Exfoliation Technology for Scalable Ligand-Free Core-Semishell Metal Nanoparticle Films.

Core-shell metallic nanoparticles (NPs) are considered promising materials for their multifunctional properties. However, traditionally synthesized NPs have crucial issues that their ligands interfere with the direct interaction between NPs and neighboring materials, and it is very difficult to form a uniform film without the mixture of a template. In this article, we report an unprecedented exfoliation technology for fabricating a scalable ligand-free core-semishell metal NP film based on the evaporation system through a self-assembled monolayer-assisted surface energy control combined with a deep ultraviolet surface treatment around the core NPs. Owing to fabrication merits, the properties of the core-semishell NPs can be easily modulated depending on the shell material; the ligand-free core-shell NPs are directly attached to the surface of a material by Scotch tape, allowing interfacial interactions. Therefore, the proposed technique presents a new scientific method for studying interfacial interactions with heterogeneous materials and can be universally applied in optoelectronic devices, biopatches, photocatalysts, and so on.

Intense Near-Infrared Light-Emitting NaYF4:Nd,Yb-Based Nanophosphors for Luminescent Solar Concentrators.

In this study, we synthesized NaYF4-based downshifting nanophosphors (DSNPs), and fabricated DSNP-polydimethylsiloxane (PDMS) composites. Nd3+ ions were doped into the core and shell to increase absorbance at 800 nm. Yb3+ ions were co-doped into the core to achieve intense near-infrared (NIR) luminescence. To further enhance the NIR luminescence, NaYF4:Nd,Yb/NaYF4:Nd/NaYF4 core/shell/shell (C/S/S) DSNPs were synthesized. The C/S/S DSNPs showed a 3.0-fold enhanced NIR emission at 978 nm compared with core DSNPs under 800 nm NIR light. The synthesized C/S/S DSNPs showed high thermal stability and photostability against the irradiation with ultraviolet light and NIR light. Moreover, for application as luminescent solar concentrators (LSCs), C/S/S DSNPs were incorporated into the PDMS polymer, and the DSNP-PDMS composite containing 0.25 wt% of C/S/S DSNP was fabricated. The DSNP-PDMS composite showed high transparency (average transmittance = 79.4% for the visible spectral range of 380-750 nm). This result demonstrates the applicability of the DSNP-PDMS composite in transparent photovoltaic modules.

Elemental-Migration-Assisted Full-Color-Tunable Upconversion Nanoparticles for Video-Rate Three-Dimensional Volumetric Displays.

Herein, we demonstrate video-rate color three-dimensional (3D) volumetric displays using elemental-migration-assisted full-color-tunable upconversion nanoparticles (UCNPs). In the heavily doped NaErF4:Tm-based core@multishell UCNPs, erbium migration was observed. By tailoring this migration through adjustment of the intermediate shell thickness between the core and the sensitizer-doped second shell, red-green orthogonal upconversion luminescence (UCL) was achieved. Furthermore, highly efficient red-green-blue orthogonal UCL and full-color tunability were achieved in the UCNPs through a combination of elemental-migration-assisted color tuning and selective photon blocking. Finally, 3D volumetric displays were fabricated using a UCNP-polydimethylsiloxane composite. More specifically, 3D color images were created and motion pictures based on the expansion, rotation, and up/down movement of the displayed images were realized in the display matrix. Overall, our study provides new insights into upconversion color tuning and the achievement of motion pictures in the UCNP-polydimethylsiloxane composite is expected to accelerate the further development of solid-state full-color 3D volumetric displays.

Environmentally friendly, highly efficient, and large stokes shift-emitting ZnSe:Mn2+/ZnS core/shell quantum dots for luminescent solar concentrators.

In this study, heavy-metal-free orange light-emitting ZnSe:Mn2+/ZnS doped-core/shell (d-C/S) quantum dots (QDs) were synthesized using a nucleation doping strategy. To synthesize high quality d-C/S QDs with high photoluminescence (PL) quantum yield (QY), the Mn2+ concentration was optimized. The resulting ZnSe:Mn2+(5%)/ZnS d-C/S QDs showed a high PL QY of 83.3%. The optical properties of the synthesized QDs were characterized by absorption and PL spectroscopy. Their structural and compositional properties were studied by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. After doping Mn2+ into a ZnSe core, the ZnSe:Mn2+/ZnS d-C/S QDs showed a large Stokes shift of 170 nm. The ZnSe:Mn2+/ZnS d-C/S QDs were embedded in a poly(lauryl methacrylate) (PLMA) polymer matrix and the ZnSe:Mn2+/ZnS-based polymer film was fabricated. The fabricated ZnSe:Mn2+/ZnS-PLMA film was highly transparent in the visible spectral region (transmittance > 83.8% for λ ≥ 450 nm) and it exhibited bright orange light under air mass (AM) 1.5G illumination using a solar simulator. The optical path-dependent PL measurement of the ZnSe:Mn2+/ZnS-PLMA film showed no PL band shift and minimal PL decrease under variation of excitation position. These results indicate that the highly efficient and large Stokes shift-emitting ZnSe:Mn2+/ZnS QDs are promising for application to luminescent solar concentrators.

Biocompatible Yb3+/Er3+ Co-activated La2(WO4)3 Upconversion Nanophosphors for Optical Thermometry, Biofluorescent, and Anticancer Agents.

Non-cytotoxic upconversion nanocrystals are preferred candidates because they offer exceptional advantages for numerous applications, ranging from optical thermometry to bioimaging/biomedical applications. In this report, we demonstrate the luminescence characteristics and practical utility of a multifunctional upconversion nanophosphor based on Yb3+/Er3+:La2(WO4)3 (LWO) flakes. Strong upconversion green emission was observed from 6-mol % Er3+-doped LWO nanophosphor flakes excited by a 980 nm laser. We further enhanced the upconversion emission considerably by co-doping LWO nanophosphors with Yb3+/Er3+ to exploit energy migration from Yb3+ to Er3+ ions. The exceptional improvement in upconversion green and near-infrared emission was achieved by Yb3+ ion co-doping up to 6 mol %; beyond 6 mol %, emission intensities remarkably dropped due to concentration quenching. Photometric parameters were evaluated with and without Yb3+ ion-doped LWO nanophosphors, which exhibited a high green color purity of 95.6%, to elucidate their energy transfer mechanism. In addition, temperature-dependent upconversion emission trends were evaluated by analyzing the fluorescence intensity ratio, exhibiting higher temperature sensitivity than that previously reported. This suggests the applicability of our proposed nanophosphors to optical thermometry. As for bioimaging applications, the non-cytotoxicity of the optimized nanophosphor was confirmed based on distinct fluorescence images of a normal fibroblast cell line (L929). Furthermore, we demonstrated the strong cytotoxicity of nanophosphors against human colon cancer (HCT-116) cells. Based on the results, non-cytotoxic Yb3+(6 mol %)/Er3+ (6 mol %):LWO upconversion nanophosphor flakes are expected to be exceptional candidates owing to their extensive suitability to the fields of upconversion lasers, optical thermometry, and biomedical and anticancer applications. The results indicate the potential of upconversion materials in the effective execution of multiple strategic applications.

A Super-Boosted Hybrid Plasmonic Upconversion Process for Photodetection at 1550 nm Wavelength.

A super-boosted hybrid plasmonic upconversion (UC) architecture comprising a hierarchical plasmonic upconversion (HPU) film and a polymeric microlens array (MLA) film is proposed for efficient photodetection at a wavelength of 1550 nm. Plasmonic metasurfaces and Au core-satellite nanoassembly (CSNA) films can strongly induce a more effective plasmonic effect by providing numerous hot spots in an intense local electromagnetic field up to wavelengths exceeding 1550 nm. Hence, significant UC emission enhancement is realized via the amplified plasmonic coupling of an HPU film comprising an Au CSNA and UC nanoparticles. Furthermore, an MLA polymer film is synergistically coupled with the HPU film, thereby focusing the incident near-infrared light in the micrometer region, including the plasmonic nanostructure area. Consequently, the plasmonic effect super-boosted by microfocusing the incident light, significantly lowers the detectable power limit of a device, resulting in superior sensitivity and responsivity at weak excitation powers. Finally, a triple-cation perovskite-based photodetector coupled with the hybrid plasmonic UC film exhibits the excellent values of responsivity and detectivity of 9.80 A W-1 and 8.22 × 1012 Jones at a weak power density of ≈0.03 mW cm-2 , respectively, demonstrating that the device performance is enhanced by more than 104 magnitudes over a reference sample.

Orthogonal R/G/B Upconversion Luminescence-based Full-Color Tunable Upconversion Nanophosphors for Transparent Displays.

Here, excitation orthogonalized red/green/blue upconversion luminescence (UCL)-based full-color tunable rare-earth (RE) ion-doped upconversion nanophosphors (UCNPs) are reported. The LiREF4-based core/sextuple-shell (C/6S) UCNPs are synthesized, and they consist of a blue-emitting core, green-emitting inner shell, and red-emitting outer shell, with inert intermediate and outermost shells. The synthesized C/6S UCNPs emit blue, green, and red light under 980, 800, and 1532 nm, respectively. Importantly, by combining incident near-infrared (NIR) light with various wavelengths (800, 980, and 1532 nm), full-color UCL including blue, cyan, green, yellow, orange, red, purple, and white UCL is achieved from the single C/6S UCNP composition. The color gamut obtained from the C/6S UCNPs shows 101.6% of the sRGB standard color gamut. Furthermore, transparent C/6S UCNP-polydimethylsiloxane (PDMS) composite is prepared. Full-color display realized in the transparent C/6S UCNP-PDMS composite indicates the feasibility of constructing the C/6S UCNP-based three-dimensional volumetric displays with wide color gamut.

Bright Blue, Green, and Red Luminescence from Dye-Sensitized Core@Shell Upconversion Nanophosphors under 800 nm Near-Infrared Light.

In this study, Li-based blue- and green-emitting core@shell (C@S) upconversion nanophosphors (UCNPs) and NaGdF4-based red-emitting C@S UCNPs were synthesized, and IR-808 dyes were conjugated with the C@S UCNPs to enhance upconversion (UC) luminescence. The surface of the as-synthesized C@S UCNPs, which was originally capped with oleic acid, was modified with BF4- to conjugate the IR-808 dye having a carboxyl functional group to the surface of the UCNPs. After the conjugation with IR-808 dyes, absorbance of the UCNPs was significantly increased. As a result, dye-sensitized blue (B)-, green (G)-, and red (R)-emitting UCNPs exhibited 87-fold, 10.8-fold, and 110-fold enhanced UC luminescence compared with B-, G-, and R-emitting Nd3+-doped C@S UCNPs under 800 nm near-infrared (NIR) light excitation, respectively. Consequently, dye-sensitized UCNPs exhibiting strong UC luminescence under 800 nm NIR light excitation have high applicability in a variety of biological applications.

Plasmonic-tape-attached multilayered MoS2 film for near-infrared photodetection.

Molybdenum disulfide has been intensively studied as a promising material for photodetector applications because of its excellent electrical and optical properties. We report a multilayer MoS2 film attached with a plasmonic tape for near-infrared (NIR) detection. MoS2 flakes are chemically exfoliated and transferred onto a polymer substrate, and silver nanoparticles (AgNPs) dewetted thermally on a substrate are transferred onto a Scotch tape. The Scotch tape with AgNPs is attached directly and simply onto the MoS2 flakes. Consequently, the NIR photoresponse of the MoS2 device is critically enhanced. The proposed tape transfer method enables the formation of plasmonic structures on arbitrary substrates, such as a polymer substrate, without requiring a high-temperature process. The performance of AgNPs-MoS2 photodetectors is approximately four times higher than that of bare MoS2 devices.

Large-scale nanoporous metal-coated silica aerogels for high SERS effect improvement.

We investigate the optical properties and surface-enhanced Raman scattering (SERS) characteristics of metal-coated silica aerogels. Silica aerogels were fabricated by easily scalable sol-gel and supercritical drying processes. Metallic nanogaps were formed on the top surface of the nanoporous silica network by controlling the thickness of the metal layer. The optimized metallic nanogap structure enabled strong confinement of light inside the gaps, which is a suitable property for SERS effect. We experimentally evaluated the SERS enhancement factor with the use of benzenethiol as a probe molecule. The enhancement factor reached 7.9 × 107 when molecules were adsorbed on the surface of the 30 nm silver-coated aerogel. We also theoretically investigated the electric field distribution dependence on the structural geometry and substrate indices. On the basis of FDTD simulations, we concluded that the electric field was highly amplified in the vicinity of the target analyte owing to a combination of the aerogel's ultralow refractive index and the high-density metallic nanogaps. The aerogel substrate with metallic nanogaps shows great potential for use as an inexpensive, highly sensitive SERS platform to detect environmental and biological target molecules.

High quality chalcogenide-silica hybrid wedge resonator.

Chalcogenide glasses, with high nonlinearity and low loss, have captured research interest as an integrated device platform for near- and mid-infrared nonlinear optical devices. Compared to silicon-based microfabrication technologies, chalcogenide fabrication processes are less mature and a major challenge is obtaining high quality devices. In this paper, we report a hybrid resonator design leveraging a high quality silica resonator to achieve high Q factors with chalcogenide. The device is composed of a thin chalcogenide layer deposited on a silica wedge resonator. The hybrid resonators exhibit loaded Q factors up to 1.5 x 105 in the near-infrared region. We also measured the effective thermo-optic coefficient of the device to be 5.5x10-5/K, which agreed well with the bulk value. Thermal drift of the device can be significantly reduced by introducing a titanium dioxide cladding layer with a negative thermo-optic coefficient.

Scalable variable-index elasto-optic metamaterials for macroscopic optical components and devices.

Optical metamaterials with an artificial subwavelength structure offer new approaches to implement advanced optical devices. However, some of the biggest challenges associated with the development of metamaterials in the visible spectrum are the high costs and slow production speeds of the nanofabrication processes. Here, we demonstrate a macroscale (>35 mm) transformation-optics wave bender (293 mm2) and Luneburg lens (855 mm2) in the broadband white-light visible wavelength range using the concept of elasto-optic metamaterials that combines optics and solid mechanics. Our metamaterials consist of mesoscopically homogeneous chunks of bulk aerogels with superior, broadband optical transparency across the visible spectrum and an adjustable, stress-tuneable refractive index ranging from 1.43 down to nearly the free space index (∼1.074). The experimental results show that broadband light can be controlled and redirected in a volume of >105λ × 105λ × 103λ, which enables natural light to be processed directly by metamaterial-based optical devices without any additional coupling components.

Resolution enhancement using plasmonic metamask for wafer-scale photolithography in the far field.

Resolution enhancement in far-field photolithography is demonstrated using a plasmonic metamask in the proximity regime, in which Fresnel diffraction is dominant. The transverse magnetic component of the diffracted wave from the photomask, which reduces the pattern visibility and lowers the resolution, was successfully controlled by coupling with the anti-symmetric mode of the excited surface plasmon. We obtained a consistently finely-patterned photoresist surface at a distance of up to 15 µm from the mask surface for 3-µm-pitch slits because of conserved field visibility when propagating from the near-field to the proximity regime. We confirmed that sharp edge patterning is indeed possible when using a wafer-scale photomask in the proximity photolithography regime. Our plasmonic metamask method produces cost savings for ultra-large-scale high-density display fabrication by maintaining longer photomask lifetimes and by allowing sufficient tolerance for the distance between the photomask and the photoresist.

Lithography-Free Broadband Ultrathin-Film Absorbers with Gap-Plasmon Resonance for Organic Photovoltaics.

Strategies to confine electromagnetic field within ultrathin film emerge as essential technologies for applications from thin-film solar cells to imaging and sensing devices. We demonstrate a lithography-free, low-cost, large-scale method to realize broadband ultrathi-film metal-dielectric-metal (MDM) absorbers, by exploiting gap-plasmon resonances for strongly confined electromagnetic field. A two-steps method, first organizing Au nanoparticles via thermal dewetting and then transferring the nanoparticles to a spacer-reflector substrate, is used to achieve broader absorption bandwidth by manipulating geometric shapes of the top metallic layer into hemiellipsoids. A fast-deposited nominal Au film, instead of a conventional slow one, is employed in the Ostwald ripening process to attain hemiellipsoidal nanoparticles. A polymer supported transferring step allows a wider range of dewetting temperature to manipulate the nanoparticles' shape. By incorporating circularity with ImageJ software, the geometries of hemiellipsoidal nanoparticles are quantitatively characterized. Controlling the top geometry of MDM structure from hemisphere to hemiellipsoid increases the average absorption at 500-900 nm from 23.1% to 43.5% in the ultrathin film and full width at half-maximum of 132-324 nm, which is consistently explained by finite-difference time-domain simulation. The structural advantages of our scheme are easily applicable to thin-film photovoltaic devices because metal electrodes can act as metal reflectors and semiconductor layers as dielectric spacers.

Improvement of Light Extraction Efficiency in Flip-Chip Light Emitting Diodes on SiC Substrate via Transparent Haze Films with Morphology-Controlled Collapsed Alumina Nanorods.

We demonstrate GaN-based flip-chip light emitting diodes (FC-LEDs) on SiC substrate achieving high extraction efficiency by simply attaching the optically transparent haze films consisting of collapsed alumina nanorods. Through controlled etching time of alumina nanorods, we obtain four types of films that have different morphologies with different optical transmittance and haze properties. We show that the light output power of the FC-LEDs with film, which has 95.6% transmittance and 62.7% haze, increases by 20.4% in comparison to the bare LEDs. The angular radiation pattern of the LEDs also follows the Lambertian emission pattern without deteriorating the electrical properties of the device. The improvement of light extraction is mainly attributed to the reduced total internal reflection (TIR) via efficient out-coupling of guided light from SiC substrate to air by collapsed alumina nanorod structures in the film. The high transparency of film and reduced Fresnel reflection via graded refractive index transition between the film and SiC substrate also contribute to the extraction enhancement of the device. We systematically investigate the influence of haze film's geometrical or optical properties on the extraction efficiency of FC-LEDs, and this study will provide a novel approach to enhance the performance of various optoelectronic devices.

Flexible thin-film black gold membranes with ultrabroadband plasmonic nanofocusing for efficient solar vapour generation.

Solar steam generation has been achieved by surface plasmon heating with metallic nanoshells or nanoparticles, which have inherently narrow absorption bandwidth. For efficient light-to-heat conversion from a wider solar spectrum, we employ adiabatic plasmonic nanofocusing to attain both polarization-independent ultrabroadband light absorption and high plasmon dissipation loss. Here we demonstrate large area, flexible thin-film black gold membranes, which have multiscale structures of varying metallic nanoscale gaps (0-200 nm) as well as microscale funnel structures. The adiabatic nanofocusing of self-aggregated metallic nanowire bundle arrays produces average absorption of 91% at 400-2,500 nm and the microscale funnel structures lead to average reflection of 7% at 2.5-17 µm. This membrane allows heat localization within the few micrometre-thick layer and continuous water provision through micropores. We efficiently generate water vapour with solar thermal conversion efficiency up to 57% at 20 kW m(-2). This new structure has a variety of applications in solar energy harvesting, thermoplasmonics and related technologies.

Broadband light-trapping enhancement in an ultrathin film a-Si absorber using whispering gallery modes and guided wave modes with dielectric surface-textured structures.

An embedded nanosphere dielectric structure on an a-Si ultrathin film improves weighted absorption from 23.8% to 39.9%. The PMMA embedding layer offers a guided wave mode as well as mechanical robustness, in addition to the resonant whispering gallery modes coupling. Broadband light-trapping enhancements are observed by dielectric surface textured structures of hemispheres, nanocones, nanospheres, or embedded nanospheres.

Broadband electromagnetic cloaking with smart metamaterials.

The ability to render objects invisible with a cloak that fits all objects and sizes is a long-standing goal for optical devices. Invisibility devices demonstrated so far typically comprise a rigid structure wrapped around an object to which it is fitted. Here we demonstrate smart metamaterial cloaking, wherein the metamaterial device not only transforms electromagnetic fields to make an object invisible, but also acquires its properties automatically from its own elastic deformation. The demonstrated device is a ground-plane microwave cloak composed of an elastic metamaterial with a broad operational band (10-12 GHz) and nearly lossless electromagnetic properties. The metamaterial is uniform, or perfectly periodic, in its undeformed state and acquires the necessary gradient-index profile, mimicking a quasi-conformal transformation, naturally from a boundary load. This easy-to-fabricate hybrid elasto-electromagnetic metamaterial opens the door to implementations of a variety of transformation optics devices based on quasi-conformal maps.

Broadband optical antireflection enhancement by integrating antireflective nanoislands with silicon nanoconical-frustum arrays.

Based on conventional colloidal nanosphere lithography, we experimentally demonstrate novel graded-index nanostructures for broadband optical antireflection enhancement including the near-ultraviolet (NUV) region by integrating residual polystyrene antireflective (AR) nanoislands coating arrays with silicon nano-conical-frustum arrays. This is a feasible optimized integration method of two major approaches for antireflective surfaces: quarter-wavelength AR coating and biomimetic moth's eye structure.

Tunable subwavelength focusing with dispersion-engineered metamaterials in the terahertz regime.

We develop a terahertz lens with both subwavelength resolution and tunable far-field focal length by extending the surface plasmon (SP) diffraction theory into spoof SPs of slit-groove-structure terahertz metamaterials. The dispersion properties of terahertz groove structures are engineered in the curved depth profile to produce a directional beaming feature and mimic SPs at the same time. The finite-difference time-domain simulation results confirm that the far-field focal position can be tuned by controlling the curvature of the relative electric field phase distribution profile on the output surface.