Enabling Active Nanotechnologies by Phase Transition: From Electronics, Photonics to Thermotics.

Phase transitions can occur in certain materials such as transition metal oxides (TMOs) and chalcogenides when there is a change in external conditions such as temperature and pressure. Along with phase transitions in these phase change materials (PCMs) come dramatic contrasts in various physical properties, which can be engineered to manipulate electrons, photons, polaritons, and phonons at the nanoscale, offering new opportunities for reconfigurable, active nanodevices. In this review, we particularly discuss phase-transition-enabled active nanotechnologies in nonvolatile electrical memory, tunable metamaterials, and metasurfaces for manipulation of both free-space photons and in-plane polaritons, and multifunctional emissivity control in the infrared (IR) spectrum. The fundamentals of PCMs are first introduced to explain the origins and principles of phase transitions. Thereafter, we discuss multiphysical nanodevices for electronic, photonic, and thermal management, attesting to the broad applications and exciting promises of PCMs. Emerging trends and valuable applications in all-optical neuromorphic devices, thermal data storage, and encryption are outlined in the end.

Engineering Dynamic Structural Color Pixels at Microscales by Inhomogeneous Strain-Induced Localized Topographic Change.

Structural colors in homogeneous elastomeric materials predominantly exhibit uniform color changes under applied strains. However, juxtaposing mechanochromic pixels that exhibit distinct responses to applied strain remains challenging, especially on the microscale where the demand for miscellaneous spectral information increases. Here, we present a method to engineer microscale switchable color pixels by creating localized inhomogeneous strain fields at the level of individual microlines. Trenches produced by transfer casting from 2.5D structures into elastomers exhibit a uniform structural color in the unstretched state due to interference and scattering effects, while they show different colors under an applied uniaxial strain. This programmable topographic change resulting in color variation arises from strain mismatch between layers and trench width. We utilized this effect to achieve the encryption of text strings with Morse code. The effective and facile design principle is promising for diverse optical devices based on dynamic structures and topographic changes.

Metasurface-Driven Optically Variable Devices.

Optically variable devices (OVDs) are in tremendous demand as optical indicators against the increasing threat of counterfeiting. Conventional OVDs are exposed to the danger of fraudulent replication with advances in printing technology and widespread copying methods of security features. Metasurfaces, two-dimensional arrays of subwavelength structures known as meta-atoms, have been nominated as a candidate for a new generation of OVDs as they exhibit exceptional behaviors that can provide a more robust solution for optical anti-counterfeiting. Unlike conventional OVDs, metasurface-driven OVDs (mOVDs) can contain multiple optical responses in a single device, making them difficult to reverse engineered. Well-known examples of mOVDs include ultrahigh-resolution structural color printing, various types of holography, and polarization encoding. In this review, we discuss the new generation of mOVDs. The fundamentals of plasmonic and dielectric metasurfaces are presented to explain how the optical responses of metasurfaces can be manipulated. Then, examples of monofunctional, tunable, and multifunctional mOVDs are discussed. We follow up with a discussion of the fabrication methods needed to realize these mOVDs, classified into prototyping and manufacturing techniques. Finally, we provide an outlook and classification of mOVDs with respect to their capacity and security level. We believe this newly proposed concept of OVDs may bring about a new era of optical anticounterfeit technology leveraging the novel concepts of nano-optics and nanotechnology.

Full Geometric Control of Hidden Color Information in Diffraction Gratings under Angled White Light Illumination.

Under white light illumination, gratings produce an angular distribution of wavelengths dependent on the diffraction order and geometric parameters. However, previous studies of gratings are limited to at least one geometric parameter (height, periodicity, orientation, angle of incidence) kept constant. Here, we vary all geometric parameters in the gratings using a versatile nanofabrication technique, two-photon polymerization lithography, to encode hidden color information through two design approaches. The first approach hides color information by decoupling the effects of grating height and periodicity under normal and oblique incidence. The second approach hides multiple sets of color information by arranging gratings in sectors around semicircular pixels. Different images are revealed with negligible crosstalk under oblique incidence and varying sample rotation angles. Our analysis shows that an angular separation of ≥10° between adjacent sectors is required to suppress crosstalk. This work has potential applications in information storage and security watermarks.

Stiff Shape Memory Polymers for High-Resolution Reconfigurable Nanophotonics.

Reconfigurable metamaterials require constituent nanostructures to demonstrate switching of shapes with external stimuli. Yet, a longstanding challenge is in overcoming stiction caused by van der Waals forces in the deformed configuration, which impedes shape recovery. Here, we introduce stiff shape memory polymers. This designer material has a storage modulus of ∼5.2 GPa at room temperature and ∼90 MPa in the rubbery state at 150 °C, 1 order of magnitude higher than those in previous reports. Nanopillars with diameters of ∼400 nm and an aspect ratio as high as ∼10 were printed by two-photon lithography. Experimentally, we observe shape recovery as collapsed and touching structures overcome stiction to stand back up. We develop a theoretical model to explain the recoverability of these sub-micrometer structures. Reconfigurable structural color prints with a resolution of 21150 dots per inch and holograms are demonstrated, indicating potential applications of the stiff shape memory polymers in high-resolution reconfigurable nanophotonics.

Hierarchical Colorful Structures by Three-Dimensional Printing of Inverse Opals.

Structural coloration is a recurring solution in biological systems to control visible light. In nature, basic structural coloration results from light interacting with a repetitive nanopattern, but more complex interactions and striking results are achieved by organisms incorporating additional hierarchical structures. Artificial reproduction of single-level structural color has been achieved using repetitive nanostructures, with flat sheets of inverse opals being very popular because of their simple and reliable fabrication process. Here, we control photonic structures at several length scales using a combination of direct laser writing and nanosphere assembly, producing freeform hierarchical constructions of inverse opals with high-intensity structural coloration. We report the first 3D prints of stacked, overhanging and slanted microstructures of inverse opals. Among other characteristics, these hierarchical photonic structures exhibit geometrically tunable colors, focal-plane-dependent patterns, and arbitrary alignment of microstructure facet with self-assembled lattice. Based on those results, novel concepts of multilevel information encoding systems are presented.

Silicon Nanoantenna Mix Arrays for a Trifecta of Quantum Emitter Enhancements.

Dielectric nanostructures have demonstrated optical antenna effects due to Mie resonances. Previous work has exhibited enhancements in absorption, emission rates and directionality with practical limitations. In this paper, we present a Si mix antenna array to achieve a trifecta enhancement of ∼1200-fold with a Purcell factor of ∼47. The antenna design incorporates ∼10 nm gaps, within which fluorescent molecules strongly absorb the pump laser energy through a resonant mode. In the emission process, the antenna array increases the radiative decay rates of the fluorescence molecules via a Purcell effect and provides directional emission through a separate mode. This work could lead to novel CMOS-compatible platforms to enhance fluorescence for biological and chemical applications.

Full Color and Grayscale Painting with 3D Printed Low-Index Nanopillars.

Sculpting nanostructures into different geometries in either one or two dimensions produces a wide range of colorful elements in microscopic prints. However, achieving different shades of gray and control of color saturation remain challenging. Here, we report a complete approach to color and grayscale generation based on the tuning of a single nanostructure geometry. Through two-photon polymerization lithography, we systematically investigated color generation from the basic single nanopillar geometry in low-refractive-index (n < 1.6) material. Grayscale and full color palettes were achieved that allow decomposition onto hue, saturation, and brightness values. This approach enabled the "painting" of arbitrary colorful and grayscale images by mapping desired prints to precisely controllable parameters during 3D printing. We further extend our understanding of the scattering properties of the low-refractive-index nanopillar to demonstrate grayscale inversion and color desaturation and steganography at the level of single nanopillars.

Multiphoton Upconversion Enhanced by Deep Subwavelength Near-Field Confinement.

Efficient generation of anti-Stokes emission within nanometric volumes enables the design of ultracompact, miniaturized photonic devices for a host of applications. Many subwavelength crystals, such as metal nanoparticles and two-dimensional layered semiconductors, have been coupled with plasmonic nanostructures for augmented anti-Stokes luminescence through multiple-harmonic generation. However, their upconversion process remains inefficient due to their intrinsic low absorption coefficients. Here, we demonstrate on-chip, site-specific integration of lanthanide-activated nanocrystals within gold nanotrenches of sub-25 nm gaps via bottom-up self-assembly. Coupling of upconversion nanoparticles to subwavelength gap-plasmon modes boosts 3.7-fold spontaneous emission rates and enhances upconversion by a factor of 100 000. Numerical investigations reveal that the gap-mode nanocavity confines incident excitation radiation into nanometric photonic hotspots with extremely high field intensity, accelerating multiphoton upconversion processes. The ability to design lateral gap-plasmon modes for enhanced frequency conversion may hold the potential to develop on-chip, background-free molecular sensors and low-threshold upconversion lasers.

Direct Color Printing with an Electron Beam.

The direct patterning of colors using the bombardment of a focused beam of electrons onto a thin-film stack consisting of poly(methyl methacrylate) coated with a thin nickel film is demonstrated. This direct electron-beam color printing approach creates variations in the height of a Fabry-Perot (FP) cavity, resulting directly in a color print without the need for prepatterned substrates, distinct from some direct laser writing methods. Notably, the resolution of the color prints is defined by the electron beam. Height measurements with ∼5 nm accuracy through color image analysis of an electron-beam-patterned FP cavity were carried out. This technique also introduces a reflectance-based measurement of the point exposure function of a focused electron beam, aiding in rapid proximity effect corrections. In addition, the grayscale lithographic nature of this process was used to produce blazed gratings and could enable the fabrication of other 2.5D nanostructures with precise height control.

In-Plane Direct-Write Assembly of Iridescent Colloidal Crystals.

Materials made by directed self-assembly of colloids can exhibit a rich spectrum of optical phenomena, including photonic bandgaps, coherent scattering, collective plasmonic resonance, and wave guiding. The assembly of colloidal particles with spatial selectivity is critical for studying these phenomena and for practical device fabrication. While there are well-established techniques for patterning colloidal crystals, these often require multiple steps including the fabrication of a physical template for masking, etching, stamping, or directing dewetting. Here, the direct-writing of colloidal suspensions is presented as a technique for fabrication of iridescent colloidal crystals in arbitrary 2D patterns. Leveraging the principles of convective assembly, the process can be optimized for high writing speeds (≈600 µm s-1 ) at mild process temperature (30 °C) while maintaining long-range (cm-scale) order in the colloidal crystals. The crystals exhibit structural color by grating diffraction, and analysis of diffraction allows particle size, relative grain size, and grain orientation to be deduced. The effect of write trajectory on particle ordering is discussed and insights for developing 3D printing techniques for colloidal crystals via layer-wise printing and sintering are provided.

Ultraviolet Interband Plasmonics With Si Nanostructures.

Although Si acts as an electrical semiconductor, it has properties of an optical dielectric. Here, we revisit the behavior of Si as a plasmonic metal. This behavior was previously shown to arise from strong interband transitions that lead to negative permittivity of Si across the ultraviolet spectral range. However, few have studied the plasmonic characteristics of Si, particularly in its nanostructures. In this paper, we report localized plasmon resonances of Si nanostructures and the observation of plasmon hybridization in the UV (∼250 nm wavelength). In addition, simulation results show that Si nanodisk dimers can achieve a local intensity enhancement greater than ∼500-fold in a 1 nm gap. Lastly, we investigate hybrid Si-Al nanostructures to achieve sharp resonances in the UV, due to the coupling between plasmon resonances supported by Si and Al nanostructures. These results will have potential applications in the UV range, such as nanostructured devices for spectral filtering, plasmon-enhanced Si photodetectors, interrogation of molecular chirality, and catalysis. It could have significant impact on UV photolithography on patterned Si structures.

Noninterleaved Metasurface for (26-1) Spin- and Wavelength-Encoded Holograms.

Nanostructured metasurfaces demonstrate extraordinary capabilities to control light at the subwavelength scale, emerging as key optical components to physical realization of multitasked devices. Progress in multitasked metasurfaces has been witnessed in making a single metasurface multitasked by mainly resorting to extra spatial freedom, for example, interleaved subarrays, different angles. However, it imposes a challenge of suppressing the cross-talk among multiwavelength without the help of extra spatial freedom. Here, we introduce an entirely novel strategy of multitasked metasurfaces with noninterleaved single-size Si nanobrick arrays and minimalist spatial freedom demonstrating massive information on 6-bit encoded color holograms. The interference between electric dipole and magnetic dipole in individual Si nanobricks with in-plane orientation enables manipulating six bases of incident photons simultaneously to reconstructed 6-bit wavelength- and spin-dependent multicolor images. Those massively reconstructed images can be distinguished by pattern recognition. It opens an alternative route for integrated optics, data encoding, security encryption, and information engineering.

Printing Beyond sRGB Color Gamut by Mimicking Silicon Nanostructures in Free-Space.

Localized optical resonances in metallic nanostructures have been increasingly used in color printing, demonstrating unprecedented resolution but limited in color gamut. Here, we introduce a new nanostructure design, which broadens the gamut while retaining print resolution. Instead of metals, silicon nanostructures that exhibit localized magnetic and electric dipole resonances were fabricated on a silicon substrate coated with a Si3N4 index matching layer. Index matching allows a suppression of substrate effects, thus enabling Kerker's conditions to be met, that is, sharpened transitions in the reflectance spectra leading to saturated colors. This nanostructure design achieves a color gamut superior to sRGB, and is compatible with CMOS processes. The presented design could enable compact high-resolution color displays and filters, and the use of a Si3N4 antireflection coating can be readily extended to designs with nanostructures fabricated using other high-index materials.

On the correlation of absorption cross-section with plasmonic color generation.

Through numerical simulations, we investigate the correlation between the absorption cross-section and the color saturation of plasmonic nanostructures of varying density. Understanding this correlation, enables the prediction of an optimal nanostructure separation, or combinations of different nanostructure sizes for plasmonic color printing applications. Here, we use metal-insulator-metal (MIM) aluminum nanostructures that support gap-plasmons. Large absorption cross-sections were observed that exceed twelve times the physical cross-section of the nanostructure disks. We derive a set of equations to determine the optimal separation for a periodic array using the absorption cross-section of an individual structure to realize saturated colors. Using the optimum pitch and enabled by the large absorption cross-sections of our structures, we employ color mixing strategies to realize a wider color gamut. The simulated color gamut exceeds the sRGB gamut for some colors, and includes dark tones. Color mixing using structures with large absorption cross-sections is a practical approach to generate a broad range of colors, in comparison to fabricating structures with continuously varying sizes.

Directed self-assembly of sub-10 nm particle clusters using topographical templates.

Directed self-assembly of nanoparticles (DSA-n) is an approach that creates suitable conditions to capture nanoparticles randomly dispersed in a liquid and position them into predefined locations on a solid template. Although DSA-n is emerging as a potential bottom-up patterning technique to build nanostructures using nanoparticles of various sizes, geometries and material compositions, there are still several outstanding challenges. In this paper, we focus on the DSA-n of sub-10 nm particles using topographical templates to guide them into 1D and 2D ordered arrays. The process mechanism leading DSA-n at sub-10 nm size scale has been reviewed and experimental evidence of the impact of the template on the positioning both individual and clusters of particles with low level of structure defects have also been demonstrated. Furthermore, by controlling the drying direction of the liquid within polygonal traps, we are also able to tune the spacing between the trapped nanoparticle clusters. This self-structuring phenomenon is of crucial importance for various applications such as plasmonics and charge transport within quantum circuits, whereby the coupling effects are highly dependent on the size of the nanoparticles and their separation.

Large Area Directed Self-Assembly of Sub-10 nm Particles with Single Particle Positioning Resolution.

Directed self-assembly of nanoparticles (DSA-n) holds great potential for device miniaturization in providing patterning resolution and throughput that exceed existing lithographic capabilities. Although nanoparticles excel at assembling into regular close-packed arrays, actual devices on the other hand are often laid out in sparse and complex configurations. Hence, the deterministic positioning of single or few particles at specific positions with low defect density is imperative. Here, we report an approach of DSA-n that satisfies these requirements with less than 1% defect density over micrometer-scale areas and at technologically relevant sub-10 nm dimensions. This technique involves a simple and robust process where a solvent film containing sub-10 nm gold nanoparticles climbs against gravity to coat a prepatterned template. Particles are placed individually into nanoscale cavities, or between nanoposts arranged in varying degrees of geometric complexity. Brownian dynamics simulations suggest a mechanism in which the particles are pushed into the template by a nanomeniscus at the drying front. This process enables particle-based self-assembly to access the sub-10 nm dimension, and for device fabrication to benefit from the wealth of chemically synthesized nanoparticles with unique material properties.

Second-Harmonic Generation from Sub-5 nm Gaps by Directed Self-Assembly of Nanoparticles onto Template-Stripped Gold Substrates.

Strong field enhancement and confinement in plasmonic nanostructures provide suitable conditions for nonlinear optics in ultracompact dimensions. Despite these enhancements, second-harmonic generation (SHG) is still inefficient due to the centrosymmetric crystal structure of the bulk metals used, e.g., Au and Ag. Taking advantage of symmetry breaking at the metal surface, one could greatly enhance SHG by engineering these metal surfaces in regions where the strong electric fields are localized. Here, we combine top-down lithography and bottom-up self-assembly to lodge single rows of 8 nm diameter Au nanoparticles into trenches in a Au film. The resultant "double gap" structures increase the surface-to-volume ratio of Au colocated with the strong fields in ∼2 nm gaps to fully exploit the surface SHG of Au. Compared to a densely packed arrangement of AuNPs on a smooth Au film, the double gaps enhance SHG emission by 4200-fold to achieve an effective second-order susceptibility χ((2)) of 6.1 pm/V, making it comparable with typical nonlinear crystals. This patterning approach also allows for the scalable fabrication of smooth gold surfaces with sub-5 nm gaps and presents opportunities for optical frequency up-conversion in applications that require extreme miniaturization.

All-metal nanostructured substrates as subtractive color reflectors with near-perfect absorptance.

All-metal structures consisting of nanoprotrusions on a bulk silver layer are theoretically investigated and shown to have narrow near-perfect absorption peaks (>95%). Within the constraints of constant nanostructure height (50 nm) and pitch (250 nm), these peaks are tunable across the visible spectrum by adjusting the width and shape of the protrusion. The peaks are caused by localized surface plasmon resonances leading to dissipation on the surface of the protrusions. As the peaks occur in the visible range, they produce subtractive colors with high saturation, in accordance with Schrödinger's rule for maximum pigment purity.

Plasmon excitation on flat graphene by s-polarized beams using four-wave mixing.

Graphene plasmons have received significant attention recently due to its attractive properties such as high spatial confinement and tunability. However, exciting plasmons on graphene effectively still remains a challenge owing to the large wave-vector mismatch between the optical beam in air and graphene plasmon. In this paper, we present a novel scheme capable of exciting graphene surface plasmons (GSPs) on a flat suspended graphene by using only s-polarized optical beams through four-wave mixing (FWM) process, where the GSPs fields were derived analytically based on the Green's function analysis, under the basis of momentum conservation. By incorporating the merits of nonlinear optics, the presented scheme avoids any patterning of either graphene or substrate. We believe that the proposed scheme potentially paves the way towards an efficient pure optical excitation, switching and modulation of GSPs for realizing graphene-based nano-photonic and optoelectronic integrated circuits.