Direct hierarchical assembly of nanoparticles
View Patent ↗The present invention provides hierarchical assemblies of a block copolymer, a bifunctional linking compound and a nanoparticle. The block copolymers form one micro-domain and the nanoparticles another micro-domain.
1. A composition comprising:
a plurality of nanoparticles each having a ligand linked to a surface of each of the nanoparticles;
a plurality of block copolymers, each block copolymer comprising a first block and a second block; and
a plurality of bifunctional linking compounds, each bifunctional linking compound non-covalently links to one block of one of the block copolymers and to the ligand on the surface of each of the nanoparticles, wherein the plurality of nanoparticles are arranged in an array to form a first micro-domain, and the block copolymers form a second micro-domain, and the composition is a solid below the glass transition temperature of the plurality of block copolymers.
2. The composition of matter of claim 1 , wherein the nanoparticles are selected from the group consisting of a metal, a semiconductor, a magnetic material, a metal chalcogenide, a metal oxide, and a combination thereof.
3. The composition of matter of claim 1 , wherein the nanoparticles are selected from the group consisting of CdS, CdSe, PbS, Au, and CoFe 2 O 4 .
4. The composition of matter of claim 1 , wherein the nanoparticles are selected from the group consisting of quantum dots, spherical and pseudo-spherical particles, faceted particles, nanorods, nanowires, tetrapods, anisotropic particles, and a combination thereof.
5. The composition of matter of claim 1 , wherein the ligand covers the surface of the nanoparticles.
6. The composition of matter of claim 1 , wherein the second block of the block copolymer comprises a hydrogen-bond acceptor.
7. The composition of matter of claim 1 , wherein the block copolymer comprises polystyrene-block poly-4-vinylpyridine (PS-b-P4VP).
8. The composition of matter of claim 1 , wherein the bifunctional linking compound comprises a hydrogen-bond donor selected from the group consisting of OH, NH 2 and SH.
9. The composition of matter of claim 1 , wherein the bifunctional linking compound comprises a member selected from the group consisting of C 6-20 alkyl and C 6-20 haloalkyl.
10. The composition of matter of claim 1 , wherein the bifunctional linking compound is selected from the group consisting of 3-n-pentadecylphenol (PDP), 4-(4′-Octylphenyl)azophenol (OPAP), 5′″-(3,7-dimethyloctyl)-5-(3-(3-hydroxyphenyl)propyl)-[2,2′;5′,2″;5″,2′″] quaterthiophene (4T), 4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecylthio)phenol (FDP) and (8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl (3-hydroxyphenyl) succinate (ChHP).
11. The composition of matter of claim 1 , wherein the bifunctional linking compound is selected from the group consisting of 3-n-pentadecylphenol (PDP) and 4-(4′-Octylphenyl)azophenol (OPAP).
12. The composition of matter of claim 1 , wherein the bifunctional linking compound is selected from the group consisting of octadecylphosphonic acid and oleic acid.
13. The composition of matter of claim 1 , wherein the array comprises a one dimensional array.
14. The composition of matter of claim 13 , wherein the nanoparticles are arranged in a closed packed structure in the one dimensional array.
15. The composition of matter of claim 1 , wherein the array comprises a two dimensional array.
16. The composition of matter of claim 1 , wherein the array comprises a three dimensional array.
17. The composition of matter of claim 1 , wherein the second micro-domain forms a matrix that separates a plurality of first micro-domains from each other.
18. A method of making a nanocomposite comprising:
forming a solution of a plurality of block copolymers each comprising a first block and a second block, a plurality of bifunctional linking compounds, and a plurality of nanoparticles; and
annealing the solution to produce the nanocomposite comprising:
the plurality of nanoparticles each having a ligand linked to a surface of each nanoparticle;
the plurality of block copolymers; and
the plurality of bifunctional linking compounds that non-covalently link to one block of one of the block copolymers and to the ligand on the surface of each of the plurality of nanoparticles, wherein the plurality of nanoparticles are arranged in an array to form a first micro-domain, and the plurality of block copolymers form a second micro-domain, and the nanocomposite is a solid below the glass transition temperature of the plurality of block copolymers.
19. The method of claim 18 wherein annealing the solution comprises a solvent anneal.
20. The method of claim 18 wherein annealing the solution comprises a thermal anneal.