of poly(acrylonitrile) matrix at calcination temperatures of 850 °C and 1000 °C. XRD analysis also showed the complete disappearance of poly(acrylonitrile) at calcination temperatures above 850 °C. SEM micrographs taken after calcination of the precursor showed that calcination around 850 °C leads to the formation of spherical gold clusters, whereas, calcination at 1000 °C produces gold flake clusters.