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This study proposes a methodology for the fabrication of two-dimensional assembled colloidal nanocrystals based on the classical theory for the surface excess of a short-chain alcohol (butanol) in an aqueous mixture and Rayleigh-Bénard-Marangoni convection caused by temperature and/or surface tension gradients due to the volatilization of butanol at the air-water interface. When polyvinylpyrrolidone (PVP)-modified anisotropic silver nanoprisms dispersed in butanol were added into the water phase, the nanoprisms were guided to the air-water interface

Field-induced ionic motions in all-inorganic CsPbBr3 perovskite quantum dots (QDs) strongly dictate not only their electro-optical characteristics but also the ultimate optoelectronic device performance. Here, we show that the functionality of a single Ag/CsPbBr3/ITO device can be actively switched on a sub-millisecond scale from a resistive random-access memory (RRAM) to a light-emitting electrochemical cell (LEC), or vice versa, by simply modulating its bias polarity. We then realize for the first time a fast, all-perovskite light-emitting memory (LEM) operating at 5 kHz by pairing such two identical devices in series, in which one functions as an RRAM to electrically read the encoded data while the other simultaneously as an LEC for a parallel, non-contact optical reading. We further show that the digital status of the LEM can be perceived in real time from its emission color. Our work opens up a completely new horizon for more advanced all-inorganic perovskite optoelectronic technologies., Electric field induced ion migration is a well-known phenomenon in perovskite, but the consequences are notorious, and thus needs to be prevented. Here, on the other hand, the authors cleverly manipulate this event for realising resistive random-access memory and light-emitting electrochemical cell in one device based on CsPbBr3 quantum dots.

Understanding chemical effects on the plasmonic properties of a metal nanomaterial due to the surface molecules on that metal is of great importance in the field of plasmonics and these effects have yet to be completely elucidated. Here, we report mechanisms of the chemically induced change in the electronic state at the metal-ligand interface of silver nanoparticles due to the ligand molecules, and the effect of this change on the plasmonic properties of those nanoparticles. It was found that changes in the electron density of states at the metal-ligand interface cause alterations in the induced and permanent dipole moments, and eventually to the permittivity at the interface, when the wave function near the Fermi level is localized at the interface. These alterations play a key role in determining the plasmonic properties of silver nanoparticles. The present findings provide a more precise understanding of the interconnection between the electronic states at the metal-organic interface and the plasmonic properties of the metal. Studying the bonding of organic molecules onto the surface of metal nanomaterials is important for understanding their plasmonic properties. Here, changes in the electron density of states at the metal-ligand interface of Ag nanoparticles are linked to variations in localized dipole moments and interface permittivity.

A rapid and simple cancer detection method independent of cancer type is an important technology for cancer diagnosis. Although the expression profiles of biological molecules contained in cancer cell-derived extracellular vesicles (EVs) are considered candidates for discrimination indexes to identify any cancerous cells in the body, it takes a certain amount of time to examine these expression profiles. Here, we report the shape distributions of EVs suspended in a solution and the potential of these distributions as a discrimination index to discriminate cancer cells. Distribution analysis is achieved by low-aspect-ratio nanopore devices that enable us to rapidly analyze EV shapes individually in solution, and the present results reveal a dependence of EV shape distribution on the type of cells (cultured liver, breast, and colorectal cancer cells and cultured normal breast cells) secreting EVs. The findings in this study provide realizability and experimental basis for a simple method to discriminate several types of cancerous cells based on rapid analyses of EV shape distributions.

High-density colloidal quantum dot (QD) thin films are promising materials for optoelectronic devices. Our experimental data revealed a unique layer number-dependent photoluminescence (PL) from mul...

We demonstrate a flexible transmissive color filter based on a hybrid metallic–optical Tamm state device composed of a thin metallic film on top of dual dielectric distributed Bragg reflectors (DBR...

We propose a unique random metal nanohemisphere on mirror (NHoM) structure to tune the surface plasmon (SP) resonance in a flexible manner. The SP resonance peak was split into two peaks owing to the strong coupling between the SP mode in the metal nanohemisphere and the mirror image mode generated in the metal substrate. This phenomenon is based on the fact that the strong coupling and the induced electromagnetic effects are similar to those pertaining to the Rabi splitting, Fano resonance, and electromagnetically induced transparency, thus providing quantum effect analogies. These phenomena have recently attracted increased attention and have been studied with nanocavities fabricated with top-down nanotechnologies. Compared with previous reports, NHoM structures can be fabricated in a much easier manner and are tunable in rather wider wavelength regions without nanofabrication technologies. The SP resonance peaks were enhanced, sharpened dramatically, and tuned flexibly, based on the optimization of the thickness of the spacer layer between the metal hemisphere and metal substrate. Experimental results were reproduced and were explained based on finite difference time domain (FDTD) simulations. These phenomena have never been observed previously on similar nanosphere on mirror (NSoM) because nanohemispherical structures were required. The NHoM nanocavity structure has a quality factor >200 that is surprisingly high for the localized SP mode of nanoparticles. Flexible tuning of the SP resonance with the use of NHoM is envisaged to lead to the development of new applications and technologies in the field of plasmonics and nanophotonics.

The authors acknowledge the facilities, as well as the scientific and technical assistance, from the NSW Node of the Australian National Fabrication Facility (ANFF) and the Research & Prototype Foundry Core Research Facility at the University of Sydney, part of the ANFF. The authors also thank the Electron Microscope Unit within the Mark Wainwright Analytical Centre at UNSW Sydney for the use of facilities. N.S. is grateful to the advanced graduate course on molecular systems for devices, a program for leading graduate schools, Kyushu University, Japan.

Synthesis of anisotropic Ag nanoprisms (AgPRs) contributes to the development of high performance plasmonic devices. The localized surface plasmon resonance wavelength of AgPRs was successfully tun...

Size control is critical in the synthesis of quantum-confined semiconductor nanocrystals, otherwise known as quantum dots. The achievement of size-uniformity and narrow spectral line-width in quantum dots conventionally relies on a very precise kinetic control of the reactions, where reaction time plays a significant role in defining the final crystal sizes and distribution. Here, we show that synthesis of quantum-confined perovskite nanostrips could be achieved through a thermodynamically controlled reaction, using a low-temperature and ligand-rich approach. The nanostrip growth proceeds through an initial one-dimensional (1D) nanorod stage, followed by the lateral widening of the rod to form a two-dimensional (2D) nanostrip. The spectral characteristics of the final product remain unchanged after prolonged reaction, indicating no signs of crystal ripening and confirming the thermodynamic nature of this reaction. The CsPbBr3 perovskite nanostrips were highly uniform and emit at a deep-blue wavelength of 462 nm with a remarkably narrow line-width of 13 nm. This corresponds to color coordinates of (0.136, 0.049) on the CIE 1931 color space, which fulfils the stringent Rec. 2020 standard for next-generation color displays. The well-passivated nanostrips also possess negligible defects and provide a near-unity photoluminescence quantum yield at 94%. Crucially, the achievement of blue emission through a pure-halide perovskite circumvents the problems of spectral instability that are frequently experienced in mixed-halide perovskite systems. The convenience and scalability of our thermodynamic approach, coupled with the excellent optical attributes, would likely enable these quantum-confined perovskite systems to be the preferred method toward color control in trichromatic display applications.

Homogeneously self-assembled colloidal semiconductor quantum dot monolayers (QD-SAMs) over large areas are promising materials for thin film optoelectronic device applications, especially for displ...

Recently we have developed LSPR-mediated high resolution live-cell imaging techniques for adhesive cells on plasmonic metasurface composed of self-assembled gold or silver nanoparticles. Compared with other super-resolution microscopy techniques, our LSPR-mediated imaging is extremely simple but quite effective for monitoring the molecular dynamics at a nanointerface. The LSPR of the plasmonic metasurface provides high-contrast interfacial images due to the confined light within a region a few tens of nanometers from the particles and the enhancement of fluorescence. The improved lateral resolution reaches down to the theoretical limit even during cell movement due to the properties of the metasurface with an extremely high refractive index. In the presentation, we will present our latest imaging data concerning molecular dynamics in live cells, which were not visualized by other super-resolution imaging methods with low temporal resolution.

Field-induced ionic motions in all-inorganic CsPbBr3 perovskite quantum dots (QDs) strongly dictate not only their electro-optical characteristics but also the ultimate device performance of the CsPbBr3 optoelectronics. Novel device concepts with multiple functionalities can as a result be achieved based on CsPbBr3 by carefully controlling the ionic flow under different bias conditions. Here, we show that by manipulating the ion migrations in two nominally identical, series-connected Ag/CsPbBr3/ITO devices, one device can operate as a resistive random-access memory (RRAM) while the other simultaneously as a light-emitting electrochemical cell (LEC), or vice versa, simply through the polarity switching of the external bias across the entire structure. We further show that this electrically switchable, series-connected perovskite memories and light emitters can be employed as a novel all-perovskite light-emitting memory (LEM) device for simultaneous electronic and optical reading of the encoded information in communication and computation applications. We present a physical picture that clearly depicts the movements of each ionic species and their reduction or oxidation processes in the perovskite LEM responsible for the observed electronic and optical characteristics. The demonstrated bifunctionality of the simple metal-perovskite-metal structures and the novel device concept derived from their creative synergy opens up a completely new horizon for more advanced all-inorganic perovskite optoelectronics with novel functionalities.

Size control is critical in the synthesis of quantum-confined semiconductor nanocrystals, otherwise known as quantum dots. The achievement of size-uniformity and narrow spectral line-width in quantum dots conventionally relies on a very precise kinetic control of the reactions, where reaction time plays a significant role in defining the final crystal sizes and distribution. Here, we show that synthesis of quantum-confined perovskite nanostrips could be achieved through a thermodynamically controlled reaction, using a low-temperature and ligand-rich approach. The nanostrip growth proceeds through an initial one-dimensional (1D) nanorod stage, followed by the lateral widening of the rod to form a two-dimensional (2D) nanostrip. The spectral characteristics of the final product remain unchanged after prolonged reaction, indicating no signs of crystal ripening and confirming the thermodynamic nature of this reaction. The CsPbBr

The interactions between colloidal particles and nanoparticles determine solution stability and the structures formed when the particles are unstable to flocculation. Therefore, knowledge of the interparticle interactions is important for understanding the transport, dissolution, and fate of particles in the environment. The interactions between particles are governed by the surface properties of the particles, which are altered when species adsorb to the surface. The important interactions in the environment are almost never those between the bare particles but rather those between particles that have been modified by the adsorption of natural organic materials. Citric acid is important in this regard not only because it is present in soil but also as a model of humic and fulvic acids. Here we have studied the surface forces between the model metal oxide surface hafnia in the presence of citric acid in order to understand the stability of colloidal particles and nanoparticles. We find that citric acid stabilizes the particles over a wide range of pH at low to moderate ionic strength. At high ionic strength, colloidal particles will flocculate due to a secondary minimum, resulting in aggregates that are dense and easily redispersed. In contrast, nanoparticles stabilized by citric acid remain stable at high ionic strengths and therefore exist in solution as individual particles; this will contribute to their dispersion in the environment and the uptake of nanoparticles by mammalian cells.

Monolayer graphene exhibits impressive in-plane thermal conductivity (> 1000 W m–1 K–1). However, the out-of-plane thermal transport is limited due to the weak van der Waals interaction, indicating the possibility of constructing a vertical thermoelectric (TE) device. Here, we propose a cross-plane TE device based on the vertical heterostructures of few-layer graphene and gold nanoparticles (AuNPs) on Si substrates, where the incorporation of AuNPs further inhibits the phonon transport and enhances the electrical conductivity along vertical direction. A measurable Seebeck voltage is produced vertically between top graphene and bottom Si when the device is put on a hot surface and the figure of merit ZT is estimated as 1 at room temperature from the transient Harman method. The polarity of the output voltage is determined by the carrier polarity of the substrate. The device concept is also applicable to a flexible and transparent substrate as demonstrated.

A liquid crystal (LC) phase with P213 symmetry, the lowest so far in a cubic LC, was obtained in a system of CdS quantum dots (QDs) modified with a two-layer corona of aliphatic thiols (inner) and LC aromatic dendrons (outer). We propose that the unusual low symmetry of this cubic mesophase is a result of the multi-layered corona, which prefers to adopt an anisotropic radial profile because of the combination of long and short “bristles.” The anisotropic distribution of dendrons (long bristles) in the P213 phase is thought to facilitate π-π interaction among the aromatic moieties. The interaction gives rise to non-radiative exciton energy-transfer pathways that induce photoluminescence quenching of the CdS QDs. This is believed to be the first example of structure-dependent emission-quenching behavior.

A glycopolymer with different mannose incorporation ratios was synthesized via a reversible addition fragmentation chain transfer with acrylamide. The polymers were immobilized onto a gold substrate by the thiol terminate. The glycopolymer layer structures and the glycopolymer–protein interactions were analyzed using a surface plasmon resonance technique. The glycopolymers formed pancake-like structures under dry conditions and were swollen in water. The interaction between the glycopolymer and the protein was enhanced by the cluster effect of the mannose units.

Photocatalysts are practically used for decomposition of harmful and fouling organic compounds. Among the photocatalytic reactions, remote oxidation via airborne species is a relatively slow process, so that a sensitive technique for its detection has been awaiting. Here, we investigated an airborne remote photocatalytic reaction of a TiO2 photocatalyst modified with Pt nanoparticles as co-catalysts via the color change caused by a decomposition of a multilayered silver nanoparticle sheet. The silver nanoparticle sheet fabricated by the Langmuir-Schaefer method on a gold substrate exhibits a unique multicolor depending upon the number of layers. The color originates from multiple light trapping in the stratified sheets that has a metamaterial characteristic along with an intra- and interlayer coupling of localized surface plasmon resonance (LSPR). The stepwise decomposition of the sheets was confirmed by the colorimetric data, which exhibited not only a monotonic decrease but also a maximized absorption of light when the film thickness reached the optimal thickness for light trapping or when the oxidation of the Ag core started. Scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and surface plasmon resonance (SPR) spectroscopy data provided a complete view of the decomposition process of this inorganic-organic nanocomposite film, and simulation by the transfer-matrix method explained a simultaneous plasmonic response rationally. The influence of the humidity and gas flow rate on the airborne remote photocatalytic reaction kinetics was examined by this colorimetric detection method, and it suggests that H2O in air plays an essential role in the reaction.

Plasmonic nanopore structures have been expected to play a key role in next-generation nanopore devices because plasmonic-enhanced electric fields inside nanopores potentially enable the measurement of surface-enhanced Raman scattering (SERS) spectra of a single analyte passing through a nanopore. However, sufficient enhancement of the electric field inside a nanopore for SERS measurements has not been obtained. Here, we report finite-difference time-domain simulation studies of inverted cone-shaped plasmonic nanopore structures, which maximally show an ∼1000 times stronger SERS enhancement factor than that of a conventional cylindrical plasmonic nanopore structure. The enhancement was found to be achieved via nanofocusing and structural effects, causing a 1.3 and 4.7 times stronger plasmonic-enhanced electric field than that of a cylindrical structure, respectively. The present study suggests a high potential of inverted cone shapes as plasmonic nanopore structures for SERS measurement of an analyte passing through a nanopore.

In this study, we investigated the viscoelastic properties of metal nanoparticle monolayers at the air/water interface by dilational rheology under periodic oscillation of surface area. Au nanoparticles capped with oleylamine form a stable, dense monolayer on a Langmuir film balance. The stress response function of a nanoparticle monolayer was first analyzed using the classical Kelvin-Voigt model, yielding the spring constant and viscosity. The obtained results suggest that the monolayer of nanoparticles is predominantly elastic, forming a two-dimensional physical gel. As the global shape of the signal exhibited a clear nonlinearity, we further analyzed the data with the higher modes in the Fourier series expansion. The imaginary part of the higher mode signal was stronger than the real part, suggesting that the dissipative term mainly causes the nonlinearity. Intriguingly, the response function measured at larger strain amplitude became asymmetric, accompanied by the emergence of even modes. The significance of interactions between nanoparticles was quantitatively assessed by calculating the potential of mean force, indicating that the lateral correlation could reach up to the distance much larger than the particle diameter. The influence of surface chemical functions and core metal has also been examined by using Au nanoparticles capped with partially fluorinated alkanethiolate and Ag nanoparticles capped with myristic acid. The combination of dilational rheology and correlation analyses can help us precisely control two-dimensional colloidal assembly of metal nanoparticles with fine-adjustable localized surface plasmon resonance.

Surface Plasmon resonance (SPR) is widely utilized as a surface sensitive detection method, especially for label-free detection of biomolecules via refractive index change at metal–dielectric interface.

Colorimetric plasmon sensors for naked-eye detection of molecular recognition events have been proposed. Here, 3-layered Ag nanoparticle (NP) sheets on a Au substrate fabricated using the Langmuir-Schaefer method were utilized as the detection substrates. A drastic color change was observed following the binding of Au NPs via avidin-biotin interactions at less than 30% surface coverage. The color change was attributed not only to the localized surface plasmon resonance (LSPR) of the adsorbed Au NPs but also to the multiple light trapping effect derived from the stratified Au and Ag NPs, as predicted by a finite-difference time-domain (FDTD) simulation. This plasmonic multi-color has great potential in the development of simple and highly sensitive diagnostic systems.

In this paper, we report different coordinations of citrates on gold (AuNP) and silver (AgNP) nanoparticles, as determined using Fourier transform infrared spectroscopy (FTIR) and molecular orbital (MO) calculations. AuNPs and AgNPs are found to have completely different interactions with the carboxylate anchoring groups, as indicated by their unique asymmetric stretching vibrations in the FTIR spectra. The νas (COO−) of citrate exhibits a high-frequency shift resulting from the formation of a unidentate coordination on AuNPs, whereas this vibration exhibits a low-frequency shift as a result of ionic bond formation on AgNPs, as predicted from the MO calculations of the corresponding metal complex salts. The enhancement in the IR signals when their vibration direction was perpendicular to the nanoparticle surface revealed the influence of localized surface plasmons excited on the metal nanoparticles.

Techniques for micro/nano-scale patterning of large metal nanoparticle sheets can potentially be used to realize high-performance photoelectronic devices because the sheets provide greatly enhanced electrical fields around the nanoparticles due to localized surface plasmon resonances. However, no single metal nanoparticle sheet currently exists with sufficient durability for conventional lithographical processes. Here, we report large photo and/or e-beam lithographic patternable metal nanoparticle sheets with improved durability by incorporating molecular cross-linked structures between nanoparticles. The cross-linked structures were easily formed by a one-step chemical reaction; immersing a single nanoparticle sheet consisting of core metals, to which capping molecules ionically bond, in a dithiol ethanol solution. The ligand exchange reaction processes were discussed in detail, and we demonstrated 20 μm wide line and space patterns, and a 170 nm wide line of the silver nanoparticle sheets.

This paper proposes a simple, effective, non-scanning method for the visualization of a cell-attached nanointerface. The method uses localized surface plasmon resonance (LSPR) excited homogeneously on a two-dimensional (2D) self-assembled gold-nanoparticle sheet. The LSPR of the gold-nanoparticle sheet provides high-contrast interfacial images due to the confined light within a region a few tens of nanometers from the particles and the enhancement of fluorescence. Test experiments on rat basophilic leukemia (RBL-2H3) cells with fluorescence-labeled actin filaments revealed high axial and lateral resolution even under a regular epifluorescence microscope, which produced higher quality images than those captured under a total internal reflection fluorescence (TIRF) microscope. This non-scanning-type, high-resolution imaging method will be an effective tool for monitoring interfacial phenomena that exhibit relatively rapid reaction kinetics in various cellular and molecular dynamics.

The surface plasmon (SP) resonance was used to increase the emission efficiencies toward high efficiency light-emitting diodes (LEDs). We obtained the enhancements of the electroluminescence from the fabricated plasmonic LED device structure by employing the very thin p+-GaN layer. The further enhancements should be achievable by optimization of the metal and device structures. Next important challenge is to extend this method from the visible to the deep UV region. By using Aluminum, we obtained the enhancements of emissions at ~260 nm from AlGaN/AlN quantum wells. We succeeded to control the SP resonance by using the various metal nanostructures. These localized SP resonance spectra in the deep-UV regions presented here would be useful to enhance deep UV emissions of super wide bandgap materials such as AlGaN/AlN. We believe that our approaches based on ultra-deep UV plasmonics would bring high efficiency ultra-deep UV light sources.

Micro-photoluminescence (PL) mapping was investigated to elucidate the detailed mechanism of surface plasmon (SP)-enhanced emissions from InGaN/GaN quantum wells (QWs) with Ag or Al coating. The PL wavelengths were obviously red-shifted with Ag films, while the PL peak wavelengths were not changed with Al coating. The relationship between the PL peak intensity and the PL wavelength at each pixel showed a positive or negative correlation for the uncoated part of the InGaN/GaN QWs with blue or green emission, respectively. We found that these correlations disappeared in the Ag-coated regions. These results suggest that the energy transfer from the excitons to the SPs should be much faster than that in the exciton localization and charge screening processes of the piezoelectric field in QWs. These effects were not observed for the Al-coated regions because the mechanism of PL enhancement should be quite different as we have suggested previously.

In this short communication, we report a procedure for the fabrication of microscale pores on a rigid self-assembled Ag nanoparticle monolayer with nanothickness. Here, condensed water droplets on a hydrophobic substrate are used as a pore formation template for Langmuir-Schaefer film deposition. The optical properties of the Ag nanoparticle monolayer were influenced by the porous structure, e.g., the localized surface plasmon resonance (LSPR) peak was weakened and broadened for the porous monolayer compared with the homogeneous monolayer, even though the number of particles on the substrate should be the same between them. The pores obtained by this method were robust and could be used as a mask for metal deposition or local fluorescence imaging. This environmentally friendly technique can provide a micropatterned surface with a minimal cytotoxicity, which has high potential for LSPR mediated biosensing and bioimaging applications.

Micro-photoluminescence (PL) mapping was investigated for Al-coated InGaN/GaN quantum wells (QWs), which showed huge PL enhancement by the surface plasmon (SP) resonance. The obtained images show inhomogeneity at the micro-meter scale; in addition, the region with lower PL intensities tend to have a longer PL wavelength for bare QWs. This correlation changed with an Al coating, positive correlations were observed in an area with a relatively short peak wavelength with blue-shift. Conversely, negative correlations were observed at longer peak wavelengths. These results suggest that the quantum-confined Stark effect (QCSE) was screened by the enhanced electrical-field of the SP resonance.