Method for patterning metal using nanoparticle containing precursors
Continuous, conducting metal patterns can be formed from metal nanoparticle containing films by exposure to radiation ( FIG. 1 ). The metal patterns can be one, two, or three dimensional and have high resolution resulting in feature sizes in the order of micron down to nanometers. Compositions containing the nanoparticles coated with a ligand and further including a dye, a metal salt, and either a matrix or an optional sacrificial donor are also disclosed.
1. A method, comprising:
subjecting a metal nanoparticles containing composition to radiation, thereby effecting a growth of said nanoparticles; and forming a continuous or semi-continuous metal phase, said metal nanoparticle containing composition, including:
a ligand coated metal nanoparticle;
a dye;
a metal salt; and
optionally a sacrificial donor.
2. A method, comprising:
subjecting a metal nanoparticles containing composition to radiation, thereby effecting a growth of said nanoparticles; and
forming a continuous or semi-continuous metal phase, said metal nanoparticle containing composition including:
a ligand coated metal nanoparticle;
a dye;
a metal salt; and
a matrix.
3. The method according to claim 2 , wherein said nanoparticle is a silver nanoparticle with a mixture of ligands having the formula A-B-C, wherein
A is a molecular or ionic fragment that has at least one atom having a lone pair of electrons that can bond to a metal nanoparticle surface, or is an unsaturated molecular or ionic fragment that can bond to the metal nanoparticle surface, and includes a point of attachment to connect the fragment to B,
B is a single bond or an organic fragment that has two points of attachment, one for connecting to part A and one for connecting to part C, and
C is a molecular fragment with one point of attachment that connects to fragment B.
4. The method according to claim 3 , wherein A and C are each independently selected from the group consisting of σ S, σ O, σ O 2 C—, σ S—S—R, σ O 3 S—, σ S 2 C—NR—, σ O 2 C—NR—, P(R 1 R 2 )—, N(R 1 R 2 )—, O(R 1 )—, P(OR 1 )(OR 2 )O—, and S 2 (R)—;
wherein R, R 1 , and R 2 may be independently selected from the group consisting of —H, a linear or branched alkyl chain containing 1 to 50 carbon atoms, a phenyl group, an aryl group other than a phenyl group, and a hetero aromatic group;
wherein each of A and C independently has one point of attachment to B.
5. The method according to claim 3 , wherein B is an organic fragment that has two points of attachment, one for connecting to part A and one for connecting to part C.
6. The method according to claim 3 , wherein B is a single bond.
7. The method according to claim 3 , wherein B and C are each independently selected from the group consisting of a methylene chain with 1 to 50 carbon atoms, a phenylene chain with 1 to 20 phenyls, a thiophenylene chain with 1 to 20 thiophenylenes, a phenylene vinylene chain with 1 to 20 phenyl vinylenes, a branched hydrocarbon chain, an ethylene oxide chain with 1 to 20 ethylene oxides, an oligo (vinyl carbazole) chain with 1 to 20 vinyl carbazole units;
wherein B has two points of attachment; and
wherein C has one point of attachment.
8. The method according to claim 3 , wherein C is selected from the group consisting of —H, an aryl group, N-carbazoyl, α-fluorenyl, —SiOR 3 , —SiCl 3 , a dye, a donor-acceptor dye, a photoreducing dye, a multi-photon absorbing chromophore, methylene blue, an oligonucleotide strand, a peptide chain.
9. The method according to claim 3 , wherein C is selected from the group consisting of a carbazole, a bis-styrylbenzene, a cyanine and a thiophene.
10. The method according to claim 3 , wherein said ligand A-B-C is selected from the group consisting of octanethiol, dodecanthiol, heptanethiol, 8-(9H-carbazol-9-yl)octane-1-thiol, 8-(9H-carbazol-9-yl)dodecane-1-thiol, 3-mercaptopropionic acid, Bis[2-(dimethylamino)ethyl]2-mercaptopentadioate, 3 {2,5-bis[(E)-2-(4-formyl-(phenyl)etheny]phenoxy}propyl-4-(1,2-dithiolane-3-yl)butanoate and a mixture thereof.
11. The method according to claim 2 , wherein said metal salt is AgBF 4 .
12. The method according to claim 2 , wherein said dye is a multi-photon absorbing dye.
13. A method, comprising:
forming a film from a metal nanoparticle, a metal salt, a dye and a polymer matrix; and
exposing said film to radiation, thereby producing a pattern of a conductive metal.
14. The method according to claim 13 , wherein said nanoparticle is a silver nanoparticle with a mixture of ligands having the formula A-B-C, wherein
A is a molecular or ionic fragment that has at least one atom having a lone pair of electrons that can bond to a metal nanoparticle surface, or is an unsaturated molecular or ionic fragment that can bond to the metal nanoparticle surface, and includes a point of attachment to connect the fragment to B,
B is a single bond or an organic fragment that has two points of attachment, one for connecting to part A and one for connecting to part C, and
C is a molecular fragment with one point of attachment that connects to fragment B.
15. The method according to claim 14 , wherein A and C are each independently selected from the group consisting of σ S—, σ O—, σ O 2 C—, σ S—S—R, σ O 3 S—, σ S 2 C—NR—, σ O 2 C—NR—, P(R 1 R 2 )—, N(R 1 R 2 )—, O(R 1 )—, P(OR 1 )(OR 2 )O—, and S 2 (R)—;
wherein R, R 1 , and R 2 may be independently selected from the group consisting of —H, a linear or branched alkyl chain containing 1 to 50 carbon atoms, a phenyl group, an aryl group other than a phenyl group, and a hetero aromatic group;
wherein each of A and C independently has one point of attachment to B.
16. The method according to claim 14 , wherein B is an organic fragment that has two points of attachment, one for connecting to part A and one for connecting to part C.
17. The method according to claim 14 , wherein B is a single bond.
18. The method according to claim 14 , wherein B and C are each independently selected from the group consisting of a methylene chain with 1 to 50 carbon atoms, a phenylene chain with 1 to 20 phenyls, a thiophenylene chain with 1 to 20 thiophenylenes, a phenylene vinylene chain with 1 to 20 phenyl vinylenes, a branched hydrocarbon chain, an ethylene oxide chain with 1 to 20 ethylene oxides, an oligo (vinyl carbazole) chain with 1 to 20 vinyl carbazole units;
wherein B has two points of attachment; and
wherein C has one point of attachment.
19. The method according to claim 14 , wherein C is selected from the group consisting of —H, an aryl group, N-carbazoyl, α-fluorenyl, —SiOR 3 , —SiCl 3 , a dye, a donor-acceptor dye, a photoreducing dye, a multi-photon absorbing chromophore, methylene blue, an oligonucleotide strand, a peptide chain.
20. The method according to claim 14 , wherein C is selected from the group consisting of a carbazole, a bis-styrylbenzene, a cyanine and a thiophene.
21. The method according to claim 14 , wherein said ligand A-B-C is selected from the group consisting of octanethiol, dodecanthiol, heptanethiol, 8-(9H-carbazol-9-yl)octane-1-thiol, 8-(9H-carbazol-9-yl)dodecane-1-thiol, 3 -mercaptopropionic acid, Bis[2-(dimethylamino)ethyl]2-mercaptopentadioate, 3 {2,5-bis[(E)-2-(4-formyl-(phenyl)ethenyl]phenoxy}propyl-4-(1,2-dithiolane-3-yl)butanoate and a mixture thereof.
22. The method according to claim 13 , wherein said metal salt is AgBF 4 .
23. The method according to claim 13 , wherein said dye is a multi-photon absorbing dye.
24. The method according to claim 23 , wherein a two-photon cross section is in excess of 1×10 50 cm 4 photon −1 sec −1 .