TW201708322A - Polymer, radiation-sensitive composition, and method of forming pattern - Google Patents

Abstract

The present invention provides a polymer which is highly sensitive and is capable of forming a fine pattern, a photoresist material comprising the polymer, a radiation-sensitive composition comprising the polymer, and a method of forming a photoresist pattern. The present invention provides a polymer comprising a structural unit represented by general formula (1): in general formula (1), m1, m2=1 to 8, n1, n2=0 to 7, m1+n1, m2+n2=4 to 8; y is 0 to 2; R1 is a hydroxy group, a substituted or unsubstituted straight, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a hlogen atom; R3 is a hydrogen atom, a substituted or unsubstituted straight, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group; R2 is any of the structures represented by general formula (2) shown in the specification. At least one of R2 has an acid-dissociable group. R5 is a hydroxy group, -O-R2-O-*, -O-R2-O-R55. R6 is a hydroxy group or -O-R2-O-*.

Description

Polymer compound, radiation sensitive linear composition and pattern forming method

The present invention relates to a polymer compound and a radiation-sensitive linear composition and a photoresist pattern forming method using the same.

With the miniaturization of semiconductor elements, development of a lithography process using, for example, extreme ultraviolet light (13.5 nm) or electron lines has been intensively developed. On the basis of the base material of the base of the chemically sensitized positive type resist, the novolak type phenol type resin and the polyhydroxy styrene type resin which are the polymer type photoresist materials are mainly reviewed. (Meth)acrylic resin. However, the polymer photoresist material has a molecular weight of about 10,000 to 100,000 and a broad molecular weight distribution. Therefore, the use of the lithography of the polymer-based photoresist material has a problem that roughness is generated on the surface of the fine pattern. Therefore, recently, a polyphenol-based compound or a calixarene-based compound of a low-molecular-based photoresist material has been introduced into a compound which can be decomposed by an acid to be decomposed, and its development is prosperous. A report example of a polymer-based photoresist material which can reduce the roughness of a fine pattern. Also, used as a low molecular weight photoresist material Since the calixarene-based compound has a rigid ring structure on the main skeleton, it is expected to have sufficient heat resistance required for pattern formation.

As the acid dissociable functional group, a monofunctional alkoxymethyl group, an alkoxyethyl group, and a tertiary alkoxy group can be mainly used (for example, refer to Patent Document 1 below).

In addition, in order to reduce the roughness of the pattern obtained by using the polymer material or to suppress the collapse of the pattern, there are many reviews using polyfunctional acid dissociable functional groups (for example, refer to the following Patent Documents 2 to 7). ).

In addition, a positive-type photoresist material having a main chain-cut type is proposed by reacting a calixarene-based compound having a rigid ring-shaped structure with a polyfunctional acid-dissociable functional group (for example, refer to Patent Document 8).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-173623

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-344808

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-098613

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-308977

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2006-2073

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2006-3846

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2007-206371

[Patent Document 8] International Publication No. 2012/014435

However, when a compound having an acid-dissociable functional group described in Patent Document 1 is introduced, there is a problem that a fine pattern is liable to collapse. Further, the photoresist material described in Patent Document 8 is limited in resolution, and there is room for improvement from this viewpoint.

An object of the present invention is to provide a polymer compound having high sensitivity and obtaining a fine pattern, and a radiation-sensitive composition and a pattern forming method containing the compound.

The present inventors have found that a polymer having a specific structure can solve the above problems, and the present invention has been made in order to solve the above problems.

That is, the present invention is as follows.

<1> A polymer compound comprising a unit structure represented by the following general formula (1).

(In general formula (1), m ₁ is an integer from 1 to 8, n ₁ is an integer from 0 to 7, m ₁ + n ₁ = an integer from 4 to 8, m ₂ is an integer from 1 to 8, and n ₂ is An integer from 0 to 7, m ₂ +n ₂ = an integer from 4 to 8, y each independently an integer from 0 to 2, and R ¹ are each independently a hydroxyl group, a substituted or unsubstituted carbon number of 1 to 20 a branch having a carbon number of 3 to 20 or a cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a halogen atom, and each of R ^{3 is} independently a hydrogen atom. , substituted or unsubstituted, a straight chain having a carbon number of 1 to 20, a branched chain having a carbon number of 3 to 20, a cyclic alkyl group having a carbon number of 3 to 20, or a substituted or unsubstituted carbon number of 6 to 20 Each of R ^{2 is} independently a structure represented by the following general formula (2): However, at least one R ² has an acid dissociable moiety. R ⁵ is a hydroxyl group, -OR ² -O-* (* indicates a bonding site between the unit structures.), or -OR ² -OR ⁵⁵ (R ⁵⁵ is another R ⁵ in the general formula (1)). R ⁶ is a hydroxyl group, or -OR ² -O-* (* indicates The bonding part between the above unit structures.))

(In the general formula (2), R ⁴ is a substituted or unsubstituted linear group having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, or substituted. Or an unsubstituted carbon number of 6 to 20 aryl.)

<2> The polymer compound according to the above <1>, wherein, in the general formula (1), R ³ is substituted or unsubstituted, and has a linear chain of 1 to 10 carbon atoms and a branch of 3 to 20 carbon atoms. a cyclic or alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

<3> A radiation-sensitive linear composition comprising the polymer compound according to <1> or <2> above.

<4> The radiation sensitive composition according to <3> above, which further comprises a solvent.

<5> A pattern forming method comprising: a film forming step of forming a film on a substrate using the radiation sensitive composition of <3> or <4>, an exposure step of exposing the film, and The exposed film in the aforementioned exposure step is developed to form a pattern development step.

According to the present invention, it is possible to provide a polymer compound having a high sensitivity and a fine pattern, a photoresist material containing the compound, a radiation sensitive composition, and a photoresist pattern forming method.

Fig. 1 is a chart showing the ¹ H-NMR spectrum of the compound obtained in Example 1.

Fig. 2 is a graph showing the IR spectrum of the compound obtained in Example 1.

[Formation of the Invention]

Hereinafter, an embodiment of the present invention will be described (hereinafter referred to as "this embodiment"). Further, the present embodiment is intended to be illustrative of the present invention, and the present invention is not limited to the embodiment.

[polymer compound]

The polymer compound of the present embodiment contains a polymer having a unit structure represented by the following general formula (1).

(In general formula (1), m ₁ is an integer from 1 to 8, n ₁ is an integer from 0 to 7, m ₁ + n ₁ = an integer from 4 to 8, m ₂ is an integer from 1 to 8, and n ₂ is An integer from 0 to 7, m ₂ +n ₂ = an integer from 4 to 8, y each independently an integer from 0 to 2, and R ¹ are each independently a hydroxyl group, a substituted or unsubstituted carbon number of 1 to 20 a branch having a carbon number of 3 to 20 or a cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a halogen atom, and each of R ^{3 is} independently a hydrogen atom. , substituted or unsubstituted, a straight chain having a carbon number of 1 to 20, a branched chain having a carbon number of 3 to 20, a cyclic alkyl group having a carbon number of 3 to 20, or a substituted or unsubstituted carbon number of 6 to 20 Each of R ^{2 is} independently a structure represented by the following general formula (2): However, at least one R ² has an acid dissociable moiety. R ⁵ is a hydroxyl group, -OR ² -O-* (* indicates a bonding site between the unit structures.), or -OR ² -OR ⁵⁵ (R ⁵⁵ is another R ⁵ in the general formula (1)). R ⁶ is a hydroxyl group, or -OR ² -O-* (* indicates The bonding part between the above unit structures.))

(In the general formula (2), R ⁴ is a substituted or unsubstituted linear group having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, or substituted. Or an unsubstituted carbon number of 6 to 20 aryl.)

As described above, the polymer compound of the present embodiment has a specific structure and is highly sensitive, and when used as a radiation-sensitive composition, a fine pattern can be obtained. Further, the polymer compound of the present embodiment can improve the solubility in a safe solvent as needed, can easily control the production, and can easily stabilize the quality.

First, the structure of the polymer compound of the present embodiment will be described. As shown below, the polymer compound of the present embodiment contains a unit structure (hereinafter referred to as "C") represented by the general formula (1). The number of the unit structures represented by the general formula (1) contained in the polymer compound of the present embodiment is not particularly limited, but from the viewpoint of resolution, it is preferably from 1 to 100, and from the viewpoint of roughness. It is better from 1 to 50, and from the point of view of sensitivity, it is particularly good from 1 to 10. When the polymer compound of the present embodiment has a plural unit structure, the unit structures are bonded to each other by "-OR ² -O-*" in R ⁵ or R ⁶ in the general formula (1). In other words, when the polymer compound of the present embodiment has a plural unit structure, the structural unit represented by the general formula (1) has -OR ² -O-* as R ⁵ or R ⁶ . The polymer compound of the present embodiment may include a constituent unit other than the unit structure represented by the general formula (1), within a range that does not inhibit the effects of the present invention. The unit structure other than the unit structure represented by the general formula (1) may be, for example, a structure formed only by an upper or lower annular structure as described later. Further, the polymer compound of the present embodiment may be composed only of the same unit structure, or may be composed of two or more constituent units.

Further, the unit structure of the polymer compound of the present embodiment is composed of two annular structures. In the present specification, in the above general formula (1), the annular structure in the direction on the paper surface is the "upper annular structure" (the aforementioned "A"), and the annular structure in the downward direction of the paper surface is "Lower ring structure"("B" above). However, among the actual compounds, the upper annular structure and the lower annular structure are not distinguishable. Each of the ring structures has two kinds of benzene ring structures. For example, the upper annular structure includes a benzene ring structure (the aforementioned "A1") having a portion bonded to the lower annular structure and R ⁵ , and a benzene ring structure having the R ⁶ (the aforementioned "A2"). Similarly, the lower annular structure includes a benzene ring structure (the aforementioned "B1") having a portion bonded to the upper annular structure and R ⁵ , and a benzene structure having the R ⁶ (the aforementioned "B2"). In the present specification, these are appropriately referred to as benzene ring structures A1 to B2.

In the polymer compound of the present embodiment, the upper annular structure and the lower annular structure are each a benzene ring structure bond to form a ring structure. That is, m ₁ benzene ring structure A1 is bonded to n ₁ benzene ring structure A2 to form an upper ring structure. Similarly, the lower annular structure is composed of m ₂ benzene ring structures B1 and n ₂ benzene ring structures B2. At this time, the upper ring configuration m ₁ benzene rings structure A1 with n ₁ or the arrangement structure of benzene ring A2, the lower ring configuration m ₂ benzene rings structure B1 and n ₂ benzene rings The arrangement of the structures B2 may be arranged arbitrarily or regularly, or may be arranged randomly.

In the general formula (1), m ₁ is an integer of 1 to 8, n ₁ is an integer of 0 to 7, and m ₁ + n ₁ = an integer of 4 to 8. Although it is not particularly limited, it is preferable that m ₁ is an integer of 2 to 6, n ₁ is an integer of 2 to 6, and m ₁ + n ₁ is preferably an integer of 2 to 8.

In the general formula (1), m ₂ is an integer of 1 to 8, n ₂ is an integer of 0 to 7, and m ₂ + n ₂ = an integer of 4 to 8. Although it is not particularly limited, it is preferable that m ₂ is an integer of 2 to 6, n ₂ is an integer of 2 to 6, and m ₁ + n ₁ is preferably an integer of 2 to 8.

Further, when the polymer compound of the present embodiment contains a plurality of constituent units represented by the general formula (1), m ¹ , m ² , n ¹ and n ² in each constituent unit may be the same between the respective constituent units. Can also be different.

For example, in the upper ring structure, the benzene ring structures A1 and A2 can be used as a bonding site for the upper ring structure with carbon at the 3 position of the benzene ring and carbon at the 5 position. The benzene ring structures B1 and B2 in the lower ring structure are also the same.

R ^{1 is} independently a hydroxyl group, a substituted or unsubstituted linear chain having a carbon number of 1 to 20, a branched carbon number of 3 to 20 or a cyclic alkyl group having a carbon number of 3 to 20; a substituted or unsubstituted carbon a number of 6 to 20 aryl groups; or a halogen atom. Further, y each independently represents an integer of 0 to 2.

The unsubstituted alkyl group having a linear number of carbon atoms of 1 to 20 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group or a hexadecyl group. Alkyl, octadecyl, and the like.

Examples of the linear alkyl group having 1 to 20 carbon atoms substituted include a fluoromethyl group, a 2-hydroxyethyl group, a 3-cyanopropyl group, and a 20-nitrooctadecyl group.

In the case of the above-mentioned unsubstituted or substituted linear alkyl group, those having 1 to 10 carbon atoms are preferably used.

The unsubstituted alkyl group having 3 to 20 carbon atoms may, for example, be isopropyl, isobutyl, tert-butyl, neopentyl, 2-hexyl, 2-octyl, 2-indenyl, 2 - dodecyl, 2-hexadecyl, 2-octadecyl, and the like.

Examples of the branched alkyl group having 3 to 20 carbon atoms are substituted, and examples thereof include 1-fluoroisopropyl group and 1-hydroxy-2-octadecyl group.

The unsubstituted carbon group having 3 to 20 carbon atoms may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group or a cyclodecene. Hexaalkyl, cyclooctadecyl and the like.

Examples of the substituted alkyl group having 3 to 20 carbon atoms include a 2-fluorocyclopropyl group and a 4-cyanocyclohexyl group.

The unsubstituted aryl group having 6 to 20 carbon atoms may, for example, be a phenyl group or a naphthyl group.

The substituted aryl group having 6 to 20 carbon atoms may, for example, be 4-isopropylphenyl, 4-cyclohexylphenyl, 4-methylphenyl or 6-fluoronaphthyl. In the case of the above-mentioned unsubstituted or substituted aryl group, those having 6 to 10 carbon atoms are preferably used.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In addition, the term "substitution" as used in the specification means, without any other definition, means that one or more hydrogen atoms in the functional group are bonded to a halogen atom, a hydroxyl group, a cyano group, a nitro group, a heterocyclic group, or a carbon number of 1 to 20 a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms , alkoxy group having 1 to 20 carbon atoms, amine group having 0 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, mercapto group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbon The alkyleneoxy group having 1 to 20 alkyl groups, the aryl fluorenyloxy group having 7 to 30 carbon atoms or the alkyl fluorenyl group having 1 to 20 carbon atoms is substituted.

In the general formula (1), each of R ^{3 is} independently a hydrogen atom, a substituted or unsubstituted linear chain having a carbon number of 1 to 20, a branched carbon number of 3 to 20, or a cyclic alkane having a carbon number of 3 to 20. A aryl group having 6 to 20 carbon atoms, substituted or unsubstituted.

In R ³ , a substituted or unsubstituted carbon number of 1 to 20, a branched carbon number of 3 to 20, a cyclic alkyl group having 3 to 20 carbon atoms, and a substituted or unsubstituted carbon number of 6~ The aryl group of 20 may be the same as those exemplified in the above R ¹ .

(1), any configuration shown each R ² is independently R ² are each independently the general formula (2) of the general formula. However, at least one R ² has an acid dissociable moiety. R ² has an acid dissociable site and can be used as a polymer-cuttable main chain-cut positive photoresist material by the action of an acid.

In the general formula (2), R ⁴ is a substituted or unsubstituted linear chain having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or substituted group. An unsubstituted aryl group with a carbon number of 6 to 20.

An unsubstituted alkyl group having 1 to 20 carbon atoms, and examples thereof include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, and a fluorenyl group. , dodecyl, hexadecyl, octadecyl and the like.

a linear alkyl group having 1 to 20 carbon atoms substituted, and examples thereof include a fluoromethylene group, a 2-hydroxyethylidene group, a 3-cyanopropyl group, and a 20-nitrolevole octadecane. Base.

An unsubstituted alkyl group having 3 to 20 carbon atoms, and examples thereof include an isopropyl group, an isobutyl group, an exo-tert-butyl group, a neopentyl group, a 2-extended hexyl group, a 2-extended octyl group, and 2-extended fluorenyl group, 2-extended dodecyl group, 2-extended hexadecyl group, 2-extended octadecyl group and the like.

The branched alkyl group having 3 to 20 carbon atoms is substituted, and examples thereof include 1-fluoroextension isopropyl group and 1-hydroxy-2- stearyl group.

The unsubstituted alkyl group having 3 to 20 carbon atoms may, for example, be a cyclic propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodextylene group, a ring-extension group, or a ring extension. Dodecyl, cyclohexadecyl, cyclohexadecyl and the like.

The cyclic alkyl group having 3 to 20 carbon atoms is substituted, and examples thereof include a 2-fluorocyclopropyl group and a 4-cyanocyclohexyl group.

The unsubstituted aryl group having 6 to 20 carbon atoms may, for example, be a phenyl group or a naphthyl group.

The substituted aryl group having 6 to 20 carbon atoms may, for example, be 4-isopropylphenylene, 4-cyclohexylphenylene, 4-methylphenylene or 6-fluoronaphthyl.

In the general formula (1), at least one R ² has an acid dissociable moiety. In the present specification, the term "acid dissociable site" means a site which is cleaved in the presence of an acid to cause a change in an alkali-soluble group or the like. The alkali-soluble group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. The phenolic hydroxyl group and the carboxyl group are preferred, and the phenolic hydroxyl group is particularly preferred. The general formula (2) having the acid dissociable moiety described above may, for example, be as follows.

R ⁵ in the general formula (1) is a hydroxyl group, -OR ² -O-* (* represents a bonding site between the unit structures described above), or -OR ² -OR ⁵⁵ (R ⁵⁵ is a general formula (1) Other R ⁵ ). That is, the benzene ring structures A1 and B1 are bonded to the upper ring structure and the lower ring structure in the same unit structure by at least one "-OR ² -O-" on the benzene ring. Further, the other bond of the benzene ring structure A1 and B1 (that is, R ⁵ ) may be a hydroxyl group (OH-), or may be a "-OR ² -O bonded with "*" to other unit structures. -*", which may be "-OR ² -OR ⁵⁵ ", and may be bonded to other R ⁵ in the upper or lower annular structure of the same unit structure or in the same unit structure. The upper annular structure and the lower annular structure are bonded.

Further, in the general formula (1), R ⁶ is a hydroxyl group or -OR ² -O-* (* represents a bonding site between the unit structures).

As described above, when the polymer compound of the present embodiment has a plural unit structure, at least one of R ⁵ and R ⁶ in the unit structure represented by at least one general formula (1) is "-OR ² -O-*". And the plural unit structure is bonded through the R ⁵ or R ⁶ . In -OR ² O-*, "*" indicates the bonding portion in the unit structure. For example, when the polymer compound of the present embodiment has two unit structures represented by the general formula (1), at least one of R ⁵ and R ⁶ in the unit structure represented by one general formula (1) (- The * part of OR ² -O-*) and the other side are bonded to the carbon atom constituting the benzene ring in the unit structure represented by the general formula (1).

Further, in the general formula (1), when R ⁵ is "-OR ² -OR ⁵⁵ ", it means that one of the benzene ring structures A1 or B1 is bonded to the upper ring structure and the lower ring structure. When there are two -OR ² -O-", two of "-OR ² -O-" may be bonded to different benzene ring structures, or may be bonded to the same benzene ring structure.

Further, when a plurality of R ⁵ to R ⁶ have "-OR ² -O-*", each of R ⁵ to R ⁶ may be bonded to the same unit structure by "-OR ² -O-*". , or the respective key sections can be constructed in different units.

The polymer compound of the present embodiment can be obtained, for example, by reacting a compound represented by the following general formula (3) with any one selected from the group represented by the following general formula (4).

(In the general formula (3), R ¹ , R ³ , m ₁ , m ₂ , and y are synonymous with the above general formula (1).)

(In the general formula (4), R ⁴ is synonymous with the above general formula (2), X ¹ is a halogen atom, and X ² is a halogen atom or a hydroxyl group.)

The halogen atom represented by X ¹ and X ² in the general formula (4) is the same as the above-mentioned R ¹ .

The compound represented by the above formula (3) is preferably one selected from the group represented by the following compounds.

The compound represented by the above formula (4) is preferably One compound selected from the group shown by the following compounds.

(In the formula (4-1), the R ⁴ system is synonymous with the above general formula (2).)

The above-mentioned R ⁴ is preferably one selected from the group represented by the following formula (4-2) from the viewpoint of heat resistance.

The reaction of the compound represented by the above formula (3) with any of the compounds selected from the group represented by the general formula (4) is not particularly limited, and the two compounds may be dissolved in a solvent as needed, and may be used as a catalyst. It is preferred to carry out the reaction in the presence of it.

The solvent used in the reaction of the compound represented by the general formula (3) with any of the compounds selected from the group represented by the general formula (4) may, for example, be acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. An aprotic solvent such as ester, dimethylacetamide or N-methylpyrrolidone. For example, the compound represented by the general formula (3) can be dissolved or suspended in these solvents. Next, a divinyl alkyl ether such as divinyloxymethyladamantane (a compound represented by the general formula (4)) is added, and an acid touch such as trifluoroacetic acid or pyridinium p-toluenesulfonate is added. In the presence of the medium, the reaction is carried out at atmospheric pressure at 20 to 60 ° C for 6 to 72 hours. The reaction solution is neutralized with an alkali compound, added to distilled water to precipitate a white solid, and the separated white solid is The distilled water is washed, and the desired polymer compound is obtained by drying.

Further, for example, the compound represented by the general formula (3) may be dissolved or suspended in an aprotic solvent, and then an alkyl halide such as ethyl chloromethyl ether (general formula (4)) The compound is added and reacted at 20 to 110 ° C for 6 to 72 hours in the presence of a base catalyst such as potassium carbonate at normal pressure. The reaction liquid is neutralized with an acid such as hydrochloric acid, and added to distilled water to precipitate a white solid. Then, the separated white solid is washed with distilled water, and the desired polymer compound is obtained by drying.

In the present embodiment, it is preferred to synthesize a polymer compound by using two or more compounds represented by the general formula (3) and/or any one selected from the group represented by the general formula (4). By using two or more compounds represented by the general formula (3) and/or any one selected from the group represented by the general formula (4), the solubility of the obtained polymer in a semiconductor safe solvent is improved.

In order to reduce the amount of residual metal of the polymer, it may be subjected to purification treatment as needed. Further, if the acid catalyst remains, generally, the storage stability of the radiation-sensitive composition is lowered, or if the basic catalyst remains, generally, the sensitivity of the radiation-sensitive composition is lowered, and therefore, it is also possible to Purification is carried out for the purpose of reduction. In terms of purification, the polymer can be carried out by a known method, and is not particularly limited, and examples thereof include a method of washing with water, a method of washing with an acidic aqueous solution, and an alkaline aqueous solution. A method of washing, a method of treating with an ion exchange resin, a method of treating with a cerium oxide colloidal column, and the like. These purification methods are preferably carried out by combining two or more kinds. Acidic aqueous solution, alkaline aqueous solution, ion The exchange resin and the cerium oxide colloidal column chromatography can be appropriately selected depending on the amount or type of the metal, the acidic compound and/or the basic compound to be removed, the type of the dissolution inhibitor to be purified, and the like. For example, examples of the acidic aqueous solution include hydrochloric acid, nitric acid, and acetic acid aqueous solution having a concentration of 0.01 to 10 mol/L, and an aqueous alkaline solution having a concentration of 0.01 to 10 mol/L, and an ion exchange resin. A cation exchange resin such as Amberlyst 15J-HG Dry manufactured by ORGANO is used. It can also be dried after purification. The drying can be carried out by a known method, and is not particularly limited. Examples of the polymer invariability include vacuum drying and hot air drying.

The polymer compound of the present embodiment is at normal pressure, 100 ° C or lower, preferably 120 ° C or lower, more preferably 130 ° C or lower, still more preferably 140 ° C or lower, and particularly preferably 150 ° C or lower. The lower is better. The sublimation property is low, and in the thermogravimetric analysis, the weight loss at 10 minutes at a predetermined temperature is 10%, preferably 5%, more preferably 3%, still more preferably 1%, and particularly preferably 0.1. % is better. Due to the low sublimation, it can prevent contamination of the exposure device due to exhaust gas during exposure. The low line edge roughness (hereinafter, simply referred to as "LER") imparts a good pattern shape.

The polymer compound of the present embodiment preferably satisfies F<3.0 (F represents the total number of atoms/(all carbon number - total oxygen atom number)), and more preferably satisfies F<2.5. By satisfying the foregoing conditions, the dry etching resistance can be improved.

It can also be high in the range that does not impair the effects of the present invention. A non-acid dissociable functional group is introduced into at least one of the phenolic hydroxyl group and/or the carboxyl group of the molecular compound. The non-acid dissociable functional group means a characteristic group which does not crack in the presence of an acid and does not form an alkali-soluble group. For example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms which are not decomposed by the action of an acid may be mentioned. a group, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen atom, a carboxyl group, an alkyl group having 1 to 20 carbon atoms, a functional group selected from the group of such derivatives, and the like.

The polystyrene-equivalent number average molecular weight (Mn) of the polymer compound of the present embodiment is preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000, particularly preferably from 2,500 to 7,500. When the number average molecular weight of the polymer compound of the present embodiment is in the above range, the film forming property necessary for the photoresist can be maintained, and the pattern collapse can be further suppressed to improve the resolution.

Further, the degree of dispersion (weight average molecular weight/number average molecular weight (hereinafter, simply referred to as "Mw/Mn") of the polymer compound of the present embodiment is preferably Mw/Mn < 1.7, more preferably Mw/Mn < 1.5. From the viewpoint of sensitivity, it is more preferable that Mw/Mn is <1.3, and from the viewpoint of low roughness, Mw/Mn is more preferably 1.2, particularly preferably, Mw/Mn is <1.1.

In the polymer compound of the present embodiment, it is preferred that the compound represented by the general formula (3) is reacted with any of the compounds selected from the group represented by the general formula (4), and then the general formula (3) The compound of the following general formula (5) obtained by the reaction of the compound shown is shown.

Since the polymer compound of the present embodiment has a large number of pores, the polymer compound of the present embodiment is not colloidal, and the solvent solubility is excellent, and the pores are extremely high.

(In the general formula (5), R ¹ , R ² , R ³ and y are synonymous with the above and the general formula (1), and n is an integer of 4 to 8.)

Further, the polymer compound of the present embodiment is preferably a compound represented by the following general formula (X).

Specific examples of the polymer compound of the present embodiment are shown below. However, the polymer compound of the present embodiment is not limited to the following specific examples.

When the polymer compound of the present embodiment is used, the strength of the obtained photoresist pattern or the adhesion to the substrate is improved, so that the problem of pattern collapse seen in a low molecular system can be suppressed. Further, in the polymer compound of the present embodiment, the molecular weight is lowered by the detachment of the cross-linking type protective group in the exposed portion, and the low molecular weight can also reduce the roughness of the photoresist pattern. Further, the polymer compound of the present embodiment is excellent in film formability because of its high heat resistance and amorphous property, and has excellent sublimation property, excellent development property, etching resistance, and the like, and is suitable as a photoresist material, particularly Applicable as the main component (substrate) of the photoresist material.

The polymer compound of the present embodiment does not colloidal due to its tubular structure, and has excellent solvent solubility and a high sensitivity because it has more pores. Moreover, on the manufacturing surface, it is also possible to make the compound represented by the above general formula (3) and the industrial product easy to obtain. Any of the compounds selected in the group represented by the general formula (4) is produced by a known method and is produced in a high yield, and is extremely excellent in practical use.

[Sense Radiation Composition]

The radiation sensitive composition of the present embodiment has the polymer compound of the above embodiment. The radiation sensitive composition of the present embodiment may contain a solvent as needed. The radiation sensitive composition of the present embodiment is preferably any one selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The acid generator (C), the acid diffusion controlling agent (E), and the solvent are directly or indirectly generated by irradiation of radiation.

In the radiation sensitive composition of the present embodiment, an amorphous film can be formed by a method such as spin coating. Further, in the radiation sensitive linear composition of the present embodiment, any of the positive photoresist pattern and the negative photoresist pattern may be used depending on the type of the developing liquid to be used. For example, when an alkali developing solution is used, a positive pattern can be obtained, and when an organic developing solution is used, a negative pattern can be obtained.

When the positive photoresist pattern is formed, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment preferably has a dissolution rate of 5 Å/sec or less for the developing solution at 23 ° C. More preferably 0.05~5Å/sec, more preferably 0.0005~5Å/sec. When the dissolution rate is 5 Å/sec or less, it may be a photoresist which is insoluble to the developing solution. Further, when the radiation-sensitive linear composition of the present embodiment has a dissolution rate of 0.0005 Å/sec or more, the resolution can be improved. It can be speculated that this is the form of this embodiment. The change in solubility of the polymer compound before and after exposure causes the interface portion dissolved in the developing solution to be more contrasted with the interface of the unexposed portion which is not dissolved in the developing liquid. Further, when the radiation sensitive composition of the present embodiment is used, the line edge roughness is reduced and the effect of reducing defects is obtained.

When the negative photoresist pattern is formed, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment preferably has a dissolution rate of 10 Å/sec or more for the developing solution at 23 ° C. If the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is more suitable for the photoresist. Further, if the dissolution rate is 10 Å/sec or more, the resolution is improved. In this case, it is presumed that the minute surface portion of the polymer compound of the present embodiment is dissolved, and the line edge roughness is reduced. Further, when the radiation sensitive composition of the present embodiment is used, there is an effect of reducing defects.

The dissolution rate is such that the amorphous film is immersed in the developing solution at a predetermined time at 23 ° C, and the film thickness before and after the immersion can be measured by a known method such as visual inspection, ellipsometry or QCM method. And calculated based on the measured value.

When a positive photoresist pattern is formed, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment is made of KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The portion exposed by the radiation is preferably at a rate of 10 Å/sec or more for the dissolution rate of the developing solution at 23 ° C. If the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is more suitable for the photoresist. Further, if the dissolution rate is 10 Å/sec or more, the resolution is improved. It is presumed that the minute surface portion of the polymer compound of the present embodiment is dissolved and the line edge is reduced. The reason for the roughness of the edge. Further, when the radiation sensitive composition of the present embodiment is used, there is an effect of reducing defects.

When a negative photoresist pattern is formed, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment is made of KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The portion to be exposed by the radiation has a dissolution rate of 5 Å/sec or less at 23 ° C, preferably 0.05 to 5 Å / sec, more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å/sec or less, it may be a photoresist which is insoluble to the developing solution. Further, if the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. In this case, it is presumed that the change in the solubility of the polymer compound of the present embodiment before and after the exposure causes the interface between the unexposed portion which is dissolved in the developing liquid and the exposed portion which is not dissolved in the developing liquid to become larger. Therefore. Further, when the radiation sensitive composition of the present embodiment is used, the line edge roughness is reduced and the effect of reducing defects is obtained.

The radiation sensitive composition of the present embodiment can be formed, for example, in a solid content of 1 to 80% by mass and a solvent of 20 to 99% by mass, preferably 1 to 50% by mass of the solid content and 50 to 99% by mass of the solvent, and more preferably The solid content is 2 to 40% by mass and the solvent is 60 to 98% by mass, particularly preferably 2 to 10% by mass of the solid component and 90 to 98% by mass of the solvent.

The content of the radiation sensitive composition of the polymer compound of the present embodiment is 10 to 90% by mass, preferably 30 to 90% by mass, more preferably 50 to 80% by mass, particularly preferably the total mass of the solid content. It is 70 to 75 mass%. When the content of the radiation-sensitive composition of the polymer compound of the present embodiment is as described above, a higher resolution can be obtained, and Line edge roughness will become smaller.

(acid generator (C))

The radiation sensitive composition of the present embodiment contains at least one type of radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. It is preferred that the acid generator (C) which directly or indirectly produces an acid is irradiated.

In this case, in the radiation sensitive composition of the present embodiment, the content of the acid generator (C) is preferably 0.001 to 50% by mass based on the total mass of the solid content, more preferably 10 to 37.5% by mass, and 10 to 30% by weight. The quality % is particularly good. By using the acid generator (C) in the range of the aforementioned content, a pattern profile of higher sensitivity and lower edge roughness can be obtained.

In the photoresist composition of the present embodiment, when an acid is generated in the system, the method of generating the acid is not limited. If an excimer laser is used instead of ultraviolet rays such as g-line or i-line, finer processing can be realized, and if an electron beam, an extreme ultraviolet ray, an X-ray, or an ion beam is used as a high-energy line, it can be finer. machining.

The acid generator (C) is preferably at least one selected from the group consisting of the compounds represented by the following formulas (7-1) to (7-8).

(In the formula (7-1), R ¹³ may be the same or different, and each independently represents a hydrogen atom, a linear chain, a branched or a cyclic alkyl group, a linear chain, a branched chain or a cyclic alkoxy group. group, a hydroxyl group or a halogen atom; X ^- an alkyl group, an aryl group, a halogen-substituted alkyl or halogen halide ion or sulfonate ion the aryl group).

The compound represented by the above formula (7-1) is composed of triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro- N-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-tri Methylphenylphosphonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylphosphonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylphosphonium nonafluoro- N-butanesulfonate, diphenyl-4-hydroxyphenylphosphonium trifluoromethanesulfonate, bis(4-fluorophenyl)-4-hydroxyphenylphosphonium trifluoromethanesulfonate, diphenyl 4-hydroxyphenylphosphonium nonabutane sulfonate, bis(4-hydroxyphenyl)-phenylindole trifluoromethanesulfonate, tris(4-methoxyphenyl)phosphonium trifluoride Methanesulfonate, tris(4-fluorophenyl)phosphonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2,4,6 -trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylphosphonium-2-trifluoromethylbenzenesulfonate, diphenyl-2,4, 6-trimethylphenylphosphonium-4-trifluoromethylbenzenesulfonate, two Phenyl-2,4,6-trimethylphenylphosphonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, Diphenylnaphthylfluorene trifluoromethanesulfonate, diphenyl-4-hydroxyphenylphosphonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxybenzene It is preferred that at least one type selected from the group consisting of 10-camphorsulfonate and cyclo(1,3-perfluoropropanedifluoride) sulfanilide.

(In the formula (7-2), R ¹⁴ may be the same or different, and each independently represents a hydrogen atom, a linear chain, a branched or a cyclic alkyl group, a linear chain, a branched or a cyclic alkoxy group. a group, a hydroxyl group or a halogen atom. The X ^- line is synonymous with the above formula (7-1).)

The compound represented by the above formula (7-2) is composed of bis(4-t-butylphenyl)phosphonium trifluoromethanesulfonate, bis(4-t-butylphenyl)phosphonium nonfluoride-n. -butane sulfonate, bis(4-t-butylphenyl)phosphonium perfluoro-n-octane sulfonate, bis(4-t-butylphenyl)pyridinium-toluenesulfonate, double (4-t-butylphenyl) anthracenesulfonate, bis(4-t-butylphenyl)indole-2-trifluoromethylbenzenesulfonate, bis(4-t-butylphenyl)錪-4-trifluoromethylbenzenesulfonate, bis(4-t-butylphenyl)indole-2,4-difluorobenzenesulfonate, bis(4-t-butylphenyl)phosphonium Hexafluorobenzenesulfonate, bis(4-t-butylphenyl)indole 10-camphorsulfonate, diphenylsulfonium trifluoromethanesulfonate, diphenylphosphonium nonabutanesulfonate Acid salt, diphenylsulfonium perfluoro-n-octanesulfonate, diphenylphosphonium p-toluenesulfonate, diphenylsulfonium benzenesulfonate, diphenylphosphonium 10-camphorsulfonate, two Phenylfluorene-2-trifluoromethylbenzenesulfonate, diphenylphosphonium-4-trifluoromethylbenzenesulfonate, diphenylphosphonium-2,4-difluorobenzenesulfonate, diphenyl Hexafluorobenzenesulfonate, bis(4-trifluoromethylphenyl)phosphonium trifluoromethanesulfonate, bis(4-trifluoromethylphenyl)phosphonium nonabutanesulfonate, Bis(4-trifluoromethylphenyl)phosphonium perfluoro-n-octanesulfonate, bis(4-trifluoromethylphenyl)phosphonium p-toluenesulfonate, bis(4-trifluoromethyl) At least one selected from the group consisting of phenyl) anthracenesulfonate and bis(4-trifluoromethylphenyl)phosphonium 10-camphorsulfonate is preferred.

(In the formula (7-3), Q is an alkylene group, an extended aryl group or an alkylene group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.)

The compound represented by the above formula (7-3) is composed of N-(trifluoromethylsulfonyloxy)butaneimine, N-(trifluoromethylsulfonyloxy)-o-phenylene Formammine, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)naphthyl quinone imine, N-(10-camphorsulfonyloxy)butanediimide, N -(10-樟 Cerebral sulfonyloxy) phthalimide, N-(10-camphorsulfonyloxy)diphenylmaleimide, N-(10-camphorsulfonyloxy)bicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(10-camphorsulfonyloxy)naphthyl quinone imine, N-(n-octanesulfonyloxy) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(n-octanesulfonyloxy)naphthylimine, N-(p-toluenesulfonate) Bisyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(p-toluenesulfonyloxy)naphthyl quinone imine, N-(2-three Fluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-trifluoromethylbenzenesulfonyloxy)naphthyl Yttrium, N-(4-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(4-trifluoromethyl) Benzosulfonyloxy)naphthylimine, N-(perfluorobenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N- (Perfluorobenzenesulfonyloxy)naphthylimine, N-(1-naphthalenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(1-naphthalenesulfonyloxy)naphthylimine, N-(nonafluoro-n-butanesulfonyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(nonafluoro-n-butanesulfonyloxy)naphthyl quinone imine, N-(all Fluorine-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine and N-(perfluoro-n-octanesulfonyloxy) It is preferred that at least one of the groups selected from the group consisting of naphthylimine is preferred.

(In the formula (7-4), R ¹⁶ may be the same or different, and each independently may be an optionally substituted straight-chain, branched or cyclic alkyl group, optionally substituted aryl group, optionally a substituted heteroaryl group or an optionally substituted aralkyl group.)

The compound represented by the above formula (7-4) is composed of diphenyl difluorene, bis(4-methylphenyl) difluorene, dinaphthyl difluorene, and di(4-tert-butylphenyl). Diterpene, bis(4-hydroxyphenyl)difluorene, bis(3-hydroxynaphthyl)difluorene, bis(4-fluorophenyl)difluorene, bis(2-fluorophenyl)difluorene and di(4) At least one type selected from the group consisting of -trifluoromethylphenyl)diguanidine is preferred.

(In the formula (7-5), R ¹⁷ may be the same or different, and each independently may be an optionally substituted linear, branched or cyclic alkyl group, optionally substituted aryl group, optionally a substituted heteroaryl group or an optionally substituted aralkyl group.)

The compound represented by the above formula (7-5) is composed of α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino)-4. -methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-4-methoxy Phenyl acetonitrile, α-(ethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-4-methylphenyl At least one selected from the group consisting of acetonitrile and α-(methylsulfonyloxyimino)-4-bromophenylacetonitrile is preferred.

In the formula (7-6), R ¹⁸ may be the same or different, and each independently is a halogenated alkyl group having 1 or more chlorine atoms and 1 or more bromine atoms. The carbon number of the halogenated alkyl group is preferably from 1 to 5.

In the formulae (7-7) and (7-8), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and a cyclopentane group. An alkoxy group having 1 to 3 carbon atoms such as a cycloalkyl group, a methoxy group, an ethoxy group or a propoxy group, or an aryl group such as a phenyl group, a tolyl group or a naphthyl group; An aryl group having 6 to 10 carbon atoms. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. With respect to the organic group having a 1,2-naphthoquinonediazide group, specifically, 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-naphthoquinonediazide are preferably mentioned. a 1,2-quinonediazidesulfonyl group such as a 5-sulfonyl group or a 1,2-naphthoquinonediazide-6-sulfonyl group. In particular, 1,2-naphthoquinonediazide-4-sulfonyl and 1,2-naphthoquinonediazide-5-sulfonyl are preferred. p is each independently an integer of 1 to 3, and q is independently an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ¹⁹ is a single bond, a polymethylene group having a carbon number of 1 to 4, a cycloalkyl group, a phenyl group, a group represented by the following formula (7-7-1), a carbonyl group, an ester group, an anthranyl group or The ether group, Y ¹⁹ is a hydrogen atom, an alkyl group or an aryl group, and each of X ^{20 is} independently a group represented by the following formula (7-8-1).

(In the formula (7-8-1), Z ^{22 is} independently an alkyl group, a cycloalkyl group or an aryl group, R ²² is an alkyl group, a cycloalkyl group or an alkoxy group, and r is an integer of 0 to 3.)

Examples of other acid generators include bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and bis(tert-butyl). Sulfhydryl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazo Methane, bis(n-propylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, 1,3-double ( Cyclohexylsulfonylazomethylsulfonyl)propane, 1,4-bis(phenylsulfonylazomethylsulfonyl)butane, 1,6-bis(phenylsulfonylazo) 2-sulfonyldiazomethane, 2-(4-methoxyl) such as methylsulfonyl)hexane or 1,10-bis(cyclohexylsulfonylazomethylsulfonyl)decane Phenyl)-4,6-(bistrichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-(bistrichloromethyl)-1 , 3,5-triazine, ginseng (2,3-dibromopropyl)-1,3,5-triazine, ginseng (2,3-dibromopropyl)isocyanate, etc. Triazine derivatives and the like.

Among the acid generators, the acid generator (C) used in the radiation sensitive composition of the present embodiment is preferably an acid generator having an aromatic ring, and the formula (7-1) or (7-2) is preferable. The acid generator shown is more preferred. X-based acid generator having the formula (7-1) or (7-2) ^- A is substituted with an aryl group or a halogen acid ion and still more preferably those of aryl groups, again having a sulfonic acid generator having an aryl group of Acid ions are particularly preferred, and diphenyltrimethylphenylphosphonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium Nonafluoromethanesulfonate is particularly preferred. By using the acid generator, the line edge roughness can be reduced.

The acid generator (C) may be used singly or in combination of two or more.

(acid diffusion control agent (E))

In the radiation sensitive composition of the present embodiment, the diffusion of the acid generated by the acid generator in the photoresist film can be controlled by radiation irradiation, and the chemical reaction which prevents the poor in the unexposed field can be prevented by blending. An acid diffusion controlling agent (E) such as an action. By using such an acid diffusion controlling agent (E), the storage stability of the radiation sensitive composition is enhanced. In addition, as the resolution is improved, the line width change of the photoresist pattern due to the change of the standing time before the electron beam irradiation and the standing time after the electron beam irradiation can be suppressed, and it is excellent in the process stability. Examples of the acid diffusion controlling agent (E) include an electron beam radiolysis-decomposable basic compound containing a basic compound, a basic cerium compound, and a basic cerium compound in a nitrogen atom. The acid diffusion controlling agent may be used singly or in combination of two or more.

The acid diffusion controlling agent may, for example, be a nitrogen-containing organic compound or a basic compound which can be decomposed by exposure. The aforementioned nitrogen-containing organic Examples of the compound include a compound represented by the following general formula (10) (hereinafter referred to as "nitrogen-containing compound (I)"), and a diamine compound having two nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen-containing compound" a compound (II)"), a polyamine compound or a polymer having three or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (III)"), a guanamine-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound Wait. Further, the acid diffusion controlling agent may be used alone or in combination of two or more.

In the above general formula (10), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear chain, a branched or a cyclic alkyl group, an aryl group or an aralkyl group. Further, the alkyl group, the aryl group or the aralkyl group may be unsubstituted or substituted with another functional group such as a hydroxyl group. Here, the linear, branched or cyclic alkyl group may, for example, be a carbon number of 1 to 15, preferably 1 to 10, and specific examples thereof include a methyl group, an ethyl group, and an n- group. Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, tert-hexyl, n-heptyl, n-octyl Base, n-ethylhexyl, n-fluorenyl, n-fluorenyl and the like. Further, examples of the aryl group include those having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumyl group, and a 1-naphthyl group. Further, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples thereof include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthyl group. Base.

Specific examples of the nitrogen-containing compound (I) include n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and n-dodecane. Mono(cyclo)alkylamines such as alkamine, cyclohexylamine, etc.; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di- N-octylamine, di-n-decylamine, di-n-decylamine, methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, Di(cyclo)alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-ten a tri(cyclo)alkylamine such as a dialkylmethylamine, a dicyclohexylmethylamine or a tricyclohexylamine; an alkanolamine such as a monoethanolamine, a diethanolamine or a triethanolamine; an aniline or an N-methyl group; Aniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthylamine Aromatic amines, etc.

Specific examples of the nitrogen-containing compound (II) include ethyl diamine, N, N, N', N'-tetramethylethylidene diamine, N, N, N', N'. -肆(2-hydroxypropyl)-extended ethyldiamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3 -aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl) )-2-(4-hydroxyphenyl)propane, 1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, 1,3-bis[1-(4- Aminophenyl)-1-methylethyl]benzene and the like.

Specific examples of the nitrogen-containing compound (III) include a polymer of polyethylenimine, polyallylamine, and N-(2-dimethylaminoethyl)acrylamide.

Specific examples of the amide group-containing compound include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzoguanamine, pyrrolidone, N-methylpyrrolidone, and the like.

Specific examples of the urea compound include urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1 , 3-diphenylurea, tri-n-butylthiourea, and the like.

Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and 2-phenylbenzimidazole. Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, a pyridine such as nicotine, nicotinic acid, nicotinic acid decylamine, quinoline, 8-oxyquinoline or acridine; and pyrazine, pyrazole, pyridazine, quinizarin, hydrazine, pyrrole Pyridine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and the like.

In addition, the hydrazine compound represented by the following general formula (11-1) and the hydrazine compound represented by the following general formula (11-2), etc. are mentioned, for example, the basic compound which can be decomposed by the exposure.

In the above general formulas (11-1) and (11-2), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 1; ~6 alkoxy, hydroxy or halogen atom. Z ^- represents HO ^- , R-COO ^- (only, R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms or an aryl group having 1 to 6 carbon atoms) or the following general formula (11- 3) The anion shown.

Specific examples of the basic compound which can be decomposed by exposure include triphenylsulfonium hydroxide, triphenylsulfonium acetate, and trisole. Phenylhydrazine salicylate, diphenyl-4-hydroxyphenylhydrazine hydroxide, diphenyl-4-hydroxyphenylhydrazine acetate, diphenyl-4-hydroxyphenylhydrazine salicylate, Bis(4-t-butylphenyl)phosphonium hydroxide, bis(4-t-butylphenyl)phosphonium acetate, bis(4-t-butylphenyl)phosphonium hydroxide, double (4 -t-butylphenyl)indole acetate, bis(4-t-butylphenyl)hydrazine salicylate, 4-t-butylphenyl-4-hydroxyphenylhydrazine hydroxide, 4- T-butylphenyl-4-hydroxyphenyl hydrazine acetate, 4-t-butylphenyl-4-hydroxyphenylhydrazine salicylate, and the like.

The content of the acid diffusion controlling agent (E) is preferably 0.001 to 50% by mass of the total mass of the solid content in the radiation sensitive composition, more preferably 0.001 to 10% by mass, more preferably 0.001 to 5% by mass, and more preferably 0.001%. 3% by mass is particularly good. When the content of the acid diffusion controlling agent (E) is within the above range, deterioration in resolution, deterioration in pattern shape, dimensional fidelity, and the like can be prevented. In addition, even if the standing time from the irradiation of the electron beam to the irradiation after the radiation irradiation becomes long, the shape of the upper portion of the pattern does not deteriorate. In addition, when the content of the acid-diffusion controlling agent (E) is 10% by mass or less, it is possible to prevent the sensitivity and the development of the unexposed portion from being lowered. Further, by using such an acid diffusion controlling agent, the storage stability of the positive-type radiation-radiating composition is improved, and the resolution of the place before the radiation irradiation and the standing time after the radiation irradiation can be suppressed while the resolution is improved. The line width of the resulting photoresist pattern changes, and it becomes excellent in process stability.

(Other ingredients (F))

In the radiation-sensitive linear composition of the present embodiment, one or two or more kinds may be added as needed in the range which does not inhibit the object of the present invention. Various additives such as a dissolution promoter, a dissolution controlling agent, a sensitizer, a surfactant, and an oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof of the other component (F).

[1] dissolution promoter

When the solubility of the alkali or the like of the photoresist substrate to the developing solution is too low, the low molecular weight dissolution promoter has an effect of improving the solubility and appropriately increasing the dissolution rate of the cyclic compound at the time of development. The ingredients can be used without departing from the scope of the effects of the present invention. The solvent accelerator may, for example, be a low molecular weight phenolic compound such as bisphenol or hydroxyphenylmethane. These dissolution promoters may be used singly or in combination of two or more. The blending amount of the dissolution promoter can be appropriately adjusted depending on the type of the photoresist base material to be used, and the photoresist base material (polymer, hereinafter referred to as the polymer compound of the present embodiment) is used per 100 parts by mass. 0 to 100 parts by mass is preferred, preferably 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, still more preferably 0 to 2 parts by mass.

[2] dissolution control agent

When the solubility of the photoresist base material to a developing solution such as alkali is too high, the dissolution controlling agent has a function of controlling the solubility thereof so as to appropriately reduce the dissolution rate at the time of development. In the case of such a dissolution controlling agent, it is preferred that the chemical conversion does not occur in the steps of firing, radiation irradiation, development, or the like of the photoresist film. Examples of the dissolution controlling agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and anthracene naphthalene; acetophenone, benzophenone, and phenylnaphthyl group; A ketone such as a ketone; an anthracene such as methylphenylhydrazine, diphenylanthracene or dinaphthylfluorene. These dissolution control agents may be used singly or in combination of two or more.

The blending amount of the dissolution controlling agent can be appropriately adjusted depending on the type of the polymer compound of the present embodiment to be used, but it is preferably 0 to 100 parts by mass per 100 parts by mass of the polymer compound of the present embodiment. Preferably, it is 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 2 parts by mass.

[3] sensitizer

The sensitizer is a component which has the function of absorbing the energy of the irradiated radiation, and transmitting the energy to the acid generator (C), thereby increasing the amount of acid generated and enhancing the visible sensitivity of the photoresist. Examples of such a sensitizer include, but are not limited to, benzophenones, acetophenones, anthraquinones, phenothiazines, anthracenes, and the like.

These sensitizers may be used alone or in combination of two or more. The blending amount of the sensitizer can be appropriately adjusted depending on the type of the polymer compound of the present embodiment to be used, but it is preferably 0 to 100 parts by mass per 100 parts by mass of the polymer compound of the present embodiment. Preferably, it is 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 2 parts by mass.

[4] surfactants

The surfactant is a component which has an effect of improving the coatability or streaks of the positive-type radiation-sensitive composition of the present invention and the development of the photoresist. Such a surfactant may be anionic, cationic, nonionic or Any of the two sexes. Preferred surfactants are nonionic surfactants. The nonionic surfactant is more compatible with the solvent used for the production of the positive-type radiation-linear composition, and is more effective. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. . For the commercial product, Eftop (manufactured by JEMCO), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad (manufactured by Sumitomo 3M), Asahiguard, Surflon (above, Asahi Glass Co., Ltd.), Peporu (manufactured by Toho Chemical Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Oil & Fat Chemical Industry Co., Ltd.), and the like.

The blending amount of the surfactant may be appropriately adjusted depending on the type of the polymer compound of the present embodiment to be used, but it is preferably 0 to 100 parts by mass per 100 parts by mass of the polymer compound of the present embodiment. Preferably, it is 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 2 parts by mass.

[5] An oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof

The radiation-sensitive composition of the present embodiment may further contain an organic acid or phosphorus oxyacid as an optional component for the purpose of preventing sensitivity deterioration, improving the shape of the photoresist pattern, and setting stability. derivative. Further, it may be used in combination with an acid diffusion controlling agent, or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like is preferable. In terms of phosphorus oxyacids or their derivatives, Examples thereof include phosphoric acid such as phosphoric acid, di-n-butyl phosphate or diphenyl phosphate, derivatives such as these esters, phosphonic acid, dimethyl phosphonate, and di-n-butyl phosphonate. a phosphonic acid such as an ester, phenylphosphonic acid, diphenyl phosphonate or dibenzyl phosphonate; a derivative such as an ester thereof; a phosphinic acid such as phosphinic acid or phenylphosphinic acid; Among the derivatives such as esters, etc., among these, phosphonic acid is particularly preferred.

The oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof may be used alone or in combination of two or more. The blending amount of the oxyacid or the derivative of the organic carboxylic acid or phosphorus can be appropriately adjusted depending on the type of the polymer compound of the present embodiment to be used, but the polymer compound of the present embodiment is used per 100 parts by mass. It is preferably from 0 to 100 parts by mass, preferably from 0 to 30 parts by mass, more preferably from 0 to 10 parts by mass, still more preferably from 0 to 2 parts by mass.

[6] The above-mentioned dissolution control agent, sensitizer, surfactant, and other additives other than an oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof

Further, in the positive-type radiation-sensitive linear composition of the present invention, one or two or more kinds of the above-mentioned dissolution controlling agents, sensitizing agents, and surfactants may be blended as needed within a range not inhibiting the object of the present invention. Additives other than those. Examples of such additives include dyes, pigments, and auxiliaries. For example, if a dye or a pigment is blended, it is preferable to visualize the latent image of the exposed portion to alleviate the influence of halation during exposure. Further, when the auxiliary agent is blended, it is preferable because the adhesion to the substrate can be improved. In addition, as for the other additives, a halo preventing agent, a storage stabilizer, an antifoaming agent, a shape improving agent and the like, and specific examples thereof include 4-hydroxy-4'-methylchalcone.

Blending of the radiation sensitive composition of the present embodiment (this The polymer compound/acid generator (C)/acid diffusion control agent (E)/other component (F) according to the embodiment is preferably 10 to 90/0.001 to 50/ by mass based on the solid content. 0.01~50/0~50, more preferably 30~90/0.001~50/0.01~5/0~15, and even more preferably 50~80/10~37.5/0.01~3/0~1, especially good 70~75/10~30/0.01~3/0.

When the elements contained in the radiation-sensitive linear composition of the present embodiment are blended as described above, the performance such as sensitivity, resolution, and alkali developability can be further improved.

In the radiation-sensitive composition of the present embodiment, a component is usually dissolved in a solvent to form a uniform solution, and then, if necessary, it can be prepared by, for example, filtration using a filter having a pore diameter of about 0.2 μm.

(solvent)

Examples of the solvent used in the preparation of the radiation sensitive composition of the present embodiment include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol mono-n. Ethylene glycol monoalkyl ether acetate such as propyl ether acetate or ethylene glycol mono-n-butyl ether acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. Ethylene glycol monoalkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetic acid Propylene glycol monoalkyl ether acetates such as esters; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate Lactic acid esters of esters, n-butyl lactate, n-pentyl lactate, etc.; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate An aliphatic carboxylic acid ester such as an ester, n-hexyl acetate, methyl propionate or ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, 3-methoxy-2-methylpropionic acid methyl ester, 3-methoxybutyl acetate, 3 -methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropionic acid butyl ester, 3-methoxy-3-methylbutyric acid butyl ester, acetamidine acetate Other esters such as base ester, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, Ketones such as cyclohexanone; amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone A lactone or the like such as γ-lactone, but is not particularly limited. These solvents may be used singly or in combination of two or more.

Preferred examples of the solvent used in the radiation sensitive composition of the present embodiment include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), and a ring. A solvent selected from pentanone (CPN), 2-heptanone, methylphenyl ether, butyl acetate, ethyl propionate and ethyl lactate. The solvent is preferably a polymer compound of the present embodiment at 23 ° C, preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably 20% by mass or more. The solvent to be dissolved is preferred. It is preferably selected from PGMEA, PGME, and CHN, and it is preferred to use a solvent which exhibits the highest solubility in the polymer compound of the present embodiment. Use satisfied The solvent of the foregoing conditions can be used in the semiconductor manufacturing step in actual production, and the preservation stability is also good.

The radiation sensitive composition of the present embodiment may contain a resin soluble in an aqueous alkali solution, within a range not inhibiting the object of the present invention. Examples of the resin soluble in the aqueous alkali solution include novolac resin, polyvinyl phenol, polyacrylic acid, polyvinyl alcohol, styrene-anhydrous maleic acid resin, and acrylic acid, vinyl alcohol or vinyl phenol. A polymer as a monomer unit or a derivative thereof or the like. The blending amount of the resin soluble in the aqueous alkali solution can be appropriately adjusted depending on the type of the cyclic compound to be used, and the cyclic compound is preferably 0 to 30 parts by mass per 100 parts by mass, more preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, particularly preferably 0 parts by mass.

[Formation method of photoresist pattern]

The method for forming a pattern (photoresist pattern) of the present embodiment may include a film forming step of forming a film (photoresist film) on a substrate by using the radiation sensitive composition of the present embodiment. An exposure step of exposing the film (photoresist film) and a development process of forming the pattern (photoresist pattern) by exposing the exposed film (photoresist film) in the exposure step. By the photoresist pattern obtained by the pattern forming method of the present embodiment, the upper layer photoresist can be formed as a multilayer photoresist process.

The method for forming the pattern is not particularly limited, and examples thereof include the following methods. First, the formation of a photoresist pattern is The radiation sensitive film of the present embodiment is applied to a conventionally known substrate by a coating means such as spin coating, cast coating, or roll coating to form a photoresist film. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for an electronic component or a pattern in which a predetermined wiring pattern can be formed. More specifically, a metal substrate such as a ruthenium wafer, copper, chromium, iron, or aluminum, or a glass substrate can be given. Examples of the material of the wiring pattern include copper, aluminum, nickel, gold, and the like. Further, an inorganic-based and/or organic-based film may be provided on the substrate as needed. An inorganic antireflection film (inorganic BARC) is mentioned as an inorganic film. An organic antireflection film (organic BARC) is mentioned as an organic film. Surface treatment with hexamethylene diazane or the like can also be carried out.

The coated substrate is then heated as needed. The heating condition may be changed by the blending composition of the radiation sensitive composition, etc., but it is preferably 20 to 250 ° C, more preferably 20 to 150 ° C. By heating, it is preferable because the adhesion to the photoresist substrate can be improved. Then, the photoresist film is exposed to a desired state by any one of radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. Graphic type. The exposure conditions and the like can be appropriately selected depending on the blending composition of the radiation-sensitive composition. In the present invention, in order to stabilize the high-precision fine pattern during exposure, it is preferable to heat it after radiation irradiation. The heating condition may be changed by the blending composition of the radiation sensitive composition, etc., but it is preferably 20 to 250 ° C, more preferably 20 to 150 ° C.

Next, by alkali imaging the exposed photoresist film The liquid is developed to form a predetermined positive photoresist pattern. As the alkali imaging liquid, for example, mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH) can be used. An alkaline aqueous solution in which one or more kinds of the basic compounds such as choline are dissolved so as to have a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable to suppress dissolution of the exposed portion in the developing liquid.

Further, in the alkali developing solution, an alcohol such as methanol, ethanol or isopropyl alcohol or the above surfactant may be added in an appropriate amount. Among them, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. Therefore, it is preferable to improve the wettability of the developer to the photoresist. Further, when a developing solution made of such an alkaline aqueous solution is used, it is generally washed with water after development.

On the other hand, a predetermined positive or negative photoresist pattern can be formed by developing an exposed photoresist film as an organic developing solution. The organic developing solution contains a developing solution of at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent, because the solution of the photoresist pattern can be improved. Photoresist properties such as image or roughness are preferred.

The vapor pressure of the developing liquid is not particularly limited. For example, it is preferably 5 kPa or less at 20 ° C, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By suppressing the evaporation of the developing liquid on the substrate or in the developing cup by setting the vapor pressure of the developing liquid to 5 kPa or less, the temperature uniformity in the wafer surface can be improved, and as a result, the dimensional uniformity in the wafer surface can be optimized. .

A developing solution having a vapor pressure of 5 kPa or less, and specific examples thereof include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, and a ketone solvent such as isobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, Glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxy Ester of butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Solvent; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentyl An alcohol solvent such as an alcohol, n-heptyl alcohol, n-octyl alcohol or n-nonyl alcohol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; Ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol a glycol ether solvent such as monoethyl ether or methoxymethylbutanol; an ether solvent such as tetrahydrofuran; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N An amine-based solvent of N-dimethylformamide; an aromatic hydrocarbon solvent such as toluene or xylene; and an aliphatic hydrocarbon solvent such as octane or decane.

Specific examples of the developing solution having a vapor pressure of 2 kPa or less in a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, and 4-heptanone. a ketone solvent such as 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone or phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, lactate propyl Ester solvent such as ester; n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol An alcohol solvent such as n-octyl alcohol or n-nonyl alcohol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; ethylene glycol monomethyl ether and propylene glycol monomethyl a glycol ether solvent such as ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol; -methyl-2-pyrrolidone, N,N-dimethylacetamide, amide-based solvent of N,N-dimethylformamide; aromatic hydrocarbon solvent such as xylene; octane, An aliphatic hydrocarbon solvent such as decane.

In the developing solution, a surfactant may be appropriately added as needed. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. For example, Japanese Patent Laid-Open No. Sho 62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-61-226745 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 5988, U.S. Patent No. 5,405,720, the same as No. 5,360,692, the same as No. 5,529,881, the same as No. 5,296,330, the same as No. 5,546,098, the same as No. 5,576,143, the same as No. 5,294,511, the same as the description of the 5842541 Preferably, it is a nonionic surfactant. Nonionic The surfactant is not particularly limited, and it is more preferable to use a fluorine-based surfactant or a quinone-based surfactant.

The amount of the surfactant to be used is usually about 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass based on the total amount of the developing solution.

In the development method, for example, a method of immersing the substrate in a bath filled with a developing solution for a certain period of time (dipping method), and displaying the developing solution on the surface of the substrate by a surface tension for a certain period of time can be used for display. The method (paddle stirrer method), the method of spraying the developing liquid on the surface of the substrate (spray method), moving the developing liquid at a constant speed, and applying the developing solution to the nozzle at a constant speed Method on a rotating substrate (mobile distribution method) or the like. There is no particular limitation on the time for performing pattern development, and it is preferably between 10 seconds and 90 seconds.

Further, after the developing step, a step of stopping the development while replacing the solvent with another solvent may be carried out.

Further, after the developing step, the step of washing with an organic solvent-containing lotion may be included. In the rinsing liquid used in the rinsing step after the development, if the photoresist pattern which is hardened by crosslinking is not dissolved, it is not particularly limited, and a solution containing a general organic solvent or water can be used. In the above-mentioned rinse liquid, it is preferred to use a rinse liquid containing at least one organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. More preferably, after the development, a step of washing with a rinsing liquid containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent is carried out. Better yet After the development, a step of washing with a rinse liquid containing an alcohol solvent or an ester solvent is carried out. More preferably, after the development, the step of washing with a lotion containing a monovalent alcohol is carried out. It is particularly preferable to carry out the step of washing with a rinsing liquid containing a monovalent alcohol having 5 or more carbon atoms after development. The time for performing the rinsing of the pattern is not particularly limited, and is preferably between 10 seconds and 90 seconds.

Here, the monovalent alcohol used in the rinsing step after development is not particularly limited, and for example, a linear, branched, or cyclic monovalent alcohol can be used. Specifically, 1-butanol, 2 -butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., especially good C5 or higher As the monovalent alcohol, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol or the like can be used.

Each of the above components may be used in combination or in combination with an organic solvent other than the above.

The water content in the rinse liquid is not particularly limited, and is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. Since the water content is 10% by mass or less, more excellent development characteristics can be obtained.

The vapor pressure of the rinse liquid used after the development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and still more preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface can be Furthermore, it is possible to further suppress the swelling caused by the penetration of the washing liquid, and to optimize the dimensional uniformity in the wafer surface.

In the rinse solution, an appropriate amount of a surfactant may be added and used.

In the rinsing step, the developed wafer is washed with a rinsing liquid containing the organic solvent. The method of the washing treatment is not particularly limited, and for example, a method of continuously applying a rinsing liquid to a substrate rotating at a constant speed (spin coating method), and immersing the substrate in a tank filled with the rinsing liquid must be applied. a method of time (dipping method), a method of spraying a lotion onto the surface of a substrate (spray method), etc., wherein the substrate is washed by a spin coating method, and the substrate is rotated at 2000 rpm to 4000 rpm after washing. The number of rotations is good for removing the lotion from the substrate.

After the photoresist pattern is formed, the pattern wiring substrate can be obtained by performing etching. The etching method can be carried out by dry etching using a plasma gas or by a known method such as wet etching using an alkali solution, a copper dichloride solution or a ferric chloride solution.

After the photoresist pattern is formed, plating can be performed. Examples of the plating method include copper plating, solder plating, nickel plating, gold plating, and the like.

The residual photoresist pattern after etching can be peeled off by an organic solvent or an aqueous solution for developing a more alkaline than the aqueous alkali solution. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), and the like, and the strong alkali aqueous solution may, for example, be 1 to 20 mass. % aqueous sodium hydroxide solution or 1 to 20% by mass aqueous potassium hydroxide solution. In terms of the aforementioned peeling method, For example, a dipping method, a spraying method, and the like. Further, the wiring substrate on which the photoresist pattern is formed may be a multilayer wiring substrate or may have a small diameter through hole.

The wiring board obtained by the present invention may be formed by a method in which a photoresist pattern is formed, a metal is vapor-deposited in a vacuum, and then a photoresist pattern is dissolved in a solution, that is, a lift off method.

[Examples]

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the embodiments.

[Example 1] -Poly(tBCRA[4]-co-ADB) synthesis -

Using a 200 mL eggplant type flask, 1.02 g (1.0 mmol) of Ct-butylphenyl [4] cup-resorcinol aromatic hydrocarbon (hereinafter referred to as "tBCRA [4]") was dissolved in N-methylpyrrolidone 20 ml. in. Next, 0.8 g (0.25 mmol) of tetrabutylammonium bromide and 0.288 g (12 mmol) of sodium hydride were added, and the mixture was stirred at 80 ° C for 2 hours. Thereafter, 1.63 g (4.0 mmol) of bromoacetic acid-2-methyladamantan-2-yl ester was added, and the mixture was reacted at 80 ° C for 48 hours. After completion of the reaction, the mixture was reprecipitated with a 1 N-HCl aqueous solution, and then filtered, and then washed with water to give a solid. Next, the obtained solid was dissolved in ethyl acetate and purified by column chromatography. The structure of the obtained solid (compound) was confirmed by ¹ H-NMR (Nuclear Magnetic Resonance) and IR (Infrared absorption spectrometry). Fig. 1 is a chart showing the ¹ H-NMR spectrum of the compound synthesized in Synthesis Example 1. Fig. 2 is a view showing the IR spectrum of the compound obtained in Synthesis Example 1.

As a result of confirming the structure, it was confirmed that the obtained compound is in the above general formula (1), R ¹ is hydrogen, R ² is a bond group derived from bromoacetic acid-2-methyladamantan-2-yl ester, and R ³ is a compound of t-butylphenyl, m ₁ + n ₁ = m ₂ + n ₂ = 4 (Ct-butylphenyl [4] cup resorcinol aromatic hydrocarbon and bromoacetic acid-2-methyl adamantane-2 A mixture of a condensation reaction of a base ester (hereinafter referred to as "Poly (tBCRA [4]-co-ADB)")). Further, the mixture contains the following compounds. Poly(tBCRA[4]-co-ADB) has a four-dimensional structure as described below.

Further, the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the obtained solid (compound) can be calculated by SEC (Size Exclusion Chromatography) measurement using dimethylformamide in the eluate. For the compound, the introduction rate of adamantane was calculated from ¹ H-NMR due to the integrated intensity ratio of the signal of the aromatic proton of tBCA [4] and the signal of the proton derived from the adamantyl ester.

From the above measurement results, it was found that Poly(tBCRA[4]-co-ADB) yielded 1.1 g, yield 49%, Mn=3360 (Mw/Mn=1.54), and the reaction rate of hydroxyl groups of tBCRA[4]=70%. Tdi = 216 ° C, Td 5% (5 mass % heat reduction temperature) = 280 ° C.

[Embodiment 2] -Poly (CCRA[4]-co-ADB) synthesis -

The tBCRA [4] was changed to 4-C-cyclohexylphenyl [4] cup resorcinol aromatic hydrocarbon (hereinafter referred to as "CCRA [4]"), and the other was also carried out in the same manner as in Example 1. In the above general formula (1), R ¹ is hydrogen, R ² is a bond group derived from bromoacetic acid-2-methyladamantan-2-yl ester, and R ³ is 4-C-cyclohexylphenyl group, m ₁ a condensation reaction of a compound of +n ₁ =m ₂ +n ₂ =4 (4-C-cyclohexylphenyl[4] cup resorcinol arene and bromoacetic acid-2-methyladamantan-2-yl ester (hereinafter referred to as "Poly (CCRA [4]-co-ADB)")). Further, it has been confirmed that the following compounds are contained in the mixture. Poly (CCRA [4]-co-ADB) has a four-body structure as described below.

[Example 3] -Poly (iPCRA[4]-co-ADB) synthesis -

tBCRA [4] was changed to 4-Ci-propylphenyl [4] cup resorcinol arene (hereinafter referred to as "iPCRA [4]"), and the other was also carried out in the same manner as in Example 1, and it was confirmed that it was obtained. In the above general formula (1), R ¹ is hydrogen, R ² is a bond group derived from bromoacetic acid-2-methyladamantan-2-yl ester, and R ³ is a 4-Ci-propylphenyl group, m ₁ a condensation reaction of a compound of +n ₁ =m ₂ +n ₂ =4 (4-Ci-propylphenyl[4] cup resorcinol arene and bromoacetic acid-2-methyladamantan-2-yl ester (hereinafter referred to as "Poly (iPCRA [4]-co-ADB)"))). Further, it has been confirmed that the following compounds are contained in the mixture. Poly (iPCRA [4]-co-ADB) has a 4-body structure as described below.

[Example 4] -Poly(BCRA[4]-co-mXG) synthesis -

The bromoacetic acid-2-methyladamantan-2-yl ester was changed to 1,3-bis[(chloromethoxy)methyl]benzene (hereinafter referred to as "mXG"), and the others were also the same as in Example 1. It was confirmed that R ^{1 in the} above general formula (1) is hydrogen, R ² is a bond group derived from 1,3-bis[(chloromethoxy)methyl]benzene, and R ³ is a t-butyl group. a compound of phenyl, m ₁ +n ₁ =m ₂ +n ₂ =4 (4-t-butylphenylcalix[4]arene and 1,3-bis[(chloromethoxy)methyl]benzene A mixture of a condensation reaction product (hereinafter referred to as "Poly (BCRA [4]-co-mXG)"). It has been confirmed that the following compound is contained in the mixture. Poly (BCRA [4]-co-mXG) is as follows. It has a 4-body structure.

<Modulation and Evaluation of Radiation-Linear Compositions> [Picture test]

The components described in the following Table 1 were blended to form a homogeneous solution. Thereafter, the mixture was filtered through a membrane filter made of Teflon (registered trademark) having a pore size of 0.1 μm to prepare a radiation sensitive composition. The following evaluation was performed about the obtained radiation sensitive composition. The results are shown in Table 2.

(1) Evaluation of sensitivity

After the radiation-sensitive composition (photoresist) was spin-coated on a clean tantalum wafer, prebake baking was performed in an oven to form a photoresist film having a thickness of 60 nm. An electron beam drawing device (product name: ELS-7500, manufactured by ELIONIX Co., Ltd.) was used, and the obtained photoresist film was irradiated with an electron beam set at a line and pitch of 1:1 at intervals of 100 nm. After the electron beam was irradiated, the photoresist film was heated at a predetermined temperature (PEB shown in Table 2 below) for 90 seconds, and developed in an aqueous solution of 2.38 mass% tetramethylammonium hydroxide (TMAH). Seconds. Thereafter, it was washed with water for 30 seconds and dried to form a positive photoresist pattern. The line and the pitch of the obtained photoresist pattern were observed by a scanning electron microscope (manufactured by HITACHI HIGHTECHNOLOGIES, product name: S-4800), and evaluated based on the absorbed dose (μC/cm ² ) according to the following evaluation criteria. The sensitivity of the obtained polymer compound.

[evaluation benchmark]

A: Absorbed dose ≦30μC/cm ² (excellent sensitivity)

B: 30 μC/cm ² <Absorbing dose ≦ 40 μC/cm ² (good sensitivity)

C: 40 μC/cm ² < absorbed dose (bad sensitivity)

(2) Evaluation of line edge roughness (LER)

A positive photoresist pattern was prepared by the same method as the evaluation of the sensitivity of the above (1) at a line and pitch of 1:1 at intervals of 100 nm. Hitachi Semiconductor SEM TERMINAL PC V5 OFFLINE MEASUREMENT SOFTWARE (manufactured by Hitachi Science Systems Co., Ltd.) was used to measure the edge and the reference line at any of the 300 points of the 100 nm interval and the pitch of the 1:1 line (0.75 μm). distance. The standard deviation (3σ) was calculated from the measurement results, and the LER of the pattern was evaluated according to the following evaluation criteria.

[evaluation benchmark]

A: LER (3σ) ≦ 3.5nm (good LER)

C: 3.5 nm < LER (3σ) (bad LER)

(3) Evaluation of pattern collapse

In the same manner as the evaluation of the sensitivity of the above (1), a positive-type photoresist pattern of a line and a pitch of 1:1 at intervals of 30 nm was formed in a region of 1 μm. The line and the pitch were observed by a scanning electron microscope (manufactured by HITACHI HIGHTECHNOLOGIES, product name: S-4800), and the pattern collapse was evaluated according to the following evaluation criteria.

[evaluation benchmark]

A: No picture collapse

C: Part of the pattern collapses

As a result of the above-described patterning test, it was found that the positive-type radiation-sensitive composition of the polymer compound of the present embodiment is excellent in sensitivity and LER, and can suppress collapse in the fine pattern.

In the above Table 1, the acid generator, the acid diffusion controlling agent, and the solvent are as follows.

(acid generator)

P-1: Triphenylphenylhydrazine trifluoromethanesulfonate (Midori Chemical Co., Ltd.)

(acid diffusion control agent)

Q-1: Trioctylamine (Tokyo Chemical Industry Co., Ltd.)

(solvent)

S-1: propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

[Industrial availability]

The polymer compound of the present invention can be suitably used, for example, as an acid-amplifying radiation sensitive composition and a photoresist pattern forming method using the composition.

Claims (5)

A polymer compound comprising a unit structure represented by the following general formula (1), (In general formula (1), m ₁ is an integer from 1 to 8, n ₁ is an integer from 0 to 7, m ₁ + n ₁ = an integer from 4 to 8, m ₂ is an integer from 1 to 8, and n ₂ is An integer from 0 to 7, m ₂ + n ₂ = an integer from 4 to 8, y each independently an integer from 0 to 2; and R ¹ are each independently a hydroxyl group, a substituted or unsubstituted carbon number of 1 to 20 a branched, a carbon number of 3 to 20 or a cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a halogen atom; and each of R ^{3 is} independently a hydrogen atom; a substituted or unsubstituted linear group having 1 to 20 carbon atoms, a branched carbon number of 3 to 20, a cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. R ^{2 is} each independently a structure represented by the following general formula (2), except that at least one R ² has an acid dissociable moiety; R ⁵ is a hydroxyl group, -OR ² -O-* (* indicates the foregoing a bonding site between unit structures), or -OR ² -OR ⁵⁵ (R ⁵⁵ is the other R ⁵ in the general formula (1)); R ⁶ is a hydroxyl group, or -OR ² -O-* (* indicates the aforementioned unit Bonding between structures)) (In the general formula (2), R ⁴ is a substituted or unsubstituted linear group having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, or substituted. Or unsubstituted carbon number 6~20 aryl group). The polymer compound according to claim 1, wherein in the general formula (1), R ³ is a substituted or unsubstituted carbon number of 1 to 10, a carbon number of 3 to 20, or a carbon number of 3 to 3 a cyclic alkyl group of 20, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. A radiation sensitive composition comprising the polymer compound of claim 1 or 2. A radiation-sensitive composition according to claim 3, which further comprises a solvent. A pattern forming method comprising the steps of: using a radiation-sensitive composition such as claim 3 or claim 4; A film forming step of forming a film on the substrate, an exposing step of exposing the film, and a developing step of forming a pattern by developing the film exposed in the exposure step.