# US 12,009,217 B2 · Substrate processing method and substrate processing apparatus

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- Number: US 12,009,217 B2
- Document ID: US12009217B2
- Status: Granted
- Kind: B2
- Application number: 17/593,071
- Filed: 2020-03-04
- Published: 2022-06-16
- Granted: 2024-06-11
- Earliest claimed: 2019-03-13
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Tsuyoshi Takahashi; Yu Nunoshige
- Web page: https://patentgrep.com/patent/US12009217B2

## CPC

- H10P 14/418: {the conductive layers comprising transition metals}
- C23C 14/0617: {AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi}
- C23C 16/34: Nitrides {(C23C16/303 takes precedence)}
- C23C 16/4554: {Plasma being used non-continuously in between ALD reactions (C23C16/56 takes precedence)}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/45561: {Gas plumbing upstream of the reaction chamber}
- C23C 16/505: using radio frequency discharges
- C23C 16/5096: {Flat-bed apparatus}
- H01J 37/32082: {Radio frequency generated discharge (H01J37/32357, H01J37/32366, H01J37/32394 and H01J37/32403 take precedence)}
- H01J 37/3244: {Gas supply means}
- H10P 14/432: {using selective deposition}
- H01J 2237/338: Changing chemical properties of treated surfaces
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT 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)

## Abstract

Provided are a substrate processing method and a substrate processing apparatus for forming a low-resistance metal-containing nitride film. The substrate processing method includes: a step of providing a substrate in a processing container; a step of forming a metal-containing nitride film on the substrate by repeating supplying an organic metal-containing gas and a nitrogen-containing gas alternately for a first predetermined number of cycles; a step of modifying the metal-containing nitride film by generating plasma in the processing container; and a step of repeating the step of forming the metal-containing nitride film and the step of modifying the metal-containing nitride film for a second predetermined number of cycles.

## Claims

### Claim 1

A substrate processing method comprising:
providing a substrate in a processing container;
forming a metal-containing nitride film on the substrate by repeating supplying an organic metal-containing gas and a nitrogen-containing gas alternately for a first predetermined number of cycles;
modifying the metal-containing nitride film by generating plasma in the processing container; and
repeating the forming the metal-containing nitride film and the modifying the metal-containing nitride film for a second predetermined number of cycles,
wherein a cycle ratio between the supplying the organic metal-containing gas and the nitrogen-containing gas alternately and the modifying the metal-containing nitride film is in a range of 5:1 to 10:1.

### Claim 2 (depends on 1)

The substrate processing method of claim 1, wherein the organic metal-containing gas is at least one of TDMAT, TEMAT, TDEAT, and a cyclopentadienyl Ti complex.

### Claim 3 (depends on 2)

The substrate processing method of claim 2, wherein the nitrogen-containing gas is at least one of NH3, monomethylhydrazine, and hydrazine.

### Claim 4 (depends on 3)

The substrate processing method of claim 3, further comprising:
stabilizing a pressure in a processing space in the processing container before the plasma is generated.

### Claim 5 (depends on 4)

The substrate processing method of claim 4, wherein, in the modifying the metal-containing nitride film, plasma of ammonia radicals and hydrogen radicals is generated.

### Claim 6 (depends on 1)

The substrate processing method of claim 1, wherein the nitrogen-containing gas is at least one of NH3, monomethylhydrazine, and hydrazine.

### Claim 7 (depends on 1)

The substrate processing method of claim 1, further comprising:
stabilizing a pressure in a processing space in the processing container before the plasma is generated.

### Claim 8 (depends on 1)

The substrate processing method of claim 1, wherein, in the modifying the metal-containing nitride film, plasma of ammonia radicals and hydrogen radicals is generated.