TWI707030B - Chemical solution for forming water-repellent protective film and wafer surface treatment method - Google Patents

Abstract

The present invention provides a chemical liquid for forming a water-repellent protective film that can further improve the effect of imparting water-repellency. The chemical solution for forming a water-repellent protective film of the present invention has (I) an aminosilane compound represented by the following general formula [1], (II) a silicon compound represented by the following general formula [2], and (III) Protic solvent, and the content of (I) relative to the total amount of (I) to (III) is 0.02 to 0.5% by mass.

Description

Chemical solution for forming water-repellent protective film and wafer surface treatment method

The present invention relates to a water-repellent protective film forming chemical solution for forming a water-repellent protective film on the surface of a fine concave-convex pattern on the surface of a substrate (wafer) and a surface treatment method for wafers.

For semiconductor devices used in networks or digital home appliances, further high performance, high functionality, or low power consumption are required. Therefore, the miniaturization of circuit patterns has been advanced, and the problem of the pattern aspect ratio becoming higher with the miniaturization of semiconductor devices has emerged. That is, after washing or rinsing, the phenomenon of pattern collapse (hereinafter sometimes referred to as "pattern collapse") when passing through the pattern at the gas-liquid interface, the yield rate is greatly reduced, and this situation becomes a serious problem.

The pattern collapse occurs when the cleaning solution or the rinse solution is dried and removed from the wafer surface. It is believed that the reason is that there is a difference in the height of the residual liquid between the part with a high aspect ratio and a low part of the pattern, and thus the capillary force acting on the pattern is different. Therefore, if the water-repellent protective film is formed on the pattern surface by replacing the cleaning liquid or rinsing liquid with the chemical liquid for forming a water-repellent protective film, and the capillary force acting on the pattern is reduced, the difference in the height of the residual liquid can be expected. The resulting difference in capillary force is reduced, and pattern collapse is eliminated.

(R分別相互獨立地為選自包含碳數為1～18之烴基之1價有機基、及包含碳數為1～8之氟烷基鏈之1價有機基中之至少1種基，X分別相互獨立地為鍵結於Si元素之元素為氮之1價有機基，a係1～3之整數，b係0～2之整數，且a與b合計為1～3)。 先前技術文獻 專利文獻The applicant disclosed in Patent Document 1 a chemical solution for forming a water-repellent protective film or a method for cleaning a wafer using the chemical solution. The chemical solution is used to clean the surface with fine uneven patterns and the unevenness When at least a part of the pattern contains silicon on the wafer, a water-repellent protective film is formed on the surface of at least the concave portion of the concave-convex pattern, characterized in that it contains an acidic silicon compound A and an acid A represented by the following general formula. The acid A is Selected from trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethyl trifluoroacetate Silane ester, butyl dimethyl silyl trifluoromethanesulfonate, hexyl dimethyl silyl trifluoroacetate, hexyl dimethyl silyl trifluoromethanesulfonate, octyl dimethyl silyl trifluoroacetate, three At least one of the group consisting of octyl dimethyl silyl fluoromethanesulfonate, decyl dimethyl silyl trifluoroacetate, and decyl dimethyl silyl trifluoromethanesulfonate, and one of the above-mentioned liquids The total amount of moisture in the starting material is 100 mass ppm or less relative to the total amount of the material. [化1]

(R is each independently at least one group selected from a monovalent organic group containing a hydrocarbon group with 1 to 18 carbons and a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbons, X Each independently of each other is a monovalent organic group in which the element bonded to the Si element is nitrogen, a is an integer of 1 to 3, b is an integer of 0 to 2, and the total of a and b is 1 to 3). Prior Art Document Patent Document

Patent Document 1: Japanese Patent No. 5821844

[The problem to be solved by the invention]

In the manufacturing of semiconductor devices, especially in the cleaning technology of substrates (wafers) aimed at improving the manufacturing yield of circuit patterned devices with fine and high aspect ratios, a chemical solution for forming a water-repellent protective film has been developed. The chemical solution for forming a protective film described in Patent Document 1 reliably exerts an excellent water repellency imparting effect, and the total amount of water in the starting material of the chemical solution is 100 mass ppm or less relative to the total amount of the material. The storage stability of the liquid is excellent. However, in recent years, the trend toward higher integration and miniaturization of semiconductor devices has increased, and the miniaturization and high aspect ratio of wafer patterns have been advancing. Therefore, water-repellent protective film formation chemicals that reduce pattern collapse are expected to impart water-repellency The effect is further improved. [Technical means to solve the problem]

[式[1]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；a係1～3之整數，b係0～2之整數，且a與b合計為1～3]。 [化3]

[式[2]中，R² 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；又，X表示選自由鹵基、-OC(=O)R³ 、-OS(=O)₂ -R³ 、-N(S(=O)₂ -R³ )₂ 、-C(S(=O)₂ -R³ )₃ 所組成之群中之至少1種基；R³ 係碳數為1至6之1價全氟烷基，c係1～3之整數，d係0～2之整數，且c與d合計為1～3]。The present invention is a chemical solution for forming a water-repellent protective film (hereinafter, sometimes only referred to as "a chemical solution for forming a protective film" or "a chemical solution"), which has (I) an amine group represented by the following general formula [1] Silane compound, (II) silicon compound represented by the following general formula [2], and (III) aprotic solvent, and the content of (I) relative to the total amount of (I) to (III) is 0.02～ 0.5% by mass. [化2]

[In formula [1], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; a is an integer of 1 to 3, b is an integer of 0-2, and the total of a and b is 1-3]. [化3]

[In formula [2], R ^{2 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with a carbon number of 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; and X represents selected from halogen groups , -OC(=O)R ³ , -OS(=O) ₂ -R ³ , -N(S(=O) ₂ -R ³ ) ₂ , -C(S(=O) ₂ -R ³ ) ₃ At least one group in the group; R ³ is a monovalent perfluoroalkyl group with carbon number of 1 to 6, c is an integer of 1 to 3, d is an integer of 0 to 2, and the sum of c and d is 1～3].

[式[3]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；e係1～3之整數，f係0～2之整數，且e與f合計為3]。In addition, if the above-mentioned (I) is a compound represented by the following general formula [3], the above-mentioned protective film can be formed homogeneously, which is more preferable. [化4]

[In formula [3], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3].

[式[4]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；e係1～3之整數，f係0～2之整數，且e與f合計為3]。From the viewpoint of the ease of preparing the drug solution, the drug solution preferably further contains (IV) the silazane compound represented by the following general formula [4]. [化5]

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3].

In addition, the content of (II) relative to the total amount of (I) to (III) above is preferably 0.05% by mass or more from the viewpoint of improving the effect of imparting water repellency, and it is higher from the viewpoint of cost. Preferably, it is 20% by mass or less.

[式[5]中，R² 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基，R³ 係碳數為1至6之1價全氟烷基；又，g係1～3之整數]。In addition, from the viewpoint of improving the water repellency imparting effect, the above (II) is preferably at least one compound selected from the group consisting of the following general formula [5]. [化6]

[In formula [5], R ^{2 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with a carbon number of 1 to 18 that can be substituted with a part or all of hydrogen elements and fluorine elements, and R ³ is a monovalent organic group with a carbon number of 1 to 6 is a monovalent perfluoroalkyl group; and, g is an integer of 1 to 3].

[式[1]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；a係1～3之整數，b係0～2之整數，且a與b合計為1～3]。 [化8]

[式[2]中，R² 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；又，X表示選自由鹵基、-OC(=O)R³ 、-OS(=O)₂ -R³ 、-N(S(=O)₂ -R³ )₂ 、-C(S(=O)₂ -R³ )₃ 所組成之群中之至少1種基；R³ 係碳數為1至6之1價全氟烷基，c係1～3之整數，d係0～2之整數，且c與d合計為1～3]。In addition, the present invention is a wafer surface treatment method, which has a water-repellent protective film forming step and a drying step. The water-repellent protective film forming step is composed of a cleaning solution and a rinsing solution on the wafer surface. In the state of at least one liquid in the group, the liquid is replaced with a chemical solution for forming a water-repellent protective film and the chemical solution is held on the surface of the wafer. The chemical solution for forming a water-repellent protective film has the following characteristics (I) The aminosilane compound represented by formula [1], (II) the silicon compound represented by the following general formula [2], and (III) aprotic solvent, relative to the total amount of (I) to (III) The content of (I) is 0.02 to 0.5 mass%. [化7]

[In formula [1], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; a is an integer of 1 to 3, b is an integer of 0-2, and the total of a and b is 1-3]. [化8]

[In formula [2], R ^{2 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with a carbon number of 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; and X represents selected from halogen groups , -OC(=O)R ³ , -OS(=O) ₂ -R ³ , -N(S(=O) ₂ -R ³ ) ₂ , -C(S(=O) ₂ -R ³ ) ₃ At least one group in the group; R ³ is a monovalent perfluoroalkyl group with carbon number of 1 to 6, c is an integer of 1 to 3, d is an integer of 0 to 2, and the sum of c and d is 1～3].

[式[3]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；e係1～3之整數，f係0～2之整數，且e與f合計為3]。In addition, if the above-mentioned (I) is a compound represented by the following general formula [3], the above-mentioned protective film can be formed homogeneously, which is more preferable. [化9]

[In formula [3], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3].

[式[4]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；e係1～3之整數，f係0～2之整數，且e與f合計為3]。In the above method, from the viewpoint of the ease of preparing a chemical solution, the chemical solution for forming a water-repellent protective film preferably further contains (IV) a silazane compound represented by the following general formula [4]. [化10]

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3].

[式[4]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；e係1～3之整數，f係0～2之整數，且e與f合計為3]。In addition, from the viewpoint of the ease of preparing the drug solution, the above method preferably includes a drug solution preparation step before the water-repellent protective film formation step, and the drug solution preparation step is to make the protic compound and the (II) above The silicon compound represented by the general formula [2], (IV) the silazane compound represented by the following general formula [4], and (III) the crude drug solution of the aprotic solvent are compared to (II), (III) The total amount of 1 kg of) and (IV) is contacted at a ratio of 0.001 to 0.3 mol, thereby preparing (I) having the above (I) to (III) and relative to the total amount of (I) to (III) The content is 0.02-0.5% by mass of the water-repellent protective film forming liquid. [化11]

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3].

[式[4]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；e係1～3之整數，f係0～2之整數，且e與f合計為3]。In addition, from the viewpoint of the ease of preparing the drug solution, the above method preferably includes a drug solution preparation step before the water-repellent protective film formation step, and the drug solution preparation step is to make the protic compound and the (II) above The silicon compound represented by the general formula [2], (IV) the silazane compound represented by the following general formula [4], and (III) the crude drug solution of the aprotic solvent are compared to (II), (III) The total amount of 1 kg of ), (IV) is contacted at a ratio of 0.001 to 0.3 mol, thereby preparing (I) having the above (I) to (IV) and relative to the total amount of (I) to (III) The content is 0.02-0.5% by mass of the water-repellent protective film forming liquid. [化12]

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3].

Furthermore, in the above method, it is preferable that the above-mentioned drug solution preparation step introduces the above-mentioned raw drug solution into the space containing the protic compound to bring the two into contact, so that the two can be brought into uniform contact easily. Furthermore, the protic compound contained in the aforementioned space may be in a liquid state or in a gas state. When the protic compound is in a gas state, it is better to manage the concentration (vol%) of the protic compound in the space and the contact time.

In the above method, from the viewpoint of improving the effect of imparting water repellency, the protic compound is preferably a compound having an -OH group and/or -NH ₂ group, and more preferably water, and/or, 2- Propanol is particularly preferably water.

[式[4]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；e係1～3之整數，f係0～2之整數，且e與f合計為3]。 [化14]

[式[6]中，X表示鹵基、-OC(=O)R³ 、-OS(=O)₂ -R³ 、-N(S(=O)₂ -R³ )₂ 、-C(S(=O)₂ -R³ )₃ ；且R³ 係碳數為1至6之1價全氟烷基]。In addition, if the above method has a chemical solution preparation step before the water-repellent protective film formation step, the chemical solution preparation step is to combine the acidic compound represented by the following general formula [6] with the acid compound having (IV) the following general formula [4 ] The indicated silazane compound and (III) aprotic solvent raw material liquid are contacted at a ratio of 0.001 to 0.3 mol relative to the total amount of (III) and (IV) 1 kg, thereby preparing The water-repellent protective film forming chemical solution having the above (I) to (III) and the content of (I) relative to the total amount of (I) to (III) is 0.02 to 0.5% by mass, which can reduce the raw materials used Quantity, so it is better from a cost point of view. [化13]

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3]. [化14]

[In formula [6], X represents a halogen group, -OC(=O)R ³ , -OS(=O) ₂ -R ³ , -N(S(=O) ₂ -R ³ ) ₂ , -C( S(=O) ₂ -R ³ ) ₃ ; and R ³ is a monovalent perfluoroalkyl group having 1 to 6 carbon atoms].

[式[4]中，R¹ 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基；e係1～3之整數，f係0～2之整數，且e與f合計為3]。 [化16]

[式[6]中，X表示鹵基、-OC(=O)R³ 、-OS(=O)₂ -R³ 、-N(S(=O)₂ -R³ )₂ 、-C(S(=O)₂ -R³ )₃ ，且R³ 係碳數為1至6之1價全氟烷基]。In addition, if the above method has a chemical solution preparation step before the water-repellent protective film formation step, the chemical solution preparation step is to combine the acidic compound represented by the following general formula [6] with the acid compound having (IV) the following general formula [4 ] The indicated silazane compound and (III) aprotic solvent raw material liquid are contacted at a ratio of 0.001 to 0.3 mol relative to the total amount of (III) and (IV) 1 kg, thereby preparing The water-repellent protective film forming chemical solution having the above (I) to (IV) and the content of (I) relative to the total amount of (I) to (III) is 0.02 to 0.5% by mass, which can reduce the raw materials used The quantity is better in terms of cost. [化15]

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3]. [化16]

[In formula [6], X represents a halogen group, -OC(=O)R ³ , -OS(=O) ₂ -R ³ , -N(S(=O) ₂ -R ³ ) ₂ , -C( S(=O) ₂ -R ³ ) ₃ , and R ³ is a monovalent perfluoroalkyl group having 1 to 6 carbon atoms].

Furthermore, in the above method, the content of (II) relative to the total amount of (I) to (III) above is preferably 0.05% by mass or more from the viewpoint of improving the effect of imparting water repellency, and in terms of cost From a viewpoint, it is preferably 20% by mass or less.

[式[5]中，R² 分別相互獨立地為包含部分或全部氫元素可取代為氟元素之碳數為1至18之1價烴基之1價有機基，R³ 係碳數為1至6之1價全氟烷基；又，g係1～3之整數]。 [發明之效果]Moreover, in the above method, if the above (II) is at least one compound selected from the group consisting of the following general formula [5], it is preferable from the viewpoint of improving the water repellency imparting effect. [化17]

[In formula [5], R ^{2 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with a carbon number of 1 to 18 that can be substituted with a part or all of hydrogen elements and fluorine elements, and R ³ is a monovalent organic group with a carbon number of 1 to 6 is a monovalent perfluoroalkyl group; and, g is an integer of 1 to 3]. [Effects of Invention]

According to the present invention, there is provided a water-repellent protective film forming chemical solution with a novel composition that can exert a more excellent water-repellency imparting effect, and a surface treatment method of a wafer using the chemical solution.

1. Chemical solution for forming water-repellent protective film The chemical solution for forming a water-repellent protective film is used when a water-repellent protective film (hereinafter, only referred to as "protective film") is formed on the surface of the object to be treated. The type of the object to be processed is not particularly limited. The object to be processed is preferably a "substrate (wafer)". Here, as the "wafer" to be processed, a wafer used for the production of semiconductor devices is exemplified. The so-called "surface of the wafer" exemplifies the inorganic pattern and resin pattern provided on the wafer in addition to the surface of the wafer itself. The surface of the inorganic layer and the surface of the organic layer without patterning.

As the inorganic pattern provided on the wafer, an etching mask is made on the surface of the inorganic layer existing on the wafer by a photoresist method, and then a pattern formed by an etching process. As the inorganic layer, in addition to the wafer itself, an oxide film of the elements constituting the wafer, and a film or layer of inorganic substances such as silicon nitride, titanium nitride, and tungsten formed on the surface of the wafer are exemplified. Such a film or layer is not particularly limited, and is exemplified by an inorganic film or layer formed in the production process of a semiconductor element.

As the resin pattern provided on the wafer, a resin pattern formed on the wafer by a photoresist method is exemplified. Such a resin pattern is formed, for example, by forming an organic layer as a photoresist film on a wafer, and exposing and developing the organic layer through a photomask. As the organic layer, in addition to the surface of the wafer itself, an organic layer such as the surface of a laminated film provided on the surface of the wafer is exemplified. The organic layer is not particularly limited, and is exemplified in a film of an organic substance provided to form an etching mask during the production process of a semiconductor device.

The drug solution of the present invention prepared in advance can be applied to the surface of a processed object such as a wafer by means of a spin coating method or a dipping method, etc., so that it can be held on the surface. In addition, the above-mentioned chemical solution may be vaporized and supplied to the surface of the object to be processed such as a wafer (hereinafter, sometimes referred to as a "vapor method") to be held on the surface.

Furthermore, it is also possible to contact the raw chemical solution with the protic compound in a state where the raw chemical solution is applied to the surface of the object to be processed such as a wafer by means of spin coating, dipping, or steam. The chemical solution for forming a water-repellent protective film is prepared by the reaction described later, and is held on the surface of the object to be treated. In addition, in a space containing a protic compound in advance, the above-mentioned raw chemical solution may be applied to the surface of a processed object such as a wafer by means of spin coating, dipping, or steam, and prepared by the reaction described below. The water-repellent protective film is formed with a chemical solution, and it is kept on the surface of the object to be treated.

The chemical solution for forming a water-repellent protective film of the present invention contains at least (I) an aminosilane compound, (II) a silicon compound, and (III) an aprotic solvent. Hereinafter, each component will be described.

[(I) Aminosilane compound and (II) Silicon compound] R ¹ of the general formula [1] and R ² of the general formula [2] are water-repellent functional groups. And, for example, when the object to be processed is a wafer containing silicon, the -NH ₂ group of the general formula [1] or the -X group of the general formula [2] reacts with the silanol group on the wafer surface , The part having the above water-repellent functional group is fixed on the surface of the wafer, thereby forming a water-repellent protective film on the surface of the wafer. By using both the above (I) and (II), both react quickly with the wafer surface, and a more excellent water repellency imparting effect can be obtained.

If R ¹ of the above general formula [1] is a linear alkyl group, when a protective film is formed on the surface of the wafer as the object to be processed, it can impart more excellent water repellency to the surface, which is preferable.

As specific examples of the aminosilane compound represented by the general formula [1], for example, CH ₃ Si(NH ₂ ) ₃ , C ₂ H ₅ Si(NH ₂ ) ₃ , C ₃ H ₇ Si(NH ₂ ) ₃ , C ₄ H ₉ Si(NH ₂ ) ₃ , C ₅ H ₁₁ Si(NH ₂ ) ₃ , C ₆ H ₁₃ Si(NH ₂ ) ₃ , C ₇ H ₁₅ Si(NH ₂ ) ₃ , C ₈ H ₁₇ Si(NH ₂ ) ₃ , C ₉ H ₁₉ Si(NH ₂ ) ₃ , C ₁₀ H ₂₁ Si(NH ₂ ) ₃ , C ₁₁ H ₂₃ Si(NH ₂ ) ₃ , C ₁₂ H ₂₅ Si(NH ₂ ) _3. C ₁₃ H ₂₇ Si(NH ₂ ) ₃ , C ₁₄ H ₂₉ Si(NH ₂ ) ₃ , C ₁₅ H ₃₁ Si(NH ₂ ) ₃ , C ₁₆ H ₃₃ Si(NH ₂ ) ₃ , C ₁₇ H ₃₅ Si(NH ₂ ) ₃ , C ₁₈ H ₃₇ Si(NH ₂ ) ₃ , (CH ₃ ) ₂ Si(NH ₂ ) ₂ , C ₂ H ₅ Si(CH ₃ )(NH ₂ ) ₂ , (C ₂ H ₅ ) ₂ Si(NH ₂ ) ₂ , C ₃ H ₇ Si(CH ₃ )(NH ₂ ) ₂ , (C ₃ H ₇ ) ₂ Si(NH ₂ ) ₂ , C ₄ H ₉ Si(CH ₃ )(NH ₂ ) ₂ , (C ₄ H ₉ ) ₂ Si(NH ₂ ) ₂ , C ₅ H ₁₁ Si(CH ₃ )(NH ₂ ) ₂ , C ₆ H ₁₃ Si(CH ₃ )(NH ₂ ) ₂ , C ₇ H ₁₅ Si(CH ₃ )(NH ₂ ) ₂ , C ₈ H ₁₇ Si(CH ₃ )(NH ₂ ) ₂ , C ₉ H ₁₉ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₀ H ₂₁ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₁ H ₂₃ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₂ H ₂₅ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₃ H ₂₇ Si(CH ₃ )(NH ₂ ) _2. C ₁₄ H ₂₉ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₅ H ₃₁ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₆ H ₃₃ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₇ H ₃₅ Si(CH ₃ )(NH ₂ ) ₂ , C ₁₈ H ₃₇ Si(CH ₃ )(NH ₂ ) ₂ , (CH ₃ ) ₃ SiNH ₂ , C ₂ H ₅ Si(CH ₃ ) ₂ NH ₂ , (C ₂ H ₅ ) ₂ Si(CH ₃ )NH ₂ , (C ₂ H ₅ ) ₃ SiNH ₂ , C ₃ H ₇ Si(CH ₃ ) ₂ NH ₂ , (C ₃ H ₇ ) ₂ Si(CH ₃ )NH ₂ , (C ₃ H ₇ ) ₃ SiNH ₂ , C ₄ H ₉ Si(CH ₃ ) ₂ NH ₂ , (C ₄ H ₉ ) ₃ SiNH ₂ , C ₅ H ₁₁ Si(CH ₃ ) ₂ NH ₂ , C ₆ H ₁₃ Si(CH ₃ ) ₂ NH ₂ , C ₇ H ₁₅ Si(CH ₃ ) ₂ NH ₂ , C ₈ H ₁₇ Si(CH ₃ ) ₂ NH ₂ , C ₉ H ₁₉ Si(CH ₃ ) ₂ NH ₂ , C ₁₀ H ₂₁ Si(CH ₃ ) ₂ NH ₂ , C ₁₁ H ₂₃ Si(CH ₃ ) ₂ NH ₂ , C ₁₂ H ₂₅ Si(CH ₃ ) ₂ NH ₂ , C ₁₃ H ₂₇ Si(CH ₃ ) ₂ NH ₂ , C ₁₄ H ₂₉ Si(CH ₃ ) ₂ NH ₂ , C ₁₅ H ₃₁ Si(CH ₃ ) ₂ NH ₂ , C ₁₆ H ₃₃ Si(CH ₃ ) ₂ NH ₂ , C ₁₇ H ₃₅ Si(CH ₃ ) ₂ NH ₂ , C ₁₈ H ₃₇ Si(CH ₃ ) ₂ NH ₂ , (CH ₃ ) ₂ Si(H)NH ₂ , CH ₃ Si(H) ₂ NH ₂ , (C ₂ H ₅ ) ₂ Si(H)NH ₂ , C ₂ H ₅ Si(H) ₂ NH ₂ , C ₂ H ₅ Si(CH ₃ )(H)NH ₂ , (C ₃ H ₇ ) ₂ Si(H)NH ₂ , C ₃ H ₇ Si(H) ₂ NH ₂ , CF ₃ CH ₂ CH ₂ Si( NH ₂ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(NH ₂ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(NH ₂ ) ₃ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )(NH ₂ ) ₂ , CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH _2. CF ₃ CH ₂ CH ₂ Si(CH ₃ )(H)NH ₂ and so on.

In addition, if the number of -NH ₂ groups represented by 4-ab in the general formula [1] is 1, the protective film can be uniformly formed, which is more preferable.

In addition, if b in the above general formula [1] is 0, it is easier to maintain water repellency even when washing (rinsing) after formation of the protective film described later is performed, which is preferable.

Furthermore, if the above-mentioned R ¹ is a combination of two -CH ₃ groups and one linear alkyl group, the above-mentioned protective film can be formed homogeneously, which is more preferable. Furthermore, it is particularly preferable that the above-mentioned R ¹ is three -CH ₃ groups.

In addition, the aminosilane compound represented by the general formula [1] may be obtained by reaction.

The (I) aminosilane compound is 0.02 to 0.5% by mass relative to the total amount of (I) to (III). If it is less than 0.02% by mass, further improvement of the water repellency imparting effect cannot be achieved. In addition, if it exceeds 0.5% by mass, aminosilanes are likely to react with each other, making it difficult to prepare a chemical solution. It is preferably 0.03 to 0.4% by mass, and more preferably 0.03 to 0.3% by mass.

In addition, as specific examples of the silicon compound represented by the general formula [2], CH ₃ Si(OC(=O)CF ₃ ) ₃ , C ₂ H ₅ Si(OC(=O)CF ₃ ) ₃ , C ₃ H ₇ Si(OC(=O)CF ₃ ) ₃ , C ₄ H ₉ Si(OC(=O)CF ₃ ) ₃ , C ₅ H ₁₁ Si(OC(=O)CF ₃ ) ₃ , C ₆ H ₁₃ Si(OC(=O)CF ₃ ) ₃ , C ₇ H ₁₅ Si(OC(=O)CF ₃ ) ₃ , C ₈ H ₁₇ Si(OC(=O)CF ₃ ) ₃ , C ₉ H ₁₉ Si(OC(=O)CF ₃ ) ₃ , C ₁₀ H ₂₁ Si(OC(=O)CF ₃ ) ₃ , C ₁₁ H ₂₃ Si(OC(=O)CF ₃ ) ₃ , C ₁₂ H ₂₅ Si (OC(=O)CF ₃ ) ₃ , C ₁₃ H ₂₇ Si(OC(=O)CF ₃ ) ₃ , C ₁₄ H ₂₉ Si(OC(=O)CF ₃ ) ₃ , C ₁₅ H ₃₁ Si(OC (=O)CF ₃ ) ₃ , C ₁₆ H ₃₃ Si(OC(=O)CF ₃ ) ₃ , C ₁₇ H ₃₅ Si(OC(=O)CF ₃ ) ₃ , C ₁₈ H ₃₇ Si(OC(= O)CF ₃ ) ₃ , (CH ₃ ) ₂ Si(OC(=O)CF ₃ ) ₂ , C ₂ H ₅ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , (C ₂ H ₅ ) ₂ Si(OC(=O)CF ₃ ) ₂ , C ₃ H ₇ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , (C ₃ H ₇ ) ₂ Si(OC(=O)CF ₃ ) _2. C ₄ H ₉ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , (C ₄ H ₉ ) ₂ Si(OC(=O)CF ₃ ) ₂ , C ₅ H ₁₁ Si(CH ₃ ) (OC(=O)CF ₃ ) ₂ 、C ₆ H ₁₃ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ 、C ₇ H ₁₅ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₈ H ₁₇ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₉ H ₁₉ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₀ H ₂₁ Si(CH ₃ ) (OC(=O)CF ₃ ) ₂ 、C ₁₁ H ₂₃ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₂ H ₂₅ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₃ H ₂₇ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₄ H ₂₉ Si( CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₅ H ₃₁ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₆ H ₃₃ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₇ H ₃₅ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₈ H ₃₇ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , (CH ₃ ) ₃ SiOC (=O)CF ₃ , C ₂ H ₅ Si(CH ₃ ) ₂ OC(=O)CF ₃ , (C ₂ H ₅ ) ₂ Si(CH ₃ )OC(=O)CF ₃ , (C ₂ H ₅ ) ₃ SiOC(=O)CF ₃ , C ₃ H ₇ Si(CH ₃ ) ₂ OC(=O)CF ₃ , (C ₃ H ₇ ) ₂ Si(CH ₃ )OC(=O)CF ₃ , (C ₃ H ₇ ) ₃ SiOC(=O)CF ₃ , C ₄ H ₉ Si(CH ₃ ) ₂ OC(=O)CF ₃ , (C ₄ H ₉ ) ₃ SiOC(=O)CF ₃ , C ₅ H ₁₁ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₆ H ₁₃ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₇ H ₁₅ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₈ H ₁₇ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₉ H ₁₉ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₀ H ₂₁ Si(CH ₃ ) ₂ OC(=O )CF ₃ , C ₁₁ H ₂₃ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₂ H ₂₅ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₃ H ₂₇ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₄ H ₂₉ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₅ H ₃₁ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₆ H ₃₃ Si( CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₇ H ₃₅ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₈ H ₃₇ Si(CH ₃ ) ₂ OC(=O)CF ₃ , (CH ₃ ) ₂ Si(H)OC(=O)CF ₃ , CH ₃ Si(H) ₂ OC(=O)CF ₃ , (C ₂ H ₅ ) ₂ Si(H)OC(=O)CF ₃ , C ₂ H ₅ Si(H) ₂ OC(=O)CF ₃ , C ₂ H ₅ Si(CH ₃ )(H)OC(=O)CF ₃ , (C ₃ H ₇ ) ₂ Si(H)OC (=O)CF ₃ , C ₃ H ₇ Si(H) ₂ OC(=O)CF ₃ , CF ₃ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ 、CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ 、C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O) CF ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O) CF ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O) CF ₃ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )(H)OC(=O)CF ₃ and other trifluoroacetoxysilane, or replace the -OC(=O)CF ₃ group of the above trifluoroacetoxysilane with halogen group, -OC (= O) -OC ( = O) CF ₃ group other than the group R _{^3, -OS (= O) 2 -R} 3 group, -N (S (= O) 2 -R 3) 2 group , -C(S(=O) ₂ -R ³ ) ₃ group (R ³ is a monovalent perfluoroalkyl group having 1 to 6 carbon atoms), etc.

Furthermore, if the number of -X groups represented by 4-c-d in the general formula [2] is 1, the protective film can be uniformly formed, which is more preferable.

In addition, if d in the above general formula [2] is 0, it is easier to maintain water repellency even when washing (rinsing) after formation of the protective film described later is performed, which is preferable.

Furthermore, if the above-mentioned R ² is a combination of two -CH ₃ groups and one linear alkyl group, the above-mentioned protective film can be uniformly formed, which is more preferable. Furthermore, it is particularly preferable that the above-mentioned R ² is three -CH ₃ groups.

In addition, the silicon compound represented by the above general formula [2] may be obtained by reaction.

In addition, the content of (II) silicon compound relative to the total amount of (I) to (III) is preferably 0.05% by mass or more from the viewpoint of improving the effect of imparting water repellency, and from the viewpoint of cost Preferably it is 20 mass% or less. More preferably, it is 0.1-15 mass %, More preferably, it is 0.2-10 mass %.

[(III) Aprotic solvent] The chemical solution for forming a water-repellent protective film of the present invention contains an aprotic solvent. By containing an aprotic solvent, it is possible to easily perform surface treatment of the object to be treated by spin coating, dipping, or steam. In addition, it is easy to ensure the storage stability of the liquid medicine.

As the aforementioned aprotic solvents, for example, hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfite-based solvents, sulfite-based solvents, lactone-based solvents, carbonate-based solvents, and derivatives of polyols are suitably used. Those that do not have OH groups, nitrogen-containing solvents that do not have NH groups, organic solvents such as silicone solvents, terpene-based solvents, or their mixtures. Among them, if hydrocarbons, esters, ethers, halogen-containing solvents, polyol derivatives that do not have OH groups, or their mixtures are used, the above-mentioned protection can be formed on the surface of the object to be treated in a short time The film is therefore better.

As examples of the above hydrocarbons, there are n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane Alkane, n-eicosane, and branched hydrocarbons corresponding to their carbon numbers (for example, isododecane, isocyclobutane, etc.), cyclohexane, methylcyclohexane, decalin, Benzene, toluene, xylene, (ortho-, m-, or p-)diethylbenzene, 1,3,5-trimethylbenzene, etc., as examples of the above esters, ethyl acetate, n-propyl acetate Ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate Ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl caprate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl Acetate, Ethyl Acetate, Ethyl 2-oxobutyrate, Dimethyl Adipate, Methyl 3-Methoxy Propionate, Ethyl 3-Methoxy Propionate, 3 -Methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, etc., as examples of the above ethers, there are di-n-propyl ether, ethyl-n-butyl ether, and di- N-butyl ether, ethyl-n-pentyl ether, di-n-pentyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether, and diisopropyl ether and diisopropyl ether corresponding to their carbon numbers Ethers having branched hydrocarbon groups such as amyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, methyl cyclopentyl ether, diphenyl ether, tetrahydrofuran, dioxane, etc. As examples of the above ketones, acetone , Acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, etc., as examples of the above halogen-containing solvents, perfluorooctane, perfluorononane , Perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene and other perfluorocarbons, 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoro Hydrofluorocarbons such as pentane, ZEORORA H (manufactured by Zeon Corporation in Japan), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asahiklin AE-3000 (Manufactured by Asahi Glass), Novec7100, Novec7200, Novec7300, Novec7600 (all manufactured by 3M), hydrofluoroethers, chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, 1,1- Dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoro Hydrochlorofluorocarbons such as propylene, 1,2-dichloro-3,3,3-trifluoropropene, perfluoroethers, perfluoropolyethers, etc., as examples of the above-mentioned sulfite-based solvents, dimethyl sulfite, etc. As examples of the above-mentioned stubborn solvents, there are dimethyl stubborn, diethyl stubborn, bis(2-hydroxyethyl) stubborn, tetramethylene stubborn, etc., as examples of the aforementioned lactone-based solvents, there are β-propane Lactone, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolide, γ-caprolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolide Ester, γ-laurolactone, δ-pentane Lactone, δ-caprolactone, δ-caprolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolide, δ-laurolactone, ε-caprolactone, etc., as the above Examples of carbonate-based solvents include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, etc. As examples of the derivatives of the above polyols that do not have OH groups, there are ethylene glycol two Methyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diethyl Ester, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether ether, diethylene glycol dibutyl ether, diethylene glycol mono Methyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether , Triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, Triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether ethyl Ester, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetic acid Ester, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, Dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, Tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol two Methyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerol triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-Methyl-3-methoxybutyl propionate, etc. As examples of the above-mentioned solvents containing nitrogen elements without NH groups, there are N,N-dimethylformamide and N,N-dimethyl Acetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone , 1,3-Diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, triethylamine, pyridine, etc. As examples of silicone solvents, there are hexamethyl two Silicone, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, etc. Examples of terpene-based solvents include p-menthane, diphenyl menthane, and limonene , Terpinene, campane, norbornane, pinane, etc.

In addition, if a solvent with a flash point of more than 70°C is used as the aprotic solvent, it is preferable from the viewpoint of safety in the fire protection law. For example, carbonate-based solvents or polyhydric alcohol derivatives that do not have OH groups are mostly those with a higher flash point, so that the danger of the chemical liquid can be reduced, so it is preferred. From the viewpoint of the above-mentioned safety, specifically, it is more preferable to use propylene carbonate, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, and ethylene glycol diethyl having a flash point of more than 70°C. Ester, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethyl Glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether , Triethylene glycol butyl methyl ether ether, Triethylene glycol monomethyl ether acetate, Triethylene glycol monoethyl ether acetate, Triethylene glycol monobutyl ether acetate, Triethylene glycol diacetate , Tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol mono Butyl ether acetate, tetraethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol methyl propyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl Ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl Ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol diacetate, glycerol triacetate, etc. are used as the above Solvent.

The liquid medicine for forming a water-repellent protective film of the present invention may further contain additives such as polymerization inhibitors, chain transfer agents, and antioxidants to further improve the stability of the liquid medicine.

In addition, the number of particles larger than 0.2 μm in the particle measurement using a light scattering type particle detector in the liquid phase in the liquid drug solution is preferably 100 or less per 1 mL of the drug solution. If the number of particles larger than 0.2 μm above exceeds 100 per 1 mL of the chemical solution, the particles may induce damage to the pattern of the wafer to be processed, which may cause a decrease in the yield and reliability of the device The reason for the reduction is therefore not good. In addition, if the number of particles larger than 0.2 μm is less than 100 per 1 mL of the chemical solution, the washing of the wafer surface (protective film surface) with solvent or water after forming the protective film can be omitted or reduced. Clean (rinse), so it is better. Furthermore, the number of particles larger than 0.2 μm should be as small as possible. If it is within the above content range, there can be more than one per 1 mL of the drug solution. Furthermore, the measurement of particles in the liquid phase in the drug solution in the present invention is performed by a commercially available measurement device in the light scattering type particle measurement method in the liquid using a laser as a light source. The so-called particle size means PSL (polystyrene latex) standard particle standard light scattering equivalent diameter. Here, the above-mentioned particles refer to dust, dust, organic solids, inorganic solids and other particles contained in the form of impurities in the raw materials, or dust, dust, organic solids mixed in the form of pollutants in the preparation of the chemical solution Particles, inorganic solids and other particles are equivalent to those that do not dissolve but exist in the liquid medicine in the form of particles.

In addition, the content of each element (metal impurity) of Na, Mg, K, Ca, Mn, Fe, Cu, Li, Al, Cr, Ni, Zn and Ag in the above-mentioned chemical solution is better than the total amount of the chemical solution Each is 0.1 mass ppb or less. If the metal impurity content exceeds 0.1 mass ppb with respect to the total amount of the chemical solution, the bonding leakage current of the device may increase, which may cause a decrease in the yield and reliability of the device, which is not good. In addition, if the metal impurity content relative to the total amount of the chemical solution is 0.1 mass ppb or less, the wafer surface using solvent or water after the protective film is formed on the surface of the wafer to be processed can be omitted or reduced (Protective film surface) cleaning (rinsing), so it is better. Therefore, the smaller the content of the above-mentioned metal impurities, the better, but if it is within the above-mentioned content range, the total amount of each element relative to the chemical solution may be 0.001 mass ppb or more.

2. Surface treatment method of wafer The surface treatment method of the present invention is characterized in that it has a water-repellent protective film forming step, and a drying step. The water-repellent protective film forming step is maintained on the surface of the wafer selected from the group consisting of a cleaning solution and a rinsing solution In the state of at least one liquid, replace the liquid with a chemical liquid for forming a water-repellent protective film and hold the chemical liquid on the wafer surface, The above-mentioned water-repellent protective film formation chemical solution has (I) The aminosilane compound represented by the general formula [1], (II) The silicon compound represented by the general formula [2], and (III) aprotic solvent, and The content of (I) relative to the total amount of (III) is 0.02 to 0.5% by mass.

(Surface treatment aspect 1) As shown in Figure 1, at least (I), (II), and (III) are mixed to form a solution (a chemical solution for forming a water-repellent protective film), and the chemical solution is supplied to the wafer surface in a liquid or gas state The liquid chemical for forming a water-repellent protective film is held on the surface of the wafer. The supply of the above-mentioned chemical liquid is carried out in a state where a liquid such as a cleaning liquid or a rinse liquid is held on the surface of the wafer, and the liquid is replaced with a chemical liquid. At the time of replacement, there is no particular limitation on the liquid such as a cleaning solution or a rinsing solution maintained on the surface of the wafer, and it is generally 2-propanol (iPA). A water-repellent protective film is formed on the surface of the wafer by holding the chemical solution on the surface of the wafer by using the above replacement. If necessary, the above-mentioned chemical solution on the surface of the wafer can be replaced with a rinse solution for further rinse processing. Then, the liquid is removed from the wafer surface by drying. Since the water-repellent protective film is formed on the surface of the wafer, the excellent water-repellency can reduce pattern collapse during drying. Furthermore, as the liquid to be removed by drying, the above-mentioned water-repellent protective film forming chemical liquid, rinse liquid, or a mixed liquid thereof can be cited. Furthermore, when the liquid to be removed is a rinsing liquid, there are cases in which the above-mentioned chemical liquid is replaced with a rinsing liquid to further perform a rinsing process. In addition, when the liquid to be removed is a mixed liquid of the above-mentioned chemical liquid and the rinse liquid, it may be the case where the above-mentioned chemical liquid is replaced with a "mixed liquid" in the middle of the rinse liquid, or the raw material of the chemical liquid is dissolved in advance When the "mixed solution" made from the rinse solution replaces the above-mentioned chemical solution. The same applies to surface treatment aspects 2 to 6 described later. Furthermore, in the surface treatment aspect 1, the order of mixing (I) to (III) as the raw materials of the chemical liquid is not particularly limited, and it is preferable to mix (I) or (II) to (III) Aprotic solvent.

可採用後述表面處理態樣2～3作為該表面處理方法。In addition, the surface treatment method of the present invention may further have a chemical solution preparation step before the water-repellent protective film formation step. The chemical solution preparation step is to combine a protic compound with a compound having (II) represented by the general formula [2] Silicon compound, (IV) silazane compound represented by the general formula [4], and (III) aprotic solvent raw material drug liquid relative to the total amount of (II), (III), (IV) 1 kg is contacted at a ratio of 0.001 to 0.3 mol, thereby preparing (I) having the above (I) to (III) or having the above (I) to (IV) relative to the total amount of (I) to (III) ) The content of the water-repellent protective film is 0.02-0.5% by mass. The method of bringing the protic compound into contact with the raw drug solution is not particularly limited, and a known method can be used. Furthermore, when the chemical solution for forming a water-repellent protective film is prepared by the above contact, although the details are not clear, it is thought that the silicon compound represented by the above general formula [2] and the protic compound (AH ) The reaction product (XH; acidic compound) produced by the reaction reacts with the silazane compound represented by the general formula [4], thereby producing the aminosilane compound represented by the general formula [1], as a result To obtain water repellency with the above (I) to (III) or the above (I) to (IV) and the content of (I) relative to the total amount of (I) to (III) of 0.02 to 0.5% by mass Chemical solution for forming protective film. [化18]

The surface treatment modes 2 to 3 described later can be used as the surface treatment method.

(Surface treatment aspect 2) As shown in Figure 2, at least (II), (III), and (IV) are mixed to form a solution (raw drug solution), and the protic compound is compared with (II), (III), (IV) The total amount of 1 kg is contacted with the raw drug solution at a ratio of 0.001 to 0.3 mol to prepare a drug solution for forming a water-repellent protective film. The protic compound used in the above-mentioned contact may be diluted with an aprotic solvent (in the case of immiscibility, it is in a dispersed state). Examples of the aprotic solvent used for this dilution include those described in (III) of the present invention. The crude drug solution and protic compound used in the preparation step of the drug solution may be in a liquid state or a gas state. For example, the two liquid states can be mixed in the container, tank, or pipe below the junction point in the chamber, and the gas state can be mixed in the chamber, in the vaporization chamber, or in the pipe below the junction point after vaporization. When the two are mixed, the liquid raw material drug solution in the liquid state of the container in the chamber can be exposed to the gaseous protic compound to make contact. Furthermore, (I) may be contained in the bulk drug solution.

From the viewpoint of improving the effect of imparting water repellency, the protic compound is preferably a compound having an -OH group and/or a -NH ₂ group, and particularly preferably a compound having an -OH group and/or NH ₃ . Furthermore, water and/or an alcohol having 6 or less carbon atoms is preferable, and water and/or 2-propanol are more preferable.

As examples of the alcohols with 6 or less carbon atoms, in addition to methanol, ethanol, linear or branched propanol, butanol, pentanol, and hexanol, polyhydric alcohols or polyhydric alcohols with OH groups can also be cited derivative. As examples of the above-mentioned polyols, there are ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butane Glycol, 1,4-butanediol, glycerin, etc., as examples of the derivatives of the above-OH group-containing polyhydric alcohols, include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropylene Ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, butylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.

In addition, if the protic compound is brought into contact at a ratio of 0.001 to 0.3 mol with respect to 1 kg of the total amount of (II), (III), and (IV), it will be easier to use in the above-mentioned water-repellent protective film formation chemical solution The content of (I) relative to the total amount of (I) to (III) is found to be 0.02 to 0.5% by mass, which is preferable. The ratio at which the protic compound is brought into contact is more preferably a ratio of 0.003 to 0.2 mol, and particularly preferably a ratio of 0.003 to 0.1 mol.

Then, the obtained chemical solution is supplied to the surface of the wafer in a liquid state or a gas state, and the chemical solution for forming a water-repellent protective film in a liquid state is held on the wafer surface. Furthermore, the chemical solution in a state in which the content of (I) relative to the total amount of (I) to (III) is in the range of 0.02 to 0.5% by mass is supplied to the wafer surface to generate (I) by the reaction as described above. ) Aminosilane. On the other hand, since the influence of side reactions on the composition of the chemical solution can be easily ignored, it is preferable to supply the chemical solution to the wafer surface within 1 day from the above contact, and it is more preferable to supply the chemical solution to the wafer surface since the contact The chemical solution within 5 hours is particularly preferred to supply the chemical solution to the wafer surface within 1 hour from the above contact. The supply of the above-mentioned chemical liquid is carried out in a state where a liquid such as a cleaning liquid or a rinse liquid is maintained on the surface of the wafer, and the liquid is replaced with the chemical liquid. Furthermore, when the liquid such as the washing liquid or the rinse liquid is a protic compound, there is a possibility that the protic compound is further contacted during the replacement process, and the above (II) reacts with the protic compound, The reaction product (acidic compound) further reacts with the above (IV), thereby newly forming the above (I). However, in the above replacement, the liquid such as the cleaning liquid or the rinse liquid is quickly replaced with the water-repellent protective film forming chemical liquid, so there is almost no influence of the reaction of the above-mentioned (II) with the protic compound. Therefore, in the above replacement, the influence of the new generation (I) described above is negligible. There is no particular limitation on the liquid such as cleaning liquid or rinsing liquid that remains on the surface of the wafer during replacement, and is generally 2-propanol (iPA). A water-repellent protective film is formed on the surface of the wafer by holding the chemical solution on the surface of the wafer by using the above replacement. Optionally, the above-mentioned chemical solution on the surface of the wafer can be replaced with a rinse solution for further rinse treatment. Then, the liquid is removed from the wafer surface by drying. Since the water-repellent protective film is formed on the surface of the wafer, the excellent water-repellency can reduce pattern collapse during drying. Furthermore, as the liquid to be removed by drying, the above-mentioned water-repellent protective film forming chemical liquid, rinse liquid, or a mixed liquid thereof can be cited.

(Surface treatment aspect 3) As shown in FIG. 3, at least (II), (III), and (IV) are mixed to form a solution (raw drug solution), and the bulk drug solution is supplied to the wafer surface in a liquid state or a gas state to make the liquid state The raw material liquid is kept on the surface of the wafer. The supply of the above-mentioned bulk chemical solution is performed in a state in which a liquid such as a cleaning solution or a rinse liquid is maintained on the wafer surface, and the bulk chemical solution is used to replace the liquid. Furthermore, when the liquid such as the washing liquid or the rinsing liquid is a protic compound such as water or alcohol, there is a possibility that the above-mentioned (II) reacts with the protic compound in the above-mentioned replacement process, and the reaction product The (acidic compound) further reacts with the above (IV) to thereby produce the above (I). However, in the above-mentioned replacement, since the liquid such as the cleaning liquid or the rinse liquid is quickly replaced with the bulk chemical liquid, there is almost no influence of the reaction of the above-mentioned (II) with the protic compound. Therefore, in the above replacement, the influence of the new generation (I) described above is negligible. There is no particular limitation on the liquid such as cleaning liquid or rinsing liquid that remains on the surface of the wafer during replacement, and is generally 2-propanol (iPA). Next, the protic compound is brought into contact with the raw chemical solution at a ratio of 0.001 to 0.3 mol relative to 1 kg of the total amount of (II), (III), and (IV) to prepare a water-repellent protective film forming drug on the wafer surface liquid. Furthermore, in order to produce (I) aminosilane by the reaction as described above, the drug is added so that the content of (I) relative to the total amount of (I) to (III) is in the range of 0.02 to 0.5 mass% The liquid remains on the surface of the wafer. The protic compound used in the above-mentioned contact may be diluted with an aprotic solvent (in the case of immiscibility, it is in a dispersed state). Examples of the aprotic solvent used for this dilution include those described in (III) of the present invention. The protic compound used in the liquid preparation step may be in a liquid state or in a gas state. For example, it is possible to add a protic compound in the liquid state to the chemical raw material in the liquid state maintained on the wafer surface in the chamber, or to expose the chemical raw material in the liquid state maintained on the wafer surface to the gaseous state in the chamber. Protic compounds are brought into contact. In the latter case, for example, the chamber may be made into a vapor environment of a protic compound with a specific concentration to supply the crude drug solution. In addition, in the case of contacting the chemical raw material with the protic compound in the gas state, if the chemical raw material in the solution state is diffused on the surface of the wafer to contact the protic compound in the gas state, the contact area can be enlarged. It is preferable to introduce protic compounds in a short time. At this time, the concentration of the protic compound in the gas state in the space is preferably 0.05-5 vol%, and more preferably 0.1-2 vol%. In addition, the contact time is preferably 0.1 to 600 seconds, and more preferably 2 to 180 seconds. The method of spreading the raw material liquid on the surface of the wafer can appropriately use a known method, and a spin coating method is particularly preferred. The water-repellent protective film is formed on the surface of the wafer by holding the chemical solution prepared in the above manner on the surface of the wafer. Optionally, the above-mentioned chemical solution on the surface of the wafer can be replaced with a rinse solution for further rinse treatment. Then, the liquid is removed from the wafer surface by drying. Since the water-repellent protective film is formed on the surface of the wafer, the excellent water-repellency can reduce pattern collapse during drying. Furthermore, as the liquid to be removed by drying, the above-mentioned water-repellent protective film forming chemical liquid, rinse liquid, or a mixed liquid thereof can be cited.

又，若使酸性化合物以相對於(III)、(IV)之總量1 kg為0.001～0.3莫耳之比率進行接觸，則於上述撥水性保護膜形成用藥液中，容易將相對於(I)～(III)之總量之(I)之含量控制為0.02～0.5質量%，因此較佳。上述使酸性化合物進行接觸之比率更佳為0.003～0.2莫耳之比率，尤佳為0.003～0.1莫耳之比率。 可採用後述之表面處理態樣4～5作為該表面處理方法。In addition, the surface treatment method of the present invention may also have a chemical solution preparation step before the water-repellent protective film forming step. The chemical solution preparation step is to combine the acidic compound represented by the general formula [6] with the acid compound having the general formula (IV) The silazane compound represented by formula [4] and (III) aprotic solvent raw material liquid are contacted at a ratio of 0.001 to 0.3 mol relative to the total amount of (III) and (IV) 1 kg. Thereby, the water repellency having the above (I) to (III) or the above (I) to (IV) and the content of (I) relative to the total amount of (I) to (III) is prepared with a water repellency of 0.02 to 0.5% by mass Chemical solution for forming protective film. The method of bringing the acidic compound into contact with the crude drug solution is not particularly limited, and a known method can be used. Furthermore, when the chemical solution for forming a water-repellent protective film is prepared by the above contact, although the details are not clear, it is believed that the silazane compound represented by the above general formula [4] is as shown in the following reaction formula. The acidic compound represented by the formula [6] reacts to produce the aminosilane compound represented by the general formula [1] and the silicon compound represented by the general formula [2]. As a result, the compound having the above (I ) To (III) or having the above (I) to (IV) and the content of (I) relative to the total amount of (I) to (III) is 0.02 to 0.5% by mass for forming a water-repellent protective film. [化19]

In addition, if the acidic compound is brought into contact at a ratio of 0.001 to 0.3 mol relative to 1 kg of the total amount of (III) and (IV), it will be easier to compare the chemical solution for forming a water-repellent protective film with respect to (I). The content of (I) in the total amount of) to (III) is controlled to be 0.02 to 0.5% by mass, which is preferable. The above-mentioned ratio of contacting the acidic compound is more preferably a ratio of 0.003 to 0.2 mol, and particularly preferably a ratio of 0.003 to 0.1 mol. The surface treatment modes 4 to 5 described later can be used as the surface treatment method.

(Surface treatment aspect 4) As shown in Figure 4, at least (III) and (IV) are mixed to form a solution (raw drug solution), and the acidic compound represented by the general formula [6] is relative to the total of (III) and (IV) The amount of 1 kg is 0.001-0.3 mol in a ratio of 0.001 to 0.3 mol to contact the raw material liquid to prepare a water-repellent protective film forming liquid. The acidic compound used in the aforementioned contact may be diluted with an aprotic solvent (in the case of immiscibility, it is in a dispersed state). Examples of the aprotic solvent used for this dilution include those described in (III) of the present invention. The crude drug solution and acidic compound used in the drug solution preparation step may be in a liquid state or in a gas state. For example, the two liquid states can be mixed in the container, tank, or pipe below the junction point in the chamber, and the gas state can be mixed in the chamber, in the vaporization chamber, or in the pipe below the junction point after vaporization. When the two are mixed, the liquid raw material in the container in the chamber can also be exposed to the acidic compound in the gaseous state to make contact. Then, the obtained chemical solution is supplied to the surface of the wafer in a liquid state or a gas state, and the chemical solution for forming a water-repellent protective film in a liquid state is held on the wafer surface. Furthermore, in order to produce (I) aminosilane by reaction as described above, the content of (I) relative to the total amount of (I) to (III) is supplied to the wafer surface in the range of 0.02 to 0.5 mass% The state of the liquid medicine. On the other hand, since the influence of side reactions on the composition of the chemical solution can be easily ignored, it is preferable to supply the chemical solution to the wafer surface within 1 day from the above contact, and it is more preferable to supply the chemical solution to the wafer surface since the contact The chemical solution within 5 hours is particularly preferred to supply the chemical solution to the wafer surface within 1 hour from the above contact. The supply of the above-mentioned chemical liquid is carried out in a state where a liquid such as a cleaning liquid or a rinse liquid is maintained on the surface of the wafer, and the liquid is replaced with the chemical liquid. There is no particular limitation on the liquid such as cleaning liquid or rinsing liquid that remains on the surface of the wafer during replacement, and is generally 2-propanol (iPA). A water-repellent protective film is formed on the surface of the wafer by holding the chemical solution on the surface of the wafer by using the above replacement. Optionally, the above-mentioned chemical solution on the surface of the wafer can be replaced with a rinse solution for further rinse treatment. Then, the liquid is removed from the wafer surface by drying. Since the water-repellent protective film is formed on the surface of the wafer, the excellent water-repellency can reduce pattern collapse during drying. Furthermore, as the liquid to be removed by drying, the above-mentioned water-repellent protective film forming chemical liquid, rinse liquid, or a mixed liquid thereof can be cited.

(Surface treatment aspect 5) As shown in Figure 5, at least (III) and (IV) are mixed to form a solution (raw drug solution), and the drug substance is supplied to the surface of the wafer in a liquid or gas state to keep the drug substance in a liquid state On the surface of the wafer. The supply of the above-mentioned bulk chemical solution is performed in a state in which a liquid such as a cleaning solution or a rinse liquid is maintained on the wafer surface, and the bulk chemical solution is used to replace the liquid. There is no particular limitation on the liquid such as cleaning liquid or rinsing liquid that remains on the surface of the wafer during replacement, and is generally 2-propanol (iPA). Next, the acidic compound is brought into contact with the raw chemical solution at a ratio of 0.001 to 0.3 mol relative to the total amount of (III) and (IV) 1 kg to prepare a water-repellent protective film forming chemical solution on the wafer surface. Furthermore, in order to produce (I) aminosilane by the reaction as described above, the drug is added so that the content of (I) relative to the total amount of (I) to (III) is in the range of 0.02 to 0.5 mass% The liquid remains on the surface of the wafer. The acidic compound used in the aforementioned contact may be diluted with an aprotic solvent (in the case of immiscibility, it is in a dispersed state). Examples of the aprotic solvent used for this dilution include those described in (III) of the present invention. The acidic compound used in the preparation step of the liquid medicine may be in a liquid state or in a gas state. For example, it is possible to add an acidic compound in the liquid state to the chemical raw material in the liquid state maintained on the wafer surface in the chamber, or to expose the chemical raw material in the liquid state maintained on the wafer surface to the acidic acid in the gas state in the chamber Compound and bring it into contact. In the latter case, for example, the chamber may be made into a vapor environment with a specific concentration of acidic compound to supply the raw chemical liquid. In addition, when the raw chemical liquid is brought into contact with the acidic compound in the gaseous state, if the raw chemical liquid in the solution state is diffused on the surface of the wafer to make it contact with the acidic compound in the gas state, the contact area can be enlarged, and the contact area can be shortened. It is better to introduce acidic compounds within time. At this time, the concentration of the acidic compound in the gas state in the space is preferably 0.05 to 5% by volume, and more preferably 0.1 to 2% by volume. In addition, the contact time is preferably 0.01 to 600 seconds, and more preferably 0.1 to 180 seconds. The method of spreading the raw material liquid on the surface of the wafer may appropriately use a known method, and a spin coating method is particularly preferred. The water-repellent protective film is formed on the surface of the wafer by holding the chemical solution prepared in the above manner on the surface of the wafer. Optionally, the above-mentioned chemical solution on the surface of the wafer can be replaced with a rinse solution for further rinse treatment. Then, the liquid is removed from the wafer surface by drying. Since the water-repellent protective film is formed on the surface of the wafer, the excellent water-repellency can reduce pattern collapse during drying. Furthermore, as the liquid to be removed by drying, the above-mentioned water-repellent protective film forming chemical liquid, rinse liquid, or a mixed liquid thereof can be cited.

In addition, the surface treatment aspect 6 described later can also be used as the surface treatment method.

(Surface treatment aspect 6) If, for example, the SC-1 with ammonia component is used for the pretreatment, the component (protic compound) containing the NH ₂ group derived from the ammonia component is molecular level and easy to remain on the wafer surface tendency. As shown in FIG. 6, the above-mentioned NH ₂ group-containing component (protic compound) is at the molecular level and remains in a specific amount on the wafer surface, and at least (II), (III), and (IV) The solution (raw drug solution) obtained by mixing, so as to replace the above-mentioned SC-1 or the cleaning solution replaced after SC-1 treatment with a liquid bulk drug solution. Then, there is a water-repellent protective film forming step and a drying step. The water-repellent protective film forming step involves contacting the crude drug solution with a component (protic compound) containing an NH ₂ group remaining in a specific amount at the molecular level. The water-repellent protective film forming chemical solution described in the present invention is prepared on the wafer surface, and the chemical solution is maintained on the wafer surface.

From the viewpoint of easily suppressing the exotherm of the reaction, the surface treatment aspect 3 is preferable.

Specific examples of the silazane compound represented by the general formula [4] include: [(CH ₃ ) ₃ Si] ₂ NH, [(CH ₃ ) ₂ Si(H)] ₂ NH, [CH ₃ Si(H) ₂ ] ₂ NH, [C ₂ H ₅ Si(CH ₃ ) ₂ ] ₂ NH, [(C ₂ H ₅ ) ₂ Si(CH ₃ )] ₂ NH, [(C ₂ H ₅ ) ₃ Si ] ₂ NH, [C ₃ H ₇ Si(CH ₃ ) ₂ ] ₂ NH, [(C ₃ H ₇ ) ₂ Si(CH ₃ )] ₂ NH, [(C ₃ H ₇ ) ₃ Si] ₂ NH, [ C ₄ H ₉ Si(CH ₃ ) ₂ ] ₂ NH, [C ₅ H ₁₁ Si(CH ₃ ) ₂ ] ₂ NH, [C ₆ H ₁₃ Si(CH ₃ ) ₂ ] ₂ NH, [C ₇ H ₁₅ Si (CH ₃ ) ₂ ] ₂ NH, [C ₈ H ₁₇ Si(CH ₃ ) ₂ ] ₂ NH, [C ₉ H ₁₉ Si(CH ₃ ) ₂ ] ₂ NH, [C ₁₀ H ₂₁ Si(CH ₃ ) ₂ ] ₂ NH, [C ₁₁ H ₂₃ Si(CH ₃ ) ₂ ] ₂ NH, [C ₁₂ H ₂₅ Si(CH ₃ ) ₂ ] ₂ NH, [C ₁₃ H ₂₇ Si(CH ₃ ) ₂ ] ₂ NH, [ C ₁₄ H ₂₉ Si(CH ₃ ) ₂ ] ₂ NH, [C ₁₅ H ₃₁ Si(CH ₃ ) ₂ ] ₂ NH, [C ₁₆ H ₃₃ Si(CH ₃ ) ₂ ] ₂ NH, [C ₁₇ H ₃₅ Si (CH ₃ ) ₂ ] ₂ NH, [C ₁₈ H ₃₇ Si(CH ₃ ) ₂ ] ₂ NH, [(C ₂ H ₅ ) ₂ Si(H)] ₂ NH, [C ₂ H ₅ Si(H) ₂ ] ₂ NH, [C ₂ H ₅ Si(CH ₃ )(H)] ₂ NH, [(C ₃ H ₇ ) ₂ Si(H)] ₂ NH, [C ₃ H ₇ Si(H) ₂ ] ₂ NH , [CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ ] ₂ NH, [C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ ] ₂ NH, [C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ ] ₂ NH, [C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ ] ₂ NH, [C ₅ F ₁₁ CH ₂ CH ₂ Si(C H ₃ ) ₂ ] ₂ NH, [C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ ] ₂ NH, [C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ ] ₂ NH, [C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ ] ₂ NH, [CF ₃ CH ₂ CH ₂ Si(CH ₃ )(H)] ₂ NH, etc., among which, especially [(CH ₃ ) ₃ Si] ₂ NH, [C ₂ H ₅ Si(CH ₃ ) ₂ ] ₂ NH, [C ₃ H ₇ Si(CH ₃ ) ₂ ] ₂ NH, [C ₄ H ₉ Si(CH ₃ ) ₂ ] ₂ NH, [CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ ] ₂ NH is preferred, and [(CH ₃ ) ₃ Si] ₂ NH is particularly preferred.

Specific examples of the acidic compound represented by the general formula [6] include, for example, HCl, HBr, HI, CF ₃ COOH, C ₂ F ₅ COOH, C ₃ F ₇ COOH, C ₄ F ₉ COOH, and C ₅ F ₁₁ COOH, C ₆ F ₁₃ COOH, CF ₃ S(=O) ₂ OH, C ₂ F ₅ S(=O) ₂ OH, C ₃ F ₇ S(=O) ₂ OH, C ₄ F ₉ S( =O) ₂ OH, C ₅ F ₁₁ S(=O) ₂ OH, C ₆ F ₁₃ S(=O) ₂ OH, {CF ₃ S(=O) ₂ } ₂ NH, {C ₂ F ₅ S( =O) ₂ } ₂ NH, {C ₃ F ₇ S(=O) ₂ } ₂ NH, {C ₄ F ₉ S(=O) ₂ } ₂ NH, {C ₅ F ₁₁ S(=O) ₂ } ₂ NH, {C ₆ F ₁₃ S(=O) ₂ } ₂ NH, {CF ₃ S(=O) ₂ } ₃ CH, {C ₂ F ₅ S(=O) ₂ } ₃ CH, {C ₃ F ₇ S(=O) ₂ } ₃ CH, {C ₄ F ₉ S(=O) ₂ } ₃ CH, {C ₅ F ₁₁ S(=O) ₂ } ₃ CH, {C ₆ F ₁₃ S(=O ) ₂ } ₃ CH, etc. Among them, CF ₃ COOH, C ₂ F ₅ COOH, C ₃ F ₇ COOH, C ₄ F ₉ COOH are particularly preferred, and CF ₃ COOH is particularly preferred. Example

Hereinafter, there will be shown an example that more specifically discloses the embodiment of the present invention. Furthermore, the present invention is not limited to these embodiments.

Setting the surface of the wafer as a surface with a concave-convex pattern, and replacing the cleaning solution holding at least the concave portion of the concave-convex pattern with another cleaning solution has been variously studied in other documents, and it is an established technology. Therefore, in the present invention, the effect of imparting water repellency when the wafer is surface-treated with the chemical solution for forming a water repellent protective film is evaluated. Furthermore, in the examples, as the liquid that contacts the wafer surface when evaluating the contact angle, water, which is a representative water-based cleaning liquid, was used.

However, in the case of a wafer with a concave-convex pattern on its surface, it is impossible to accurately evaluate the contact angle of the water-repellent protective film itself formed on the surface of the concave-convex pattern.

The evaluation of the contact angle of the water droplets is as described in JIS R 3257 "Test Method for Wettability of the Glass Surface of the Substrate". A few μl of water droplets are dropped on the surface of the sample (substrate) and formed by the water droplets and the substrate surface. The angle measurement is carried out. However, in the case of patterned wafers, the contact angle is very large. The reason is that due to the Wenzel effect or the Cassie effect, and the contact angle is affected by the surface shape (roughness) of the substrate, the apparent contact angle of the water droplets increases.

Therefore, in this embodiment, the above-mentioned chemical solution is applied to a wafer with a smooth surface to form a protective film on the surface of the wafer, and the protective film is regarded as a protective film formed on the surface of the wafer with a concave-convex pattern formed on the surface , In order to carry out various evaluations. Furthermore, in this embodiment, a "wafer with SiO ₂ film" having an SiO ₂ layer on a smooth surface silicon wafer is used as a smooth surface wafer.

The details are described below. The following describes the evaluation method, the preparation of the water-repellent protective film formation chemical solution or raw material chemical liquid, the surface treatment method of the wafer using the water-repellent protective film formation chemical solution, and the evaluation results.

[Evaluation method] Contact angle evaluation of the protective film formed on the wafer surface (evaluation of the effect of imparting water repellency) Put about 2 μl of pure water on the surface of the wafer with the protective film, and measure the angle (contact angle) between the water drop and the wafer surface with a contact angle meter (manufactured by Kyowa Interface Science: CA-X type). Set 80° or more to pass.

[Example 1-1] (1-1) Preparation of chemical solution for forming water-repellent protective film will be (II) trimethylsilyl trifluoroacetate as a silicon compound [TMS-TFA: (CH ₃ ) ₃ Si-OC (=O)CF ₃ ]: 15 g, hexamethyldisilazane as (IV) silazane compound [HMDS: (CH ₃ ) ₃ Si-NH-Si(CH ₃ ) ₃ ]: 70 g, (III) Propylene glycol monomethyl ether acetate (PGMEA) as an aprotic solvent: 915 g was mixed to obtain a crude drug solution in a solution state. Secondly, add water as a protic compound to the bulk drug solution: 3.6 g, thereby making 0.2 mol of the protic compound (water in liquid state) and the raw material relative to the total of 1 kg of TMS-TFA, HMDS, and PGMEA The chemical solution is contacted to prepare a chemical solution for forming a water-repellent protective film.

(1-2) Cleaning of silicon wafer A smooth silicon wafer with thermal oxide film (Si wafer with a thermal oxide film layer of 1 μm thick on the surface) is immersed in a 1% by mass hydrofluoric acid aqueous solution for 10 minutes at room temperature, Soak in water for 1 minute and immerse in 2-propanol (iPA) for 1 minute at room temperature.

(1-3) Surface treatment of silicon wafer surface with protective film forming chemical solution The cleaned silicon wafer was immersed in the water-repellent protective film formation chemical solution prepared in the above "(1-1) Preparation of water-repellent protective film formation chemical solution" at 25°C for 30 seconds, and placed in the chamber Soak in iPA for 30 seconds at warm temperature. Finally, the silicon wafer is taken out from the iPA, and air is blown to remove the iPA on the surface, thereby drying the silicon wafer.

This embodiment uses the method of surface treatment mode 2 for surface treatment. The obtained wafers were evaluated, and the results are shown in Table 1. The initial contact angle before surface treatment was less than 10°, and the contact angle after surface treatment was 90°, showing an excellent water repellency imparting effect.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[Table 1]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Examples 1-2~1-23] The type, contact method, or contact amount of the protic compound used in Example 1-1, and the type or content of aminosilane compound, silicon compound, or silazane compound were changed. Otherwise, the same as in Example 1-1 The surface treatment of the wafer was carried out in the same way, and then the evaluation was carried out. The results are shown in Table 1. Furthermore, in the table, "iPA" refers to 2-propanol, "MeOH" refers to methanol, "EtOH" refers to ethanol, "nBuOH" refers to 1-butanol, and "PGME" refers to propylene glycol monomethyl ether. "TFAcA" refers to trifluoroacetamide.

Furthermore, in Examples 1-18, first, dibutyltetramethyldisilazane as a silazane compound [DBTMDS: C ₄ H ₉ (CH ₃ ) ₂ Si-NH-Si(CH ₃ ) ₂ C ₄ H ₉ ]: 86 g, PGMEA as an aprotic solvent: 900 g, and trifluoroacetic anhydride: 14 g are mixed to obtain a raw drug solution in a solution state by the reaction described below. Trifluoroacetic anhydride immediately reacts with DBTMDS to become butyldimethylsilyl trifluoroacetate [BDMS-TFA: C ₄ H ₉ (CH ₃ ) ₂ Si-OC(=O)CF ₃ ] and butyl dimethyl Base silyl trifluoroacetamide [BDS-TFAcA: C ₄ H ₉ (CH ₃ ) ₂ Si-NH-C(=O)CF ₃ ]. That is, the type of silicon compound or silazane compound of the bulk drug solution of this embodiment is different, and BDS-TFAcA is contained as other silicon compound. Secondly, by adding water as a protic compound to the crude drug solution: 0.9 g, the protic compound (water in liquid state) and the raw material are 0.05 mol relative to the total amount of BDMS-TFA, DBTMDS, and PGMEA 1 kg The chemical liquid is contacted to prepare a chemical liquid for forming a water-repellent protective film.

In addition, in Examples 1-19, first, dioctyltetramethyldisilazane [DOTMDS: C ₈ H ₁₇ (CH ₃ ) ₂ Si-NH-Si(CH ₃ ) as a silazane compound ₂ C ₈ H ₁₇ ]: 89 g, PGMEA as an aprotic solvent: 900 g, and trifluoroacetic anhydride: 11 g are mixed to obtain a raw drug solution in a solution state by the reaction described later. Trifluoroacetic anhydride immediately reacts with DOTMDS to become octyldimethylsilyl trifluoroacetate [ODMS-TFA: C ₈ H ₁₇ (CH ₃ ) ₂ Si-OC(=O)CF ₃ ] and octyldimethylsilyl Trifluoroacetamide [ODS-TFAcA: C ₈ H ₁₇ (CH ₃ ) ₂ Si-NH-C(=O)CF ₃ ]. That is, the type of silicon compound or silazane compound in the bulk drug solution of this embodiment is different, and ODS-TFAcA is contained as other silicon compound. Secondly, by adding water as a protic compound to the bulk drug solution: 0.9 g, the protic compound (water in liquid state) and the raw material are 0.05 mol relative to 1 kg of the total of ODMS-TFA, DOTMDS, and PGMEA. The chemical liquid is contacted to prepare a chemical liquid for forming a water-repellent protective film.

Also, in Example 1-22, first, HMDS as a silazane compound: 83 g, PGMEA as an aprotic solvent: 900 g, and trifluoroacetic anhydride: 17 g were mixed to obtain a solution by the reaction described below The raw material liquid in the state. Trifluoroacetic anhydride immediately reacts with HMDS to become TMS-TFA and trimethylsilyl trifluoroacetamide [TMS-TFAcA: (CH ₃ ) ₃ Si-NH-C(=O)CF ₃ ]. That is, the bulk drug solution of this embodiment contains TMS-TFAcA as a silicon compound other than a silicon compound or a silazane compound.

Furthermore, in Examples 1-20, 1-21, 1-23, the ratio of the protic compound concentration to the total amount of (II), (III), (IV) 1 kg less than 0.001 mol The crude drug liquid is placed in a pre-controlled space, and a specific amount of gaseous protic compound is introduced into the space to make the two contact, thereby preparing a water-repellent protective film forming drug solution.

In any embodiment, the initial contact angle before the surface treatment is less than 10°, and the contact angle after the surface treatment is 80° or more, showing an excellent water repellency imparting effect.

[Comparative Examples 1-1 to 1-3] Except that the type or contact amount of the protic compound used in Example 1-1 was changed, the surface treatment of the wafer was performed in the same manner as in Example 1-1, and the evaluation was performed. The results are shown in Table 1. The contact angle after surface treatment did not reach 80°, and the effect of imparting water repellency was worse than that of the examples.

Based on the results of Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2, the contact angle after surface treatment relative to the contact amount of the protic compound (water in liquid state) is shown in the figure 7. The contact angle after surface treatment relative to the content of (I) aminosilane compound (TMS-NH ₂ ) in the total amount of (I) to (III) is shown in FIG. 8. According to Figures 7 and 8, in Comparative Example 1-1 where the protic compound (water in liquid state) is not exposed, or Comparative Example 1-2 where the contact amount is too much, the total amount of (I) to (III) (I) The content of aminosilane compound (TMS-NH ₂ ) is too small (the content of (I) deviates from the range of 0.02 to 0.5 mass% relative to the total amount of (I) to (III)), so surface treatment The subsequent contact angle did not reach 80°. On the other hand, by contacting the protic compound (liquid state water), a water-repellent protective film formation chemical solution with a content of (I) of 0.02 to 0.5 mass% relative to the total amount of (I) to (III) is used In Examples 1-1 to 1-3, the contact angles after surface treatment all exceeded 80°, showing a more excellent water repellency imparting effect.

In addition, the same tendency was confirmed when the types of protic compounds were changed. According to the results of Examples 1-4 to 1-6, and Comparative Examples 1-1, 1-3, the contact angle after surface treatment relative to the contact amount of the protic compound (iPA in liquid state) is shown in the figure 9. The contact angle after surface treatment with respect to the content of (I) aminosilane compound (TMS-NH ₂ ) in the total amount of (I) to (III) is shown in FIG. 10. According to Figures 9 and 10, in Comparative Example 1-1 without contact with protic compounds (iPA in liquid state), or Comparative Example 1-3 with too much contact, among the total amount of (I) to (III) (I) The content of aminosilane compound (TMS-NH ₂ ) is too small (the content of (I) deviates from the range of 0.02 to 0.5 mass% relative to the total amount of (I) to (III)), so surface treatment The subsequent contact angle did not reach 80°. In contrast, by contacting with protic compounds (iPA in liquid state), a chemical solution for forming a water-repellent protective film with a content of (I) of 0.02 to 0.5% by mass relative to the total amount of (I) to (III) is used In Examples 1-4 to 1-6, the contact angle after surface treatment did not exceed 80°, showing a more excellent water repellency imparting effect.

[Example 2-1] (2-1) Preparation of API liquid Mix TMS-TFA as (II) silicon compound: 15 g, HMDS as (IV) silazane compound: 70 g, and PGMEA as (III) aprotic solvent: 915 g to obtain a solution state API liquid.

(2-2) Preparation of water-repellent protective film forming chemical solution and surface treatment of silicon wafer surface using protective film forming chemical solution The silicon wafer cleaned by the same method as in Example 1-1 was immersed in the bulk drug solution prepared in the above "(2-1) Preparation of bulk drug solution", and then the bulk drug solution was added as a protic compound Water in liquid state: 3.6 g, by which a protic compound (water in liquid state) of 0.2 mol relative to the total amount of 1 kg of TMS-TFA, HMDS, and PGMEA is brought into contact with the crude drug solution to prepare water repellent protection Membrane formation liquid. After immersing in the water-repellent protective film formation chemical for 30 seconds, the silicon wafer was taken out, and then immersed in iPA for 30 seconds at room temperature. Then the silicon wafer was taken out from the iPA, and air was blown to remove the iPA on the surface to make the silicon The wafer is dry.

This embodiment uses the method of surface treatment mode 3 for surface treatment. The obtained wafers were evaluated, and the results are shown in Table 2. The initial contact angle before surface treatment was less than 10°, and the contact angle after surface treatment was 90°, showing an excellent water repellency imparting effect.

﹡胺基矽烷化合物之含量係相對於(I)～(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[Table 2]

﹡The content of aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Examples 2-2～2-16] The type, contact method, or contact amount of the protic compound used in Example 2-1, and the type or content of aminosilane compound, silicon compound, or silazane compound were changed. Otherwise, the same as in Example 2-1 The surface treatment of the wafer was carried out in the same way, and then the evaluation was carried out. The results are shown in Table 2.

Furthermore, in Examples 2-13, 2-14, and 2-16, the silicon wafers cleaned by the same method as in Example 1-1 were placed on the protic compound introduced in advance in a specific amount of gaseous state In the space, and on the surface of the silicon wafer (the side surface of the SiO ₂ film), the raw material liquid is filled, so that the raw material liquid is brought into contact with the protic compound to prepare the water-repellent protective film forming liquid.

In any embodiment, the initial contact angle before the surface treatment is less than 10°, and the contact angle after the surface treatment is 80° or more, showing an excellent water repellency imparting effect.

[Comparative Examples 2-1 to 2-3] Except for changing the type or contact amount of the protic compound used in Example 2-1, the surface treatment of the wafer was performed in the same manner as in Example 2-1, and the evaluation was performed. The results are shown in Table 2. The contact angle after surface treatment did not reach 80°, and the effect of imparting water repellency was worse than that of the examples.

[Example 3-1] HMDS as (IV) silazane compound: 71 g, and PGMEA as (III) aprotic solvent: 929 g were mixed to obtain a raw drug solution in a solution state. Secondly, by adding trifluoroacetic acid [TFA: CF ₃ COOH]: 22.8 g as an acidic compound to the crude drug solution, the acidic compound (TFA in liquid state) is 0.2 mol relative to the total amount of HMDS and PGMEA 1 kg. ) Contact with the raw chemical liquid to prepare a chemical liquid for forming a water-repellent protective film. Except for this, the surface treatment of the wafer was performed in the same manner as in Example 1-1, and the evaluation was further performed. The results are shown in Table 3.

In this embodiment, the surface treatment has been performed by the method of surface treatment mode 4. The obtained wafers were evaluated, and the results are shown in Table 3. The contact angle after the surface treatment of those whose initial contact angle before surface treatment was less than 10° was 90°, showing excellent water repellency imparting effect.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[table 3]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Examples 3-2 to 3-6] In addition to changing the type or contact amount of acidic compound used in Example 3-1, and the type or content of aminosilane compound, silicon compound or silazane compound, The surface treatment of the wafer was performed in the same manner as in Example 3-1, and the evaluation was performed. The results are shown in Table 3. Furthermore, in the table, "TFMSA" refers to trifluoromethanesulfonic acid [CF ₃ SO ₃ H], and "TMS-TFMSA" refers to trimethylsilyl trifluoromethanesulfonate [(CH ₃ ) ₃ Si-OS (=O) ₂ CF ₃ ].

In any embodiment, the initial contact angle before the surface treatment is less than 10°, and the contact angle after the surface treatment is 80° or more, showing an excellent water repellency imparting effect.

[Comparative Examples 3-1, 3-2] Except for changing the contact amount of the acidic compound used in Example 3-1, the surface treatment of the wafer was performed in the same manner as in Example 3-1, and the evaluation was performed. The results are shown in Table 3. The contact angle after surface treatment did not reach 80°, and the effect of imparting water repellency was worse than that of the examples.

[Example 4-1] (4-1) Preparation of API liquid Mix HMDS as (IV) silazane compound: 71 g, and PGMEA as (III) aprotic solvent: 929 g to obtain a raw drug solution in a solution state.

(4-2) Preparation of water-repellent protective film formation chemical solution and surface treatment of silicon wafer surface using protective film formation chemical solution The silicon wafers cleaned by the same method as in Example 1-1 were immersed in the bulk drug solution prepared in the above "(4-1) Preparation of bulk drug solution", and then added to the bulk drug solution as an acid compound Liquid TFA: 22.8 g, so that 0.2 mol of acidic compound (TFA in liquid state) relative to the total amount of HMDS and PGMEA 1 kg is brought into contact with the raw drug solution to prepare a water-repellent protective film formation drug solution. After being immersed in the water-repellent protective film formation chemical for 30 seconds, the silicon wafer was taken out, and then immersed in iPA for 30 seconds at room temperature. Then the silicon wafer was taken out of the iPA, and air was blown to remove the iPA on the surface, thereby making the silicon crystal Round dry.

This embodiment uses the method of surface treatment mode 5 for surface treatment. The obtained wafers were evaluated, and the results are shown in Table 4. The contact angle after surface treatment with the initial contact angle before surface treatment less than 10° was 90°, showing excellent water repellency imparting effect.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[Table 4]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Examples 4-2 to 4-6] The type or contact amount of acidic compound used in Example 4-1, and the type or content of aminosilane compound, silicon compound, or silazane compound were changed, except that it was performed in the same manner as in Example 4-1. The surface treatment of the wafer, and then the evaluation. The results are shown in Table 4.

In any embodiment, the initial contact angle before the surface treatment is less than 10°, and the contact angle after the surface treatment is 80° or more, showing an excellent water repellency imparting effect.

[Comparative Examples 4-1, 4-2] Except for changing the contact amount of the acidic compound used in Example 4-1, the surface treatment of the wafer was performed in the same manner as in Example 4-1, and the evaluation was performed. The results are shown in Table 4. The contact angle after surface treatment did not reach 80°, and the effect of imparting water repellency was worse than that of the examples.

As described above, even with different surface treatments, the water-repellent protective film forming chemical solution of the present invention and the wafer surface treatment method of the present invention can further improve the effect of imparting water-repellent properties.

[Example 1-1a] In the "preparation of a chemical solution for forming a water-repellent protective film", water as a protic compound is added to the drug substance in a state that it is diluted with PGMEA as an aprotic solvent (in the case of incompatible conditions, it is dispersed) Except for this, the same operation as in Example 1-1 was performed, and the same evaluation was performed. Furthermore, the amount of water added is 0.2 mol relative to the total amount of 1 kg of TMS-TFA, HMDS, PGMEA contained in the bulk drug solution, and PGMEA used for dilution. The results are shown in Table 5. Furthermore, the amount of PGMEA used for dilution is the same as the amount of PGMEA contained in the bulk drug solution.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[table 5]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Examples 1-2a to 1-22a, Comparative Examples 1-2a to 1-3a] The type, contact method or contact amount of the protic compound used in Example 1-1a, and the type or content of aminosilane compound, silicon compound, or silazane compound were changed. Otherwise, the same as in Example 1-1a The surface treatment of the wafer was carried out in the same way, and then the evaluation was carried out. Furthermore, for Examples 1-20a and 1-21a, the protic compound in the gaseous state was diluted in the aprotic solvent in the gaseous state to make it contact with the crude drug solution. The results are shown in Table 5. In addition, the results of Comparative Example 1-1 are described for comparative examples that are not exposed to protic compounds.

[Example 2-1a] In "Preparation of the chemical solution for forming a water-repellent protective film and surface treatment of the surface of a silicon wafer with the chemical solution for forming a protective film", water as a protic compound is diluted in the state of PGMEA as an aprotic solvent ( In the case of incompatibility, it is in a dispersed state) was added to the bulk drug solution, except that the same operation as in Example 2-1 was performed, and the same evaluation was performed. Furthermore, the amount of water added is 0.2 mol relative to the total amount of 1 kg of TMS-TFA, HMDS, PGMEA contained in the bulk drug solution, and PGMEA used for dilution. The results are shown in Table 6. Furthermore, the amount of PGMEA used for dilution is the same as the amount of PGMEA contained in the bulk drug solution.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[Table 6]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Examples 2-2a to 2-15a, Comparative Examples 2-2a to 2-3a] The type, contact method, or contact amount of the protic compound used in Example 2-1a, and the type or content of aminosilane compound, silicon compound, or silazane compound were changed. Otherwise, the same as in Example 2-1a The surface treatment of the wafer was carried out in the same way, and then the evaluation was carried out. Furthermore, for Examples 2-13a and 2-14a, the protic compound in the gaseous state was diluted in the aprotic solvent in the gaseous state and brought into contact with the crude drug solution. The results are shown in Table 6. In addition, the results of Comparative Example 2-1 are described for comparative examples that are not exposed to protic compounds.

[Example 3-1a] In the "Preparation of the chemical solution for forming a water-repellent protective film", add TFA as an acidic compound in a state of being diluted with PGMEA as an aprotic solvent (in a dispersed state when it is incompatible), and add it to the raw drug solution Except for this, the same operation as in Example 3-1 was performed, and the same evaluation was performed. Furthermore, the added amount of TFA is 0.2 mol relative to the total 1 kg of HMDS, PGMEA contained in the bulk drug solution, and PGMEA used for dilution. The results are shown in Table 7. Furthermore, the amount of PGMEA used for dilution is the same as the amount of PGMEA contained in the bulk drug solution.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[Table 7]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Examples 3-2a to 3-6a, Comparative Example 3-2a] The type or contact amount of acidic compound used in Example 3-1a, and the type or content of aminosilane compound, silicon compound, or silazane compound were changed, except that it was performed in the same manner as in Example 3-1a The surface treatment of the wafer, and then the evaluation. The results are shown in Table 7. In addition, the results of Comparative Example 3-1 are described for comparative examples that are not exposed to acidic compounds.

[Example 4-1a] In "Preparation of water-repellent protective film forming chemical solution and surface treatment of silicon wafer surface using protective film forming chemical solution", TFA as an acid compound is diluted in the state of PGMEA as an aprotic solvent (in In the case of immiscibility, it is in a dispersed state) was added to the bulk drug solution, except that the same operation as in Example 4-1 was performed, and the same evaluation was performed. Furthermore, the added amount of TFA is 0.2 mol relative to the total 1 kg of HMDS, PGMEA contained in the bulk drug solution, and PGMEA used for dilution. The results are shown in Table 8. Furthermore, the amount of PGMEA used for dilution is the same as the amount of PGMEA contained in the bulk drug solution.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[Table 8]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Examples 4-2a to 4-6a, Comparative Example 4-2a] The type or contact amount of acidic compound used in Example 4-1a, and the type or content of aminosilane compound, silicon compound or silazane compound were changed, except that the same procedure as in Example 4-1a was performed. The surface treatment of the wafer, and then the evaluation. The results are shown in Table 8. In addition, the results of Comparative Example 4-1 are described for comparative examples that are not exposed to acidic compounds.

[Example 5-1] In "Preparation of a chemical solution for forming a water-repellent protective film", the protic compound was set to NH ₃ and added to the raw chemical solution in a state of being diluted in dioxane as an aprotic solvent, Otherwise, the same operation as in Example 1-2 was performed, and the same evaluation was performed. Furthermore, the addition amount of NH ₃ is 0.05 mol relative to 1 kg of the total amount of TMS-TFA, HMDS, PGMEA contained in the bulk drug solution, and dioxane used for dilution. The results are shown in Table 9. Furthermore, the concentration of the NH ₃ /dioxane solution when added to the bulk drug solution is set to 0.4 mol/liter.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[Table 9]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Example 5-2] Except that the type of aprotic solvent used for dilution in Example 5-1 was changed to tetrahydrofuran [THF], the surface treatment of the wafer was performed in the same manner as in Example 5-1, and the evaluation was performed. The results are shown in Table 9. In addition, regarding the comparative example not exposed to the protic compound, the result of the comparative example 1-1 is described.

[Example 6-1] In "Preparation of a chemical solution for forming a water-repellent protective film and surface treatment of a silicon wafer surface using a chemical solution for forming a protective film", the protic compound was set to NH ₃ and diluted in The aprotic solvent, dioxane, was added to the raw drug solution in the state of addition, and the same operation as in Example 2-2 was performed, and the same evaluation was performed except that. Furthermore, the addition amount of NH ₃ is 0.05 mol relative to 1 kg of the total amount of TMS-TFA, HMDS, PGMEA contained in the bulk drug solution, and dioxane used for dilution. The results are shown in Table 10. Furthermore, the concentration of the NH ₃ /dioxane solution when added to the bulk drug solution is set to 0.4 mol/liter.

﹡胺基矽烷化合物之含量係相對於(I)〜(III)之總量。其他成分之含量係相對於撥水性保護膜形成用藥液之總量。[Table 10]

*The content of the aminosilane compound is relative to the total amount of (I) ~ (III). The content of other components is relative to the total amount of the liquid medicine for forming the water-repellent protective film.

[Example 6-2] Except that the type of aprotic solvent used for dilution in Example 6-1 was changed to tetrahydrofuran [THF], the surface treatment of the wafer was performed in the same manner as in Example 6-1, and the evaluation was performed. The results are shown in Table 10. In addition, the results of Comparative Example 2-1 are described for comparative examples that do not contact the protic compound.

As mentioned above, even if the protic compound or acidic compound added to the bulk drug solution is diluted in an aprotic solvent (in the case of incompatible conditions, it is in a dispersed state), the water repellency can be further improved than before. Give effect.

Figure 1 is a flow chart of surface treatment mode 1. Figure 2 is a flow chart of the surface treatment mode 2. Figure 3 is a flowchart of the surface treatment mode 3. FIG. 4 is a flowchart of surface treatment mode 4. Figure 5 is a flowchart of the surface treatment mode 5. FIG. 6 is a flowchart of the surface treatment mode 6. Fig. 7 is a graph of contact angle after surface treatment with respect to the amount of water added (Comparative Example 1-1, Example 1-3, Example 1-2, Example 1-1, Comparative Example 1-2). Figure 8 is a graph of the contact angle after surface treatment relative to the concentration of the aminosilane compound after water addition (Comparative Example 1-1, Comparative Example 1-2, Example 1-3, Example 1-2, Implementation Example 1-1). Fig. 9 is a graph of the contact angle after surface treatment relative to the amount of iPA added (Comparative Example 1-1, Example 1-6, Example 1-5, Example 1-4, Comparative Example 1-3). Figure 10 is a graph of the contact angle after surface treatment relative to the concentration of the aminosilane compound after iPA addition (Comparative Example 1-1, Comparative Example 1-3, Example 1-6, Example 1-5, Implementation Example 1-4).

Claims (19)

A chemical solution for forming a water-repellent protective film, comprising (I) an aminosilane compound represented by the following general formula [1], (II) a silicon compound represented by the following general formula [2], and (III) Protic solvent, and the content of (I) relative to the total amount of (I) to (III) is 0.02 to 0.5% by mass,

[In formula [1], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; a is an integer of 1 to 3, b is an integer of 0-2, and the total of a and b is 1-3],

[In the formula [2], R ^{2 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon numbers from 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; and X represents a halogen group,- OC(=O)R ³ , -OS(=O) ₂ -R ³ , -N(S(=O) ₂ -R ³ ) ₂ , -C(S(=O) ₂ -R ³ ) ₃ At least one group in the group; R ³ is a monovalent perfluoroalkyl group with carbon number of 1 to 6, c is an integer of 1 to 3, d is an integer of 0 to 2, and the total of c and d is 1 to 3]. The chemical solution for forming a water-repellent protective film according to claim 1, wherein the above (I) is a compound represented by the following general formula [3],

[In formula [3], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3]. The chemical solution for forming a water-repellent protective film of claim 1, which further contains (IV) a silazane compound represented by the following general formula [4],

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3]. The water-repellent protective film forming chemical solution of claim 1, wherein the content of (II) relative to the total amount of (I) to (III) above is 0.05-20% by mass. The chemical solution for forming a water-repellent protective film according to claim 1, wherein the above (II) is at least one compound in the group consisting of the following general formula [5],

[In formula [5], R ^{2 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with a carbon number of 1 to 18 that can be substituted with a part or all of hydrogen elements and fluorine elements, and R ³ is a monovalent organic group with a carbon number of 1 to 6 is a monovalent perfluoroalkyl group; and, g is an integer of 1 to 3]. A method for surface treatment of a wafer, which has a water-repellent protective film forming step and a drying step. The water-repellent protective film forming step maintains at least one selected from the group consisting of a cleaning solution and a rinse solution on the surface of the wafer In the state of one liquid, replace the liquid with a chemical solution for forming a water-repellent protective film and hold the chemical solution on the wafer surface. The chemical solution for forming a water-repellent protective film has (I) the following general formula [1] (II) the silicon compound represented by the following general formula [2], and (III) aprotic solvent, and relative to the total amount of (I) to (III) (I) The content is 0.02～0.5% by mass,

[In formula [1], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; a is an integer of 1 to 3, b is an integer of 0-2, and the total of a and b is 1-3],

[In the formula [2], R ^{2 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon numbers from 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; and X represents a halogen group,- OC(=O)R ³ , -OS(=O) ₂ -R ³ , -N(S(=O) ₂ -R ³ ) ₂ , -C(S(=O) ₂ -R ³ ) ₃ At least one group in the group; R ³ is a monovalent perfluoroalkyl group with carbon number of 1 to 6, c is an integer of 1 to 3, d is an integer of 0 to 2, and the total of c and d is 1 to 3]. The surface treatment method of a wafer according to claim 6, wherein the above (I) is a compound represented by the following general formula [3],

[In formula [3], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with a part or all of hydrogen elements, which can be substituted with fluorine; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3]. The method for surface treatment of a wafer according to claim 6, wherein the chemical solution for forming a water-repellent protective film further contains (IV) a silazane compound represented by the following general formula [4],

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3]. Such as the surface treatment method of the wafer of claim 6, which has a chemical solution preparation step before the water-repellent protective film forming step, and the chemical solution preparation step is to combine the protic compound with the formula (II) described in [2] above The silicon compound represented by (IV) the silazane compound represented by the following general formula [4], and (III) the raw material drug solution of the aprotic solvent are compared with the ratio of (II), (III), (IV) The total amount of 1 kg is contacted at the ratio of 0.001 to 0.3 mol, thereby preparing the preparation having the above (I) to (III) and the content of (I) relative to the total amount of (I) to (III) is 0.02 to 0.5 The mass% of the water-repellent protective film forming liquid,

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3]. Such as the surface treatment method of the wafer of claim 8, which has a chemical solution preparation step before the water-repellent protective film formation step, and the chemical solution preparation step is to combine the protic compound with the formula (II) described above in [2] The silicon compound represented by (IV) the silazane compound represented by the following general formula [4], and (III) the raw material drug solution of the aprotic solvent are compared with the ratio of (II), (III), (IV) The total amount of 1 kg is contacted at a ratio of 0.001 to 0.3 mol, whereby the preparation has the above (I) to (IV) and the content of (I) relative to the total amount of (I) to (III) is 0.02 to 0.5 The mass% of the water-repellent protective film forming liquid,

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer of 0-2, and the total of e and f is 3]. The method for surface treatment of wafers according to claim 9 or 10, wherein the liquid chemical preparation step is to introduce the raw chemical liquid into the space containing the protic compound to bring the two into contact. According to claim 9 or 10, the surface treatment method of a wafer, wherein the protic compound is in a gas state. According to claim 9 or 10, the wafer surface treatment method, wherein the protic compound is in a liquid state. According to claim 9 or 10, the surface treatment method of a wafer, wherein the protic compound is a compound having an -OH group and/or a -NH ₂ group. According to claim 9 or 10, the surface treatment method of a wafer, wherein the protic compound is water and/or 2-propanol. The surface treatment method of a wafer according to claim 6, which has a chemical solution preparation step before the water-repellent protective film formation step, and the chemical solution preparation step is to make the acidic compound represented by the following general formula [6] and have ( IV) The silazane compound represented by the following general formula [4] and the raw material liquid medicine of (III) aprotic solvent are 0.001-0.3 mol relative to the total 1 kg of (III) and (IV) To prepare a water-repellent protective film forming chemical solution having the above (I) to (III) and the content of (I) relative to the total amount of (I) to (III) of 0.02 to 0.5% by mass. ,

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer from 0 to 2, and the total of e and f is 3],

[In formula [6], X represents a halogen group, -OC(=O)R ³ , -OS(=O) ₂ -R ³ , -N(S(=O) ₂ -R ³ ) ₂ , -C( S(=O) ₂ -R ³ ) ₃ ; R ³ is a monovalent perfluoroalkyl group having 1 to 6 carbon atoms]. The surface treatment method of a wafer according to claim 8, which has a chemical solution preparation step before the water-repellent protective film formation step, and the chemical solution preparation step is to make the acidic compound represented by the following general formula [6] and have ( IV) The silazane compound represented by the following general formula [4] and the raw material liquid medicine of (III) aprotic solvent are 0.001-0.3 mol relative to the total 1 kg of (III) and (IV) To prepare a water-repellent protective film forming chemical solution having the above (I) to (IV) and the content of (I) relative to the total amount of (I) to (III) of 0.02 to 0.5% by mass. ,

[In formula [4], R ^{1 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with carbon number 1 to 18, which can be substituted with fluorine, part or all of the hydrogen elements; e is an integer of 1 to 3, f is an integer from 0 to 2, and the total of e and f is 3],

[In formula [6], X represents a halogen group, -OC(=O)R ³ , -OS(=O) ₂ -R ³ , -N(S(=O) ₂ -R ³ ) ₂ , -C( S(=O) ₂ -R ³ ) ₃ ; R ³ is a monovalent perfluoroalkyl group having 1 to 6 carbon atoms]. Such as claim 6, wherein the content of (II) relative to the total amount of (I) to (III) above is 0.05-20% by mass. The surface treatment method of wafer according to claim 6, wherein the above (II) is at least one compound in the group consisting of the following general formula [5],

[In formula [5], R ^{2 is} each independently a monovalent organic group containing a monovalent hydrocarbon group with a carbon number of 1 to 18 that can be substituted with a part or all of hydrogen elements and fluorine elements, and R ³ is a monovalent organic group with a carbon number of 1 to 6 is a monovalent perfluoroalkyl group; and, g is an integer of 1 to 3].

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