Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film

• US 20030148871A1
• Filed: 11/25/2002
• Published: 08/07/2003
• Est. Priority Date: 08/31/1998
• Status: Active Grant

• Current Assignee: Idemitsu Kosan Company Limited
• Original Assignee: Idemitsu Kosan Company Limited
• Inventors: Inoue, Kazuyoshi
• Granted Patent: US 6,689,477 B2
• Time in Patent Office: Days
• US Class Current: 501/134
• CPC Class Codes: C03C 17/2453 Coating containing SnO2
• CPC Class Codes: C03C 2217/23 Mixtures
• CPC Class Codes: C03C 2217/231 In2O3/SnO2
• CPC Class Codes: C03C 2218/154 by sputtering
• CPC Class Codes: C04B 2235/3239 Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
• CPC Class Codes: C04B 2235/3251 Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3256 Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
• CPC Class Codes: C04B 2235/3262 Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
• CPC Class Codes: C04B 2235/3284 Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
• CPC Class Codes: C04B 2235/3286 Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
• CPC Class Codes: C04B 2235/3289 Noble metal oxides
• CPC Class Codes: C04B 2235/3293 Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
• CPC Class Codes: C04B 2235/763 Spinel structure AB2O4
• CPC Class Codes: C04B 2235/767 Hexagonal symmetry, e.g. beta-Si3N4, beta-Sialon, alpha-SiC or hexa-ferrites
• CPC Class Codes: C04B 2235/77 Density
• CPC Class Codes: C04B 2235/80 Phases present in the sintered or melt-cast ceramic products other than the main phase
• CPC Class Codes: C04B 2235/96 Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
• CPC Class Codes: C04B 2235/9653 Translucent or transparent ceramics other than alumina
• CPC Class Codes: C04B 35/01 based on oxide ceramics
• CPC Class Codes: C04B 35/453 based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
• CPC Class Codes: C04B 35/457 : based on tin oxides or stannates
• CPC Class Codes: C08J 2369/00 : Characterised by the use of polycarbonates; Derivatives of polycarbonates
• CPC Class Codes: C08J 7/0423 : with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
• CPC Class Codes: C08J 7/044 : Forming conductive coatings; Forming coatings having anti-static properties
• CPC Class Codes: C23C 14/086 : of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 14/3414 : Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
• CPC Class Codes: G02F 1/13439 : characterised by their electrical, optical, physical properties; materials therefor; method of making
• CPC Class Codes: H01L 31/022466 : made of transparent conductive layers, e.g. TCO, ITO layers
• CPC Class Codes: H10K 50/81 : Anodes

Abstract

The invention includes sintered products for transparent electroconductive films, which are formed into films in a stable and efficient manner through sputtering or the like, sputtering targets of the sintered products, and transparent electroconductive glass and films formed from the targets. The transparent electroconductive glass and films have good transparency, good electroconductivity and good workability into electrodes, and are therefore favorable to transparent electrodes in organic electroluminescent devices as realizing good hole injection efficiency therein. The sintered products contain constituent components of indium oxide, tin oxide and zinc oxide in specific atomic ratios of the metal atoms, and optionally contain specific metal oxides of ruthenium oxide, molybdenum oxide, vanadium oxide, etc.

Claims

1. A sintered product that comprises constituent components of indium oxide, tin oxide and zinc oxide in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.20 to 0.45, Zn/(In+Sn+Zn)=0.03 to 0.30,

and contains a hexagonal layer compound of In₂O₃.(ZnO)m with m indicating an integer of from 2 to 20, and a spinel-structured compound of Zn₂SnO₄.

2. The sintered product as claimed in claim 1, which has a specific resistance of smaller than 2 mΩ

·

cm.

5. A sputtering target for transparent electroconductive films, which comprises the sintered product of any of claims 1 to 4.

6. An electron-beaming target for transparent electroconductive films, which comprises the sintered product of any of claims 1 to 4.

7. An ion-plating target for transparent electroconductive films, which comprises the sintered product of any of claims 1 to 4.

3. A sintered product that comprises constituent components of indium oxide, tin oxide and zinc oxide in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.20 to 0.45, Zn/(In+Sn+Zn)=0.03 to 0.30,

and from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of an oxide of a positive tetra-valent or higher poly-valent metal, and contains a hexagonal layer compound of In₂O₃.(ZnO)m with m indicating an integer of from 2 to 20, and a spinel-structured compound of Zn₂SnO₄.

4. The sintered product as claimed in claim 3, in which the oxide of a positive tetra-valent or higher poly-valent metal is ruthenium oxide, molybdenum oxide or vanadium oxide.

8. Transparent electroconductive glass prepared by coating the surface of glass with an amorphous transparent electroconductive film that comprises constituent components of indium oxide, tin oxide and zinc oxide in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.20 to 0.45, Zn/(In+Sn+Zn)=0.03 to 0.30,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of an oxide of a positive tetra-valent or higher poly-valent metal.

9. The transparent electroconductive glass as claimed in claim 8, in which the oxide of a positive tetra-valent or higher poly-valent metal is ruthenium oxide, molybdenum oxide or vanadium oxide.

10. The transparent electroconductive glass as claimed in claim 8 or 9, which has a light transmittance of at least 75% and a specific resistance of at most 5 mΩ

·

cm, and in which the transparent electroconductive film has a work function of at least 5.45.

11. A transparent electroconductive film prepared by coating the surface of a transparent resin film with an amorphous transparent electroconductive layer that comprises constituent components of indium oxide, tin oxide and zinc oxide in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.20 to 0.45, Zn/(In+Sn+Zn)=0.03 to 0.30,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of an oxide of a positive tetra-valent or higher poly-valent metal.

12. The transparent electroconductive film as claimed in claim 11, in which the oxide of a positive tetra-valent or higher poly-valent metal is ruthenium oxide, molybdenum oxide or vanadium oxide.

13. The transparent electroconductive film as claimed in claim 11 or 12, which has a light transmittance of at least 75% and a specific resistance of at most 5 mΩ

·

cm, and in which the transparent electroconductive layer has a work function of at least 5.45.

17. A sputtering target comprising the sintered product of any of claims 13 to 16.

18. An electron-beaming target comprising the sintered product of any of claims 13 to 16.

19. An ion-plating target comprising the sintered product of any of claims 13 to 16.

14. A sintered product of a composition that comprises indium oxide, or indium oxide and zinc oxide and/or tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00, Zn/(In+Zn+Sn)=0.00 to 0.20, Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of a metal oxide selected from ruthenium oxide, molybdenum oxide and vanadium oxide.

15. A sintered product of a composition that comprises indium oxide and zinc oxide, or tin oxide in addition to the former two oxides in the following atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00, Zn/(In+Zn+Sn)=0.05 to 0.20, Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of a metal oxide selected from ruthenium oxide, molybdenum oxide and vanadium oxide.

16. A sintered product of a composition that comprises indium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00, Zn/(In+Zn+Sn)=0.05 to 0.20, Sn/(In+Zn+Sn)=0.02 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of a metal oxide selected from ruthenium oxide, molybdenum oxide and vanadium oxide.

20. Transparent electroconductive glass prepared by coating the surface of glass with a transparent electroconductive film of a composition that comprises indium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00, Zn/(In+Zn+Sn)=0.00 to 0.20, Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of a metal oxide selected from ruthenium oxide, molybdenum oxide and vanadium oxide.

21. The transparent electroconductive glass as claimed in claim 20, which has a light transmittance of at least 75% and a specific resistance of at most 5 mΩ

·

cm, and in which the transparent electroconductive film has a work function of at least 5.45 electron volts.

22. A transparent electroconductive film prepared by coating the surface of a transparent resin film with a transparent electroconductive layer that comprises indium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00, Sn/(In+Zn+Sn)=0.00 to 0.20, Zn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of a metal oxide selected from ruthenium oxide, molybdenum oxide and vanadium oxide.

23. The transparent electroconductive film as claimed in claim 22, which has a light transmittance of at least 75% and a specific resistance of at most 5 mΩ

·

cm, and in which the transparent electroconductive layer has a work function of at least 5.45 electron volts.

24. A transparent electroconductive material of a composition that comprises one or more metal oxides selected from indium oxide, zinc oxide and tin oxide and contains from 0.5 to 20 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide.

28. A sintered product prepared by sintering the composition of any of claims 24 to 27.

29. A sputtering target comprising the sintered product of claim 28.

25. A transparent electroconductive material of a composition that comprises metal oxide(s) of indium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.00 to 1.00, Zn/(In+Zn+Sn)=0.00 to 0.25, Sn/(In+Zn+Sn)=0.00 to 1.00,

and contains from 0.5 to 20 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide.

26. A transparent electroconductive material of a composition that comprises metal oxides of indium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.50 to 1.00, Zn/(In+Zn+Sn)=0.05 to 0.25, Sn/(In+Zn+Sn)=0.00 to 0.50,

and contains from 0.5 to 20 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide.

27. A transparent electroconductive material of a composition that comprises metal oxides of indium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.75 to 0.95, Zn/(In+Zn+Sn)=0.05 to 0.20, Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 20 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide.

30. Transparent electroconductive glass prepared by coating the surface of glass with a transparent electroconductive film of a composition that comprises one or more metal oxides selected from indium oxide, zinc oxide and tin oxide and contains from 0.5 to 20 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide.

31. The transparent electroconductive glass as claimed in claim 30, which has a light transmittance of at least 70% and in which the transparent electroconductive film has a work function of at least 5.4 electron volts.

32. A transparent electroconductive film prepared by coating the surface of a transparent resin film with a transparent electroconductive layer that comprises one or more metal oxides selected from indium oxide, zinc oxide and tin oxide and contains from 0.5 to 20 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from iridium oxide, rhenium oxide and palladium oxide.

33. The transparent electroconductive film as claimed in claim 32, which has a light transmittance of at least 70% and in which the transparent electroconductive layer has a work function of at least 5.4 electron volts.

34. A transparent electroconductive material of a composition that comprises metal oxide(s) of tin oxide, indium oxide and zinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 1.00, In/(Sn+In+Zn)=0.00 to 0.45, Zn/(Sn+In+Zn)=0.00 to 0.25,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from vanadium oxide, molybdenum oxide and ruthenium oxide.

35. The transparent electroconductive material as claimed in claim 34, in which tin oxide, indium oxide and zinc oxide are in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 0.95, In/(Sn+In+Zn)=0.00 to 0.40, Zn/(Sn+In+Zn)=0.05 to 0.25.

36. The transparent electroconductive material as claimed in claim 34, in which tin oxide, indium oxide and zinc oxide are in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 0.95, In/(Sn+In+Zn)=0.00 to 0.40, Zn/(Sn+In+Zn)=0.05 to 0.20.

37. The transparent electroconductive material as claimed in claim 34, in which tin oxide, indium oxide and zinc oxide are in the following atomic ratios:

Sn/(Sn+In+Zn)=0.60 to 0.95, In/(Sn+In+Zn)=0.00 to 0.35, Zn/(Sn+In+Zn)=0.05 to 0.20.

38. A sintered product prepared by sintering the composition of any of claims 34 to 37 at a temperature of not lower than 1200°

C.

39. A sputtering target comprising the sintered product of claim 38, which has a specific resistance of at most 10 mΩ

·

cm.

40. Transparent electroconductive glass prepared by forming, on the surface of a glass substrate, a transparent electroconductive film of a composition that comprises metal oxide(s) of tin oxide, indium oxide and zinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 1.00, In/(Sn+In+Zn)=0.00 to 0.45, Zn/(Sn+In+Zn)=0.00 to 0.25,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from vanadium oxide, molybdenum oxide and ruthenium oxide.

41. The transparent electroconductive glass as claimed in claim 40, in which the transparent electroconductive film has a light transmittance of at least 70% and a work function of at least 5.4 electron volts.

42. A transparent electroconductive film prepared by forming, on the surface of a transparent resin film, a transparent electroconductive layer of a composition that comprises metal oxide(s) of tin oxide, indium oxide and zinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 1.00, In/(Sn+In+Zn)=0.00 to 0.45, Zn/(Sn+In+Zn)=0.00 to 0.25,

and contains from 0.5 to 10 atomic %, relative to the total of all metal atoms therein, of one or more metal oxides selected from vanadium oxide, molybdenum oxide and ruthenium oxide.

43. The transparent electroconductive film as claimed in claim 42, in which the transparent electroconductive layer has a light transmittance of at least 70% and a work function of at least 5.4 electron volts.