Method for patterning metal using nanopraticle containing percursors

• US 20040079195A1
• Filed: 12/15/2003
• Published: 04/29/2004
• Est. Priority Date: 12/15/2000
• Status: Active Grant

• Current Assignee: Arizona Board of Regents (University of Arizona)
• Original Assignee: Arizona Board of Regents (University of Arizona)
• Inventors: Stellacci, Francesco, Marder, Seth R., Perry, Joseph W.
• Granted Patent: US 7,252,699 B2
• Time in Patent Office: Days
• US Class Current: 75/345
• CPC Class Codes: B22F 1/0545 Dispersions or suspensions of nanosized particles
• CPC Class Codes: B22F 1/056 Submicron particles having a size above 100 nm up to 300 nm
• CPC Class Codes: B22F 2998/00 Supplementary information concerning processes or compositions relating to powder metallurgy
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: H01B 1/02 mainly consisting of metals or alloys
• CPC Class Codes: H01B 1/22 the conductive material comprising metals or alloys
• CPC Class Codes: H01L 21/76838 characterised by the formation and the after-treatment of the conductors etching for patterning the conductors H01L21/3213
• CPC Class Codes: Y10S 977/783 Organic host/matrix, e.g. lipid
• CPC Class Codes: Y10T 428/12181 Composite powder [e.g., coated, etc.]
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31942 Of aldehyde or ketone condensation product

Abstract

Continous, conducting metal patterns can be formed from metal nanoparticle containing fils by exposure to radiation. The metal patterns can be one, two, or three dimensional and have high resolution resulting in feature sizes in the order of micron to nanometers

Claims

1. A method for growth of a pre-nucleated metal nanoparticle, comprising:

providing said pre-nucleated metal nanoparticle in a composite;

generating a metal atom by reducing a metal ion by exposure to radiation;

reacting said metal atom with said pre-nucleated metal nanoparticle, thereby growing a metal nanoparticle.

2. The method according to claim 1, further comprising collapsing of at least two metal nanoparticles, thereby obtaining a metallic continuous phase.

3. The method according to claim 1, wherein said metal atom is generated from the metal ion by using an electron-beam.

4. The method according to claim 1, wherein said metal atom is generated by laser excitation of a molecule, thereby generating heat and causing thermal reduction of the metal ion.

5. The method according to claim 1, wherein said metal atom is generated by photo-excitation of a molecule, thereby creating an excited state of said molecule and increasing a reducing potential of said molecule;

and

reducing of said metal ion by said molecule in said excited state to obtain the metal atom.

6. A method for growth of a pre-nucleated metal nanoparticle, comprising:

forming a film from said pre-nucleated metal nanoparticle, a metal salt, a dye and a polymer matrix;

generating a metal atom by reducing a metal ion of said metal salt by exposure to radiation;

reacting said metal atom with said pre-nucleated metal nanoparticle, thereby growing a metal nanoparticle.

7. A metal nanoparticle containing composition, comprising:

a ligand coated metal nanoparticle;

a dye;

a metal salt; and

optionally a sacrificial donor.

8. The composition according to claim 7, wherein said dye is capable of reducing a metal ion from said metal salt under exposure to radiation.

9. The composition according to claim 7, wherein said metal nanoparticle is selected from the group consisting of a nanoparticle of a metal coated with an organic ligand, a nanoparticle of an alloy of metals coated with an organic ligand, and a metallic nanoshell nanoparticle coated with an organic ligand.

10. The composition according to claim 9, wherein a core of said metallic nanoshell nanoparticle is selected from the group consisting of a semiconductor nanoparticle, a metal oxide nanoparticle, a SiO_x nanoparticle, a polymer nanoparticle and a protein nanoparticle;

and

wherein an outer shell of said metallic nanoshell is metallic and coated with an organic ligand coating.

11. The composition according to claim 7, wherein said metal nanoparticle is stabilized by an organic ligand or a mixture of organic ligands.

12. The composition according to claim 11, wherein said organic ligand is a molecule of formula A-B-C.

13. The composition according to claim 12, 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.

14. The composition according to claim 12, wherein A and C are each independently selected from the group consisting of ^eS, ^eO—

, ^eO₂C—

, ^eS—

S—

R, ^eO₃S—

, ^eS₂C—

NR—

, ^eO₂C—

NR—

, P(R₁R₂)—

, N(R₁R₂)—

, O(R₁)—

, P(OR₁)(OR₂)O—

, and S₂(R)—

;

wherein R, R₁, and R₂ 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.

15. The composition according to claim 12, 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.

16. The composition according to claim 12, wherein B is a single bond.

17. The composition according to claim 12, 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.

18. The composition according to claim 12, wherein C is a molecular fragment with one point of attachment that connects to fragment B.

19. The composition according to claim 18, wherein C is selected from the group consisting of —

H, an aryl group, N-carbazoyl, α

-fluorenyl, —

SiOR₃, —

SiCl₃, a dye, a donor-acceptor dye, a photoreducing dye, a multi-photon absorbing chromophore, methylene blue, an oligonucleotide strand, a peptide chain.

20. The composition according to claim 18, wherein C is selected from the group consisting of a carbazole, a bis-styrylbenzene, a cyanine and a thiophene.

21. The composition according to claim 18, 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 composition according to claim 7, wherein said dye is attached to said metal nanoparticle.

23. The composition according to claim 7, wherein said dye is selected from the group consisting of a centrosymmetric bisaldehyde-bistyrylbenzene, a non-centrosymmetric bisaldehyde-bistyrylbenzene, a centrosymmetric acceptor terminated bistyrylbenzene, a non-centrosymmetric acceptor terminated bistyrylbenzene and a mixture thereof.

46. A method, comprising:

subjecting said metal nanoparticles containing composition of claim 7 to radiation, thereby effecting a growth of said nanoparticles; and

forming a continuous or semi-continuous metal phase.

24. A metal nanoparticle containing composition, comprising:

a ligand coated metal nanoparticle;

a dye;

a metal salt; and

a matrix.

25. The composition according to claim 24, wherein said matrix is selected from the group consisting of a polymer, a glass, a liquid crystalline material, a liquid and a porous crystalline solid.

26. The composition according to claim 24, wherein said matrix is a polymer selected from the group consisting of polyvinylcarbazole, poly(2-{[11-(9H-carbazole-9-yl)undecanoyl]oxy}ethyl-2-methacrylate), poly(p-chlorostyrene), poly(methylmethacrylate) and a mixture thereof.

27. The composition according to claim 24, wherein said matrix is 1-[11-(9H-carbazole-9-yl)]-4-methoxybenzene, 1-[11-(9H-carbazole-9-yl)]-4-methylbenzene or a mixture thereof.

28. The composition of claim 24, further comprising a plasticizer.

29. The composition according to claim 28, wherein said plasticizer is N-ethylcarbazole, p,p′

-formyl-N-octyl-carbazole or a mixture thereof.

30. The composition according to claim 24, wherein said dye is capable of reducing a metal ion from said metal salt under exposure to radiation.

31. The composition according to claim 24, wherein said metal nanoparticle is selected from the group consisting of a nanoparticle of a metal coated with an organic ligand, a nanoparticle of an alloy of metals coated with an organic ligand, and a metallic nanoshell nanoparticle coated with an organic ligand.

32. The composition according to claim 24, wherein a core of said metallic nanoshell nanoparticle is selected from the group consisting of a semiconductor nanoparticle, a metal oxide nanoparticle, a SiO_x nanoparticle, a polymer nanoparticle and a protein nanoparticle;

and

wherein an outer shell of said metallic nanoshell is metallic and coated with an organic coating.

33. The composition according to claim 24, wherein said metal nanoparticle is stabilized by an organic ligand or a mixture of organic ligands.

34. The composition according to claim 33, wherein said organic ligand is a molecule of formula A-B-C.

35. The composition according to claim 34, 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.

36. The composition according to claim 34, wherein A and C are each independently selected from the group consisting of ^eS, ^eO, ^eO₂C—

, ^eS—

S—

R, ^eO₃S—

, ^eS₂C—

NR—

, ^eO₂C—

NR—

, P(R₁R₂)—

, N(R₁R₂)—

, O(R₁)—

, P(OR₁)(OR₂)O—

, and S₂(R)—

;

wherein R, R₁, and R₂ 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.

37. The composition according to claim 34, 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.

38. The composition according to claim 34, wherein B is a single bond.

39. The composition according to claim 34, 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.

40. The composition according to claim 34, wherein C is a molecular fragment with one point of attachment that connects to fragment B.

41. The composition according to claim 40, wherein C is selected from the group consisting of —

H, an aryl group, N-carbazoyl, α

-fluorenyl, —

SiOR₃, —

SiCl₃, a dye, a donor-acceptor dye, a photoreducing dye, a multi-photon absorbing chromophore, methylene blue, an oligonucleotide strand, a peptide chain.

42. The composition according to claim 40, wherein C is selected from the group consisting of a carbazole, a bis-styrylbenzene, a cyanine and a thiophene.

43. The composition according to claim 40, 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.

44. The composition according to claim 24, wherein said dye is attached to said metal nanoparticle.

45. The composition according to claim 24, wherein said dye is selected from the group consisting of a centrosymmetric bisaldehyde-bistyrylbenzene, a non-centrosymmetric bisaldehyde-bistyrylbenzene, a centrosymmetric acceptor terminated bistyrylbenzene, a non-centrosymmetric acceptor terminated bistyrylbenzene and a mixture thereof.

47. A method, comprising:

subjecting said metal nanoparticles containing composition of claim 24 to radiation, thereby effecting a growth of said nanoparticles; and

forming a continuous or semi-continuous metal phase.

48. The method according to claim 47, wherein said nanoparticle is a silver nanoparticle with a mixture of ligands having the formula A-B-C.

49. The method according to claim 48, 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.

50. The method according to claim 48, wherein A and C are each independently selected from the group consisting of ^eS, ^eO, ^eO₂C—

, ^eS—

S—

R, ^eO₃S—

, ^eS₂C—

NR—

, ^eO₂C—

NR—

, P(R₁R₂)—

, N(R₁R₂)—

, O(R₁)—

, P(OR₁)(OR₂)O—

, and S₂(R)—

;

wherein R, R₁, and R₂ 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.

51. The method according to claim 48, 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.

52. The method according to claim 48, wherein B is a single bond.

53. The method according to claim 48, 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.

54. The method according to claim 48, wherein C is a molecular fragment with one point of attachment that connects to fragment B.

55. The method according to claim 54, wherein C is selected from the group consisting of —

H, an aryl group, N-carbazoyl, α

-fluorenyl, —

SiOR₃, —

SiCl₃, a dye, a donor-acceptor dye, a photoreducing dye, a multi-photon absorbing chromophore, methylene blue, an oligonucleotide strand, a peptide chain.

56. The method according to claim 54, wherein C is selected from the group consisting of a carbazole, a bis-styrylbenzene, a cyanine and a thiophene.

57. The method according to claim 54, 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.

58. The method according to claim 47, wherein said metal salt is AgBF₄.

59. The method according to claim 47, wherein said dye is a multi-photon absorbing dye.

60. 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.

61. The method according to claim 60, wherein said nanoparticle is a silver nanoparticle with a mixture of ligands having the formula A-B-C.

62. The method according to claim 61, 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.

63. The method according to claim 61, wherein A and C are each independently selected from the group consisting of ^eS, ^eO—

, ^eO₂C—

, ^e—

S—

R, ^eO₃S—

, ^eS₂C—

NR—

, ^eO₂C-NR—

, P(R₁R₂)—

, N(R₁R₂)—

, O(R₁)—

, P(OR₁)(OR₂)O—

, and S₂(R)—

;

wherein R, R₁, and R₂ 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.

64. The method according to claim 61, 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.

65. The method according to claim 61, wherein B is a single bond.

66. The method according to claim 61, 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.

67. The method according to claim 61, wherein C is a molecular fragment with one point of attachment that connects to fragment B.

68. The method according to claim 67, wherein C is selected from the group consisting of —

H, an aryl group, N-carbazoyl, α

-fluorenyl, —

SiOR₃, —

SiCl₃, a dye, a donor-acceptor dye, a photoreducing dye, a multi-photon absorbing chromophore, methylene blue, an oligonucleotide strand, a peptide chain.

69. The method according to claim 67, wherein C is selected from the group consisting of a carbazole, a bis-styrylbenzene, a cyanine and a thiophene.

70. The method according to claim 67, 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.

71. The method according to claim 60, wherein said metal salt is AgBF₄.

72. The method according to claim 60, wherein said dye is a multi-photon absorbing dye.

73. The method according to claim 72, wherein a two-photon cross section is in excess of 1×

10<sup>−

50</sup> cm⁴ photon<sup>−

1</sup> sec<sup>−

1</sup>.