CN111524790A - Process method for improving silicon wafer recoverability through high-temperature wet oxygen oxidation method - Google Patents
Process method for improving silicon wafer recoverability through high-temperature wet oxygen oxidation method Download PDFInfo
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- CN111524790A CN111524790A CN202010336959.8A CN202010336959A CN111524790A CN 111524790 A CN111524790 A CN 111524790A CN 202010336959 A CN202010336959 A CN 202010336959A CN 111524790 A CN111524790 A CN 111524790A
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- 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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
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- H01L21/02019—Chemical etching
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- H01L21/02032—Preparing bulk and homogeneous wafers by reclaiming or re-processing
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/02079—Cleaning for reclaiming
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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Abstract
The invention provides a process method for improving the recoverability of a silicon wafer by a high-temperature wet oxygen oxidation method, which comprises the steps of providing a silicon wafer to be recovered, wherein a SiCN film layer is arranged on the silicon wafer; placing the silicon wafer in a high-temperature wet oxygen environment for thermal oxidation treatment until the SiCN film layer is completely oxidized into SiOCN; and removing SiOCN on the silicon wafer by using a wet etching process of acid washing. The process method adopted by the invention carries out thermal oxidation treatment on the silicon wafer to be recovered in the environment of high-temperature wet oxygen, so that the films of SiCN and the like are completely oxidized into SiOCN, then the SiOCN is completely removed by utilizing the acid-washing wet etching process, and finally the high-efficiency recovery of the silicon wafer containing the films of SiCN and the like is realized, the recovery and reuse times of the silicon wafer are increased, and the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a process method for improving silicon wafer recoverability through a high-temperature wet oxygen oxidation method.
Background
The silicon carbon nitride (SiCN) film is a novel functional film material, is often used as a gate side wall (offset spacer) in the technical field of integrated circuit manufacturing, has the characteristics of good corrosion resistance and the like, and is difficult to directly remove by directly utilizing a wet etching process, thereby influencing the recycling of silicon wafers containing the SiCN film.
Because of the characteristics of high SiCN hardness, good corrosion resistance and the like, the method of chemical mechanical grinding or ion etching is mostly adopted for directly removing the SiCN film at present, but the chemical mechanical grinding and the ion etching are single-chip single-side operation, and for the recycling of the silicon chip containing the SiCN film, the problems of low efficiency, high cost and large times of recycling are existed; the wet etching can control the etching selection ratio, and simultaneously, the film layers on the front side and the back side of the silicon wafer are etched in batch, so that the recovery effect and the recovery efficiency can be obviously improved, but the SiCN film layer is difficult to directly remove by the wet etching process.
Therefore, in order to solve the above problems, it is necessary to provide a new process for improving the silicon wafer recycling property.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a process for improving the recyclability of silicon wafers by a high temperature wet oxygen oxidation method, which is used to solve the problem of low recycling efficiency of the silicon wafers recycled in the prior art due to the fact that the SiCN film layer of the silicon wafers is difficult to remove in the conventional wet etching process.
To achieve the above and other related objects, the present invention provides a process for improving the recyclability of silicon wafers by a high temperature wet oxygen oxidation process, the process comprising at least the steps of:
providing a silicon wafer to be recovered, wherein a SiCN film layer exists on the silicon wafer;
secondly, placing the silicon wafer in a high-temperature wet oxygen environment for thermal oxidation treatment until the SiCN film layer is completely oxidized into SiOCN;
and step three, removing SiOCN on the silicon wafer by using a wet etching process.
Preferably, in the step one, the SiCN film layer exists on the front side and the back side of the silicon wafer to be recycled.
Preferably, the temperature of the high-temperature wet oxygen environment in the second step is 980 ℃.
Preferably, the high temperature humid oxygen environment in step two comprises water vapor and oxygen components.
Preferably, the volume ratio of the water vapor to the oxygen in the second step is: h2O:O2＝2:1。
Preferably, the thickness of the SiCN film in the first step is 100A.
Preferably, the time for performing thermal oxidation treatment on the silicon wafer in the second step is 60 min.
Preferably, in the third step, the SiOCN is removed by wet etching with hydrofluoric acid.
Preferably, the ratio of the H2O to the HF of the hydrofluoric acid used in the third step is 1: 1-10: 1.
Preferably, in the third step, the SiOCN is removed by wet etching with concentrated phosphoric acid.
As described above, the process for improving the recyclability of silicon wafers by the high-temperature wet oxygen oxidation method according to the present invention has the following beneficial effects: the process method adopted by the invention carries out thermal oxidation treatment on the silicon wafer to be recovered in the environment of high-temperature wet oxygen, so that the films of SiCN and the like are completely oxidized into SiOCN, then the SiOCN is completely removed by utilizing the acid-washing wet etching process, and finally the high-efficiency recovery of the silicon wafer containing the films of SiCN and the like is realized, the recovery and reuse times of the silicon wafer are increased, and the production cost is reduced.
Drawings
FIG. 1 is a schematic flow chart of the process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to the present invention;
FIG. 2 is a schematic diagram showing the thermal oxidation of a silicon wafer to be recovered with a SiCN film layer on the surface according to the present invention;
FIG. 3 is a schematic view showing a silicon wafer to be recovered after acid washing and thermal oxidation in the present invention;
FIG. 4 is a schematic view of a silicon wafer to be recycled after the SiOCN on the surface is removed after cleaning in the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 4. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
Example one
The invention provides a process method for improving silicon wafer recoverability by a high-temperature wet oxygen oxidation method, as shown in fig. 1, fig. 1 is a schematic flow chart of the process method for improving silicon wafer recoverability by the high-temperature wet oxygen oxidation method, and the process method comprises the following steps in the embodiment:
providing a silicon wafer to be recovered, wherein a SiCN film layer exists on the silicon wafer; furthermore, in the first step, the SiCN film layers exist on the front side and the back side of the silicon wafer to be recovered. Because the SiCN film layer on the silicon wafer generally has an anti-corrosion effect in the integrated circuit manufacturing process, the formed SiCN film layer is generally used as a side wall of a grid electrode, and the SiCN film layer on the front side and the back side of the silicon wafer is required to be removed to have a recycling value when the silicon wafer is recycled. Therefore, the following steps are required to remove the SiCN film layer on the silicon wafer. In this embodiment, the thickness of the SiCN film in the first step is 100A.
Secondly, placing the silicon wafer in a high-temperature wet oxygen environment for thermal oxidation treatment until the SiCN film layer is completely oxidized into SiOCN; further, the temperature of the high-temperature wet oxygen environment in the step two is 980 ℃. And in the second step, the high-temperature wet oxygen environment comprises water vapor and oxygen components. In still another aspect of the present invention, the water vapor and oxygen in step twoThe volume ratio of gas is: h2O:O2Further, the thermal oxidation time of the silicon wafer in the second step is 60min, that is, in this embodiment, the thermal oxidation time is 60min for the silicon wafer with the SiCN film layer with the thickness of 100A. The step enables the silicon wafer to be subjected to thermal oxidation treatment in a high-temperature wet oxygen environment, because the size of water molecules is smaller than that of oxygen molecules, the water molecules can enter a SiCN film layer structure more easily than the oxygen molecules to form SiOCN, and because the H2 generated by the reaction of the water molecules and the SiCN is generated, the formed SiOCN structure is loose, the oxidation of deeper SiCN to SiOCN is further facilitated, and finally the SiCN can be completely oxidized to SiOCN. The addition of O2 can regulate the quality of the generated SiOCN film layer to be more uniform and consistent, and avoid the damage of the surface quality (such as flatness, roughness and the like) of the silicon wafer after recovery, which is possibly caused by the non-uniform quality of the SiOCN film layer. Referring to fig. 2, fig. 2 is a schematic view illustrating thermal oxidation of a silicon wafer to be recycled, in which a SiCN film layer is present on the surface thereof according to the present invention. Therefore, in this embodiment, a high temperature environment with a temperature of 980 ℃ is used, and the silicon wafer is placed in an environment containing water vapor and oxygen, wherein the volume ratio of water vapor to oxygen in this environment is: h2O:O22:1, placing the silicon wafer at a high temperature of 980 ℃ in a volume ratio of H2O:O2The duration of the run in 2:1 water vapor and oxygen was 60min for a SiCN thermal oxidation of thickness 100A. Under the above conditions, the SiCN film on the silicon wafer can be completely oxidized to form SiOCN. Since SiOCN is easier to remove than SiCN, the subsequent steps are directed to the removal of SiOCN.
And step three, removing SiOCN on the silicon wafer by utilizing a wet etching process of acid washing. Because the SiOCN formed on the silicon wafer is easy to be cleaned by acid, the SiOCN is removed by utilizing a wet cleaning method of acid cleaning in the third step of the invention. As shown in FIG. 3, the acid for removing SiOCN shown in FIG. 3 as a schematic view of the silicon wafer to be recovered after the acid cleaning and the thermal oxidation in the present invention may be various, and the acid in the present invention includes hydrofluoric acid or concentrated phosphoric acid. Further, in the third step of this embodiment, the SiOCN is removed by wet etching with hydrofluoric acid. The invention further provides hydrofluoric acid used in the third step, wherein the ratio (concentration) of H2O to HF is 1: 1-10: 1. In the third step of this embodiment, a wet cleaning (etching) process with hydrofluoric acid is used to completely remove SiOCN on the front and back sides of the silicon wafer. FIG. 4 is a schematic view of a silicon wafer to be recycled after the SiOCN on the surface is removed after cleaning in the present invention.
Example two
This example provides a process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation, as shown in fig. 1, and fig. 1 is a schematic flow chart of the process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to the present invention, and the process comprises the following steps in this example:
providing a silicon wafer to be recovered, wherein a SiCN film layer exists on the silicon wafer; furthermore, in the first step, the SiCN film layers exist on the front side and the back side of the silicon wafer to be recovered. Because the SiCN film layer on the silicon wafer generally has an anti-corrosion effect in the integrated circuit manufacturing process, the formed SiCN film layer is generally used as a side wall of a grid electrode, and the SiCN film layer on the front side and the back side of the silicon wafer is required to be removed to have a recycling value when the silicon wafer is recycled. Therefore, the following steps are required to remove the SiCN film layer on the silicon wafer.
Secondly, placing the silicon wafer in a high-temperature wet oxygen environment for thermal oxidation treatment until the SiCN film layer is completely oxidized into SiOCN; further, the temperature of the high-temperature wet oxygen environment in the step two is 980 ℃. And in the second step, the high-temperature wet oxygen environment comprises water vapor and oxygen components. The invention still further provides that the volume ratio of the water vapor to the oxygen in the second step is H2O:O22:1, further, the time for performing thermal oxidation treatment on the silicon wafer in the second step is as follows: SiCN with the thickness of 100A is thermally oxidized for 60 min. The step enables the silicon wafer to be subjected to thermal oxidation treatment in a high-temperature wet oxygen environment, because the size of water molecules is smaller than that of oxygen molecules, the water molecules can enter a SiCN film layer structure more easily than the oxygen molecules to form SiOCN, and because the H2 generated by the reaction of the water molecules and the SiCN is generated, the formed SiOCN structure is loose, the deeper SiCN is further oxidized into the SiOCN, and finally the SiCN can be completely oxidized into the SiOCNTo SiOCN. The addition of O2 can regulate the quality of the generated SiOCN film layer to be more uniform and consistent, and avoid the damage of the surface quality (such as flatness, roughness and the like) of the silicon wafer after recovery, which is possibly caused by the non-uniform quality of the SiOCN film layer. Referring to fig. 2, fig. 2 is a schematic view illustrating thermal oxidation of a silicon wafer to be recycled, in which a SiCN film layer is present on the surface thereof according to the present invention. Therefore, in this example, a high temperature environment of 980 ℃ is used, and the silicon wafer is placed in an environment containing water vapor and oxygen, wherein the volume ratio of water vapor to oxygen in this environment is H2O:O22:1, placing the silicon wafer at a high temperature of 980 ℃ in a volume ratio of: h2O:O2Run in 2:1 steam and oxygen for a period of time: the thermal oxidation time was 60min for a thickness of 100A SiCN. Under the above conditions, the SiCN film on the silicon wafer can be completely oxidized to form SiOCN. Since SiOCN is easier to remove than SiCN, the subsequent steps are directed to the removal of SiOCN.
And step three, removing SiOCN on the silicon wafer by utilizing a wet etching process of acid washing. Because the SiOCN formed on the silicon wafer is easy to be cleaned by acid, the SiOCN is removed by utilizing a wet cleaning method of acid cleaning in the third step of the invention. As shown in FIG. 3, the acid for removing SiOCN shown in FIG. 3 as a schematic view of the silicon wafer to be recovered after the acid cleaning and the thermal oxidation in the present invention may be various, and the acid in the present invention includes hydrofluoric acid or concentrated phosphoric acid. Further, in the third step of this embodiment, the SiOCN is removed by wet etching with concentrated phosphoric acid. In the third step of this embodiment, a wet cleaning (etching) process of concentrated phosphoric acid is used to completely remove SiOCN on the front and back sides of the silicon wafer. FIG. 4 is a schematic view of a silicon wafer to be recycled after the SiOCN on the surface is removed after cleaning in the present invention.
In conclusion, the process method adopted by the invention carries out thermal oxidation treatment on the silicon wafer to be recovered under the environment of high-temperature wet oxygen, so that the film layers of SiCN and the like are completely oxidized into SiOCN, and then the SiOCN is completely removed by utilizing the acid-washing wet etching process, so that the high-efficiency recovery of the silicon wafer containing the film layers of SiCN and the like is finally realized, the recovery and reuse times of the silicon wafer are increased, and the production cost is reduced. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation, the process comprising at least the steps of:
providing a silicon wafer to be recovered, wherein a SiCN film layer exists on the silicon wafer;
secondly, placing the silicon wafer in a high-temperature wet oxygen environment for thermal oxidation treatment until the SiCN film layer is completely oxidized into SiOCN;
and step three, removing SiOCN on the silicon wafer by utilizing a wet etching process of acid washing.
2. The process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to claim 1 wherein: in the first step, the SiCN film layers exist on the front side and the back side of the silicon wafer to be recovered.
3. The process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to claim 1 wherein: and the temperature of the high-temperature wet oxygen environment in the second step is 980 ℃.
4. The process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to claim 1 wherein: and in the second step, the high-temperature wet oxygen environment comprises water vapor and oxygen components.
5. According toThe process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation as set forth in claim 4 wherein: the volume ratio of the water vapor to the oxygen in the step two is as follows: h2O:O2＝2:1。
6. The process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to claim 1 wherein: the thickness of the SiCN film layer in the first step is 100A.
7. The process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to claim 6 wherein: and in the second step, the time for performing thermal oxidation treatment on the silicon wafer is 60 min.
8. The process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to claim 1 wherein: and step three, carrying out wet etching by using hydrofluoric acid to remove the SiOCN.
9. The process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to claim 8 wherein: the hydrofluoric acid used in the third step has a ratio of H2O to HF of 1: 1-10: 1.
10. The process for improving the recyclability of silicon wafers by high temperature wet oxygen oxidation according to claim 1 wherein:
and step three, removing the SiOCN by wet etching by using concentrated phosphoric acid.
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| US6693047B1 (en) * | 2002-12-19 | 2004-02-17 | Taiwan Semiconductor Manufacturing Co. Ltd. | Method for recycling semiconductor wafers having carbon doped low-k dielectric layers |
| JP2004363516A (en) * | 2003-06-09 | 2004-12-24 | Sony Corp | Method for forming embedded wiring |
| US20060016786A1 (en) * | 2004-07-26 | 2006-01-26 | Bing-Yue Tsui | Method and apparatus for removing SiC or low k material film |
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| TW200816304A (en) * | 2006-09-21 | 2008-04-01 | United Microelectronics Corp | Method of recycling dummy wafer |
| CN102468228A (en) * | 2010-11-19 | 2012-05-23 | 中芯国际集成电路制造(上海)有限公司 | Semiconductor structure and forming method thereof |
| CN102610562A (en) * | 2012-03-23 | 2012-07-25 | 上海华力微电子有限公司 | Method for removing carbon element in carbon-contained thin film and regenerating method of SiOC control baffle plate |
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- 2020-04-26 CN CN202010336959.8A patent/CN111524790A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6693047B1 (en) * | 2002-12-19 | 2004-02-17 | Taiwan Semiconductor Manufacturing Co. Ltd. | Method for recycling semiconductor wafers having carbon doped low-k dielectric layers |
| JP2004363516A (en) * | 2003-06-09 | 2004-12-24 | Sony Corp | Method for forming embedded wiring |
| US20060016786A1 (en) * | 2004-07-26 | 2006-01-26 | Bing-Yue Tsui | Method and apparatus for removing SiC or low k material film |
| US20070082497A1 (en) * | 2005-08-08 | 2007-04-12 | Lee Chun-Deuk | Composition for removing an insulation material and related methods |
| TW200816304A (en) * | 2006-09-21 | 2008-04-01 | United Microelectronics Corp | Method of recycling dummy wafer |
| CN102468228A (en) * | 2010-11-19 | 2012-05-23 | 中芯国际集成电路制造(上海)有限公司 | Semiconductor structure and forming method thereof |
| CN102610562A (en) * | 2012-03-23 | 2012-07-25 | 上海华力微电子有限公司 | Method for removing carbon element in carbon-contained thin film and regenerating method of SiOC control baffle plate |
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Application publication date: 20200811 |