TY - JOUR
T1 - Fabrication of Ultrafine, Highly Ordered Nanostructures Using Carbohydrate-Inorganic Hybrid Block Copolymers
AU - Nishimura, Taiki
AU - Katsuhara, Satoshi
AU - Lee, Chaehun
AU - Ree, Brian J.
AU - Borsali, Redouane
AU - Yamamoto, Takuya
AU - Tajima, Kenji
AU - Satoh, Toshifumi
AU - Isono, Takuya
N1 - Publisher Copyright:
© 2022 by the authors. Licensee MDPI, Basel, Switzerland.
PY - 2022/5/1
Y1 - 2022/5/1
N2 - Block copolymers (BCPs) have garnered considerable interest due to their ability to form microphase-separated structures suitable for nanofabrication. For these applications, it is critical to achieve both sufficient etch selectivity and a small domain size. To meet both requirements concurrently, we propose the use of oligosaccharide and oligodimethylsiloxane as hydrophilic and etch-resistant hydrophobic inorganic blocks, respectively, to build up a novel BCP system, i.e., carbohydrate-inorganic hybrid BCP. The carbohydrate-inorganic hybrid BCPs were synthesized via a click reaction between oligodimethylsiloxane with an azido group at each chain end and propargyl-functionalized maltooligosaccharide (consisting of one, two, and three glucose units). In the bulk state, small-angle X-ray scattering revealed that these BCPs microphase separated into gyroid, asymmetric lamellar, and symmetric lamellar structures with domain-spacing ranging from 5.0 to 5.9 nm depending on the volume fraction. Additionally, we investigated microphase-separated structures in the thin film state and discovered that the BCP with the most asymmetric composition formed an ultrafine and highly oriented gyroid structure as well as in the bulk state. After reactive ion etching, the gyroid thin film was transformed into a nanoporous-structured gyroid SiO2 material, demonstrating the material’s promising potential as nanotemplates.
AB - Block copolymers (BCPs) have garnered considerable interest due to their ability to form microphase-separated structures suitable for nanofabrication. For these applications, it is critical to achieve both sufficient etch selectivity and a small domain size. To meet both requirements concurrently, we propose the use of oligosaccharide and oligodimethylsiloxane as hydrophilic and etch-resistant hydrophobic inorganic blocks, respectively, to build up a novel BCP system, i.e., carbohydrate-inorganic hybrid BCP. The carbohydrate-inorganic hybrid BCPs were synthesized via a click reaction between oligodimethylsiloxane with an azido group at each chain end and propargyl-functionalized maltooligosaccharide (consisting of one, two, and three glucose units). In the bulk state, small-angle X-ray scattering revealed that these BCPs microphase separated into gyroid, asymmetric lamellar, and symmetric lamellar structures with domain-spacing ranging from 5.0 to 5.9 nm depending on the volume fraction. Additionally, we investigated microphase-separated structures in the thin film state and discovered that the BCP with the most asymmetric composition formed an ultrafine and highly oriented gyroid structure as well as in the bulk state. After reactive ion etching, the gyroid thin film was transformed into a nanoporous-structured gyroid SiO2 material, demonstrating the material’s promising potential as nanotemplates.
KW - block copolymer
KW - gyroid structure
KW - microphase-separated structure
KW - organic–inorganic hybrid
KW - self-assembly
UR - http://www.scopus.com/inward/record.url?scp=85129888189&partnerID=8YFLogxK
U2 - 10.3390/nano12101653
DO - 10.3390/nano12101653
M3 - Article
AN - SCOPUS:85129888189
SN - 2079-4991
VL - 12
JO - Nanomaterials
JF - Nanomaterials
IS - 10
M1 - 1653
ER -