Miniature reference electrode

• US 6,419,809 B1
• Filed: 03/24/2000
• Issued: 07/16/2002
• Est. Priority Date: 06/24/1999
• Status: Expired due to Fees

• Current Assignee: Katayanagi Institute
• Original Assignee: Katayanagi Institute
• Inventors: Karube, Masao, Suzuki, Hiroaki
• Primary Examiner(s): Tung, T.
• Application Number:
  US09/535,906
• Time in Patent Office: 844 Days
• Field of Search: 204/402, 204/420, 204/435
• US Class Current: 204/435
• CPC Class Codes: G01N 27/301 Reference electrodes
• CPC Class Codes: G01N 27/401 Salt-bridge leaks; Liquid junctions

Abstract

A miniature reference electrode with improved stability and durability formed of a miniature silver/silver chloride reference electrode with high stability and general applicability as a reference electrode. The miniature reference electrode includes, on electrode substrate, a thin-film backbone metal pattern and a thin-film silver pattern formed in electrical contact with a portion of the thin-film backbone metal pattern. A silver chloride layer is set on a portion of the thin-film silver pattern. The silver chloride layer is in contact with a portion of thin-film electrolyte layer via hydrophobic thin-film insulating layer. The thin-film electrolyte layer is impregnated with a saturated solution of potassium chloride for making contact to the outside via a thin-film liquid junction pattern. When in use, the thin-film liquid junction pattern (31) is impregnated with the electrolyte, while its end portion is recessed in an aqueous solution.

Claims

1. A miniature reference electrode, comprising:

a thin-film backbone metal pattern set on an electrode substrate;

a thin-film electrode metal pattern on said thin-film backbone metal pattern and in electrical contact with a portion of said thin-film backbone metal pattern;

a metal salt region on a portion of said thin-film electrode metal pattern and made of a salt of the structural metal of said thin-film electrode metal pattern;

a thin-film electrolyte layer impregnated with a saturated solution of an electrolyte having an anion common with an anion of the metal salt of said metal salt region;

a hydrophobic layer intervening between said metal salt region and said electrolyte layer, said hydrophobic layer having at least one opening which cause a portion of the electrolyte layer to be in contact with the metal salt region; and

a thin-film liquid junction pattern in contact with a portion of said thin-film electrolyte layer and impregnated with an electrolyte solution containing the electrolyte of said thin-film electrolyte layer.

2. The miniature electrode of claim 1, further comprising a protective film covering the electrode, at least a portion of said thin-film backbone metal pattern is exposed through the protective film as the electrode terminal portion, and a portion of said thin-film liquid junction pattern is exposed through the protective film as a contact portion with the external liquid.

3. The miniature reference electrode of claim 2 wherein said thin-film electrolyte layer comprises a thin-film electrolyte layer having said electrolyte carried in the form of solid particles.

4. The miniature reference electrode of claim 1 wherein the metal of said thin-film electrode metal pattern is formed of silver, the metal salt of said metal salt region is silver chloride, and the electrolyte of said thin-film electrolyte layer is potassium chloride.

5. The miniature reference electrode of claim 4 wherein the metal of said thin-film backbone metal pattern is gold.

6. The miniature reference electrode of claim 1, further comprising a plurality of holes formed in said thin-film electrode metal pattern, and, as said hydrophobic thin-film insulating layer is bonded with said electrode substrate through said plurality of holes, the adhesion of said thin-film electrode metal pattern on said electrode substrate is increased.

7. The miniature reference electrode of claim 1, further comprising, on the electrode substrate, an auxiliary electrode pattern formed from another metal pattern and a thin-film insulating layer.

8. A one-touch potentiometric sensor comprising,

a miniature reference electrode, said reference electrode comprising:

a thin-film backbone metal patter set on an electrode substrate;

a thin-film electrode metal pattern on said thin-film backbone metal pattern and in electrical contact with a portion of said thin-film backbone metal pattern;

a metal salt region on a portion of said thin-film electrode metal pattern and made of a salt of the structural metal of said thin-film electrode metal pattern;

a thin-film electrolyte layer impregnated with a saturated solution of an electrolyte of said metal salt region;

a hydrophobic layer intervening between said metal salt region and said electrolyte layer, said hydrophobic layer having at least one opening which causes a portion of the electrolyte layer to be in contact with the metal salt region;

a thin-film liquid junction pattern in contact with a portion of said thin-film electrolyte layer and impregnated with an electrolyte solution containing the electrolyte of said thin-film electrolyte layer;

said potentiometric sensor further comprising a sensor based on the potentiometric measurement principle integrated with the miniature reference electrode.

9. A one-touch electrochemical measurement system comprising:

a function electrode;

a counter electrode; and

a miniature reference electrode integrated on a single chip, the miniature reference electrode comprising;

a thin-film backbone metal pattern set on an electrode substrate;

a thin-film electrode metal pattern on said thin-film backbone metal pattern and in electrical contact with a portion of said thin-film backbone metal pattern;

a metal salt region on a portion of said thin-film electrode metal pattern and made of a salt of the structural metal of said thin-film electrode metal pattern;

a thin-film electrolyte layer impregnated with a saturated solution of an electrolyte having an anion common with an anion of the metal salt of said metal salt region;

a hydrophobic layer intervening between said metal salt region and said electrolyte layer, said hydrophobic layer having at least one opening which causes a portion of the electrolyte layer to be in contact with the metal salt region; and

a thin-film liquid junction pattern in contact with a portion of said thin-film electrolyte layer and impregnated with an electrolyte solution containing the electrolyte of said thin-film electrolyte layer.

10. A method for prolonging the lifetime of a miniature reference electrode made of plural thin-film layers, comprising:

forming a thin-film electrode metal pattern, with a portion of the thin-film electrode metal pattern formed of a metal salt region made of a salt of the structural metal of the thin-film electrode metal pattern, with the metal salt region exposed on the surface of the thin-film electrode metal pattern;

forming a thin-film electrolyte layer impregnated with a saturated solution of an electrolyte having an anion common with an anion of the metal salt of said metal salt region, the metal salt region being in contact with a portion of the thin-film electrolyte layer which has said electrolyte carried in the form of solid particles;

forming a portion of said thin-film electrolyte layer to include a liquid junction exposed to the exterior of the miniature reference electrode; and

forming a hydrophobic layer intervening between said metal salt region and said electrolyte layer, said hydrophobic layer having at least one opening which provides the contact between the electrolyte layer and the metal salt region.

11. A miniature reference electrode, comprising:

a thin-film backbone metal pattern set on an electrode substrate;

a thin-film electrode metal pattern on said thin-film backbone metal pattern and in electrical contact with a portion of said thin-film backbone metal pattern;

a metal salt region on a portion of said electrode metal pattern and made of a salt of the structural metal of said thin-film electrode metal pattern;

a thin-film electrolyte layer impregnated with a saturated solution of an electrolyte having an anion common with an anion of the metal salt of said metal salt region;

a hydrophobic layer intervening between said metal salt region and said electrolyte layer, said hydrophobic layer having at least one opening which causes a portion of the electrolyte layer to be in contact with the metal salt region;

a thin film liquid junction pattern in contact with a portion of said thin-film electrolyte layer and impregnated with an electrolyte solution containing the electrolyte of said thin-film electrolyte layer; and

a protective film covering the electrode, at least a portion of the thin-film backbone metal pattern exposed through the protective film as an electrode terminal portion, and a portion of the thin-film liquid junction pattern exposed through the protective film as a contact portion with an external liquid.