# US 10,865,311 B2 · Coating liquid for forming piezoelectric thin film, method of producing coating liquid for forming piezoelectric thin film, piezoelectric thin film, method of manufacturing piezoelectric thin film, and liquid ejection head

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- Number: US 10,865,311 B2
- Document ID: US10865311B2
- Status: Granted
- Kind: B2
- Application number: 15/493,426
- Filed: 2017-04-21
- Published: 2017-11-23
- Granted: 2020-12-15
- Earliest claimed: 2016-05-18
- Assignees: Canon Kabushiki Kaisha
- Applicants: Canon Kabushiki Kaisha; Fuji Chemical Co., Ltd.
- Inventors: Motokazu Kobayashi; Minako Nakasu; Naoyuki Koketsu; Chiemi Shimizu; Fumio Uchida
- Web page: https://patentgrep.com/patent/US10865311B2

## CPC

- C09D 1/00: Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- B41J 2/161: {of film type, deformed by bending and disposed on a diaphragm}
- B41J 2/164: {thin film formation}
- C23C 18/1216: {Metal oxides (C23C18/1212 takes precedence)}
- C23C 18/1241: {Metallic substrates}
- C23C 18/1283: {Control of temperature, e.g. gradual temperature increase, modulation of temperature}
- C23C 18/1291: {by heating of the substrate}
- H10N 30/078: by sol-gel deposition
- H10N 30/704: {based on piezoelectric or electrostrictive films or coatings}
- H10N 30/8554: {Lead-zirconium titanate [PZT] based}
- B41J 2202/03: Specific materials used
- H10N 30/2047: {Membrane type}
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B41J: TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR

## Abstract

Provided is a coating liquid for forming a piezoelectric thin film containing lead zirconate titanate, the coating liquid including a complex precursor containing at least three kinds of metal elements of Pb, Ti, and Zr, the coating liquid being free from an exothermic peak at a temperature of 450° C. or more, or having a heat generation amount at a temperature of from 400° C. to 450° C., which is larger than a heat generation amount at a temperature of from 450° C. to 500° C., in differential thermal analysis of the coating liquid.

## Claims

### Claim 1

A coating liquid for forming a piezoelectric thin film containing lead zirconate titanate, the coating liquid comprising a complex precursor containing Pb, Ti, and Zr, and at least one selected from the group consisting of 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]non-5-ene, and 1,4-diazabicyclo[2.2.2]octane,
wherein an exothermic peak of the coating liquid is at a temperature of 400° C. to 450° C. in differential thermal analysis of the coating liquid.

### Claim 2 (depends on 1)

The coating liquid according to claim 1, wherein the coating liquid has a peak position of particle size distribution of 100 nm or less.

### Claim 3 (depends on 1)

The coating liquid according to claim 1, wherein the coating liquid is free from a liquid having a boiling point of 100° C. or less.

### Claim 4

A method of producing a coating liquid for forming a piezoelectric thin film, comprising:
heating at least three raw material compounds containing each of Pb, Ti, and Zr, or at least two raw material compounds including a complex raw material compound containing any two of Pb, Ti, and Zr and a raw material compound containing the remaining one of Pb Ti, and Zr, at a temperature of 120° C. or more in an organic solvent, to thereby form a complex metal compound containing Pb, Ti, and Zr; and
hydrolyzing the complex metal compound by adding water to a system after the heating, to thereby form a complex precursor containing Pb, Ti, and Zr;
wherein the heating is performed in the presence of at least one selected from the group consisting of 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]non-5-ene, and 1,4-diazabicyclo[2.2.2]octane, and
wherein an exothermic peak of the coating liquid formed after the hydrolyzing is at a temperature of 400° C. to 450° C. in differential thermal analysis of the coating liquid.

### Claim 5 (depends on 4)

The method according to claim 4, further comprising, after the hydrolyzing:
removing a liquid containing the water, the liquid having a boiling point of 100° C. or less; and
adding an organic solvent having a boiling point of more than 100° C. to the complex precursor, to thereby adjust a concentration of the complex precursor.

### Claim 6

A method of manufacturing a piezoelectric thin film, comprising:
applying a coating liquid for forming a piezoelectric thin film containing lead zirconate titanate onto a substrate, the coating liquid comprising a complex precursor containing Pb, Ti, and Zr, and at least one selected from the group consisting of 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]non-5-ene, and 1,4-diazabicyclo[2.2.2]octane; and
forming the piezoelectric thin film containing lead zirconate titanate by a sol-gel method,
wherein an exothermic peak of the coating liquid is at a temperature of 400° C. to 450° C. in differential thermal analysis of the coating liquid.