# US 10,246,776 B2 · Layer-forming device and layer-forming method

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- Number: US 10,246,776 B2
- Document ID: US10246776B2
- Status: Granted
- Kind: B2
- Application number: 14/770,782
- Filed: 2014-02-21
- Published: 2016-01-07
- Granted: 2019-04-02
- Earliest claimed: 2013-02-28
- Assignees: Mitsui E&S Machinery Co., Ltd.
- Applicants: Mitsui Engineering & Shipbuilding Co., Ltd.
- Inventors: Yasunari Mori; Naomasa Miyatake; Nozomu Hattori
- Web page: https://patentgrep.com/patent/US10246776B2

## CPC

- C23C 16/45544: {characterized by the apparatus}
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C23C 16/545: {for coating elongated substrates}
- H01J 37/32091: {the radio frequency energy being capacitively coupled to the plasma}
- H01J 37/32422: {Arrangement for selecting ions or species in the plasma}
- H01J 37/32761: {Continuous moving}
- C03C 2218/153: by plasma-enhanced cvd
- 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)
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- 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 layer-forming device that enables highly efficient layer formation and has a simplified configuration includes: a substrate feeding mechanism; a plasma-generating electrode; a space-partitioning wall; and a plurality of injectors. The plasma-generating electrode faces towards a feeding pathway of the substrate, and generates plasma using a reactive gas upon a supply of electric power. The space-partitioning wall is disposed between the feeding pathway and the plasma-generating electrode. A plurality of slit-shaped through-holes, through which radicals, ions generated from the plasma, or a portion of the plasma can pass, are formed at predetermined intervals in the space-partitioning wall. The plurality of injectors are sandwiched between the space-partitioning wall and the feeding pathway, such that each of the injectors is sandwiched between two adjacent through-holes from both sides of the two through-holes in the feeding direction, and the layer-forming gas is supplied toward the substrate through a layer-forming gas supply port.

## Claims

### Claim 1

A layer-forming device that forms a thin layer in atomic layer unit using a layer-forming gas and a reactive gas, the layer forming device comprising:
a layer-forming container;
a feeding mechanism configured to feed a substrate for layer-forming inside the layer-forming container;
a plasma-generating electrode disposed to face a feeding pathway of the substrate during feeding, the plasma-generating electrode configured to receive a supply of electric power to generate plasma using a reactive gas inside the layer-forming container;
a space-partitioning wall disposed between the feeding pathway of the substrate and the plasma-generating electrode, the space-partitioning wall forming a plasma-generating space between the plasma-generating electrode and the space-partitioning wall, the space-partitioning wall having a plurality of slit-shaped through holes for communicating the plasma-generating space and a space between the feeding pathway of the substrate and the space-partitioning wall, the through holes being disposed at intervals along a feeding direction of the substrate;
gas injectors, each of the gas injectors being disposed between the space-partitioning wall and the feeding pathway, and being sandwiched from both sides of a feeding direction by adjacent through holes of the plurality of through holes, each of the gas injectors including a layer-forming gas supply opening through which the layer-forming gas is supplied to the substrate and a pair of gas exhaust openings through which an excess gas including the supplied layer-forming gas above the substrate is sucked, the layer-forming gas supply opening being sandwiched between the pair of gas exhaust openings in the feeding direction, the layer-forming gas supply opening and the pair of the gas exhaust openings elongated in a lateral direction perpendicular to the feeding direction, having an identical length in the lateral direction respectively; and
a pair of inert gas supply openings through which inert gas is supplied, and the layer-forming gas supply opening and the pair of gas exhaust openings sandwiched between the pair of the inert gas supply openings in the feeding direction, and a member that blocks a portion of each of the inert gas supply openings provided on each of the inert gas supply openings along a lateral direction perpendicular to the feeding direction, the member dividing each of the inert gas supply openings into two sections.

### Claim 2 (depends on 1)

The layer-forming device according to claim 1, wherein an opposing surface of the space-partitioning wall that faces the plasma-generating electrode is composed of a grounding electrode.

### Claim 3 (depends on 2)

The layer-forming device according to claim 2, wherein each of the gas injectors is disposed on a surface of the space-partitioning wall opposite to an opposing surface of the space-partitioning wall that faces the plasma-generating electrode.

### Claim 4 (depends on 3)

The layer-forming device according to claim 3, wherein a gas supply hole for supplying the reactive gas inside the plasma-generating space is disposed in a side wall of the layer-forming container.

### Claim 5 (depends on 2)

The layer-forming device according to claim 2, wherein a gas supply hole for supplying the reactive gas inside the plasma-generating space is disposed in a side wall of the layer-forming container.

### Claim 6 (depends on 2)

The layer-forming device according to claim 2, wherein a dummy injector configured not to supply the layer-forming gas to the substrate is disposed further on a downstream side of the feeding direction than a furthest downstream gas injector positioned at a furthest downstream side of the feeding direction of the substrate, and the dummy injector is disposed so as to be spaced at an interval away from the furthest downstream gas injector, such that a furthest downstream through hole positioned on a furthest downstream side of the feeding direction of the plurality of through holes is positioned between the dummy injector and the furthest downstream injector.

### Claim 7 (depends on 1)

The layer-forming device according to claim 1, wherein each of the gas injectors is disposed on a surface of the space-partitioning wall opposite to an opposing surface of the space-partitioning wall that faces the plasma-generating electrode.

### Claim 8 (depends on 7)

The layer-forming device according to claim 7, wherein a gas supply hole for supplying the reactive gas inside the plasma-generating space is disposed in a side wall of the layer-forming container.

### Claim 9 (depends on 7)

The layer-forming device according to claim 7, wherein a dummy injector configured not to supply the layer-forming gas to the substrate is disposed further on a downstream side of the feeding direction than a furthest downstream gas injector positioned at a furthest downstream side of the feeding direction of the substrate, and the dummy injector is disposed so as to be spaced at an interval away from the furthest downstream gas injector, such that a furthest downstream through hole positioned on a furthest downstream side of the feeding direction of the plurality of through holes is positioned between the dummy injector and the furthest downstream injector.

### Claim 10 (depends on 1)

The layer-forming device according to claim 1, wherein a gas supply hole for supplying the reactive gas inside the plasma-generating space is disposed in a side wall of the layer-forming container.

### Claim 11 (depends on 10)

The layer-forming device according to claim 10, wherein a dummy injector configured not to supply the layer-forming gas to the substrate is disposed further on a downstream side of the feeding direction than a furthest downstream gas injector positioned at a furthest downstream side of the feeding direction of the substrate, and the dummy injector is disposed so as to be spaced at an interval away from the furthest downstream gas injector, such that a furthest downstream through hole positioned on a furthest downstream side of the feeding direction of the plurality of through holes is positioned between the dummy injector and the furthest downstream injector.

### Claim 12 (depends on 1)

The layer-forming device according to claim 1, wherein a dummy injector configured not to supply the layer-forming gas to the substrate is disposed further on a downstream side of the feeding direction than a furthest downstream gas injector positioned at a furthest downstream side of the feeding direction of the substrate, and the dummy injector is disposed so as to be spaced at an interval away from the furthest downstream gas injector, such that a furthest downstream through hole positioned on a furthest downstream side of the feeding direction of the plurality of through holes is positioned between the dummy injector and the furthest downstream injector.

### Claim 13 (depends on 1)

The layer-forming device according to claim 1, wherein the feeding mechanism includes a pair of rotary rollers, the substrate is a long flexible film, and the film is wound onto one rotary roller before feeding.

### Claim 14 (depends on 13)

The layer-forming device according to claim 13, wherein each rotary roller is configured to rotate in different directions.

### Claim 15 (depends on 1)

The layer-forming device according to claim 1, wherein a member that blocks a portion of the layer-forming gas supply opening is provided on the layer-forming gas supply opening along a lateral direction perpendicular to the feeding direction, the member dividing the layer-forming gas supply opening being into two sections.

### Claim 16 (depends on 1)

The layer-forming device according to claim 1, wherein each of the inert gas supply openings is elongated in the lateral direction perpendicular to the feeding direction, having a length in the lateral direction identical to the length of the layer-forming gas supply opening and the pair of the gas exhaust openings.

### Claim 17

A layer-forming method conducted using a layer-forming device that includes:
a layer-forming container,
a feeding mechanism configured to feed a substrate for layer-forming inside the layer-forming container,
a plasma-generating electrode disposed to face a feeding pathway of the substrate during feeding, the plasma-generating electrode configured to receive a supply of electric power to generate plasma using a reactive gas inside the layer-forming container,
a space-partitioning wall disposed between the feeding pathway of the substrate and the plasma-generating electrode, the space-partitioning wall forming a plasma-generating space between the plasma-generating electrode and the space-partitioning wall, the space-partitioning wall having a plurality of slit-shaped through holes for communicating the plasma-generating space and a space between the feeding pathway of the substrate and the space-partitioning wall disposed at intervals along a feeding direction of the substrate, and
gas injectors, each of the gas injectors being disposed between the space-partitioning wall and the feeding pathway, and being sandwiched from both sides of a feeding direction by adjacent through holes of the plurality of through holes, each of the gas injectors including a layer-forming gas supply opening through which the layer-forming gas is supplied to the substrate and a pair of gas exhaust openings through which an excess gas including the supplied layer-forming gas above the substrate is sucked, the layer-forming gas supply opening being sandwiched between the pair of gas exhaust openings in the feeding direction, the substrate being a film from a roll of film, the layer-forming gas supply opening and the pair of the gas exhaust openings elongated in a lateral direction perpendicular to the feeding direction, having an identical length in the lateral direction respectively, and a pair of inert gas supply openings through which inert gas is supplied, and the layer-forming gas supply opening and the pair of gas exhaust openings sandwiched between the pair of the inert gas supply openings in the feeding direction, and a member that blocks a portion of each of the inert gas supply openings provided on each of the inert gas supply openings along a lateral direction perpendicular to the feeding direction, the member dividing each of the inert gas supply openings into two sections,
the layer deposition method comprising:
producing a roll of processed film by unwinding the film from the roll of film, then feeding the film for layer-forming process, and winding the film processed during feeding; and
making a new roll of processed film by again unwinding the processed film from the roll of processed film, then feeding the processed film in order to increase a layer thickness on the processed film, and winding the processed film,
such that a target layer thickness is obtained by repeating the making operation.

### Claim 18 (depends on 17)

The layer-forming method according to claim 17, wherein
in the producing and the making, a plurality of sets of sub-processes are conducted to the film, each set of sub-processes including:
a layer-forming component deposition, in which a layer of a layer-forming component is formed on the film by supplying the layer-forming gas from the gas injector to the film, and
a reaction, in which the layer of the layer-forming component formed on the film is reacted with the plasma or a radical generated from the plasma supplied to the film, and wherein
a final sub-process before winding the film is the reaction.