CN101656191B - Method for removing silicon oxynitride film - Google Patents
Method for removing silicon oxynitride film Download PDFInfo
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- CN101656191B CN101656191B CN2008100418835A CN200810041883A CN101656191B CN 101656191 B CN101656191 B CN 101656191B CN 2008100418835 A CN2008100418835 A CN 2008100418835A CN 200810041883 A CN200810041883 A CN 200810041883A CN 101656191 B CN101656191 B CN 101656191B
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- silicon oxynitride
- oxynitride film
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- hydrofluoric acid
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Abstract
The invention provides a method for removing a silicon oxynitride film. The method comprises the following steps: providing a control wafer on which the silicon oxynitride film is formed; cleaning the surface of the silicon oxynitride film with 0.2 to 0.5 percent hydrofluoric acid; removing the silicon oxynitride film with phosphoric acid; removing the residual silicon oxynitride film with 45 to 50 percent hydrofluoric acid; and cleaning the surface of the control wafer with solution containing ammonia, hydrogen peroxide and water. The method improves the utilization rate of the control wafer and reduces the process cost.
Description
Technical field
The present invention relates to field of semiconductor manufacture, relate in particular to the method for removing silicon oxynitride film on the control sheet.
Background technology
Along with dwindling gradually of the device size of integrated circuit, especially behind deep sub-micron technique, the accuracy for figure in the semiconductor fabrication also improves constantly.Because lithographic dimensioned dwindling, in exposure process because the difference of the luminous reflectivity of various media can cause the deviation of figure after the photoetching.The application of anti-reflecting layer (ARC) can reduce or eliminate and cause photoresist uneven sense reflection of light light, improves the control ability of critical size.Because the characteristics of optical parameter value be controlled and be adjusted to silicon oxynitride (SiON) film can by adjusting each constituent content in forming process, become more valued anti-reflecting layer material just gradually, the patent No. is that 200310108409 Chinese patent discloses with the scheme of silicon oxynitride film as anti-reflecting layer.In addition, because etching gas or liquid are slow to the etch rate of silicon oxynitride film, therefore, in the process of making metal connecting line, be used to usually as etching barrier layer.
Along with the application of silicon oxynitride film more and more widely, require also to improve constantly for the depositing operation of silicon oxynitride film.In order in technology, constantly to monitor the quality of silicon oxynitride film, must before form silicon oxynitride film on the wafer,, detect it and whether meet the requirements prior to forming the silicon oxynitride film of same size on the control sheet.
Yet,, after having detected the quality of silicon oxynitride film, silicon oxynitride film need be removed in order to make the recycling of control sheet.The existing concrete processing step of removing silicon oxynitride film on the control sheet as shown in Figure 1, execution in step S1 provides the control that is formed with silicon oxynitride layer sheet.Described control sheet is blank wafer.
Execution in step S2 is that 49% hydrofluoric acid solution carries out wet etching after 30 seconds to silicon oxynitride film with concentration, cleans silicon oxynitride film 5 minutes with the mixed solution of ammoniacal liquor, hydrogen peroxide and water.Wherein, be that 49% hydrofluoric acid solution carries out wet etching to silicon oxynitride film and removed the part silicon oxynitride film after 30 seconds with concentration, mixed solution with ammoniacal liquor, hydrogen peroxide and water cleaned 5 minutes silicon oxynitride film then, removed residual nitrogen silicon oxide film surface because the particle that etching produces.
Execution in step S3 is that 49% hydrofluoric acid carries out wet etching after 20 seconds to remaining silicon oxynitride film with concentration, cleans silicon oxynitride film 5 minutes with the mixed solution of ammoniacal liquor, hydrogen peroxide and water.Wherein, at the hydrofluoric acid that with concentration is 49% remaining silicon oxynitride film was carried out wet etching after 20 seconds, silicon oxynitride film still has residual on the control sheet.
Execution in step S4 is that 49% hydrofluoric acid carries out wet etching after 10 seconds to residual silicon oxynitride film with concentration, cleans the control sheet 5 minutes with the mixed solution of ammoniacal liquor, hydrogen peroxide and water.After residual silicon oxynitride film being carried out 10 seconds wet etching, intact basically being eliminated; Then, control sheet 5 minutes, the silicon oxynitride particle that residues in behind the wet etching on the control sheet is cleaned removal with the mixed solution cleaning of ammoniacal liquor, hydrogen peroxide and water.
Yet, owing to when the silicon oxynitride film of control on the sheet handled, be not that monolithic is handled, but the control sheet of 50 multi-discs is placed on the removal of carrying out silicon oxynitride film in the same acid tank together.When removing the silicon oxynitride film of these controls on sheets simultaneously with prior art, because silicon oxynitride film is more intense with the binding ability of control sheet silicon face, when the hydrofluoric acid that with concentration is 49% is removed, silicon oxynitride film on all control sheets can not be removed fully, promptly have only 20%～30% control sheet qualified, the residual particles on surface is less than 100, and 70%～80% control sheet is defective, and the surface nitrogen silicon oxide particle is residual more than 5000 (as shown in Figure 2).Most control sheets can not be reused, and the technology cost improves.
Summary of the invention
The problem that the present invention solves provides a kind of method of removing silicon oxynitride film, and it is too much to prevent to control sheet surface nitrogen silica residual particles, causes the technology cost to improve.
The invention provides a kind of method of removing silicon oxynitride film, comprising: the control that is formed with silicon oxynitride film sheet is provided; It with concentration 0.2%～0.5% hydrofluoric acid clean silicon oxynitride film surface; Remove silicon oxynitride film with phosphoric acid; With concentration is that 45%～50% hydrofluoric acid is removed the residual nitrogen silicon oxide film; Clean control sheet surface with the solution that comprises ammoniacal liquor, hydrogen peroxide and water.
Optionally, be that 0.2%～0.5% the hydrofluoric acid clean silicon oxynitride film used time of surface is 8 minutes～12 minutes with concentration.
Optionally, described concentration of phosphoric acid is 55%～65%.Removing the used time of silicon oxynitride film with phosphoric acid is 20 minutes～40 minutes.
Optionally, be that to remove the residual nitrogen used time of silicon oxide film be 8 seconds～12 seconds for 45%～50% hydrofluoric acid with concentration.
Optionally, the ratio of ammoniacal liquor, hydrogen peroxide and water is 1: 1: 50.The mixed solution cleaning control sheet used time of surface with ammoniacal liquor, hydrogen peroxide and water is 4 minutes～7 minutes.
Compared with prior art, the present invention has the following advantages: the present invention is earlier 0.2%～0.5% hydrofluoric acid clean silicon oxynitride film surface with concentration, the in-situ oxidation silicon layer that oxidation generates of can removing silicon oxynitride film surface because be exposed in the air; Then, remove silicon oxynitride film, the silicon oxynitride film on all control sheets almost completely can be removed with phosphoric acid, only residual a little silicon oxynitride film, promptly the silicon oxynitride particle probably is less than 5000 more than 100; With concentration is that 45%～50% hydrofluoric acid is removed the residual nitrogen silicon oxide film, and silicon oxynitride particles of all control sheet remained on surface are further removed, and makes the residual nitrogen silicon oxide particle near 100; Mixed solution with ammoniacal liquor, hydrogen peroxide and water cleans control sheet surface, can further remove the silicon oxynitride particle on the control sheet, make the silicon oxynitride particle on all the control sheet surfaces on the processing line reach requirement, be less than 100, all like this control sheets can utilize once more.With process of the present invention the utilance of control sheet is improved, cost descends.
Description of drawings
Fig. 1 is the flow chart that existing technology is removed silicon oxynitride film on the control sheet;
Fig. 2 removes the design sketch of controlling residual nitrogen silicon oxide particle on the sheet on the control sheet behind the silicon oxynitride film with existing technology;
Fig. 3 is the embodiment flow chart that the present invention removes silicon oxynitride film on the control sheet;
Fig. 4 to Fig. 7 is the embodiment schematic diagram that the present invention removes silicon oxynitride film on the control sheet;
Fig. 8 removes the design sketch of controlling residual nitrogen silicon oxide particle on the sheet on the control sheet behind the silicon oxynitride film with technology of the present invention.
Embodiment
In order to improve the utilance of control sheet, the present invention makes the silicon oxynitride granule number on all the control sheet surfaces on the processing line meet the requirement that the control sheet utilizes again by improving process, is less than 100.
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.
The invention provides a kind of method of silicon oxynitride film on the control sheet of removing, embodiment as shown in Figure 3, execution in step S11 provides the control that is formed with silicon oxynitride film sheet.
With reference to figure 4, described control sheet 100 is a negative crystal circle.The method that forms silicon oxynitride film 102 is a chemical vapour deposition technique, and the thickness of described silicon oxynitride film 102 is 500 dusts～4000 dusts.Because silicon oxynitride film 102 is exposed in the air, the surface is easy to oxidized, forms the in-situ oxidation silicon layer 104 of one deck 3 dusts～5 dusts.
Execution in step S12 is 0.2%～0.5% hydrofluoric acid clean silicon oxynitride film surface with concentration.
With reference to figure 5, because there is in-situ oxidation silicon layer 104 on the surface of silicon oxynitride film 102, therefore, need be earlier that 0.2%～0.5% hydrofluoric acid solution is removed in-situ oxidation silicon layer 104 with concentration value, removing the in-situ oxidation 104 used times of silicon layer is 8 minutes～12 minutes.Wherein, it is relevant with the concentration of hydrofluoric acid solution to be with concentration that 0.2%～0.5% hydrofluoric acid solution is removed the in-situ oxidation 104 concrete times of silicon layer; Optimize embodiment as one, if be 0.25% hydrofluoric acid with concentration value, clean silicon oxynitride film 102 surfaces with removal in-situ oxidation silicon layer 104, the used time is 10 minutes.
Execution in step S13 removes silicon oxynitride film with phosphoric acid.
As shown in Figure 6, with concentration be 55%～65% phosphoric acid solution etching silicon oxynitride film 102 to exposing control sheet 100, removing the 102 used times of silicon oxynitride film with phosphoric acid is 20 minutes～40 minutes.With concentration is that 55%～65% phosphoric acid solution can not be removed silicon oxynitride film 102 fully, and all control sheet 100 surfaces on processing line are still residual more than 100 but be less than 5000 silicon oxynitride particle 102a.
In the present embodiment, the time of phosphoric acid etching silicon oxynitride film 102 is relevant with concentration of phosphoric acid, and for example, when concentration of phosphoric acid was 60%, removing the 102 used times of silicon oxynitride film with the phosphoric acid solution of this concentration was 30 minutes.
Execution in step S14 is that 45%～50% hydrofluoric acid is removed the residual nitrogen silicon oxide film with concentration.
Execution in step S15 is with the mixed solution cleaning control sheet surface of ammoniacal liquor, hydrogen peroxide and water.
As shown in Figure 7, be the most of the nitrogen silicon oxide particle 102a that 45%～50% hydrofluoric acid will be controlled sheet 100 remained on surface earlier with concentration, make the number of residual silicon oxynitride particle 102a approach 100, removing the residual used time of silicon oxynitride particle 102a is 8 seconds～12 seconds.As a preferred embodiment, removing the residual used time of silicon oxynitride particle 102a when the hydrofluoric acid that with concentration is 49% is 10 seconds.
Then, the mixed solution with ammoniacal liquor, hydrogen peroxide and water cleans control sheet 100 surfaces again, further removes residual silicon oxynitride particle 102a, makes the silicon oxynitride particle 102a on all control sheet 100 surfaces on the processing line reach requirement, is less than 100.
In the present embodiment, the ratio of ammoniacal liquor, hydrogen peroxide and water is 1:1:50.The mixed solution cleaning control 100 surperficial used times of sheet with ammoniacal liquor, hydrogen peroxide and water are 4 minutes～7 minutes, and the preferred time is 5 minutes.
The scheme of present embodiment makes all the control sheets on the processing line meet the requirements through cleaning, and then the utilance of control sheet is improved, and cost descends.
Fig. 8 removes the design sketch of controlling residual nitrogen silicon oxide particle on the sheet on the control sheet behind the silicon oxynitride film with technology of the present invention.As shown in Figure 8, adopt process of the present invention: be 0.2%～0.5% hydrofluoric acid clean silicon oxynitride film surface 8 minutes～12 minutes earlier with concentration, the in-situ oxidation silicon layer of oxidation generation of can removing the silicon oxynitride film surface because be exposed in the air; Then, with concentration is 55%～65% phosphoric acid etching silicon oxynitride film, and the used time is 20 minutes～40 minutes, silicon oxynitride film almost completely can be removed, only residual a little silicon oxynitride particle, promptly the silicon oxynitride particle probably is less than 5000 more than 100; With concentration is that 45%～50% hydrofluoric acid is removed the residual nitrogen silicon oxide particle, and the used time is 8 seconds～12 seconds, through this step, can make the silicon oxynitride particle of all the control sheet remained on surface on the processing line approach 100; At last, be that the mixed solution of ammoniacal liquor, hydrogen peroxide and the water of 1:1:50 cleans control sheet surface with ratio, further remove the silicon oxynitride particle on the control sheet, make the silicon oxynitride particle on all the control sheet surfaces on the processing line reach requirement, be less than 100.With process of the present invention the utilance of control sheet is improved, cost descends.
Though the present invention discloses as above with preferred embodiment, the present invention is defined in this.Any those skilled in the art without departing from the spirit and scope of the present invention, all can do various changes and modification, so protection scope of the present invention should be as the criterion with claim institute restricted portion.
Claims (7)
1. a method of removing silicon oxynitride film is characterized in that, comprising:
The control that is formed with silicon oxynitride film sheet is provided;
It with concentration 0.2%～0.5% hydrofluoric acid clean silicon oxynitride film surface;
Remove silicon oxynitride film with phosphoric acid;
With concentration is that 45%～50% hydrofluoric acid is removed the residual nitrogen silicon oxide film;
Clean control sheet surface with the solution that comprises ammoniacal liquor, hydrogen peroxide and water.
2. according to the method for the described removal silicon oxynitride film of claim 1, it is characterized in that, is that 0.2%～0.5% the hydrofluoric acid clean silicon oxynitride film used time of surface is 8 minutes～12 minutes with concentration.
3. according to the method for the described removal silicon oxynitride film of claim 1, it is characterized in that described concentration of phosphoric acid is 55%～65%.
4. according to the method for claim 1 or 3 described removal silicon oxynitride films, it is characterized in that removing the used time of silicon oxynitride film with phosphoric acid is 20 minutes～40 minutes.
5. according to the method for the described removal silicon oxynitride film of claim 1, it is characterized in that, is that to remove the residual nitrogen used time of silicon oxide film be 8 seconds～12 seconds for 45%～50% hydrofluoric acid with concentration.
6. according to the method for the described removal silicon oxynitride film of claim 1, it is characterized in that the ratio of ammoniacal liquor, hydrogen peroxide and water is 1: 1: 50.
7. according to the method for claim 1 or 6 described removal silicon oxynitride films, it is characterized in that controlling the sheet used time of surface with the mixed solution cleaning of ammoniacal liquor, hydrogen peroxide and water is 4 minutes～7 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2008100418835A CN101656191B (en) | 2008-08-19 | 2008-08-19 | Method for removing silicon oxynitride film |
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| CN2008100418835A CN101656191B (en) | 2008-08-19 | 2008-08-19 | Method for removing silicon oxynitride film |
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| CN101656191A CN101656191A (en) | 2010-02-24 |
| CN101656191B true CN101656191B (en) | 2011-06-15 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101799381B (en) * | 2010-03-02 | 2012-03-14 | 上海新傲科技股份有限公司 | Method for forming oxide layer on surface of silicon wafer |
| CN102716867B (en) * | 2012-06-21 | 2015-01-14 | 苏州阿特斯阳光电力科技有限公司 | Method for cleaning crystalline silicon slice of solar battery |
| CN103894362A (en) * | 2014-01-10 | 2014-07-02 | 浙江晶科能源有限公司 | Method for cleaning coating film reworked sheet |
| CN105551940A (en) * | 2016-01-11 | 2016-05-04 | 上海华虹宏力半导体制造有限公司 | Method of removing photoetching anti-reflective layer containing particle defects |
| CN111540670B (en) * | 2020-05-11 | 2023-10-24 | 粤芯半导体技术股份有限公司 | Wet cleaning method for wafer and manufacturing method for semiconductor device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6521549B1 (en) * | 2000-11-28 | 2003-02-18 | Lsi Logic Corporation | Method of reducing silicon oxynitride gate insulator thickness in some transistors of a hybrid integrated circuit to obtain increased differential in gate insulator thickness with other transistors of the hybrid circuit |
| CN1778991A (en) * | 2004-11-17 | 2006-05-31 | 上海华虹Nec电子有限公司 | Selective silicon nitrogen oxide sculpturing liquid by wetting method |
| CN1794432A (en) * | 2005-11-11 | 2006-06-28 | 中国电子科技集团公司第五十五研究所 | Semiconductor platform technology |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6521549B1 (en) * | 2000-11-28 | 2003-02-18 | Lsi Logic Corporation | Method of reducing silicon oxynitride gate insulator thickness in some transistors of a hybrid integrated circuit to obtain increased differential in gate insulator thickness with other transistors of the hybrid circuit |
| CN1778991A (en) * | 2004-11-17 | 2006-05-31 | 上海华虹Nec电子有限公司 | Selective silicon nitrogen oxide sculpturing liquid by wetting method |
| CN1794432A (en) * | 2005-11-11 | 2006-06-28 | 中国电子科技集团公司第五十五研究所 | Semiconductor platform technology |
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