TW201840837A - Semiconductor aqueous composition and use of the same - Google Patents

Abstract

Problem: To provide a semiconductor aqueous composition which comprises a surfactant having high solubility in water and does not adversely affect a pattern shape. To provide a method for producing a resist pattern and a method for manufacturing a semiconductor, using the composition. Means for Solution: A semiconductor aqueous composition comprising:a surfactant comprising an organic compound comprising a ring structure, said ring structure comprising peptide,or a salt thereof, and water. A method for producing a resist pattern and a method for manufacturing a semiconductor, using the same.

Description

 Semiconductor water soluble composition and its use  

The present invention relates to a semiconductor water-soluble composition comprising a surfactant and water. The surfactant comprises an organic compound or a salt thereof, and the organic compound comprises a ring structure containing a peptide. One embodiment of the present invention relates to the use of the semiconductor water-soluble composition for cleaning in a semiconductor manufacturing step.

Further, another embodiment of the present invention relates to a method of producing a resist pattern or a semiconductor using the semiconductor water-soluble composition.

In a semiconductor device such as an LSI (Large Scale Integration, semiconductor integrated circuit), it is required to form a finer pattern as the degree of integration increases.

By exposing with light of a short wavelength, a finer pattern can be formed, but in order to create a very fine structure, there is a problem of yield such as collapse of a fine pattern. It is considered that the narrower the interval width between the stress-based patterns applied to the pattern walls, the higher the height of the pattern, is, for example, one of the causes of the pattern collapse (Non-Patent Document 1). Therefore, in Patent Document 1, it is attempted to suppress pattern collapse of a resist pattern of 20 to 500 nm or to improve unevenness of pattern width by using a rinse agent containing a specific linear alkanediol (LWR: Line width roughness).

On the other hand, in the manufacturing process of the liquid crystal panel, when a liquid crystal material is injected between two substrates, there is a problem that the liquid crystal material is immersed in the μm-level void portion of the substrate due to capillary action (Patent Document 2). In Patent Document 2, it is attempted to clean a liquid crystal panel in which a liquid crystal material is sealed in a portion having a gap of 5 μm by using a cleaning agent for a liquid crystal panel containing a specific surface surfactant.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-44298

[Patent Document 2] Japanese Patent No. 3758613

 [Non-patent literature]  

[Non-Patent Document 1] "Dimensional limitations of silicon nanolines resulting from pattern distortion due to surface tension of rinse water" Namatsu et al. Appl. Phys. Lett. 1995(66) p2655-2657

The inventors of the present invention considered that the water-soluble composition used in the semiconductor process step is useful as a surfactant having high solubility in water, and the water-soluble composition can be effectively used without adversely affecting the shape of the pattern. By. Further, attention has been paid to the fact that the water-soluble composition can not only remove the residue but also increase the barrier width when the water-soluble composition is removed in the cleaning step after development.

The inventors reviewed the use of a surfactant having a large molecular weight to invade the wall of the resist pattern and expand it. However, such a surfactant is not excellent in solubility in water. Therefore, a surfactant having a large molecular weight is required, but a surfactant having a polar group (for example, a nonionic surfactant to which ethylene oxide is added) is tried.

However, although they have high solubility in water, there are other problems such as the polar group dissolves the barrier pattern wall.

As a result of the review, the present inventors have found that a surfactant containing an organic compound containing a ring structure containing a peptide or a salt thereof is excellent in solubility in water, and is used as a semiconductor water-soluble composition. Therefore, problems such as dissolution of the wall of the resist pattern can be suppressed. Further, the resist pattern produced by the method of the present invention can reduce the interval width (more finer). Further, it was confirmed that the occurrence of defects such as bridges in the resist pattern was suppressed, and cleaning was more preferably performed. Further, it was confirmed that the resist pattern LWR was improved.

According to the above review, the inventors completed the invention described later. That is, an object of the present invention is to provide a useful water-soluble composition used in a semiconductor manufacturing step, and to provide a method of using the water-soluble composition in a cleaning step, a resist pattern, and a method for producing a semiconductor.

The semiconductor water-soluble composition according to the present invention comprises a surfactant and water, and the surfactant comprises an organic compound or a salt thereof, and the organic compound comprises a ring structure containing a peptide. The amount of the amino acid constituting the organic compound is 5 to 15.

As an aspect of the semiconductor water-soluble composition of the present invention, the organic compound is represented by the following formula (1).

The semiconductive water-soluble composition of the present invention may further comprise an antibacterial agent, a bactericide, a preservative, an antifungal agent, or a mixture thereof. Further, a surfactant other than the aforementioned surfactant, an acid, a base, an organic solvent, or a mixture thereof may be further included.

The semiconductor water-soluble composition of the present invention is suitable as a semiconductor water-soluble cleaning composition. Further, other suitable embodiments of the present invention are a resist pattern cleaning composition.

Further, the present invention provides a method for producing a resist pattern using the semiconductor water-soluble composition.

For example, the manufacturing method includes the following steps.

(1) A photosensitive resin composition is laminated on a substrate by one or a plurality of intermediate layers or without passing through an intermediate layer to form a photosensitive resin layer.

(2) Exposing the photosensitive resin layer to radiation.

(3) The exposed photosensitive resin layer is developed.

(4) The developed layer is washed with the aforementioned semiconductor water-soluble composition.

Further, the present invention provides a method for producing a semiconductor including the method for producing the resist pattern.

The surfactant contained in the semiconductor water-soluble composition of the present invention is excellent in solubility, and can suppress problems such as dissolution of the barrier pattern wall. Further, the resist pattern produced by using the composition of the present invention can reduce the interval width. Further, the pattern is suppressed from being generated such as bridging, and the composition can be more preferably washed. Furthermore, the pattern can improve the LWR by using the composition.

Figure 1 is a SEM photograph comparing the resist pattern of Composition 1 which produced a bridged spacer width.

2 is a SEM photograph of a resist pattern comparing the minimum interval width of the composition 1.

Figure 3 is an enlarged view of Figure 1.

Figure 4 is an enlarged view of Figure 2.

 [Formation of the Invention]  

The above description and the following details are illustrative of the invention and are not intended to limit the invention claimed.

In the present specification, in the case where ~ is used to indicate a numerical range, unless otherwise specified, they include both ends, and the units are common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

In the present specification, the descriptions of "C _x~y ", "C _x ~C _y ", and "C _x " mean the number of carbons in a molecule or a substituent. For example, C _{1 to 6} alkyl means an alkyl chain (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.) having 1 or more and 6 or less carbons.

In the present specification, in the case where the polymer has a plurality of repeating units, these repeating units are copolymerized. These copolymerizations may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof, unless otherwise specified.

In the present specification, as long as there is no particular limitation, the unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

Semiconductor water soluble composition

The semiconductor water-soluble composition of the present invention means a water-soluble composition used in the semiconductor manufacturing step, and is particularly preferably used in the lithography step. The composition may not be a semiconductor material dissolved in a solution.

The substance which accounts for the most mass ratio as a whole of the composition according to the present invention is water. The water content is preferably 90 to 99.995 mass%, more preferably 95 to 99.995 mass%, and more preferably 98 to 99.99 mass%, as compared with the entire composition. Water can be suitably exemplified by pure water, DW, and deionized water.

The surfactant of the present invention is suitably a cyclic polypeptide type biosurfactant.

The composition according to the present invention may also contain a solvent other than water. The solvent other than water will be described later.

The surfactant in the present case means a component (hereinafter referred to as an interface active component) or a salt thereof which acts on the interface to change the properties. The surfactant in this case contains no solvent (the interface active ingredient or its salt is excluded from the beginning when it is liquid). Further, when a solid interface active component is dissolved in a solvent and added to the composition, such a solvent is contained in the semiconductor water-soluble composition in the form of "water or a solvent other than the solvent". The details are as follows.

Since the surfactant of the present invention is suitable as a biosurfactant, it may not be a single compound or a mixture of a plurality of interfacial active ingredients as long as the effects of the present invention are exerted. Further, the surfactant in the present case also contains a state in which a surfactant and a salt thereof are blended.

An organic compound or a salt thereof comprising a ring structure containing a peptide

The semiconductor water-soluble composition of the present invention contains a surfactant and water, and the surfactant contains an organic compound or a salt thereof, and the organic compound contains a ring structure containing a peptide.

In the semiconductor water-soluble composition of the present invention, the organic compound or a salt thereof is also contained in a water-soluble state in which ion-separation is carried out in an aqueous solvent of the water-soluble composition.

The amount of the amino acid constituting the organic compound is 5 to 15. The number is suitable for 6~12, more suitable for 7~10. If required by the present invention, the organic compound is not necessarily a single organic compound, but may be a combination of a plurality of different organic compounds.

The ring structure including the organic compound is preferably composed of a plurality of amino acids and one or a plurality of auxiliary chains. The amino acid groups constituting the ring structure are each independently selected from the group consisting of: alanine, arginine, aspartic acid, aspartic acid, cysteine, glutamine, glutamic acid, glycine, Histamine, isoleucine, leucine, lysine, methionine, phenylalanine, valine, serine, threonine, tryptophan, tyrosine or valine. The same amino acid can be selected several times. Suitably, these amino acids are peptide bonded. Suitably, all of the amino acids contained in the ring structure constitute a peptide.

The amino acids constituting the ring structure are suitably selected from the group consisting of: alanine, aspartic acid, aspartic acid, glutamic acid, histidine, isoleucine, leucine, lysine. , phenylalanine, threonine or valine.

Each of the amino acids may be either L or D.

As a suitable aspect, the peptide constituting the loop structure is represented by "L glutamic acid-L leucine-D leucine-L-proline-L-aspartic acid-D-leucine-X" X is any of leucine, isoleucine or valine.

The auxiliary chain is each independently composed of -O-, -NH-, -C(=O)-, -CH ₂ -, -C(CH ₃ )H-, -CR ⁰ H- or a combination thereof. R ⁰ is a linkage bond (single bond) to the side chain. These constituent units are the same and can be selected several times. For example, in the organic compound having the following structure, the auxiliary chain is "-O-CR ⁰ H-CH ₂ -C(=O)-".

In the organic compound of the present invention structured as described above, it is preferred that the ring structure is one.

The ring structure is preferably hydrophilic as a whole. It is considered that such a ring structure has an effect of helping the organic compound dissolve in water.

The organic compound is one or a plurality of side chains, and is preferably one side chain. The side chain may be a linear alkyl group, a branched alkyl group, -NH-, -C(=O)-, -CH(NH ₂ )-, -CH(OH)-, a heterocyclic compound, an amino acid. Or a combination of them. These constituent units are the same and can be selected several times.

The linear alkyl group is preferably C _{1 to 10} , more preferably C _{1 to 9} . The branched alkyl group is preferably C _{3 to 10} , more preferably C _{3 to 6} , and still more preferably C _{3 to 4} . The heterocyclic compound is suitably thiazole or pyrrolidine, more preferably thiazole. The heterocyclic compound may form a side chain as a linker or may constitute a side chain as a modifying group. Suitably, the heterocyclic compound forms a side chain as a linker.

The amino acids constituting the side chain are each independently selected from the group consisting of: alanine, arginine, aspartic acid, aspartic acid, cysteine, glutamine, glutamic acid, glycine, Histamine, isoleucine, leucine, lysine, methionine, phenylalanine, valine, serine, threonine, tryptophan, tyrosine or valine. The same amino acid can be selected several times. Suitably, these amino acids are peptide bonded. Suitably, all of the amino acids contained in the side chain constitute a peptide.

The amino acids constituting the side chain are suitably selected from the group consisting of: alanine, aspartic acid, aspartic acid, glutamic acid, histidine, isoleucine, leucine, lysine. , phenylalanine, threonine or valine.

Each of the amino acids may be either L or D.

One of the side chains is bonded to one amino acid or an auxiliary chain constituting the ring structure, respectively. Suitably, one of the side chains is bonded to one auxiliary chain constituting the ring structure, respectively.

The side chain is suitable for those who exhibit hydrophobicity as a whole. It is believed that such side chains have the effect of helping the organic compound invade the walls of the resist pattern to increase the fat pattern.

For example, in an organic compound of the following configuration. The side chain can be read as "-NH-amino acid-amino acid-amino acid-C(=O)-heterocyclic compound-CH(NH ₂ )-branched alkyl group".

The molecular weight of the organic compound of the present invention is preferably from 700 to 2,000, more preferably from 800 to 1,500.

This organic compound is preferably one embodiment by the following formula (1).

The organic compound of the formula (1) is composed of one peptide and one auxiliary chain, and one side chain is bonded to the auxiliary chain. The side chain may comprise an amino acid. Further, the surfactant of the present invention also contains a salt of the organic compound represented by the formula (1).

The organic compound can be obtained, produced and synthesized by a known method. For example, the organic compound enables it to be produced in a prokaryotic or animal cell line. For the prokaryote to be used for the production of the organic compound, for example, Bacillus subtilis IAM1213 strain, IAM1069 strain, IAM1260 strain, IFO3035 strain, ATCC21332 strain or the like can be used. The organic compound can be obtained by culturing and purifying the microorganism. It is also possible to produce a target organic compound by using a genetic engineering method such as vector injection to produce a prokaryotic or animal cell strain.

The organic compound of the present invention is not necessarily a single compound. In the case where an organism produces an organic compound, there is a case where a modified variation or the like occurs, and even if such a variation occurs, the effect of exerting the effect of the present invention is not large. For example, A3 used in the examples described below is not a single compound, but the effects of the present invention can still be exerted.

A well-known method can be used for refining. For example, the culture solution can be made acidic by adding hydrochloric acid or the like, and the precipitated organic compound can be separated by filtration, dissolved in an organic solvent such as methanol, and then subjected to ultrafiltration and activated carbon. Treatment, crystallization, etc. The addition of acid can also be replaced by the addition of a calcium salt.

The refining can be effectively used to remove the organism or culture liquid from which the organic compound is produced. The organic compound is preferably an organic compound after purification. In the semiconductor manufacturing step, tight control is important, and it is not desirable to produce unexpected residues in each step.

a surfactant comprising an organic compound containing a ring structure containing a peptide or a salt thereof

The surfactant of the present invention may contain a salt of an organic compound containing a ring structure containing a peptide. The organic compound can use a metal salt, an ammonium salt, an organic ammonium salt, an acid salt or a mixture thereof. For example, the sodium salt of the organic compound can also be used by changing it to an ammonium salt. A known method can be used for the change of the salt.

As the metal salt, an organic compound such as an alkali metal such as sodium or potassium, an alkaline earth metal such as calcium or magnesium, or a salt-forming compound can be used.

As the organic ammonium salt, a salt such as trimethylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, lysine, arginine or choline can be used.

As the acid salt, a sulfate, a hydrochloride, a phosphate, a nitrate, or the like can be used.

The salt is preferably a sodium salt, an ammonium salt, a sulfate salt or a mixture thereof, more preferably a sodium salt or an ammonium salt.

Specific examples of the surfactant of the present invention are listed below, but the intention of the invention is not limited.

The proportion of the surfactant of the present invention in the water-soluble semiconductor composition is preferably 0.005 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, still more preferably 0.005 to 0.5% by mass, and still more preferably It is 0.01 to 0.4% by mass. These ratios do not include water or other solvents.

Solvent

The composition according to the present invention may contain a solvent other than water. For example, an organic solvent can be effectively used to dissolve the solute contained in the composition according to the present invention. As the organic solvent, a known organic solvent can be used.

For example, suitable are cyclohexanone, cyclopentanone, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether , propylene glycol-1-methyl ether-2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate (EL), Or a mixture of them. They are preferred in terms of storage stability of the solution.

The amount of the organic solvent (in the case of a plurality of cases, the sum of them) is preferably from 0 to 9.985 mass%, more preferably from 0 to 5 mass%, more preferably than the entire composition according to the present invention. Good is 0~1% by mass.

The solvent which is the most abundant solvent in the composition of the present invention is preferably water, and the amount of the organic solvent in the present composition is preferably 0.1% by mass or less, more preferably 0.01% by mass or less. The solvent preferably does not contain an organic solvent in relation to other layers or films, and the amount of the organic solvent in the composition according to the present invention is 0.00% by mass as one aspect of the present invention.

Antibacterial agents, fungicides, preservatives, antifungals

The composition according to the present invention may further contain an antibacterial agent, a preservative, a bactericide, an antifungal agent or a mixture thereof (hereinafter referred to as an antibacterial agent or the like) as needed. These agents are used to prevent bacteria or fungi from multiplying in water-soluble compositions that pass through time. In particular, since the organic compound according to the present invention contains a peptide, it is important to use an antibacterial agent or the like in order to secure the stability of the composition. Examples of the antibacterial agent and the like include an alcohol such as phenoxyethanol or isothiazolinone. As a commercially available antibacterial agent, etc., Pesticide (trade name) of Japan Soda Co., Ltd. is mentioned. According to a suitable aspect of the semiconductor water-soluble composition of the present invention, a composition comprising one antibacterial agent can be mentioned.

The amount of the antibacterial agent or the like (in the case of a plurality of cases, the total amount thereof) is preferably 0.0001 to 1% by mass, and more preferably 0.0001 to 0.01% by mass, as compared with the entire composition.

Other surfactants

The composition of the present invention may further contain a surfactant other than a surfactant (hereinafter referred to as another surfactant) including an organic compound having a ring structure containing a peptide or a salt thereof.

Other surfactants are effective for improving coatability or solubility. The amount of the surfactant in the present composition is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, as compared with the entire composition.

Examples of other surfactants include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octylphenol ether. And polyoxyethylene alkyl aryl ether compounds such as polyoxyethylene nonylphenol ether; polyoxyethylene ‧ polyoxypropylene block copolymer compound, sorbitan monolaurate, sorbitan monopalmitate, a sorbitan fatty acid ester compound such as sorbitan monostearate, sorbitan trioleate and sorbitan tristearate; polyoxyethylene sorbitan monolaurate Polyoxyethylene sorbitan fatty acid such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan tristearate Ester compound. In addition, trade names EFTOP EF301, EF303, EF352 (made by Tohkem Products), trade names Megafac F171, F173, R-08, R-30, R-2011 (made by Dainipa Ink Co., Ltd.) Fluoride FC430, FC431 (Sumitomo 3M (share) system), trade name Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants And an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Acid and alkali

The acid or the base is used to adjust the pH of the treatment liquid or to improve the solubility of the additive component. The acid or the base to be used can be arbitrarily selected within the range which does not impair the effects of the present invention, and examples thereof include a carboxylic acid, an amine, and an ammonium compound. These include a fatty acid, an aromatic carboxylic acid, a primary amine, a secondary amine, a tertiary amine, and an ammonium compound, which may or may not be substituted with any substituent. More specifically, formic acid, acetic acid, propionic acid, benzoic acid, phthalic acid, salicylic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, and Malay can be mentioned. Acid, aconitic acid, glutaric acid, adipic acid, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, ethylenediamine, diethylenetriamine, pentaethylenehexamine, piperidine, pyridyl , morpholine, tetramethylammonium hydroxide, and the like.

The amount of the acid is preferably 0.005 to 0.1% by mass as compared with the entire composition.

Further, the amount of the base is preferably 0.01 to 0.3% by mass as compared with the entire composition.

The semiconductor water-soluble composition of the present invention can be filtered by a filter to remove insoluble matter after the solute is dissolved.

Semiconductor water-soluble cleaning composition

For cleaning in a semiconductor manufacturing step, a preferred aspect of the composition according to the present invention. That is, the semiconductor water-soluble composition is preferably a semiconductor water-soluble cleaning composition. Further, a resist pattern for cleaning a resist film by exposure and development (lithography) is an aspect of the present invention. That is, the semiconductor water-soluble composition is more preferably a resist pattern cleaning composition. Of course, the cleaning composition is used in the semiconductor manufacturing step.

These resist patterns are not only those which have been exposed to the resist film, but also those who thicken the wall by further coating other layers or films (the spacing width is further refined).

As a technique for further thickening the wall by further covering another layer or film, a known technique can be used. For example, in Japanese Patent No. 5,098,494, the resist pattern is further refined by the resin composition.

Method for manufacturing resist pattern

Next, a method of producing the resist pattern of the present invention will be described. The lithography step in the method may be any one of a method of forming a resist pattern by using a known positive or negative photosensitive resin composition (resist composition) of a type developed by an aqueous alkali solution. As a representative pattern forming method to which the semiconductor water-soluble composition of the present invention is applied, the following method can be mentioned.

First, a photosensitive resin composition is laminated on a substrate such as a ruthenium substrate or a glass substrate which is pretreated as necessary to form a photosensitive resin layer. A known method can be used for the laminate, but it is suitable for a coating method such as spin coating. It is also possible to laminate a photosensitive resin composition directly on the substrate, or to laminate one or a plurality of intermediate layers (for example, a BARC layer). Further, an antireflection film (for example, a TARC layer) may be laminated on the photosensitive resin layer (on the side opposite to the substrate). The layer other than the photosensitive resin layer will be described later. By forming an antireflection film above or below the photosensitive resin film, the cross-sectional shape and the exposure margin can be improved.

A typical example of a known positive or negative photosensitive resin composition of the type developed by the alkaline developer used in the method for producing a resist pattern of the present invention is, for example, a ruthenium containing ruthenium. A chemically amplified photosensitive resin composition of a diazide-based sensitizer and an alkali-soluble resin. From the viewpoint of forming a fine resist pattern having a high resolution, a chemically amplified photosensitive resin composition is preferable, and examples thereof include a chemically amplified PHS-acrylate hybrid EUV resist composition.

An example of the quinonediazide-based sensitizer used in the positive photosensitive resin composition containing the quinonediazide-based sensitizer and the alkali-soluble resin is 1,2-benzopyrene a nitrogen-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, an ester of such a sulfonic acid or a guanamine, and the like, Examples of the alkali-soluble resin include a phenol resin, a polyvinyl phenol, a polyvinyl alcohol, a copolymer of acrylic acid or methacrylic acid, and the like. The phenolic resin may be one or more selected from the group consisting of phenols such as phenol, o-cresol, m-cresol, p-cresol, and xylenol, and aldehydes such as formaldehyde and paraformaldehyde. The above-mentioned manufacturers are preferred.

In addition, examples of the chemically amplified photosensitive resin composition include a compound (photoacid generator) which generates an acid by irradiation with active rays or radiation, and an acid which is generated by a photoacid generator. a chemically amplified photosensitive resin composition having a positive effect on the resin having a change in solubility in a developing portion and an unexposed portion; or an alkali-soluble resin, a photoacid generator, and a crosslinking agent, A cross-linking of a crosslinking agent-based resin by an action of an acid, a negative-type chemically amplified photosensitive resin composition in which the solubility in a developing solution is changed in an exposed portion and an unexposed portion, and the like.

The resin whose polarity is increased by the action of an acid and which changes the solubility in the developer in the exposed portion and the unexposed portion may be a main chain or a side chain of the resin, or both a main chain and a side chain. A resin having a base which is decomposed by the action of an acid to generate an alkali-soluble group. A representative example of the acetal-based polymer (PHS) is a acetal group or a ketal-based polymer which is a protective group (for example, JP-KEP) Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The same polymer having an oxy group as an acid-decomposing group, and a carboxylic acid such as acrylic acid or methacrylic acid, is disclosed in JP-A-2002-209977, JP-A-3-206458, JP-A No. 2-19847. a monomer having an acid moiety or a resin having a hydroxyl group or a cyano group in a molecule and a monomer having an alicyclic hydrocarbon group, a base containing an alkali-insoluble group protected by a structure containing an alicyclic group, and the base An acid-inductive resin which is insoluble in the insoluble acid, and which is an alkali-soluble structural unit (Japanese Unexamined Patent Publication No. Hei 9-73173, JP-A No. Hei 9-90637, Japanese Patent Application Laid-Open No. Hei No. Hei 10-161313).

Further, the photoacid generator may be any compound which generates an acid by irradiation with active light or radiation, and examples thereof include a diazonium salt, an ammonium salt, a phosphonium salt, and a phosphonium salt. Photodegradation represented by sulfonium salts, selenium salts, strontium salts, cesium salts, organohalogen compounds, organometallic/organic halides, photoacid generators with o-benzylic-type protecting groups, iminosulfonates, etc. A sulfonic acid-producing compound, a disulfonic acid, a diazoketyl hydrazine, a diazodiamine compound, or the like. Further, a compound in which these groups which generate an acid by light or a compound is introduced into a main chain or a side chain of a polymer can also be used.

Further, the chemically amplified photosensitive resin composition may further contain a compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, and a promotion pair which prevent acid decomposition and dissolution, if necessary. A compound or the like which is soluble in a developer.

The photosensitive resin composition is applied, for example, to a substrate by a suitable coating device or a coating method such as a spinner or a coater, and soft bake on a hot plate to remove the photosensitive resin. The solvent in the composition forms a photosensitive resin layer. The soft baking temperature varies depending on the solvent to be used or the composition of the resist, and can generally be carried out at a temperature of 70 to 150 ° C, preferably 90 to 150 ° C, for 10 to 180 seconds using a heating plate. Preferably, it is 30 to 90 seconds, and is carried out for 1 to 30 minutes in the case of using a clean oven.

Layer other than photosensitive resin layer

In the method for producing a resist pattern of the present invention, the presence of a film or layer other than the photosensitive resin layer is also allowed. The substrate and the photosensitive resin layer may be interposed between the intermediate layers without direct contact. The intermediate layer refers to a layer formed between the substrate and the photosensitive resin layer, which is also referred to as an underlayer film. Examples of the underlayer film include a substrate modified film, a planarizing film, a Bottom anti-reflecting coating (BARC layer), and an inorganic hard mask intermediate layer (an oxide film, a tantalum nitride film, and a tantalum oxide). Nitrogen film) or close to the film. For the formation of the inorganic hard mask intermediate layer, Japanese Patent No. 5336306 can be referred to. The intermediate layer may be composed of one layer or a plurality of layers. Further, an upper anti-reflective coating (TARC layer) may be formed on the photosensitive resin layer.

In the resist pattern manufacturing step of the present invention, the layer configuration can be a known method in accordance with the process conditions, and for example, the following laminated structure can be cited.

Substrate/underlayer/resist film

Substrate/planarization film/BARC layer/resist film

Substrate/planarization film/BARC layer/resist film/TARC layer

Substrate/flattening film/inorganic hard mask intermediate layer/resist film/TARC layer

Substrate/flattening film/inorganic hard mask intermediate layer/BARC layer/resist film/TARC layer

Substrate/flattening film/close film/BARC layer/resist film/TARC layer

Substrate/substrate modification layer/planarization film/BARC layer/resist film/TARC layer

Substrate/substrate modification layer/planarization film/adhesion film/BARC layer/resist film/TARC layer

These layers can be cured by heating and/or exposure after coating, and can be formed by a known method such as a CVD method. These layers can be removed by a known method (etching or the like), and the upper layer can be patterned as a mask.

Exposure of photosensitive resin layer

Exposure of the photosensitive resin layer is performed by a predetermined mask. In the case where other layers are also included (TARC layer, etc.), they are exposed together. The wavelength of light used for the exposure is not particularly limited, and it is preferred to perform exposure with light having a wavelength of 13.5 to 248 nm. Specifically, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), and an extreme ultraviolet (wavelength: 13.5 nm) can be used, and more preferably, it is extremely ultraviolet. These wavelengths allow a range of ± 5%, preferably a range of ± 1%. After exposure, post exposure bake can also be performed as needed. The temperature which can be heated from the exposure is 70 to 150 ° C, preferably 80 to 120 ° C, and the heating time is 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

Next, development is carried out using a developing solution. The development of the resist pattern producing method of the present invention preferably uses a 2.38 mass% aqueous solution of TMAH. Further, a surfactant or the like can also be added to these developing solutions. The temperature from the developer is usually 5 to 50 ° C, preferably 25 to 40 ° C, and the development time is usually 10 to 300 seconds, preferably 20 to 60 seconds. A known method such as puddle development can be used for the development method.

As described above, the resist pattern of the present invention is not only exposed to the resist film. The developer also includes a person who thickens the wall by further coating other layers or films.

Cleaning

The resist pattern (developed photosensitive resin layer) formed up to the above step is in an unwashed state. The resist pattern can be cleaned with the semiconductive composition of the semiconductor of the present invention. The time during which the semiconductor water-soluble composition is brought into contact with the resist pattern, that is, the treatment time, is preferably 1 second or longer. Further, the processing temperature may be arbitrary. The method of bringing the washing liquid into contact with the resist is also arbitrary, and for example, it can be carried out by immersing the resist substrate in the washing liquid or dropping the washing liquid on the surface of the rotating resist substrate.

In the method for producing a resist pattern of the present invention, the developed resist pattern can be washed with another cleaning liquid before and/or after the cleaning treatment using the semiconductor water-soluble composition. Other cleaning solutions are suitable for water and are more suitable for pure water. The pre-treatment cleaning can be effectively used to clean the developer attached to the resist pattern. This post-treatment cleaning can be effectively used to clean the semiconductor water-soluble composition. By replacing the developer with pure water injected into the developed resist pattern, while cleaning the pattern, the pure water is replaced by injecting the semiconductor water-soluble composition while maintaining the pattern immersed in pure water. The method of cleaning the pattern is a suitable aspect of the manufacturing method of the present invention.

The cleaning using the semiconductor water-soluble composition can be carried out by any method known in the art.

For example, the resist substrate may be immersed in the semiconductor water-soluble composition or the semiconductor water-soluble composition may be dropped on the surface of the resist substrate that is rotating. These methods can be carried out in an appropriate combination.

The resist pattern produced by the method of the present invention is suppressed in the generation of defects such as bridges, and can be washed more satisfactorily. In the present specification, bridging refers to the presence of a structure other than the purpose in the groove of the resist pattern, which is a type of defect. For the reason, it is possible that the resist patterns (walls) are connected to each other, or the foreign matter that should be flowed off is caught by the grooves and remains. If the intended trench is buried by the bridge, it becomes impossible to design the intended circuit in a subsequent step such as etching.

In order to manufacture a semiconductor having a high degree of integration, if the interval width is narrowed, it becomes easy to bridge the trench between the resist patterns, which is a problem.

Semiconductors appearing on the market have complex circuits unlike circuits in which the lines are simply advanced at equal intervals. In such a complicated environment, there is a narrowest interval between the wall and the wall of the resist pattern which is one of the conditions for easily causing defects such as bridging. Where the walls of the resist pattern are parallel to the wall, it becomes a strict condition. In the present specification, the distance of the interval at which the interval is the smallest on one circuit unit is set to the minimum interval size. Preferably, one circuit unit becomes one semiconductor in the subsequent step. Further, it is preferable that one semiconductor includes one circuit unit in the horizontal direction and a plurality of circuit elements in the vertical direction. Of course, unlike the test sample, if the frequency of occurrence of a narrow space between the wall and the wall is lowered, the frequency of occurrence of the defect is lowered, so that the frequency of occurrence of defective products is reduced.

In the present invention, the minimum interval size of the resist pattern in one circuit unit is preferably 10 to 30 nm, more preferably 15 to 25 nm, still more preferably 18 to 22 nm.

The resist pattern produced by the method of the present invention can reduce the interval width (more finer) than the case of washing with pure water. In the present specification, the interval width means the width of a trench between the wall and the wall of the resist pattern. Compared with the case of cleaning with pure water, the resist pattern which can be manufactured by using the method of the present invention is suitable for a gap width of 0.5 to 5 nm, more preferably 1.0 to 2.0 nm, and more suitable for being able to be reduced. 1.3~2.4nm.

The resist pattern produced by the method of the present invention can reduce the LWR.

It is considered to be effective for improving yield.

Substrate processing, device manufacturing

The intermediate layer and the substrate can be patterned by using the resist pattern produced by the manufacturing method of the present invention as a mask. As the pattern formation, a known method such as etching (dry etching, wet etching) can be used. For example, the intermediate layer can be etched using the resist pattern as an etch mask, and the obtained intermediate layer pattern can be used as an etch mask to etch the substrate to form a pattern on the substrate. In addition, the photoresist pattern can also be used as an etch mask to etch a layer under the photoresist layer (for example, an intermediate layer) while directly etching the substrate. Wiring can be formed on the substrate using the formed pattern.

These layers are suitably removed by dry etching with O ₂ , CF ₄ , CHF ₃ , Cl ₂ or BCl ₃ , and it is suitable to be able to use O ₂ or CF ₄ .

Thereafter, the substrate is further processed as needed to form a device. These further processing can apply well-known methods. After the device is formed, the substrate is cut into wafers as needed, connected to a lead frame, and packaged with a resin. In the present invention, this encapsulated material is referred to as a semiconductor.

 [Examples]  

Hereinafter, the present invention will be described by way of specific examples. These examples are for illustrative purposes, and are not intended to limit the scope of the invention.

 Surfactant  

In this embodiment, the following surfactants were used.

A1 (sodium surface, model 197-12691, manufactured by Wako Pure Chemical Industries, Ltd.)

A2 (subtilisin, model 022-07701, manufactured by Wako Pure Chemical Industries, Ltd.)

A3 (colistin sulfate, model C2930, manufactured by Tokyo Chemical Industry Co., Ltd.)

A4 (superficial ammonium)

Further, A4 was prepared by changing A1 to an ammonium salt as a solution by the following procedure.

100 g of A1 was added to 900 g of pure water, and stirred to completely dissolve. 80 g of a 10% aqueous hydrochloric acid solution was added thereto, and the mixture was stirred and allowed to stand. This liquid was filtered with a filter paper to obtain a precipitate. The precipitate was allowed to stand in a desiccator overnight and allowed to dry. 48.4 g of the dried powder and 16 g of a 10% aqueous ammonia solution were placed in 935.6 g of pure water and stirred. In this step, sodium was changed to ammonium to obtain 1000 g of an A4 solution having a concentration of 5% by mass.

As the surfactant of the comparative example, tetraglycine (hereinafter referred to as B1) of Tokyo Chemical Industry Co., Ltd. and Surfynol 2502 (hereinafter referred to as B2) of Nissin Chemical Industry Co., Ltd. were used.

B1 (tetraglycine)

 Preparation Example 1 of Semiconductor Water-Soluble Composition  

0.2 g of A1 was added to 1,000 g of pure water, and the mixture was stirred and completely dissolved to obtain a 0.02% by mass aqueous solution of A1. This was taken as the composition of Example 1. The additives and concentrations of the example compositions are summarized in Table 1.

 Preparation examples 2 to 6 of semiconductor water-soluble composition, comparative preparation examples 1 to 3  

The composition was prepared in the same manner as in Preparation Example 1 except that the surfactant and the concentration were changed as described in Table 1. Comparative Preparation Example 1 No surfactant was added.

The compositions 2 to 6 and the comparative compositions 1 to 3 were respectively used as the examples.

 Preparation Example 7 of Semiconductor Water-Soluble Composition  

5.0 g of the above A4 solution was taken. This was added to 245 g of pure water and stirred to completely dissolve. This was taken as the composition of Example 7. The mass % of Table 1 represents the mass % of the organic compound as a solute.

 Evaluation of the substrate  

The evaluation substrate used in the following evaluation was prepared in the following manner.

The surface of the ruthenium substrate (manufactured by SUMCO, 12 Å) was treated at 1,0 °C for 30 seconds using a 1,1,1,3,3,3-hexamethyldioxane solution. On top of this, a chemically amplified PHS-acrylate hybrid EUV resist composition was spin-coated, and soft baked at 110 ° C for 60 seconds to form a resist film having a film thickness of 50 nm on the substrate. It was exposed by a mask of a line: interval = 3:1 (78 nm: 26 nm) by an extreme ultraviolet exposure apparatus NXE: 3100 (manufactured by ASML). A plurality of exposure amounts are set to obtain substrates of various conditions. Further, when the exposure amount is increased, the interval width of the resist pattern formed by development is increased.

The substrate was subjected to post exposure bake (PEB) at 100 ° C for 60 seconds. Thereafter, the resist film was subjected to a puddle development using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds. The pure water is allowed to flow on the substrate while the pulverizing developer is being pulverized on the substrate, and the pulverizing developer is replaced with pure water while being rotated, and is stopped while being pulverized with pure water. Each of the components of Table 1 was flowed thereinto, and the substrate was rotated at a high speed to perform spin drying.

 Evaluation example of the shape of the resist pattern  

The shape of the resist pattern on the evaluation substrate which was exposed under the conditions of an exposure amount of 46 mJ/cm ^{2 was} evaluated by SEM apparatus CG5000 (manufactured by Hitachi High-Technologies Corporation). The evaluation criteria are as follows.

A: No pattern dissolution is confirmed

B: Confirm the pattern is dissolved

The evaluation results are shown in Table 1. The same is true below. The problem of the pattern dissolution was not confirmed in the example composition. Further, since the comparative composition 3-based resist pattern was dissolved, the measurement could not be performed without performing the following evaluation.

 Evaluation example of the interval width reduction amount  

Using the resist pattern on the evaluation substrate which was exposed under the conditions of an exposure amount of 46 mJ/cm ² , the amount of decrease in the interval width was evaluated in the following manner. The interval width of the comparative composition 1 to which no surfactant was added was measured by SEM apparatus CG5000 (manufactured by Hitachi High-Technologies Corporation), and it was 26.0 nm. Using this as a control, the interval widths of the compositions of Examples 1 to 7 and Comparative Composition 2 were measured in the same manner. The difference between the obtained interval width and the interval width of the comparative composition 1 is defined as the interval width reduction amount and is shown in Table 1.

For example, the interval width treated with the composition of Example 1 was 24.2 nm, and the interval width was narrower by 1.8 nm than that of Comparative Composition 1 (26.0 nm). It was confirmed that the resist pattern on the evaluation substrate treated with the example compositions 1 to 7 can narrow the interval width compared to water (comparative composition 1).

 Evaluation example of minimum interval width  

The minimum interval width was evaluated in the following manner using the resist pattern on the evaluation substrate treated with each of the compositions of Table 1.

Evaluation was performed from the evaluation substrate having a large amount of exposure, and the interval width of the resist pattern was measured by the above-described SEM apparatus CG5000, and whether or not bridging occurred during the observation interval occurred. When the occurrence of bridging cannot be confirmed, the evaluation substrate having the second exposure amount is evaluated. This step is repeated until the bridge generation can be confirmed. Once the bridge generation can be confirmed, the interval width of the resist pattern of the evaluation substrate is taken as the interval width at which the bridge is generated. Further, the interval width of the evaluation substrate (the number of exposures) of the previous evaluation of the evaluation substrate was defined as the minimum interval width.

For example, the comparative composition 1 to which no surfactant was added had a minimum interval width of 22.6 nm, and it was found that the interval width of the evaluation substrate (the gap width at which bridging occurred) was 21.8 nm. The evaluation substrate after which the exposure amount became smaller was not evaluated.

A SEM photograph of the resist pattern of the composition 1 in which the bridged interval width and the minimum interval width were compared is shown in FIGS. 1 to 4.

 Evaluation example of LWR  

The LWR of the resist pattern on the evaluation substrate which was exposed under the conditions of an exposure amount of 46 mJ/cm ^{2 was} measured by the above SEM apparatus CG5000. Use the ITRS recommendation program.

Claims (19)

 A semiconductor water-soluble composition comprising a surfactant and water, the surfactant comprising an organic compound or a salt thereof, wherein the organic compound comprises a ring structure comprising a peptide, wherein the composition is The amount of the amino acid of the organic compound is 5 to 15.    The semi-semiconductor water-soluble composition of claim 1, wherein the amino acid constituting the organic compound is each independently from the group consisting of alanine, arginine, aspartic acid, aspartic acid, cysteine, and bran Indoleamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, valine, serine, threonine, tryptamine A group of acids, tyrosine and proline were selected.   The semi-semiconductor water-soluble composition of claim 1 or 2, wherein the ring structure is composed of a plurality of amino acids and one or a plurality of auxiliary chains each independently from -O-, -NH- a group selected from the group consisting of -C(=O)-, -CH ₂ -, -C(CH ₃ )H-, -CR ⁰ H-, and combinations thereof; wherein R ⁰ is a linked chain to the side chain. The semi-semiconductor water-soluble composition according to any one of claims 1 to 3, wherein the organic compound comprises one or a plurality of side chains, the side chain comprising from a linear alkyl group, a branched alkyl group, Selected from the group of NH-, -C(=O)-, -CH(NH ₂ )-, -CH(OH)-, heterocyclic compound, amino acid, and combinations thereof, the side chains are bonded separately An amino acid or an auxiliary chain constructed in the ring.  The semi-semiconductor water-soluble composition according to any one of claims 1 to 4, wherein the organic compound has a molecular weight of from 700 to 2,000.   The semiconductor water-soluble composition according to any one of claims 1 to 5, wherein the organic compound is represented by the following formula (1),  The semi-semiconductor water-soluble composition according to any one of claims 1 to 6, wherein the salt is selected from the group consisting of a metal salt, an ammonium salt, an organic ammonium salt, an acid salt, and a mixture thereof.    The semiconductor water-soluble composition according to any one of claims 1 to 7, wherein the ratio of the surfactant to the semiconductor water-soluble composition is 0.005 to 2.0% by mass.    The semi-semiconductor water-soluble composition according to any one of claims 1 to 8, which further comprises an antibacterial agent, a bactericide, a preservative, an antifungal agent, or a mixture thereof.    The semiconductor water-soluble composition according to any one of claims 1 to 9, which further comprises a surfactant other than the surfactant, an acid, a base, an organic solvent, or a mixture thereof.    A semiconductor water-soluble cleaning composition comprising the semiconductor water-soluble composition according to any one of claims 1 to 10.    A resist pattern cleaning composition comprising the semiconductive water-soluble composition of any one of claims 1 to 10.    A method of producing a resist pattern using the semiconductor water-soluble composition according to any one of claims 1 to 10.    A method for producing a resist pattern comprising the steps of: (1) passing a photosensitive resin composition on a substrate by passing through one or a plurality of intermediate layers or without interposing an intermediate layer to form a photosensitive resin layer; (2) exposing the photosensitive resin layer to radiation; (3) developing the exposed photosensitive resin layer; and (4) cleaning and developing with the semiconductor water-soluble composition according to any one of claims 1 to 10. Layer.    The method for producing a resist pattern according to claim 14, wherein the photosensitive resin composition is a chemically amplified photosensitive resin composition, and the exposure system is extremely ultraviolet ray.    A method of manufacturing a resist pattern according to claim 14 or 15, wherein a minimum size of a resist pattern in one circuit unit is 10 to 30 nm.    A method of producing a semiconductor comprising the method of producing a resist pattern according to any one of claims 14 to 16.    The method of manufacturing a semiconductor according to claim 17, which comprises the step of etching the resist pattern produced by the method of any one of claims 14 to 16 as a mask to process the substrate.    A method of manufacturing a semiconductor according to claim 18, comprising the step of forming a wiring on the processed substrate.