TW201405251A - Resist overlayer film forming composition for lithography - Google Patents

Abstract

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

Microfilm resisting agent upper film forming composition

The present invention relates to a lithographic resistive upper layer film forming composition which is used in a manufacturing step of a semiconductor device using photolithography to reduce adverse effects caused by an exposure light source, and to obtain a good resist pattern. The type is effective; and a resist pattern forming method for forming a composition using the resist film upper film, and a method of manufacturing a semiconductor device using the forming method.

Conventionally, in the manufacture of semiconductor devices, fine processing using photolithography has been carried out. The microfabrication is a film in which a photoresist composition is formed on a substrate to be processed such as a germanium wafer, and a mask pattern having a pattern of a semiconductor device is formed thereon to perform ultraviolet rays. The processing method of etching the substrate to be processed, such as a germanium wafer, by irradiating and developing the active light, and using the obtained photoresist pattern as a protective film (mask). In recent years, the progress of high integration of semiconductor devices has led to the use of KrF excimer lasers (248 nm) for short wavelengths to ArF excimer lasers (193 nm). Accompany Here, the influence of the disordered reflection or standing wave of the active light from the substrate becomes a big problem, and as an underlayer film which acts as a role of preventing reflection between the photoresist and the substrate to be processed, an antireflection film has been widely used. (Bottom Anti-Reflective Coating, BARC) method.

As the antireflection film, an inorganic antireflection film such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon, or α-tellurium, or an organic antireflection film composed of a light absorbing material and a polymer compound is known. In the former, it is necessary to have a vacuum vapor deposition device, a CVD device, a sputtering device, and the like at the time of film formation. In contrast, the latter does not require special equipment, which is advantageous in this point and is being reviewed most.

In recent years, as a new generation of photolithography technology following the use of ArF excimer laser (193nm) photolithography technology, ArF liquid immersion lithography technology exposed by water is being grandly reviewed. However, the use of light lithography has gradually reached the limit. In the new lithography technology after ArF immersion lithography, EUV lithography using EUV (wavelength 13.5 nm) has attracted attention.

In the semiconductor device fabrication step using EUV lithography, the substrate coated with the EUV resist is irradiated with EUV light for exposure and development to form a resist pattern.

In order to protect EUV resists from contaminating substances or to occlude poor radiation such as UV or DUV (OUT of BAND/Out-of-Band, OOB), a method of containing a copolymer in the upper layer of the EUV resist has been disclosed. Wherein the copolymer contains one or more groups including ruthenium, boron, carbon, ruthenium, zirconium, hafnium and molybdenum (Patent Document 1 and Patent Literature) 2).

Further, in order to block the OOB, there has been an example in which a top coat formed by using 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); or to apply a film that is an EUV resolution enhancement layer to the EUV resist to absorb OOB to improve the resolution of the EUV resist (Non-Patent Document 2), but Reveal which composition is optimal.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-348133

[Patent Document 2] Japan Special Open 2008-198788

[Non-patent literature]

[Non-Patent Document 1] Shimizu, M., Maruyama, K., Kimura, T., Nakagawa, H., Sharma, S., "Development of Chemically Amplified EUV resist for 22nm half pitch and beyond" Extreme Ultraviolet Lithography Symposium. Miami. (Oct.2011)

[Non-Patent Document 2] Proc. of SPIE Vol.7969 796916-1

The present invention is directed to the above problems to provide an optimum resistive upper film forming composition. That is, the present invention provides a resistive upper film forming composition for a lithography process, which is used as a resist upper film. In particular, as an EUV resist overlayer film, it is not intermixed with the resist, especially at the time of EUV exposure, interrupting a poor exposure light source such as UV or DUV, and selectively passing only EUV, Moreover, after exposure, the developer can be developed.

A first aspect of the present invention provides a resist-upper layer film-forming composition comprising a resin selected from the group consisting of (a) a tetracarboxylic dianhydride compound and (b), and an alcohol-based solvent. An acid dihalide compound and (c) one or more compounds having a dicarboxylic anhydride group and an acid halide group, and (d) one or more kinds of diamine compounds Manufactured and included at least one of a guanamine bond and a quinone bond.

According to a second aspect of the invention, the resin of the first aspect includes one or more selected from the group consisting of the following formula (1-1), formula (1-2), and formula (1-3). Unit structure resin, (in the formulae (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 resin has a weight average molecular weight of from 500 to 100,000.

According to a third aspect, in the first aspect or the second aspect, the resist upper layer film forming composition, wherein the resin end structure of the first viewpoint or the second viewpoint is represented by the formula (1-4), (In the formula (1-4), R ₁ is an organic group containing an aromatic ring or an alkyl group having 1 to 5 carbon atoms, B ₁ is synonymous with the definition of the second viewpoint, and the wavy line portion is shown as the second viewpoint. One part of the resin).

According to a fourth aspect, the composition of the resistive upper layer film of the first aspect or the second aspect, wherein the resin end structure of the first viewpoint or the second viewpoint is a formula (1-5) or a formula (1-6) Show, (In the formula (1-5) or the formula (1-6), R ₂ is an organic group containing an aromatic ring or an alkyl group having 1 to 5 carbon atoms, and A ₁ and B ₁ are synonymous with the definition of the second viewpoint. The wavy line portion is shown as part of the resin of the second viewpoint).

The resistive upper layer film forming composition according to any one of the first aspect to the fourth aspect, wherein the alcohol solvent is a linear chain having 1 to 20 carbon atoms and a branch having 3 to 20 carbon atoms. Or a cyclic saturated alkyl alcohol or an aromatic alcohol having 6 to 20 carbon atoms.

The resistive upper layer film forming composition according to any one of the first aspect to the fifth aspect, wherein the alcohol solvent is 1-heptanol, 2-methyl-2-butanol, 4-methyl Base-2-pentanol or cyclopentanol.

According to a seventh aspect, the composition of the resistive upper layer film of the first aspect, wherein the compound (a) is represented by the following formula (1-7) to formula (1-10), (In the formulae (1-7) to (1-10), X ₁ to X ₅ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms or a branched halogenated alkyl group, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzhydryl group (the hydrogen atom of the aforementioned phenoxy group and benzhydryl group may be passed through 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxyl groups; m1 is shown as an integer from 0 to 8, and n1, m3 and m4 are shown An integer from 0 to 3, n2 and n3 are shown as integers from 0 to 2, and m2 and m5 are shown as integers from 0 to 4; W _{1 is} shown as a single bond, an oxygen atom, a linear or branched carbon number of 1 to 10. An alkyl group, a linear or branched halogenated alkyl group having 1 to 10 carbon atoms, a sulfonyl group or a carbonyl group), and the compound (b) is represented by the following formula (1-11) to formula (1-13) As shown, (In the formulae (1-11) to (1-13), Z ₁ is a halogen atom, and X ₆ to X ₉ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a carbon number. a straight or branched halogenated alkyl group of 1 to 10, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzamyl group (the aforementioned phenoxy group and benzhydryl group) The hydrogen atom may be substituted by 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxyl groups; m6 and m7 are shown as 0 to 10 The integers, n4 and n5 are shown as integers from 0 to 3, m8 and m9 are shown as integers from 0 to 4; W _{2 is} shown as a single bond, an oxygen atom, a linear or branched alkyl group having a carbon number of 1 to 10, carbon a straight or branched halogenated alkyl group, a sulfonyl group or a carbonyl group of 1 to 10, and the compound (c) is represented by the following formula (1-14) to formula (1-15), (In the formulae (1-14) to (1-15), Z ₁ is a halogen atom, and X ₁₀ to X ₁₂ are independently shown as a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a carbon number. a straight or branched halogenated alkyl group of 1 to 10, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzamyl group (the aforementioned phenoxy group and benzhydryl group) The hydrogen atom may be substituted by 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxyl groups; m10 is shown as an integer from 0 to 9. , n6 and m11 are shown as integers from 0 to 3, m12 is shown as an integer from 0 to 4; W _{3 is} shown as a single bond, an oxygen atom, a linear or branched alkyl group having a carbon number of 1 to 10, and a carbon number of 1 to 10 a straight chain or a branched halogenated alkyl group, a sulfonyl group or a carbonyl group), and the compound (d) is represented by the following formula (1-16) or formula (1-17), (In the formulae (1-16) and (1-17), X ₁₃ to X ₁₅ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms or a branched halogenated alkyl group, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzhydryl group (the hydrogen atom of the aforementioned phenoxy group and benzhydryl group may be passed through 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxyl groups; m13 to m15 are shown as integers from 0 to 4, and n7 is shown as 0. An integer of up to 3; W ₄ is represented by a single bond, an oxygen 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, a sulfonyl group or a carbonyl group. Any one of them), and the unit structure of the resin has at least one hydroxyl group, carboxyl group or a combination thereof.

As a eighth aspect, the resistive upper layer film forming composition of the third aspect, wherein the terminal blocking agent for forming the partial structure of the formula (1-4) is the following formula (1-18) to (1) 21) the compound shown, (In the formulae (1-18) to (1-21), Z ₁ is a halogen atom, and X ₁₆ to X ₂₁ 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 halogenated alkyl group to 10, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a phenoxy group, a cyano group or a nitro group; m16 is an integer of 0 to 10, and n8, n9 and m17 are shown An integer from 0 to 3, m18 and m21 are shown as integers from 0 to 5, m19 is an integer from 0 to 11, m20 is an integer from 0 to 4; W ₅ and W _{6 are} shown as single bond, oxygen atom, carbon A linear or branched alkyl group having 1 to 10 or a straight or branched halogenated alkyl group having a carbon number of 1 to 10, a sulfonyl group or a carbonyl group).

As a ninth aspect, the resist superposed film forming composition of the fourth aspect, wherein the terminal blocking agent for forming a partial structure of the formula (1-5) or the formula (1-6) is the following formula (1) -22) or a compound represented by formula (1-23), (In the formulae (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 chain having 1 to 10 carbon atoms or Branched halogenated alkyl group, alkoxy group having 1 to 30 carbon atoms, hydroxyl group, carboxyl group, phenoxy group, cyano group or nitro group; m22 is shown as an integer from 0 to 11, n10 is an integer from 0 to 3, and m23 is shown as An integer from 0 to 4, m24 is shown as an integer from 0 to 5; W _{7 is} shown as a single bond, an oxygen atom, a linear or branched alkyl group having a carbon number of 1 to 10, and a linear or branched halogenation having a carbon number of 1 to 10. Any of an alkyl group, a sulfonyl group or a carbonyl group).

The resistive upper layer film forming composition according to any one of the first aspect to the ninth aspect, further comprising an acid compound.

According to a tenth aspect, the composition of the resistive upper layer film of the tenth aspect, wherein the acid compound is a sulfonic acid compound or a sulfonic acid ester compound.

According to a twelfth aspect, the composition of the resistive upper layer film of the tenth aspect, wherein the acid compound is an iodonium salt acid generator or a phosphonium salt acid generator.

The resistive upper layer film forming composition according to any one of the first aspect to the twelfth aspect, further comprising a basic compound.

A resistive upper layer film forming composition according to any one of the first aspect to the thirteenth aspect, wherein the composition is used together with the above composition The resist is a resist for EUV (wavelength 13.5 nm).

A fifteenth aspect is a method for producing a semiconductor device, comprising the steps of: forming a resist film on a substrate; and forming a resist superposed film from any one of the first to the fourteenth aspects. a step of coating the resist film on the resist film to form a resist upper film, exposing the semiconductor substrate covered with the resist upper film and the resist film, and developing the resist to the resist film The step of removing the resist film.

A method of manufacturing a semiconductor device according to the fifteenth aspect, wherein the exposure is performed by EUV (wavelength: 13.5 nm).

The invention relates to a resist film upper layer forming composition, which is used as a resisting upper layer film forming composition, in particular as an EUV resisting upper layer film forming composition, which is not mixed with an EUV resist agent, especially at the time of EUV exposure. The poor exposure light source such as UV or DUV is interrupted, and only EUV is selectively passed through, and after exposure, the developer is developable.

Generally, when EUV light is used for exposure, if EUV light is used, UV light or DUV light is emitted together with EUV light. That is, the EUV light may contain about 5% of light having a wavelength of 300 nm or less other than EUV light, but light having a wavelength of, for example, 190 to 300 nm, particularly in the vicinity of 220 to 260 nm, has the highest intensity, and thus causes sensitivity of the EUV resist. Decreased or degraded shape of the pattern. When the line width is 22 nm or less, the influence of this UV light or DUV light (OUT of BAND/out-of-band radiation) starts to occur, which adversely affects the resolution of the EUV resist. In order to remove 220 to 260 nm In the vicinity of the wavelength light, there is also a method of setting the filter to the lithography system, but the steps become complicated. In contrast, the present invention is a DUV light (OUT of BAND/out-of-band radiation) contained in an EUV exposure light source, and even an undesired DUV light of 220 to 260 nm can be absorbed by a resist upper film. It can improve the resolution of EUV resist.

Further, in the case of covering the upper layer of the EUV resist, in order to prevent intermixing with the EUV resist (mixing of the layers), the resist upper layer is a solvent for not using the EUV resist, and an alcohol solvent is preferably used. In this case, the resin for forming a composition of the upper film of the resist of the present invention is composed of an organic group having a hydroxyl group or a carboxyl group or a group containing the same for improving the solubility to an alcohol solvent. Since it has a hydrophilic group, it has high solubility in an alcohol solvent.

That is, the resin for forming a composition of the upper layer film of the present invention is a hydrophilic group composed of a hydroxyl group or a carboxyl group or an organic group containing the group, so that it can be developed after exposure. It is removed together with the EUV resist by dissolution of a developing solution (for example, an alkaline developing solution).

[Best Mode for Carrying Out the Invention]

The present invention relates to a resist superposed film forming composition comprising the following resin and an alcohol-based solvent, wherein the resin is selected from the group consisting of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) a compound obtained by reacting one or more compounds having a dicarboxylic anhydride group and an acid halide group with (d) one or more kinds of diamine compounds, and comprising a guanamine bond and a ruthenium bond At least one of them. The invention is suitable as a general resist upper layer The film-forming composition is particularly suitable as a composition for forming an upper layer film of an EUV lithography step using EUV as an exposure wavelength.

The resist superposed film forming composition contains the above-mentioned resin and an alcohol-based solvent, and may further contain an acid compound, a basic compound, a crosslinking agent, a crosslinking catalyst, a surfactant, a rheology modifier, and a subsidizing agent.

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

The content of the solid content of the upper film forming composition of the above-mentioned resin 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. %. In the above resin, (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) a component having a compound of a dicarboxylic anhydride group and an acid halide group, A ₁ , (d) a diamine At least one of B ₁ of the constituent units of the compound 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. Since the hydroxyl group and the carboxyl group are hydrophilic groups, it is necessary to exhibit a function of solubility in an alcohol solvent and solubility of a developer.

The following is a detailed description of the resist film formation film of the present invention.

The resin of the present invention is one or more selected from the group consisting of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) a compound having both a dicarboxylic anhydride group and an acid halide group. Compound, and (d) one or more The amine compound is produced by a reaction and is at least one of a guanamine bond and a quinone bond. The resin is one or more unit structures selected from the group consisting of the following formula (1-1), formula (1-2), and formula (1-3).

A ₁ and B _{1 in} the formulae (1-1) to (1-3) are as defined above. Specifically as follows:

(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 is a case of containing an aromatic ring and having a hydroxyl group, a carboxyl group or an organic group of such a combination.

(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 a case of containing an aromatic ring but having no hydroxyl group, a carboxyl group or an organic group of such a combination.

(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 a case of not containing an aromatic ring but having a hydroxyl group, a carboxyl group or an organic group of such a combination.

(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 a case which does not contain an aromatic ring and does not have a hydroxyl group, a carboxyl group or an organic group of such a combination.

(v) A ₁ is an aromatic ring but contains no hydroxyl group, a carboxyl group, or a combination of such an organic group; B ₁ is a case of containing an aromatic ring and having an organic group of hydroxyl, carboxyl, or a combination of these.

(vi) A ₁ is an organic group containing an aromatic ring but having no hydroxyl group, a carboxyl group or a combination thereof; and B ₁ is a case of not containing an aromatic ring but having a hydroxyl group, a carboxyl group or an organic group of such a combination.

(vii) A ₁ is an organic group which does not contain an aromatic ring but has a hydroxyl group, a carboxyl group or a combination thereof; and B ₁ is a case which contains an aromatic ring and has a hydroxyl group, a carboxyl group or an organic group of such a combination.

(viii) A ₁ is an organic group which does not contain an aromatic ring but has a hydroxyl group, a carboxyl group or a combination thereof; and B ₁ is a case which contains an aromatic ring but does not have a hydroxyl group, a carboxyl group or an organic group of such a combination.

(ix) A ₁ is an organic group which does not contain an aromatic ring and does not have a hydroxyl group, a carboxyl group or a combination thereof; and B ₁ is a case which contains an aromatic ring and has a hydroxyl group, a carboxyl group or an organic group of such a combination.

The end of the resin of the present invention is adjusted by selecting one of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) a compound having both a dicarboxylic anhydride group and an acid halide group. The reaction amount (mounting amount) of the above-mentioned compound and (d) one or more kinds of diamine compounds may be the case of the terminal of the amine group, and the case of the terminal of the dicarboxylic anhydride group or the acid halide group. In the case of an amine terminal, the terminal blocking may be carried out by reacting an end-capping agent having an organic group which has a reactive group reactive with an amine group and which contains an aromatic ring or a carbon number. 1 to 5 alkyl groups. In the case of a dicarboxylic anhydride group or an acid halide group terminal, an end blocking agent having the following organic group may be used to carry out the reaction and end-capping, the foregoing The organic group is a group having a reactive group reactive with a dicarboxylic anhydride group or an acid halide group and containing an aromatic ring or an alkyl group having 1 to 5 carbon atoms. By adjusting the amount of the reactive group of the amine group, the dicarboxylic anhydride group or the acid halide group at the end of the resin, the molecular weight of the resin can be adjusted, the physical properties of the resin (parent, hydrophobicity, etc.) can be controlled, and the preservation stability can be improved. .

As A ₁ in the formula (1-1) to the formula (1-3), for example, the formulae (2-1) to (2-8) are exemplified. Wherein X ₂₅ to X ₃₄ are each independently represented by 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, and an alkoxy group having 1 to 30 carbon atoms. a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzhydryl group (the hydrogen atom of the aforementioned phenoxy group and benzamidine group may have 1 to 5 halogen atoms, 1 to 5 carbon atoms 1 Up to 5 straight or branched alkyl groups, or 1 to 5 hydroxyl groups are substituted). M25 to m34 are integers from 0 to 4. The present invention is not limited to this and the like.

As B ₁ , for example, the formulae (3-1) to (3-14) are exemplified. Wherein X ₃₅ to X ₅₀ are each independently represented by 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, and an alkoxy group having 1 to 30 carbon atoms. a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzhydryl group (the hydrogen atom of the aforementioned phenoxy group and benzamidine group may have 1 to 5 halogen atoms, 1 to 5 carbon atoms 1 The linear or branched alkyl group of 5 or the hydroxyl group of 1 to 5 is substituted. m35 to m50 are shown as an integer of 0 to 4. The present invention is not limited thereto.

Further, in the present specification, the halogen atom is represented by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Further, in the present specification, as the linear or branched alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i- are exemplified. Butyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n- Propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3- Methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n -hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl -n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-di Methyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl -n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl , cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3 -ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl Base-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl Base, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl Base-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl and the like.

Further, a linear or branched alkyl group having 1 to 5 carbon atoms, for example, a carbon number of 1 to 5 in the above-exemplified examples is preferably a methyl group, an ethyl group, an isopropyl group or the like.

Further, examples of the linear or branched halogenated alkyl group having 1 to 10 carbon atoms are, for example, those substituted by one or more halogen atoms as exemplified above.

Further, in the present specification, as the alkoxy group having 1 to 30 carbon atoms, exemplified For example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, pentyloxy, Oxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, hexadecyloxy, octadecyloxy, nonadecanyloxy, icosyloxy, twentieth Pentameryloxy, hexadecyloxy, octadecyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy 1,1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n -propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n -pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2 - dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1- Methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group and the like.

The (a) tetracarboxylic dianhydride compound to be 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. As a specific example, for example, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride An aromatic tetracarboxylic acid such as 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride or 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride; 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetra 1,2-,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid An alicyclic tetracarboxylic dianhydride such as dianhydride or 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride; such as 1,2,3,4-butane An aliphatic tetracarboxylic dianhydride like a tetracarboxylic dianhydride.

The (b) acid dihalogen 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. As a specific example, for example, 4-bromoisophthalonitrile chloride, 5-tert-butyl metaxylylene chloride, 5-hydroxym-xylylene chloride, m-xylylene chloride, 5-methoxy Alkyl phthalocyanine chloride, 5-nitrom-xylylene chloride, 5-methylm-xylylene chloride, tetrafluorom-xylylene chloride, bromine-p-xylylene chloride, 2,5 - Dichloro-p-xylylene chloride, 2,5-dimethyl-p-xylylene chloride, nitro-p-xylylene chloride, tetrafluoro-p-xylylene chloride, tetrachloro-p-xylylene chloride , tetrabromo-p-xylylene chloride; 4-bromo-xylylene fluorene, 5-tert-butyl metaxyl fluorofluoride, 5-hydroxym-xylylene fluorene, m-xylylene fluorene, 5-methoxym-xylylene fluorene, 5-nitroisophthalocylidene fluoride, 5-methylm-xylylene fluorene fluoride, tetrafluorom-xylylene fluorene fluoride, bromine terephthalic acid fluoride , 2,5-dichloro-p-xylylene fluoride, 2,5-dimethyl-p-xylylene fluoride, nitro-p-xylylene fluoride, tetrafluoro-p-xylylene fluoride, tetrachloro-p-benzene Dimethyl fluorene fluoride, tetrabromo-p-xylylene fluorene; 4-bromoisophthalonitrile bromine, 5-tert-butyl meta-xylylene bromide, 5-hydroxym-xylylene bromide, m-phenylene Formamidine bromide, 5-methoxyl Dimethyl bromo, 5-nitrom-xylylene bromide, 5-methylm-xylylene bromide, tetrafluorom-xylylene bromide, bromine-p-xylylene bromide, 2,5-dichloro Parathylene bromide, 2,5-dimethyl-p-xylylene bromide, nitro-p-xylylene bromide, tetrafluoro-p-xylylene bromide, tetrachloro-p-xylylene bromide, tetrabromo Parathylene bromo bromide; 4-bromoisophthalate iodide, 5-tert-butyl metaxyl hydrazine iodine, 5-hydroxy m-xylylene hydrazine iodine, m-xylylene hydrazine iodine, 5-methyl Oxime m-xylylene iodide, 5-nitroisophthalate iodide, 5-methylm-xylylene dioxime iodide, tetrafluoro Isophthalic acid iodine, bromine terephthalic acid iodine, 2,5-dichloro-p-xylylene iodine, 2,5-dimethyl-p-xylylene iodine, nitro-p-xylylene iodine , tetrafluoro-p-xylylene iodine, tetrachloro-p-xylylene iodine, tetrabromo-p-benzoquinone iodine.

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

(In the formula (4-1) to the formula (4-5), Z ₁ is represented by a halogen atom).

In addition, the (d) diamine compound used in the production of the resin to be used in the present invention is not particularly limited, and these may be used alone or in combination of two or more. As a specific example, for example, 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcin, 2,5-di Aminohydroquinone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxyphenyl)ether, bis(4-amino-3,5-dihydroxyphenyl) Ether, double (3-Amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis (3) -amino-4-hydroxyphenyl)anthracene, bis(4-amino-3-hydroxyphenyl)anthracene, bis(4-amino-3,5-dihydroxyphenyl)anthracene, 2,2-double (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-4-hydroxyphenoxy)phenyl]anthracene, bis[4-(3-amino-4) a diamine compound having a phenolic hydroxyl group such as -hydroxyphenoxy)phenyl]propane or 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane; 3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-indole) a thiophenol group-containing diamine compound such as phenyl)ether or 2,2-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-aminophenyl-3-sulfonic acid) ether, 4,4'-diamino group a diamine having a sulfonic acid group such as biphenyl-3,3'-disulfonic acid or 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid Compound; 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, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, double (4-Amino-3-carboxyphenyl)indole, bis(4-amino-3,5-dicarboxyphenyl)anthracene, 4,4'-diamino-3,3'-dicarboxybiphenyl 4,4'-diamine -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]anthracene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3- A diamine compound having at least one carboxyl group such as carboxyphenoxy)phenyl]hexafluoropropane.

Further, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylamine benzene), 4,4'-methylene-bis (2) -isopropyl-6-methylamine benzene) 4,4'-methylene-bis(2,6-diisopropylamine benzene), 2,4,6-trimethyl-1,3-benzene Diamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-three M-three ,3,3',5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(3-aminophenoxyl) Phenyl)propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-dimethylbicyclo Hexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aniline) Hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-toluamyl)hexafluoropropane, 1,4-double (4 -aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4 -(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,2-naphthalenediamine, 1,4 a diamine compound such as naphthalene diamine, 2,4-naphthalenediamine or 1,5-diaminonaphthalene.

Further, the compound (end capping agent) which reacts at the terminal end of the resin is reacted, and the resin is obtained by adjusting the amount of the reactive group of the amine group, the dicarboxylic anhydride group or the acid halide group at the terminal of the resin. It The adjustment of the molecular weight, the control of the physical properties of the resin (parent, hydrophobicity, etc.), and the improvement of the preservation stability. As a method of terminally capping, (d) one or more kinds of diamine compounds in the resin of the present invention are selected from (a) a tetracarboxylic dianhydride compound, (b) an acid dihalide compound, and ( c) One or more compounds having a dicarboxylic anhydride group and a halogen group may be formed by reacting an organic group with an amine group after adding an excess amount to the organic group. The group is a group having a reactive group capable of bonding to the terminal of the resin and comprising an aromatic ring or an alkyl group having 1 to 5 carbon atoms. More preferably, a dicarboxylic anhydride compound or an acid halogen compound having an aromatic ring or an alkyl group having 1 to 5 carbon atoms can be formed by reacting with the terminal of the resin.

The dicarboxylic acid anhydride is, for example, a compound represented by the following formula (5-1) to the formula (5-30); and as the acid halogen compound, for example, the formula (5-31) to the formula (5-60) are exemplified. The compound shown. In particular, when a dicarboxylic acid anhydride is used, since a carboxyl group is formed at the terminal, the affinity and hydrophobicity of the entire resin can be controlled by the carboxyl group. The present invention is not limited to such compounds.

(In the above formula, Z ₁ is a halogen atom, and n11 to n42 are represented by a maximum number of bonds to the compound and an integer of 0 or more).

As another method of end capping, the tree of the present invention is made One or more compounds selected from the group consisting of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) a compound having both a dicarboxylic anhydride group and a halogen group, in terms of (d) The diamine compound may be formed by reacting an organic group with a dicarboxylic acid anhydride group or an acid halide group in such a manner that an excess amount thereof is added, wherein the organic group is capable of The resin is bonded to the terminal end of the resin and contains an aromatic ring or an alkyl group having 1 to 5 carbon atoms. More preferably, an amine group-containing compound having an aromatic ring or an alkyl group having 1 to 5 carbon atoms may be formed by reacting with the terminal of the resin. Specifically, for example, a compound represented by the following formula (6-1) to formula (6-30). The present invention is not limited to this and the like.

(In the above formula, Z ₁ is a halogen atom, and n43 to n60 are represented by a maximum number of bonds to the compound and an integer of 0 or more).

The following is a specific example of the structure of the poly-proline or polyamine contained in the resist formation film of the resist of the present invention, but the present invention is not limited by any of the following examples. The polylysine which is contained in the upper film formation composition of the resist of the present invention may, for example, be the following polyaminic acid (7-1) to (7-13) (wherein, p ₁ , p ₂ , p ₃ and p _{4 are} shown as the ratio of each structure in the poly-proline. Here, (7-1) to (7-8) are polyglycines produced from one type of tetracarboxylic dianhydride compound and two kinds of diamine compounds; (7-9) and (7-10) a polyphthalic acid produced from two kinds of tetracarboxylic dianhydride compounds and one type of diamine compound; (7-11) is a tetracarboxylic dianhydride compound and two kinds of diamine compounds The produced polyamic acid; (7-12) and (7-13) are polyamines produced from one type of tetracarboxylic dianhydride compound and one type of diamine compound.

The polyaminic acid can also be used as a polyimine by using other methods such as thermal hydrazide or chemical hydrazide.

The polyamine which is contained in the upper film formation composition of the resist of the present invention may, for example, be polyamines (8-1) to (8-11) described below. Here, (8-1) to (8-7) are polyamines produced from one type of acid dihalide compound and two kinds of diamine compounds; (8-8) and (8-9) are Polyamine produced by two kinds of acid dihalogen compounds and one type of diamine compound; (8-10) is a polydecylamine produced from two kinds of acid dihalogen compounds and two kinds of diamine compounds; (8-11) is a polydecylamine produced from one type of acid dihalogen compound and one type of diamine compound.

Further, the structural formula of the resin in which the terminal blocking agent is introduced at the terminal of the polyamic acid may, for example, be an amine terminal or an acid halogen compound or an acid anhydride compound, as in the formula (9-1) to the formula (9-13). An example of the reaction; or an example of reacting a terminal of a dicarboxylic anhydride with an amine group-containing compound, for example, by the formula (10-1) to the formula (10-13).

The polyaminic acid can also be used as a polyimine by using other methods such as thermal hydrazide or chemical hydrazide.

Further, the structural formula of the resin in which the terminal blocking agent is introduced at the end of the polyamine can be, for example, reacted with an acid halide compound or an acid anhydride like the formula (11-1) to the formula (11-11). For example, an example in which an acid halide terminal is reacted with an amine group-containing compound, such as the formula (12-1) to the formula (12-10), may be mentioned.

The resin used in the present invention is one or more selected from the group consisting of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) a compound having both a dicarboxylic anhydride group and a halogen group. When the compound is produced by reacting (d) one or more kinds of diamine compounds, the tetracarboxylic dianhydride, the acid dihalide compound and the dicarboxylic anhydride group and the acid halide group with respect to the total molar number of the diamine compound. The ratio of the total moles of the compounds of both parties is preferably from 0.8 to 1.2. As in the case of the general polycondensation reaction, when the molar ratio is closer to 1, the degree of polymerization of the resulting resin becomes larger, and the molecular weight increases.

Further, when a terminal blocking agent is added, for example, in the case of synthesizing an amine-terminated resin, (d) one or more kinds of diamine compounds are selected from (a) a tetracarboxylic dianhydride compound, (b) The acid dihalide compound and (c) the total mole number of one or more compounds of the compound having both the dicarboxylic anhydride group and the halogen group is a method of adding an excess amount in the range of 1.1 to 1.6 of the total mole number. After the reaction is carried out, the terminal blocking agent is further added to the two sides selected from the group consisting of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) a dicarboxylic anhydride group and a halogen group. The total mole number 1 of one or more compounds in the compound is synthesized by adding the total molar number of 0.1 to 2.0.

Conversely, in the case of synthesizing a resin of a dicarboxylic anhydride group or an acid halide group, a compound selected from the group consisting of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) has a dicarboxylic anhydride group and One or more compounds of the compounds of the halogen group are added in an excess amount of the total mole number of 1.1 to 1.6 with respect to (d) the total mole number of one or more kinds of diamine compounds. After the reaction, the terminal blocking agent was further synthesized in such a manner that the total molar number of the diamine compound was from 0.1 to 2.0 in terms of total moles.

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

Among the resins of the present invention, those having a quinone imine bond can be obtained by heating a polylysine in a resin and subjecting it to dehydration ring closure (thermal imidization). In this case, the polyaminic acid is converted into a quinone imine in a solvent, and it can also be used as a solvent-soluble polyimine-containing resin.

Further, a chemical ring closure method using a conventional dehydration ring-closing catalyst can also be employed.

The heating can be carried out at any temperature of from 100 to 350 ° C, preferably from 120 to 300 ° C.

The chemical ring closure method can be carried out, for example, in the presence of pyridine or triethylamine and acetic anhydride, and the temperature can be selected from any temperature of from -20 to 200 °C.

The polyimine-containing resin obtained by the above operation may be used as it is, or a weak solvent such as methanol, ethanol or water may be added, and the resin may be precipitated and isolated as a resin solid. Alternatively, the resin solid can be re-dissolved in a suitable solvent for use.

The weight average molecular weight of the resin of the present invention measured by a GPC (Gel Permeation Chromatography) method is, for example, 500 to 100,000, or 1,000 to 50,000, preferably 2,000 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 diffuse in the photoresist to cause deterioration of lithographic properties. When the weight average molecular weight is 100,000 or more, the solubility of the formed resist film on the photoresist developer becomes not The foot will develop a residue after development.

One or more compounds selected from the group consisting of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c) a compound having both a dicarboxylic anhydride group and a halogen group, and (d) 1 The reaction of the above various diamine compounds can be carried out in a solvent. As the solvent which can be used at this time, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate Ester, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3-ethoxy Ethyl propyl propionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Ether, 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 glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl stilbene acetate, Cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and the like. These may be used alone or in combination. Further, even if the resin is a solvent which is insoluble, the resin produced by the polymerization reaction may be used in the above solvent as long as it does not precipitate.

The resin-containing solution obtained by such a procedure can be directly used for the modulation of the resist upper film forming composition. Alternatively, the resin precipitate can be isolated from methanol, ethanol, ethyl acetate, hexane, toluene, and B. It is recovered after use in a weak solvent such as nitrile or water. The drying conditions after separating the resin are preferably dried at 50 to 100 ° C for 8 to 48 hours using an oven or the like. After the resin is recovered, it can be redissolved in any solvent, and is preferably dissolved in an alcohol-based solvent described below as a resist upper layer film composition.

In the resist film upper layer forming composition of the present invention, in order to prevent intermixing (layer mixing) when the composition is applied and the film is formed on the resist, the resin is preferably an alcohol solvent as described below. Instead of the solvent generally used in the resist, the alcohol solvent is a linear one having a carbon number of 1 to 20, a branched or cyclic saturated alkyl alcohol having 3 to 20 carbon atoms, or a carbon number of 6 to 20. Aromatic alcohol.

For example, as a saturated alkyl alcohol, for example, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2- Heptyl alcohol, tert-pentanol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butene Alcohol, 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-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 cyclohexanol.

Examples of the aromatic alcohol include 1-phenylpropanol, 2-phenylpropanol, 3-phenylpropanol, 2-phenoxyethanol, phenylethyl alcohol, and ethylphenylethanol.

These alcohol solvents may be used singly or as a mixture.

Further, for example, a factor for synthesizing the resin of the present invention, the above alcohol The solvent may also be mixed together with the solvent described below. The solvent can be used, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl sarbuta acetate, ethyl sirolimus acetate, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone , 2-hydroxypropionic acid ethyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate Ester, butyl acetate, ethyl lactate, butyl lactate, and the like. These organic solvents may be used alone or in combination of two or more. The above other solvent can be contained in an amount of 0.01 to 30.00% by mass based on the alcohol solvent.

The resist film upper layer forming composition of the present invention may further contain an acid compound in order to conform to the acidity of the resist present in the lower layer in the lithography step. As the acid compound, a sulfonic acid compound or a sulfonic acid ester compound can be used. For example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfinic acid, citric acid, benzoic acid, hydroxybenzoic acid, and the like, and/or 2, A thermal acid generator such as 4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate or the like is 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.

Moreover, the resist film upper layer forming composition of the present invention can be used to produce acid acid generated by an exposure light source (for example, EUV irradiation or electron beam irradiation) in order to conform to the acidity of the resist existing in the lower layer in the lithography step. The agent acts as an acid compound. Preferred examples of the acid generator include sulfonium-based acid generators such as bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate and triphenylsulfonium trifluoromethanesulfonate. Class, phenyl-bis(trichloromethyl)-s-three The halogen includes a compound acid generator, a benzoin tosylate, a sulfonic acid generator such as N-hydroxysuccinimide trifluoromethanesulfonate, and the like. The amount of the above-mentioned acid generator added is 0.02 to 10% by mass, preferably 0.04 to 5% by mass, per 100% by mass.

The resist superposed film forming composition of the present invention may further comprise a basic compound. The sensitivity adjustment of the resist exposure can be performed by adding a basic compound. That is, a basic compound such as an amine is reacted with an acid generated by a photoacid generator during exposure, and the shape of the upper portion of the resist after exposure and development can be controlled by reducing the sensitivity of the underlayer film of the resist (exposure, The shape of the resist after development is preferably rectangular).

As the basic compound, for example, an amine can be exemplified. For example, there is an aminobenzene compound represented by the formula (13-1).

In the formula (13-1), r ₁ to r ₅ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an amine group.

As the above alkyl group, for example, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, Cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl Base-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl -n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2 ,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n- Pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1 ,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl , 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl , 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl , 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-Dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2, 3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl -cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl -cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2- Ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl and the like.

Among them, a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group is preferred, and examples thereof include a methyl group, an ethyl group, and an isopropyl group.

As the above compound, the following formula (13-2) to formula (13-47) are exemplified.

Further, for example, triethanolamine, tributylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, a tertiary amine such as tri-n-octylamine, triisopropanolamine, phenyldiethanolamine, stearyl diethanolamine, and diazabicyclooctane, or pyridine or 4-dimethylaminopyridine Aromatic amines. More, too For example, a monoamine such as benzylamine or n-butylamine or a secondary amine such as diethylamine or di-n-butylamine. These compounds may be used alone or in combination of two or more.

In addition to the above, the rheology adjusting agent, the auxiliary agent, the surfactant, and the like may be further added as needed in the resist superposed film forming composition of the present invention.

The rheology modifier is mainly added for the purpose of improving the fluidity of the resist film forming composition. Specific examples include dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, and the like. Phthalic acid derivatives; di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate, etc.; a maleic acid derivative such as butyl ester, diethyl maleate or dinonyl maleate; an oleic acid derivative such as methyl oleate, butyl oleate or tetrahydrofurfuryl oleate; or a hard fat A stearic acid derivative such as n-butyl acrylate or glyceryl stearate. These rheology modifiers are usually blended in an amount of less than 30% by mass based on 100% by mass of the total composition of the resist superposed film forming composition.

In the resist upper layer film-forming composition of the present invention, a surfactant may be blended in order to prevent pinholes, striations, and the like from occurring, and to further improve coating properties against surface unevenness. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octylphenol; Polyoxyethylene alkyl allyl ethers such as ethers, polyoxyethylene nonylphenol ethers, etc.; polyoxyethylene. Polyoxypropylene block copolymers; sorbitan Monolaurate, sorbitan monohexadecanate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Desorbed sorbitan fatty acid esters such as acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monohexadecanate, polyoxyethylene sorbitan monostearate, Non-ionic surfactants such as polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.; F-Top EF301, EF303, EF352 (manufactured by Tokem Products), MEGAFACEF171, F173 (made by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), AashiGuard AG710, Surflon S-382, SC101, SC102, A fluorine-based surfactant such as SC103, SC104, SC105, or SC106 (made by Asahi Glass Co., Ltd.); Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The blending amount of the above-mentioned surfactant 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 film forming composition of the present invention. These surfactants may be added singly or in combination of two or more.

EUV resists can be used in the present invention. As the EUV resist applied to the lower layer of the upper film of the resist of the present invention, both a negative type and a positive type can be used. As such resists, there are the following types: chemically amplified resists composed of an acid generator and a binder having a base which is decomposed by an acid to cause a change in the rate of alkali dissolution; an alkali-soluble binder and an acid are produced. a chemically amplified resist composed of a low molecular compound which is decomposed by an acid to cause a change in the alkali dissolution rate of the resist; and an alkali generator which is decomposed by an acid generating agent to cause alkali a chemically amplified resist composed of a binder having a change in dissolution rate and a low molecular compound which is decomposed by an acid to cause a change in the alkali dissolution rate of the resist; and a base having a base which undergoes decomposition by EUV and which causes a change in alkali dissolution rate. A non-chemically amplified resist composed of a binder; a non-chemically amplified resist composed of a binder having a portion which is cut by EUV and which causes a change in alkali dissolution rate.

For example, as a material of the EUV resist, there are a methacrylic acid type, a polyhydroxy styrene (PHS) system, and the like. When such an EUV resist is used, a resist pattern can be formed in the same manner as a resist using an electron beam as an irradiation source.

A KrF resist or an ArF resist can be used in the present invention. As the KrF resist or the ArF resist applied to the lower layer of the resist film of the present invention, a negative photoresist or a positive photoresist can be used arbitrarily. As such resists, there are the following types: a positive photoresist composed of a phenol resin and 1,2-diazide naphthoquinone sulfonate; the decomposition rate is increased by the decomposition of the acid. a chemically amplified photoresist composed of a binder and a photoacid generator; a low molecular compound, an alkali soluble binder, and a photoacid generator which are decomposed by an acid to increase the alkali dissolution rate of the photoresist a chemically amplified photoresist composed of a binder having a base which is decomposed by permeation to increase the rate of alkali dissolution, and a low molecular compound which is decomposed by an acid to increase the alkali dissolution rate of the photoresist, and light A chemically amplified photoresist composed of an acid generator. For example, the product name APEX-E manufactured by The Dow Chemical Company (formerly Rohm and Haas Electronic Materials Co., Ltd.), the product name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and the Shin-Etsu Chemical Co., Ltd. product may be mentioned. Name SEPR430 and so on. Further, for example, it can be described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000) or Proc. SPIE, Vol. 3999, 365-374 ( 2000) Fluorine-containing atomic polymer photoresist.

An electron line resist can be used in the present invention. As the electron line resist applied to the lower layer of the upper film of the resist of the present invention, a negative photoresist or a positive photoresist can be used arbitrarily. As such resists, there are the following types: chemically amplified resists composed of an acid generator and a binder having a base which is decomposed by an acid to cause a change in the rate of alkali dissolution; an alkali-soluble binder and an acid are produced. a chemically amplified resist composed of a low molecular compound which is decomposed by an acid to cause a change in the alkali dissolution rate of the resist; an acid generator, a binder having a base which is decomposed by an acid to change the alkali dissolution rate, a chemically amplified resist composed of a low molecular compound which is decomposed by an acid to cause a change in the alkali dissolution rate of the resist; a non-chemical increase consisting of a binder having a base which is decomposed by an electron beam and which causes a change in the rate of alkali dissolution. A resisting agent; a non-chemically amplified resist composed of a binder having a portion which is cut by an electron beam and which causes a rate of alkali dissolution to change. When such an electron beam resist is used, a resist pattern can be formed in the same manner as a photoresist using KrF or ArF light as an irradiation source.

The resistive upper layer forming composition is used to form the resist upper layer film, and as the developing solution having the positive resist of the above resist upper layer film, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate can be used. , inorganic bases such as sodium metasilicate, ammonia, etc.; first amines such as ethylamine and n-propylamine; second amines such as diethylamine and di-n-butylamine; Amine a third amine such as methyl diethylamine; an alcohol amine such as dimethylethanolamine or triethanolamine; a fourth ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline; An aqueous alkali solution such as a cyclic amine such as pyrrole or piperidine. Further, an aqueous solution of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the aqueous alkali solution. The preferred developer among these is a fourth-order ammonium salt, more preferably tetramethylammonium hydroxide and choline.

In the present invention, for example, on a substrate having a film to be processed which forms a transfer pattern, a semiconductor device can be manufactured by the steps including the steps of forming an EUV resist film with or without an EUV resist underlayer film. a step of coating an EUV resist upper film forming composition on the resist film and firing to form an EUV resist upper film; and exposing the semiconductor substrate covered with the resist upper film and the resist film And a step of removing the resist upper film and the resist film after exposure. The exposure was carried out by EUV (wavelength 13.5 nm).

The formation of the resist upper layer film is generally performed by a spin coating method in the same manner as the formation of a resist film or the like. For example, a substrate to be processed (for example, a ruthenium/cerium oxide-coated substrate, a glass substrate, an ITO substrate, or the like) is placed in a spin coater manufactured by Tokyo Electron Co., Ltd., and a resist film is formed on the substrate to be processed, and the number of revolutions is rotated. The resist superposed film forming composition (varnish) is applied to the substrate to be processed at 700 rpm to 3000 rpm, and then fired at 50 ° C to 150 ° C for 30 to 300 seconds using a hot plate to form the resist superposed film. The resist upper layer is formed to have a film thickness of 3 to 100 nm, or 5 to 100 nm, or 5 to 50 nm.

As a resistive upper film formed for the photoresist The dissolution rate of the shadow liquid 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 upper film of the resist becomes long, which leads to a decrease in productivity. After forming a pattern using a suitable exposure light source, the resist and the resist upper layer are not partially removed by development using a resist developer to form a resist pattern.

A semiconductor device to which the EUV resist superposed film forming composition of the present invention is applied is formed by sequentially forming a film to be processed having a transfer pattern, a resist film, and a resist upper film on a substrate. The resist upper layer is a resist pattern which forms a good linear shape by reducing the adverse effect caused by the base substrate or EUV, and a sufficient margin with respect to the EUV irradiation amount can be obtained. Further, the upper film of the resist has a wet etching rate which is equal to or larger than that of the resist film formed on the lower layer, and the unnecessary portion of the resist film after the exposure can be easily removed using an alkali developing solution or the like.

Further, the substrate to be processed of the semiconductor device can be processed by any step of dry etching or wet etching, and a good resist pattern formed by using the resist upper film can be used as a mask. Dry etching or wet etching can transfer a good shape onto the substrate to be processed.

In the present invention, for example, on a substrate having a film to be processed which forms a transfer pattern, the semiconductor device can be manufactured by the steps including the steps of forming a KrF resist film with or without a KrF resist underlayer film. a step of coating a KrF resist upper film forming composition on the resist film and firing to form a KrF resist upper film; the resist upper film and a step of exposing the semiconductor substrate covered by the resist film; and developing the film after exposure to remove the resist upper film and the resist film. Exposure is performed by KrF. The formation of the resist upper layer film was carried out in the same manner as in the case of the above EUV exposure.

In the present invention, for example, on a substrate having a film to be processed which forms a transfer pattern, the semiconductor device can be manufactured by the steps including the steps of forming an ArF resist film with or without an ArF resist underlayer film. a step of coating an ArF resist upper film forming composition on the resist film and firing to form an ArF resist upper film; and exposing the semiconductor substrate covered with the resist upper film and the resist film And a step of removing the resist upper film and the resist film after exposure. Exposure is performed by ArF. The formation of the resist upper layer film was carried out in the same manner as in the case of the above EUV exposure.

In the present invention, for example, on a substrate having a film to be processed which forms a transfer pattern, the semiconductor device can be manufactured by including the following steps: forming an electron line resist film with or without an electron line resist underlayer film a step of coating an electron beam resist superposed film forming composition on the resist film and firing to form an electron linear resist upper film; and covering the semiconductor coated with the resist upper film and the resist film a step of exposing the substrate; developing the film after exposure to remove the resist film and the resist film. Exposure is performed by electronic wires. The formation of the resist upper layer film was carried out in the same manner as in the case of the above EUV exposure.

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

The resin (polymer) shown in the following Synthesis Example 1 to Synthesis Example 11 of the present specification has a weight average molecular weight (Mw) as a result of measurement by a GPC (Gel Permeation Chromatography) method. The measurement was carried out using a GPC apparatus manufactured by Tosoh Co., Ltd., and the measurement conditions were as follows. Moreover, the degree of dispersion shown in the following synthesis examples of the present specification is calculated from the measured weight average molecular weight and the number average molecular weight.

Measuring device: HLC-8320GPC [trade name] (manufactured by Tosoh Co., Ltd.)

GPC pipe column: TSKgel SuperMultipore HZ-N (P0009) [trade name] (made by Tosoh Co., Ltd.)

TSKgel SuperMultipore HZ-N (P0010) [trade name] (made by Tosoh Corporation)

Column temperature: 40 ° C

Solvent: tetrahydrofuran (THF)

Flow rate: 0.35ml/min

Standard sample: polystyrene (manufactured by Tosoh Corporation)

[Examples] <Synthesis Example 1>

10.0 g of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 1.9 g of 3,5-diaminobenzoic acid, and 3.11 g of bis(4-aminophenyl)anthracene in C two The alcohol monomethyl ether was reacted at 40 ° C for 24 hours in 85.1 g. Next, 1.7 g of tetrafluorophthalic anhydride and 9.4 g of propylene glycol monomethyl ether were added, and a solution containing polylysine was obtained by reacting at room temperature for 20 hours. The weight average molecular weight (Mw) obtained by the GPC method was 7509. The obtained polyaminic acid has a structure represented by the formula (14-1).

<Synthesis Example 2>

10.0 g of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 1.0 g of 3,5-diaminobenzoic acid, and bis(4-aminophenyl)anthracene 3.11 g, 4 2.4 g of octadecyloxy-1,3-diaminobenzene in 93.1 g of propylene glycol monomethyl ether was reacted 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 a solution containing polylysine was obtained by reacting at room temperature for 20 hours. The weight average molecular weight (Mw) obtained by the GPC method was 6,728. The obtained polyaminic acid has a knot represented by the formula (14-2) Structure.

<Synthesis Example 3>

10.0 g of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 1.9 g of 3,5-diaminobenzoic acid, 4-octadecyloxy-1,3-diamine 4.7 g of phenylbenzene was reacted in propylene glycol monomethyl ether 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 a solution containing polylysine was obtained by reacting at room temperature for 22 hours. The weight average molecular weight (Mw) obtained by the GPC method was 8,925. The obtained polyaminic acid has a structure represented by the formula (14-3).

<Synthesis Example 4>

2.2 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.4 g of isophthalic acid dichloride, and 0.2 g of bis(4-aminophenyl)anthracene in N-methylpyrrolidone In 15.5 g, a solution containing polyamine was obtained by reacting at room temperature for 17 hours. The obtained solution was added to methanol to reprecipitate, and then dried at 50 ° C for 12 hours to obtain a solid of polyamine having a structural unit represented by the following formula (14-4). The weight average molecular weight (Mw) obtained by the GPC method was 4,502.

<Synthesis Example 5>

2.0 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 1.1 g of dichloroisophthalic acid were added to 12.4 g of N-methylpyrrolidone, and the mixture was reacted at 50 ° C for 30 minutes. Thereafter, a solution containing polyamine was obtained by reacting at room temperature for 18 hours. The obtained solution was added to a solution of methanol:water = 9:1 to reprecipitate, and then dried at 50 ° C for 12 hours to obtain a polyamine having a structural unit represented by the following formula (14-5). solid. The weight average molecular weight (Mw) obtained by the GPC method was 4362.

<Synthesis Example 6>

5.0 g of pyromellitic dianhydride, 1.52 g of 3,5-diaminobenzoic acid, and 0.7 g of bis(3-amino-4-hydroxyphenyl)anthracene in 40.93 g of propylene glycol monomethyl ether, The reaction was carried out at 40 ° C for 24 hours. Next, 0.82 g of tetrafluorophthalic anhydride and 4.68 g of propylene glycol monomethyl ether were added, and a solution containing polylysine was obtained by reacting at room temperature for 20 hours. The weight average molecular weight (Mw) obtained by the GPC method was 1249. The obtained polyaminic acid has a structure represented by the formula (14-6).

<Synthesis Example 7>

5.0 g of pyromellitic dianhydride, 1.52 g of 3,5-diaminobenzoic acid, and 0.62 g of bis(4-aminophenyl)anthracene in 40.48 g of propylene glycol monomethyl ether were reacted at 40 ° C. hour. Next, add tetrafluorophthalic anhydride 0.82 g and 4.68 g of propylene glycol monomethyl ether were obtained by reacting at room temperature for 20 hours to obtain a solution containing polylysine. The weight average molecular weight (Mw) obtained by the GPC method was 1552. The obtained polyaminic acid has a structure represented by the formula (14-7).

<Synthesis Example 8>

5.0 g of pyromellitic dianhydride, 1.52 g of 3,5-diaminobenzoic acid, and 0.80 g of 2,2'-bis(trifluoromethyl)benzidine in 41.49 g of propylene glycol monomethyl ether, The reaction was carried out at 40 ° C for 24 hours. Next, 0.82 g of tetrafluorophthalic anhydride and 4.68 g of propylene glycol monomethyl ether were added, and a solution containing polylysine was obtained by reacting at room temperature for 20 hours. The weight average molecular weight (Mw) obtained by the GPC method was 1894. The obtained polyaminic 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, and reacted at 40 ° C for 24 hours. Next, 0.83 g of 4-amino benzoic acid and 4.75 g of propylene glycol monomethyl ether were added, and a solution containing polylysine was obtained by reacting at room temperature for 20 hours. The weight average molecular weight (Mw) obtained by the GPC method was 5,647. The obtained polyaminic acid has a structure represented by the formula (14-9).

<Synthesis Example 10>

4.06 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, and reacted at 40 ° C for 24 hours. Next, 0.53 g of 4-amino benzoic acid and 3.06 g of propylene glycol monomethyl ether were added, and a solution containing polylysine was obtained by reacting at room temperature for 20 hours. The weight average molecular weight (Mw) obtained by the GPC method was 2,826. The obtained polyaminic acid has a structure represented by the formula (14-10).

<Synthesis Example 11>

3.5 g of pyromellitic dianhydride, 0.47 g of trimellitic anhydride chloride, 1.49 g of 3,5-diaminobenzoic acid, and bis(3-amino-4-hydroxyphenyl)fluorene 0.55 g The reaction was carried out at 40 ° C for 24 hours in 31.17 g of propylene glycol monomethyl ether. Next, 0.74 g of tetrafluorophthalic anhydride and 4.21 g of propylene glycol monomethyl ether were added, and a solution containing polylysine was obtained by reacting at room temperature for 20 hours. The weight average molecular weight (Mw) obtained by the GPC method was 4,556. The obtained polyaminic acid has a structure represented by the formula (14-11).

(Example 1)

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

(Example 2)

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

(Example 3)

20.4 g of 4-methyl-2-pentanol was added to 1.0 g of a solution containing 0.32 g of the resin obtained in the above Synthesis Example 3, and dissolved. After that, use the hole A polyethylene microfilter having a diameter of 0.05 μm was filtered to form a composition for forming a resist film on the lithography.

(Example 4)

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

(Example 5)

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

(Example 6)

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

(Example 7)

24.4 g of 4-methyl-2-pentanol was added to 2.5 g of a solution containing 0.42 g of the resin obtained in the above Synthesis Example 7, and dissolved. After using A polyethylene microfilter having a pore diameter of 0.05 μm was filtered to form a composition for forming a resist film on the lithography.

(Example 8)

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

(Example 9)

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

(Embodiment 10)

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

(Example 11)

24.4 g of 2-methyl-2-butanol was added to 2.5 g of a solution containing 0.42 g of the resin obtained in the above Synthesis Example 6, and dissolved. After that, use the hole A polyethylene microfilter having a diameter of 0.05 μm was filtered to form a composition for forming a resist film on the lithography.

(Embodiment 12)

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

(Example 13)

24.4 g of 4-methyl-2-pentanol was added to 2.5 g of a solution containing 0.42 g of the resin obtained in the above Synthesis Example 10, and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to form a composition for forming a resist film on the lithography.

(Example 14)

20.4 g of 4-methyl-2-pentanol was added to 1.0 g of a solution containing 0.32 g of the resin obtained in the above Synthesis Example 11, and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 μm to form a composition for forming a resist film on the lithography.

(Comparative Example 1)

1 g of a 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. The upper film forms a composition solution.

(Comparative Example 2)

Propylene glycol monomethyl ether acetate was used.

(Comparative Example 3)

Use ethyl acetate.

(Comparative Example 4)

Use cyclohexanone.

(Comparative Example 5)

Γ-butyrolactone was used.

(intermix test with resist)

A rotator was used to coat the EUV resist solution (methacrylic resist). A resist film was formed on the hot plate by heating at 100 ° C for 1 minute, and the film thickness was measured (film thickness A: resist film thickness).

The resist upper layer film forming composition solution prepared in Example 1 to Example 14 or Comparative Example 1 of the present invention was applied onto the resist film using a rotator, or only the solvent was used in Comparative Example 2 to Comparative Example 5. The film was coated on a resist film and heated on a hot plate at 100 ° C for 1 minute to measure the film thickness (film thickness B: the sum of the film thicknesses of the resist and the resist upper film).

On the upper film of the resist, 2.38 of a commercially available general-purpose alkaline developer A wt% tetramethylammonium hydroxide aqueous solution (trade name: NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) was dropped, placed for 60 seconds, and rotated at 3000 rpm while being rinsed with pure water for 30 seconds. After the 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 it is not mixed with the resist. The film thickness A of Example 1 to Example 14 was equal to the film thickness C, and it was confirmed that it was not mixed with the resist. On the other hand, in Comparative Example 2 to Comparative Example 5, since the film thickness B was 0, it was suggested that the resist upper layer film composition using these solvents would cause mutual mixing.

[Optical parameter test]

The resist upper layer film forming composition solution prepared in Example 1 to Example 11 and Example 14 of the present invention and the resist upper layer film forming composition solution shown in Comparative Example 1 were applied by using a rotator, respectively. On the quartz substrate. On the hot plate, a resist upper film (film thickness: 30 nm) was formed by heating at 100 ° C for 1 minute. Thereafter, the absorption ratio of the upper film of the resist at a wavelength of 190 nm to 240 nm was measured using a spectrophotometer.

The transmittance at 13.5 nm is calculated from the relationship between the elemental composition ratio and the film density by simulation.

Regarding the light-shielding property of DUV light, in the wavelength range of 220 to 260 nm, the maximum value of the absorptance is 40% or more, and the defect is set to be less than 40%. Further, the transmittance of EUV light (13.5 nm) was set to be good for a transmittance of 80% or more, and was set to be less than 80%.

The resist upper layer film obtained by forming the composition from the resist upper layer film of each example has excellent light-shielding property of DUV light compared to the resist upper film obtained by forming the composition of the resist upper film of Comparative Example 1. The result.

[Industry Utilization]

The present invention is a composition for forming an upper layer film of an EUV resist used in an EUV lithography process, or a composition for forming a resist film for a lithography process at other exposure wavelengths, the composition of the present invention It is not intermixed with the resist, for example, when the EUV is exposed, the poor exposure light source such as UV or DUV is interrupted, and only EUV is selectively passed through, and after exposure, the developer is developable.

Claims (16)

A resist superposed film forming composition comprising a resin selected from the group consisting of (a) a tetracarboxylic dianhydride compound, (b) an acid dihalogen compound, and (c), wherein the resin is selected from the group consisting of: One or more compounds having a dicarboxylic anhydride group and an acid halide group are produced by reacting (d) one or more kinds of diamine compounds, and at least one of a guanamine bond and a ruthenium bond. One. The resist superposed film forming composition of claim 1, wherein the resin of claim 1 contains one selected from the group consisting of the following formula (1-1), formula (1-2), and formula (1-3) The resin of the above unit structure, (in the formulae (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 resin has a weight average molecular weight of from 500 to 100,000. The resist superposed film forming composition of claim 1 or claim 2, wherein the resin end structure of claim 1 or claim 2 is represented by formula (1-4), (In the formula (1-4), R ₁ is an organic group containing an aromatic ring or an alkyl group having 1 to 5 carbon atoms, B ₁ is synonymous with the definition of the claim 2, and a wavy line portion is shown as claim 2 One part of the resin). The resist superposed film forming composition of claim 1 or claim 2, wherein the resin end structure of claim 1 or claim 2 is represented by formula (1-5) or formula (1-6), (In the formula (1-5) or the formula (1-6), R ₂ is an organic group containing an aromatic ring or an alkyl group having 1 to 5 carbon atoms, and A ₁ and B ₁ are synonymous with the definition of the claim 2 The wavy line portion is shown as part of the resin of claim 2. The resist superposed film forming composition according to any one of Claims 1 to 4, wherein the alcohol solvent is a linear one having a carbon number of 1 to 20, a branch having a carbon number of 3 to 20, or a cyclic saturated alkane A base alcohol, or an aromatic alcohol having 6 to 20 carbon atoms. The resist superposed film forming composition according to any one of Claims 1 to 5, wherein the alcohol solvent is 1-heptanol, 2-methyl-2-butanol, 4-methyl-2-pentyl Alcohol or cyclopentanol. The resist film upper layer forming composition of claim 1, wherein the compound (a) is represented by the following formula (1-7) to formula (1-10), (In the formulae (1-7) to (1-10), X ₁ to X ₅ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms or a branched halogenated alkyl group, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzhydryl group (the hydrogen atom of the aforementioned phenoxy group and benzhydryl group may be passed through 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxyl groups; m1 is shown as an integer from 0 to 8, and n1, m3 and m4 are shown An integer from 0 to 3, n2 and n3 are shown as integers from 0 to 2, and m2 and m5 are shown as integers from 0 to 4; W _{1 is} shown as a single bond, an oxygen atom, a linear or branched carbon number of 1 to 10. An alkyl group, a linear or branched halogenated alkyl group having 1 to 10 carbon atoms, a sulfonyl group or a carbonyl group), and the compound (b) is represented by the following formula (1-11) to formula (1-13) As shown, (In the formulae (1-11) to (1-13), Z ₁ is a halogen atom, and X ₆ to X ₉ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a carbon number. a straight or branched halogenated alkyl group of 1 to 10, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzamyl group (the aforementioned phenoxy group and benzhydryl group) The hydrogen atom may be substituted by 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxyl groups; m6 and m7 are shown as 0 to 10 The integers, n4 and n5 are shown as integers from 0 to 3, m8 and m9 are shown as integers from 0 to 4; W _{2 is} shown as a single bond, an oxygen atom, a linear or branched alkyl group having a carbon number of 1 to 10, carbon a straight or branched halogenated alkyl group, a sulfonyl group or a carbonyl group of 1 to 10, and the compound (c) is represented by the following formula (1-14) to formula (1-15), (In the formulae (1-14) to (1-15), Z ₁ is a halogen atom, and X ₁₀ to X ₁₂ are independently shown as a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a carbon number. a straight or branched halogenated alkyl group of 1 to 10, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzamyl group (the aforementioned phenoxy group and benzhydryl group) The hydrogen atom may be substituted by 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxyl groups; m10 is shown as an integer from 0 to 9. , n6 and m11 are shown as integers from 0 to 3, m12 is shown as an integer from 0 to 4; W _{3 is} shown as a single bond, an oxygen atom, a linear or branched alkyl group having a carbon number of 1 to 10, and a carbon number of 1 to 10 a straight chain or a branched halogenated alkyl group, a sulfonyl group or a carbonyl group), and the compound (d) is represented by the following formula (1-16) or formula (1-17), (In the formulae (1-16) and (1-17), X ₁₃ to X ₁₅ are each independently a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms or a branched halogenated alkyl group, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a phenoxy group or a benzhydryl group (the hydrogen atom of the aforementioned phenoxy group and benzhydryl group may be passed through 1 to 5 halogen atoms, 1 to 5 linear or branched alkyl groups having 1 to 5 carbon atoms, or 1 to 5 hydroxyl groups; m13 to m15 are shown as integers from 0 to 4, and n7 is shown as 0. An integer of up to 3; W ₄ is represented by a single bond, an oxygen 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, a sulfonyl group or a carbonyl group. Any one of them), and the unit structure of the resin has at least one hydroxyl group, carboxyl group or a combination thereof. The resist film upper layer forming composition of claim 3, wherein the terminal blocking agent for forming the partial structure of the formula (1-4) is represented by the following formulas (1-18) to (1-21) Compound, (In the formulae (1-18) to (1-21), Z ₁ is a halogen atom, and X ₁₆ to X ₂₁ 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 halogenated alkyl group to 10, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, a phenoxy group, a cyano group or a nitro group; m16 is an integer of 0 to 10, and n8, n9 and m17 are shown An integer from 0 to 3, m18 and m21 are shown as integers from 0 to 5, m19 is an integer from 0 to 11, m20 is an integer from 0 to 4; W ₅ and W _{6 are} shown as single bond, oxygen atom, carbon A linear or branched alkyl group having 1 to 10 or a straight or branched halogenated alkyl group having a carbon number of 1 to 10, a sulfonyl group or a carbonyl group). The resist film upper layer forming composition of claim 4, wherein the terminal blocking agent for forming a partial structure of the formula (1-5) or the formula (1-6) is a formula (1-22) or a formula a compound shown in (1-23), (In the formulae (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 chain having 1 to 10 carbon atoms or Branched halogenated alkyl group, alkoxy group having 1 to 30 carbon atoms, hydroxyl group, carboxyl group, phenoxy group, cyano group or nitro group; m22 is shown as an integer from 0 to 11, n10 is an integer from 0 to 3, and m23 is shown as An integer from 0 to 4, m24 is shown as an integer from 0 to 5; W _{7 is} shown as a single bond, an oxygen atom, a linear or branched alkyl group having a carbon number of 1 to 10, and a linear or branched halogenation having a carbon number of 1 to 10. Any of an alkyl group, a sulfonyl group or a carbonyl group). The resist superposed film forming composition according to any one of claims 1 to 9, which further comprises an acid compound. The resist superposed film forming composition according to claim 10, wherein the acid compound is a sulfonic acid compound or a sulfonic acid ester compound. The resist superposed film forming composition according to claim 10, wherein the acid compound is an iodonium salt-based acid generator or a phosphonium-based acid generator. The resist superposed film forming composition according to any one of Claims 1 to 12, which further comprises a basic compound. The resist superposed film forming composition according to any one of Claims 1 to 13, wherein the resist used together with the above composition is a resist for EUV (wavelength 13.5 nm). A method of manufacturing a semiconductor device comprising the steps of: forming a resist film on a substrate, and applying a resist film forming composition of any one of claim 1 to claim 14 to the resist a step of firing the film to form a resist upper layer, exposing the semiconductor substrate covered with the resist upper film and the resist film, and developing after exposure to remove the resist upper film and the resist film The steps. The method of manufacturing a semiconductor device according to claim 15, wherein the exposure is performed by EUV (wavelength 13.5 nm).