IP Library › Granted Patent US 9,536,633
Granted Patent B2
US 9,536,633 · App. 13/263,220 · Granted Jan 3, 2017

Metallic composite and composition thereof

Inventors: Hideyuki Higashimura (Tsukuba, JP); Takayuki Iijima (Tsukuba, JP); Masahiro Fujioka (Wakayama, JP); Kenta Tanaka (Tsukuba, JP)
Assignee: SUMITOMO CHEMICAL COMPANY, LIMITED
H01B1/128B22F1/0025B22F1/0062B82Y30/00C07F5/025C08G61/02C08K3/08C09D5/24H01L51/009H01L51/0039H01L51/0043B22F2999/00C08G2261/143C08G2261/145C08G2261/149C08G2261/1424C08G2261/1426C08G2261/3142C08G2261/411C08G2261/51C08G2261/95C08G2261/964C08K2201/016C08L65/00Y02E10/549Y02P70/521
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Quick Facts
Patent No.
US 9,536,633
App. No.
13/263,220
Granted
Jan 3, 2017
Kind
B2
Abstract

A metallic composite in which a conjugated compound having a molecular weight of 200 or more is adsorbed to a metallic nanostructure having an aspect ratio of 1.5 or more, for example, a metallic composite in which a compound having a group represented by the formula (I) or a repeating unit represented by the formula (II) or both of them is adsorbed to a metallic nanostructure having an aspect ratio of 1.5 or more, is useful for electronic devices such as a light-emitting device, a solar cell and an organic transistor.

Claims (47)

1. A metallic composite in which a conjugated compound having a molecular weight of 200 or more is adsorbed to a metallic nanosheet, a metallic nanorod, or a metallic nanowire having an aspect ratio of 10 or more and a largest diameter of 2000 nm or more.

2. The metallic composite of claim 1 , wherein the conjugated compound is an aromatic compound and the metallic nanosheet, the metallic nanorod, or the metallic nanowire is a metallic nanosheet, a metallic nanorod, or a metallic nanowire of a metal of Group 11 of the Periodic Table, respectively.

3. The metallic composite of claim 1 , wherein the conjugated compound is an aromatic compound having a hetero atom-containing group and the metallic nanosheet, the metallic nanorod, or the metallic nanowire is a metallic nanosheet, a metallic nanorod, or a metallic nanowire of a metal of Group 11 of the Periodic Table, respectively.

4. The metallic composite of claim 3 , wherein the hetero atom-containing group is a monovalent group selected from Group 1, wherein the groups of the Group 1 are a mercapto group, a mercaptocarbonyl group, a mercaptothiocarbonyl group, an optionally substituted hydrocarbylthio group, an optionally substituted hydrocarbylthiocarbonyl group, an optionally substituted hydrocarbyldithio group, a hydroxy group, an optionally substituted hydrocarbyloxy group, a carboxyl group, an optionally substituted hydrocarbylcarbonyl group, a cyano group, an amino group, an (optionally substituted hydrocarbyl)amino group, an (optionally substituted dihydrocarbyl)amino group, a phosphino group, an (optionally substituted hydrocarbyl)phosphino group, an (optionally substituted dihydrocarbyl)phosphino group, a group represented by formula: —P(═O)(OH) 2 , a sulfo group, a heterocyclic group, a halogen atom, a formyl group, an optionally substituted hydrocarbyloxycarbonyl group, an optionally substituted hydrocarbylcarbonyloxy group, a nitro group, a group represented by formula: —OP(═O)(OH) 2 , a phosphono group, a carbamoyl group, an optionally substituted hydrocarbylcarbamoyl group, an (optionally substituted dihydrocarbyl)carbamoyl group, a group represented by formula: —C(═S)NR 2 , a group represented by formula: —B(OH) 2 , a group represented by formula: —BR 2 , a boric acid ester group, a group represented by formula: —Si(OR) 3 , an optionally substituted hydrocarbylsulfo group, an optionally substituted hydrocarbylsulfonyl group, a sulfino group, an optionally substituted hydrocarbylsulfino group, a group represented by formula: —NRC(═O)OR, a group represented by formula: —NRC(═O)SR, a group represented by formula: —NRC(═S)OR, a group represented by formula:

—NRC(═S)SR, a group represented by formula: —OC(═O)NR 2 , a group represented by formula: —SC(═O)NR 2 , a group represented by formula: —OC(═S)NR 2 , a group represented by formula: —SC(═S)NR 2 , a group represented by formula:

—NRC(═O)NR 2 , and a group represented by formula:

—NRC(═S)NR 2 , wherein R represents a hydrogen atom or an optionally substituted hydrocarbyl group.

5. The metallic composite of claim 3 , wherein the hetero atom-containing group is a monovalent group selected from Group 2, wherein the groups of the Group 2 are a hydrocarbyl group having two or more ether bonds, a hydrocarbyl group having two or more ester bonds, a hydrocarbyl group having two or more amido bonds, a group represented by formula: —SM, a group represented by formula: —C(═O)SM, a group represented by formula: —CS 2 M, a group represented by formula: —OM, a group represented by formula: —CO 2 M, a group represented by formula: —NM 2 , a group represented by formula: —NHM, a group represented by formula: —NRM, a group represented by formula: —PO 3 M, a group represented by formula: —OP(═O)(OM) 2 , a group represented by formula: —P(═O)(OM) 2 , a group represented by formula: —C(═O)NM 2 , a group represented by formula:

—C(═O)NHM, a group represented by formula: —C(═O)NRM, a group represented by formula: —C(═S)NHM, a group represented by formula: —C(═S)NRM, a group represented by formula: —C(═S)NM 2 , a group represented by formula: —B(OM) 2 , a group represented by formula: —BR 3 M, a group represented by formula: —B(OR) 3 M, a group represented by formula: —SO 3 M, a group represented by formula: —SO 2 M, a group represented by formula: —NRC(═O)OM, a group represented by formula:

—NRC(═O)SM, a group represented by formula: —NRC(═S)OM, a group represented by formula: —NRC(═S)SM, a group represented by formula: —OC(═O)NM 2 , a group represented by formula: —OC(═O)NRM, a group represented by formula:

—OC(═S)NM 2 , a group represented by formula: —OC(═S)NRM, a group represented by formula: —SC(═O)NM 2 , a group represented by formula: —SC(═O)NRM, a group represented by formula: —SC(═S)NM 2 , a group represented by formula:

—SC(═S)NRM, a group represented by formula: —NRC(═O)NM 2 , a group represented by formula: —NRC(═O)NRM, a group represented by formula: —NRC(═S)NM 2 , a group represented by formula: —NRC(═S)NRM, a group represented by formula:

—NR 3 M′, a group represented by formula: —PR 3 M′, a group represented by formula: —OR 2 M′, a group represented by formula: —SR 2 M′, a group represented by formula: —IRM′, and a heterocyclic group having a cationized nitrogen atom within the heterocycle, wherein R represents a hydrogen atom or an optionally substituted hydrocarbyl group, M represents a metal cation or an optionally substituted ammonium cation, and M′ represents an anion.

6. The metallic composite of claim 3 , wherein the conjugated compound comprises at least one type of group in the Group 1 and at least one type of group in the Group 2.

7. The metallic composite of claim 1 , wherein the conjugated compound comprises a group represented by the formula (I) below, or a repeating unit represented by the formula (II) below, or both of them:

—Ar 1 R 1 (X 1 ) m 1 ) n 1   (I)

wherein

Ar 1 is an (n 1 +1) valent aromatic group,

R 1 is a direct bond or an (m 1 +1) valent group,

X 1 is a hetero atom-containing group,

m 1 and n 1 , which are the same as or different from each other, are an integer of 1 or more, and

when R 1 , X 1 and m 1 are plurally present, they each may be the same as or different from each other;

wherein

Ar 2 is an (n 2 +2) valent aromatic group,

R 2 is a direct bond or an (m 2 +1) valent group,

X 2 is a hetero atom-containing group,

m 2 and n 2 , which are the same as or different from each other, are an integer of 1 or more, and

when R 2 , X 2 and m 2 are plurally present, they each may be the same as or different from each other.

8. The metallic composite of claim 7 , wherein the (n 1 +1) valent aromatic group represented by Ar 1 is a residue remaining after removing (n 1 +1) hydrogen atoms on an aromatic ring of aromatic compounds of the formulae below, the (n 2 +2) valent aromatic group represented by Ar 2 is a residue remaining after removing (n 2 +2) hydrogen atoms on an aromatic ring of aromatic compounds of the formulae below, and the aromatic groups are optionally substituted.

9. The metallic composite of claim 8 , wherein the conjugated compound comprises at least one type of group in the Group 1 and at least one type of group in the Group 2.

10. The metallic composite of claim 1 , wherein the conjugated compound is a macromolecular compound having a repeating unit represented by the following formulae:

wherein n 3 represents an integer of 2 to 30, n 4 represents an integer of 1 to 10, and R represents a hydrogen atom or an optionally substituted hydrocarbyl group.

11. The metallic composite of claim 10 , wherein the conjugated compound is a macromolecular compound having a repeating unit represented by the formula (b-6), (b-34), (b-37), (c-1), (c-2), (c-3), (c-4), (d-38), (d-41) or (d-42).

12. The metallic composite of claim 10 , wherein the metallic nanosheet, the metallic nanorod, or the metallic nanowire is a metallic nanosheet, a metallic nanorod, or a metallic nanowire of a metal of Group 11 of the Periodic Table, respectively.

13. The metallic composite of claim 10 , wherein the metallic nanosheet, the metallic nanorod, or the metallic nanowire is a silver nanosheet, a silver nanorod, or a silver nanowire, respectively.

14. The metallic composite of claim 11 , wherein the metallic nanosheet, the metallic nanorod, or the metallic nanowire is a silver nanosheet, a silver nanorod, or a silver nanowire, respectively.

15. The metallic composite of claim 1 , wherein a peak position measured by an X-ray photoelectron spectrometry for one or more atoms existing in the composite is detected at a peak position attributed to the conjugated compound as well as at a peak position of atoms existing in the metallic nanosheet, the metallic nanorod, or the metallic nanowire and a precursor of metallic nanosheet, metallic nanorod, or metallic nanowire, on a basis of a peak position of Ag3d.

16. The metallic composite of claim 1 , wherein a highest occupied molecular orbital (HOMO) level of the conjugated compound is −4.5 eV or less, where the highest occupied molecular orbital is a value obtained by attaching “− (minus)” to a value of an ionization potential of the conjugated compound measured by a photoelectron spectrometer in the atmosphere.

17. The metallic composite of claim 1 , wherein a lowest unoccupied molecular orbital (LUMO) level of the conjugated compound is −3.5 eV or more, where the lowest unoccupied molecular orbital is a value obtained from an ionization potential of the conjugated compound measured by a photoelectron spectrometer and a HOMO-LUMO gap measured by an ultraviolet-visible-near-infrared spectrophotometer.

18. A composition comprising the metallic composite of claim 1 and a conjugated compound having a molecular weight of 200 or more.

19. A cathode material comprising the metallic composite of claim 1 .

20. A light-emitting device comprising a light-emitting layer between an anode and a cathode, in which the cathode is the metallic composite of claim 1 .

21. A light-emitting device comprising a light-emitting layer between an anode and a cathode, in which the cathode is the composition of claim 18 .

22. A photoelectric conversion device comprising a charge separation layer between an anode and a cathode, in which the cathode is the metallic composite of claim 1 .

23. A photoelectric conversion device comprising a charge separation layer between an anode and a cathode, in which the cathode is the composition of claim 18 .

24. A layered structure comprising a substrate and a layer produced with using the metallic composite of claim 1 formed on the substrate.

25. A method for manufacturing a transparent cathode, characterized by forming a transparent cathode by an application method with using a dispersion liquid of a conductive material having an aspect ratio of 10 or more and a largest diameter of 2000 nm or more.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 6, 2011
From: HIGASHIMURA, HIDEYUKI; IIJIMA, TAKAYUKI; FUJIOKA, MASAHIRO; TANAKA, KENTA
To: SUMITOMO CHEMICAL COMPANY, LIMITED
Reel/Frame 027027/0845 →
Priority Claims (1)
JP 2009-095657 · Apr 10, 2009 · national
Continuity (1)
Related Publication 20120032121A1 · Feb 9, 2012