# US 7,612,015 B2 · Member having photocatalytic function and method for manufacture thereof

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- Number: US 7,612,015 B2
- Document ID: US7612015B2
- Status: Granted
- Kind: B2
- Application number: 10/499,462
- Filed: 2002-12-24
- Published: 2005-10-20
- Granted: 2009-11-03
- Earliest claimed: 2001-12-21
- Assignees: Nippon Sheet Glass Co., Ltd.
- Inventors: Toshiaki Anzaki; Yoshifumi Kijima; Kenji Mori
- Web page: https://patentgrep.com/patent/US7612015B2

## CPC

- C23C 14/083: {of refractory metals or yttrium}
- A01N 59/16: Heavy metals; Compounds thereof
- B01J 35/39: Photocatalytic properties
- B01J 37/0244: {Coatings comprising several layers}
- C03C 17/3417: {all coatings being oxide coatings}
- C23C 14/024: {Deposition of sublayers, e.g. to promote adhesion of the coating (C23C14/027 takes precedence)}
- C03C 2217/71: Photocatalytic coatings
- C03C 2218/36: Underside coating of a glass sheet
- 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)
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS

## Abstract

A photocatalyst layer (TiO2) is formed on the surface of a substrate (glass plate) through the intermediary of a monoclinic undercoat layer (ZrO2), and no dead layer is substantially present between the photocatalyst layer and the undercoat layer. Also, by providing a peel preventing layer between the substrate and the undercoat layer, it is possible to eliminate film peeling between the photocatalyst layer and the substrate, defects and discoloration. A metal element may be doped in the photocatalyst layer, and it is preferable that the metal element is at least one of Sn, Zn, Mo and Fe. The phrase “no dead layer is substantially present” means that the thickness of the dead layer is 20 nm or less. The thickness of the photocatalyst layer is preferably from 1 nm to 1,000 nm, more preferably from 1 nm to 500 nm.

## Claims

### Claim 1

A member having a photocatalytic function comprising:
a substrate;
an undercoat layer provided on said substrate, the undercoat layer including monoclinic zirconium oxide; and
a photocatalyst layer formed on said undercoat layer, the photocatalyst layer including anatase type titanium dioxide,
wherein said undercoat layer is crystalline, said photocatalyst layer is constituted of a crystalline phase, and no dead layer which is observed as a halo pattern in an electron diffraction image is substantially present between said undercoat layer and said photocatalyst layer,
wherein an electron diffraction image obtained by perpendicularly irradiating a cross section of the undercoat layer includes an electron diffraction image from a (111) orientation plane or a (−111) plane of the monoclinic zirconium oxide, an interplanar spacing with respect to the (111) orientation plane measured by an electron diffraction image or by a bright-field image of a transmission electron microscope (TEM) is 2.6 to 3.0 Å, and an interplanar spacing with respect to the (−111) orientation plane measured by the an electron diffraction image or by a bright field image of a transmission electron microscope (TEM) is 3.0 to 3.5 Å, and wherein at least one of the distances between oxygen atoms in crystals which constitute the undercoat layer is in the range from 90 to 110%with respect to at least one of the distances between oxygen atoms in crystals which constitute the photocatalyst layer.

### Claim 2

A member having a photocatalytic function comprising:
a substrate;
a peel preventing layer, whose main component is an oxide, an oxynitride or a nitride of at least one of silicon and tin, provided on a surface of said substrate;
an undercoat layer provided on said peel preventing layer, the undercoat layer including monoclinic zirconium oxide; and
a photocatalyst layer formed on a surface of said undercoat layer, the photocatalyst layer including anatase type titanium dioxide,
wherein said undercoat layer is crystalline, said photocatalyst layer is constituted of a crystalline phase, and no dead layer which is observed as a halo pattern in an electron diffraction image is substantially present between said undercoat layer and said photocatalyst layer,
wherein an electron diffraction image obtained by perpendicularly irradiating a cross section of the undercoat layer includes an electron diffraction image from a (111) orientation plane or a (−111) plane of the monoclinic zirconium oxide, an interplanar spacing with respect to the (111) orientation plane measured by an electron diffraction image or by a bright-field image of a transmission electron microscope (TEM) is 2.6 to 3.0 Å, and an interplanar spacing with respect to the (−111) orientation plane measured by the an electron diffraction image or by a bright field image of a transmission electron microscope (TEM) is 3.0 to 3.5 Å, and wherein at least one of the distances between oxygen atoms in crystals which constitute the undercoat layer is in the range from 90 to 110%with respect to at least one of the distances between oxygen atoms in crystals which constitute the photocatalyst layer.

### Claim 3 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein said peel preventing layer has a thickness of from 2 nm to 200 nm.

### Claim 4 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein said substrate is a glass plate manufactured by a float process, and said peel preventing layer is a tin modification layer formed on a bottom face of said glass plate at a time of manufacturing said glass plate.

### Claim 5 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein said dead layer has a thickness of 0 nm or more and 20 nm or less.

### Claim 6 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein said photocatalyst layer has a thickness of from 1 nm to 1,000 nm.

### Claim 7 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein said undercoat layer has a thickness of from 1 nm to 500 nm.

### Claim 8 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein particulates which constitute said photocatalyst layer are formed continuously from an interface with the undercoat layer to a surface of the photocatalyst layer.

### Claim 9 (depends on 8)

The member having a photocatalytic function according to claim 8, wherein a width of the particulates which constitute said photocatalyst layer along a direction parallel to the substrate is 5 nm or more.

### Claim 10 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein an electron diffraction image obtained by perpendicularly irradiating a cross section of the photocatalyst layer includes an electron diffraction pattern from the (101) plane of the anatase type titanium oxide, and an interplanar spacing with respect to the (101) orientation plane measured by an electron diffraction image or by a bright-field image of a transmission electron microscope (TEM) is 3.3 to 3.7 Å.

### Claim 11 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein a metal element is doped in said photocatalyst layer.

### Claim 12 (depends on 11)

The member having a photocatalytic function according to claim 11, wherein said metal element is at least one of Sn, Zn and Mo.

### Claim 13 (depends on 11)

The member having a photocatalytic function according to claim 11, wherein an addition amount of said metal element is 0.1 mass % or more and 1.0 mass % or less.

### Claim 14 (depends on 11)

The member having a photocatalytic function according to claim 11, wherein an addition amount of said metal element is 0.2 mass % or more and 0.5 mass % or less.

### Claim 15 (depends on 11)

The member having a photocatalytic function according to claim 11, wherein said metal element is Fe and an addition amount thereof is 0.001 mass % or more and 1.0 mass % or less.

### Claim 16 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein a hydrophilic thin film is formed on the surface of said photocatalyst layer.

### Claim 17 (depends on 16)

The member having a photocatalytic function according to claim 16, wherein said hydrophilic thin film is made of at least one oxide selected from the group consisting of silicon oxide, zirconium oxide, germanium oxide and aluminum oxide.

### Claim 18 (depends on 17)

The member having a photocatalytic function according to claim 17, wherein said hydrophilic thin film is made of silicon oxide.

### Claim 19 (depends on 16)

The member having a photocatalytic function according to claim 16, wherein said hydrophilic thin film is porous.

### Claim 20 (depends on 16)

The member having a photocatalytic function according to claim 16, wherein said hydrophilic thin film has a thickness of 1 nm or more and 30 nm or less.

### Claim 21 (depends on 16)

The member having a photocatalytic function according to claim 16, wherein said hydrophilic thin film has a thickness of 1 nm or more and 20 nm or less.

### Claim 22 (depends on 2)

The member having a photocatalytic function according to claim 2, wherein at least said undercoat layer and said photocatalyst layer are formed by a vapor phase method.

### Claim 23 (depends on 22)

The member having a photocatalytic function according to claim 22, wherein said vapor phase method is a sputtering method.

### Claim 24

A method for manufacturing a photocatalytic member comprising the steps of:
forming a peel preventing layer whose main component is an oxide, an oxynitride or a nitride containing at least one of silicon and tin on the surface of a substrate;
forming an undercoat layer including monoclinic zirconium oxide at low temperature on said peel preventing layer; and
forming a photocatalyst layer including anatase type titanium dioxide on said undercoat layer, wherein said undercoat layer is crystalline, said photocatalyst layer is constituted of a crystalline phase, and no dead layer which is observed as a halo pattern in an electron diffraction image is substantially present between said undercoat layer and said photocatalyst layer,
wherein an electron diffraction image obtained by perpendicularly irradiating a cross section of the undercoat layer includes an electron diffraction image from a (111) orientation plane or a (−111) plane of the monoclinic zirconium oxide, an interplanar spacing with respect to the (111) orientation plane measured by an electron diffraction image or by a bright-field image of a transmission electron microscope (TEM) is 2.6 to 3.0 Å, and an interplanar spacing with respect to the (−111) orientation plane measured by the an electron diffraction image or by a bright field image of a transmission electron microscope (TEM) is 3.0 to 3.5 Å.

### Claim 25 (depends on 24)

The method for manufacturing a photocatalytic member according to claim 24, wherein said undercoat layer is formed at temperature of 150C. or below.

### Claim 26 (depends on 24)

The method for manufacturing a photocatalytic member according to claim 24, wherein said undercoat layer is formed by a sputtering method.