# US 12,191,193 B2 · Method of manufacturing semiconductor device and film forming apparatus

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- Number: US 12,191,193 B2
- Document ID: US12191193B2
- Status: Granted
- Kind: B2
- Application number: 17/444,775
- Filed: 2021-08-10
- Published: 2022-02-24
- Granted: 2025-01-07
- Earliest claimed: 2020-08-20
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Tatsuya Yamaguchi
- Web page: https://patentgrep.com/patent/US12191193B2

## CPC

- H10W 10/20: Air gaps
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/4412: {Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps}
- C23C 16/45557: {Pulsed pressure or control pressure}
- C23C 16/46: characterised by the method used for heating the substrate (C23C16/48, C23C16/50 take precedence)
- C23C 16/482: {using incoherent light, UV to IR, e.g. lamps}
- C23C 16/509: using internal electrodes
- C23C 16/511: using microwave discharges
- C23C 16/56: After-treatment
- H01J 37/32522: {Temperature}
- H01J 37/32834: {Exhausting}
- H10P 14/6334: {using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition (deposition by physical ablation of a target H10P14/6329)}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/683: {carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC}
- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- H10P 50/287: {by chemical means}
- H10P 72/0432: {mainly by conduction}
- H10P 72/0434: {mainly by convection}
- H10P 72/72: using electrostatic chucks
- H10W 10/021: {of air gaps}
- B05D 1/32: using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
- B05D 1/34: Applying different liquids or other fluent materials simultaneously
- B05D 1/60: {Deposition of organic layers from vapour phase (vapour phase deposition in general C23C14/00, C23C16/00)}
- B05D 1/62: {Plasma-deposition of organic layers (plasma deposition in general C23C14/00, C23C16/00)}
- H01J 2237/3321: CVD [Chemical Vapor Deposition]
- H10P 14/662: {Laminate layers, e.g. stacks of alternating high-k metal oxides (adhesion layers or buffer layers H10P14/6508, H10P14/6548)}
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)

## Abstract

A method of manufacturing a semiconductor includes adjusting a temperature of a substrate having a recess formed therein and accommodated in a container to a temperature within a range of 200 degrees C. or higher and 280 degrees or lower, and laminating a polyurea film in the recess in the substrate by supplying isocyanate gas and amine gas into the container.

## Claims

### Claim 1

A method of manufacturing a semiconductor, the method comprising:
adjusting a temperature of a substrate having recesses formed therein and accommodated in a container to a temperature within a first temperature range of 220 degrees C. or higher and 280 degrees or lower, the recesses including a first recess with a width and a second recess with a width wider than the width of the first recess;
laminating polyurea films in the first recess and the second recess in the substrate at the temperature within the first temperature range by supplying isocyanate gas and amine gas into the container;
removing the polyurea films by stopping supplying the isocyanate gas and the amine gas while maintaining the substrate at the temperature within the first temperature range, the removing the polyurea films being performed such that the polyurea film laminated in the second recess is thermally decomposed;
laminating a sealing film on the substrate; and
desorbing the polyurea film in the first recess by heating the substrate to a temperature within a second temperature range, to form an air gap in the first recess.

### Claim 2 (depends on 1)

The method of claim 1,
wherein the temperature of the desorbing the polyurea film is a temperature higher than 280 degrees C.

### Claim 3 (depends on 2)

The method of claim 2, wherein, in the adjusting the temperature of the substrate, the temperature of the substrate is adjusted to a temperature within a range of 220 degrees C. or higher and 250 degrees C. or lower.

### Claim 4 (depends on 3)

The method of claim 3, wherein, in laminating the polyurea films, each of partial pressures of the isocyanate gas and the amine gas is adjusted to a pressure within a range of 0.01 Torr or higher and 1 Torr or lower.

### Claim 5 (depends on 1)

The method of claim 1, wherein, in the adjusting the temperature of the substrate, the temperature of the substrate is adjusted to a temperature within a range of 220 degrees C. or higher and 250 degrees C. or lower.

### Claim 6 (depends on 1)

The method of claim 1, wherein, in laminating the polyurea films, each of partial pressures of the isocyanate gas and the amine gas is adjusted to a pressure within a range of 0.01 Torr or higher and 1 Torr or lower.

### Claim 7

A film forming apparatus comprising:
a container in which a substrate having a recess formed therein is accommodated;
a gas supply configured to supply isocyanate gas and amine gas into the container;
a heater configured to heat the substrate; and
a controller, wherein the controller is configured to execute:
controlling the heater to adjust a temperature of the substrate having recesses formed therein and accommodated in the container to a temperature within a first temperature range of 220 degrees C. or higher and 280 degrees or lower, the recesses including a first recess with a width and a second recess with a width wider than the width of the first recess;
laminating polyurea films in the first recess and the second recess in the substrate at the temperature within the first temperature range by controlling the gas supply to supply the isocyanate gas and the amine gas into the container;
removing the polyurea films by controlling the gas supply to stop supplying the isocyanate gas and the amine gas while maintaining the substrate at the temperature within the first temperature range, the removing the polyurea films being performed such that the polyurea film laminated in the second recess is thermally decomposed;
laminating a sealing film on the substrate by controlling the gas supply; and
desorbing the polyurea film in the first recess by controlling the heater to heat the substrate to a temperature within a second temperature range, to form an air gap in the first recess.

### Claim 8 (depends on 7)

The film forming apparatus of claim 7, further comprising:
an exhaust duct configured to exhaust the gases in the container;
an exhaust shield provided between a processing space, which is a space in the container and to which the substrate is exposed, and an exhaust space, which is a space in the exhaust duct,
wherein the exhaust shield maintains a pressure in the exhaust space to be lower than the pressure in the processing space.

### Claim 9 (depends on 8)

The film forming apparatus of claim 8, wherein the pressure in the processing space is maintained at a pressure higher than the pressure in the exhaust space by 1 Torr or higher by the exhaust shield.