JP3044620B2 - Developer for resist - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resist developer. More specifically, images (patterns) using positive or negative resists such as azide compounds and chemical amplification systems
The present invention relates to a resist developer that can be suitably used in the formation.

[0002]

2. Description of the Related Art In lithography technology in the technical fields of semiconductor devices and liquid crystal display devices, there is a demand for further improvement in the dissolution selectivity of photoresist and the uniformity of fine patterns to be formed. In response to this request, high-resolution resists such as azide compound-based and chemically amplified resists using an alkali-soluble polymer as a base resin have been developed as positive or negative resists, and quaternary ammonium hydroxide or the like as a developing solution. Are known.

However, when only an aqueous solution of a quaternary ammonium hydroxide is used as a developing solution, the dissolution selectivity to the resist is reduced due to the miniaturization of the resist pattern, and application in a field where high resolution is required. Is no longer satisfactory.

Therefore, in order to further improve the dissolution selectivity with respect to a resist, a developer in which an alkylene oxide compound is added to an aqueous solution of a quaternary ammonium hydroxide or the like has been proposed [Japanese Patent Publication No. 6-38159, JP-B 5-73228 and JP-A-60-223120], the dissolution selectivity of the resist has not been satisfied.

[0005]

SUMMARY OF THE INVENTION The present invention has excellent dissolution selectivity by promoting solubility in a dissolving part and suppressing solubility in a non-dissolving part, even in a fine resist pattern. It is an object of the present invention to provide a resist developer that can be developed in a shorter time.

[0006]

The gist of the present invention is to provide: (1) a basic organic compound A and a compound B having a carboxyl group capable of forming a salt with the basic compound [hereinafter simply referred to as organic compound B] Ri Na is prepared with, said base
Organic compound A is a quaternary ammonium hydroxide
And the organic compound B is a compound of the formula (I) having a molecular weight of 46 to 200.
In represented, resist developer for use in the fabrication of printed circuit, (2) and the basic organic compound A, Ri Na contain salt C formed from an organic compound B, said basic organic compound A But
A quaternary ammonium hydroxide, the organic compound B
Is a wiring circuit represented by the formula (I) having a molecular weight of 46 to 200.
Resist developer for use in the preparation of the road, (3) Furthermore, basic organic compounds A and / or comprising the organic compound B above (2) Existing image solution according, (4) Furthermore, an alkylene oxide compound And (5) a developing method for developing using the developer according to any one of (1) to (4).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The salt C formed from a basic organic compound A and an organic compound B referred to in the present specification is a salt of the basic organic compound A and the organic compound B and / or a salt formed from the salt. Dissociated material.

The raw materials used in the developer of the present invention include, for example, basic organic compound A and organic compound B; salt C; basic organic compound A, organic compound B and salt C; basic organic compound A and salt C. The developer can be prepared, for example, by dissolving the raw materials in water.

The developer contains a salt C, but may further contain a basic organic compound A and / or an organic compound B.

Representative examples of the basic organic compound A include ammonia, primary amine, secondary amine, tertiary amine, imine, alkanolamine, amide, basic heterocyclic compound and quaternary ammonium hydroxide. These can be used alone or in combination of two or more.

Specific examples of the basic organic compound A include ammonia; primary amines such as ethylamine, n-propylamine, n-butylamine and 1,3-diaminopropane;
Secondary amines such as diethylamine, di-n-propylamine, di-n-butylamine, and 4,4'-diaminodiphenylamine; tertiary amines such as n, n-dimethylethylamine, n, n-diethylmethylamine and triethylamine; Imines such as bis (dialkylamino) imine; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, diethylethanolamine and propanolamine; amides such as formamide and acetamide; pyrrole, pyrrolidine, pyrrolidone, pyridine, morpholine and pyrazine; A basic heterocyclic compound having at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom in a ring skeleton containing 3 to 5 carbon atoms such as piperidine, oxazole and thiazole;
I):

[0012]

Embedded image

(Wherein R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, 7 to 8 carbon atoms)
Aralkyl group, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms)
And the like.

Specific examples of the quaternary ammonium hydroxide represented by the formula (II) include tetramethylammonium hydroxide (hereinafter referred to as TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and tributylmethylammonium hydroxide. , Trimethylhydroxyethylammonium hydroxide (hereinafter referred to as choline), tetraethanolammonium hydroxide, methyltriethanolammonium hydroxide and the like. Among these basic organic compounds A, quaternary ammonium hydroxides are preferred from the viewpoint of solubility selectivity, and each of R ^{2 to} R in the formula (II)
The carbon number of ⁵ is preferably 1 to 4, and more preferably 1 or 2. Specifically, TMA
H and choline are particularly preferred.

[0015] The "dissolution selectivity" of the developer referred to in the present specification means a property of promoting the solubility of a resist in a dissolved portion and suppressing the solubility of a non-dissolved portion. .
For example, in the case of a positive resist, a portion irradiated with ultraviolet rays, far ultraviolet rays, excimer laser, X-rays, an electron beam, or the like corresponds to a dissolved portion, and a non-exposed portion corresponds to a non-dissolved portion.

Examples of the basic compound capable of forming a salt with the organic compound B include a basic organic compound A and a basic inorganic compound. Examples of the basic inorganic compound include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like.

Specific examples of the organic compound B include an organic compound containing a carboxyl group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfino group, or a sulfeno group in a molecule, and the organic compound B and the basic inorganic compound. Salts.

Further, specific examples of the organic compound B include:
Examples include ethers, esters, amides or imides having a carboxyl group, a thiocarboxyl group, a dithiocarboxy group, a sulfo group, a sulfino group or a sulfeno group in the molecule, and salts of these with basic inorganic compounds.

Examples of the ether, ester, amide or imide include an ester of polycarboxylic acid, polythiocarboxylic acid or polydithiocarboxylic acid with an alcohol or an alkylene oxide adduct thereof, an amidate of an amine or an alkylene oxide adduct thereof, Examples include imidized compounds and esterified compounds.

Examples of the alcohol and its alkylene oxide adduct include straight-chain saturated alcohol, branched-chain saturated alcohol, straight-chain unsaturated alcohol, branched-chain unsaturated alcohol, alcohol having an aromatic ring, alcohol having an alicyclic or heterocyclic ring, Examples include polyhydric alcohols and their ethylene oxide and / or propylene oxide adducts.

Examples of the amine and its alkylene oxide adduct include a linear saturated amine, a branched saturated amine, a linear unsaturated amine, a branched unsaturated amine, an amine having an aromatic ring, an amine having an alicyclic or heterocyclic ring, Examples thereof include polyamines, and ethylene oxide and / or propylene oxide adducts thereof.

Specific examples of the organic compound B include acidic esters of inorganic acids (carbonic acid esters, sulfate esters, phosphoric acid esters, etc.), complex compounds of borate esters, acidic esters of inorganic acids and basic inorganic compounds. And salts of a boric acid ester complex compound with a basic inorganic compound.

Further, specific examples of the organic compound B include:
Organic acids and salts of organic acids and basic inorganic compounds are exemplified. Specific examples of the organic acid include carboxylic acid, thiocarboxylic acid, dithiocarboxylic acid, peracid, mercaptan, sulfonic acid, sulfinic acid, sulfenic acid, phosphonic acid, phosphatidic acid, and phosphine.

Among the organic compounds B, an organic compound having a carboxyl group, a thiocarboxyl group or a dithiocarboxyl group in the molecule and a salt of the organic compound and a basic inorganic compound are preferable from the viewpoint of solubility selectivity. Among them, an organic compound having a carboxyl group in the molecule and a salt of the organic compound and a basic inorganic compound are more preferable.
Carboxylic acids and salts thereof are more preferred, with carboxylic acids being particularly preferred.

Examples of the carboxylic acid include linear saturated monocarboxylic acids, linear unsaturated monocarboxylic acids, branched saturated monocarboxylic acids, branched unsaturated monocarboxylic acids, saturated polycarboxylic acids, and unsaturated polycarboxylic acids. , Hydroxycarboxylic acid,
One or more selected from the group consisting of aminocarboxylic acids, alkoxycarboxylic acids, carboxylic acids having an aromatic ring, carboxylic acids having an alicyclic ring, and carboxylic acids having a heterocyclic ring are exemplified.

The molecular weight of the carboxylic acid is preferably from 46 to 10000, more preferably from 46 to 1000, particularly preferably from 46 to 200, from the viewpoint of solubility selectivity.

Further, from the viewpoint of further dissolution selectivity, the carboxylic acid is represented by the formula (I): A-[(R ¹ ) _K- (COOH) _m ] _n (I) wherein R ¹ is a hydrogen atom, A saturated or unsaturated hydrocarbon group having a linear, branched or cyclic skeleton having 1 to 40 carbon atoms, wherein the hydrocarbon group of R ¹ has 1 to 5 oxygen atoms, nitrogen atoms or sulfur atoms. A hydrogen atom bonded to the carbon atom of R ¹ may be —OH group, —NH ₂
Group, -SH group or -NO ₂ group may be substituted,
Each of the m —COOH groups may be bonded to the same carbon atom of R ¹ , k is 0 or 1, m is an integer of 1 to 40, n is an integer of 1 to 3 (when A does not exist, n is 1,
When A is present, n is 2 or 3), A is not present or -O-, -CO-, -NH-, -S- or

[0028]

Embedded image

It is preferable to use a carboxylic acid represented by the following formula:

R ¹ is an alkylene group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. Is preferably an aryl group or an alkoxyalkyl group having 2 to 20 carbon atoms.

In the formula (I), when A does not exist,
Specific examples of the carboxylic acid include linear saturated monocarboxylic acids having 1 to 18 carbon atoms, such as formic acid, acetic acid, and propionic acid;
Acrylic acid, crotonic acid, vinyl acetic acid, 4-pentenoic acid,
Linear unsaturated monocarboxylic acids such as 6-heptenoic acid, 2-octenoic acid, undecylenic acid and oleic acid; isobutyric acid, isovaleric acid, pivalic acid, 2-methylbutyric acid, 2-methylvaleric acid, 2,2-dimethyl Butyric acid, 2-ethylbutyric acid, tert-butylbutyric acid, 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid,
2-methylhexanoic acid, 2-ethylhexanoic acid, 2,4-dimethylhexanoic acid, 2-methylheptanoic acid, 2-propylpentanoic acid, 3,5,5-trimethylhexanoic acid, 2-methyloctanoic acid, 2-methylhexanoic acid Branched saturated monocarboxylic acids such as ethylheptanoic acid, 2-ethyl-2,3,3-trimethylbutyric acid, 2,2,4,4-tetramethylpentanoic acid and 2,2-diisopropylpropionic acid; methacrylic acid, tiglic acid , 3,3-dimethylacrylic acid, 2,2-
Branched unsaturated monocarboxylic acids such as dimethyl-4-pentenoic acid, 2-ethyl-2-hexenoic acid and citronellic acid; oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid Acid, 2,2-dimethylsuccinic acid, glutaric acid, adipic acid, 3-methyladipic acid, sebacic acid, hexadecandioic acid, 1,2,3
-Saturated polycarboxylic acids such as propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, polyacrylic acid and polymaleic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, cis-aconitic acid, trans -Unsaturated polycarboxylic acids such as aconitic acid; hydroxycarboxylic acids such as lactic acid, gluconic acid, tartaric acid, malic acid and citric acid;
Aminocarboxylic acids such as glycine, DL-alanine, 4-aminobutyric acid, DL-3-aminobutyric acid, and sarcosine; alkoxycarboxylic acids such as methoxyacetic acid and ethoxyacetic acid; benzoic acid, terephthalic acid, trimellitic acid, and naphthoic acid A carboxylic acid having an aromatic ring; cyclohexanecarboxylic acid,
Carboxylic acids having an alicyclic ring, such as cyclohexanepropionic acid, cyclohexanebutyric acid, and cyclopentanecarboxylic acid;
Carboxylic acids having a heterocyclic ring such as furic acid, tenic acid, nicotinic acid and the like can be mentioned.

In the formula (I), when A is present, specific examples of the carboxylic acid include diglycolic acid,
Thiodiglycolic acid, 4,6-dioxoheptanoic acid, iminodiacetic acid, nitrotriacetic acid and the like.

Among these carboxylic acids, the solubility selectivity
From the viewpoint of formula (I), R ¹Is a hydrogen atom, carbon
Linear saturated hydrocarbon group having 1 to 18 carbon atoms, 3 to 18 carbon atoms
Branched saturated hydrocarbon group, straight-chain having 2 to 18 carbon atoms
Unsaturated hydrocarbon group, branched chain unsaturated having 3 to 18 carbon atoms
Saturated or having an alicyclic group having 3 to 18 carbon atoms,
Unsaturated hydrocarbon group, having an aromatic ring having 6 to 18 carbon atoms
It is preferably a sum or unsaturated hydrocarbon group. further
Is R¹Is a linear saturated hydrocarbon group having 1 to 12 carbon atoms,
A branched saturated hydrocarbon group having 3 to 12 carbon atoms, 2 carbon atoms
-12 straight-chain unsaturated hydrocarbon groups, 3-12 carbon atoms
A branched unsaturated hydrocarbon group, an alicyclic ring having 3 to 12 carbon atoms;
Saturated or unsaturated hydrocarbon groups having 6 to 12 carbon atoms
It may be a saturated or unsaturated hydrocarbon group having an aromatic ring.
Is more preferable. In particular, R¹Is linear saturated having 1 to 6 carbon atoms
Hydrocarbon group, branched saturated hydrocarbon having 3 to 6 carbon atoms
Group, linear unsaturated hydrocarbon group having 2 to 6 carbon atoms, carbon number
3 to 6 branched unsaturated hydrocarbon groups, 3 to 6 carbon atoms
A saturated or unsaturated hydrocarbon group having an alicyclic ring, having 6 to 8 carbon atoms
A saturated or unsaturated hydrocarbon group having an aromatic ring
Is most preferred.

When the hydrocarbon group for R ¹ has an oxygen atom, a nitrogen atom or a sulfur atom, the number of such atoms is more preferably 1 or 2 respectively.

In the formula (I), from the viewpoint of solubility selectivity, m is an integer of 1 to 40, more preferably an integer of 1 to 20, more preferably an integer of 1 to 12, and an integer of 1 to 6. Is particularly preferred.

As the thiocarboxylic acid, o-thioacetic acid,
Hexanebis (thioic acid) and the like. Examples of the dithiocarboxylic acid include dithiobenzoic acid. Examples of the ester having a carboxyl group include monoethyl succinate, acetylsalicylic acid, and the like. Examples of the amide having a carboxyl group include oxamic acid and DL-alanyl-DL-alanine.

The salt C in the developer is prepared by adding a salt C formed from a basic organic compound A and an organic compound B to water, adding the basic organic compound A and the organic compound B to water, A method of forming C, adding an organic compound B present as a salt with a basic inorganic compound to a developer containing a basic organic compound A, and adding an anion in the salt to a base in the developer. It can be prepared by a method such as a method of forming a salt C by substituting an anion in the organic compound A with an anion. Among these methods, the method and the method are preferable from the viewpoint of avoiding corrosion of a wiring circuit due to a metal derived from the basic inorganic compound as compared with the method.

Among the salts C, from the viewpoint of dissolution selectivity, the preferred basic organic compound A and the organic compound B
Among these, salts formed from those preferred are more preferred.

2% by weight TMAH of organic compound B and salt C
The solubility at 25 ° C. with respect to 100 parts by weight of the aqueous solution is preferably 0.001 part by weight or more, preferably 0.05 part by weight or more, and more preferably 0.1 part by weight or more, from the viewpoint of solubility selectivity. . From the viewpoint of solubility selectivity, the first dissociation constant at 25 ° C. of the pKa of the organic compound B is desirably 0.1 to 10, preferably 0.5 to 6.

The sum of the content of the basic organic compound A in the developer and the content of the basic organic compound A forming the salt C (total content) is a factor that promotes the dissolution of the resist in the dissolution part. From the viewpoint, it is desirably 0.5% by weight or more, preferably 1% by weight or more, and more preferably 1.5% by weight or more. From the viewpoint of suppressing dissolution in the non-dissolved portion of the resist, it is preferably 20% by weight or less. Is 10% by weight or less,
More preferably, it is desirably 5.5% by weight or less. The total content is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, and still more preferably 1.5 to 10% by weight.
5.5% by weight.

The content of the basic organic compound A in the developer is from 0.1 to 19.
It is preferably 5% by weight, more preferably 0.5 to 10% by weight, further preferably 1 to 5% by weight, and particularly preferably 1.5 to 2.5% by weight.

The sum of the content of the organic compound B in the developer and the content of the organic compound B forming the salt C (total content) is from 0.001 to 0.001 from the viewpoint of solubility selectivity.
15% by weight is preferable, 0.001 to 4% by weight is more preferable, and 0.05 to 2.0% by weight is more preferable.
0.05 to 1% by weight is particularly preferred.

The sum of the equivalent of the basic organic compound A in the developer and the equivalent of the basic organic compound A forming the salt C (total equivalent), and the equivalent of the organic compound B and the formation of the salt C The ratio of the organic compound B to the sum (total equivalent) of the organic compound B is preferably from 1: 0.001 to 1: 0.80, more preferably from 1: 0.005 to 1: from the viewpoint of dissolution selectivity. 0.
60, particularly preferably 1: 0.01 to 1: 0.50.

The ratio of the equivalent of the basic organic compound A in the developer of the present invention to the sum of the equivalent of the organic compound B and the equivalent of the organic compound B forming the salt C (total equivalent) is as follows: From the viewpoint of dissolution selectivity, the ratio is preferably from 1: 0.001 to 1: 4, more preferably from 1: 0.005 to 1: 1.
5, particularly preferably 1: 0.01 to 1: 1.

The content of the salt C in the developing solution is preferably from 0.001 to 4.5% by weight, more preferably from 0.01 to 15% by weight, and more preferably from 0.05 to 15% by weight, from the viewpoint of solubility selectivity.
10% by weight is more preferable, and 0.1 to 5% by weight is particularly preferable.

When the developer contains the basic organic compound A and the salt C, the content of the basic organic compound A in the developer, the content of the organic compound B forming the salt C and the salt The content of the basic organic compound A forming C can be quantified, for example, as follows.

The total amine value (KOH mg / g) of the developer is titrated with a 0.2N alcoholic hydrochloric acid standard solution using a potentiometric titrator and measured by a known method described in ASTM D2073-66 and the like.

Since the salt C is contained in the developing solution, two or more inflection points are observed in a pH titration curve obtained by titration with a standard solution of alcoholic hydrochloric acid.

The amine value having the lowest value among the obtained total amine values is defined as the amine value (KOH mg / g) of the basic organic compound A in the developer.

The value obtained by subtracting the lowest amine value from the highest amine value is calculated as the salt C in the developer.
Value of the basic organic compound A (KOH
mg / g).

Next, the total amine value of the basic organic compound A itself is measured by the above method.

The acid value (KO) of the organic compound B itself
Hmg / g) is measured by a known method described in JIS K0070 (1992) and the like.

The content (% by weight) of the basic organic compound A in the developer, the content (% by weight) of the organic compound B in the salt C in the developer, and the basic content in the salt C in the developer The content (% by weight) of the organic compound A can be determined according to the following equation. [Content (% by weight) of basic organic compound A in developer] = [Amine value (KOH mg
/ G)] ÷ [total amine value of basic organic compound A itself (KOH mg / g)] × 100 [content (% by weight) of organic compound B in salt C in developing solution] = [in developing solution Amine value of basic organic compound A in salt C (KOH mg / g)] ÷ [organic compound B
Acid value of itself (KOH mg / g)] × 100 [Content (% by weight) of basic organic compound A in salt C in developer] = [basic organic compound A in salt C in developer] Amine value (KOH mg / g)] ÷ [total amine value of basic organic compound A itself (KOH mg / g)
g)] × 100 By adding an alkylene oxide compound to the developer, the dissolution selectivity of the developer and the development speed can be further improved. As used herein, the term "alkylene oxide compound" refers to a compound obtained by adding an alkylene oxide to a compound having active hydrogen such as an alcohol, a phenol compound, an amine, or a carboxylic acid, and a derivative thereof.

Specific examples of the alcohol include methanol, ethanol, n-propanol, n-butanol,
linear saturated alcohols such as n-pentanol, hexyl alcohol, n-octanol and n-dodecanol;
Methyl-1-propanol, neopentyl alcohol,
Amyl alcohol, 3-methyl-1-pentanol, 2
Branched saturated alcohols such as -ethyl-1-hexanol; linear unsaturated alcohols such as allyl alcohol, crotyl alcohol and oleyl alcohol; 2-methyl-2
-Propen-1-ol, 4-methyl-3-pentene-
Branched-chain unsaturated alcohols such as 1-ol; alcohols having an aromatic ring such as benzyl alcohol; alcohols having an alicyclic or heterocyclic ring such as cyclohexanol, cyclohexylmethanol, cyclooctanol, decahydro-2-naphthol and furfuryl alcohol; Examples include polyhydric alcohols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerol, pentaerythritol, arabitol, and sorbitol.

Specific examples of the phenol compound include phenol, ortho-cresol, nonylphenol and the like.

Specific examples of the amine include ethylamine,
Linear saturated amines such as propylamine, octylamine and dodecylamine; branched-chain saturated amines such as isopropylamine and tert-butylamine; linear unsaturated amines such as allylamine and oleylamine; aniline, n-methylaniline, p-toluidine; Amines having an aromatic ring such as benzylamine; amines having an alicyclic or heterocyclic ring such as cyclopropylamine, cyclohexylamine and furfurylamine; ethylenediamine, diethylenetriamine,
And polyamines such as triethylenetetramine.

Specific examples of the carboxylic acid include straight-chain saturated monocarboxylic acids, straight-chain unsaturated monocarboxylic acids, branched-chain saturated monocarboxylic acids, and branched-chain unsaturated monocarboxylic acids exemplified above as the carboxylic acid used in the present invention. Saturated monocarboxylic acid, saturated polycarboxylic acid, unsaturated polycarboxylic acid, hydroxycarboxylic acid, aminocarboxylic acid, alkoxycarboxylic acid,
Examples thereof include carboxylic acids having an aromatic ring, carboxylic acids having an alicyclic or heterocyclic ring, and the like.

The alkylene oxide used in the alkylene oxide compound includes ethylene oxide and propylene oxide, and these can be used alone or in combination. These may be added in random or block units.

Among the alkylene oxide compounds, from the viewpoint of solubility selectivity, formula (III): R ⁶ _p Y ¹ -[(AO) _r -Y ² R ⁷ ] _q (III) (wherein R ⁶ is Hydrogen atom, alkyl group having 1 to 18 carbon atoms, aralkyl group having 7 to 18 carbon atoms, 2 to 18 carbon atoms
An alkenyl group or an aryl group having 6 to 18 carbon atoms, Y ¹
Is a -O- group, a -COO- group, or

[0060]

Embedded image

The group A is an ethylene group and / or a propylene group, r is an integer of 1 to 60, Y ² is absent or -C
An O- group, R ⁷ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, p is 1 or 2, q
Is 1 or 2, and when Y ¹ is a —O— group or a —COO— group, p is
And the sum of q is 2 and Y ¹ is

[0062]

Embedded image

In the case of a group, the sum of p and q is 3).

R ⁶ is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkyl group having 6 to 12 carbon atoms, from the viewpoint of solubility selectivity. It is preferably an aryl group, and is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 6 to 8 carbon atoms.
Is more preferably an aryl group.

R ⁷ is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, and is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 to 2 carbon atoms. More preferably, it is 6 alkenyl groups. R is an integer of 1 to 30, preferably 1 to 15
And more preferably an integer of 1 to 6.

The content of the alkylene oxide compound in the developer is from 0.001 to
It is desirably 5.0% by weight, preferably 0.01 to 2.0% by weight, and more preferably 0.01 to 0.5% by weight.

The developing solution of the present invention can be used in a developing step performed after the step of exposing the positive and negative resists. In particular, when the developer is used in a development step during a lithography step in a manufacturing process of a semiconductor element or a liquid crystal display element in which a fine resist pattern is required, the effect of the developer is easily exerted. preferable.

When developing using the developing solution of the present invention,
For example, a substrate such as a wafer to be processed may be developed one by one by a paddle method or the like using a spinner or a plurality of sheets by a cassette method by a dipping method or the like, or a spray method or rotation of a spinner or the like. May be performed by applying a mechanical stress such as a flow of a developing solution due to the above. Among these developing methods, a method of processing wafers one by one by a paddle method is preferable from the viewpoint of reducing the consumption of the developing solution and improving the dissolution selectivity. Further, the development temperature is preferably from 10 to 60 ° C, particularly preferably from 15 to 30 ° C.

The type of the resist to which the resist developing solution of the present invention is applied is not particularly limited. Examples thereof include a positive resist containing an alkali-soluble novolak resin and a photolytic agent such as a naphthoquinonediazide compound as components, and an alkali-insoluble resin (p-te
a chemically amplified positive resist containing, as constituents, rt-butoxycarbonyloxystyrene and the like; and an acid generator (triphenylsulfonium triflate and the like).
A negative resist containing, as constituents, an alkali-soluble novolak resin and an azide compound as a photosensitizer,
Chemically amplified negative resists containing, as constituents, an alkali-soluble polyvinylphenol resin or a novolak resin, an acid-reactive crosslinking agent (melamine-based, silanol-based acid-reactive crosslinking agent, etc.) and a photoacid generator, etc. No.

The use of the resist developing solution of the present invention promotes the solubility in the dissolved portion of the resist and suppresses the solubility in the non-dissolved portion, that is, improves the dissolution selectivity. Thus, a fine pattern with high resolution can be formed in a shorter time.

[0071]

Examples 1-28 The basic organic compound A which is a main component of the developer is, for example, TM
In the case of AH, the resolution of the resist after development greatly changes depending on the amount of TMAH existing in a free state in the developer.

Here, the “content of free TMAH in the developer” refers to “the content of all TMAH in the developer” and “the content of TMAH in the developer neutralized with the organic compound B”. ].

Accordingly, in each of the examples, by making the content of TMAH existing in a free state in the developing solution constant, the resolution of the resist by components other than TMAH can be relatively evaluated. The amount of TMAH added is
The total amount was the sum of the amount of TMAH existing in a free state and the amount of TMAH neutralized by the organic compound B.

In each of the examples, after mixing the TMAH and the carboxylic acid in the amounts set as described above, pure water was added to the mixture to prepare a developer having a predetermined concentration shown in Table 1 or Table 2. did.

For example, the content of free TMAH in the developer is 2.00% by weight, and the content of formic acid is 0.05% by weight.
When 1,000 g of the developing solution (Example 1) was prepared, the developing solution was prepared as follows. Free T in developer
The amount of TMAH (2
0g), the amount of TMAH (0.99) required for neutralizing formic acid was added.
g (free TMAH content in the developer is 0.0
This corresponds to 99% by weight. )) Plus TMAH
(20.99 g), a TMAH aqueous solution (139.93 g) containing 15% by weight of TMAH was prepared. Formic acid (0.50 g) in an amount of 0.05% by weight was added thereto, and finally, pure water was added to make the total amount 1000 g, thereby preparing a developer having a predetermined concentration.

The carboxylic acid used in Examples 1 to 28 had a solubility in 100 parts by weight of a 2% by weight aqueous TMAH solution of not less than 0.005 parts by weight at 25 ° C. Also, p
The first dissociation constant of Ka was 0.5-6 at 25 ° C.

The obtained developer was evaluated for a positive photoresist in the following manner.

Positive photoresist (novolak resin,
Diazonaphthoquinone compound, solvent) was applied on a 4-inch silicon wafer using a spinner. Next, using a hot plate, prebaking was performed at 110 ° C. for 90 seconds to obtain a photoresist film having a thickness of 1.5 μm.

The resist film was exposed to a reduction projection exposure apparatus (stepper) via a test chart. Thereafter, paddle development was performed at 23 ° C. for a certain time using a developer. After the developed photoresist film was rinsed with pure water for 30 seconds, it was dried under a nitrogen stream.

The resist pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the presence or absence of a resist film residue on the exposed portion was evaluated. In the table, ○ indicates that no residue was confirmed, Δ indicates that a small amount of residue was observed, and x indicates that a large amount of residue was observed.

Further, the film thickness of the resist film in the non-exposed area was measured using an ellipsometer, and the residual film ratio of the resist in the non-exposed area was calculated. The residual film ratio is determined by the resist film thickness before development (1.
5 μm) from the change in the resist film thickness of the unexposed portion after development. The results are shown in Tables 1 and 2.

The developer having excellent dissolution selectivity is excellent in that no residue of the resist film in the exposed portion is confirmed, and the resist remaining ratio in the unexposed portion is large.

[0083]

[Table 1]

[0084]

[Table 2]

Examples 29 to 35 In the same manner as in Example 1, a resist developer of the present invention was prepared, and the resist film was developed in the same manner as in Example 1.

The organic compound B capable of forming a salt with TMAH was other than carboxylic acid. Table 3 shows the composition of the obtained developer and the evaluation results.

The solubility of the organic compound B used in Examples 29 to 35 in 100 parts by weight of a 2% by weight aqueous TMAH solution was 0.005 parts by weight or more at 25 ° C. The first dissociation constant of pKa was 0.5 to 6 at 25 ° C.

[0088]

[Table 3]

Comparative Examples 1 to 8 An aqueous solution of TMAH alone was prepared and used as a developer. Using the obtained developer, the resist film was developed in the same manner as in Example 1. Table 4 shows the composition of the obtained developer and the evaluation results.

[0090]

[Table 4]

Examples 36 to 50 A developer having the composition shown in Table 5 was prepared by adding a salt of a basic compound and a carboxylic acid to a TMAH aqueous solution containing a predetermined amount of TMAH. The solubility of the carboxylate used in Examples 36 to 50 in 100 parts by weight of a 2% by weight TMAH aqueous solution was 0.005 parts by weight or more at 25 ° C. Using the obtained developer, the resist film was developed in the same manner as in Example 1. Table 5 shows the composition, evaluation results, and the like of the obtained developer.

[0092]

[Table 5]

From the above results, when the resist was developed using the resist developer of the present invention (Examples 1 to 50) prepared by adding the organic compound B or a salt thereof to the TMAH aqueous solution, the development of TMAH alone As compared with the case where the development was performed using the liquids (Comparative Examples 1 to 8), a resist pattern having high dissolution selectivity was formed while suppressing the reduction of the resist film in the non-exposed area. Further, the use of the developer of the present invention could shorten the development time.

The results of Comparative Examples 1 to 8 indicate that TMAH
It was found that in the case of development using only the above, the dissolution selectivity was not improved even if the content was increased.

Example 51 and Comparative Example 9 A developer for resist prepared in the same manner as in Example 1 [free TMAH (2.38% by weight), formic acid (4% by weight)] (Example 51) and TMAH alone Using the developing solution [2.38% by weight] (Comparative Example 9), the resist film was developed in the same manner as in Example 1. However, the prebake temperature was set to 135 ° C.

As a result, a developer containing only TMAH (Comparative Example 9)
In the case of using, a development time of 3.0 minutes was required to complete the development, and the residual film ratio of the non-exposed portion resist at that time was 95.0%.

On the other hand, the developer of the present invention (Example 5)
When 1) was used, it took only a short time of 1.0 minute to complete the development, and the residual film ratio of the non-exposed portion resist at that time was 97.0%.

Examples 52 to 61 and Comparative Examples 10 to 11 Developers were prepared using choline as the basic organic compound A in accordance with the method using TMAH.

Using the obtained developing solution, the resist film was developed in the same manner as in Example 1. The composition of the resulting developer,
Table 6 shows the evaluation results and the like.

[0100]

[Table 6]

As a result, the developer of the present invention (Examples 52 to 52)
61), the dissolution selectivity can be reduced while suppressing the reduction of the resist film in the non-exposed area, as compared with the case of developing using the developer containing only choline (Comparative Examples 10 to 11). A high resist pattern was formed.

Further, when the developing solution of the present invention was used, the developing time could be shortened.

Examples 62 to 73 and Comparative Example 12 A TMAH aqueous solution containing an alkylene oxide compound (Comparative Example 12) and a developer prepared in Examples (Examples 2, 9, and 16) containing an alkylene oxide compound The resist film of the invention was developed in the same manner as in Example 1. Table 7 shows the composition of each developer and the evaluation results.

In Table 7, MG is ethylene glycol monomethyl ether, BDG is diethylene glycol monobutyl ether, BEDG is diethylene glycol monobutyl ethyl ether, HDG is diethylene glycol monohexyl ether, EPE is 5 moles of ethylene oxide and 5 moles of propylene oxide. Lauryl ether of block copolymer of EGEO is polyethylene glycol (ethylene oxide 4 mol adduct),
PhDG is diethylene glycol monophenyl ether, POEH is polyoxyethylene (addition of 6 moles of ethylene oxide) hexyl ether acetate, POEB
Represents polyoxyethylene (addition of 10 moles of ethylene oxide) butylamine, and EOPO represents an ethylene oxide-propylene oxide copolymer (tylene oxide / propylene oxide (molar ratio): 7/1, average molecular weight: about 3000, pluronic type).

[0105]

[Table 7]

From the results shown in Table 7, when the resist was developed using the resist developer of the present invention (Examples 62 to 73), the development was performed using an aqueous solution of an alkylene oxide compound and TMAH (Comparative Example 12). As compared with the case, a resist pattern having high dissolution selectivity was formed while suppressing the reduction of the resist film in the non-exposed portion. Also, the use of the developer of the present invention could shorten the development time.

Examples 74 to 91 and Comparative Examples 13 to 17 Aqueous TMAH solution and Examples (Examples 1 to 4, 6, 8, 9,
The resist developing solution of the present invention prepared in 11, 12, 16, 18 to 25) was evaluated for a chemically amplified negative resist as follows.

Chemically amplified negative photoresist (composition:
Polyvinylphenol, melamine-based compound, bromine-based photoacid generator and solvent) were applied on a 4-inch silicon wafer using a spinner, and the wafer was pre-baked at 125 ° C. for 60 seconds using a hot plate to obtain a film thickness of 1 A photoresist film having a thickness of 0.0 μm was obtained.

After exposing this photoresist film using a KrF excimer laser, post exposure bake (PEB) was performed at 130 ° C. for 60 seconds using a hot plate.

Next, paddle development was performed using a developing solution at 23 ° C. for a certain period of time. The developed photoresist film was rinsed with pure water for 30 seconds, and then dried under a nitrogen stream.

The resist pattern on the obtained silicon wafer was observed using a scanning electron microscope, and the presence or absence of a resist film residue in the unexposed area was evaluated in the same manner as in Examples 1-28.

The thickness of the resist film in the exposed area was measured using an ellipsometer, and the residual film ratio of the resist in the exposed area was calculated. The residual film ratio was determined based on the resist film thickness before development (1.0 μm).
m) was determined from the change in the resist film thickness of the exposed portion after development. Table 8 shows the results.

The developer having excellent dissolution selectivity is excellent in that no residual film of the resist is observed in the non-exposed area, and the resist remaining rate in the exposed area is large.

[0114]

[Table 8]

From the results shown in Table 8, when the resist was developed using the resist developing solution of the present invention (Examples 74 to 91) prepared by adding carboxylic acid to the TMAH aqueous solution, T
Compared with the case where the developing was performed using only the MAH developer (Comparative Examples 13 to 17), a resist pattern having high dissolution selectivity was formed while suppressing the decrease in the thickness of the resist film in the exposed portion.

When the developing solution of the present invention was used, the developing time could be shortened.

Further, from the results of Comparative Examples 13 to 17, TM
In the case of development using only AH, it was found that dissolution selectivity was not improved even if the content was increased.

[0118]

According to the present invention, the resist developing solution of the present invention promotes solubility in a dissolved portion of a resist and suppresses solubility in a non-dissolved portion as compared with a conventional developing solution. The effect is excellent in selectivity and the development time can be reduced.

Continuation of the front page (56) References JP-A-8-95257 (JP, A) JP-A-7-333386 (JP, A) JP-A-7-181690 (JP, A) JP-A-6-266119 (JP) JP-A-6-222569 (JP, A) JP-A-62-159148 (JP, A) JP-A-59-142547 (JP, A) JP-A-11-109609 (JP, A) 10-198047 (JP, A) Special table 59-501482 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42 H01L 21/027

Claims (8)

(57) [Claims] [Claim 1] with a compound B having a basic organic compound A and a basic compound and a carboxyl group capable of forming a salt
Ri Na is prepared Te, said basic organic compound A quaternary ammonium
And has the carboxyl group
The compound B is a compound represented by the formula (I) having a molecular weight of 46 to 200: A-[(R ¹ ) _K- (COOH) _m ] _n (I) ( wherein R ¹ is a hydrogen atom and a straight chain having 1 to 12 carbon atoms ) Satiating
Japanese hydrocarbon group, branched saturated hydrocarbon having 3 to 12 carbon atoms
A hydrogen atom, a linear unsaturated hydrocarbon group having 2 to 12 carbon atoms,
A branched chain unsaturated hydrocarbon group having a prime number of 3 to 12, having 3 carbon atoms
A saturated or unsaturated hydrocarbon group having an alicyclic ring of 12 to 12 carbon atoms
A saturated or unsaturated hydrocarbon group having an aromatic ring of the number 6 to 12
Wherein the hydrocarbon group for R ¹ is 1-5 oxygen atoms, nitrogen
May have an atom or a sulfur atom, and a carbon atom of R ¹
Hydrogen atom bonded to the -OH group, -NH ₂ group, -S
May be substituted with an H group or a —NO ₂ group,
The COOH group may be bonded to the same carbon atom of R ¹
K is 0 or 1, m is an integer of 1 to 6, and n is an integer of 1 to 3.
The number A is absent or -O-, -CO-, -N
H-group, -S- group or A developer for use in the production of wiring circuits . Wherein the basic organic compound A, Ri Na contain salt C formed from a compound B having a carboxyl group capable of forming a basic compound and a salt, said basic organic compound A
Is a quaternary ammonium hydroxide, and the carboxy is
Is a compound having a molecular weight of 46 to 200.
(I): A-[(R ¹ ) _K- (COOH) _m ] _n (I) ( wherein R ¹ is a hydrogen atom, a linear saturated group having 1 to 12 carbon atoms )
Japanese hydrocarbon group, branched saturated hydrocarbon having 3 to 12 carbon atoms
A hydrogen atom, a linear unsaturated hydrocarbon group having 2 to 12 carbon atoms,
A branched chain unsaturated hydrocarbon group having a prime number of 3 to 12, having 3 carbon atoms
Saturated or unsaturated hydrocarbon group have a 12 alicyclic carbon
A saturated or unsaturated hydrocarbon group having an aromatic ring of the number 6 to 12
Wherein the hydrocarbon group for R ¹ is 1-5 oxygen atoms, nitrogen
May have an atom or a sulfur atom, and a carbon atom of R ¹
Hydrogen atom bonded to the -OH group, -NH ₂ group, -S
May be substituted with an H group or a —NO ₂ group,
The COOH group may be bonded to the same carbon atom of R ¹
K is 0 or 1, m is an integer of 1 to 6, and n is an integer of 1 to 3.
The number A is absent or -O-, -CO-, -N
H-group, -S-group or A developer for use in the production of wiring circuits . 3. Furthermore, the basic organic compound A and / or basic compound and comprising a <br/> compound B having a carboxyl group salts capable of forming Claim 2 current image solution according. 4. A quaternary ammonium hydroxide of the formula (I)
I): (Wherein R ² , R ³ , R ⁴ and R ⁵ are each independently
C1-C6 alkyl group, C7-C8 aralkyl
Group, alkenyl group having 2 to 6 carbon atoms, ant having 6 to 8 carbon atoms
Or a hydroxyalkyl group having 1 to 6 carbon atoms or carbon
Which represents an alkoxyalkyl group of Formulas 2 to 6)
The developer according to any one of claims 1 to 3, which is a compound. 5. Further, the developing solution according to claim 1-4, wherein one comprising an alkylene oxide compound. 6. A process for manufacturing a semiconductor device or a liquid crystal display device.
Developer according to any 請 Motomeko 1-5 for use in. 7. A method for preparing a basic organic compound A in a developer
And the equivalent of the basic organic compound A forming the salt C
(Total equivalent) and a salt capable of forming a salt with a basic compound
A salt C is formed with an equivalent of the compound B having a boxyl group.
Has a carboxyl group capable of forming a salt with a basic compound
Ratio of the compound B to the sum (total equivalent) of the compound B is 1: 0.0
7. The method according to claim 1, wherein the ratio is from 01 to 1: 0.80.
Developer. 8. A developing method for developing using the developer according to claim 1.