TWI802624B - Surface treatment method, surface treatment agent and method for area-selective film formation on substrate - Google Patents

Abstract

The present invention provides a method for surface treatment of a substrate surface that can be modified in different degrees of modification (such as imparting hydrophobicity, etc.) corresponding to the material of each region of the surface of a substrate having a plurality of regions, the surface treatment agent used therefor and its use. The ALD method is a method of area-selective film formation on a substrate. The surface treatment method of the present invention is a surface treatment method for the surface of a substrate, and includes exposing the aforementioned surface to a surface treating agent comprising a silylating agent (A) and a nitrogen-containing heterocyclic compound (B), wherein the aforementioned surface comprises two In the above regions, the materials of the adjacent regions among the two or more aforementioned regions are different from each other, and the water contact angles of the adjacent regions among the two or more aforementioned regions are different from each other by the reaction of the aforementioned silanizing agent with the two or more aforementioned regions.

Description

Surface treatment method, surface treatment agent and method for area-selective film formation on substrate

The present invention relates to a surface treatment method for regioselective modification of the substrate surface used in the manufacture of semiconductor integrated circuits, a surface treatment agent used therein, and a method for regioselective film formation on a substrate by atomic layer growth.

In recent years, the trend of high integration and miniaturization of semiconductor devices has become higher, and the miniaturization of inorganic patterns produced by organic patterns and etching processes that have become masks has progressed, and films at the atomic layer level are required thick control. Atomic Layer Growth (ALD (Atomic Layer Deposition) method; hereinafter also abbreviated as "ALD method") is known as a method for forming a thin film at the atomic layer level on a substrate. Compared with general CVD (Chemical Vapor Deposition) method, ALD method is known to have high step coverage and film thickness control.

The ALD method is a thin-film formation technique that alternately supplies two kinds of gases mainly composed of elements constituting the film to be formed on the substrate, and repeats the formation of a thin film on the substrate several times in units of atomic layers to form a film with a desired thickness. In the ALD method, only one or several layers of raw material gas components are adsorbed on the surface of the substrate when the raw material gas is supplied, and the excess raw material gas does not contribute to growth, and the self-control function (self-limiting function) of growth is used. For example, when forming an Al ₂ O ₃ film on a substrate, a raw material gas composed of TMA (trimethylaluminum) and an oxidizing gas containing O are used. Also, when forming a nitride film on a substrate, a nitride gas is used instead of an oxidizing gas. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent No. 4043785 [Non-Patent Document]

[Non-Patent Document 1] J.Phys.Chem.C 2014,118,10957-10962

[Problem to be solved by the invention]

In recent years, attempts have been made to form a region-selective film on the substrate surface using the ALD method (see Patent Document 1 and Non-Patent Document 1). Accompanied by this, there is a demand for a substrate that can be better applied to the region-selective modification of the substrate surface region, such as the method of region-selective film formation on the substrate by the ALD method. In the film forming method, by using the ALD method, it is expected to control the film thickness at the atomic layer level, step coverage and miniaturization of patterning.

The present invention was made in view of the above situation, and the object is to provide a surface treatment method of a substrate surface that can be modified in different degrees of modification (such as imparting hydrophobicity, etc.) corresponding to the material of each region of the substrate surface having a plurality of regions. , the surface treatment agent used therein and the method for forming a region-selective film on the substrate by the ALD method. [Means to solve the problem]

The inventors of the present invention found that the degree of modification can be changed according to the surface material of the substrate by treating with a silanizing agent and a nitrogen-containing heterocyclic compound, and thus completed the present invention. That is, the present invention is as follows.

The first aspect of the present invention is a surface treatment method, which is a surface treatment method for the surface of a substrate, and includes exposing the surface to a surface treatment agent containing a silylating agent (A) and a nitrogen-containing heterocyclic compound (B). , The above-mentioned surface includes two or more regions, the adjacent regions in the two or more above-mentioned regions have different materials from each other, and the adjacent regions among the two or more above-mentioned regions are made The water contact angles are different from each other.

The second aspect of the present invention is a surface treatment agent, which is the surface treatment agent used in the surface treatment method of the first aspect, and contains a silylation agent (A) and a nitrogen-containing heterocyclic compound (B).

The third aspect of the present invention is a region-selective film-forming method on the surface of a substrate, which includes treating the above-mentioned surface of the above-mentioned substrate by the surface treatment method of the first aspect; The film is formed by the atomic layer growth method, and the material deposition amount of the above film is selectively different from region to region. [Invention effect]

The surface treatment method of the present invention can provide different modification degrees corresponding to the material of each region of the substrate surface with multiple regions (such as imparting hydrophobicity, etc.), and is especially suitable for the use of ALD method. A substrate on which a film is selectively formed on a region of the substrate surface. The surface treatment agent of the present invention can provide the above-mentioned surface treatment method. The region-selective film formation method on the substrate of the present invention can selectively form a film with excellent step coverage on the substrate by controlling the film thickness at the atomic layer level.

Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is by no means limited to the following embodiments, and can be implemented with appropriate changes within the scope of the purpose of the present invention.

<<Surface treatment method for the surface of the substrate>> The surface treatment method of the first aspect is a surface treatment method for the surface of the substrate, and includes exposing the above-mentioned surface to a silylating agent (A) and a nitrogen-containing heterocyclic compound (B). ) surface treatment agent, the above-mentioned surface includes two or more regions, the materials of adjacent regions in the two or more above-mentioned regions are different from each other, and the two or more above-mentioned regions are made The water contact angles of adjacent regions among the regions are different from each other.

Examples of the "substrate" to be subjected to surface treatment include substrates used for manufacturing semiconductor devices, such as silicon (Si) substrates, silicon nitride (SiN) substrates, silicon oxide film (Ox) substrates, tungsten (W) substrates, Cobalt (Co) substrate, titanium nitride (TiN) substrate, tantalum nitride (TaN) substrate, germanium (Ge) substrate, silicon germanium (SiGe) substrate, aluminum (Al) substrate, nickel (Ni) substrate, ruthenium (Ru ) substrate, copper (Cu) substrate, etc. In addition to the surface of the substrate itself, the so-called "substrate surface" can also be, for example, the surface of the inorganic pattern and the organic pattern provided on the substrate, and the surface of the non-patterned inorganic layer or organic layer.

An example of the inorganic pattern provided on the substrate is a pattern formed by forming an etching mask on the surface of the inorganic layer existing in the substrate using a photoresist method, and then etching. In addition to the surface of the substrate itself, examples of the inorganic layer include oxide films of elements constituting the substrate, SiN, Ox, W, Co, TiN, TaN, Ge, SiGe, Al, Ni, Ru, Cu, etc. formed on the surface of the substrate. A film or layer of an inorganic substance, etc. These films or layers are not particularly limited, but examples include films or layers of inorganic substances formed in the process of manufacturing semiconductor devices.

Examples of the organic pattern provided on the substrate include a resin pattern formed on the substrate by photolithography using a photoresist or the like. These organic patterns can be formed, for example, by forming an organic layer of a photoresist film on a substrate, exposing and developing the organic layer through a photomask. In addition to the surface of the substrate itself, the organic layer may be an organic layer provided on the surface of a laminated film provided on the surface of the substrate or the like. These organic layers are not particularly limited, but examples include films of organic substances used to form etching masks provided in the manufacturing process of semiconductor devices.

(Aspect in which the surface of the substrate includes two regions) In the surface treatment method of the first aspect, the surface of the substrate includes two or more regions, and the adjacent regions of the two or more regions have different materials from each other.

Between the above two or more regions, the region where the contact angle of water (preferably hydrophobicity) tends to be larger than the other regions is, for example, a group consisting of Si, SiN, Ox, TiN, TaN, Ge, and SiGe An area of at least one of the selected ones. Between the above two or more regions, as a region where the contact angle of water (preferably hydrophobicity) tends to be smaller than that of other regions, for example, it is composed of W, Co, Al, Ni, Ru, Cu, TiN, and TaN. An area of at least one selected from the group.

For example, when one of the above two or more regions is set as the first area and the adjacent area is set as the second area, the materials of the first area and the second area are different. Here, each of the first area and the second area may be divided into plural areas, or may not be divided. As an example of the first region and the second region, for example, the surface of the substrate itself is set as the first region, and the surface of the inorganic layer formed on the surface of the substrate is set as the second region, and the first inorganic layer formed on the surface of the substrate is The surface is defined as the first region, and the surface of the second inorganic layer formed on the surface of the substrate is defined as the second region. Also, similarly, an aspect in which an organic layer is formed instead of the formation of these inorganic layers can also be exemplified. As an aspect in which the surface of the substrate itself is used as the first region and the surface of the inorganic layer formed on the surface of the substrate is used as the second region, the water repellency can be selectively improved between two or more adjacent regions with different materials on the substrate surface, and water repellency can be improved. From the viewpoint of the difference in contact angle, it is preferable to set the surface of at least one substrate selected from the group consisting of Si substrate, SiN substrate, Ox substrate, TiN substrate, TaN substrate, Ge substrate, and SiGe substrate as the first region. The surface of the inorganic layer comprising at least one selected from the group consisting of W, Co, Al, Ni, Ru, Cu, TiN, and TaN formed on the surface of the substrate is set as the second region. In addition, as an aspect in which the surface of the first inorganic layer formed on the surface of the substrate is set as the first region, and the surface of the second inorganic layer formed on the surface of the substrate is set as the second region, based on two or more substrates having different materials on the surface of the substrate, From the viewpoint of selectively increasing hydrophobicity between adjacent regions and increasing the difference in contact angle of water, it is preferable to form a substrate composed of SiN, Ox, TiN, TaN, Ge, and SiGe to be formed on the surface of any substrate (such as a Si substrate). The surface of the first inorganic layer of at least one selected from the group is set as the first region, and is selected from the group consisting of W, Co, Al, Ni, Ru, Cu, TiN, and TaN to be formed on the surface of the above-mentioned substrate. The surface of the at least one second inorganic layer is in the form of the second region.

(Aspects where the surface of the substrate includes three regions) One of the above two or more regions is defined as the first region, the region adjacent to it is defined as the second region, and the region adjacent to the second region is defined as In the case of the third area, the materials of the first area and the second area are different from each other, and the materials of the second area and the third area are different from each other. Here, when the first area and the third area are adjacent, the materials of the first area and the third area are different from each other. When the first area and the third area are not adjacent, the materials of the first area and the third area can be different or the same. Also, each of the first area, the second area, and the third area may be divided into plural areas, or may not be divided. As examples of the first area, the second area, and the third area, for example, the surface of the substrate itself is set as the first area, the surface of the first inorganic layer formed on the surface of the substrate is set as the second area, and the surface of the first inorganic layer formed on the surface of the substrate is set as the second area. 2. The surface of the inorganic layer is set in the form of the third region, etc. Also, similarly, an aspect in which an organic layer is formed instead of the formation of these inorganic layers can also be exemplified. In addition, an embodiment including both the inorganic layer and the organic layer can be similarly exemplified by changing only any one of the second inorganic layer and the third inorganic layer into an organic layer. From the viewpoint of selectively increasing hydrophobicity and increasing the difference in contact angle of water between two or more adjacent regions with different materials on the surface of the substrate, it is preferable to set the surface of any substrate (such as a Si substrate) itself as the first region, and The surface of the first inorganic layer comprising at least one selected from the group consisting of SiN, Ox, TiN, TaN, Ge, and SiGe formed on the surface of the above-mentioned substrate is set as the second region, and the surface of the above-mentioned substrate including The surface of the second inorganic layer of at least one selected from the group consisting of W, Co, Al, Ni, Ru, Cu, TiN, and TaN is set as the third region. The same way of thinking can also be applied to the case where there are four or more regions. The upper limit of the number of regions with different materials is not limited as long as it does not impair the effect of the present invention. For example, it can be 7 or less or 6 or less, typically 5 or less.

(Exposure) As a method of exposing the substrate surface to a surface treatment agent, for example, a surface treatment agent (typically a liquid surface treatment agent) that may contain a solvent is applied by, for example, a dipping method, a spin coating method, or a roll coating method. A method of applying (for example, coating) on the surface of a substrate and exposing it by means of coating methods such as the blade method and the doctor blade method. The exposure temperature is, for example, from 10°C to 90°C, preferably from 20°C to 80°C, more preferably from 30°C to 70°C, more preferably from 40°C to 60°C. The above-mentioned exposure time is preferably at least 20 seconds, more preferably at least 1 minute, and more preferably at least 10 minutes, from the viewpoint of selectively improving hydrophobicity between two or more adjacent regions of different materials on the surface of the substrate. The upper limit of the exposure time is not particularly limited, but may be, for example, 6 hours or less, typically 2 hours or less. After the above-mentioned exposure, cleaning (such as cleaning with water, active agent cleaning, etc.) and/or drying (cleaning with nitrogen blowing, etc.) can be carried out as necessary. For example, as the cleaning treatment of the surface of the substrate with inorganic patterns or organic patterns, the cleaning solution itself used in the cleaning treatment of inorganic patterns or organic patterns can be directly used. Regarding inorganic patterns Examples of molds include SPM (sulfuric acid-hydrogen peroxide solution), APM (ammonia-hydrogen peroxide solution), etc., and examples of organic patterns include water, active agent cleaning solution, etc. Also, heat treatment at 100°C to 300°C can be added to the processed substrate after drying as needed.

Through the above-mentioned exposure, the material area corresponding to each area on the surface of the substrate can be selectively silanized. After the surface treatment agent is exposed, the contact angle of the substrate surface to water can be set at 5° to 140°. By controlling the material of the substrate surface, the type and amount of silanizing agent (A) and nitrogen-containing heterocyclic compound (B), and exposure conditions, the contact angle to water can be set to 50° or more, preferably 60° ° or more, more preferably 70° or more, more preferably 90° or more, particularly preferably 100° or more, most preferably 101° or more. The upper limit of the contact angle is not particularly limited, but is, for example, 140° or less, typically 130° or less.

In the surface treatment method of the first aspect, since the materials of two or more adjacent regions on the surface of the substrate are different, the above-mentioned exposure can selectively increase the hydrophobicity between the above two or more adjacent regions, and the contact angle of water can be improved. different from each other. The difference in water contact angle between the two or more adjacent regions is not particularly limited as long as it does not impair the effect of the present invention, for example, it is 10° or more, based on the selectivity improvement between the above two or more adjacent regions From the viewpoint of hydrophobicity, the difference in the contact angle of water is preferably at least 20°, more preferably at least 30°, still more preferably at least 40°. As the upper limit of the above-mentioned contact angle difference, as long as it does not impair the effect of the present invention, it is not particularly limited, for example, it is 80° or less or 70° or less, and typically it is 60° or less.

<Surface treatment agent> Next, the surface treatment agent used in the surface treatment method of the first aspect will be described. The surface treatment agent of this aspect includes a silanizing agent (A) and a nitrogen-containing heterocyclic compound (B). The following describes each component.

[Silylation agent (A)] The silanization agent (A) is a component used to silanize the substrate surface to increase the hydrophobicity of the substrate surface. The silylating agent (A) is not particularly limited, and all known silanizing agents can be used. As such silylating agents, for example, alkoxymonosilane compounds having a hydrophobic group bonded to a silicon atom, compounds having a hydrophobic group bonded to a silicon atom and a leaving group bonded to a silicon atom can be used (In more detail, for example, a compound represented by the general formula (2) described below, etc.).

(Alkoxymonosilane compound having a hydrophobic group bonded to a silicon atom) The alkoxymonosilane compound having a hydrophobic group bonded to a silicon atom means having one silicon atom and having A compound having at least one hydrophobic group on an atom and at least one alkoxy group bonded to the aforementioned silicon atom. By using an alkoxymonosilane compound having a hydrophobic group bonded to a silicon atom as the silylating agent (A), the alkoxymonosilane compound having a hydrophobic group can be bonded to the substrate surface. By binding the alkoxymonosilane compound to the substrate surface, a monomolecular film derived from the alkoxymonosilane compound can be formed on the substrate surface. The monomolecular film is preferably a self-assembled monomolecular film (self-assembled monolayer; SAM) in which a network of siloxane bonds is formed in the plane direction of the substrate. The monomolecular film and the self-organized monomolecular film will be described in detail later.

The above-mentioned hydrophobic group possessed by the above-mentioned alkoxymonosilane compound is preferably a chain having 3 to 20 carbon atoms from the viewpoint of selectively improving hydrophobicity between two or more adjacent regions having different materials on the surface of the substrate. An aliphatic hydrocarbon group, more preferably a chain aliphatic hydrocarbon group with 6 to 18 carbon atoms, more preferably a chain aliphatic hydrocarbon group with 7 to 12 carbon atoms, particularly preferably a chain aliphatic hydrocarbon group with 8 to 11 carbon atoms The chain aliphatic hydrocarbon group is preferably a chain aliphatic hydrocarbon group having 8 to 10 carbon atoms. A part or all of the hydrogen atoms of the above-mentioned chain aliphatic hydrocarbon group may be substituted by halogen atoms (fluorine atoms, etc.), and may be linear or branched, but preferably a part or all of the hydrogen atoms may be substituted by fluorine atoms. Substituted linear aliphatic hydrocarbon group.

The alkoxy group of the alkoxymonosilane compound mentioned above is represented by the general formula RO-(R represents an alkyl group). As the alkyl group represented by this R, it is preferably a linear or branched alkyl group, more preferably a straight chain group. Alkanes. In addition, the number of carbon atoms of the alkyl group represented by R is not particularly limited, but it is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from the viewpoint of controlling hydrolysis and condensation. 1 or 2. As the alkoxy group of the alkoxy monosilane compound, specific examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, second butoxy and third butoxy wait.

(上述通式中，R¹ 各獨立為1價有機基，R¹ 中之至少1個係氫原子之一部分或全部可經氟原子取代之碳原子數3以上20以下之鏈狀脂肪族烴基，X係烷氧基，n為1以上3以下之整數)。 　　作為R¹ 之1價有機基舉例為烷基、芳香族烴基、胺基、單烷胺基、二烷胺基等。As the above-mentioned alkoxymonosilane compound, a compound represented by the following formula (1) is preferable.

(In the above general formula, each of ^R1 is independently a monovalent organic group, and at least one of ^R1 is a chain aliphatic hydrocarbon group with 3 to 20 carbon atoms that can be replaced by a part or all of hydrogen atoms, X is an alkoxy group, and n is an integer ranging from 1 to 3). The monovalent organic group as R ¹ is exemplified by an alkyl group, an aromatic hydrocarbon group, an amino group, a monoalkylamino group, a dialkylamino group, and the like.

The following describes the case where ^R1 is an organic group other than a chain aliphatic hydrocarbon group with 3 to 20 carbon atoms, in which part or all of the hydrogen atoms may be substituted by fluorine atoms. The above-mentioned alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms (preferably having 1 to 8 carbon atoms), more preferably methyl, ethyl, n-propyl and Isopropyl. As the above-mentioned aromatic hydrocarbon group, phenyl, naphthyl, biphenyl, anthracenyl and phenanthrenyl are preferred, phenyl and naphthyl are more preferred, and phenyl is particularly preferred. The alkyl group contained in the above-mentioned monoalkylamino group or dialkylamino group may also contain a nitrogen atom, an oxygen atom or a carbonyl group in the chain, and may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or the dialkylamino group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 1 to 6.

Next, the case where R ¹ is a chain aliphatic hydrocarbon group with 3 to 20 carbon atoms in which part or all of the hydrogen atoms may be substituted by fluorine atoms will be described. The number of carbon atoms in the chain aliphatic hydrocarbon group is, as described above, more preferably from 6 to 18, more preferably from 7 to 12, particularly preferably from 8 to 11, most preferably from 8 to 10. The chain aliphatic hydrocarbon group may be linear or branched, preferably linear. Preferable examples of chain aliphatic hydrocarbon groups in which part or all of the above-mentioned hydrogen atoms may be substituted by fluorine atoms are n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl , straight-chain alkyl groups such as n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl, and Fluorinated straight-chain alkyl groups in which hydrogen atoms on the straight-chain alkyl groups are replaced by fluorine atoms.

X is preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of X include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, and 3-butoxy. Among these, methoxy, ethoxy, isopropoxy or butoxy are preferred especially from the viewpoint of control during hydrolysis and condensation. Also, the above-mentioned alkoxymonosilane compound is preferably a trialkoxymonosilane compound.

The above-exemplified alkoxymonosilane compounds may be used alone or in combination of two or more. Specific examples of such alkoxymonosilane compounds include propyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane , n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, etc., preferably n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane or n-octadecyltrimethoxysilane, more preferably n-octyltrimethoxysilane, n-dodecyltrimethoxysilane or n-octadecyltrimethoxysilane.

By using the above-mentioned alkoxymonosilane compound, a monomolecular film can be formed on the surface of the substrate. When a monomolecular film derived from an alkoxy monosilane compound having a hydrophobic group is formed on the substrate surface, the hydrophobicity of the substrate surface can be highly improved, and as a result, the gap between two or more adjacent regions with different materials on the substrate surface can be improved. Selectivity for enhanced hydrophobicity. In particular, from the viewpoint of highly improving hydrophobicity, in the monomolecular film, it is preferable to form a network of siloxane bonds in the plane direction of the substrate. This monomolecular film is a so-called self-organized monomolecular film. In the self-organized monomolecular film, the residues derived from the alkoxymonosilane compound are densely contained, and since the residues are bonded to each other through siloxane bonds, the monomolecular film can be strongly bonded to the surface of the substrate. As a result, especially high hydrophobicity can be exhibited. As mentioned above, the self-organized monomolecular film can be formed by using a trialkoxymonosilane compound and/or a dialkoxymonosilane compound as the silylating agent (A).

Formation of the monomolecular film can be confirmed by, for example, changes in film thickness, changes in contact angle, and X-ray photoelectron spectroscopy (XPS). Also, the film thickness of the above-mentioned hydrophobic monomolecular film can be, for example, 20 nm or less, preferably 10 nm or less, more preferably 5 nm or less, and more preferably 3 nm or less. The lower limit is not particularly limited unless the effect of the present invention is impaired, but is, for example, 0.1 nm or more, typically 0.5 nm or more.

(Compound represented by general formula (2)) As an example of the silylating agent used in this aspect, the compound represented by the following general formula (2) is mentioned.

(上述通式(2)中，R⁴ 、R⁵ 及R⁶ 分別獨立表示氫原子、含氮基或有機基，R⁴ 、R⁵ 及R⁶ 所含之碳原子數之合計個數為1個以上，LG表示離去基)。

(In the above general formula (2), R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, a nitrogen-containing group or an organic group, and the total number of carbon atoms contained in R ⁴ , R ⁵ and R ⁶ is 1 more than one, LG means leaving group).

The compound represented by the general formula (2) reacts with a functional group (typically -OH group, _-NH2 group, etc.) on the surface of the substrate while leaving the leaving group contained in its structure to form a chemical bond. As the leaving group, for example, a nitrogen-containing group or a halogen group having a nitrogen atom bonded to a silicon atom in the general formula (2), and a halogen group having an oxygen atom bonded to a silicon atom in the general formula (2) are exemplified. Acyloxy group or sulfoxyl group (sulfoxy group) or their derivatives, hydrogen atom, azido group.

As a compound which has a substituent represented by said general formula (2), the compound represented by following general formula (3)-(6) can be used more specifically.

(上述通式(3)中，R⁴ 、R⁵ 及R⁶ 與上述通式(2)相同，R⁷ 及R⁸ 分別獨立表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、乙醯基、或是飽和或不飽和雜環烷基，R⁷ 及R⁸ 亦可相互鍵結形成含氮原子之環構造，構成該環構造之環構成原子亦可包含氮原子以外之雜原子)。

(In the above general formula (3), R ⁴ , R ⁵ and R ⁶ are the same as the above general formula (2), R ⁷ and R ⁸ independently represent a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkane group, acetyl group, or saturated or unsaturated heterocycloalkyl group, R ⁷ and R ⁸ can also be bonded to each other to form a ring structure containing a nitrogen atom, and the ring constituent atoms constituting the ring structure can also include other than nitrogen atoms heteroatoms).

(上述通式(4)中，R⁴ 、R⁵ 及R⁶ 與上述通式(2)相同，R⁹ 表示氫原子、甲基、三甲基矽烷基或二甲基矽烷基，R¹⁰ 、R¹¹ 及R¹² 分別獨立表示氫原子或有機基，R¹⁰ 、R¹¹ 及R¹² 中所含之碳原子合計個數為1個以上)。

(In the above general formula (4), R ⁴ , R ⁵ and R ⁶ are the same as the above general formula (2), R ⁹ represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or an organic group, and the total number of carbon atoms contained in R ¹⁰ , R ¹¹ and R ¹² is 1 or more).

(上述通式(5)中，R⁴ 、R⁵ 及R⁶ 與上述通式(2)相同，X表示O、CHR¹⁴ 、CHOR¹⁴ 、CR¹⁴ R¹⁴ 或NR¹⁵ ，R¹³ 及R¹⁴ 分別獨立表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、三烷基矽烷基、三烷基矽氧基、烷氧基、苯基、苯基乙基或乙醯基，R¹⁵ 表示氫原子、烷基或三烷基矽烷基)。

(In the above general formula (5), R ⁴ , R ⁵ and R ⁶ are the same as the above general formula (2), X represents O, CHR ¹⁴ , CHOR ¹⁴ , CR ¹⁴ R ¹⁴ or NR ¹⁵ , R ¹³ and R ¹⁴ are respectively independently represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trialkylsilyl group, a trialkylsilyloxy group, an alkoxy group, a phenyl group, a phenylethyl group or an acetyl group, R ¹⁵ represents a hydrogen atom, an alkyl group or a trialkylsilyl group).

(上述通式(6)中，R⁴ 、R⁵ 及R⁶ 與上述通式(2)相同，R⁹ 與上述通式(4)相同，R¹⁶ 表示氫原子、飽和或不飽和烷基或三烷基矽烷基胺基)。

(In the above general formula (6), R ⁴ , R ⁵ and R ⁶ are the same as the above general formula (2), R ⁹ is the same as the above general formula (4), R ¹⁶ represents a hydrogen atom, a saturated or unsaturated alkyl group or trialkylsilylamino).

In addition, the alkyl and cycloalkyl groups in the general formulas (3) to (6) may be substituted with fluorine atoms for part or all of the hydrogen atoms bonded to the carbon atoms constituting the alkyl and cycloalkyl groups.

Examples of compounds represented by the above general formula (3) include N,N-dimethylaminotrimethylsilane, N,N-dimethylaminodimethylsilane, N,N-dimethylaminomono Methylsilane, N,N-diethylaminotrimethylsilane, tert-butylaminotrimethylsilane, allylaminotrimethylsilane, trimethylsilylacetamide, N,N -Dimethylaminodimethylvinylsilane, N,N-Dimethylaminodimethylpropylsilane, N,N-Dimethylaminodimethyloctylsilane, N,N-di Methylaminodimethylphenylethylsilane, N,N-Dimethylaminodimethylphenylsilane, N,N-Dimethylaminodimethylphenylethylsilane, N,N -Dimethylaminotriethylsilane, Trimethylsilylamine, Monomethylsilylimidazole, Dimethylsilylimidazole, Trimethylsilylimidazole, Monoethylsilyltriazole, Dimethylsilane Trimethylsilyl triazole, trimethylsilyl triazole, N-(trimethylsilyl) dimethylamine, trimethylsilyl morpholine, etc.

Examples of compounds represented by the above general formula (4) include hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1, 3-Dimethyldisilazane, 1,2-di-N-octyltetramethyldisilazane, 1,2-divinyltetramethyldisilazane, heptamethyldisilazane , nonamethyltrisilazane, ginseng (dimethylsilyl) amine, ginseng (trimethylsilyl) amine, pentamethylethyldisilazane, pentamethylvinyldisilazane, five Methylpropyldisilazane, pentamethylphenylethyldisilazane, pentamethyl-tert-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane Disilazane, etc.

Examples of the silylating agent represented by the above general formula (5) include trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl propionate, Trimethylsilyl butyrate, trimethylsiloxy-3-penten-2-one, etc.

Examples of the silylating agent represented by the above general formula (6) include bis(trimethylsilyl)urea, N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide Amide, etc.

Among the various compounds described above, the compound represented by the general formula (3) and the compound represented by the general formula (4) are particularly preferably used from the viewpoint of ease of acquisition and high handling properties.

Moreover, among the compounds represented by the above-mentioned general formula (4), a compound having a hydrogen atom as R ⁴ and/or R ¹⁰ is also a preferable example. When these compounds are used, it is considered that an intermolecular network is easily formed after the compounds are spread out on the substrate. There are also these benefits. Once bonded on the substrate, it tends to be difficult to remove even if heated. Thereby, as shown below, even when the surface-treated substrate is delivered to a high-temperature process such as atomic layer growth, the silylation site is stably maintained.

(上述通式(3-a)中，R⁴ 及R⁶ 分別獨立表示氫原子、含氮基或有機基，R⁴ 及R⁶ 中所含之碳原子合計之個數為1個以上，R⁷ 、R⁸ 、R¹⁷ 、R¹⁸ 分別表示氫原子、飽和或不飽和烷基、飽和或不飽和環烷基、乙醯基、或是飽和或不飽和雜環烷基，R⁷ 及R⁸ 或R¹⁷ 及R¹⁸ 亦可相互鍵結形成含氮原子之環構造，構成該環構造之環構成原子亦可含有氮原子以外之雜原子)。Also, among the compounds represented by the above-mentioned general formula (3), it is also preferable to use a silazane compound represented by the following general formula (3-a) having a nitrogen-containing group as R ⁵ and having two nitrogen atoms bonded to the silicon atom . When these compounds are used, the two nitrogen atoms contained in the compounds respectively form chemical bonds with the functional groups on the substrate. That is, two bonding bonds of one nitrogen atom can be bonded to the substrate, and a stronger bond can be formed between the substrates. Furthermore, since such a strong bond can be formed, once bonded on the substrate, it tends to be difficult to remove even by heating. Thereby, as will be shown later, even when the surface-treated substrate is subjected to a high-temperature process such as atomic layer growth, the silylation site is stably maintained. Also, as defined below, R ⁴ and R ⁶ in the general formula (3-a) can be the same nitrogen-containing group as R ⁵ of the general formula (3), which can also enhance the bonding between the silylation agent and the substrate according to the application. interaction.

(In the above general formula (3-a), R ⁴ and R ⁶ independently represent a hydrogen atom, a nitrogen-containing group or an organic group, the total number of carbon atoms contained in R ⁴ and R ⁶ is 1 or more, and R ⁷ , R ⁸ , R ¹⁷ , and R ¹⁸ respectively represent a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an acetyl group, or a saturated or unsaturated heterocycloalkyl group, R ⁷ and R ⁸ Alternatively, R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring structure containing a nitrogen atom, and the ring constituting atoms constituting the ring structure may also contain heteroatoms other than nitrogen atoms).

Also, when focusing on a substituent bonded to a silicon atom, it is preferable to use a so-called bulky (bulky) silylating agent in which the number of carbon atoms contained in the substituent is bonded to a silicon atom. By containing such a silanizing agent in the surface treatment agent, the hydrophobicity of the surface of the substrate to be treated can be increased by the surface treatment agent. Thereby, the improvement of hydrophobicity between two or more types of adjacent regions having different materials on the surface of the substrate can be selectively enhanced.

Therefore, in the above general formula (2), the total number of carbon atoms contained in R ⁴ , R ⁵ and R ⁶ is preferably 3 or more. Among them, based on the viewpoint of obtaining sufficient reactivity in the silylation reaction, it is more preferable that in the above general formula (2), any one of R ⁴ , R ⁵ and R ⁶ is an organic group with 2 or more carbon atoms (hereinafter In this paragraph, referred to as "specific organic group"), and the remaining two are independently methyl or ethyl. Examples of the specific organic group include an alkyl group having 2 to 20 carbon atoms which may have a branch and/or a substituent, a vinyl group which may have a substituent, an aryl group which may have a substituent, and the like. The number of carbon atoms in the specific organic group is more preferably from 2 to 12, still more preferably from 2 to 10, particularly preferably from 2 to 8.

Based on these viewpoints, among the silylating agents with substituents represented by the general formula (2) exemplified above, N,N-dimethylaminodimethylvinylsilane, N,N-dimethyl Aminodimethylpropylsilane, N,N-Dimethylaminodimethyloctylsilane, N,N-Dimethylaminodimethylphenylethylsilane, N,N-Dimethyl Aminodimethylphenylsilane, N,N-Dimethylaminodimethyltert-butylsilane, N,N-Dimethylaminotriethylsilane, N,N-Dimethylamino Trimethylsilane, etc.

(Cyclic silazane) Examples of cyclic silazane compounds include 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, 2,2,6 , Cyclic disilazane compounds such as 6-tetramethyl-2,6-disila-1-azacyclohexane; 2,2,4,4,6,6-hexamethylcyclotrisil Cyclic trisilazane compounds such as azane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; 2,2,4,4,6,6,8 , Cyclic tetrasilazane compounds such as 8-octamethylcyclotetrasilazane; etc. Among these cyclic silazane compounds, compounds having a partial structure in which two or more nitrogen-containing groups are bonded to one silicon atom can be preferably used. In this case, similar to the aforementioned general formula (3-a), a stronger bond can be formed between the silylation agent and the substrate, and once bonded to the substrate, it tends to be difficult to remove even by heating. Thereby, as will be shown later, even when the surface-treated substrate is subjected to a high-temperature process such as atomic layer growth, the silanization site is stably maintained.

(Other silylating agents) In addition to the above compounds, compounds represented by the following general formula (7), (8) or (9) can also be used as silylating agents.

(上述通式(7)中，R¹⁹ 及R²⁰ 分別獨立表示氫原子、烷基、三烷基矽烷基，R¹⁹ 及R²⁰ 之至少1個表示三烷基矽烷基，且R²¹ 表示氫原子之一部分或全部可藉由氟原子取代之碳原子數1以上10以下之脂肪族烴基)。

(In the above general formula (7), R ¹⁹ and R ²⁰ independently represent a hydrogen atom, an alkyl group, and a trialkylsilyl group, at least one of R ¹⁹ and R ²⁰ represents a trialkylsilyl group, and R ²¹ represents a hydrogen atom An aliphatic hydrocarbon group having 1 to 10 carbon atoms in which some or all of the atoms may be substituted by fluorine atoms).

(上述通式(8)中，R²² 表示三烷基矽烷基，R²³ 及R²⁴ 分別獨立表示氫原子或有機基)。

(In the above general formula (8), R ²² represents a trialkylsilyl group, and R ²³ and R ²⁴ independently represent a hydrogen atom or an organic group).

(上述通式(9)中，R⁴ 、R⁵ 及R⁶ 與上述通式(2)同樣，R²⁵ 表示單鍵或有機基，R²⁶ 不存在，或於存在時，表示-SiR²⁷ R²⁸ R²⁹ ，R²⁷ 、R²⁸ 及R²⁹ 分別獨立表示氫原子、含氮基或有機基)。

(In the above general formula (9), R ⁴ , R ⁵ and R ⁶ are the same as the above general formula (2), R ²⁵ represents a single bond or an organic group, R ²⁶ does not exist, or when present, it represents -SiR ²⁷ R ²⁸ R ²⁹ , R ²⁷ , R ²⁸ and R ²⁹ each independently represent a hydrogen atom, a nitrogen-containing group or an organic group).

Examples of the compound represented by the above formula (7) include bis(trimethylsilyl)trifluoroacetamide, trimethylsilylmethylacetamide, bistrimethylsilylacetamide, etc., as the above-mentioned The compound represented by the general formula (8) is exemplified by 2-trimethylsiloxypent-2-en-4-one and the like. Examples of the compound represented by the above formula (9) include 1,2-bis(dimethylchlorosilyl)ethane, tert-butyldimethylchlorosilane, and the like.

The above exemplified silylation agents may be used alone or in combination of two or more.

The content of the silanizing agent (A) as the above-mentioned surface treatment agent is not particularly limited as long as the effect of the present invention is not impaired, but it is preferably at least 0.001% by mass, more preferably at least 0.01% by mass, based on the total amount of the above-mentioned surface treatment agent , more preferably at least 0.1% by mass, particularly preferably at least 0.5% by mass, most preferably at least 1.0% by mass. The upper limit of the content of the silanizing agent (A) in the surface treatment agent is not particularly limited as long as the effect of the present invention is not impaired, but it may be, for example, 30% by mass or less, 15% by mass or less, or 10% by mass or less, Typically, it is 8 mass % or less.

[Nitrogen-Containing Heterocyclic Compound (B)] The surface treatment agent contains a nitrogen-containing heterocyclic compound (B). By including the nitrogen-containing heterocyclic compound (B) in the surface treatment agent, the silylation reaction of the silylation agent, the hydrolysis and condensation of the above-mentioned alkoxymonosilane compound, and the bonding to the substrate surface can be promoted. The surface of the substrate can be activated by dehydrogenation of the hydroxyl group, and as a result, the hydrophobicity between two or more adjacent regions of different materials on the surface of the substrate can be selectively increased.

The nitrogen-containing heterocyclic compound (B) is not particularly limited as long as it is a compound containing a nitrogen atom in the ring structure, but from the viewpoint of selectively improving the hydrophobicity between two or more adjacent regions having different materials on the surface of the substrate, the nitrogen atom is more Preferably more than 2 and less than 5, more preferably more than 2 and less than 4, more preferably 2 or 3. The nitrogen-containing heterocyclic compound (B) may also contain heteroatoms other than nitrogen atoms such as oxygen atoms and sulfur atoms in the ring. As the nitrogen-containing heterocyclic compound (B), typically, a compound that does not contain a silicon atom in its structure can be used. The nitrogen-containing heterocyclic compound (B) is preferably a compound containing an aromatic nitrogen-containing heterocyclic ring from the viewpoint of surface hydrophobization.

The nitrogen-containing heterocyclic compound (B) may be a compound in which two or more plural rings are bonded by a single bond or a polyvalent linking group having a valence of two or more. In this case, two or more plural rings bonded via a linking group need only contain at least one nitrogen-containing heterocycle. Among the polyvalent linking groups, a divalent linking group is preferred from the viewpoint that the steric barrier between the rings is small. Specific examples of divalent linking groups include alkylene groups having 1 to 6 carbon atoms, -CO-, -CS-, -O-, -S-, -NH-, -N=N-, - CO-O-, -CO-NH-, -CO-S-, -CS-O-, -CS-S-, -CO-NH-CO-, -NH-CO-NH-, -SO- and - SO ₂ -etc. The number of rings contained in the compound in which two or more plural rings are bonded by a polyvalent linking group is preferably at most 4, more preferably at most 3, most preferably 2, from the viewpoint of ease of preparation of a uniform surface treatment agent. Also, for example, in a condensed ring such as a naphthalene ring, the number of rings is two.

The nitrogen-containing heterocyclic compound (B) may be a nitrogen-containing heterocyclic compound in which two or more plural rings are condensed. In this case, at least one of the rings constituting the condensed ring should just be a nitrogen-containing heterocyclic ring. The number of rings contained in the nitrogen-containing heterocyclic compound having condensed plural rings of two or more rings is preferably at most 4, more preferably at most 3, most preferably at most 2, in view of the ease of preparation of a uniform surface treatment agent.

From the viewpoint of surface hydrophobization, the nitrogen-containing heterocyclic compound (B) preferably contains a nitrogen-containing 5-membered ring or a condensed polycyclic ring including a nitrogen-containing 5-membered ring skeleton.

The nitrogen-containing heterocycle contained in the nitrogen-containing heterocyclic compound (B) is preferably imidazole which may have a substituent, triazole which may have a substituent, tetrazole which may have a substituent, and benzo which may have a substituent. Triazole or optionally substituted pyrazole, more preferably one or more selected from the group consisting of optionally substituted imidazole, optionally substituted triazole, and optionally substituted tetrazole.

Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkyl group having 3 to 8 carbon atoms. Cycloalkoxy group, aryl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms, halogenated alkyl group with 1 to 6 carbon atoms, aliphatic group with 2 to 7 carbon atoms Acyl group, halogenated aliphatic acyl group with 2 to 7 carbon atoms, arylcarbonyl group with 7 to 20 carbon atoms, carboxyalkyl group with 2 to 7 carbon atoms, halogen atom, hydroxyl group, mercapto group, carbon number Alkylthio groups of 1 to 6, amino groups, monoalkylamino groups containing alkyl groups with 1 to 6 carbon atoms, dialkylamino groups with alkyl groups with 1 to 6 carbon atoms, nitro groups and cyano groups base. The nitrogen-containing heterocyclic compound (B) may have multiple substituents on the heterocyclic ring. When the number of substituents is plural, the plural substituents may be the same or different. When these substituents include aliphatic hydrocarbon rings or aromatic hydrocarbon rings, etc., these rings may further have the same substituents as the nitrogen-containing heterocyclic compound (B) may have.

Particularly preferred specific examples of the heterocyclic compound include compounds of the following formulae.

The content of the nitrogen-containing heterocyclic compound (B) in the surface treatment agent is not particularly limited as long as it does not impair the effect of the present invention, and is preferably at least 0.001% by mass, more preferably 0.01% by mass, based on the total amount of the surface treatment agent or more, more preferably at least 0.1% by mass, particularly preferably at least 0.5% by mass, most preferably at least 1.0% by mass. The upper limit of the nitrogen-containing heterocyclic compound (B) content in the surface treatment agent is not particularly limited as long as the effect of the present invention is not impaired, but may be, for example, 30% by mass or less, 15% by mass or less, or 10% by mass Below, typically 5% by mass or less.

[Solvent] Since the surface treatment agent contains a solvent, it is preferable that the surface treatment agent contains a solvent from the viewpoint of easiness of substrate surface treatment by a dipping method, a spin coating method, or the like.

Specific examples of solvents include dimethylphenoxide, etc.; dimethylsulfide, diethylsulfone, bis(2-hydroxyethyl)sulfone, tetramethylenesulfone, etc.; N, Amides of N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide, etc. Class; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxy Lactamides such as ethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl imidazolidinones such as 2-imidazolidinone; Dimethyl glycol, diethyl diethylene glycol, dimethyl triethylene glycol, methyl ethyl diethylene glycol, diethyl glycol, triethyl glycol Dialkyl glycol ethers such as glycol butyl methyl ether; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, Pentanol, 2-methylbutanol, 2-pentanol, 3-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, n-hexanol, 2-methylpentanol , second hexanol, 2-ethylbutanol, second heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl -4-heptanol, n-decyl alcohol, second-undecanol, trimethylnonanol, second-tetradecanol, second-heptadecanol, phenol, cyclohexanol, methylcyclohexyl alcohol Monoalcohol solvents such as alcohol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbitol, diacetone alcohol, and cresol; Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, etc. Diethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly) alkylene glycol monoalkyl ethers; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. (poly) alkylene glycol monoalkyl ether acetates; Dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol di Methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran and other ethers; Methyl ethyl ketone, cyclohexanone, 2-heptanone, Ketones such as 3-heptanone; Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate and 3-methoxypropionate Methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, 2-hydroxy- Methyl 3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, 3-methyl-3-methoxybutyl propionate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, isoacetic acid Amyl ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl caprate, methyl pyruvate, ethyl pyruvate Other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, dimethyl adipate, propylene glycol diacetate, etc.; Lactones, γ-butyrolactone, δ-valerolactone and other lactones; n-hexane, n-heptane, n-octane, n-nonane, methyl octane, n-decane, n-undecane, n- Dodecane, 2,2,4,6,6-pentamethylheptane, 2,2,4,4,6,8,8-heptamethylnonane, cyclohexane, methylcyclohexane, etc. straight-chain, branched-chain or cyclic aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, naphthalene, etc.; p-menthane, diphenyl Terpenes such as menthane, limonene, terpinene, bornane, norbornane, pinane, etc.; etc. These solvents can be used individually or in mixture of 2 or more types.

Among the above-mentioned solvents, solvents that can dissolve the silylation agent (A) and the nitrogen-containing heterocyclic compound (B) and cause less damage to the surface of the substrate (organic patterns, inorganic patterns, etc.) are preferred. As a solvent, a dielectric is preferable from the viewpoint of dissolving both the silylation agent (A) and the nitrogen-containing heterocyclic compound (B) and selectively improving the hydrophobicity between two or more adjacent regions of different substrate surface materials. Solvents with a dielectric ratio of 1 to 25, more preferably solvents with a dielectric ratio of 2 to 20, more preferably solvents with a dielectric ratio of 3 to 15, particularly preferably solvents with a dielectric ratio of 4 to 10, most preferably Solvents with a dielectric ratio of 5 to 8.

As a solvent satisfying the above dielectric ratio, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol Monomethyl ether, isopropanol or methyl ethyl ketone, more preferably 3-methyl-3-methoxy-1-butyl acetate, ethyl acetate or propylene glycol monomethyl ether acetate.

＜<Regioselective film formation method on the substrate>> Next, the method of regioselective film formation on the substrate using the surface treatment method of the first aspect will be described. In this aspect, the region-selective film-forming method on the substrate includes treating the above-mentioned surface of the above-mentioned substrate by the surface treatment method of the above-mentioned first aspect; Membranes, making the material accumulation amount of the above-mentioned membranes regionally different selectively.

As a result of the surface treatment of the method of the above-mentioned first aspect, the contact angle of water (preferably hydrophobicity) between the above-mentioned two or more regions becomes different. In the present invention, the formation of the above-mentioned The accumulation amount of the material of the film is different according to the region selectivity of the surface of the substrate. Specifically, the contact angle of water between the above two or more regions is better (preferably hydrophobic) in a region larger than the other regions, and the film forming material by ALD method is difficult to adsorb (preferably chemical adsorption) ) in the aforementioned regions on the surface of the substrate, and as a result of differences in the deposited amount of the film-forming material between the above-mentioned two or more regions, the deposited amount of the regioselective film-forming material on the substrate is different. Examples of the above-mentioned chemical adsorption include chemical adsorption with hydroxyl groups and the like.

Between the above two or more regions, the region where the contact angle of water (preferably hydrophobicity) tends to be larger than the other regions is, for example, a group consisting of Si, SiN, Ox, TiN, TaN, Ge, and SiGe An area of at least one of the selected ones. Between the above two or more regions, as a region where the contact angle of water (preferably hydrophobicity) tends to be smaller than that of other regions, for example, it is composed of W, Co, Al, Ni, Ru, Cu, TiN, and TaN. An area of at least one selected from the group.

(Film Formation by ALD Method) The film formation method by ALD method is not particularly limited, but it is preferably adsorption ( Preferably, it is a film forming method of chemical adsorption). Specifically, a method including the following steps (a) and (b) and repeating the following steps (a) and (b) at least once (1 cycle) until a desired film thickness is obtained is exemplified. (a) a step of exposing the substrate surface-treated by the method of the first aspect above to pulses of the first precursor gas, and (b) after the above step (a), exposing the substrate to the second precursor gas steps in the pulse.

After the above step (a) and before the above step (b), it may also include a plasma treatment step, removing or exhausting (blowing) the first precursor gas and its reactants by carrier gas, second precursor gas, etc. steps, etc., may not include these steps. After the above step (b), the step of plasma treatment, the step of removing or degassing the second precursor gas and its reactants by means of carrier gas, etc. may also be included, or these steps may not be included. Examples of carrier gas include inert gases such as nitrogen, argon, and helium.

Preferably the pulses of each cycle and the layers formed are self-controlled, more preferably the layers formed are monoatomic layers. The film thickness of the monoatomic layer is, for example, not more than 5 nm, preferably not more than 3 nm, more preferably not more than 1 nm, more preferably not more than 0.5 nm.

Examples of the first precursor gas include organic metals, metal halides, and metal oxide halides, and specifically, tantalum pentaethoxide, tetrakis(dimethylamino)titanium, and pentano(dimethylamino)tantalum , Si(dimethylamino)zirconium, Si(dimethylamino)hafnium, Si(dimethylamino)silane, copper hexafluoroacetylacetonate vinyltrimethylsilane, Zn(C ₂ H ₅ ) ₂ , Zn(C ₂ H ₅ ) ₂ , Zn(CH ₃ ) ₂ , TMA (trimethylaluminum), TaCl ₅ , WF ₆ , WOCl ₄ , CuCl, ZrCl ₄ , AlCl ₃ , TiCl ₄ , SiCl ₄ , HfCl _{4 ,} etc. .

The second precursor gas is, for example, a precursor gas that can decompose the first precursor or a precursor gas that can remove the ligand of the first precursor. Specific examples are H ₂ O, H ₂ O ₂ , O ₂ , O _3. NH ₃ , H ₂ S, H ₂ Se, PH ₃ , AsH ₃ , C ₂ H ₄ or Si ₂ H ₆ etc.

The exposure temperature of the step (a) is not particularly limited, for example, it is 100°C to 800°C, preferably 150°C to 650°C, more preferably 200°C to 500°C, and more preferably 225°C to 375°C. below ℃.

The exposure temperature in the step (b) is not particularly limited, and is, for example, a temperature substantially equal to or higher than the exposure temperature in the step (a).

The film formed by the ALD method is not particularly limited, and examples include films containing pure elements (such as Si, Cu, Ta, W), films containing oxides (such as SiO ₂ , GeO ₂ , HfO ₂ , ZrO ₂ , Ta ₂ O ₅ , TiO ₂ , Al ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₅ , B ₂ O ₃ , In ₂ O ₃ , WO ₃ ), films containing nitrides (such as Si ₃ N ₄ , TiN , AlN, BN, GaN, NbN), carbide-containing film (such as SiC), sulfide-containing film (such as CdS, ZnS, MnS, WS ₂ , PbS), selenide-containing film (such as CdSe, ZnSe) , phosphide-containing film (GaP, InP), arsenide-containing film (such as GaAs, InAs) or a mixture thereof, etc. [Example]

The following examples are shown to further describe the present invention in detail, but the scope of the present invention is not limited to these examples.

[Examples 1 to 4 and Comparative Example 1] (Preparation of surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate (MMBA), uniformly mix the silylating agent (A) 7.8% by mass of n-octyltrimethoxysilane and 1.0% by mass of the nitrogen-containing heterocyclic compound (B) (hereinafter also referred to as "compound (B)") listed in Table 1 below to prepare Examples 1 to 4 and compare The surface treatment agent of Example 1.

(Surface treatment) Using the surface treatment agents obtained in Examples 1 to 4 and Comparative Example 1, the surfaces of silicon nitride substrates (SiN), silicon thermal oxide film substrates (Ox) and tungsten substrates (W) were treated in the following manner. deal with. Specifically, each substrate was pretreated by immersing each substrate in an aqueous HF solution with a concentration of 0.5% by mass at 25°C for 1 minute. After the above pretreatment, the substrate was washed with ion-exchanged distilled water for 1 minute. The substrate washed with water was dried by nitrogen flow. After drying, the substrates were immersed in the above-mentioned surface treatment agents at 60°C for 10 minutes to perform surface treatment of the substrates. The surface-treated substrate was washed with isopropanol for 1 minute, and then with ion-exchanged distilled water for 1 minute. The cleaned substrate was dried by nitrogen flow to obtain a surface-treated substrate.

(Measurement of Water Contact Angle) The water contact angle was measured for each of the substrates after the HF pretreatment and each of the substrates after the surface treatment. The measurement of the contact angle of water is to drop pure water droplets (2.0μL) on the surface of the surface-treated substrate using Dropmaster700 (manufactured by Kyowa Interface Science Co., Ltd.), and measure the contact angle after 2 seconds of dropping. The results are shown in Table 1 below. The contact angle difference (°) in Table 1 is the value obtained by subtracting the value of the water contact angle of the latter substrate after the treatment from the water contact angle of the former substrate after treatment.

As understood from the results shown in Table 1 above, it can be seen that the surface treatment of Examples 1 and 2 containing Compound (B) together with the silanizing agent (A) was compared to Comparative Example 1 not containing Compound (B). For those with different agents, the water contact angle difference between the W substrate and the SiN or Ox substrate is relatively large. In particular, it can be seen that the surface treatment agents of Examples 1 and 2, which contain compound (B) together with the silylation agent (A), can be preferably used for regioselective film formation on the surface of the substrate by the ALD method.

[Example 3~7] (Preparation of surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate, each silylating agent (A) recorded in the following Table 2 was uniformly mixed 7.8% by mass, 1.0% by mass of imidazole as the compound (B), prepared the surface treatment agents of Examples 3-7.

(Surface treatment) Using the obtained surface treatment agents of Examples 3 to 7, as in Examples 1, 2 and Comparative Example 1, after pretreatment with HF aqueous solution, SiN substrate, Ox substrate, W substrate and titanium nitride substrate were performed. For the surface treatment of the substrate (TiN), the contact angle of water was measured for each substrate after the above-mentioned HF pretreatment and each substrate after the above-mentioned surface treatment. The measurement of the contact angle of water was carried out in the same manner as above. The results are shown in Table 2 below. In addition, the contact angle difference (°) in Table 2 is the value obtained by subtracting the value of the water contact angle of the latter substrate after the treatment from the water contact angle of the former substrate after treatment.

As can be understood from the results shown in Table 2 above, it can be known that the SiN substrate, Ox substrate, W substrate, and TiN substrate before the surface treatment with the silanizing agent (after the HF pretreatment) have a small difference in water contact angle between the substrates. . On the other hand, it can be seen that after surface treatment with the surface treatment agents of Examples 3 to 7 containing various silylation agents (A) and imidazoles, for example, between the substrates shown in the contact angle difference column of Table 2, the water contact angle difference is relatively small. big. From this result, it can be said that the use of surface treatment agents containing various silanizing agents (A) and compounds (B) on substrates containing multiple different regions is better suitable for the region-selective film formation on the substrate surface using the ALD method. . In particular, when using the surface treatment agents of Examples 5 and 6 in which the linear alkyl group has 8 or 11 carbon atoms, it can be seen that the difference in water contact angle between the W substrate and the SiN substrate, Ox substrate, or TiN substrate tends to be particularly large. .

[Example 8] (Preparation of surface treatment agent) In the following solvents, 7.8% by mass of n-octyltrimethoxysilane as a silylating agent (A) and 1.0% by mass of imidazole as a compound (B) were uniformly mixed , modulation surface treatment agent. Isopropyl alcohol (IPA) Methyl ethyl ketone (MEK) Ethyl acetate 3-methyl-3-methoxybutanol (MMB) Propylene glycol monomethyl ether (PGME) Diethylene glycol monomethyl ether (MDG) Propylene glycol Monomethyl ether acetate (PGMEA) 3-methyl-3-methoxy-1-butyl acetate (MMBA)

(Surface treatment) Using the obtained surface treatment agent, the same as in Examples 1, 2 and Comparative Example 1, after pre-treatment with HF aqueous solution, carry out the surface treatment of the Ox substrate and the W substrate, for each substrate after the above-mentioned surface treatment, Measure the contact angle of water. The measurement of the contact angle of water was carried out in the same manner as above. Subsequently, the relationship between the water contact angle difference between the Ox substrate and the W substrate and the dielectric constant of each solvent is summarized in FIG. 1 .

Based on the relationship between the water contact angle difference between the Ox substrate and the W substrate and the dielectric constants of various solvents shown in Figure 1, it can be known that the water contact angle difference becomes larger for solvents with a dielectric constant of 1 to 25 tendency. Specifically, from the viewpoint of the selectivity of hydrophobicity improvement between substrate surfaces of different materials, it can be known that 3-methyl-3-methoxy-1-butyl acetate, ethyl acetate, or propylene glycol monomethyl ether acetate Excellent.

[Examples 9 and 10 and Comparative Examples 2 and 3] (Preparation of surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate, 5.0% by mass of hexamethyldisilane was uniformly mixed Azane (HMDS) prepared the surface treatment agent of Comparative Example 2. The surface treatment agent of Example 9 was prepared in the same manner as in Comparative Example 2, except that 3.5% by mass of imidazole as compound (B) was further mixed. The surface treatment agent of Comparative Example 3 was prepared in the same manner as in Comparative Example 3, except that 5.0% by mass of n-octyltrimethoxysilane was uniformly mixed instead of 5.0% by mass of HMDS. The surface treatment agent of Example 10 was prepared in the same manner as in Comparative Example 3, except that 3.5% by mass of imidazole as compound (B) was further mixed.

(Surface treatment) Using the surface treatment agents obtained in Examples 9 and 10 and Comparative Examples 2 and 3, as in Examples 1, 2 and Comparative Example 1, after pre-treatment with HF aqueous solution, Si substrates, SiN substrates, The surface treatment of Ox substrate, W substrate, cobalt substrate (Co), titanium nitride substrate (TiN) and tantalum nitride substrate (TaN) was measured for each substrate after the above HF pretreatment and each substrate after the above surface treatment. water contact angle. The measurement of the contact angle of water was carried out in the same manner as above. The results are shown in Tables 3 and 4 below. In addition, Tables 4 and 6 below show differences in contact angles of water between substrates of different materials. Also, the contact angle difference (°) in Table 4 and Table 6 is the value obtained by subtracting the contact angle of water after substrate treatment in the former from the contact angle of water after substrate treatment in the latter.

As understood from the results shown in Table 3 above, it can be seen that when the surface is treated with the surface treatment agent of Example 9 containing imidazole, compared with the surface treatment with the surface treatment agent of Comparative Example 2 that does not contain imidazole, for example The water contact angle difference between the substrates shown in the contact angle difference column of Table 4 is relatively large. The use of the surface treatment agent of Example 9, which contains the compound (B) together with the silylation agent (A), can be said to be suitable for regioselective film formation on the substrate surface using the ALD method.

As understood from the results shown in Table 5 above, it can be seen that when the surface is treated with the surface treatment agent of Example 10 containing imidazole, compared to the surface treatment with the surface treatment agent of Comparative Example 3 that does not contain imidazole, for example The water contact angle difference between the substrates shown in the contact angle difference column of Table 6 is relatively large. The use of the surface treatment agent of Example 10, which contains the compound (B) together with the silylation agent (A), can be said to be suitable for regioselective film formation on the surface of the substrate using the ALD method.

In addition, except that the imidazole content was changed to 0.5% by mass, 1% by mass, and 3% by mass, the same surface treatment agent as in Example 10 was used to treat Si substrates, SiN substrates, Ox substrates, W substrates, and Co substrates. As a result of surface treatment of the substrate, TiN substrate, and TaN substrate, the same results as those shown in Table 5 and Table 6 were obtained.

[Example 11] (Preparation of surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate, 5.0% by mass of the conventional silylation agent HMDS and 3.5% by mass of imidazole were uniformly mixed to prepare The surface treatment agent of embodiment 4.

(Surface treatment) Using the surface treatment agent obtained in Example 11, the surface treatment of Si substrates, SiN substrates, Ox substrates and W substrates was carried out by the following method. Specifically, each substrate was pretreated by immersing each substrate in an aqueous HF solution with a concentration of 0.5% by mass at 25°C for 1 minute. After the above pretreatment, the substrate was washed with ion-exchanged distilled water for 1 minute. The substrate washed with water was dried by nitrogen flow. After drying, each substrate was immersed in the above-mentioned surface treatment agents at 25°C for the time shown in Table 5 below to perform surface treatment of the substrate, and the water contact angle of each immersion time was measured for each substrate. The measurement of the water contact angle was carried out in the same manner as above. The results are shown in Table 7 below.

As understood from the results shown in Table 7 above, it can be seen that the water contact angle of the W substrate has a large difference from the water contact angle of the Si, SiN, or Ox substrate regardless of the immersion time.

[Examples 12 to 14] (Surface treatment agent) In the solvent 3-methyl-3-methoxy-1-butyl acetate 91.5g, HMDS and imidazole 3.5 mass% were uniformly mixed at 5.0 mass%, and Example 12 was prepared. surface treatment agent. The surface treatment agent of Example 13 was prepared in the same manner as in Example 12, except that 5.0% by mass of tetramethyldisilazane (TMDS) was uniformly mixed instead of 5.0% by mass of HMDS. The surface treatment agent of Example 14 was prepared in the same manner as in Example 12, except that 5.0% by mass of bis(dimethylamino)dimethylsilane (BDMADMS) was uniformly mixed instead of 5.0% by mass of HMDS.

(Surface Treatment) Using the obtained surface treatment agents of Examples 12 to 14, the surface treatment of SiN substrates, Ox substrates, Co substrates and TiN substrates was carried out by the following method. Specifically, each substrate was pretreated by immersing each substrate in an aqueous HF solution with a concentration of 0.5% by mass at 25°C for 1 minute. After the above pretreatment, the substrate was washed with ion-exchanged distilled water for 1 minute. The substrate washed with water was dried by nitrogen flow. After drying, the substrates were immersed in the above-mentioned surface treatment agents at 60°C for 10 minutes to perform surface treatment of the substrates. The surface-treated substrate was washed with isopropanol for 1 minute, and then washed with ion-exchanged distilled water for 1 minute. The cleaned substrate was dried by nitrogen flow to obtain a surface-treated substrate. The measurement of the water contact angle was carried out in the same manner as above. The results are shown in Table 8 below.

As can be understood from the results shown in Table 8 above, after surface treatment with the surface treatment agents of Examples 12 to 14 containing various silanizing agents (A) and imidazoles, the difference in water contact angle with SiN or Ox substrates is relatively large . On the other hand, since the difference of the water contact angle with the Co or TiN substrate is reduced, it can be seen that Examples 12 to 14 have selectivity.

(Evaluation of heat resistance) Using the surface treatment agents obtained in Examples 12 to 14, the heat resistance evaluations on SiN substrates and Ox substrates were performed by the following method. Specifically, immerse in each of the above-mentioned surface treatment agents for 1 minute at a temperature of 25°C to perform surface treatment of the SiN substrate and the Ox substrate. Subsequently, under a nitrogen atmosphere, a heating plate was used to bake at 300° C., and the water contact angle was measured for each substrate after each baking time. The results are shown in Table 9.

As is clear from the results shown in Table 9 above, when TMDS or BDMADMS is used, water contact can be maintained at a high level even when heated. From this, it is considered that the use of these silanizing agents can stably maintain the silanized sites even when the surface-treated substrate is subjected to a high-temperature process such as atomic layer growth method, and it is expected to be better used in industrial process.

FIG. 1 is a graph showing the relationship between the water contact angle difference between an Ox substrate and a W substrate and the dielectric constant of various solvents.

Claims (10)

A surface treatment method, which is a surface treatment method for the surface of a substrate, and includes exposing the aforementioned surface to a surface treating agent comprising a silylating agent (A), a nitrogen-containing heterocyclic compound (B) and a solvent, and the dielectric of the aforementioned solvent The ratio is 3 or more and less than 8, the surface includes 2 or more regions, the materials of adjacent regions of the 2 or more regions are different from each other, and the silanization agent reacts with the 2 or more regions to make 2 or more regions Among the aforementioned regions, the water contact angles of adjacent regions are different from each other. The surface treatment method as in Claim 1, wherein the aforementioned solvent is 3-methyl-3-methoxy-1-butyl acetate or ethyl acetate. The surface treatment method according to claim 1 or 2, wherein the nitrogen-containing heterocyclic compound (B) is selected from the group consisting of imidazole that may have substituents, triazole that may have substituents, and tetrazole that may have substituents One or more of them. The surface treatment method according to claim 1 or 2, wherein the aforementioned silylating agent (A) is an alkoxy monosilane compound having a hydrophobic group bonded to a silicon atom. Such as the surface treatment method of claim 4, wherein the aforementioned alkoxy monosilane The compound is a trialkoxy monosilane compound. The surface treatment method according to claim 4, wherein the aforementioned hydrophobic group possessed by the aforementioned alkoxymonosilane compound is a chain aliphatic hydrocarbon group having 3 to 20 carbon atoms. The surface treatment method according to claim 1 or 2, wherein the silylating agent (A) is a compound having a hydrophobic group bonded to a silicon atom and a leaving group bonded to a silicon atom. The surface treatment method according to claim 1 or 2, wherein, on the surface exposed to the surface treatment agent, the difference in water contact angle between two or more adjacent regions is 20° or more. A method for forming a region-selective film on the surface of a substrate, which includes treating the aforementioned surface of the aforementioned substrate by the surface treatment method according to any one of claims 1 to 8; The layer growth method forms a film in which the amount of material deposited in the film is selectively different from region to region. A surface treatment agent, which is the surface treatment agent used in the surface treatment method according to any one of claims 1 to 8, and comprises a silanizing agent (A) and a nitrogen-containing heterocyclic compound (B).

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