Plasmonic Color Printing via Bottom-Up Laser-Induced Photomodification Process.

Plasmonic color printing has received significant attention owing to its advantages such as nonfading and nontoxic color expression, without necessitating the use of chemical dyes. Recently, color generation from laser-induced plasmonic nanostructures has been extensively explored because of its simplicity, cost-effectiveness, and large-scale processability. However, these methods usually utilize a top-down method that causes unexpected background colors. Here, we proposed a novel method of plasmonic color printing via a bottom-up type laser-induced photomodification process. In the proposed method, selective silver nanoparticles (Ag NPs) structure could be fabricated on a transparent substrate through a unique organometallic solution-based laser patterning process. A set of color palettes was formed on the basis of different processing parameters such as laser fluence, scanning speed, and baking time. This color change was verified by finite-difference time-domain (FDTD) simulations via monitoring the spectral peak shift of the localized surface plasmon resonance (LSPR) at Ag NPs. It was also confirmed that the colors can be fabricated at a relatively high scanning speed (≥10 mm/s) on a large substrate (>300 mm2). Since semitransparent color images can be patterned on various transparent substrates, this process will broaden the application range of laser-induced plasmonic color generation.

Long-distance transmission of broadband near-infrared light guided by a semi-disordered 2D array of metal nanoparticles.

Near-infrared (NIR) waveguides are a key component of planar photonic devices such as optical communication couplers, image sensors, and spectroscopes for chemical or biological molecules. Conventional NIR waveguides used for signal transmission include silicon-on-insulator (SOI) waveguides and channel/ridge-type metal micro-strips. However, these waveguides usually have limitations of either signal delay or signal loss in optically integrated devices. In this study, a novel NIR waveguide composed of a semi-disordered array of metal nanoparticles (sDAMNPs) on Si substrate was proposed, fabricated, and tested. The disordered metallic nanoparticles array is geometrically localized in the form of 1D metal strips, thus replacing sDAMNPs with less lossy micro strip channel waveguides. From the measurements supported by various computational models, the fabricated waveguides operate effectively in the broadband NIR region (1100 to 1700 nm). The waveguide does not support signal transmission in the ultra violet-visible spectrum due to strong signal absorption, scattering, and localization effects inside the metal nanoparticles. Instead, it is capable of transmitting NIR over a distance longer than 100 µm (signal loss ∼3.85 dB per 100 µm for NIR from 1200 to 1600 nm), which is also sufficiently longer than the conventional surface plasmon polariton propagation distance at the metal-Si interface. Compared to a waveguide-free reference, the waveguide exhibited greatly improved signal transmission efficiency up to a factor of 7.42 × 104 at 1367 nm. It also exhibits a high deflection angle sensitivity of 1.89 dB per 0.01 rad, thus efficiently and straightly guiding the broadband NIR signal over a long distance.

A Plasmonic Platform with Disordered Array of Metal Nanoparticles for Three-Order Enhanced Upconversion Luminescence and Highly Sensitive Near-Infrared Photodetector.

Three-order enhanced upconversion luminescence from upconversion nanoparticles is suggested by way of a promising platform utilizing a disordered array of plasmonic metal nanoparticles. Its application toward highly sensitive NIR photodetectors is discussed.

Upconversion luminescence enhancement in plasmonic architecture with random assembly of metal nanodomes.

We report an experimental study on the highly enhanced upconversion luminescence (UCL) of ß-NaYF4:Yb(3+)/Er(3+) nanocrystals (NCs) in a plasmonic architecture. For the architecture, we designed a thin film device composed of a thin layer of NCs capped with an upper layer of a plasmonic nanodome array (pNDA) and lower substrate of a back reflector (BR). Compared to the UCL intensity observed in a glass reference substrate, the designed plasmonic architecture exhibits distinctively strong luminescence enhanced by up to 800-fold. The intensity considerably exceeds the previously reported luminescence intensity regardless of the excitation power. We elucidated a mechanism explaining the large UCL enhancement, which quantitatively analyzes the combination of plasmonic effects as well as multiple large scattering. More importantly, we provided a detailed analysis of the Ag NDA-derived and BR-assisted plasmonic effects that contribute to an increase in the radiative decay rate and an enhancement of the absorption of incident light. The present study is expected to be beneficial for designing a thin film-based plasmonic structure with a randomized metal nanostructure for high-efficiency photovoltaic devices and infrared detectors.

A luminescent down-shifting and moth-eyed anti-reflective film for highly efficient photovoltaic devices.

Adhesive polydimethylsiloxane (PDMS) films were developed to increase the performance of photovoltaic devices. The films combined two separate features of moth-eye patterns to reduce the reflection of incident light at the film surface and luminescent down-shifting (LDS) CdZnS/ZnS-core/shell quantum dots (QDs) to convert ultraviolet (UV) radiation into visible light at 445 nm. The films were both flexible and self-adhesive, easily attachable to any surface of a solar cell module. By simply attaching the developed films on high-efficiency GaAs solar cells, the short circuit current density and power conversion efficiency of the solar cells increased to 33.8 mA cm(-2) and 28.7%, by 1.1 mA cm(-2) and 0.9 percentage points in absolute values, respectively. We showed that the enhancement of the GaAs solar cells was attributed to both the anti-reflection (AR) properties of the moth-eye patterns and the LDS of QDs using a scattering matrix method and external quantum efficiency measurements. The developed films are versatile in application for solar cells, and expected to aid in overcoming limits of material absorption and device structures.

Enhanced triplet-triplet annihilation in bicomponent organic systems by using a gap plasmon resonator.

The triplet-triplet annihilation (TTA) efficiency in bicomponent organic systems is investigated by employing a gap plasmon resonator. In our structure, strong absorption peaks arising from coupling between localized surface plasmons and surface plasmon polaritons closely overlap the Q band of porphyrin, leading to higher triplet concentrations within the film. We find that at ultralow excitation intensities on the order of watts per square centimeter (W cm(-2)), TTA becomes predominant for the organic system on a gap plasmon resonator. A strong surface-enhanced Raman scattering intensity is observed in this substrate, verifying the near-field enhancement.

Structural Origin of the Band Gap Anomaly of Quaternary Alloy Cd(x)Zn(1-x)S(y)Se(1-y) Nanowires, Nanobelts, and Nanosheets in the Visible Spectrum.

Single-crystalline alloy II-VI semiconductor nanostructures have been used as functional materials to propel photonic and optoelectronic device performance in a broad range of the visible spectrum. Their functionality depends on the stable modulation of the direct band gap (Eg), which can be finely tuned by controlling the properties of alloy composition, crystallinity, and morphology. We report on the structural correlation of the optical band gap anomaly of quaternary alloy CdxZn1-xSySe1-y single-crystalline nanostructures that exhibit different morphologies, such as nanowires (NWs), nanobelts (NBs), and nanosheets (NSs), and cover a wide range of the visible spectrum (Eg = 1.96-2.88 eV). Using pulsed laser deposition, the nanostructures evolve from NWs via NBs to NSs with decreasing growth temperature. The effects of the growth temperature are also reflected in the systematic variation of the composition. The alloy nanostructures firmly maintain single crystallinity of the hexagonal wurtzite and the nanoscale morphology, with no distortion of lattice parameters, satisfying the virtual crystal model. For the optical properties, however, we observed distinct structure-dependent band gap anomalies: the disappearance of bowing for NWs and maximum and slightly reduced bowing for NBs and NSs, respectively. We tried to uncover the underlying mechanism that bridges the structural properties and the optical anomaly using an empirical pseudopotential model calculation of electronic band structures. From the calculations, we found that the optical bowings in NBs and NSs were due to residual strain, by which they are also distinguishable from each other: large for NBs and small for NSs. To explain the origin of the residual strain, we suggest a semiempirical model that considers intrinsic atomic disorder, resulting from the bond length mismatch, combined with the strain relaxation factor as a function of the width-to-thickness ratio of the NBs or NSs. The model agreed well with the observed optical bowing of the alloy nanostructures in which a mechanism for the maximum bowing for NBs is explained. The present systematic study on the structural-optical properties correlation opens a new perspective to understand the morphology- and composition-dependent unique optical properties of II-VI alloy nanostructures as well as a comprehensive strategy to design a facile band gap modulation method of preparing photoconverting and photodetecting materials.

Hotspot-engineered 3D multipetal flower assemblies for surface-enhanced Raman spectroscopy.

Novel 3D metallic structures composed of multipetal flowers consisting of nanoparticles are presented. The control of surface plasmon hotspots is demonstrated in terms of location and intensity as a function of petal number for uniform and reproducible surfaceenhanced Raman spectroscopy (SERS) with high field enhancement.

Large-area assembly of three-dimensional nanoparticle structures via ion assisted aerosol lithography with a multi-pin spark discharge generator.

We present an approach utilizing ion assisted aerosol lithography (IAAL) with a newly designed multi-pin spark discharge generator (SDG) for fabricating large-area three-dimensional (3D) nanoparticle-structure (NPS) arrays. The design of the multi-pin SDG allows us to uniformly construct 3D NPSs on a large area of 50 mm × 50 mm in a parallel fashion at atmospheric pressure. The ion-induced focusing capability of IAAL significantly reduces the feature size of 3D NPSs compared to that of the original pre-patterns formed on a substrate. The spatial uniformity of 3D NPSs is above 95% using the present multi-pin SDG, which is far superior to that of the previous single-pin SDG with less than 32% uniformity. The effect of size distributions of nanoparticles generated via the multi-pin SDG on the 3D NPSs also has been studied. In addition, we measured spectral reflectance for the present 3D NPSs coated with Ag, demonstrating enhanced diffuse reflectance.

Plasmonic organic solar cells employing nanobump assembly via aerosol-derived nanoparticles.

We report the effect of a nanobump assembly (NBA) constructed with molybdenum oxide (MoO3) covering Ag nanoparticles (NPs) under the active layer on the efficiency of plasmonic polymer solar cells. Here, the NPs with precisely controlled concentration and size have been generated by an atmospheric evaporation/condensation method and a differential mobility classification and then deposited on an indium tin oxide electrode via room temperature aerosol method. NBA structure is made by enclosing NPs with MoO3 layer via vacuum thermal evaporation to isolate the undulated active layer formed onto the underlying protruded NBA. Simulated scattering cross sections of the NBA structure reveal higher intensities with a strong forward scattering effect than those from the flat buffer cases. Experimental results of the device containing the NBA show 24% enhancement in short-circuit current density and 18% in power conversion efficiency compared to the device with the flat MoO3 without the NPs. The observed improvements are attributed to the enhanced light scattering and multireflection effects arising from the NBA structure combined with the undulated active layer in the visible and near-infrared regions. Moreover, we demonstrate that the NBA adopted devices show better performance with longer exciton lifetime and higher light absorption in comparison with the devices with Ag NPs incorporated flat poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). Thus, the suggested approach provides a reliable and efficient light harvesting in a broad range of wavelength, which consequently enhances the performance of various organic solar cells.