WO2014017331A1

WO2014017331A1 - Resist upper layer film forming composition for lithography and method for manufacturing semiconductor device using same

Info

Publication number: WO2014017331A1
Application number: PCT/JP2013/069278
Authority: WO
Inventors: 竜慈大西; 徳昌藤谷; 木村　茂雄; 坂本　力丸
Original assignee: 日産化学工業株式会社
Priority date: 2012-07-25
Filing date: 2013-07-16
Publication date: 2014-01-30
Also published as: JP2015172606A; TW201411288A

Abstract

[Problem] To provide a resist upper layer film forming composition to be used for a lithography process in a manufacturing procedure of a semiconductor device, which is free from intermixing with a resist and selectively transmits EUV only, while blocking undesirable exposure light such as UV and DUV especially during EUV exposure. This resist upper layer film forming composition can be developed with a developer liquid after the exposure. [Solution] Provided is a resist upper layer film forming composition which contains: a derivative obtained by reacting a cyanurate derivative with a compound containing a naphthalene ring or an anthracene ring; and an alcohol solvent.

Description

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

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

Conventionally, fine processing using a photolithography technique has been performed in the manufacture of semiconductor devices. In the fine processing, a thin film of a photoresist composition is formed on a substrate to be processed such as a silicon wafer, and then actinic rays such as ultraviolet rays are irradiated and developed through a mask pattern on which a semiconductor device pattern is drawn. In this processing method, the substrate to be processed such as a silicon wafer is etched using the obtained photoresist pattern as a protective film (mask). In recent years, the degree of integration of semiconductor devices has increased, and the active light used has also been shortened from a KrF excimer laser (wavelength 248 nm) to an ArF excimer laser (wavelength 193 nm). Along with this, the influence of diffuse reflection and standing wave of actinic rays from the substrate becomes a big problem, and 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, and α-silicon, and an organic antireflection film made of a light-absorbing substance and a polymer compound are known. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation, whereas the latter is advantageous in that no special equipment is required, and many studies have been made.

In recent years, an ArF immersion lithography technique in which exposure is performed through water has been put into practical use as a next-generation photolithography technique that bears the photolithography technique using an ArF excimer laser (wavelength 193 nm). However, photolithographic technology using light is reaching its limit, and EUV lithography technology using EUV (wavelength 13.5 nm) is attracting attention as a new lithography technology after ArF immersion lithography technology.
In a semiconductor device manufacturing process using EUV lithography, a substrate coated with an EUV resist is irradiated with EUV, exposed, developed, and a resist pattern is formed.
To protect the EUV resist from contaminants and to block unwanted radiation such as UV and DUV (OUT of BAND / Out of Band, OOB), the upper layer of the EUV resist is beryllium, boron, carbon, silicon, zirconium, niobium. And a method comprising a polymer comprising a group comprising one or more of 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 that solves the above-mentioned problems, and is used as a resist upper layer film, particularly as an upper layer film of an EUV resist, without intermixing with the resist. In particular, a composition for forming a resist upper layer film used in a lithography process for manufacturing a semiconductor device, which is capable of selectively transmitting only EUV by blocking exposure light, such as UV or DUV, which is not preferable in EUV exposure, and capable of developing with a developer after exposure. Offer things.

As a first aspect of the present invention, (Formula 1-1):

(Substituents A _{1 to} A _{3 in} (Formula 1-1) are each a substituent containing at least one hydroxyl group, and at least one substituent is a naphthalene ring or an anthracene ring. A benzene ring, the hydrogen atoms of the naphthalene ring, anthracene ring or benzene ring are each independently substituted with a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms. And a resist upper layer film-forming composition comprising a cyanurate derivative represented by formula (II) and an alcohol solvent,
As a second aspect, the resist upper layer film-forming composition according to the first aspect, wherein the cyanurate derivative is synthesized from 1,3,5-tris- (2,3-epoxypropyl) isocyanurate,
As a third aspect, the cyanurate derivative is a cyanurate derivative synthesized from 1,3,5-tris- (2,3-epoxypropyl) isocyanurate and a hydroxyl group-containing compound D. A resist upper layer film-forming composition,
The hydroxyl group-containing compound D is a compound represented by i) or a combination of compounds represented by ii).
i) 1 selected from naphthoic acid or anthracenecarboxylic acid which contains at least one hydroxyl group as a substituent and may contain a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms as a substituent. More than one species,
ii) 1 selected from naphthoic acid or anthracenecarboxylic acid which contains at least one hydroxyl group as a substituent and may contain a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms as a substituent. One or more compounds and at least one hydroxyl group as a substituent, and one or more benzoic acid which may contain a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms as a substituent, A combination of
As a fourth aspect, the cyanurate derivative may be 1,3,5-tris- (2,3-epoxypropyl) isocyanurate and a compound represented by the following (formula 1-2), or (formula 1-2): A combination of the compound represented by (Formula 1-3) and

(In (Formula 1-2) or (Formula 1-3), n1 and n4 are each independently an integer of 1 to 5, n2 and n3 are each independently an integer of 0 to 8, n6 is each independently an integer of 0 to 4, (n1 + n2 + n3) is an integer of 1 to 9, (n4 + n5 + n6) is an integer of 1 to 5, and (n1 + n4) is an integer of 2 to 9 M1 represents 1 or 2. X represents a halogen atom), and is a cyanurate derivative synthesized from the first 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, the alcohol solvent is 1-heptanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, or cyclopentanol. The resist upper layer film-forming composition according to any one of the five aspects,
As a seventh aspect, the resist upper layer film-forming composition according to any one of the first aspect to the sixth aspect, further including an acid compound,
As an eighth aspect, the resist upper layer film-forming composition according to the seventh aspect, in which the acid compound is a sulfonic acid compound or a sulfonic acid ester compound,
As a ninth aspect, the resist upper layer film-forming composition according to the seventh aspect, wherein the acid compound is an onium salt-based acid generator, a halogen-containing compound-based acid generator, or a sulfonic acid-based acid generator,
As a tenth aspect, the resist upper layer film-forming composition according to any one of the first to ninth aspects, further including a basic compound,
As an eleventh aspect, the resist upper layer film forming composition according to any one of the first aspect to the tenth aspect, wherein the resist used together with the composition is a resist for EUV (wavelength 13.5 nm),
As a twelfth aspect, a step of forming a resist film on a substrate, a resist upper layer film formed by applying and baking the resist upper layer film forming composition according to any one of the first aspect to the eleventh aspect on the resist film A method of manufacturing a semiconductor device, comprising: a step of exposing a semiconductor substrate coated with the resist upper layer film and the resist film; a step of developing after exposure to remove the resist upper layer film and the resist film;
A thirteenth aspect is the method for manufacturing a semiconductor device according to the twelfth aspect, in which the exposure is performed by EUV (wavelength: 13.5 nm).

The present invention provides a resist upper layer film-forming composition, in particular, an EUV resist upper layer film-forming composition, which does not intermix with the EUV resist, and blocks EUV exposure, such as UV or DUV, which is not preferable 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.
In particular, when the EUV resist is exposed, the EUV light emits UV light and DUV light 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 EUV light. For example, the wavelength region in the vicinity of 190 nm to 300 nm, particularly 220 nm to 260 nm has the highest intensity. Deteriorating the shape. Specifically, 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 adversely affects the resolution of the EUV resist.
Although there is a method of installing a filter in the lithography system in order to remove light having a wavelength in the vicinity of 220 nm to 260 nm, the process is complicated. In the present invention, among DUV light (OUTofBAND / out-of-band radiation) contained in EUV exposure light, unwanted DUV light of 220 nm to 260 nm is used as cyanurate containing a naphthalene ring or anthracene ring contained in the composition of the present invention. By absorbing with a derivative, the resolution of the EUV resist can be improved.

In addition, 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, and the resist upper layer film forming composition is an alcohol solvent. It is better to use In this case, in the resist upper layer film forming composition of the present invention, a cyanurate derivative containing a hydroxyl group is used in order to enhance the solubility in an alcohol solvent.
Since the cyanurate derivative used in the resist upper layer film-forming composition of the present invention contains a hydroxyl group, it can be dissolved in a developer (for example, an alkaline developer) together with an EUV resist during development after exposure. Dissolution removal with a liquid is possible.

The present invention is a resist upper layer film-forming composition containing a cyanurate derivative and an alcohol solvent. Although suitable as a resist upper layer film, it is particularly suitable as a resist upper layer film forming composition used in an EUV lithography process using EUV as an exposure wavelength.

Details of the resist upper layer film-forming composition of the present invention will be described below.
The cyanurate compound for forming the cyanurate derivative used in the resist upper layer film-forming composition of the present invention has the following structure.

In the compound of formula (3-1), each of R ₁ , R ₂ , and R ₃ is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a benzene derivative group, vinyl Derivative group or epoxy derivative group is represented. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-octyl, and n-dodecyl. Is done. Examples of the benzene derivative group include a phenyl group, a benzyl group, a tolyl group, a methoxyphenyl group, a xylyl group, a biphenyl group, a naphthyl group, and an anthryl group. Examples of the vinyl derivative group include an ethenyl group, a propenyl group, a butenyl group, a butadienyl group, a hexenyl group, and an octadienyl group. Examples of the epoxy derivative group include a glycidyl group and a β-methyl-glycidyl group.
These alkyl groups, benzene derivative groups, and vinyl derivative groups may be substituted in addition to unsubstituted groups. Examples of the substituents include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, Examples are a hydroxyl group, an alkoxy group and an acyl group. A particularly preferred substituent is a hydroxyl group.

Among these, 1,3,5-tris- (2,3-epoxypropyl) isocyanurate represented by (Formula 3-2) is more preferably used.

The above isocyanurate compound is reacted with an aromatic ring compound having a specific structure described below to synthesize a cyanurate derivative used in the resist upper layer film-forming composition of the present invention.

The cyanurate derivative used in the present invention has the following structure (formula 1-1).

The compound of the formula (1-1) is synthesized by reacting a cyanurate compound with an aromatic ring compound having a specific structure. The aromatic ring compound having a specific structure is a compound containing a naphthalene ring or anthracene ring containing at least one hydroxyl group in the structure.
Substituents A ₁ to substituents A ₃ (Formula 1-1) are each a substituent containing at least one hydroxyl group, further at least one substituent is a naphthalene ring or an anthracene ring, the other When a substituent is present, it is a benzene ring. When a compound containing a naphthalene ring or an anthracene ring and a compound containing a benzene ring are reacted at the same time, a compound containing a naphthalene ring or an anthracene ring and a benzene ring coexists in the substituent A _{1 to the} substituent A _3. . The hydrogen atoms of the naphthalene ring, anthracene ring or benzene ring may be each independently substituted with a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms. The hydroxyl group is a hydrophilic group and is excellent in solubility in an alcohol solvent and in a developer. The reason for introducing a naphthalene ring or an anthracene ring into the cyanurate derivative is to absorb the UV light or DUV light.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the linear or branched saturated alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. It is done.

In order to synthesize the cyanurate derivative used in the present invention, the hydroxyl group-containing compound D to be reacted with the cyanurate compound is a compound represented by the following i) or a combination of compounds represented by ii).
i) 1 selected from naphthoic acid or anthracenecarboxylic acid which contains at least one hydroxyl group as a substituent and may contain a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms as a substituent. Two or more kinds of compounds, or ii) naphthoic acid or anthracene which contains at least one hydroxyl group as a substituent and may contain a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms as a substituent 1 or more types of compounds chosen from carboxylic acid, 1 type which may contain at least 1 hydroxyl group as a substituent, and may contain a halogen atom or a C1-C4 linear or branched saturated alkyl group as a substituent A combination with the above benzoic acid.
When the compound represented by i) or the combination of compounds represented by ii) includes a compound containing two or more carboxyl groups, a compound in which two or more cyanurate compounds are linked by the compound is formed. This is not preferable as the composition component of the present invention.
The compound constituting i) may be one kind or a combination of two or more kinds, but is preferably within 4 kinds, more preferably within 3 kinds.
The compound constituting ii) may be a combination of one or more compounds selected from the naphthoic acid or anthracene carboxylic acid and one or more combinations of the benzoic acid, more preferably the naphthoic acid or anthracene carboxylic acid. A combination of 3 or less compounds selected from acids and 3 or less of the above benzoic acids.

In order to synthesize the cyanurate derivative used in the present invention, the compound to be reacted with the cyanurate compound is a compound represented by the general formula (formula 1-2), or a compound represented by the formula (1-2) A compound containing one carboxyl group represented by a combination of compounds represented by 1-3) is preferably used. The compound having the structure of (Formula 1-2) may be one kind or a combination of two or more kinds, but is preferably within 4 kinds, more preferably within 3 kinds. The compound having the structure of (Formula 1-3) may be one kind or a combination of two or more kinds, but preferably within 4 kinds, more preferably within 3 kinds. Moreover, when these compounds contain two or more carboxyl groups, a compound in which two or more cyanurate compounds are linked with each other may be formed, which is not preferable as the composition component of the present invention. The carboxyl group in the compound represented by (Formula 1-2) or (Formula 1-3) reacts with a cyanurate derivative, particularly preferably reacts with an epoxy group to form a trimethyl group such as (Formula 1-1). An ester compound is produced.

In (Formula 1-2) or (Formula 1-3), n1 and n4 are each independently an integer of 1 to 5, preferably an integer of 1 to 3, and n2 and n3 are each independently 0 Is an integer from 1 to 8, more preferably an integer from 0 to 3, n5 and n6 are each independently an integer from 0 to 4, more preferably an integer from 0 to 3, and (n1 + n2 + n3) is 1. Is an integer from 1 to 9, (n4 + n5 + n6) is an integer from 1 to 5, and (n1 + n4) is an integer from 2 to 9. m1 represents 1 or 2. X represents a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom).

Specific examples of the compound represented by (Formula 1-2) or (Formula 1-3) include those represented by the following (Formula 2-1) to (Formula 2-10).

The resist upper layer film-forming composition of the present invention contains the above cyanurate derivative 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 and the like.
The molecular weight of the cyanurate compound used in the present invention is 129 to 1000, preferably 129 to 600. Moreover, although the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method of the cyanurate derivative synthesize | combined from a cyanurate compound is fluctuate | varied with the coating solvent to be used, solution viscosity, film | membrane shape, etc., it is 500 to 10000 in polystyrene conversion, for example. Or 1000 to 5000, preferably 1000 to 2000. When the weight average molecular weight is 500 or less, the resist upper layer film using the cyanurate derivative may diffuse into the photoresist to deteriorate the lithography performance. When the weight average molecular weight is 10,000 or more, the solubility of the resist upper layer film to be formed in the photoresist developer is insufficient, and a residue may be present after development.
In order to synthesize the cyanurate derivative used in the present invention having the structure of (formula 1-1), it is necessary to react the cyanurate compound with a compound containing a naphthalene ring or an anthracene ring containing at least one hydroxyl group. As a ratio when the total compound to be reacted with the cyanurate compound is 100% by mass, 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, More preferably, it is 76 mass% to 100 mass%.
The content of the cyanurate derivative in the resist upper layer film forming composition in the solid content 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. %.

The solid content of the resist upper layer film-forming composition of the present invention is 0.1 to 50% by mass, preferably 0.3 to 30% by mass. The solid content is obtained by removing the solvent component from the resist upper layer film-forming composition. *

In the production of the cyanurate derivative used in the present invention, the reaction between the cyanurate compound and the aromatic ring-containing compound is preferably performed in a nitrogen atmosphere. The reaction temperature may be selected from 50 ° C. to 200 ° C., preferably 80 ° C. to 180 ° C. A high molecular weight cyanurate derivative can be obtained in a reaction time of 1 to 48 hours. In order to obtain a cyanurate derivative having a low molecular weight and high storage stability, a reaction time of 1 to 24 hours at 80 to 150 ° C. is more preferable.

The reaction between the cyanurate compound and the aromatic ring-containing compound can be performed in a solvent. Solvents that can be used in this case include alcohol solvents such as 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-me 2-Pentanol, 2-Methyl-3-pentanol, 3-Methyl-1-pentanol, 3-Methyl-2-pentanol, 3-Methyl-3-pentanol, 4-Methyl-1-pen Examples include butanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, 1-butoxy-2-propanol, and cyclohexanol.

Other solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxyethyl propionate, 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyethyl acetate, 2-hydroxy-3-methylbutanoate, 3-methoxy Methyl propionate 3 over methoxypropionate, ethyl 3 over ethyl ethoxypropionate, 3 over ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, can be used butyl lactate and the like.
These may be used alone or in combination. Further, even a solvent that does not dissolve the cyanurate derivative may be used by mixing with the above solvent as long as the cyanurate derivative produced by the polymerization reaction does not precipitate.

The solution containing the cyanurate derivative thus obtained can be used as it is for the preparation of the resist upper layer film-forming composition. In addition, the cyanurate derivative may 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 cyanurate derivative are preferably 6 to 48 hours at 40 to 100 ° C. in an oven or the like. After the cyanurate derivative is recovered, it can be redissolved in an arbitrary 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 cyanurate derivative in place of a solvent usually used for resists and the film is formed on the resist. The following alcohol solvents are preferably used.
For example, the saturated alkyl alcohol may be a straight chain having 1 to 20 carbon atoms, a branched or cyclic saturated alkyl alcohol having 3 to 20 carbon atoms, such as 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-butane 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl -2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, 1-butoxy-2-propanol and And cyclohexanol. Examples of the aromatic alcohol include aromatic alcohols having 6 to 20 carbon atoms such as 1-phenylpropanol, 2-phenylpropanol, 3-phenylpropanol, 2-phenoxyethanol, phenethyl alcohol, and styryl alcohol.
Preferred alcohol solvents are 1-heptanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol or cyclopentanol.
These alcohol solvents can be used alone or as a mixture.

Further, for example, for the convenience of synthesis of the cyanurate derivative used in 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% by 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, bis (4-hydroxyphenyl) sulfone, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid and other acidic compounds, and / or Alternatively, a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate can be blended. The blending amount is 0.02 to 10% by mass, preferably 0.04 to 5% by mass, per 100% by mass of the total solid content.

In order to make the acidity of the resist upper layer film-forming composition of the present invention coincide with the acidity of the resist present in the lower layer in the lithography process, an acid is irradiated by exposure light (for example, ArF excimer laser irradiation, EUV irradiation, electron beam irradiation, etc.). A generated acid generator can be added. Preferred acid generators include, for example, onium salt acid generators such as bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, and phenyl-bis (trichloromethyl) -s-triazine. And halogen-containing compound acid generators such as benzoin tosylate and sulfonic acid acid generators such as N-hydroxysuccinimide trifluoromethanesulfonate. The amount of the acid generator added is 0.02 to 10% by mass, preferably 0.04 to 5% by mass, per 100% by mass of the total solid content.

The resist upper layer film-forming composition of the present invention can contain a basic compound. By adding a basic compound, the sensitivity can be adjusted during exposure of the resist. That is, a basic compound such as amine reacts with an acid generated from a photoacid generator during exposure to reduce the sensitivity of the resist underlayer film, thereby controlling the upper shape of the resist after exposure and development (after exposure and development). The resist shape is preferably rectangular.
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 each independently represents 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 addition to the above, the composition for forming a resist upper layer film of the present invention may contain additional rheology modifiers, surfactants and the like as necessary.
The rheology modifier is added mainly for the purpose of improving the fluidity of the resist upper layer film-forming composition. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; Mention may be made of maleic acid derivatives such as normal butyl maleate, diethyl maleate and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate, or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. it can. These rheology modifiers are usually blended at a ratio of less than 30% by mass with respect to 100% by mass of the total composition of the resist upper layer film-forming composition.

In the resist upper layer film forming composition of the present invention, 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 aryl ethers such as phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc., EFTOP EF301, EF303, EF352 (Manufactured by Tochem Products Co., Ltd.), Megafuk F171, F173 (manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, Fluorosurfactants such as SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), and Footent Series (Neos Co., Ltd.), organosiloxane polymer KP341 (Shinsei) Chemical Industries Co., Ltd.), and the like. The compounding amount of these surfactants is usually 0.2% by mass or less, preferably 0.1% by mass or less, per 100% by mass of the total composition of the resist upper layer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

In the present invention, an EUV resist can be used. As the EUV resist applied to the lower layer of the resist upper layer film formed from the composition of the present invention, either a negative type or a positive type can be used. Chemically amplified resist comprising a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist A chemically amplified resist comprising: a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate; and a chemically amplified resist comprising a low-molecular compound that decomposes with an acid to change the alkali dissolution rate of the resist, There are non-chemically amplified resists composed of binders having groups that decompose by EUV to change the alkali dissolution rate, and non-chemically amplified resists composed of binders having sites that are cut by EUV to change the alkali dissolution rate.
For example, as the material system of EUV resist, there are methacrylic system, polyhydroxystyrene (PHS) system, and the like. 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 formed from the composition of the present invention, either a negative photoresist or a positive photoresist can be used. A positive photoresist comprising a novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist comprising a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, an acid A chemically amplified photoresist comprising a low-molecular compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate There is a chemically amplified photoresist composed of a low molecular weight compound that decomposes with an acid to increase the alkali dissolution rate of the photoresist and a photoacid generator. For example, the Dow Chemical Company (formerly Rohm and Haas Electronic Materials Co., Ltd.) trade name APEX-E, Sumitomo Chemical Co., Ltd. trade name PAR710, and Shin-Etsu Chemical Co., Ltd. trade name SEPR430 Etc. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), Proc. SPIE, Vol. 3999, 365-374 (2000), and fluorine-containing polymer-based photoresists.

In the present invention, an electron beam resist can be used. As the electron beam resist applied to the lower layer of the resist upper layer film formed from the composition of the present invention, either a negative photoresist or a positive photoresist can be used. Chemically amplified resist comprising a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist A chemically amplified resist comprising: a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate; and a chemically amplified resist comprising a low-molecular compound that decomposes with an acid to change the alkali dissolution rate of the resist, There are non-chemically amplified resists composed of a binder having a group that changes the alkali dissolution rate by being decomposed by an electron beam, and non-chemically amplified resists composed of a binder having a portion that is cut by an electron beam to change the alkali dissolution rate. Even when these electron beam resists are used, a resist pattern can be formed in the same manner as when a photoresist is used as the irradiation source with KrF and ArF light.

As a developer for a positive resist having a resist upper layer film formed using the resist upper layer film-forming composition of the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia Inorganic amines such as ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine Alcohol amines such as alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, and cyclic amines such as pyrrole and piperidine, and alkaline aqueous solutions can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution. Of these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.

In the present invention, for example, a step of forming an EUV resist film on a substrate having a film to be processed for forming a transfer pattern, with or without using an EUV resist lower layer film, the EUV resist upper layer of the present invention on the resist film A step of applying and baking a film-forming composition 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, and 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).

In the present invention, the resist upper layer film is generally formed by a spin coating method in the same manner as the resist film formation. For example, a resist coat is formed 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 the resist upper layer film of the present invention is formed. The forming composition (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 formed from the composition of the present invention 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 to transfer a pattern, a resist film, and a resist upper layer film formed from the composition are sequentially formed on a substrate. Have 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. The resist upper layer film according to the present invention has a wet etching rate equal to or greater 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. Is possible.
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 with or without a KrF resist underlayer film on a substrate having a processing target film for forming a transfer pattern, and the KrF resist according to the present invention on the resist film A step of applying and baking an upper layer film-forming composition to form a KrF resist upper layer film, a step of exposing a semiconductor substrate covered with the resist upper layer film and the resist film, and developing after exposure to develop 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, an ArF resist film is formed on a substrate having a film to be processed on which a transfer pattern is to be formed, with or without an ArF resist underlayer film, and the ArF resist according to the present invention is formed on the resist film. A step of applying and baking an upper layer film forming composition to form an ArF 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 develop 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, an electron beam resist film is formed on a substrate having a processing target film for forming a transfer pattern, with or without an electron beam resist underlayer film, and the present invention is applied to the resist film. A step of applying and baking an electron beam resist upper layer film forming composition to form an electron beam resist upper layer film, a step of exposing the resist upper layer film and a semiconductor substrate coated with the resist film, and developing after exposure to the resist upper layer film And a step of removing 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.

EXAMPLES Hereinafter, although a synthesis example and an Example are given and explained in full detail about this invention, this invention is not limited to the following description at all.
The weight average molecular weight shown in the following synthesis examples of this specification is a measurement result by gel permeation chromatography (hereinafter abbreviated as GPC). The measurement conditions etc. are as follows using the GPC apparatus by Tosoh Corporation for the measurement. 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.
GPC column: Shodex (registered trademark) Asahipak (registered trademark) (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Solvent: N, N-dimethylformamide (DMF)
Flow rate: 0.6 ml / min Standard sample: Standard polystyrene sample (manufactured by Tosoh Corporation)
Detector: RI detector (manufactured by Tosoh Corporation, RI-8020)

<Synthesis Example 1>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g, 1,4-dihydroxy-2- 6.1 g of naphthoic acid (Formula 2-1) and 0.17 g of benzyltriethylammonium chloride were added to 13.9 g of cyclohexanol and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 1673 in terms of standard polystyrene and a dispersity of 1.69.
<Synthesis Example 2>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g, 3,5-dihydroxy-2- 6.1 g of naphthoic acid (Formula 2-2) and 0.17 g of benzyltriethylammonium chloride were added to 13.9 g of cyclohexanol and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 1453 and a dispersity of 1.41 in terms of standard polystyrene.
<Synthesis Example 3>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g 3,7-dihydroxy-2- Naphthoic acid (formula 2-3) 6.1 g and benzyltriethylammonium chloride 0.17 g were added to cyclohexanol 13.9 g and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 1373 in terms of standard polystyrene and a dispersity of 1.25.
<Synthesis Example 4>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g, 6-hydroxy-1-naphthoic acid 5.6 g of (Formula 2-4) and 0.17 g of benzyltriethylammonium chloride were added to 13.1 g of cyclohexanol and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. When GPC analysis was performed, the obtained cyanurate derivative had a weight average molecular weight of 1073 and a dispersity of 1.41 in terms of standard polystyrene.

<Synthesis Example 5>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g, 1-hydroxy-2-naphthoic acid 5.6 g of (Formula 2-5) and 0.17 g of benzyltriethylammonium chloride were added to 13.1 g of cyclohexanol and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 1546 in terms of standard polystyrene and a dispersity of 1.90.
<Synthesis Example 6>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g, 2-hydroxy-1-naphthoic acid 5.6 g of (Formula 2-6) and 0.17 g of benzyltriethylammonium chloride were added to 13.1 g of cyclohexanol and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 1559 in terms of standard polystyrene and a dispersity of 1.75.
<Synthesis Example 7>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g, 6-hydroxy-2-naphthoic acid 5.6 g of (Formula 2-7) and 0.17 g of benzyltriethylammonium chloride were added to 13.1 g of cyclohexanol and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 1166 in terms of standard polystyrene and a dispersity of 1.40.
<Synthesis Example 8>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (Product name: TEPIC (registered trademark) -SS, manufactured by Nissan Chemical Industries, Ltd.) 2.0 g, 3,7-dihydroxy-2- 3.6 g of naphthoic acid (Formula 2-8), 1.1 g of 3,5-di-tert-butylsalicylic acid hydrate (Formula 2-9) and 0.113 g of benzyltriethylammonium chloride were added to 27.1 g of cyclohexanol. Added and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 1225 and a dispersity of 1.11.

<Comparative Synthesis Example 1>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g, benzoic acid 4.01 g and benzyltriethyl 0.17 g of ammonium chloride was added to 10.7 g of cyclohexanol and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 756 and a dispersity of 1.05 in terms of standard polystyrene.
<Comparative Synthesis Example 2>
1,3,5-tris- (2,3-epoxypropyl) isocyanurate (product name: TEPIC [registered trademark] -SS, manufactured by Nissan Chemical Industries, Ltd.) 3.0 g, 6-bromo-2-naphthoic acid 7.75 g and 0.17 g of benzyltriethylammonium chloride were added to 16.3 g of cyclohexanol and dissolved. The reaction vessel was purged with nitrogen and reacted at 135 ° C. for 4 hours to obtain a cyanurate derivative solution. The cyanurate derivative solution does not cause white turbidity even when cooled to room temperature, and has good solubility in cyclohexanol. As a result of GPC analysis, the obtained cyanurate derivative had a weight average molecular weight of 1265 and a dispersity of 1.12.

(Example 1)
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 1 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 2)
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 2 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 3)
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 3 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
Example 4
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 4 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 5)
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 5 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 6)
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 6 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 7)
To 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 7, 20.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 8)
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 8 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
Example 9
20.4 g of 1-heptanol was added to 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 1 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 10)
20.4 g of cyclopentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 1 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 11)
20.4 g of 2-methyl-1-butanol was added to 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 1 and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
Example 12
To 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 1 above and 0.0032 g of bis (4-hydroxyphenyl) sulfone, 20.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 13)
To 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 1 and 0.0032 g of 2,6-diisopropylaniline, 20.4 g of 4-methyl-2-pentanol was added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Example 14)
20.4 g of 2-methyl-2-butanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Synthesis Example 1 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Comparative Example 1)
1 g of polyhydroxystyrene resin (commercial product, weight average molecular weight: 8,000) was dissolved in 99 g of 4-methyl-2-pentanol to obtain an EUV resist upper layer film forming composition solution.
(Comparative 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 cyanurate derivative obtained in Comparative Synthesis Example 1 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.
(Comparative Example 3)
20.4 g of 4-methyl-2-pentanol was dissolved in 1.0 g of a solution containing 0.32 g of the cyanurate derivative obtained in Comparative Synthesis Example 2 above. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.05 μm to obtain a resist upper layer film forming composition for lithography.

(Intermixing test with resist)
An EUV resist solution (methacrylic resist) was applied onto a quartz substrate using a spinner. A resist film was formed by heating at 100 ° C. for 1 minute on a hot plate, and the film thickness was measured (film thickness A: resist film thickness).
The resist upper layer film forming composition solutions prepared in Examples 1 to 14 and Comparative Examples 1 to 3 of the present invention were applied onto the resist film using a spinner, and then on a hot plate at 100 ° C. Heating was performed for 1 minute to form a resist upper layer film, and the film thickness was measured (film thickness B: sum of film thickness of resist and resist upper layer film).
A commercially available developer (product name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was placed on the resist upper layer film, allowed to stand for 60 seconds, and rinsed with pure water for 30 seconds while rotating at 3000 rpm. After rinsing, the film was baked at 100 ° C. for 60 seconds to measure the film thickness (film thickness C).
When the film thickness A is equal to the film thickness C, it can be said that there is no intermixing with the resist. In Examples 1 to 14 or Comparative Examples 1 and 2, no intermixing with the resist was observed. In Comparative Example 3, the material was not dissolved by the developer.
[Table 1]

[Optical parameter test]
The resist upper layer film-forming composition solution prepared in Examples 1 to 14 of the present invention and the resist upper layer film-forming composition solution shown in Comparative Examples 1 to 3 were each applied to 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 absorptance in wavelength 190nm thru | or 260nm was measured for these 17 types of resist upper layer films | membranes using the spectrophotometer.
The transmittance at 13.5 nm was calculated by simulation from the relationship between the elemental composition ratio and the film density.
Regarding the light shielding property of DUV light, in the wavelength range of 220 nm to 260 nm, the maximum value of the absorptance was 40% or more as good and less than 40% as bad. In addition, regarding the transmittance of EUV light (13.5 nm), a transmittance of 80% or more was considered 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 is superior to the resist upper layer film obtained from the resist upper layer film forming composition of Comparative Example 1 and Comparative Example 2 in DUV light shielding properties. It became the result. In Comparative Example 3, the light shielding property of the DUV light was good, but it did not dissolve in the developer in the resist intermixing test described above, and thus the desired required characteristics were not satisfied.
[Table 2]

The present invention provides an EUV lithography process that selectively transmits only EUV by blocking unwanted exposure light, such as UV and DUV, for example, without intermixing with a resist, and developing with a developer after exposure. It can be used as a composition for forming an EUV resist upper layer film to be used or a resist upper layer film for a lithography process at other exposure wavelengths.

Claims

(Formula 1-1):

(Substituents A 1 to A 3 in (Formula 1-1) are each a substituent containing at least one hydroxyl group, and at least one substituent is a naphthalene ring or an anthracene ring. A benzene ring, the hydrogen atoms of the naphthalene ring, anthracene ring or benzene ring are each independently substituted with a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms. And a resist upper layer film-forming composition comprising a cyanurate derivative represented by formula (II) and an alcohol solvent.
The resist upper layer film-forming composition according to claim 1, wherein the cyanurate derivative is synthesized from 1,3,5-tris- (2,3-epoxypropyl) isocyanurate.
2. The resist upper layer film formation according to claim 1, wherein the cyanurate derivative is a cyanurate derivative synthesized from 1,3,5-tris- (2,3-epoxypropyl) isocyanurate and a hydroxyl group-containing compound D. Composition.
The hydroxyl group-containing compound D is a compound represented by i) or a combination of compounds represented by ii).
i) 1 selected from naphthoic acid or anthracene carboxylic acid which contains at least one hydroxyl group as a substituent and may contain a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms as a substituent. More than one compound.
ii) 1 selected from naphthoic acid or anthracenecarboxylic acid which contains at least one hydroxyl group as a substituent and may contain a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms as a substituent. One or more compounds and at least one hydroxyl group as a substituent, and one or more benzoic acid which may contain a halogen atom or a linear or branched saturated alkyl group having 1 to 4 carbon atoms as a substituent, Combination.
The cyanurate derivative is 1,3,5-tris- (2,3-epoxypropyl) isocyanurate and a compound represented by the following (formula 1-2) or a compound represented by (formula 1-2) And a combination of compounds represented by (Formula 1-3)

(In (Formula 1-2) or (Formula 1-3), n1 and n4 are each independently an integer of 1 to 5, n2 and n3 are each independently an integer of 0 to 8, n6 is each independently an integer of 0 to 4, (n1 + n2 + n3) is an integer of 1 to 9, (n4 + n5 + n6) is an integer of 1 to 5, and (n1 + n4) is an integer of 2 to 9 2. The resist upper layer film-forming composition according to claim 1, wherein m1 represents 1 or 2. X represents a halogen atom.
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 alcohol solvent according to claim 1, wherein the alcohol solvent is 1-heptanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, or cyclopentanol. 2. The resist upper layer film-forming composition according to item 1.
The resist upper layer film-forming composition according to any one of claims 1 to 6, further comprising an acid compound.
The resist upper layer film-forming composition according to claim 7, 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 7, wherein the acid compound is an onium salt acid generator, a halogen-containing compound acid generator, or a sulfonic acid generator.
The composition for forming a resist upper layer film according to any one of claims 1 to 9, further comprising a basic compound.
The resist upper film | membrane formation composition of any one of Claims 1 thru | or 10 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 11 on the resist film, and forming a resist upper layer film; A method for manufacturing a semiconductor device, comprising: exposing the resist upper layer film and a semiconductor substrate coated with the resist film; and developing the resist upper layer film and the resist film after exposure.
The method of manufacturing a semiconductor device according to claim 12, wherein the exposure is performed by EUV (wavelength: 13.5 nm).