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.

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.

Fabrication of Various Plasmonic Pt Nanostructures via Indium Assisted Solid-State Dewetting: From Small Nanoparticles to Widely Connected Networks.

In this paper, the modified solid-state dewetting (MSSD) of well-defined and various uniform Pt nanostructures is demonstrated by the auxiliary diffusion enhancement. The MSSD utilizes the introduction of metallic indium (In) layers with high diffusivity in between sapphire and platinum (Pt) layer, through which the global diffusion and dewetting of metallic atoms can be significantly enhanced. Subsequently, the In atoms can be sublimated from the NP matrix, resulting in the formation of pure Pt NPs. By the systematic control of In and Pt bi-layer thickness, various areal density, size and configuration of Pt NPs are demonstrated. The In2 nm / Pt2 nm bilayers establish very small and highly dense NPs throughout the temperature range due to the early maturation of growth. Intermediate size of NPs is demonstrated with the In45 nm / Pt15 nm bilayers with the much improved interparticle spacings by annealing between 650 and 900 oC for 450 s. Finally, the In30 nm / Pt30 nm bilayers demonstrate the widely connected network-like nanostructures. In addition, the finite difference time domain (FDTD) simulation is employed to exploit the local electric field distributions at resonance wavelengths. The dewetting characteristics of In/Pt bilayers is systematically controlled by the modifications of layer thickness and annealing temperature and is systematically described based on the diffusion of atoms, Rayleigh instability and surface energy minimization mechanism. The optical properties demonstrate dynamic and widely tunable localized surface plasmon resonance (LSPR) responses depending upon the various surface morphologies of Pt nanostructures.

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.

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.

Modification of dewetting characteristics for the improved morphology and optical properties of platinum nanostructures using a sacrificial indium layer.

Metal nanoparticles (NPs) fabricated by means of the solid state dewetting (SSD) approach are applicable in many optoelectronic, biomedical and catalytical applications. However, the fabrication of metallic NPs with the low diffusivity elements such as platinum (Pt) has been challenging for the well-defined configuration and uniformity due to the low diffusivity of Pt atoms and thus the optical properties suffer. In this paper, the evolution of well-defined configuration and improved uniformity of Pt NPs are demonstrated by the altered solid state dewetting (ASSD) approach using a sacrificial indium (In) layer. Upon annealing, the high diffusivity In atoms can lead to the formation of In-Pt alloy due to the inter-mixing at the interface and the dewetting process advances along with the enhanced diffusion of In-Pt alloy atoms. Eventually, well-defined Pt NPs are formed by means of complete desorption of In atoms by sublimation. By the control of In and Pt ratio in the bilayers with the fixed total thickness such as In4.5 nm/Pt1.5 nm, In3 nm/Pt3 nm, In1.5 nm/Pt4.5 nm, the isolated dome shaped Pt NPs of various size are demonstrated, which reflects the significant impact of In component in the dewetting process. The optical characterization of Pt NPs exhibits the formation of quadrupolar resonance and strong dipolar resonance bands in the UV and VIS regions respectively, which are tunable based on the morphology of Pt NPs. In specific, the dipolar resonance peaks demonstrate a red shifting behavior with the increment of size of Pt NPs and gradually become narrower along with the improvement of uniformity of Pt NPs.