WO2013141046A1

WO2013141046A1 - Resist upper layer film-forming composition for lithography

Info

Publication number: WO2013141046A1
Application number: PCT/JP2013/056471
Authority: WO
Inventors: 竜慈大西; 友輝臼井; 坂本　力丸; 邦慶何
Original assignee: 日産化学工業株式会社
Priority date: 2012-03-22
Filing date: 2013-03-08
Publication date: 2013-09-26
Also published as: TW201405251A; JP2015108644A

Abstract

[Problem] To provide a resist upper layer film-forming composition which is used in a lithography process during the production procedure of a semiconductor device, and which selectively transmits EUV only, while blocking exposure light such as UV or DUV that is undesirable especially for EUV exposure, and is able to be developed with a developer liquid after the exposure without being intermixed with the resist. [Solution] Provided is a resist upper layer film-forming composition which contains an alcohol-based solvent and a resin that contains an amide bond and/or an imide bond and is produced by reacting (d) at least one kind of diamine compound with at least one kind of compound selected from among (a) tetracarboxylic acid dianhydride compounds, (b) acid dihalide compounds and (c) compounds having both a dicarboxylic acid anhydride group and an acid halide group. A terminal of the resin may be blocked with an organic group that has an aromatic ring or an alkyl group having 1-5 carbon atoms.

Description

Composition for forming resist upper layer film for lithography

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, microfabrication 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 actinic rays used have also been shortened in wavelength from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). Along with this, the influence of diffuse reflection and standing wave of actinic rays from the substrate becomes a big problem, and as a resist underlayer film that plays a role of preventing reflection between the photoresist and the substrate to be processed, an antireflection film (Bottom Anti-Reflective Coating, The method of providing BARC) has been widely adopted.
As the antireflection film, an inorganic antireflection film such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon and the like, 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 actively studied as a next-generation photolithography technique to be followed by a photolithography technique using an ArF excimer laser (193 nm). However, photolithography 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 EUV resolution enhancement layer film is applied to 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.

JP 2004-348133 A JP2008-198788

The present invention has been made to provide an optimal resist upper layer film forming composition with respect to the above-mentioned problems. That is, the present invention intermixes with a resist as a resist upper layer film, particularly as an upper layer film of an EUV resist. In particular, a resist upper layer film forming composition for use in a lithography process, which is capable of selectively transmitting only EUV by blocking exposure light, such as UV and DUV, which is not preferable in EUV exposure, and capable of being developed with a developer after exposure. provide.

As a first aspect of the present invention, one or more selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a compound having both a dicarboxylic anhydride group and an acid halide group (D) a resist upper layer film-forming composition comprising a resin containing at least one of an amide bond and an imide bond, and an alcohol solvent, produced by reacting the compound of (d) with one or more diamine compounds,
As a second aspect, the resin according to the first aspect is a resin including one or more unit structures selected from the following formulas (1-1), (1-2), and (1-3). Resist upper layer film-forming composition described in the first aspect

(In the formulas (1-1) to (1-3), at least one of A ₁ and B ₁ is an organic group containing an aromatic ring, and at least one is an organic group having a hydroxyl group, a carboxyl group, or a combination thereof. The weight average molecular weight of the resin is 500 to 100,000).
As a third aspect, the resist upper layer film-forming composition according to the first aspect or the second aspect, wherein the resin terminal structure according to the first aspect or the second aspect is represented by the formula (1-4)

(In the formula (1-4), R ₁ represents an aromatic ring or an organic group containing an alkyl group having 1 to 5 carbon atoms, B ₁ has the same definition as described in the second aspect, Represents a part of the resin described in the second viewpoint).
As a fourth aspect, the resist upper layer according to the first aspect or the second aspect, wherein the resin terminal structure according to the first aspect or the second aspect is represented by the formula (1-5) or the formula (1-6) Film-forming composition

(In Formula (1-5) or Formula (1-6), R ₂ represents an aromatic ring or an organic group containing an alkyl group having 1 to 5 carbon atoms, and A ₁ and B ₁ are those described in the second aspect. The wavy line part represents the part of the resin described in the second aspect).
As a fifth aspect, the alcohol solvent is a straight chain having 1 to 20 carbon atoms, a branched or cyclic saturated alkyl alcohol having 3 to 20 carbon atoms, or an aromatic alcohol having 6 to 20 carbon atoms. The resist upper layer film-forming composition according to any one of the viewpoints to the fourth aspect,
As a sixth aspect, in any one of the first to fifth aspects, the alcohol solvent is 1-heptanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, or cyclopentanol. The composition for forming a resist upper layer film according to the description,
As a seventh aspect, the compound (a) is represented by the following formulas (1-7) to (1-10),

(In the formulas (1-7) to (1-10), X _{1 to} X ₅ are each independently a halogen atom, a straight or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 1 to 10 carbon atoms, or Branched halogenated alkyl group, alkoxy group having 1 to 30 carbon atoms, hydroxy group, carboxyl group, cyano group, nitro group, phenoxy group or benzoyl group (the hydrogen atom of the phenoxy group and benzoyl group is 1 to 5 halogen atoms) M1 represents an integer of 0 to 8. n1 represents an atom, which may be substituted with 1 to 5 straight-chain or branched alkyl groups having 1 to 5 carbon atoms or 1 to 5 hydroxy groups. m3 and m4 represent an integer of 0 to 3. n2 and n3 represent an integer of 0 to 2. m2 and m5 represent an integer of 0 to 4.
W ₁ represents any of a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. ),
Compound (b) is represented by the following formulas (1-11) to (1-13),

(In the formulas (1-11) to (1-13), Z ₁ is a halogen atom, X _{6 to} X ₉ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and 1 carbon atom. A linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxy group, a carboxyl group, a cyano group, a nitro group, a phenoxy group, or a benzoyl group (the hydrogen atoms of the phenoxy group and benzoyl group are M6 and m7 may be substituted with 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxy groups. It represents an integer of 10. n4 and n5 represent an integer of 0 to 3. m8 and m9 represent an integer of 0 to 4.
W ₂ represents any of a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. ),
Compound (c) is represented by the following formula (1-14) or formula (1-15),

(In the formulas (1-14) to (1-15), Z ₁ is a halogen atom, X _{10 to} X ₁₂ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a carbon number of 1 A linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxy group, a carboxyl group, a cyano group, a nitro group, a phenoxy group, or a benzoyl group (the hydrogen atoms of the phenoxy group and benzoyl group are M10 represents 0 to 9 and may be substituted with 1 to 5 halogen atoms, 1 to 5 straight-chain or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxy groups. N6 and m11 represent an integer of 0 to 3. m12 represents an integer of 0 to 4.
W ₃ represents any of a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. ),
Compound (d) is represented by the following formula (1-16) or formula (1-17),

(In the formulas (1-16) and (1-17), X _{13 to} X ₁₅ are each independently a halogen atom, a straight or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 1 to 10 carbon atoms, or Branched halogenated alkyl group, alkoxy group having 1 to 30 carbon atoms, hydroxy group, carboxyl group, cyano group, nitro group, phenoxy group or benzoyl group (the hydrogen atom of the phenoxy group and benzoyl group is 1 to 5 halogen atoms) M13 to m15 each represents an integer of 0 to 4, and may be substituted with 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms or 1 to 5 hydroxy groups. n7 represents an integer of 0 to 3.
W ₄ represents a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. And the resist upper layer film-forming composition according to the first aspect, having at least one hydroxyl group, carboxyl group, or a combination thereof in the unit structure of the resin,
As an eighth aspect, end-capping agents for forming the partial structure of the formula (1-4) are represented by the following formulas (1-18) to (1-21),

(In the formulas (1-18) to (1-21), Z ₁ is a halogen atom, X _{16 to} X ₂₁ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, 10 represents a linear or branched halogenated alkyl group, an alkoxy group having 1 to 30 carbon atoms, a hydroxy group, a carboxyl group, a phenoxy group, a cyano group, or a nitro group, and m16 represents an integer of 0 to 10. n8, n9 And m17 represents an integer of 0 to 3. m18 and m21 represent an integer of 0 to 5. m19 represents an integer of 0 to 11. m20 represents an integer of 0 to 4.
W ₅ and W _{6 each} represent a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. . A composition for forming a resist upper layer film according to the third aspect, which is a compound represented by:
As a ninth aspect, an end-capping agent for forming a partial structure of formula (1-5) or formula (1-6) is represented by the following formula (1-22) or formula (1-23),

(In the formulas (1-22) and (1-23), X _{22 to} X ₂₄ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, or A branched halogenated alkyl group, an alkoxy group having 1 to 30 carbon atoms, a hydroxy group, a carboxyl group, a phenoxy group, a cyano group or a nitro group, m22 represents an integer of 0 to 11, and n10 represents an integer of 0 to 3 M23 represents an integer of 0 to 4, and m24 represents an integer of 0 to 5.
W ₇ represents any of a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. A composition for forming a resist upper layer film according to the fourth aspect, which is a compound represented by:
As a tenth aspect, the resist upper layer film-forming composition according to any one of the first to ninth aspects, further comprising 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, in which the acid compound is an iodonium salt acid generator or a sulfonium salt acid generator,
As a thirteenth aspect, the resist upper layer film-forming composition according to any one of the first to twelfth aspects, further including a basic compound,
As a fourteenth aspect, the resist upper layer film forming composition according to any one of the first to thirteenth aspects, wherein the resist used together with the composition is a resist for EUV (wavelength 13.5 nm),
As a fifteenth aspect, a step of forming a resist film on a substrate, the resist upper layer film forming composition according to any one of the first aspect to the fourteenth aspect is applied on the resist film and baked to form a resist upper layer 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;
As a sixteenth aspect, there is provided the method for manufacturing a semiconductor device according to the fifteenth aspect, wherein the exposure is performed by EUV (wavelength: 13.5 nm).

The present invention provides a resist upper layer film-forming composition, particularly an EUV resist upper layer film-forming composition, without intermixing with an EUV resist, and blocking only EUV by blocking exposure light, such as UV and DUV, which is not desirable for EUV exposure. 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.
Normally, when EUV light is used for exposure of an EUV resist, UV light and DUV light are emitted together with the EUV light. That is, this EUV light contains about 5% of light having a wavelength of 300 nm or less in addition to the EUV light. For example, light in a wavelength region of about 190 to 300 nm, particularly 220 to 260 nm, has the highest intensity. It leads to a decrease in sensitivity and pattern shape. When the line width is 22 nm or less, the influence of the UV light or DUV light (OUTofBAND / out-of-band radiation) starts to appear, and the resolution of the EUV resist is adversely affected.
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 to 260 nm, but this is complicated in the process. On the other hand, in the present invention, among the DUV light (OUTofBAND / out-of-band radiation) included in the EUV exposure light, unwanted DUV light of 220 to 260 nm is absorbed by the resist upper layer film, and the resolution of the EUV resist is improved. It can be performed.

Also, in order to prevent intermixing (mixing of layers) with the EUV resist when coating the upper layer of the EUV resist, the solvent used for the EUV resist is not used for the resist upper layer film, and an alcohol solvent is used. It is better to use it. In such a case, the resin used in the resist upper layer film-forming composition of the present invention has a hydrophilic group comprising a hydroxyl group, a carboxyl group, or an organic group containing these groups in order to increase the solubility in an alcohol solvent. It has high solubility in alcohol solvents.
That is, the resin used in the resist upper layer film-forming composition of the present invention has a hydrophilic group composed of a hydroxyl group, a carboxyl group, and an organic group containing these groups, so that a developer is developed together with an EUV resist during development after exposure. It can be dissolved and removed with (for example, an alkaline developer).

The present invention includes one or more compounds selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a compound having both a dicarboxylic anhydride group and an acid halide group, (D) A resist upper layer film-forming composition comprising a resin containing at least one of an amide bond and an imide bond and an alcohol solvent, which is produced by reacting with one or more diamine compounds. The present invention is suitable as a general resist upper layer film forming composition, but is particularly suitable as a resist upper layer film forming composition used in an EUV lithography process using EUV as an exposure wavelength.

The resist upper layer film-forming composition contains the resin and an alcohol solvent, and may further contain an acid compound, a basic compound, a crosslinking agent, a crosslinking catalyst, a surfactant, a rheology modifier, an adhesion aid, and the like. .

The solid content of the resist upper layer film-forming composition of the present invention is 0.1 to 50% by mass, preferably 0.1 to 30% by mass. Here, the solid content is obtained by removing the solvent component from the resist upper layer film-forming composition.

The content of the resin 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, or 60 to 80% by mass. It is. A ₁ , (d) diamine, which is a structural unit of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a compound having both a dicarboxylic anhydride group and an acid halide group in the resin. B ₁ which is a structural unit of the compound is an organic group in which at least one includes an aromatic ring, and at least one is an organic group having a hydroxyl group, a carboxyl group, or a combination thereof. A hydroxyl group and a carboxyl group are hydrophilic groups, and are essential for expressing solubility in alcohol solvents and developer-soluble functions.

Details of the resist upper layer film forming composition of the present invention will be described below.

The resin of the present invention comprises at least one compound selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a compound having both a dicarboxylic acid anhydride group and an acid halide group. And (d) a resin containing at least one of an amide bond and an imide bond produced by reacting one or more diamine compounds. The resin contains one or more unit structures selected from the following formulas (1-1), (1-2), and (1-3).

The definitions of A ₁ and B _{1 in} the formulas (1-1) to (1-3) are as described above. Specifically, (i) A ₁ is an organic group containing an aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ contains an aromatic ring and has a hydroxyl group, a carboxyl group or a combination thereof If it is an organic group,
(ii) A ₁ is an organic group containing an aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ is an organic group containing an aromatic ring and having no hydroxyl group, a carboxyl group or a combination thereof. If it is,
(iii) A ₁ is an organic group containing an aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ is an organic group not containing an aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof If there is
(iv) A ₁ is an organic group containing an aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ is an organic group containing no aromatic ring and having no hydroxyl group, a carboxyl group or a combination thereof If it is a group,
(v) A ₁ is an organic group containing an aromatic ring and not having a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ is an organic group containing an aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof If it is,
(vi) An organic group in which A ₁ contains an aromatic ring and does not have a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ does not contain an aromatic ring and has a hydroxyl group, a carboxyl group or a combination thereof If it is a group,
(Vii) A ₁ is an organic group not containing an aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ is an organic group containing an aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof If there is
(viii) A ₁ is an organic group having no aromatic ring and having a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ is an organic group having an aromatic ring and having no hydroxyl group, a carboxyl group or a combination thereof. If it is a group,
(ix) An organic group in which A ₁ does not contain an aromatic ring and does not have a hydroxyl group, a carboxyl group or a combination thereof, and B ₁ contains an aromatic ring and has a hydroxyl group, a carboxyl group or a combination thereof If it is a group,
It is.

About the resin terminal of this invention, 1 or more types chosen from (a) tetracarboxylic dianhydride compound, (b) acid dihalide compound, and (c) the compound which has both dicarboxylic anhydride group and acid halide group By adjusting the reaction amount (preparation amount) of (d) one or more diamine compounds, it may be an amino group terminal or a dicarboxylic acid anhydride group or an acid halide group terminal. . In the case of an amino group terminal, it may be end-capped by reacting an end-capping agent having a reactive group that reacts with the amino group and an aromatic ring or an organic group containing an alkyl group having 1 to 5 carbon atoms. Good. In the case of a dicarboxylic acid anhydride group or acid halide group terminal, it has a reactive group that reacts with the dicarboxylic acid anhydride group or acid halide group and has an organic group containing an aromatic ring or an alkyl group having 1 to 5 carbon atoms. The end capping agent may be reacted to end cleave. By adjusting the amount of the reactive group of the amino group, dicarboxylic acid anhydride group or acid halide group at the end of the resin, it is possible to adjust the molecular weight of the resin, control the physical properties (hydrophobicity etc.) of the resin, and improve the storage stability. Become.

Examples of A _{1 in} formulas (1-1) to (1-3) include formulas (2-1) to (2-8). In the formula, X _{25 to} X ₃₄ each independently represent a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy having 1 to 30 carbon atoms. Group, hydroxy group, carboxyl group, cyano group, nitro group, phenoxy group or benzoyl group (the phenoxy group and the benzoyl group have 1 to 5 halogen atoms, 1 to 5 carbon atoms having 1 to 5 carbon atoms, A linear or branched alkyl group or optionally substituted with 1 to 5 hydroxy groups). m25 to m34 represent an integer of 0 to 4. The present invention is not limited to these.

Examples of B ₁ include formulas (3-1) to (3-14). In the formula, X _{35 to} X ₅₀ each independently represent a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy having 1 to 30 carbon atoms. Group, hydroxy group, carboxyl group, cyano group, nitro group, phenoxy group or benzoyl group (the phenoxy group and benzoyl group have 1 to 5 halogen atoms, 1 to 5 carbon atoms having 1 to 5 carbon atoms, A linear or branched alkyl group or optionally substituted with 1 to 5 hydroxy groups). m35 to m50 represent an integer of 0 to 4). The present invention is not limited to these.

In the present specification, a halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
In this specification, examples of the linear or branched alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, i -Butyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 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, 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-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 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-cyclopropyl group.
Further, the linear or branched alkyl group having 1 to 5 carbon atoms is, for example, one having 1 to 5 carbon atoms among those listed above, and preferred examples include a methyl group, an ethyl group, and an isopropyl group. .
Further, examples of the linear or branched alkyl halide group having 1 to 10 carbon atoms include groups substituted with one or more halogen atoms among those listed above.
In the present specification, examples of the alkoxy group having 1 to 30 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, hexadecyloxy group, octadecyloxy group, nonadecyloxy group, heicosyloxy group, pentacosyl Oxy group, hexacosyloxy group, nonacosyloxy 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 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, 2,3-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 and the like.

The (a) tetracarboxylic dianhydride compound used in the production of the resin used in the present invention is not particularly limited, and these may be used alone or in combination of two or more. Specific examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3, Aromatic tetracarboxylic acids such as 3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2 , 3 Alicyclic tetracarboxylic dianhydrides such as 4-tetrahydro-1-naphthalene succinic dianhydride, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride Things.

The (b) acid dihalide compound used in the production of the resin used in the present invention is not particularly limited, and these may be used alone or in combination of two or more. Specific examples include 4-bromoisophthaloyl chloride, 5-tert-butylisophthaloyl chloride, 5-hydroxyisophthaloyl chloride, isophthaloyl chloride, 5-methoxyisophthaloyl chloride, 5-nitroisophthaloyl. Chloride, 5-methylisophthaloyl chloride, tetrafluoroisophthaloyl chloride, bromoterephthaloyl chloride, 2,5-dichloroterephthaloyl chloride, 2,5-dimethylterephthaloyl chloride, nitroterephthaloyl chloride, tetra Fluoroterephthaloyl chloride, tetrachloroterephthaloyl chloride, tetrabromoterephthaloyl chloride,
4-bromoisophthaloyl fluoride, 5-tert-butylisophthaloyl fluoride, 5-hydroxyisophthaloyl fluoride, isophthaloyl fluoride, 5-methoxyisophthaloyl fluoride, 5-nitroisophthaloyl Fluoride, 5-methylisophthaloyl fluoride, tetrafluoroisophthaloyl fluoride, bromoterephthaloyl fluoride, 2,5-dichloroterephthaloyl fluoride, 2,5-dimethylterephthaloyl fluoride, nitro Terephthaloyl fluoride, tetrafluoroterephthaloyl fluoride, tetrachloroterephthaloyl fluoride, tetrabromoterephthaloyl fluoride,
4-bromoisophthaloyl bromide, 5-tert-butylisophthaloyl bromide, 5-hydroxyisophthaloyl bromide, isophthaloyl bromide, 5-methoxyisophthaloyl bromide, 5-nitroisophthaloyl bromide, 5-methyl Isophthaloyl bromide, tetrafluoroisophthaloyl bromide, bromoterephthaloyl bromide, 2,5-dichloroterephthaloyl bromide, 2,5-dimethyl terephthaloyl bromide, nitroterephthaloyl bromide, tetrafluoroterephthaloyl bromide Tetrachloroterephthaloyl bromide, tetrabromoterephthaloyl bromide,
4-bromoisophthaloyl iodide, 5-tert-butylisophthaloyl iodide, 5-hydroxyisophthaloyl iodide, isophthaloyl iodide, 5-methoxyisophthaloyl iodide, 5-nitroisophthaloyl Iodide, 5-methylisophthaloyl iodide, tetrafluoroisophthaloyl iodide, bromoterephthaloyl iodide, 2,5-dichloroterephthaloyl iodide, 2,5-dimethylterephthaloyl iodide, nitro Examples include terephthaloyl iodide, tetrafluoroterephthaloyl iodide, tetrachloroterephthaloyl iodide, and tetrabromoterephthaloyl iodide.

(C) The compound having both a dicarboxylic anhydride group and an acid halide group used in the production of the resin used in the present invention is not particularly limited, and these may be used alone or in combination of two or more. Can be used. Specific examples thereof include compounds represented by the following formulas (4-1) to (4-5).

(In formulas (4-1) to (4-5), Z ₁ represents a halogen atom.)

Moreover, there is no limitation in particular as (d) diamine compound used for manufacture of resin used by this invention, These may be used 1 type and can use 2 or more types simultaneously. Specific examples include 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ) Ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-) 3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3-amino -4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy -5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1,4-bis (4 -Amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino No-4-hydroxyphenoxy) phenyl] sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexa A diamine compound having a phenolic hydroxyl group such as fluoropropane,
1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2- A diamine compound having a thiophenol group, such as bis (3-amino-4-mercaptophenyl) hexafluoropropane,
1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ether, Diamine compounds having a sulfonic acid group such as 4,4′-diaminobiphenyl-3,3′-disulfonic acid, 4,4′-diamino-3,3′-dimethylbiphenyl-6,6′-disulfonic acid,
2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid Acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino- 3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethylbiphenyl, 4, , 4′-diamino-3,3′-dicarboxy-5,5′-dimethoxybiphenyl, 1,4-bis (4-amino-3-carboxyphenoxy) benzene, 1,3-bis (4 Amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis Examples thereof include diamine compounds having at least one carboxyl group such as [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane.
Further, p-phenylenediamine, m-phenylenediamine, 4,4′-methylene-bis (2,6-ethylaniline), 4,4′-methylene-bis (2-isopropyl-6-methylaniline) 4,4 '-Methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-tolidine , M-tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′- Aminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2- Bis (3-amino-4-toluyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) Phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,2-naphthalenediamine, 1 , 4-naphthalenediamine, 2,4-naphthalenediamine, 1,5-diaminonaphthalene, etc. It can be mentioned Min compound.

Furthermore, by reacting a compound (terminal blocking agent) that seals the terminal reaction with the resin terminal, and adjusting the amount of the reactive group of the amino group, dicarboxylic anhydride group or acid halide group at the resin terminal, It is possible to adjust the molecular weight of the resin, control the physical properties (hydrophobicity etc.) of the resin, and improve the storage stability. As a method for end-capping, (d) one or more diamine compounds in the resin of the present invention are converted into (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a dicarboxylic acid anhydride. One or more compounds selected from compounds having both a group and a halide group, in addition to making the resin terminal an amino group in excess, having a reactive group bonded thereto and an aromatic ring or having 1 to It can be formed by reacting an organic group containing 5 alkyl groups. More preferably, it can be formed by reacting an end of the resin with a dicarboxylic anhydride compound or acid halide compound having an aromatic ring or an alkyl group having 1 to 5 carbon atoms.

Examples of the dicarboxylic acid anhydride include the following formulas (5-1) to (5-30), and examples of the acid halide compound include compounds represented by the formulas (5-31) to (5-60). In particular, when a dicarboxylic acid anhydride is used, a carboxyl group is generated at the terminal, and thus the hydrophilicity / hydrophobicity of the entire resin can be controlled by this carboxyl group. The present invention is not limited only to these compounds.

(In the above formula, Z ₁ represents a halogen atom, and n11 to n42 represent an integer of 0 or more, which is not more than the maximum number that can be bonded to the compound.)

As another method, it is selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a compound having both a dicarboxylic anhydride group and a halide group in the resin of the present invention. (D) One or more diamine compounds are added in excess to make the resin end of the resin a dicarboxylic anhydride group or acid halide group, and then have a reactive group that binds to it. And an organic group containing an aromatic ring or an alkyl group having 1 to 5 carbon atoms can be reacted. More preferably, it can be formed by reacting an aromatic ring or an amino group-containing compound having an alkyl group having 1 to 5 carbon atoms with a resin terminal. Specific examples include compounds represented by the following formulas (6-1) to (6-30). The present invention is not limited to these.

(In the above formula, Z ₁ represents a halogen atom, and n43 to n60 represent an integer of 0 or more, which is not more than the maximum number that can be bonded to the compound.)

Specific examples of the structure of the polyamic acid or polyamide contained in the resist upper layer film-forming composition of the present invention are shown below, but the present invention is not limited to the following examples.
Examples of the polyamic acid contained in the resist upper layer film-forming composition of the present invention include the following polyamic acids (7-1) to (7-13) (wherein p ₁ , p ₂ , p ₃ and p ₄ represent the proportion of each structure in the polyamic acid). Here, (7-1) to (7-8) are polyamic acids produced from one kind of tetracarboxylic dianhydride compound and two kinds of diamine compounds, and (7-9) and (7-10) Is a polyamic acid produced from two tetracarboxylic dianhydride compounds and one diamine compound, and (7-11) is produced from two tetracarboxylic dianhydride compounds and two diamine compounds. (7-12) and (7-13) are polyamic acids produced from a kind of tetracarboxylic dianhydride compound and a kind of diamine compound.
The polyamic acid can be converted to polyimide by a method such as thermal imidization or chemical imidization described separately.

Examples of the polyamide contained in the resist upper layer film forming composition of the present invention include the following polyamides (8-1) to (8-11). Here, (8-1) to (8-7) are polyamides produced from one kind of acid dihalide compound and two kinds of diamine compounds, and (8-8) and (8-9) are two kinds of acids. A polyamide produced from a dihalide compound and one kind of diamine compound, (8-10) is a polyamide produced from two kinds of acid dihalide compounds and two kinds of diamine compounds, and (8-11) is one kind It is a polyamide produced from an acid dihalide compound and a kind of diamine compound.

The structural formula of the resin in which the end-capping agent is introduced at the end of the polyamic acid is, for example, an acid halide compound or an acid anhydride compound at the amino group end as in the formulas (9-1) to (9-13). Examples of the reaction include examples in which an amino group-containing compound is reacted with the terminal of the dicarboxylic acid anhydride, such as formula (10-1) to formula (10-13).
The polyamic acid can be converted to polyimide by a method such as thermal imidization or chemical imidization described separately.

In addition, the structural formula of a resin in which an end-capping agent is introduced at the end of polyamide is, for example, a reaction of an acid halide compound or acid anhydride with an amino group end such as formula (11-1) to formula (11-11). And examples in which an amino group-containing compound is reacted with the terminal of the acid halide group, such as formula (12-1) to formula (12-10).

The resin used in the present invention is one or more selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound and (c) a compound having both a dicarboxylic anhydride group and a halide group. Compound and (d) when produced from one or more diamine compounds, tetracarboxylic dianhydride, acid dihalide compound and compound having both dicarboxylic anhydride group and halide group, based on the total number of moles of diamine compound The ratio to the total number of moles is preferably 0.8 to 1.2. As in the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the resin produced and the higher the molecular weight.

Further, when adding an end-capping agent, for example, when synthesizing an amino group-terminated resin, (d) one or more diamine compounds are converted into (a) tetracarboxylic dianhydride, (b) acid dihalide. Compound (c) and an excess of 1 to 1.6 total moles relative to 1 total mole of one or more compounds selected from compounds having both dicarboxylic anhydride groups and halide groups In addition, after the reaction, end-capping agent is selected from (a) tetracarboxylic dianhydride compound, (b) acid dihalide compound, and (c) compound having both dicarboxylic anhydride group and halide group. The synthesis is performed by adding a total number of moles of 0.1 to 2.0 with respect to a total number of moles of one or more selected compounds.

Conversely, when synthesizing a resin having a dicarboxylic acid anhydride group or an acid halide group terminal, (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) both a dicarboxylic acid anhydride group and a halide group. One or more compounds selected from among the compounds having (d) one or more diamine compounds are added in excess in the range of a total number of moles of 1.1 to 1.6 with respect to a total number of moles of one or more diamine compounds. In addition, the end capping agent is synthesized by adding a total number of moles of 0.1 to 2.0 with respect to a total number of moles of the diamine compound.

In the production of the resin of the present invention, at least one selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a compound having both a dicarboxylic anhydride group and a halide group. The reaction temperature of the reaction between the compound and (d) one or more diamine compounds can be selected from -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. A high molecular weight resin can be obtained at a reaction temperature of 5 to 40 ° C. and a reaction time of 1 to 48 hours. In order to obtain a resin having a low molecular weight and high storage stability, a reaction time of 10 hours or longer at 40 to 80 ° C. is more preferable.

Of the resins of the present invention, those having an imide bond can be obtained by dehydrating and ring-closing (thermal imidization) of the polyamic acid in the resin. At this time, it is also possible to convert the polyamic acid into an imide in a solvent and use it as a solvent-soluble polyimide-containing resin.
Moreover, the method of chemically ring-closing using a well-known dehydration ring-closing catalyst is also employable.
The heating method can be performed at an arbitrary temperature of 100 to 350 ° C., preferably 120 to 300 ° C.
The chemical ring closure can be carried out, for example, in the presence of pyridine, triethylamine or the like and acetic anhydride, and the temperature at this time can be selected from -20 to 200 ° C. .

The solution containing the polyimide-containing resin thus obtained can be used as it is, and a poor solvent such as methanol, ethanol and water is added to precipitate the resin, which is isolated as a resin solid, Alternatively, the resin solid can be used after re-dissolving in a suitable solvent.

The weight average molecular weight of the resin of the present invention measured by GPC (Gel Permeation Chromatography) method is, for example, 500 to 100,000, or 1000 to 50,000, preferably 2000 to 50,000 in terms of polystyrene. When the weight average molecular weight is 500 or less, the resist upper layer film using the resin may be diffused into the photoresist to deteriorate the lithography performance. When the weight average molecular weight is 100,000 or more, the formed resist upper layer film has insufficient solubility in a photoresist developer, and a residue may be present after development.
One or more compounds selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a compound having both a dicarboxylic anhydride group and a halide group, and (d) one type The reaction with the above diamine compound can be carried out in a solvent. Solvents that can be used in this case include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ester Ter, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene Examples include glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These may be used alone or in combination. Furthermore, even if it is a solvent which does not melt | dissolve resin, you may mix and use it for the said solvent in the range in which the resin produced | generated by the polymerization reaction does not precipitate.

The solution containing the resin thus obtained can be used as it is for the preparation of the resist upper layer film-forming composition. In addition, the resin can be precipitated and isolated in a poor solvent such as methanol, ethanol, ethyl acetate, hexane, toluene, acetonitrile, water, and recovered for use. The drying conditions after isolating the resin are desirably 8 to 48 hours at 50 to 100 ° C. in an oven or the like. After the resin is recovered, it can be redissolved in any solvent, preferably the alcohol solvent described below, and used as a resist upper layer film composition.

In order to prevent intermixing (layer mixing) when the resist upper layer film-forming composition of the present invention is applied to the above resin, instead of the solvent usually used for resist, and the film is formed on the resist. An alcohol solvent such as the following, which is a straight chain having 1 to 20 carbon atoms, a branched or cyclic saturated alkyl alcohol having 3 to 20 carbon atoms or an aromatic alcohol having 6 to 20 carbon atoms is preferably used.
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 can be used alone or as a mixture.

Also, for example, for the convenience of the synthesis of the resin of the present invention, the following solvents may be mixed together with the alcohol solvent. The solvent is 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, methyl 2-hydroxy-3-methylbutanoate, 3-methoxypropionic acid Methyl, 3-methoxy Ethyl propionate, 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 30.00 mass% with respect to the alcohol solvent.

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 p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and / or 2,4,4,6- Thermal acid generators such as tetrabromocyclohexadienone, benzoin tosylate, and 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 addition, the resist upper layer film-forming composition of the present invention generates an acid that generates acid by exposure light (for example, EUV irradiation, electron beam irradiation) in order to match the acidity with the resist present in the lower layer in the lithography process. An agent can be added as an acid compound. 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 may further 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.

Examples of the basic compound include amines. For example, there is an aminobenzene compound represented by the formula (13-1).

In formula (13-1), r _{1 to} r ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an amino group.

Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, -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 , 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, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl 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 may 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 the resist upper layer film forming composition of the present invention, in addition to the above, further rheology adjusting agents, adhesion assistants, surfactants and the like can be added 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, adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate, 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, there is no occurrence of pinholes or striations, and a surfactant can be blended in order to further improve the applicability to surface unevenness. 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 allyl 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 sol Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, EFTTOP EF301, EF303, EF352 (Manufactured by Tochem Products Co., Ltd.), Megafuk F171, F173 (manufactured by Dainippon Ink Co., Ltd.), 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.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned. 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. These resists include chemically amplified resists composed of a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, and an alkali dissolution rate of the resist that decomposes with an alkali-soluble binder, an acid generator, and an acid. A chemically amplified resist composed of a low molecular weight compound that changes the acid, a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, and a low molecular weight compound that decomposes with an acid to change the alkali dissolution rate of the resist A chemically amplified resist comprising: a non-chemically amplified resist comprising a binder having a group that is decomposed by EUV to change the alkali dissolution rate; and a non-chemically amplified resist comprising a binder having a portion that is cut by EUV to change the alkali dissolution rate. and so on. .

For example, the material system of EUV resist includes methacrylic and polyhydroxystyrene (PHS). 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. These resists include a positive photoresist composed of novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemical amplification composed of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator. -Type photoresist, chemically amplified photoresist composed of low molecular weight compound, alkali-soluble binder and photoacid generator that decomposes with acid to increase alkali dissolution rate of photoresist, and acid decomposes to increase alkali dissolution rate There is a chemically amplified photoresist composed of a low molecular weight compound that decomposes with a binder having an acid group and 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 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. These resists include chemically amplified resists composed of a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, and an alkali dissolution rate of the resist that decomposes with an alkali-soluble binder, an acid generator, and an acid. A chemically amplified resist composed of a low molecular weight compound that changes the acid, a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, and a low molecular weight compound that decomposes with an acid to change the alkali dissolution rate of the resist A chemically amplified resist, a non-chemically amplified resist composed of a binder having a group that is decomposed by an electron beam to change the alkali dissolution rate, and a non-chemically amplified composed of a binder having a site that is cut by the electron beam to change the alkali dissolution rate There are mold resists. 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, 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 resist upper layer film is generally formed 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 to 100 nm, 5 to 100 nm, or 5 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.

The 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.

Hereinafter, the present invention will be described in detail with reference to synthesis examples and examples, but the present invention is not limited to the following description.

The weight average molecular weights (Mw) of the resins (polymers) shown in the following Synthesis Examples 1 to 11 of the present specification are measurement results by 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) [trade name] (manufactured by Tosoh Corporation)
TSKgel SuperMultipore HZ-N (P0010) [trade name] (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow rate: 0.35 ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

<Synthesis Example 1>
10.0 g of 4,4 ′-(hexafluoroisopropylidene) bisphthalic dianhydride, 1.9 g of 3,5-diaminobenzoic acid and 3.11 g of bis (4-aminophenyl) sulfone were added to 85.1 g of propylene glycol monomethyl ether. The mixture was reacted at 40 ° C. for 24 hours. Next, 1.7 g of tetrafluorophthalic anhydride and 9.4 g of propylene glycol monomethyl ether were added and reacted at room temperature for 20 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 7509. The obtained polyamic acid has a structure represented by the formula (14-1).

<Synthesis Example 2>
10.0 g of 4,4 ′-(hexafluoroisopropylidene) bisphthalic dianhydride, 1.0 g of 3,5-diaminobenzoic acid, 3.11 g of bis (4-aminophenyl) sulfone, 4-octadecyloxy-1, 2.4 g of 3-diaminobenzene was reacted in 93.1 g of propylene glycol monomethyl ether at 40 ° C. for 24 hours. Next, 1.1 g of phthalic anhydride and 6.3 g of propylene glycol monomethyl ether were added and reacted at room temperature for 20 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 6728. The obtained polyamic acid has a structure represented by the formula (14-2).

<Synthesis Example 3>
Propylene glycol monomethyl ether containing 10.0 g of 4,4 ′-(hexafluoroisopropylidene) bisphthalic dianhydride, 1.9 g of 3,5-diaminobenzoic acid, and 4.7 g of 4-octadecyloxy-1,3-diaminobenzene The reaction was carried out in 94.1 g at 40 ° C. for 24 hours. Next, 4.7 g of tetrafluorophthalic anhydride and 9.4 g of propylene glycol monomethyl ether were added and reacted at room temperature for 22 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 8925. The obtained polyamic acid has a structure represented by the formula (14-3).

<Synthesis Example 4>
Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (2.2 g), isophthalic acid dichloride (1.4 g) and bis (4-aminophenyl) sulfone (0.2 g) in N-methylpyrrolidone (15.5 g) at room temperature for 17 hours By reacting, a solution containing polyamide was obtained. The obtained solution was added to methanol and reprecipitated, followed by drying at 50 ° C. for 12 hours to obtain a polyamide solid having a structural unit represented by the following formula (14-4). The weight average molecular weight (Mw) obtained by GPC method was 4502.

<Synthesis Example 5>
Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (2.0 g) and isophthalic acid dichloride (1.1 g) were reacted in 1-2.4 g of N-methylpyrrolidone at 50 ° C. for 30 minutes. Then, the solution containing polyamide was obtained by reacting at room temperature for 18 hours. The obtained solution was added to a methanol: water = 9: 1 solution and reprecipitated, followed by drying at 50 ° C. for 12 hours to obtain a polyamide solid having a structural unit represented by the following formula (14-5). . The weight average molecular weight (Mw) obtained by GPC method was 4362.

<Synthesis Example 6>
Pyromellitic dianhydride 5.0 g, 3,5-diaminobenzoic acid 1.52 g, and bis (3-amino-4-hydroxyphenyl) sulfone 0.7 g in propylene glycol monomethyl ether 40.93 g at 40 ° C. The reaction was performed for 24 hours. Next, 0.82 g of tetrafluorophthalic anhydride and 4.68 g of propylene glycol monomethyl ether were added and reacted at room temperature for 20 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 1249. The obtained polyamic acid has a structure represented by the formula (14-6).

<Synthesis Example 7>
Pyromellitic dianhydride 5.0 g, 3,5-diaminobenzoic acid 1.52 g, and bis (4-aminophenyl) sulfone 0.62 g were reacted in propylene glycol monomethyl ether 40.48 g at 40 ° C. for 24 hours. It was. Next, 0.82 g of tetrafluorophthalic anhydride and 4.68 g of propylene glycol monomethyl ether were added and reacted at room temperature for 20 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 1552. The obtained polyamic acid has a structure represented by the formula (14-7).

<Synthesis Example 8>
Pyromellitic dianhydride 5.0 g, 3,5-diaminobenzoic acid 1.52 g, and 2,2′-bis (trifluoromethyl) benzidine 0.80 g in propylene glycol monomethyl ether 41.49 g at 40 ° C. The reaction was performed for 24 hours. Next, 0.82 g of tetrafluorophthalic anhydride and 4.68 g of propylene glycol monomethyl ether were added and reacted at room temperature for 20 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 1894. The obtained polyamic acid has a structure represented by the formula (14-8).

<Synthesis Example 9>
4.0 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2.79 g of 3,5-diaminobenzoic acid were reacted in 38.49 g of propylene glycol monomethyl ether at 40 ° C. for 24 hours. Next, 0.83 g of 4-aminobenzoic acid and 4.75 g of propylene glycol monomethyl ether were added and reacted at room temperature for 20 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 5647. The obtained polyamic acid has a structure represented by the formula (14-9).

<Synthesis Example 10>
4.0 g of 4,4′-oxydiphthalic anhydride and 1.76 g of 3,5-diaminobenzoic acid were reacted in 32.67 g of propylene glycol monomethyl ether at 40 ° C. for 24 hours. Next, 0.53 g of 4-aminobenzoic acid and 3.06 g of propylene glycol monomethyl ether were added and reacted at room temperature for 20 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 2826. The obtained polyamic acid has a structure represented by the formula (14-10).

<Synthesis Example 11>
Propylene glycol monomethyl containing 3.5 g of pyromellitic dianhydride, 0.47 g of trimellitic anhydride chloride, 1.49 g of 3,5-diaminobenzoic acid, and 0.55 g of bis (3-amino-4-hydroxyphenyl) sulfone The reaction was carried out in 31.17 g of ether at 40 ° C. for 24 hours. Next, 0.74 g of tetrafluorophthalic anhydride and 4.21 g of propylene glycol monomethyl ether were added and reacted at room temperature for 20 hours to obtain a solution containing polyamic acid. The weight average molecular weight (Mw) obtained by GPC method was 4556. The obtained polyamic acid has a structure represented by the formula (14-11).

(Example 1)
To 1.0 g of a solution containing 0.32 g of the resin obtained in Synthesis Example 1, 20.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 2)
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the resin obtained in Synthesis Example 2 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 3)
To 1.0 g of a solution containing 0.32 g of the resin obtained in Synthesis Example 3, 20.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 4)
20.4 g of 4-methyl-2-pentanol was added to 0.32 g of the resin obtained in Synthesis Example 4 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 5)
To 0.32 g of the resin obtained in Synthesis Example 5, 20.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 6)
To 2.5 g of a solution containing 0.42 g of the resin obtained in Synthesis Example 6, 24.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 7)
To 2.5 g of a solution containing 0.42 g of the resin obtained in Synthesis Example 7, 24.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 8)
To 2.5 g of a solution containing 0.42 g of the resin obtained in Synthesis Example 8, 24.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

Example 9
22.5 g of cyclopentanol was added to 2.5 g of a solution containing 0.42 g of the resin obtained in Synthesis Example 6 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 10)
To 2.5 g of the solution containing 0.42 g of the resin obtained in Synthesis Example 6 above, 24.4 g of 1-heptanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 11)
To 2.5 g of a solution containing 0.42 g of the resin obtained in Synthesis Example 6 above, 24.4 g of 2-methyl-2-butanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

Example 12
To 2.5 g of a solution containing 0.42 g of the resin obtained in Synthesis Example 9, 24.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Example 13)
To 2.5 g of a solution containing 0.42 g of the resin obtained in Synthesis Example 10, 24.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 14)
To 1.0 g of a solution containing 0.32 g of the resin obtained in Synthesis Example 11, 20.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Comparative Example 1)
1 g of polyhydroxystyrene resin (commercial product, weight average molecular weight 8000) was dissolved in 99 g of 4-methyl-2-pentanol to obtain an EUV resist upper layer film forming composition solution.
(Comparative Example 2)
Propylene glycol monomethyl ether acetate was used.
(Comparative Example 3)
Ethyl acetate was used.
(Comparative Example 4)
Cyclohexanone was used.
(Comparative Example 5)
Gamma butyl lactone was used.

(Intermixing test with resist)
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).
In the resist upper layer film forming composition solution prepared in Example 1 to Example 14 or Comparative Example 1 of the present invention, or in Comparative Examples 2 to 5, only the solvent was applied onto the resist film using a spinner, The film thickness was measured by heating on a hot plate at 100 ° C. for 1 minute (film thickness B: sum of film thickness of resist and resist upper layer film).
A 2.38 wt% tetramethylammonium hydroxide aqueous solution (trade name: NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)), which is a commercially available general-purpose alkaline developer, is deposited on the resist upper layer film and left for 60 seconds. Then, rinsing was performed 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 can be said that there is no intermixing with the resist. In Examples 1 to 14, it was confirmed that the film thickness A was equal to the film thickness C and there was no resist and intermixing. On the other hand, in Comparative Examples 2 to 5, since the film thickness B was 0, it is suggested that the resist upper layer film composition using these solvents causes intermixing.
[Table 1]

[Optical parameter test]
The resist upper layer film-forming composition solution prepared in Examples 1 to 11 and Example 14 of the present invention and the resist upper layer film-forming composition solution shown in Comparative Example 1 were each formed on a quartz substrate using a spinner. It was applied to. 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 absorptivity in wavelength 190nm thru | or 240nm was measured for these 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 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 better light shielding property of DUV light than the resist upper layer film obtained from the resist upper layer film forming composition of Comparative Example 1. It was.
[Table 2]

EUV resist used in an EUV lithography process that can selectively pass through EUV exposure light, such as UV or DUV, without being intermixed 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

One or more compounds selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and (c) a compound having both a dicarboxylic anhydride group and an acid halide group, and (d) 1 A resist upper layer film-forming composition comprising a resin containing at least one of an amide bond and an imide bond, which is produced by reacting at least one kind of diamine compound, and an alcohol solvent.
The resin according to claim 1, wherein the resin comprises one or more unit structures selected from the following formulas (1-1), (1-2), and (1-3): Resist upper layer film forming composition.

(In formulas (1-1) to (1-3), at least one of A 1 and B 1 is an organic group containing an aromatic ring, and at least one of them is an organic group having a hydroxyl group, a carboxyl group, or a combination thereof. (The weight average molecular weight of the resin is 500 to 100,000.)
The resist upper layer film-forming composition according to claim 1 or 2, wherein the resin terminal structure according to claim 1 or 2 is represented by formula (1-4).

(In the formula (1-4), R 1 represents an aromatic ring or an organic group containing an alkyl group having 1 to 5 carbon atoms, B 1 has the same definition as described in claim 2, This represents a part of the resin according to claim 2.)
The resist upper layer film-forming composition according to claim 1 or 2, wherein the resin terminal structure according to claim 1 or 2 is represented by formula (1-5) or formula (1-6).

(In Formula (1-5) or Formula (1-6), R 2 represents an aromatic ring or an organic group containing an alkyl group having 1 to 5 carbon atoms, and A 1 and B 1 are defined in claim 2. The definition is the same, and the wavy line represents a part of the resin according to claim 2.)
5. The alcohol solvent is a straight chain having 1 to 20 carbon atoms, a branched or cyclic saturated alkyl alcohol having 3 to 20 carbon atoms, or an aromatic alcohol having 6 to 20 carbon atoms. The resist upper layer film forming composition of any one of these.
6. The resist upper layer film according to claim 1, wherein the alcohol solvent is 1-heptanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, or cyclopentanol. Forming composition.
Compound (a) is represented by the following formulas (1-7) to (1-10),

(In the formulas (1-7) to (1-10), X 1 to X 5 are each independently a halogen atom, a straight or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 1 to 10 carbon atoms, or Branched halogenated alkyl group, alkoxy group having 1 to 30 carbon atoms, hydroxy group, carboxyl group, cyano group, nitro group, phenoxy group or benzoyl group (the hydrogen atom of the phenoxy group and benzoyl group is 1 to 5 halogen atoms) M1 represents an integer of 0 to 8. n1 represents an atom, which may be substituted with 1 to 5 straight-chain or branched alkyl groups having 1 to 5 carbon atoms or 1 to 5 hydroxy groups. m3 and m4 represent an integer of 0 to 3. n2 and n3 represent an integer of 0 to 2. m2 and m5 represent an integer of 0 to 4.
W 1 represents any of a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. ),
Compound (b) is represented by the following formulas (1-11) to (1-13),

(In the formulas (1-11) to (1-13), Z 1 is a halogen atom, X 6 to X 9 are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and 1 carbon atom. A linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxy group, a carboxyl group, a cyano group, a nitro group, a phenoxy group, or a benzoyl group (the hydrogen atoms of the phenoxy group and benzoyl group are M6 and m7 may be substituted with 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxy groups. It represents an integer of 10. n4 and n5 represent an integer of 0 to 3. m8 and m9 represent an integer of 0 to 4.
W 2 represents any of a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. ),
Compound (c) is represented by the following formula (1-14) or formula (1-15),

(In the formulas (1-14) to (1-15), Z 1 is a halogen atom, X 10 to X 12 are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a carbon number of 1 A linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxy group, a carboxyl group, a cyano group, a nitro group, a phenoxy group, or a benzoyl group (the hydrogen atoms of the phenoxy group and benzoyl group are M10 represents 0 to 9 and may be substituted with 1 to 5 halogen atoms, 1 to 5 straight-chain or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxy groups. N6 and m11 represent an integer of 0 to 3. m12 represents an integer of 0 to 4.
W 3 represents any of a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. ),
Compound (d) is represented by the following formula (1-16) or formula (1-17),

(In the formulas (1-16) and (1-17), X 13 to X 15 are each independently a halogen atom, a straight or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 1 to 10 carbon atoms, or Branched halogenated alkyl group, alkoxy group having 1 to 30 carbon atoms, hydroxy group, carboxyl group, cyano group, nitro group, phenoxy group or benzoyl group (the hydrogen atom of the phenoxy group and benzoyl group is 1 to 5 halogen atoms) M13 to m15 each represents an integer of 0 to 4, and may be substituted with 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms or 1 to 5 hydroxy groups. n7 represents an integer of 0 to 3.
W 4 represents a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. The composition for forming a resist upper layer film according to claim 1, wherein the unit structure of the resin has at least one hydroxyl group, carboxyl group, or a combination thereof.
End capping agents for forming the partial structure of the formula (1-4) are represented by the following formulas (1-18) to (1-21),

(In the formulas (1-18) to (1-21), Z 1 is a halogen atom, X 16 to X 21 are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, 10 represents a linear or branched halogenated alkyl group, an alkoxy group having 1 to 30 carbon atoms, a hydroxy group, a carboxyl group, a phenoxy group, a cyano group, or a nitro group, and m16 represents an integer of 0 to 10. n8, n9 And m17 represents an integer of 0 to 3. m18 and m21 represent an integer of 0 to 5. m19 represents an integer of 0 to 11. m20 represents an integer of 0 to 4.
W 5 and W 6 each represent a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. . The resist upper layer film forming composition of Claim 3 which is a compound represented by this.
The end-capping agent for forming the partial structure of formula (1-5) or formula (1-6) is represented by the following formula (1-22) or formula (1-23),

(In the formulas (1-22) and (1-23), X 22 to X 24 are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, or A branched halogenated alkyl group, an alkoxy group having 1 to 30 carbon atoms, a hydroxy group, a carboxyl group, a phenoxy group, a cyano group or a nitro group, m22 represents an integer of 0 to 11, and n10 represents an integer of 0 to 3 M23 represents an integer of 0 to 4, and m24 represents an integer of 0 to 5.
W 7 represents any of a single bond, an oxygen atom, a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched halogenated alkylene group having 1 to 10 carbon atoms, a sulfonyl group, or a carbonyl group. The resist upper layer film forming composition of Claim 4 which is a compound represented by this.
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 iodonium salt acid generator or a sulfonium salt acid generator.
The composition for forming a resist upper layer film according to any one of claims 1 to 12, further comprising a basic compound.
The resist upper layer film formation composition of any one of Claims 1 thru | or 13 whose resist used with the said composition is a resist for EUV (wavelength 13.5nm).
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 14 on the resist film to form 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).