KR101405552B1 - Resist composition - Google Patents

Abstract

The present invention provides a resist composition which not only improves the solubility in the preparation of a resist and the resist film adhesion property at the time of development but also improves the resist stability and is also excellent in safety.

The present invention relates to a resist composition comprising a resist component and an organic solvent, wherein the organic solvent comprises (a) a hydroxydecarboxylic acid ester (B) an acetoxycarboxylic acid ester compound group consisting of an acetoxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety, and (c) an alkoxycarboxylic acid ester compound group in which the carboxylic acid moiety has 2 to 6 carbon atoms And at least one organic solvent selected from the group of alkoxycarboxylic acid ester compounds composed of carboxylic acid esters.

A resist composition, a semiconductor device, a liquid crystal display element

Description

RESIST COMPOSITION [0001]

The present invention relates to a resist composition which is sensitive to radiation such as ultraviolet rays, deep ultraviolet rays, X-rays, electron beams and the like and is excellent in safety at the time of use and has excellent properties such as coatability, residual film ratio at the time of development, And at the same time, excellent adhesion at the time of development.

In the production of integrated circuits, color filters, liquid crystal devices and the like, microfabrication is required. Resists have hitherto been used to satisfy this demand. Generally, resists include positive and negative types, and any of them can be usually dissolved in a solvent to form a resist composition in a solution state.

The resist composition is applied onto a substrate such as a silicon substrate or a glass substrate by a known coating method such as spin coating, roller coating, slit coating, or ink jetting, and then prebaked to form a resist film. Thereafter, Depending on the region, it is exposed by a particle beam such as ultraviolet ray, far ultraviolet ray, X-ray or electron beam, and is developed, and then dry etching is performed if necessary to form a desired resist pattern.

As the solvent used in the resist composition, various conventional ones have been used and are selected and used in consideration of solubility, coating properties, sensitivity, developability, pattern characteristics to be formed, and the like. For example, ethylene glycol monoethyl ether acetate has been known as a solvent excellent in various properties such as solubility, coating property, resist formation property and the like. In recent years, however, a safety problem has been pointed out to the human body and safety has been high, There is a demand for a solvent having improved performance such as resist formation properties excellent in solubility.

As a solution to these problems, propylene glycol monomethyl ether acetate and the like have been disclosed as a solvent for replacing ethylene glycol monoethyl ether acetate (see, for example, Patent Document 1). However, there is a problem in that the properties such as resist formation properties and solubility are insufficient for a solvent which is considered to have higher safety than ethylene glycol monoethyl ether acetate. For example, in the case of propylene glycol monomethyl ether acetate, when the resist is coated on a substrate, the amount of residual solvent in the film is small, resulting in abnormal film thickness distribution, or uniformity of line width, .

Further, although a technique for improving the resin solubility and the initiator solubility by using β-propylene glycol monomethyl ether acetate has been disclosed, it is still insufficient in terms of resin solubility and initiator solubility (for example, Patent Document 2).

[Patent Document 1] Japanese Patent Application Laid-Open No. 3-1659

[Patent Document 2] JP-A-6-324483

It is an object of the present invention to provide a resist composition which not only improves the solubility in the preparation of a resist and the resist film adhesion property upon development but also improves the resist stability and is also excellent in safety.

As a result of intensive studies, the inventors of the present invention have found that the above objects can be achieved by using a specific organic solvent, and have reached the present invention.

That is, the present invention is a resist composition comprising a resist component and an organic solvent, wherein (a) the hydroxycarboxylic acid having a carboxylic acid moiety having 2 to 6 carbon atoms and a hydroxydicarboxylic acid ester (B) an acetoxycarboxylic acid ester compound group composed of an acetoxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety, and (c) a group of an acetoxycarboxylic acid ester compound in which the carboxylic acid moiety has 2 to 6 carbon atoms And at least one organic solvent selected from the group of alkoxycarboxylic acid ester compounds composed of alkoxycarboxylic acid esters.

In the resist composition, two or more kinds of organic solvents may be combined. The resist composition may further contain, as the organic solvent, (a ') a hydroxycarboxylic acid ester compound group composed of a hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety, (b) An acetoxycarboxylic acid ester compound group composed of an acetoxycarboxylic acid ester having 2 to 6 carbon atoms and (c) an alkoxycarboxylic acid ester compound composed of an alkoxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety And a plurality of organic solvents selected from at least one compound group of two or more of the three compound groups.

The resist composition may further contain, as an organic solvent, a group of a hydroxydicarboxylic acid ester compound comprising a 2-hydroxysuccinic acid dialkyl ester, an acetoxy group comprising a dialkyl 2-acetoxysuccinic acid ester and a 2-acetoxypropionic acid alkyl ester At least one compound group selected from at least two compounds out of the three compound groups of the carboxylic acid ester compound group and the alkoxycarboxylic acid ester compound group consisting of the 2-methoxy succinic acid dialkyl ester and the 2-methoxypropionic acid alkyl ester And may include a plurality of organic solvents.

The resist composition may further contain at least one solvent selected from carboxylic acid alkyl esters and aliphatic ketones as the organic solvent.

According to the present invention, the solubility at the time of preparing a resist is improved, the stability of the resist is drastically improved, and the drying rate is adjusted by maintaining the amount of the residual solvent in the resist film at the time of application of the resist to improve the uniformity of the film thickness, A resist composition with improved properties such as resist film adhesion at the time of development and high stability can be provided.

In the present invention, as the organic solvent, there may be mentioned (a) a hydroxydecarboxylic acid ester compound group composed of a hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety, (b) a hydroxycarboxylic acid ester compound group in which the carbon number of the carboxylic acid moiety is 2 To (6), and (c) an alkoxycarboxylic acid ester compound group composed of an alkoxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety, in an alkoxycarboxylic acid ester compound group composed of an acetoxycarboxylic acid ester group One or more selected organic solvents are used.

These organic solvents may be used alone or in combination of two or more kinds of organic solvents in consideration of the solubility of the resin and the like. It may also be used in combination with other organic solvents. (A ') a hydroxycarboxylic acid ester compound group composed of a hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety, (b) An acetoxycarboxylic acid ester compound group consisting of an acetoxycarboxylic acid ester having 2 to 6 carbon atoms in the acid moiety and (c) an alkoxycarboxylic acid ester group comprising an alkoxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety And a plurality of organic solvents selected from at least one compound group of at least two compounds out of the three compound groups of the compound of the acid ester group. Among them, a mixed system of the organic solvent contained in the alkoxycarboxylic acid ester compound group and the organic solvent contained in the acetoxycarboxylic acid ester compound group is preferable.

In the above (a '), (b) and (c), the "hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety" means a carboxylic acid ester of a carboxylic acid having 2 to 6 carbon atoms, Is a compound in which one or more hydroxyl groups are combined with one or more (preferably one) hydroxyl groups on the carbon atom of the carboxylic acid moiety, and "acetoxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety" A compound in which an acetoxy group is bonded to the carbon atom of the carboxylic acid moiety in an ester of a carboxylic acid having 2 to 6 carbon atoms with 1 or 2 or more (preferably 1) of the carbon atom, and the carbon number of the carboxylic acid moiety is 2 Refers to a compound in which one or two or more (preferably one) alkoxy groups are bonded to the carbon atom of the carboxylic acid moiety in the ester of the carboxylic acid having 2 to 6 carbon atoms. As the "carboxylic acid" in the above (a '), (b) and (c), an aliphatic carboxylic acid or an alicyclic carboxylic acid is preferable and an aliphatic carboxylic acid (particularly, an aliphatic saturated carboxylic acid) desirable. The "carboxylic acid" may be a monocarboxylic acid, or a polycarboxylic acid such as dicarboxylic acid or tricarboxylic acid. As the "ester" in the above (a '), (b) and (c), an alkyl ester is preferable, and an alkyl ester having 1 to 4 carbon atoms such as methyl ester, ethyl ester, propyl ester and butyl ester is preferable . The carboxyl group of the carboxylic acid is preferably all esterified. The "alkoxy" in the above (c) is preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy groups. The "hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety" in the above (a) means a hydroxycarboxylic acid having a carboxylic acid moiety having 2 to 6 carbon atoms Ester "is a polycarboxylic acid moiety.

Examples of the hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety in (a) include dimethyl hydroxymonate, diethyl hydroxymalonate, dipylyl hydroxymalonic acid, Hydroxymalonic acid diesters such as butyl, methylmethyl hydroxymalonate, methylpropylhydroxymalonate and methylbutyl hydroxymalonate; Hydroxysuccinic acid diesters such as dimethyl hydroxysuccinate, diethyl hydroxysuccinate, dipropyl hydroxysuccinate, dibutyl hydroxysuccinate, methyl ethyl hydroxysuccinate, methyl propyl hydroxysuccinate and methyl butyl hydroxysuccinate; Dimethyl hydroxyglutarate, diethyl hydroxy glutarate, dipropyl hydroxy glutarate, di butyl hydroxy glutarate, methyl butyl hydroxy glutarate, methyl propyl hydroxy glutarate, methyl hydroxysultarate Hydroxyglutaric acid diesters such as butyl (2-hydroxyglutaric acid diester, 3-hydroxyglutaric acid diester); Dimethyl hydroxyadipate, diethylhydroxyadipate, dipropylhydroxyadipate, dibutylhydroxyadipate, methylhydroxyadipate, methylpropylhydroxyadipate, methylhydroxyadipate Butyl dicarboxylic acid diester (e.g., 2-hydroxyadipic acid diester, 3-hydroxyadipic acid diester, 4-hydroxyadipic acid diester); 2-hydroxy-1,2,3-propanetricarboxylic acid trimethyl ester, 2-hydroxy-1,2,3-propanetricarboxylic acid triethyl ester, 2-hydroxy- Propane tricarboxylic acid triphenyl ester, 2-hydroxy-1,2,3-propanetricarboxylic acid tributyl ester, 2-hydroxy-1,2,3-propanetricarboxylic acid dimethylethyl ester, 2 -Hydroxy-1,2,3-propanetricarboxylic acid dimethyl ester, 2-hydroxy-1,2,3-propanetricarboxylic acid dimethyl butyl ester, 2-hydroxy- 2-hydroxy-1,2,3-propanetricarboxylic acid triester such as propane tricarboxylic acid methyl ethyl propyl ester and 2-hydroxy-1,2,3-propanetricarboxylic acid methyl ethyl butyl ester And the like. Among them, a hydroxy polycarboxylic acid alkyl ester such as 2-hydroxysuccinic acid dialkyl ester such as dimethyl 2-hydroxysuccinate is particularly preferable.

As the hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety in the formula (a '), in addition to the hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety, methylhydroxyacetic acid methyl , Hydroxyacetic acid esters such as ethylhydroxyacetate, propylhydroxyacetate, and butylhydroxyacetate; Hydroxypropionic acid esters such as methyl hydroxypropionate, ethyl hydroxypropionate, propyl hydroxypropionate and butyl hydroxypropionate (2-hydroxypropionic acid ester, 3-hydroxypropionic acid ester); Hydroxybutyric acid esters (2-hydroxybutyric acid ester, 3-hydroxybutyric acid ester, 4-hydroxybutyric acid ester) such as methyl hydroxybutyrate, ethyl hydroxybutyrate, propylhydroxybutyrate and butyl hydroxybutyrate; Hydroxy valeric acid esters such as 2-hydroxyvaleric acid esters, 3-hydroxyvaleric acid esters, 4-hydroxystearic acid esters, 4-hydroxybutyric acid esters such as methyl hydroxy valerate, ethyl hydroxy valerate, propyl hydroxy valerate and butyl hydroxy valerate Hydroxybutyric acid ester, hydroxybutyric acid ester, and 5-hydroxyvaleric acid ester), and the like (hydroxymonocarboxylic acid alkyl ester and the like).

Examples of the acetoxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety in (b) include acetoxy such as methyl acetoxyacetate, ethyl acetoxyacetate, propyl acetoxyacetate and butyl acetoxyacetate. Acetic acid esters; Acetoxypropionic acid esters (2-acetoxypropionic acid ester, 3-acetoxypropionic acid ester) such as methyl acetoxipropionate, ethyl acetoxypropionate, propyl acetoxypropionate and butyl acetoxypropionate; Acetoxybutyric acid esters (2-acetoxybutyric acid ester, 3-acetoxybutyric acid ester, 4-acetoxybutyric acid ester) such as methyl acetoxybutyrate, ethyl acetoxybutyrate, propyl acetoxybutyrate, and butyl acetoxybutyrate; Acetoxy valeric acid esters such as 2-acetoxy valeric acid ester, 3-acetoxy valeric acid ester, 4-acetoxy valeric acid ester such as methyl acetoxy valerate, ethyl acetoxy valerate, propyl acetoxy valerate and butyl butyl acetoxy valerate Ethoxyvaleric acid ester, 5-acetoxy valeric acid ester); Such as dimethyl acetoxymalonate, diethyl acetoxymalonate, dipropyl acetoxymalonate, dibutyl acetoxymalonate, methylethyl acetoxymalonate, methylpropylmethacrylate, methylbutyl acetoxymalonate, and the like, Diesters; Acetoxysuccinic acid diesters such as dimethyl acetoxysuccinic acid, diethyl acetosuccinic acid, dipropyl acetosuccinic acid, dibutyl acetosuccinic acid, methyl ethyl acetosuccinate, methylpropyl acetosuccinate and methylbutyl acetosuccinate; Dimethyl acetoxy glutarate, diethyl acetoxy glutarate, dipropyl acetoxy glutarate, dibutyl acetoxy glutarate, methyl ethyl acetoxy glutarate, methyl propyl acetoxy glutarate, methyl ethyl acetoxy glutarate, An acetoxyglutaric acid diester such as butyl (2-acetoxyglutaric acid diester, 3-acetoxyglutaric acid diester); Dimethyl acetoxyanaphthalate, dimethyl acetoxyanaphthalate, diethyl acetoxydipdate, dipropyl acetoxyadipate, dibutyl acetoxyadipate, methylethyl acetoxydipate, methylpropyl acetoxydapropylate, methyl acetoxydapropylate An acetoxy diphosphate diester such as butyl (2-acetoxy dicarboxylic acid diester, 3-acetoxy dicarboxylic acid diester, 4-acetoxy dicarboxylic acid diester); Acetoxy-1,2,3-propanetricarboxylic acid trimethyl ester, 2-acetoxy-1,2,3-propanetricarboxylic acid triethyl ester, 2-acetoxy- Propane tricarboxylic acid tripropyl ester, 2-acetoxy-1,2,3-propanetricarboxylic acid tributyl ester, 2-acetoxy-1,2,3-propanetricarboxylic acid dimethylethyl ester, 2 Acetoxy-1,2,3-propanetricarboxylic acid dimethyl ester, 2-acetoxy-1,2,3-propanetricarboxylic acid dimethyl butyl ester, 2-acetoxy- 2-acetoxy-1,2,3-propanetricarboxylic acid triester such as propane tricarboxylic acid methyl ethyl propyl ester and 2-acetoxy-1,2,3-propanetricarboxylic acid methyl ethyl butyl ester And the like. Of these, 2-acetoxypropionic acid alkyl esters such as methyl 2-acetoxypropionate and 2-acetoxy succinic acid dialkyl esters such as dimethyl 2-acetoxy succinate are particularly preferable.

(c) Examples of the alkoxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety include methyl methoxyacetate, methyl ethoxyacetate, methyl propoxyacetate, methyl butoxyacetate, methoxyacetate, Propoxy ethyl acetate, propoxy ethyl acetate, ethyl butoxyacetate, propyl methoxyacetate, propyl ethoxyacetate, propoxypropylacetate, propoxyacetate, butyl methoxyacetate, butyl ethoxyacetate, butyloxypropoxyacetate, Alkoxyacetic acid esters such as butyl methoxyacetate; Propoxy propionate, methyl methoxypropionate, methyl ethoxypropionate, methyl propoxypropionate, methyl butoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl propoxypropionate, ethyl butoxypropionate, propyl methoxypropionate, propyl ethoxypropionate, Alkoxypropionic acid esters such as propoxy propionic acid propylate, propyl butoxy propionate, butyl methoxypropionate, butyl ethoxypropionate, butyl propoxypropionate, and butyl butoxy propionate; And examples thereof include methyl methoxybutyrate, methyl ethoxybutyrate, methyl propoxybutyrate, methyl butoxybutyrate, ethyl methoxybutyrate, ethyl ethoxybutyrate, ethyl propoxybutyrate, ethyl butoxybutyrate, methoxybutyric acid propyl, ethoxybutyric acid, Alkoxybutyric acid esters such as propoxybutyric acid propyl, propoxybutyric acid propyl, butyl methoxybutyric acid, butyl ethoxybutyric acid, butyl propoxybutyric acid, and butyl butoxybutyric acid; Methyl methoxy valerate, methyl methoxy valerate, methyl ethoxy valerate, methyl propoxy valerate, methyl butoxy valerate, ethyl methoxy valerate, ethyl ethoxy valerate, ethyl propoxy valerate, ethyl butoxy valerate, methoxy Examples of the alkoxy valeric acid such as valeric acid propyl, ethoxy valeric acid, propoxy valeric acid, propoxy valeric acid, butyl methoxy valeric acid, butyl ethoxy valeric acid, butyl propoxyvaleric acid and butyl butoxy valeric acid ester; But are not limited to, dimethyl methoxymonate, dimethyl ethoxymalonate, dimethyl propoxymalonic acid, dimethyl butoxymalonate, diethyl methoxymalonate, diethyl ethoxymalonate, diethyl propoxymalonate, diethyl butoxy malonate, methoxy But are not limited to, diethyl malonate, dipropyl methoxylate, dipropyl methoxylate, dipropyl methoxylate, dipropyl butoxide, dibutyl methoxymaleate, dibutyl ethoxymaleate, dibutyl propoxymalonate, dibutyl butoxy malonate, methoxymalonic acid But are not limited to, methyl ethyl, ethoxymalonate methylethyl, propoxymalonic acid methylethyl, butoxymalonic acid methylethyl, methoxymalonic acid methylpropyl, ethoxymalonic acid methylpropyl, propoxymalonic acid methylpropyl, butoxymalonic acid methyl Propyl methoxymonate, methyl butyl methoxymonate, methyl butyl ethoxymalonate, methyl butyl propoxymalonate, and methyl butyl butyl butoxymalonate; Examples of the organic solvent include dimethyl dimethyl methoxysuccinate, dimethyl ethoxysuccinate, dimethyl propoxysuccinate, dimethyl butoxysuccinate, diethyl methoxysuccinate, diethyl ethoxysuccinate, diethyl propoxysuccinate, diethyl butoxy succinate, dipropyl methoxysuccinate, But are not limited to, dipropyl ethoxysuccinate, dipropyl propoxysuccinate, dipropyl butoxy succinate, dibutyl methoxysuccinate, dibutyl ethoxysuccinate, dibutyl propoxysuccinate, dibutyl butoxy succinate, methyl ethyl methoxysuccinate, ethoxy But are not limited to, methyl ethyl succinate, methyl ethyl propoxysuccinate, methyl ethyl butoxy succinate, methyl propyl methoxysuccinate, methyl propyl ethoxysuccinate, methyl propyl propoxysilate, methyl propyl butoxy succinate, methyl butyl methoxysuccinate, methyl ethoxysuccinate Alkoxysuccinic acid diesters such as butyl, methylbutyl propoxysuccinate and methylbutyl butoxysuccinate; Examples thereof include dimethyl methoxy glutarate, dimethyl ethoxy glutarate, dimethyl propoxy glutarate, dimethyl butoxy glutarate, diethyl methoxy glutarate, diethyl ethoxy glutarate, diethyl propoxy glutarate, diethyl methoxy glutarate, Diethyl methoxy glutarate, dipropyl methoxy glutarate, dipropyl ethoxy glutarate, dipropyl methoxy glutarate, dipropyl methoxy glutarate, dipropyl methoxy glutarate, dibutyl methoxy glutarate, dibutyl methoxy glutarate, dibutyl ethoxy glutarate, Dibutyl glutarate, dibutyl butoxybutyl glutarate, methylethyl methoxy glutarate, methyl ethyl ethoxy glutarate, methyl ethyl propoxy glutarate, methyl ethyl butoxy glutarate, methyl methoxy glutarate Propyl succinic acid, propyl succinic acid, propyl succinic acid, propyl succinic acid, propyl succinic acid, propyl succinic acid, propyl succinic acid, Alkoxyglutaric acid diesters such as methylbutyl tartarate and methylbutylbutoxyglutarate (2-alkoxyglutaric acid diester, 3-alkoxyglutaric acid diester); Dimethyl dimethyl methoxydiacetate, dimethyl methoxydaphosphate, dimethyl propoxyadipate, dimethyl butoxyadipate, diethyl methoxyadipate, diethyl ethoxyadipate, diethyl propoxyadipate, diethyl butoxyadipate , Dipropyl methoxyadipate, dipropyl ethoxyadipate, dipropyl propoxyadipate, dipropyl dipropionate, dibutyl dipropionate, dibutyl dipropionate, dibutyl dipropionate, dibutyl dipropionate, dibutyl dipropionate, dibutyl dipropionate, dibutyl dipropionate, dibutyl dipropionate, dibutyl dipropionate, dibutyl dipropionate , Methyl methoxyadipate methylethyl, ethoxyadipic acid methylethyl, propoxyadipic acid methylethyl, butoxyadipic acid methylethyl, methoxyadipic acid methylpropyl, ethoxyadipic acid methylpropyl, propoxyadipic acid methyl Propyl adipate, propyl adipate, propyl adipate, propyl adipate, propyl adipate, propyl adipate, propyl adipate, propyl adipate, Acid di-ester (2-alkoxy adipic acid diester, adipic acid diester, 3-alkoxy, 4-alkoxy-adipic acid diester); 2-methoxy-1,2,3-propanetricarboxylic acid trimethyl ester, 2-methoxy-1,2,3-propanetricarboxylic acid triethyl ester, 2-methoxy- Propane tricarboxylic acid triphenyl ester, 2-methoxy-1,2,3-propanetricarboxylic acid tributyl ester, 2-methoxy-1,2,3-propanetricarboxylic acid dimethylethyl ester, 2 Methoxy-1,2,3-propanetricarboxylic acid dimethyl ester, 2-methoxy-1,2,3-propanetricarboxylic acid dimethyl butyl ester, 2-methoxy-1,2,3- Propane tricarboxylic acid methyl ethyl ester, 2-methoxy-1,2,3-propanetricarboxylic acid methyl ethyl butyl ester, 2-ethoxy-1,2,3-propanetricarboxylic acid trimethyl ester, Ethoxy-1,2,3-propanetricarboxylic acid triethyl ester, 2-ethoxy-1,2,3-propanetricarboxylic acid tripropyl ester, 2-ethoxy-1,2,3 -Propane tricarboxylic acid tributyl ester, 2- Ethoxy-1,2,3-propanetricarboxylic acid dimethyl ester, 2-ethoxy-1,2,3-propanetricarboxylic acid dimethyl ester, 2-ethoxy-1,2,3-propanetricarboxylic acid methylethylpropyl ester, 2-ethoxy-1,2,3-propanetricarboxylic acid methylethylbutyl ester, 2 -Propoxy-1,2,3-propanetricarboxylic acid trimethyl ester, 2-propoxy-1,2,3-propanetricarboxylic acid triethyl ester, 2-propoxy-1,2,3-propane Tricarboxylic acid tripropyl ester, 2-propoxy-1,2,3-propanetricarboxylic acid tributyl ester, 2-propoxy-1,2,3-propanetricarboxylic acid dimethylethyl ester, 2- Propoxy-1,2,3-propane tricarboxylic acid dimethyl ester, 2-propoxy-1,2,3-propanetricarboxylic acid dimethyl butyl ester, 2-propoxy-1,2,3-propane Tricarboxylic acid Propyl tricarboxylic acid methyl ethyl butyl ester, 2-butoxy-1,2,3-propanetricarboxylic acid trimethyl ester, 2-butoxy-1,2,3- 1,2,3-propanetricarboxylic acid triethyl ester, 2-butoxy-1,2,3-propanetricarboxylic acid tripropyl ester, 2-butoxy-1,2,3-propanetricarboxyl Butoxy-1,2,3-propanetricarboxylic acid dimethyl ester, 2-butoxy-1,2,3-propanetricarboxylic acid dimethyl ester, 2-butoxy- Propane tricarboxylic acid dimethyl butyl ester, 2-butoxy-1,2,3-propanetricarboxylic acid methyl ethyl ester, 2-butoxy-1,2,3-propanetricarboxylic acid And methyl ethyl ketoxylate. Of these, 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate and 2-alkoxy succinic acid dialkyl esters such as dimethyl 2-methoxy succinate are particularly preferred.

When two kinds of organic solvents are used in combination, the ratio between them is appropriately selected depending on the type and purpose of the solvent. For example, when the organic solvent contained in the alkoxycarboxylic acid ester compound group and the organic solvent contained in the acetoxycarboxylic acid ester compound group are used in combination, the ratio of the former to the latter is 1 / (weight ratio) = 1 / 99 to 99/1, preferably 5/95 to 95/5, and more preferably 10/90 to 90/10. When the organic solvent contained in the hydroxycarboxylic acid ester compound group and the organic solvent included in the alkoxycarboxylic acid ester compound group are used in combination, or when the organic solvent contained in the hydroxycarboxylic acid ester compound group and the acetoxy When the organic solvents contained in the carboxylic acid ester compound group are used in combination, it is preferable to use them in the same ratio as described above.

As long as the effect of the present invention is not impaired, another organic solvent (d) can be added (concurrently) to the organic solvent in the present invention. Examples of other organic solvents (d) which can be added include carboxylic acid alkyl esters, aliphatic ketones and the like. Examples of the carboxylic acid esters include alkyl esters of aliphatic carboxylic acids having about 1 to 4 carbon atoms (for example, C _{1 -6} alkyl esters and the like) such as alkyl acetate esters and propionic acid alkyl esters.

More specifically, such as the alkyl esters such as ethyl acetate as the propyl acetate, n- butyl acetate, amyl acetate, such as n- C _{1 -6} alkyl ester, propionic acid alkyl ester as methyl propionate, ethyl propionate, propyl propionate, butyl Propionic acid C _{1 -6} alkyl ester, and the like. Examples of the aliphatic ketone include aliphatic ketones having about 3 to 10 carbon atoms such as 2-butanone, 2-pentanone, 2-hexanone and 2-heptanone.

In addition to the above, other organic solvents (d) which can be added include glycol ethers such as monopropylene glycol alkyl ether and dipropylene glycol alkyl ether; And glycol ether acetates such as monopropylene glycol alkyl ether acetate (propylene glycol methyl ether acetate and the like).

The amount of the other organic solvent (d) can be appropriately selected within a range that does not impair the solubility of the resin and other properties as a solvent for a resist, but is usually 80% by weight or less, preferably 70% More preferably not more than 50% by weight, particularly preferably not more than 10% by weight, and may be substantially 0% by weight.

The resist component in the resist composition of the present invention may be any one of conventionally known or well-known positive or negative type resists. Representative examples of the resist usable in the present invention include, for example, a quinone diazide-based photosensitive agent and an alkali-soluble resin, a chemically amplified resist, and the like, Those containing an aromatic azide compound or those containing azide compounds such as those containing a cyclic rubber and a bisazide compound, those containing a diazo resin , A photopolymerizable composition containing an addition polymerizable unsaturated compound, a chemically amplified negative resist comprising an alkali soluble resin, a crosslinking agent, and an acid generator.

In the present invention, those containing a quinonediazide photosensitive agent and an alkali-soluble resin are preferable as a resist material to be used. A variety of positive resists including a quinonediazide photosensitive agent and an alkali-soluble resin have been known in the past, but the present invention is not limited thereto.

Examples of quinonediazide-based photosensitizers used in positive resists comprising these quinonediazide photosensitizers and alkali-soluble resins include, for example, 1,2-benzoquinonediazide-4-sulfonic acid, 1,2- 4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, esters or amides of these sulfonic acids, and the like. The ester or amide compound of the sulfonic acid is obtained by a condensation reaction of the corresponding quinonediazide sulfonic acid or quinonediazide sulfonyl chloride with a compound having a hydroxyl group or a compound having an amino group.

Examples of the compound having a hydroxyl group include dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phenol, naphthol, p-methoxyphenol, bisphenol A, pyrocatechol, pyrogallol, pyrogallol methyl ether, , tris (hydroxyphenyl) methane, and the like. Examples of the compound having an amino group include aniline, p-amino Diphenylamine, etc. These quinone diazide-based photosensitizers can be used alone or as a mixture of two or more thereof.

On the other hand, examples of the alkali-soluble resin include novolak resins, polyvinyl phenol, polyvinyl alcohol, copolymers of acrylic acid and methacrylic acid, and the like.

Examples of the novolak resin include phenol, o-cresol, m-cresol, p-cresol, xylenol, trimethylphenol, t-butylphenol, ethylphenol, 2-naphthol, 1,3-dihydroxynaphthalene , And condensation products of one or more phenols with aldehydes such as formaldehyde and paraformaldehyde. These alkali-soluble resins such as novolac resins can be used in combination of two or more kinds as needed, and further, other resins can be added for improving the film formability and the like. As the quinone diazide sulfonic acid ester, esters of quinone diazidesulfonic acid with a polycondensation product of phenols and aldehydes or ketones may also be used.

The ratio of the quinone diazide-based photosensitive agent to the alkali-soluble resin differs depending on the photosensitive agent and alkali-soluble resin specifically used and is generally in the range of 1: 1 to 1:20 by weight, .

A chemically amplified resist is also a positive resist which can be preferably used in the present invention. The chemically amplified resist is used to generate an acid by irradiation with radiation and to change the solubility of the irradiated portion in the developer by a chemical change caused by a catalytic action of the acid to form a pattern. For example, An acid-generating compound which generates an acid, and an acid-sensitive group-containing resin which is decomposed in the presence of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group.

Examples of the acid generating compound that generates an acid by irradiation with radiation include bis-sulfonyldiazomethanes such as bis (isopropylsulfonyl) diazomethane, bis-sulfonyl methanes such as methylsulfonyl p-toluenesulfonylmethane , Sulfonylcarbonyldiazomethanes such as cyclohexylsulfonylcyclohexylcarbonyldiazomethane, sulfonylcarbonylalkanes such as 2-methyl-2- (4-methylphenylsulfonyl) propiophenone, 2-nitro Nitrobenzyl sulfonates such as benzyl p-toluenesulfonate, alkyl or aryl sulfonates such as pyrogallol tris methanesulfonate, benzoin sulfonates such as benzoin tosylate, N- (trifluoromethylsulfonyl) (4-fluoro-benzenesulfonyloxy) -3,4,6-trimethyl-2-pyridone, 2,2,2,2-tetramethyl- -Trifluoro-1-trifluoromethyl-1- (3-vinylphenyl) -ethyl-4- Sulfonic acid esters such as chlorobenzene sulfonate, and onium salts such as triphenylsulfonium methanesulfonate. These compounds may be used alone or in admixture of two or more.

The acid-sensitive group-containing resin which is decomposed in the presence of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group includes an alkali-soluble resin portion having an acid sensitive group and an alkali-soluble group which are decomposed in the presence of an acid. Examples of the acid-sensitive group include substituted methyl groups such as benzyl groups, 1-substituted ethyl groups such as 1-methoxyethyl group and 1-benzyloxyethyl group, 1-branched alkyl groups such as t-butyl group, silyl groups such as trimethylsilyl group, An acyl group such as an acetyl group, a cyclic acid decomposing group such as a tetrahydropyranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiopyranyl group, or a tetrahydrothiopuranyl group; And the like. Preferred among these acid decomposable groups are a benzyl group, a t-butyl group, a t-butoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydrothiopuranyl group.

Examples of the alkali-soluble resin having an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group include hydroxystyrene, hydroxy-? -Methylstyrene, hydroxymethylstyrene, hydroxyadamantyl (meth) acrylate, A polymer from vinyl monomers such as methyl (meth) acrylate, vinyl benzoic acid, carboxymethyl styrene, carboxymethoxystyrene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, Or copolymers thereof, copolymers of one or more of these monomers with other monomers, and condensation polymerization resins such as novolak resins.

Examples of the chemically amplified resist include a compound which decomposes in the presence of an alkali-soluble resin, an acid generator and an acid to lower the solubility-controlling effect of the alkali-soluble resin or accelerate the solubility of the alkali-soluble resin It is known and can be used.

These resist components may be dissolved in the organic solvent to prepare the resist composition of the present invention. The ratio of the resist component can be appropriately set according to the type of the resist to be used and the kind of the solvent. Usually, 50 to 3000 parts by weight, preferably 70 to 2000 parts by weight, more preferably 100 to 100 parts by weight, To 1000 parts by weight of an organic solvent is used. In particular, when 100 to 500 parts by weight of the organic solvent is used, the solubility of the alkali-soluble resin is often exhibited.

In addition, various conventionally known additives such as a surfactant, a sensitizer, and the like may be appropriately added to these resist compositions, depending on the purpose of use. When water is used, water may be added.

The resist composition of the present invention can be used in various applications such as the production of semiconductor devices or the production of liquid crystal display elements, but is preferably used as a photoresist composition for semiconductor production or liquid crystal display device production. Formation of a resist pattern using the resist composition of the present invention is performed, for example, as follows.

First, the resist composition of the present invention is prepared by dissolving a resist material in the above solvent. However, insolubles are removed by filtration of the resist composition of the present invention as required, and the resist composition is subjected to spin coating, roll coating, , Flexible coating, doctor coating, or the like, to a substrate such as silicon, glass or the like so that the film thickness after the pre-baking becomes, for example, 0.01 to 1000 mu m.

The resist composition applied to the substrate is pre-baked, for example, on a hot plate to remove the solvent, and a resist film is formed. The prebaking temperature differs depending on the type of the solvent or resist to be used, and is usually 30 to 200 ° C, preferably about 50 to 150 ° C.

After the resist film is formed, exposure is performed. Since the photosensitive regions are different depending on the resist used, exposure is performed using an exposure source along the photosensitive region of the resist. Exposure can be performed by using a known irradiation device such as a high-pressure mercury lamp, a metal halide lamp, an ultra-high pressure mercury lamp, a KrF excimer laser, an ArF excimer laser, an F2 laser, a soft X-ray irradiating device, an electron beam drawing device, Irradiation with a predetermined pattern shape is performed by ultraviolet rays, far ultraviolet rays, X-rays, electron beams or the like through a mask. After exposure, in order to improve developability, resolution, pattern shape and the like, after-baking is performed as necessary, and development is performed. After the development, if necessary, dry etching using a gas plasma or the like is performed to remove the antireflection film and the like, and a resist pattern is formed.

The development of the resist is usually carried out by using a developing solution and using a difference in solubility in a solvent for an exposed region and in an unexposed region or in an alkali solution. Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium silicate; amines such as ammonia, ethylamine, diethylamine, triethylamine, diethylethanolamine, triethanolamine, benzylamine, An aqueous solution or an aqueous solution in which quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperazine are dissolved is used.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

Examples 1 to 10 and Comparative Examples 1 to 3

2 g of the esterification reaction product of 1 mole of 2,4,4,4'-tetrahydroxybenzophenone and 3 moles of naphthoquinone-1,2-diazide-5-sulfonyl chloride and 8 g of cresol novolak resin Was dissolved in 40 g of a solvent having the composition shown in the following Table 1 (number ratio: weight ratio) to prepare a coating liquid for a positive photoresist composition. The coating liquid thus obtained was subjected to the following evaluation tests (1) to (4). The results are shown in Table 1.

(1) Presence or absence of precipitate

The prepared coating liquid was filtered with a 0.2 탆 membrane filter and allowed to stand at 40 캜, and the presence or absence of precipitates in the coating liquid at the lapse of 2 months was examined.

(2) Sensitivity change

The presence or absence of a change in sensitivity of the photoresist composition after 3 months was examined. That is, the case where the coating liquid immediately after preparation is applied to the substrate and dried, and the minimum exposure amount (sensitivity) when the coating liquid which has been dried for three months after the preparation is coated on the substrate and dried is compared, Quot ;, and " x "

(3) Cross-sectional shape

The prepared coating liquid was slit coated on a glass substrate and dried on a hot plate at 90 DEG C for 90 seconds to form a resist film having a film thickness of 1.3 mu m and exposed to light through a predetermined mask using a stepper, The plate was heated on a plate at 110 캜 for 90 seconds, then developed with 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH), rinsed with water for 30 seconds and dried, and evaluated by the following criteria.

: No undercut occurs at the contact portion between the glass substrate and the resist pattern.

X: Undercut occurred at the contact portion between the glass substrate and the resist pattern (see Fig. 1).

(4) Coating condition

The coating liquid thus prepared was slit-coated on a glass substrate, and the film thickness of the substrate dried at 90 DEG C for 90 seconds on a hot plate was measured to find that the coating was uniformly applied to the surface, and the " Bad ".

The abbreviations in the table are as follows.

SMH: Dimethyl 2-hydroxysuccinate

SMHA: Dimethyl 2-acetoxysuccinate

PMHA: methyl 2-acetoxypropionate

SMHM: Dimethyl 2-methoxysuccinate

PMHM: methyl 2-methoxypropionate

PGMEA: Propylene glycol methyl ether acetate

EL: Ethyl lactate

Examples 11 to 12 and Comparative Example 4

Monohydroxyadamantyl acrylate and tetrahydropyranyl methacrylate were copolymerized to obtain a copolymer of monohydroxyadamantyl acrylate unit having 70 mol% and tetrahydropyranyl methacrylate unit having 30 mol% and having a weight average molecular weight of 8,000 To obtain a copolymer. A solvent having the composition shown in Table 2 was added to the obtained resin so that the solid component became 25 wt%, and the dissolution rate (solubility) of the resin was examined by heating at 50 캜 for 10 minutes. The results are shown in Table 2. The abbreviations in the tables are the same as above.

○: A homogeneous transparent solution was obtained.

X: Insoluble resin of the granule remained on the wall.

The resist composition of the present invention is useful as a photoresist composition for producing a semiconductor device, a liquid crystal display element and the like because it is excellent in solvent solubility, safe to human body and excellent in stability.

1 is a schematic diagram showing a state (evaluation: X) in which an undercut is formed at a contact portion between a glass substrate and a resist pattern in an evaluation test of a cross-sectional shape.

DESCRIPTION OF THE REFERENCE NUMERALS

1: glass substrate

2: Resist pattern

3: undercut portion

Claims (4)

A resist composition comprising a resist component and an organic solvent, wherein the organic solvent includes (a) a hydroxycarboxylic acid ester compound group composed of a hydroxycarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety, (b) an acetoxycarboxylic acid ester compound group consisting of an acetoxycarboxylic acid ester having a carboxylic acid moiety having 2 to 6 carbon atoms, and (c ') an alkoxydicarboxylic acid ester compound group having a carboxylic acid moiety having 2 to 6 carbon atoms Wherein the resist composition comprises at least one organic solvent selected from the group consisting of alkoxydecarboxylic acid ester compounds composed of a carboxylic acid ester and a carboxylic acid ester. The organic solvent according to claim 1, wherein the organic solvent is selected from the group consisting of (a) a hydroxydecarboxylic acid ester compound group having a carboxylic acid moiety having 2 to 6 carbon atoms, (b) An acetoxycarboxylic acid ester compound group consisting of an acetoxycarboxylic acid ester group having 2 to 6 carbon atoms, and (c ') an alkoxydarboxylic acid ester group composed of an alkoxydecarboxylic acid ester having 2 to 6 carbon atoms in the carboxylic acid moiety And a plurality of organic solvents selected from at least one compound group of two or more of the three compound groups of the carboxylic acid ester compound group. The organic electroluminescent device according to claim 1, wherein the organic solvent is selected from the group consisting of a hydroxy polycarboxylic acid ester compound group composed of a 2-hydroxysuccinic acid dialkyl ester, an acetoxy group consisting of a dialkyl 2-acetoxysuccinic acid ester and a 2-acetoxypropionic acid alkyl ester A carboxylic acid ester compound group, and a 2-methoxy-succinic acid dialkyl ester alkoxydecarboxylic acid ester compound group, each of which contains at least one organic solvent selected from at least two compound groups, Composition. The resist composition according to any one of claims 1 to 3, further comprising at least one solvent selected from carboxylic acid alkyl esters and aliphatic ketones as the organic solvent.

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