Miniaturizing color-sensitive photodetectors via hybrid nanoantennas toward submicrometer dimensions.

Digital camera sensors use color filters on photodiodes to achieve color selectivity. As the color filters and photosensitive silicon layers are separate elements, these sensors suffer from optical cross-talk, which sets limits to the minimum pixel size. Here, we report hybrid silicon-aluminum nanostructures in the extreme limit of zero distance between color filters and sensors. This design could essentially achieve submicrometer pixel dimensions and minimize the optical cross-talk arising from tilt illuminations. The designed hybrid silicon-aluminum nanostructure has dual functionalities. Crucially, it supports a hybrid Mie-plasmon resonance of magnetic dipole to achieve color-selective light absorption, generating electron hole pairs. Simultaneously, the silicon-aluminum interface forms a Schottky barrier for charge separation and photodetection. This design potentially replaces the traditional dye-based filters for camera sensors at ultrahigh pixel densities with advanced functionalities in sensing polarization and directionality, and UV selectivity via interband plasmons of silicon.

Gold Nanostars-AIE Theranostic Nanodots with Enhanced Fluorescence and Photosensitization Towards Effective Image-Guided Photodynamic Therapy.

Dual-functional aggregation-induced photosensitizers (AIE-PSs) with singlet oxygen generation (SOG) ability and bright fluorescence in aggregated state have received much attention in image-guided photodynamic therapy (PDT). However, designing an AIE-PS with both high SOG and intense fluorescence via molecular design is still challenging. In this work, we report a new nanohybrid consisting of gold nanostar (AuNS) and AIE-PS dots with enhanced fluorescence and photosensitization for theranostic applications. The spectral overlap between the extinction of AuNS and fluorescence emission of AIE-PS dots (665 nm) is carefully selected using five different AuNSs with distinct localized surface plasmon (LSPR) peaks. Results show that all the AuNSs can enhance the 1O2 production of AIE-PS dots, among which the AuNS with LSPR peak at 585 nm exhibited the highest 1O2 enhancement factor of 15-fold with increased fluorescence brightness. To the best of our knowledge, this is the highest enhancement factor reported for the metal-enhanced singlet oxygen generation systems. The Au585@AIE-PS nanodots were applied for simultaneous fluorescence imaging and photodynamic ablation of HeLa cancer cells with strongly enhanced PDT efficiency in vitro. This study provides a better understanding of the metal-enhanced AIE-PS nanohybrid systems, opening up new avenue towards advanced image-guided PDT with greatly improved efficacy.

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.

Simulation guided design of silver nanostructures for plasmon-enhanced fluorescence, singlet oxygen generation and SERS applications.

Plasmonic nanostructures such as gold and silver could alter the intrinsic properties of fluorophores, photosensitizers or Raman reporters in their close vicinity. In this study, we have conducted systematic simulations to provide insight for the design of silver nanostructures with appropriate geometrical features for metal-enhanced fluorescence (MEF), metal-enhanced singlet oxygen generation (ME-SOG) and surface-enhanced Raman scattering (SERS) applications. The size-dependent optical properties and electric field enhancement of single and dimeric nanocubes were simulated. The extinction spectra of silver nanocubes were analysed by the multipole expansion method. Results show that a suitable size of Ag nanocubes for MEF and ME-SOG can be selected based on their maximum light scattering yield, the excitation and emission wavelengths of a particular fluorophore/photosensitizer and their maximum spectral overlap. Simulations of the 'hot-spot' or gap distance between two silver nanocubes with different configurations (i.e., face-to-face, edge-to-edge and corner-to-corner) were also performed. A direct correlation was found between the size and enhanced electric field around the Ag nanocubes simulated under 15 common Raman laser wavelengths from the UV to near-infrared region. The maximum SERS enhancement factor can be achieved by selecting the silver nanocubes with the right orientation, suitable edge length and gap distance that give the highest electric field at a specific Raman laser wavelength. It was also found that the higher order of silver nanostructures, e.g., trimer and tetramer, can lead to better enhancement effects. These simulation results can serve as generic guidelines to rationally design metal-enhancement systems including MEF, ME-SOG and SERS for different application needs without cumbersome optimization and tedious trial-and-error experimentation.

Metal-enhancement study of dual functional photosensitizers with aggregation-induced emission and singlet oxygen generation.

Photosensitizers with aggregation-induced emission (AIE-PS) are attractive for image-guided photodynamic therapy due to their dual functional role in generating singlet oxygen and producing high fluorescent signal in the aggregated state. However, their brightness and treatment efficiency maybe limited in current practice. Herein we report the first systematic investigation on the metal-enhanced fluorescence (MEF) and singlet oxygen generation (ME-SOG) ability of our newly synthesized AIE-photosensitizers. The Ag@AIE-PS of varied sizes were prepared via layer-by-layer assembly with controlled distance between silver nanoparticles (AgNPs) and AIE-PS. A maximum of 6-fold enhancement in fluorescence and 2-fold increment in SOG were observed for the 85nmAg@AIE-PS. Comprehensive characterization and simulation were conducted to unravel the plasmon-enhancement mechanisms of Ag@AIE-PS. Results show that MEF of AIE-PS is determined by the enhanced electric field around AgNPs, while ME-SOG is dictated by the scattering efficiency of the metal core, where bigger AgNPs would result in larger enhancement factor. Furthermore, the optimum distance between AgNPs and AIE-PS to achieve maximum SOG enhancement is shorter than that required for the highest MEF. The correlation of MEF and ME-SOG found in this study is useful for designing new a generation of AIE-photosensitizers with high brightness and treatment efficiency towards practical theranostic application in the future.