WO2006040922A1

WO2006040922A1 - Composition for forming bottom anti-reflective coating containing aromatic sulfonic acid ester compound and light photoacid-generating agent

Info

Publication number: WO2006040922A1
Application number: PCT/JP2005/017734
Authority: WO
Inventors: Tadashi Hatanaka; Tomoyuki Enomoto; Shigeo Kimura
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2004-10-14
Filing date: 2005-09-27
Publication date: 2006-04-20
Also published as: CN101040221A; TWI375868B; CN101040221B; KR20070065316A; JPWO2006040922A1; KR101195468B1; JP4525940B2; TW200622498A

Abstract

[PROBLEMS] To provide a bottom anti-reflective coating forming composition for forming a bottom anti-reflective coating which is used in a lithography process for manufacturing a semiconductor device and can be developed with an alkaline developing solution for a photoresist, and a method for forming a photoresist pattern using the bottom anti-reflective coating forming composition. [MEANS FOR SOLVING PROBLEMS] A composition for forming a bottom anti-reflective coating which comprises a polyamide acid, a crosslinkable compound having two or more epoxy groups, an aromatic sulfonic acid ester compound, a photoacid-generating agent and a solvent.

Description

Specification

Lower layer antireflection film-forming composition comprising an aromatic sulfonate compound and a photoacid generator

Technical field

TECHNICAL FIELD [0001] The present invention relates to a lower antireflection film forming composition used in a lithography process for manufacturing a semiconductor device, and a photoresist pattern forming method using the lower antireflection film forming composition. More specifically, the present invention relates to a lower antireflection film forming composition for forming a lower antireflection film that can be developed with an alkaline developer used for developing a photoresist. Further, the present invention relates to a method for forming a photoresist pattern by simultaneously developing a photoresist and a lower antireflection film using the lower antireflection film forming composition. Background art

In the manufacture of semiconductor devices, microfabrication by lithography 1 using a photoresist is performed. Microfabrication is obtained by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating it with actinic rays such as ultraviolet rays through a mask pattern on which a device pattern is drawn, and developing it. In this processing method, fine concaves and convexes corresponding to the pattern are formed on the substrate surface by etching the substrate using the photoresist pattern as a protective film. However, in these lithography processes, the dimensional accuracy of the photoresist pattern decreases due to the influence of standing waves caused by reflection of the light used for exposure from the substrate and the effect of irregular reflection due to the step of the substrate. The problem of doing was occurring. Therefore, a method of providing a bottom anti-reflective coating between the photoresist and the substrate that should solve this problem has been studied.

[0003] These lower antireflection films are often formed using a thermally crosslinkable composition in order to prevent intermixing with the photoresist applied thereon. As a result, the antireflection film becomes insoluble in an alkaline developer for photoresist, and the lower antireflection film must be removed by dry etching prior to semiconductor substrate processing (see, for example, Patent Document 1). .

However, simultaneously with the removal of the lower antireflection film by dry etching, the photoresist is also removed. It is removed by touching. As a result, there arises a problem that it is difficult to secure the photoresist film thickness necessary for the substrate strength. This is a particularly serious problem when thin film photoresists are used to improve resolution.

[0005] On the other hand, the ion implantation process in semiconductor device manufacturing is a process of introducing impurities into a semiconductor substrate using a photoresist pattern as a saddle, and avoids damaging the substrate surface. In the formation, a dry etching process cannot be performed. Therefore, in forming a photoresist pattern for the ion implantation process, an antireflection film that needs to be removed by dry etching cannot be used as a lower layer of the photoresist. The photoresist pattern that has been used as a vertical pattern in the ion implantation process so far is the influence of standing wave caused by reflection of exposure irradiation light from the substrate whose line width is wide, and exposure irradiation due to the step of the substrate. Reflection problems have been solved by using dye-containing photoresists and anti-reflection coatings on the top of the photoresist because they are less susceptible to diffuse reflection of light. However, with the recent miniaturization of the pattern size, the photoresist used in the ion implantation process has begun to require a fine pattern, and it has become necessary to use an antireflection film under the photoresist. .

[0006] For these reasons, it has been desired to develop a lower antireflection film that can be dissolved in an alkaline developer used for developing a photoresist and developed and removed simultaneously with the photoresist. By the way, studies have been made on the lower antireflection film that can be developed and removed simultaneously with the photoresist (see, for example, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6). .) ₀ However, per cent in terms of butter over emissions shape applied resistance and formation of microfabrication Te, it was not sufficient.

Patent Document 1: US Patent No. 6156479

Patent Document 2: Japanese Patent No. 2686898

Patent Document 3: Japanese Patent Laid-Open No. 9-78031

Patent Document 4: Japanese Patent Laid-Open No. 11-72925

Patent Document 5: International Publication No. 03Z057678 Pamphlet

Patent Document 6: International Publication No. 03Z058345 Pamphlet Disclosure of the invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and is a lower antireflection film soluble in an alkaline developer used for developing a photoresist, and a composition for forming the lower antireflection film The purpose is to provide goods.

[0008] That is, an object of the present invention is to provide a composition for forming a lower antireflection film used for manufacturing a semiconductor device. The lower layer can be dissolved in an alkaline developer without being intermixed with the photoresist applied and formed on the upper layer, can be developed and removed simultaneously with the photoresist, and can provide a photoresist pattern with a good shape. It is to provide an antireflection film. It is another object of the present invention to provide a method for forming a photoresist pattern used for manufacturing a semiconductor device using the lower antireflection film forming composition.

Means for solving the problem

[0009] In view of the current situation, the present inventors have conducted extensive research and have found that an underlayer antireflection film superior to a composition containing an aromatic sulfonic acid ester compound and a photoacid generator can be formed. The title and the present invention have been completed.

[0010] That is, the present invention provides, as a first aspect, a composition for forming an underlayer antireflection film for forming an underlayer antireflection film that is developed together with a photoresist with an alkaline developer. Formula (2):

[0011] [Chemical 1]

[In the formula, A and A represent a tetravalent organic group, B represents a trivalent organic group, and B represents a divalent organic group.

1 2 1 2

A lower layer characterized in that it contains a polyamic acid having a structure represented by the following formula: a bridged compound having two or more epoxy groups, an aromatic sulfonic acid ester compound, a photoacid generator and a solvent. Antireflection film-forming composition,

As a second aspect, the composition for forming an underlayer antireflection film according to the first aspect, further comprising a light-absorbing compound,

As a third aspect, the composition for forming a lower antireflection film according to the first aspect, further comprising an aromatic carboxylic acid compound,

As a fourth aspect, the lower layer antireflection film-forming composition according to the first aspect, wherein the crosslinkable compound is a compound having two to four epoxy groups,

As a fifth aspect, the composition for forming an antireflection film for a lower layer according to the first aspect, wherein the photoacid generator is a iodine salt compound or a sulfo-chloride compound, As a viewpoint, the aromatic sulfonate ester compound is represented by the formula (3):

[0013] [Chemical 2]

(In the formula, Ar is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a nitro group, a cyan group, an amino group, a halogen group, a carboxyl group, and carbon. Substituted by a group selected from alkoxy groups having 1 to 6 atoms !, may be! /, Represents a benzene ring, a naphthalene ring or an anthracene ring, and R and R are each independently ,

1 2

Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R and R are bonded to each other.

1 2

Then, a ring having 3 to 8 carbon atoms may be formed. A composition for forming an underlayer antireflection film according to the first aspect, which is a compound having a structure represented by:

As a seventh aspect, the lower layer reflection according to the first aspect is characterized in that the aromatic sulfonate ester compound is a compound having two to four structures represented by the formula (3). Prevention film forming composition, As an eighth aspect, the antireflective film-forming composition according to the second aspect, wherein the light-absorbing compound is a naphthalenecarboxylic acid ester compound,

As a ninth aspect, the lower layer antireflection according to the eighth aspect, characterized in that the naphthalenecarboxylic acid ester compound is a compound produced by reacting a naphthalenecarboxylic acid compound and an epoxy compound. A film-forming composition,

As a tenth aspect, the lower-layer antireflection film-forming composition according to the third aspect, wherein the aromatic carboxylic acid compound is an aromatic carboxylic acid compound having a phenolic hydroxyl group,

As an eleventh aspect, the lower-layer antireflection film-forming composition according to the third aspect, wherein the aromatic carboxylic acid compound is a naphthalenecarboxylic acid compound having a phenolic hydroxyl group,

As a twelfth aspect, the polyamic acid is represented by formulas (4) and (5):

[0015] [Chemical 3]

(Five)

[0016] (wherein A and A represent a tetravalent organic group) is a polyamic acid having a structure represented by

1 2

The lower-layer antireflection film-forming composition as described in the first aspect,

As a thirteenth aspect, the polyamic acid is represented by formulas (6) and (7):

[0017] [Chemical 4]

[0018] (wherein B represents a trivalent organic group and B represents a divalent organic group)

1 2

A composition for forming a lower antireflection film according to the first aspect, characterized in that it is a polyamic acid,

As a fourteenth aspect, a process of forming a lower antireflection film by applying the lower layer antireflection film forming composition according to any one of the first to thirteenth aspects on a semiconductor substrate and baking the composition, the lower layer antireflection Manufacturing a semiconductor device, comprising: forming a photoresist layer on the film; exposing the semiconductor substrate covered with the lower antireflection film and the photoresist layer; and developing with an alkaline developer after the exposure A method for forming a photoresist pattern used in the above.

The invention's effect

[0019] By using the composition for forming an underlayer antireflection film of the present invention, it does not cause intermixing with the photoresist, dissolves in an alkaline developer used for developing the photoresist, and develops and removes at the same time as the photoresist. A possible lower antireflection film can be formed.

[0020] The lower antireflection film formed from the lower antireflection film-forming composition of the present invention can be removed without dry etching. Therefore, it can be used in a semiconductor device manufacturing process including a process sensitive to damage to the substrate surface by dry etching, such as an ion implantation process.

[0021] The lower layer reaction of the present invention comprising an aromatic sulfonic acid ester compound and a photoacid generator. The lower antireflective coating formed from the anti-reflective coating forming composition can easily adjust its acidity to the same level as the acidity of the photoresist, so that a more rectangular photoresist pattern can be formed. Can do.

BEST MODE FOR CARRYING OUT THE INVENTION

[0022] The composition for forming a lower antireflection film of the present invention comprises a polyamic acid having a structure represented by the above formula (1) and the above formula (2), a crosslinkable compound having two or more epoxy groups, an aromatic Group sulfonic acid ester compounds, photoacid generators and solvents. In addition, the lower layer antireflection film-forming composition of the present invention can contain a light-absorbing compound, an aromatic carboxylic acid compound, a surfactant, and the like.

[0023] The ratio of the solid content in the lower antireflection film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved, but is, for example, 1 to 50 mass%, or 3 to 30 It is mass%, or 5 to 25 mass%, or 10 to 15 mass%. Here, the solid content is a value obtained by removing the solvent component from all the components of the lower layer antireflection film-forming composition.

[0024] The composition for forming a lower antireflection film of the present invention will be specifically described.

[0025] <Polyamide acid>

The underlayer antireflection film-forming composition of the present invention comprises a polyamic acid having a structure represented by the formula (1) and a structure represented by the formula (2).

In the above formula (1), A represents a tetravalent organic group, and B represents a trivalent organic group. As A

1 1 1 includes, for example, formulas (8) to (16) (wherein X is an alkyl group having 1 to 5 carbon atoms, chlorine atom, bromine atom, fluorine atom, 1 to 5 carbon atoms) Represents an alkoxy group, a hydroxyl group, a ruboxyl group, a phenoxy group, a trifluoromethyl group or a -tro group, and m is 0, 1 or

1 represents the number 2).

[0027] [Chemical 5]

(12) ( ^x ) ^m i (13)

[0028] Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a cyclopentyl group, and a normal pentyl group. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, a cyclopentyloxy group, and a normal pentyloxy group.

[0029] Examples of B include formulas (17) to (24) (wherein Y is a group having 1 to 5 carbon atoms)

1

An alkyl group, a chlorine atom, a bromine atom, a fluorine atom, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, a carboxyl group, a phenoxy group, a trifluoromethyl group or a -tro group, and m is 0, 1 or 2 Represents a number).

H H2 H2 H H2

(23) (24)

[0031] In the formula (2), A represents a tetravalent organic group, and B represents a divalent organic group. As A

Examples of 2 2 2 include the above formulas (8) to (16).

[0032] Examples of B include formulas (25) to (34) (wherein Z is a group having 1 to 5 carbon atoms)

2

Three

[0033] [Chemical 7]

(Z) m ₃ (26) (Z) m ^

(33) () The weight average molecular weight of the polyamic acid used in the present invention is, for example, 1000 to 100,000, or 1500 to 50000, or 2000 to 30000, or 5000 to 10,000 in terms of polystyrene. . When the weight average molecular weight is smaller than the above value, the solubility of the lower antireflection film to be formed in the solvent used for the photoresist is increased. As a result, the lower antireflection film is intermixed with the photoresist. If force ^s to cause is there. When the weight average molecular weight is larger than the above value, the lower antireflection film to be formed is insufficiently soluble in an alkaline developer used for developing the photoresist, and the residue of the lower antireflection film after development is insufficient. May exist.

[0035] The method for obtaining the polyamic acid contained in the composition for forming an underlayer antireflection film of the present invention is not particularly limited, and can be produced by an existing method. For example, a polyamic acid can be produced by reacting and polymerizing a diamine compound with a tetracarboxylic dianhydride compound such as tetra-strength rubonic acid or a derivative thereof or a dicarboxylic acid dihalogen compound. Moreover, after synthesizing a polyamic acid silyl ester by polymerization using a bissilylidamine compound and a tetracarboxylic dianhydride compound, a polyamic acid can be produced by decomposing the silyl ester moiety with an acid.

[0036] The polyamic acid contained in the lower antireflection film-forming composition of the present invention includes (a) a tetracarboxylic dianhydride compound, (b) a diamine compound having at least one carboxyl group, and (c) ) Can be manufactured from Giamny compound.

[0037] The (a) tetracarboxylic dianhydride compound used in the production of the polyamic acid used in the present invention is not particularly limited. (A) The tetracarboxylic dianhydride compound may be used alone or in combination of two or more. Specific examples include pyromellitic dianhydride, 3, 3 ', 4, 4, biphenyl tetracarboxylic dianhydride, 3, 3', 4, 4, monobenzophenone tetracarboxylic dianhydride 3, 3 ', 4, 4'-diphenyl ether tetracarboxylic dianhydride, 4, 4' (hexafluoroisopropylidene) diphthalic dianhydride and 3, 3 ', 4, 4'-diphenol -Aromatic tetra force such as sulfone tetracarboxylic dianhydride Rubonic dianhydride, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 1, 2 dimethyl-1, 2, 3, 4 Cyclobutane tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl- 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride, 1 , 2, 3, 4 Cyclohexanetetracarboxylic dianhydride and 3, 4 dicarboxy 1, 2, 3, 4-tetrahydride Rho 1 Alicyclic tetracarboxylic dianhydrides such as naphthalene succinic dianhydride and aliphatic tetracarboxylic dianhydrides such as 1, 2, 3, 4 butanetetracarboxylic dianhydride it can.

[0038] (b) At least one carboxylic acid used in the production of the polyamic acid used in the present invention The diamine compound having a syl group is not particularly limited. Examples of the diamine compound having at least one carboxyl group (b) include diamine compounds having 1 to 3 carboxyl groups. (B) The diamine compound having at least one carboxyl group may be used alone or in combination of two or more. Specific examples include 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, bis (4 amino-3-carboxyphenyl) sulfone, bis (4- Amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5, monodimethylbiphenyl, 4, 4, 1, diamino 1, 3, 3, 1 dicarboxy 1, 5, 5, 1, dimethoxy biphenyl, 1, 4 bis (4 amino-3 carboxyphenoxy) benzene, 1, 3-bis (4-amino 3 —Carboxyphenoxy) benzene, bis [4— (4-amino-3-carboxyphenoxy) phenol] sulfone, bis [4- (4-amino-3-carboxyphenol) phenol] propane, and 2,2bis [4- (4 amino-3-carboxy) Phenoxy) and hexafluoropropane.

The (c) diamine compound used in the production of the polyamic acid used in the present invention is not particularly limited. (C) A diamine compound may be used alone, or two or more diamine compounds may be used simultaneously. Specific examples include 2,4 diaminophenol, 3,5 diaminophenol, 2,5 diaminophenol, 4,6 diaminole: / noresinole, 2,5 diaminohydroquinone, bis (3-amino-4- Hydroxyphenol) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenol) ether, bis (3-amino-4-hydroxyphenol) ) Methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-1,3,5-dihydroxyphenol) methane, bis (3-amino-4-hydroxyphenol) sulfone Bis (4-amino-3-hydroxyphenol) sulfone, bis (4 amino-3,5 dihydroxyphenol) sulfone, 2, 2 bis (3-amino-4-hydroxyphenol) hexafluoro Propane, 2, 2 screws ( 4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) Hexyl) fluoropropane, 4,4, -diamino-3,3, -dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy 5,5,1 dimethylbiphenyl, 4,4'-diamino 3 , 3'-dihydroxy-1,5,5,1-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-1-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenol] sulfone Bis [4- (3-amino-4-hydroxyphenoxy) phenol] propan and 2,2bis [4- (3-amino-4-hydroxyphenoxy) phenol] hexafluoropropane, etc. Di having a phenolic hydroxyl group Amin compounds, 1, ₃ Jiamino 4-mercapto benzene, 1, 3-diamino 5-mercapto benzene, 1, 4 Jiamino 2-mercapto benzene, bis (4-amino-3 Merukaputofue - Le) ether, and 2, 2-bis (3-Amino 4-mercapto Phenol) Hexafluoropropane and other diamine compounds having a thiophenol group, 1,3 diaminobenzene-4-sulfonic acid, 1,3 diaminobenzene 5-snorephonic acid, 1,4-diamino Benzene 2-sunolephonic acid, bis (4-aminobenzene 3-sulfonic acid) ether, 4,4'-diaminobiphenyl 3, 3, -disulfonic acid, and 4,4'-diamino-3,3, -dimethylbiphenyl 6 , 6, -disulfonic acid-containing diamine compounds having sulfonic acid groups, 3,5-diaminobenzoic acid tert-butyl ester, 3,5-diaminobenzoic acid ethoxy Examples thereof include diamine compounds containing carboxylic acid esters such as methyl ester, 3,5-diaminobenzoic acid methyl ester, 3,5-diaminobenzoic acid normal propyl ester, and 3,5-diaminobenzoic acid isobutyl ester. P-Phenylenediamine, m-Phenylenediamine, 4,4, -Methylenebis (2,6 ethylamine), 4,4, Methylenebis (2-isopropyl-6-methylamine) 4,4'-methylene bis (2,6 diisopropyl-line), 2, 4, 6 —trimethyl 1,3 phenylene diamine, 2, 3, 5, 6-tetramethyl 1,1,4 phenylenediamine, o tolidine , M-tolidine, 3, 3 ', 5, 5, monotetramethylbenzidine, bis [4— (3-aminophenoxy) phenol] sulfone, 2,2bis [4- (3-aminophenoxy) phenol ] Propane, 2, 2 bis [4- (3-Aminophenoxy) phenol] hexafluorol Bread, 4,4'-diamino-3,3,1-dimethyldicyclohexylmethane, 4,4'-damino Diphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 2, 2 bis (4 lino) hexafluoropropane, 2, 2 bis (3 lino) Hexafluoropropane, 2, 2 bis (3 amino-4 toluyl) hexafluoropropane, 1, 4 bis (4 aminophenoxy) benzene, 1, 3 bis (4 aminophenoxy) benzene, bis (4-aminophenol) Sulfone, bis [4- (4-aminophenoxy) phenol] Sulfone, 2,2bis [4- (4-aminophenoxy) phenol] propane, and 2,2bis [4- (4-aminophenoxy) phenol] ] Diamine compounds such as hexafluoropropane can be mentioned.

[0040] In the production of the polyamic acid used in the present invention, the ratio of (b) the diamine compound having at least one carboxyl group in the total diamine compound used is, for example, 1 to 99% by mass, or 5 -80 mass%, or 10-60 mass%, or 20-50 mass%, or 30-40 mass%. (B) When the ratio of the diamine compound having at least one carboxyl group is less than this, the lower antireflection film to be formed has insufficient solubility in an alkaline developer.

[0041] The polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound, (b) a diamine compound having at least one carboxyl group, and (c) a diamine compound. In this case, the ratio of the total number of moles of the diamine compound used to the total number of moles of the tetracarboxylic dianhydride compound is preferably 0.8 to 1.2. As in the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the polyamic acid produced and the higher the molecular weight.

[0042] In the production of polyamic acid, the reaction temperature of the diamine compound and the tetracarboxylic dianhydride compound is 20 ° C to 150 ° C, preferably 5 ° C to 100 ° C. You can choose. High molecular weight polyamic acid can be obtained at a reaction temperature of 5 ° C to 40 ° C and a reaction time of 1 to 48 hours. In order to obtain a polyamic acid having a low molecular weight and high storage stability, a reaction time of 10 hours or longer at 40 ° C. to 80 ° C. is more preferable.

[0043] The reaction of the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used include N, N dimethylformamide, N, N dimethylacetamide, N-methylpyrrolidone, N vinylpyrrolidone, N-methylcaprolacta Dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, y butyrolatatane, ethyl acetate, butyl acetate, ethyl lactic acid, methyl 3-methoxypropionate, methyl 2-methoxypropionate, 3-ethyl methoxypropionate, 2-methoxypropionate, 3 ethoxypropionate, 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glyconoresin methinoate ethere, diethylene glycono lesino enoate, Diethylene glycol methyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomono Chinoleatenore, diethyleneglycololemonomethinoatenore, diethyleneglycololemonomethinoleatenore, propyleneglycolenomonomethinoleatenore, propyleneglycolenolemonothenoreether, dipropyleneglycololemonomethinoreether, Dipropylene glycolenomonoethylenole ether, propylene glycolenomonomethylenoate tenoleacetate, canolebitonoreacetate, ethinoreserosonolebuacetate, cyclohexanone, methylethylketone, methylisobutylketone, and 2- And heptanone. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyamic acid, it may be mixed with the above solvent as long as the polyamic acid produced by the polymerization reaction does not precipitate.

[0044] The solution containing the polyamic acid thus obtained can be used as it is for the preparation of the lower antireflection film-forming composition. Alternatively, the polyamic acid can be poured into a poor solvent such as methanol or ethanol, precipitated, isolated and used.

[0045] Examples of the polyamic acid contained in the lower antireflection film-forming composition of the present invention include polyamic acids having structures represented by the above formulas (4) and (5). The polyamic acid having the structure represented by the formula (4) and the formula (5) includes, for example, (a) a tetracarboxylic dianhydride compound, 3,5-diaminobenzoic acid and bis (4 aminophenol). It can be obtained by reacting with sulfone.

[0046] Examples of the polyamic acid contained in the composition for forming an underlayer antireflection film of the present invention include polyamic acids having structures represented by the above formulas (6) and (7). Polyamic acids having the structures represented by the above formulas (6) and (7) are, for example, 4, 4 ′ (hexafluoro (Luoroisopropylidene) diphthalic dianhydride can be obtained by reacting (b) a diamine compound having at least one carboxyl group and (C) a diamine compound.

[0047] The polyamic acid contained in the lower antireflection film-forming composition of the present invention is basically represented by the structure represented by the formula (1) and the formula (2) except for the terminal portion. Or a structure represented by the formula (4) and a structure represented by the formula (5), or a structure represented by the formula (6) and the structure represented by the formula (6) Polyamic acid having a structure and a force represented by the formula (7) can be preferably used.

[0048] Examples of the polyamic acid contained in the composition for forming an underlayer antireflection film of the present invention include the following polyamic acids and formulas (35) to (43) (wherein p, p, p and p are poly

1 2 3 4 represents the proportion of each structure in the amic acid). Here, the formulas (35) to (42) are one kind of tetracarboxylic dianhydride compound and two kinds of diamine compounds, and the polyamic acid produced, and the formula (43) is two kinds of tetracarboxylic dianhydrides. It is a polyamic acid produced from a compound and two diamine compounds.

[0049] [Chemical 8]

[6 ^] [oeoo]

£ LLl0 / S00Zdr / 13d LY

(38)

[0052] [Chemical 11]

(41)

(42) 2]

[0054] <Crosslinking compound>

The underlayer antireflection film-forming composition of the present invention contains a crosslinkable compound having two or more epoxy groups.

[0055] Such a crosslinkable compound is not particularly limited as long as it is a compound having two or more epoxy groups. For example, a compound having 2 to 4 epoxy groups.

[0056] Specific examples of the crosslinkable compound having two or more epoxy groups include tris (2,3 epoxypropyl) isocyanurate, 1,4 butanediol diglycidyl ether, 1,2 epoxy 4 (epoxy ethinole ) Cyclohexane, glyceron tritriglycidino rea Ter, diethylene glycol diglycidyl ether, 2, 6 diglycidyl phenyl glycidyl ether, 1, 1, 3 tris [p— (2, 3 epoxypropoxy) phenol] propane, 1, 2 cyclohexanedicarboxylic acid di Glycidyl ester, 4,4,1-methylenebis (N, N diglycidyl dilin), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether and bisphenol A Examples thereof include diglycidyl ether and pentaerythritol polyglycidyl ether.

[0057] As the compound having two or more epoxy groups, a polymer having an epoxy group can be used. As such a polymer, any polymer having an epoxy group can be used without particular limitation. The polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. Further, it can be produced by a reaction between a polymer compound having a hydroxyl group and a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate. For example, addition polymers such as polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, And polycondensation polymers such as epoxy novolac. The weight average molecular weight of such a polymer is, for example, 500-200000, or 1000-50000.

[0058] Examples of the compound having two or more epoxy groups include YH-434, YH434L (manufactured by Toto Kasei Co., Ltd.), which are epoxy resins having an amino group, and epoxy resins having a cyclohexene oxide structure. EPOLID GT-401, GT-403, GT-301, GT-302, GT 302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.), Epicoat, a bisphenol A type epoxy resin, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, manufactured by Japan Epoxy Resin Co., Ltd.), Epicoat 807, a bisphenol F type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd. Epicoat 152, 154 (above, made by Japan Epoxy Resin Co., Ltd.), EPPN201, 202 (above, made by Nihon Shakuyaku Co., Ltd.), cresol novolac EOCN—102, EOCN—103S, EOCN—104S, EOCN — 1020, EOCN— 1025, EOCN— 1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 18 OS 75 (Japan Epoxy Resin Co., Ltd.), Denacol EX — 252 (Nagase) Chemtex Co., Ltd.), CY175, CY177, CY179 (above, manufactured by CIBA—GEIGY AG), Araldite CY—182, CY—192, CY—184 (above, manufactured by CIBA—GEIGY AG), Epiclon 200 400 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Epicoat 871, 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED 5662 (above, manufactured by Celanese Coating Co., Ltd.) ) And Denacol EX-611, EX-612, EX-612, EX-622, EX-622, EX-411, EX-512, EX-522 and EX--, which are aliphatic polyglycidyl ethers 421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation) are commercially available. Mention may be made of things

[0059] When a non-polymer compound is used as the compound having two or more epoxy groups, for example, 2 to 10, or 2 to 4, or 2 to 3, or 3 to 5 epoxy groups are used. A compound having is preferably used.

[0060] The content of the crosslinkable compound having two or more epoxy groups in the lower antireflection film-forming yarn composition of the present invention is, for example, 5 to 70 parts by mass with respect to 100 parts by mass of the polyamic acid. Or 10 to 60 parts by mass, preferably 15 to 45 parts by mass, or 20 to 40 parts by mass. When the content of the crosslinkable compound having two or more epoxy groups is smaller than the above value, the curing degree of the lower antireflection film is insufficient, which may dissolve in the photoresist solvent and cause intermixing. When the content of the crosslinkable compound having two or more epoxy groups is larger than the above value, sufficient solubility in an alkaline developer used for developing a photoresist cannot be obtained. There is.

[0061] <Aromatic sulfonate ester compound>

The underlayer antireflection film-forming composition of the present invention contains an aromatic sulfonic acid ester compound.

[0062] The aromatic sulfonic acid ester compound is not particularly limited. For example, sulfonic acid alkyl ester compounds having an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a naphthacene ring, and a sulfonic acid aryl ester. Louis compound. Further, examples thereof include sulfonic acid alkyl ester compounds and sulfonic acid aryl ester compounds having an aromatic hetero ring such as a pyridine ring, a furan ring, a quinoline ring, a thiophene ring, a pyrimidine ring, a quinoxaline ring, and a thiadiazole ring.

[0063] The aromatic sulfonic acid ester compound contained in the composition for forming an underlayer antireflection film of the present invention can be obtained by a known method. For example, an aromatic sulfonic acid ester compound can be obtained by reacting an aromatic sulfonyl chloride compound with an alcohol compound or a phenol compound in the presence of a base.

[0064] Here, there are no particular limitations on the aromatic sulfourekudo lydo compound, but examples thereof include benzene senorephonino rechloride, 4-tono reneno enore nonino rechloride, bistrobenzene senorephonyl chloride, 2 , 5 Diclonal benzene sulphonyl chloride, 1, 3 Benzene disreno phononyl chloride, 4 (2-phthalimido) phenol sulphonyl chloride, 2, 4, 6 Trimethylbenzen sulphonyl chloride, 1, 3, 5 Benzene tri Sulfo-chloride, 2, 3, 5, 6-tetramethylbenzene sulphonyl chloride, 4 (trifluoromethyl) benzene sulphonyl chloride, pentamethyl benzene sulphonyl chloride, 4-normal propyl benzene sulphonyl chloride, 4-ethinorebenzene Sunolehoninorechloride, 4-nonolemanolebutinorebenzenesnorejo- Luchloride, 4-biphenylsulfuryl chloride, 4 tert butylbenzenesulfuryl chloride, 4-styrenesulfonyl chloride, 4,4,1 methylenebis (benzenesulphononole chloride), 4,4'-biphenyldisulfuryl chloride, and 4, Benzenesulfuryl chloride compounds such as 4 'bis (chlorosulfuryl) diphenyl ether, naphthalene 1-sulphonyl chloride, naphthalene mono 2-sulfol chloride, 2, 6 naphthalenedisulfuryl chloride, and 1,5 naphthalenedisulfonyl And naphthalenesulfonyl chloride compounds such as chloride. In addition, anthracenesulfuryl chloride compounds such as 2 anthracenesulfuryl chloride and 9 anthracenesulfuryl chloride, and fluorenesulfuryl chloride compounds such as fluorene 2,7 disulfol chloride are exemplified. In addition, thiophene 2-sulfo chloride, 8 quinoline sulfo chloride, 5 quinoline sulfonyl chloride, 2 dibenzofuran sulfo chloride, benzo-2,1,3 triazole 4-sulfo chloride, benzofuran 4 sulfo chloride and 5-isoquinoline sulfonyl chloride, etc. Sulfonyl chloride compounds having an aromatic heterocycle The

[0065] As the alcoholic compound and phenolic compound, there can be used a compound capable of reacting with an aromatic sulfonyl chloride compound without particular limitation to give an aromatic sulfonic acid ester.

[0066] Examples of the alcohol compound include methanol, ethanol, normal pentanol, cyclohexanol, cyclooctanol, decalin 2-ol, 2-ethyl-1-hexanol, 2-ethyl-1,3-hexanediol, 1, Examples include aliphatic alcohol compounds such as 2-cyclohexanediol, 2,2,2-trifluoroethanol, 1H, 1H-perfluoro-1-octanol, 1,2-cyclohexanedimethanol, and 2-tridecanol. . It also has an aromatic hydrocarbon ring or aromatic heterocycle such as benzyl alcohol, 9-hydroxymethylanthracene, phenylethyl alcohol, 1,2-benzenedimethanol, 2-hydroxymethylthiophene, and 2-naphthalenemethanol. Alcohol compound to be used.

[0067] Examples of the phenol compound include phenol, cresol, 2-naphthol, and hydroxyanthracene.

[0068] As the aromatic sulfonic acid ester compound in the lower antireflection film-forming composition of the present invention, a compound having a structure represented by the formula (3) can be used. In the formula (3), Ar is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a nitro group, a cyano group, an amino group, a halogen group, a carboxyl group, and carbon. Substituted with a group selected from the group consisting of 1 to 6 alkoxycarbonyl groups! Represents a benzene ring, naphthalene ring or anthracene ring. R and R are each a hydrogen atom or charcoal

1 2

An alkyl group having 1 to 6 elementary atoms is represented. R and R are bonded to each other to form 3 to

1 2

8 rings may be formed. Examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a normal hexyl group, and a cyclopentyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropyloxy group, a normal hexyloxy group, and a cyclopentyloxy group. Examples of the alkoxycarbo yl group include a methoxy carbo ol group, an ethoxy carbo ol group, an isopropyloxy carbo ol group, and a cyclopentyloxy carbonyl group. Rings with 3 to 8 carbon atoms formed by R and R include cyclo A propyl ring, a cyclobutyl ring, a cyclohexyl ring, and the like. The halogen group includes a fluoro group, a black mouth group, a bromo group, and an iodine group.

[0069] Examples of the compound having the structure represented by the formula (3) include a compound having a structure represented by the formula (44) and a compound represented by the formula (45):

[0070] [Chemical 13]

Ri

—— C-OH (44)

R ₂

O

II

Ar— S-CI (45)

II

o

[0071] can be obtained by reaction with [0071]. The compound having the structure represented by the formula (44) is an alcohol compound, and various alcohol compounds can be used.

[0072] As the aromatic sulfonic acid ester compound in the lower antireflection film-forming composition of the present invention, a compound having 2 to 4, or 2 to 3 structures represented by the formula (3) is used. can do. Such a compound can be obtained, for example, by reacting an alcohol compound having 2 to 4 structures of the formula (44) with a compound of the formula (45).

[0073] Examples of the alcoholic compound having two to four structures of the formula (44) include ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, 1,2,3 propanetriol. , Diethylene glycol, triethylene glycol, pentaerythritol, 1,3 benzenedimethanol, 1,4 benzenedimethanol, 1,2 cyclohexanediol, 1,4-cyclohexanediol, 1,3 cyclopentanediol 1,2-dicyclohexyl lu, 1,2-ethanediol, 1,2-diphenyldiol, 1,2-ethanediol, 3,4 furandol, 1,4 dioxane 2,3 diol, and 1,4 dioxane 2, 5-diol, trimethylolpropane and the like.

[0074] The compound of the formula (45) includes the benzenesulfonyl chloride compound, the na Examples thereof include a phthalene sulfochloride compound and the anthracene sulfochloride compound.

[0075] A compound having two to four structures represented by the formula (3) is synthesized by reacting a compound having the structure represented by the formula (44) with a compound represented by the formula (45). In this case, the compound of the formula (45) can be used alone or in combination of two or more.

[0076] When the lower antireflection film is formed from the lower antireflection film-forming composition of the present invention, a baking step is performed as described below. Therefore, it is more preferable that the aromatic sulfonic acid ester compound used in the composition for forming an underlayer antireflection film of the present invention is not a compound that is easily decomposed by heat. The aromatic sulfonate ester compound used in the lower antireflection film-forming composition of the present invention has a thermal decomposition starting temperature of 100 ° C or higher, or 150 ° C or higher, or 200 ° C or higher, or An aromatic sulfonic acid ester compound having a temperature of 220 ° C or higher or 245 ° C or higher is preferably used. Here, the thermal decomposition start temperature is the weight decrease start temperature obtained by TG measurement (thermogravimetry).

[0077] Specific examples of the aromatic sulfonic acid ester compound used in the composition for forming an underlayer antireflection film of the present invention include, for example, 1, 3 bis (p-toschioxy) propane, 1, 2 bis. (P—Tosioxy) ethane, 1,4 Diol o Tosyl 1,3— o—Isopropylidenethreitol, Triethylene glycol ditosylate, 2,3 Dihydroxybutane 1,4 Dirubis (p—Toluenesulfona 1), tetra (p-toluenesulfo-loxymethyl) methane, 1,2-propanediol p-tosylate, 1,2,4 tritosylbutanetriol, 2,3 butanediol p-tosylate, diethylene glycol di-p-tosylate, N, N-bis (2- (toxixy) ethyl) toluene-4-sulfonamide and 1,3-adamantandi methanoly p-tosylate, 1 monobenzyloxy 3- (p-tosyloxy) -2pronol V-l and the like.

[0078] In the composition for forming a lower antireflection film of the present invention, the aromatic sulfonic acid ester compound can be used alone or in combination of two or more. The content thereof is, for example, 0.1 to 100 parts by mass of polyamic acid, LOO parts by mass, 1 to 50 parts by mass, 2 to 30 parts by mass, or 3 to 20 Parts by mass, and Is 5 to 15 parts by mass. When the content of the aromatic sulfonate ester compound is larger than the above value, the photoresist pattern may be large and undercut, and the dissolution rate of the lower antireflection film in the alkaline developer may be low. May cause problems in removing the lower antireflection coating.

[0079] <Photoacid generator>

The underlayer antireflection film-forming composition of the present invention contains a photoacid generator.

[0080] The photoacid generator is a compound that generates an acid by the action of light when the upper-layer photoresist is exposed by a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or the like. If so, V, deviation can also be used.

[0081] Examples of such a photoacid generator include form salt compounds, sulfonimide compounds, and disulfonyl diazomethane compounds.

[0082] Examples of salt salts include, for example, diphenol rhododone hexafluorophosphatate, diphenyl rhodonordotriolenoroleomethane sulphonate, diphenyl rhododomono nafnoroleolonorema. Norebutans norephonate, diphenol-nouleo-muppernoleolol-normal octane sulfonate, diphenol-nodum camphor sulfonate, bis (4 —tert butylphenol) odonium camphor sulfonate and bis ( 4-tert-butyl) iodo-umtrifluoromethanesulfonate and other ododonium salt compounds; , Triphenylsulfo-mucamphor sulfonate and tri Et - Rusuruho - © beam triflate Ruo B sulfonyl Umushioi 匕合 of such as methane sulfonates.

[0083] Examples of the sulfonimide compound include N- (trifluoromethanesulfo-loxy) succinimide, N- (nonafluoro-normalbutanesulfo-loxy) succinimide, N (camphorsulfo-loxy) succinimide and N (trifluoro Chloromethanesulfoloxy) naphthalimide and the like.

Examples of the disulfo-diazomethane compound include bis (trifluoromethylsulfo) diazomethane, bis (cyclohexylsulfo) diazomethane, bis (phenylsulfo) diazomethane, and bis (p toluenesulfo- ) Diazomethane, bis (2,4 dimethyl) Benzenesulfol) diazomethane, and methylsulfolulu p-toluenesulfol diazomethane.

[0085] In the underlayer antireflection film-forming composition of the present invention, these photoacid generators can be used alone or in combination of two or more. The content of the photoacid generator is, for example, 0.01 to 20 parts by mass, or 0.05 to 10 parts by mass, for example, 0.1 to 100 parts by mass of the polyamic acid. Or 5 to 3 parts by mass, or 0.5 to 3 parts by mass. By adding a photoacid generator, the acidity of the lower antireflection film can be adjusted, and thereby the shape of the photoresist can be controlled. That is, by adding a photoacid generator, a rectangular photoresist pattern can be formed.

[0086] Solvent>

As the solvent used in the composition for forming an underlayer antireflection film of the present invention, any solvent that can dissolve solids can be used. Such solvents include, for example, ethylene glycol monomethenore etherenole, ethylene glycol monomethenore etherenole, methinorecello sonoleb acetate, ethyl acetate sorbacetate, diethylene glycol monomethyl ether, diethylene glycol monorenoethylenore. Ether, Propylene glycol, Propylene glycol monomethinole ether, Propylene glycol nomonomethino ethenore acetate, Propylene glycol propyl ether acetate, Toluene, Xylene, Methyleno ethinoreketone, Cyclopentanone, Cyclohexanone, 2 —Ethyl hydroxypropionate, 2-hydroxyethyl 2-methylpropionate, ethoxy ethoxy acetate, ethyl oxyacetate, 2-hydroxy 3-methylbutanoic acid Til, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, Butyl lactate, N, N dimethylformamide, N, N dimethylacetamide, N-methylpyrrolidone and the like can be used. These solvents can be used alone or in combination of two or more. Further, a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate can be mixed and used. [0087] The prepared solution of the lower antireflection coating resin composition can be used after being filtered using a filter having a pore size of about 0.2 m to 0.05 m. The lower antireflective coating resin composition thus prepared is excellent in long-term storage stability at room temperature.

[0088] <Light Absorbing Compound>

The composition for forming an underlayer antireflection film of the present invention may contain a light-absorbing compound.

The light-absorbing compound is not particularly limited as long as it is a compound having absorption at the wavelength of light used for exposure of a photoresist. A compound having an aromatic ring structure such as an anthracene ring, naphthalene ring, benzene ring, quinoline ring, and triazine ring is preferably used.

[0090] A naphthalene carboxylic acid ester compound can be used as the light-absorbing compound because it has a large absorption with respect to light having a wavelength of 248 nm. For example, 2-hydroxy-3-naphthalenecarboxylic acid methyl ester, 6-hydroxy-2-naphthalenecarboxylic acid benzyl ester, 3-hydroxy-7 methoxy-2-naphthalenecarboxylic acid propyl ester, 3,7 dihydroxy-2 naphthalenecarboxylic acid ethyl ester, etc. Is mentioned.

[0091] Naphthalene carboxylic acid ester compounds other than the above are 1 naphthoic acid, 2 naphthoic acid, 1-hydroxy-2 naphthoic acid, 3 hydroxy-2 naphthoic acid, 3, 7-dihydroxy-2 naphthoic acid, 1,2 naphthalene dicarboxylic acid 1,3 naphthalene dicarboxylic acid, 1,4 naphthalene dicarboxylic acid, 1,5 naphthalene dicarboxylic acid, 1,6 naphthalene dicarboxylic acid, 1,7 naphthalene dicarboxylic acid, 1,8 naphthalene dicarboxylic acid, 2, 3 naphthalene Dicarboxylic acid, 2, 6 Naphthalenedicarboxylic acid, 6 Hydroxy 1 Naphthoic acid, 1-Hydroxy-2 Naphthoic acid, 3 Hydroxy-2 Naphthoic acid, 6 Hydroxy-2 Naphthoic acid, 1-bromo-2 Hydroxy-3 naphthoic acid, 1-bromo 4-hydroxy-3 naphthoic acid 1,6 Jib mouth Moe 2 Hydroxy-3 Naphthoic acid, 3-H Droxy-7-methoxy-2-naphthoic acid, 1, 4, 5, 8 naphthalenetetracarboxylic acid, 3,5 dihydroxy-2 naphthoic acid, 1,4-dihydroxy-2 naphthoic acid, 2 ethoxy 1 naphthoic acid, and 6-acetoxy 2 naphthoic acid Naphthalenecarboxylic acid compounds such as methanol, ethanol, normal pentanol, 9-hydroxymethylan Examples thereof include naphthalenecarboxylic acid ester compounds obtained by esterification with alcohol compounds such as tracene, cyclohexanol and benzyl alcohol.

[0092] Further, naphthalenecarboxylic acid ester compounds obtained by the reaction of the naphthalenecarboxylic acid compound and the epoxy compound are mentioned. In this reaction, a reaction takes place between the carboxyl group of the naphthalene strength rubonic acid compound and the epoxy ring, and a naphthalene strength rubonic acid ester compound is obtained.

[0093] Examples of the epoxy compound include tris (2,3 epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2 epoxy 1-4 (epoxyethyl) hexane, glycerol triglycidyl ether, diethylene glycol diglycidyl. Ether, 2,6-diglycidylphenol-glycidyl ether, 1,1,3 tris (p- (2,3 epoxypropoxy) phenyl) propane, 1,2 dicyclohexylidenoleestenole, 1,2 cyclohexanedicarboxylic acid, 4 , 4'-methylenebis (N, N-diglycidyl dilin), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, trimethylol ethane triglycidyl ether, bisphenol A-diglycidyl ether, and Pentaerythritol polyglycidylate The compounds of the like. Moreover, as an epoxy compound, the polymer containing the structure which has epoxy groups, such as glycidyl metatalylate, can be mentioned.

[0094] The reaction of the naphthalenecarboxylic acid compound with the epoxy compound is carried out by reacting benzene, toluene, xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and N-methyl. It can be carried out in an organic solvent such as pyrrolidone. In this reaction, a quaternary ammonium salt such as benzyltriethylammonium chloride, tetraptylammonium chloride, and tetraethylammonium chloride can be used as a catalyst. The reaction temperature and reaction time depend on the compound used, concentration, etc. Force Reaction time 0.1 to: LOO time, reaction temperature 20 ° C to 200 ° C. When a catalyst is used, it can be used in the range of 0.001 to 30% by mass with respect to the total mass of the compound to be used.

[0095] Obtained by reacting the naphthalenecarboxylic acid compound with the epoxy compound Examples of the light-absorbing compound include a polymer having a unit structure represented by formula (46) and formula (47), a compound represented by formula (48), and the like. In formula (48), Np represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a hydroxyl group, or a carboxyl group. A naphthalene ring group which may be substituted with a group, a phenoxy group, a acetyl group or an alkoxycarbo group having 1 to 5 carbon atoms. The compound represented by the formula (48) can be obtained by reacting tris (2,3 epoxypropyl) isocyanurate with a naphthalenecarboxylic acid compound.

[0096] [Chemical 14]

[0097] Further, as the light-absorbing compound, tris (2,3 epoxypropyl) isocyanurate, 1-hydroxy 2 naphthoic acid, 3 hydroxy 2 naphthoic acid, 3, 7 dihydroxy 2 naphthoic acid, 1,2 naphthalene Dicarboxylic acid, 1,4 Naphthalenedicarboxylic acid, 1,5 Naphthalene dicarboxylic acid, 2,3 naphthalene dicarboxylic acid, 2,6 naphthalene dicarboxylic acid, 6 hydroxy-1 naphthoic acid, 3 hydroxy-2 naphthoic acid, 1 bromo 2 hydroxy-3 naphthoic acid, 1-bromo 4-hydroxy-3 naphthoic acid, 1,6 Naphthalene carboxylic acid compounds such as -dibromo 2 hydroxy 3 naphthoic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,5 dihydroxy-2 naphthoic acid, and 1,4-dihydroxy-2 naphthoic acid A naphthalenecarboxylic acid ester compound obtained by reacting is preferred.

[0098] The absorbent compound can be used alone or in combination of two or more. When a light-absorbing compound is used, the content thereof is, for example, 1 to 300 parts by weight, or 3 to 200 parts by weight, for example 5 parts to 100 parts by weight of polyamic acid. ~: LOO parts by mass or 10-50 parts by mass. When the content of the absorbent composite is larger than the above value, the solubility of the lower antireflection film in the alkaline developer may be lowered. By changing the type and content of the light-absorbing compound, the attenuation coefficient (k value) of the lower-layer anti-reflection film can be adjusted.

[0099] <Aromatic carboxylic acid compound>

The lower antireflection film-forming composition of the present invention can contain an aromatic carboxylic acid compound. By using the aromatic carboxylic acid compound, the dissolution rate of the lower antireflection film to be formed in the alkaline developer can be adjusted.

[0100] The aromatic carboxylic acid compound is not particularly limited, and examples thereof include aromatic rings such as a benzene ring, naphthalene ring, anthracene ring, pyridine ring, thiophene ring, quinoxaline ring, quinoline ring, and benzothiazole ring. The aromatic carboxylic acid compound having the above can be used.

[0101] Examples of aromatic carboxylic acid compounds include, for example, benzoic acid, pyromellitic acid, phthalic acid, trimeric acid, 4 sulfophthalic acid, benzenehexacarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 3, 3 ', 4, 4,-biphenyl tetracarboxylic acid, 3, 3', 4, 4,-benzophenol tetracarboxylic acid, 3, 3 ', 4, 4, diphenyl ether tetracarboxylic acid, 3, 3 4,4'-diphenylsulfonetetracarboxylic acid, 2 naphthoic acid, thiophene 2 carboxylic acid and 9 anthracene carboxylic acid.

[0102] Further, from the viewpoint of solubility in alkaline developer and! / ヽぅ, it has a phenolic hydroxyl group. Aromatic carboxylic acid compounds can be used.

[0103] Examples of aromatic carboxylic acid compounds having a phenolic hydroxyl group include phenols such as hydroxybenzoic acid, 4-hydroxyphthalic acid, 3,4-dihydroxyphthalic acid, and 4,5-dihydroxyphthalic acid. Benzoic acid compounds having a reactive hydroxyl group, and 2-hydroxy-3 naphthoic acid, 2-hydroxy-1 naphthoic acid, 8 hydroxy-1 naphthoic acid and 3,7 dihydroxy 2 naphthoic acid-containing naphthalene carboxylic acid Examples of such compounds are listed.

[0104] The aromatic carboxylic acid compound can be used alone or in combination of two or more. When an aromatic carboxylic acid compound is used, the content thereof is, for example, 1 to: LOO parts by mass, or 3 to 50 parts by mass with respect to 100 parts by mass of polyamic acid. -30 mass parts, or 10-20 mass parts. If the content of the aromatic carboxylic acid compound is larger than the above value !, the solubility of the lower antireflection film in the alkaline developer becomes too high, which may cause problems such as poor pattern shape.

[0105] The lower-layer antireflection film-forming composition of the present invention may further contain a surfactant, a rheology adjusting agent, an adhesion aid, and the like, if necessary.

[0106] Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene ethylene ether, polyoxyethylene octyl phenol ether, Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sonorebitan monostearate, sorbitan monooleate, Sorbitan fatty acid esters such as sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxy Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (manufactured by Gemco Co., Ltd.), Mega-Fac F171, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo) Fluorosurfactants such as Asamhiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), Organosiloxane polymer KP341 (Shin-Etsu)匕を挙げる学工業 Co., Ltd.). The amount of these surfactants to be added is generally 0.2% by mass or less, preferably 0.1% by mass or less, based on all components of the composition for forming an underlayer antireflection film of the present invention. These surfactants may be added singly or in combination of two or more.

[0107] Hereinafter, the use of the lower antireflection film-forming composition of the present invention will be described.

[0108] On a semiconductor substrate (for example, a silicon Z-dioxide-silicon-coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, etc.) The lower-layer antireflection film-forming composition of the invention is applied and then baked to form a lower-layer antireflection film. As conditions for firing, medium strength of firing temperature of 80 ° C to 300 ° C and firing time of 0.3 to 60 minutes is appropriately selected. Preferably 150. C-250. C, 0.5-2 minutes.

[0109] The dissolution rate in the alkaline developer used to develop the lower antireflection film and photoresist formed is 0. Inn! ˜50 nm, preferably 0.2 nm to 40 nm per second, more preferably 0.3ηπ! ~ 20nm. If the dissolution rate is smaller than this, the time required to remove the lower antireflection film becomes longer, leading to a decrease in productivity. If the dissolution rate is higher than this, the lower antireflection film below the unexposed portion of the photoresist also dissolves, and as a result, a photoresist pattern may not be formed.

[0110] The lower antireflection film formed from the lower antireflection film-forming composition of the present invention can control the dissolution rate of the lower antireflection film in an alkaline developer by changing the baking conditions at the time of formation. it can. In the case of a certain baking time, the lower the antireflection film having a lower dissolution rate in the alkaline developer, the higher the baking temperature.

Next, a photoresist layer is formed on the lower antireflection film. The formation of the photoresist layer can be performed by a general method, that is, by applying a photoresist solution onto the lower antireflection film and baking.

[0112] The photoresist formed on the lower antireflection film of the present invention is used for exposure. As long as it is sensitive to light, there is no particular limitation, and a shift between negative and positive photoresists can be used. Examples of such photoresists include novolak resin, 1,2-naphthoquinonediazide sulfonate ester and powerful positive photoresist, a binder having a group that decomposes with an acid to increase the alkali dissolution rate, and a photoacid generator. Chemically amplified photoresist that can be decomposed by acid, chemically amplified photoresist composed of a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator. There are chemically amplified photoresists composed of a photoacid generator and a low molecular weight compound that decomposes with a noinder having a group that increases the rate and an acid to increase the alkali dissolution rate of the photoresist. Further, for example, trade name A PEX-E manufactured by Shipley Co., Ltd., trade name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and trade name SE PR430 manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.

[0113] Next, exposure is performed through a predetermined mask. For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 ηm), or the like can be used. After exposure, if necessary, post exposure bake can be performed.

[0114] Next, development is performed with an alkaline developer. Thus, for example, when a positive photoresist is used, the exposed portion of the photoresist and the lower layer antireflection film in the lower layer portion are removed by development to form a photoresist pattern.

[0115] Alkaline developers used for developing photoresists include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, hydroxide tetramethylammonium, water. Examples include aqueous solutions of quaternary ammonium hydroxides such as tetraethyl ammonium oxide and choline, and alkaline aqueous solutions such as aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 ° C to 50 ° C and a time of 10 to 300 seconds.

[0116] bottom anti-reflective coating which is bottom anti-reflective coating forming composition mosquitoゝet form of the invention, Mizusani匕tetramethylammonium of 2.38 mass ^_0/0, which is widely used as the alkaline developer - Development can be easily carried out at room temperature using an aqueous solution of sulfur. [0117] The lower antireflection film of the present invention is a layer for preventing the interaction between the semiconductor substrate and the photoresist, the material used for the photoresist, or the adverse effect on the substrate of the substance generated during exposure to the photoresist. As a layer for preventing diffusion of the material generated from the substrate during heating and baking into the upper photoresist, and a noria layer for reducing the bisting effect of the photoresist layer by the semiconductor substrate dielectric layer It can also be used.

[0118] Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example

[0119] Example 1

(Synthesis of polyamic acid)

4,4,1 (Hexafluoroisopropylidene) diphthalic dianhydride 17.8 g, 3,5-diaminobenzoic acid 3.12 g and bis (4-aminophenol) sulfone 4.92 g A solution [A] containing polyamic acid was obtained by reacting in 145.6 g of coal monomethyl ether at 80 ° C. for 20 hours. The obtained polyamic acid had a structure represented by formula (49) and formula (50).

[0120] [Chemical 15]

(50) [0121] (Synthesis of light absorbing compounds)

3, 7-Dihydroxy-1-naphthoic acid 19. Og, 10 g of tris (2,3-epoxypropyl) isocyanurate and benzyltriethylammonium chloride 0.552 g in 118 g of cyclohexanone at 130 ° C The mixture was reacted for 24 hours to obtain a solution [a] containing the light-absorbing compound represented by the formula (51).

[0122] [Chemical 16]

[0123] (Preparation of composition for forming antireflection film for lower layer)

Solution containing polyamic acid [A] 25. Og and solution containing light-absorbing compound [a] 4. 15 g, 4, 4, 1 methylene bis (N, N-diglycidyl dilin) 1. 13 g, 3, 7-dihydroxynaphthoic acid 0.825 g, 1,3-bis (p-tosuccinoxy) pronone 0.206 g, triphenylsulfur trifluoromethanesulfonate 0.124 g, propylene glycol monomethyl ether 82.8 g, 127 g of propylene glycol monomethyl ether acetate and 10. Og of cyclohexanone were added, and the mixture was stirred at room temperature for 30 minutes to prepare a solution [1] of the lower antireflection film forming composition.

[0124] Thermogravimetric measurement of 1,3-bis (p-toshiguchixy) propane was performed (device used; SSCZ5200, manufactured by Seiko Instruments Inc., measurement conditions; measurement range 30 ° C) The starting temperature of weight reduction was 250 ° C.

[0125] (Evaluation of lower antireflection film) After applying the lower-layer antireflection film-forming composition solution [1] onto a silicon wafer substrate using a spinner, baking was performed on a hot plate at 175 ° C for 1 minute to form a 40-nm-thick lower-layer antireflection film. did. The resulting underlayer anti-reflection film was insoluble in propylene glycol, ethyl lactate and propylene glycol monomethyl ether acetate. As a result of measuring the lower antireflection film with an ellipsometer, the refractive index (n value) at a wavelength of 248 nm was 1.80, and the attenuation coefficient (k value) was 0.44. The refractive index (n value) at a wavelength of 193 nm was 1.52, and the attenuation coefficient (k value) was 0.44.

[0126] In addition, a lower antireflection film was formed in the same manner as described above at a firing temperature of 170 ° C and 180 ° C. Then, it was confirmed that these lower antireflection films were insoluble in ethyl lactate and propylene glycol monomethyl ether acetate.

[0127] Next, the dissolution rate of the lower antireflection film in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution: Tokyo Oka Kogyo Co., Ltd., product name NMD-3) was measured using a resist developer analyzer (litho Measured using Tech Japan Co., Ltd. The dissolution rate of the lower antireflection film formed at a firing temperature of 175 ° C. and a firing time of 1 minute was 1.74 nm per second. The dissolution rate of the lower antireflection film formed at a firing temperature of 170 ° C and a firing time of 1 minute is 2.35 nm per second, and the dissolution rate of the lower antireflection film formed at a firing temperature of 180 ° C and a firing time of 1 minute is 1.48 nm per second.

[0128] The lower layer antireflection film-forming composition solution [1] was applied onto a silicon wafer substrate using a spinner and then baked on a hot plate at 175 ° C for 1 minute to prevent the lower layer antireflection film with a thickness of 40 nm. A film was formed. A positive photoresist for ArF was formed on the lower antireflection film, and exposed with an ArF excimer laser (wavelength: 193 nm) through a mask set to form a 7 Onm line Z space pattern. After exposure and heating at 110 ° C. for 60 seconds, paddle development was performed for 60 seconds using 2.38% tetramethylammonium hydroxide aqueous solution (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.). The exposed part of the lower anti-reflective coating as well as the photoresist was dissolved, and the residual film of the lower anti-reflective coating was strong even in the 70 nm line Z space. The pattern formed was a rectangular shape for both the photoresist and the lower antireflection film.

[0129] Comparative Example 1 (Preparation of lower antireflection film-forming composition)

Solution containing polyamic acid [A] 25. Og and solution containing light-absorbing compound [a] 4. 15 g, 4, 4, 1 methylene bis (N, N-diglycidyl dilin) 1. 13 g, 3, 7-dihydroxynaphthoic acid 0.825 g, propylene glycol monomethyl ether 82.8 g, propylene glycol monomethyl ether acetate 127 g, and cyclohexanone 10. Og was added and stirred at room temperature for 30 minutes to form a lower antireflection film composition A product solution [2] was prepared.

[0130] (Evaluation of lower antireflection film)

The lower antireflection film-forming composition solution [2] was applied onto a silicon wafer substrate using a spinner, and then baked on a hot plate at 175 ° C. for 1 minute to form a lower antireflection film having a thickness of 40 nm. Formed. The obtained lower antireflection film was insoluble in propylene glycol, lactate ethyl and propylene glycol monomethyl ether acetate. As a result of measuring this lower antireflection film with an ellipsometer, the refractive index (n value) at a wavelength of 248 nm is 1.82, the attenuation coefficient (k value) is 0.42, and the refractive index (n value) at a wavelength of 193 nm is The coefficient of attenuation was 1.51, and the attenuation coefficient (k value) was 0.42.

[0131] Further, a lower antireflection film was similarly formed at a firing temperature of 170 ° C and 180 ° C. Then, it was confirmed that these lower antireflection films were insoluble in ethyl acetate and propylene glycol monomethyl ether acetate.

[0132] Next, the dissolution rate of the lower antireflection film in 2.38% tetramethylammonium hydroxide aqueous solution (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used as a resist development analyzer (Risotech Japan Co., Ltd.) ). The dissolution rate of the lower antireflection film formed at a firing temperature of 175 ° C and a firing time of 60 seconds was 2.40 nm per second. The dissolution rate of the lower antireflection film formed at a firing temperature of 170 ° C and a firing time of 1 minute was 2.65 nm per second, the dissolution rate of the lower antireflection film formed at a firing temperature of 180 ° C and a firing time of 1 minute. Was 2.03 ηm per second.

[0133] The lower antireflection film forming composition solution [2] was applied onto a silicon wafer substrate using a spinner and then baked on a hot plate at 175 ° C for 1 minute to prevent the lower layer antireflection film with a thickness of 40 nm. A film was formed. A positive photoresist for ArF is formed on the lower antireflection film, and the ArF is passed through a mask set to form a 7 Onm line Z space pattern. Exposed with an excimer laser (wavelength 193 nm). After exposure and heating at 110 ° C. for 60 seconds, paddle development was performed for 60 seconds using 2.38% tetramethylammonium hydroxide aqueous solution (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.). The photoresist was in the footing shape. Further, the lower antireflection film was not completely dissolved, and the presence of a residual film was observed.

[0134] Comparative Example 2

(Preparation of lower antireflection film-forming composition)

Solution containing polyamic acid [A] 25. Og and solution containing light-absorbing compound [a] 4. 15 g, 4, 4, 1 methylene bis (N, N-diglycidyl dilin) 1. 13 g, 3, 7-Dihydroxynaphthoic acid 0.825 g, Triphenylsulfo-mu-trifluoromethanesulfonate 0. 124 g, Propylene glycol-monoremonomethinoreether 82.8 g, Propyleneglycololemonomethylenoatenole acetate 127 g, and Cyclohe Xanone 10. Og was added, and the mixture was stirred at room temperature for 30 minutes to prepare a solution [3] of the lower antireflection film-forming composition.

[0135] (Evaluation of lower antireflection film)

After applying this lower-layer antireflection film-forming composition solution [3] onto a silicon wafer substrate using a spinner, it was baked on a hot plate at 175 ° C. for 1 minute to form a lower-layer antireflection film having a thickness of 40 nm. Formed. The obtained lower antireflection film was insoluble in propylene glycol, lactate ethyl and propylene glycol monomethyl ether acetate. As a result of measuring this lower antireflection film with an ellipsometer, the refractive index (n value) at a wavelength of 248 nm is 1.80, the attenuation coefficient (k value) is 0.44, and the refractive index (n value) at a wavelength of 193 nm is 1. 50 and the damping coefficient (k value) was 0.44.

[0136] Further, an antireflection film was similarly formed at a firing temperature of 170 ° C and 180 ° C. Then, it was confirmed that these lower antireflection films were insoluble in ethyl lactate and propylene glycol monomethyl ether acetate.

[0137] Next, the dissolution rate of the lower antireflection film in 2.38% tetramethylammonium hydroxide aqueous solution (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used as a resist development analyzer (Risotech Japan Co., Ltd.) ). The dissolution rate of the lower antireflection film formed at a firing temperature of 175 ° C and a firing time of 1 minute was 2. OOnm per second. In addition, the dissolution rate of the lower antireflection film formed at a baking temperature of 170 ° C. and a baking time of 1 minute was 2.35 nm per second. The dissolution rate of the lower antireflection film formed at a deposition temperature of 180 ° C. and a baking time of 1 minute was 1.8 2 nm per second.

After applying the lower-layer antireflection film-forming composition solution [3] onto a silicon wafer substrate using a spinner, baking is performed at 175 ° C for 1 minute on a hot plate to form a 40-nm-thick lower-layer antireflection film. did. A positive photoresist for ArF was formed on the underlayer anti-reflection film, and exposed with an ArF excimer laser (wavelength: 193 nm) through a mask set to form a 70 nm line Z space pattern. After exposure and heating at 110 ° C. for 60 seconds, paddle development was performed for 60 seconds using 2.38% tetramethylammonium hydroxide aqueous solution (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.). The photoresist was in the footing shape. Further, the lower antireflection film was not completely dissolved, and the presence of a residual film was observed.

Claims

Claims In the composition for forming an underlayer antireflection film for forming an underlayer antireflection film that is developed together with a photoresist with an alkaline developer, the formulas (1) and (2):

[Chemical 1]

(In the formula, A and A represent a tetravalent organic group, B represents a trivalent organic group, and B represents a divalent organic group.

1 2 1 2

A lower layer characterized in that it contains a polyamic acid having a structure represented by the following formula: a bridged compound having two or more epoxy groups, an aromatic sulfonic acid ester compound, a photoacid generator and a solvent. Anti-reflective film forming composition.

[2] The lower-layer antireflection film-forming composition according to claim 1, further comprising a light-absorbing compound.

[3] The composition for forming an underlayer antireflection film according to claim 1, further comprising an aromatic carboxylic acid compound.

[4] The composition for forming an underlayer antireflection film according to [1], wherein the crosslinkable compound is a compound having 2 to 4 epoxy groups.

[5] The composition for forming a lower antireflection film according to [1], wherein the photoacid generator is an iodine salt compound or a sulfoyuum salt compound.

[6] The aromatic sulfonic acid ester compound is represented by the formula (3):

[Chemical 2]

(In the formula, Ar is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a nitro group, a cyano group, an amino group, a halogen group, a carboxyl group, and 1 carbon atom. Group power consisting of an alkoxy carbo group of ~ 6 substituted with a selected group !, may! /, Represents a benzene ring, a naphthalene ring or an anthracene ring, and R and R are each independently

1 2

Then, a ring having 3 to 8 carbon atoms may be formed. 2. The composition for forming an underlayer antireflection film according to claim 1, wherein the composition has a structure represented by:

[7] The lower antireflection film forming set according to [1], wherein the aromatic sulfonic acid ester compound is a compound having two to four structures represented by the formula (3).

Adult.

[8] The antireflection film-forming composition according to [2], wherein the light-absorbing compound is a naphthalenecarboxylic acid ester compound.

[9] The composition for forming an underlayer antireflection film according to claim 8, wherein the composition is a compound produced by reacting a naphthalenecarboxylic acid compound with an epoxy compound. .

10. The lower antireflection film-forming composition according to claim 3, wherein the aromatic carboxylic acid compound is an aromatic carboxylic acid compound having a phenolic hydroxyl group.

[11] The composition for forming a lower antireflection film according to [3], wherein the aromatic carboxylic acid compound is a naphthalenecarboxylic acid compound having a phenolic hydroxyl group.

[12] The polyamic acid is represented by the formula (4) and the formula (5):

[Chemical 3]

(Wherein Α and Α represent a tetravalent organic group) is a polyamic acid having a structure represented by

1 2

The composition for forming an underlayer antireflection film according to claim 1, wherein:

[13] The polyamic acid is represented by the formula (6) and the formula (7):

[Chemical 4]

(Wherein B represents a trivalent organic group and B represents a divalent organic group).

1 2

2. The composition for forming a lower antireflection film according to claim 1, wherein the composition is a polyamic acid.

A process of forming a lower antireflection film by applying the lower layer antireflection film-forming composition according to any one of claims 1 to 13 on a semiconductor substrate and baking the composition, the lower antireflection film Manufacturing a semiconductor device, comprising: forming a photoresist layer on the film; exposing the semiconductor substrate covered with the lower antireflection film and the photoresist layer; and forming an image with an alkaline developer after the exposure Of forming a photoresist pattern for use in the process.