JPH0573228B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a developer, and more particularly to a photosensitive resin that becomes soluble or insoluble in an alkaline aqueous solution upon irradiation with light such as ultraviolet rays,
Ionizing radiation-sensitive resins that become soluble or insoluble in alkaline aqueous solutions when irradiated with ionizing radiation such as electron beams, X-rays, neutron beams, and molecular beams (hereinafter, these sensitive resins and ionizing radiation-sensitive resins are collectively referred to as " This invention relates to a developer suitable for a radiation-sensitive resin (referred to as "radiation-sensitive resin"). [Prior art] In recent years, as integrated circuits have become smaller, positive resists with higher resolution than conventional cyclized isoprene-based negative resists have been used as resists for photolithography technology in the integrated circuit manufacturing process. There is a tendency to A typical positive resist includes a resist made of a composition of an alkali-soluble novolac resin and a 1,2-quinonediazide compound. In photolithography using this resist, a 1,2-quinonediazide compound undergoes a transfer reaction by irradiation with light or ionizing radiation (hereinafter simply referred to as "radiation"), and becomes soluble in an alkaline aqueous solution. It uses development. That is, the substrate coated with the resist is partially irradiated with radiation,
A substrate having a desired resist pattern can be obtained by eluting the radiation irradiated area using a developer consisting of an alkaline aqueous solution. [Problems to be Solved by the Invention] Resists developed with a developer made of an alkaline aqueous solution as described above have high resolution because the resist pattern is not swelled by the developer, but unexposed areas are often left unexposed during development. The surface layer of a fine resist pattern may peel off (hereinafter, this development is referred to as "surface layer peeling"), and this surface layer may adhere to the exposed areas, or the exposed areas that should originally be removed by development may not be sufficiently removed. Development occurs in which a thin film remains without being removed (hereinafter, this phenomenon is referred to as "thin film remaining"). Even if a substrate having a resist pattern with surface layer peeling or thin film residue is etched, the areas that should be etched will not be etched (hereinafter referred to as "etching residue"), and as a result 1
The ratio of the number of defective chips to the total number of chips within a single wafer increases. Conventionally, methods such as increasing the alkaline concentration of the alkaline aqueous developer solution or raising the development temperature have been taken to solve these problems, but this has resulted in a decrease in the residual film rate of the resist pattern. , this resulted in negative effects such as a decrease in contrast. In addition, because the surface tension of the conventional developing solution consisting of an alkaline aqueous solution is quite high with respect to the resist, the wettability of the current solution to the resist film surface is poor (hereinafter, this phenomenon is referred to as "poor wettability"), and the pattern is It may be difficult for the developer to penetrate into the minute parts of the resist film, or the developer may not be spread over the entire resist film during development using the paddle development method, in which the developer is placed on the resist film, left to stand for a predetermined period of time, and then washed away. In some cases, good development could not be achieved. Another drawback is that when the developer is placed on the resist film, the film becomes thick and the developer is wasted. The present invention has been made against the background of the above-mentioned conventional technical problems, and an object of the present invention is to provide a developer that does not cause the above-mentioned surface layer peeling, thin film remaining, and poor wettability. [Means for Solving the Problems] As a result of intensive studies to improve the drawbacks of the prior art, the present inventors have discovered that when a nonionic surfactant having a specific structure is added to a developer consisting of an alkaline aqueous solution, The present invention was achieved by discovering that the above-mentioned drawbacks can be improved. The present invention provides a developer characterized in that at least one nonionic surfactant selected from the following general formulas (), (), and () is blended into an alkaline aqueous solution. General formula ();

[In the general formula (), R ¹ represents an alkylene group, R ² represents a hydrogen atom or -COR ³ , where R ³ represents an alkyl group, an aryl group, an alkenyl group, or an alkynyl group, and n is 1 represents an integer of ~100, m is an integer of 1 to 6, m X's may be the same or different, and are selected from a hydrogen atom or -O-( ^R1O )n- ^R2 group, but at least Contains one -O-(R ¹ O) _o -R ² group. Furthermore, if the number of -O-(R ¹ O) _o -R ² groups contained in one molecule is l, then l R ¹ may be the same or different, and l R ² may also be the same. May be different. Furthermore, the l n's may be the same or different. ]

General formula ();

[In the general formula (), R ¹ , R ² and n have the same meanings as in the general formula (), the three R ¹ may be the same or different, and the four R ² may also be the same or different. Furthermore, the three n's may be the same or different. ]

General formula ();

[In the general formula (), R ¹ , R ² and n have the same meanings as in the general formula (), the three R ¹ may be the same or different, and the four R ² may also be the same or different. Furthermore, the three n's may be the same or different. ]

The nonionic surfactant used in the present invention is
It is at least one type of compound selected from the general formulas () to (). Here, the alkylene group for R ¹ is -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ - or -C ₄ H ₈ -
etc., with _-C2H4- or _-C3H6- being _{preferred .} Examples of the alkyl group constituting R ³ in R ² include CH ₃ −, CH ₃ CH ₂ −, CH ₃ (CH ₂ ) ₂ −, CH ₃ (CH ₂ ) ₃ −, CH ₃ (CH ₂ ) ₄ -,

【formula】

【formula】

[Formula] CH ₃ (CH ₂ ) ₆ −, CH ₃ (CH ₂ ) ₇ −, CH ₃ (CH ₂ ) ₈ −, CH ₃ (CH ₂ ) ₉ −, CH ₃ (CH ₂ ) ₁₀ −, CH ₃ (CH ₂ ) ₁₁ −, CH ₃ (CH ₂ ) ₁₂ −, CH ₃ (CH ₂ ) ₁₃ −, CH ₃ (CH ₂ ) ₁₄ −, CH 3 (CH ₂ ) ₁₅ −, _{CH 3 (} CH ₂ ) ₁₆ −, CH ₃ (CH ₂ ) ₁₇ −, CH ₃ (CH ₂ ) ₁₈ −, CH ₃ (CH ₂ ) ₁₉ −, CH ₃ (CH ₂ ) ₂₀ −, CH ₃ (CH ₂ ) ₂₁ −, CH ₃ ( 1 carbon number, such as CH ₂ ) ₂₃ −, CH ₃ (CH ₂ ) ₂₅ −, etc.
-30 linear or branched alkyl groups are preferred, and among these, alkyl groups having 10-20 carbon atoms are preferred. Further, as the aryl group constituting R ³ , for example,

【formula】

[ka]

[ka]

[ka]

【formula】

【formula】

[ka]

[ka]

[ka]

[ka]

[ka]

An aryl group having 6 to 35 carbon atoms, preferably 10 to 25 carbon atoms, and containing 1 to 2 aromatic rings, such as [Formula], and an aryl group having a linear or branched alkyl group substituent thereon. can be mentioned. Furthermore, examples of the alkenyl group or _alkynyl group constituting ^R3 include _CH2 =CH( _CH2 ) _7- , _CH3CH2 =CH( _CH2 ) _7- , _CH3 ( _CH2 ) ₅ CH=CH−, CH ₃ (CH ₂ ) ₇ CH=CH
−, CH ₃ (CH ₂ ) ₇ CH=CH−(CH ₂ ) ₇ −, CH ₃ (CH ₂ ) ₉ CH=CH−(CH ₂ ) ₇ −, CH ₃ (CH ₂ ) ₁₀ = CH−(CH ₂ ) ₄ −, CH ₃ (CH ₂ ) ₄ CH=CHCH ₂ CH=CH (CH ₂ ) ₇ −, CH ₃ CH ₂ CH=CHCH ₂ CH=CHCH ₂ CH=CH
(CH ₂ ) ₇ −, CH ₃ (CH ₂ ) ₃ (CH=CH) ₃ (CH ₂ ) ₇ −, CH ₃
Those having 5 to 30 carbon atoms such as (CH ₂ ) ₇ C≡C(CH ₂ ) ₇ − are preferable, and those having 10 to 20 carbon atoms are particularly preferable. In the present invention, the nonionic surfactant preferably contains 10 or more -R ¹ O- in the -O-(R ¹ O)n-R ² group, for example, 30 or more. It is particularly preferred that it be included. Examples of nonionic surfactants made of compounds represented by the general formulas () to () include the Rheodol TW series such as Rheodol TW-L106, Rheodol TW-P120, and Rheodol TW-S120, Rheodol 430, Rheodol 440, Leodor
Emazol series such as 460, Emazol L-120, Emazol P-120 (all manufactured by Kao Soap Co., Ltd.)
manufactured by Sorbon); Sorbon TR series such as Sorbon TR-824, Sorbon TR-834, and Sorbon TR-843; Sorbon T series such as Sorbon T-60;
(manufactured by Toho Chemical Industry Co., Ltd.). Among these, Leodor 430, Leodor
440, Rheodor 460 and Sorbon TR series are based on the above general formula (), and Rheodor TW series and Emazol series are based on the above general formula ().
In addition, the Sorbon T series corresponds to the above general formula (). Note that if these nonionic surfactants contain a large amount of metal, they may be used without the metal content. Among these, especially the Sorbon TR series, Reodore 430, Reodore 440 and Reodore
It is preferable to use 460 or the like from which metals have been removed by ion exchange treatment. In the present invention, the amount of the nonionic surfactant made of a compound having -O-(R ¹ O)n-R ² groups is preferably 0.001 to 1% by weight based on the alkaline aqueous solution as the developer. is 0.02 to 0.2% by weight, and if it is less than 0.001%, it will have little effect on the surface peeling layer, remaining thin film, or poor wettability, while if it exceeds 1% by weight, the remaining film rate will tend to decrease. 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, dimethyl ethanol Amine, triethanolamine, aqueous solution of alcohol amines such as diethyl hydroxylamine, tetramethyl ammonia hydroxide, tetraethylammonia hydroxide, 2
-Aqueous solutions of quaternary ammonium salts such as -hydroxyethyltrimethylammonium hydroxide, and aqueous ammonia. Among the inorganic alkalis, potassium hydroxide, trisodium phosphate, sodium phosphate, sodium metasilicate and mixtures thereof are included; among the organic alkalis,
Preferred are tetramethyl ammonia hydroxide, 2-hydroxyethyltrimethyl ammonia hydroxide, and the like. These alkaline aqueous solutions contain, for example, the above-mentioned -
Surfactants made of compounds other than compounds having O-(R ¹ O) n-R ² groups, stabilizers such as sodium sulfite and ammonium sulfite, alcohols, ketones,
Hydrophilic organic solvents such as esters and ethers, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetra-n-butylammonium hydroxide, tetra-n-butylammonium chloride, trimethylbenzylammonium hydroxide, trimethylbenzylammonium iodide, Quaternary ammonium hydroxide or quaternary ammonium salts such as tetrapentylammonium hydroxide, tetrapentylammonium bromide, etc. can be added. The concentration of these alkaline aqueous solutions is generally
0.1-0.5% by weight, preferably 0.2-4% by weight, particularly preferably 0.5-3% by weight. The photoresist to which the developer of the present invention is applied is a radiation-sensitive resin containing an alkali-soluble resin, and is a radiation-sensitive resin that becomes insoluble or soluble in the developer of the present invention after irradiation with an alkali. A positive radiation-sensitive resin comprising a soluble resin and a 1,2-quinonediazide compound can be mentioned. Examples of the alkali-soluble resin include addition condensation of phenols such as phenol, cresol, ethylphenol, xylenol, p-phenylphenol, resorcinol, pyrogallol, and phloroglucinol, and aldehydes such as formaldehyde, acetaldehyde, and benzaldehyde. alkali-soluble novolac resin, hydroxylstyrene and/or α
- Mention may be made of polymers of hydroxystyrene derivatives such as methylhydroxystyrene. Among the alkali-soluble novolak resins,
An alkali-soluble novolak resin obtained by condensing a cresol isomer mixture containing 55 to 97% by weight of m-cresol and 3 to 45% by weight of p-cresol with formaldehyde, in particular, a resin containing no o-cresol and a mixture of m-cresol and p-cresol. - Preferred is an alkali-soluble novolak resin obtained by condensing a cresol isomer mixture containing only cresol with formaldehyde. Further, the number average molecular weight of the alkali-soluble novolac resin is preferably 400 to 900. Alkali-soluble novolak resins are produced by reacting phenols and aldehydes in the presence of an acidic catalyst by a conventional method. Examples of the acidic catalyst used in this case include oxalic acid, acetic acid, hydrochloric acid, and sulfuric acid, and these are usually used in an amount smaller than the stoichiometric equivalent of the aldehyde to be subjected to the reaction. The reaction is 80
It is preferably carried out at ~150°C and under a pressure of 1 to 3 atmospheres, and is usually completed in about 1 to 7 hours. In addition, polymers of hydroxystyrene and/or hydroxystyrene derivatives are made of hydroxystyrene, hydroxystyrene derivatives, etc., and azo compounds such as azobisisobutyrolitrile, and peroxides such as benzoyl peroxide and lauroyl persulfide. A method of radical polymerization in the presence of a radical generator, silylation or acetylation of the hydroxyl group contained in hydroxystyrene or a hydroxystyrene derivative, and silylation or acetylation of the hydroxyl group in the presence of the radical generator, or n-butyllithium, sec.
- It is produced by a method of polymerizing in the presence of an anionic polymerization initiator such as butyl lithium or sodium naphthalene, followed by desilylation or deacetylation. These polymers of hydroxystyrene and/or hydroxystyrene derivatives may be copolymers with other polymerizable monomers. At this time, examples of monomers that can be copolymerized include styrene monomers such as styrene and aminostyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, acrylic acid, methyl acrylate,
Examples include (meth)acrylic acid monomers such as ethyl acrylate, diene monomers such as butadiene and isoprene, and two or more of these monomers may be copolymerized in combination. The preferred (co)polymerization ratio of hydroxystyrene and/or hydroxystyrene derivative in the polymer of hydroxystyrene and/or hydroxystyrene derivative is preferably 30 to 100 mol%. Further, 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, a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-4-sulfonyl group,
-naphthoquinonediazide-5-sulfonyl group,
Alkali-soluble novolak resin into which a 1,2-quinonediazide sulfonyl group such as a 1,2-benzoquinone diazido-4-sulfonyl group is introduced, 1.
It may be a polymer of hydroxystyrene and/or a hydroxystyrene derivative into which a 2-quinonediazide sulfonyl group has been introduced, but these alkali-soluble resins imparted with radiation sensitivity may be , 2-quinonediazide sulfonyl group content is preferably 10% by weight or less. The alkali-soluble resins may be used alone or in combination of two or more kinds, 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 imparted with radiation sensitivity. Examples include novolac resins, hydroxystyrene polymers and alkali-soluble novolac resins imparted with radiation sensitivity. Examples of the 1,2-quinonediazide compound to be mixed with the alkali-soluble resin include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-
Examples include naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, and specific examples include the above-mentioned esters of mono- or polyhydroxybenben or derivatives of these compounds. It will be done. In addition, as a specific example of hydroxybenzene,
Examples include p-cresol, resorcinol, pyrogallol, and phloroglucinol. Furthermore, as a 1,2-quinonediazide compound, for example, the following general formula (i)

[Formula, q is an integer of 1 to 3, R ³ is an alkyl group,
In all or part of the hydroxyl group of the compound represented by (representing an aryl group or an aralkyl group),
1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-
A 1,2-quinonediazide compound obtained by subjecting sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride to a condensation reaction can be used. Examples of the compound represented by general formula (i) include 2,3,4-trihydroxyphenylemethylketone, 2,3,4-trihydroxyphenylethylketone, 2,3,4-trihydroxyphenyl Butyl ketone, 2,3,4-trihydroxyphenyl-n-hexyl ketone, 3,
4,5-trihydroxyphenylmethylketone,
3,4,5-trihydroxyphenyl ethyl ketone, 3,4,5-trihydroxyphenyl butyl ketone, 3,4,5-trihydroxyphenyl-
n-hexylketone, 2,4,6-trihydroxyphenylmethylketone, 2,4,6-trihydroxyphenylethylketone, 2,4,6-trihydroxyphenylbutylketone, 2,4,6-
trihydroxyphenyl-n-hexyl ketone,
2,3,4-trihydroxyphenyldecyl ketone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxyphenylbenzyl ketone, 3,4,5-trihydroxybenzyl ketone, 2,4,6-trihydroxyphenylbenzyl ketone, 2,4-dihydroxyphenylpropyl ketone, 2,4-dihydroxyphenyl-n
-hexylketone, 2,4-dihydroxybenzophenone, and the like. In addition, as a 1,2-quinonediazide compound, for example, 2,4,2',4'-tetrahydroxy-
6,6'-dimethyl-diphenylmethane, 2,6,
2',6'-tetrahydroxy-3,5,3',5'-tetrachloro-diphenylmethane, 2,2'-dihydroxy-4,4'-dimethyl-diphenylmethane-
(1,1), 2,2'-dihydroxy-4,4'-dimethoxy-diphenylethane-(1,1), 2,4,
2′,4′-tetrahydroxy-diphenylethane-
(1,1), 2,2'-dihydroxy-4,4'-dimethoxy-triphenylmethane, 2,2'-dihydroxy-dinaphthylmethane, 2,4,2',4'-tetrahydroxy-diphenyl sulfoxide, 2,
4,2',4'-tetrahydroxy-6,6'-dimethyl-diphenylethane-(1,1), 2,4,2',
4'-tetrahydroxy-6,6'-dicarbomethoxy-diphenylmethane-2,4,2',4'-tetrahydroxy-6,6'-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-diphenylpentane-(1,1), 2,4,
2′,4′-tetradroxy-diphenylpropane-
(2,2), 2,4,2',4'-tetrahydroxy-
Triphenylmethane, 2,2'-dihydroxy-
5,5'-dibromo-diphenylmethane, 2,2-
Dihydroxy-5,5'-dichloro-diphenylethane (1,1), 2,2-dihydroxy-5,
5'-dibromo-diphenylethane (1,1) etc., 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-
A 1,2-quinonediazide compound obtained by a condensation reaction with 5-sulfonyl chloride or 1,2-benzoquinonediazide-5-sulfonyl chloride can be used. Furthermore, poly(polymeryl) such as lauryl 3,5-dihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate, etc. ) hydroxybenzoic acid alkyl ester or aryl ester, 1,2-naphthoquinonediazide-4-sulfonyl chloride,
1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-benzoquinonediazide-
A 1,2-quinonediazide compound obtained by a condensation reaction with 5-sulfonyl chloride can be used. The amount of the 1,2-quinonediazide compound added is 100 parts by weight of the alkali-soluble resin, considering the heat resistance, plasma resistance, solubility of the end-exposed area, and sensitivity range to radiation when the radiation-sensitive resin is used as a resist. Usually, the amount is 10 to 40 parts by weight. Examples of photoresists other than those mentioned above to which the developer of the present invention is applied include negative-tone radiation-sensitive resins comprising an alkali-soluble resin and an azide-based radiation crosslinking agent. Here, examples of the alkali-soluble resin include those similar to the alkali-soluble resin used in the above-mentioned positive radiation-sensitive resin. In addition, as an azide-based radiation crosslinking agent, for example, the general formula ()

[Chemical formula] (However, R ⁴ is an element or substituent that is conjugated or non-conjugated with the two benzene rings, X' is a hydrogen atom or an azide group, and Y is an azide group when X' is a hydrogen atom.) , when X' is an azide group, it is a hydrogen atom or a halogen atom such as a chlorine atom, when Y is a hydrogen atom, Z is a hydrogen atom, -SO ₃ Na or

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, in the examples, the sensitivity is manufactured by OAI, light meter model 205 U-V power meter (MODEL205-UV POWERMETER) (365nm)
This is the exposure amount that resolves the 1L/1S pattern measured in , and the evaluation of surface layer peeling and thin film remaining is expressed as follows. Surface peeling development or peeling film residue development ○: Not observed △: Only a small portion observed ×: Quite a lot observed: Wettability ○: No wetting residue ×: Wetting residue Examples 1 to 12 and Comparative Examples 1 to 6 In a three-necked separable flask with an internal volume of 500ml
- After charging 75 g of cresol and 25 g of p-cresol, 66 ml of a 37% by weight formalin aqueous solution and 0.04 g of oxalic acid were added, and the reaction temperature was adjusted while stirring.
The mixture was kept at 100°C and reacted for 10 hours. After the reaction is complete,
Reduce the pressure to 300mmHg to distill off the water, and further lower the internal temperature.
The temperature was raised to 130°C to remove unreacted substances. Then,
The reaction product, an alkali-soluble novolak resin, was recovered. Next, 1.1 g of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid triester was added as a photosensitizer to 43 g of this novolak resin, and dissolved in 21 g of ethyl cellosolve acetate to adjust the pore size. The mixture was filtered through a 0.2 μm membrane filter to prepare a radiation-sensitive resin solution. 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. Using a test pattern mask with equal line width and space width (1L/1S) on this radiation-sensitive resin film,
Manufactured by Canon Inc. with a 250W ultra-high pressure mercury lamp.
After exposure with PLA501F mask liner, 2.4% by weight of tetramethylammonium hydroxide
Using a developer prepared by adding the nonionic surfactant shown in Table 1 to an aqueous solution, development was performed at 21° C. for 1 minute, and then developed by a static immersion method. Next, after rinsing with running water, the obtained resist pattern was observed with an optical microscope, and sensitivity, resolution, developability (surface layer peeling, thin film remaining), and film remaining rate were measured. The results are shown in Tables 1 and 2. Further, as a comparative example, Table 3 shows the results when the nonionic surfactant of the present invention was not added to the developer. Furthermore, using the same developer as above, the substrate was coated, prebaked, and exposed in the same manner as above, and then developed by the paddle development method, and the wettability was determined by the presence or absence of wet residue when the solution was piled up. At this time, using a 4-inch silicon wafer,
The amount of developer was approximately 12 c.c.

【table】

【table】

【table】

〔Effect of the invention〕

The developer of the present invention does not cause surface layer peeling or thin film residue when developing a resist made of a radiation-sensitive resin containing an alkali-soluble resin, and
Moreover, a resist pattern with a high residual film rate can be obtained. Further, the surface tension of the developer of the present invention is much lower than that of water due to the action of a specific nonionic surfactant, and the developer has good wettability to the resist. Therefore, there is no wastage of the developing solution, and since the permeability is good, good development can be performed even when producing ultra-fine patterns, and a clear resist pattern can be obtained. Furthermore, even if the amount of radiation irradiated is smaller than before, good development can be performed.

Claims (1)

[Claims] 1. In an alkaline aqueous solution, the following general formula (),
A developer characterized in that it contains at least one nonionic surfactant selected from () and (). General formula (); [In the general formula (), R ¹ represents an alkylene group,
^R2 represents a hydrogen atom or ^-COR3 , where ^R3 represents an alkyl group, aryl group, alkenyl group, or alkynyl group, n represents an integer of 1 to 100, m is an integer of 1 to 6, The m Xs may be the same or different and are selected from hydrogen atoms or -O-(R ¹ O) _o -R ² groups, but at least one -O-(R ¹ O) _o -R ² Contains groups. Also, -O-(R ¹ O) _o -R ² contained in one molecule
When the number of groups is l, l R ¹ may be the same or different, and l R ² may also be the same or different. Furthermore, the l n's may be the same or different. [In the general formula (), R ¹ , R ² and n have the same meaning as in the general formula (), the three R ¹ may be the same or different, and the four R 1 ² may be the same or different. Furthermore, the three n's may be the same or different. [In the general formula (), R ¹ , R ² and n have the same meaning as in the general formula (), the three R ¹ may be the same or different, and the four R 1 ² may be the same or different. Furthermore, the three n's may be the same or different. ]