Photoresponse of CVD grown crystalline quantum dot-embedded covalent organic framework thin film.

Covalent organic frameworks (COFs) are a new family of novel 2D materials which are highly sought after for integration into future sensors and other devices for their highly porous structures and large surface areas. However, low-temperature large-area growth of these semiconductive materials with a clean surface for direct device applications is still a challenging task. To provide an on-chip photonic device, a COF366-Quantum dot (COF366-QDs) thin-film-based device fabricated by in situ chemical vapor deposition (CVD) is presented. The high-resolution transmission electron microscopy (HRTEM) displays the formation of the periodic, crystalline and porous framework of the COF layer with mono-dispersed QDs of average particle size of ∼2.5-3 nm. The fabricated COF366-QD layer acts as a photoactive layer in the photonic device with an Au-COFQD-Au structure where a conduction path is formed between the metal electrodes through a network of COF layer with embedded QDs. The device shows photoactive response under 514 nm visible light with a very low dark current of 4.36 × 10-11 A with a minimum light detection capability of 160 nW and a responsivity of ∼3.42 A W-1. The photonic device was highly stable for successive switching cycles with very low attenuation. To our knowledge, this is the first report of a Quantum dot embedded COF366 thin-film by chemical vapor deposition. The proposed interfacing of COF366-QD thin-films on silicon substrate using in situ low-temperature CVD technique can be highly valuable for the development of transfer-free, clean, and low-cost preparation of industrial-scale organic electronics, optoelectronic device applications, and lab-on-chip based technologies for a wide range of future applications.

Constructing covalent organic frameworks in water via dynamic covalent bonding.

The formation of keto-enamine based crystalline, porous polymers in water is investigated for the first time. Facile access to the Schiff base reaction in water has been exploited to synthesize stable porous structures using the principles of Dynamic Covalent Chemistry (DCC). Most credibly, the water-based Covalent Organic Frameworks (COFs) possess chemical as well as physical properties such as crystallinity, surface area and porosity, which is comparable to their solvothermal counterparts. The formation of COFs in water is further investigated by understanding the nature of the monomers formed using hydroxy and non-hydroxy analogues of the aldehyde. This synthetic route paves a new way to synthesize COFs using a viable, greener route by utilization of the DCC principles in conjunction with the keto-enol tautomerism to synthesize useful, stable and porous COFs in water.