Plasmonic Core-Shell-Satellites with Abundant Electromagnetic Hotspots for Highly Sensitive and Reproducible SERS Detection.

In this work, we develop a Ag@Al2O3@Ag plasmonic core-shell-satellite (PCSS) to achieve highly sensitive and reproducible surface-enhanced Raman spectroscopy (SERS) detection of probe molecules. To fabricate PCSS nanostructures, we employ a simple hierarchical dewetting process of Ag films coupled with an atomic layer deposition (ALD) method for the Al2O3 shell. Compared to bare Ag nanoparticles, several advantages of fabricating PCSS nanostructures are discovered, including high surface roughness, high density of nanogaps between Ag core and Ag satellites, and nanogaps between adjacent Ag satellites. Finite-difference time-domain (FDTD) simulations of the PCSS nanostructure confirm an enhancement in the electromagnetic field intensity (hotspots) in the nanogap between the Ag core and the satellite generated by the Al2O3 shell, due to the strong core-satellite plasmonic coupling. The as-prepared PCSS-based SERS substrate demonstrates an enhancement factor (EF) of 1.7 × 107 and relative standard deviation (RSD) of ~7%, endowing our SERS platform with highly sensitive and reproducible detection of R6G molecules. We think that this method provides a simple approach for the fabrication of PCSS by a solid-state technique and a basis for developing a highly SERS-active substrate for practical applications.

Enhanced Spatial Light Confinement of All Inorganic Perovskite Photodetectors Based on Hybrid Plasmonic Nanostructures.

3D incident light confinement by radical electromagnetic fields offers a facile and novel way to break through the performance limit of inorganic perovskite CsPbBr3 quantum dots (QDs). Herein, metallic nanoparticles decorated anodic aluminum oxide (AAO) hybrid plasmonic nanostructures with geometric control are first proposed for cyclic light utilization of perovskite photodetectors, enabled by spatially extended light confinement. The drastic multiple interference induced by plasmonic coupling within AAO matrixes are generated as a function of pore sizes, which can effectively collect the transmitted photons back to the surface. In addition, the self-assembled metallic nanoparticles simultaneously concentrate the incident and reflected light beams into the CsPbBr3 QD layers. The light confinement inherently stems from the metallic nanoparticles due to the variation of the near surface electromagnetic fields. As a result, perovskite photodetectors based on Al nanoparticles/AAO hybrid plasmonic nanostructures with a pore size of 220 nm exhibit enhanced photoresponse behavior with remarkably increased photocurrent by ≈43× and maintain low dark current under 490 nm light illumination at 1 V.

Effect of Annealing Temperature on Morphological and Optical Transition of Silver Nanoparticles on c-Plane Sapphire.

As a promising candidate for the improved performance, silver nanoparticles (Ag NPs) have been successfully adapted in various applications such as photovoltaics, light emitting diodes (LEDs), sensors and catalysis by taking the advantage of their controllable plasmonic properties. In this paper, the control on the morphologies and optical properties of Ag NPs on c-plane sapphire (0001) is demonstrated by the systematic control of annealing temperature (between 200 and 950 °C) with 20 and 6 nm thick Ag films through the solid state dewetting. With the relatively thicker film of 20 nm, various configuration and size of Ag NPs are fabricated such as irregular, round dome-shaped and tiny Ag NPs depending on the annealing temperature. In a shrill contrast, the 6 nm Ag set exhibits a sharp distinction with the formation of densely packed small NPs and ultra-highly dense tiny Ag NPs due to the higher dewetting rate. While, the surface diffusion assumes the main driving force in the evolution process of Ag NP morphologies up to 550 °C, the sublimation of Ag atoms has played a significant role on top on the surface diffusion between 600 and 950 °C. The reflectance spectra of Ag NPs exhibit the quadrupolar resonance and dipolar resonance peaks, and the evolution of peaks, shift and average reflectance were discussed based on the Ag NPs size and surface coverage. In particular, the dipolar resonance peak in the reflectance spectra red shifts from ~475 to ~570 nm due to the size increment of Ag NPs (38.31 to 74.68 nm). The wide surface coverage of Ag NPs exhibits the highest average reflectance (~27%) and the lowest Raman intensity.

Morphological and optical properties of PdxAg1-x alloy nanoparticles.

Alloy nanoparticles (NPs) can offer a wide range of opportunities for various applications due to their composition and structure dependent properties such as multifunctionality, electronic heterogeneity, site-specific response, and multiple plasmon resonance bands. In this work, the fabrication of self-assembled PdxAg1-x NPs alloy nanostructures with distinct size, density, shape, and composition is demonstrated via the solid-state dewetting of sputtered Pd/Ag thin films on c-plane sapphire. The initial stage of bilayer dewetting exhibits the nucleation of voids, followed by the expansion of voids and cluster breakdown and finally shape transformation along with the temperature control. Bilayer composition shows a substantial influence on the dewetting such that the overall dewetting is enhanced along with the increased Ag composition, i.e. Pd0.25Ag0.75 > Pd0.5Ag0.5 > Pd0.75Ag0.25. On the other hand, the size and density of NPs can be efficiently controlled by varying the initial thickness of bilayers. Reflectance peaks in UV and near-infrared (NIR) regions and a wide absorption band in the visible region arisen from the surface plasmon resonance are observed in reflectance spectra. The peak intensity depends on the composition of PdxAg1-x NPs and the NIR peaks gradually blue-shift with the size decrement.

Determination of growth regimes of Pd nanostructures on c-plane sapphire by the control of deposition amount at different annealing temperatures.

Metallic nanoparticles (NPs) with tunable physical, optical and catalytic properties have a wide range of applications including various optoelectronics, sensors and fuel cells. In this paper, we demonstrate the evolution of various physical properties, configurations, size and density of palladium (Pd) nanostructures on sapphire(Al2O3) (0001) by the systematic control of deposition amount (DA) at distinct annealing temperatures. The transformation of the deposited thin films into various Pd NPs is achieved by the dewetting of the thin film by means of surface diffusion, nucleation, Volmer-Weber growth and surface energy minimization mechanism. Depending on the evolution of size, density and configuration, five distinctive regimes of Pd nanostructures are demonstrated: (i) nucleation and evolution of small NPs between 1 and 3 nm, (ii) medium NPs with the dominating vertical growth between 5 and 20 nm, (iii) laterally expanded large NPs between 30 and 40 nm, (iv) irregular coalesced Pd NPs between 50 and 80 nm and (v) voids evolution between 100 and 200 nm. Initial film thickness and annealing temperature play major roles on the dewetting process and the resulting Pd nanostructures are notably distinguished. The fabricated Pd nanostructures influence the lattice vibration modes of sapphire(0001) such as gradual decrement in the intensity and left-shift of the peak position with increased surface coverage. In addition, the optical properties are studied by UV-VIS-NIR (300-1100 nm) reflectance spectra, which shows the reflectance, absorption and scattering over the wavelength and are closely related to the morphology evolution of Pd nanostructures.

Reconfigurable Resistive Switching in VO2/La0.7Sr0.3MnO3/Al2O3 (0001) Memristive Devices for Neuromorphic Computing.

The coexistence of nonvolatile and volatile switching modes in a single memristive device provides flexibility to emulate both neuronal and synaptic functions in the brain. Furthermore, such a device structure may eliminate the need for additional circuit elements such as transistor-based selectors, enabling low-power consumption and high-density device integration in fully memristive spiking neural networks. In this work, we report dual resistive switching (RS) modes in VO2/La0.7Sr0.3MnO3 (LSMO) bilayer memristive devices. Specifically, the nonvolatile RS is driven by the movement of oxygen vacancies (Vo) at the VO2/LSMO interface and requires a higher biasing voltage, whereas the volatile RS is controlled by the metal-insulator transition (MIT) of VO2 under a lower biasing voltage. The simple device structure is electrically driven between the two RS modes and thus can operate as a one selector-one resistor (1S1R) cell, which is a desirable feature in memristive crossbar arrays to avoid the sneak-path current issue. The RS modes are found to be stable and repeatable and can be reconfigured by exploiting the interfacial and phase transition properties, and thus, they hold great promise for applications in memristive neural networks and neuromorphic computing.

MoS2 Nanoplatelets on Hybrid Core-Shell (HyCoS) AuPd NPs for Hybrid SERS Platform for Detection of R6G.

In this work, a novel hybrid SERS platform incorporating hybrid core-shell (HyCoS) AuPd nanoparticles (NPs) and MoS2 nanoplatelets has been successfully demonstrated for strong surface-enhanced Raman spectroscopy (SERS) enhancement of Rhodamine 6G (R6G). A significantly improved SERS signal of R6G is observed on the hybrid SERS platform by adapting both electromagnetic mechanism (EM) and chemical mechanism (CM) in a single platform. The EM enhancement originates from the unique plasmonic HyCoS AuPd NP template fabricated by the modified droplet epitaxy, which exhibits strong plasmon excitation of hotspots at the nanogaps of metallic NPs and abundant generation of electric fields by localized surface plasmon resonance (LSPR). Superior LSPR results from the coupling of distinctive AuPd core-shell NP and high-density background Au NPs. The CM enhancement is associated with the charge transfer from the MoS2 nanoplatelets to the R6G. The direct contact via mixing approach with optimal mixing ratio can effectively facilitate the charges transfer to the HOMO and LUMO of R6G, leading to the orders of Raman signal amplification. The enhancement factor (EF) for the proposed hybrid platform reaches ~1010 for R6G on the hybrid SERS platform.

Hybrid UV Photodetector Design Incorporating AuPt Alloy Hybrid Nanoparticles, ZnO Quantum Dots, and Graphene Quantum Dots.

A hybrid device scheme is an attractive strategy in the construction of advanced UV photodetectors due to the flexibility in selecting the components and correspondingly improved optoelectronic properties by the cooperation of various components, which cannot be achieved by a single component device. In this work, a novel hybrid UV photodetector (PD) is demonstrated by adapting AuPt alloy hybrid nanoparticles (AHNPs), ZnO quantum dots (QDs), and graphene quantum dots (GQDs), namely, GQD/ZnO/AHNP PD. The optimized device achieves high-end figure-of-merit performance with a responsivity of 2299 mA/W, detectivity of 7.04 × 1010 jones, and external quantum efficiency of 741%. Enhanced photocurrent can be associated with the hot electron generation around the AuPt AHNPs and swift transfer to the conduction band of ZnO QDs. At the same time, the added carrier injection is achieved by a thin layer of GQDs. High density of hotspots and electromagnetic fields are generated by the strong localized surface plasmon resonance (LSPR) by the uniquely designed AuPt AHNPs with the fully alloyed AuPt NPs and adjacent small background Au NPs. The e-field distribution of various NP configurations is systematically investigated with finite-difference time-domain (FDTD) simulations.

Manipulating topological Hall-like signatures by interface engineering in epitaxial ruthenate/manganite heterostructures.

Topologically protected non-trivial spin textures (e.g. skyrmions) give rise to a novel phenomenon called the topological Hall effect (THE) and have promising implications in future energy-efficient nanoelectronic and spintronic devices. Here, we have studied the Hall effect in SrRuO3/La0.42Ca0.58MnO3 (SRO/LCMO) bilayers. Our investigation suggests that pure SRO has hard and soft magnetic characteristics but the anomalous Hall effect (AHE) in SRO is governed by the high coercivity phase. We have shown that the proximity effect of a soft magnetic LCMO on SRO plays a critical role in interfacial magnetic coupling and transport properties in SRO. Upon reducing the SRO thickness in the bilayer, the proximity effect becomes the dominant feature, enhancing the magnitude and temperature range of THE-like signatures. The THE-like features in bilayers can be explained by a diffusive Berry phase transition model in the presence of an emergent magnetic state due to interface coupling. This work provides an alternative understanding of THE-like signatures and their manipulation in SRO-based heterostructures, bilayers and superlattices.

Anisotropic Properties of Epitaxial Ferroelectric Lead-Free 0.5[Ba(Ti0.8Zr0.2)O3]-0.5(Ba0.7Ca0.3)TiO3 Films.

As the energy demand is expected to double over the next 30 years, there has been a major initiative towards advancing the technology of both energy harvesting and storage for renewable energy. In this work, we explore a subset class of dielectrics for energy storage since ferroelectrics offer a unique combination of characteristics needed for energy storage devices. We investigate ferroelectric lead-free 0.5[Ba(Ti0.8Zr0.2)O3]-0.5(Ba0.7Ca0.3)TiO3 epitaxial thin films with different crystallographic orientations grown by pulsed laser deposition. We focus our attention on the influence of the crystallographic orientation on the microstructure, ferroelectric, and dielectric properties. Our results indicate an enhancement of the polarization and strong anisotropy in the dielectric response for the (001)-oriented film. The enhanced ferroelectric, energy storage, and dielectric properties of the (001)-oriented film is explained by the coexistence of orthorhombic-tetragonal phase, where the disordered local structure is in its free energy minimum.

Hybrid Device Architecture Using Plasmonic Nanoparticles, Graphene Quantum Dots, and Titanium Dioxide for UV Photodetectors.

In this work, a nanoscale device architecture is demonstrated for a UV photodetector application on sapphire (0001), incorporating the plasmonic hybrid nanoparticles (HNPs), graphene quantum dots (GQDs), and titanium oxide (TiO2) for the first time. The hybrid GQDs/TiO2/HNPs photodetector exhibits the photocurrent of 1.58 × 10-5 A under the 1.64 mW/mm2 of 275 nm illumination at 10 V, which is around two order increase from the bare TiO2 device. The proposed architecture demonstrates a low dark current of ∼1 × 10-10 A at 10 V and thus the device demonstrates an excellent photo to dark current ratio along with the improved rise and fall time on the order of several hundred millisecond. The enhanced performance of device architecture is attributed to the efficient utilization of localized surface plasmon resonance (LSPR) induced hot carriers as well as scattered photons from the plasmonic HNPs that are fully encapsulated by the photoactive TiO2 layers. Furthermore, the addition of GQDs on the TiO2 can offer an additional photon absorption pathway. The proposed hybrid architecture of GQDs/TiO2/HNPs demonstrates the integration of the photon absorption and carrier transfer properties of plasmonic HNPs, GQDs, and TiO2 for an enhanced ultraviolet (UV) photoresponse. The photocurrent enhancement mechanisms of the hybrid device architecture are thoroughly investigated based on the finite-difference time domain (FDTD) simulation along with the energy band analysis. This work demonstrates a great potential of the hybrid device architecture for high-performance UV photodetectors.

Improved Photoresponse of UV Photodetectors by the Incorporation of Plasmonic Nanoparticles on GaN Through the Resonant Coupling of Localized Surface Plasmon Resonance.

Very small metallic nanostructures, i.e., plasmonic nanoparticles (NPs), can demonstrate the localized surface plasmon resonance (LSPR) effect, a characteristic of the strong light absorption, scattering and localized electromagnetic field via the collective oscillation of surface electrons upon on the excitation by the incident photons. The LSPR of plasmonic NPs can significantly improve the photoresponse of the photodetectors. In this work, significantly enhanced photoresponse of UV photodetectors is demonstrated by the incorporation of various plasmonic NPs in the detector architecture. Various size and elemental composition of monometallic Ag and Au NPs, as well as bimetallic alloy AgAu NPs, are fabricated on GaN (0001) by the solid-state dewetting approach. The photoresponse of various NPs are tailored based on the geometric and elemental evolution of NPs, resulting in the highly enhanced photoresponsivity of 112 A W-1, detectivity of 2.4 × 1012 Jones and external quantum efficiency of 3.6 × 104% with the high Ag percentage of AgAu alloy NPs at a low bias of 0.1 V. The AgAu alloy NP detector also demonstrates a fast photoresponse with the relatively short rise and fall time of less than 160 and 630 ms, respectively. The improved photoresponse with the AgAu alloy NPs is correlated with the simultaneous effect of strong plasmon absorption and scattering, increased injection of hot electrons into the GaN conduction band and reduced barrier height at the alloy NPs/GaN interface.

Hydrogen Peroxide Detection by Super-Porous Hybrid CuO/Pt NP Platform: Improved Sensitivity and Selectivity.

A super-porous hybrid platform can offer significantly increased number of reaction sites for the analytes and thus can offer advantages in the biosensor applications. In this work, a significantly improved sensitivity and selectivity of hydrogen peroxide (H2O2) detection is demonstrated by a super-porous hybrid CuO/Pt nanoparticle (NP) platform on Si substrate as the first demonstration. The super-porous hybrid platform is fabricated by a physiochemical approach combining the physical vapor deposition of Pt NPs and electrochemical deposition of super-porous CuO structures by adopting a dynamic hydrogen bubble technique. Under an optimized condition, the hybrid CuO/Pt biosensor demonstrates a very high sensitivity of 2205 µA/mM·cm2 and a low limit of detection (LOD) of 140 nM with a wide detection range of H2O2. This is meaningfully improved performance as compared to the previously reported CuO-based H2O2 sensors as well as to the other metal oxide-based H2O2 sensors. The hybrid CuO/Pt platform exhibits an excellent selectivity against other interfering molecules such as glucose, fructose, dopamine, sodium chloride and ascorbic acid. Due to the synergetic effect of highly porous CuO structures and underlying Pt NPs, the CuO/Pt architecture offers extremely abundant active sites for the H2O2 reduction and electron transfer pathways.

Enhanced Localized Surface Plasmon Resonance of Fully Alloyed AgAuPdPt, AgAuPt, AuPt, AgPt, and Pt Nanocrystals: Systematical Investigation on the Morphological and LSPR Properties of Mono-, Bi-, Tri-, and Quad-Metallic Nanoparticles.

Multi-metallic alloy nanoparticles (NPs) can offer tunable or modifiable localized surface plasmon resonance (LSPR) properties depending upon their configurational and elemental alterations, which can be utilized in various applications, that is, in photon energy harvesting, optical sensing, biomedical imaging, photocatalysis, and spectroscopy. In this work, a systematic investigation on the morphological and LSPR properties of multi-metallic alloy NPs incorporating Ag, Au, Pd, and Pt is presented on c-plane sapphire (0001). The resulting NPs exhibit much enhanced and tunable LSPR bands in the UV-VIS wavelength as compared to the previously reported mono-metallic NPs based on the considerable improvement in size and shape of nanostructures along with the electronic heterogeneity. Solid-state dewetting of sputtered bilayers (Ag/Pt), tri-layers (Ag/Au/Pt), and quad-layers (Ag/Au/Pd/Pt) is employed to demonstrate a wide variety of configurations, sizes, densities, and elemental compositions of Pt, AgPt, AuPt, AgAuPt, AgAuPt, and AgAuPdPt NPs by the systematic control of annealing temperature and deposition schemes. The distinct morphology and elemental composition of surface nanostructures are obtained by means of surface diffusion, intermixing, and surface/interface energy minimization along with the applied thermal energy. In addition, the sublimation of Ag atoms from the alloy nanostructure matrix significantly influences the structural, elemental, and thus optical properties of NPs by reducing the average size and Ag percentage in the alloy NPs. Based on the specific size, shape, and elemental composition of NPs, the excitation of LSPR is correlated to the dipolar, quadrupolar, multi-polar, and higher order (HO) modes along with the finite difference time domain simulation of local electric-field. The LSPR intensity is generally stronger with a higher percentage of Ag atoms in the alloy NPs and gradually diminished by the sublimation loss. However, even the mono-metallic and alloy NPs without Ag exhibited significantly improved and dynamic nature of plasmonic bands in the UV and VIS wavelength.

Strongly confined localized surface plasmon resonance (LSPR) bands of Pt, AgPt, AgAuPt nanoparticles.

Multi-metallic alloy nanoparticles (NPs) can enable the advanced applications in the energy, biology, electronics, optics and catalysis due to their multi-functionality, wide tunable range and electronic heterogeneity. In this work, various mono-, bi- and tri-metallic nanostructures composed of Ag, Au and Pt are demonstrated on transparent c-plane sapphire (0001) substrates and the corresponding morphological and optical characteristics are thoroughly investigated. The resulting Pt and AuPt NPs in this study demonstrate much enhanced LSPR responses as compared to the pure Pt NPs from the previous studies, which was contributed by the synergistic effect of Au and Pt and improved surface morphology. These results are sharply distinct in terms of surface morphology and elemental variability from those obtained by the dewetting of monometallic Ag, Au and Pt films under the similar growth conditions, which is due to the distinct dewetting kinetics of the bi-layer and tri-layer films. These NPs exhibit strongly enhanced localized surface plasmon resonance (LSPR) bands in the UV-VIS wavelengths such as dipolar, quadrupolar, multipolar and higher order resonance modes depending upon the size and elemental composition of NPs. The LSPR bands are much stronger with the high Ag content and gradually attenuated with the Ag sublimation. Furthermore, the VIS region LSPR bands are readily blue shifted along with the reduction of NP size. The Ag/Pt bi-layers and Ag/Au/Pt tri-layers are systematically dewetted and transformed into various AgPt and AgAuPt nanostructures such as networked, elongated and semispherical configurations by means of enhanced surface diffusion, intermixing and energy minimization along with the temperature control. The sublimation of Ag atoms plays a significant role in the structural and elemental composition of NPs such that more isolated and semispherical Pt and AuPt NPs are evolved from the AgPt and AgAuPt NPs respectively.

Improved Morphological and Localized Surface Plasmon Resonance (LSPR) Properties of Fully Alloyed Bimetallic AgPt and Monometallic Pt NPs Via the One-Step Solid-State Dewetting (SSD) of the Ag/Pt Bilayers.

Multi-metallic alloy nanoparticles (NPs) can offer a promising route for the integration of multi-functional elements by the adaptation of advantageous individual NP properties and thus can exhibit the multi-functional dynamic properties arisen from the electronic heterogeneity as well as configurational diversity. The integration of Pt-based metallic alloy NPs are imperative in the catalytic, sensing, and energy applications; however, it usually suffers from the difficulty in the fabrication of morphologically well-structured and elementally well-alloyed NPs, which yields poor plasmonic responses. In this work, the improved morphological and localized surface plasmon resonance (LSPR) properties of fully alloyed bimetallic AgPt and monometallic Pt NPs are demonstrated on sapphire (0001) via the one-step solid-state dewetting (SSD) of the Ag/Pt bilayers. In a sharp contrast to the previous studies of pure Pt NPs, the surface morphology of the resulting AgPt and Pt NPs in this work are significantly improved such that they possess larger size, increased interparticle gaps, and improved uniformity. The intermixing of Ag and Pt atoms, AgPt alloy formation, and concurrent sublimation of Ag atoms plays the major roles in the fabrication of bimetallic AgPt and monometallic Pt NPs along with the enhanced global diffusion and energy minimization of NP system. The fabricated AgPt and Pt NPs show much-enhanced LSPR responses as compared to the pure Pt NPs in the previous studies, and the excitation of dipolar, quadrupolar, multipolar and higher-order resonance modes is realized depending upon the size, configuration, and elemental compositions. The LSPR peaks demonstrate drastic alteration along with the evolution of AgPt and Pt NPs, i.e., the resonance peaks are shifted and enhanced by the variation of size and Ag content.

Systematic investigation on quad-metallic AgAuPdPt and tri-metallic AuPdPt NPs through the solid-state dewetting of quad-layer Ag/Au/Pd/Pt thin films on c-plane sapphire.

Multi-metallic alloy nanoparticles (MNPs) can offer valuable opportunities to meet the various demands of applications. MNPs consist of various noble metallic elements can combine diverse electronic, optical and catalytic properties in a single NP configuration, thus taking the advantage of each element. In this paper, the fabrication of tri- and quad- metallic alloy NPs with noble elements (Ag, Au, Pd and Pt) and the corresponding localized surface plasmon resonance (LPSR) properties are systematically demonstrated. Tri- and quad-metallic alloy NPs come in various size and configurations by the solid-state dewetting of Ag/Au/Pd/Pt quad-layers on sapphire (0001). Tri-metallic AuPdPt NPs are demonstrated by the systematic control of growth temperature along with the significant Ag atom sublimation. Strongly enhanced and tunable LPSR is exerted in the UV-VIS regions depending upon the size, configuration, spacing and elemental composition of the MNPs. The size dependent LSPR response of MNPs is discussed based on the absorption and scattering along with the excitation of dipolar, quadrupolar, high order and multipolar resonance modes. The MNPs exhibit much stronger and dynamic LSPR bands as compared with the monometallic Pt and Pd NPs with the comparable size and configurations.

Improved control on the morphology and LSPR properties of plasmonic Pt NPs through enhanced solid state dewetting by using a sacrificial indium layer.

Platinum (Pt) nanoparticles (NPs) are important nano-material components in various catalytic, photonic and electronic applications, yet face challenges in the fabrication of desired morphology and uniformity with the conventional solid-state dewetting approach. Specifically, the necessity of high annealing temperatures, typically above 800 °C due to the low diffusivity of Pt atoms, limits the morphological and functional tunability of Pt NPs. In this work, the fabrication of Pt NPs with an improved configuration, spacing and uniformity is demonstrated through the enhancement of solid state dewetting by using a sacrificial indium (In) layer on sapphire (0001). The well-defined Pt NPs demonstrate the dynamic localized surface plasmon (LSPR) bands in the visible range between ∼400 and 700 nm depending on the size and spacing of NPs. The LSPR peak intensity and width are also varied depending on the uniformity of Pt NPs. The overall dewetting magnitude is significantly enhanced through the inter-mixing of In and Pt atoms at the In/Pt interface that eventually results in the formation of an In-Pt alloy. During the dewetting process the In atoms desorb from the NP matrix by atomic sublimation, which gives rise to pure Pt NP fabrication. In sharp contrast to the pure Pt film dewetting, the Pt NPs in this approach demonstrate significantly improved spatial arrangement with well-defined configuration and uniformity. In addition, the ratio of In can be readily controlled along with the thickness of the Pt layer to alter the dewetting kinetics and thereby the surface morphology of Pt NPs. Specifically, large hexagonal, semi-spherical and small hexagonal Pt NPs are obtained through the dewetting of In75 nm/Pt25 nm, In20 nm/Pt20 nm and In2.5 nm/Pt7.5 nm bilayers respectively.

Improved Configuration and LSPR Response of Platinum Nanoparticles via Enhanced Solid State Dewetting of In-Pt Bilayers.

Noble metallic nanoparticles (NPs) can exhibit valuable properties such as localized surface plasmon resonance (LSPR) and large surface to volume ratio, which can find various optoelectronic and catalytic applications. In this work, the improved configuration and uniformity of platinum (Pt) NPs are demonstrated by using a sacrificial indium (In) layer via the enhanced solid state dewetting of In-Pt bilayers on sapphire (0001). In a sharp contrast to the conventional dewetting of intrinsic Pt film, the introduction of In component can significantly enhance the global dewetting process and thus can result in the fabrication of well-defined Pt NPs with the improved uniformity. This can be due to the fact that In possess high diffusivity, low surface energy and low sublimation temperature. Upon annealing, the intermixing of In and Pt atoms can occur at the interface due to the inter-diffusion, which forms In-Pt alloy system. As a result, the overall diffusivity and dewetting degree of system can be significantly improved and this can produce more isolated, uniform and semispherical Pt NPs at much lower temperatures as compared to the pure Pt film dewetting. Conveniently, the In atoms preferentially can be removed from the NP matrix by the sublimation even at relatively low temperatures. These Pt NPs exhibit dynamic LSPR band in the UV-visible wavelength based on the excitation of dipolar, quadrupolar and higher order resonance modes. Specifically, the LSPR wavelength can be tuned between ~480 and 580 nm by the fabrication of small to large size Pt NPs with the distinct configuration and interparticle spacing. Furthermore, at a constant Pt thickness, the size, spacing and density of Pt NPs can be readily tuned by the control of In layer thickness. The introduction of sacrificial In component can enable an additional flexibility for the control of surface morphologies of metallic NPs with the low diffusivity materials.