Octupolar Cyclotriphosphazene-Cored Self-Standing Covalent Organic Framework Membranes as Nonlinear Optical Materials: Impact of Linkage Types and Material Forms.

Conjugated and processable self-standing vinylene-linked covalent organic framework membranes (COFMs) are highly demanding for photonics and optoelectronics. In this work, we have fabricated the first cyclotriphosphazene (CTP) cored vinylene-linked self-standing COFM (CTP-PDAN). For comparison purposes, we have successfully fabricated the imine-linked congener (CTP-PDA). Leveraging the inherent nonlinear optical (NLO) response of the CTP core, both membranes were directly mounted to evaluate NLO parameters using the open-aperture (OA) Z-scan technique. Direct measurement of NLO responses on membranes is advantageous and free from solvent and scattering effects, making it a more practical approach compared to the conventional dispersion mode. The OA Z-scan transmission yields a reverse saturable absorption signature exhibiting a higher NLO absorption coefficient (ß) of 58.37 cm/GW for CTP-PDAN, compared to that of the imine-linked CTP-PDA COFM (ß = 8.5 cm/GW). These results can be correlated to the efficient conjugation through the vinylene linkage in CTP-PDAN compared to the imine linked congener.

Exploring the superhydrophilicity of nanosecond laser textured silicon: a Raman analysis.

We present Raman analysis of nanosecond laser textured silicon. The samples have also been characterized by field emission scanning electron microscopy (FESEM) and x ray diffraction. Contact angles (CAs) are measured to trace the hydrophilic nature. Characterization of the textured samples in argon and air shows that cleavage cracks are developed during texturing. CA measurements reveal the superhydrophilic nature of textured samples obtained in the presence of ambient oxygen and argon. In vacuum, however, the hydrophilicity is decreased. Micro-Raman analysis indicates the formation of nano-sized cleavage cracks that impart stable superhydrophilic properties to textured silicon is supported from FESEM images also. On the other hand, in vacuum textured silicon, evidence of such cracks is not noticed, which is also supported by Raman analysis. Further, the hydrophilicity is decreased. A definitive trend appears to exist between Raman signatures and hydrophilicity. We believe that the study will further the understanding of the mechanistic aspect in designing textured silicon with a high degree of self-cleaning capability.