Boosted Second Harmonic Generation and Cascaded Sum Frequency Generation from a Surface Crystallized Glass Ceramic Microcavity.

The development of novel materials and structures for efficient second-order nonlinear micro/nano devices remains a significant challenge. In this study, the remarkable enhancement of second-harmonic generation (SHG) and cascaded sum frequency generation in whispering gallery mode microspheres made of surface-crystallized glass with a 6-µm Ba2TiSi2O8 crystal layer are demonstrated. Attributed to the core-shell design, the Ba2TiSi2O8 located on the surface can be efficiently coupled with whispering gallery modes, resulting in a highly efficient micron-scale cavity-enhanced second-order optical nonlinearity. Greatly enhanced SHG of the microcavity is observed, which is up to 80 times stronger than that of a non-resonant sample. Furthermore, owing to the wavelength non-selectivity of random quasi-phase matching, ultra-wideband SHG with a strong response ranging from 860 to 1600 nm and high-contrast polarization characteristics is demonstrated. The glass-ceramic-based microsphere cavity also boosts the cascading optical nonlinearity, manifested by a two-magnitude enhancement of cascaded sum frequency generation. This work delineates an efficient strategy for boosting nonlinear optical response in glass ceramics, which will open up new opportunities for applications in photonics and optical communications.

Reversible Growth of Halide Perovskites via Lead Oxide Hydroxide Nitrates Anchored Zeolitic Imidazolate Frameworks for Information Encryption and Decryption.

The low formation energies of metal halide perovskites endow them with potential luminescent materials for applications in information encryption and decryption. However, reversible encryption and decryption are greatly hindered by the difficulty in robustly integrating perovskite ingredients into carrier materials. Here, we report an effective strategy to realize information encryption and decryption by reversible synthesis of halide perovskites, on the lead oxide hydroxide nitrates (Pb13O8(OH)6(NO3)4) anchored zeolitic imidazolate framework composites. Benefiting from the superior stability of ZIF-8 in combination with the strong bond between Pb and N evidenced by X-ray absorption spectroscopy and X-ray photoelectron spectroscopy, the as-prepared Pb13O8(OH)6(NO3)4-ZIF-8 nanocomposites (Pb-ZIF-8) can withstand common polar solvent attack. Taking advantage of blade-coating and laser etching, the Pb-ZIF-8 confidential films can be readily encrypted and subsequently decrypted through reaction with halide ammonium salt. Consequently, multiple cycles of encryption and decryption are realized by quenching and recovery of the luminescent MAPbBr3-ZIF-8 films with polar solvents vapor and MABr reaction, respectively. These results provide a viable approach to integrate the state-of-the-art materials perovskites and ZIF for applications in information encryption and decryption films with large scale (up to 6 × 6 cm2), flexibility, and high resolution (approximate 5 µm line width).

Coupling Localized Laser Writing and Nonlocal Recrystallization in Perovskite Crystals for Reversible Multidimensional Optical Encryption.

The ability to generate and manipulate photoluminescence (PL) with high spatial resolution has been of primary importance for applications in micro-optoelectronics, while the emerging metal halide perovskites offer novel material platforms where diverse photonic functionalities and fine structuring are constantly explored. Herein, micro-PL patterns consisting of highly luminescent CsPbBr3 nanocrystals (NCs) in nonluminescent perovskite crystals are directly fabricated by focused femtosecond laser irradiation. Further modulation with a moisture field leads to the selective dissolution of the laser-destabilized perovskite structures as revealed by density functional theory simulations, thus allowing for facile control of the reversible PL from the recrystallization of moisture-induced CsPbBr3 NCs. By leveraging the coupled laser writing and moisture modulation, multimodal information encryption is realized by reversible encryption-reading and repeatable erasing-refreshing. This optical storage mechanism is also extended to 3D and 4D by realizing spatially and temporally resolved optical encryption. The coupled multifield modulation on perovskite crystals can enable potential applications in optical storage and encryption, and offer a novel solution for the creation and manipulation of localized PL structures with high temporal and spatial resolutions.

Reversible 3D optical data storage and information encryption in photo-modulated transparent glass medium.

Transparent glass has been identified as a vital medium for three-dimensional (3D) optical information storage and multi-level encryption. However, it has remained a challenge for directly writing 3D patterning inside a transparent glass using semiconductor blue laser instead of high-cost femtosecond laser. Here, we demonstrate that rare earth ions doped transparent glass can be used as 3D optical information storage and data encryption medium based on their reversible transmittance and photoluminescence manipulation. The color of tungsten phosphate glass doped with rare earth ions change reversibly from light yellow to blue upon alternating 473 nm laser illumination and temperature stimulation, resulting in the reversible luminescence modulation. The information data could be repeatedly written and erased in arbitrary 3D space of transparent glass, not only showing the ability of the excellent reproducibility and storage capacity, but also opening opportunities in information security. The present work expands the application fields of luminescent glass, and it is conducive to develop a novel 3D data storage and information encryption media.

Three-Dimensional Laser-Assisted Patterning of Blue-Emissive Metal Halide Perovskite Nanocrystals inside a Glass with Switchable Photoluminescence.

The high-precision patterning of metal halide perovskites (MHPs) is of paramount importance for their device application. Here, we demonstrate the femtosecond (fs)-laser-assisted formation of three-dimensional MHP nanocrystal (NC) patterns with strong blue photoluminescence (PL) inside an oxide glass. Our strategy enables the crystallization and erasing of CsPb(Cl/Br)3 NCs inside a glass localized around the laser focal area through a combination of fs laser irradiation and thermal treatment processes. These recoverable patterns exhibit a switchable PL associated with the laser-induced defect and the thermal healing of MHP NCs that are benefits from the soft ionic crystal structure and low formation energy of the MHPs. Due to the high stability offered by the protection of the oxide glass matrix, the laser printing of fine-structured MHP micropatterns can be repeated over multiple cycles with a high robustness compared with their colloidal process counterparts. Our results demonstrate a simple strategy for creating emissive patterns inside a stable and transparent solid matrix that could be promising for applications including information storage, three-dimensional displays, anticounterfeit labels, and information security protection.

Anisotropic Excitation Polarization Response from a Single White Light-Emitting ß-NaYF4 :Yb3+ ,Pr3+ Microcrystal.

Precise knowledge about optical and structural performance of individual rare earth (RE)-doped particles is extremely important for the optimization of luminescent particles and for fully exploiting their capability as multifunctional probes for interdisciplinary applications. In this work, optical and structural anisotropy of individual particles through RE-doped single fluoride microcrystals with controllable morphology is reported. Unique luminescent phenomena, for example, white light-emission from Pr3+ at single particle level and different photoluminescent spectra variation dependence on excitation polarization orientation at different excitation direction are observed upon excitation with a 980 nm linearly polarized laser. Based on the analysis of local site symmetry and electron cloud distribution of REs in hexagonal structure by density functional theory calculations, an exciting mechanism of excitation polarization response anisotropy is given for the first time, providing a guidance for emission polarization simultaneously. The structural anisotropy is presented in Raman spectra with obvious differing Raman curves, revealing the reason why there are differences between powder groups. Taking advantage of anisotropic crystals, potential applications in microscopic multi-information transportation are suggested for the optical and structural performance anisotropy from RE-doped fluoride single nano/microcrystals to ordered nano/microcrystal arrays, such as local rate probing in a flowing liquid.

Formation, element-migration and broadband luminescence in quantum dot-doped glass fibers.

All solid-state PbS quantum dot (QD)-doped glass precursor fibers avoiding crystallization during fiber-drawing process are successfully fabricated by melt-in-tube technique. By subsequent heat treatment schedule, controllable crystallization of PbS QDs can be obtained in the glass precursor fibers, contributing to broad near-infrared emissions from PbS QD-doped glass fibers. Nevertheless, we find that element-migration and volatilization of sulfur simultaneously happen during the whole fiber-drawing process, because of the huge difference between the melting temperature of core glass and the fiber-drawing temperature. Element-migration pathways along the fiber length were revealed. Such PbS QD-doped glass fiber with broadband emissions will be a potential application as gain medium of broadband fiber amplifiers and fiber lasers.