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All forms of energy follow the law of conservation of energy, by which they can be neither created nor destroyed. Light-to-heat conversion as a traditional yet constantly evolving means of converting light into thermal energy has been of enduring appeal to researchers and the public. With the continuous development of advanced nanotechnologies, a variety of photothermal nanomaterials have been endowed with excellent light harvesting and photothermal conversion capabilities for exploring fascinating and prospective applications. Herein we review the latest progresses on photothermal nanomaterials, with a focus on their underlying mechanisms as powerful light-to-heat converters. We present an extensive catalogue of nanostructured photothermal materials, including metallic/semiconductor structures, carbon materials, organic polymers, and two-dimensional materials. The proper material selection and rational structural design for improving the photothermal performance are then discussed. We also provide a representative overview of the latest techniques for probing photothermally generated heat at the nanoscale. We finally review the recent significant developments of photothermal applications and give a brief outlook on the current challenges and future directions of photothermal nanomaterials.
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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.
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Heterogeneous metal nanostructures with excellent plasmonic performance and catalytic activity are urgently needed to realize efficient light-driven catalysis. Herein, we demonstrate the preparation of hollow Au nanobipyramid (NBP)@AgPd nanostructures by employing Au NBP@Ag nanorods as templates. The products could transform from Au NBP@AgPd nanoframes to nanocages, along with the redshift and broadening of the plasmon wavelength. Particularly, the plasmon intensity of these nanostructures remained considerable among the shape evolution process. Based on the selective absorption of CTAB, the Ag atoms on the side surfaces of the Au NBP@Ag nanorods were employed as the sacrificial templates to reduce Pd atoms through galvanic replacement. The reduced Pd and Ag atoms produced through the reduction reaction were preferably co-deposited on the corners and edges at the early stage and later deposited directly on the defect sites of the side facets, as more Ag atoms were released. The discontinued distribution of the Pd atoms gives an opportunity to etch away the Ag atoms in the cores, leading to the formation of hollow Au NBP@AgPd nanostructures after the etching process. It is worth noting that the deposition of the ultrathin AgPd nanoframe had little influence on the plasmonic properties of Au NBPs, as verified by electrodynamic simulations. The Au NBP@AgPd nanoframe showed great photocatalytic activity toward Suzuki coupling reactions under laser irradiation. Taken together, these results suggest that the hot electrons successfully transfer from Au NBP to the AgPd nanoframes to participate in the photocatalytic reactions. This study affords a promising route for the synthesis of anisotropic bimetallic nanostructures with excellent plasmonic performances.
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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.
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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 â¼5.2 GPa at room temperature and â¼90 MPa in the rubbery state at 150 °C, 1 order of magnitude higher than those in previous reports. Nanopillars with diameters of â¼400 nm and an aspect ratio as high as â¼10 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.
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Nanoestruturas , Materiais Inteligentes , Polímeros/química , Impressão , Nanoestruturas/química , FótonsRESUMO
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.
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Nanoestruturas , Fótons , Luz , Óptica e Fotônica , Impressão TridimensionalRESUMO
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.
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Au nanostructures are remarkably important in a wide variety of fields for decades. The fabrication of Au nanostructures typically requires time-consuming and expensive electron-beam lithography (EBL) that operates in vacuum. To address this challenge, this paper reports the development of massive dip-pen nanodisplacement lithography (DNL) as a desktop fabrication tool, which allows high-throughput and rational design of arbitrary Au nanopatterns in ambient condition. Large-area (1 cm2 ) and uniform (<10% variation) Au nanostructures as small as 70 nm are readily fabricated, with a throughput 100-fold higher than that of conventional EBL. As a proof-of-concept of the applications in the opitcal field, we fabricate discrete Au nanorod arrays that show significant plasmonic resonance in the visible range, and interconnected Au nanomeshes that are used for transparent conductive electrode of solar cells.
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The mode volume and Purcell factor are two important parameters to assess the performance of optical nanocavities. Achieving small mode volumes and high Purcell factors for nanocavity structures while simplifying their fabrication has been a major task to realize high-performance and large-scale photonic devices and systems. Different optical resonators based on nanoparticle-on-mirror (NPoM) structures are systematically analyzed, which are easy to fabricate and flexible to use. Direct comparison of these optical resonators is made through finite-difference time-domain (FDTD) simulations. The achievement of ultrasmall mode volumes below 10-7 (λ/n)3 based on the NPoM structure through FDTD simulations is demonstrated by rationally selecting the structural parameters. Such NPoM structures provide a decent Purcell factor on the order of 107 , which can effectively enhance spontaneous emission and facilitate a number of photonic applications. The simulation results are confirmed by dark field scattering and second-harmonic generation measurements. This work is scientifically important and offers practical guidelines for the design of optical resonators for state-of-the-art optical and photonic devices.
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Absorption-dominant small Au nanorods with diameters of less than 10 nm are prepared using a facile seed-mediated growth method. The diameters of the small gold nanorods range from 6 to 9 nm, and their lengths vary from 16 to 45 nm. Their aspect ratios can be tailored from 2.7 to 4.7. As a result, the longitudinal plasmon resonance wavelengths are readily tunable from â¼720 nm to â¼830 nm by changing the seed-to-Au(III) molar ratio in the growth solution. The fractions of the scattering in the total extinction of the small Au nanorods are found to be in the range of 0.005 to 0.025 with finite-difference time-domain simulations, confirming that the extinction values of these small Au nanorods are dominantly contributed to by the light absorption. Moreover, the small Au nanorod sample is coated with a dense silica layer for photothermal therapy with three cell lines. It shows improved photothermal therapy performance compared to a large Au nanorod sample for the same cellular Au contents. Our study suggests that small Au nanorods are promising light absorbers and photothermal therapy agents.
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Absorção de Radiação , Ouro/química , Nanotecnologia , Nanotubos/química , Transporte Biológico , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos da radiação , Ouro/metabolismo , Ouro/farmacologia , Humanos , Espaço Intracelular/metabolismo , Dióxido de Silício/químicaRESUMO
Noble metal nanostructures, especially gold nanocrystals, have attracted intensive interest due to their rich plasmonic properties and enormous potential technological applications. The preparation process of gold nanocrystals can strongly affect their plasmonic properties and therefore their performances in various applications. Chemically synthesized colloidal gold nanocrystals are usually employed in biomedical fields, while lithographically fabricated ones are highly preferred for constructing optical meta-structures. A detailed careful comparison of the plasmonic performances between lithographical and chemical metal nanostructures is strongly desired for using them for different applications. Herein, we experimentally measured and quantitatively compared the plasmonic properties, including longitudinal localized surface plasmon wavelengths (LLSPWs) and plasmon peak widths, scattering intensities, and local electric field enhancements, of lithographically fabricated and chemically grown gold nanorods. The lithographical nanorods exhibit much weaker scattering, largely broadened spectral widths, and considerably reduced electric field enhancements. Electrodynamic simulations suggest that the reduction in the plasmonic performance of the lithographical nanorods is caused mainly by the use of an adhesive metal layer and slightly by their polycrystalline nature. Our quantitative comparison results will be very helpful in guiding the selection of proper types of metal nanostructures for targeted technological applications.
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Colloidal noble metal nanocrystals are promising for a large number of optical and biotechnological applications. Many practical applications require the formation of large-area, high-density, and uniformly distributed metal nanocrystal arrays on various substrates, to overcome the limitations brought by the instability of colloidal metal nanocrystal solutions and the high cost of single-particle spectroscopy characterizations. A method is developed for directly depositing colloidal metal nanocrystals, including Au nanospheres, Au nanorods, Au nanobipyramids, and (Au core)/(Ag shell) nanorods, from their solutions onto different substrates. The resultant nanocrystal arrays are relatively uniform and dense, with the peak extinction value of a single layer reaching 0.3. Their areas are up to 10 cm by 10 cm and can be further increased if larger-size containers are utilized. The refractive index sensitivities are studied for Au nanorod arrays supported on glass slides, mesoporous silica and titania films, and capped with different molecules. Au nanorods deposited on mesoporous titania films are found to exhibit the highest index sensitivities, comparable to those of the same nanorod sample in solutions. It is expected that this approach will greatly facilitate plasmonic applications that require large-area arrays of noble metal nanocrystals.
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Técnicas Biossensoriais/métodos , Coloides/química , Ouro/química , Nanopartículas Metálicas/química , Refratometria , Prata/química , Nanopartículas Metálicas/ultraestrutura , Nanotubos/química , Nanotubos/ultraestrutura , Porosidade , Dióxido de Silício/química , Titânio/químicaRESUMO
Optical transparency is rare in terrestrial organisms, and often originates through loss of pigmentation and reduction in scattering. The coloured wings of some butterflies and moths have repeatedly evolved transparency, offering examples of how they function optically and biologically. Because pigments are primarily localized in the scales that cover a colourless wing membrane, transparency has often evolved through the complete loss of scales or radical modification of their shape. Whereas bristle-like scales have been well documented in glasswing butterflies, other scale modifications resulting in transparency remain understudied. The butterfly Phanus vitreus achieves transparency while retaining its scales and exhibiting blue/cyan transparent zones. Here, we investigate the mechanism of wing transparency in P. vitreus by light microscopy, focused ion beam milling, microspectrophotometry and optical modelling. We show that transparency is achieved via loss of pigments and vertical orientation in normal paddle-like scales. These alterations are combined with an anti-reflective nipple array on portions of the wing membrane being more exposed to light. The blueish coloration of the P. vitreus transparent regions is due to the properties of the wing membrane, and local scale nanostructures. We show that scale retention in the transparent patches might be explained by these perpendicular scales having hydrophobic properties.
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Borboletas , Animais , Asas de Animais , Pigmentação , Microscopia Eletrônica de Varredura , Visão OcularRESUMO
Plasmonic metal nanocrystals (e.g., Au, Ag, and Cu) hold great promise for driving photocatalytic reactions, but little is known about the plasmonic properties of Pd nanocrystals. Herein, we constructed a plasmonic Pd/Ru antenna-reactor photocatalyst through the controllable growth of a Ru nanoarray 'reactor' on a Pd nano-octahedron 'antenna' and demonstrated a plasmonic Pd-driven N2 photofixation process. The plasmonic properties of Pd nano-octahedrons were verified using finite-difference time-domain (FDTD) simulations and refractive index sensitivity tests in water-glycerol mixtures. Notably, the constructed plasmonic antenna-reactor nanostructures exhibited superior photocatalytic activities during N2 photofixation, with a maximum ammonia production rate of 117.5 ± 15.0 µmol g-1 h-1 under visible and near-infrared (NIR) light illumination. The mechanism can be attributed to the ability of the plasmonic Pd nanoantennas to harvest light to generate abundant hot electrons and the Ru nanoreactors to provide active sites for adsorption and activation of N2. This work paves the way for the development of Pd-based plasmonic photocatalysts for efficient N2 photofixation and sheds new light on the optimal design and construction of antenna-reactor nanostructures.
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The orbital angular momentum is a fundamental degree of freedom of light wavefronts, currently exploited in applications where information capacity is a key requirement, such as optical communication, super-resolution imaging and high-dimensional quantum computing. However, generating orbital angular momentum beams requires spatio-temporally coherent light sources (lasers or supercontinuum sources), because incoherent light would smear out the doughnut features of orbital angular momentum beams, forming polychromatic or obscured orbital angular momentum beams instead. Here we show generation of coloured orbital angular momentum beams using incoherent white light. Spatio-temporal coherence is achieved by miniaturizing spiral phase plates and integrating them with structural colour filters, three-dimensionally printed at the nanoscale. Our scheme can in principle generate multiple helical eigenstates and combine colour information into orbital angular momentum beams independently. These three-dimensional optical elements encoded with colour and orbital angular momentum information substantially increase the number of combinations for optical anti-counterfeiting and photonic lock-key devices in a pairwise fashion.
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Flat optics consisting of nanostructures of high-refractive index materials produce lenses with thin form factors that tend to operate only at specific wavelengths. Recent attempts to achieve achromatic lenses uncover a trade-off between the numerical aperture (NA) and bandwidth, which limits performance. Here, we propose a new approach to design high-NA, broadband, and polarization-insensitive multilayer achromatic metalenses (MAMs). We combine topology optimization and full-wave simulations to inversely design MAMs and fabricate the structures in low-refractive index materials by two-photon polymerization lithography. MAMs measuring 20 µm in diameter operating in the visible range of 400 to 800 nm with 0.5 and 0.7 NA were achieved with efficiencies of up to 42%. We demonstrate broadband imaging performance of the fabricated MAM under white light and RGB narrowband illuminations. These results highlight the potential of the 3D-printed multilayer structures for realizing broadband and multifunctional meta-devices with inverse design.
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Au-Pd hollow nanostructures have attracted a lot of attention because of their excellent ethanol electrooxidation performance. Herein, we report a facile preparation of Au nanoframe@Pd array electrocatalysts in the presence of cetylpyridinium chloride. The reduced Pd atoms were directed to mainly deposit on the surface of the Au nanoframes in the form of rods, leading to the formation of Au nanoframe@Pd arrays with a super-large specific surface area. The red shift and damping of the plasmon peak were ascribed to the deposition of the Pd arrays on the surface of the Au nanoframes and nanobipyramids, which was verified by electrodynamic simulations. Surfactants, temperature and reaction time determine the growth process and thereby the architecture of the obtained Au-Pd hollow nanostructures. Compared with the Au nanoframe@Pd nanostructures and Au nanobipyramid@Pd arrays, the Au nanoframe@Pd arrays exhibit an enhanced electrocatalytic performance towards ethanol electrooxidation due to an abundance of catalytic active sites. The Au NF@Pd arrays display 4.1 times higher specific activity and 13.7 times higher mass activity than the commercial Pd/C electrocatalyst. Moreover, the nanostructure shows improved stability towards the ethanol oxidation reaction. This study enriches the manufacturing technology to increase the active sites of noble metal nanocatalysts and promotes the development of direct ethanol fuel cells.
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Color changes can be achieved by straining photonic crystals or gratings embedded in stretchable materials. However, the multiple repeat units and the need for a volumetric assembly of nanostructures limit the density of information content. Inspired by surface reliefs on oracle bones and music records as a means of information archival, here, surface-relief elastomers are endowed with multiple sets of information that are accessible by mechanical straining along in-plane axes. Distinct from Bragg diffraction effects from periodic structures, trenches that generate color due to variations in trench depth, enabling individual trench segments to support a single color, are reported. Using 3D printed cuboids, trenches of varying geometric parameters are replicated in elastomers. These parameters determine the initial color (or lack thereof), the response to capillary forces, and the appearance when strained along or across the trenches. Strain induces modulation in trench depth or the opening and closure of a trench, resulting in surface reliefs with up to six distinct states, and an initially featureless surface that reveals two distinct images when stretched along different axes. The highly reversible structural colors are promising in optical data archival, anti-counterfeiting, and strain-sensing applications.
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It remains a challenge to directly print arbitrary three-dimensional shapes that exhibit structural colors at the micrometer scale. Woodpile photonic crystals (WPCs) fabricated via two-photon lithography (TPL) are elementary building blocks to produce 3D geometries that generate structural colors due to their ability to exhibit either omnidirectional or anisotropic photonic stop bands. However, existing approaches produce structural colors on WPCs when illuminating from the top, requiring print resolutions beyond the limit of commercial TPL, which necessitates postprocessing techniques. Here, we devised a strategy to support high-order photonic cavity modes upon side illumination on WPCs that surprisingly generate prominent reflectance peaks in the visible spectrum. Based on that, we demonstrate one-step printing of 3D photonic structural colors without requiring postprocessing or subwavelength features. Vivid colors with reflectance peaks exhibiting a full width at half-maximum of â¼25 nm, a maximum reflectance of 50%, a gamut of â¼85% of sRGB, and large viewing angles were achieved. In addition, we also demonstrated voxel-level manipulation and control of colors in arbitrary-shaped 3D objects constituted with WPCs as unit cells, which has potential for applications in dynamic color displays, colorimetric sensing, anti-counterfeiting, and light-matter interaction platforms.
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While structural colors are ubiquitous in nature, saturated reds are mysteriously absent. This long-standing problem of achieving Schrödinger's red demands sharp transitions from "stopband" to a high-reflectance "passband" with total suppression of higher-order resonances at blue/green wavelengths. Current approaches based on nanoantennas are insufficient to satisfy all conditions simultaneously. Here, we designed Si nanoantennas to support two partially overlapping quasi-bound-states-in-the-continuum modes with a gradient descent algorithm to achieve sharp spectral edges at red wavelengths. Meanwhile, high-order modes at blue/green wavelengths are suppressed via engineering the substrate-induced diffraction channels and the absorption of amorphous Si. This design produces possibly the most saturated and brightest reds with ~80% reflectance, exceeding the red vertex in sRGB and even the cadmium red pigment. Its nature of being sensitive to polarization and illumination angle could be potentially used for information encryption, and this proposed paradigm could be generalized to other Schrödinger's color pixels.