CN111489954A - Method for removing nitride after semiconductor substrate etching - Google Patents
Method for removing nitride after semiconductor substrate etching Download PDFInfo
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- CN111489954A CN111489954A CN201910071391.9A CN201910071391A CN111489954A CN 111489954 A CN111489954 A CN 111489954A CN 201910071391 A CN201910071391 A CN 201910071391A CN 111489954 A CN111489954 A CN 111489954A
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- Prior art keywords
- semiconductor substrate
- mixed solution
- mixed gas
- difluoromethane
- nitrogen
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 74
- 239000000758 substrate Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 33
- 238000005530 etching Methods 0.000 title claims abstract description 19
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 42
- 239000011259 mixed solution Substances 0.000 claims abstract description 41
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention provides a method for removing nitride after etching a semiconductor substrate, which comprises the following steps: (1) uniformly covering the mixed solution of hydrofluoric acid, carbon dioxide and deionized water on the surface of the semiconductor substrate in the atmosphere of mixed gas of difluoromethane, nitrogen and oxygen to form a uniform liquid film on the surface of the semiconductor substrate; (2) and under the pressure of 600-900mTorr, keeping the mixed gas continuously flowing through the semiconductor substrate covered with the mixed solution to perform reaction, wherein the reaction temperature is 50-70 ℃, the volume ratios of the difluoromethane, the nitrogen and the oxygen to the mixed gas are respectively 60-90%, 5-30% and 5-10%, and the flow rate of the mixed gas is 500-800 SCCM. The method has good removal effect on nitride after the semiconductor substrate is etched, and can ensure the integrity of the semiconductor substrate.
Description
Technical Field
The invention belongs to the technical field of semiconductor preparation processes, and particularly relates to a method for removing nitride after etching a semiconductor substrate.
Background
In the microelectronics industry, semiconductor substrates are etched to form desired features and patterns. The etching process typically employs liquid chemistry, reactive gases, and plasma. Nitride is generated on the surface of the substrate after etching. To prevent the yield of the final device from decreasing, the nitride generated after etching must be removed before the next stage of the process is started. The removal of these residues is usually accomplished by using a liquid mixture of an acid and an oxidizing agent, however, these prior art methods are not effective in completely removing these nitrides.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for removing nitride after etching a semiconductor substrate.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for removing nitride from a semiconductor substrate after etching, the method comprising the steps of:
(1) uniformly covering the mixed solution of hydrofluoric acid, carbon dioxide and deionized water on the surface of the semiconductor substrate in the atmosphere of mixed gas of difluoromethane, nitrogen and oxygen to form a uniform liquid film on the surface of the semiconductor substrate;
(2) and under the pressure of 600-900mTorr, keeping the mixed gas continuously flowing through the semiconductor substrate covered with the mixed solution to perform reaction, wherein the reaction temperature is 50-70 ℃, the volume ratios of the difluoromethane, the nitrogen and the oxygen to the mixed gas are respectively 60-90%, 5-30% and 5-10%, and the flow rate of the mixed gas is 500-800 SCCM.
The method combines hydrofluoric acid solution etching and difluoromethane (CH)2F2) Nitride on the surface of the semiconductor substrate is removed through chemical reaction, and difluoromethane is mixed with nitrogen and oxygen to react, the nitrogen can clean the removed nitride, and the oxygen assists the difluoromethane to react, so that the reaction efficiency and effect are improved; the inclusion of carbon dioxide gas in the hydrofluoric acid solution protects the conductors, such as copper coils, inside the substrate from corrosion during cleaning.
Preferably, the reaction time is 5 to 40 minutes.
Preferably, the difluoromethane accounts for 70-80% of the volume of the mixed gas.
Preferably, the reaction is carried out in step (2) while maintaining the continuous flow of the mixed gas through the semiconductor substrate covered with the mixed solution at a pressure of 800 mTorr.
Preferably, the concentration of hydrofluoric acid in the mixed solution is: the volume ratio of the hydrofluoric acid to the deionized water is 1:45000-1: 60000.
Preferably, the concentration of hydrofluoric acid in the mixed solution is: the volume ratio of the hydrofluoric acid to the deionized water is 1: 50000.
Preferably, when the mixed solution is uniformly covered on the surface of the semiconductor substrate, the temperature of the mixed solution is 20-25 ℃, and the concentration of the carbon dioxide is that the carbon dioxide is saturated in the mixed solution.
Preferably, the volume ratio of the difluoromethane, nitrogen and oxygen to the mixed gas is 80%, 15% and 5% or 70%, 20% and 10%, respectively.
Preferably, the reaction time is 10 to 25 minutes.
Preferably, the method for uniformly covering the surface of the semiconductor substrate with the mixed solution comprises the following steps: and when the semiconductor substrate rotates at the rotating speed of 1000-1500rpm, uniformly spraying the mixed solution on the surface of the semiconductor substrate.
The invention has the beneficial effects that: the invention provides a method for removing nitride after etching a semiconductor substrate, which combines hydrofluoric acid solution corrosion and difluoromethane (CH)2F2) Nitride on the surface of the semiconductor substrate is removed through chemical reaction, and difluoromethane is mixed with nitrogen and oxygen to react, the nitrogen can clean the removed nitride, and the oxygen assists the difluoromethane to react, so that the reaction efficiency and effect are improved; the hydrofluoric acid solution contains carbon dioxide gas, so that a conductor such as a copper coil in the substrate can be protected from being corroded in the cleaning process.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The method for removing the nitride after the semiconductor substrate is etched, which is provided by the embodiment of the invention, comprises the following steps of:
(1) uniformly covering the mixed solution of hydrofluoric acid, carbon dioxide and deionized water on the surface of the semiconductor substrate in the atmosphere of mixed gas of difluoromethane, nitrogen and oxygen to form a uniform liquid film on the surface of the semiconductor substrate;
(2) keeping the mixed gas to continuously flow through the semiconductor substrate covered with the mixed solution under the pressure of 800mTorr, and reacting for 10 minutes at the temperature of 60 ℃, wherein the difluoromethane, the nitrogen and the oxygen respectively account for 80%, 15% and 5% of the mixed gas by volume, and the flow rate of the mixed gas is 700 SCCM;
the reaction is carried out in a process treatment cavity, and the method for uniformly covering the surface of the semiconductor substrate with the mixed solution comprises the following steps: placing the semiconductor substrate on a sample table rotating at the rotating speed of 1300rpm, and uniformly spraying the mixed solution on the surface of the semiconductor substrate;
and introducing mixed gas into the process treatment chamber to continuously flow through the semiconductor substrate covered with the mixed solution.
Example 2
The method for removing the nitride after the semiconductor substrate is etched, which is provided by the embodiment of the invention, comprises the following steps of:
(1) uniformly covering the mixed solution of hydrofluoric acid, carbon dioxide and deionized water on the surface of the semiconductor substrate in the atmosphere of mixed gas of difluoromethane, nitrogen and oxygen to form a uniform liquid film on the surface of the semiconductor substrate;
(2) keeping the mixed gas to continuously flow through the semiconductor substrate covered with the mixed solution under the pressure of 800mTorr, and reacting for 7 minutes at the temperature of 60 ℃, wherein the difluoromethane, the nitrogen and the oxygen respectively account for 90%, 5% and 5% of the mixed gas by volume, and the flow rate of the mixed gas is 700 SCCM;
the reaction is carried out in a process treatment cavity, and the method for uniformly covering the surface of the semiconductor substrate with the mixed solution comprises the following steps: placing the semiconductor substrate on a sample table rotating at the rotating speed of 1300rpm, and uniformly spraying the mixed solution on the surface of the semiconductor substrate;
and introducing mixed gas into the process treatment chamber to continuously flow through the semiconductor substrate covered with the mixed solution.
Example 3
The method for removing the nitride after the semiconductor substrate is etched, which is provided by the embodiment of the invention, comprises the following steps of:
(1) uniformly covering the mixed solution of hydrofluoric acid, carbon dioxide and deionized water on the surface of the semiconductor substrate in the atmosphere of mixed gas of difluoromethane, nitrogen and oxygen to form a uniform liquid film on the surface of the semiconductor substrate;
(2) keeping the mixed gas to continuously flow through the semiconductor substrate covered with the mixed solution under the pressure of 800mTorr, and reacting for 25 minutes at the temperature of 60 ℃, wherein the difluoromethane, the nitrogen and the oxygen respectively account for 70%, 20% and 10% of the mixed gas by volume, and the flow rate of the mixed gas is 700 SCCM;
the reaction is carried out in a process treatment cavity, and the method for uniformly covering the surface of the semiconductor substrate with the mixed solution comprises the following steps: placing the semiconductor substrate on a sample table rotating at the rotating speed of 1300rpm, and uniformly spraying the mixed solution on the surface of the semiconductor substrate;
and introducing mixed gas into the process treatment chamber to continuously flow through the semiconductor substrate covered with the mixed solution.
Example 4
The method for removing the nitride after the semiconductor substrate is etched, which is provided by the embodiment of the invention, comprises the following steps of:
(1) uniformly covering the mixed solution of hydrofluoric acid, carbon dioxide and deionized water on the surface of the semiconductor substrate in the atmosphere of mixed gas of difluoromethane, nitrogen and oxygen to form a uniform liquid film on the surface of the semiconductor substrate;
(2) keeping the mixed gas to continuously flow through the semiconductor substrate covered with the mixed solution under the pressure of 800mTorr, and reacting for 40 minutes at the temperature of 60 ℃, wherein the difluoromethane, the nitrogen and the oxygen respectively account for 60%, 30% and 10% of the mixed gas by volume, and the flow rate of the mixed gas is 700 SCCM;
the reaction is carried out in a process treatment cavity, and the method for uniformly covering the surface of the semiconductor substrate with the mixed solution comprises the following steps: placing the semiconductor substrate on a sample table rotating at the rotating speed of 1300rpm, and uniformly spraying the mixed solution on the surface of the semiconductor substrate;
and introducing mixed gas into the process treatment chamber to continuously flow through the semiconductor substrate covered with the mixed solution.
Example 5
As a method for removing nitride after etching a semiconductor substrate according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the temperature of the reaction in the step (2) was 50 ℃.
Example 6
As a method for removing nitride after etching a semiconductor substrate according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the temperature of the reaction in the step (2) was 55 ℃.
Example 7
As a method for removing nitride after etching a semiconductor substrate according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the temperature of the reaction in the step (2) was 65 ℃.
Example 8
As a method for removing nitride after etching a semiconductor substrate according to an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is: the temperature of the reaction in the step (2) was 70 ℃.
Comparative example 1
The only difference between the method for removing nitride after etching the semiconductor substrate as the comparative example of the invention and the embodiment 1 is that: the mixed solution does not contain carbon dioxide.
Comparative example 2
The only difference between the method for removing nitride after etching the semiconductor substrate as the comparative example of the invention and the embodiment 1 is that: the mixed gas does not contain oxygen.
Comparative example 3
The only difference between the method for removing nitride after etching the semiconductor substrate as the comparative example of the invention and the embodiment 1 is that: the mixed gas does not contain nitrogen.
Experimental example 1
The nitride removing effects of examples 1 to 8 and comparative examples 1 to 3 were observed by a 1000-fold microscope, and the nitride removing effect by cleaning was examined by comparing the size and number of nitride particles on the surface of the semiconductor under a microscope, and it was found that all of examples 1 to 8 had a good removing effect, and the observation results are shown in table 1.
Table 1 removal effects on nitride of examples 1 to 8 and comparative example 1
Note: the particle diameters in Table 1 are the sizes of the nitride particles which are 1000 times larger under a 1000-fold microscope, and the number of the particle diameters in Table is 4.5mm2Area calculation (i.e., the size of the area of one semiconductor).
From the removal effects of comparative example 1 and comparative example 1, it was found that the removal effect was good for nitride, but it was found that corrosion occurred in the conductor inside the semiconductor substrate.
By comparing the removal effects of example 1 and comparative examples 2 and 3, it was found that the removal effects of comparative examples 2 and 3 were poor.
By comparing the removal effects of examples 1 to 4, it was found that the removal effect of example 1 was the best, and the removal effect of example 3 was the second best.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A method for removing nitride after etching a semiconductor substrate is characterized by comprising the following steps:
(1) uniformly covering the mixed solution of hydrofluoric acid, carbon dioxide and deionized water on the surface of the semiconductor substrate in the atmosphere of mixed gas of difluoromethane, nitrogen and oxygen to form a uniform liquid film on the surface of the semiconductor substrate;
(2) and under the pressure of 600-900mTorr, keeping the mixed gas continuously flowing through the semiconductor substrate covered with the mixed solution to perform reaction, wherein the reaction temperature is 50-70 ℃, the volume ratios of the difluoromethane, the nitrogen and the oxygen to the mixed gas are respectively 60-90%, 5-30% and 5-10%, and the flow rate of the mixed gas is 500-800 SCCM.
2. The method of claim 1, wherein the reaction time is 5 to 40 minutes.
3. The method as claimed in claim 1, wherein the difluoromethane is 70-80% by volume of the mixed gas.
4. The method according to claim 1, wherein the concentration of hydrofluoric acid in the mixed solution is: the volume ratio of the hydrofluoric acid to the deionized water is 1:45000-1: 60000.
5. The method according to claim 1, wherein the mixed solution is at a temperature of 20 to 25 ℃ and the concentration of the carbon dioxide is such that the carbon dioxide is saturated in the mixed solution when the mixed solution is uniformly coated on the surface of the semiconductor substrate.
6. The method of claim 1, wherein the difluoromethane, nitrogen and oxygen are present in 80%, 15% and 5% or 70%, 20% and 10% by volume of the mixed gas, respectively.
7. The method of claim 6, wherein the reaction time is 10 to 25 minutes.
8. The method according to any one of claims 1 to 7, wherein the method for uniformly coating the mixed solution on the surface of the semiconductor substrate comprises the steps of: and when the semiconductor substrate rotates at the rotating speed of 1000-1500rpm, uniformly spraying the mixed solution on the surface of the semiconductor substrate.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5279705A (en) * | 1990-11-28 | 1994-01-18 | Dainippon Screen Mfg. Co., Ltd. | Gaseous process for selectively removing silicon nitride film |
US5858861A (en) * | 1998-05-15 | 1999-01-12 | Taiwan Semiconductor Manufacturing Company, Ltd. | Reducing nitride residue by changing the nitride film surface property |
US20040266210A1 (en) * | 2003-06-30 | 2004-12-30 | Sang-Mi Lee | Etchant for etching nitride and method for removing a nitride layer using the same |
CN1767154A (en) * | 2004-07-23 | 2006-05-03 | 气体产品与化学公司 | Method for removing carbon-containing residues from a substrate |
CN101651116A (en) * | 2008-08-14 | 2010-02-17 | 中芯国际集成电路制造(北京)有限公司 | Method for forming contact hole |
CN103137415A (en) * | 2011-11-21 | 2013-06-05 | Psk有限公司 | Apparatus and method for manufacturing semiconductor devices |
CN108242388A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院微电子研究所 | Method and device for removing residues after substrate etching |
-
2019
- 2019-01-25 CN CN201910071391.9A patent/CN111489954A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5279705A (en) * | 1990-11-28 | 1994-01-18 | Dainippon Screen Mfg. Co., Ltd. | Gaseous process for selectively removing silicon nitride film |
US5858861A (en) * | 1998-05-15 | 1999-01-12 | Taiwan Semiconductor Manufacturing Company, Ltd. | Reducing nitride residue by changing the nitride film surface property |
US20040266210A1 (en) * | 2003-06-30 | 2004-12-30 | Sang-Mi Lee | Etchant for etching nitride and method for removing a nitride layer using the same |
CN1767154A (en) * | 2004-07-23 | 2006-05-03 | 气体产品与化学公司 | Method for removing carbon-containing residues from a substrate |
CN101651116A (en) * | 2008-08-14 | 2010-02-17 | 中芯国际集成电路制造(北京)有限公司 | Method for forming contact hole |
CN103137415A (en) * | 2011-11-21 | 2013-06-05 | Psk有限公司 | Apparatus and method for manufacturing semiconductor devices |
CN108242388A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院微电子研究所 | Method and device for removing residues after substrate etching |
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Application publication date: 20200804 |