Double perovskites are a promising family of lead-free materials that not only replace lead but also enable new optoelectronic applications beyond photovoltaics. Recently, a titanium (Ti)-based vacancy-ordered double perovskite, Cs2TiBr6, has been reported as an example of truly sustainable and earth-abundant perovskite with controversial results in terms of photoluminescence and environmental stability. Our work looks at this material from a new perspective, i.e., at the nanoscale. We demonstrate the first colloidal synthesis of Cs2TiX6 nanocrystals (X = Br, Cl) and observe tunable morphology and size of the nanocrystals according to the set reaction temperature. The Cs2TiBr6 nanocrystals synthesized at 185 °C show a bandgap of 1.9 eV and are relatively stable up to 8 weeks in suspensions. However, they do not display notable photoluminescence. The centrosymmetric crystal structure of Cs2TiBr6 suggests that this material could enable third-harmonic generation (THG) responses. Indeed, we provide a clear evidence of THG signals detected by the THG microscopy technique. As only a few THG-active halide perovskite materials are known to date and they are all lead-based, our findings promote future research on Cs2TiBr6 as well as on other lead-free double perovskites, with stronger focus on currently unexplored nonlinear optical applications.

For modern tissue engineering, we need not only develop new hydrogels but also suitable processing methods for them. Polypeptides and polysaccharides are potential candidates because they can be methacrylated, processed before photocross-linking, and yielded into hydrogels with given shape and form. In this study, we successfully methacrylated collagen, gelatin, hyaluronan, and alginate to 30 and 60% degree of modification. We studied methacrylated compositions (i.e., precursors) to investigate their processability. The precursors of collagen and gelatin with 60% methacrylation exhibited suitable yield stress, shear-thinning properties, and fiber-forming capability for injecting and 3D bioprinting. On the contrary, the 30% methacrylated precursors had properties suitable for casting purposes. Our study also showed that the mechanical properties of hydrogels corresponded to the used photocross-linking conditions and the degree of modification. These results underline the importance of tunability of the precursors and resulting hydrogels according to the specific fabrication method and tissue engineering application.

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Third-harmonic generation (THG) microscopy is demonstrated as a powerful technique to visualize undeveloped photopolymerized microstructures within a negative photoresist film. By comparing the THG microscopy images of developed and undeveloped single-photon polymerized structures in a SU-8 film, THG was found to provide sufficient contrast for distinguishing polymerized and unpolymerized regions. This also suggests that the technique can be used as a complementary technique to visualize the effect of photoresist development where microstructure shrinkage could occur. In addition, we applied the technique to visualize a three-photon polymerized microstructure that was fabricated in the same microscopy setup. This demonstrates the potential of the technique for in situ microscopy of photopolymerized microstructures in three dimensions.

Using three-dimensional (3D) second-harmonic generation (SHG) scanning microscopy, we unravel the formation and distribution of distinct and highly localized persistent luminescent (PeL) microparticles of varied hierarchical levels in glasses prepared using the direct doping method. The PeL microparticles were added in the glasses at different doping temperatures and the glasses were quenched after different dwell time. The SHG maps of the PeL microparticles in the glass, prepared with a doping temperature of 975°C and a dwell time of 3 min, reveal grating-like microscopic domains. This suggests that a large arrangement of PeL crystals spanning several micrometers in three dimensions is manifested by the imbued PeL microparticle. In contrast, the SHG maps of the PeL microparticles inside the glass prepared at doping temperature of 1025°C and dwell time of 10 min, show the existence of single, highly localized and most importantly, submicrometer-sized PeL crystals. These findings substantiate well with the expected behavior of the PeL microparticles in glasses and their physical disintegration in the form of nanoparticles at high doping temperatures and dwell times. The SHG microscopy technique is shown to circumvent the fundamental challenges of traditional and usually destructive imaging methods to detect and visualize PeL nanoparticles in a glass matrix and expected to open a new avenue to evidence the presence of crystals in glasses.