JP6119983B2 - Composition for forming resist upper layer film for lithography and method for manufacturing semiconductor device using the same - Google Patents

Description

  The present invention is used in a manufacturing process of a semiconductor device using photolithography, reduces an adverse effect exerted by exposure light, and is effective for obtaining a good resist pattern. The present invention relates to a resist pattern forming method using a resist upper layer film forming composition and a method for manufacturing a semiconductor device using the forming method.

Conventionally, fine processing using a photolithography technique has been performed in the manufacture of semiconductor devices. In the fine processing, a thin film of a photoresist composition is formed on a substrate to be processed such as a silicon wafer, and then actinic rays such as ultraviolet rays are irradiated and developed through a mask pattern on which a semiconductor device pattern is drawn. In this processing method, the substrate to be processed such as a silicon wafer is etched using the obtained photoresist pattern as a protective film (mask). In recent years, the degree of integration of semiconductor devices has increased, and the active light used has also been shortened from a KrF excimer laser (wavelength 248 nm) to an ArF excimer laser (wavelength 193 nm). Along with this, the influence of diffuse reflection and standing wave of actinic rays from the substrate becomes a big problem, and a bottom anti-reflection film (Bottom Anti- A method of providing reflective coating (BARC) has been widely adopted.
As an antireflection film, an inorganic antireflection film such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and α-silicon, and an organic antireflection film made of a light-absorbing substance and a polymer compound are known. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation, whereas the latter is advantageous in that no special equipment is required, and many studies have been made.
In recent years, an ArF immersion lithography technique in which exposure is performed through water has been put into practical use as a next-generation photolithography technique that bears the photolithography technique using an ArF excimer laser (wavelength 193 nm). However, photolithographic technology using light is reaching its limit, and EUV lithography technology using EUV (wavelength 13.5 nm) is attracting attention as a new lithography technology after ArF immersion lithography technology. In a semiconductor device manufacturing process using EUV lithography, a substrate coated with an EUV resist is irradiated with EUV, exposed, developed, and a resist pattern is formed.
In order to protect the EUV resist from contaminants and to block unwanted radiation such as UV and DUV (OUT of BAND / Out-of-band radiation, OOB), an upper layer of the EUV resist is coated with beryllium, boron, carbon, silicon, zirconium, A method is disclosed that includes a polymer that includes a group that includes one or more of niobium and molybdenum (Patent Document 1, Patent Document 2).
In order to block OOB, a top coat formed of a polyhydroxystyrene (PHS) compound or an acrylic compound is applied to the upper layer of the EUV resist to reduce OOB (Non-patent Document 1), There is an example in which a film called EUV resolution enhancement layer is applied on the upper layer of the EUV resist, and the EUV resist resolution is improved by absorbing OOB (Non-Patent Document 2), but what composition is optimal is disclosed. Absent. Further, a novolak-based material containing a naphthalene ring is disclosed as a resist upper layer film forming composition for EUV lithography (Patent Document 3).
Further, as a resist upper layer protective film having hydrophobicity optimal for immersion lithography and soluble in an alkaline aqueous solution, a resist protective film material containing an acrylic polymer containing a hexafluoroisopropyl alcohol group (Patent Document 4), a solvent As a resist protective film material using an ester compound having a fluoroalkyl group (Patent Document 5), a photoresist upper layer film-forming composition containing a solvent having an ether structure (Patent Document 6), and immersion for coating on the upper surface of the photoresist A topcoat material containing a hexafluoroalcohol unit that can be used as a topcoat for a process or a top anti-reflective coating (TARC) and an alcohol solvent is disclosed (Patent Document 7).
Patent Document 8 discloses an upper layer film for immersion exposure comprising a resin containing a fluorine atom in a side chain and a solvent containing a monohydric alcohol having 6 or less carbon atoms, which is dissolved in a developer using an alkaline aqueous solution. A forming composition is disclosed.
Patent Document 9 discloses a composition for forming a liquid immersion upper layer film containing a polymer component (A) and a solvent (B), and as at least a part of all repeating units of the polymer component (A), Having a repeating unit (c) having a carboxyl group and a repeating unit (s) having a sulfo group,
A liquid immersion upper layer film-forming composition containing an ether solvent (B1) having 2 to 8 carbon atoms as a solvent (B) is disclosed.
Patent Document 10 discloses a photoresist upper layer containing (A) a resin soluble in a developer and (B) a solvent component containing 1 to 15% by mass of a solvent having a specific boiling point and vapor pressure (B1). A film-forming composition is disclosed.
However, it is unclear whether the resist upper layer film used in EUV lithography has sufficient characteristics as a material that can transmit EUV light, block the OOB, and is excellent in blocking outgas from the resist.

JP 2004-348133 A JP2008-198788 International Publication WO2012 / 053302 Pamphlet JP 2006-70244 A JP2007-241053 JP2012-103738 Special table 2008-532067 JP2010-211226 JP2012-215721 International Publication WO2011 / 034099 Pamphlet

Shimizu, M .; , Maruyama, K .; Kimura, T .; Nakagawa, H .; , Sharma, S .; , “Development of Chemically Amplified EUV resist for 22 nm half pitch and beyond” Extreme Ultraviolet Symposium, Mi. Proc. of SPIE Vol. 7969 796916-1

  The present invention has been made to provide an optimum resist upper layer film-forming composition for the above-mentioned problems, and this composition intermixes with a resist as a resist upper layer film, particularly as an upper layer film of an EUV resist. Without being particularly unfavorable in EUV exposure, for example, UV and DUV are blocked, and only EUV is selectively transmitted, it is excellent in degassing blocking from the resist, and can be developed with a developer after exposure. Provided is a resist upper layer film forming composition used in a lithography process for manufacturing a semiconductor device, which can be applied to either a positive resist or a negative resist.

As a first aspect of the present invention, a novolak polymer containing a saturated straight chain or branched alkyl group having 4 to 20 carbon atoms or a saturated straight chain or branched alkoxy group having 4 to 20 carbon atoms and a solvent may be substituted. And a noblek polymer having a unit structure containing 35 mol% or more of the alkyl group or the alkoxy group in the entire unit structure. Composition,
As a second aspect, the novolak polymer has the following (formula 1-1) to (formula 1-4):

(In (Formula 1-1) to (Formula 1-4), Ar ¹ is an organic group containing an aromatic ring having 6 to 18 carbon atoms. Ar ² is via a methylene group or a tertiary carbon atom. Te represents an organic group containing a bond to having 6 to carbon atom 18 aromatic rings and Ar ^1. the hydrogen atoms of the aromatic ring which the Ar ¹ and Ar ² include the carbon atoms 4 to 20 It is substituted with a saturated linear or branched alkyl group, a saturated linear or branched alkoxy group having 4 to 20 carbon atoms, or a combination thereof, and the number of substituents is an integer of 1 to 10. Ar ¹ or Ar ² The hydrogen atom of the above aromatic ring is a hydroxy group, a halogen atom, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a saturated straight chain or branched alkoxy group having 1 to 6 carbon atoms, and a hydrogen atom is carbon. 1 to 3 atoms An amino group which may be substituted with a linear alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms and a straight chain having 1 to 6 carbon atoms, in which a hydrogen atom may be substituted with a hydroxy group Or a branched halogenated alkyl group or a combination of these groups, and the number of substituents is an integer of 0 to 10). A resist upper layer film-forming composition,
As a third aspect, Ar ₁ is represented by the following (formula 2-a) to (formula 2-e) or a combination thereof, and Ar ₂ is represented by a methylene group or the following (formula 3), The resist upper layer film forming composition according to the first aspect or the second aspect,

(In (Formula 2-a) to (Formula 2-e) or (Formula 3), R _{3 to} R ₁₅ are each independently a saturated linear or branched alkyl group having 4 to 20 carbon atoms, or 4 carbon atoms. Represents a saturated straight-chain or branched alkoxy group or a combination of these groups of 20 to 20. T _{3 to} T ₁₆ are each independently a hydroxy group, a halogen atom, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a carbon A saturated linear or branched alkoxy group having 1 to 6 atoms, an amino group in which a hydrogen atom may be substituted with a linear alkyl group having 1 to 3 carbon atoms, and a hydrogen atom may be substituted with a hydroxy group .Q ₁ and Q ₂ represents a linear or branched alkyl group or a linear or branched halogenated alkyl group, or a combination thereof having 1 to 6 carbon atoms of 1 to 6 carbon atoms is a single bond, Elementary atom, sulfur atom, sulfonyl group, carbonyl group, imino group, arylene group having 1 to 40 carbon atoms, linear or branched alkylene group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a halogen atom Or the above alkylene group may form a ring, m1 to m3, r4, r5, r8 to r14, t4, t5 or t8 to t14 each independently represents 0 to 2; R3, r6, r7, t3, t6 or t7 each independently represents an integer of 0 to 8. r15 and t15 each independently represents an integer of 0 to 9. The sum of r3 to r15 is An integer from 1 to 10),
As a fourth aspect, the novolak polymer includes, in all unit structures, Ar ₁ in which each of r3 to r14 in (Formula 2-a) to (Formula 2-e) is 0, and (Formula 3) r15 are those that contain more than 35 mole% of the unit structure represented by the Ar ₂ is an integer of 1 to 9, the resist upper layer film forming composition according to the third aspect,
As a fifth aspect, the including (Formula 2-a) to (Formula 2-e) or _{T 3} to _{T 16} are one or more hydroxy groups of (Formula 3), according to the third aspect or the fourth aspect Resist upper layer film-forming composition,
As a sixth aspect, the resist upper layer film-forming composition according to any one of the first aspect to the fifth aspect, wherein the weight average molecular weight in terms of polystyrene measured by the GPC method of the novolak polymer is 800 to 50000,
As a seventh aspect, the resist upper layer film formation according to any one of the first to sixth aspects, wherein the ether compound according to the first aspect includes dibutyl ether, diisoamyl ether, diisobutyl ether, or a combination thereof. Composition,
As an eighth aspect, the resist upper layer film-forming composition according to any one of the first to seventh aspects, wherein the proportion of the ether compound in the solvent according to the first aspect is 87% by mass or more and 100% by mass. ,
As a ninth aspect, the resist upper layer film-forming composition according to any one of the first aspect to the eighth aspect, further including a basic compound,
As a tenth aspect, the resist upper layer film forming composition according to any one of the first aspect to the ninth aspect, further including an acid compound,
As an eleventh aspect, the resist upper layer film-forming composition according to the tenth aspect, in which the acid compound is a sulfonic acid compound or a sulfonic acid ester compound,
As a twelfth aspect, the resist upper layer film-forming composition according to the tenth aspect, wherein the acid compound is an onium salt acid generator, a halogen-containing compound acid generator, or a sulfonic acid generator.
As a thirteenth aspect, the resist upper layer film forming composition according to any one of the first to twelfth aspects, wherein the resist used together with the composition is a resist for EUV (wavelength 13.5 nm),
As a fourteenth aspect, a step of forming a resist upper layer film by applying and baking the resist upper layer film forming composition according to any one of the first aspect to the thirteenth aspect on a resist formed on a semiconductor substrate. A method of forming a resist pattern used for manufacturing a semiconductor device,
As a fifteenth aspect, a step of forming a resist film on a substrate, a resist upper film formed by applying and baking the resist upper film forming composition according to any one of the first to thirteenth aspects on the resist film A method of manufacturing a semiconductor device, comprising: a step of exposing a semiconductor substrate coated with the resist upper layer film and the resist film; a step of developing after exposure to remove the resist upper layer film and the resist film;
A sixteenth aspect is the method for manufacturing a semiconductor device according to the fifteenth aspect, in which the exposure is performed by EUV (wavelength: 13.5 nm).

The present invention is a resist upper layer film forming composition, particularly as an upper layer film forming composition of an EUV resist. The present invention relates to a resist upper layer film-forming composition that is selectively transmitted and can be developed with a developer after exposure.
In particular, when the EUV resist is exposed, the EUV light emits UV light and DUV light together with the EUV light. This EUV light contains about 5% of light having a wavelength of 300 nm or less in addition to the EUV light. For example, the wavelength region of 190 nm to 300 nm, particularly 220 nm to 260 nm, has the highest intensity, which reduces the sensitivity of the EUV resist and the pattern shape. Connected. When the line width becomes 22 nm or less, the influence of the UV light and DUV light (OUTof BAND / out-of-band radiation) starts to appear, and the resolution of the EUV resist is adversely affected.
Although there is a method of installing a filter in the lithography system in order to remove light having a wavelength in the vicinity of 220 nm to 260 nm, there is a problem that the process becomes complicated. In the present invention, among the DUV light (OUTof BAND / out-of-band radiation) contained in the EUV exposure light, unwanted DUV light of 220 nm to 260 nm is absorbed by the aromatic hydrocarbon ring contained in the composition of the present application. The resolution of the EUV resist can be improved.

  In addition, in order to prevent intermixing (mixing of layers) with the EUV resist when the upper layer of the EUV resist is coated, the solvent used for the EUV resist is not used, and the resist upper layer film forming composition has the number of carbon atoms. It is better to use a solvent having 8 to 16 ether bonds.

The ether solvent has low solubility in the resin constituting the resist regardless of the type of resin (methacrylate type, PHS type, hybrid type containing both methacrylate and hydroxystyrene (HS)). Therefore, when the resist upper layer film forming composition of the present application is used, it can be applied to various types of resists regardless of the resist type (positive type, negative type).
The resist upper layer film-forming composition of the present application is a saturated straight chain or branched alkyl group having 4 to 20 carbon atoms or a saturated straight chain having 4 to 20 carbon atoms in order to enhance the solubility in a solvent having an ether bond. Alternatively, a novolak polymer containing a branched alkoxy group (hereinafter referred to as “alkyl group or alkoxy group”) is used.
The resist upper layer film forming composition of the present application containing a novolak polymer containing an alkyl group or an alkoxy group can be dissolved in a developing solvent (butyl acetate, 2-heptanone, etc.) used in a negative developing process. Removal is possible. Such a negative resist development process is called NTD (Negative Tone Development).
Furthermore, when the novolak polymer used in the resist upper layer film-forming composition of the present application contains a hydroxy group, a carboxyl group, a sulfonic acid group, etc., it may be soluble in an alkaline developer together with the EUV resist during development after exposure. In this case, the composition using the novolak polymer can be dissolved and removed with an alkaline developer. Such a positive resist development process is called PTD (Positive Tone Development).
Furthermore, since it has an excellent barrier against degassing from the resist, particularly during EUV exposure, contamination by the degassing component to the exposure machine can be prevented.

The present invention includes a novolak polymer containing a saturated straight-chain or branched alkyl group having 4 to 20 carbon atoms or a saturated straight-chain or branched alkoxy group having 4 to 20 carbon atoms, and a solvent. This is a resist upper layer film-forming composition containing 35 mol% or more of a unit structure containing the alkyl group or the alkoxy group in the entire unit structure.
As the solvent, an ether compound having 8 to 16 carbon atoms is suitable for preventing intermixing (mixing of layers) with the resist. Although suitable as a resist upper layer film, it is particularly suitable as a resist upper layer film forming composition used in an EUV lithography process using EUV as an exposure wavelength.
When the unit structure containing the alkyl group or alkoxy group is contained in the entire unit structure in an amount of 34.9 mol% or less, the solubility of the novolak polymer in an ether solvent is lowered, and the preparation of the resist upper layer film-forming composition is reduced. It becomes difficult.
The maximum value of the ratio of the unit structure containing the alkyl group or alkoxy group to the entire unit structure is 100 mol%. Further, the proportion of the unit structure containing a more preferable alkyl group or alkoxy group in the total unit structure is 40 mol% to 100 mol%. The novolak polymer having a unit structure containing the alkyl group or alkoxy group within this range becomes soluble in the solvent having the ether bond, and the resist upper layer film forming composition of the present invention can be prepared.

Details of the resist upper layer film forming composition of the present invention will be described below.
The general formula of the novolak polymer containing an alkyl group or an alkoxy group used in the present application is represented by the following formula.

In (Formula 1-1) to (Formula 1-4), Ar ¹ is an organic group containing an aromatic ring having 6 to 18 carbon atoms. Ar ² represents an organic group containing an aromatic ring having 6 to 18 carbon atoms bonded to Ar ¹ via a methylene group or a tertiary carbon atom. The hydrogen atom in the aromatic ring in Ar ¹ and Ar ² is a saturated linear or branched alkyl group having 4 to 20 carbon atoms, a saturated linear or branched alkoxy group having 4 to 20 carbon atoms, or a combination thereof. The number of substituents is an integer of 1 to 10.
The aromatic ring represents an aromatic hydrocarbon ring or a heteroaromatic ring.
Examples of the aromatic hydrocarbon ring of the present invention include benzene, naphthalene, anthracene, phenanthrene, naphthacene, triphenylene, pyrene, chrysene, and the like, preferably benzene, naphthalene, anthracene, or pyrene.
Examples of the heteroaromatic ring of the present invention include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, Although phenazine or carbazole is mentioned, carbazole is preferable.
Examples of the saturated straight chain or branched alkyl group having 4 to 20 carbon atoms include n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, and 1-methyl-n-butyl group. 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group Group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group Group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3- Dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group Tyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group 1-ethyl-2-methyl-n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, n-undecanyl group, n-dodecanyl group, n-tridecanyl group, n -Tetradecanyl group, n-pentadecanyl group, n-hexadecanyl group, n-heptadecanyl group, n-octadecanyl group, n-nonadecanyl group, n-icosanyl group and the like.
Examples of the saturated linear or branched alkoxy group having 4 to 20 carbon atoms include n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, and 1-methyl-n-butoxy group. 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group Group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl -N-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group , 2, -Dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2, -trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, n-heptyloxy group, n-octyloxy Group, n-nonyloxy group, n-decanyloxy group, n-undecanyloxy group, n-dodecanyloxy group, n-tridecanyloxy group, n-tetradecanyloxy group, n-pentadecanyloxy group N-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosanoxy group and the like.
The hydrogen atom of the aromatic ring in Ar ¹ or Ar ² is a hydroxy group, a halogen atom, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, or a saturated linear or branched alkoxy group having 1 to 6 carbon atoms. An amino group in which a hydrogen atom may be substituted with a linear alkyl group having 1 to 3 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with a hydroxy group Alternatively, it may be substituted with a linear or branched alkyl group having 1 to 6 carbon atoms or a combination of these groups, and the number of substituents is an integer of 0 to 10.
Examples of the saturated linear or branched alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, and t-butoxy group. Group, n-pentoxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl -N-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group and the like can be mentioned.
Examples of the linear alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.
Examples of the linear or branched saturated alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t -Butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2 -Dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl Group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl- -Butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2, Examples include 2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, and the like.
In the present invention, some or all of the hydrogen atoms of the linear or branched saturated alkyl group having 1 to 6 carbon atoms may be substituted with a hydroxy group.
Furthermore, in this invention, you may use the halogenated alkyl group by which all the hydrogen atoms of the said C1-C6 linear or branched saturated alkyl group were substituted by the halogen atom.
More preferably, the above Ar ₁ is represented by the following (formula 2-a) to (formula 2-e) or a combination thereof, and the above Ar ₂ is represented by a methylene group or the following (formula 3). It is a film-forming composition.

In (Formula 2-a) to (Formula 2-e) or (Formula 3), R _{3 to} R ₁₅ are each independently a saturated linear or branched alkyl group having 4 to 20 carbon atoms, or 4 to 4 carbon atoms. 20 saturated linear or branched alkoxy groups or a combination of these groups are represented. T _{3 to} T ₁₆ are each independently a hydroxy group, a halogen atom, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a saturated linear or branched alkoxy group having 1 to 6 carbon atoms, and a hydrogen atom is a carbon atom. An amino group which may be substituted with a linear alkyl group having 1 to 3 carbon atoms, a linear or branched alkyl group with 1 to 6 carbon atoms whose hydrogen atom may be substituted with a hydroxy group, or 1 to 1 carbon atoms; 6 straight-chain or branched halogenated alkyl groups or a combination thereof. Q ₁ and Q ₂ are each a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, an arylene group having 1 to 40 carbon atoms, or an optionally substituted carbon atom having 1 to 10 carbon atoms. A linear or branched alkylene group or a combination of these groups is represented. The alkylene group may form a ring. m1 to m3, r4, r5, r8 to r14, t4, t5 or t8 to t14 each independently represents an integer of 0 to 2. r3, r6, r7, t3, t6 or t7 each independently represents an integer of 0 to 8. r15 and t15 each independently represents an integer of 0 to 9. The sum of r3 to r15 is an integer of 1 to 10.
Examples of the arylene group having 6 to 40 carbon atoms include phenylene group, o-methylphenylene group, m-methylphenylene group, p-methylphenylene group, o-chlorophenylene group, m-chlorophenylene group, and p-chloro group. Phenylene group, o-fluorophenylene group, p-fluorophenylene group, o-methoxyphenylene group, p-methoxyphenylene group, p-nitrophenylene group, p-cyanophenylene group, α-naphthylene group, β-naphthylene group, o -Biphenylylene group, m-biphenylylene group, p-biphenylylene group, 1-anthrylene group, 2-anthrylene group, 9-anthrylene group, 1-phenanthrylene group, 2-phenanthrylene group, 3-phenanthrylene group, 4-phenanthrylene group and 9 -A phenanthrylene group.
Examples of the linear or branched alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n -Propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl- n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2, -Dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1, 1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, An n-heptylene group, an n-octylene group, an n-nonylene group or an n-decanylene group may be mentioned.
The linear or branched alkylene group having 1 to 10 carbon atoms may form a ring, for example, 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group. , A 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, or a cycloalkylene group or a cycloalkylidene group. Ten alicyclic hydrocarbons may be used.
Specific structural formulas of (Formula 2-a) to (Formula 2-e) include, for example, the following (Formula 4-1) to (Formula 4-40).

Specific structural formulas of (Formula 3) include, for example, the following (Formula 5-1) to (Formula 5-14) or (Formula 5-2) to (Formula 5-57).

Examples of the unit structure of the synthesized novolak polymer include the following (Formula 6-1) to (Formula 6-25).

More preferably, in the novolak polymer, Ar1 in which each of r3 to r14 in (Formula 2-a) to (Formula 2-e) is 0 in all unit structures and r15 in (Formula 3) is 1 It is a resist upper layer film forming composition which contains 35 mol% or more of unit structures represented by Ar2 which is the integer of thru | or 9.
Further, in order to make the resist upper layer film-forming composition of the present application soluble in an alkaline developer and applicable to a positive resist, the above (formula 2-a) to (formula 2-e) or (formula 3) It is desirable that T _{3 to} T ₁₆ of the group contain one or more hydroxy groups.
The number of hydroxy groups contained in the unit structure of the novolak polymer selected from the above (formula 2-a) to (formula 2-e) or (formula 3) is preferably 1 to 20, more preferably 1 to The number is 15, more preferably 1 to 10, more preferably 1 to 9, more preferably 1 to 8, and further preferably 1 to 7.
For example, when the resist upper layer film forming composition of the present application is applicable to a positive resist, it is as follows.
In the novolak polymer, in the entire unit structure, for example, Ar ¹ is 1,5-dihydroxynaphthalene (compound of formula 4-1), phloroglicinol (compound of formula 4-7) or 2,2′-biphenol ( When the compound selected from (compound of formula 4-10) and, for example, Ar ² includes a unit structure synthesized from 3,4-dihydroxybenzaldehyde (compound of formula 5-2), the entire unit structure of the novolak polymer When the content is 15 mol% or more based on (a), the resist upper layer film forming composition of the present application can be applied to a positive resist. More preferably, the unit structure in this case is 20% by mole or more based on the total unit structure of the novolak polymer. In this case, the maximum ratio of the unit structure (a) to the entire unit structure of the novolak polymer is 65 mol% or less, more preferably 60 mol% or less.
In addition, Ar ¹ is, for example, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (compound of formula 4-21) or 4,4 ′, 4 ″ -trihydroxytriphenylmethane (formula 4-25). (B), even if there is no compound containing a hydroxy group in Ar ² , it is soluble in an alkali developer and applicable to a positive resist.
When Ar ₂ is a methylene group, formaldehyde is used as the compound to be reacted with Ar ₁ .

As a method for synthesizing a novolak polymer containing an alkyl group or an alkoxy group used in the present application, “monomer group A” which is a monomer group constituting Ar ₁ and “monomer group B” which is a monomer group constituting Ar _2. Is generally subjected to condensation polymerization in the presence of an acid catalyst.
Each of the monomer A group and the monomer B group is one type or two or more types, preferably 3 types or less, more preferably 2 types or less. In addition, the charge molar ratio of the monomer A group to the novolak polymer synthesis with respect to the monomer B group is 20/100 or more and 80/20 or less, more preferably 20/80 or more and 70/30 or less for the monomer A group / monomer B group. I can do it.
When the monomer group A or the monomer group B is composed of two or more monomers, the charged molar ratio of each monomer containing an alkyl group or an alkoxy group contained in the group is 3.5 / 10 or more and 5 or less. More preferably, it is 4/10 or more and 4 or less.
Furthermore, the charged molar ratio of each monomer with respect to the entire monomer A group or monomer B group is at least 1/20 or more, more preferably 1/10 or more.
In the production of the novolak polymer containing an alkyl group or an alkoxy group according to the present invention, the reaction between the monomer A group and the monomer B group is preferably performed in a nitrogen atmosphere. The reaction temperature may be selected from 50 ° C. to 200 ° C., preferably 80 ° C. to 180 ° C. A novolak polymer containing a high molecular weight alkyl group or alkoxy group can be obtained in a reaction time of 1 to 48 hours. In order to obtain a novolak polymer containing an alkyl group or alkoxy group having a low molecular weight and high storage stability, a reaction time of 1 to 24 hours is more preferable at 80 to 150 ° C.
Examples of the acid catalyst used in the condensation reaction include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate, Carboxylic acids such as formic acid and oxalic acid are used.
Of these, methanesulfonic acid and p-toluenesulfonic acid monohydrate are preferably used.
The amount of the acid catalyst used is variously selected depending on the type of acids used. Usually, it is 0.001 to 10000 parts by mass, preferably 0.01 to 1000 parts by mass, and more preferably 0.05 to 100 parts by mass with respect to 100 parts by mass of the total of the monomer A group and the monomer B group.
Solvents used during polymerization include dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutane Methyl acid, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc. can be used .

The weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method of the novolak polymer used in the present invention varies depending on the coating solvent used, the solution viscosity, etc., but is preferably 800 to 50000 in terms of polystyrene, for example. Is 900 to 20000. When the weight average molecular weight is 800 or less, the resist upper layer film using the novolak polymer having an alkyl group or an alkoxy group of the present application may diffuse into the photoresist and deteriorate the lithography performance. When the weight average molecular weight is 50000 or more, the solubility of the resist upper layer film to be formed in the photoresist developer is insufficient, and a residue may be present after development.
The solution containing the novolak polymer having an alkyl group or alkoxy group thus obtained can be used as it is for the preparation of the resist upper layer film-forming composition. In addition, a novolak polymer having an alkyl group or an alkoxy group can be recovered by precipitation by precipitation in a poor solvent such as methanol, ethanol, ethyl acetate, hexane, toluene, acetonitrile, water, or a mixed solvent thereof.
After isolating the novolak polymer having an alkyl group or an alkoxy group, it may be used after being redissolved in the solvent used in the composition of the present application or may be used after being dried. Desirable drying conditions are 40 to 100 ° C. for 6 to 48 hours in an oven or the like. After recovering the novolak polymer having the alkyl group or alkoxy group, it is redissolved in an arbitrary solvent, preferably a solvent having an ether bond of 8 to 16 carbon atoms described below, and used as a resist upper layer film composition. I can do it.
The resist upper layer film-forming composition of the present invention is an intermixing when the novolak polymer containing an alkyl group or an alkoxy group is coated on the resist in place of the solvent usually used for the resist, and the film is formed. In order to prevent (layer mixing), the following solvent having an ether bond having 8 to 16 carbon atoms which may be substituted is preferably used.
The term “optionally substituted” means that a hydrogen atom of an alkyl group described later may be substituted with any monovalent organic group or halogen atom. The case where it is substituted is more preferably the case where it is substituted with a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).
The solvent having an ether bond having 8 to 16 carbon atoms is represented by the following (formula 1-8) in the general formula.

(In (Formula 1-8), A ₁ and A ₂ each independently represent a linear, branched or cyclic saturated alkyl group having 1 to 15 carbon atoms which may be substituted.
Examples of the linear, branched or cyclic saturated alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decanyl group, n-undecanyl group, n-dodecanyl group, n-tridecanyl group, n-tetradecanyl group, n-pentadecanyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl Group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n- Propyl , Cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclo Propyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl Group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3- Dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1 , 2,2-Trimethyl-n-propi Group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl- Cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1- i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3- Limethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl- A cyclopropyl group, a 2-ethyl-3-methyl-cyclopropyl group, and the like. A part or all of the hydrogen atoms of these hydrocarbon groups are halogen atoms (fluorine atoms, chlorine atoms, bromine atoms or iodine atoms). May be substituted.
Among these, preferred solvents include dibutyl ether, diisobutyl ether, di-tert-butyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, cyclopentyl methyl ether, and more preferred solvents are dibutyl ether, diisoamyl. Ether and diisobutyl ether.
These ether solvents can be used alone or as a mixture.
The ratio of the ether solvent to the solvent in the composition of the present application is preferably 100% by mass, but may be 90% by mass to 100% by mass, and further 87% by mass to 100% by mass.
In addition to the solvent having an ether bond having 8 to 16 carbon atoms, the following alcohol solvent or water may be mixed as necessary.
For example, as saturated alkyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol Neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentano 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl Examples include 2-pentanol, 4-methyl-3-pentanol, 1-butoxy-2-propanol, and cyclohexanol.
Examples of the aromatic alcohol include 1-phenylpropanol, 2-phenylpropanol, 3-phenylpropanol, 2-phenoxyethanol, phenethyl alcohol, and styryl alcohol.
These alcohol solvents or water are used alone or in combination of two or more. The above-mentioned other solvents can be contained at a ratio of 0.01 to 13% by mass with respect to the solvent having an ether bond having 8 to 16 carbon atoms.
Further, for example, for the purpose of synthesizing a novolak polymer containing an alkyl group or an alkoxy group of the present invention, the following organic solvents may be mixed with the solvent having an ether bond having 8 to 16 carbon atoms. Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl. Ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxypropionic acid ethyl, 2-hydroxy-2-methylpropionic acid ethyl, ethyl ethioacetate, hydroxyacetic acid ethyl, 2-hydroxy-3-methylbutanoic acid methyl, 3-methoxypropion Methyl acid 3- Tokishipuropion ethyl, 3 over ethyl ethoxypropionate, 3 over ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, can be used butyl lactate and the like. These organic solvents are used alone or in combination of two or more. The above-mentioned other solvents can be contained at a ratio of 0.01 to 13% by mass with respect to the solvent having an ether bond having 8 to 16 carbon atoms.
The content of the novolak polymer having an alkyl group or alkoxy group in the solid content in the resist upper layer film-forming composition is 20% by mass or more, for example, 20 to 100% by mass, or 30 to 100% by mass, or 50 to 90% by mass. %, More preferably 60 to 80% by mass.
The solid content of the resist upper layer film-forming composition of the present invention is 0.1 to 50% by mass, preferably 0.3 to 30% by mass. The solid content is obtained by removing the solvent component from the resist upper layer film-forming composition.

The resist upper layer film-forming composition contains the novolak polymer containing the alkyl group or alkoxy group and the ether solvent, and further includes an acid compound, a basic compound, a crosslinking agent, a crosslinking catalyst, a surfactant, a rheology modifier, and the like. Can be included.
The resist upper layer film-forming composition of the present invention may further contain an acid compound in order to match the acidity with the resist present in the lower layer in the lithography process. As the acid compound, a sulfonic acid compound or a sulfonic acid ester compound can be used. For example, acidic compounds such as bis (4-hydroxyphenyl) sulfone, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and / or Alternatively, a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate can be blended. The blending amount is 0.02 to 10% by mass, preferably 0.04 to 5% by mass, per 100% by mass of the total solid content.
In order to make the acidity of the resist upper layer film-forming composition of the present invention coincide with the acidity of the resist present in the lower layer in the lithography process, an acid is irradiated by exposure light (for example, ArF excimer laser irradiation, EUV irradiation, electron beam irradiation, etc.). A generated acid generator can be added. Preferred acid generators include, for example, onium salt acid generators such as bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, and phenyl-bis (trichloromethyl) -s-triazine. And halogen-containing compound acid generators such as benzoin tosylate and sulfonic acid acid generators such as N-hydroxysuccinimide trifluoromethanesulfonate. The amount of the acid generator added is 0.02 to 10% by mass, preferably 0.04 to 5% by mass, per 100% by mass of the total solid content.

The resist upper layer film-forming composition of the present invention can contain a basic compound. By adding a basic compound, the sensitivity can be adjusted during exposure of the resist. That is, a basic compound such as amine reacts with an acid generated from a photoacid generator during exposure to reduce the sensitivity of the resist underlayer film, thereby controlling the upper shape of the resist after exposure and development (after exposure and development). The resist shape is preferably rectangular. Furthermore, by adding the basic compound to a novolak polymer containing an alkyl group or an alkoxy group, a salt is formed between the novolak polymer containing an alkyl group or an alkoxy group and the basic compound, and the salt becomes soluble in water.
Examples of the basic compound include amines.
Amine compounds include ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, 2-aminophenol, 3-aminophenol, 4-aminophenol, benzyltrimethylammonium hydroxide. Benzyltriethylammonium hydroxide, benzyltripropylammonium hydroxide, benzyltributylammonium hydroxide, N-benzyldimethylamine, N-benzyldiethylamine, N-benzylmethylamine, N-benzylethylamine, N-benzylisopropylamine, N- tert-butylbenzylamine,
Pyridine, 4-methylpyridine, 4-ethylpyridine, 4-isopropylpyridine, 3-fluoropyridine, 4-bromopyridine, 4-fluoropyridine, 4-iodopyridine, 4-aminopyridine, 4- (bromomethyl) pyridine, 4 -Cyanopyridine, 4-methoxypyridine, N- (4-pyridyl) dimethylamine, 3,4-dimethylpyridine, 4- (methylamino) pyridine, 2-bromo-5-iodopyridine, 2-chloro-4-iodo Pyridine, 4- (aminomethyl) pyridine, 2,4,6-trimethylpyridine, 2,6-diaminopyridine, 1,5-naphthyridine,
Diethylamine, N-tert-butylethylamine, N, N-diethylmethylamine, N-ethylisopropylamine, N-ethylmethylamine, diisopropylamine, N, N-dimethylethylamine, triethylamine, N-diisopropylethylamine, N, N- Diethylethylenediamine, ethylamine,
2- (dimethylamino) ethanol, N-methyldiethanolamine, 2- (methylamino) ethanol, triethanolamine, 2-diethylaminoethanol, N-ethyldiethanolamine, diethanolamine, N-tert-butyldiethanolamine, 1-dimethylamino-2 -Propanol, 2- (diisopropylamino) ethanol, 2- (dimethylamino) isobutanol, 2- (ethylamino) ethanol,
2,2,2-trifluoroethylamine, trifluoroacetamide, N-methyltrifluoroacetamide, bistrifluoroacetamide, N, N-bis (trifluoroacetyl) methylamine, N-methyl-N-trimethylsilyltrifluoroacetamide, penta Decafluorotriethylamine,
4-methylmorpholine, 4-ethylmorpholine, bis (2-morpholinoethyl) ether, 4- (2-aminoethyl) morpholine, N-cyanomethylmorpholine, 4- (2-hydroxyethyl) morpholine, 4-isobutylmorpholine, 4-acetylmorpholine, N- (2-cyanoethyl) morpholine, N- (3-aminopropyl) morpholine, 4- (3-chloropropyl) morpholine, N- (2-hydroxypropyl) morpholine, 4- (3-hydroxy Propyl) morpholine, 3-morpholino-1,2-propanediol, 1-morpholino-1-cyclohexene,
Ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3-butanediamine, 1,4 -Butanediamine, 1,3-pentanediamine (DAMP), 1,5-pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1,5-pentanediamine ( C11-neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2,4-trimethylhexamethylenediamine (TMD), 2,4,4-trimethylhexamethylenediamine ( TMD), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decandia 1,11-undecanediamine, 1,12-dodecanediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane (H12-MDA) Bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino-3,5-dimethylcyclohexyl) methane, bis (4-amino-3-) Ethyl-5-methylcyclohexyl) methane (M-MECA), 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine or IPDA), 2-methyl-1,3-diaminocyclohexane, 4 -Methyl-1,3-diaminocyclohexane, 1,3-bis ( Minomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane (NBDA), 3 (4), 8 (9 ) -Bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8-menthanediamine, 3,9- Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3-xylylenediamine, 1,4-xylylenediamine,
Bis (2-aminoethyl) ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane-2,9-diamine, 4,9 -Dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine,
4-aminomethyl-1,8-octanediamine, 1,3,5-tris (aminomethyl) benzene, 1,3,5-tris (aminomethyl) -cyclohexane, tris (2-aminoethyl) amine, tris ( 2-aminopropyl) amine, tris (3-aminopropyl) amine,
Diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), dipropylenetriamine (DPTA), bishexamethylenetriamine (BHMT), 3- (2-aminoethyl) Aminopropylamine (N3-amine), N, N′-bis (3-aminopropyl) ethylenediamine (N4-amine), N3- (3-aminopentyl) -1,3-pentanediamine, N5- (3-amino Propyl) -2-methyl-1,5-pentanediamine and N5- (3-amino-1-ethylpropyl) -2-methyl-1,5-pentanediamine,
N, N′-bis (aminopropyl) piperazine, N, N-bis (3-aminopropyl) methylamine, N, N-bis (3-aminopropyl) ethylamine, N, N-bis (3-aminopropyl) Propylamine, N, N-bis (3-aminopropyl) cyclohexylamine, N, N-bis (3-aminopropyl) -2-ethylhexylamine, N, N-bis (3-aminopropyl) dodecylamine, N, N-bis (3-aminopropyl) tallow alkylamine,
Methylamine, ethylamine, 1-propylamine, 2-propylamine, 1-butylamine, 2-butylamine, tert-butylamine, 3-methyl-1-butylamine, 3-methyl-2-butylamine, cyclopentylamine, hexylamine, cyclohexyl Amine, octylamine, 2-ethyl-1-hexylamine, benzylamine, 1-phenylethylamine, 2-phenylethylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine, coco Alkylamine, C16-C22-alkylamine, soyaalkylamine, oleylamine, tallow alkylamine,
2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3- (2-methoxyethoxy) propylamine, 2 (4) -methoxy Phenylethylamine N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl-1,2-ethanediamine, N-hexyl-1,2-ethanediamine, N-butyl- 1,6-hexanediamine, N-cyclohexyl-1,2-ethanediamine, 4-aminomethylpiperidine, 3- (4-aminobutyl) piperidine, N- (2-aminoethyl) piperazine (N-AEP), N -(2-aminopropyl) piperazine,
N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-hexyl-1,3-propanediamine, N- (2-ethylhexyl) ) -1,3-propanediamine, N-dodecyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 3-methylamino-1-pentylamine, 3-ethylamino-1-pentylamine 3-butylamino-1-pentylamine, 3-hexylamino-1-pentylamine, 3- (2-ethylhexyl) amino-1-pentylamine, 3-dodecylamino-1-pentylamine, 3-cyclohexylamino- 1-pentylamine, N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanedia N-soyaalkyl-1,3-propanediamine, N-tallowalkyl-1,3-propanediamine, cocoalkyldipropylenetriamine, oleyldipropylenetriamine, tallowalkyldipropylenetriamine, oleyltripropylenetetramine, tallowalkyltriamine Propylenetetramine, N, N-diethyl-1,2-ethanediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-diethyl-1, 4-pentanediamine,
Butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine, 2-ethyl-1-hexylamine, benzylamine, 1- Phenylethylamine, 2-phenylethylamine, N-hexyl-1,2-ethanediamine, N- (2-ethylhexyl) -1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, N-butyl-1 , 3-propanediamine, N-hexyl-1,3-propanediamine, N- (2-ethylhexyl) -1,3-propanediamine, N-dodecyl-1,3-propanediamine, N-cyclohexyl-1,3 -Propanediamine, cocoa Killamine, soyaalkylamine, oleylamine, N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propanediamine, and the like are more preferable. Ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, 2- (dimethylamino) ethanol, 2,2,2-trifluoroethylamine, pyridine, 4-methylmorpholine Can be mentioned.
Further, for example, there is an aminobenzene compound represented by the formula (13-1).

In formula (13-1), U _{1 to} U ₅ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an amino group.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1 -Methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1 -Dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2 -Methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group Pyr group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl- n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3 1,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n -Propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl -Cyclopentyl group, 1-ethyl-cyclobutyl group, 2- Ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2, 4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i- Propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl- Cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclo A propyl group etc. are mentioned.
Of these, a linear alkyl group having 1 to 5 carbon atoms and a branched alkyl group are preferable, and examples thereof include a methyl group, an ethyl group, and an isopropyl group.
Examples of the compound include the following formulas (13-2) to (13-47).

Also, triethanolamine, tributanolamine, trimethylamine, triethylamine, trinormalpropylamine, triisopropylamine, trinormalbutylamine, tri-tert-butylamine, trinormaloctylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and dia There can be mentioned tertiary amines such as zabicyclooctane and aromatic amines such as pyridine and 4-dimethylaminopyridine. Further, primary amines such as benzylamine and normal butylamine, and secondary amines such as diethylamine and dinormalbutylamine are also included. These compounds can be used alone or in combination of two or more.
In addition to the above, the composition for forming a resist upper layer film of the present invention may contain additional rheology modifiers, surfactants and the like as necessary.
The rheology modifier is added mainly for the purpose of improving the fluidity of the resist upper layer film-forming composition. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; Mention may be made of maleic acid derivatives such as normal butyl maleate, diethyl maleate and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate, or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. it can. These rheology modifiers are usually blended at a ratio of less than 30% by mass with respect to 100% by mass of the total composition of the resist upper layer film forming composition.
In the resist upper layer film-forming composition of the present invention, a surfactant can be blended in order to further improve the applicability to surface unevenness without generating pinholes or striations. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonyl Polyoxyethylene alkyl aryl ethers such as phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc., EFTOP EF301, EF303, EF352 (Manufactured by Tochem Products Co., Ltd.), Megafuk F171, F173 (manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, Fluorosurfactants such as SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), and Footent Series (Neos Co., Ltd.), organosiloxane polymer KP341 (Shinsei) Chemical Industries Co., Ltd.), and the like. The compounding amount of these surfactants is usually 0.2% by mass or less, preferably 0.1% by mass or less, per 100% by mass of the total composition of the resist upper layer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.
In the present invention, an EUV resist can be used. As the EUV resist applied to the lower layer of the resist upper layer film in the present invention, either a negative type or a positive type can be used. Chemically amplified resist comprising a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist A chemically amplified resist comprising: a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate; and a chemically amplified resist comprising a low-molecular compound that decomposes with an acid to change the alkali dissolution rate of the resist, There are non-chemically amplified resists composed of binders having groups that decompose by EUV to change the alkali dissolution rate, and non-chemically amplified resists composed of binders having sites that are cut by EUV to change the alkali dissolution rate.
Examples of EUV resist material systems include methacrylate systems, PHS systems, and hybrid systems containing both methacrylate and hydroxystyrene (HS). When these EUV resists are used, a resist pattern can be formed in the same manner as when a resist is used with the irradiation source as an electron beam.
In the present invention, a KrF resist or an ArF resist can be used. As the KrF resist or ArF resist applied to the lower layer of the resist upper layer film in the present invention, either a negative photoresist or a positive photoresist can be used. A positive photoresist comprising a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist comprising a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, an acid A chemically amplified photoresist comprising a low-molecular compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate There is a chemically amplified photoresist composed of a low molecular weight compound that decomposes with an acid to increase the alkali dissolution rate of the photoresist and a photoacid generator. For example, the Dow Chemical Company (formerly Rohm and Haas Electronic Materials Co., Ltd.) trade name APEX-E, Sumitomo Chemical Co., Ltd. trade name PAR710, and Shin-Etsu Chemical Co., Ltd. trade name SEPR430 Etc. Also, for example, ProC. SPIE, Vol. 3999, 330-334 (2000), ProC. SPIE, Vol. 3999, 357-364 (2000), ProC. SPIE, Vol. 3999, 365-374 (2000), and fluorine-containing polymer-based photoresists.
In the present invention, an EB (electron beam) resist can be used. As the electron beam resist applied to the lower layer of the resist upper layer film in the present invention, either a negative photoresist or a positive photoresist can be used. Chemically amplified resist comprising a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist A chemically amplified resist comprising: a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate; and a chemically amplified resist comprising a low-molecular compound that decomposes with an acid to change the alkali dissolution rate of the resist, There are non-chemically amplified resists composed of a binder having a group that changes the alkali dissolution rate by being decomposed by an electron beam, and non-chemically amplified resists composed of a binder having a portion that is cut by an electron beam to change the alkali dissolution rate. Even when these electron beam resists are used, a resist pattern can be formed in the same manner as when a photoresist is used as the irradiation source with KrF and ArF light.
As a developer for a positive resist having a resist upper layer film formed using the resist upper layer film-forming composition of the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia Inorganic amines such as ethylamine, primary amines such as N-propylamine, secondary amines such as diethylamine and di-N-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine Alcohol amines such as alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, and cyclic amines such as pyrrole and piperidine, and alkaline aqueous solutions can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution. Of these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.
In the present invention, for example, a step of forming an EUV resist film with or without an EUV resist underlayer film on a substrate having a film to be processed for forming a transfer pattern, an EUV resist upper layer film forming composition on the resist film A step of applying and baking an object to form an EUV resist upper layer film, a step of exposing a semiconductor substrate coated with the resist upper layer film and the resist film, a step of developing after exposure to remove the resist upper layer film and the resist film, A semiconductor device can be manufactured. Exposure is performed by EUV (wavelength 13.5 nm).
The formation of the resist upper layer film is generally performed by a spin coating method in the same manner as the resist film formation. For example, it is set on a substrate to be processed (for example, a silicon / silicon dioxide coated substrate, a glass substrate, an ITO substrate, etc.) on a spin coater manufactured by Tokyo Electron, and a resist film is formed on the substrate to be processed. An object (varnish) is applied to the substrate to be processed at a spin speed of 700 rpm to 3000 rpm and then baked on a hot plate at 50 ° C. to 150 ° C. for 30 to 300 seconds to form the resist upper layer film. The film thickness of the resist upper layer film is 3 nm to 100 nm, 5 nm to 100 nm, or 5 nm to 50 nm.
The dissolution rate of the resist upper layer film to be formed in the photoresist developer is 1 nm or more per second, preferably 3 nm or more per second, and more preferably 10 nm or more per second. When the dissolution rate is smaller than this, the time required for removing the resist upper layer film becomes longer, resulting in a decrease in productivity. Thereafter, after pattern formation with appropriate exposure light, development is performed using a resist developer, thereby removing the resist and unnecessary portions of the resist upper layer film to form a resist pattern.
A semiconductor device to which the composition for forming an EUV resist upper layer film of the present invention is applied has a structure in which a film to be processed for transferring a pattern, a resist film, and a resist upper layer film are sequentially formed on a substrate. This resist upper layer film can form a resist pattern having a good straight shape by reducing adverse effects exerted by the base substrate and EUV, and can provide a sufficient margin for the EUV irradiation amount. In addition, this resist upper layer film has a wet etching rate equal to or higher than that of the resist film formed in the lower layer, and can be easily removed with an alkali developer together with unnecessary portions of the resist film after exposure. .
In addition, the substrate to be processed of the semiconductor device can be processed by either dry etching or wet etching. Using the resist upper layer film as a mask, a resist pattern that is well formed can be used as a mask, and dry etching or wet etching can be used. It is possible to transfer a good shape to the substrate to be processed.
In the present invention, for example, a step of forming a KrF resist film on a substrate having a film to be processed for forming a transfer pattern, with or without a KrF resist lower layer film, and a composition for forming a KrF resist upper layer film on the resist film A step of applying and baking an object to form a KrF resist upper layer film, a step of exposing a semiconductor substrate coated with the resist upper layer film and the resist film, a step of developing after exposure to remove the resist upper layer film and the resist film, A semiconductor device can be manufactured. Exposure is performed with KrF. The resist upper layer film is formed in the same manner as in the EUV exposure.
In the present invention, for example, a step of forming an ArF resist film on a substrate having a film to be processed for forming a transfer pattern, with or without using an ArF resist lower layer film, an ArF resist upper layer film forming composition on the resist film A step of forming an ArF resist upper layer film by applying and baking an object, a step of exposing a semiconductor substrate coated with the resist upper layer film and the resist film, a step of developing after exposure to remove the resist upper layer film and the resist film, A semiconductor device can be manufactured. Exposure is performed with ArF. The resist upper layer film is formed in the same manner as in the EUV exposure.
In the present invention, for example, a step of forming an electron beam resist film with or without an electron beam resist lower layer film on a substrate having a film to be processed for forming a transfer pattern, an electron beam resist upper layer on the resist film A step of applying a film-forming composition and baking to form an electron beam resist upper layer film; a step of exposing a semiconductor substrate coated with the resist upper layer film and the resist film; and developing after exposure to form the resist upper layer film and the resist film. A semiconductor device can be manufactured. Exposure is performed with an electron beam. The resist upper layer film is formed in the same manner as in the EUV exposure.

The weight average molecular weight (Mw) of the novolak polymer shown in the following Synthesis Examples 1 to 33 in the present specification is a measurement result by a GPC (Gel Permeation Chromatography) method. For measurement, a GPC apparatus manufactured by Tosoh Corporation is used, and the measurement conditions are as follows. Further, the dispersity shown in the following synthesis examples of the present specification is calculated from the measured weight average molecular weight and number average molecular weight.
Measuring device: HLC-8320GPC [trade name] (manufactured by Tosoh Corporation)
GPC column: TSKgel SuperMultipore HZ-N (P0009)
[Product Name] (Tosoh Corporation)
TSKgel SuperMultipore HZ-N (P0010) [Product Name] (East
Saw Co., Ltd.)
Column temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow rate: 0.35 ml / min
Standard sample: Polystyrene (manufactured by Tosoh Corporation)
<Synthesis Example 1>
1,5-dihydroxynaphthalene (compound of formula 4-1) (4.0 g, 0.025 mol), 4-butoxybenzaldehyde (compound of formula 5-3) (4.45 g, 0.025 mol), p-toluenesulfone Acid monohydrate (0.497 g, 0.0025 mol) was dissolved in 20.87 g of propylene glycol monomethyl ether. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-1). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2655.
<Synthesis Example 2>
1,5-dihydroxynaphthalene (compound of formula 4-1) (7.5 g, 0.0468 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.587 g, 0.0187 mol), 4- n-Octyloxybenzaldehyde (compound of formula 5-8) (6.58 g, 0.0281 mol), p-toluenesulfonic acid monohydrate (0.933 g, 0.0047 mol) was added to 41.07 g of propylene glycol monomethyl ether. Added and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-6). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2,498.
<Synthesis Example 3>
1,5-dihydroxynaphthalene (compound of formula 4-1) (7.5 g, 0.0468 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.587 g, 0.0187 mol), 4- Heptyloxybenzaldehyde (compound of formula 5-7) (6.19 g, 0.0281 mol), p-toluenesulfonic acid monohydrate (0.929 g, 0.047 mol) was added to 40.15 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-4). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2566.
<Synthesis Example 4>
1,5-dihydroxynaphthalene (compound of formula 4-1) (7.5 g, 0.0468 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.587 g, 0.0187 g), 4- Hexyloxybenzaldehyde (compound of formula 5-6) (5.79 g, 0.0281 mol), p-toluenesulfonic acid monohydrate (0.933 g, 0.047 mol) was added to 39.23 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-3). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2477.
<Synthesis Example 5>
1,5-dihydroxynaphthalene (compound of formula 4-1) (8.0 g, 0.0499 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.759 g, 0.020 mol), 4- Butylbenzaldehyde (compound of formula 5-4) (4.86 g, 0.030 mol), p-toluenesulfonic acid monohydrate (0.995 g, 0.0050 mol) was added to propylene glycol monomethyl ether 38.77 g and dissolved. . The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-5). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2921.
<Synthesis Example 6>
1,5-dihydroxynaphthalene (compound of formula 4-1) (4.5 g, 0.0281 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (0.77 g, 0.0056 mol), 4- Butoxybenzaldehyde (compound of formula 5-3) (4.00 g, 0.0225 mol), p-toluenesulfonic acid monohydrate (0.559 g, 0.0028 mol) was added to 22.70 g of propylene glycol monomethyl ether and dissolved. . The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-1) and (Formula 6-2). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2463.
<Synthesis Example 7>
1,5-dihydroxynaphthalene (compound of formula 4-1) (3.4 g, 0.0212 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (1.17 g, 0.085 mol), 4- Octadecyloxybenzaldehyde (compound of formula 5-14) (4.77 g, 0.0127 mol) and p-toluenesulfonic acid monohydrate (0.422 g, 0.0049 mol) are added to 22.78 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-10). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3577.
<Synthesis Example 8>
1,5-dihydroxynaphthalene (compound of formula 4-1) (7.5 g, 0.0468 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.71 g, 0.0197 mol), 4- n-Octyloxybenzaldehyde (compound of formula 5-8) (6.91 g, 0.0295 mol), p-toluenesulfonic acid monohydrate (0.979 g, 0.0049 mol) to 42.25 g of propylene glycol monomethyl ether Added and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-6). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2560.
<Synthesis Example 9>
1,5-dihydroxynaphthalene (compound of formula 4-1) (7.5 g, 0.0468 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.71 g, 0.0197 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (7.74 g, 0.0295 mol), p-toluenesulfonic acid monohydrate (0.979 g, 0.0049 mol) was added to 44.18 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-7). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2809.
<Synthesis Example 10>
1,5-dihydroxynaphthalene (compound of formula 4-1) (3.0 g, 0.0187 mol), 4-n-octyloxybenzaldehyde (compound of formula 5-8) (4.61 g, 0.0197 mol), p -Toluenesulfonic acid monohydrate (0.391 g, 0.0020 mol) was added to 18.66 g of propylene glycol monomethyl ether and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-6). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3641.
<Synthesis Example 11>
1,5-dihydroxynaphthalene (compound of formula 4-1) (3.0 g, 0.0187 mol), 4-decyloxybenzaldehyde (compound of formula 5-10) (5.16 g, 0.0197 mol), p-toluene Sulfonic acid monohydrate (0.391 g, 0.0020 mol) was added to 19.95 g of propylene glycol monomethyl ether and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-7). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 4164.
<Synthesis Example 12>
Phloroglucinol (compound of formula 4-7) (4.0 g, 0.0317 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (1.75 g, 0.0127 mol), 4-n-octyl Oxybenzaldehyde (compound of formula 5-8) (4.46 g, 0.0190 mol), p-toluenesulfonic acid monohydrate (0.632 g, 0.0032 mol) was added to 25.30 g of propylene glycol monomethyl ether acetate and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-11) and (Formula 6-11-1). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2164.
<Synthesis Example 13>
Phloroglucinol (compound of formula 4-7) (4.0 g, 0.0317 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (1.75 g, 0.0127 mol), 4-decyloxybenzaldehyde (Compound of formula 5-10) (4.99 g, 0.0190 mol) and p-toluenesulfonic acid monohydrate (0.632 g, 0.0032 mol) were added to 26.54 g of propylene glycol monomethyl ether acetate and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-11) and (Formula 6-12). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2619.
<Synthesis Example 14>
2,2′-biphenol (compound of formula 4-10) (5.0 g, 0.0269 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (1.55 g, 0.0113 mol), 4- n-Octyloxybenzaldehyde (compound of formula 5-8) (3.96 g, 0.0169 mol) and methanesulfonic acid (0.812 g, 0.0085 mol) were added to 17.00 g of propylene glycol monomethyl ether acetate and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-14) and (Formula 6-15). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2116.
<Synthesis Example 15>
2,2′-biphenol (compound of formula 4-10) (5.0 g, 0.0269 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (1.55 g, 0.0113 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (4.43 g, 0.0169 mol) and methanesulfonic acid (0.812 g, 0.0085 mol) were added to 17.71 g of propylene glycol monomethyl ether acetate and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-14) and (Formula 6-16). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2295.
<Synthesis Example 16>
1,5-dihydroxynaphthalene (compound of formula 4-1) (4.5 g, 0.0281 mol), carbazole (compound of formula 4-13) (0.522 g, 0.0031 mol), 3,4-dihydroxybenzaldehyde ( Compound of formula 5-2) (1.81 g, 0.0131 mol), 4-decyloxybenzaldehyde (compound of formula 5-10) (5.16 g, 0.0197 mol), p-toluenesulfonic acid monohydrate ( 0.653 g, 0.0033 mol) was added to 29.50 g of propylene glycol monomethyl ether and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-2), (Formula 6-7), (Formula 6-17), and (Formula 6-18). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 1183.
<Synthesis Example 17>
1,5-dihydroxynaphthalene (compound of formula 4-1) (6.0 g, 0.0375 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.58 g, 0.0187 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (4.91 g, 0.0187 mol), p-toluenesulfonic acid monohydrate (0.783 g, 0.0037 mol) was added to 34.20 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-7). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2,727.
<Synthesis Example 18>
1,5-dihydroxynaphthalene (compound of formula 4-1) (6.0 g, 0.0375 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (3.10 g, 0.0225 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (3.93 g, 0.015 mol), p-toluenesulfonic acid monohydrate (0.746 g, 0.0037 mol) was added to 33.06 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-7). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2704.
<Synthesis Example 19>
1,5-dihydroxynaphthalene (compound of formula 4-1) (5.0 g, 0.0312 mol), 3,5-di-tert-butyl-4-hydroxybenzaldehyde (compound of formula 5-25) (7.68 g) 0.0328 mol), p-toluenesulfonic acid monohydrate (0.653 g, 0.0033 mol) was added to 31.11 g of propylene glycol monomethyl ether and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-19). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2369.
<Synthesis Example 20>
Phloroglucinol (compound of formula 4-7) (5.0 g, 0.0396 mol), 3,5-di-tert-butyl-4-hydroxybenzaldehyde (compound of formula 5-25) (9.75 g, .0. 0416 mol), p-toluenesulfonic acid monohydrate (0.829 g, 0.0042 mol) was added to 36.36 g of propylene glycol monomethyl ether acetate and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-20). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 1771.
<Synthesis Example 21>
1,5-dihydroxynaphthalene (compound of formula 4-1) (5.0 g, 0.0312 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (0.91 g, 0.0066 mol), 3, 5-Di-tert-butyl-4-hydroxybenzaldehyde (compound of formula 5-25) (6.14 g, 0.0262 mol), p-toluenesulfonic acid monohydrate (0.653 g, 0.0033 mol) in propylene Dissolved in 50.81 g of glycol monomethyl ether. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-19). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3623.
<Synthesis Example 22>
1,5-dihydroxynaphthalene (compound of formula 4-1) (5.0 g, 0.0312 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (1.81 g, 0.0131 mol), 3, 5-Di-tert-butyl-4-hydroxybenzaldehyde (compound of formula 5-25) (4.60 g, 0.0197 mol), p-toluenesulfonic acid monohydrate (0.653 g, 0.0033 mol) in propylene It was dissolved in 48.29 g of glycol monomethyl ether. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-19). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 1856.
<Synthesis Example 23>
Phloroglucinol (compound of formula 4-7) (5.0 g, 0.0396 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (1.15 g, 0.0083 mol), 3,5-di -Tert-butyl-4-hydroxybenzaldehyde (compound of formula 5-25) (7.80 g, 0.0333 mol), 0.829 g of p-toluenesulfonic acid monohydrate was added to 34.49 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-11) and (Formula 6-20). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3408.
<Synthesis Example 24>
Phloroglucinol (compound of formula 4-7) (5.0 g, 0.0396 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.30 g, 0.0167 mol), 3,5-di -Tert-butyl-4-hydroxybenzaldehyde (compound of formula 5-25) (5.85 g, 0.025 mol), p-toluenesulfonic acid monohydrate (0.829 g, 0.0042 mol) in propylene glycol monomethyl ether Added to 32.62 g and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-11) and (Formula 6-20). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 1316.
<Synthesis Example 25>
1,5-dihydroxynaphthalene (compound of formula 4-1) (5.0 g, 0.0312 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (2.16 g, 0.0156 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (3.27 g, 0.0125 mol), 3,5-bis (trifluoromethyl) benzaldehyde (compound of formula 5-27) (0.75 g, 0.0031 mol), p-Toluenesulfonic acid monohydrate (0.62 g, 0.0031 mol) was added to 27.55 g of propylene glycol monomethyl ether and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-2), (Formula 6-7), and (Formula 6-21). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2902.
<Synthesis Example 26>
1,5-dihydroxynaphthalene (compound of formula 4-1) (5.0 g, 0.0312 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (0.43 g, 0.0031 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (7.37 g, 0.0281 mol), p-toluenesulfonic acid monohydrate (0.621 g, 0.0031 mol) was added to 31.32 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-7). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3486.
<Synthesis Example 27>
1,5-dihydroxynaphthalene (compound of formula 4-1) (5.0 g, 0.0312 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (0.86 g, 0.0062 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (6.55 g, 0.025 mol), p-toluenesulfonic acid monohydrate (0.621 g, 0.031 mol) was added to 30.42 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-7). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3302.
<Synthesis Example 28>
1,5-dihydroxynaphthalene (compound of formula 4-1) (5.0 g, 0.0312 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (1.29 g, 0.0094 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (5.79 g, 0.0219 mol), p-toluenesulfonic acid monohydrate (0.621 g, 0.0031 g) was added to 29.51 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-7). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3355.
<Synthesis Example 29>
1,5-dihydroxynaphthalene (compound of formula 4-1) (6.0 g, 0.0375 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (3.62 g, 0.0262 mol), 4- Decyloxybenzaldehyde (compound of formula 5-10) (2.95 g, 0.0112 mol), p-toluenesulfonic acid monohydrate (0.746 g, 0.0037 mol) was added to 31.92 g of propylene glycol monomethyl ether and dissolved. did. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The unit structure of the novolak polymer is represented by (Formula 6-2) and (Formula 6-7). The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a brown novolak polymer. As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2512.
<Synthesis Example 30>
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (compound of formula 4-21) (product name: TEP-DF, manufactured by Asahi Organic Materials Co., Ltd.) (6.0 g, 0.0151 mol) , 4-decyloxybenzaldehyde (compound of formula 5-10) (7.90 g, 0.0301 mol), p-toluenesulfonic acid monohydrate (1.2 g, 0.0060 mol) with 22.65 g of propylene glycol monomethyl ether And dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a black novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-22). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2358.
<Synthesis Example 31>
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (compound of formula 4-21) (product name: TEP-DF, manufactured by Asahi Organic Materials Co., Ltd.) (3.5 g, 0.0088 mol) , 4-decyloxybenzaldehyde (compound of formula 5-10) (9.22 g, 0.0351 mol), p-toluenesulfonic acid monohydrate (1.4 g, 0.0070 mol) with 22.65 g of propylene glycol monomethyl ether And dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a black novolak polymer. The unit structure of the novolak polymer is represented by (Formula 6-23). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3914.
<Synthesis Example 32>
4,4 ′, 4 ″ -trihydroxytriphenylmethane (compound of formula 4-25) (3.5 g, 0.0120 mol), 4-decyloxybenzaldehyde (compound of formula 5-10) (9.42 g, 0 0.0359 mol), p-toluenesulfonic acid monohydrate (1.43 g, 0.0072 mol) was dissolved in 21.53 g of propylene glycol monomethyl ether, and the reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours, A novolak polymer solution was obtained and added to a methanol: water = 1: 9 solution to obtain a black novolak polymer, whose unit structure is represented by (formula 6-24). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 2177.
<Synthesis Example 33>
1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (compound of formula 4-21) (product name: TEP-DF, manufactured by Asahi Organic Materials Co., Ltd.) (4.0 g, 0.01 mol) , 4-decyloxybenzaldehyde (compound of formula 5-10) (9.48 g, 0.0361 mol), 3,4-dihydroxybenzaldehyde (compound of formula 5-2) (0.55 g, 0.0040 mol), p- Toluenesulfonic acid monohydrate (1.44 g, 0.0072 mol) was added to 23.21 g of propylene glycol monomethyl ether and dissolved. The reaction vessel was purged with nitrogen and reacted at 140 ° C. for 4 hours to obtain a novolak polymer solution. The obtained solution was added to a solution of methanol: water = 1: 9 to obtain a black novolak polymer. The main unit structure of the novolak polymer is represented by (Formula 6-23) and (Formula 6-25). As a result of GPC analysis, the obtained novolak polymer had a weight average molecular weight of 3701.

Example 1
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 1 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 2)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 2 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 3)
To 0.6 g of the novolak polymer obtained in Synthesis Example 3 above, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
Example 4
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 4 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 5)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 5 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 6)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 6 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 7)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 7 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 8)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 8 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
Example 9
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 9 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 10)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 10 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 11)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 11 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 12)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 12 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 13)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 13 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 14)
10.6 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 14 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 15)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 15 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 16)
To 0.6 g of the novolak polymer obtained in Synthesis Example 16, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 17)
To 0.6 g of the novolak polymer obtained in Synthesis Example 17, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 18)
To 0.6 g of the novolak polymer obtained in Synthesis Example 18, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 19)
To 0.6 g of the novolak polymer obtained in Synthesis Example 19, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 20)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 20 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 21)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 21 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 22)
10.6 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 22 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 23)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 23 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 24)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 24 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 25)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 25 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 26)
To 0.6 g of the novolak polymer obtained in Synthesis Example 26, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 27)
To 0.6 g of the novolak polymer obtained in Synthesis Example 27, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 28)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 28 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 29)
10.6 g of dibutyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 28 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 30)
To 0.6 g of the novolak polymer obtained in Synthesis Example 28, 19.4 g of diisobutyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 31)
To 0.6 g of the novolak polymer obtained in Synthesis Example 28, 18.4 g of diisoamyl ether and 0.97 g of 4-methyl-2-pentanol were added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 32)
To 0.6 g of the novolak polymer obtained in Synthesis Example 28, 17.4 g of diisoamyl ether and 1.97 g of 4-methyl-2-pentanol were added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 33)
To 0.6 g of the novolak polymer obtained in Synthesis Example 28, 16.5 g of diisoamyl ether and 2.91 g of 4-methyl-2-pentanol were added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 34)
To 0.6 g of the polymer obtained in Synthesis Example 30, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 35)
To 0.6 g of the polymer obtained in Synthesis Example 31, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 36)
To 0.6 g of the polymer obtained in Synthesis Example 32, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 37)
To 0.6 g of the polymer obtained in Synthesis Example 33, 19.4 g of diisoamyl ether was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Comparative Example 1)
19.4 g of diisoamyl ether was added to 0.6 g of the novolak polymer obtained in Synthesis Example 29 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Comparative Example 2)
1 g of polyhydroxystyrene resin (commercial product, weight average molecular weight: 8,000) was dissolved in 99 g of 4-methyl-2-pentanol to obtain a resist upper layer film forming composition solution.

[Test for confirming insolubility of resist in ether solvents]
An EUV resist solution (hydroxystyrene (HS) -containing resist) was applied using a spinner. A resist film was formed by heating at 100 ° C. for 1 minute on a hot plate, and the film thickness was measured.
Solvent for resist upper layer film forming composition (dibutyl ether, diisoamyl ether, diisobutyl ether) and resist upper layer film forming compositions of Example 30, Example 31, Example 32, and Example 33 on a resist film using a spinner And heated on a hot plate at 100 ° C. for 1 minute, and then on the resist (in the case of the solvent for the resist upper layer film-forming composition) or on the resist upper layer film (Example 30, Example 31, Example 32 and Example) In the case of Example 33), a commercially available alkaline developer (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name: NMD-3) was added and left for 60 seconds, and rinsed with pure water for 30 seconds while rotating at 3000 rpm. . After rinsing, the film was baked at 100 ° C. for 60 seconds to measure the film thickness.
The degree of resist film rubbing was determined as shown in Table 1. When there is almost no film slippage, ◎, and when there is no problem in implementation, the amount of film slippage is indicated by ◯.
[Table 1]
Table 1 Resist Insolubility Confirmation Test ――――――――――――――――――――――――――――――――――――
Dibutyl ether ◎
Diisoamyl ether ◎
Diisobutyl ether ◎
Example 30
Example 31
Example 32
Example 33
――――――――――――――――――――――――――――――――――――
[Solubility test of polymer in upper layer solvent]
The resist upper layer film-forming composition of Example 9, Example 17, Example 18 and Comparative Example 1 of the present invention was applied on a wafer at 1500 rpm for 1 minute using a spinner, and then on a hot plate at 100 ° C. for 1 minute. After heating, the thickness of the resist upper layer film was measured. The degree of film thickness of the resist upper layer film was determined as shown in Table 2. When the film thickness is 30 nm or more, it is indicated as “◯”, and when the film thickness is 30 nm or less, it is indicated as “X”. When the film thickness is 30 nm or less, it cannot be used as a resist upper layer film.
[Table 2]
Table 2 Measurement of film thickness ――――――――――――――――――――――――――――――――――――
Film thickness (nm)
Example 9 ○
Example 17
Example 18
Comparative Example 1 ×
――――――――――――――――――――――――――――――――――――
[Intermixing Test with Resist (PTD (Positive Tone Development))
An EUV resist solution (methacrylic resist) was applied using a spinner. A resist film was formed by heating at 100 ° C. for 1 minute on a hot plate, and the film thickness was measured (film thickness A: resist film thickness).
The resist upper layer film forming composition solution prepared in Examples 1 to 37 and Comparative Example 2 of the present invention was applied onto the resist film using a spinner and heated at 100 ° C. for 1 minute on a hot plate. Then, a resist upper layer film was formed, and the film thickness was measured (film thickness B: sum of film thickness of resist and resist upper layer film).
On the resist upper layer film, a commercially available developer (product name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was poured, left for 60 seconds, and rinsed with pure water for 30 seconds while rotating at 3000 rpm. After rinsing, the film was baked at 100 ° C. for 60 seconds to measure the film thickness (film thickness C).
When the film thickness A is equal to the film thickness C, it indicates that there is no intermixing with the resist and it can be applied as a resist upper layer film for the PTD process.
[Table 3]
Table 3 Measurement of film thickness ――――――――――――――――――――――――――――――――――――
Film thickness A (nm) Film thickness B (nm) Film thickness C (nm)
Example 1 56 86 86
Example 2 56 86 56
Example 3 56 86 56
Example 4 56 86 56
Example 5 56 86 56
Example 6 56 86 56
Example 7 56 86 56
Example 8 56 86 56
Example 9 56 86 56
Example 10 56 86 86
Example 11 56 86 86
Example 12 56 86 56
Example 13 56 86 56
Example 14 56 86 56
Example 15 56 86 56
Example 16 56 86 56
Example 17 56 86 56
Example 18 56 86 56
Example 19 56 86 86
Example 20 56 86 86
Example 21 56 86 56
Example 22 56 86 56
Example 23 56 86 56
Example 24 56 86 56
Example 25 56 86 56
Example 26 56 86 86
Example 27 56 86 56
Example 28 56 86 56
Example 29 56 86 56
Example 30 56 86 56
Example 31 56 86 56
Example 32 56 86 56
Example 33 56 86 56
Example 34 56 86 56
Example 35 56 86 56
Example 36 56 86 56
Example 37 56 86 56
Comparative Example 2 56 86 56
――――――――――――――――――――――――――――――――――――
[Application test to NTD (Negative tone Development) process]
The resist upper layer film forming composition solution prepared in Examples 1 to 37 and Comparative Example 2 of the present invention was applied onto a wafer using a spinner, and heated on a hot plate at 100 ° C. for 1 minute. A resist upper layer film was formed, and the film thickness was measured (film thickness A: film thickness of resist upper layer film).
On the resist upper layer film, butyl acetate (solvent developer) often used in the NTD process was added and allowed to stand for 60 seconds, and rotated at 3000 rpm. Thereafter, the film was baked at 100 ° C. for 60 seconds, and the film thickness was measured (film thickness B).
When the film thickness B is 0 nm, it can be said that the resist upper layer film was removed by the developer. This indicates that the composition of the present application is applicable as a resist upper layer film for NTD process.
[Table 4]
Table 4 Film thickness measurement ――――――――――――――――――――――――――――――――――――
Film thickness A (nm) Film thickness B (nm)
Example 1 30 0
Example 2 30 0
Example 3 30 0
Example 4 30 0
Example 5 30 0
Example 6 30 0
Example 7 30 0
Example 8 30 0
Example 9 30 0
Example 10 30 0
Example 11 30 0
Example 12 30 0
Example 13 30 0
Example 14 30 0
Example 15 30 0
Example 16 30 0
Example 17 30 0
Example 18 30 0
Example 19 30 0
Example 20 30 0
Example 21 30 0
Example 22 30 0
Example 23 30 0
Example 24 30 0
Example 25 30 0
Example 26 30 0
Example 27 30 0
Example 28 30 0
Example 29 30 0
Example 30 30 0
Example 31 30 0
Example 32 30 0
Example 33 30 0
Example 34 30 0
Example 35 30 0
Example 36 30 0
Example 37 30 0
Comparative Example 2 30 30
――――――――――――――――――――――――――――――――――――

[Optical parameter test]
The resist upper layer film forming composition solutions prepared in Examples 1 to 37 and Comparative Example 2 of the present invention were each applied onto a quartz substrate using a spinner. On the hot plate, it heated at 100 degreeC for 1 minute, and formed the resist upper layer film | membrane (film thickness of 30 nm). And the absorptance in wavelength 190nm thru | or 260nm was measured for these 38 types of resist upper layer films | membranes using the spectrophotometer.
The transmittance at 13.5 nm was calculated by simulation from the relationship between the elemental composition ratio and the film density.
Regarding the light shielding property of DUV light, in the wavelength range of 220 nm to 260 nm, the maximum value of the absorptance was 40% or more as good and less than 40% as bad. In addition, regarding the transmittance of EUV light (13.5 nm), a transmittance of 80% or more was regarded as good, and less than 80% was regarded as defective.
The resist upper layer film obtained from the resist upper layer film forming composition of each example had a result of better DUV light shielding performance than the resist upper layer film obtained from the resist upper layer film forming composition of Comparative Example 2. It was.
[Table 4]
Table 4 EUV transmission and DUV blocking properties ――――――――――――――――――――――――――――――――――――
Film thickness (nm) EUV light transmittance DUV light shielding properties Example 1 30 Good Good Example 2 30 Good Good Example 3 30 Good Good Example 4 30 Good Good Example 5 30 Good Good Example 6 30 Good Good Example 7 30 Good Good Example 8 30 Good Good Example 9 30 Good Good Example 10 30 Good Good Example 11 30 Good Good Example 12 30 Good Good Example 13 30 Good Good Example 14 30 Good Good Example Example 15 30 Good Good Example 16 30 Good Good Example 17 30 Good Good Example 18 30 Good Good Example 19 30 Good Good Example 20 30 Good Good Example 21 30 Good Good Example 22 30 Good Good Example 23 30 Good Good Example 24 30 Good Good Example 25 30 Good Good Example 26 30 Good Good Example 27 30 Good Good Example 28 30 Good Good Example 29 30 Good Good Example 30 30 Good Good Example 31 30 Good Good Example 32 30 Good Good Example 33 30 Good Good Example 34 30 Good Good Example 35 30 Good Good Example 36 30 Good Good Example 37 30 Good Good Comparative Example 2 30 Good Bad ――――――――――――――――――――――――――――――― ――――

  EUV resist used in an EUV lithography process that can selectively transmit only EUV by blocking exposure light, such as UV or DUV, which is not desirable for EUV exposure without intermixing with the resist, and can be developed with a developer after exposure. It is a composition for forming an upper layer film and a resist upper layer film for a lithography process at other exposure wavelengths.

Claims (16)

A novolak polymer containing a saturated straight-chain or branched alkyl group having 4 to 20 carbon atoms or a saturated straight-chain or branched alkoxy group having 4 to 20 carbon atoms, and having 8 to 16 carbon atoms optionally substituted as a solvent A composition for forming a resist upper layer film comprising an ether compound, wherein the novolak polymer contains 35 mol% or more of a unit structure containing the alkyl group or the alkoxy group in the entire unit structure. The novolak polymer is represented by the following (formula 1-1) to (formula 1-4):

(In (Formula 1-1) to (Formula 1-4), Ar ¹ is an organic group containing an aromatic ring having 6 to 18 carbon atoms. Ar ² is via a methylene group or a tertiary carbon atom. Te represents an organic group containing a bond to having 6 to carbon atom 18 aromatic rings and Ar ^1. the hydrogen atoms of the aromatic ring which the Ar ¹ and Ar ² include the carbon atoms 4 to 20 It is substituted with a saturated linear or branched alkyl group, a saturated linear or branched alkoxy group having 4 to 20 carbon atoms, or a combination thereof, and the number of substituents is an integer of 1 to 10. Ar ¹ or Ar ² The hydrogen atom of the above aromatic ring is a hydroxy group, a halogen atom, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a saturated straight chain or branched alkoxy group having 1 to 6 carbon atoms, and a hydrogen atom is carbon. 1 to 3 atoms An amino group which may be substituted with a linear alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms and a straight chain having 1 to 6 carbon atoms, in which a hydrogen atom may be substituted with a hydroxy group Or a branched halogenated alkyl group or a combination of these groups, and the number of substituents is an integer of 0 to 10. Resist upper layer film forming composition. The Ar ₁ is represented by the following (Formula 2-a) to (Formula 2-e) or a combination thereof, and the Ar ₂ is represented by a methylene group or the following (Formula 3). 2. The resist upper layer film-forming composition according to 2.

(In (Formula 2-a) to (Formula 2-e) or (Formula 3), R _{3 to} R ₁₅ are each independently a saturated linear or branched alkyl group having 4 to 20 carbon atoms, or 4 carbon atoms. Represents a saturated straight-chain or branched alkoxy group or a combination of these groups of 20 to 20. T _{3 to} T ₁₆ are each independently a hydroxy group, a halogen atom, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a carbon A saturated linear or branched alkoxy group having 1 to 6 atoms, an amino group in which a hydrogen atom may be substituted with a linear alkyl group having 1 to 3 carbon atoms, and a hydrogen atom may be substituted with a hydroxy group .Q ₁ and Q ₂ represents a linear or branched alkyl group or a linear or branched halogenated alkyl group, or a combination thereof having 1 to 6 carbon atoms of 1 to 6 carbon atoms is a single bond, Elementary atom, sulfur atom, sulfonyl group, carbonyl group, imino group, arylene group having 1 to 40 carbon atoms, linear or branched alkylene group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a halogen atom Or the above alkylene group may form a ring, m1 to m3, r4, r5, r8 to r14, t4, t5 or t8 to t14 each independently represents 0 to 2; R3, r6, r7, t3, t6 or t7 each independently represents an integer of 0 to 8. r15 and t15 each independently represents an integer of 0 to 9. The sum of r3 to r15 is (It is an integer from 1 to 10) In the novolak polymer, Ar ₁ in which each of r3 to r14 in (Formula 2-a) to (Formula 2-e) is 0 and r15 in (Formula 3) is 1 to 9 in the entire unit structure. The composition for forming a resist upper layer film according to claim 3, which contains 35 mol% or more of a unit structure represented by Ar ₂ which is an integer of. The resist upper layer film-forming composition according to claim 3 or 4, wherein T _{3 to} T _{16 of} (Formula 2-a) to (Formula 2-e) or (Formula 3) include one or more hydroxy groups. object. The resist upper layer film-forming composition according to any one of claims 1 to 5, wherein the novolak polymer has a weight average molecular weight in terms of polystyrene measured by GPC method of 800 to 50000. The resist upper layer film-forming composition according to any one of claims 1 to 6, wherein the ether compound according to claim 1 comprises dibutyl ether, diisoamyl ether, diisobutyl ether, or a combination thereof. The composition for forming a resist upper layer film according to any one of claims 1 to 7, wherein a proportion of the ether compound in the solvent according to claim 1 is 87% by mass or more and 100% by mass. The composition for forming a resist upper layer film according to any one of claims 1 to 8, further comprising a basic compound. The composition for forming a resist upper layer film according to any one of claims 1 to 9, further comprising an acid compound. The resist upper layer film-forming composition according to claim 10, wherein the acid compound is a sulfonic acid compound or a sulfonic acid ester compound. The resist upper layer film-forming composition according to claim 10, wherein the acid compound is an onium salt acid generator, a halogen-containing compound acid generator, or a sulfonic acid generator. The resist upper layer film forming composition according to any one of claims 1 to 12, wherein the resist used together with the composition is a resist for EUV (wavelength: 13.5 nm). A resist upper layer film forming composition according to claim 1 is applied onto a resist formed on a semiconductor substrate and baked to form a resist upper layer film. A method for forming a resist pattern used in manufacturing. A step of forming a resist film on the substrate, a step of applying and baking the resist upper layer film-forming composition according to any one of claims 1 to 13 on the resist film, and forming a resist upper layer film; A method for manufacturing a semiconductor device, comprising: exposing the resist upper layer film and a semiconductor substrate coated with the resist film; and developing the resist upper layer film and the resist film after exposure. The method of manufacturing a semiconductor device according to claim 15, wherein the exposure is performed by EUV (wavelength: 13.5 nm).