TY - JOUR
T1 - Understanding and Controlling Polymer-Organometallic Precursor Interactions in Sequential Infiltration Synthesis
AU - Weisbord, Inbal
AU - Shomrat, Neta
AU - Azoulay, Rotem
AU - Kaushansky, Alexander
AU - Segal-Peretz, Tamar
N1 - Publisher Copyright: Copyright © 2020 American Chemical Society.
PY - 2020/6/9
Y1 - 2020/6/9
N2 - Sequential infiltration synthesis (SIS) is an emerging method for vapor-phase growth of inorganic materials within polymers that is utilized for hybrid organic-inorganic and inorganic nanostructure fabrication. The range of SIS applications has been continuously expanding for the past decade. A fundamental understanding of precursor-polymer interactions is, however, essential to expand the use of SIS to additional chemistries and move beyond thin film polymer templates. This work utilizes density functional theory (DFT) calculations and in situ gravimetric analysis to probe the growth mechanism of trimethylaluminum (TMA) within poly(methyl methacrylate) (PMMA) and poly(2-vinylpyridine) (P2VP). The theoretical and experimental analyses reveal that each precursor-polymer pair is characterized by a balance point temperature at which rates of forward and reverse precursor-polymer binding enable maximum mass gain at thermodynamic equilibrium. At short exposure times, mass gain is significantly influenced by the pressure profile of the process chamber. Mechanism comprehension enabled nanopatterning of a previously unsuitable block copolymer (BCP), polystyrene-block-P2VP (PS-b-P2VP), at elevated temperatures. It was proven possible to grow significant mass while maintaining the pattern by stabilizing the morphology via a single cycle at low-temperature SIS, thus overcoming self-assembly sensitivity to temperature.
AB - Sequential infiltration synthesis (SIS) is an emerging method for vapor-phase growth of inorganic materials within polymers that is utilized for hybrid organic-inorganic and inorganic nanostructure fabrication. The range of SIS applications has been continuously expanding for the past decade. A fundamental understanding of precursor-polymer interactions is, however, essential to expand the use of SIS to additional chemistries and move beyond thin film polymer templates. This work utilizes density functional theory (DFT) calculations and in situ gravimetric analysis to probe the growth mechanism of trimethylaluminum (TMA) within poly(methyl methacrylate) (PMMA) and poly(2-vinylpyridine) (P2VP). The theoretical and experimental analyses reveal that each precursor-polymer pair is characterized by a balance point temperature at which rates of forward and reverse precursor-polymer binding enable maximum mass gain at thermodynamic equilibrium. At short exposure times, mass gain is significantly influenced by the pressure profile of the process chamber. Mechanism comprehension enabled nanopatterning of a previously unsuitable block copolymer (BCP), polystyrene-block-P2VP (PS-b-P2VP), at elevated temperatures. It was proven possible to grow significant mass while maintaining the pattern by stabilizing the morphology via a single cycle at low-temperature SIS, thus overcoming self-assembly sensitivity to temperature.
UR - http://www.scopus.com/inward/record.url?scp=85088369432&partnerID=8YFLogxK
U2 - https://doi.org/10.1021/acs.chemmater.0c00026
DO - https://doi.org/10.1021/acs.chemmater.0c00026
M3 - مقالة
SN - 0897-4756
VL - 32
SP - 4499
EP - 4508
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 11
ER -