USRE37960E1 - Method for forming an oxynitride film in a semiconductor device - Google Patents
Method for forming an oxynitride film in a semiconductor device Download PDFInfo
- Publication number
- USRE37960E1 USRE37960E1 US08/824,879 US82487997A USRE37960E US RE37960 E1 USRE37960 E1 US RE37960E1 US 82487997 A US82487997 A US 82487997A US RE37960 E USRE37960 E US RE37960E
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- United States
- Prior art keywords
- containing gas
- temperature
- oxidation
- ammonia
- nitrous oxide
- Prior art date
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02321—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer
- H01L21/02323—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of oxygen
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
- H01L21/3144—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers on silicon
Definitions
- the present invention relates to a method for forming an oxide film in a semiconductor device, more particularly to a method for forming an oxide film, which can obtain an oxide film of good quality by growing an oxide film under environment of mixed gas of N 2 O gas and NH 3 gas during a main oxidation process and by using N 2 O gas during a pre-oxidation process and a post-oxidation process.
- N 2 O gas is resolved into 64.3% of N 2 , 31.0% of O 2 gas and 4.7% of NO gas in the oxidation chamber under a temperature of 950 degree Celsius.
- a method for forming an oxide film comprises the steps of:
- the FIGURE is a flow chart illustrating the method of oxidation according to the present invention.
- a wafer is loaded in an oxidation chamber containing N 2 gas at a temperature of 700 degree Celsius. Temperature in the oxidation chamber is increased to 900 degree Celsius and then stabilized. Then a pre-oxidation process, main oxidation process and post-oxidation process are executed successively in the oxidation chamber in order to form an oxide film on the surface of the wafer.
- the pre-oxidation process is executed with N 2 O gas
- the main oxidation process is performed with a mixed gas of N 2 O gas and NH 3 gas
- the post-oxidation process is done with N 2 O gas.
- the temperature of interior of the oxidation chamber is dropped to 700 degree Celsius, and N 2 gas is supplied in the oxidation chamber.
- the oxidation process is completed, and the wafer is unloaded from the oxidation chamber.
- temperature in the oxidation chamber pressure and flow rate of process gases(N 2 O gas and NH 3 gas) are varied according to the condition(thickness) of the oxide film.
- the pre-oxidation and post-oxidation processes using N 2 O gas are performed prior to and after the main oxidation process using the mixed gas of N 2 O gas and NH 3 gas.
- the post-oxidation process is undertaken so as to prevent a nitridation of the surface of the wafer.
- the post-oxidation process is done to prevent penetration of any remaining NH 3 to the oxide film and to prevent degeneration of the interface characteristic by hydrogen.
- NH 3 gas is mixed with N 2 O gas, the proper ratio of NH 3 gas in the mixed gas is 0.5-20%. Because of the lower activation energy of NH 3 gas, the influx of nitrogen depends upon amount of NH 3 gas. Therefore, enough nitrogen can be introduced in the oxide film by the mixed gas of a small quantity of NH 3 gas and N2 O, and the incorporated amount of nitrogen can be controlled by a rate of NH 3 gas. Also, hydrogen is acted upon oxygen which is resolved into N 2 O gas, and then is made OH as a wet oxidizer, OH accelerates the oxidation process.
- the insulation characteristics of an oxide film is increased by an introducing nitrogen
- the amount of nitrogen can be regulated by controlling of the amount of NH 3 gas.
- the present invention can solve the problems encountered when NH 3 gas and N 2 O gas are used separately for the oxidation process, by using of the mixed gas of NH 3 gas and N 2 O gas.
Abstract
A method for forming an oxide film in a semiconductor device comprises a pre-oxidation process, a main oxidation process and a post-oxidation process. N2O gas is used for the pre-oxidation process, a mixed gas of N2O gas and NH3 gas is used for the main oxidation process, and N2O gas is used for the post-oxidation process. The insulation characteristics of the oxide film are increased by introducing nitrogen, and amount of introduced nitrogen can be regulated by the controlling of amount of NH3 gas. Also, the problems encountered when NH3 gas and N2O gas are used separately for the oxidation process can be solved by using of the mixed gas of NH3 gas and N2O gas.
Description
1. Field of the Invention
The present invention relates to a method for forming an oxide film in a semiconductor device, more particularly to a method for forming an oxide film, which can obtain an oxide film of good quality by growing an oxide film under environment of mixed gas of N2O gas and NH3 gas during a main oxidation process and by using N2O gas during a pre-oxidation process and a post-oxidation process.
2. Information Disclosure Statement
In general, in order to enhance the reliability of oxide film in a semiconductor device, nitrogen is introduced in an oxide film. In the method for forming an oxide film using NH3 gas, the long-term reliability of the oxide film is deteriorated due to hydrogen ions contained in NH3 gas. There is another method for forming an oxide film using N2O gas, however, an high temperature process is required because of the high activation energy of N2O gas. Also it is impossible to control independently the oxidation rate and influx of the nitrogen. That is, N2O gas is resolved into 64.3% of N2, 31.0% of O2 gas and 4.7% of NO gas in the oxidation chamber under a temperature of 950 degree Celsius. The NO gas is needed to introduce nitrogen into the oxide film, however, NO gas exists in extremely small quantities of 4.7%. Also, most of the NO gas acts upon the O2 gas, and NO2 gas is formed according to the chemical reaction formula: (2NO+O2=2NO2). Therefore, because the influx of nitrogen depends on the degree of reaction of NO gas and O2 gas, it is impossible to control independently the oxidation rate and influx of the nitrogen.
It is an object of the present invention to provide a method for forming an oxide film using N2O gas, and mixed gas of N2O gas and NH3 gas, so that it is possible to control the oxidation rate and influx of the nitrogen and obtain an oxide film of good quality.
To achieve the above object, a method for forming an oxide film comprises the steps of:
a) initiating oxide film formation by introducing an NITROUS OXIDE containing gas;
b) controlling the oxidation rate and influx of nitrogen by introducing ammonia into the nitrous oxide containing gas; and
c) halting the introducing of ammonia gas while maintaining the flow of nitrous oxide containing gas until formation of the oxide film is complete.
The present invention will now be described with reference to the attached drawings, in which:
The FIGURE is a flow chart illustrating the method of oxidation according to the present invention.
A more complete understanding of the present invention can be obtained by considering the following detailed description.
A method for forming an oxide film according to the present invention is described in detail conjunction with the FIGURE.
A wafer is loaded in an oxidation chamber containing N2 gas at a temperature of 700 degree Celsius. Temperature in the oxidation chamber is increased to 900 degree Celsius and then stabilized. Then a pre-oxidation process, main oxidation process and post-oxidation process are executed successively in the oxidation chamber in order to form an oxide film on the surface of the wafer.
The pre-oxidation process is executed with N2O gas, the main oxidation process is performed with a mixed gas of N2O gas and NH3 gas, and the post-oxidation process is done with N2O gas.
Thereafter, the temperature of interior of the oxidation chamber is dropped to 700 degree Celsius, and N2 gas is supplied in the oxidation chamber. The oxidation process is completed, and the wafer is unloaded from the oxidation chamber.
In the above oxidation processes, temperature in the oxidation chamber, pressure and flow rate of process gases(N2O gas and NH3 gas) are varied according to the condition(thickness) of the oxide film.
As noted, prior to and after the main oxidation process using the mixed gas of N2O gas and NH3 gas, the pre-oxidation and post-oxidation processes using N2O gas are performed. The post-oxidation process is undertaken so as to prevent a nitridation of the surface of the wafer. The post-oxidation process is done to prevent penetration of any remaining NH3 to the oxide film and to prevent degeneration of the interface characteristic by hydrogen.
In the main oxidation process, NH3 gas is mixed with N2O gas, the proper ratio of NH3 gas in the mixed gas is 0.5-20%. Because of the lower activation energy of NH3 gas, the influx of nitrogen depends upon amount of NH3 gas. Therefore, enough nitrogen can be introduced in the oxide film by the mixed gas of a small quantity of NH3 gas and N2 O, and the incorporated amount of nitrogen can be controlled by a rate of NH3 gas. Also, hydrogen is acted upon oxygen which is resolved into N2O gas, and then is made OH as a wet oxidizer, OH accelerates the oxidation process.
Because nitrogen is incorporated into the oxide film simultaneously with the oxidation process, it therefore is possible to obtain .an oxide film of good quality.
According to the present invention as described above, the insulation characteristics of an oxide film is increased by an introducing nitrogen, the amount of nitrogen can be regulated by controlling of the amount of NH3 gas. Also, the present invention can solve the problems encountered when NH3 gas and N2O gas are used separately for the oxidation process, by using of the mixed gas of NH3 gas and N2O gas.
Claims (40)
1. A method for forming an oxide film in a semiconductor device comprising:
a) initiating oxide film formation by introducing an nitrous oxide containing gas;
b) controlling the oxidation rate and influx of nitrogen by introducing ammonia into said nitrous oxide containing gas; and
c) halting the introducing of ammonia gas while maintaining the flow of nitrous oxide containing gas until formation of said oxide film is complete.
2. The method of claim 1 further comprising the steps of:
prior to said initiating oxide film formation step, loading the semiconductor device into an oxidation chamber; and
introducing a nitrogen containing gas into said oxidation chamber.
3. The method of claim 2 further comprising the step of increasing a temperature in said oxidation chamber from a first temperature to a second temperature during said introducing nitrogen containing gas step.
4. The method of claim 3 wherein said first temperature is 700 degrees Celsius.
5. The method of claim 3 wherein said second temperature is 900 degrees Celsius.
6. The method of claim 1 further comprising the steps of:
supplying a nitrogen containing gas to an oxidation chamber containing said semiconductor device after said halting step; and
reducing a temperature in said oxidation chamber.
7. The method of claim 1 wherein said initiating step is a pre-oxidation process.
8. The method of claim 1 wherein said controlling step is a main oxidation process.
9. The method of claim 1 wherein said halting step is a post-oxidation process.
10. The method of claim 9 wherein said post-oxidation process prevents a possibility of nitridation in a substrate of said semiconductor device.
11. The method of claim 9 wherein said post-oxidation process prevents a possibility of said ammonia penetrating said oxide film after said halting step.
12. The method of claim 9 wherein said post-oxidation process prevents a possibility of degeneration of said oxide film by hydrogen ions in said ammonia.
13. The method of claim 1 wherein during said controlling step, said ammonia and said nitrous oxide in said nitrous oxide containing gas are provided at a ratio which ranges between 0.5% and 20 %.
14. The method of claim 1 wherein said controlling step produces an OH.
15. The method of claim 14 wherein said OH accelerates said oxide film formation.
16. The method of claim 1 wherein said controlling step is provided at a temperature of 900 degrees Celsius.
17. A method for forming an oxide film in a semiconductor device comprising the steps of:
introducing a nitrous oxide containing gas to the semiconductor device to initiate the film formation;
after introducing said nitrous oxide containing gas, mixing an ammonia containing compound with said nitrous oxide containing gas to control an oxidation rate and influx of nitrogen; and
halting the introduction of said ammonia containing compound while maintaining a flow of the nitrous oxide containing gas until formation of said oxide film is complete.
18. The method of claim 17 further comprising the step of maintaining a flow rate of said nitrous oxide during said halting step until said film formation is complete.
19. The method of claim 17 further comprising the steps of:
prior to said introducing step, loading a wafer into an oxidation chamber; and
introducing a nitrogen containing gas into said oxidation chamber.
20. The method of claim 19 further comprising the step of:
raising a temperature in said oxidation chamber during said introducing nitrogen containing gas step from a first temperature to a second temperature.
21. The method of claim 20 wherein said first temperature is 700 degrees Celsius.
22. The method of claim 20 wherein said second temperature is 900 degrees Celsius.
23. The method of claim 17 further comprising the steps of:
supplying a nitrogen containing gas after said halting step to an oxidation chamber containing the semiconductor device; and
dropping a temperature in said oxidation chamber.
24. The method of claim 17 wherein said introducing a nitrous oxide containing gas is a pre-oxidation process.
25. The method of claim 17 wherein said mixing step is a main oxidation process.
26. The method of claim 17 wherein said halting step is a post-oxidation process.
27. The method of claim 26 wherein said post-oxidation process prevents a possibility of nitridation in a substrate of said semiconductor device.
28. The method of claim 26 wherein said post-oxidation process prevents a possibility of said ammonia in said ammonia containing compound penetrating said film after said halting step.
29. The method of claim 17 wherein during said mixing step, said ammonia in said ammonia containing compound and said nitrous oxide in said nitrous oxide containing gas is at a ratio which ranges from 0.5% to 20 %.
30. The method of claim 17 wherein said mixing step is performed at 900 degrees Celsius.
31. The method of claim 17 wherein said OH accelerates said film formation.
32. A method for forming an oxide film on a semiconductor device comprising the steps of:
loading the semiconductor device into an oxidation chamber containing a nitrogen containing gas;
increasing a temperature of said oxidation chamber from a first temperature to a second temperature;
introducing a nitrous oxide containing gas into said oxidation chamber to initiate the film formation; said introducing step being a pre-oxidation process;
after introducing said nitrous oxide containing gas into said oxidation chamber, mixing an ammonia containing compound with said nitrous oxide containing gas to control an oxidation rate and influx of nitrogen, said mixing step being a main oxidation process;
halting the introduction of said ammonia containing compound while maintaining a flow of the nitrous oxide containing gas until formation of said oxide film is complete, said halting step being a post-oxidation process;
dropping a temperature in said oxidation chamber; and
supplying a nitrogen containing gas to said oxidation chamber.
33. The method of claim 32 wherein during said halting step, a flow rate of said nitrous oxide containing gas is maintained after the halting of said ammonia until said film formation is completed.
34. The method of claim 32 wherein said first temperature is 700 degrees Celsius.
35. The method of claim 32 wherein said second temperature is 900 degrees Celsius.
36. The method of claim 32 wherein said post-oxidation process prevents a possibility of said ammonia penetrating said film after said main oxidation process.
37. The method of claim 32 wherein during said mixing step, said ammonia in said ammonia containing compound and said nitrous oxide in said nitrous oxide containing gas is at a ratio which ranges from 0.5% to 20 %.
38. The method of claim 32 wherein during said mixing step produces an OH.
39. The method of claim 38 wherein said OH accelerates said film formation.
40. The method of claim 32 wherein said mixing step is performed at 900 degrees Celsius.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/824,879 USRE37960E1 (en) | 1995-02-27 | 1997-03-26 | Method for forming an oxynitride film in a semiconductor device |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/394,607 US5541141A (en) | 1995-02-27 | 1995-02-27 | Method for forming an oxynitride film in a semiconductor device |
| US08/824,879 USRE37960E1 (en) | 1995-02-27 | 1997-03-26 | Method for forming an oxynitride film in a semiconductor device |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/394,607 Reissue US5541141A (en) | 1995-02-27 | 1995-02-27 | Method for forming an oxynitride film in a semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE37960E1 true USRE37960E1 (en) | 2003-01-07 |
Family
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/394,607 Ceased US5541141A (en) | 1995-02-27 | 1995-02-27 | Method for forming an oxynitride film in a semiconductor device |
| US08/824,879 Expired - Lifetime USRE37960E1 (en) | 1995-02-27 | 1997-03-26 | Method for forming an oxynitride film in a semiconductor device |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/394,607 Ceased US5541141A (en) | 1995-02-27 | 1995-02-27 | Method for forming an oxynitride film in a semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| US (2) | US5541141A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080299780A1 (en) * | 2007-06-01 | 2008-12-04 | Uv Tech Systems, Inc. | Method and apparatus for laser oxidation and reduction |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3660391B2 (en) * | 1994-05-27 | 2005-06-15 | 株式会社東芝 | Manufacturing method of semiconductor device |
| KR100187674B1 (en) * | 1994-07-07 | 1999-06-01 | 김주용 | Quartz for fabricating semiconductor device and method of forming gate oxide using the same |
| US6362114B1 (en) * | 1996-11-12 | 2002-03-26 | Micron Technology, Inc. | Semiconductor processing methods of forming an oxynitride film on a silicon substrate |
| US5821172A (en) * | 1997-01-06 | 1998-10-13 | Advanced Micro Devices, Inc. | Oxynitride GTE dielectrics using NH3 gas |
| US5851888A (en) * | 1997-01-15 | 1998-12-22 | Advanced Micro Devices, Inc. | Controlled oxide growth and highly selective etchback technique for forming ultra-thin oxide |
| US5840610A (en) * | 1997-01-16 | 1998-11-24 | Advanced Micro Devices, Inc. | Enhanced oxynitride gate dielectrics using NF3 gas |
| US5877057A (en) * | 1997-01-17 | 1999-03-02 | Advanced Micro Devices, Inc. | Method of forming ultra-thin oxides with low temperature oxidation |
| JPH10209168A (en) * | 1997-01-24 | 1998-08-07 | Nec Corp | Manufacture of semiconductor device |
| US5851892A (en) * | 1997-05-07 | 1998-12-22 | Cypress Semiconductor Corp. | Fabrication sequence employing an oxide formed with minimized inducted charge and/or maximized breakdown voltage |
| US6147011A (en) | 1998-02-28 | 2000-11-14 | Micron Technology, Inc. | Methods of forming dielectric layers and methods of forming capacitors |
| US6316316B1 (en) * | 1998-03-06 | 2001-11-13 | Texas Instruments-Acer Incorporated | Method of forming high density and low power flash memories with a high capacitive-coupling ratio |
| US6114258A (en) * | 1998-10-19 | 2000-09-05 | Applied Materials, Inc. | Method of oxidizing a substrate in the presence of nitride and oxynitride films |
| KR100682190B1 (en) * | 1999-09-07 | 2007-02-12 | 동경 엘렉트론 주식회사 | Method and apparatus for forming insulating film containing silicon oxy-nitride |
| US6211045B1 (en) * | 1999-11-30 | 2001-04-03 | Vlsi Technology, Inc. | Incorporation of nitrogen-based gas in polysilicon gate re-oxidation to improve hot carrier performance |
| KR100933835B1 (en) * | 2007-11-12 | 2009-12-24 | 주식회사 하이닉스반도체 | Manufacturing Method of Flash Memory Device |
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-
1995
- 1995-02-27 US US08/394,607 patent/US5541141A/en not_active Ceased
-
1997
- 1997-03-26 US US08/824,879 patent/USRE37960E1/en not_active Expired - Lifetime
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|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080299780A1 (en) * | 2007-06-01 | 2008-12-04 | Uv Tech Systems, Inc. | Method and apparatus for laser oxidation and reduction |
Also Published As
| Publication number | Publication date |
|---|---|
| US5541141A (en) | 1996-07-30 |
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