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

Abstract

Provided are 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 toplayer film composition, a resist toplayer film pattern, and a method for producing a resist pattern. [Background technology]

[0002] In recent years, the need for higher integration of LSIs has increased, and so has the need for finer resist patterns. To meet these needs, lithography processes using short-wavelength light such as KrF excimer lasers, ArF excimer lasers, extreme ultraviolet rays, X-rays, and electron beams are becoming more and more common.

[0003] In order to obtain a finer pattern, there is a method in which a resist pattern formed in a range that can be stably obtained by a conventional method is covered with a composition containing a polymer to widen the resist pattern and thereby make the hole diameter or separation width finer. This method is mainly aimed at widening the width of the resist pattern, and involves developing the resist pattern once and then applying a composition containing a polymer.

[0004] Resist top layer film compositions that selectively transmit only EUV or electron beams and block outgassing from the resist have been proposed (e.g., Patent Documents 1 to 3). These compositions are applied before exposure, and there is no disclosure of increasing the film thickness of the resist. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication 2016 / 013598 [Patent Document 2] International Publication 2014 / 115843 [Patent Document 3] International Publication No. 2015 / 129486 Summary of the Invention

Problems to be Solved by the Invention

[0006] The inventors of the present invention considered that there are one or more problems that still need to be improved in the method for manufacturing a resist pattern. For example, they include the following: thickening a fine resist pattern; obtaining a fine resist pattern useful as an etching mask; obtaining sufficient resolution even when using an exposure apparatus with an increased numerical aperture; obtaining a fine pattern with a good shape; obtaining a resist pattern with a high aspect ratio; widening the process window; being able to develop and pattern the upper layer film itself; not significantly reducing the thickness of the resist film even when applying a resist upper layer film composition; being able to form a resist upper layer film on the resist film; being able to apply the resist upper layer film composition to the resist film after exposure; being able to apply the resist upper layer film composition to the resist film before development; the resist upper layer film being able to receive an acid from the resist film; being able to change the solubility of the resist upper layer film by the acid received from the resist film; the resist upper layer film hardly containing a component that generates a strong acid; being able to generate an acid with a long diffusion distance by ion-exchanging with the acid received from the resist film; improving the manufacturing yield.

[0007] The inventors of the present invention considered and studied as follows. DOF (Depth of Focus) refers to the range of the depth of focus within which a resist pattern can be formed with a deviation within a predetermined range with respect to the target dimension when exposing with the focus shifted up and down at the same exposure amount. DOF is represented by the following formula. k2×λ / NA 2 (In the formula, k2 is a constant, λ is the exposure wavelength, and NA represents the numerical aperture) The larger the DOF, the wider the process window, which is preferable. However, in high-precision lithography technologies such as ICs, the NA of exposure apparatuses tends to increase in the future, and it is expected that the DOF will become increasingly narrow.

[0008] In EUV lithography, which is expected to be a high-precision technology, the formation of fine patterns on a thin film is being achieved. The inventors considered that it is preferable to thicken the resist pattern in order to make it more resistant when using a high-precision pattern as a mask in subsequent processes. If the resist pattern is thin, for example, when used as an etching mask, it may not be able to fulfill its durability as a mask, and it may be etched away to the object to be masked at the end of the etching process.

[0009] When the resist film thickness is thick, the process window tends to become narrow. For example, if the focus shifts due to a slight thickness variation of the substrate, the shape of the resist pattern formed will change, becoming far from rectangular, and pattern collapse etc. may easily occur. Another example is that if the exposure dose (Dose) fluctuates, the line width will fluctuate, and pattern bridging and pattern collapse may easily occur. In high-precision technologies that require high resolution, a thinner resist film thickness is more likely to be used.

[0010] The present invention has been made based on the above-described technical background, and provides a developable resist upper layer film composition capable of achieving thickening of the resist pattern, and a method for manufacturing a resist upper layer film pattern and a resist pattern.

Means for Solving the Problems

[0011] The developable resist upper layer film composition according to the present invention comprises a hydrocarbon compound (A) and a solvent (B). The hydrocarbon compound (A) is a compound represented by the formula (0) or a polymer comprising a structure derived from the compound represented by the formula (0) as a repeating unit; and The solvent (B) is a composition comprising a solvent (B1) represented by the formula (b1).

Chemical formula

Chemical Structure

[0012] The method for producing a resist upper layer film pattern and a resist pattern according to the present invention comprises the following steps. (1) Applying a resist composition above a substrate, heating the resist composition to form a resist film; (2) Optionally, exposing the resist film; (3) Applying a developable resist upper layer film composition directly above the resist film, heating the resist upper layer film composition to form a resist upper layer film; (4) Optionally, exposing the resist film and the resist upper layer film; However, at least one of the exposures in (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, develop the upper resist film and the resist film to form an upper resist pattern and a resist pattern.

[0013] The method for manufacturing a device according to the present invention includes the above method. [Advantages of the Invention]

[0014] According to the present invention, it is possible to achieve one or more of the following effects. Thicken a fine resist pattern; obtain a fine resist pattern useful as an etching mask; obtain sufficient resolution even when using an exposure machine with an increased numerical aperture; obtain a fine pattern with a good shape; obtain a resist pattern with a high aspect ratio; widen the process window; develop and pattern the upper layer film itself; the thickness of the resist film does not decrease significantly even when applying the upper resist film composition; it is possible to form an upper resist film on the resist film; the upper resist film composition can be applied to the resist film after exposure; the upper resist film composition can be applied to the resist film before development; the upper resist film can receive an acid from the resist film; the solubility of the upper resist film can be changed by the acid received from the resist film; the upper resist film may contain almost no component that generates a strong acid; by ion-exchanging with the acid received from the resist film, an acid with a long diffusion distance can be generated; improve the manufacturing yield. [Brief Description of the Drawings]

[0015]

Figure 1

[0016] [Definitions] In this specification, unless otherwise specifically limited, follow the definitions and examples described in this paragraph. The singular form includes the plural form, and "one" or "the" means "at least one". The elements of a concept can be expressed by multiple types, and when the amount (e.g., mass %, mole %) is described, the amount means the sum of those multiple types. "And / or" includes all combinations of elements and also includes use alone. When indicating a numerical range using "~" or "-", these include both endpoints and the units are common. For example, 5~25 mol% means 5 mol% or more and 25 mol% or less. "C x-y ", "C x ~C y " and "C x " and such descriptions mean the number of carbons in the molecule or substituent. For example, C 1-6 alkyl means an alkyl chain having 1 to 6 carbons (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units copolymerize. These copolymerizations may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When showing a polymer or resin by a structural formula, n, m, etc. written in parentheses indicate the number of repetitions. The unit of temperature uses Celsius. For example, 20 degrees means 20 degrees Celsius. An additive refers to the compound itself having that function (for example, if it is a base generator, it is the compound itself that generates a base). There may also be a mode in which the compound is dissolved or dispersed in a solvent and added to the composition. As one form of the present invention, such a solvent is preferably contained in the composition according to the present invention as solvent (B) or as other components.

[0017] Hereinafter, embodiments of the present invention will be described in detail.

[0018] [Developable resist upper layer film composition] The developable resist upper layer film composition according to the present invention (hereinafter sometimes referred to as the composition) comprises a hydrocarbon compound (A) and a solvent (B). The hydrocarbon compound (A) is a compound represented by formula (0) or a polymer comprising, as a repeating unit, a structure derived from the compound represented by formula (0), and the solvent (B) comprises a solvent (B1) represented by formula (b1). The composition according to 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-type EUV resist film formed from a positive-type EUV resist composition. The resist upper layer film formed on the resist film using the composition according to the present invention can be developed with a developer. A pattern (resist upper layer film pattern) derived from the composition according to the present invention is formed on the developed resist pattern. Thus, by applying the composition according to the present invention, the resist pattern is thickened. The composition according to the present invention is not applied between the developed resist patterns. However, the "development" after development as used herein does not include the development when the already removed resist layer is patterned. For example, in the case of a design in which a plurality of resist patterning steps are performed continuously, it is possible to use the composition according to the present invention to thicken the resist layer in the subsequent step after the development of the resist in the previous step.

[0019] (A) Hydrocarbon compound The composition according to the present invention comprises a hydrocarbon compound (A) (hereinafter sometimes referred to as component (A). The same applies to other components). The hydrocarbon compound (A) is a compound represented by formula (0) or a polymer comprising, as a repeating unit, a structure derived from the compound represented by formula (0). It is also one of the preferred embodiments of the present invention that the hydrocarbon compound (A) includes both the compound represented by formula (0) and the polymer comprising, as a repeating unit, a structure derived from the compound represented by formula (0).

[0020] Formula (0) is as follows. [Chemical formula] Here, X is a C 1-60 hydrocarbon group. X is preferably a C 5-10 group consisting of a combination of aryl and linear or branched C 1-6 alkyl, a group consisting of a combination of aryl and cyclic C 5-10 alkyl, a group consisting of cyclic C 5-6 alkyl, a group consisting of a combination of linear or branched C 5-10 alkyl and cyclic C 1-6 alkyl, or a group consisting of linear or branched C 5-6 alkyl (more preferably a group consisting of a combination of phenyl and branched C 1-6 alkyl, a group consisting of a combination of phenyl and cyclohexyl, a group consisting of cyclic C 1-6 alkyl, a group consisting of a combination of methyl and cyclohexyl, a group consisting of a combination of methyl and cyclopentyl, or a group consisting of linear C 5-6 alkyl; even more preferably a group consisting of a combination of phenyl and branched C 1-6 alkyl, cyclohexyl, or a group consisting of linear C 2-3 alkyl). For the sake of clarity, it is noted that H in the C 3-5 hydrocarbon group of X is substituted to bond with Y. The same applies to R 1-60 . 02

[0021] The elements constituting X can be read as a linker according to the number of other groups to which it binds. This will be detailed below. The following compound can be read by formula (0). X consists of three phenyls and C 2 alkyl. The C 2 alkyl is read as a linker that binds three phenyls. n 02 is 0. n 01 is 3. 100% of the total number of Ys is a group represented by formula (1), and there is no Y that is -OH. In all Ys, n 11 and n​12 is 1, and n 13 and n 14 is 0, and L 12 is -CH 2 -C(=O)-, and R 15 is t-butyl.

Chemical Structure

[0022] n 01 is a number from 1 to 10 (preferably a number from 1 to 5; more preferably a number from 1 to 3; even more preferably 1, 2 or 3). n 02 is a number from 0 to 10 (preferably a number from 0 to 3; more preferably a number from 0 to 1; even more preferably 0 or 1; even more preferably 0). Y is a group represented by formula (1) or -OH, provided that 40 to 100% of the total number of Y is a group represented by formula (1) (preferably 45 to 100%; more preferably 75 to 100%; even more preferably 100%). It is preferable to calculate the "total number of Y" in terms of molar ratio.

[0023] R 02 is C 1-6 alkoxy (excluding t-butoxy), -(C=O)-R 03 -(C=O)-O-R 04 -(C=O)-N(R 05 ) 2 -O-(C=O)-R 06 or -NR 07 -(C=O)-R 08 is. Without being bound by theory, modifications that do not interfere with the reaction of the group represented by formula (1) are acceptable for R 02 . The above groups are more preferable than functional groups of strong acids such as carboxylic acids and sulfonic acids or basic functional groups. R 02 is preferably C 1-6 alkoxy (even more preferably methoxy). R 03 is H or C 1-4is alkyl (preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl or t-butyl; more preferably H, methyl, n-propyl, or n-butyl; even more preferably H or methyl). R 04 is C 1-4 alkyl (excluding t-butyl). R 04 is preferably H, methyl, ethyl, isopropyl, n-propyl, or n-butyl (more preferably H, methyl, n-propyl, or n-butyl; even more preferably H or methyl).

[0024] R 05 are each independently H or C 1-4 alkyl, and two R 05 may combine to form a ring structure. R 05 are each independently preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl or t-butyl (more preferably H, methyl, n-propyl, or n-butyl; even more preferably H or methyl). The following compound can be read by formula (0). X consists of three phenyls and C 2 alkyl. n 01 is 2. 100% of the total number of Y is a group represented by formula (1). In one of the groups of formula (1), n 11 and n 12 are 1, n 13 and n 14 are 0, L 12 is -CH 2 -C(=O)-, and R 15 is t-butyl. In the other group of formula (1), n 11 , n 12 , n 13 and n 14 are 0, R 15 is vinyl (C 2 alkenyl). n 02 is 1. R 02 is -(C=O)-N(R 05 ) 2 is. R 05 is C 2 alkyl and C3 is alkyl and forms a ring structure.

Chemical formula

[0025] R 06 is H, C 1-4 alkyl, or C 1-4 alkoxy (excluding t-butoxy) (preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, or methoxy; more preferably H, methyl, n-propyl, n-butyl, or methoxy). R 07 is H or C 1-4 alkyl (preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl, or t-butyl; more preferably H, methyl, n-propyl, or n-butyl). R 08 is H, C 1-4 alkyl, or -N(R 09 ) 2 and when R 07 and R 08 are alkyl, they may be bonded together to form a ring structure; and R 09 are each independently H or C 1-4 alkyl, and two R 09 may be bonded together to form a ring structure. R 08 is preferably H, methyl, t-butyl or -N(R 09 ) 2 R 09 is preferably H, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, or methoxy (more preferably H, methyl, n-propyl, n-butyl, or methoxy).

[0026] Formula (1) is as follows.

Chemical formula

[0027] Examples of the formula (1) include the following structures.

Chemical formula

[0028] The following compound can be read as the formula (0). The following compound has three Ys, and 2 / 3 (about 67%) are groups represented by the formula (1). The groups represented by the formula (1) are the same. n11 = n12 = 1, n13 = n14 = 0, and L 12 is -CH(CH 3 ) - and R 15 is C 3 which can be read as alkyl (n-propyl). The methyl of L 12 and the methyl of R 15 are bonded to form a ring.

Chemical formula

[0029] (A) component has a group represented by the formula (1) as one of the features. Without being bound by theory, the group represented by the formula (1) or the binding site using the same is deprotected or de-crosslinked by accepting an acid. Assuming that the number of groups represented by the formula (1) among the total number of Y is the protection rate, the protection rate is preferably 40 to 100% (more preferably 45 to 100%; still more preferably 75 to 100%; even more preferably 100%). Without being bound by theory, when the acid in the resist film moves to the upper resist film, by the said deprotection or de-crosslinking, the solubility of that part in the developer changes, while the part where there is no movement of the acid (in the case of a positive resist film, directly above the unexposed part) does not change in solubility in the developer. Thus, it is considered that the pattern of the upper layer film is formed.

[0030] As one of the forms of the present invention, R in the formula (1) 15 is C 1-15 alkyl. Without being bound by theory, when the acid moves from the resist film to the upper resist film, R 15 is deprotected by accepting the acid, and the acid-accepting part can be solubilized in the developer. For example, when R 15 is t-butyl, it is deprotected by accepting the acid and changes to a carboxylic acid group, and there is a form in which it is deprotected. Suitable examples suitable for this form include the following independently. X is a group composed of a combination of C 5-10 aryl and linear or branched C 1-6 alkyl, or a group composed of a combination of C 5-10 aryl and cyclic C 1-6 alkyl (more preferably a group composed of a combination of phenyl and branched C 1-6 alkyl; still more preferably a group composed of a combination of phenyl and branched C 2-3 alkyl). It is preferable that X is represented by the formula (X-1). n 01 is a number from 1 to 3 (more preferably 1, 2 or 3; still more preferably 2 or 3; even more preferably 3). n 11 =n 12= 1. n 13 = n 14 = 0. L 12 The group of -C(=O)-, -CH 2 -C(=O)- and -CH(CH 3 )- is selected from (more preferably -CH 2 -C(=O)- and -CH(CH 3 )- is selected from; even more preferably -CH 2 -C(=O)-). R 15 is C 1-15 alkyl (more preferably ethyl, n-propyl, t-butyl, ethyl-cyclopentyl, ethyl-cyclohexyl, or ethyl-adamantyl; even more preferably t-butyl, ethyl-cyclopentyl, ethyl-cyclohexyl, or ethyl-adamantyl; even more preferably t-butyl). R 21 and R 24 are linear or branched C 2-4 aliphatic hydrocarbon groups (more preferably linear or branched C 2 , C 3 or C 4 aliphatic hydrocarbon groups; even more preferably branched C 2 , C 3 or C 4 aliphatic hydrocarbon groups; even more preferably ethynyl group). n 22 is 0, 1, 2 or 3 (more preferably 0, 2 or 3; even more preferably 2 or 3; even more preferably 3). Component (A) is a compound represented by formula (0). The content of the following component (C) is more preferably 0 to 100% by mass (even more preferably 0 to 10% by mass; even more preferably 0 to 1% by mass) based on the hydrocarbon compound (A). It is also preferable not to contain component (C) (0.000% by mass).

[0031] The compound represented by formula (0) has at least one Y and has X as a mother skeleton. X which is the mother skeleton is C 1-60It is one of the aspects of the present invention that it is a hydrocarbon group and is composed of a linear or branched aliphatic hydrocarbon group, a cyclic hydrocarbon group, or a combination thereof. X is preferably represented by formula (X-1) or formula (X-2). Formula (X-1) is as follows. [Chemical formula] Here, R 21 and R 24 are each independently a linear or branched C 1-10 aliphatic hydrocarbon group (preferably a linear or branched C 1-4 aliphatic hydrocarbon group; more preferably a linear or branched C 2ー4 aliphatic hydrocarbon group; even more preferably a linear or branched C 2 , C 3 or C 4 aliphatic hydrocarbon group). The parent skeleton represented by formula (X-1) preferably takes a form that extends and / or branches starting from R 21 . When the parent skeleton represented by formula (X-1) has a branch as a structure, it is a preferred form that the branch point is R 21 . Here, the aliphatic hydrocarbon group also includes cases other than monovalent. For example, when n22 of R 21 is 2, it is divalent. n 22 is a number from 0 to 5 (preferably a number from 0 to 3; more preferably 0, 1, 2, or 3; even more preferably 0, 2, or 3; even more preferably 0 or 3). When n 22 is 2 or more, the groups in the parentheses listed together with n 22 may be the same or different. When there are multiple branches, when looking at the whole formula, n 23 , n 24 and n 25 use the average value. When n 22 is 1 or more, at least one of n 23 , n 24 and n 25 is preferably greater than 0. When the group represented by formula (1) is Cy 23 or Cy25 The mode of bonding at the para position is preferred. Cy 23 and Cy 25 are each independently a cyclic hydrocarbon group having ring atoms of C 5―10 (preferably cyclopentyl, cyclohexyl, phenyl, or naphthyl; more preferably cyclohexyl or phenyl; still more preferably phenyl). n 23 are each independently a number from 0 to 1 (preferably 0 or 1). n 24 and n 25 are each independently a number from 0 to 3 (preferably each independently a number from 0 to 1; more preferably 0 or 1). When n 24 is 2 or 3, R 24 is not bonded to Cy 23 in series, but two R 24 are each bonded to Cy 23 . The same applies to n 25 .

[0032] The compound on the left below is a C 1-60 hydrocarbon group, which can be read as X in formula (0) and further can be read as formula (X-1) which is a lower concept (middle concept). In formula (X-1), R 21 is a C 2 aliphatic hydrocarbon group, n 22 is 3, and around R 21 there are three groups enclosed in brackets noted together with n 22 . In the groups enclosed in brackets noted together with two n , n 22 = 1, n 23 = n 24 = n 25 = 0, and Cy 23 is phenyl. In the group enclosed in brackets noted together with the third n 22 , n 23 = n 24 = n 25 = 1, and Cy 23 and Cy 25 are phenyl, and R 24 is C3 It is an aliphatic hydrocarbon group. Looking at the whole formula, n 23 = 1, and n 24 = n 25 = 1 / 3. The compound on the right below can be read as having three Ys in the compound on the left below. Two of the Ys are groups represented by formula (1), and one of the Ys is -OH. That is, 2 / 3 (about 67%) of the total number of Ys are groups represented by formula (1).

Chemical formula

[0033] The compound on the left below is a C 1-60 hydrocarbon group, which can be read as X in formula (0), and can further be read as formula (X-1) which is a lower concept (middle concept). R 21 is a straight-chain C 4 aliphatic hydrocarbon group (n-butyl), and n 22 = 0. The compound on the right below has two Ys in the parent skeleton represented by formula (X-1). The two Ys are represented by formula (1) and are the same group. n 11 = n 12 = n 13 = n 14 = 0, and R 15 is vinyl. Since two Ys replace and bond with the H of R 21 , R 21 can be read as n-butylene.

Chemical formula

[0034] Examples of the structure represented by formula (X-1) include the following.

Chemical formula

[0035] Formula (X-2) is as follows.

Chemical formula

[0036] The compound on the left below is a C 1-60 hydrocarbon group, which can be read as X in formula (0) and can further be read as formula (X-2), which is a lower concept (middle concept). In formula (X-2), Cy 31 is cyclohexyl, n 32 = 2, and the groups in the parentheses where n 32 is listed together are the same. n 33 = 1, n 34 = n 35 = 0, and R 33 is methyl. The compound on the right below has a parent skeleton represented by formula (X-2) and has two Ys, and both Ys are groups represented by formula (1) and are the same group. n 11 = n 12 = n 13 = n 14 = 0, and R 15 is vinyl. Y is bonded to the methyl of R 33 , and R 33 becomes a methylene linker.

Chemical formula

[0037] The compound on the left below is a C 1-60It is a hydrocarbon group, can be read as X in formula (0), and can further be read as formula (X-2) which is a lower concept (medium concept). In formula (X-2), Cy 31 is cyclohexyl, and n 32 = 0. The compound on the lower right below has a mother skeleton represented by formula (X-2) and has three Ys, and all three Ys are groups represented by formula (1) and are the same group. n 11 = 0, and n 12 = n 13 = n 14 = 1. L 12 is -C(=O)-, and L 14 is C 4 alkylene. R 15 is vinyl.

Chemical formula

[0038] Examples of the structure represented by formula (X-2) include the following.

Chemical formula

[0039] In a preferred embodiment of the present invention, the component (A) is a compound represented by formula (0).

[0040] In a preferred embodiment of the present invention, the component (A) is a polymer (hereinafter sometimes referred to as polymer (A)) comprising, as a repeating unit, a structure derived from a compound represented by formula (0) (hereinafter sometimes referred to as the formula (0) structure). Polymer (A) may be a copolymer containing repeating units other than the formula (0) structure within a range not impairing the scope of the present invention. Examples of the repeating units other than the formula (0) structure include, for example, a structure derived from a compound represented by formula (c) described later. Specific examples of polymer (A) include, for example, polymers having the following structures.

Chemical formula

[0041] The molecular weight of the component (A) is preferably 100 to 80,000. When the component (A) is a polymer, the molecular weight means the weight-average molecular weight (Mw), and refers to the polystyrene-equivalent average mass molecular weight measured using gel permeation chromatography. When the component (A) is a compound represented by formula (0), its molecular weight is more preferably 100 to 1,000 (even more preferably 100 to 900; still more preferably 120 to 800). When the component (A) is a polymer, its molecular weight (Mw) is more preferably 5,000 to 60,000 (even more preferably 10,000 to 50,000; still more preferably 20,000 to 40,000).

[0042] As one of the forms of the present invention, R in formula (1) 15 is C 2-7 alkenyl. Without being bound by theory, the cross-linked site via R 15 accepts the acid that has migrated from the resist film to the upper resist film and is thereby de-cross-linked, and the acid acceptor part can be solubilized in the developer. For example, when R 15 is vinyl, the cross-linked site can be de-cross-linked by accepting an acid. Suitable examples suitable for this form include the following independently. X is preferably a group consisting of cyclic C 5-10 alkyl, a group consisting of linear C 1-6 alkyl, branched C3-6 A group consisting of alkyl, or a group consisting of any combination thereof (more preferably cyclic C 5-10 A group consisting of alkyl, linear C 1-6 A group consisting of alkyl, or a group consisting of a combination thereof; more preferably cyclic C 5-6 A group consisting of alkyl, or linear C 1-6 A group consisting of alkyl; even more preferably cyclohexyl or n-butyl). It is preferable that X is represented by the formula (X-1). As another form, it is also preferable that X is represented by the formula (X-2). n 01 Is a number from 1 to 3 (more preferably 1, 2 or 3; even more preferably 2 or 3; even more preferably 2). n 11 Is 0 or 1 (more preferably 0). n 12 Is 0 or 1 (more preferably 0). L 12 Is selected from -C(=O)- or -C(=O)-CH 2 -(more preferably -C(=O)-). n 13 Is 0 or 1 (more preferably 0). n 14 Is 0 or 1 (more preferably 0). L 14 Is methylene, ethylene or n-butylene (more preferably methylene or n-butylene; even more preferably n-butylene). R 15 Is C 2-7 Alkenyl (more preferably vinyl). R 21 And R 24 Are each independently a linear or branched C 1-4 Aliphatic hydrocarbon group (more preferably linear or branched C 2 , C 3 Or C 4 Aliphatic hydrocarbon group; even more preferably n-butyl group). n 22is 0, 1, 2 or 3 (more preferably 0, 2 or 3; even more preferably 0 or 3; still even more preferably 0). Cy 23 and Cy 25 are each independently cyclohexyl or phenyl (more preferably cyclohexyl). n 23 is 0 or 1 (more preferably 0). n 24 and n 25 are each independently 0 or 1 (more preferably 0). A more preferred embodiment is that the composition of the present invention contains the component (C) described below, or the polymer (A) is a copolymer further comprising a structure derived from the compound represented by the formula (c). The inclusion of the component (C) as used herein preferably means that the content of the component (C) is 50 to 200% by mass based on the component (A).

[0043] The content of the component (A) is preferably 0.01 to 15% by mass based on the composition according to the present invention (more preferably 0.05 to 10% by mass; even more preferably 0.10 to 5% by mass; still even more preferably 0.10 to 4% by mass). As described above, the polymer (A) may be a copolymer containing repeating units other than the structure of the formula (0) within the scope not impairing the present invention. It is a preferred form of the present invention that a structure derived from the compound represented by the formula (c) constitutes the polymer (A) as a repeating unit among the repeating units other than the structure of the formula (0). A more preferred example of the structure derived from the compound represented by the formula (c) is the compound represented by the formula (c) itself. In that case, the molecular weight and content are described as the polymer (A) rather than the component (C). The details are as described above. When the polymer (A) is a copolymer, preferably, (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%; even more preferably 150 to 250%). It is preferable to determine the ratio of the number of repeating units in terms of molar ratio. When the polymer (A) is a copolymer, the molar ratio of the hydroxy group in the structure derived from the compound represented by formula (c) to the group represented by formula (1) in the structure of formula (0) is preferably 2:1 to 1:2 (more preferably 3:2 to 2:3; even more preferably 4:3 to 3:4).

[0044] (B) Solvent The composition according to the present invention comprises a solvent (B). The solvent (B) comprises a solvent (B1) represented by formula (b1). R 21 -O―R 22 (b1) Herein,[[]]END]] R 21 and R 22 are each independently C 1-8 alkyl (preferably C 3-6 alkyl). These may be linear, branched or cyclic (preferably linear or cyclic; more preferably linear). R 21 and R 22 may be different or the same, but are preferably the same. R 21 and R 22 are each independently preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, isopentyl, cyclopentyl, or cyclohexyl (more preferably methyl, n-butyl, n-pentyl, isopropyl, cyclopentyl, or cyclohexyl; even more preferably n-butyl). Examples of the solvent (B1) include dibutyl ether, dipentyl ether, diisopentyl ether, dicyclopentyl ether, dicyclohexyl ether, cyclopentyl methyl ether, and the like. As one embodiment of the present invention, the solvent (B) preferably consists essentially of only the solvent (B1) (more preferably consists of only the solvent (B1)).

[0045] The solvent (B) preferably comprises a solvent (B2) different from the solvent (B1) (more preferably consists essentially of only the solvent (B1) and the solvent (B2); even more preferably consists of only the solvent (B1) and the solvent (B2)). Preferably, the 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. The solvent (B2) is preferably PGME, PGMEA, or a combination thereof. When the solvent contained in the solvent (B2) is two types, the mass ratio thereof is preferably 100:1 to 1:100 (more preferably 50:1 to 1:50; even more preferably 30:1 to 1:30). The solvent (B2) may contain water. The water content is preferably 5% by mass or less (more preferably 1% by mass or less; even more 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). Without being bound by theory, it is considered that the solvent (B) of the composition according to the present invention can contribute to the formation of a thick film pattern by dissolving the solid component (components other than the solvent (B)) while avoiding dissolving the underlying resist film.

[0046] The content of the solvent (B) is preferably 70 to 99.99% by mass (more preferably 80 to 99.99% by mass; still more preferably 95 to 99.99% by mass; even more preferably 95 to 99.90% by mass) based on the composition according to the present invention. The content of the solvent (B1) is preferably 70 to 100% by mass (more preferably 80 to 100% by mass; still more preferably 90 to 100% by mass) based on the solvent (B). The content of the solvent (B2) is preferably 0 to 30% by mass (more preferably 0 to 20% by mass; still more preferably 0.1 to 10% by mass) based on the solvent (B).

[0047] (C) Hydroxy-containing compound The composition according to the present invention may further contain a (C) hydroxy-containing compound represented by the formula (c). The formula (c) is as follows.

Chemical formula

[0048] The (C) hydroxy-containing compound (component (C)) represented by the formula (c) has at least one OH and has X as the mother skeleton. X which is the mother skeleton is C 1-60 is a hydrocarbon group, and being composed of an aliphatic hydrocarbon group, a cyclic hydrocarbon group or a combination thereof is one of the preferred forms of the present invention. X in the component (C) is preferably represented by the formula (X-1) or the formula (X-2) (more preferably (X-2)).

[0049] Examples of the component (C) include the following compounds.

Chemical formula

[0050] The molecular weight of component (C) is preferably from 200 to 800 (more preferably from 200 to 600; even more preferably from 200 to 450).

[0051] The content of component (C) is preferably from 50 to 200% by mass based on the hydrocarbon compound (A) (more preferably from 60 to 150% by mass; even more preferably from 60 to 110% by mass). It is also a preferred form of the present invention that component (C) is not contained (0.000% by mass). In the composition of the present invention, the molar ratio of the hydroxy group of component (C) to the group represented by formula (1) of component (A) is preferably from 2:1 to 1:2 (more preferably from 3:2 to 2:3; even more preferably from 4:3 to 3:4).

[0052] As one form of the present invention, R in formula (1) 15 is C 2-7 alkenyl, and the composition of the present invention substantially does not contain component (C). Without being bound by theory, when there is a resist film having a hydroxy group on the surface, R 15 is protected by bonding with the hydroxy group, and the bonding site is deprotected by receiving an acid that has migrated from the resist film to the resist upper layer film, and the acid receiving portion can be solubilized in the developer. For example, when R 15 is vinyl, the bonding site with hydroxy (acetal structure) can be deprotected by receiving an acid. It is a preferred form of the present invention that the migration of the "acid that has migrated from the resist film to the resist upper layer film" is promoted by heating in step (3). As a preferred form, the surface of the resist film to which the composition of the present invention is applied has a hydroxy group. Suitable examples suitable for this form include the following independently of each other. X is preferably a group consisting of cyclic C 5-10 alkyl, a group consisting of linear C 1-6 alkyl, a group consisting of branched C 3-6 alkyl, or a group consisting of any combination thereof (more preferably a group consisting of cyclic C 5-10 alkyl, linear C 1-6A group consisting of an alkyl group or a combination thereof; more preferably a cyclic C 5-6 A group consisting of an alkyl group, or a linear C 1-6 A group consisting of an alkyl group; even more preferably cyclohexyl). It is preferable that X is represented by the formula (X-2). As another form, it is also preferable that X is represented by the formula (X-1). n 01 Is a number from 1 to 3 (more preferably 1, 2 or 3; even more preferably 1 or 2; even more preferably 1). n 11 Is 0 or 1 (more preferably 0). n 12 Is 0 or 1 (more preferably 0). L 12 Is selected from -C(=O)- or -C(=O)-CH 2 -(more preferably -C(=O)-). n 13 Is 0 or 1 (more preferably 0). n 14 Is 0 or 1 (more preferably 0). L 14 Is methylene, ethylene or n-butylene (more preferably methylene or n-butylene; even more preferably n-butylene). R 15 Is C 2-7 Alkenyl (more preferably vinyl). Cy 31 And Cy 34 Are each independently cyclohexyl or phenyl (more preferably cyclohexyl). n 32 Is 0, 1, 2 or 3 (more preferably 0, 1 or 2; even more preferably 0 or 2; even more preferably 0). R 33 And R 35 Are each independently methyl, ethyl, isopropyl or n-propyl (more preferably methyl or ethyl; even more preferably methyl). n 33 Is 0 or 1 (more preferably 1). n34 and n 35 is, independently of each other, 0 or 1 (more preferably 0). The composition of the present invention substantially does not contain the component (C). Substantially not containing means that the content of the component (C) is 0 to 5% by mass (more preferably 0.00 to 1% by mass; even more preferably 0.00 to 0.1% by mass; even more preferably 0.000% by mass) based on the component (A). When the component (A) of the present invention is a polymer, the polymer does not contain a structure derived from the compound represented by the formula (c). The component (A) of the composition of the present invention is not a polymer but a compound represented by the formula (0).

[0053] (D) Acid generator The composition according to the present invention may further contain a (D) acid generator. In a preferred embodiment, when the component (D) reacts with an acid, it releases an acid having an acid dissociation constant pKa(H 2 O) - 14 to 8 (more preferably - 14 to 4; even more preferably - 12 to 2; even more preferably - 10 to 1). More preferably, the resist film formed under the resist upper layer film contains PAG (D'), and PAG (D') releases an acid having an acid dissociation constant pKa(H 2 O) - 20 to 1.4 (preferably - 16 to 1.4; more preferably - 16 to 1.2; even more preferably - 16 to 1.1) upon exposure. Without being bound by theory, it is considered that the acid derived from the component (D') moves from the resist film to the resist upper layer film and undergoes salt exchange with the component (D), thereby diffusing the resist upper layer film for a longer time and thus more effectively exerting the effect according to the present invention. An acid generated from the component (D) by salt exchange is a weak acid, and it is one aspect of the present invention that the acidity is lower than that of the strong acid generated from the (E) photoacid generator by photoreception described below.

[0054] A preferred form of the (D) acid generator includes a salt of an m-valent Cation and an m-valent Anion. m is preferably 1 or 2 (more preferably 2). The Cation is preferably obtained from triarylsulfonium or diaryliodonium (more preferably triarylsulfonium). The aryl group of the Cation is preferably phenyl or naphthyl (more preferably phenyl). The aryl group may be unsubstituted or substituted (more preferably unsubstituted). The number of substituents bonded to one aryl group to be substituted is preferably an integer of 1 to 5 (more preferably 1, 2 or 3; even more preferably 1), and the substituents are preferably halogen, methyl or methoxy (more preferably fluorine, methyl or methoxy; even more preferably methyl). The Anion is preferably obtained from sulfonic acid or carboxylic acid (more preferably sulfonic acid). The sulfonic acid or carboxylic acid has an alkyl or aryl group (more preferably an alkyl group). The alkyl group is preferably C 1-4 alkyl (more preferably methyl). The H in the alkyl group may be unsubstituted or substituted (preferably substituted). All or part (more preferably all) of the H of one alkyl group to be substituted is replaced by a substituent. The substituent is preferably halogen (more preferably fluorine). The aryl group is preferably C 6-10 aryl (more preferably phenyl or naphthyl; even more preferably phenyl). The H in the aryl group may be unsubstituted or substituted (preferably substituted). The number of substituents bonded to one aryl group to be substituted is preferably an integer of 1 to 5 (more preferably 1, 2 or 3; even more preferably 1), and the substituents are preferably halogen, methyl or methoxy (more preferably fluorine, methyl or methoxy; even more preferably methyl).

[0055] Examples of the component (D) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium methanesulfonate, triphenylsulfonium 4-methylbenzenesulfonate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and the like.

[0056] The composition of the present invention may or may not contain component (D). The content of component (D) is preferably 0.01 to 40% by mass (more preferably 0.10 to 20% by mass; still more preferably 0.20 to 10% by mass) based on component (A).

[0057] (E) Photoacid generator The composition according to the present invention may further contain (E) a photoacid generator, but preferably does not substantially contain it. Here, component (E) releases an acid having an acid dissociation constant pKa(H 2 O) of -20 to 1.4 (preferably -16 to 1.4; still more preferably -16 to 1.2; even more preferably -16 to 1.1). The content of component (E) is preferably 0 to 1.00% by mass (more preferably 0.00 to 0.005% by mass; still more preferably 0.00 to 0.001% by mass) based on component (A). It is also a preferred form according to the present invention not to contain component (E) (0.000% by mass). Without being bound by theory, it is considered possible to accept the acid migrating from the underlying resist film even if the upper layer film of the present invention does not contain component (E) that generates a strong acid.

[0058] (F) Surfactant The composition according to the present invention may further contain a surfactant (F). By including the surfactant (F), the coatability can be improved. Examples of the surfactant that can be used in the present invention include (I) anionic surfactants, (II) cationic surfactants, or (III) nonionic surfactants. More specifically, (I) alkyl sulfonates, alkylbenzene sulfonic acids, and alkylbenzene sulfonates, (II) lauryl pyridinium chloride and lauryl methyl ammonium chloride, and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene acetylenic glycol ether, fluorine-containing surfactants (e.g., Fluorad (3M), MAGAFACE (DIC), Sulfron (Asahi Glass)), and organosiloxane surfactants (e.g., KF-53, KP341 (Shin-Etsu Chemical Co., Ltd.)) can be mentioned. These surfactants can be used alone or in combination of two or more.

[0059] The content of the surfactant (F) is preferably 0 to 10% by mass (more preferably 0.001 to 10% by mass; still more preferably 0.1 to 5% by mass) based on the hydrocarbon compound (A). It is also one form of the present invention not to contain the surfactant (F) (0.00% by mass).

[0060] (G) Additive The composition according to the present invention may further contain other additives (G) different from the above components (A) to (F). The additive (G) is preferably a surface smoothing agent, an acid, a base, a substrate adhesion enhancer, an antifoaming agent, or a combination of any of these (more preferably a base). Examples of the base include trialkylamine.

[0061] The content of the additive (G) is preferably 0 to 10% by mass (more preferably 0.001 to 10% by mass; still more preferably 0.001 to 1% by mass; even more preferably 0.01 to 0.5% by mass) based on the hydrocarbon compound (A). In a preferred form of the present invention, the additive (G) is not contained (0.000% by mass).

[0062] [Method for manufacturing resist upper layer film pattern and resist pattern] The method for manufacturing a resist upper layer film pattern and a resist pattern according to the present invention comprises the following steps. (1) Apply a resist composition above a substrate, heat the resist composition, and form a resist film; (2) Optionally, expose the resist film; (3) Apply a developable resist upper layer film composition directly above the resist film, heat the resist upper layer film composition, and form a resist upper layer film; (4) Optionally, expose the resist film and the resist upper layer film; However, at least one of the exposures in (2) and (4) must be performed. (5) Acid in the resist film moves to the resist upper layer film; and (6) Develop the resist upper layer film and the resist film using a developer to form a resist upper layer pattern and a resist pattern. Hereinafter, each step will be described with reference to the drawings. The numbers in () indicating the steps mean the order.

[0063] Step (1) In step (1), a resist composition is applied above the substrate, the resist composition is heated, and a resist film is formed. 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. The resist composition is not particularly limited, but from the viewpoint of forming a high-resolution fine resist pattern, a chemically amplified resist composition is preferably used, and examples thereof include a chemically amplified PHS-acrylate hybrid type EUV resist composition. It is also a preferred embodiment that the resist composition contains a photoacid generator (D') (the above-mentioned PAG (D')). As the resist composition usable in the production method of the present invention, the pattern forming composition or the radiation-sensitive resin composition described in JP-A-2021-73367 or JP-A-2020-8842 can be used. The resist composition of the production method of the present invention is preferably a positive type. A general high-resolution positive resist composition includes a combination of an alkali-soluble resin having side chains protected by a protecting group and a photoacid generator. When a resist layer formed from 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 protecting group bonded to the alkali-soluble resin is dissociated by the acid (hereinafter referred to as deprotection). Since the deprotected alkali-soluble resin is soluble in an alkali developer, it is removed by development processing.

[0064] The resist composition is applied above the substrate by an appropriate method. Here, in the present invention, "above the substrate" includes the case of applying directly above the substrate and the case of applying through other layers. For example, a resist underlayer film (for example, SOC (Spin On Carbon) and / or an adhesion enhancing film) may be formed directly above the substrate, and the resist composition may be applied directly above it. Preferably, the resist composition is applied directly above the substrate. In another preferred embodiment, SOC is formed directly above the substrate, an adhesion enhancing film is formed directly above SOC, and the resist composition is applied directly above it. The application method is not particularly limited, and examples thereof include coating by spin coating. The substrate to which the resist composition is applied forms a resist layer by heating. This heating is also called pre-baking and is performed, for example, by a hot plate. The heating temperature is preferably 90 to 250 °C (more preferably 90 to 200 °C; even more 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; even more preferably 45 to 90 seconds). The heating is preferably performed in an atmosphere of air or nitrogen gas (more preferably in an air atmosphere). Figure 1(i) is a schematic diagram showing a resist film 2 formed on a substrate 1. The film thickness of the resist layer is preferably 10 to 50 nm (more preferably 25 to 50 nm).

[0065] Step (2) In step (2), optionally, the resist film is exposed. The exposure is performed through a mask if desired. The wavelength of the radiation (light) used for exposure is not particularly limited, but it is preferable to expose with light having a wavelength of 13.5 to 248 nm. Specifically, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and EUV (extreme ultraviolet light, wavelength 13.5 nm), etc. can be used. EUV light is more preferable. A range of ±1% is allowed for these wavelengths. After exposure, post-exposure baking (PEB) can also be performed as necessary. The temperature of PEB can be selected from the range of 70 to 150 °C (preferably 100 to 140 °C). The heating time of PEB can be selected from the range of 0.3 to 5 minutes (preferably 0.5 to 2 minutes). Figure 1(ii) is a schematic diagram showing a state in which the resist film 2 in the case of using a typical positive chemically amplified resist composition is exposed through a mask. In the exposed portion 3, an acid is released from the photoacid generator, whereby the polymer is deprotected and its alkali solubility is increased. The alkali solubility of the unexposed portion 4 has not changed.

[0066] Step (3) In step (3), a developable resist upper layer film composition is applied directly on the resist film, and then the resist upper layer film composition is heated to form a resist upper layer film. The developable resist upper layer film composition is preferably a composition comprising the hydrocarbon compound (A) and the solvent (B) according to the present invention described above. The application method is not particularly limited, and examples thereof include coating by spin coating. For the substrate to which the developable resist upper layer film composition is applied, a resist upper layer film is formed by heating. The heating is performed, for example, on 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 an atmosphere of air or nitrogen gas (more preferably in an air atmosphere). Without being bound by theory, when the exposure in step (2) is performed, it is considered that the acid generated from the photoacid generator in the resist film diffuses by the heating in step (3). A form in which the acid moves from the resist film to the resist upper layer film of the present invention by this diffusion, as in step (5) described later, is more preferable. The thickness of the resist upper layer film formed in step (3) is preferably 1 to 10 nm (more preferably 2 to 8 nm; still more preferably 5 to 7 nm). A preferred embodiment is that the thickness of the resist film does not substantially decrease even when the resist upper layer film composition of the present invention is applied. Specifically, the reduction amount of the thickness of the resist film (excluding the resist upper layer film) before and after the application is preferably 0 to 15% (more preferably 0 to 10%; still more preferably 0.1 to 5%; even more preferably 0.1 to 1%). Another preferred embodiment of the present invention is that the thickness of the resist film does not decrease (the reduction amount is 0%) before and after the application.

[0067] Step (4) In step (4), optionally, the resist film and the resist upper layer film are exposed. However, at least one of the exposures in steps (2) and (4) must be performed. The exposure conditions in step (4) are the same as those in step (2). Preferably, the exposure in step (2) is performed, and the exposure in step (4) is not performed. In this case, the resist film before the formation of the upper resist film is exposed, and is not exposed after the formation of the upper resist film. That is, in the manufacturing method of the present invention, step (4) may be removed. Fig. 1(iii) is a schematic diagram of a state in which, after the resist film 2 is formed, it is exposed, and then the upper resist film 5 is formed.

[0068] It is also preferable to perform heating (PEB) after the exposure. Preferably, heating in step (2-2) is performed following step (2) and / or heating in step (4-2) is performed following step (4). By PEB, the acid generated in the exposed portion can be diffused, and for example, the presence of the acid within the exposed portion can be made more uniform. Not performing the heating in (2-2) and (4-2) is also a preferred form. When the exposure is performed in step (2), it is possible to diffuse the acid by heating in step (3).

[0069] Step (5) In step (5), the acid in the resist film moves to the upper resist film. The movement of the acid can also be promoted by heating. The movement of the acid may occur during the heating of the upper resist film in step (3) (that is, step (5) may occur simultaneously with step (3)), or may occur after step (3). More preferably, the movement of the acid in step (5) occurs during the heating of the upper resist film in step (3). Preferably, the solubility of the upper resist film in the developer is changed by the acid that has moved in this step (5). In a preferred form, the acid generated from the photoacid generator (E) in the resist film is ion-exchanged with the acid generator (D) in the upper resist film, and the acid derived from the acid generator (D) diffuses in the upper resist film, changing the solubility of the upper resist film in the developer. In a more preferred embodiment, in a region where no acid migration occurs (the unexposed portion in the case of a positive resist), when forming the resist upper layer film in step (3), the hydrocarbon compound (A) in the developable resist upper layer film composition binds to the resist film, becoming insoluble in the developer. In a region where acid migration occurs (the exposed portion in the case of a positive resist), the acid that has 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. Figure 1(iv) is a schematic diagram of a state where acid migration occurs from the resist film to the resist upper layer film. In the positive type, acid migrates to the exposed portion of the resist film and the resist upper layer film directly above the exposed portion, and the portion where the acid has migrated becomes alkali-soluble like the resist film. However, in the unexposed portion, no acid migration occurs, and the solubility of the resist upper layer film in the developer does not change.

[0070] After step (5) and before development, it is also preferable to perform surface cleaning on the resist upper layer film to remove the upper part of the resist upper layer film. For the surface cleaning, a composition having the same composition as the solvent (B) of the composition according to the present invention can be used.

[0071] Step (6) In step (6), using a developer, the resist upper layer film and the resist film are developed to form a resist upper layer film pattern and a resist pattern (hereinafter sometimes referred to as a thick film pattern). Examples of the method for applying the developer include the paddle method, the dip method, and the spray method. The temperature of the developer 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 applying the developer, the developer is removed. The developer is preferably an alkaline aqueous solution or an organic solvent (more preferably an alkaline aqueous solution). Examples of the alkaline aqueous solution include aqueous solutions containing inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium silicate, organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, and triethylamine, and quaternary amines such as tetramethylammonium hydroxide (TMAH) (more preferably an aqueous TMAH solution; even more preferably a 2.38 mass% TMAH aqueous solution). The above-described surfactant can also be added to the developer.

[0072] Figure 1(v) shows a state where the developer is applied to the resist film and the upper resist film, the developer is removed, and the resist pattern 6 and the upper resist film pattern 7 are formed. When the resist pattern 6 and the upper layer film pattern 7 are viewed together, they form a thickening pattern. Assuming that the thickening amount is (the film thickness of the resist pattern and the film thickness of the upper resist film) - (the resist pattern film thickness formed in the same manner except that the thickening solution is not applied), the thickening amount is preferably 1 to 10 nm; more preferably 2 to 8 nm; even more preferably 3 to 7 nm; and even more preferably 4 to 6 nm. Without being bound by theory, in high-precision lithography techniques such as EUV exposure, the thickness of the resist film is generally thin. By thickening according to the present invention, it is considered possible to ensure the durability as a mask when used as an etching mask, for example, in a subsequent process.

[0073] The method according to the present invention can further include the following step (7). (7) Wash the upper resist film pattern and the resist pattern with a cleaning solution and remove the cleaning solution between the patterns. In order to remove local film residues, the resist upper layer film pattern and the resist pattern can be cleaned using a cleaning liquid. Examples of the cleaning liquid include a water-soluble cleaning liquid or an organic solvent cleaning liquid (e.g., IPA, PGME, PGMEA, PGEE, nBA). In a preferred embodiment of the present invention, the cleaning liquid is a rinse liquid, and the developer is replaced with the rinse liquid for rinsing. The rinsing process can preferably be performed with a water-soluble rinse liquid. The lower limit of the content of water (DIW) in the water-soluble rinse liquid, based on the whole liquid, is preferably 90% by mass (more preferably 95% by mass; even more preferably 98% by mass; still more preferably 99.99% by mass). The components other than water contained in the water-soluble rinse liquid are preferably 1,000 ppm or less (more preferably 100 ppm or less) based on the whole liquid.

[0074] [Method for manufacturing a processed substrate and a device] The method for manufacturing a processed substrate according to the present invention includes the following steps. Forming a resist upper layer film pattern and a resist pattern by the method described above; and (8) Processing using the resist upper layer film pattern and the resist pattern as a mask.

[0075] Step (8) In step (8), processing is performed using the resist upper layer film pattern and the resist pattern as a mask. The resist upper layer film pattern and the resist pattern are preferably used as a mask for performing a processing treatment on the resist lower layer film or the substrate (more preferably the substrate). Specifically, various substrates serving as a base can be processed using a dry etching method, a wet etching method, an ion implantation method, a metal plating method, etc., using the thickening pattern as a mask. Since the resist pattern is thickened, it can function as a mask even under more severe conditions, and thus it is preferably used for processing by the dry etching method. When processing the resist underlayer film using a thick film pattern, the processing may be performed step by step. For example, using the thick film pattern, the adhesion enhancement film and the SOC may be processed, and using the SOC pattern, the substrate may be processed. As the adhesion enhancement film, for example, SiARC (Si antireflection film) can be used. A form of directly processing the substrate using the thick film pattern is a more preferred embodiment.

[0076] The method for manufacturing a device according to the present invention includes the above method, and preferably further includes a step of forming wiring on the processed substrate. These processes can apply known methods. Thereafter, if necessary, the substrate is cut into chips, connected to a lead frame, and packaged with resin. In the present invention, this packaged product is referred to as a device. Examples of the device include a semiconductor element, a liquid crystal display element, an organic EL display element, a plasma display element, and a solar cell element. The device is preferably a semiconductor element.

[0077] [Examples] The present invention will be described by way of examples as follows. The forms of the present invention are not limited to only these examples.

[0078] [Preparation of Compositions of Examples 101 to 107] As shown in Table 1, each component is mixed in each blending amount. First, the components (B1) and (B2) are mixed to obtain the solvent (B). The components (A), (D), and (F) are added to the solvent (B). The numerical values in Table 1 are the contents (parts by mass) of the respective components based on the total mass of the composition. The obtained solution is stirred at room temperature for 30 minutes. After visually confirming that the solute is completely dissolved, this solution is filtered through a 0.2 μm fluororesin filter to obtain the compositions of Examples 101 to 107.

Table 1

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0079] B1-1 is dibutyl ether. B2-1 is PGMEA. B2-2 is PGME. D1 is triphenylsulfonium trifluoromethanesulfonate. D2 is triphenylsulfonium trifluoroacetate. D3 is triphenylsulfonium methanesulfonate. D4 is triphenylsulfonium 4-methylbenzenesulfonate. D5 is (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate. F1 is an acetylene diol polyoxyalkylene ether having the following structure.

Chemical formula

[0080] [Preparation of the compositions of Examples 201 to 206] As shown in Table 2, each component is mixed in each compounding 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 numerical values in Table 2 are the contents (parts by mass) of the respective components based on the total mass of the composition. The obtained solution is stirred at room temperature for 30 minutes. After visually confirming that the solute is completely dissolved, this solution is filtered through a 0.2 μm fluororesin filter to obtain the compositions of Examples 201 to 206.

Table 2

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0081] [Preparation of Compositions of Examples 301 to 305] 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 numerical values in Table 3 are the contents (parts by mass) of the respective components based on the total mass of the composition. The obtained solution is stirred at room temperature for 30 minutes. After visually confirming that the solute is completely dissolved, this solution is filtered through a 0.2 μm fluororesin filter to obtain the compositions of Examples 301 to 305. [Table 3]

[0082] The compounds described in Table 3 are as follows. A10 is cyclohexyl vinyl ether. [Chemical Formula] A11 is 1,4-cyclohexanedimethanol divinyl ether. [Chemical Formula] A9, B1-1, B2-2, D1 and F1 are the same as in Tables 1 and 2.

[0083] [Manufacture of Resist Upper Layer Film Pattern and Resist Pattern] The silicon substrate is subjected to HMDS (hexamethyldisilazane) treatment at 90°C for 30 seconds. The HMDS-treated substrate is coated with a chemically amplified PHS-acrylate hybrid resist composition by spin coating and heated on a hot plate at 110°C for 60 seconds to form a resist film with a thickness of 35 nm. The resist film is exposed using an EUV exposure apparatus (NXE:3300B, ASML) through a mask with a size of 18 nm (line:space = 1:1) while changing the exposure dose. Then, PEB is performed at 100°C for 60 seconds. Thereafter, the composition of the above example is applied onto the resist layer by spin coating and heated at 90°C for 60 seconds to form a resist upper layer film. Then, paddle development is performed for 30 seconds using a 2.38 mass% TMAH aqueous solution as the developer. Water is dropped while the developer is being paddled on the substrate, and water dropping is continued while rotating the substrate to replace the developer with water. Thereafter, the substrate is rotated at high speed to dry the thickened resist pattern (resist upper layer film pattern and resist pattern).

[0084] For comparison, a resist pattern is formed without applying the composition of the example. Specifically, a resist pattern is formed in the same manner as above, except that the composition of the example is not applied and subsequent heating is not performed. This is referred to as a comparative resist pattern.

[0085] [Evaluation of thickening amount] Cross-sections of the substrate are prepared for the thickened resist pattern and the comparative resist pattern, respectively, and the cross-sectional shape is observed with an SEM (SU8230, Hitachi High-Tech Fielding) to measure the height of the pattern. (Thickness of the resist pattern + thickness of the resist upper layer film pattern) - (thickness of the comparative resist pattern) is calculated as the thickening amount. The obtained results are shown in Tables 1 to 3.

Explanation of reference numerals

[0086] 1. Substrate 2. Resist film 3. Exposed portion 4. Unexposed portion 5. Resist upper layer film 6. Resist pattern 7. Resist upper layer film pattern

Claims

1. A developable resist upper film composition comprising a hydrocarbon compound (A) and a solvent (B), The hydrocarbon compound (A) is a polymer comprising a compound represented by formula (0), or a structure derived from the compound represented by formula (0), as repeating units; and A composition comprising solvent (B) represented by formula (b1). 【Chemistry 1】 (Here, X is C １－６０ It is a hydrocarbon group; n ０１ n is a number between 1 and 10. ０２ is a number between 0 and 10; Y is a group represented by formula (1) or -OH, wherein 40 to 100% of the total number of Y are groups represented by formula (1); R ０２ is C １－６ alkoxy (excluding t-butoxy), -(C=O)-R ０３ , -(C=O)-O-R ０４ , -(C=O)-N(R ０５ ) ２ , -O-(C=O)-R ０６ , or -NR ０７ -(C=O)-R ０８ ; R ０３ is H or C １－４ It is alkyl; R ０４ C １－４ Alkyl (except t-butyl); R ０５ These are, independently, H or C １－４ It is alkyl, and has two R ０５ They may also bond to form a ring structure; R ０６ H, C １－４ Alkyl, or C １－４ It is an alkoxy (except t-butoxy); R ０７ is H or C １－４ It is alkyl; R ０８ H, C １－４ Alkyl, or -N(R) ０９ ) ２ And; R ０７ and R ０８ When is alkyl, they may bond together to form a ring structure; and R ０９ These are, independently, H or C １－４ It is alkyl, and has two R ０９ They may both bond together to form a ring structure. 【Chemistry 2】 (Here, n １１ , n １２ , n １３ and n １４ Each of these is independently a number between 0 and 1; L １２ -C(=O)-, -CH ２ -C(=O)-, -C(=O)-CH ２ - and -CH(CH ３ Selected from the group consisting of: L １４ C １－５ It is alkylene; and R １５ C １－１５ Alkyl or C ２－７ It is an alkenil; L １２ The methyl and R that it possesses １５ (The methyl atoms present may bond to form a ring.) R ２１ -O-R ２２ (A1) (Here, R ２１ and R ２２ Each of them independently, C １－８ (It is alkyl.)

2. The composition according to claim 1, wherein X is represented by formula (X-1) or formula (X-2): 【Transformation 3】 (Here, R ２１ and R ２４ Each of these is independently a linear or branched C １－１０ It is an aliphatic hydrocarbon group; n ２２ These are numbers from 0 to 5; Cy ２３ and Cy ２５ Each of them independently, C ５―１０ It is a cyclic hydrocarbon group having a ring atom; n ２３ Each of these is independently a number between 0 and 1; n ２４ and n ２５ (Each of these is an independent number between 0 and 3.) 【Chemistry 4】 (Here, Cy ３１ and Cy ３４ Each of them independently, C ５―１０ It is a cyclic hydrocarbon group having a ring atom; n ３２ These are numbers from 0 to 5; R ３３ Each of these is independently a linear or branched C １－１０ It is alkyl; R ３５ Each of these is independently a linear or branched C １－１０ It is alkyl; n ３３ These are each independently a number between 0 and 1; n ３４ and n ３５ Each of these is independently a number between 0 and 3): Preferably, the molecular weight of the hydrocarbon compound (A) is 100 to 80,000.

3. The composition according to claim 1 or 2, further comprising a hydroxyl-containing compound (C) represented by formula (c): 【Transformation 5】 (Here, 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 And; n ４１ n is a number between 1 and 10. ４２ These are numbers from 0 to 10; X, R ０３ , R ０４ , R ０５ , R ０６ , R ０７ and R ０８ each independently has the meaning described in claim 1): Preferably, the molecular weight of the hydroxyl-containing compound (C) is 200 to 800; or Preferably, the content of the hydroxyl-containing compound (C) is 50 to 200% by mass, based on the hydrocarbon compound (A).

4. The composition according to claim 1 or 2, wherein solvent (B) further comprises solvent (B2): Preferably, the solvent (B2) is 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. The composition according to claim 1 or 2, further comprising an acid generator (D): Preferably, when the acid generator (D) reacts with the acid, the acid dissociation constant pKa(H) ２ O) Releases an acid of -14 to -8; Preferably, the resist film formed beneath the resist upper layer film contains PAG(D'), and PAG(D') undergoes an acid dissociation constant pKa(H) upon exposure. ２ O) Releases an acid of -20 to 1.4; or Preferably, the content of the acid generator (D) is 0.01 to 40% by mass, based on the hydrocarbon compound (A).

6. The composition according to claim 1 or 2, substantially free of the photoacid generator (E): Here, the photoacid generator (E) reacts to exposure, and the acid dissociation constant pKa(H) ２ It releases an acid of O)-20 to 1.4; and The content of the photoacid generator (E) is 0 to 1.00% by mass, based on the hydrocarbon compound (A).

7. The composition according to claim 1 or 2, further comprising a surfactant (F): Preferably, the content of surfactant (F) is 0 to 10% by mass, based on hydrocarbon compound (A).

8. The composition according to claim 1 or 2, further comprising other additives (G): Preferably, additive (G) is a surface smoothing agent, an acid, a base, a substrate adhesion enhancer, an antifoaming agent, or a combination thereof; or Preferably, the content of additive (G) is 0 to 10% by mass, based on hydrocarbon compound (A).

9. The composition according to claim 1 or 2, wherein the content of hydrocarbon compound (A) is 0.01 to 15% by mass, based on the composition. Preferably, the content of solvent (B) is 70 to 99.99% by mass based on the composition; Preferably, the content of solvent (B1) is 70 to 100% by mass, based on solvent (B), or Preferably, the content of solvent (B2) is 0 to 30% by mass, based on solvent (B).

10. The composition according to claim 1 or 2, which is a developable resist upper layer film composition formed on a resist film after exposure: Preferably, the composition is a developable resist top layer composition formed on a resist film after EUV exposure; or Preferably, the resist film is a positive-type EUV resist film.

11. A resist upper layer film pattern and a method for manufacturing the resist pattern comprising the following steps: (1) Apply the resist composition to the substrate, heat the resist composition, and form a resist film; (2) Optionally, expose the resist film; (3) Apply a developable resist upper layer composition directly on the resist film, heat the resist upper layer composition, and form a resist upper layer; (4) Optionally, expose the resist film and the resist upper layer film; However, at least one of the exposures in (2) and (4) must be performed. (5) Acid in the resist film moves to the upper resist film; and (6) Using a developer, develop the resist upper layer film and the resist film to form the resist upper layer pattern and the resist pattern: Preferably, step (2-2) heating is performed following step (2), and / or step (4) heating is performed following step (4).

12. The method according to claim 11, wherein the developable resist upper layer film composition is the composition described in claim 1.

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: Preferably, the thickness of the resist film formed in step (1) is 10 to 50 nm.

14. The method according to claim 11 or 12, wherein the solubility of the resist upper layer film in the developer is changed by the acid moved in step (5): Preferably, the acid generated from the photoacid generator (E) in the resist film is exchanged with the acid generator (D) in the resist upper layer film through ion exchange, and the acid derived from the acid generator (D) diffuses into the resist upper layer film, changing the solubility of the resist upper layer film in the developer.

15. In step (3), the hydrocarbon compound (A) in the developable resist upper layer composition becomes insoluble in the developer solution by bonding with the resist film, and The method according to claim 11 or 12, wherein the resist upper layer film becomes soluble in the developer due to the acid moved in step (5).

16. The method according to claim 11 or 12, further comprising step (7): (7) Clean the resist upper layer pattern and the resist pattern with the cleaning solution and remove the cleaning solution from between the patterns.

17. A method for manufacturing a processed substrate, comprising the following steps. Forming a resist upper layer film pattern and a resist pattern by the method of claim 11 or 12; and (8) Process the resist upper layer pattern and the resist pattern as a mask: Preferably, step (8) processes the resist underlayer or substrate.

18. A method for manufacturing a device comprising the method of claim 11 or 12: Preferably, the process further includes the step of forming wiring on the processed substrate; or Preferably, the device is a semiconductor element.

Images