# US 9,520,295 B2 · Metal doping of amorphous carbon and silicon films used as hardmasks in substrate processing systems

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- Number: US 9,520,295 B2
- Document ID: US9520295B2
- Status: Granted
- Kind: B2
- Application number: 14/612,750
- Filed: 2015-02-03
- Published: 2016-08-04
- Granted: 2016-12-13
- Earliest claimed: 2015-02-03
- Assignees: Lam Research Corporation
- Applicants: Lam Research Corporation
- Inventors: Fayaz Shaikh; Sirish Reddy; Alice Hollister
- Web page: https://patentgrep.com/patent/US9520295B2

## CPC

- C23C 16/458: characterised by the method used for supporting substrates in the reaction chamber
- C23C 16/24: Deposition of silicon only
- C23C 16/26: Deposition of carbon only
- C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)}
- C23C 16/52: Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)}
- H01J 37/32082: {Radio frequency generated discharge (H01J37/32357, H01J37/32366, H01J37/32394 and H01J37/32403 take precedence)}
- H01J 37/32449: {Gas control, e.g. control of the gas flow}
- H10P 14/416: {of highly doped semiconductor materials, e.g. polysilicon layers or amorphous silicon layers}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6902: {composed of carbon, e.g. alpha-C, diamond or hydrogen doped carbon}
- H10P 76/40: of masks comprising inorganic materials
- 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

## Abstract

Systems and methods for depositing a metal-doped amorphous carbon hardmask film or a metal-doped amorphous silicon hardmask film includes arranging a substrate in a processing chamber; supplying a carrier gas to the processing chamber; supplying a hydrocarbon precursor gas or a silicon precursor gas to the processing chamber, respectively; supplying a metal-based precursor gas to the processing chamber; one of creating or supplying plasma in the processing chamber; and depositing a metal-doped amorphous carbon hardmask film or a metal-doped amorphous silicon hardmask film on the substrate, respectively.

## Claims

### Claim 1

A method for depositing a metal-doped amorphous carbon hardmask film, comprising:
arranging a substrate on a pedestal in a processing chamber;
supplying a carrier gas to the processing chamber;
supplying a hydrocarbon precursor gas to the processing chamber;
supplying a metal-based precursor gas to the processing chamber;
providing, to the pedestal, first RF power at a first frequency;
providing, to the pedestal, second RF power at a second frequency less than the first frequency;
one of creating plasma in or supplying plasma to the processing chamber; and
depositing a metal-doped amorphous carbon hardmask film on the substrate, wherein the carbon hardmask film includes metal carbide.

### Claim 2 (depends on 1)

The method of claim 1, wherein the processing chamber comprises a plasma enhanced chemical vapor deposition (PECVD) processing chamber.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metal-based precursor gas comprises a metal halide precursor gas.

### Claim 4 (depends on 3)

The method of claim 3 wherein the metal halide precursor gas is selected from a group consisting of WFa, TiClb, WClC, HfCld, and TaCle, where a, b, c, d and e are integers greater than or equal to one.

### Claim 5 (depends on 1)

The method of claim 1, wherein the metal-based precursor gas comprises tetrakis(dimethylamino)titanium (TDMAT) precursor gas.

### Claim 6 (depends on 1)

The method of claim 1, wherein the metal-based precursor gas comprises bis(tert-butylimido)-bis-(dimethylamido)tungsten (BTBMW) precursor gas.

### Claim 7 (depends on 1)

The method of claim 1, wherein the carrier gas is selected from a group consisting of molecular hydrogen (H2), argon (Ar), molecular nitrogen (N2), helium (He), and/or combinations thereof.

### Claim 8 (depends on 1)

The method of claim 1, wherein the hydrocarbon precursor gas comprises CxHy, wherein x is an integer from 2 to 10 and y is an integer from 2 to 24.

### Claim 9 (depends on 1)

The method of claim 1, wherein the hydrocarbon precursor gas is selected from a group consisting of methane, acetylene, ethylene, propylene, butane, cyclohexane, benzene and toluene.

### Claim 10 (depends on 1)

The method of claim 1, wherein the metal-based precursor gas comprises tungsten hexafluoride, the hydrocarbon precursor gas comprises methane and the carrier gas comprises molecular hydrogen.

### Claim 11

A method for depositing a metal-doped amorphous silicon hardmask film, comprising:
arranging a substrate in a processing chamber;
supplying a carrier gas to the processing chamber;
supplying a silicon precursor gas to the processing chamber;
supplying a metal-based precursor gas to the processing chamber;
one of creating plasma in or supplying plasma to the processing chamber; and
depositing a metal-doped amorphous silicon hardmask film on the substrate.

### Claim 12 (depends on 11)

The method of claim 11, wherein the processing chamber comprises a plasma enhanced chemical vapor deposition (PECVD) processing chamber.

### Claim 13 (depends on 11)

The method of claim 11, wherein the metal-based precursor gas comprises a metal halide precursor gas.

### Claim 14 (depends on 13)

The method of claim 13, wherein the metal halide precursor gas is selected from a group consisting of WFa, TiClb, WClc, HfCld, and TaCle, where a, b, c, d and e are integers greater than or equal to one.

### Claim 15 (depends on 11)

The method of claim 11, wherein the metal-based precursor gas comprises tetrakis(dimethylamino)titanium (TDMAT) precursor gas.

### Claim 16 (depends on 11)

The method of claim 11, wherein the metal-based precursor gas comprises bis(tert-butylimido)-bis-(dimethylamido)tungsten (BTBMW) precursor gas.

### Claim 17 (depends on 11)

The method of claim 11, wherein the carrier gas is selected from a group consisting of molecular hydrogen (H2), argon (Ar), molecular nitrogen (N2), helium (He), and/or combinations thereof.

### Claim 18 (depends on 11)

The method of claim 11, wherein the silicon precursor gas is selected from a group consisting of silane and tetraethylorthosilicate.

### Claim 19

A substrate processing system for depositing a metal-doped amorphous carbon hardmask film, comprising:
a processing chamber including a substrate support configured to support a substrate;
a gas supply system configured to selectively supply process gas to the processing chamber;
a plasma generator configured to selectively create plasma in or supply plasma to the processing chamber;
a controller configured to control the gas supply system and the plasma generator and configured to:
supply a carrier gas to the processing chamber;
supply a hydrocarbon precursor gas to the processing chamber;
supply a metal-based precursor gas to the processing chamber;
provide, to the substrate support, first RF power at a first frequency;
provide, to the substrate support, second RF power at a second frequency less than the first frequency;
control the plasma generator to create plasma in or supply plasma to the processing chamber; and
deposit a metal-doped amorphous carbon hardmask film on the substrate, wherein the carbon hardmask film includes metal carbide.

### Claim 20 (depends on 19)

The substrate processing system of claim 19, wherein the processing chamber comprises a plasma enhanced chemical vapor deposition (PECVD) processing chamber.

### Claim 21 (depends on 19)

The substrate processing system of claim 19, wherein the metal-based precursor gas comprises a metal halide precursor gas.

### Claim 22 (depends on 21)

The substrate processing system of claim 21, wherein the metal halide precursor gas is selected from a group consisting of WFa, TiClb, WClc, HfCld, and TaCle, where a, b, c, d and e are integers greater than or equal to one.

### Claim 23 (depends on 19)

The substrate processing system of claim 19, wherein the metal-based precursor gas comprises tetrakis(dimethylamino)titanium (TDMAT) precursor gas.

### Claim 24 (depends on 19)

The substrate processing system of claim 19, wherein the metal-based precursor gas comprises bis(tert-butylimido)-bis-(dimethylamido)tungsten (BTBMW) precursor gas.

### Claim 25 (depends on 19)

The substrate processing system of claim 19, wherein the carrier gas is selected from a group consisting of molecular hydrogen (H2), argon (Ar), molecular nitrogen (N2), helium (He), and/or combinations thereof.

### Claim 26 (depends on 19)

The substrate processing system of claim 19, wherein the hydrocarbon precursor gas comprises CxHy, wherein x is an integer from 2 to 10 and y is an integer from 2 to 24.

### Claim 27 (depends on 19)

The substrate processing system of claim 19, wherein the hydrocarbon precursor gas is selected from a group consisting of methane, acetylene, ethylene, propylene, butane, cyclohexane, benzene and toluene.

### Claim 28 (depends on 19)

The substrate processing system of claim 19, wherein the metal-based precursor gas comprises tungsten hexafluoride, the hydrocarbon precursor gas comprises methane and the carrier gas comprises molecular hydrogen.

### Claim 29

A substrate processing system for depositing a metal-doped amorphous silicon hardmask film, comprising:
a processing chamber including a substrate support configured to support a substrate;
a gas supply system configured to selectively supply process gas to the processing chamber;
a plasma generator configured to selectively create plasma in or supply plasma to the processing chamber;
a controller configured to control the gas supply system and the plasma generator and configured to:
supply a carrier gas to the processing chamber;
supply a silicon precursor gas to the processing chamber;
supply a metal-based precursor gas to the processing chamber;
control the plasma generator to create plasma in or supply plasma to the processing chamber; and
deposit a metal-doped amorphous silicon hardmask film on the substrate.

### Claim 30 (depends on 29)

The substrate processing system of claim 29, wherein the processing chamber comprises a plasma enhanced chemical vapor deposition (PECVD) processing chamber.

### Claim 31 (depends on 29)

The substrate processing system of claim 29, wherein the metal-based precursor gas comprises a metal halide precursor gas.

### Claim 32 (depends on 31)

The substrate processing system of claim 31, wherein the metal halide precursor gas is selected from a group consisting of WFa, TiClb, WClc, HfCld, and TaCle, where a, b, c, d and e are integers greater than or equal to one.

### Claim 33 (depends on 29)

The substrate processing system of claim 29, wherein the metal-based precursor gas comprises tetrakis(dimethylamino)titanium (TDMAT) precursor gas.

### Claim 34 (depends on 29)

The substrate processing system of claim 29, wherein the metal-based precursor gas comprises bis(tert-butylimido)-bis-(dimethylamido)tungsten (BTBMW) precursor gas.

### Claim 35 (depends on 29)

The substrate processing system of claim 29, wherein the carrier gas is selected from a group consisting of molecular hydrogen (H2), argon (Ar), molecular nitrogen (N2), helium (He), and/or combinations thereof.

### Claim 36 (depends on 29)

The substrate processing system of claim 29, wherein the silicon precursor gas is selected from a group consisting of silane and tetraethylorthosilicate.