Substrate material for self-assembled materials

Abstract

A lower layer film which is a fired product of a coated film of a lower layer film-forming composition containing a polysiloxane which is a hydrolytic condensate of a hydrolyzable silane, the hydrolyzable silane containing a compound represented by the following formula (1) and can contain a compound represented by the following formula (2), the molar proportion of the compound represented by the formula (1) in the hydrolyzable silane being 45 mol% or more, and the molar proportion of the total of the compound represented by the formula (1) and the compound represented by the formula (2) in the hydrolyzable silane being 65 mol% or more (Note that the case where the molar proportion of the compound represented by the formula (2) in the hydrolyzable silane is 0 mol% is included.)(In the formula (1), Ar represents an aromatic hydrocarbon group which can have a substituent. n represents an integer of 1 to 3. When n is 1, R a represents a single bond or an alkylene group having 1 to 6 carbon atoms. When n is 2 or 3, R a represents a saturated hydrocarbon group having (n + 1) valences and having 1 to 6 carbon atoms. X's independently represent a hydrolyzable group. When n is 2 or 3, the plurality of Ar's can be the same or different.)(In the formula (2), R b represents a non-aromatic hydrocarbon group having 1 to 6 carbon atoms. X's independently represent a hydrolyzable group.)

Description

Technical Field

[0001] The present invention relates to compositions and underlying films for photolithography using resist films and self-assembled films for forming underlying films, and methods for manufacturing semiconductor devices using them. Background Technology

[0002] In recent years, with the further miniaturization of large-scale integrated circuits (LSI), there has been a demand for technologies that fabricate finer structures. To address this demand, efforts have begun to explore the formation of finer patterns using phase-separated structures formed by the self-assembly of block copolymers, which are obtained by bonding immiscible polymers together. For example, a patterning method has been proposed in which a lower layer film forming composition is coated on a substrate, a lower layer film is formed from the composition, a self-assembled film comprising a block copolymer of two or more polymers is formed on the surface of the lower layer film, and the block copolymer phases in the self-assembled film are separated, selectively removing the phase of at least one polymer constituting the block copolymer.

[0003] Patent Document 1 discloses a composition for forming the lower layer of a self-assembled membrane comprising polysiloxane and a solvent.

[0004] Patent document 2 discloses a method for forming microelectronic structures, which utilizes induced self-assembly to form microelectronic structures. The method includes: A wafer stack is supplied, the stack comprising: A substrate with a surface; One or more optional intermediate layers located on the aforementioned substrate surface; and A hard mask layer adjacent to the intermediate layer when the intermediate layer is present, or a hard mask layer on the substrate surface when the intermediate layer is absent; and The self-assembly composition is directly coated onto the aforementioned hard mask layer. The self-assembling composition is directly adjacent to the hard mask layer and self-assembles into a self-assembling layer, wherein the self-assembling layer includes a first self-assembling region and a second self-assembling region different from the first self-assembling region.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2013 / 146600

[0008] Patent Document 2: Japanese Patent Publication No. 2015-516686 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] When using self-assembled films for microfabrication, they are sometimes used in the same photoresists (photoresists, electron beam resists) used in conventional microfabrication. In this case, when the underlying film of the resist film also serves as the underlying film of the self-assembled film, the underlying film is required to ensure that the self-assembled film forms a vertical alignment even when exposed to the exposure and development processes used to form the resist pattern.

[0011] The object of the present invention is to provide a lower layer film that serves as both a resist film and a self-assembled film, a lower layer film in which the self-assembled film can be formed vertically even when exposed to exposure and development during the formation of a resist pattern, a lower layer film forming composition capable of forming the lower layer film, and a method for manufacturing a semiconductor device using the lower layer film forming composition.

[0012] Methods for solving problems

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved, and completed the present invention with the following main points.

[0014] That is, the present invention includes the following solutions.

[0015] [1] A lower layer film, which is a sintered product of a coated film of a lower layer film forming composition, In photolithography using either photoresist film or electron beam resist film and a self-assembled film, the lower layer film, after being used as the lower layer film of the aforementioned resist film, is further used as the lower layer film of the aforementioned self-assembled film. The above-mentioned composition for forming the lower film contains a polysiloxane as a hydrolytic condensate of a hydrolyzable silane. The above-mentioned hydrolyzable silanes include compounds represented by formula (1) below, and may include compounds represented by formula (2) below. The molar proportion of the compound represented by formula (1) in the above-mentioned hydrolyzable silane is 45 mol% or more. The total molar percentage of the compound shown in formula (1) and the compound shown in formula (2) in the above-mentioned hydrolyzable silane is 65 mol% or more (it should be noted that this includes cases where the molar percentage of the compound shown in formula (2) in the above-mentioned hydrolyzable silane is 0 mol%).

[0016]

[0017] In formula (1), Ar represents an aromatic hydrocarbon group that can have substituents. n represents an integer from 1 to 3. When n is 1, R a Indicates a single bond or an alkylene group with 1 to 6 carbon atoms. When n is 2 or 3, R aThis represents a saturated hydrocarbon group with a valence of (n+1) carbon atoms (1-6). Each X independently represents a hydrolyzable group. When n is 2 or 3, multiple Ar groups can be the same or different.

[0018] (In equation (2), R) b Represents non-aromatic hydrocarbon groups with 1 to 6 carbon atoms. Each X independently represents a hydrolyzable group.

[0019] [2] According to the lower membrane described in [1], n in the above formula (1) is 1, R a Indicates alkylene groups having 1 to 6 carbon atoms.

[0020] [3] According to the lower membrane described in [2], the molar proportion of the compound represented by the above formula (1) in the above hydrolyzable silane is 65 mol% or more.

[0021] [4] According to any one of [1] to [3], the total molar ratio of the compound shown in formula (1) and the compound shown in formula (2) in the hydrolyzable silane is 80 mol% or more (it should be noted that this includes the case where the molar ratio of the compound shown in formula (2) in the hydrolyzable silane is 0 mol%).

[0022] [5] The lower layer film according to any one of [1] to [4] is formed of a positive resist.

[0023] [6] The lower membrane according to any one of [1] to [5], wherein the self-assembled membrane is a membrane comprising a block copolymer.

[0024] [7] The thickness of the lower layer film according to any one of [1] to [6] is 30 nm or less.

[0025] [8] A composition for forming a lower layer film, wherein the lower layer film is used in photolithography, after being used as a lower layer film for the aforementioned photoresist film and an electron beam photoresist film and a self-assembled film, and is further used as a lower layer film for the aforementioned self-assembled film. The composition for forming the lower film contains a polysiloxane as a hydrolytic condensate of a hydrolyzable silane. The above-mentioned hydrolyzable silanes include compounds represented by formula (1) below, and may include compounds represented by formula (2) below. The molar proportion of the compound represented by formula (1) in the above-mentioned hydrolyzable silane is 45 mol% or more. The total molar percentage of the compound shown in formula (1) and the compound shown in formula (2) in the above-mentioned hydrolyzable silane is 65 mol% or more (it should be noted that this includes cases where the molar percentage of the compound shown in formula (2) in the above-mentioned hydrolyzable silane is 0 mol%).

[0026]

[0027] In formula (1), Ar represents an aromatic hydrocarbon group that can have substituents. n represents an integer from 1 to 3. When n is 1, R a Indicates a single bond or an alkylene group with 1 to 6 carbon atoms. When n is 2 or 3, R a This represents a saturated hydrocarbon group with a valence of (n+1) carbon atoms (1-6). Each X independently represents a hydrolyzable group. When n is 2 or 3, multiple Ar groups can be the same or different.

[0028] (In equation (2), R) b Represents non-aromatic hydrocarbon groups with 1 to 6 carbon atoms. Each X independently represents a hydrolyzable group.

[0029] [9] According to the composition for forming the lower film described in [8], n in the above formula (1) is 1, R a Indicates alkylene groups having 1 to 6 carbon atoms.

[0030]

[10] In the composition for forming the lower layer film according to [9], the molar proportion of the compound represented by the above formula (1) in the above hydrolyzable silane is 65 mol% or more.

[0031]

[11] In any one of [8] to

[10] , the total molar percentage of the compound represented by formula (1) and the compound represented by formula (2) in the hydrolyzable silane is 80 mol% or more (it should be noted that this includes cases where the molar percentage of the compound represented by formula (2) in the hydrolyzable silane is 0 mol%).

[0032]

[12] The composition for forming a lower layer film according to any one of [8] to

[11] , wherein the resist film is formed from a positively developing resist.

[0033]

[13] The composition for forming a lower layer film according to any one of [8] to

[12] , wherein the self-assembled film is a film comprising a block copolymer.

[0034]

[14] The composition for forming a lower layer film according to any one of [8] to

[13] , wherein the thickness of the lower layer film is 30 nm or less.

[0035]

[15] A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a lower layer film on a semiconductor substrate using the composition for forming a lower layer film as described in any one of [8] to

[14] The process of forming either a photoresist film or an electron beam resist film on the aforementioned lower layer film. The process of subjecting the above-mentioned resist film to light or electron beam irradiation, followed by developing the above-mentioned resist film to obtain a resist pattern, and... The process of forming a self-assembled film on at least a portion of the lower film after the process of obtaining the resist pattern described above.

[0036]

[16] According to the semiconductor device manufacturing method described in

[15] , the step of forming the self-assembled film is a step of forming the self-assembled film between the resist patterns and on at least a portion of the lower film.

[0037]

[17] The semiconductor device manufacturing method according to

[15] includes, between the above-mentioned step of obtaining the resist pattern and the above-mentioned step of forming the self-assembled film, the following steps are sequentially included: a step of forming a brush layer between the above-mentioned resist patterns and on at least a portion of the above-mentioned lower film, and a step of removing the above-mentioned resist pattern.

[0038]

[18] The semiconductor device manufacturing method according to

[17] includes, between the above-described process of obtaining the resist pattern and the above-described process of forming the brush layer, a process of performing surface modification on the lower film exposed between the above-described resist patterns using a dry process.

[0039]

[19] The semiconductor device manufacturing method according to

[15] includes, between the above-mentioned step of obtaining the resist pattern and the above-mentioned step of forming the self-assembled film, the following steps are included in sequence: a step of performing surface modification on the lower film exposed between the above-mentioned resist patterns using a dry process, and a step of removing the above-mentioned resist patterns.

[0040] Invention Effects

[0041] According to the present invention, a lower layer film that serves as both a resist film and a self-assembled film can be provided; a lower layer film in which the self-assembled film can be formed vertically even when exposed to exposure and development during the formation of a resist pattern; a lower layer film forming composition capable of forming the lower layer film; and a method for manufacturing a semiconductor device using the lower layer film forming composition. Attached Figure Description

[0042] Figure 1A A cross-sectional schematic diagram (1) is provided for illustrating an example of a method for manufacturing a semiconductor element according to the present invention.

[0043] Figure 1B A cross-sectional schematic diagram (2) is provided for illustrating an example of a method for manufacturing a semiconductor element according to the present invention.

[0044] Figure 1C This is a cross-sectional schematic diagram (3) illustrating an example of a method for manufacturing a semiconductor element according to the present invention.

[0045] Figure 1D A cross-sectional schematic diagram (4) illustrating an example of a method for manufacturing a semiconductor element according to the present invention.

[0046] Figure 1E A cross-sectional schematic diagram (5) illustrating an example of a method for manufacturing a semiconductor element according to the present invention.

[0047] Figure 1F A cross-sectional schematic diagram (6) illustrating an example of a method for manufacturing a semiconductor element according to the present invention.

[0048] Figure 2A This is a cross-sectional schematic diagram (1) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0049] Figure 2B This is a cross-sectional schematic diagram (2) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0050] Figure 2C This is a cross-sectional schematic diagram (3) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0051] Figure 2D This is a cross-sectional schematic diagram (4) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0052] Figure 2E This is a cross-sectional schematic diagram (5) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0053] Figure 2F This is a cross-sectional schematic diagram (6) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0054] Figure 2G This is a cross-sectional schematic diagram (7) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0055] Figure 2H This is a cross-sectional schematic diagram (8) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0056] Figure 3AThis is a cross-sectional schematic diagram (1) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0057] Figure 3B This is a cross-sectional schematic diagram (2) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0058] Figure 3C This is a cross-sectional schematic diagram (3) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0059] Figure 3D This is a cross-sectional schematic diagram (4) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0060] Figure 3E This is a cross-sectional schematic diagram (5) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0061] Figure 3F This is a cross-sectional schematic diagram (6) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0062] Figure 3G This is a cross-sectional schematic diagram (7) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0063] Figure 3H This is a cross-sectional schematic diagram (8) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0064] Figure 3I This is a cross-sectional schematic diagram (9) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0065] Figure 4A This is a cross-sectional schematic diagram (1) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0066] Figure 4B This is a cross-sectional schematic diagram (2) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0067] Figure 4C This is a cross-sectional schematic diagram (3) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0068] Figure 4D This is a cross-sectional schematic diagram (4) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0069] Figure 4E This is a cross-sectional schematic diagram (5) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0070] Figure 4F This is a cross-sectional schematic diagram (6) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0071] Figure 4G This is a cross-sectional schematic diagram (7) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0072] Figure 4H This is a cross-sectional schematic diagram (8) illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0073] Figure 5 Electron microscopy (SEM) images of the microphase separation structure of the self-assembled membrane prepared using self-assembled membrane forming composition 1 in Comparative Example 1.

[0074] Figure 6 SEM images of the microphase separation structure of the self-assembled membranes prepared using self-assembled membrane formation composition 1 in Examples 2-5. Detailed Implementation

[0075] The lower film of the present invention is a fired product of a coated film of a lower film forming composition. Therefore, after describing the lower film forming composition, the lower film of the present invention will be described.

[0076] (Composition for lower layer film formation)

[0077] The composition for forming a lower layer film of the present invention is a composition for forming a lower layer film.

[0078] In photolithography, which uses either a photoresist film or an electron beam resist film and a self-assembled film, the lower layer film is used as a lower layer film for self-assembled films after being used as a resist film.

[0079] The composition for forming the lower layer film of the present invention contains polysiloxane.

[0080] Polysiloxanes are hydrolytic condensates of hydrolyzable silanes.

[0081] Hydrolyzable silanes include compounds represented by formula (1) below, and may include compounds represented by formula (2) below.

[0082] The molar proportion of the compound represented by formula (1) in the hydrolyzable silane is 45 mol% or more.

[0083] The total molar percentage of the compound shown in formula (1) and the compound shown in formula (2) in the hydrolyzable silane is 65 mol% or more (it should be noted that this includes cases where the molar percentage of the compound shown in formula (2) in the hydrolyzable silane is 0 mol%).

[0084]

[0085] In formula (1), Ar represents an aromatic hydrocarbon group that can have substituents. n represents an integer from 1 to 3. When n is 1, R a Indicates a single bond or an alkylene group with 1 to 6 carbon atoms. When n is 2 or 3, R a This represents a saturated hydrocarbon group with a valence of (n+1) carbon atoms (1-6). Each X independently represents a hydrolyzable group. When n is 2 or 3, multiple Ar groups can be the same or different.

[0086] (In equation (2), R) b Represents non-aromatic hydrocarbon groups with 1 to 6 carbon atoms. Each X independently represents a hydrolyzable group.

[0087] Even if the lower layer of the self-assembled film is able to form a vertically aligned layer, the alignment of the self-assembled film may sometimes decrease when the lower layer is exposed to exposure and development.

[0088] The polysiloxane contained in the composition for forming the lower film contains, to a certain extent, the compound shown in formula (1) as a constituent component, thereby enabling the formation of a vertically aligned lower film by self-assembling film even when exposed to exposure and development during the formation of a resist pattern. Furthermore, the polysiloxane may contain, to a certain extent, the compound shown in formula (2) as a constituent component, in combination with the compound shown in formula (1).

[0089] The inventors believe that the ability to obtain a self-assembled film that forms a vertically aligned lower layer even when exposed to exposure and development during the formation of a resist pattern is due to the presence of (Ar) in the compound represented by formula (1). n -R a The base, R in the compound shown in formula (2) b Even when exposed to light and development, the base is not easily denatured.

[0090] <Polysiloxane>

[0091] Polysiloxanes are hydrolytic condensates of hydrolyzable silanes.

[0092] Hydrolyzable silanes include compounds represented by formula (1) below, and may include compounds represented by formula (2) below.

[0093] The molar proportion of the compound represented by formula (1) in the hydrolyzable silane is 45 mol% or more.

[0094] The total molar percentage of the compound shown in formula (1) and the compound shown in formula (2) in the hydrolyzable silane is 65 mol% or more (it should be noted that this includes cases where the molar percentage of the compound shown in formula (2) in the hydrolyzable silane is 0 mol%).

[0095]

[0096] In formula (1), Ar represents an aromatic hydrocarbon group that can have substituents. n represents an integer from 1 to 3. When n is 1, R a Indicates a single bond or an alkylene group with 1 to 6 carbon atoms. When n is 2 or 3, R a This represents a saturated hydrocarbon group with a valence of (n+1) carbon atoms (1-6). Each X independently represents a hydrolyzable group. When n is 2 or 3, multiple Ar groups can be the same or different.

[0097] (In equation (2), R) b Represents non-aromatic hydrocarbon groups with 1 to 6 carbon atoms. Each X independently represents a hydrolyzable group.

[0098] <<Ar in formula (1)>>

[0099] The aromatic hydrocarbon ring in the Ar group of formula (1) can be a monocyclic ring, a fused ring, or a polycyclic ring composed of two or more monocyclic rings bonded together by single bonds. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, biphenyl rings, anthracene rings, and phenanthrene rings.

[0100] As an aromatic hydrocarbon group of Ar in formula (1), examples include a monovalent group obtained by removing a hydrogen atom from any of the benzene ring, naphthalene ring, biphenyl ring, anthracene ring and phenanthrene ring.

[0101] Examples of substituents for Ar in formula (1) include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, and alkoxyalkyl groups with a total carbon number of 2 to 6. Among these, alkyl groups with 1 to 6 carbon atoms and alkenyl groups with 2 to 6 carbon atoms are preferred from the viewpoint of suitably obtaining the effects of the present invention.

[0102] When there are two or more substituents in Ar, the two or more substituents can be the same or different.

[0103] Furthermore, from the viewpoint of suitably obtaining the effects of the present invention, Ar is preferably unsubstituted. That is, Ar preferably represents an aromatic hydrocarbon group.

[0104] <<R in equation (1) a >>

[0105] When n is 1, R in equation (1) a It is a single bond or an alkylene group having 1 to 6 carbon atoms.

[0106] When n is 2 or 3, R in equation (1) a It is a saturated hydrocarbon group with a valence of (n+1) and 1 to 6 carbon atoms.

[0107] Alkylenes having 1 to 6 carbon atoms can be either straight-chain or branched. Alkylenes can have 1 to 4 carbon atoms. Examples of alkylenes having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene.

[0108] Saturated hydrocarbon groups with 1 to 6 carbon atoms and a valence of (n+1) are trivalent when n is 2 and tetravalent when n is 3. The carbon chain constituting the saturated hydrocarbon group can be either straight or branched.

[0109] The preferred value for n is 1.

[0110] As R in equation (1) a From the perspective of excellent arrangement of the self-assembled film even when the lower film is exposed to exposure and development, it is preferably an alkylene group with 1 to 6 carbon atoms, and more preferably an alkylene group with 1 to 4 carbon atoms.

[0111] <<X in equations (1) and (2)>>

[0112] In formulas (1) and (2), X is a hydrolyzable group. Examples of hydrolyzable groups include alkoxy, arylalkoxy, acyloxy, and halogen atoms.

[0113] Examples of alkoxy groups include, for instance, alkoxy groups having at least one alkyl moiety among straight-chain, branched, and cyclic forms having 1 to 20 carbon atoms.

[0114] Examples of linear or branched alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-propoxy Pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc.

[0115] Aranealkyl groups are monovalent groups derived from the hydroxyl groups of aralkyl alcohols by removing a hydrogen atom.

[0116] The number of carbon atoms in the arylalkoxy group is not particularly limited; for example, it can be set to 40 or less, preferably 30 or less, and more preferably 20 or less.

[0117] Acyloxy groups are monovalent groups derived from the carboxyl group (-COOH) of a carboxylic acid compound by removing a hydrogen atom. Examples of alkyl carbonyloxy, aryl carbonyloxy, or aralkyl carbonyloxy derived from the carboxyl group of an alkyl carboxylic acid, aryl carboxylic acid, or aralkyl carboxylic acid are typical, but not limited to, these.

[0118] Specific examples of acyloxy groups include those with 2 to 20 carbon atoms.

[0119] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0120] <<R in equation (2) b >>

[0121] R in equation (2) b It represents a non-aromatic hydrocarbon group with 1 to 6 carbon atoms.

[0122] Examples of non-aromatic hydrocarbon groups include aliphatic saturated hydrocarbon groups and aliphatic unsaturated hydrocarbon groups.

[0123] Aliphatic saturated hydrocarbon groups are alkyl groups with 1 to 6 carbon atoms.

[0124] As an alkyl group having 1 to 6 carbon atoms, it can be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, and 2-methyl-n-pentyl. 3-Methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc.

[0125] Examples of aliphatic unsaturated hydrocarbon groups include alkenyl groups with 2 to 6 carbon atoms and alkynyl groups with 2 to 6 carbon atoms.

[0126] Specific examples of alkenyl groups having 2 to 6 carbon atoms include, for example, vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, etc. Alkenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4- -Pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3-dimethyl- 1-Butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentene The list includes 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, among others.

[0127] Examples of alkynyl groups with 2 to 6 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, and hexynyl.

[0128] Examples of compounds represented by formula (1) include, for instance, compounds represented by formula (1-1) below.

[0129] (In equation (1-1), R) a Indicates a single bond or an alkylene group having 1 to 6 carbon atoms. R c Indicates a substituent. Each X independently represents a hydrolyzable group. n represents an integer from 0 to 5. When n is 2 or more, there are two or more R groups. c They can be the same or different.

[0130] n represents an integer from 0 to 5, preferably 0.

[0131] Examples of compounds that can be cited as compounds represented by formula (1) include the following compounds.

[0132]

[0133] (In the formula, X independently represents each hydrolyzable group.)

[0134] Examples of compounds that can be cited as compounds represented by formula (2) include the following.

[0135]

[0136] (In the formula, X independently represents each hydrolyzable group.)

[0137] The molar percentage of the compound represented by formula (1) in the hydrolyzable silane can be 45 mol% or more, or 65 mol% or more. The molar percentage of the compound represented by formula (1) in the hydrolyzable silane can be 100 mol% or less, or 100 mol%.

[0138] In equation (1) R a When the alkylene group having 1 to 6 carbon atoms is represented, from the viewpoint of more effectively obtaining the effects of the present invention, the molar percentage of the compound represented by formula (1) in the hydrolyzable silane is preferably 65 mol% or more.

[0139] The total molar percentage of the compound represented by formula (1) and the compound represented by formula (2) in the hydrolyzable silane is 65 mol% or more, and preferably 80 mol% or more, more preferably 90 mol% or more, from the viewpoint of more effectively obtaining the effects of the present invention (Note that this includes the case where the molar percentage of the compound represented by formula (2) in the hydrolyzable silane is 0 mol%).

[0140] The total molar ratio of the compound shown in formula (1) and the compound shown in formula (2) in the hydrolyzable silane can be less than 100 mol% or 100 mol%.

[0141] It should be noted that the molar proportion of the compound represented by formula (1) in the hydrolyzable silane can be 100 mol%. The molar proportion of the compound represented by formula (2) in the hydrolyzable silane can be 0 mol.

[0142] When a hydrolyzable silane contains a compound of formula (2), the molar proportion of the compound of formula (1) in the hydrolyzable silane is less than 100 moles.

[0143] When the hydrolyzable silane does not contain the compound shown in formula (2), the molar proportion of the compound shown in formula (1) in the hydrolyzable silane may be less than 100 mol%.

[0144] Polysiloxanes may include modified polysiloxanes in which a portion of the silanol group has been modified, such as polysiloxanes modified by alcohol modification or protected by acetal.

[0145] Additionally, as an example, polysiloxanes may also comprise hydrolyzed condensates of hydrolyzable silanes, or modified polysiloxanes obtained by modifying at least a portion of the silanol groups present in the hydrolyzed condensate with alcohol or protecting them with acetal. The hydrolyzed silanes involved in the hydrolyzed condensate may comprise one or more hydrolyzable silanes.

[0146] Furthermore, the polysiloxane can have a main chain structure of any of the following: cage-like, ladder-like, linear, and branched. Commercially available polysiloxanes can also be used as polysiloxanes.

[0147] It should be noted that in this invention, the "hydrolysis condensate" of the hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only the polyorganosiloxane polymer as a condensate with complete condensation, but also the polyorganosiloxane polymer as a partially hydrolyzed condensate with incomplete condensation. Such partially hydrolyzed condensates, like the fully condensed condensates, are polymers obtained through the hydrolysis and condensation of the hydrolyzable silane, but the hydrolysis is partially stopped, and no condensation occurs; therefore, Si-OH groups remain. Furthermore, in the composition for forming the lower film, in addition to the hydrolyzed condensate, uncondensed hydrolysates (completely hydrolyzed products, partially hydrolyzed products) and monomers (hydrolyzable silanes) may also remain.

[0148] It should be noted that in this specification, "hydrolyzable silane" is sometimes simply referred to as "silane compound".

[0149] Additionally, in this specification, "polysiloxane" is sometimes referred to as "hydrolysis condensate".

[0150] The polysiloxane may be a hydrolytic condensate of a hydrolytic silane containing other silane compounds besides those exemplified above, without impairing the effects of the present invention.

[0151] As described above, as a polysiloxane, a modified polysiloxane in which at least a portion of the silanol group has been modified can be used. For example, a polysiloxane modified by modifying a portion of the silanol group with an alcohol or a polysiloxane modified by protecting with an acetal can be used.

[0152] Examples of such modified polysiloxanes include reaction products obtained by reacting at least a portion of the silanol groups in the hydrolytic condensate of the aforementioned hydrolytic silane with the hydroxyl groups of an alcohol, dehydration products of the condensate and an alcohol, and modified products obtained by protecting at least a portion of the silanol groups in the condensate with acetal groups.

[0153] As an alcohol, monohydric alcohols can be used, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-pentanol, neopentanol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-prop ... -Dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol and cyclohexanol.

[0154] Alternatively, alcohols containing alkoxy groups, such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol), can be used.

[0155] The reaction of the silanol groups in the condensate with the hydroxyl groups of the alcohol is achieved by contacting the polysiloxane with the alcohol at a temperature of 40–160°C, for example 60°C, for 0.1–48 hours, for example 24 hours, to obtain a modified polysiloxane with blocked silanol groups. In this case, the alcohol, acting as a blocking agent, can be used as a solvent in the composition containing the polysiloxane.

[0156] In addition, the dehydration reaction product of polysiloxane composed of hydrolytic condensate of hydrolyzable silane and alcohol can be produced by reacting polysiloxane with alcohol in the presence of acid as a catalyst, blocking silanol groups with alcohol, and removing the generated water produced by dehydration from the reaction system.

[0157] The acid can be an organic acid with an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5. Examples of acids include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, etc., especially benzoic acid, isobutyric acid, acetic acid, etc.

[0158] In addition, acids with boiling points of 70 to 160°C can be used, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid.

[0159] Therefore, the preferred acid is one with a dissociation constant (pKa) of 4 to 5 or a boiling point of 70 to 160°C. That is, a weak acid or an acid with a strong acidity but a low boiling point can be used.

[0160] Furthermore, as an acid, it can also utilize any property based on the acid dissociation constant and boiling point.

[0161] The acetal protection of the silanol group of the condensate can be achieved by using vinyl ethers, such as the vinyl ether shown in formula (5) below, through which a partial structure shown in formula (6) below can be introduced into the polysiloxane by their reaction.

[0162]

[0163] In equation (5), R 1a R 2a and R 3a R represents either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 4a R represents an alkyl group having 1 to 10 carbon atoms. 2a With R 4a They can combine with each other to form rings. Alkyl groups can be exemplified by the above examples.

[0164]

[0165] In equation (6), R 1’ R 2’ and R 3’ R represents either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 4’ R represents an alkyl group with 1 to 10 carbon atoms. 2’ With R 4’ They can combine to form a ring. In equation (6) This indicates a bond with an adjacent atom. Examples of adjacent atoms include, for example, the oxygen atom in a siloxane bond, the oxygen atom in a silanol group, and R derived from formula (1). 1 The carbon atom. Alkyl groups can be exemplified by the above examples.

[0166] As the vinyl ether represented by formula (5), aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, as well as cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran can be used. Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran are particularly preferred.

[0167] Silanol acetal protection can be achieved using polysiloxanes, vinyl ethers, and solvents such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, and 1,4-dimethylformamide. Aprotic solvents such as alkanes are used with pyridine. It is carried out using catalysts such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, and sulfuric acid.

[0168] It should be noted that the alcohol blocking and acetal protection of these silanol groups can be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silanes described later.

[0169] In a preferred embodiment of the present invention, the polysiloxane comprises at least one of a hydrolytic silane containing a hydrolytic silane of formula (1), a hydrolytic condensate of a hydrolytic silane according to a desired formula (2), and other hydrolytic silanes, and a modified thereof.

[0170] In a preferred embodiment, the polysiloxane comprises a dehydration reaction product of a hydrolysis condensate and an alcohol.

[0171] The weight-average molecular weight of the polysiloxane, which is a hydrolysis condensate (which may also include a modifier) ​​of a hydrolyzable silane, can be set to, for example, 500 to 1,000,000. From the viewpoint of suppressing the precipitation of hydrolysis condensates in the composition, it is preferable to have a weight-average molecular weight of 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of combining storage stability and coatability, it is preferable to have a weight-average molecular weight of 500 or more, and more preferably 600 or more.

[0172] It should be noted that the weight-average molecular weight is the molecular weight obtained from polystyrene analysis using GPC. GPC analysis can be performed using, for example, a GPC apparatus (trade name HLC-8220GPC). The column was made of GPC (trade name Shodex KF803L, KF802, KF801, manufactured by Showa Denko Corporation), the column temperature was set to 40°C, tetrahydrofuran was used as the eluent, the flow rate was set to 1.0 mL / min, and polystyrene (Shodex manufactured by Showa Denko Corporation, registered trademark) was used as the standard sample.

[0173] Hydrolysis condensates of hydrolyzable silanes can be obtained by hydrolyzing and condensing the above-mentioned silane compounds (hydrolyzable silanes).

[0174] The aforementioned silane compounds (hydrolyzable silanes) contain alkoxy, arylalkoxy, acyloxy, or halogen atoms that are directly bonded to silicon atoms, namely alkoxysilyl, arylalkoxysilyl, acyloxysilyl, or halosilyl (hereinafter referred to as hydrolyzable groups).

[0175] In the hydrolysis of these hydrolyzable groups, 0.1 to 100 moles, for example 0.5 to 100 moles, preferably 1 to 10 moles of water are typically used relative to 1 mole of the hydrolyzable group.

[0176] During hydrolysis and condensation, a hydrolysis catalyst may be used for purposes such as promoting the reaction, or hydrolysis and condensation may be carried out without using a hydrolysis catalyst. When using a hydrolysis catalyst, 0.0001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolytic group can be used per mole.

[0177] The reaction temperature for hydrolysis and condensation is typically above room temperature and below the reflux temperature of the organic solvent that can be used for hydrolysis at atmospheric pressure, for example, 20 to 110°C, or 20 to 80°C.

[0178] Hydrolysis can be complete, meaning all hydrolyzable groups are converted into silanol groups, or it can be partial, meaning that unreacted hydrolyzable groups remain.

[0179] Examples of hydrolysis catalysts that can be used to hydrolyze and condense these substances include metal chelates, organic acids, inorganic acids, organic bases, and inorganic bases.

[0180] Metal chelates that can serve as hydrolysis catalysts include, for example, triethoxy-mono(acetylacetone)titanium, tri-n-propoxy-mono(acetylacetone)titanium, triisopropoxy-mono(acetylacetone)titanium, tri-n-butoxy-mono(acetylacetone)titanium, tri-sec-butoxy-mono(acetylacetone)titanium, tri-tert-butoxy-mono(acetylacetone)titanium, diethoxy-bis(acetylacetone)titanium, di-n-propoxy-bis(acetylacetone)titanium, diisopropoxy-bis(acetylacetone)titanium, and di-n-butoxy-bis(acetylacetone)titanium. Di-sec-butoxy-bis(acetylacetone)titanium, di-tert-butoxy-bis(acetylacetone)titanium, monoethoxy-tri(acetylacetone)titanium, mono-n-propoxy-tri(acetylacetone)titanium, monoisopropoxy-tri(acetylacetone)titanium, mono-n-butoxy-tri(acetylacetone)titanium, mono-sec-butoxy-tri(acetylacetone)titanium, mono-tert-butoxy-tri(acetylacetone)titanium, tetra(acetylacetone)titanium, triethoxy-mono(ethyl acetoacetate)titanium, tri-n-propoxy-mono(ethyl acetoacetate)titanium, triisopropoxy- Titanium chelates including mono(ethyl acetoacetate) titanium, tri-n-butoxy-mono(ethyl acetoacetate) titanium, tri-sec-butoxy-mono(ethyl acetoacetate) titanium, tri-tert-butoxy-mono(ethyl acetoacetate) titanium, diethoxy-bis(ethyl acetoacetate) titanium, di-n-propoxy-bis(ethyl acetoacetate) titanium, diisopropoxy-bis(ethyl acetoacetate) titanium, di-n-butoxy-bis(ethyl acetoacetate) titanium, di-sec-butoxy-bis(ethyl acetoacetate) titanium, di-tert-butoxy-bis(ethyl acetoacetate) titanium, monoethoxy-tri(ethyl acetoacetate) titanium, mono-n-propoxy-tri(ethyl acetoacetate) titanium, monoisopropoxy-tri(ethyl acetoacetate) titanium, mono-n-butoxy-tri(ethyl acetoacetate) titanium, mono-sec-butoxy-tri(ethyl acetoacetate) titanium, mono-tert-butoxy-tri(ethyl acetoacetate) titanium, tetra(ethyl acetoacetate) titanium, mono(acetylacetone)tri(ethyl acetoacetate) titanium, bis(acetylacetone)bis(ethyl acetoacetate) titanium, and tri(acetylacetone)mono(ethyl acetoacetate) titanium;Triethoxy-mono(acetylacetone)zirconium, tri-n-propoxy-mono(acetylacetone)zirconium, triisopropoxy-mono(acetylacetone)zirconium, tri-n-butoxy-mono(acetylacetone)zirconium, tri-sec-butoxy-mono(acetylacetone)zirconium, tri-tert-butoxy-mono(acetylacetone)zirconium, diethoxy-bis(acetylacetone)zirconium, di-n-propoxy-bis(acetylacetone)zirconium, diisopropoxy-bis(acetylacetone)zirconium, di-n-butoxy-bis(acetylacetone)zirconium, di-sec-butoxy-bis(acetylacetone)zirconium, di-tert-butoxy-bis(acetylacetone)zirconium Zirconium acetylacetone, zirconium monoethoxytris(acetylacetone), zirconium mono-n-propoxytris(acetylacetone), zirconium monoisopropoxytris(acetylacetone), zirconium mono-n-butoxytris(acetylacetone), zirconium mono-sec-butoxytris(acetylacetone), zirconium mono-tert-butoxytris(acetylacetone), zirconium tetra(acetylacetone), zirconium triethoxymono(ethyl acetoacetate), zirconium tri-n-propoxymono(ethyl acetoacetate), zirconium triisopropoxymono(ethyl acetoacetate), zirconium tri-n-butoxymono(ethyl acetoacetate) Zirconium chelates including tri-sec-butoxy-mono(ethyl acetoacetate)zirconium, tri-tert-butoxy-mono(ethyl acetoacetate)zirconium, diethoxy-bis(ethyl acetoacetate)zirconium, di-n-propoxy-bis(ethyl acetoacetate)zirconium, diisopropoxy-bis(ethyl acetoacetate)zirconium, di-n-butoxy-bis(ethyl acetoacetate)zirconium, di-sec-butoxy-bis(ethyl acetoacetate)zirconium, di-tert-butoxy-bis(ethyl acetoacetate)zirconium, monoethoxy-tri(ethyl acetoacetate)zirconium, mono-n-propoxy-tri(ethyl acetoacetate)zirconium, monoisopropoxy-tri(ethyl acetoacetate)zirconium, mono-n-butoxy-tri(ethyl acetoacetate)zirconium, mono-sec-butoxy-tri(ethyl acetoacetate)zirconium, mono-tert-butoxy-tri(ethyl acetoacetate)zirconium, tetra(ethyl acetoacetate)zirconium, mono(acetylacetone)tri(ethyl acetoacetate)zirconium, bis(acetylacetone)bis(ethyl acetoacetate)zirconium, tri(acetylacetone)mono(ethyl acetoacetate)zirconium, etc.; aluminum chelates including tri(acetylacetone)aluminum, tri(ethyl acetoacetate)aluminum, etc.; etc., but not limited to these. ;

[0181] Organic acids that can serve as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0182] Inorganic acids that can act as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0183] Examples of organic bases that can serve as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, methylpyridine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0184] Inorganic bases that can act as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0185] The preferred catalysts are metal chelates, organic acids, and inorganic acids. One of these catalysts can be used alone, or two or more can be used in combination.

[0186] In this invention, nitric acid can be suitable as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, the molecular weight change of the hydrolysis condensate can be suppressed. It is known that the stability of hydrolysis condensates in liquids depends on the pH of the solution. In-depth research has shown that by using an appropriate amount of nitric acid, the pH of the solution becomes within a stable range.

[0187] In addition, as mentioned above, nitric acid can also be used when obtaining modified hydrolysis condensates, for example, when blocking silanol groups with alcohols. Therefore, it is preferred from the viewpoint that it can be a substance that can help both the hydrolysis and condensation of hydrolyzable silanes and the alcohol blocking of hydrolysis condensates.

[0188] During hydrolysis and condensation, organic solvents can be used as solvents. Specific examples include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; and aromatic solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-pentylnaphthalene. Hydrocarbon solvents: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecyl alcohol, sec-heptadecane Monohydric alcohol solvents such as phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol; acetone, methyl ethyl ketone, methyl- Ketone solvents including n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone-acetone, diacetone alcohol, acetophenone, fentanyl ketone, etc.; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, dioxolane, 4-methyldioxolane, etc. Alkane, dimethyl di Alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl Ether solvents such as propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, etc. Benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetyl glycol diethyl ether, diacetyl glycol diethyl ether, methoxytriethylene glycol acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, etc. Ester solvents such as isoamyl ester, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesulfonyl lactone, etc., but not limited to these. One or more of these solvents may be used.

[0189] After the hydrolysis and condensation reactions are completed, the reaction solution is either directly diluted or concentrated and then neutralized. It is then treated with an ion exchange resin to remove hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation processes. Additionally, before or after this treatment, byproducts such as alcohols, water, and the hydrolysis catalysts used can be removed from the reaction solution by means of vacuum distillation.

[0190] The resulting hydrolysis condensate is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, which can be directly used in the preparation of the composition for the lower layer film formation. That is, the reaction solution can be used directly (or diluted) in the preparation of the composition for the lower layer film formation. In this case, the hydrolysis catalyst, byproducts, etc., used in the hydrolysis and condensation can remain in the reaction solution as long as they do not impair the effects of the present invention. For example, the hydrolysis catalyst and the nitric acid used in the silanol group blocking can remain in the polymer varnish solution at a concentration of approximately 100 ppm to 5,000 ppm.

[0191] The resulting polysiloxane varnish can be solvent-displaced and, in addition, diluted with a suitable solvent. It should be noted that if the resulting polysiloxane varnish has good storage stability, the organic solvent can also be removed by distillation to achieve a film-forming component concentration of 100%. It should be noted that the film-forming component refers to the component remaining after removing the solvent from all components of the composition.

[0192] The organic solvents used for solvent displacement and dilution of polysiloxane varnishes can be the same as or different from those used for the hydrolysis and condensation reactions of hydrolyzable silanes. There are no particular limitations on the dilution solvent; one or more solvents can be used, and any selection is acceptable.

[0193] <<Solvent>>

[0194] The solvent contained in the composition for forming the lower layer film can be used without particular restriction, as long as it is a solvent capable of dissolving / mixing the polysiloxane and other components contained in the composition for forming the lower layer film as needed.

[0195] Examples of solvents include organic solvents and water.

[0196] Examples of organic solvents include alcohols, carboxylic acids having hydroxyl groups, straight-chain or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic esters (monocarboxylic esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic esters of alkylene glycol monoalkyl ethers).

[0197] Examples of alcohols include monohydric alcohol solvents and polyhydric alcohol solvents.

[0198] Examples of monohydric alcohol solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecyl alcohol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, cresol, etc.

[0199] Examples of polyol solvents include ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol.

[0200] Examples of carboxylic acids having a hydroxyl group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, etc.

[0201] Examples of linear or cyclic alkyl ketones include, for example, methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0202] Examples of cyclic lactones include, for instance, γ-butyrolactone.

[0203] Examples of alkylene glycol alkyl ethers include, for example, alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0204] Examples of monoalkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl methanol, and propylene glycol monobutyl ether.

[0205] Examples of alkylene glycol dialkyl ethers include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc.

[0206] Examples of monoalkylene glycol monoalkyl ether carboxylic esters include, for example, monocarboxylic esters of monoalkylene glycol monoalkyl ethers and alkoxycarboxylic esters of monoalkylene glycol monoalkyl ethers.

[0207] Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include, for instance, alkylene glycol monoalkyl ether acetates.

[0208] Examples of alkylene glycol monoalkyl ether acetates include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0209] Examples of alkoxycarboxylic acid esters that are monoalkylene glycol ethers include, for example, 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0210] Specific examples of other solvents include toluene, xylene, ethyl ethoxylate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, isopropyl butyrate, butyl glycolate, isobutyl butyrate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, isopropyl butyrate, ethyl glycolate, ethyl glycolate, ethyl glycolate, isobutyl glycolate ... ethyl glycolate, isobutyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl glycolate, ethyl Esters, methyl 3-methoxy-2-methylpropionate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, etc.

[0211] These solvents can be used alone or in combination of two or more.

[0212] Furthermore, the composition for forming the lower film may contain water as a solvent. When water is contained as a solvent, its content relative to the total mass of the solvent contained in the composition for forming the lower film may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0213] <<Civilized Catalyst>>

[0214] The composition for forming the lower film can be prepared without a curing catalyst, but preferably contains a curing catalyst.

[0215] As a curing catalyst, ammonium salts, phosphine compounds, etc. can be used. Salt, matte salt, iodine Salt, oxygen Salts, etc. It should be noted that the following salts, described as an example of a curing catalyst, may be added in the form of salts, or may be any of the substances that form salts in the composition (substances added as other compounds at the time of addition that form salts in the system).

[0216] Examples of ammonium salts include quaternary ammonium salts having the structure shown in formula (D-1), quaternary ammonium salts having the structure shown in formula (D-2), quaternary ammonium salts having the structure shown in formula (D-3), quaternary ammonium salts having the structure shown in formula (D-4), quaternary ammonium salts having the structure shown in formula (D-5), and tertiary ammonium salts having the structure shown in formula (D-6).

[0217]

[0218] (where m) a n represents an integer from 2 to 11. a R represents integers from 2 to 3. 21 Y represents alkyl, aryl, or aralkyl. - (This indicates anion.)

[0219] (where R is in the formula) 22 R 23 R 24 and R 25 Each can be independently represented as alkyl, aryl, or aralkyl, Y - Represents anion, and R 22 R 23 R 24 and R 25 They each combine with a nitrogen atom.

[0220] (where R is in the formula) 26 and R 27 Each can be independently represented as alkyl, aryl, or aralkyl, Y - (This indicates anion.)

[0221] (where R is in the formula) 28 Y represents alkyl, aryl, or aralkyl. - (This indicates anion.)

[0222] (where R is in the formula) 29 and R 30 Each can be independently represented as alkyl, aryl, or aralkyl, Y - (This indicates anion.)

[0223] (where m) a n represents an integer from 2 to 11. a Y represents an integer from 2 to 3. - (This indicates anion.)

[0224] In addition, as mentioned above Salt, as exemplified by the quaternary salts shown in equation (D-7), can be used as a reference. Salt.

[0225]

[0226] (where R is in the formula) 31 R 32 R 33 and R 34 Each can be independently represented as alkyl, aryl, or aralkyl, Y - Represents anion, and R 31 R 32 R 33 and R 34 They bond with phosphorus atoms respectively.

[0227] In addition, as a matte salt, the tertiary matte salt shown in formula (D-8) can be cited as an example.

[0228]

[0229] (where R is in the formula) 35 R 36 and R 37 Each can be independently represented as alkyl, aryl, or aralkyl, Y - Represents anion, and R 35 R 36 and R 37 They bond with sulfur atoms respectively.

[0230] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m a n represents an integer from 2 to 11. a Represents an integer from 2 to 3. The R of this quaternary ammonium salt... 21This refers to, for example, alkyl groups with 1 to 18 carbon atoms, preferably 2 to 10, aryl groups with 6 to 18 carbon atoms, or aralkyl groups with 7 to 18 carbon atoms. Examples include linear alkyl groups such as ethyl, propyl, and butyl, benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. Additionally, anionic (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - (e.g., acid radicals).

[0231] The compound of formula (D-2) is R. 22 R 23 R 24 R 25 N + Y - The quaternary ammonium salt shown. The R of this quaternary ammonium salt... 22 R 23 R 24 and R 25 Examples include alkyl groups with 1-18 carbon atoms such as ethyl, propyl, butyl, cyclohexyl, and cyclohexylmethyl; aryl groups with 6-18 carbon atoms such as phenyl; and aralkyl groups with 7-18 carbon atoms such as benzyl. Anion (Y - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - (e.g., tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, etc.)

[0232] The compound of formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 The number of carbon atoms is, for example, 1 to 18, preferably R. 26 and R 27 The total number of carbon atoms is 7 or more. For example, R 26 Examples of possible compounds include alkyl groups such as methyl, ethyl, and propyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. 27 Examples include aryl groups such as benzyl, octyl, and octadecyl. Anion (Y) - Examples include chloride ions (Cl).- ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - The compound can be obtained commercially, but it can also be produced by reacting imidazole compounds such as 1-methylimidazole and 1-benzylimidazole with aralkyl halides, alkyl halides, and aryl halides such as benzyl bromide, bromomethane, and bromobenzene.

[0233] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, R 28 For example, it can be an alkyl group with 1 to 18 carbon atoms, preferably an aryl group with 4 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms, such as butyl, octyl, benzyl, lauryl. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - This compound is available as a commercially available product, but it can also be prepared, for example, by reacting pyridine with alkyl halides or aryl halides such as lauryl chloride, benzyl chloride, benzyl bromide, bromomethane, and bromooctane. Examples of this compound include N-laurylpyridine chloride. N-Benzylpyridine bromide wait.

[0234] The compound of formula (D-5) is a quaternary ammonium salt derived from substituted pyridines, such as methylpyridine, R 29 For example, it can be an alkyl group with 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms, such as methyl, octyl, lauryl, benzyl, etc. 30 For example, it can be an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. For example, in the case where the compound shown in formula (D-5) is a quaternary ammonium salt derived from methylpyridine, R 30 It is a methyl group. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3)- ), alcohol radical (-O) - This compound can be obtained as a commercially available product, but it can also be produced, for example, by reacting substituted pyridines such as methylpyridine with alkyl halides or aryl halides such as bromomethane, bromooctane, lauryl chloride, benzyl chloride, and benzyl bromide. Examples of this compound include N-benzylmethylpyridine. Chloride, N-benzylmethylpyridine bromide, N-laurylmethylpyridine Chlorides, etc.

[0235] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m a n represents an integer from 2 to 11. a It indicates 2 or 3. Additionally, the anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - This compound can be produced by reacting amines with weak acids such as carboxylic acids and phenols. Examples of carboxylic acids include formic acid and acetic acid. When formic acid is used, the anion (Y)... - ) is (HCOO) - In the case of using acetic acid, the anion (Y) - (CH3COO) - Additionally, when phenol is used, the anion (Y) - (C6H5O) - ).

[0236] The compound of formula (D-7) is a compound with R 31 R 32 R 33 R 34 P + Y - The structure of the season Salt. R 31 R 32 R 33 and R 34 Examples include alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, and cyclohexylmethyl; aryl groups with 6 to 18 carbon atoms such as phenyl; or aralkyl groups with 7 to 18 carbon atoms such as benzyl, preferably R. 31 ~R 34Of the four substituents, three are unsubstituted phenyl groups or substituted phenyl groups, such as phenyl or tolyl. The remaining substituent is an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Additionally, the anion (Y...) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - Anions such as ) and ) are present. These compounds are available commercially, for example, tetra-n-butyl halide. Tetrapropylhalogenated isohalogenated tetraalkyl , triethylbenzyl halide isohalogenated trialkylbenzyl , triphenylmethyl halogenated Triphenyl ethyl halide Isohalogenated triphenylmonyl , triphenylbenzyl halide Tetraphenylhalide Halogenated trimethylyl monoaryl or halogenated trimethylyl monoalkyl (The halogen atom is either a chlorine atom or a bromine atom). A particularly preferred option is triphenylmethyl halide. Triphenyl ethyl halide Isohalogenated triphenylmonyl , triphenylbenzyl halide isohalogenated triphenyl monoaryl , Trimethylyl monophenyl halogenated Isohyetalized trimethylolyl monoaryl , Trimethylhalogenated Isohyetalized trimethylyl monoalkyl (The halogen atom is either a chlorine atom or a bromine atom).

[0237] In addition, examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0238] The compound of formula (D-8) is one with R 35 R 36 R 37 S + Y - Tertiary sulfonium salts with a structure of R.35 R 36 and R 37 Examples include alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, and cyclohexylmethyl; aryl groups with 6 to 18 carbon atoms such as phenyl; or aralkyl groups with 7 to 18 carbon atoms such as benzyl, preferably R. 35 ~R 37 Two of the three substituents are unsubstituted phenyl groups or substituted phenyl groups, such as phenyl or tolyl. The remaining substituent is an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Additionally, the anion (Y...) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - The compound contains anions such as maleic acid anions and nitrate anions. Examples of commercially available compounds include tri-n-butylsulfonium halide, tri-n-propylsulfonium halide, dialkylbenzylsulfonium halide, diphenylmethylsulfonium halide, diphenylethylsulfonium halide, triphenylmonoalkylsulfonium halide (where the halogen atom is a chlorine or bromine atom), tri-n-butylsulfonium carboxylates, trialkylsulfonium carboxylates, dialkylbenzylsulfonium carboxylates, diphenylmethylsulfonium carboxylates, diphenylethylsulfonium carboxylates, and triphenylmonoalkylsulfonium carboxylates. Triphenylsulfonium halide and triphenylsulfonium carboxylates are preferred.

[0239] In addition, nitrogen-containing silane compounds can be added as curing catalysts. Examples of nitrogen-containing silane compounds include silane compounds containing an imidazole ring, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0240] The content of the curing catalyst in the composition for forming the lower film is preferably 0.01 to 30 parts by weight relative to 100 parts by weight of polysiloxane, more preferably 0.01 to 25 parts by weight, and even more preferably 0.01 to 20 parts by weight.

[0241] <<Acid>>

[0242] The composition for forming the lower film preferably contains an acid.

[0243] Acids can be added when preparing the composition for forming the lower layer film. However, if the composition for forming the lower layer film contains polysiloxanes, substances that are used as hydrolysis catalysts in the manufacture of the polysiloxanes or as alcohols with silanol groups and that remain in the polysiloxane varnish can also be treated as acids.

[0244] Examples of acids include organic acids and inorganic acids.

[0245] Examples of organic acids include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, etc.

[0246] Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0247] The amount of acid mixed (residual acid) is based on the total mass of the composition for forming the lower film, and can be set to, for example, 0.0001% to 1% by mass, or 0.001% to 0.1% by mass, or 0.005% to 0.05% by mass.

[0248] <<Amines and Hydroxides>>

[0249] The composition for forming the lower film may contain at least one selected from amines and hydroxides.

[0250] Examples of amines include ammonia; primary amines such as monomethanolamine, monoethanolamine, monopropanolamine, methylamine, ethylamine, propylamine, and butylamine; secondary amines such as dimethylamine, ethylmethylamine, and diethylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine, dimethylethylamine, methyldiisopropylamine, diisopropylethylamine, diethylethanolamine, and triethanolamine; amines such as ethylenediamine and tetramethylethylenediamine; and cyclic amines such as pyridine and morpholine.

[0251] Examples of hydroxides include inorganic base hydroxides and organic base hydroxides.

[0252] Examples of inorganic base hydroxides include sodium hydroxide and potassium hydroxide.

[0253] Examples of organic base hydroxides include, for example, tetraalkylammonium hydroxide, triarylsulfonium hydroxide, and diaryliodophosphate. Hydroxides, etc. Examples of tetraalkylammonium hydroxides include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Examples of triarylsulfonium hydroxides include, for example, triphenylsulfonium hydroxide and tris(tert-butylphenyl)sulfonium hydroxide. Diaryliodocyanine hydroxides... Hydroxides, such as diphenyl iodide, can be cited as an example. Hydroxide, bis(tert-butylphenyl)iodine Hydroxides, etc.

[0254] The content of amines and hydroxides in the composition for forming the lower film is not particularly limited, but it can be preferably set to 0.05 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight relative to 100 parts by weight of polysiloxane.

[0255] <<Other Additives>>

[0256] In the composition for forming the lower layer film, various additives may be mixed in depending on the intended use of the composition.

[0257] Examples of additives include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid-generating agents, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology modifiers, adhesive aids, etc., and known additives that are blended into materials (compositions) of various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, antireflective films, and pattern reversal films.

[0258] It should be noted that the following examples illustrate various additives, but are not limited to them.

[0259] -Stabilizer-

[0260] When the composition for forming the lower film contains polysiloxane, a stabilizer can be added for purposes such as stabilizing the hydrolytic condensate of the hydrolytic silane mixture. As a specific example, an organic acid, water, alcohol, or a combination thereof can be added.

[0261] Examples of organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Oxalic acid and maleic acid are preferred. When an organic acid is added, its amount is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the hydrolyzable silane mixture. These organic acids can also function as pH adjusters.

[0262] As water, pure water, ultrapure water, ion-exchanged water, etc. can be used. When used, the amount added can be set to 0.1 to 20 parts by mass relative to 100 parts by mass of the composition for forming the lower membrane.

[0263] The preferred alcohol is one that is easily dispersed by heating after coating, such as methanol, ethanol, propanol, isopropanol, butanol, etc. When an alcohol is added, the amount added can be set to 0.1 to 20 parts by weight relative to 100 parts by weight of the composition for forming the underlying film.

[0264] -Organic polymers-

[0265] When the composition for forming the lower layer film contains polysiloxane, by adding an organic polymer to the composition, the dry etching rate (the amount of reduction in film thickness per unit time), as well as the attenuation coefficient, refractive index, etc., of the lower layer film formed by the composition can be adjusted. There are no particular limitations on the organic polymer; it can be appropriately selected from various organic polymers (condensation polymers and addition polymers) depending on its purpose of addition.

[0266] Specific examples include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyvinyl ether, phenolic varnish, naphthol varnish, polyether, polyamide, and polycarbonate.

[0267] In this invention, organic polymers containing aromatic or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be used when such functionality is required. Specific examples of such organic polymers include addition polymers containing addition monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as their structural units, as well as condensation polymers such as phenolic varnishes and naphtholic varnishes, but are not limited to these.

[0268] When using an addition polymer as an organic polymer, the polymer can be either a homopolymer or a copolymer.

[0269] When manufacturing addition polymers, addition polymerizable monomers are used. Specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, etc.

[0270] Specific examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0271] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0272] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0273] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthraylmethacrylamide.

[0274] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc.

[0275] Specific examples of styrene compounds include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetystyrene, etc., but are not limited to these.

[0276] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but are not limited to these.

[0277] When using condensation polymers as the polymer, examples of such polymers include condensation polymers of diol compounds and dicarboxylic acid compounds. Examples of diol compounds include diethylene glycol, 1,6-hexanediol, and butanediol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Additionally, examples of polyesters, polyamides, and polyimides include, but are not limited to, polypyroxene tetramethylimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate.

[0278] When an organic polymer contains hydroxyl groups, these hydroxyl groups can undergo cross-linking reactions with hydrolytic condensates, etc.

[0279] The weight-average molecular weight of organic polymers can typically be set to 1,000 to 1,000,000. When organic polymers are blended, from the viewpoint of fully obtaining the function of the polymer while suppressing precipitation in the composition, their weight-average molecular weight can be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000.

[0280] Such organic polymers can be used alone or in combination of two or more.

[0281] When the composition for forming the lower film contains an organic polymer and is used in conjunction with a polysiloxane, its content is appropriately determined considering the function of the organic polymer, etc., and therefore cannot be specified in general terms. However, it can generally be set to a range of 1 to 200% by mass relative to the mass of the polysiloxane. From the viewpoint of suppressing precipitation in the composition, it can be set to, for example, 100% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less. From the viewpoint of fully obtaining its effect, it can be set to, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more.

[0282] -Acid-producing agents-

[0283] Examples of acid-producing agents include thermal acid-producing agents and photo-producing acid-producing agents, with photo-producing acid-producing agents being preferred.

[0284] Examples of photoacid-producing agents include sulfonium salts, Salts, ammonium salts, iodine Salt, oxygen Salt, etc. Salt compounds, sulfonylimide compounds, disulfonyldiazomethane compounds, etc., but not limited to these. It should be noted that photoacid-generating agents, such as those described later... Salt compounds such as nitrates, maleates, and other carboxylates, as well as hydrochlorides, can also act as curing catalysts, depending on their type.

[0285] In addition, examples of heat-generating acid agents include tetramethylammonium nitrate, but it is not limited to these.

[0286] As A specific example of a salt compound is diphenyliodide. Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate, bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Sulfonate compounds, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro n-butane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium trifluoromethane sulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, triphenylsulfonium chloride, and other sulfonate compounds, but not limited to these.

[0287] Specific examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide, but are not limited to these.

[0288] Specific examples of disulfonyl diazonium methane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyl diazonium methane, etc., but are not limited to these.

[0289] When the composition for forming the lower film contains an acid-generating agent, its content is appropriately determined considering the type of acid-generating agent, etc., and therefore cannot be specified in general. However, generally, it is in the range of 0.01 to 5% by mass relative to the mass of polysiloxane. From the viewpoint of suppressing the precipitation of the acid-generating agent in the composition, it is preferably 3% by mass or less, more preferably 1% by mass or less. From the viewpoint of fully obtaining its effect, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

[0290] It should be noted that one type of acid-producing agent can be used alone or in combination with two or more types. In addition, photo-acid-producing agents and thermal acid-producing agents can be used together.

[0291] -surfactant-

[0292] When coating a composition for forming a lower film onto a substrate, surfactants are effective in suppressing the formation of pinholes, streaks, etc. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, and UV-curable surfactants. More specifically, examples include, for instance, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, and sorbitol monostearate. Oleate, sorbitol trioleate, sorbitol tristearate, and other sorbitol fatty acid esters; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate, and other polyoxyethylene sorbitol fatty acid esters, etc., nonionic surfactants, trade names (Registered Trademarks) EF301, EF303, EF352 (strain) (old (strain)) (Manufactured) (Product Name) (Registered Trademarks) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation) FC430, FC431 (Company) Manufacturer, Product Name (Registered Trademark) AG710 (manufactured by AGC Corporation), (Registered Trademarks) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC) Fluorinated surfactants such as those manufactured by Shin-Etsu Chemical Co., Ltd., and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), but not limited to these.

[0293] Surfactants can be used alone or in combination of two or more.

[0294] When the composition for forming the lower film contains a surfactant, its content relative to the mass of the polysiloxane is typically set to 0.0001 to 5% by mass, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass.

[0295] -Rheology modifier-

[0296] Rheology modifiers are primarily added to improve the flowability of the composition used for forming the lower film, especially during the baking process, to enhance the uniformity of the film thickness and improve the filling ability of the composition into pores. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, di-isobutyl adipate, di-isooctyl adipate, and octyl decyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate.

[0297] When using these rheology modifiers, the amount added is typically less than 30% by mass relative to the total film-forming components of the underlying film-forming composition.

[0298] -Adhesive Additives-

[0299] Adhesion aids are mainly added to improve the adhesion between the substrate or resist and the underlying film formed by the composition for forming the underlying film, especially to inhibit / prevent resist peeling during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium; other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; and benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzo[]. Heterocyclic compounds such as azoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds.

[0300] When using these adhesive additives, the amount added is typically less than 5% by mass, preferably less than 2% by mass, relative to the film-forming component of the underlying film-forming composition.

[0301] pH adjuster-

[0302] In addition, examples of pH adjusters include organic acids and acids having one or more carboxylic acid groups, which are also mentioned as stabilizers. When using a pH adjuster, the amount added relative to 100 parts by weight of polysiloxane can be set to a ratio of 0.01 to 20 parts by weight, 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight.

[0303] -Metal oxides-

[0304] In addition, as metal oxides that can be added to the composition for forming the lower film, examples include oxides of one or more of the following metals: tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and w (tungsten), and metalloids such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te), but these are not limited to these.

[0305] The concentration of the film-forming component in the composition for forming the lower layer film can be set, for example, 0.01 to 50% by mass, 0.01 to 30% by mass, 0.01 to 25% by mass, or 0.01 to 20.0% by mass relative to the total mass of the composition.

[0306] The content of polysiloxane in the film-forming component is usually 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and further preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the above-mentioned additives.

[0307] In addition, the composition for forming the lower membrane preferably has a pH of 1 to 5, and more preferably a pH of 2 to 4.

[0308] The composition for forming the lower film can be manufactured by mixing it with polysiloxane and solvent, as well as other desired components. In this case, a solution containing polysiloxane can be prepared in advance, and this solution can be mixed with the solvent and other components.

[0309] In the preparation of the composition for lower film formation, appropriate heating can be carried out within a range that does not decompose or deteriorate the components.

[0310] During the manufacturing process of the composition for forming the lower membrane layer, or after mixing all the components, filtration can be performed using a submicron-sized filter or similar material. It should be noted that there are no restrictions on the type of filter material used at this time; for example, filters made of polyethylene, nylon, fluoropolymer, or polyimide can be used.

[0311] In this invention, the resist film can be formed by either a positively developing resist or a negatively developing resist.

[0312] In the case of a positively developing resist, the exposed portion is developed. Therefore, if the lower layer film is one in which the alignment of the self-assembled film decreases when exposed to exposure and development during resist pattern formation, then in the case where the resist film is formed by a positively developing resist, the lower layer film exposed after development is also exposed, thus reducing the alignment of the self-assembled film on the lower layer film.

[0313] On the other hand, the lower layer film formed by the composition for forming the lower layer film of the present invention is a lower layer film in which the self-assembled film can be formed in a vertically aligned manner even when exposed to exposure and development during the formation of the resist pattern. Therefore, even if the resist film is formed by a positively developing resist and the lower layer film exposed after development is also exposed, the alignment of the self-assembled film formed on the lower layer film is not easily reduced, and the self-assembled film can still be formed in a vertically aligned manner.

[0314] (Lower membrane)

[0315] The lower layer film of the present invention is a sintered product of the coated film of the above-described lower layer film forming composition.

[0316] In photolithography, the lower layer of the present invention is used as a lower layer for the self-assembly film after being used as a photoresist film, in the case of photolithography using any one of photoresist film and electron beam photoresist film and self-assembly film.

[0317] The lower layer film of the present invention can be manufactured, for example, by coating a lower layer film forming composition onto a semiconductor substrate and then firing it.

[0318] Examples of semiconductor substrates for coating the lower film forming composition of the present invention include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0319] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed by methods such as ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, and spin coating (SOG). Examples of such inorganic films include polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phospho Silicate Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0320] Semiconductor substrates can also have films containing silicon and organic groups. A film containing silicon and organic groups is a film formed from the hydrolysis condensation of hydrolyzable silanes (also called organosilicon compounds) containing organic groups. For example, a film containing silicon and organic groups may contain a hydrolysis condensation of a hydrolyzable silane comprising a compound shown in formula (A) below.

[0321]

[0322] (In formula (A), R) a Represents alkyl, aryl, haloalkyl, haloaryl, alkoxyaryl, alkenyl, epoxide-containing organic groups, acryloyl-containing organic groups, methacryloyl-containing organic groups, mercapto-containing organic groups, or cyano-containing organic groups, R b (This represents an alkoxy, acyloxy, or halogen atom, where x represents an integer from 0 to 3.)

[0323] Films containing silicon and organic groups can be formed, for example, from a silicon-containing photoresist underlayer film forming composition. Examples of such silicon-containing photoresist underlayer film forming compositions include, for example, the silicon-containing photoresist underlayer film forming compositions described below.

[0324] Japanese Patent Application Publication No. 2020-076999, Booklet No. WO2019 / 181873, Booklet No. WO2019 / 082934, Booklet No. WO2019 / 009413, Booklet No. WO2018 / 181989, Booklet No. WO2018 / 079599, Booklet No. WO2016 / 080217, Booklet No. WO2016 / 009965, Booklet No. WO2016 / 009939, Booklet No. WO2015 / 194555, Booklet No. WO2014 / 098076, Booklet No. WO2014 / 069329, Booklet No. WO2014 / 046055, Booklet No. WO2013 / 191203 Booklet No. WO2013 / 115032, Booklet No. WO2013 / 022099, Booklet No. WO2012 / 102261, Booklet No. WO2012 / 053600, Booklet No. WO2012 / 039337, Booklet No. WO2011 / 105368, Booklet No. WO2011 / 102470, Booklet No. WO2011 / 033965, Booklet No. WO2010 / 140551, Booklet No. WO2010 / 071155, Booklet No. WO2010 / 021290, Booklet No. WO2009 / 104552, Booklet No. WO2009 / 088039, Booklet No. WO2009 / 069712

[0325] On such a semiconductor substrate, the composition for forming the lower layer film of the present invention is coated using a suitable coating method such as a spin coater or a coating machine. Then, it is baked using a heating device such as a heating plate to form the lower layer film. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes; more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0326] The thickness of the lower layer can be less than 30 nm, less than 25 nm, less than 20 nm, or less than 15 nm. Alternatively, the thickness of the lower layer can be greater than 1 nm, greater than 2 nm, or greater than 3 nm.

[0327] When a brush layer is formed in the gaps between the patterns of the patterned lower film, the brush layer becomes a thin layer (e.g., about 1 nm). From the viewpoint of minimizing the difference in film thickness between the brush layer and the lower film, a thin film thickness is preferred. From this viewpoint, a film thickness of 15 nm or less is preferred.

[0328] Furthermore, by making the lower layer thin, it is easier to transfer the pattern of the patterned self-assembled film to the lower layer. From this perspective, the thickness of the lower layer is preferably 15 nm or less.

[0329] On the other hand, when the lower layer film is used as an etching mask, it is preferable that the lower layer film is thick. From this perspective, the thickness of the lower layer film is preferably 30 nm or less.

[0330] The method for determining the thickness of the lower membrane in this specification is as follows.

[0331] • Measuring device name: Elliptic film thickness measuring device RE-3100 (SCREEN Co., Ltd.)

[0332] • SWE (Single Wavelength Ellipsometry) Mode

[0333] • Arithmetic mean of 8 points (e.g., measured at 1 cm intervals along the X direction of the wafer)

[0334] (Semiconductor device manufacturing methods)

[0335] The method for manufacturing a semiconductor element according to the present invention includes steps 1 to 4.

[0336] Step 1: The step of forming a lower layer film on a semiconductor substrate using the lower layer film forming composition of the present invention.

[0337] • Step 2: The process of forming either a photoresist film or an electron beam resist film on the lower layer film.

[0338] Step 3: Irradiating the resist film with light or electron beam, followed by developing the resist film to obtain the resist pattern.

[0339] • Step 4: After obtaining the resist pattern, a self-assembled film is formed on at least a portion of the underlying film.

[0340] An example of a method for manufacturing a semiconductor device (first embodiment) is a step (fourth step) in which a self-assembled film is formed between resist patterns and on at least a portion of an underlying film.

[0341] In other words, an example of a method for manufacturing a semiconductor device (first embodiment) includes the following 4A step as the fourth step.

[0342] • Step 4A: The process of forming a self-assembled film between the resist patterns and on at least a portion of the underlying film.

[0343] An example of a method for manufacturing a semiconductor device (second embodiment) is a step of forming a brush layer on at least a portion of a lower film between a step of obtaining a resist pattern (second step) and a step of forming a self-assembled film (fourth step), and a step of removing the resist pattern.

[0344] In other words, an example of a method for manufacturing a semiconductor device (the second embodiment) includes steps 4B to 6B as described below in place of step 4.

[0345] • Step 4B: A step of forming a brush layer between the resist patterns and on at least a portion of the underlying film. • Step 5B: The process of removing the resist pattern. • Step 6B: The process of forming a self-assembled film on the brushed layer and the exposed underlayer film. An example of a method for manufacturing a semiconductor device (the third embodiment) includes a step between the step of obtaining a resist pattern (the third step) and the step of forming a brush layer (the fourth step) to perform surface modification on the underlying film exposed between the resist patterns using a dry process.

[0346] In other words, an example of a method for manufacturing a semiconductor device (the third embodiment) includes steps 4C to 7C as described below in place of step 4.

[0347] • Step 4C: A process that uses a dry process to modify the surface of the underlying film exposed between the resist patterns.

[0348] • Step 5C: The process of forming a brush layer on the surface-modified lower film. • Step 6C: The process of removing the resist pattern. • Step 7C: The process of forming a self-assembled film on the brushed layer and the exposed underlayer film. In the third embodiment, the adhesion between the brush layer and the underlying film can be improved by using a dry process to modify the surface of the underlying film exposed between the resist patterns.

[0349] An example of a method for manufacturing a semiconductor device (the fourth embodiment) includes, between the step of obtaining a resist pattern (the third step) and the step of forming a self-assembled film (the fourth step), a step of performing surface modification on the underlying film exposed between the resist patterns using a dry process, and a step of removing the resist patterns.

[0350] In other words, an example of a method for manufacturing a semiconductor device (the fourth embodiment) includes steps 4D to 6D as described below in place of step 4.

[0351] • Step 4D: A process that uses a dry process to modify the surface of the underlying film exposed between the resist patterns.

[0352] • Step 5D: The process of removing the resist pattern.

[0353] • Step 6D: The process of forming a self-assembled film on the lower layer film.

[0354] In the fourth embodiment, by performing surface modification on a portion of the lower film, the vertical alignment of that portion of the lower film is lost, thereby allowing that portion to replace the brush layer. By doing so, the brush layer is no longer required.

[0355] <Step 1>

[0356] The first step is the step of forming a lower layer film on a semiconductor substrate using the lower layer film forming composition of the present invention. There are no particular limitations on the method for forming the lower layer film, and the methods described above can be cited as examples. That is, the lower layer film can be manufactured, for example, by coating the lower layer film forming composition onto a semiconductor substrate and then firing it.

[0357] <Process 2 and Process 3>

[0358] The second step is to form either a photoresist film or an electron beam resist film on the lower layer film.

[0359] The third step is to irradiate the resist film with light or electron beam, and then develop the resist film to obtain the resist pattern.

[0360] The thickness of the resist film is not particularly limited, but is preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 80 nm or less. Furthermore, the thickness of the resist film is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more.

[0361] As a photoresist formed by coating and firing on a lower film using known methods, there are no particular limitations as long as the photoresist responds to the light or electron beam (EB) used for irradiation. Both negative and positive photoresists can be used.

[0362] It should be noted that in this specification, resists that respond to EB are sometimes also referred to as photoresists.

[0363] As photoresists, there are positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazonium sulfonate; chemically amplified photoresists composed of binders and photoacid generators having groups that increase the rate of alkali dissolution through acid decomposition; chemically amplified photoresists composed of low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition; alkali-soluble binders and photoacid generators; chemically amplified photoresists composed of binders that increase the rate of alkali dissolution through acid decomposition; low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition; and photoacid generators; as well as photoresists containing metal elements. Examples include JSR Corporation's V146G, Sprint Corporation's APEX-E, Sumitomo Chemical Co., Ltd.'s PAR710, and Shin-Etsu Chemical Co., Ltd.'s AR2772 and SEPR430. Additionally, examples include fluorinated polymer photoresists as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0364] Alternatively, you can use WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO2019 / 172054, W O2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Special Opening 2018-180525, WO2018 / 190088, Japanese Special Opening 2018-070596, Japanese Special Opening 2018-028090, Japanese Special Opening 2016-153409, Japanese Special Opening 2016-130240, Japanese Special Opening 2016-108325, Japanese Special Opening 2016-047920, Japanese Special Opening 2016-035570, Japan This special issue 2016-035567, Japan’s special issue 2016-035565, Japan’s special issue 2019-101417, Japan’s special issue 2019-117373 , Japanese Special Opening 2019-052294, Japanese Special Opening 2019-008280, Japanese Special Opening 2019-008279, Japanese Special Opening 2019-003176, Japanese Special Opening 2019-003175, Japanese Special Opening 2018-197853, Japanese Special Opening 2019-191298, Japanese Special Opening 2019-0 61217, Japanese Special Opening 2018-045152, Japanese Special Opening 2018-022039, Japanese Special Opening 2016-090441, Japanese Special Opening 2015-10878, Japanese Special Opening 2012-168279, Japanese Special Opening 2012-022261, Japanese Special Opening 2012-022258, Japanese Special Opening 20 The so-called resist compositions, such as resist compositions, radiosensitive resin compositions, and compositions for high-resolution patterning based on organometallic solutions, as described in Japanese Patent Application Publications (JP2010-181857, JP2010-128369, WO2018 / 031896, JP2019-113855, WO2017 / 156388, WO2017 / 066319, JP2018-41099, WO2016 / 065120, WO2015 / 026482, JP2016-29498, and JP2011-253185, are not limited to these.

[0365] Examples of resist compositions include the following.

[0366] An active light-sensitive or radiation-sensitive resin composition comprising resin A and a compound represented by the following general formula (21), wherein resin A has repeating units having acid-degradable groups that protect polar groups with protecting groups that are deactivated by the action of acid.

[0367]

[0368] In general formula (21), m represents an integer from 1 to 6.

[0369] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0370] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0371] L2 indicates that it can have alkylene groups or single bonds that have substituents.

[0372] W1 represents a cyclic organic group that can have substituents.

[0373] M ＋ It represents a cation.

[0374] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to the 3rd to 7th periods of Groups 3 to 15 of the periodic table.

[0375] A radiation-sensitive resin composition comprising a polymer and an acid-producing agent, said polymer having a first structural unit as shown in formula (31) and a second structural unit as shown in formula (32) containing an acid-dissociating group.

[0376]

[0377] In formula (31), Ar is a group from aromatic hydrocarbons with 6 to 20 carbon atoms from which (n+1) hydrogen atoms have been removed. 1 It is a hydroxyl group, a thiol group, or a monovalent organic group with 1 to 20 carbon atoms. n is an integer from 0 to 11. When n is 2 or more, multiple R... 1 Same or different. R 2 It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 It is a monovalent group containing 1 to 20 carbon atoms, including the aforementioned acid-dissociative group. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 (It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0378] An anti-corrosion composition comprising a resin (A1) and an acid-generating agent, wherein the resin (A1) comprises structural units having a cyclic carbonate structure, structural units represented by the following formula, and structural units having an acid-instantaneous group.

[0379]

[0380] [In the formula,] R 2 X represents an alkyl group, hydrogen atom, or halogen atom that can have 1 to 6 carbon atoms and may contain halogen atoms. 1 Indicates a single bond, -CO-O- or -CO-NR 4 - , R represents the bond with -Ar. 4 [Ar represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have one or more groups selected from hydroxyl and carboxyl groups.] Examples of resist films include the following.

[0381] A photoresist film comprising a base resin containing repeating units as shown in formula (a1) and / or repeating units as shown in formula (a2), and repeating units of acid bonded to the polymer backbone by exposure.

[0382]

[0383] (In equations (a1) and (a2), R) A Each can be independently a hydrogen atom or a methyl group. R 1 and R 2 Each is an independent tertiary alkyl group having 4 to 6 carbon atoms. R 3 Each atom can be independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. X 1 It is a single bond, a phenylene or naphthylene group, or a linker containing 1 to 12 carbon atoms selected from at least one of ester bonds, lactone rings, phenylene, and naphthylene groups. X 2 (These can be single bonds, ester bonds, or amide bonds.)

[0384] Examples of corrosion-resistant materials include the following.

[0385] A corrosion-resistant material comprising a polymer having repeating units as shown in formula (b1) or formula (b2).

[0386]

[0387] (In equations (b1) and (b2), R) AIt can be a hydrogen atom or a methyl group. X 1 It is a single bond or an ester group. X 2 It is a linear, branched, or cyclic alkylene group with 1 to 12 carbon atoms or an aryl group with 6 to 10 carbon atoms. A portion of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group, or a group containing an lactone ring. Additionally, X 2 At least one hydrogen atom is replaced by a bromine atom. X 3 It is a single bond, an ether group, an ester group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, wherein a portion of the methylene group constituting the alkylene group may be substituted with an ether group or an ester group. Rf 1 ~Rf 4 Each atom can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom, but at least one of them must be a fluorine atom or a trifluoromethyl atom. Additionally, Rf... 1 and Rf 2 They can combine to form a carbonyl group. R 1 ~R 5 Each group is independently a linear, branched, or cyclic alkyl group with 1 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, an alkynyl group with 2 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or an aryloxyalkyl group with 7 to 12 carbon atoms. Some or all of the hydrogen atoms in these groups may be substituted with hydroxyl, carboxyl, halogen, oxo, cyano, amide, nitro, sulopentalide, sulfonic acid, or a group containing a sulfonate. A portion of the methylene group constituting these groups may be substituted with ether, ester, carbonyl, carbonate, or sulfonate groups. Additionally, R... 1 With R 2 They can combine with the sulfur atoms they are bonded to to form rings.

[0388] A corrosion resist material comprising a base resin, said base resin comprising a polymer containing repeating units as shown in formula (a).

[0389]

[0390] (In equation (a), R) A It can be a hydrogen atom or a methyl group. R 1 It is a hydrogen atom or an acid-instable group. R 2 It is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1 It is a single bond or a phenylene group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms that may contain an ester group or an lactone ring. X 2 It can be -O-, -O-CH2-, or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. Where m + u is an integer from 1 to 4.

[0391] A photoresist composition that generates acid upon exposure, thereby altering the solubility of the photoresist in a developer through the action of the acid. It contains a substrate component (A) whose solubility in the developer changes due to the action of acid, and a fluorinated additive component (F) that exhibits decomposition properties in alkaline developers. The above-mentioned fluorinated additive component (F) contains a fluoropolymer component (F1), which has a structural unit (f1) containing a base-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0392]

[0393] In equation (f2-r-1), Rf 21 Each is independently a hydrogen atom, alkyl group, alkoxy group, hydroxy group, hydroxyalkyl group, or cyano group. n” is an integer from 0 to 2. [This is a bonding bond.]

[0394] The above structural unit (f1) includes the structural unit shown in the following general formula (f1-1) or the structural unit shown in the following general formula (f1-2).

[0395]

[0396] In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms. X is a divalent linker without an acid-dissociating site. A aryl It is a divalent aromatic cyclic group that can have substituents. X 01 It is a single-bond or divalent linker. R 2 Each is an organic group containing a fluorine atom.

[0397] Examples of substances that can be cited as coatings, coating solutions, and coating compositions include the following.

[0398] A coating comprising a network of metal oxygen-hydroxyl groups having organic ligands via metal carbon bonds and / or metal carboxylate bonds.

[0399] Compositions based on inorganic oxygen / hydroxyl groups.

[0400] A coating solution comprising an organic solvent, a first organometallic composition, and a hydrolyzable metal compound, wherein the first organometallic composition is of formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (Here, 0 < z ≤ 2 and 0 < (z + x) ≤ 4), Equation R' n SnX 4-n(Here, n = 1 or 2), or a mixture thereof, where R and R' are independently hydrocarbon groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolytic bond to Sn or a combination thereof; the hydrolytic metal compound is of formula MX' v (Here, M is a metal selected from groups 2 to 16 of the periodic table, v is a number from 2 to 6, and X' is a ligand of an MX bond with hydrolytic properties or a combination thereof.)

[0401] A coating solution comprising an organic solvent and the formula RSnO (3 / 2-x / 2) (OH) x The coating solution of the first organometallic compound shown in the formula (where 0 < x < 3) contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, wherein the alkyl or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0402] An aqueous precursor solution for inorganic pattern formation comprises water, a metal low oxide cation, a polyatomic inorganic anion, and a mixture of a radiation-sensitive ligand containing a peroxide group.

[0403] Another example of a metal-containing corrosion resist is the composition described in Japanese Patent Application Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Application Publication No. 2020-122959, Japanese Patent Application Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229.

[0404] These contents are incorporated herein by reference to all that are expressly stated.

[0405] There are no particular limitations on the method for forming a metal-containing resist film from a metal-containing resist. For example, a method can be used to coat and fire a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist.

[0406] Furthermore, metal-containing resist films can be formed by vapor deposition. As a method for forming metal-containing resist films based on vapor deposition, the method described in Japanese Patent Application Publication No. 2017-116923 can be cited as an example. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein by reference to the entirety of the invention. It should be noted that in Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film of the present invention is referred to as a film containing metal oxides.

[0407] Irradiation with light or an electron beam is performed, for example, through a mask (photomask) used to form a prescribed pattern. There are no particular limitations on the wavelength of the light. I-beams, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet) or EB (electron beam) can be used.

[0408] There are no particular restrictions on the irradiation energy and light exposure of the EB.

[0409] Baking (PEB: Post Exposure Bake) can also be performed after exposure to light or an electron beam but before development.

[0410] There are no particular limitations on the baking temperature, but it is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C.

[0411] There are no particular restrictions on the baking time, but it is preferred to be 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0412] For example, alkaline developing solutions or organic solvents can be used for developing.

[0413] Examples of developing temperatures include 5°C to 50°C.

[0414] Examples of development times include 10 seconds to 300 seconds.

[0415] As an alkaline developer, aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alkanolamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, cyclic amines such as pyrrole and piperidine, and other bases can be used. Furthermore, an appropriate amount of an alcohol such as isopropanol or a nonionic surfactant can be added to the above-mentioned alkaline aqueous solutions. Among these, aqueous solutions of quaternary ammonium salts are preferred, and aqueous solutions of tetramethylammonium hydroxide and choline are more preferred. Furthermore, surfactants can be added to these developers. Alternatively, an organic solvent such as butyl acetate can be used instead of an alkaline developer to develop the portion of the photoresist whose alkaline dissolution rate has not been increased.

[0416] As a developer for a metal-containing photoresist, an organic solvent can be used, and development is performed using the developer (solvent) after irradiation with light or an electron beam. Thus, for example, when using a negative metal-containing photoresist film, the unexposed portions of the metal-containing photoresist film are removed, forming a pattern of the metal-containing photoresist film.

[0417] Examples of organic solvents used as developers include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-methoxybutyl acetate, 4-methoxybutyl acetate -Ethoxybutylacetic acid ester, 4-propoxybutylacetic acid ester, 2-methoxypentylacetic acid ester, 3-methoxypentylacetic acid ester, 4-methoxypentylacetic acid ester, 2-methyl-3-methoxypentylacetic acid ester, 3-methyl-3-methoxypentylacetic acid ester, 3-methyl-4-methoxypentylacetic acid ester, 4-methyl-4-methoxypentylacetic acid ester, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate Examples include esters, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, surfactants can also be added to these developing solutions.

[0418] There are no particular restrictions on the type of resist pattern that can be formed; it can be a line pattern or a hole pattern.

[0419] When the resist pattern is a line pattern, there is no particular limitation on the line width, and examples include 30nm to 200nm.

[0420] When the resist pattern is a hole pattern, the diameter of the hole can be, for example, 30 nm to 200 nm.

[0421] <Step 4>

[0422] The fourth step is a step of forming a self-assembled film on at least a portion of the underlying film after the process of obtaining the resist pattern.

[0423] An example of a method for manufacturing a semiconductor device (first embodiment) is a process of forming a self-assembled film that includes forming a self-assembled film between resist patterns and on at least a portion of an underlying film.

[0424] Self-assembling films, for example, can be formed by coating and drying a self-assembling film forming composition.

[0425] Self-assembled membranes are, for example, membranes containing block copolymers.

[0426] The thickness of the self-assembled membrane is not particularly limited, but is preferably 10 nm to 100 nm, more preferably 30 nm to 80 nm, and particularly preferably 40 nm to 60 nm.

[0427] <<Compositions for Self-Assembly Film Formation>>

[0428] Compositions for self-assembling film formation, for example, contain block copolymers.

[0429] Compositions for self-assembling film formation typically contain solvents.

[0430] The solid content of the composition for self-assembling film formation can be 0.1 to 10% by mass, or 0.1 to 5% by mass, or 0.1 to 3% by mass. The solid content is the proportion of the remaining components after removing the solvent from the composition for film formation.

[0431] The proportion of block copolymers in the solid component can be 30-100% by mass, or 50-100% by mass, or 50-90% by mass, or 50-80% by mass.

[0432] The block copolymer may contain 2 or more types of blocks. Moreover, the number of blocks present in the block copolymer may be 2 or more.

[0433] <<<Block Copolymers>>>

[0434] As block polymers, there are combinations such as AB, ABAB, ABA, and ABC.

[0435] One method for synthesizing block copolymers includes living radical polymerization and living cationic polymerization, where the polymerization process consists only of initiation and propagation reactions without side reactions that deactivate the propagation ends. The propagation ends can maintain their propagation activity throughout the polymerization reaction. By preventing chain transfer, polymers (PA) of uniform length can be obtained. By adding different monomers (mb), the polymerization of the monomers (mb) can be carried out using the propagation ends of the polymer (PA), forming block copolymers (AB).

[0436] For example, when the block types are PA and PB, the molar ratio of polymer chain (PA) to polymer chain (PB) can be 1:9 to 9:1, preferably 3:7 to 7:3.

[0437] The volume ratio of the block copolymer is, for example, 30:70 to 70:30.

[0438] Homopolymers PA or PB are polymers of polymeric compounds having at least one reactive group (vinyl or an organopolymer containing vinyl) capable of free radical polymerization.

[0439] The weight-average molecular weight (Mw) of the block copolymer is preferably 1,000 to 100,000 or 5,000 to 100,000. When it is above 1,000, it has excellent coatability to the substrate, and when it is below 100,000, it has excellent solubility in solvents.

[0440] The polydispersity (Mw / Mn) of the block copolymer is preferably 1.00 to 1.50, more preferably 1.00 to 1.20.

[0441] The block copolymers used in this invention can be known block copolymers.

[0442] As a specific example of a block copolymer, for instance, in the case of combining silicon-containing polymer chains and non-silicon-containing polymer chains, the difference in dry etching rate can be large, for example, which is therefore preferred.

[0443] Examples of silicon-containing polymer chains include silylated polystyrene derivatives. Examples of silylated polystyrene derivatives include polysilanes (e.g., polydihexylsilane), polysiloxanes (e.g., polydimethylsiloxane), poly(trimethylsilylstyrene), and poly(pentamethyldimethylsilylstyrene).

[0444] In particular, the above-mentioned silylated polystyrene derivatives are preferably poly(4-trimethylsilylstyrene) or poly(4-pentamethyldimethylsilylstyrene) with a substituent at the 4 position.

[0445] A preferred example of a block copolymer is a block copolymer formed by combining a silicone-free polymer with styrene, which can be substituted with organic groups, as a structural unit, or a silicone-free polymer with a structure derived from lactide as a structural unit, with a silicone-containing polymer with styrene, which is substituted with silicon-containing groups, as a structural unit.

[0446] Among them, combinations of silylated polystyrene derivatives and polystyrene derivatives, or combinations of silylated polystyrene derivatives and polylactide, are preferred.

[0447] Among them, a combination of a silylated polystyrene derivative having a substituent at the 4-position and a polystyrene derivative having a substituent at the 4-position, or a combination of a silylated polystyrene derivative having a substituent at the 4-position and polylactide is preferred.

[0448] More preferred examples of block copolymers include combinations of poly(trimethylsilylstyrene) and polyoxymethylene styrene, combinations of polystyrene and poly(trimethylsilylstyrene), and combinations of poly(trimethylsilylstyrene) and poly(D,L-lactide).

[0449] More preferred specific examples of block copolymers include combinations of poly(4-trimethylsilylstyrene) and poly(4-methoxystyrene), combinations of polystyrene and poly(4-trimethylsilylstyrene), and combinations of poly(4-trimethylsilylstyrene) and poly(D,L-lactide).

[0450] Specific examples of block copolymers that are the most preferred choices include poly(4-methoxystyrene) / poly(4-trimethylsilylstyrene) block copolymers and polystyrene / poly(4-trimethylsilylstyrene) block copolymers.

[0451] All publicly available information contained in WO2018 / 135456 is incorporated herein by reference.

[0452] Alternatively, the block copolymer described above may also be a block copolymer formed by combining a silicon-free polymer with a silicon-containing polymer whose structural unit is styrene substituted with silicon-containing groups, wherein the silicon-free polymer comprises the unit structure shown in formula (1-1c) or formula (1-2c).

[0453]

[0454] (In equation (1-1c) or equation (1-2c), R) 1 and R 2 Each independently represents a hydrogen atom, a halogen atom, and an alkyl group having 1 to 10 carbon atoms, R 3 ~R 5 Each group independently represents a hydrogen atom, hydroxyl group, halogen atom, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, cyano group, amino group, amide group, or carbonyl group.

[0455] The aforementioned silicon-containing groups may contain one silicon atom.

[0456] The aforementioned silicon-containing polymers may contain the unit structure shown in formula (2c).

[0457]

[0458] (In equation (2c), R) 6 ~R 8 Each can independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0459] Furthermore, as the aforementioned block copolymer, block copolymers comprising [BCP11] to [BCP14] described in Japanese Patent Application Publication No. 2019-507815 may also be used. All disclosures described in Japanese Patent Application Publication No. 2019-507815 are incorporated herein by reference.

[0460] [BCP11] is a block copolymer containing 5-vinylbenzo[d][1,3]dioxane.

[0461] [BCP12] According to the block copolymer of [BCP11], the block copolymer further comprises silicon-containing blocks.

[0462] [BCP13] According to the block copolymer described in [BCP12], the block copolymer further comprises pentamethyldimethylsilyl styrene.

[0463] [BCP14] According to the block copolymer described in [BCP13], the block copolymer is poly(5-vinylbenzo[d][1,3]dioxane)-b-poly(pentamethyldimethylsilylstyrene).

[0464] The synthesis of poly(5-vinylbenzo[d][1,3]dioxane-block-4-pentamethyldimethylsilylstyrene) described above is shown in the following figure 1.

[0465]

[0466] Me represents methyl.

[0467] Preferably, the aforementioned silicon-containing polymer or silicon-containing block is poly(4-trimethylsilylstyrene) derived from 4-trimethylsilylstyrene. Preferably, the aforementioned silicon-containing polymer or silicon-containing block is poly(pentamethyldimethylsilylstyrene) derived from pentamethyldimethylstyrene. An aryl group with 6 to 40 carbon atoms refers to a monovalent group of a monocyclic or polycyclic aromatic hydrocarbon with 6 to 40 carbon atoms; specific examples include phenyl, naphthyl, or anthracene.

[0468] All publicly available information contained in WO2020 / 017494 is incorporated herein by reference.

[0469] Alternatively, block copolymers formed from combinations of the monomers described below may also be used: styrene, methyl methacrylate, dimethylsiloxane, propylene oxide, ethylene oxide, vinylpyridine, vinylnaphthalene, D,L-lactide, methoxystyrene, methylenedioxystyrene, trimethylsilylstyrene, and pentamethyldisilylstyrene.

[0470] Useful block copolymers contain at least two blocks, which can be diblock, triblock, tetrablock, etc., copolymers with different blocks, and each block can be a homopolymer, a random copolymer, or an alternating copolymer.

[0471] Typical block copolymers include polystyrene-b-polyvinylpyridine, polystyrene-b-polybutadiene, polystyrene-b-polyisoprene, polystyrene-b-polymethyl methacrylate, polystyrene-b-polyalkenyl aromatic, polyisoprene-b-polyethylene oxide, polystyrene-b-poly(ethylene-propylene), polyethylene oxide-b-polycaprolactone, polybutadiene-b-polyethylene oxide, polystyrene-b-poly(tert-butyl methacrylate), polymethyl methacrylate-b-poly(tert-butyl methacrylate), polyethylene oxide-b-polypropylene oxide, and polystyrene-b-polytetrahydrocarbonyl methacrylate. Furan, polystyrene-b-polyisoprene-b-polyethylene oxide, poly(styrene-b-dimethylsiloxane), poly(methyl methacrylate-b-dimethylsiloxane), poly((methyl methacrylate-r-styrene)-b-polymethyl methacrylate, poly((methyl methacrylate-r-styrene)-b-polystyrene, poly(p-hydroxystyrene-r-styrene)-b-polymethyl methacrylate, poly(p-hydroxystyrene-r-styrene)-b-polyethylene oxide, polyisoprene-b-polystyrene-b-polyferrocene silane, or a combination comprising at least one of the above block copolymers.

[0472] In addition, block copolymers formed from combinations of the organic polymers and / or metal-containing polymers described below are also exemplified.

[0473] As typical organic polymers, they include poly(9,9-bis(6'-N,N,N-trimethylammonium)-hexyl)-fluorenephenylene (PEP), poly(4-vinylpyridine) (4PVP), hydroxypropyl methylcellulose (HPMC), polyethylene glycol (PEG), poly(ethylene oxide)-poly(propylene oxide) diblock or multiblock copolymers, polyvinyl alcohol (PVA), poly(ethylene-vinyl alcohol) (PEVA), polyacrylic acid (PAA), polylactic acid (PLA), and poly(ethyl... (e.g., azoline), poly(alkyl acrylate), polyacrylamide, poly(N-alkylacrylamide), poly(N,N-dialkylacrylamide), polypropylene glycol (PPG), polypropylene oxide (PPO), partially or fully hydrogenated poly(vinyl alcohol), dextran, polystyrene (PS), polyethylene (PE), polypropylene (PP), polyisoprene (PI), polychloroprene (CR), polyvinyl ether (PVE), polyvinyl acetate (PVA), polyvinyl chloride (PVC), polyurethane (PU), polyacrylate, polymethacrylate, oligosaccharides or polysaccharides, but not limited to these.)

[0474] As a metal-containing polymer, it includes, but is not limited to, polymers containing silicon—such as polydimethylsiloxane (PDMS), silsesquioxane cage (POSS), or poly(trimethylsilylstyrene) (PTMSS)—or polymers containing silicon and iron—such as poly(ferrocene dimethylsilane) (PFS).

[0475] Typical block copolymers (copolymers) include, but are not limited to, diblock copolymers—such as polystyrene-b-polydimethylsiloxane (PS-PDMS), poly(2-vinylpropylene)-b-polydimethylsiloxane (P2VP-PDMS), polystyrene-b-poly(ferrocene dimethylsilane) (PS-PFS), or polystyrene-b-polyDL lactic acid (PS-PLA)—or triblock copolymers—such as polystyrene-b-poly(ferrocene dimethylsilane)-b-poly(2-vinylpyridine) (PS-PFS-P2VP), polyisoprene-b-polystyrene-b-poly(ferrocene dimethylsilane) (PI-PS-PFS), or polystyrene-b-poly(ferrocene dimethylsilane)-b-polystyrene (PS-PTMSS-PS). In one embodiment, the PS-PTMSS-PS block copolymer comprises a poly(trimethylsilyl styrene) polymer block consisting of two chains of PTMSS linked by linkers comprising four styrene units. Modifications of block copolymers, such as those disclosed in U.S. Patent Application Publication No. 2012 / 0046415, are also contemplated.

[0476] Other examples of block copolymers include, for instance, block copolymers formed by combining a polymer with styrene or a derivative thereof as structural units with a polymer with (meth)acrylate as structural units; block copolymers formed by combining a polymer with styrene or a derivative thereof as structural units with a polymer with siloxane or a derivative thereof as structural units; and block copolymers formed by combining a polymer with an olefin oxide as structural unit with a polymer with (meth)acrylate as structural units. It should be noted that "(meth)acrylate" refers to one or both of acrylates with a hydrogen atom bonded at the α-position and methacrylates with a methyl group bonded at the α-position.

[0477] Examples of (meth)acrylates include substances in which alkyl, hydroxyalkyl, or other substituents are bonded to the carbon atoms of (meth)acrylic acid. Examples of alkyl groups used as substituents include straight-chain, branched, or cyclic alkyl groups having 1 to 10 carbon atoms. Specifically, examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, anthracene (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, and propyltrimethoxysilane (meth)acrylate.

[0478] Examples of styrene derivatives include, for example, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethylstyrene, 4-methoxystyrene, 4-tert-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxyvinylstyrene, vinylcyclohexane, 4-vinylbenzyl chloride, 1-vinylnaphthalene, 4-vinylbiphenyl, 1-vinyl-2-pyrrolidone, 9-vinylanthracene, vinylpyridine, etc.

[0479] Examples of siloxane derivatives include dimethylsiloxane, diethylsiloxane, diphenylsiloxane, and methylphenylsiloxane.

[0480] Examples of olefin oxides include ethylene oxide, propylene oxide, isopropylene oxide, and butene oxide.

[0481] Examples of block copolymers include polystyrene / poly(methyl methacrylate) block copolymers, styrene-polyethyl methacrylate block copolymers, styrene-(polytert-butyl methacrylate) block copolymers, styrene-polymethyl methacrylate block copolymers, styrene-polyethyl methacrylate block copolymers, styrene-(polytert-butyl methacrylate) block copolymers, and styrene-polyacrylate block copolymers.

[0482] All publicly available information from WO2022 / 039187 is incorporated into this specification.

[0483] <<<Solvent>>>

[0484] Examples of solvents used as solvents in compositions for self-assembling film formation include the following organic solvents.

[0485] • Aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane.

[0486] Aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, and trimethylbenzene.

[0487] Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecyl alcohol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, cresol, and other monohydric alcohol solvents.

[0488] Polyol solvents such as ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptaethylenediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol.

[0489] Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone-based acetone, diacetone alcohol, acetophenone, and ketone.

[0490] Ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, dioxolane, 4-methyldioxolane, di... Alkane, dimethyl di Alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and other ether-based solvents.

[0491] Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diacetate Ester solvents including glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc.

[0492] Nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone

[0493] Sulfur-containing solvents such as dimethyl sulfide, ethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sulpholactone

[0494] In particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate are preferred in terms of the stability of the composition in solution storage.

[0495] In addition, the solvent contained in the composition for self-assembling film formation may be a combination of a low-boiling-point solvent (A) with a boiling point of less than 160°C and a high-boiling-point solvent (B) with a boiling point of more than 170°C, as described in WO2018 / 135456.

[0496] As a low-boiling-point solvent (A) with a boiling point below 160°C, preferred examples include propylene glycol monomethyl ether acetate (boiling point: 146°C), n-butyl acetate (boiling point: 126°C), and methyl isobutyl ketone (boiling point: 116°C).

[0497] As a high-boiling-point solvent (B) with a boiling point of 170°C or higher, preferred examples include N-methylpyrrolidone (boiling point: 204°C), diethylene glycol monomethyl ether (boiling point: 193°C), N,N-dimethylisobutyramide (boiling point: 175°C), 3-methoxy-N,N-dimethylpropionamide (boiling point: 215°C), and γ-butyrolactone (boiling point: 204°C).

[0498] Low-boiling-point solvent (A) and high-boiling-point solvent (B) can also be selected and mixed together for use.

[0499] As a preferred embodiment, the high-boiling-point solvent (B) comprises 0.3 to 2.0% by weight relative to the total solvent contained in the above composition. Most preferably, it comprises 0.5 to 1.5% by weight of the high-boiling-point solvent (B).

[0500] All publicly available information from WO2018 / 135456 is incorporated into this instruction manual.

[0501] <<Phase Separation of Self-Assembled Membranes>>

[0502] Phase separation of self-assembled membranes (e.g., block copolymer membranes) can be achieved through treatments that induce rearrangement of the self-assembled membranes, such as ultrasonic treatment, solvent treatment, thermal annealing, etc. In many applications, it is desirable to achieve phase separation of self-assembled membranes simply by heating or so-called thermal annealing.

[0503] Hot annealing can be carried out in the atmosphere or in an inert gas, under normal pressure, reduced pressure or increased pressure.

[0504] There are no particular restrictions on the conditions for hot annealing, but it is preferably 180°C to 300°C under atmospheric conditions, more preferably 210°C to 280°C, and particularly preferably 230°C to 270°C.

[0505] There is no particular limitation on the processing time, but it is usually 1 to 30 minutes, preferably 3 to 10 minutes.

[0506] Phase separation of the self-assembled film creates domains that are substantially perpendicular to the substrate or the surface of the underlying film. The morphology of these domains can be, for example, layered, spherical, or cylindrical. The domain spacing is, for example, 50 nm or less.

[0507] <<Patterning of Self-Assembled Films>>

[0508] By selectively removing a portion of the phase-separated self-assembled membrane, a pattern corresponding to the morphology of the domain is obtained.

[0509] Examples of methods for selectively removing a portion of a phase-separated self-assembled membrane include, for instance, oxygen plasma treatment of the phase-separated self-assembled membrane and hydrogen plasma treatment.

[0510] <Process for forming the brush layer>

[0511] One example of a semiconductor device manufacturing method includes a step of forming a brush layer.

[0512] An example of a method for manufacturing a semiconductor device (second embodiment) includes a step between the step of obtaining a resist pattern and the step of forming a self-assembled film, wherein a brush layer is formed on at least a portion of the underlying film between the resist pattern and the step of forming a resist pattern.

[0513] An example of a method for manufacturing a semiconductor device (the third embodiment) includes a step of forming a brush layer on a surface-modified lower film.

[0514] There are no particular limitations on the method for forming the brush layer; for example, a method of coating a composition for forming the brush layer and then drying it can be cited.

[0515] <<Composition for Brush Layer Forming>>

[0516] Compositions for forming brush layers may contain, for example, a brush polymer and a solvent.

[0517] Compositions for forming brush layers are, for example, compositions comprising polymer chains capable of directly bonding to the surface of a substrate. Films or layers formed by polymer chains brush-like disposed on a substrate are sometimes referred to as brush layers.

[0518] The composition for forming a brush layer is, for example, a composition for forming a lower layer film for forming a lower layer film containing a block copolymer layer.

[0519] Furthermore, the film formed by the brush layer forming composition, for example, functions as a guide to control the generation location of the polymer phase formed through self-assembly. For instance, the film formed by the brush layer forming composition is a sidewall of a recess in a grapho-epitaxy, a physical guide for forming microphase separation patterns in the recesses. Additionally, for example, the film formed by the brush layer forming composition is a chemical guide formed in the lower layer of a self-assembled material, controlling the formation location of the microphase separation pattern based on differences in surface energy.

[0520] <<<Brush-type polymer>>>

[0521] As a brush-type polymer, there are no particular restrictions as long as it is used for the formation of the underlying film.

[0522] As an example of a brush-type polymer, one could cite the polymer contained in a neutral, wettable substrate as described in Japanese Patent Application Publication No. 2011-515537. Examples of such polymers include, for instance, the random copolymer described in claim 15 of Japanese Patent Application Publication No. 2011-515537, and the blend of multiple grafted homopolymers described in claim 16. The contents of Japanese Patent Application Publication No. 2011-515537 are incorporated herein by reference to the entirety of what is explicitly stated.

[0523] Another example of a brush-type polymer is the random copolymer described in Japanese Patent Application Publication No. 2011-518652. One example of the random copolymer described in Japanese Patent Application Publication No. 2011-518652 is the photocrosslinkable random PS-r-PMMA described in paragraph

[0028] . The contents of Japanese Patent Application Publication No. 2011-518652 are incorporated herein by reference to the entirety of this specification.

[0524] As another example of a brush-type polymer, one could cite, for instance, a resin in which 20 mol% to 80 mol% of the overall structural unit is derived from a monomer containing an aromatic ring. Such a resin is, for example, the resin component contained in the base agent described in International Publication No. 2012 / 036121. The contents of International Publication No. 2012 / 036121 are incorporated herein by reference to the entirety of what is expressly stated.

[0525] As another example of a brush-type polymer, one can cite, for instance, the random copolymer described in claim 1 of Japanese Patent Application Publication No. 2013-166934. The contents of Japanese Patent Application Publication No. 2013-166934 are incorporated herein by reference to the entirety of what is expressly stated.

[0526] As another example of a brush-type polymer, a polymer having a unit structure containing 0.2 mol% or more of a polycyclic aromatic vinyl compound relative to the total unit structure can be cited. Examples of such polymers include those contained in the lower film-forming composition described in International Publication No. 2014 / 097993. The contents of International Publication No. 2014 / 097993 are incorporated herein by reference to the entirety of what is expressly stated.

[0527] Another example of a brush-type polymer is the polymer contained in the brush backfill composition disclosed in Japanese Patent Application Publication No. 2015-130496 (e.g., a poly(alkyl acrylate)) having functional groups capable of reacting with a semiconductor substrate). The contents of Japanese Patent Application Publication No. 2015-130496 are incorporated herein by reference to the entirety of what is explicitly stated.

[0528] As another example of a brush-type polymer, the addition polymer described in claim 1 of Japanese Patent Application Publication No. 2016-148024 is cited. The contents of Japanese Patent Application Publication No. 2016-148024 are incorporated herein by reference to the entirety of what is expressly stated.

[0529] Another example of a brush-type polymer can be cited as the polymer contained in the staple material described in claim 1 of Japanese Patent Application Publication No. 2016-528713. Another example of such a polymer can be cited as the polymer described in claim 3 of Japanese Patent Application Publication No. 2016-528713. The contents of Japanese Patent Application Publication No. 2016-528713 are incorporated herein by reference to the entirety of what is explicitly stated.

[0530] As another example of a brush-type polymer, one can cite, for instance, the acid-sensitive copolymer comprising acid-degradable groups, adhesion groups, and functional groups as described in claim 1 of Japanese Patent Application Publication No. 2018-139007. The contents of Japanese Patent Application Publication No. 2018-139007 are incorporated herein by reference to the entirety of what is explicitly stated.

[0531] As another example of a brush-type polymer, the hydrophobic polymer brush precursor described in claim 1 of Japanese Patent Application Publication No. 2018-503241 is cited. The contents of Japanese Patent Application Publication No. 2018-503241 are incorporated herein by reference to the entirety of what is explicitly stated.

[0532] The brush-type polymer preferably has functional groups that can bond with the substrate.

[0533] Examples of functional groups that can bind to a substrate include hydroxyl, amino, and sulfonic acid groups.

[0534] Brush-type polymers may have functional groups at the ends of the polymer chains that can bind to the substrate, or they may have functional groups at other locations besides the ends of the polymer chains that can bind to the substrate.

[0535] There are no particular limitations on the method of introducing functional groups that can bind to the substrate to the end of the polymer chain. For example, in the case of addition polymers, methods using polymerization initiators and chain transfer agents that have compounds with functional groups that can bind to the substrate can be cited.

[0536] The brush-type polymer is preferably an addition polymer.

[0537] Addition polymers are obtained, for example, by polymerizing one or more free radical polymerizable monomers.

[0538] There are no particular limitations on monomers that can be polymerized on a free radical basis; examples include (meth)acrylic acid compounds and vinyl compounds containing aromatic groups.

[0539] Examples of (meth)acrylic acid compounds include, for example, (meth)acrylic acid and (meth)acrylates. Examples of (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, etc.

[0540] Examples of vinyl compounds containing aromatic groups include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethylstyrene, 4-methoxystyrene, 4-tert-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxyvinylstyrene, vinylcyclohexane, 4-vinylbenzyl chloride, 1-vinylnaphthalene, 4-vinylbiphenyl, 1-vinyl-2-pyrrolidone, 9-vinylanthracene, vinylpyridine, etc.

[0541] <<<<Polymer (P)>>>>

[0542] Brush-type polymers are preferred as polymers (P) containing the following structural units (A) and (B) in order to induce microphase separation structures of block copolymers in a manner perpendicular to the substrate.

[0543] Structural unit (A): A structural unit derived from a (meth)acryloyl group and a functional group capable of binding to a substrate in a (meth)acrylic acid compound.

[0544] Structural unit (B): Structural unit derived from vinyl compounds containing aromatic groups.

[0545] The molar proportion of structural unit (A) relative to all structural units in polymer (P) is greater than 0% and less than 5%.

[0546] By ensuring that the molar proportion of structural unit (A) relative to all structural units in polymer (P) is greater than 0% and less than 5%, a film inducing microphase separation structure of the block copolymer in a perpendicular manner to the substrate can be formed. If the molar proportion of structural unit (A) relative to all structural units in polymer (P) exceeds 5%, the arrangement of the microphase separation structure of the block copolymer is disordered, and the microphase separation structure of the block copolymer cannot be induced in a perpendicular manner to the substrate.

[0547] As for the polymer (P), there are no particular limitations as long as it contains structural units (A) and (B), but it is preferred to be an addition polymer obtained by polymerization of a compound having a polymerizable unsaturated group. Examples of polymerizable unsaturated groups include, for example, olefinic unsaturated groups. Examples of olefinic unsaturated groups include, for example, vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadimide, (meth)acryloyl, etc.

[0548] The polymer (P) is, for example, a random copolymer.

[0549] Polymer (P) may also contain structural units other than structural units (A) and (B).

[0550] Structural unit (A) is derived from (meth)acrylic acid compounds.

[0551] (Meth)acrylic acid compounds have (meth)acryloyl groups.

[0552] (Meth)acrylic acid compounds have functional groups that can bind to a substrate.

[0553] The term (meth)acryloyl is used to represent acryloyl and methacryloyl groups. Acryloyl refers to the group represented by CH2=CH-CO-, while methacryloyl refers to the group represented by CH2=C(CH3)-CO-.

[0554] There are no particular limitations on the functional groups that can bind to the substrate, and examples include hydroxyl, amino, and sulfonic acid groups.

[0555] The number of functional groups in structural unit (A) that can bond with the substrate can be one or more, but one is preferred.

[0556] The (meth)acryloyl group in (meth)acrylic acid compounds can be one or more, but one is preferred.

[0557] Structural unit (A) is a different structural unit from structural unit (B). Therefore, structural unit (B) does not have an aromatic ring.

[0558] The structural unit (A) in the polymer (P) can be one type or two or more types.

[0559] As a structural unit (A), it is preferable to include the structural unit (A-1) shown in the following formula (1).

[0560]

[0561] (In formula (1), X represents -O- or -NH-. Y represents a hydroxyl, amino, or sulfonic acid group. R) 1 R represents an alkylene group with 1 to 10 carbon atoms that can be substituted by a halogen atom. 2 (This indicates a hydrogen atom or a methyl group.)

[0562] As for the amino group, primary amino or secondary amino groups are preferred.

[0563] The term "primary amino group" refers to a monovalent functional group (-NH2) that has had a hydrogen atom removed from ammonia.

[0564] The term secondary amine refers to a monovalent functional group (-NHR, where R represents an organogroup) that has had a hydrogen atom removed from a primary amine. R represents, for example, an alkyl group having 1 to 6 carbon atoms.

[0565] Alkyl groups with 1 to 10 carbon atoms that can be substituted by halogen atoms can be straight-chain, branched, or cyclic.

[0566] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0567] The number of halogen atoms in an alkylene group with 1 to 10 carbon atoms substituted by halogen atoms can be one or more.

[0568] As an alkylene group having 1 to 10 carbon atoms, it can be a straight-chain or branched alkylene group, and examples include methylene, ethylene, 1,3-propylene (trimethylene), 1-methylethylene (1,2-propylene), 1,4-butylene, 1-ethylethylene, 1-methylpropylene, 2-methylpropylene, 1,5-pentylene, 1-methylbutylene, 2-methylbutylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1-ethylpropylene, 2-ethylpropylene, 1,6-hexylene, 1,4-cyclohexylene, 1,8-octylene, 2-ethyloctylene, 1,9-nonylene, 1,10-decylene, etc.

[0569] The molar percentage of structural unit (A) relative to all structural units in polymer (P) is more than 0% and less than 5%, preferably more than 0.1% and less than 5%, more preferably more than 0.3% and less than 4.5%, and particularly preferably more than 0.5% and less than 4.0%.

[0570] Examples of (meth)acrylic acid compounds include those shown in formula (1-1) below.

[0571]

[0572] (In formula (1-1), X represents -O- or -NH-. Y represents a hydroxyl, amino, or sulfonic acid group. R) 1 R represents an alkylene group with 1 to 10 carbon atoms that can be substituted by a halogen atom. 2 (This indicates a hydrogen atom or a methyl group.)

[0573] Examples of (meth)acrylic acid compounds include, for example, (meth)acrylates containing hydroxyl groups, (meth)acrylates containing amino groups, (meth)acrylates containing sulfonic acid groups, (meth)acrylamides containing hydroxyl groups, and (meth)acrylamides containing sulfonic acid groups.

[0574] Examples of hydroxyl-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, and 1,4-cyclohexanediethanol mono(meth)acrylate.

[0575] Examples of (meth)acrylates containing amino groups include, for example, (meth)acrylates containing primary amino groups and (meth)acrylates containing secondary amino groups.

[0576] Examples of (meth)acrylates containing a primary amino group include, for example, aminomethyl (meth)acrylate and aminoethyl (meth)acrylate.

[0577] Examples of (meth)acrylates containing a secondary amino group include, for example, tert-butylaminoethyl (meth)acrylate and tert-butylaminopropyl (meth)acrylate.

[0578] Examples of (meth)acrylates containing sulfonic acid groups include 2-sulfoethyl (meth)acrylate and 3-sulfopropyl (meth)acrylate.

[0579] Examples of (meth)acrylamides containing hydroxyl groups include N-(hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, and N-(4-hydroxybutyl)acrylamide.

[0580] Structural unit (B) is derived from a vinyl compound containing an aromatic group.

[0581] The aromatic ring in a vinyl compound containing an aromatic group can be an aromatic hydrocarbon ring or an aromatic heterocycle, but an aromatic hydrocarbon ring is preferred.

[0582] Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings.

[0583] Vinyl compounds containing aromatic groups, for example, do not have functional groups that can bind to a substrate.

[0584] Vinyl compounds containing aromatic groups, for example, do not have hydroxyl, amino, or sulfonic acid groups.

[0585] Structural unit (B) for example does not have functional groups that can bond with the substrate.

[0586] Structural unit (B) may not have hydroxyl, amino, or sulfonic acid groups, for example.

[0587] The structural unit (B) in the polymer (P) can be one type or two or more types.

[0588] As a structural unit (B), it is preferable to include the structural unit (B-1) shown in the following formula (2).

[0589] As a structural unit (B), it is preferable to include the structural unit (B-2) shown in the following formula (3).

[0590]

[0591] (In equation (2), each of the n Y atoms independently represents a halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, or alkylthio group, and n represents an integer from 0 to 7.)

[0592] (In equation (3), R) 3 ~R 5 Each can independently represent a hydrogen atom or a tert-butyl group. Wherein, R... 3 ~R 5 One or two of them represent tert-butyl.

[0593] Examples of halogen atoms in Y in formula (2) include fluorine, chlorine, bromine, and iodine atoms.

[0594] As for the alkyl group in formula (2), it is preferably an alkyl group with 1 to 15 carbon atoms, more preferably an alkyl group with 1 to 10 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and particularly preferably an alkyl group with 1 to 3 carbon atoms. The alkyl group can be straight-chain, branched, or cyclic.

[0595] As for the alkoxy group in formula (2), it is preferred to be an alkoxy group with 1 to 15 carbon atoms, more preferably an alkoxy group with 1 to 10 carbon atoms, even more preferably an alkoxy group with 1 to 6 carbon atoms, and particularly preferably an alkoxy group with 1 to 3 carbon atoms. The alkyl group in the alkoxy group can be straight-chain, branched, or cyclic.

[0596] As for the alkoxycarbonyl group in formula (2), it is preferred to be an alkoxycarbonyl group with 2 to 15 carbon atoms, more preferably an alkoxycarbonyl group with 2 to 10 carbon atoms, even more preferably an alkoxycarbonyl group with 2 to 6 carbon atoms, and particularly preferably an alkoxycarbonyl group with 2 to 3 carbon atoms. The alkyl group in the alkoxycarbonyl group can be straight-chain, branched, or cyclic.

[0597] As an alkylthio group in Y in formula (2), examples can be found where the -O- of the above alkoxy group is replaced with a -S- group.

[0598] There are no particular limitations on the molar ratio of structural unit (B) to all structural units in polymer (P), but it is preferably 80% or more and less than 100%, more preferably 90% or more and less than 100%, and particularly preferably more than 95% and less than 100%.

[0599] The molar ratio (structural unit (A): structural unit (B)) of structural unit (A): structural unit (B) in polymer (P) is not particularly limited, but is preferably 1:200 to 1:10, more preferably 1:150 to 1:20.

[0600] When the polymer (P) contains the structural unit (B-1) shown in formula (2), there is no particular limitation on the molar ratio (structural unit (A): structural unit (B-1)) of structural unit (A): structural unit (B-1) in the polymer (P), but it is preferably 1:100 to 1:5, and more preferably 1:75 to 1:10.

[0601] When the polymer (P) contains the structural unit (B-2) shown in formula (3), there is no particular limitation on the molar ratio (structural unit (A): structural unit (B-2)) of structural unit (A): structural unit (B-2) in the polymer (P), but it is preferably 1:100 to 1:5, and more preferably 1:75 to 1:10.

[0602] When the polymer (P) contains the structural unit (B-1) shown in formula (2) and the structural unit (B-2) shown in formula (3), there is no particular limitation on the molar ratio (structural unit (B-1): structural unit (B-2)) of structural unit (B-1): structural unit (B-2) in the polymer (P), but it is preferably 1.0:0.1 to 0.1:1.0, more preferably 1.0:0.5 to 0.5:1.0, and particularly preferably 1.0:0.7 to 0.7:1.0.

[0603] Examples of vinyl compounds containing aromatic groups include, for example, compounds represented by formula (2-1) and compounds represented by formula (3-1).

[0604]

[0605] (In equation (2-1), each of the n Y atoms independently represents a halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, or alkylthio group, and n represents an integer from 0 to 7.)

[0606] (In equation (3-1), R) 3 ~R 5 Each can independently represent a hydrogen atom or a tert-butyl group. Wherein, R... 3 ~R 5 One or two of them represent tert-butyl.

[0607] There are no particular limitations on the weight-average molecular weight of the brush polymer as determined by gel permeation chromatography (GPC), but when converted to polystyrene, it is, for example, 1,000 to 50,000, preferably 2,000 to 20,000.

[0608] <<<<Method for Manufacturing Brush-Type Polymers>>>>

[0609] There are no particular restrictions on the manufacturing method of brush-type polymers.

[0610] For example, in the case where the brush polymer is an addition polymer, it can be manufactured by polymerizing the monomer using conventional methods such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Solution polymerization is particularly preferred, in which, for example, polymerization can be carried out by adding the desired monomer to a solvent containing a polymerization initiator.

[0611] For example, in the case where the brush polymer is an addition-polymerized random copolymer, it can be manufactured by copolymerizing various monomers in a manner that is appropriate in molar ratio using conventional methods such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

[0612] Examples of such polymerization include free radical polymerization.

[0613] The manufacturing method of brush-type polymers can also be a polymerization method other than free radical polymerization. For example, it can be a manufacturing method using ionic (anionic, cationic) addition polymerization, or a manufacturing method using condensation polymerization or addition polymerization.

[0614] The polymer (P) can be manufactured, for example, by solution polymerization of a mixture of monomers containing a (meth)acryloyl compound having a (meth)acrylyl group and a functional group capable of binding to a substrate, and a vinyl compound containing an aromatic group.

[0615] [Polymerization initiator]

[0616] Organic peroxides and diazo compounds can be used as polymerization initiators.

[0617] Examples of organic peroxides include peroxydiacyl peroxides, peroxydicarbonate peroxides, peroxyester peroxides, and peroxysulfonate peroxides.

[0618] Examples of peroxide diacyl groups include, for example, diacetyl peroxide, diisobutyl peroxide, didecyl peroxide, benzoyl peroxide, and succinic acid peroxide.

[0619] Examples of dicarbonate peroxides include, for example, diisopropyl dicarbonate peroxide, di-2-ethylhexyl dicarbonate peroxide, and diallyl dicarbonate peroxide.

[0620] Examples of peroxide esters include tert-butyl peroxide, tert-butyl neodecanoate, and cumyl peroxide neodecanoate.

[0621] Examples of peroxide sulfonates include, for example, acetylcyclohexylsulfonyl peroxide.

[0622] Examples of diazo compounds include 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanopentaic acid), 2,2'-azobis(4-methoxy-2,4-dimethoxypentanone), and 2,2'-azobis(2-cyclopropylpropionitrile).

[0623] When it is desired to end the polymerization in a short time, a polymerization initiator with a decomposition half-life of 10 hours or less at 80°C is preferred. Benzoyl peroxide, 2,2'-azobisisobutyronitrile, and more preferably 2,2'-azobisisobutyronitrile are preferred polymerization initiators.

[0624] The amount of polymerization initiator used relative to the total amount of monomer used is, for example, 0.0001 to 0.2 equivalents, preferably 0.0005 to 0.1 equivalents.

[0625] [Solvent]

[0626] As for the solvent used in the polymerization, there are no particular restrictions as long as it does not participate in the polymerization reaction and is compatible with the resulting brush polymer. Examples include aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, esters, amides, sulfoxides, alcohols, and polyol derivatives.

[0627] Examples of aromatic hydrocarbons include benzene, toluene, and xylene.

[0628] Examples of alicyclic hydrocarbons include cyclohexane.

[0629] Examples of aliphatic hydrocarbons include n-hexane and n-octane.

[0630] Examples of ketones include acetone, methyl ethyl ketone, and cyclohexanone.

[0631] Examples of ethers include tetrahydrofuran and dihydrofuran. Alkane, etc.

[0632] Examples of esters include ethyl acetate and butyl acetate.

[0633] Examples of amides include N,N-dimethylformamide and N,N-dimethylacetamide.

[0634] Examples of sulfoxides include, for example, dimethyl sulfoxide.

[0635] Examples of alcohols include methanol and ethanol.

[0636] Examples of polyol derivatives include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate.

[0637] They can be used individually or in combination of two or more.

[0638] There are no particular restrictions on the polymerization temperature, as long as it is within the range where no side reactions such as transfer reactions or termination reactions occur and the polymerization is completed without the consumption of monomers. However, it is preferred to carry out the polymerization in a temperature range above -100°C and below the boiling point of the solvent.

[0639] Furthermore, there are no particular limitations on the concentration of the monomer relative to the solvent, but it is typically 1 to 40% by mass, preferably 10 to 30% by weight.

[0640] The time for the polymerization reaction can be selected appropriately, but it is usually in the range of 2 to 50 hours.

[0641] <<<Solvent>>>

[0642] There are no particular restrictions on the solvent contained in the composition for forming the brush layer, as long as it is a solvent that dissolves the brush-type polymer.

[0643] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monopropyl ether, methyl ethyl ketone, ethyl lactate, cyclohexanone, N,N-2-trimethylpropionamide, γ-butyrolactone, N-methyl-2-pyrrolidone, methyl 2-hydroxyisobutyrate, and ethyl 3-ethoxypropionate.

[0644] They can be used individually or in combination of two or more.

[0645] The content of the solvent in the composition for forming the brush layer is not particularly limited, but is, for example, 90% by mass or more and 99.9% by mass or less.

[0646] <<<Other Ingredients>>>

[0647] The brush layer forming composition preferably does not contain a crosslinking agent. For example, by reacting a brush-type polymer with a substrate, the film obtained from the brush layer forming composition becomes a film that is insoluble in the solvent contained in a self-assembled film forming composition containing a block copolymer. Therefore, the brush layer forming composition does not need to contain a crosslinking agent.

[0648] In this invention, the term "not containing a crosslinking agent" may also include cases where the crosslinking agent is present only slightly to the extent that its function as a crosslinking agent is not fully realized. As an option for a brush layer forming composition not containing a crosslinking agent, the content of the crosslinking agent in the brush layer forming composition is preferably less than 0.1% by mass, more preferably less than 0.01% by mass, and particularly preferably less than 0.001% by mass, relative to the brush-type polymer.

[0649] Examples of crosslinking agents include nitrogen-containing compounds having two to four nitrogen atoms substituted with hydroxymethyl or alkoxymethyl groups.

[0650] Examples of crosslinking agents include hexamethoxymethyl melamine, tetramethoxymethyl glycourea, tetramethoxymethyl guanidine, 1,3,4,6-tetra(methoxymethyl)glycourea, 1,3,4,6-tetra(butoxymethyl)glycourea, 1,3,4,6-tetra(hydroxymethyl)glycourea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea, and 1,1,3,3-tetra(methoxymethyl)urea.

[0651] The composition for forming the brush layer may also contain a surfactant. A surfactant is an additive used to improve the coatability to a substrate.

[0652] As a surfactant, well-known surfactants such as nonionic surfactants and fluorinated surfactants can be used.

[0653] Examples of surfactant content in the composition for forming the brush layer include 0.1% to 5% by mass relative to the brush-type polymer.

[0654] In a composition for forming a brush layer, if the components other than the solvent are defined as solid components, the solid components include a brush-type polymer and additives added as needed.

[0655] The concentration of the solid component in the composition for forming the brush layer is not particularly limited, but is, for example, 0.1% to 15% by mass, preferably 0.1% to 10% by mass.

[0656] <Process for implementing surface modification>

[0657] One example of a semiconductor device manufacturing method includes a process of performing surface modification.

[0658] Dry processes are preferred for surface modification.

[0659] Examples of dry processes include plasma treatment, corona treatment, and UV treatment.

[0660] In plasma processing, for example, O2, CO2, CO, etc. are used. Plasma processing is sometimes referred to as plasma etching.

[0661] There are no specific restrictions on the conditions for dry process.

[0662] For example, the adhesion between the underlying film of the surface-modified portion and the brush layer formed thereon is improved.

[0663] The underlying membrane at the site where surface modification has been performed loses its function as a membrane capable of forming vertically aligned membranes (e.g., a neutral membrane).

[0664] <Process for removing the resist pattern>

[0665] One example of a method for manufacturing a semiconductor device includes a step of removing a resist pattern.

[0666] The removal of the resist pattern is performed, for example, by etching. Etching can be dry etching or wet etching.

[0667] An example of a method for manufacturing a semiconductor element according to the present invention is illustrated with figures.

[0668] Figures 1A-1F This is a cross-sectional schematic diagram illustrating an example of a method for manufacturing a semiconductor element according to the present invention.

[0669] A lower film 2 is formed on a semiconductor substrate 1 using the lower film formation composition of the present invention. Figure 1A ).

[0670] Next, a resist film 3 is formed on the lower film 2. Figure 1B ).

[0671] Next, the resist film 3 is subjected to light irradiation or electron beam irradiation, followed by development to obtain a resist pattern (patterned resist film) 3a. Figure 1C ).

[0672] Next, a self-assembled film 4 is formed between the resist patterns 3a and on at least a portion of the underlying film 2. Figure 1D The self-assembled membrane 4 is, for example, a block copolymer having A-blocks and B-blocks. By subjecting the self-assembled membrane 4 to phase separation, a microphase-separated structure having domain 4a of A-blocks and domain 4b of B-blocks is obtained. Figure 1D ).

[0673] Next, by selectively removing a portion of the self-assembled membrane 4 that has undergone microphase separation (e.g., domain 4b of the B-block), a pattern corresponding to the morphology of the microphase-separated domain is obtained. Figure 1E ).

[0674] Next, the pattern corresponding to the morphology of the microphase-separated domain is used as a mask to etch the lower film 2, resulting in the patterned lower film 2a. Figure 1F ).

[0675] Although not shown, the patterned lower film 2a can be used as a mask to process the semiconductor substrate 1 as a further step.

[0676] Another example of the method for manufacturing a semiconductor element according to the present invention is illustrated using figures.

[0677] Figures 2A-2H This is a cross-sectional schematic diagram illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0678] A lower film 2 is formed on a semiconductor substrate 1 using the lower film formation composition of the present invention. Figure 2A ).

[0679] Next, a resist film 3 is formed on the lower film 2. Figure 2B ).

[0680] Next, the resist film 3 is subjected to light irradiation or electron beam irradiation, followed by development to obtain a resist pattern (patterned resist film) 3a. Figure 2C ).

[0681] Next, a brush layer 5 is formed between the resist patterns 3a and on at least a portion of the underlying film 2. Figure 2D ).

[0682] Next, the resist pattern 3a is removed. Figure 2E ).

[0683] Next, a self-assembled membrane 4 is formed on the brush layer 5 and the exposed lower membrane 2. Figure 2F The self-assembled membrane 4 is, for example, a block copolymer having A-blocks and B-blocks. By causing phase separation of the self-assembled membrane 4 on the lower membrane 2, a microphase-separated structure having domain 4a with A-blocks and domain 4b with B-blocks is obtained. On the other hand, since the self-assembled membrane 4 on the brush layer 5 does not undergo phase separation, a domain 4c that has not undergone phase separation is formed on the brush layer 5. Figure 2F ).

[0684] Next, by selectively removing a portion of the self-assembled membrane 4 that has undergone microphase separation (e.g., domain 4b of the B-block), a pattern corresponding to the morphology of the microphase-separated domain is obtained. Figure 2G ).

[0685] Next, the pattern corresponding to the morphology of the microphase-separated domain is used as a mask to etch the lower film 2, resulting in the patterned lower film 2a. Figure 2H ).

[0686] Although not shown, the patterned lower film 2a can be used as a mask to process the semiconductor substrate 1 as a further step.

[0687] Another example of the method for manufacturing a semiconductor element according to the present invention is illustrated using figures.

[0688] Figures 3A to 3I This is a cross-sectional schematic diagram illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0689] A lower film 2 is formed on a semiconductor substrate 1 using the lower film formation composition of the present invention. Figure 3A ).

[0690] Next, a resist film 3 is formed on the lower film 2. Figure 3B ).

[0691] Next, the resist film 3 is subjected to light irradiation or electron beam irradiation, followed by development to obtain a resist pattern (patterned resist film) 3a. Figure 3C).

[0692] Next, the surface of the underlying film 2 exposed between the resist patterns 3a is modified using a dry process. Figure 3D ).

[0693] Next, a brush layer 5 is formed on the surface-modified lower film 2 (surface-modified region 2x). Figure 3E ).

[0694] Next, the resist pattern 3a is removed. Figure 3F ).

[0695] Next, a self-assembled membrane 4 is formed on the brush layer 5 and the exposed lower membrane 2. Figure 3G The self-assembled membrane 4 is, for example, a block copolymer having A-blocks and B-blocks. By causing phase separation of the self-assembled membrane 4 on the lower membrane 2, a microphase-separated structure having domain 4a with A-blocks and domain 4b with B-blocks is obtained. On the other hand, since the self-assembled membrane 4 on the brush layer 5 does not undergo phase separation, a domain 4c that has not undergone phase separation is formed on the brush layer 5. Figure 3G ).

[0696] Next, by selectively removing a portion of the self-assembled membrane 4 that has undergone microphase separation (e.g., domain 4b of the B-block), a pattern corresponding to the morphology of the microphase-separated domain is obtained. Figure 3H ).

[0697] Next, the pattern corresponding to the morphology of the microphase-separated domain is used as a mask to etch the lower film 2, resulting in the patterned lower film 2a. Figure 3I ).

[0698] Although not shown, the patterned lower film 2a can be used as a mask to process the semiconductor substrate 1 as a further step.

[0699] Another example of the method for manufacturing a semiconductor element according to the present invention is illustrated using figures.

[0700] Figures 4A-4H This is a cross-sectional schematic diagram illustrating another example of a method for manufacturing a semiconductor element according to the present invention.

[0701] A lower film 2 is formed on a semiconductor substrate 1 using the lower film formation composition of the present invention. Figure 4A ).

[0702] Next, a resist film 3 is formed on the lower film 2. Figure 4B ).

[0703] Next, the resist film 3 is subjected to light irradiation or electron beam irradiation, followed by development to obtain a resist pattern (patterned resist film) 3a. Figure 4C ).

[0704] Next, the surface of the underlying film 2 exposed between the resist patterns 3a is modified using a dry process. Figure 4D ).

[0705] Next, the resist pattern 3a is removed. Figure 4E ).

[0706] Next, a self-assembled film 4 is formed on the lower film 2 containing the surface-modified region 2x. Figure 4F The self-assembled film 4 is, for example, a block copolymer having A-blocks and B-blocks. By causing phase separation of the self-assembled film 4 on the lower film 2 outside the surface-modified region 2x, a microphase-separated structure of domain 4a having A-blocks and domain 4b having B-blocks is obtained. On the other hand, since the self-assembled film 4 on the surface-modified region 2x does not undergo phase separation, a domain 4c that has not undergone phase separation is formed on the surface-modified region 2x. Figure 4F ).

[0707] Next, by selectively removing a portion of the self-assembled membrane 4 that has undergone microphase separation (e.g., domain 4b of the B-block), a pattern corresponding to the morphology of the microphase-separated domain is obtained. Figure 4G ).

[0708] Next, the pattern corresponding to the morphology of the microphase-separated domain is used as a mask to etch the lower film 2, resulting in the patterned lower film 2a. Figure 4H ).

[0709] Although not shown, the patterned lower film 2a can be used as a mask to process the semiconductor substrate 1 as a further step.

[0710] Example

[0711] The following examples and embodiments illustrate the invention in more detail, but the invention is not limited to the following embodiments.

[0712] It should be noted that, in the embodiments, the apparatus and conditions used for the analysis of the physical properties of the samples are as follows.

[0713] (1) Molecular weight determination

[0714] The molecular weight of the polysiloxane used in this invention is calculated based on the molecular weight of polystyrene obtained from GPC analysis.

[0715] The determination conditions for GPC can be performed using a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Co., Ltd.), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Co., Ltd.), a column temperature of 40°C, a tetrahydrofuran eluent (dissolution solvent), a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko Co., Ltd.) as the standard sample.

[0716] Compounds 1-4 used in each synthesis are shown below.

[0717]

[0718] In the above formula, Me represents methyl and Et represents ethyl.

[0719] [1] Synthesis of hydrolysis condensate (polysiloxane)

[0720] <Synthesis example 1>

[0721] 22.9 g of compound 1, 8.8 g of compound 2 and 47.5 g of 1-ethoxy-2-propanol were added to a 200 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 20.8 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0722] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 20 hours. Then, the reaction solution was cooled to room temperature, and 50 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolytic condensate (polymer 1) using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150°C, exceeds 20% by mass.

[0723] The weight-average molecular weight (Mw) of the resulting hydrolysis condensate (polymer 1: polysiloxane) obtained by GPC is 1000 when converted to polystyrene.

[0724] <Synthesis example 2>

[0725] 16.6 g of compound 1, 14.9 g of compound 2 and 47.3 g of 1-ethoxy-2-propanol were added to a 200 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 21.1 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0726] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 20 hours. Then, the reaction solution was cooled to room temperature, and 50 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolytic condensate (polymer 2) using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150°C, exceeds 20% by mass.

[0727] The weight-average molecular weight (Mw) of the resulting hydrolysis condensate (polymer 2: polysiloxane) obtained by GPC was 1200 when converted to polystyrene.

[0728] <Synthesis example 3>

[0729] 8.2 g of compound 2, 24.2 g of compound 3 and 48.5 g of 1-ethoxy-2-propanol were added to a 200 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 19.2 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0730] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 20 hours. Then, the reaction solution was cooled to room temperature, and 50 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolytic condensate (polymer 3) using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150°C, exceeds 20% by mass.

[0731] The weight-average molecular weight (Mw) of the resulting hydrolysis condensate (polymer 3: polysiloxane) obtained by GPC was 1200 when converted to polystyrene.

[0732] <Synthesis example 4>

[0733] 32.7 g of compound 3 and 49.1 g of 1-ethoxy-2-propanol were added to a 200 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 18.2 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0734] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 20 hours. Then, the reaction solution was cooled to room temperature, and 50 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolytic condensate (polymer 4) using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150°C, exceeds 20% by mass.

[0735] The weight-average molecular weight (Mw) of the resulting hydrolysis condensate (polymer 4: polysiloxane) obtained by GPC was 1000 in polystyrene form.

[0736] <Comparative Synthesis Example 1>

[0737] 21.0 g of compound 2, 10.5 g of compound 4 and 47.3 g of 1-ethoxy-2-propanol were added to a 200 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 21.2 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0738] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 20 hours. Then, the reaction solution was cooled to room temperature, and 50 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and ethanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolytic condensate (polymer 5) using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150°C, exceeds 20% by mass.

[0739] The weight-average molecular weight (Mw) of the resulting hydrolysis condensate (polymer 5: polysiloxane) obtained by GPC was 1300 in polystyrene form.

[0740] [2] Modulation Examples 1-4 and Comparative Modulation Example 1: Modulation of the composition (coating solution) for forming a silicon-containing lower layer film

[0741] The hydrolysis condensates (polymers) 1-4 obtained in the above synthesis examples and the hydrolysis condensates (polymers) of the comparative synthesis examples were mixed with additives and solvents in the proportions shown in Table 1, and filtered using a 0.02 μm polyethylene filter to prepare compositions for forming silicon-containing lower layer films. The amounts added in Table 1 are expressed in parts by mass.

[0742] It should be noted that in Table 1, the 0.5 parts by mass of each polymer listed in the composition column refers to 0.5 parts by mass of the hydrolysate condensate.

[0743] The abbreviations in Table 1 are shown below.

[0744] PGEE: Propylene Glycol Monoethyl Ether

[0745] ·PGME: Propylene Glycol Monomethyl Ether

[0746] ·DIW: Ultrapure Water

[0747] • Add.1: The following structural formula (Add.1)

[0748] •Add.2: The following structural formula (Add.2)

[0749] [Table 1]

[0750] <Preparation of Composition 1 for Self-Assembly Film Formation>

[0751] In 24.5 g of propylene glycol monomethyl ether acetate, 0.5 g of polystyrene / poly(methyl methacrylate) copolymer (made by POLYMER SOURCE INC., PS (Mw: 39,800, Mn: 37,500)-b-PMMA (Mw: 19,100, Mn: 18,000), polydispersity = 1.06) was dissolved to prepare a 2% by mass solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a self-assembled membrane forming composition 1 containing block copolymer 1.

[0752] <Evaluation of Self-Assembly of Block Copolymers 1>

[0753] [Example A]

[0754] The silicon-containing lower layer film forming compositions obtained in Modulation Examples 1-4 and Comparative Modulation Example 1 were coated onto a silicon wafer and heated at 240°C for 1 minute on a heating plate to obtain a coated film with a thickness of 5-10 nm.

[0755] The self-assembled film forming composition 1, prepared by spin coating, was coated on the composition and heated on a heating plate at 260°C for 5 minutes under a nitrogen atmosphere, thereby inducing a microphase separation structure of a self-assembled film with a thickness of 40 nm.

[0756] <Observation of Microphase Separation Structure>

[0757] Using an etching apparatus (Lam 2300 Versys Kiyo45) manufactured by Lam Resachi, an etching unit was used to etch a silicon wafer with induced microphase separation structure for 3 seconds using O2 / N2 gas as the etching gas, thereby preferentially etching the poly(methyl methacrylate) region. The shape was then observed using an electron microscope (Hitachi Hightech CG-4100 scanning electron microscope for length measurement). The alignment direction and arrangement of the block copolymers (BCPs) as observed are shown in Table 2. "Good" is defined as the case where the BCPs show a vertical alignment of the target; "Extremely Good" is defined as the case where the BCPs only show a vertical alignment in the overall observed image; and "Poor" is defined as the case where a non-vertical alignment is shown.

[0758] Regarding Comparative Example 1, the results observed at a magnification of 200,000 are presented below. Figure 5 .

[0759] [Table 2]

[0760] <Evaluation of Self-Assembly of Block Copolymers 2>

[0761] [Example B]

[0762] The silicon-containing lower layer film forming compositions obtained in Examples 1-4 were coated onto silicon wafers, and heated at 240°C for 1 minute on a hot plate to obtain coated films with a thickness of 5-10 nm. The coated film was then exposed to the left half of the silicon wafer under specified conditions using an ArF exposure apparatus (Nicon). After exposure, development was performed, followed by rinsing with ultrapure water. Butyl acetate or NMD-3 (a developer based on tetramethylammonium hydroxide, Tokyo Ohka Kogyo Co., Ltd.) was used as the developer. It should be noted that a neutral film remains after development.

[0763] The self-assembled film forming composition 1, prepared by spin coating, was coated on the composition and heated on a heating plate at 260°C for 5 minutes under a nitrogen atmosphere, thereby inducing a microphase separation structure of a self-assembled film with a thickness of 40 nm.

[0764] It should be noted that ArF exposure and development of the neutral film are performed because, in semiconductor manufacturing processes using self-assembled films, exposure and development are sometimes performed during the patterning of neutral films using photoresist, and conditions similar to those processes are used in this evaluation.

[0765] <Observation of Microphase Separation Structure>

[0766] Using an etching apparatus (Lam 2300 Versys Kiyo45) manufactured by Lam Resachi, an etching unit was used to etch a silicon wafer with induced microphase separation structure for 3 seconds using O2 / N2 gas as the etching gas, thereby preferentially etching the poly(methyl methacrylate) region. The shape was then observed using an electron microscope (Hitachi Hightech CG-4100 scanning electron microscope for length measurement). The alignment direction and arrangement of the block copolymers (BCPs) as observed are shown in Table 3. "Good" is defined as the case where the BCPs show a vertical alignment of the target; "Extremely Good" is defined as the case where the BCPs show only a vertical alignment in the overall observed image; and "Poor" is defined as the case where a non-vertical alignment is shown.

[0767] Regarding Examples 2-5, the results observed at a magnification of 200,000 are presented below. Figure 6 .

[0768] [Table 3]

[0769] Symbol Explanation

[0770] 1. Semiconductor substrate

[0771] 2. Lower membrane

[0772] 2a Patterned lower layer film

[0773] 2x Surface Modification Regions

[0774] 3. Resist film

[0775] 3a Resist Pattern

[0776] 4 Self-assembling membrane

[0777] 4a A segment field

[0778] 4b B-section field

[0779] 4c Domains where phase separation did not occur

[0780] 5. Apply a layer.

Claims

1. A lower layer film, which is a sintered product of a coated film of a lower layer film forming composition, In photolithography using either photoresist film or electron beam resist film and a self-assembled film, the lower layer film, after being used as the lower layer film of the resist film, is further used as the lower layer film of the self-assembled film. The composition for forming the lower film contains a polysiloxane as a hydrolytic condensate of a hydrolyzable silane. The hydrolyzable silane comprises a compound represented by formula (1) below, and may also comprise a compound represented by formula (2) below. The molar proportion of the compound represented by formula (1) in the hydrolyzable silane is 45 mol% or more. The total molar percentage of the compound represented by formula (1) and the compound represented by formula (2) in the hydrolyzable silane is 65 mol% or more. It should be noted that this includes cases where the molar percentage of the compound represented by formula (2) in the hydrolyzable silane is 0 mol%. In formula (1), Ar represents an aromatic hydrocarbon group that can have substituents, n represents an integer from 1 to 3, and when n is 1, R a R represents a single bond or an alkylene group with 1 to 6 carbon atoms, where n is 2 or 3. a It represents a saturated hydrocarbon group with a valence of (n+1) carbon atoms from 1 to 6. Each X independently represents a hydrolyzable group. When n is 2 or 3, multiple Ar can be the same or different. In equation (2), R b The group represents a non-aromatic hydrocarbon group with 1 to 6 carbon atoms, and each X represents a hydrolyzable group independently.

2. The lower membrane according to claim 1, wherein n in formula (1) is 1, and R a Indicates alkylene groups having 1 to 6 carbon atoms.

3. The lower membrane according to claim 2, wherein the molar proportion of the compound represented by formula (1) in the hydrolyzable silane is 65 mol% or more.

4. According to claim 1, the total molar ratio of the compound represented by formula (1) and the compound represented by formula (2) in the hydrolyzable silane is 80 mol% or more. It should be noted that this includes the case where the molar ratio of the compound represented by formula (2) in the hydrolyzable silane is 0 mol%.

5. The lower layer film according to claim 1, wherein the resist film is formed of a positively reflective resist.

6. The lower membrane according to claim 1, wherein the self-assembled membrane is a membrane comprising a block copolymer.

7. The lower layer film according to claim 1, wherein the film thickness is less than 30 nm.

8. A composition for forming a lower layer film, wherein the lower layer film is used in photolithography, after being used as a lower layer film for the photoresist film and an electron beam photoresist film and a self-assembled film, further serves as a lower layer film for the self-assembled film. The composition for forming the lower film contains a polysiloxane as a hydrolytic condensate of a hydrolyzable silane. The hydrolyzable silane comprises a compound represented by formula (1) below, and may also comprise a compound represented by formula (2) below. The molar proportion of the compound represented by formula (1) in the hydrolyzable silane is 45 mol% or more. The total molar percentage of the compound represented by formula (1) and the compound represented by formula (2) in the hydrolyzable silane is 65 mol% or more. It should be noted that this includes cases where the molar percentage of the compound represented by formula (2) in the hydrolyzable silane is 0 mol%. In formula (1), Ar represents an aromatic hydrocarbon group that can have substituents, n represents an integer from 1 to 3, and when n is 1, R a R represents a single bond or an alkylene group with 1 to 6 carbon atoms, where n is 2 or 3. a This represents a saturated hydrocarbon group with a valence of (n+1) carbon atoms (1-6). Each X independently represents a hydrolytic group. When n is 2 or 3, multiple Ar groups can be the same or different. In equation (2), R b The group represents a non-aromatic hydrocarbon group with 1 to 6 carbon atoms, and each X represents a hydrolyzable group independently.

9. The composition for forming a lower film according to claim 8, wherein n in formula (1) is 1, and R a Indicates alkylene groups having 1 to 6 carbon atoms.

10. The composition for forming a lower film according to claim 9, wherein the molar proportion of the compound represented by formula (1) in the hydrolyzable silane is 65 mol% or more.

11. The composition for forming a lower film according to claim 8, wherein the total molar percentage of the compound represented by formula (1) and the compound represented by formula (2) in the hydrolyzable silane is 80 mol% or more, including the case where the molar percentage of the compound represented by formula (2) in the hydrolyzable silane is 0 mol%.

12. The composition for forming a lower layer film according to claim 8, wherein the resist film is formed from a positively photosensitive resist.

13. The composition for forming a lower layer film according to claim 8, wherein the self-assembled film is a film comprising a block copolymer.

14. The composition for forming a lower layer film according to claim 8, wherein the thickness of the lower layer film is 30 nm or less.

15. A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a lower layer film on a semiconductor substrate using the composition for forming a lower layer film according to any one of claims 8 to 14. The process of forming either a photoresist film or an electron beam resist film on the lower layer film. The process of irradiating the resist film with light or electron beam, followed by developing the resist film to obtain a resist pattern, and... The process of forming a self-assembled film on at least a portion of the underlying film after obtaining the resist pattern.

16. The method of manufacturing a semiconductor element according to claim 15, wherein the step of forming the self-assembled film is a step of forming the self-assembled film between the resist patterns and on at least a portion of the underlying film.

17. The method of manufacturing a semiconductor device according to claim 15, wherein between the step of obtaining the resist pattern and the step of forming the self-assembled film, the following steps are sequentially included: a step of forming a brush layer between the resist patterns and on at least a portion of the underlying film, and a step of removing the resist pattern.

18. The method for manufacturing a semiconductor device according to claim 17, wherein between the step of obtaining the resist pattern and the step of forming the brush layer, a step of performing surface modification on the underlying film exposed between the resist patterns using a dry process.

19. The method for manufacturing a semiconductor device according to claim 15, wherein between the step of obtaining the resist pattern and the step of forming the self-assembled film, the following steps are sequentially included: a step of performing surface modification on the underlying film exposed between the resist patterns using a dry process, and a step of removing the resist patterns.

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