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

Abstract

The high-precision patterning of metal halide perovskites (MHPs) is of paramount importance for their device application. Here, we demonstrate the femtosecond (fs)-laserassisted 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.

Metal Halide Perovskites Functionalized by Patterning Technologies

“…Reproduced with permission. [ 98 ] Copyright 2020, American Chemical Society. d) Illustrations (left) and optical images (right) of polarized CsPbBr 3 nanowire/copolymer nanocomposite patterns by using inkjet printing.…”

“…In this regard, our group developed a rewritable anti‐counterfeiting code composed of perovskite QDs inside a transparent glass, which can not only enhance the stability of QDs but also prevent lead leakage (Figure 9c). [ 98 ] The perovskite QD patterns can be written in the glass by femtosecond laser irradiation followed by thermal treatment. Based on the low formation energy and inherent ionic structure of perovskites, the PL of the formed QDs can be switched off by femtosecond laser irradiation and on by thermal treatment.…”

Highly luminescent and ultrastable cesium lead bromide perovskite patterns generated in phosphate glass matrices

“…[16][17][18] With regard to photonic applications, a promising approach in order to overcome these important challenges is the encapsulation of perovskite nanocrystals (PNCs) in polymer [19][20][21][22] and glass matrices. [23][24][25][26][27][28][29][30][31][32][33] Such a strategy offers tremendous advantages in terms of improving the long-term stability of the perovskite structures, as well as for minimizing the lead toxicity effects. In addition, efficient tuning of the optical properties of the perovskite-based composite materials is readily achieved upon altering the morphology and composition of the embedded PNCs.…”

“…In addition, efficient tuning of the optical properties of the perovskite-based composite materials is readily achieved upon altering the morphology and composition of the embedded PNCs. 14,[19][20][21][25][26][27][28][29][30][31][32] While both encapsulation techniques are without doubt a remarkable advancement over the stability and toxicity issues, they give rise to various drawbacks. Namely, in the case of incorporating PNCs into macroscale polymeric matrices the induction of spectral shifts and reduction in the luminescence efficiency substantially affect their use in photonic device applications.…”

“…More importantly, to date, the formation of composite perovskite glasses is based on mixing the perovskite precursors together with the chemical powders of the glass prior to melting, and then, heating all materials together at the desired melting and post-melting annealing temperatures. [23][24][25][26][27][28][29][30][31][32] In this manner, the so-formed PNCs are distributed randomly throughout the entire glass network, i.e. without offering any possible way of controlling the position, growth, and morphology of the embedded structures, [23][24][25][26][27][28][29][30][31] or requiring the employment of femtosecond laser irradiation for controlled crystal growth within the glass.…”