ABSTRACT
Stimuli-responsive organic materials with controllable luminescence are of enormous importance because of their potential applications in sensing, data security, and display devices. In this study, a multistimuli-responsive squaraine dyad (SQ-d) composed of two rigid squaraine moieties and a flexible ethylene linker was rationally designed and synthesized. SQ-d exhibits polymorphic luminescence, which can be reversibly switched by various external stimuli, including solvent vapor exposure, heat, and shear force. Unexpectedly, the weakly luminescent phase (O1) of SQ-d exhibits concentration-controlled vapochromic behavior. Film O1 can convert to a highly green-emissive phase (G1) under a low concentration of CHCl3 vapor and convert to a highly yellow-emissive phase (Y) under a high concentration of CHCl3 vapor; these originate from two distinct crystallization-induced emission enhancement processes. To the best of our knowledge, this is the first investigation of the effect of vapor concentration on the phase transitions of organic vapochromic luminophores. By analyzing the single-crystal structures and photophysical properties of SQ-d, we concluded that the green and yellow emissions probably originated from a zigzag stacking mode and an H-type π-π stacking mode, respectively. Finally, two prototypes based on SQ-d for applications in information encryption and vapor sensing were successfully demonstrated.
ABSTRACT
A large-scale sub-5 nm nanofabrication technique is developed based on double layer anodized aluminium oxide (AAO) porous membrane masking. This technique also provides a facile route to form multilayer nano-arrays (metal nanoarrays sandwiched by AAO membranes), which is very challenging for other techniques. Normally the AAO mask has to be sacrificed, yet in this work it is preserved as a part of the nanostructure. The preserved AAO layers as the support for the second/third layer of the metal arrays provide a high-refractive index background for the multilayer metal arrays. This background concentrates the local E-field more significantly and results in a much higher Surface-Enhanced Raman Spectroscopy (SERS) signal than single layer metal arrays. This technique may lead to the advent of an inexpensive, reproducible, highly sensitive SERS substrate. Moreover, the physical essence of the plasmonic enhancement is unveiled by finite element method based numerical simulations. Enhancements from the gaps and the multilayer nanostructure agree very well with the experiments. The calculated layer-by-layer electric field distribution determines the contribution from different layers and provides more insights into the 3D textured structure.