CN118726008A - Application of a fluorinated silane wafer surface treatment liquid - Google Patents
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- CN118726008A CN118726008A CN202310342769.0A CN202310342769A CN118726008A CN 118726008 A CN118726008 A CN 118726008A CN 202310342769 A CN202310342769 A CN 202310342769A CN 118726008 A CN118726008 A CN 118726008A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/28—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5018—Halogenated solvents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5027—Hydrocarbons
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Abstract
本发明公开了一种含氟硅烷晶圆表面处理液的应用。本发明的晶圆表面处理液可用于清洗刻蚀后的晶圆；该晶圆表面处理液的原料包括下列质量分数的组分：0.005％‑1％含氟硅烷、0.1％‑20％硅烷偶联剂和有机溶剂；各组分质量分数之和为100％；所述的有机溶剂补足余量。本发明的晶圆表面处理液处理晶圆之后，IPA接触角明显增大，在干燥过程中栅极间不会发生黏连，从而避免了栅极倒塌的发生。The invention discloses an application of a fluorine-containing silane wafer surface treatment liquid. The wafer surface treatment liquid of the invention can be used to clean the etched wafer; the raw materials of the wafer surface treatment liquid include the following components by mass fraction: 0.005%-1% fluorine-containing silane, 0.1%-20% silane coupling agent and organic solvent; the sum of the mass fractions of each component is 100%; the organic solvent makes up the balance. After the wafer is treated with the wafer surface treatment liquid of the invention, the IPA contact angle is significantly increased, and no adhesion occurs between the gates during the drying process, thereby avoiding the occurrence of gate collapse.
Description
Technical Field
The invention relates to application of a fluorine-containing silane wafer surface treatment liquid.
Background
With the continuous development of the semiconductor industry, integrated circuits are gradually developed towards high integration and ultra-fine line width, so that high aspect ratio structures involved in the chip manufacturing process are more and more involved (structures with a ratio of depth/height to width of greater than 10 are generally defined as high aspect ratios in the semiconductor industry). High aspect ratio structures not only present a significant challenge in etching and deposition processes, but also present significant problems in post-etch cleaning. On one hand, the current mainstream cleaning method is still wet cleaning based on water chemistry, and for micro-nano structures with small openings and large depth, liquid is difficult to enter the bottom of the groove to achieve the purpose of cleaning; on the other hand, once the cleaning liquid enters the deep groove, the liquid is difficult to remove under the action of surface tension, so that pollutant residues are left, the potential threat of subsequent processing is caused, and even the device is disabled when serious. At the same time, capillary forces present during drying of these high aspect ratio structures can also cause collapse of these structures, leading to device failure.
In the traditional IPA (isopropyl alcohol) spin-drying process, when the ratio of the gate electrode AR (aspect ratio) is more than 10, a large acting force (surface tension from IPA) is generated between the IPA and the gate electrode, and the IPA and the gate electrode are adhered in the spin-drying process, so that the gate electrode collapses in the drying process.
Disclosure of Invention
The invention aims to solve the technical problem that the grid electrode is collapsed in the spin-drying process after the wafer is processed by the traditional cleaning liquid, and provides application of the fluorine-containing silane wafer surface processing liquid. After the wafer is treated by the surface treatment liquid, the IPA contact angle is obviously increased, and the bonding between the grids can not occur in the drying process, so that the grid collapse is avoided.
The invention mainly solves the technical problems through the following technical scheme.
The invention provides application of a wafer surface treatment liquid in cleaning a wafer; the raw materials of the wafer surface treatment liquid comprise the following components in percentage by mass: 0.005% -1% of fluorine-containing silane, 0.1% -20% of silane coupling agent and organic solvent; the sum of the mass fractions of the components is 100 percent; the organic solvent is used for supplementing the balance;
The silane coupling agent is Wherein R 1、R2 and R 3 are independently H, alkyl, alkoxy, -OH, -NH 2, -COOH, or-NHC (O) NHR 4; at least one of R 1、R2 and R 3 is alkoxy;
R 4 is hydrogen or C 1-C6 alkyl;
The organic solvent is selected from one or more of Isopropanol (IPA), propylene Glycol Methyl Ether Acetate (PGMEA), N-Dimethylformamide (DMF), N-hexane, cyclohexanone, tetrahydrofuran, dichloromethane, acetone and xylene.
In some embodiments, the wafer surface treatment solution may be used to clean the etched wafer, preferably, it includes the following steps:
(1) Soaking the etched wafer in IPA cleaning solution (for example, soaking for 1 minute) and taking out;
(2) And (3) immersing the wafer obtained in the step (1) in the wafer surface treatment liquid (for example, immersing for 1 minute), taking out and drying.
In some embodiments, in the wafer surface treatment solution, R 4 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, preferably R 4 is hydrogen or methyl.
In some embodiments, the fluorine-containing silane is selected from one or more of perfluorooctyl trimethoxysilane, perfluorodecyl triethoxysilane, fluoropropyl methyl cyclotrisiloxane, (3, 3-trifluoropropyl) trimethoxysilane, (3, 3-trifluoropropyl) triethoxysilane, (3, 3-trifluoropropyl) methyldimethoxy silane and (3, 3-trifluoropropyl) methyldichloro silane, preferably, the fluorine-containing silane is selected from one or more of perfluorooctyl trimethoxysilane, perfluorodecyl triethoxysilane and (3, 3-trifluoropropyl) trimethoxysilane.
In some embodiments, the mass fraction of the fluorine-containing silane in the wafer surface treatment solution is 0.01% -0.08%, preferably 0.01% -0.05%.
In some embodiments, in the wafer surface treatment fluid, R 1、R2 and R 3 are independently C 1-C6 alkoxy, -NH 2, or-COOH, and at least one of R 1、R2 and R 3 is alkoxy; preferably, the C 1-C6 alkoxy group is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, for example methoxy.
In some embodiments, the mass fraction of the silane coupling agent in the wafer surface treatment solution is 5% -20%, preferably 5% -15%, and more preferably 10%.
In some embodiments, the silane coupling agent in the wafer surface treatment solution is
In some embodiments, the organic solvent is isopropyl alcohol and/or propylene glycol methyl ether acetate.
In some schemes, in the wafer surface treatment liquid, when the organic solvent is a mixed solution of isopropyl alcohol and propylene glycol methyl ether acetate, the mass ratio of the isopropyl alcohol to the propylene glycol methyl ether acetate is 1:1-2.
In some embodiments, the pH of the wafer surface treatment solution is 7-12.
In some aspects, the wafer is a high aspect ratio wafer.
In some embodiments, the wafer has a depth to width ratio of greater than 10, preferably 10-100, and more preferably 10-50.
In some embodiments, the wafer surface treatment liquid comprises the following raw materials in percentage by mass: 0.01% -0.05% of fluorine-containing silane, 10% of silane coupling agent and organic solvent; the sum of the mass fractions of the components is 100%; the organic solvent is used for supplementing the balance;
The fluorine-containing silane is selected from one or more of perfluorooctyl trimethoxy silane, perfluorodecyl triethoxy silane and (3, 3-trifluoropropyl) trimethoxy silane;
The silane coupling agent is
The organic solvent is isopropyl alcohol and/or propylene glycol methyl ether acetate.
In some embodiments, the raw materials of the wafer surface treatment liquid include any of the following components in percentage by mass:
Scheme 1:0.01% of perfluorooctyl trimethoxy silane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
scheme 2:0.01% of perfluorooctyl trimethoxy silane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
scheme 3:0.05% of perfluorooctyl trimethoxy silane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
scheme 4:0.05% of perfluorooctyl trimethoxy silane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
scheme 5:0.01% of perfluorodecyl triethoxysilane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
Scheme 6:0.01% of perfluorodecyl triethoxysilane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
Scheme 7:0.05% of perfluorodecyl triethoxysilane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
Scheme 8:0.05% of perfluorodecyl triethoxysilane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
Scheme 9:0.01% (3, 3-trifluoropropyl) trimethoxysilane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
Scheme 10:0.01% (3, 3-trifluoropropyl) trimethoxysilane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
Scheme 11:0.05% (3, 3-trifluoropropyl) trimethoxysilane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
Scheme 12:0.05% (3, 3-trifluoropropyl) trimethoxysilane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
Preferably, the raw material of the wafer surface treatment liquid is composed of any one of the above schemes.
The term "high aspect ratio" in the present invention; structures having a ratio of depth to width greater than 10 are generally defined in the semiconductor industry as high aspect ratios.
"Room temperature" means 20℃to 30 ℃.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: after the fluorine-containing silane wafer surface treatment liquid is used for cleaning a wafer, the IPA contact angle is obviously increased, the surface is changed from hydrophilic to hydrophobic, and the bonding between grids can not occur in the drying process, so that the grid collapse is avoided.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
The surface treatment solutions were prepared according to the components and proportions of the examples shown in Table 1, and the mixture was stirred at room temperature for 1 hour (no sequential addition).
TABLE 1
Note that: "/" indicates absence.
The test experiment method is carried out by adopting TEOS (tetraethoxysilane) and SiN (silicon nitride) respectively:
1. cutting a wafer with an aspect ratio of 10 into test pieces with 30 mm;
2. soaking the test piece in IPA cleaning solution for 1min; taking out;
3. Immersing the test pieces in the surface treatment solutions shown in table 1 for 1min, taking out and drying with nitrogen;
4. Performing contact angle test by using a contact angle tester (Attension THETA LITE), wherein the test solution is IPA; the surface roughness was also measured and the surface condition of the test piece was observed by electron microscopy, and the results are shown in table 2 below.
TABLE 2
As shown by test results, after the surface treatment liquid is soaked, the contact angle of IPA is obviously increased, and the bonding between grids can not occur in the drying process, so that the grid collapse is avoided.
Claims (10)
1. The application of the wafer surface treatment liquid in cleaning the wafer is characterized in that the raw materials of the wafer surface treatment liquid comprise the following components in percentage by mass: 0.005% -1% of fluorine-containing silane, 0.1% -20% of silane coupling agent and organic solvent; the sum of the mass fractions of the components is 100 percent; the organic solvent is used for supplementing the balance;
The silane coupling agent is Wherein R 1、R2 and R 3 are independently H, alkyl, alkoxy, -OH, -NH 2, -COOH, or-NHC (O) NHR 4; at least one of R 1、R2 and R 3 is alkoxy;
R 4 is hydrogen or C 1-C6 alkyl;
The organic solvent is one or more selected from isopropanol, propylene glycol methyl ether acetate, N-dimethylformamide, N-hexane, cyclohexanone, tetrahydrofuran, dichloromethane, acetone and xylene.
2. The use of a wafer surface treatment liquid according to claim 1 for cleaning a wafer, the wafer surface treatment liquid is used for cleaning the etched wafer, and preferably comprises the following steps:
(1) Placing the etched wafer into IPA cleaning solution for soaking and then taking out;
(2) And (3) soaking the wafer obtained in the step (1) in the wafer surface treatment liquid, and drying.
3. Use of a wafer surface treatment liquid according to claim 2 for cleaning a wafer, wherein one or more of the following conditions are met:
(1) The fluorine-containing silane is selected from one or more of perfluorooctyl trimethoxysilane, perfluorodecyl triethoxysilane, fluoropropyl methyl cyclotrisiloxane, (3, 3-trifluoropropyl) trimethoxysilane, (3, 3-trifluoropropyl) triethoxysilane, (3, 3-trifluoropropyl) methyl dimethoxy silane and (3, 3-trifluoropropyl) methyl dichloro silane;
(2) The mass fraction of the fluorine-containing silane is 0.01% -0.08%;
(3) R 4 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; and
(4) The wafer is a high aspect ratio wafer.
4. The use of a wafer surface treatment fluid according to claim 3 for cleaning a wafer, wherein the wafer surface treatment fluid satisfies one or more of the following conditions:
(1) The fluorine-containing silane is selected from one or more of perfluorooctyl trimethoxy silane, perfluorodecyl triethoxy silane and (3, 3-trifluoropropyl) trimethoxy silane;
(2) The mass fraction of the fluorine-containing silane is 0.01% -0.05%; and
(3) R 4 is hydrogen or methyl.
5. The use of a wafer surface treatment fluid according to claim 4 for cleaning a wafer, wherein the wafer surface treatment fluid satisfies one or more of the following conditions:
(1) R 1、R2 and R 3 are independently C 1-C6 alkoxy, -NH 2 or-COOH, at least one of R 1、R2 and R 3 being alkoxy;
(2) The mass fraction of the silane coupling agent is 5% -20%;
(3) The organic solvent is isopropyl alcohol and/or propylene glycol methyl ether acetate; and
(4) The pH value of the wafer surface treatment liquid is 7-12.
6. The use of a wafer surface treatment fluid according to claim 5 for cleaning a wafer, wherein the wafer surface treatment fluid satisfies one or more of the following conditions:
(1) In R 1、R2 and R 3, C 1-C6 alkoxy is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, for example methoxy;
(2) The mass fraction of the silane coupling agent is 5% -15%; and
(3) When the organic solvent is a mixed solution of isopropyl alcohol and propylene glycol methyl ether acetate, the mass ratio of the isopropyl alcohol to the propylene glycol methyl ether acetate is 1:1-2.
7. The use of a wafer surface treatment fluid according to claim 6 for cleaning a wafer, wherein the wafer surface treatment fluid satisfies one or both of the following conditions:
(1) The mass fraction of the silane coupling agent is 10%; and
(2) The silane coupling agent is
8. The use of the wafer surface treatment liquid according to claim 1, wherein the raw materials of the wafer surface treatment liquid comprise the following components in mass percent: 0.01% -0.05% of fluorine-containing silane, 10% of silane coupling agent and organic solvent; the sum of the mass fractions of the components is 100%; the organic solvent is used for supplementing the balance;
The fluorine-containing silane is selected from one or more of perfluorooctyl trimethoxy silane, perfluorodecyl triethoxy silane and (3, 3-trifluoropropyl) trimethoxy silane;
The silane coupling agent is
The organic solvent is isopropyl alcohol and/or propylene glycol methyl ether acetate.
9. Use of a wafer surface treatment liquid according to any one of claims 1 to 8 for cleaning wafers, wherein the raw materials of the wafer surface treatment liquid comprise any one of the following components in mass fraction:
Scheme 1:0.01% of perfluorooctyl trimethoxy silane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
scheme 2:0.01% of perfluorooctyl trimethoxy silane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
scheme 3:0.05% of perfluorooctyl trimethoxy silane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
scheme 4:0.05% of perfluorooctyl trimethoxy silane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
scheme 5:0.01% of perfluorodecyl triethoxysilane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
Scheme 6:0.01% of perfluorodecyl triethoxysilane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
Scheme 7:0.05% of perfluorodecyl triethoxysilane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
Scheme 8:0.05% of perfluorodecyl triethoxysilane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
Scheme 9:0.01% (3, 3-trifluoropropyl) trimethoxysilane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
Scheme 10:0.01% (3, 3-trifluoropropyl) trimethoxysilane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance;
Scheme 11:0.05% (3, 3-trifluoropropyl) trimethoxysilane, 10% And isopropyl alcohol, the balance being isopropyl alcohol;
Scheme 12:0.05% (3, 3-trifluoropropyl) trimethoxysilane, 10% And propylene glycol methyl ether acetate, the propylene glycol methyl ether acetate making up the balance.
10. Use of a wafer surface treatment liquid according to claim 9 for cleaning wafers, wherein the material of the wafer surface treatment liquid consists of any one of the solutions according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310342769.0A CN118726008A (en) | 2023-03-31 | 2023-03-31 | Application of a fluorinated silane wafer surface treatment liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310342769.0A CN118726008A (en) | 2023-03-31 | 2023-03-31 | Application of a fluorinated silane wafer surface treatment liquid |
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| CN118726008A true CN118726008A (en) | 2024-10-01 |
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