JPS63136041A - Resist developer composition - Google Patents

Abstract

PURPOSE:To improve contrast of a resist by composing the developer of the resist of an aqueous alkaline solution contg. a specific surfactant. CONSTITUTION:The developer of the resist is composed of the aqueous alkaline solution contg. the surfactant shown by formula I wherein R<1> is 5-24 C a straight chain hydrocarbon group, and said hydrocarbon group may contain <=3 oxygen atoms which are not adjacent with each other, R<2> and R<3> are each 1-3 C alkyl group, -(R<5>O)lH group [wherein R<5> is 1-3 C alkylene group, (l) is an integer of 1-20] or 2-8 C a cyclic hydrocarbon group, and said cyclic hydrocarbon group may contain <=2 heterocyclic atoms which are selected from oxygen, nitrogen and sulfur atoms and are not adjacent with each other, and also are not adjacent to a quaternary nitrogen atom shown by formula I. Thus, the contrast of resist is further improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resist developer composition, and more particularly, to a resist developer composition that can be used to develop a composition by irradiation with radiation such as ultraviolet rays, deep ultraviolet rays, electron beams, X-rays, neutron beams, and molecular beams. The present invention relates to a resist developer composition suitable for resists that are soluble or insoluble in real alkaline aqueous solutions.

(Prior Art) In recent years, as the miniaturization of integrated circuits progresses, there is a tendency to use resists with excellent resolution that use an alkaline aqueous solution as a developer as resists used in photolithography technology in the integrated circuit manufacturing process. Examples of such resists include positive resists made of an alkali-soluble resin and a 1,2-quinonediazide compound, negative resists made of an alkali-soluble resin and a bisazide compound, and positive resists made of an alkali-soluble resin and polyolefin sulfone. It has been known.

(Problems to be Solved by the Invention) Resists developed with a developer made of an alkaline aqueous solution as described above have excellent resolution because the resist pattern is less swollen by the developer. As a result, further improvement in resolution is desired.

In general, the change in solubility in the developer caused by radiation irradiation on the resist is only a relative change, and even parts that should originally be insoluble in the developer dissolve to some extent in the developer, so even if the resist is not irradiated with radiation, Resolution can be improved by increasing the difference in dissolution rate (generally referred to as contrast) in a developing solution between the portion and the radiation-exposed portion.

In conventional developing methods using developers, contrast can be increased to some extent by lowering the alkaline concentration of the developer, but in this case, this may reduce sensitivity or require longer development times. It has problems such as:

In order to solve these problems, for example, a developing solution (Japanese Patent Application Laid-Open No. 5-111001), which is an aqueous alkaline developer containing a surfactant such as methylbis(2-hydroxyethyl)codium chloride or trimethylyacyanmonium chloride, has been developed.
8-9143), a developer containing a surfactant such as tributylmethylammonium chloride or triamylmethylammonium chloride in an aqueous alkaline developer (Japanese Unexamined Patent Publication No. 61-232454), an aqueous alkaline developer containing a surfactant such as tributylmethylammonium chloride or triamylmethylammonium chloride, A developing solution containing a monohydric alcohol and a surfactant such as trimethylbis(2-hydroxyethyl)cyanmonium chloride, l.limethylcyanmonium chloride, etc. (Japanese Patent Laid-Open No. 61-232453) has been proposed. However, with these developers, the tolerance of the development process is very narrow, and depending on the development conditions, there may be large variations in pattern dimensions on the wafer surface, peeling of the surface layer, scum residue, etc. There is a problem with this.

An object of the present invention is to provide a resist developer composition that solves the problems of the prior art and can further increase the contrast of the resist without reducing the sensitivity and residual film rate of the resist film due to development. be.

(Means for Solving the Problems) The present invention provides a developer for a resist that becomes soluble or insoluble in a real alkaline aqueous solution upon irradiation with radiation, which contains a surfactant represented by the following general formula CI). A resist developer composition comprising an alkaline aqueous solution.

[Here, R1 means a chain hydrocarbon group having 5 to 24 carbon atoms, and the hydrocarbon group can have 3 or less oxygen atoms that are not adjacent to each other.

R2 and R3 are the same or different and have 1 to 3 carbon atoms
an alkyl group of the general formula (II)-(Rk O)
I) (wherein R is an alkylene group having 1 to 3 carbon atoms, and l is an integer of 1 to 20), or a cyclic hydrocarbon group having 2 to 8 carbon atoms. , the cyclic hydrocarbon group may have two or less non-adjacent heteroatoms selected from oxygen atoms, nitrogen atoms and sulfur atoms, and non-adjacent to the quaternary nitrogen in the general formula (I).

R4 is (a) a chain hydrocarbon group having 1 to 10 carbon atoms;
(b) a substituent represented by the general formula (n), (C) a substituent represented by the general formula (I group, or the general formula % formula % () (wherein m represents an integer of 1 to 4, R6 is the above (al,
(b) or (C)).

Is X an R? It means a group represented by Coo- or R8SO4 (wherein R? and R8 are the same or different and represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom). ] It is characterized by containing the surfactant shown by these.

Examples of the hydrocarbon group for R1 in the present invention include CH3 CH3CH3 CH3(CH2)6-1CH3(CH2)? -1CH5
(CH2)8-2CH3(CH2)9-1CH3(CH
2) 1O-1CH3(CH2) tt-1CH3(C
H2) 12-1CH3(CH2) 13-1CH3(C
H2) 14-1CH3(CH2) 1!1-3CH3(
CH2) 16-1CH3(CH2) 1? -1CH3
(CH2) R8-1CH3(CH2) 19-1CH
3(CH2)2o-1CH3(CH2)21-1CH5
(CH2)22-1H(OCH2CH2)3-1 and other alkyl groups having 5 to 24 carbon atoms, or general formula 〇pH2p-4- or CqH2q-3- (in the formula, p
, q each represents an integer of 5 to 24), and preferably one having 6 to 24 carbon atoms.
20 alkyl groups or alkenyl groups having 6 to 20 carbon atoms, particularly preferably alkyl groups having 6 to 20 carbon atoms.

' R2 and R3 are, for example, CH3-1C8
1 carbon atom, such as 3CH2-1CH3(CH2)2-
~3 alkyl group, or HOCH2-5H(OCH2
CH2)r-1H(OCHCH2)! -1■ CH3H(OCH2CH)t- (where r, s, t are 1 to CH
3 represents an integer of 20).

As R4, for example, CH3- as a substituent of +al
2CI3Ct12-1CH3(CH2)2-1CH3(
CH2)3-1CH3(CH2)4-1CH5CH3 CH3(CH2)2 CH-1CH3(CH2)s -
1CH3 CH3 (CH2)? -1CH5(CH2)8-1CH5
A chain alkyl group having 1 to 10 carbon atoms such as (CH2)9-, or the general formula Cu112u-t b or C
A substituent of H'0CH2-1H(OCH2CH2)w -1CH as a substituent of (b), a substituent represented by vH uv-3 (in the formula, IJ and V represent integers of 1 to 10)
Substituents for (C) include groups represented by the general formula (n) such as 3CH3 (wherein w, x, and y represent integers of 1 to 20), and aryl groups such as (C). Particularly preferable R4 is
General formula (IV) -(CH2)m-N-R6(IV) (wherein, m is an integer of 1 to 4, R6 is the above-mentioned (a), (b)
or (C)). These groups include, for example, CH2CH20HCH2C
Examples include H20H CH3CH3 CH3 -(CH2)2-N -Cto H21.

"CH3 R? and R8 included in X in formula (1) above are, for example, H-1CH3-1CH3CH2-1CH5 (
CH2)2-1CH3(CH2)3- and the like,
CfT3-1CH3CH2- is particularly preferred.

Surfactant used in the present invention, that is, general formula [I]
As the surfactant represented by, for example, commercially available products include Cortamino 86EG, Cortamin 86EPT, and Cortamin 86ESSK34B (the above are trade names manufactured by Kao Soap Co., Ltd.).
, Nopcostat 092 (trade name manufactured by San Nopco), and the like.

In the present invention, the amount of the surfactant represented by the general formula (I) to be added is set to 0.
．． 0005 to 1% by weight is preferred, particularly preferably 0.0005 to 1% by weight.
001 to 0.2% by weight.

Examples of the alkaline aqueous solution used in the present invention include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, trisodium phosphate, and sodium hydrogen phosphate; Aqueous solutions of amines such as propylamine, di-n-propylamine, di-n-butylamine, methyldiethylamine, pyrrole, 2,5-dimethylpyrrole, β-picoline, collidine, piperidine, piperazine, triethylenediamine, dimethylethanolamine , aqueous solutions of alcohol amines such as triethanolamine and diethylhydroxylamine, aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, and aqueous ammonia. It will be done. Among the inorganic alkalis, potassium hydroxide, trisodium phosphate, sodium hydrogen phosphate, sodium metasilicate and mixtures thereof are used; among the organic alkalis, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide etc. are preferable.

These alkaline aqueous solutions contain, for example, a surfactant containing a compound other than the surfactant represented by the general formula [I] used in the present invention for the purpose of improving developability and adjusting the residual film rate of the resist pattern. Surfactants such as TR series (manufactured by Toho Chemical Industry Co., Ltd.), Rheodol 430, Rheodol 440, Luodor 460 (manufactured by Kao Soap Co., Ltd.), stabilizers such as sodium sulfite and ammonium sulfite, glycerin, ethylene glycol, polyglycerin, glycol ether, etc. Polyhydric AA agents suitable for alkaline aqueous solutions, hydrophilic organic solvents such as alcohols, ketones, esters, and ethers, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetra-n-
Quaternary ammonium hydroxide or quaternary ammonium salt such as butylammonium hydroxide, tetra-n-butylammonium chloride, trimethylbenzylammonium hydroxide, trimethylbenzylammonium iodide, tetrapentylammonium hydroxide, tetrapentylammonium bromide, etc. can be added. Their concentration in alkaline aqueous solution is generally 0.1 to 5% by weight, preferably 0.2 to 4% by weight, particularly preferably 0.5 to 3% by weight.

The resist to which the developer of the present invention can be used is a radiation-sensitive resist that becomes insoluble or soluble with the developer of the present invention after irradiation with radiation, and is usually a resist containing an alkali-soluble resin.

These resists include, for example, a positive resist made of an alkali-soluble resin and a 1,2-quinonediazide compound, a negative resist made of an alkali-soluble resin and a bisazide compound, a positive resist made of an alkali-soluble resin and a polyolefin sulfone, etc. can be mentioned.

Examples of the alkali-soluble resin include phenol,
Alkali-soluble novolak resin, hydroxystyrene and/or hydroxystyrene and/or alkali-soluble novolak resin obtained by condensing phenols such as cresol, ethylphenol, xylenol, p-phenylphenol, resorcinol, pyrogallol, and phloroglycitur with aldehydes such as formaldehyde, acetaldehyde, and benzaldehyde. Alternatively, polymers of hydroxystyrene derivatives such as α-methylhydroxystyrene can be mentioned.

Among the alkali-soluble novolak resins, m-cresol is contained in an amount of 55 to 97% by weight, and p-cresol is contained in an amount of 3 to 97% by weight.
An alkali-soluble novolac resin obtained by condensing a cresol isomer mixture containing 45% by weight with formaldehyde, especially a cresol isomer mixture containing only m-cresol and p-cresol without 0-cresol and formaldehyde. The resulting alkali-soluble novolak resin is preferred.

Moreover, the number average molecular weight of the alkali-soluble novolak resin is preferably 400 to 900.

The polymer of hydroxystyrene and/or hydroxystyrene derivatives may also be used in combination with other polymerizable polymers such as styrene yarns such as styrene and aminostyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, and methacrylic acid. hydroxyethyl, acrylic acid,
It may also be a copolymer with (meth)acrylic acid monomers such as methyl acrylate and ethyl acrylate, and/or diene monomers such as butadiene and isoprene.

The preferred (co)polymerization ratio of hydroxystyrene and/or hydroxystyrene derivative in the polymer of hydroxystyrene and/or hydroxystyrene derivative is 30 to 100 mol%.

Moreover, the weight average molecular weight of the polymer of hydroxystyrene and/or hydroxystyrene derivative in terms of polystyrene is preferably 3,000 to 30,000.

The alkali-soluble resin may be one imparted with radiation sensitivity, for example, 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-
5-sulfonyl group, 1,2-benzoquinonediazide-4
- Alkali-soluble novolak resin into which a 1,2-quinonediazide sulfonyl group such as a sulfonyl group is introduced, 1.2
- Quinonediazide Polymers of hydroxystyrene and/or hydroxystyrene derivatives into which a sulfonyl group has been introduced may also be used, but these alkali-soluble resins imparted with radiation sensitivity do not contain 1,2-quinonediazide in the resin from the viewpoint of alkali solubility. Sulfonyl group content is 10
It is preferably less than % by weight.

The alkali-soluble resin may be used alone or in combination with
More than one type of resin may be used in combination, and when used in combination, it is preferable that the resins have compatibility with each other. Examples of combinations of two or more alkali-soluble resins include an alkali-soluble novolac resin and a hydroxystyrene polymer, an alkali-soluble novolac resin and an α-methylhydroxystyrene polymer, an alkali-soluble novolac resin and an alkali-soluble alkali-soluble resin that has been given radiation sensitivity. Examples include novolac resins, hydroxystyrene polymers, and alkali-soluble novolac resins imparted with radiation sensitivity.

Examples of the 1,2-quinonediazide compound mixed in the alkali-soluble resin include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1゜2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-4-sulfonic acid ester. Examples include 5-sulfonic acid esters, and specific examples include the above-mentioned esters of mono- or polyhydroxybenzene or derivatives of these compounds.

Note that specific examples of hydroxybenzene include p-cresol, resorcinol, pyrogallol, phloroglucinol, and the like.

Further, for example, 2,3.4-)lihydroxyphenylmethylketone, 2,3.4-)lihydroxyphenylethylketone, 2,3.4-trihydroxyphenylbutylketone, 2,3.4-trihydroxyphenyl -n-hexylketone, 3゜4.5-)rihydroxyphenylmethylketone, 3.4.5-)rihydroxyphenylethylketo7.3,4.5-trihydroxyphenylbutyl)rton, 3,4 .5-trihydroxyphenyl-n-
Hexylketone, 2,4.6-trihydroxyphenylmethylketone, 2.4.6-trihydroxyphenylethylketone, 2.4.6-trihydroxyphenylbutylketone, 2,4.6-drihydroxyphenylketone Eniru n-
Hexylketone, 2.3.4-1-lihydroxyphenyldecylketone, 2,3.4-)dihydroxybenzophenone, 2.4.6-trihydroxybenzophenone,
2゜3.4-1-lyhydroxyphenylbenzylketone, 3.4.5-)lyhydroxybenzylketone, 2゜4
．． 6-trihydroxyphenylbenzyl ketone, 2.4
-dihydroxyphenylpropyl ketone, 2,4-dihydroxyphenyl n-hexyl ketone, 2,4-dihydroxybenzophenone, 2゜3.4.4'-tetrahydroxybenzophenone, 2.2゜,4.4'-tetra Hydroxybenzophenone, 2,4.2", 4'-tetrahydroxy-6,6'-dimethyl-diphenylmethane, 2°6.2°, 6"-tetrahydroxy-3,5,3
1,59-tetrachloro-diphenylmethane, 2゜21
-dihydroxy-4,4f-dimethyl-diphenylmethane-(1,1), 2,2'-dihydroxy-4,41-
Dimethoxydiphenyl ethane-(1,1), 2,4.
2',4'-tetrahydroxy-diphenylethane-(
1,1), 2.21-dihydroxy-4,41-dimethoxy-triphenylmethane, 2,21-dihydroxy-dinaphthylmethane, 2.4.2',4'-tetrahydroxy-diphenyl sulfoxide, 2,4 .2'.

41-tetrahydroxy-6,61-dimethyl-diphenylethane-(1,1), 2.4.2'.

4f-tetrahydroxy-6,61-dicarbomethoxydiphenylmethane, 2.4.2',4'-tetrahydroxy-6,6g-dimethyl-triphenylmethane, 2
．． 4.2", 4'-tetrahydroxy-diphenylpropane-(1,1), 2°4.2', 4"-tetrahydroxy-diphenyl-n-butane-(1,1), 2,
4.2',4'-pentahydroxy-triphenylmethane, 2°4.2',4°-tetrahydroxy-diphenylcyclohexane-(1,1), 2.2-dihydroxy-4,4'-dimethoxy- diphenylmethane, 2.4.
2',4'-tetrahydroxy-diphenylpenkun-
(1,1), 2.4.2', 4'-tetrahydroxy-diphenylpropane-(2°2), 2,4.2', 4
“-Tetrahydroxy-triphenylmethane, 2,2-
Dihydroxy-5゜5'-dibromo-diphenylmethane, 2.2-dihydroxy-5,51-dichloro-diphenylethane (1,1), 2. 2-dihydroxy-5,
51-dibromo-diphenylethane (1,1), etc.
Using a 1,2-quinonediazide compound obtained by condensation with 1.2-naphthoquinonediazide-4-sulfonyl halide, 1,2-naphthoquinonediazide-5-sulfonyl halide, or 1.2-benzoquinonediazide-5-sulfonyl halide. I can do it.

Furthermore, lauryl 3,5-dihydroxybenzoate, 2,
3.4-) Phenyl hydroxybenzoate, 3,4.5
-) (poly)hydroxybenzoic acid alkyl esters or aryl esters, such as propyl hydroxybenzoate, 3,4.5-) phenyl hydroxybenzoate,
1.2-Naphthoquinonediazide-4-sulfonyl halide, l.

A 1,2-quinonediazide compound obtained by condensation with 2-naphthoquinonediazide-5-sulfonyl halide or 1,2-benzoquinonediazide-5-sulfonyl halide can also be used.

1. The amount of the 2-quinonediazide compound added per 1 ooii part of the alkali-soluble resin is usually determined from the viewpoints of heat resistance, plasma resistance, solubility of unirradiated areas, sensitivity range to radiation, etc. when used as a resist. 10-4
It is 0 parts by weight.

Examples of the bisazide compound to be mixed in the alkali-soluble resin include 4,4°-diazidiphenyl sulfide, 4,4'-diazidiphenyl sulfone, and 3.3
'-Diazido diphenyl sulfone, 4,4'-diazido diphenylmethane, 3,3'-dichloro-4,41-diazido diphenylmethane, 4,4'-diazido diphenyl ether, 4,4'-diazido dibenzyl, 4,4f
-Diazidostilbene-2,21-disulfonic acid sodium, 4,4'-diazidostilbene-2,2° disulfonic acid anilide, etc. can be used.

The amount of the bisazide compound added is usually 5 to 30 parts by weight per 100 parts by weight of the alkali-soluble resin, from the viewpoint of heat resistance, plasma resistance, solubility of unirradiated areas, sensitivity range to radiation, etc. when used as a resist. Parts by weight.

As the polyolefin sulfone, for example, poly(
propylene sulfone), poly(l-butenesulfone)
, poly(1-pentenesulfone), poly(1-hexenesulfone), poly(1-octensulfone), poly(2-butenesulfone), poly(2-hebutenesulfone), poly(cyclopentenesulfone), poly
(cyclohexene sulfone), poly(2-methyl-1
-pentenesulfone), poly(2-methyl-1-butenesulfone), and the like.

Further, as the polyolefin sulfone, halogenated polyolefin sulfone can also be suitably used,
This halogenated polyolefin sulfone includes chlorinated poly(propylene sulfone), chlorinated poly(1-
butenesulfone), chlorinated poly(1-pentenesulfone), chlorinated poly(1-hexenesulfone), chlorinated poly(1-octensulfone), chlorinated poly(2-
butenesulfone), chlorinated poly(2-butenesulfone), chlorinated poly(2-hebutenesulfone), chlorinated poly(cyclopentenesulfone), chlorinated poly(cyclohexenesulfone), chlorinated poly(2-methyl-1)
-pentensulfone), chlorinated poly(2-methyl-1
-butenesulfone), brominated poly(1-butenesulfone), brominated poly(2-methyl-neepentenesulfone), fluorinated poly(1-butenesulfone), fluorinated poly(2-methyl-1-pentenesulfone) ), chlorinated polyolefin sulfones, brominated polyolefin sulfones, and fluorinated polyolefin sulfones can be exemplified.

Halogenated polyolefin sulfone is obtained by halogenating polyolefin sulfone, and is carried out by a radical reaction by reacting a halogenating reagent with polyolefin sulfone in an inert organic solvent, in the presence of peroxide, or under radiation irradiation. can be done (Special application 1986)
1-180609).

The amount of polyolefin sulfone added is 100% of the alkali-soluble resin! The amount is usually 2 to 35 parts by weight, preferably 5 to 30 parts by weight.

Sensitizers used in negative and positive radiation-sensitive resists include, for example, benzotriazole and its halides, 5-methylbenzotriazole and its halides, 5,6-dimethylbenzotriazole and its halides, 1.2-naphthotriazole and its halides, cyclohexyltriazole and its halides, 1,2.3-)lyazole and its halides, 1.2.4-triazole and its halides, 4.5-dicyano-1 ,2,3-
) Triazoles such as lyazole and its halides, indazoles such as indazole and its halides, 5-nitroindazole and its halides, 6-aminoindazole and its halides, imidazole and its halides, 4-azabenzimidazole imidazoles such as and its halides, 2H-pyrido(3,2-b)-1゜4-oxazin-3(4H)ones, 10H-pyrido(3,2-
b) (1,4)-benzothiazines, urazoles such as 1-methylurazole, 1-phenylurazole, 3-methylurazole, 3-p-triurazole, 5.5
-diphenylhydantoin, 5.5-dimethylhydantoin, 5-methyl-5-phenylhydantoin, 5-methyl-3-p-)lylhydantoin, 1-methylhydantoin, ■-phenylhydantoin, 1-methyl-5-
Hydantoins such as methylhydantoin, 5-methylhydantoin, 5-ethyl-3-p-)lylhydantoin, 5,5-diethylhydantoin, 5-ethyl-3-
p-) Barbyl Mi, 1-methylglycine, 1-phenylglycine, such as lylbarbic acid, 5-nitrobarbic acid, 5,5-dimethylbarbic acid, 5,5-diphenylbarbic acid , 2-methylglycine, glycine anhydrides such as 2,2-dimethylglycine,
5-methyl-1-hydroxybenzotriazole, 5,
Examples include 1-hydroxyhencytriazoles such as 6-dimethyl-1-hydroxyhencytriazole, alloxanes such as 1-methylalloxane and 1-phenylalloxane, and maleimides such as 3-phenylmaleimide.

The amount of the sensitizer used is 0.1 to 30 parts by weight per 100 parts by weight of solid content of the resist.

The resist is applied onto the substrate by, for example, dissolving the resist in a suitable organic solvent, applying it by spin coating, flow coating, roll coating, or the like, and then heating and drying. In addition, the organic solvents used in this case include glycol ethers such as ethylene glycol methyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, Cellosolve esters such as butyl cellosolve acetate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetonylacetone, acetophenine, isophorone, benzyl ethyl ether, 1,2-dibutoxyethane , ethers such as dihexyl ether, caproic acid,
Fatty acids such as caprylic acid, alcohols such as 1-octatool, 1-nonanol, 1-decanol, benzyl alcohol, ethyl acetate, butyl acetate, isoamyl acetate, 2-ethylhexyl acetate, benzyl acetate, benzyl benzoate, oxalic acid Esters such as diethyl, dibutyl oxalate, diethyl malonate, dimethyl maleate, dibutyl maleate, diethyl maleate, dimethyl phthalate, dibutyl phthalate, ethylene carbonate, propylene carbonate, n-butyl propionate, isopropyl propionate, and lactones such as γ-butyrolactone.

The amount of the organic solvent used is generally 100 to 2000 parts by weight per 100 parts of solid content of the resist.

After the resist is applied onto the substrate and dried, a predetermined portion of the coating film is irradiated with radiation and developed using the developer of the present invention. Development is generally done by immersing the material in a developer while stirring (immersion development method), by immersing it in a developer that is left standing (static immersion development method), or by spraying a sheet or shower of developer. (spray development method), a method in which a developer is gently placed on the entire surface of the wafer, left to stand for a predetermined period of time, and then the developer is washed away with running water while rotating the wafer (paddle development method). The development time varies depending on the development method, the type of developer, the concentration of the developer, the type of resist, etc., but is usually 15 seconds to 5 minutes, preferably 15 seconds to 4 minutes. In addition, the developing temperature is usually 10 to 40°C.
, preferably 15 to 30°C.

After developing in this manner, the substrate on which the resist pattern has been formed is rinsed with water and dried.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited in any way by these Examples.

Feeling, Constance and Co1.

The sensitivity, contrast (γ), and residual film rate of the resist were measured by the following methods.

After forming a resist coating film on a wafer, irradiating it with radiation while changing exposure energy, and developing it using a prescribed developer, the remaining film rate at each exposure energy was measured.
Create the sensitivity characteristic curve of the resist film shown in the figure.

The horizontal axis of the sensitivity characteristic curve shows the exposure energy (mJ/cml
) is expressed on a logarithmic scale, and the vertical axis represents the remaining film thickness after development relative to the coating film thickness before development.

Contrast (γ) is the absolute value of the slope of the tangent to the sensitivity characteristic curve (hereinafter simply referred to as "tangent") when the remaining film thickness is 0.5, and is expressed by the following equation.

(Here, Eth represents the exposure energy at the intersection of the tangent line and the horizontal axis, and Eo represents the exposure energy at the intersection of the tangent line and the straight line with residual film thickness=1.) Sensitivity is expressed in Eth.

The residual film rate is determined by measuring the film thickness before and after development.

At this time, to measure the film thickness, Nano 3pec is usually used.
AFT (manufactured by Nanometrics, registered trademark) is used.

・1-3, 1 After charging 75 g of m-cresol and 25 g of p-cresol into a reaction vessel, 66 ml of a 37% by weight formaldehyde aqueous solution and 0.04 g of oxalic acid were added, and the reaction temperature was maintained at 100°C while stirring. The mixture was allowed to react for 10 hours. After the reaction was completed, the internal temperature was further raised to 130°C, and the pressure inside the reaction vessel was reduced to distill off volatile components. Next, the reaction product, an alkali-soluble novolak resin, was recovered.

Next, to 43 g of this novolac resin, 2
, 3.4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid triester 1.
1 g was added, dissolved in 21 g of ethyl cellosolve acetate, and filtered through a membrane filter with a pore size of 0.2 μm.
A positive resist solution was prepared. The solution was spin-coated onto a silicon wafer so that the coating thickness after drying was 1.2 μm, and then prebaked at 90° C. for 25 minutes to obtain a resist film.

This resist film was processed using a reduction projection exposure device GCA4 made by GCA.
Exposure through a pattern mask using 800DSW,
By the paddle development method using a developer containing an activator shown in Table 1 added to an aqueous solution of tetramethylammonium hydroxide (Examples 1 to 3) and a developer without adding a surfactant (Comparative Example 1). The resist film was developed for 1 minute at 21"C and rinsed with running water. Table 1 shows the sensitivity, contrast (γ), and residual film rate determined from the sensitivity characteristic curve of the resist film.

■Chlorinated poly(2-methyl-1-pentenesulfone)
7.6 g of 2-methyl-1-pentene purified by distillation and 25.8 g of sulfur dioxide purified by distillation in a synthetic glass ampoule.
After degassing, 0.08 g of cumyl peroxide was added, the tube was sealed, and the entire glass ampoule was immersed in a dry ice-methanol refrigerant at 78 DEG C., and polymerized for about 20 hours. Thereafter, the glass ampoule was opened, excess sulfur dioxide was removed, and the contents were poured into 1,500 ml of methanol for precipitation and purification to obtain 9.7 g of poly(2-methyl-1-pentenesulfone). The ceiling temperature of this poly(2-methyl-1-pentenesulfone) was -34°C.

2 g of the poly(2-methyl-1-pentenesulfone) obtained above was added to 78 g of dichloromethane in a glass container.
After dissolving 0.29 g of t-butyl hypochlorite to make a uniform solution, each glass container was immersed in a dry ice-methanol refrigerant, and the temperature of the inner solution was confirmed to be -75°C. did.

Next, a high-pressure mercury lamp equipped with a quartz water-cooling jacket on the outer periphery was placed in the glass container, and the solution was irradiated with light with a wavelength of 250 to 400 nm for 1.5 hours while maintaining the solution at -75°C. Chlorination was performed. Thereafter, the reaction product was precipitated in methanol and recovered, and then dried under reduced pressure at 40°C to obtain chlorinated poly(2-methyl-1-pentenesulfone).

The intrinsic viscosity of the obtained chlorinated poly(2-methyl-1-pentenesulfone) in methyl ethyl ketone at 30°C was 1.0 dffi/g, and the chlorine content was 2% by weight.
Met.

■Cresol mixture [m-cresol/p-cresol-6/
4 (molar ratio)), 600 g of a 37% formaldehyde aqueous solution, and 0.36 g of oxalic acid were charged. While stirring, the reaction temperature was maintained at 100 °C.
Allowed time to react.

Thereafter, the internal temperature was further raised to 180° C., and the pressure inside the reaction vessel was reduced to distill off volatile components. Then, the reaction product, an alkali-soluble novolac resin, was recovered.

■1 g of chlorinated poly (2-methyl-1-pentenesulfone) synthesized in ■, manufactured by Resist 1III, and 10 g of alkali-soluble novolac resin synthesized in ■, are dissolved in 5 g of isoamyl acetate, and a membrane filter with a pore size of 0.2 μm is filtered. - to prepare a resist-1g solution.

The solution was applied onto a silicon wafer so that the coating thickness after drying was 1
．． After spin coating so that the thickness is 0 μm, it was coated at 90℃ for 25 minutes.
Prebaking was performed for a minute to obtain a resist film.

This resist film is coated with palladium Lα rays (wavelength: 4.36).
After irradiating X-rays consisting of through a pattern mask,
By the paddle development method using a developer containing a surfactant shown in Table 2 added to an aqueous solution of tetramethylammonium hydroxide (Examples 4 to 7) and a developer without adding a surfactant (Comparative Example 2). It was developed for 3 minutes and then rinsed with running water. Table 2 shows the sensitivity, contrast (γ), and residual film rate determined from the sensitivity characteristic curve of the resist film.

Margin below

Claims (1)

[Claims] In a developer for a resist that becomes soluble or insoluble in a real alkaline aqueous solution upon irradiation with radiation, the following general formula [
A resist developer composition comprising an alkaline aqueous solution, characterized by containing a surfactant represented by [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [Here, R^1 means a chain hydrocarbon group having 5 to 24 carbon atoms, and the hydrocarbon group has 3 or less oxygen atoms that are not adjacent to each other. can have. R^2 and R^3 are the same or different and have 1 carbon atom
-3 alkyl group, general formula [II] -(R^5O)_lH[II] (wherein R^5 is an alkylene group having 1 to 3 carbon atoms, l
represents an integer of 1 to 20), or a cyclic hydrocarbon group having 2 to 8 carbon atoms, and the cyclic hydrocarbon group includes 2 or less oxygen atoms, nitrogen atoms, and It can have a heteroatom selected from sulfur atoms and not adjacent to the quaternary nitrogen in the general formula [I]. R^4 is (a) a chain hydrocarbon group having 1 to 10 carbon atoms, (b) a substituent represented by the above general formula [II], (c) general formula [III] ▲ mathematical formula, chemical formula, There are tables, etc. ▼ [III] (In the formula, n, j and k are the same or different and represent integers of 0 to 3), or a group represented by the general formula [IV] -(CH_2)_m-N- R^6 [IV] (In the formula, m represents an integer of 1 to 4, and R^6 is the above (a)
, (b), or (c)). X is R^7COO- or R^8SO4- (in the formula, R
^7 and R^8 are the same or different and have a carbon atom number of 1 to
4) represents an alkyl group or a hydrogen atom. ]