Developable resist upper layer film composition and method for manufacturing resist upper layer film pattern and resist pattern

Abstract

The invention provides a developable resist upper layer film composition, and a method for manufacturing a resist upper layer film pattern and a resist pattern.

Description

Technical Field

[0001] The present invention relates to a developable resist upper layer film composition, and a method for producing a resist upper layer film pattern and a resist pattern. Background Art

[0002] In recent years, the demand for high integration of LSI has increased, and the resist pattern has been refined. In order to meet this demand, photolithography processes using short-wavelength KrF excimer lasers, ArF excimer lasers, extreme ultraviolet rays, X-rays, electron beams, etc. are being put into practical use.

[0003] In order to obtain a finer pattern, there is a method in which a composition containing a polymer is coated on a resist pattern formed within a range that can be stably obtained by a conventional method to make the resist pattern coarser and refine the pore diameter or separation width. The main purpose is to make the width of the resist pattern coarser, and once the resist pattern is developed, the composition containing a polymer is applied.

[0004] A resist upper layer film composition has been proposed that selectively allows only EUV or electron beams to pass through and blocks outgassing from the resist (for example, Patent Documents 1 to 3). These compositions are applied before exposure and do not disclose increasing the film thickness of the resist.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: WO 2016 / 013598

[0008] Patent Document 2: WO 2014 / 115843

[0009] Patent Document 3: WO 2015 / 129486 Summary of the invention

[0010] Technical Problems to be Solved by the Invention

[0011] The present inventors have found that there are one or more problems that need to be improved regarding the method for producing a resist pattern. For example, the following can be cited: making a fine resist pattern thicker; obtaining a fine resist pattern that can be used as an etching mask; obtaining sufficient resolution even when using an exposure machine with an increased numerical aperture; obtaining a fine pattern with a good shape; obtaining a resist pattern with a high aspect ratio; expanding the process window; being able to develop and pattern the upper film itself; the thickness of the resist film is hardly reduced even if a resist upper film composition is applied; being able to form a resist upper film on the resist film; being able to apply the resist upper film composition to the resist film after exposure; being able to apply the resist upper film composition to the resist film before development; being able to receive acid from the resist film; being able to change the solubility of the resist upper film by using the acid received from the resist film; being able to contain almost no components that produce strong acids; being able to generate an acid with a long diffusion distance by ion exchange with the acid received from the resist film; and improving the manufacturing yield.

[0012] The present inventors considered and studied as follows.

[0013] DOF (Depth of Focus) refers to the range of focal depth within which a resist pattern can be formed with a size within a predetermined range relative to a target size when exposure is performed by moving the focus up and down at the same exposure amount.

[0014] DOF is expressed by the following formula.

[0015] k2×λ / NA 2

[0016] Wherein, k2 represents a constant, λ represents the exposure wavelength, and NA represents the numerical aperture.

[0017] It is preferred that the larger the DOF, the wider the process window becomes. However, in high-precision lithography technology such as IC, the NA of the exposure device tends to increase in the future, and the DOF is expected to become narrower and narrower.

[0018] In EUV exposure, which is highly anticipated as a high-definition technology, the formation of fine patterns with thin films is continuously being achieved. The inventors of the present invention believe that when a high-definition pattern is used as a mask in a subsequent process, it is preferable to thicken the resist pattern in order to have better durability. If the resist pattern is thin, it cannot achieve the durability as a mask when used as an etching mask, and the masked object may also be etched in the final stage of the etching process.

[0019] If the resist film is thicker, the process window tends to be narrower. For example, if the focus is offset due to a slight change in the thickness of the substrate, the shape of the resist pattern formed may change and deviate from the rectangle, and pattern collapse may occur easily. For another example, if the exposure dose (Dose) changes, the line width will also change, and pattern bridging or pattern collapse may occur easily. In high-precision technology that requires high resolution, it is easy to use thinner resist films.

[0020] The present invention has been accomplished based on the above technical background, and provides a developable resist upper layer film composition capable of achieving thickening of a resist pattern, and a method for producing a resist upper layer film pattern and a resist pattern.

[0021] Means used to solve problems

[0022] The developable resist top layer film composition of the present invention comprises a hydrocarbon compound (A) and a solvent (B),

[0023] The hydrocarbon compound (A) is a compound represented by the formula (0), or a polymer containing a structure derived from the compound represented by the formula (0) as a repeating unit; and

[0024] The solvent (B) is a composition containing a solvent (B1) represented by the formula (b1).

[0025]

[0026] in,

[0027] X is C 1-60 Hydrocarbon;

[0028] n 01 is a number from 1 to 10, n 02 A number from 0 to 10;

[0029] Y is a group represented by formula (1) or -OH, provided that 40 to 100% of the total number of Y are groups represented by formula (1);

[0030] R 02 It is C 1-6 Alkoxy (but excluding tert-butyloxy), -(C=O)-R 03 、-(C=O)-OR 04 、-(C=O)-N(R 05 )2. -O-(C=O)-R 06 , or -NR 07 -(C=O)-R 08 ;

[0031] R 03 Is H or C1-4 alkyl;

[0032] R 04 It is C 1-4 Alkyl (but excluding tert-butyl);

[0033] R 05 Each independently is H or C 1-4 Alkyl, 2 R 05 Can bond to form a ring structure;

[0034] R 06 It is H, C 1-4 Alkyl, or C 1-4 Alkoxy (but excluding tert-butoxy);

[0035] R 07 Is H or C 1-4 alkyl;

[0036] R 08 It is H, C 1-4 Alkyl, or -N(R 09 )2;

[0037] R 07 With R 08 When alkyl, they may be bonded together to form a ring structure; and

[0038] R 09 Each independently is H or C 1-4 Alkyl, 2 R 09 can be bonded together to form a ring structure,

[0039]

[0040] in,

[0041] n 11 、n 12 、n 13 and n 14 Each independently a number from 0 to 1;

[0042] L 12 Selected from the group consisting of -C(=O)-, -CH2-C(=O)-, -C(=O)-CH2- and -CH(CH3)-;

[0043] L 14 It is C 1-5 an alkylene group; and

[0044] R 15 It is C 1-15 Alkyl or C 2-7 alkenyl;

[0045] L 12The methyl group and R 15 The methyl groups possessed may bond to form a ring,

[0046] R 21 -OR 22 (b1)

[0047] in,

[0048] R 21 and R 22 Each independently is C 1-8 alkyl.

[0049] The method for manufacturing a resist upper film pattern and a resist pattern of the present invention comprises the following steps:

[0050] (1) applying a resist composition onto a substrate and heating the resist composition to form a resist film;

[0051] (2) Optionally, exposing the resist film to light;

[0052] (3) applying a developable resist upper layer film composition directly onto the resist film, and heating the resist upper layer film composition to form a resist upper layer film;

[0053] (4) Optionally, exposing the resist film and the resist upper film;

[0054] The condition is that at least one of the exposures (2) and (4) must be performed;

[0055] (5) causing the acid in the resist film to move to the resist upper layer film; and

[0056] (6) The resist upper layer film and the resist film are developed using a developer to form a resist upper layer pattern and a resist pattern.

[0057] A method for manufacturing a device of the present invention includes the above method.

[0058] Effects of the Invention

[0059] According to the present invention, one or more of the following effects can be expected.

[0060] The invention discloses a method for making a fine resist pattern thicker; obtaining a fine resist pattern that can be used as an etching mask; obtaining sufficient resolution even when using an exposure machine with an increased numerical aperture; obtaining a fine pattern with a good shape; obtaining a resist pattern with a high aspect ratio; expanding the process window; being able to develop and pattern the upper film itself; hardly reducing the thickness of the resist film even when a resist upper film composition is applied; being able to form a resist upper film on the resist film; being able to apply the resist upper film composition to the resist film after exposure; being able to apply the resist upper film composition to the resist film before development; being able to accept acid from the resist film; being able to change the solubility of the resist upper film by using the acid accepted from the resist film; being able to contain almost no components that generate strong acid; being able to generate an acid with a long diffusion distance by exchanging with acid ions accepted from the resist film; and improving the manufacturing yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 A schematic diagram showing one form of a method for manufacturing a resist upper layer film pattern and a resist pattern. DETAILED DESCRIPTION

[0062] [definition]

[0063] In this specification, unless otherwise specified or mentioned, the definitions or examples described in this paragraph shall apply.

[0064] The singular form includes the plural form, and “a” or “an” or “the” means “at least one.” An element of a certain concept can be expressed in plural species, and when the amount (for example, mass % or mol %) is described, the amount means the sum of these plural species.

[0065] "And / or" includes all combinations of elements and also includes the use of individual elements.

[0066] When "to" or "-" is used to express a numerical range, both endpoints are included and the unit is common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0067] “C x-y ”, “C x ~C y ” and “C x " refers to the number of carbon atoms in a molecule or a substituent. For example, C 1-6 The alkyl group means an alkyl chain having 1 or more and 6 or less carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0068] In the case where the polymer has multiple repeating units, these repeating units are copolymerized. These copolymerizations are any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, n or m outside the brackets indicates the number of repetitions.

[0069] The unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0070] The additive refers to the compound itself having the function (for example, if it is a base generator, it is the compound itself that generates the base). The compound can be dissolved or dispersed in a solvent and then added to the composition. As one aspect of the present invention, such a solvent is preferably included in the composition of the present invention as a solvent (B) or other components.

[0071] Embodiments of the present invention will be described in detail below.

[0072] [Developable resist upper layer film composition]

[0073] The developable resist top layer film composition of the present invention (hereinafter sometimes referred to as the composition) comprises a hydrocarbon compound (A) and a solvent (B), wherein the hydrocarbon compound (A) is a compound represented by formula (0) or a polymer containing a structure derived from a compound represented by formula (0) as a repeating unit, and the solvent (B) comprises a solvent (B1) represented by formula (b1).

[0074] The composition of the present invention is a composition for forming a film on a resist film (preferably a composition for forming a film on a resist film after exposure; more preferably a composition for forming a film on a resist film after EUV exposure). In a preferred embodiment, the resist film is a positive EUV resist film formed by a positive EUV resist composition.

[0075] The resist upper film formed on the resist film using the composition of the present invention can be developed using a developer. A pattern (resist upper film pattern) derived from the composition of the present invention is formed on the developed resist pattern. In this way, by applying the composition of the present invention, the resist pattern is thickened.

[0076] The composition of the present invention is not applied between the resist patterns after development. However, the "development" after development mentioned here does not include the development when the removed resist layer is patterned. For example, in the case of a design in which multiple resist patternings are performed continuously, after the resist is developed in the previous process, the composition of the present invention can be used in the subsequent process to make the resist layer thicker.

[0077] (A) Hydrocarbon compounds

[0078] The composition of the present invention contains a hydrocarbon compound (A) (hereinafter sometimes referred to as component (A). The same applies to other components).

[0079] The hydrocarbon compound (A) is a compound represented by formula (0), or a polymer containing a structure derived from the compound represented by formula (0) as a repeating unit. It is also a preferred embodiment of the present invention that the hydrocarbon compound (A) contains both a compound represented by formula (0) and a polymer containing a structure derived from the compound represented by formula (0) as a repeating unit.

[0080] Formula (0) is as follows:

[0081]

[0082] in,

[0083] X is C 1-60 X is preferably a hydrocarbon group. 5-10 Aryl with straight or branched chain C 1-6 A group consisting of a combination of alkyl groups, 5-10 Aryl and cyclic C 5-6 A group consisting of a combination of alkyl groups, a group consisting of a cyclic C 5-10 Alkyl groups, straight or branched C 1-6 Alkyl and cyclic C 5-6 A group consisting of a combination of alkyl groups, or a group consisting of a straight chain or branched C 1-6 A group composed of an alkyl group (more preferably a group composed of a phenyl group and a branched C 1-6 A group consisting of a combination of alkyl groups, a group consisting of a combination of phenyl and cyclohexyl groups, a group consisting of a cyclic C 5-6 A group consisting of an alkyl group, a group consisting of a combination of a methyl group and a cyclohexyl group, a group consisting of a combination of a methyl group and a cyclopentyl group, or a group consisting of a straight-chain C 1-6 A group composed of an alkyl group; more preferably a group composed of a phenyl group and a branched C 2-3 A group consisting of a combination of alkyl groups, a cyclohexyl group, or a straight chain C 3-5 If explicitly stated, by making the C 1-60 The H in the hydrocarbon group is replaced so as to bond to Y. 02 The same is true.

[0084] The elements constituting X can be interpreted as a linker according to the number of other groups bonded. This is described in detail below. The following compound can be interpreted as formula (0). X is composed of 3 phenyl groups and a C2 alkyl group. The C2 alkyl group is interpreted as a linker that bonds to the 3 phenyl groups. 02 is 0. 01100% of the total number of Ys are groups represented by formula (1), and there is no Y that is -OH. 11 and n 12 is 1, n 13 and n 14 =0, L 12 is -CH2-C(=O)-, R 15 It is tert-butyl.

[0085]

[0086] n 01 It is a number of 1 to 10 (preferably a number of 1 to 5; more preferably a number of 1 to 3; further preferably 1, 2 or 3).

[0087] n 02 It is a number from 0 to 10 (preferably a number from 0 to 3; more preferably a number from 0 to 1; further preferably 0 or 1; further preferably 0).

[0088] Y is a group represented by formula (1) or -OH, but 40 to 100% of the total number of Y are groups represented by formula (1) (preferably 45 to 100%; more preferably 75 to 100%; and even more preferably 100%). The "total number of Y" is preferably calculated by molar ratio.

[0089] R 02 C 1-6 Alkoxy (but excluding tert-butyloxy), -(C=O)-R 03 、-(C=O)-OR 04 、-(C=O)-N(R 05 )2. -O-(C=O)-R 06 , or -NR 07 -(C=O)-R 08 Without being bound by theory, R is defined as a modification that does not hinder the reaction of the group represented by formula (1). 02 The above groups are more preferred than strong acid functional groups such as carboxylic acid and sulfonic acid or basic functional groups. 02 Preferably C 1-6 An alkoxy group (more preferably a methoxy group).

[0090] R 03 H or C 1-4 Alkyl (preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl or tert-butyl; more preferably H, methyl, n-propyl or n-butyl; further preferably H or methyl).

[0091] R 04 C 1-4 Alkyl (but excluding tert-butyl).04 Preferred is H, methyl, ethyl, isopropyl, n-propyl, or n-butyl (more preferred is H, methyl, n-propyl, or n-butyl; further preferred is H or methyl).

[0092] R 05 Each independently is H or C 1-4 Alkyl, 2 R 05 Can bond to form a ring structure. 05 Each independently is preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl or tert-butyl (more preferably H, methyl, n-propyl or n-butyl; further preferably H or methyl).

[0093] The following compound can be interpreted as formula (0). X is composed of 3 phenyl groups and a C2 alkyl group. 01 100% of the total number of Y is the group represented by formula (1). In one group of formula (1), n 11 and n 12 is 1, n 13 and n 14 =0, L 12 is -CH2-C(=O)-, R 15 In other groups of formula (1), n 11 、n 12 、n 13 and n 14 is 0, R 15 is vinyl (C2 alkenyl). 02 is 1. 02 -(C=O)-N(R 05 )2. R 05 It is a C2 alkyl group and a C3 alkyl group, forming a ring structure.

[0094]

[0095] R 06 H, C 1-4 Alkyl, or C 1-4 Alkoxy (but excluding tert-butoxy) (preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, or methoxy; more preferably H, methyl, n-propyl, n-butyl, or methoxy).

[0096] R 07 H or C 1-4 Alkyl (preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl, or tert-butyl; more preferably H, methyl, n-propyl, or n-butyl).

[0097] R 08 H, C 1-4 Alkyl, or -N(R09 )2,R 07 With R 08 When alkyl, these may be bonded together to form a ring structure; and

[0098] R 09 Each independently is H or C 1-4 Alkyl, 2 R 09 Can bond together to form a ring structure.

[0099] R 08 Preferably H, methyl, tert-butyl or -N(R 09 )2.

[0100] R 09 Preferred is H, methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, or methoxy (more preferably H, methyl, n-propyl, n-butyl, or methoxy).

[0101] Formula (1) is as follows:

[0102]

[0103] in,

[0104] n 11 、n 12 、n 13 and n 14 Each independently represents a number from 0 to 1 (preferably 0 or 1; more preferably 0). 11 、n 12 、n 13 or 14 Each independently is 1.

[0105] L 12 Selected from the group consisting of -C(=O)-, -CH2-C(=O)-, -C(=O)-CH2- and -CH(CH3)-. 12 More preferably, it is selected from the group consisting of -C(=O)-, -CH2-C(=O)- and -CH(CH3)- (further preferably, -C(=O) or -CH2-C(=O)-; further preferably, -CH2-C(=O)-).

[0106] L 14 C 1-5 Alkylene (preferably C 1-4 Alkylene; more preferably methylene, ethylene or n-butylene; further preferably methylene or n-butylene; further preferably methylene).

[0107] R 15 C 1-15 Alkyl or C 2-7Alkenyl (more preferably ethyl, n-propyl, tert-butyl, ethyl-cyclopentyl, ethyl-cyclohexyl, or ethyl-adamantyl; further preferably ethyl, tert-butyl or vinyl; further preferably tert-butyl or vinyl). 1-15 The alkyl group may or may not include (more preferably does not include) a cycloalkyl group.

[0108] L 12 The methyl group and R 15 The methyl groups may be bonded to form a ring. A ring may or may not be formed. In the case of forming a ring, L 12 is -CH(CH3)-, R 15 C 1-15 The alkyl group and the terminal methyl group can be used for bonding. The formed ring is preferably a saturated hydrocarbon ring.

[0109] When the hydrocarbon compound (A) is a polymer containing a structure derived from a compound represented by formula (0) as a repeating unit, the structures derived from the compound represented by formula (0) may be the same or different, and are more preferably the same. The hydrocarbon compound (A) may be a mixture of a plurality of compounds represented by formula (0).

[0110] As formula (1), for example, the following structure can be mentioned:

[0111]

[0112] The following compound can be interpreted as formula (0). The following compound has 3 Ys, 2 / 3 (about 67%) of which are groups represented by formula (1). The groups represented by formula (1) are the same. 11 =n 12 =1,n 13 =n 14 =0,L 12 is -CH(CH3)-, R 15 Can be interpreted as C3 alkyl (n-propyl). 12 The methyl group and R 15 The methyl groups are bonded to form a ring.

[0113]

[0114] One of the characteristics is that component (A) has a group represented by formula (1). Although not bound by theory, the group represented by formula (1) or the bonding site using it is deprotected or cross-linked by receiving an acid. If the number of groups represented by formula (1) in the total number of Y is taken as the protection rate, the protection rate is preferably 40 to 100% (more preferably 45 to 100%; further preferably 75 to 100%; further preferably 100%). Although not bound by theory, when the acid in the resist film moves to the upper layer of the resist, the solubility of the portion in the developer changes due to the above-mentioned deprotection or cross-linking, while the solubility in the developer does not change in the portion to which the acid does not move (in the case of a positive resist film, directly above the unexposed portion). It is believed that the pattern of the upper layer is formed thereby.

[0115] As one embodiment of the present invention, R in formula (1) 15 C 1-15 Although not bound by theory, when the acid moves from the resist film to the resist upper layer film, R 15 By accepting acid and deprotecting, the acid accepting part can be soluble in the developer. 15 In the case of a tert-butyl group, there is a mode in which the group is deprotected by accepting an acid and converted into a carboxylic acid group.

[0116] Preferred examples suitable for this embodiment include the following, each independently.

[0117] X is C 5-10 Aryl with straight or branched chain C 1-6 A group consisting of a combination of alkyl groups, or a group consisting of C 5-10 Aryl and cyclic C 1-6 A group consisting of a combination of alkyl groups (more preferably a group consisting of a phenyl group and a branched C 1-6 A group composed of a combination of alkyl groups; more preferably a group composed of a phenyl group and a branched C 2-3 X is preferably represented by the formula (X-1).

[0118] n 01 It is a number of 1 to 3 (more preferably 1, 2 or 3; further preferably 2 or 3; further preferably 3).

[0119] n 11 =n 12 =1.

[0120] n 13 =n 14 =0.

[0121] L 12Selected from the group consisting of -C(=O)-, -CH2-C(=O)- and -CH(CH3)- (more preferably -CH2-C(=O)- and -CH(CH3)-; further preferably -CH2-C(=O)-).

[0122] R 15 C 1-15 Alkyl (more preferably ethyl, n-propyl, tert-butyl, ethyl-cyclopentyl, ethyl-cyclohexyl, or ethyl-adamantyl; further preferably tert-butyl, ethyl-cyclopentyl, ethyl-cyclohexyl, or ethyl-adamantyl; further preferably tert-butyl).

[0123] R 21 and R 24 C is a straight chain or branched chain 2-4 aliphatic hydrocarbon group (more preferably a linear or branched C2, C3 or C4 aliphatic hydrocarbon group; further preferably a branched C2, C3 or C4 aliphatic hydrocarbon group; further preferably an ethynyl group).

[0124] n 22 It is 0, 1, 2 or 3 (more preferably 0, 2 or 3; further preferably 2 or 3; further preferably 3).

[0125] The component (A) is a compound represented by the formula (0).

[0126] The content of the component (C) described below is more preferably 0 to 100% by mass (more preferably 0 to 10% by mass; still more preferably 0 to 1% by mass) based on the hydrocarbon compound (A). It is also preferred that the component (C) is not contained (0.000% by mass).

[0127] The compound represented by formula (0) has at least one Y and has X as a main skeleton. X of the main skeleton is C 1-60 The hydrocarbon group is composed of a linear or branched aliphatic hydrocarbon group, a cyclic hydrocarbon group, or a combination thereof, which is one embodiment of the present invention.

[0128] X is preferably represented by formula (X-1) or formula (X-2).

[0129] Formula (X-1) is as follows:

[0130]

[0131] in,

[0132] R 21 and R 24 Each independently is a linear or branched C 1-10 Aliphatic hydrocarbon group (preferably a straight chain or branched C 1-4 Aliphatic hydrocarbon group; more preferably a straight chain or branched C2-4 aliphatic hydrocarbon group; more preferably a straight-chain or branched C2, C3 or C4 aliphatic hydrocarbon group). The main skeleton represented by formula (X-1) is preferably R 21 When the main skeleton represented by formula (X-1) has branches as a structure, the branch point is R 21 Here, the aliphatic hydrocarbon group also includes cases other than monovalent. For example, in n 22 When R is 2, 21 The price is 2.

[0133] n 22 is a number from 0 to 5 (preferably a number from 0 to 3; more preferably 0, 1, 2 or 3; further preferably 0, 2 or 3; further preferably 0 or 3). 22 When n is greater than 2, 22 The groups in the brackets may be the same or different. 23 、n 24 and n 25 The average value is used. 22 When n is 1 or more, it is preferred that n 23 、n 24 and n 25 At least one of is greater than 0. Preferably, the group represented by formula (1) and Cy 23 or Cy 25 In a para-bonded manner.

[0134] Cy 23 and Cy 25 Each independently has C 5-10 cycloalkyl group having a ring atom of 4-(4-phenyl)-2-nitrogen (preferably cyclopentyl, cyclohexyl, phenyl, or naphthyl; more preferably cyclohexyl or phenyl; further preferably phenyl).

[0135] n 23 Each independently represents a number from 0 to 1 (preferably 0 or 1).

[0136] n 24 and n 25 Each independently represents a number from 0 to 3 (preferably a number from 0 to 1; more preferably 0 or 1). 24 When it is 2 or 3, 2 R 24 Respectively with Cy 23 Bonding, not R 24 In-line and with Cy 23 Bonding. For n 25 The same is true.

[0137] The compound on the left is C 1-60The hydrocarbon group can be interpreted as X in the formula (0), and can be interpreted as a lower concept (meso concept) of the formula (X-1). In the formula (X-1), R 21 is a C2 aliphatic hydrocarbon group, n 22 is 3, with R 21 Centered by n 22 There are 3 groups in the brackets. 2 of them are n 22 In the groups in brackets, n 23 =1, n 24 =n 25 =0, Cy 23 is phenyl. 22 In the groups in brackets, n 23 =n 24 =n 25 =1, Cy 23 and Cy 25 Phenyl, R 24 is a C3 aliphatic hydrocarbon group. 23 =1, n 24 =n 25 =1 / 3.

[0138] The compound on the right side below can be interpreted as the compound on the left side below having three Ys. Two Ys are groups represented by formula (1), and one Y is -OH.

[0139]

[0140] The compound on the left is C 1-60 The hydrocarbon group can be interpreted as X in the formula (0), and can be interpreted as a lower concept (meso concept) of the formula (X-1). 21 is a straight-chain C4 aliphatic hydrocarbon group (n-butyl), n 22 = 0. For the compound on the right side below, the main skeleton represented by formula (X-1) has two Ys. The two Ys are represented by formula (1) and are the same group. 11 =n 12 =n 13 =n 14 =0, R 15 It is vinyl. Since two Ys replace R 21 The H of the 21 Can be interpreted as n-butylene.

[0141]

[0142] Examples of the structure represented by formula (X-1) include the following:

[0143]

[0144] Formula (X-2) is as follows.

[0145]

[0146] in,

[0147] Cy 31 and Cy 34 Each independently has C 5-10 The main skeleton represented by formula (X-2) is preferably Cyclopentyl, cyclohexyl, phenyl, or naphthyl; more preferably cyclohexyl or phenyl; further preferably phenyl. 31 When the main skeleton represented by formula (X-2) has a branched structure, the branch point is Cy 31 It is the preferred method.

[0148] n 32 is a number from 0 to 5 (preferably a number from 0 to 3; more preferably 0, 1, 2 or 3; further preferably 0, 1 or 2; further preferably 0 or 2). 32 When n is greater than 2, 32 The groups in the brackets may be the same or different. 33 、n 34 and n 35 Use average value.

[0149] In n 32 When n is 1 or more, it is preferred that n 33 、n 34 and n 35 At least one of them is greater than 0. Preferably, the group represented by formula (1) and Cy 31 or Cy 34 In a para-bonded manner.

[0150] R 33 Each independently is a linear or branched C 1-10 Alkyl (preferably linear or branched C 1-4 alkyl; more preferably methyl, ethyl, isopropyl, or n-propyl; further preferably methyl or ethyl; further preferably ethyl).

[0151] R 35 Each independently is a linear or branched C 1-10 Alkyl (preferably linear or branched C 1-4 alkyl; more preferably methyl, ethyl, isopropyl, or n-propyl; further preferably methyl or ethyl; further preferably methyl).

[0152] n33 Each independently represents a number from 0 to 1 (preferably 0 or 1).

[0153] n 34 and n 35 Each independently represents a number from 0 to 3 (preferably a number from 0 to 1; more preferably 0 or 1). 34 When it is 2 or 3, 2 Cy 34 R 33 Bonding, not Cy 34 In-line and with R 33 Bonding. For n 35 The same is true.

[0154] The compound on the left is C 1-60 The hydrocarbon group can be interpreted as X in the formula (0), and can be interpreted as a lower concept (meso concept) of the formula (X-2). 31 is cyclohexyl, n 32 =2,n 32 The groups in the brackets are identical. 33 =1,n 34 =n 35 =0, R 33 For the compound on the right below, the main skeleton represented by formula (X-2) has two Ys, and both Ys are groups represented by formula (1) and are the same group. 11 =n 12 =n 13 =n 14 =0, R 15 For vinyl. Y and R 33 The methyl bond, R 33 Become a methylene linking group.

[0155]

[0156] The compound on the left is C 1-60 The hydrocarbon group can be interpreted as X in the formula (0), and can be interpreted as a lower concept (meso concept) of the formula (X-2). 31 is cyclohexyl, n 32 = 0. For the compound on the right side below, the main skeleton represented by formula (X-2) has three Ys, and all three Ys are groups represented by formula (1) and are the same group. 11 =0,n 12 =n 13 =n 14 =1. 12 is -C(=O)-, L 14 is a C4 alkylene group. 15For vinyl.

[0157]

[0158] Examples of the structure represented by formula (X-2) include the following.

[0159]

[0160] In a preferred embodiment of the present invention, the component (A) is a compound represented by the formula (0).

[0161] In a preferred embodiment of the present invention, the component (A) is a polymer (hereinafter sometimes referred to as polymer (A)) containing a structure derived from a compound represented by formula (0) (hereinafter sometimes referred to as formula (0) structure) as a repeating unit.

[0162] The polymer (A) may be a copolymer containing repeating units other than the structure of formula (0) within the scope of the present invention. Examples of repeating units other than the structure of formula (0) include structures derived from compounds represented by formula (c) described below.

[0163] Specific examples of the polymer (A) include polymers having the following structures:

[0164]

[0165] The above polymer can be obtained by polymerizing the following left-hand compound (represented by formula (0)) and the following right-hand compound (represented by formula (c)) at a molar ratio of 2:1.

[0166]

[0167] When the polymer (A) is a copolymer, it is preferably an alternating copolymer, a random copolymer, a block copolymer, a graft copolymer, or any mixture thereof (more preferably an alternating copolymer, a random copolymer, or a block copolymer; more preferably a random copolymer or a block copolymer; and even more preferably a random copolymer).

[0168] The molecular weight of the component (A) is preferably 100 to 80,000. When the component (A) is a polymer, the molecular weight means a mass average molecular weight (Mw), and refers to a polystyrene-equivalent mass average molecular weight measured using gel permeation chromatography.

[0169] When the component (A) is a compound represented by formula (0), the molecular weight is more preferably 100 to 1,000 (more preferably 100 to 900; more preferably 120 to 800). When the component (A) is a polymer, the molecular weight (Mw) is more preferably 5,000 to 60,000 (more preferably 10,000 to 50,000; more preferably 20,000 to 40,000).

[0170] As one embodiment of the present invention, R in formula (1) 15 C 2-7 Although not bound by theory, through R 15 The cross-linked bonded sites are de-crosslinked by accepting the acid that moves from the resist film to the resist upper layer film, making the acid-accepting sites soluble in the developer. 15 In the case of a vinyl group, the cross-linked bonded site can be decrosslinked by accepting an acid.

[0171] Preferred examples suitable for this aspect include the following, each independently being able to be listed.

[0172] X is preferably a cyclic C 5-10 The group composed of alkyl groups, straight-chain C 1-6 The group composed of alkyl groups, branched C 3-6 alkyl, or a group consisting of any combination thereof (more preferably a group consisting of a cyclic C 5-10 The group composed of alkyl groups, straight-chain C 1-6 alkyl, or a group composed of any combination thereof; more preferably a group composed of a cyclic C 5-6 A group composed of an alkyl group or a group composed of a straight chain C 1-6 Preferably, X is represented by the formula (X-1). As another embodiment, X is preferably represented by the formula (X-2).

[0173] n 01 It is a number of 1 to 3 (more preferably 1, 2 or 3; further preferably 2 or 3; further preferably 2).

[0174] n 11 is 0 or 1 (more preferably 0).

[0175] n 12 is 0 or 1 (more preferably 0).

[0176] L 12 Selected from -C(=O)- or -C(=O)-CH2- (more preferably -C(=O)-).

[0177] n 13 is 0 or 1 (more preferably 0).

[0178] n 14 is 0 or 1 (more preferably 0).

[0179] L 14 It is a methylene group, an ethylene group or an n-butylene group (more preferably a methylene group or an n-butylene group; further preferably an n-butylene group).

[0180] R 15 C 2-7 An alkenyl group (more preferably a vinyl group).

[0181] R 21 and R 24 Each independently is a linear or branched C 1-4 An aliphatic hydrocarbon group (more preferably a linear or branched C2, C3 or C4 aliphatic hydrocarbon group; further preferably an n-butyl group).

[0182] n 22 It is 0, 1, 2 or 3 (more preferably 0, 2 or 3; further preferably 0 or 3; further preferably 0).

[0183] Cy 23 and Cy 25 Each is independently a cyclohexyl group or a phenyl group (more preferably a cyclohexyl group).

[0184] n 23 is 0 or 1 (more preferably 0).

[0185] n 24 and n 25 Each is independently 0 or 1 (more preferably 0).

[0186] A more preferred embodiment is that the composition of the present invention comprises the component (C) described below, or is a copolymer in which the polymer (A) further comprises a structure derived from a compound represented by formula (c). The term "comprising the component (C)" as used herein means that the content of the component (C) is preferably 50 to 200% by mass based on the component (A).

[0187] The content of the component (A) is preferably 0.01 to 15% by mass (more preferably 0.05 to 10% by mass; further preferably 0.10 to 5% by mass; and further preferably 0.10 to 4% by mass) based on the composition of the present invention.

[0188] As described above, polymer (A) may be a copolymer containing repeating units other than the structure of formula (0) within the scope of the present invention. It is a preferred embodiment of the present invention that the repeating unit other than the structure of formula (0) is a structure derived from a compound represented by formula (c) as a repeating unit to constitute polymer (A). A more preferred example of a structure derived from a compound represented by formula (c) is the compound represented by formula (c) itself. The molecular weight or content in this case is not described with respect to component (C) but with respect to polymer (A). The details are as described above.

[0189] When the polymer (A) is a copolymer, it is preferred that (the number of repeating units of the structure of formula (0)) / {the number of repeating units other than the structure of formula (0)} is 25 to 400% (more preferably 50 to 300%; further preferably 150 to 250%). The ratio of the number of repeating units is preferably determined as a molar ratio. When the polymer (A) is a copolymer, the molar ratio of the hydroxyl group possessed by the structure of the compound represented by formula (c) to the group represented by formula (1) possessed by the structure of formula (0) is preferably 2:1 to 1:2 (more preferably 3:2 to 2:3; further preferably 4:3 to 3:4).

[0190] (B) Solvent

[0191] The composition of the present invention contains a solvent (B).

[0192] The solvent (B) contains a solvent (B1) represented by the formula (b1).

[0193] R 21 -OR 22 (b1)

[0194] in,

[0195] R 21 and R 22 Each independently is C 1-8 Alkyl (preferably C 3-6 They may be straight chain, branched chain or cyclic (preferably straight chain or cyclic; more preferably straight chain).

[0196] R 21 and R 22 They may be different or the same, and are preferably the same.

[0197] R 21 and R 22 Each independently preferably is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, or cyclohexyl (more preferably methyl, n-butyl, n-pentyl, isopropyl, cyclopentyl, or cyclohexyl; further preferably n-butyl).

[0198] Examples of the solvent (B1) include dibutyl ether, diamyl ether, diisoamyl ether, dicyclopentyl ether, dicyclohexyl ether, and cyclopentyl methyl ether.

[0199] As one embodiment of the present invention, the solvent (B) preferably consists essentially of the solvent (B1) only (more preferably consists of the solvent (B1) only).

[0200] The solvent (B) preferably contains a solvent (B2) different from the solvent (B1) (more preferably, it consists essentially of only the solvent (B1) and the solvent (B2); further preferably, it consists of only the solvent (B1) and the solvent (B2)).

[0201] Preferred solvent (B2) is cyclohexanone, cyclopentanone, propylene glycol monomethyl ether (PGME), 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 (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, 2-propanol (IPA) or any combination thereof. Solvent (B2) is preferably PGME, PGMEA, or a combination thereof. When there are two kinds of solvents contained in solvent (B2), their mass ratio is preferably 100:1 to 1:100 (more preferably 50:1 to 1:50; further preferably 30:1 to 1:30).

[0202] The solvent (B2) may contain water. The water content is preferably 5% by mass or less (more preferably 1% by mass or less; further preferably 0.001% by mass or less) based on the solvent (B). It is also a preferred embodiment of the present invention that the solvent (B2) does not contain water (0.000% by mass).

[0203] Although not being bound by theory, the solvent (B) in the composition of the present invention is believed to contribute to the formation of a thick film pattern by dissolving solid components (components other than the solvent (B)) while avoiding dissolving the underlying resist film.

[0204] The content of the solvent (B) is preferably 70 to 99.99% by mass (more preferably 80 to 99.99% by mass; further preferably 95 to 99.99% by mass; and further preferably 95 to 99.90% by mass) based on the composition of the present invention.

[0205] The content of the solvent (B1) is preferably 70 to 100% by mass (more preferably 80 to 100% by mass; further preferably 90 to 100% by mass) based on the solvent (B).

[0206] The content of the solvent (B2) is preferably 0 to 30% by mass (more preferably 0 to 20% by mass; further preferably 0.1 to 10% by mass) based on the solvent (B).

[0207] (C) Hydroxyl-containing compounds

[0208] The composition of the present invention may further contain (C) a hydroxyl group-containing compound represented by formula (c).

[0209] Formula (c) is as follows:

[0210]

[0211] R 42 C 1-6 Alkoxy (preferably excluding tert-butoxy), -(C=O)-R 03 、-(C=O)-OR 04 、-(C=O)-N(R 05 )2. -O-(C=O)-R 06 , or -NR 07 -(C=O)-R 08 . R 42 Preferably C 1-6 An alkoxy group (more preferably a methoxy group).

[0212] n 41 It is a number of 1 to 10 (preferably a number of 1 to 5; more preferably a number of 1 to 3; further preferably 1, 2 or 3).

[0213] n 42 It is a number from 0 to 10 (preferably a number from 0 to 3; more preferably a number from 0 to 1; further preferably 0 or 1; further preferably 0).

[0214] Among them, X, R 03 , R 04 , R 05 , R 06 , R 07 and R 08 Unless otherwise specified, the definitions and preferred examples of the groups having the same symbols as those in formula (0) are independently the same.

[0215] When X of the component (C) is represented by the formula (X-2), Cy of the component (C) 31 and Cy 34 Preferably, phenyl is present. If specified, X and R in component (A) 03 , R 04 , R 05 , R 06 , R 07 and R 08, and these symbols in component (C) can each independently select different groups. For example, Cy in component (A) 31 and Cy 34 , and Cy in component (C) 31 and Cy 34 can be selected independently. For example, Cy in component (A) 31 is a cyclohexyl group, Cy in the component (C) 31 and Cy 34 It is one embodiment of the present invention that the group is phenyl.

[0216] The (C) hydroxyl group-containing compound (component (C)) represented by formula (c) has at least one OH group and has X as a main skeleton. X as a main skeleton is C 1-60 It is a preferred embodiment of the present invention that the hydrocarbon group is constituted by an aliphatic hydrocarbon group, a cyclic hydrocarbon group or a combination thereof.

[0217] X in the component (C) is preferably represented by the formula (X-1) or the formula (X-2) (more preferably (X-2)).

[0218] As the component (C), for example, the following compounds can be mentioned:

[0219]

[0220] The molecular weight of the component (C) is preferably 200 to 800 (more preferably 200 to 600; further preferably 200 to 450).

[0221] The content of the component (C) is preferably 50 to 200 mass % (more preferably 60 to 150 mass %; further preferably 60 to 110 mass %) based on the hydrocarbon compound (A). It is also a preferred embodiment of the present invention that the component (C) is not contained (0.000 mass %).

[0222] In the composition of the present invention, the molar ratio of the hydroxyl group of component (C) to the group represented by formula (1) of component (A) is preferably 2:1 to 1:2 (more preferably 3:2 to 2:3; further preferably 4:3 to 3:4).

[0223] As one embodiment of the present invention, R in formula (1) 15 C 2-7 The composition of the present invention does not substantially contain the component (C). Although not being bound by theory, when a resist film has a hydroxyl group on the surface, R 15 The above-mentioned hydroxyl group is protected by bonding, and the bonding site is deprotected by accepting the acid that moves from the resist film to the resist upper layer film, so that the acid-accepting part can be soluble in the developer. 15In the case of vinyl groups, the bonding site (acetal structure) with the hydroxyl group can be deprotected by receiving an acid. The above-mentioned "acid that moves from the resist film to the resist upper film" is promoted to move by heating in step (3), which is a preferred embodiment of the present invention. As a preferred embodiment, a hydroxyl group exists on the surface of the resist film to which the composition of the present invention is applied.

[0224] As preferred examples suitable for this embodiment, the following can be mentioned independently.

[0225] X is preferably a cyclic C 5-10 The group composed of alkyl groups, straight-chain C 1-6 The group composed of alkyl groups, branched C 3-6 alkyl, or a group consisting of any combination thereof (more preferably a group consisting of a cyclic C 5-10 The group composed of alkyl groups, straight-chain C 1-6 alkyl, or a group composed of any combination thereof; more preferably a group composed of a cyclic C 5-6 A group composed of an alkyl group or a group composed of a straight chain C 1-6 Preferably, X is represented by the formula (X-2). As another embodiment, X is preferably represented by the formula (X-1).

[0226] n 01 It is a number of 1 to 3 (more preferably 1, 2 or 3; further preferably 1 or 2; further preferably 1).

[0227] n 11 is 0 or 1 (more preferably 0).

[0228] n 12 is 0 or 1 (more preferably 0).

[0229] L 12 Selected from -C(=O)- or -C(=O)-CH2- (more preferably -C(=O)-).

[0230] n 13 is 0 or 1 (more preferably 0).

[0231] n 14 is 0 or 1 (more preferably 0).

[0232] L 14 It is a methylene group, an ethylene group or an n-butylene group (more preferably a methylene group or an n-butylene group; further preferably an n-butylene group).

[0233] R 15 C 2-7 An alkenyl group (more preferably a vinyl group).

[0234] Cy31 and Cy 34 Each is independently a cyclohexyl group or a phenyl group (more preferably a cyclohexyl group).

[0235] n 32 It is 0, 1, 2 or 3 (more preferably 0, 1 or 2; further preferably 0 or 2; further preferably 0).

[0236] R 33 and R 35 Each is independently a methyl group, an ethyl group, an isopropyl group or an n-propyl group (more preferably a methyl group or an ethyl group; further preferably a methyl group).

[0237] n 33 is 0 or 1 (more preferably 1).

[0238] n 34 and n 35 Each independently is 0 or 1 (more preferably 0).

[0239] The composition of the present invention does not substantially contain component (C). Substantially free means that the content of component (C) is 0 to 5% by mass (more preferably 0.00 to 1% by mass; further preferably 0.00 to 0.1% by mass; further preferably 0.000% by mass) based on component (A). In the case where component (A) of the present invention is a polymer, the polymer does not contain a structure derived from a compound represented by formula (c). Component (A) of the composition of the present invention is not a polymer, but a compound represented by formula (0).

[0240] (D) Acid generator

[0241] The composition of the present invention can further comprise (D) an acid generator.

[0242] In a preferred embodiment, when the component (D) reacts with an acid, an acid having an acid dissociation constant pKa (H2O) of -14 to 8 (more preferably -14 to 4; further preferably -12 to 2; further preferably -10 to 1) is released.

[0243] It is more preferred that the resist film formed below the resist upper film contains PAG (D'), and PAG (D') releases an acid with an acid dissociation constant pKa (H2O) of -20 to 1.4 (preferably -16 to 1.4; more preferably -16 to 1.2; further preferably -16 to 1.1) upon exposure. Although not bound by theory, it is believed that the acid derived from the (D') component moves from the resist film to the resist upper film and undergoes salt exchange with the (D) component, thereby allowing the acid to diffuse over a longer distance on the resist upper film, thereby enabling the effect of the present invention to be more effectively exerted. The acid generated by the (D) component through salt exchange is a weak acid, and its acidity is lower than the strong acid generated by the (E) photoacid generator through light acceptance described later, and is one embodiment of the present invention.

[0244] A preferred embodiment of the acid generator (D) is a salt of an m-valent cation and an m-valent anion, wherein m is preferably 1 or 2 (more preferably 2).

[0245] The cation is preferably derived from a triarylsulfonium or diaryliodonium (more preferably a triarylsulfonium). The aryl group possessed by the above cation is preferably a phenyl group or a naphthyl group (more preferably a phenyl group). The above aryl group may be unsubstituted or substituted (more preferably unsubstituted). The number of substituents bonded to one substituted aryl group is preferably an integer of 1 to 5 (more preferably 1, 2 or 3; more preferably 1), and the substituent is preferably a halogen, a methyl group or a methoxy group (more preferably fluorine, a methyl group or a methoxy group; more preferably a methyl group).

[0246] The anion is preferably derived from a sulfonic acid or a carboxylic acid (more preferably a sulfonic acid). The sulfonic acid or the carboxylic acid has an alkyl group or an aryl group (more preferably an alkyl group). The alkyl group is preferably C 1-4 Alkyl (more preferably methyl). The H in the above alkyl may be unsubstituted or substituted (preferably substituted). All or part (more preferably all) of the H in a substituted alkyl is substituted with a substituent. The substituent is preferably halogen (more preferably fluorine). The above aryl is preferably C 6-10 Aryl (more preferably phenyl or naphthyl; more preferably phenyl). H in the above aryl may be unsubstituted or substituted (preferably substituted). The number of substituents bonded to one substituted aryl is preferably an integer of 1 to 5 (more preferably 1, 2 or 3; more preferably 1), and the substituent is preferably halogen, methyl or methoxy (more preferably fluorine, methyl or methoxy; more preferably methyl).

[0247] (D) As a component, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium methanesulfonate, triphenylsulfonium 4-methylbenzenesulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate etc. are mentioned, for example.

[0248] The composition of the present invention may or may not contain the component (D). The content of the component (D) is preferably 0.01 to 40% by mass (more preferably 0.10 to 20% by mass; and even more preferably 0.20 to 10% by mass) based on the component (A).

[0249] (E) Photogenerator

[0250] The composition of the present invention may further contain (E) a photo-induced strong acid generator, but preferably substantially no photo-induced strong acid generator, wherein the component (E) releases an acid having an acid dissociation constant pKa (H2O) of -20 to 1.4 (preferably -16 to 1.4; more preferably -16 to 1.2; and even more preferably -16 to 1.1) upon exposure.

[0251] Based on the component (A), the content of the component (E) is preferably 0 to 1.00 mass % (more preferably 0.00 to 0.005 mass %; further preferably 0.00 to 0.001 mass %). It is also a preferred embodiment of the present invention that the component (E) is not contained (0.000 mass %). Although not being bound by theory, it is believed that the upper film of the present invention can accept the acid transferred from the resist film below even if the component (E) that generates a strong acid is not contained.

[0252] (F) Surfactant

[0253] The composition of the present invention may further include a surfactant (F). The coating properties can be improved by including a surfactant (F). As surfactants that can be used in the present invention, there can be mentioned: (I) anionic surfactants, (II) cationic surfactants or (III) nonionic surfactants, more specifically, there can be mentioned: (I) alkyl sulfonates, alkylbenzene sulfonates, and alkylbenzene sulfonates, (II) lauryl pyridinium chloride and lauryl methyl ammonium chloride, and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, acetylene glycol polyoxyethylene ether, fluorinated surfactants (e.g. Fluorad (3M), MAGAFACE (DIC), Surflon (Asahi Glass), and organosiloxane surfactants (e.g. KF-53, KP341 (Shin-Etsu Chemical Industry)).

[0254] These surfactants can be used alone or in combination of two or more.

[0255] The content of the surfactant (F) is preferably 0 to 10% by mass (more preferably 0.001 to 10% by mass; further preferably 0.1 to 5% by mass) based on the hydrocarbon compound (A). Not containing the surfactant (F) (0.00% by mass) is also one embodiment of the present invention.

[0256] (G) Additives

[0257] The composition of the present invention may further contain other additives (G) different from the above-mentioned components (A) to (F). The additive (G) is preferably a surface smoothing agent, an acid, a base, a substrate adhesion enhancer, a defoaming agent, or any combination thereof (more preferably a base). Examples of the base include trialkylamines.

[0258] The content of the additive (G) is preferably 0 to 10% by mass (more preferably 0.001 to 10% by mass; further preferably 0.001 to 1% by mass; and further preferably 0.01 to 0.5% by mass) based on the hydrocarbon compound (A). In a preferred embodiment of the present invention, the additive (G) is not contained (0.000% by mass).

[0259] [Method for manufacturing resist upper layer film pattern and resist pattern]

[0260] The method for producing a resist upper layer film pattern and a resist pattern of the present invention includes the following steps.

[0261] (1) applying a resist composition onto a substrate and heating the resist composition to form a resist film;

[0262] (2) Optionally, exposing the resist film to light;

[0263] (3) applying a developable resist upper layer film composition directly onto the resist film, and heating the resist upper layer film composition to form a resist upper layer film;

[0264] (4) Optionally, exposing the resist film and the resist upper film;

[0265] The condition is that at least one of the exposures (2) and (4) must be performed;

[0266] (5) causing the acid in the resist film to move to the resist upper layer film; and

[0267] (6) The resist upper layer film and the resist film are developed using a developer to form a resist upper layer pattern and a resist pattern.

[0268] Each step is described below using a diagram. The numbers in parentheses that represent the steps indicate the order.

[0269] Process (1)

[0270] In step (1), a resist composition is applied onto a substrate, and the resist composition is heated to form a resist film.

[0271] Examples of the substrate include a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, and an ITO substrate.

[0272] The resist composition is not particularly limited. From the viewpoint of forming a fine resist pattern with high resolution, it is preferably a chemically amplified resist composition, and for example, a chemically amplified PHS-acrylate hybrid EUV resist composition can be cited. It is also preferred that the resist composition contains a photoacid generator (D') (PAG (D') described above). As a resist composition that can be used in the manufacturing method of the present invention, a pattern forming composition or a radiation-sensitive resin composition described in Japanese Patent Application No. 2021-73367 or Japanese Patent Application No. 2020-8842 can be used. The resist composition of the manufacturing method of the present invention is preferably a positive type.

[0273] In a common high-resolution positive resist composition, a combination of an alkali-soluble resin whose side chain is protected by a protecting group and a photoacid generator is included. If the resist layer formed by such a composition is irradiated with ultraviolet rays, electron beams, extreme ultraviolet rays, etc., the photoacid generator releases an acid in the irradiated portion (exposed portion), and the acid is used to dissociate the protecting group bonded to the alkali-soluble resin (hereinafter referred to as deprotection). The deprotected alkali-soluble resin is soluble in an alkaline developer, so it can be removed by development treatment.

[0274] The resist composition can be applied to the substrate by an appropriate method. Here, in the present invention, "above the substrate" includes the situation of being directly applied on the substrate and the situation of being applied via other layers. For example, a resist lower layer film (such as SOC (spin-on carbon layer) and / or a close-fitting enhancement film) can be formed directly on the substrate, and the resist composition is applied directly above it. Preferably, the resist composition is directly applied on the substrate. In another preferred embodiment, SOC is directly formed on the substrate, a close-fitting enhancement film is directly formed on the SOC, and then the resist composition is directly applied thereon.

[0275] The application method is not particularly limited, and examples thereof include coating by spin coating.

[0276] The substrate to which the resist composition is applied is heated to form a resist layer. The heating may be pre-baking, for example, using a hot plate. The heating temperature is preferably 90 to 250° C. (more preferably 90 to 200° C.; further preferably 100 to 130° C.). The temperature here is the heating surface temperature of the hot plate. The heating time is preferably 30 to 300 seconds (more preferably 30 to 120 seconds; further preferably 45 to 90 seconds). The heating is preferably performed in the atmosphere or a nitrogen environment (more preferably an atmospheric environment).

[0277] Figure 1 (i) is a schematic diagram showing that a resist film 2 is formed on a substrate 1. The thickness of the resist layer is preferably 10 to 50 nm (more preferably 25 to 50 nm).

[0278] Process (2)

[0279] In step (2), the resist film may be exposed to light. The exposure may be performed through a mask as appropriate.

[0280] The wavelength of the radiation (light) used for exposure is not particularly limited, and exposure with a wavelength of 13.5 to 248 nm is preferred. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and EUV (extreme ultraviolet light, wavelength 13.5 nm) can be used. EUV light is more preferred. These wavelengths allow a range of ±1%.

[0281] After exposure, post-exposure heating (PEB) may be performed as needed. The temperature of PEB may be selected from the range of 70 to 150° C. (preferably 100 to 140° C.). The heating time of PEB may be selected from the range of 0.3 to 5 minutes (preferably 0.5 to 2 minutes).

[0282] Figure 1 (ii) is a schematic diagram showing the state of the resist film 2 after exposure through a mask when a typical positive chemically amplified resist composition is used. The exposed portion 3 releases acid from the photoacid generator, thereby deprotecting the polymer and improving the alkali solubility. The alkali solubility of the polymer in the unexposed portion 4 does not change.

[0283] Process (3)

[0284] In the step (3), a developable resist upper layer film composition is directly applied onto the resist film, and then the resist upper layer film composition is heated to form a resist upper layer film.

[0285] The developable resist upper layer film composition is preferably a composition comprising the hydrocarbon compound (A) of the present invention and a solvent (B).

[0286] The application method is not particularly limited, and examples thereof include coating by spin coating.

[0287] A substrate to which a developable resist upper film composition is applied is heated to form a resist upper film. The heating is performed, for example, using a hot plate. The heating temperature is preferably 45 to 150° C. (more preferably 80 to 120° C.). The heating time is preferably 30 to 180 seconds (more preferably 45 to 90 seconds). The heating is preferably performed in air or nitrogen atmosphere (more preferably in air atmosphere). Although not being bound by theory, in the case of exposure in step (2), the acid generated by the photoacid generator in the resist film is believed to diffuse by heating in step (3). More preferably, the following method is used: as in step (5) described later, the acid moves from the resist film to the resist upper film of the present invention by utilizing this diffusion.

[0288] The thickness of the resist upper film formed in step (3) is preferably 1 to 10 nm (more preferably 2 to 8 nm; further preferably 5 to 7 nm). A preferred embodiment is that the thickness of the resist film does not substantially decrease even if the resist upper film composition of the present invention is applied. Specifically, the reduction in the thickness of the resist film (excluding the resist upper film) before and after the above-mentioned application is preferably 0 to 15% (more preferably 0 to 10%; further preferably 0.1 to 5%; further preferably 0.1 to 1%). It is also a preferred embodiment of the present invention that the thickness of the resist film does not decrease (the reduction is 0%) before and after the above-mentioned application.

[0289] Process (4)

[0290] In step (4), the resist film and the resist upper layer film are optionally exposed.

[0291] The condition is that at least one of the exposure in step (2) and step (4) must be performed. The exposure conditions in step (4) are the same as those in step (2).

[0292] It is preferred to perform exposure in step (2) without performing exposure in step (4). In this case, the resist film is exposed before the resist upper layer film is formed, but is not exposed after the resist upper layer film is formed. That is, step (4) can be eliminated in the manufacturing method of the present invention.

[0293] Figure 1 (iii) is a schematic diagram showing a state in which the resist film 2 is formed, and then exposed, and then the resist upper layer film 5 is formed.

[0294] It is also preferred to perform heating after exposure (PEB). It is preferred to perform heating in step (2-2) after step (2) and / or to perform heating in step (4-2) after step (4). PEB can diffuse the acid generated in the exposure area, for example, making the acid in the exposure area more uniform. It is also preferred not to perform heating (2-2) and heating (4-2). When exposure is performed in step (2), the acid can be diffused by heating in step (3).

[0295] Process (5)

[0296] In step (5), the acid in the resist film moves to the resist upper film. The movement of the acid can also be promoted by heating. The movement of the acid can occur when the resist upper film is heated in step (3) (that is, step (5) occurs simultaneously with step (3)), or it can occur after step (3). More preferably, the movement of the acid in step (5) occurs when the resist upper film is heated in step (3).

[0297] The acid migrated in step (5) is preferably used to change the solubility of the resist upper film in the developer. In a preferred embodiment, the acid generated from the photo-generated strong acid generator (E) in the resist film is ion-exchanged with the acid generator (D) in the resist upper film, and the acid derived from the acid generator (D) diffuses into the resist upper film, thereby changing the solubility of the resist upper film in the developer.

[0298] In a more preferred embodiment, in an area where acid migration does not occur (an unexposed area in the case of a positive resist), when the resist upper layer film is formed in step (3), the hydrocarbon compound (A) in the developable resist upper layer film composition becomes insoluble in the developer by bonding with the resist film, and in an area where acid migration occurs (an exposed area in the case of a positive resist), the acid that migrated in step (5) makes the resist upper layer film soluble in the developer, and it is considered that the resist upper layer film can also be patterned.

[0299] Figure 1 (iv) is a schematic diagram of a state where acid moves from the resist film to the resist upper film. In the positive type, the acid moves to the exposed portion of the resist film and the resist upper film directly above the exposed portion, and the place where the acid moves becomes alkali-soluble like the resist film, while the acid does not move to the unexposed portion, and the solubility of the resist upper film in the developer does not change.

[0300] It is also preferred that the resist upper layer film be surface cleaned before development after step (5) to remove the upper portion of the resist upper layer film. The surface cleansing may use the same composition as the solvent (B) of the composition of the present invention.

[0301] Process (6)

[0302] In step (6), the resist upper layer film and the resist film are developed using a developer to form a resist upper layer film pattern and a resist pattern (hereinafter sometimes referred to as a thickened film pattern).

[0303] The developer may be applied by a puddle method, an immersion method, or a spray method. The developer temperature is preferably 5 to 50° C. (more preferably 25 to 40° C.), and the development time is preferably 15 to 120 seconds (more preferably 20 to 60 seconds). After the developer is applied, the developer is removed.

[0304] The developer is preferably an alkaline aqueous solution or an organic solvent (more preferably an alkaline aqueous solution). As the alkaline aqueous solution, an aqueous solution containing inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, triethylamine, quaternary amines such as tetramethylammonium hydroxide (TMAH), etc. can be cited (more preferably a TMAH aqueous solution; more preferably a 2.38 mass % TMAH aqueous solution).

[0305] The above-mentioned surfactant may be further added to the developer.

[0306] Figure 1 (v) shows a state where a developer is applied to the resist film and the resist upper film, and the developer is removed to form a resist pattern 6 and a resist upper film pattern 7. The resist pattern 6 and the upper film pattern 7 together form a thickened film pattern.

[0307] If (film thickness of resist pattern and film thickness of resist upper film) - (film thickness of resist pattern formed in the same manner except that thickening solution is not applied) is taken as the film thickness amount, the film thickness amount is preferably 1 to 10 nm; more preferably 2 to 8 nm; further preferably 3 to 7 nm; and further preferably 4 to 6 nm. Although not bound by theory, the thickness of resist film is usually thin in high-definition lithography technology such as EUV exposure, and by using the present invention to thicken the resist film, it is believed that the durability as a mask can be ensured when it is used as an etching mask in a subsequent process.

[0308] The method of the present invention may further include the following step (7).

[0309] (7) The resist upper film pattern and the resist pattern are cleaned with a cleaning liquid, and the cleaning liquid is removed from between the patterns.

[0310] In order to remove local film residues, a cleaning liquid can be used to clean the resist upper film pattern and the resist pattern. As the cleaning liquid, a water-soluble cleaning liquid or an organic solvent cleaning liquid (for example, IPA, PGME, PGMEA, PGEE, nBA) can be cited. In a preferred embodiment of the present invention, the cleaning liquid is a rinse liquid, and the rinse liquid is used instead of the developer for the rinse treatment. The rinse treatment can preferably be performed with a water-soluble rinse liquid. Based on the entire liquid, the lower limit of the content of water (DIW) in the water-soluble rinse liquid is preferably 90 mass% (more preferably 95 mass%; further preferably 98 mass%; further preferably 99.99 mass%). Based on the entire liquid, the components other than water contained in the water-soluble rinse liquid are preferably less than 1,000 ppm (more preferably less than 100 ppm).

[0311] [Method for manufacturing processed substrate and device]

[0312] The method for manufacturing a processed substrate of the present invention includes the following steps.

[0313] The resist upper film pattern and the resist pattern are formed by the method described above; and (8) the resist upper film pattern and the resist pattern are processed using them as masks.

[0314] Process (8)

[0315] In step (8), the resist upper film pattern and the resist pattern are processed as a mask. The resist upper film pattern and the resist pattern are preferably used as a mask for processing the resist lower film or the substrate (more preferably the substrate). Specifically, the thick film pattern can be used as a mask to process various substrates that become the base using dry etching, wet etching, ion implantation, metal plating, etc. Since the resist pattern is thick filmed, it can function as a mask even under more severe conditions, so it is preferably suitable for processing using dry etching.

[0316] When the thick film pattern is used to process the resist lower film, the processing can be performed in stages. For example, the thick film pattern can be used to process the adhesion enhancement film and SOC, and then the SOC pattern can be used to process the substrate. The adhesion enhancement film can use, for example, SiARC (Si anti-reflection film). A more preferred method is to directly process the substrate using the thick film pattern.

[0317] The method for manufacturing a device of the present invention includes the above method, preferably further including a step of forming wiring on a processed substrate. These processes can be applied by known methods. Then, the substrate is cut into chips as needed, connected to a lead frame, and encapsulated with a resin. In the present invention, the encapsulated article is referred to as a device. As the device, semiconductor devices, liquid crystal display devices, organic EL display devices, plasma display devices, and solar cell devices can be cited. The device is preferably a semiconductor device.

[0318] [Example]

[0319] The present invention will be described below by way of examples, but the embodiments of the present invention are not limited to these examples.

[0320] [Preparation of Compositions of Examples 101 to 107]

[0321] As described in Table 1, each component is mixed in each blending amount. First, component (B1) and component (B2) are mixed to obtain solvent (B). Component (A), component (D) and component (F) are added to solvent (B). The values ​​in Table 1 are the contents (parts by mass) of each component based on the total mass of the composition.

[0322] The obtained solution was stirred at room temperature for 30 minutes. After visually confirming that the solute was completely dissolved, the solution was filtered with a 0.2 μm fluorinated resin filter to obtain the compositions of Examples 101 to 107.

[0323] [Table 1]

[0324]

[0325] The compounds described in Table 1 are as follows.

[0326] A1 and A3 are represented by the following formula, Y 1 Protection rate (in Y 1 The total number is the basis, Y 1 The probability of being a group represented by formula (1) is 78% and 50%, respectively.

[0327]

[0328] A2 is represented by the following formula, Y 2 The protection rate is 80%.

[0329]

[0330] A4 is represented by the following formula, Y 3 The protection rate is 49%.

[0331]

[0332] A5 is represented by the following formula, Y 4 The protection rate is 78%.

[0333]

[0334] B1-1 is dibutyl ether.

[0335] B2-1 is PGMEA.

[0336] B2-2 is PGME.

[0337] D1 is triphenylsulfonium trifluoromethanesulfonate.

[0338] D2 is triphenylsulfonium trifluoroacetate.

[0339] D3 is triphenylsulfonium methanesulfonate.

[0340] D4 is triphenylsulfonium 4-methylbenzenesulfonate.

[0341] D5 is (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate.

[0342] F1 is an acetylene glycol polyoxyalkylene ether having the following structure.

[0343]

[0344] [Preparation of Compositions of Examples 201 to 206]

[0345] As described in Table 2, each component is mixed in each blending amount. First, component (B1) and component (B2) are mixed to obtain solvent (B). Component (A), component (C), component (D) and component (F) are added to solvent (B). The values ​​in Table 2 are the contents (parts by mass) of each component based on the total mass of the composition.

[0346] The obtained solution was stirred at room temperature for 30 minutes. After visually confirming that the solute was completely dissolved, the solution was filtered with a 0.2 μm fluorinated resin filter to obtain the compositions of Examples 201 to 206.

[0347] [Table 2]

[0348]

[0349] The compounds described in Table 2 are as follows: A6 is 1,4-butanediol divinyl ether.

[0350]

[0351] A7 is a copolymer represented by the following formula, and is a polymer obtained by random copolymerization of 1,4-butanediol divinyl ether (same as A6) and BIP-PC (same as C1) at a molar ratio of 1:2. Mw is 20,000 to 40,000.

[0352]

[0353] A8 is 1,4-cyclohexanedimethanol divinyl ether.

[0354]

[0355] A9 is 1,3,5-tris[4-(vinyloxy)butyl 1,3,5-cyclohexanetricarboxylate (Toyo Gosei).

[0356]

[0357] C1 is BIP-PC (Asahi Organic Materials) represented by the following formula.

[0358]

[0359] B1-1, B2-1, B2-2, D1 and F1 are the same as in Table 1.

[0360] [Preparation of Compositions of Examples 301 to 305]

[0361] As described in Table 3, each component is mixed in each blending amount. First, component (B1) and component (B2) are mixed to obtain solvent (B). Component (A), component (D) and component (F) are added to solvent (B). The values ​​in Table 3 are the contents (parts by mass) of each component based on the total mass of the composition.

[0362] The obtained solution was stirred at room temperature for 30 minutes. After visually confirming that the solute was completely dissolved, the solution was filtered with a 0.2 μm fluorinated resin filter to obtain the compositions of Examples 301 to 305.

[0363] [Table 3]

[0364]

[0365] The compounds described in Table 3 are as follows.

[0366] A10 is cyclohexyl vinyl ether.

[0367]

[0368] A11 is 1,4-cyclohexanedimethanol divinyl ether.

[0369]

[0370] A9, B1-1, B2-2, D1 and F1 are the same as in Tables 1 and 2.

[0371] [Manufacturing of Resist Upper Layer Film Pattern and Resist Pattern]

[0372] The silicon substrate was treated with HMDS (hexamethyldisilazane) at 90°C for 30 seconds. The chemically amplified PHS-acrylate hybrid resist composition was applied to the HMDS-treated substrate by spin coating, and heated on a 110°C hot plate for 60 seconds to form a resist film with a thickness of 35nm. Using an EUV exposure device (NXE:3300B, ASML), the resist film was exposed while changing the exposure amount through a mask with a size of 18nm (line width: spacing = 1:1). Then, PEB was performed at 100°C for 60 seconds. Then, the composition of the above embodiment was applied to the resist layer by spin coating, and heated at 90°C for 60 seconds to form a resist upper film. Then, a 2.38% by mass TMAH aqueous solution was used as a developer, and spin immersion development was performed for 30 seconds. Water was dripped while the developer was spin-immersed on the substrate, and the developer was replaced with water while the substrate was rotated. Then, the substrate is rotated at a high speed to dry the thickened resist pattern (resist upper layer film pattern and resist pattern).

[0373] For comparison, a resist pattern without applying the composition of the example was formed. Specifically, a resist pattern was formed in the same manner as above except that the composition of the example and the subsequent heating were not performed. This is referred to as a comparative resist pattern.

[0374] [Evaluation of film thickness]

[0375] The thickened resist pattern and the comparative resist pattern were sliced ​​into substrates, and the cross-sectional shape was observed by SEM (SU8230, Hitachi High-Tech Fieldings) to measure the pattern height. The (thickness of the resist pattern + the thickness of the resist upper film pattern) - (thickness of the comparative resist pattern) was calculated as the thickening amount. The obtained results are recorded in Tables 1 to 3.

[0376] [Explanation of Reference Numerals]

[0377] 1: Substrate

[0378] 2: Resist film

[0379] 3: Exposure Department

[0380] 4: Unexposed part

[0381] 5: Resist upper film

[0382] 6: Resist pattern

[0383] 7: Resist upper film pattern.

Claims

1. A developable resist upper layer film composition comprising a hydrocarbon compound (A) and a solvent (B), The hydrocarbon compound (A) is a compound represented by the formula (0), or a polymer containing a structure derived from a compound represented by the formula (0) as a repeating unit; and The solvent (B) comprises a solvent (B1) represented by formula (b1), in, X is C 1-60 Hydrocarbon; n 01 is a number from 1 to 10, n 02 A number from 0 to 10; Y is a group represented by formula (1) or -OH, provided that 40 to 100% of the total number of Y are groups represented by formula (1); R 02 C excluding tert-butyloxy 1-6 Alkoxy, -(C=O)-R 03 、-(C=O)-OR 04 、-(C=O)-N(R 05 )2. -O-(C=O)-R 06 , or -NR 07 -(C=O)-R 08 ; R 03 H or C 1-4 alkyl; R 04 C 1-4 Alkyl, but excluding tert-butyl; R 05 Each independently is H or C 1-4 Alkyl, 2 R 05 Can bond to form ring structures; R 06 H, C 1-4 Alkyl, or C 1-4 Alkoxy, but not including tert-butoxy; R 07 H or C 1-4 alkyl; R 08 H, C 1-4 Alkyl or -N(R 09 )2; R 07 and R 08 When alkyl, they can bond together to form a ring structure; and R 09 Each independently is H or C 1-4 Alkyl, 2 R 09 can bond together to form a ring structure, in, n 11 、n 12 、n 13 and n 14 Each independently a number from 0 to 1; L 12 Selected from the group consisting of -C(=O)-, -CH2-C(=O)-, -C(=O)-CH2- and -CH(CH3)-; L 14 C 1-5 Alkylene; And R 15 C 1-15 Alkyl or C 2-7 alkenyl; L 12 The methyl group and R 15 The methyl groups can bond to form a ring. R 21 -OR 22 (b1) in, R 21 and R 22 Each independently is C 1-8 alkyl.

2. The composition according to claim 1, wherein X is represented by formula (X-1) or formula (X-2): in, R 21 and R 24 Each independently is a linear or branched C 1-10 Aliphatic hydrocarbon group; n 22 A number from 0 to 5; Cy 23 Cy 25 Each independently has C 5-10 cycloalkyl containing ring atoms of n 23 Each independently a number from 0 to 1; n 24 and n 25 are each independently a number from 0 to 3, in, Cy 31 Cy 34 Each independently has C 5-10 cycloalkyl containing ring atoms of n 32 A number from 0 to 5; R 33 Each independently is a linear or branched C 1-10 alkyl; R 35 Each independently is a linear or branched C 1-10 alkyl; n 33 Each independently a number from 0 to 1; n 34 and n 35 Each independently is a number from 0 to 3; The molecular weight of the hydrocarbon compound (A) is preferably 100 to 80,000.

3. The composition according to claim 1 or 2, wherein Further comprising a hydroxyl group-containing compound (C) represented by formula (c): in, R 42 C 1-6 Alkoxy, -(C=O)-R 03 、-(C=O)-OR 04 、-(C=O)-N(R 05 )2. -O-(C=O)-R 06 、 or -NR 07 -(C=O)-R 08 ; n 41 is a number from 1 to 10, n 42 A number from 0 to 10; X, R 03 , R 04 , R 05 , R 06 , R 07 and R 08 Each independently has the meaning stated in claim 1; The molecular weight of the hydroxyl group-containing compound (C) is preferably 200 to 800; or the content of the hydroxyl group-containing compound (C) is preferably 50 to 200% by mass based on the hydrocarbon compound (A).

4. A composition according to one or more of claims 1 to 3, wherein The solvent (B) further comprises a solvent (B2), Preferred solvents (B2) are cyclohexanone, cyclopentanone, 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, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, or any combination thereof.

5. A composition according to one or more of claims 1 to 4, wherein further comprising an acid generator (D), Preferably, the acid generator (D) releases an acid having an acid dissociation constant pKa (H2O) of -14 to 8 when reacting with an acid; Preferably, the resist film formed below the resist upper film contains PAG (D'), and PAG (D') releases an acid having an acid dissociation constant pKa (H2O) of -20 to 1.4 upon exposure; or The content of the acid generator (D) is preferably 0.01 to 40% by mass based on the hydrocarbon compound (A).

6. A composition according to one or more of claims 1 to 5, which is substantially free of photoacid generators (E), in, The photo-generated strong acid generator (E) releases an acid with an acid dissociation constant pKa (H2O) of -20 to 1.4 upon exposure; The content of the photoacid generator (E) is 0 to 1.00% by mass based on the hydrocarbon compound (A).

7. A composition according to one or more of claims 1 to 6, wherein further comprising a surfactant (F), The content of the surfactant (F) is preferably 0 to 10% by mass based on the hydrocarbon compound (A).

8. A composition according to one or more of claims 1 to 7, wherein further comprising other additives (G), The additive (G) is preferably a surface smoothing agent, an acid, a base, a substrate adhesion enhancer, a defoaming agent, or any combination thereof; and The content of the additive (G) is preferably 0 to 10% by mass based on the hydrocarbon compound (A).

9. A composition according to one or more of claims 1 to 8, wherein The content of the hydrocarbon compound (A) is 0.01 to 15% by mass based on the composition. Preferably, the content of the solvent (B) is 70 to 99.99% by mass based on the composition; Preferably, the content of the solvent (B1) is 70 to 100% by mass based on the solvent (B), and The content of the solvent (B2) is preferably 0 to 30% by mass based on the solvent (B).

10. The composition according to one or more of claims 1 to 9, which is a developable resist upper layer film composition for forming a resist film after exposure, Preferably, the composition is a developable resist upper layer film composition for forming a resist film after EUV exposure; or, It is preferred that the resist film is a positive EUV resist film.

11. A method for manufacturing a resist upper film pattern and a resist pattern, comprising the following steps: (1) applying a resist composition onto a substrate and heating the resist composition to form a resist film; (2) Optionally, exposing the resist film to light; (3) applying a developable resist upper layer film composition directly onto the resist film, and heating the resist upper layer film composition to form a resist upper layer film; (4) Optionally, exposing the resist film and the resist upper film; The condition is that at least one of the exposures (2) and (4) must be performed; (5) The acid in the resist film moves to the resist upper layer film; and (6) using a developer, developing the resist upper layer film and the resist film to form a resist upper layer pattern and a resist pattern, It is preferred that step (2-2) of heating is performed after step (2), and / or step (4-2) of heating is performed after step (4).

12. The method according to claim 11, wherein: The developable resist top film composition is a composition as claimed in one or more of claims 1 to 10.

13. The method according to claim 11 or 12, wherein: The thickness of the resist upper layer film formed in step (3) is 1 to 10 nm. The thickness of the resist film formed in step (1) is preferably 10 to 50 nm.

14. The method according to one or more of claims 11 to 13, wherein: By using the acid migrated in step (5), the solubility of the resist upper layer film in the developer is changed. It is preferred that the acid generated by the photogenerator (E) in the resist film exchanges ions with the acid generator (D) in the resist upper film, so that the acid derived from the acid generator (D) diffuses in the resist upper film, thereby changing the solubility of the resist upper film in the developer.

15. The method according to one or more of claims 11 to 14, wherein: In step (3), the hydrocarbon compound (A) in the developable resist upper layer film composition becomes insoluble in the developer by bonding to the resist film, and The acid migrated in step (5) makes the resist upper layer film soluble in the developer.

16. The method according to one or more of claims 11 to 15, wherein: Further comprising the following step (7): (7) The resist upper film pattern and the resist pattern are cleaned with a cleaning liquid, and the cleaning liquid is removed from between the patterns.

17. A method for manufacturing a processed substrate, comprising the steps of: forming a resist upper film pattern and a resist pattern by the method of one or more of claims 11 to 16; and (8) Processing using the resist upper film pattern and the resist pattern as a mask, Preferably, step (8) is to process the resist underlayer film or the substrate.

18. A method for manufacturing a device comprising the method according to one or more of claims 11 to 17, Preferably, the method further comprises the step of forming wiring on the processed substrate; Preferably the device is a semiconductor device.

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