Abstract
Bridging functionalities in periodic mesoporous organosilicas (PMOs) enable new functionalities for a wide range of applications. Bridge cleavage is frequently observed during anneals required to form porous structures, yet the mechanism of these bridge cleavages has not been completely resolved. Here, these chemical transformations and their kinetic pathways on sub-millisecond timescales induced by laser heating are revealed. By varying anneal times and temperatures, the transformation dynamics of bridge cleavage and structural transformations and their activation energies are determined. The structural relaxation time for individual reactions and their effective local heating time are determined and compared, and the results directly demonstrate the manipulation of different molecules through kinetic control of the sequence of reactions. By isolating and understanding the earliest stage of structural transformations, this study identifies the kinetic principles for new synthesis and post-processing routes to control individual molecules and reactions in PMOs and other material systems with multi-functionalities.
| Original language | English |
|---|---|
| Article number | 2310577 |
| Journal | Small |
| Volume | 20 |
| Issue number | 21 |
| DOIs | |
| State | Published - May 23 2024 |
| Externally published | Yes |
Funding
The work was supported by the Semiconductor Research Corporation (SRC), GlobalFoundries, and Intel. This work was performed in part at the Cornell NanoScale Facility, an NNCI member supported by NSF Grant NNCI‐2025233, and made use of the Cornell Center for Materials Research Shared Facilities, which are supported through the NSF MRSEC program (DMR‐1719875). Z.S. acknowledges Dr. Y. Sun and Dr. D. Zhang for experimental assistance.
Keywords
- bridge cleavage
- millisecond anneal
- periodic mesoporous organosilicas
- reaction kinetics