WO2018141944A1

WO2018141944A1 - Semiconductor aqueous composition and use of the same

Info

Publication number: WO2018141944A1
Application number: PCT/EP2018/052726
Authority: WO
Inventors: Kazuma Yamamoto; Tatsuro Nagahara; Takashi Sekito; Tomoyasu YASHIMA; Maki Ishii
Original assignee: Merck Patent Gmbh
Priority date: 2017-02-06
Filing date: 2018-02-05
Publication date: 2018-08-09
Also published as: EP3577524A1; TWI800500B; TW201840837A; JP2020507915A; JP2018127513A; JP7200110B2

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 AQUEOUS COMPOSITION AND USE OF THE

SAME

BACKGROUND OF THE INVENTION

TECHNICAL FIELD

[0001] The present invention relates to 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. One embodiment of the present invention relates to performing cleaning in a manufacturing process of semiconductor using the semiconductor aqueous composition.

Further, another embodiment of the present invention relates to a method for producing a resist pattern or a semiconductor using the semiconductor aqueous composition. BACKGROUND ART

[0002] In semiconductor devices such as LSI (Large Scale

Integration), formation of finer patterns is required as the degree of integration is improved.

Although it is possible to form finer patterns by exposure with short wavelength light, collapse of fine patterns or the li ke becomes a problem in terms of yield as a very fine structure is formed. It is thought that the stress applied to the pattern wall, which is one of the causes of pattern collapse, becomes larger as the space width between the patterns is narrower and the height of the pattern is higher (Non-Patent Document 1) . Therefore, in Patent Document 1, using a rinse agent containing a specific linear alkane diol, suppression of pattern collapse of a resist pattern of 20 to 500 nm and improvement of pattern width unevenness (LWR: Line width roughness) have been tried. On the other hand, when a liquid crystal material is injected between two substrates in a manufacturing process of liquid crystal panel, there is a problem that liquid crystal material infiltrates into the void parts of pm order in the substrate due to capillary phenomenon (Patent Document 2) . In Patent Document 2, it has been tried to clean a liquid crystal panel in which a liquid crystal material is sealed in a 5 pm void part using a cleaning agent for a liquid crystal panel, which contains a specific surfactin.

PRIOR ART DOCUMENTS

PATENT DOCUMENTS

[0004] [Patent Document 1] JP-A No. 2014-44,298

[Patent Document 2] JP-B No. 3,758,613

NON-PATENT DOCUM ENT

[0005] [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) p2, 655-2, 657

SUMMARY OF THE INVENTION

PLOBLEMS TO BE SOLVED BY THE INVENTION

The inventors of the present invention have thought that a surfactant having high solubility in water is useful for an aqueous composition used in a manufacturing process of semiconductor, and an aqueous composition that does not adversely affect a pattern shape is useful . Further, the inventors of the present invention have noticed that the space width can be reduced, if not only the aqueous composition removes residues in the cleaning step after development, but also the resist pattern wall can be made thick. The inventors of the present invention have investigated use of a surfactant having a large molecular weight for infiltrating into a resist pattern wall to inflate it, but such a surfactant was not satisfying at solubility in water. Then, the inventors of the present invention have searched for a surfactant having, regardless of a large molecular weight, high solubility in water, and tried surfactants having a polar group (for example, a nonionic surfactant to which ethylene oxide is added) .

However, although these have a high solubility in water, there was another problem that the polar group dissolves the resist pattern wall .

As the result of the investigation, the inventors of the present invention have found that a surfactant comprising an organic compound comprising a ring structure, said ring structure comprising peptide, or a salt thereof exhibits good solubility in water and that when it is used as a semiconductor aqueous composition, problems such as dissolution of the resist pattern wall and so on can be suppressed . Further, the resist pattern produced by the method of the present invention could reduce (further make finer) the space width. In addition, with respect to the resist pattern, it could be confirmed that occurrence of defects such as bridge was suppressed and better cleaning was made. As to the resist pattern, it could be also confirmed that LWR has been improved.

Through the investigation described above, the inventors of the present invention has completed an invention to be described later. That is, an object of the present invention is to provide a useful aqueous composition to be used in a manufacturing process of semiconductor, a method for using the aqueous composition in a cleaning step, and methods for producing a resist pattern and a semiconductor. MEANS FOR SOLVING THE PROBLEMS

[0009] The semiconductor aqueous composition according to the present invention comprises a surfactant comprising an organic compound comprising a ring structure, said ring structure comprising peptide, or a salt thereof, and water. The number of amino acids composing said organic compound is 5 to 15.

As one embodiment of the semiconductor aqueous composition of the present invention, the organic compound is represented by the following formula ( 1) .

^ side chain

I peptide assist chain 1 formula (1)

The semiconductor aqueous composition of the present invention may further comprise an antibacterial agent, a germicide, an antiseptic, an antifungal agent or any mixture of any of these. It may further comprise a surfactant other than said surfactant, an acid, a base, an organic solvent or any mixture of any of these.

The semiconductor aqueous composition of the present invention is preferably a semiconductor aqueous cleaning composition. Another preferred embodiment of the present invention is a resist pattern cleaning composition.

[0010] Further, the present invention provides a method for producing a resist pattern, using the semiconductor aqueous composition.

For example, the producing method comprises the following steps:

( 1) applying a photosensitive resin composition on a substrate through one or more intermediate layers or without through 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 the developed layer with said semiconductor aqueous composition.

In addition, the present invention provides a method for manufacturing a semiconductor, comprising the method for producing the resist pattern. EFFECTS OF THE INVENTION

The semiconductor aqueous composition of the present invention exhibits good solubility of the surfactant contained therein and can suppress problems such as dissolution of a resist pattern wall . Furthermore, the resist pattern produced using the composition of the present invention can reduce the space width. In addition, with respect to the resist pattern occurrence of defects such as bridge can be suppressed and better cleaning can be made by the composition. Further, as to the pattern, LWR can be improved using the composition.

DETAILED DESCRIPTION OF THE INVENTION

MODE FOR CARRYING OUT THE INVENTION

The outline described above and the details to be described below are for the purpose of explaining the present invention and are not for the purpose of limiting the claimed invention.

In the present specification, when numerical ranges are indicated using "to" or unless otherwise specifically mentioned, they include both endpoints and units thereof are common. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.

In the present specification, the descriptions such as "Cx-y" , "Cx-Cy" and "C_x" mean the number of carbons in a molecule or substituent. For example, Ci-e alkyl means an alkyl chain having 1 or more and 6 or less carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl etc.).

In the present specification, when a polymer has plural types of repeating units, these repeating units copolymerize. Unless otherwise specifically mentioned, these copolymerizations may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof.

In the present specification, unless otherwise specifically mentioned, Celsius is used as the temperature unit. For example, 20 degrees means 20 degrees Celsius.

Semiconductor aqueous composition

The semiconductor aqueous composition in the present invention means an aqueous composition used in a manufacturing process of semiconductor, and it is particularly preferably used in a lithography process. The composition of the present invention may not be one in which any semiconductor material is dissolved in a solution.

The substance which occupies the most mass ratio in whole of the composition according to the present invention is water. The amount occupied by water is preferably 90 to 99.995 mass %, more preferably 95 to 99.995 mass %, and further preferably 98 to 99.99 mass % as compared with whole of the composition. Water is preferably pure water, DW or deionized water.

The surfactant according to the present invention is preferably a cyclic polypeptide type biosurfactant.

It is also possible that the composition according to the present invention contains solvent(s) other than water. The solvents other than water are described later.

The surfactant in the present application means an ingredient, which acts on a surface to change its properties (hereinafter referred to as surface active ingredient) or its salt. The surfactant used in the present application does not include any solvent. (When a surface active ingredient or its salt is a liquid from the beginning, these are excluded.) A solid surface active ingredient may be dissolved in a solvent and added to a composition, but such a solvent is contained in the semiconductor aqueous composition as "water or a solvent other than water". Details are described below.

Since the surfactant according to the present invention is preferably a type of biosurfactant, it is not limited to be a single compound as long as the effect of the present invention is exhibited, and it may be a mixture of plural types of surface active ingredients. Further, the surfactant in the present application also includes a state in which a surface active ingredient and its salt are mixed.

Organic compound comprising a ring structure, said ring structure comprising peptide or salt thereof

The semiconductor aqueous composition in the present invention comprises a surfactant comprising an organic compound comprising a ring structure, said ring structure comprising peptide or a salt thereof, and water.

In the semiconductor aqueous composition of the present invention, the organic compound or a salt thereof also comprises an aqueous state in which it is separated into ions in an aqueous solvent of the aqueous composition.

The number of amino acids composing the organic compound is 5 to 15. The number is preferably 6 to 12, and further preferably 7 to 10. As long as it is claimed as the present invention, the organic compound is not necessary to be a single one, and it may be a combination of plural ones which are different. The ring structure comprised in the organic compound is preferably composed by a plural amino acids and one or more assist chains. The amino acids composing the ring structure are independently selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine. An identical amino acid may be selected plural times. Preferably, these amino acids form peptide bonds. Preferably, all amino acids comprised in the ring structure compose peptide.

It is preferable that the amino acids composing the ring structure are independently selected from the group consisting of alanine, asparagine, aspartic acid, glutamic acid, histidine, isoleucine, leucine, lysine, phenylalanine, threonine and valine.

The individual amino acid may be L-form or D-form.

As a preferable embodiment, peptide composing the ring structure is represented by "L-glutamic acid - L-leucine - D-leucine - L-valine - L-aspartic acid - D-leucine - X", wherein X is either one of leucine, isoleucine or valine.

The assist chain is independently selected from the group consisting of -O-, -NH-, -C(=O)-, -CH₂-, -C(CH₃)H-, -CR°H- or any combination of any of these. R° represents a bond to a side chain (single bond) . For the composing unit, an identical one may be selected plural times. For example, in the organic compound of the following structure, the assist chain is ^M-O-CR°H-CH₂-C(=O)-" .

As in the above structure, one ring structure is preferably contained in the organic compound in the present invention.

The ring structure is preferably hydrophilic as a whole. Such a ring structure is considered to have an effect of helping the organic compound to dissolve in water.

The organic compound comprises one or more side chains, preferably one side chain. The side chain is selected from the group consisting of a linear alkyl, a branched alkyl, -NH-, -C( = 0)-, -CH(NH₂)-, -CH(OH)-, a heterocyclic compound, an amino acid or any combination of any of these. For the composing unit, an identical one may be selected plural times.

The linear alkyl is preferably Ci-io, more preferably Ci-9. The branched alkyl is preferably C3-10, more preferably C3-6 , and further preferably C3-4. The heterocyclic compound is preferably thiazole or pyrrolidine, and more preferably thiazole. The heterocyclic compound may compose a side chain as a linker, or may compose a side chain as a modifying group. Preferably, the heterocyclic compound composes a side chain as a linker.

The amino acids composing the side chain are independently selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine. An identical amino acid may be selected plural times. Preferably, these amino acids form peptide bonds. Preferably, all amino acids comprised in the side chain compose peptide.

It is preferable that the amino acids composing the side chain are independently selected from the group consisting of alanine, asparagine, aspartic acid, glutamic acid, histidine, isoleucine, leucine, lysine, phenylalanine, threonine and valine.

The individual amino acid may be L-form or D-form.

One side chain bonds to one of the amino acid or the assist chain respectively composing the ring structure. Preferably, one side chain bonds to one assist chain composing the ring structure.

The side chain is preferably hydrophobic as a whole. Such a side chain is considered to have an effect of helping the organic compound to enter a resist pattern wall and to thicken the resist pattern.

For example, in the organic compound of the following structure, the side chain can be read as "- NH - amino acid - amino acid - amino acid - C( = O) - heterocyclic compound - CH(N H2) - branched alkyl".

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

The organic compound is represented by the following formula ( 1) as one preferable embodiment. side chain

peptide assist chain formula (1)

In the organic compound of the formula ( 1), one ring structure is composed of one peptide and one assist chain, and one side chain bonds to the assist chain. The side chain may contain amino acid(s) . Furthermore, 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 publicly known method. For example, it is possible to make a prokaryote or animal cell strain produce the organic compound . As the prokaryote used for the production of the organic compound, microorganisms belonging to genus Bacillus such as Bacillus subtilis IAM 1213 strain, IAM 1069 strain, IAM 1260 strain, IFO 3035 strain, ATCC 21332 strain and the like can be used. By culturing and purifying this microorganism, the organic compound can be obtained . Using genetic engineering technique such as vector injection, it is also possible to make a prokaryote or animal cell strain produce the desired organic compounds.

The organic compound according to the present invention does not have to be a single compound . In the case of making an organism produce the organic compounds, variations in the modifications and the li ke sometimes occur, and even if such variations are present, the effect of the present invention is not so much influenced . For example, A3 used in Example which is described later is not a single compound, but exhibits the effect of the present invention.

[0022] A publicly known method can be used for purification. Purification can be done, for example, by making a culture liquid acidic by adding hydrochloric acid or the like, filtering out the organic compound precipitated, dissolving it in an organic solvent such as methanol, and then conducting ultrafiltration, activated carbon treatment, crystallization, etc. The acid addition can also be substituted by adding a calcium salt.

Purification is useful for removing the organism and culture liquid that produce the organic compound .

It is preferable to use the organic compound after purification. Strict control is important for a manufacturing process of semiconductor, and it is undesirable that an unexpected residue is generated in each step.

[0023] Surfactant comprising an organic compound comprising a ring structure, said ring structure comprising peptide, or a salt thereof

The surfactant according to the present invention may comprise a salt of an organic compound comprising a ring structure, said ring structure comprising the peptide. The organic compound is selected from the group consisting of metallic salt, ammonium salt, organic ammonium salt, acid salt and any mixture of any of these. For example, the organic compound may be also used by changing its sodium salt to its ammonium salt. Publicly known methods can be used for changing the salt.

As the metal salt, alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and the like, which form a salt with the organic compound, can be used.

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

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

The salt is more preferably a sodium salt, an ammonium salt, a sulfate salt or any mixture of any of these, and more preferably a sodium salt or an ammonium salt.

024] Specific examples of the surfactant according to the present invention are shown below, but they do not intend to limit the present invention.

R— CH₃ H

[0025] The content ratio of the surfactant of the present invention is preferably 0.005 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, further preferably 0.005 to 0.5 mass %, and even more preferably 0.01 to 0.4 mass %, based on the semiconductor aqueous composition. These ratios do not contain water or other solvents.

[0026] Solvent

The composition according to the present invention may comprise solvent(s) other than water. For example, an organic solvent is useful for dissolving the solute contained in the composition according to the invention. Publicly known organic solvents can be used .

For example, 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-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate (EL), or any mixture of any of these are suitable. These are preferable in terms of storage stability of the solution.

The content ratio of the organic solvent (or sum thereof in the case of plural) as compared with whole of the composition according to the present invention is preferably 0 to 9.995 mass %, more preferably 0 to 5 mass %, and further more preferably 0 to 1 mass %.

The substance which occupies the most amount as the solvent of the composition according to the present invention is preferably water, and the content ratio of the organic solvent in the present composition is preferably 0.1 mass % or less, and further preferably 0.01 mass % or less. In relation to other layers and films, it is preferred that the present solvent contains no organic solvent, and it is one embodiment of the present invention that the content ratio of the organic solvent in the composition according to the present invention is 0.00 mass %.

Antibacterial agent, germicide, antiseptic and antifungal agent

The composition according to the present invention may further comprise an antibacterial agent, a germicide, an antiseptic, an antifungal agent or any mixture of any of these (hereinafter referred to as antibacterial agent etc.), if needed. These agents are used to prevent bacteria or fungi from breeding in the aqueous composition over time. In particular, since the organic compound according to the present invention comprises peptide, it is important to use an antibacterial agent etc. in order to ensure the stability of the present composition. Examples of antibacterial agent etc. include alcohols such as phenoxyethanol and isothiazolone. As commercially available antibacterial agent etc., BESTCIDE (trade name) of Nippon Soda Co., Ltd. can be referred. As a preferable embodiment of the semiconductor aqueous composition according to the present invention, a composition comprising one kind of antibacterial agent can be referred.

The content ratio of the antibacterial agent etc. (or sum thereof in the case of plural) as compared with whole of the composition of the present invention is preferably 0.0001 to 1 mass %, and more preferably 0.0001 to 0.01 mass %.

Other surfactant

The composition according to the present invention may further comprise a surfactant other than the surfactant comprising an organic compound comprising a ring structure, said ring structure comprising peptide, or a salt thereof (hereinafter referred to as other surfactant) .

Other surfactant is useful for improving coatability and solubility. The content ratio of the surfactant in the present composition as compared with whole of the composition of the present invention is preferably 0.01 to 5 mass %, and more preferably 0.05 to 3 mass %.

As other surfactant, polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene al kylaryl ether compounds such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymer compounds; sorbitan fatty acid ester compounds such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate and sorbitan tristearate; polyoxyethylene sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan tristearate can be referred. In addition, fluorine-based surfactants such as EFTOP EF301, EF303 and EF352 (trade name, manufactured by Tochem Products Co., Ltd. ), MEGAFAC F171, F173, R-08, R-30 and R-2011 (trade name, manufactured by DIC Corporation), FLUORAD FC430 and FC431 (trade name, manufactured by Sumitomo 3M Limited), ASAHI GUARD AG710 and SURFLON S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (trade name, manufactured by Asahi Glass Co., Ltd. ), and organosiloxane polymer KP 341 (manufactured by Shin-Etsu Chemical Co., Ltd .), and the like can be referred.

Acid and base

The acid or base is used to adjust the pH of treating liquid or to improve the solubility of adding component. The acid or base to be used can be arbitrarily selected as long as the effect of the present invention is not impaired, and examples thereof include carboxylic acids, amines and ammonium compounds. These include fatty acids, aromatic carboxylic acids, primary amines, secondary amines, tertiary amines, and ammonium compounds, and these may be substituted by any substituent or not substituted. 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, maleic acid, aconitic acid, glutaric acid, adipic acid, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, ethylenediamine, diethylenetriamine, pentaethylenehexamine, piperidine, piperazine, morpholine, tetramethylammonium hydroxide and the like can be referred.

The amount of the acid is preferably 0.005 to 0.1 mass % as compared with whole of the composition of the present invention.

Further, the amount of the base is preferably 0.01 to 0.3 mass % as compared with whole of the composition of the present invention.

[0031] In the semiconductor aqueous composition according to the present invention, after the solute is dissolved, it is possible to remove insoluble matter by filtration through a filter.

[0032] Semiconductor aqueous cleaning composition

One preferred embodiment of the composition according to the present invention is to be used for cleaning in a manufacturing process of semiconductor.

That is, the semiconductor aqueous composition is preferably a semiconductor aqueous cleaning composition. In addition, one embodiment of the present invention is to be used for cleaning a resist pattern formed by exposing / developing (lithography technique) a resist film. That is, the semiconductor aqueous composition is more preferably a resist pattern cleaning composition. Of course, the cleaning composition is used in a manufacturing process of semiconductor.

The resist pattern includes not only one obtained by exposing / developing a resist film but also one having a wall thickened by further covering it with other layer(s) or film(s) (one in which its space width is further made finer) .

As a technique for thickening the wall by further covering it with other layer(s) or film(s), a publicly known one can be used. For example, in JP-B No. 5,069,494, the resist pattern is further made finer by a resin composition.

[0033] Method for producing resist pattern

Next, the method for producing the resist pattern of the present invention is described . The lithography process in the method may be any of the method for forming a resist pattern using a publicly known positive or negative type photosensitive resin composition (resist composition), which is a type of developing with an aqueous alkaline solution. Representative pattern forming methods to which the semiconductor aqueous composition of the present invention is applied include the following methods.

[0034] First, a photosensitive resin composition is applied on a substrate such as a silicon substrate, a glass substrate, or the like, which has been optionally pretreated, to form a photosensitive resin layer. A publicly known method can be used for the application, but a coating method such as spin coating is suitable. The photosensitive resin composition may be directly applied on a substrate, or may be applied via one or more intermediate layers (for example, a BARC layer) . Further, an anti-reflective film (for example, a TARC layer) may be applied on the photosensitive resin layer (on the side opposite to the substrate) . Layers other than the photosensitive resin layer are described later. By forming an anti-reflective film on or under the photosensitive resin film, the cross-sectional shape and the exposure margin can be improved.

[0035] Typical examples of publicly known positive or negative type photosensitive resin composition of a type of developing with an al kaline developing solution used in the resist pattern producing method of the present invention include one comprising a quinone diazide type photosensitizer and an alkali soluble resin, a chemically amplified photosensitive resin composition, and the like. From the viewpoint of forming a fine resist pattern with high resolution, a chemically amplified photosensitive resin composition is preferable and, for example, a chemically amplified PHS-acrylate hybrid type EUV resist composition can be referred.

[0036] Examples of the quinone diazide type photosensitizer used in the above-described positive type photosensitive resin composition comprising the quinone diazide type photosensitizer and the alkali soluble resin include 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, esters or amides of these sulfonic acids, and examples of the alkali soluble resin include novolac resin, polyvinyl phenol, polyvinyl alcohol, copolymer of acrylic acid or methacrylic acid, and the like. Preferable examples of the novolac resin include one produced from one or more phenols such as phenol, o-cresol, m-cresol, p-cresol and xylenol, and one or more aldehydes such as formaldehyde and paraformaldehyde.

[0037] Further, the chemically amplified photosensitive resin composition includes a positive type chemically amplified photosensitive resin composition comprising a compound (photoacid generator) that generates an acid upon irradiation with active ray or radiation, and a resin whose polarity is increased by the action of the acid generated from the photoacid generator and whose solubility to a developing solution varies in an exposed part and an unexposed part; or a negative type chemically amplified photosensitive resin composition comprising an al kali soluble resin, a photo acid generator and a crosslinking agent, in which crosslinking of the resin due to the crosslinking agent is caused by action of the acid and the solubility to a developing solution varies in an exposed part and an unexposed part.

As the resin whose polarity is increased by the action of the above-described acid and whose solubility to a developing solution varies between an exposed part and an unexposed part, a resin having a group which is decomposed due to the action of acid to form an alkali soluble group in the main chain or side chain of the resin or both main chain and side chain thereof can be referred . Typical examples thereof include polymer in which an acetal group or a ketal group is introduced as a protective group to a hydroxystyrene-based polymer (PHS) (for example, JP-A No. 2- 141,636, J P-A No.

2- 19,847, JP-A No. 4-219,757 and JP-A No. 5-281,745) ; similar polymer into which a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group is introduced as an acid decomposable group (J P-A No. 2-209,977, JP-A No.

3- 206,458 and J P-A No. 2- 19,847) ; resin copolymerized a monomer having a moiety of carboxylic acid such as acrylic acid or methacrylic acid, or a monomer having a hydroxyl group or a cyano group in a molecule, with a monomer having an alicyclic hydrocarbon group; acid sensitive resin comprising an al kali insoluble group protected with a structure containing an alicyclic group and a structural unit that become alkali soluble when the alkali insoluble group is eliminated by an acid (JP-A No. 9-73, 173, JP-A No. 9-90,637 and JP-A No. 10- 161,313) ; and the like.

Further, the photoacid generator may be any compound as long as it generates an acid upon irradiation with active ray or radiation, and examples thereof include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts, organic halogen compounds, organometallic compounds / organic halides, photoacid generators having an o-nitrobenzyl type protective group, compounds capable of photolysis to generate a sulfonic acid represented by iminosulfonate and the like, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like. Compounds in which a group or compound capable of generating an acid by light is introduced into the main chain or the side chain of polymer can also be used.

Additionally, said chemically amplified photosensitive resin composition may further comprise, if needed, an acid decomposable and dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, and a compound that promotes solubility to developing solution, and the like.

For example, said photosensitive resin composition is applied onto a substrate by a suitable coating apparatus such as a spinner and a coater by means of a suitable coating method and soft-baked on a hot plate to remove the solvent in the photosensitive resin composition, thereby forming a photosensitive resin layer. The soft baking temperature varies depending on the solvent or the resist composition to be used, but is generally 70 to 150°C, and preferably 90 to 150°C. It can be carried out for 10 to 180 seconds, preferably for 30 to 90 seconds in the case of hot plate, or for 1 to 30 minutes in the case of clean oven.

Layer other than photosensitive resin layer

In the method for manufacturing the resist pattern of the present invention, the presence of film(s) or layer(s) other than the photosensitive resin layer is also allowed . Without direct contact of the substrate with the photosensitive resin layer, intermediate layer(s) may be interposed . The intermediate layer is a layer formed between a substrate and a photosensitive resin layer and is referred also to as underlayer film . As the underlayer film, a substrate modifying film, a planarizing film, a bottom anti-reflecting coating (BARC layer), an inorganic hard mask intermediate layer (silicon oxide film, silicon nitride film and silicon oxide nitride film) can be referred . As to the formation of the inorganic hard mask intermediate layer, reference can be made to JP-B No. 5,336,306. The intermediate layer may be composed of one or more layers. In addition, a top anti-reflective coating (TARC layer) may be formed on the photosensitive resin layer.

For the layer constitution in the process for manufacturing the resist pattern of the present invention, any publicly known technique can be used in accordance with process conditions. For example, the following layer constitution can be referred.

substrate / underlayer film / Photoresist film substrate / planarizing film / BARC layer / photoresist film

substrate / planarizing film / BARC layer / photoresist film / TARC layer

substrate / planarizing film / inorganic hard mask intermediate layer / photoresist film / TARC layer

substrate / planarizing film / inorganic hard mask intermediate layer / BARC layer / photoresist film / TARC layer

substrate / planarizing film / adhesive film / BARC layer / photoresist film / TARC layer

substrate / substrate modifying layer / planarizing film / BARC layer / photoresist film / TARC layer

substrate / substrate modifying layer / planarizing film / adhesive film / BARC layer / photoresist film / TARC layer

These layers can be obtained by coating and thereafter heating and / or exposing to cure, or by employing a publicly known method such as CVD method to form a film . These layers can be removed by a publicly known method (etching or the like), and can be patterned using the upper layer as a mask.

Exposure / development of photosensitive resin layer

The photosensitive resin layer is exposed through a predetermined mask. When other layers (TARC layer etc.) are also included, they may be exposed together. The wavelength of the light used for exposure is not particularly limited, but it is preferable to perform exposure with light having a wavelength of 13.5 to 248 nm. Specifically, KrF excimer laser (wavelength : 248 nm), ArF excimer laser (wavelength : 193 nm), extreme ultraviolet ray (wavelength : 13.5 nm) and the like can be used, and extreme ultraviolet ray is more preferable. These wavelengths allow a range of ±5%, and preferably a range of ± 1% . After the exposure, post exposure bake may be performed, if needed. The temperature for post-exposure heating is appropriately selected from 70 to 150°C, preferably 80 to 120°C, and the heating time is appropriately selected from 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

Thereafter, development is performed with a developing solution. For the development in the method for producing the resist pattern of the present invention, a 2.38 mass % TMAH aqueous solution is preferably used . Further, a surfactant or the like can be added to these developers. Generally, the temperature of the developing solution is appropriately selected from 5 to 50°C, preferably 25 to 40°C, and the developing time is appropriately selected from 10 to 300 seconds, preferably from 20 to 60 seconds. As the developing method, publicly known methods such as paddle development can be used.

As described above, the resist pattern of the present invention includes not only one obtained by exposing / developing a resist film but also one having a wall thickened by further covering it with other layer(s) or film(s) .

Cleaning

The resist pattern (the developed photosensitive resin layer) formed up to the above steps is in a non-cleaned state. This resist pattern can be cleaned with the semiconductor aqueous composition of the present invention. The time for bringing the semiconductor aqueous composition into contact with the resist pattern, that is, the treatment time is preferably 1 second or more. In addition, the treating temperature may be also arbitrary. The method for bringing a rinse liquid into contact with the resist is also arbitrary, and it can be done, for example, by immersing a resist substrate in a rinse liquid or dropping a rinse liquid onto a rotating resist substrate surface.

In the method for manufacturing the resist pattern of the present invention, the resist pattern after being developed can be cleaned with other cleaning liquid before and / or after the cleaning treatment with the semiconductor aqueous composition. The other cleaning liquid is preferably water, and more preferably pure water. The cleaning before the treatment is useful for cleaning the developing solution that has adhered to the resist pattern. The cleaning after the treatment is useful for cleaning the semiconductor aqueous composition. One preferred embodiment of the production method of the present invention is a method comprising, by pouring pure water onto a resist pattern, cleaning the pattern after being developed while substituting the developing solution, and further, by pouring the semiconductor aqueous composition while keeping the pattern immersed in pure water, cleaning the pattern while substituting pure water.

The cleaning with the semiconductor aqueous composition may be carried out by any conventionally known method. It can be done, for example, by immersing a resist substrate in the semiconductor aqueous composition, or by dropping the semiconductor aqueous composition onto a rotating resist substrate surface. These methods may be carried out in appropriate combination thereof.

[0048] In the resist pattern produced by the method of the present invention, occurrence of defects such as bridge was suppressed and the resist pattern could be better cleaned. In the present specification, the bridge is one in which undesired structure(s) exist in the groove(s) of a resist pattern and is a kind of defect. The reason includes that the resist patterns (walls) are connected to each other or that foreign substance which should be flowed is caught in the groove and remains therein. When a desired groove is filled with bridge(s), it becomes impossible to design a desired circuit in a following process such as etching.

Since the bridge tends to occur in the trench (groove) between the resist patterns when the space width becomes narrower, this is a problem for manufacturing a semiconductor having high degree of integration.

[0049] Semiconductors on the market have complicated circuits different from those in which lines are simply arranged side by side at equal intervals. Under such a complicated environment, as one of the conditions under which defects such as the bridge are likely to occur, there is a portion where the distance between a wall and a wall, of a resist pattern is the narrowest. At a portion where a wall and a wall, of a resist pattern are arranged in parallel, this becomes a severe condition. In the present specification, the distance of the interval at the portion where the interval is the smallest on one circuit unit is regarded as a minimum space size. It is preferable that one circuit unit becomes a semiconductor in a later process. Further, it is also preferable that one semiconductor includes one circuit unit in the horizontal direction and a plural circuit units in the vertical direction. Of course, unlike the test sample, if the occurrence frequency of the portion where the interval between a wall and a wall is narrow is low, the occurrence frequency of defects decreases, so that the occurrence frequency of defective products decreases.

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

The resist pattern produced by the method of the present invention could reduce the space width (make further finer) as compared with the case of cleaning with pure water. In the present specification, the space width means a width of a trench (groove) between a wall and a wall, of a resist pattern. The resist pattern which can be produced by using the method of the present invention can reduce the space width preferably 0.5 to 5 nm, more preferably 1.0 to 2.0 nm, and further preferably 1.3 to 2.4 nm, as compared with the case of cleaning with pure water.

The resist pattern produced by the method of the present invention could make the LWR small . This is considered to be useful for raising the yield rate.

Processing of substrate and manufacturing of device

Using the resist pattern produced by the manufacturing method of the present invention as a mask, an intermediate layer and/or a substrate can be patterned . For pattern formation, publicly known methods such as etching (dry etching and wet etching) can be used. For example, an intermediate layer is etched using a resist pattern as an etching mask, and a substrate can be etched using the obtained intermediate layer pattern as an etching mask to form a pattern on the substrate. Further, it is also possible, using a photoresist pattern as an etching mask, to etch a substrate as it is while etching layer(s) (for example, intermediate layer) lower than the photoresist layer.

Wiring can be formed on the substrate utilizing the formed pattern.

These layers can be removed, preferably by dry etching with O2, CF₄, CH F3, CI 2 or BCh, and preferably, O2 or CF₄ can be used.

[0052] Thereafter, the substrate is further processed, if needed, and a device is formed . For the further processing, publicly known methods can be applied. After formation of the device, the substrate is optionally cut into chips, connected to a lead frame, and packaged with resin. In the present invention, this packaged product is called semiconductor.

BRIEF DESCRIPTION OF THE DRAWINGS

[0053] FIG . 1 is an SEM image of a resist pattern having a space width where bridge(s) have occurred in case of Comparative Composition 1.

FIG . 2 is an SEM image of a resist pattern having a minimum space width in case of Comparative Composition 1.

FIG. 3 is an enlarged figure of FIG. 1.

FIG. 4 is an enlarged figure of FIG. 2.

[0054] Example

The present invention is explained below with reference to specific examples. These examples are for the purpose of explaining and are not for the purpose of limiting the scope of the present invention.

[0055] Surfactant

In the present example, following surfactants were used.

(sodium surfactin, model number 197- 12691, ufactured by Wako Pure Chemical Industries, Ltd .)

(Colistin sulfate A: R = CH₃, and Colistin sulfate B: R = H) A3 (colistin sulfate, model number C2930, manufactured by Tokyo Chemical Industry Co., Ltd .)

[0056]

A4 (surfactin ammonium)

A4 was prepared as a solution by changing Al to its ammonium salt in the following process.

100 g of Al was added to 900 g of pure water and completely dissolved by stirring . To this, 80 g of a 10% hydrochloric acid aqueous solution was added, and the mixture was stirred and left to stand. This liquid was filtered through a filter paper to obtain a precipitate. The precipitate was left to stand overnight in a desiccator and dried . 48.4 g of the powder obtained by drying and 16 g of a 10% aqueous ammonia solution were put into 935.6 g of pure water and stirred . In this process, sodium was changed to ammonium, thereby obtaining 1,000 g of an A4 solution having a concentration of 5 mass %.

[0057] As the surfactant of Comparative Example, tetraglycine of Tokyo Chemical Industry Co., Ltd. (hereinafter referred to as Bl) and SURFYNOL 2502 of Nissin Chemical Industries, Ltd. (hereinafter referred to as B2) were used.

Bl (tetraglycine)

[0058] Preparation Example 1 of semiconductor aqueous composition

0.2 g of Al was added to 1,000 g of pure water, and this was stirred and completely dissolved to obtain a 0.02 mass % aqueous solution of Al . This solution was designated as Example Composition 1. The additives and their concentrations in Example Compositions were summarized in Table 1.

[0059] Preparation Examples 2 to 6 and Comparative

Preparation Examples 1 to 3, of semiconductor aqueous composition

The compositions were prepared in the same manner as in Preparation Example 1 except that the surfactants and concentrations were changed as described in Table 1. In Comparative Preparation Example 1, no surfactant was added.

They were designated as Example Compositions 2 to 6 and Comparative Compositions 1 to 3, respectively.

[0060] Preparation Example 7 of semiconductor aqueous composition

5.0 g of the above-described A4 solution was batched off. This was added to 245 g of pure water, stirred, and completely dissolved . This solution was designated as Example Composition 7. The mass % in Table 1 shows the mass % of the present organic compound as a solute.

[0061] Example of forming substrate for evaluation

The substrate for evaluation used for following evaluation was prepared as shown below.

The surface of a silicon substrate (manufactured by SUMCO Corporation, 12 inches) was treated with a 1, 1, 1,3,3,3-hexamethyldisilazane solution at 90°C for 30 seconds. A chemically amplified PHS-acrylate hybrid type EUV resist composition was spin-coated thereon and soft-baked at 110°C for 60 seconds, thereby forming a resist film having a thickness of 50 nm on the substrate. This was exposed through a mask of line : space = 3 : 1 (78 nm : 26 nm) with an extreme ultraviolet stepper NXE : 3100 (manufactured by ASM L Holding N. V.) . Plural exposure amounts were set, and substrates of each condition were obtained . As the exposure amount increases, the space width of the resist pattern formed by later development increases.

This substrate was post-exposure baked (PEB) at 100°C for 60 seconds. Thereafter, the resist film was subjected to puddle development for 30 seconds using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution. In a state of a puddle developing solution being paddled on the substrate, pure water was started to flow onto the substrate, the puddle developing solution was replaced, while rotating, with pure water, and the flowing was stopped in a state of being puddled with pure water. Then, each composition shown in Table 1 was poured into this, and the substrate was rotated at a high speed, thereby spin-dried.

Evaluation example of resist pattern shape

The shape of a resist pattern on a substrate for evaluation exposed under the condition of an exposure amount of 46 mJ/cm² was evaluated with a SEM instrument, CG 5000 (manufactured by Hitachi High-Technologies Corporation) . Evaluation criteria were designated as follows:

A: dissolution of the pattern was not confirmed, and

B : dissolution of the pattern was confirmed.

The evaluation results were shown in Table 1. The same applies to the followings. With respect to Example Compositions, problem of pattern dissolution was not confirmed . With respect to Comparative Composition 3, since the resist pattern was dissolved, subsequent evaluation was not performed based on the reason that its measurement was impossible.

Evaluation example of space width reduction amount

Using a resist pattern on a substrate for evaluation exposed under the condition of an exposure amount of 46 mJ/cm², the space width reduction amount was evaluated as follows. The space width of Comparative Composition 1 to which no surfactant was added was measured with a SEM instrument, CG 5000 (manufactured by Hitachi High-Technologies Corporation), and found to be 26.0 nm. Using this as a reference, the space widths treated with Example Compositions 1 to 7 and Comparative Composition 2 were similarly measured. The difference between the obtained space width and the space width treated with Comparative Composition 1 is shown in Table 1 as the space width reduction amount.

For example, the space width treated with Example Composition 1 was 24.2 nm, and the space width was narrower by 1.8 nm than that treated with Comparative Composition 1 (26.0 nm) . It was confirmed that in the resist pattern on the substrate for evaluation, which was treated with Example Compositions 1 to 7, the space width could be made narrower than that treated with water (Comparative Composition 1) .

Evaluation example of minimum space width

Using a resist pattern on a substrate for evaluation, which was treated with each composition of Table 1, the minimum space width was evaluated as follows.

Starting the evaluation from a substrate for evaluation, which was prepared with a larger exposure amount, the space width of the resist pattern was measured with the above described SEM instrument, CG 5000, and it was observed whether or not bridge(s) had occurred in the space. When occurrence of no bridge could be confirmed, a substrate for evaluation, which was prepared with a next smaller exposure amount, was evaluated . This process was repeated until occurrence of any bridge was confirmed . When occurrence of a bridge was confirmed, the space width of the resist pattern of the substrate for evaluation was designated as space width where a bridge occurred . Further, the space width of a substrate for evaluation (that prepared with a next larger exposure amount) evaluated just before the substrate for evaluation was designated as minimum space width.

For example, with respect to Comparative Composition 1 to which no surfactant was added, the minimum space width was 22.6 nm, and the space width of the substrate for evaluation where bridge occurrence was confirmed (space width where a bridge occurred) was 21.8 nm. Substrates for evaluation, which were prepared subsequently with a smaller exposure amount, were not evaluated.

FIG. 1 to 4 show SEM images of the resist pattern with the space width and the minimum space width where a bridge occurred, in case of Comparative Composition 1.

Evaluation example of LWR

The LWR of a resist pattern on a substrate for evaluation exposed under the condition of an exposure amount of 46 mJ/cm² was measured with the above described SEM instrument, CG 5000. The ITRS recommending program was used. [0066] [Table 1]

Claims

Patent Claims

1. 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

wherein the number of amino acids composing said organic compound is 5 to 15.

2. The semiconductor aqueous composition according to claim 1, wherein said amino acids composing said organic compound are independently selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.

3. The semiconductor aqueous composition according to claims 1 or 2, wherein said ring structure is composed of a plural amino acids and one or more assist chains, and said assist chain is independently selected from the group consisting of -O-, -NH-, -C( = O)-, -CH2-, -C(CH₃)H-, -CR°H- and any combination of any of these, wherein R° represents a bond to a side chain.

4. The semiconductor aqueous composition according to any one of claims 1 to 3, wherein said organic compound comprises one or more side chains and said side chain is selected from the group consisting of a linear alkyl, a branched alkyl, -NH-, -C( = O)-, -CH(NH₂)-, -CH(OH)-, a heterocyclic compound, an amino acid and any combination of any of these, and said side chain each bonds to the amino acid or the assist chain respectively of said ring structure.

5. The semiconductor aqueous composition according to any one of claims 1 to 4, wherein the molecular weight of said organic compound is 700 to 2,000.

6. The semiconductor aqueous composition according to any one of claims 1 to 5, wherein said organic compound is represented by the following formula ( 1) .

. side chain

I peptide assist chain 1 formula (1)

7. The semiconductor aqueous composition according to any one of claims 1 to 6, wherein said salt is selected from the group consisting of metallic salt, ammonium salt, organic ammonium salt, acid salt and any mixture of any of these.

8. The semiconductor aqueous composition according to any one of claims 1 to 7, wherein the content ratio of said surfactant is 0.005 to 2.0 mass % based on the said semiconductor aqueous composition.

9. The semiconductor aqueous composition according to any one of claims 1 to 8, further comprising an antibacterial agent, a germicide, an antiseptic, an antifungal agent or any mixture of any of these.

10. The semiconductor aqueous composition according to any one of claims 1 to 9, further comprising a surfactant other than said surfactant, an acid, a base, an organic solvent or any mixture of any of these.

11. A semiconductor aqueous cleaning composition, consisting of the semiconductor aqueous composition according to any one of claims 1 to 10.

12. A resist pattern cleaning composition, consisting of the semiconductor aqueous composition according to any one of claims 1 to 10.

13. Method for producing a resist pattern, using the semiconductor aqueous composition according to any one of claims 1 to 10.

14. Method for producing a resist pattern, comprising

( 1) applying a photosensitive resin composition on a substrate through one or more intermediate layers or without through 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 the developed layer with the semiconductor aqueous composition according to any one of claims 1 to 10.

15. The method according to claim 14, said photosensitive resin composition is a chemically amplified photosensitive resin composition, and the exposure is achieved by the extreme ultraviolet radiation.

16. The method according to claim 14 or 15, wherein the minimum space size of the resist pattern in a circuit unit is 10 - 30 nm.

17. Method for manufacturing a semiconductor, comprising the method for producing the resist pattern according to any one of claims 14 to 16.

18. The method according to claim 17, comprising performing etching using the resist pattern produced by the method according to any one of claims 14 to 16 as a mask, and processing the substrate.

19. The semiconductor manufacturing method according to claim 18, comprising forming wiring on the processed substrate.