Individual Nanostructures Research Articles

Individual Nanostructures in an Epsilon-Near-Zero Material Probed with 3D-Sculpted Light

Individual Nanostructures in an Epsilon-Near-Zero Material Probed with 3D-Sculpted Light

Plasmonic coupling effect of annealed gold nanoarrays

Periodic metal nanodisc arrays have the potential to exhibit regularly spaced large local field enhancements, especially when high-Q collective plasmonic grating resonances can be obtained. Here we demonstrate how Laser interference lithography (LIL) as a maskless and high throughput technique can be used to fabricate these on square centimeter areas. The drawback of LIL is the rather fixed ratio of the size of the individual nanostructure (d) to the period of the array (p) of about d/p ∼ 0.5 for the setup used in the current article, thereby, limiting its ability to create resonances with ultra-high quality factors (Q-factors). To improve the Q-factor of the resonances of the arrays, we study the effect of thermal annealing nanodisk arrays fabricated by LIL and a lift off process. The nanodisk arrays with periods of 400 nm and 500 nm exhibited a plasmonic resonance, which was caused by the interaction of the single disk resonance and a (1 0) grating resonance. Annealing for a short duration lowered the d/p ratio from 0.5 to 0.4, and led to smoothening of the disk surfaces and growth of gold grains, resulting in lower ohmic and radiative losses and doubling of the Q-factor of the resonances. Finite element method (FEM) simulations were used to monitor this improvement in material parameters. Annealing for a longer duration disintegrated the nanodisk into several smaller particles while maintaining the overall periodicity of the array. While the plasmonic resonances of the experimentally investigated fragmented disks were basically destroyed, simulation predict that for larger periods fragmented nanodisk arrays (keeping the d/p ∼ 0.4) can exhibit extremely strong and sharp resonances whose Q-factor increases more than 58.4 times compared to the unfragmented discs. In addition, simulations show a massive enhancement of the local electric field promising immense potential for surface enhanced Raman sensing.

A Comparative Study of the individual and Mixed Oxide Nanostructures on Sunlight Driven Degradation of Methylene Blue Dye and Antimicrobial Efficacy

A Comparative Study of the individual and Mixed Oxide Nanostructures on Sunlight Driven Degradation of Methylene Blue Dye and Antimicrobial Efficacy

(Invited) Light Emission from Single Plasmonic Nanoparticles

A surface plasmon in a metal nanoparticle is the coherent oscillation of the conduction band electrons leading to both absorption and scattering as well as strong local electromagnetic fields. These fundamental properties have been exploited in many different ways, including surface enhanced spectroscopy and sensing, photothermal cancer therapy, and color display generation. The performance of plasmonic nanoparticles for a desired application not only depends on the particle size and shape, but is tunable through nanoparticle interactions on different length scales that support near- and far-field coupling. Chemical synthesis and assembly of nanostructures are able to tailor plasmonic properties that are, however, typically broadened by ensemble averaging. Single particle spectroscopy together with correlated imaging is capable of removing heterogeneity in size, shape, and assembly geometry. In this talk I will discuss our recent work on understanding the radiative properties of individual plasmonic nanostructures including its time dependence, illustrating that light emission provides a unique window into the dynamics of hot carriers.

(Invited) Photophysics and Photochemistry of Individual Plasmonic Nanostructures

A surface plasmon in a metal nanoparticle is the coherent oscillation of the conduction band electrons leading to both absorption and scattering as well as strong local electromagnetic fields. These fundamental properties have been exploited in many different ways, including surface enhanced spectroscopy and sensing, photocatalysis, photothermal cancer therapy, and color display generation. Chemical synthesis and assembly of nanostructures are able to tailor plasmonic properties that are, however, typically broadened by ensemble averaging. Single particle spectroscopy together with correlated imaging is capable of removing heterogeneity in size, shape, and assembly geometry and furthermore allows one to separate absorption and scattering contributions. In this talk I will discuss our recent work on distinguishing the different contributions that cause plasmon decay as probed by the homogeneous single-particle linewidth.[1-4] In particular, I will focus on plasmon damping due to energy and charge transfer from the metal to its environment with the goal to mechanistically understand how energy conversion from an incident photon to a plasmon and then a localized excitation can be maximized while circumventing fast metal-intrinsic internal conversion that simply leads to heat generation.

Tailoring magnon modes by extending square, kagome, and trigonal spin ice lattices vertically via interlayer coupling of trilayer nanomagnets

In this work high-frequency magnetization dynamics and statics of artificial spin-ice lattices with different geometric nanostructure array configurations are studied where the individual nanostructures are composed of ferromagnetic/non-magnetic/ferromagnetic trilayers with different non-magnetic thicknesses. These thickness variations enable additional control over the magnetic interactions within the spin-ice lattice that directly impacts the resulting magnetization dynamics and the associated magnonic modes. Specifically the geometric arrangements studied are square, kagome and trigonal spin ice configurations, where the individual lithographically patterned nanomagnets (NMs) are trilayers, made up of two magnetic layers of Ni81Fe19 of 30 nm and 70 nm thickness respectively, separated by a non-magnetic copper layer of either 2 nm or 40 nm. We show that coupling via the magnetostatic interactions between the ferromagnetic layers of the NMs within square, kagome and trigonal spin-ice lattices offers fine-control over magnetization states and magnetic resonant modes. In particular, the kagome and trigonal lattices allow tuning of an additional mode and the spacing between multiple resonance modes, increasing functionality beyond square lattices. These results demonstrate the ability to move beyond quasi-2D single magnetic layer nanomagnetics via control of the vertical interlayer interactions in spin ice arrays. This additional control enables multi-mode magnonic programmability of the resonance spectra, which has potential for magnetic metamaterials for microwave or information processing applications.

Unveiling Variations in Electronic and Atomic Structures Due to Nanoscale Wurtzite and Zinc Blende Phase Separation in GaAs Nanowires.

Phase separation is an intriguing phenomenon often found in III-V nanostructures, but its effect on the atomic and electronic structures of III-V nanomaterials is still not fully understood. Here we study the variations in atomic arrangement and band structure due to the coexistence of wurtzite (WZ) and zinc blende (ZB) phases in single GaAs nanowires by using scanning transmission electron microscopy and monochromated electron energy loss spectroscopy. The WZ lattice distances are found to be larger (by ∼1%), along both the nanowire length direction and the perpendicular direction, than the ZB lattice. The band gap of the WZ phase is ∼20 meV smaller than that of the ZB phase. A shift of ∼70 meV in the conduction band edge between the two phases is also found. The direct and local measurements in single GaAs nanowires reveal important effects of phase separation on the properties of individual III-V nanostructures.

Molecular Engineering and Morphology Control of Covalent Organic Frameworks for Enhancing Activity of Metal-Enzyme Cascade Catalysis.

Metal-enzyme integrated catalysts (MEICs) that combine metal and enzyme offer great potential for sustainable chemoenzymatic cascade catalysis. However, rational design and construction of optimal microenvironments and accessible active sites for metal and enzyme in individual nanostructures are necessary but still challenging. Herein, Pd nanoparticles (NPs) and Candida antarctica lipase B (CALB) are co-immobilized into the pores and surfaces of covalent organic frameworks (COFs) with tunable functional groups, affording Pd/COF-X/CALB (X = ONa, OH, OMe) MEICs. This strategy can regulate the microenvironment around Pd NPs and CALB, and their interactions with substrates. As a result, the activity of the COF-based MEICs in catalyzing dynamic kinetic resolution of primary amines is enhanced and followed COF-OMe > COF-OH > COF-ONa. The experimental and simulation results demonstrated that functional groups of COFs modulated the conformation of CALB, the electronic states of Pd NPs, and the affinity of the integrated catalysts to the substrate, which contributed to the improvement of the catalytic activity of MEICs. Further, the MEICs are prepared using COF with hollow structure as support material, which increased accessible active sites and mass transfer efficiency, thus improving catalytic performance. This work provides a blueprint for rational design and preparation of highly active MEICs.

Формирование наноструктур из поликристаллических пленок диоксида ванадия с помощью сканирующей зондовой литографии

Vanadium dioxide (VO2) undergoes a reversible first-order metal-insulator phase transition near room temperature, accompanied by a structural phase transition. This causes a significant change in its electrical and optical properties, making it useful for practical applications. VO2-based nanostructures exhibit notable mechanical resistance to structural transition caused by their small size and demonstrate vivid properties during the phase transition. Obtaining VO2 nanostructures is an extremely demanded objective. This research study presents the use of scanning probe lithography techniques to fabricate nanostructures on polycrystalline VO2 films. The present study focuses on the modification of VO2 films when a positive bias is applied to the sample. The effect of the value and duration of the applied voltage, relative humidity on the quality of the formed nanolithographic pattern was analyzed. The oxidation mechanism was determined. It was found that as a result of local anodic oxidation the formed oxide structures consisting of vanadium penta-oxide (V2O5) completely dissolve in water. This process leads to the separation of the continuous polycrystalline VO2 film into individual nanostructures with precise dimensions. The presented method of forming nanostructures from crystalline VO2 films is promising for nanophotonics and nanoelectronics.

Period induced reflectance tuning in transparent gold metasurfaces

Gold (Au) nanodisk arrays are modeled and fabricated for tunable near infrared reflectance with high visible transmittance. Simulations are performed in the visible and near infrared regimes between 400 and 2000 nm with varying period of nanostructures. A progressive increase in period of up to three times the diameter of the nanodisks on polymer and quartz substrates is presented. As a result, an increase in visible transmittance with a decrease in near infrared reflectance peak intensity is observed. Modeling results exhibit a high average visible transmittance of 91.5% (400–700 nm) and average reflectance of 62.9% (750–2000 nm) with diameter (D) variations from D=120 nm to D=500 nm with a period (P) equal to twice the diameter, P=2D for a polymer substrate. Electric field intensities exhibit an increase with a decrease in the period between individual nanostructures for constant unit cell dimensions. Alongside simulations, electron beam lithography and evaporation processes are utilized for the patterning and fabrication. Optical characterizations including scanning electron microscopy (SEM) and atomic force microscopy (AFM) of selected metasurfaces on quartz are performed. For a specific period and diameter, the fabricated metasurfaces exhibit near infrared reflectance having a good agreement with the simulated results about plasmonic wavelengths. Such metasurfaces offer potential to be deployed for applications that require selective reflectance intensities in the near infrared range with high visible transmittance, such as controlled environment agriculture (CEA) or multi spectral near infrared sensing. With tunability over a broadband (750–2500 nm), this simple and fabrication-friendly model may be used as a theoretical guide in quantifying specific design parameters with varying light intensity configurations.

In situ tip-guided growth of nickel nanostructures through the application of electric current

Directional growth of individual nickel nanostructures guided by a nanoindentation tip was accomplished by in situ scanning electron microscopy. Agglomerates of nickel nanoparticles supported by nickel micropillars were electrically contacted with a conductive nanoindenter. Application of an electric bias led to dielectric breakdown of native surface oxide layers covering the nanoparticles and caused the formation of conductive pathways through particle agglomerates. Joule heating and mechanical retraction of the nanoindenter enabled growth of elongated nickel nanostructures through solid-state diffusion. Finite element modeling was used to estimate the amount of Joule heating and confirmed the activation of several mass transport mechanisms. The results of this study propose the ability of tip-guided growth of individual nanostructures with complex geometries and unprecedented feature sizes.Graphical abstract

Three-dimensional surface lattice plasmon resonance effect from plasmonic inclined nanostructures via one-step stencil lithography

Abstract Plasmonic nanostructures allow the manipulation and confinement of optical fields on the sub-wavelength scale. The local field enhancement and environmentally sensitive resonance characteristics provided by these nanostructures are of high importance for biological and chemical sensing. Recently, surface lattice plasmon resonance (SLR) research has attracted much interest because of its superior quality factor (Q-factor) compared to that of localized surface plasmon resonances (LSPR), which is facilitated by resonant plasmonic mode coupling between individual nanostructures over a large area. This advantage can be further enhanced by utilizing asymmetric 3D structures rather than low-height (typically height < ∼60 nm) structure arrays, which results in stronger coupling due to an increased mode volume. However, fabricating 3D, high-aspect ratio, symmetry-breaking structures is a complex and challenging process even with state-of-the-art fabrication technology. Here, we report a plasmonic metasurface of 3D inclined structures produced via commercial TEM grid–based stencil lithography with a Q-factor of 101.6, a refractive index sensitivity of 291 nm/RIU, and a figure of merit (FOM) of 44.7 in the visible wavelength range at a refractive index of 1.5 by utilizing the 3D SLR enhancement effect, which exceeds the performance of most LSPR systems (Q < ∼10). The symmetry-breaking 3D inclined structures that are fabricated by electron beam evaporation at an angle increase the polarizability of the metasurface and the directionality of the diffractively scattered radiative field responsible for SLR mode coupling. Additionally, we explore the role of spatial coherence in facilitating the SLR effect and thus a high-Q plasmonic response from the nanostructures. Our work demonstrates the feasibility of producing 3D inclined structure arrays with pronounced SLR enhancement for high biological sensitivity by utilizing the previously unexplored inclined stencil lithography, which opens the way to fabricate highly sensitive plasmonic metasurfaces with this novel simple technique.

TEM-compatible microdevice for the complete thermoelectric characterization of epitaxially integrated Si-based nanowires.

Nanostructured materials present improved thermoelectric properties due to non-trivial effects at the nanoscale. However, the characterization of individual nanostructures, especially from the thermal point of view, is still an unsolved topic. This work presents the complete structural, morphological, and thermoelectrical evaluation of the selfsame individual bottom-up integrated nanowire employing an innovative micro-machined device compatible with transmission electron microscopy whose fabrication is also discussed. Thanks to a design that arranges the nanostructured samples completely suspended, detailed structural analysis using transmission electron microscopy is enabled. In the same device architecture, electrical collectors and isolated heaters are available at both ends of the trenches for thermoelectrical measurements of the nanowire i.e. thermal and electrical properties simultaneously. This allows the direct measurement of the nanowire power factor. Furthermore, micro-Raman thermometry measurements were performed to evaluate the thermal conductivity of the same suspended silicon nanowire. A thermal profile of the self-heating nanowire could be spatially resolved and used to compute the thermal conductivity. In this work, heavily-doped silicon nanowires were grown on this microdevices yielding a thermal conductivity of 30.8 ± 1.7 W Km-1 and a power factor of 2.8 mW mK-2 at an average nanowire temperature of 400 K. Notably, no thermal contact resistance was observed between the nanowire and the bulk, confirming the epitaxial attachment. The device presented here shows remarkable utility in the challenging thermoelectrical characterization of integrated nanostructures and in the development of multiple devices such as thermoelectric generators.

Deep Learning Design for Multiwavelength Infrared Image Sensors Based on Dielectric Freeform Metasurface

AbstractNear‐infrared multispectral imaging technology enhances target detection and recognition by distinguishing the spectral characteristics of various targets. However, traditional imaging systems heavily rely on complex optical filter designs that are often bulky and mechanically unstable, posing significant challenges for miniaturization and integration challenging. In this study, a freeform dielectric metasurface with the wavelength‐multiplexing focusing effect based on a deep learning model is designed, which can separate the mixed near‐infrared light into distinct wavelengths. To effectively modulate the complex amplitude of the transmitted light at three distinct near‐infrared wavelengths (1150, 1350, and 1550 nm), high‐index silicon freeform nanostructures supporting rich resonant modes are proposed. An inverse design model based on deep learning is utilized to generate individual freeform nanostructures pixel by pixel, satisfying the complex amplitude requirement for a multiplexed metalens design. Both the simulated and experimental results show that the wavelength‐multiplexing effect of the devices is in good agreement with the target with negligible crosstalk. Finally, a metasurface is employed to realize near‐infrared multispectral imaging, which allows for the distinct detection and decoding of images at the three target wavelengths. The proposed technology has a wide range of applications in clinical medicine, biological tissue imaging, and deep‐space exploration.

Enabling Oxidation Protection and Carrier-Type Switching for Bismuth Telluride Nanoribbons via in Situ Organic Molecule Coating.

Thermoelectric materials with high electrical conductivity and low thermal conductivity (e.g., Bi2Te3) can efficiently convert waste heat into electricity; however, in spite of favorable theoretical predictions, individual Bi2Te3 nanostructures tend to perform less efficiently than bulk Bi2Te3. We report a greater-than-order-of-magnitude enhancement in the thermoelectric properties of suspended Bi2Te3 nanoribbons, coated in situ to form a Bi2Te3/F4-TCNQ core-shell nanoribbon without oxidizing the core-shell interface. The shell serves as an oxidation barrier but also directly functions as a strong electron acceptor and p-type carrier donor, switching the majority carriers from a dominant n-type carrier concentration (∼1021 cm-3) to a dominant p-type carrier concentration (∼1020 cm-3). Compared to uncoated Bi2Te3 nanoribbons, our Bi2Te3/F4-TCNQ core-shell nanoribbon demonstrates an effective chemical potential dramatically shifted toward the valence band (by 300-640 meV), robustly increased Seebeck coefficient (∼6× at 250 K), and improved thermoelectric performance (10-20× at 250 K).

Magnetron Sputter Deposition of Nanostructured AlN Thin Films

Aluminum nitride (AlN) is a material of growing interest for power electronics, fabrication of sensors, micro-electromechanical systems, and piezoelectric generators. For the latter, the formation of nanowire arrays or nanostructured films is one of the emerging research directions. In the current work, nanostructured AlN films manufactured with normal and glancing angle magnetron sputter depositions have been investigated with scanning and transmission electron microscopy, X-ray diffraction, atomic force microscopy, and optical spectroscopy. Growth of the nanostructures was realized utilizing metal seed particles (Ag, Au, and Al), allowing the control of the nucleation and following growth of AlN. It was demonstrated how variations of seed particle material and size can be used to tune the parameters of nanostructures and morphology of the AlN films. Using normal angle deposition allowed the growth of bud-shaped structures, which consisted of pillars/lamellae with wurtzite-like crystalline structures. Deposition at a glancing angle of 85° led to a film of individual nanostructures located near each other and tilted at an angle of 33° relative to the surface normal. Such films maintained a high degree of wurtzite-like crystallinity but had a more open structure and higher roughness than the nanostructured films grown at normal incidence deposition. The developed production strategies and recipes for controlling parameters of nanostructured films pave the way for the formation of matrices to be used in piezoelectric applications.

Broadband achromatic metalens design based on predictive neural network and particle swarm optimization-genetic algorithm

The main challenge in designing broadband achromatic metalenses is to achieve the desired phase distribution at different wavelengths and positions. Finding the exact relationship between phase modulation and the size or shape of individual nanopillars is a critical but time-consuming step. This paper presents a novel joint design framework predictive neural networks and particle swarm optimization-genetic algorithms, which combines predictive neural network (PNN) and particle swarm optimization-genetic algorithm (PSO-GA). The proposed framework aims to accurately predict the phase response of nanopillars using PNN, increase the number of phase data points to establish a one-to-one correspondence between the phase and nanopillar parameters in the design of broadband achromatic metalenses, and optimize the parameters of an individual nanostructure of the metalens using PSO-GA. To validate the efficacy of the proposed method, a broadband achromatic metalens for line polarization light in the range of 260–350 nm is designed. Numerical simulations demonstrate that the designed metalens exhibits achromatic focusing. The method proposed in this paper may find wider application in the design of more complex metasurface devices.

Electrically driven light emission from single quantum dots using pulsed MOS capacitors

Robust, nanoscale light-emitting devices are attractive for emerging photonic and quantum engineering applications. However, conventional approaches suffer from fabrication challenges or lack the potential to address individual nanostructures, such as quantum dots. In this paper, we present a device that can produce electrically driven light emission from a single quantum dot using a single carbon nanotube as the charge injection contact. The device has a metal-oxide-semiconductor capacitor structure and operates based on an unconventional mechanism of electroluminescence, which relies on the use of bipolar voltage pulses. The proposed device can be fabricated in a simple manner using conventional lithographic processes, offering a scalable approach toward the development of optoelectronic devices at the single dot level.

Nanoscale Titanium Surface Engineering via Low-Temperature Hydrothermal Etching for Enhanced Antimicrobial Properties.

Bioinspired nanotopography artificially fabricated on titanium surfaces offers a solution for the rising issue of postoperative infections within orthopedics. On a small scale, hydrothermal etching has proven to deliver an effective antimicrobial nanospike surface. However, translation to an industrial setting is limited by the elevated synthesis temperature (150 °C) and associated equipment requirements. Here, for the first time, we fabricate surface nanostructures using comparatively milder synthesis temperatures (75 °C), which deliver physicochemical properties and antimicrobial capability comparable to the high-temperature surface. Using a KOH etchant, the simultaneous formation of titania and titanate crystals at both temperatures produces a one-dimensional nanostructure array. Analysis indicated that the formation mechanism comprises dissolution and reprecipitation processes, identifying the deposited titanates as hydrated layered tetra-titanates (K2Ti4O9·nH2O). A proposed nanospike formation mechanism was confirmed through the identification of a core and outer shell for individual nanostructures, primarily comprised of titanates and titania, respectively. Etching conditions dictated crystalline formation, favoring a thicker titanate core for nanorods under higher synthesis temperatures and etchant concentrations. A bactericidal investigation showed the efficacy against Gram-negative bacteria for a representative low-temperature nanosurface (34.4 ± 14.4%) was comparable to the higher temperature nanosurface (34.0 ± 17.0%), illustrating the potential of low-temperature hydrothermal synthesis. Our results provide valuable insight into the applicability of low-temperature etching protocols that are more favorable in large-scale manufacturing settings.

A two-dimensional hybrid of NiO nanowalls and reduced graphene oxide for superior field emission

The sharp and 2D nanostructure of nickel oxide (NiO) was synthesized hydrothermally on the nickel(Ni) foil and studied for field emission application. Graphene oxide (GO) and reduced graphene (rGO) is also good field emitter due to their unique electrical properties and geometry. The 2D_NiO nanostructured substrate was coated with GO solution, and it form a hetero-structure. The structure, morphology, and elemental details of as-synthesized materials, as well as hybrid samples, were determined by using X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). The field emission study of the samples was studied for NiO nanostructures samples showed field emission response. The turn-on field and maximum currents are 7.5 V/μm and 4.9 mA/cm2; for graphene oxide coated Ni foil, Ni_GO sample, 14 V/μm, and the maximum current is 2.6 mA/cm2. With a coating of GO on the NiO nanostructured surface, the field emission response enhanced abruptly. In the hybrid sample, NiO_GO, the field emission response is enhanced abruptly, the turn-on the field and the maximum current are 5.7 V/μm and 15.5 mA/ cm2, respectively. The field emission response is substantially increased than that of the individual 2D nanostructure, which has shown a low field emission. The field emission response increased further, introducing rGO on the Nanostructured substrate. In the NiO_rGO sample, the turn-on field and the maximum currents are 4.4 V/μm and 39.6 mA/ cm2, respectively.