# US 7,611,995 B2 · Method for removing silicon oxide film and processing apparatus

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- Number: US 7,611,995 B2
- Document ID: US7611995B2
- Status: Granted
- Kind: B2
- Application number: 10/552,262
- Filed: 2004-04-20
- Published: 2006-09-28
- Granted: 2009-11-03
- Earliest claimed: 2003-04-22
- Assignees: Tokyo Electron Limited
- Inventors: Kazuhide Hasebe; Mitsuhiro Okada; Takashi Chiba; Jun Ogawa
- Web page: https://patentgrep.com/patent/US7611995B2

## CPC

- H10P 50/283: {by chemical means}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A silicon dioxide film removing method is capable of removing a silicon dioxide film, such as a natural oxide film or a chemical oxide film, at a temperature considerably higher than a room temperature. The silicon dioxide film removing method of removing a silicon dioxide film formed on a workpiece in a processing vessel 18 that can be evacuated uses a mixed gas containing HF gas and NH3 gas for removing the silicon dioxide film. The silicon dioxide film can be efficiently removed from the surface of the workpiece by using the mixed gas containing HF gas and NH3 gas.

## Claims

### Claim 1

A method of removing silicon dioxide films from a surface of a workpiece having a natural oxide film thereon, said method comprising:
removing the natural oxide film from the surface of the workpiece by a chemical process;
forming a chemical oxide film on the surface as a protective film after removal of the natural oxide film, the chemical oxide film being a silicon dioxide film formed by a chemical process using a solution prepared by mixing H2O2 and NH4OH; and
removing the chemical oxide film from the surface of the workpiece, under conditions that:
a mixed gas containing HF gas and NH3 gas is used;
a processing temperature for achieving etch selectivity for the chemical oxide film to silicon is in the range of 200° C. to 400° C.;
a processing pressure at which the workpiece is processed is in the range of 26 Pa (0.2 Torr) to 53,200 Pa (400 Torr); and
the flow rate ratio of HF gas to NH3 gas is in the range of 10:1 to 1:50.

### Claim 2

A method of removing silicon dioxide films from a surface of a workpiece having a natural oxide film thereon, said method comprising:
removing the natural oxide film from the surface of the workpiece by a chemical process;
forming a chemical oxide film on the surface as a protective film after removal of the natural oxide film, the chemical oxide film being a silicon dioxide film formed by a chemical process using a solution prepared by mixing H2O2 and NH4OH; and
removing the chemical oxide film from the surface of the workpiece, under conditions that:
a mixed gas containing HF gas and NH3 gas is used;
a processing temperature for achieving etch selectivity for the chemical oxide film to a silicon nitride film is in the range of 200° C. to 600° C.;
a processing pressure at which the workpiece is processed is not more than 53,200 Pa (400 Torr); and
the flow rate ratio of HF gas to NH3 gas is in the range of 10:1 to 1:50.

### Claim 3

A method of removing silicon dioxide films from a surface of a workpiece having a natural oxide film thereon, said method comprising:
removing the natural oxide film from the surface of the workpiece by a chemical process;
forming a chemical oxide film on the surface as a protective film after removal of the natural oxide film, the chemical oxide film being a silicon dioxide film formed by a chemical process using a solution prepared by mixing H2O2 and NH4OH; and
removing the chemical oxide film from the surface of the workpiece under conditions that:
a mixed gas containing HF gas and NH3 gas is used;
a processing temperature for achieving etch selectivity for the chemical oxide film to a silicon dioxide film, which has been formed by CVD (Chemical Vapor Deposition), is in the range of 200° C. to 400° C.;
a processing pressure at which the workpiece is processed is not more than 53,200 Pa (400 Torr); and
the flow rate ratio of HF gas to NH3 gas is in the range of 10:1 to 1:50.

### Claim 4

A method of removing silicon dioxide films from a surface of a workpiece having a natural oxide film thereon, said method comprising:
removing the natural oxide film from the surface of the workpiece by a chemical process;
forming a chemical oxide film on the surface as a protective film after removal of the natural oxide film, the chemical oxide film being a silicon dioxide film formed by a chemical process using a solution prepared by mixing H2O2 and NH4OH; and
removing the chemical oxide film from the surface of the workpiece, under conditions that:
a mixed gas containing HF gas and NH3 gas is used;
a processing temperature for achieving etch selectivity for the chemical oxide film to a thermal oxide film is in the range of 100° C. to 600° C.;
a processing pressure at which the workpiece is processed is not more than 53,200 Pa (400 Torr); and
the flow rate ratio of HF gas to NH3 gas is in the range of 10:1 to 1:50.

### Claim 5 (depends on 1)

The method of claim 1, further comprising:
forming a thermal oxide film on the surface after removal of the chemical oxide film, whereby the thermal oxide film is the only film on the surface.

### Claim 6 (depends on 2)

The method of claim 2, further comprising:
forming a thermal oxide film on the surface after removal of the chemical oxide film, whereby the thermal oxide film is the only film on the surface.

### Claim 7 (depends on 3)

The method of claim 3, further comprising:
forming a thermal oxide film on the surface after removal of the chemical oxide film, whereby the thermal oxide film is the only film on the surface.

### Claim 8 (depends on 4)

The method of claim 4, further comprising:
forming a thermal oxide film on the surface after removal of the chemical oxide film, whereby the thermal oxide film is the only film on the surface.