JP2008182221A - Cleaning agent for semiconductor substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning agent for a semiconductor substrate enabling efficient high degree cleaning with the excellent re-adhesion prevention property of fine particles and organic substance detergency such as finger prints in the time of cleaning. <P>SOLUTION: The cleaning agent for a semiconductor substrate contains: one or more kinds of nonionic surfactants (A) selected from a nonionic surfactant represented by a general formula (1), and a nonionic surfactant represented by general formula (2); an anionic surfactant (B); and water (C). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a semiconductor substrate cleaning agent. More specifically, the present invention relates to a semiconductor substrate cleaning agent containing a nonionic surfactant and an anionic surfactant.

In recent years, in semiconductor substrate cleaning technology, trace amounts of impurities (metal ions, inorganic substances such as metals and organic particles such as resist resins) remaining on the substrate as microfabrication techniques such as VLSI have advanced in recent years. However, the management of impurities has become extremely important because it greatly affects device performance and yield. In particular, the particles to be cleaned have become finer particles recently, and the finer particles are more likely to adhere to the interface than before, so it is urgent to establish advanced cleaning technology. .
For this reason, in order to prevent contamination by particles, methods have been proposed in which surfactants are added to lower the zeta potential on the particle surface to reduce particle adhesion (Patent Documents 1 and 2).

JP-A-5-138142 JP-A-6-41770

However, since the surfactant proposed in Patent Document 1 is a nonionic surfactant, the zeta potential on the particle surface cannot be lowered sufficiently, and the anti-reattachment property is insufficient. In addition, the surfactant proposed in Patent Document 2 is an anionic surfactant, and although the effect of preventing the reattachment of particles can be improved to some extent by reducing the zeta potential on the particle surface, the particulate removal property is improved. It is insufficient.
In addition, there were serious problems such as severe foaming during use.

  Therefore, the object of the present invention is a semiconductor that is excellent in preventing the reattachment of fine particles that have been refined during cleaning, improves the yield rate during manufacturing, and enables highly efficient advanced cleaning that enables cleaning in a short time. It is to provide a substrate cleaning agent.

  As a result of intensive studies to obtain a cleaning agent for a semiconductor substrate that solves the above problems, the present inventors have reached the present invention.

  That is, the present invention provides at least one nonionic surfactant (A) selected from the group consisting of a nonionic surfactant represented by the general formula (1) and a nonionic surfactant represented by the general formula (2). , Anionic surfactant (B) and water (C) -containing semiconductor substrate cleaning agent; and ultrasonic cleaning, shower cleaning, spray cleaning, brush cleaning, immersion cleaning, immersion using the cleaning agent A method of manufacturing a semiconductor substrate, comprising a step of cleaning by one or more cleaning methods selected from the group consisting of rocking cleaning and single wafer cleaning.

In the formula, R ¹ is an aromatic ring-containing hydrocarbon group having 6 to 24 carbon atoms, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and AO is an oxy having 2 to 4 carbon atoms. An alkylene group, n is an integer of 1 to 5, m is an integer of 1 to 100, n (R ¹ R ² R ³ C—) may be the same or different, and m AOs are It may be the same or different.

In the formula, R ⁴ is a hydrocarbon group having 1 to 24 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, p is an integer of 1 to 7, k is an integer of 1 to 100, p R ^{4 s} may be the same or different, and k AOs may be the same or different.

  The semiconductor substrate cleaning agent of the present invention has low foaming properties, excellent cleaning properties of fine particles and wax, and excellent flatness of the substrate, thereby improving device reliability and yield. There is a possibility that you can.

  One type of nonionic surfactant (A) used in the present invention [hereinafter sometimes simply referred to as (A)] is a nonionic surfactant (A1) represented by the general formula (1). ).

Examples of the aromatic ring-containing hydrocarbon group having 6 to 24 carbon atoms represented by R ¹ in the general formula (1) include phenyl, methylphenyl, ethylphenyl, n- or i-propylphenyl, butylphenyl, pentylphenyl, and hexyl. Phenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, methylnaphthyl, ethylnaphthyl, n- or i-propylnaphthyl, butylnaphthyl, pentylnaphthyl, hexylnaphthyl, heptylnaphthyl, octylnaphthyl, Nonyl naphthyl, decyl naphthyl, undecyl naphthyl, dodecyl naphthyl group, etc. are mentioned.

Examples of the hydrocarbon group having 1 to 24 carbon atoms in R ² and R ³ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic ring-containing hydrocarbon group.
Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 24 carbon atoms and an alkenyl group having 2 to 24 carbon atoms (which may be linear or branched).
Examples of the alkyl group having 1 to 24 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl , Hecosyl, docosyl, tricosyl, tetracosyl and the like.
Examples of the alkenyl group having 2 to 24 carbon atoms include propenyl, hexenyl, heptenyl, octenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, 2-ethyldecenyl, eicosenyl, hexocetenyl, tricocenyl, Etc.

  The alicyclic hydrocarbon group includes a cycloalkyl group having 3 to 24 carbon atoms, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl, cyclohexadecyl and cyclo Examples include eicosyl.

Examples of the aromatic ring-containing hydrocarbon group include the same groups as those exemplified above for R ¹ .

  N in General formula (1) is an integer of 1-5, Preferably it is 1-3.

AO in the general formula (1) includes oxyalkylene groups having 2 to 4 carbon atoms, such as oxyethylene groups, 1,2-oxypropylene groups, 1,3-oxypropylene groups, 1,2-oxybutylene groups, and the like. Examples include 1,4-oxybutylene group.
Among AOs, oxyethylene, 1,2-oxypropylene, 1,2-oxybutylene and 1,4-oxybutylene are preferred from the viewpoint of detergency, and more preferred are oxyethylene groups. 1,2-oxypropylene groups and combinations thereof, and the combination mode of m AOs in the combination may be random bonds or block bonds.
Moreover, m in General formula (1) is an integer of 1-100, Preferably it is 1-20. The nonionic surfactant (A1) represented by the general formula (1) is usually produced as a mixture of compounds in which m represented by the general formula (1) is an integer (a mixture having a distribution in m). The surfactant containing an oxyalkylene group (AO) in the present invention is usually a mixture of a single compound, but may be a single compound.

As one type of nonionic surfactant (A) used by this invention, the nonionic surfactant (A2) shown by General formula (2) is mentioned.
The general formula (2) a hydrocarbon group having 1 to 24 carbon atoms in, the same groups as those exemplified in the above R ² or R ³ can be exemplified. Moreover, p in General formula (2) is an integer of 1-7, Preferably it is 1-3. AO includes the same ones as described above. k may be the same integer as m described above.

The nonionic surfactant (A) of the present invention may be any of (A1), (A2) and a combination of (A1) and (A2), and (A1) or (A2) is 2 of each of them. A combination of more than one species may be used.
Preference is given to a combination of two or more of (A1) or (A1).

Among specific examples of the nonionic surfactant (A) of the present invention, (A1) includes an alkylene oxide adduct of cumylphenol and an alkylene oxide adduct of (mono, di, or tri) styrenated phenol. .
Examples of (A2) include an alkylene oxide adduct of α or β-naphthol.
Among (A), from the viewpoint of detergency, (A1) is preferred, more preferred is an alkylene oxide adduct of cumylphenol and an alkylene oxide adduct of (mono, di, or tri) styrenated phenol, particularly preferred. Is an alkylene oxide adduct of cumylphenol, most preferably an ethylene oxide (hereinafter abbreviated as EO) adduct of cumylphenol.

(A) HLB value is 10-16 from a viewpoint of the detergency with respect to organic substance, Preferably it is 11-14, More preferably, it is 11.5-13.5, Most preferably, it is 12-13.
In the present invention, the HLB value is a value calculated by the following formula (1) by the Oda method. [Takehiko Fujimoto, Introduction to New Surfactant (Sanyo Chemical Industry Co., Ltd.), p197]

HLB = 10 × (inorganic / organic) (1)
In addition, the organic property and inorganic property in a formula are the total value of the numerical value defined for every atom and functional group which comprise a molecule | numerator, and can use the value described in the said literature.
Specifically, in the case of an EO 10 mol adduct of cumylphenol, p. Using the values described in Table 3/311 of 198, CH ₃ (organic 20) × 2, C (organic 20) × 1, benzene nucleus (organic 120, inorganic 15) × 2, OH (inorganic 100) × 1, oxyethylene group (organic 40, inorganic 75) × 10, calculated from the sum of the organic and inorganic values according to the above formula (1) , An HLB value of 12.6 is obtained.

The cloud point of (A) is preferably 10 ° C. or higher, more preferably 25 to 95 ° C., and particularly preferably 40 to 90 ° C. at a 2% concentration from the viewpoint of detergency. When the cloud point is in this range, (A) precipitates during cleaning and does not adhere to the substrate surface, which is preferable.
In the above and the following, unless otherwise specified,% indicates% by weight.

  The anionic surfactant (B) in the present invention [hereinafter sometimes simply referred to as (B)] is a polymer type anionic surfactant (B1) (3 or more repeating units in the molecule). And low molecular weight type anionic surfactant (B2).

  Of these, (B1), (B2) and combinations thereof are preferred from the viewpoint of low foaming properties, cleanability and flatness, and (B1) and (B2) are more preferred. An anion having one or more groups selected from the group consisting of a sulfonic acid (salt) group, a sulfate ester (salt) group, a phosphate ester (salt) group, a phosphonic acid ester (salt) group, and a carboxylic acid (salt) group It is a ionic surfactant. The “sulfonic acid (salt) group” means “sulfonic acid group and sulfonic acid group”, and the same expression is used hereinafter.

Specific examples of (B1) include the following (B1-1) to (B1-5).
(B1-1) Polymeric anionic surfactant having a sulfonic acid (salt) group:
Polystyrene sulfonic acid, styrene / styrene sulfonic acid copolymer, poly {2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid}, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / Styrene copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / acrylamide copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / (meth) acrylic acid co Polymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / (meth) acrylic acid / acrylamide copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / styrene / Acrylamide copolymer, 2- (meth) acryloylamino-2,2-dimethyl eta Sulfonic acid / styrene / (meth) acrylic acid copolymer, naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, dimethyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate Aniline sulfonic acid-phenol-formaldehyde condensates and salts thereof;

(B1-2) Polymeric anionic surfactant having a sulfate (salt) group:
Poly {2-hydroxyethyl (meth) acrylate sulfate}, 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate sulfate copolymer, sulfuric acid of poly {2-hydroxyethyl (meth) acrylate} Esterified products and sulfated products of cellulose, methylcellulose or ethylcellulose, and salts thereof;

(B1-3) Polymeric anionic surfactant having a phosphate ester (salt) group:
Poly {2-hydroxyethyl (meth) acrylate phosphate}, 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate phosphate copolymer, poly {2-hydroxyethyl (meth) acrylate} And phosphoric acid ester of cellulose, methyl cellulose or ethyl cellulose, and salts thereof;

(B1-4) Polymeric anionic surfactant having a phosphonic acid (salt) group:
Poly {(meth) acryloyloxyethanephosphonic acid}, poly {(meth) acryloyloxyethylethanephosphonate}, 2-hydroxyethyl (meth) acrylate / (meth) acryloyloxyethanephosphonic acid copolymer, 2-hydroxyethyl ( (Meth) acrylate / (meth) acryloyloxyethyl ethanephosphonate copolymer, naphthalenephosphonic acid formaldehyde condensate, methylnaphthalenephosphonic acid formaldehyde condensate, dimethylnaphthalenephosphonic acid formaldehyde condensate, anthracenephosphonic acid formaldehyde condensate, anilinephosphonic acid- Phenol-formaldehyde condensates and salts thereof;

(B1-5) Polymeric anionic surfactant having a carboxylic acid (salt) group:
Poly (meth) acrylic acid, (meth) acrylic acid-maleic acid copolymer, (meth) acrylic acid-itaconic acid copolymer, (meth) acrylic acid-fumaric acid copolymer, (meth) acrylic acid / acetic acid Vinyl copolymer, 2-hydroxyethyl (meth) acrylate / (meth) acrylic acid copolymer, carboxymethylated product of poly {2-hydroxyethyl (meth) acrylate}, carboxymethylcellulose, carboxymethylmethylcellulose, carboxymethylethylcellulose, Benzoic acid formaldehyde condensates, benzoic acid-phenol-formaldehyde condensates and their salts.

The counter ion when (B1) is a salt includes, for example, a primary amine {eg, alkylamine (such as methylamine, ethylamine and butylamine), monoethanolamine and guanidine}, secondary amine {eg, dialkylamine ( Dimethylamine, diethylamine and dibutylamine) and diethanolamine} and tertiary amines {e.g., trialkylamines (such as trimethylamine, triethylamine and tributylamine), triethanolamine, 1,8-diazabicyclo [5.4.0] -7 -Undecene (hereinafter abbreviated as DBU), 1,5-diazabicyclo [4.3.0] -5-nonene (hereinafter abbreviated as DBN), 1,4-diazabicyclo [2.2.2] octane (hereinafter, Abbreviated as DABCO), 1H-imidazole 1-ethyl-imidazole, 2-methyl-1H-imidazole and 1,4,5,6-tetrahydro-pyrimidine} cations with added protons, ammonium cations and quaternary ammonium cations (tetramethylammonium cations, tetraethylammonium cations) 1-methyl-3-methyl-imidazolium cation and 1-ethyl-3-methyl-imidazolium cation).
Among the counter ions, from the viewpoint of particle removability and residual alkali metal atom content, cations obtained by adding protons to monoethanolamine, diethanolamine, triethanolamine, DBU, DBN and DABCO, tetramethylammonium cation and tetraethyl are preferable. Particularly preferred are ammonium cations, cations obtained by adding protons to DBU, DBN and DABCO, tetramethylammonium salts and tetraethylammonium salts.

The weight average molecular weight (hereinafter abbreviated as Mw) of (B1) is preferably from 300 to 800,000, more preferably from 600 to 400,000, particularly preferably from the viewpoint of preventing reattachment of particles and low foamability. Is 1,000 to 80,000, most preferably 2,000 to 40,000.
Mw in the present invention is measured by gel permeation chromatography (hereinafter abbreviated as GPC) at 40 ° C. using polyethylene oxide as a reference material [for example, apparatus body: Waters 510 (manufactured by Japan Waters Limited), column: Tosoh Corporation. Manufactured by TSKgel G5000 PWXL, G3000 PW XL, detector: differential refractometer detector built in the apparatus body, eluent: 0.5% sodium acetate / water / methanol (volume ratio 70/30), eluent flow rate: 1.0 ml / min, column temperature: 40 ° C., sample: 0.25% eluent solution, injection amount: 200 μl, standard material: TSK TANDARD POLYETHYLENE OXIDE manufactured by Tosoh Corporation, data processing device: SC-8010 (Tosoh) Made by Corporation)].

  The low molecular weight anionic surfactant (B2) has less than 3 repeating units in the molecule. Specifically, the low molecular type anionic surfactant (B2) is a sulfonic acid-based surfactant {for example, a sulfosuccinic acid having 1 to 24 carbon atoms. Acid (mono or di) ester (salt), C3-C24 α-olefin sulfone oxide (salt) and alkylbenzene sulfonic acid (salt) having an alkyl group of 3-14 carbon atoms, petroleum sulfonate (salt) }; Sulfate ester surfactants {e.g., sulfate esters (salts) of aliphatic alcohols having 3 to 18 carbon atoms, sulfate esters (salts) of adducts of 1 to 10 moles of EO of aliphatic alcohols having 3 to 18 carbon atoms, Sulfated oil (salt), sulfated fatty acid ester (salt) and sulfated olefin (salt)}; fatty acid surfactant {for example, fatty acid (salt) having 3 to 18 carbon atoms and 3 to 3 carbon atoms An ether carboxylic acid (salt) of an aliphatic alcohol of 8; and a phosphate ester-based surfactant {for example, a phosphoric acid (mono or di) ester (salt) of an aliphatic alcohol having 3 to 24 carbon atoms and 3 to 3 carbon atoms. And phosphoric acid (mono or di) ester (salt)} of alkylene oxide adducts of 24 aliphatic alcohols.

Among these (B2), the following (B2-1) to (B2-9) are preferable from the viewpoint of low foamability, cleanability and flatness.
(B2-1) a sulfosuccinic acid (mono or di) ester (salt) of an alcohol having 1 to 8 carbon atoms;
(B2-2) C3-C12 α-olefin sulfone oxide (salt), for example, propylene tetramer sulfone oxide (salt);
(B2-3) an alkylbenzenesulfonic acid (salt) having an alkyl group having 3 to 8 carbon atoms;
(B2-4) Sulfates (salts) of aliphatic alcohols having 3 to 8 carbon atoms, such as butanol sulfate (salt), 2-ethylhexanol sulfate (salt), octanol sulfate (salt) and 1,6- Hexanediol disulfate (salt);
(B2-5) Sulfate ester (salt) of an EO 1-10 mol adduct of an aliphatic alcohol having 3 to 8 carbon atoms,
For example, 1,6-hexanediol propylene oxide (hereinafter abbreviated as PO) 5 mol adduct disulfate (salt), ethylene glycol or glycerin EO adduct monosulfate (salt) and sorbitol PO · EO Block adduct trisulfate (salt);
(B2-6) C3-C8 fatty acid (salt), such as octanoic acid (salt) and 2-ethylbutyric acid (salt);
(B2-7) an ether carboxylic acid (salt) of an aliphatic alcohol having 3 to 8 carbon atoms;
(B2-8) phosphoric acid (mono or di) ester (salt) of an aliphatic alcohol having 3 to 8 carbon atoms, for example, n-butanol phosphate (salt);
(B2-9) Phosphoric acid (mono or di) ester (salt) of an alkylene oxide adduct of an aliphatic alcohol having 3 to 8 carbon atoms.

Among (B2-1) to (B2-9), preferred are (B2-1), (B2-2), (B2-4), (B2-5), (B2-5) from the viewpoint of cleanability and flatness. B2-7), (B2-8) and (B2-9), and more preferred are (B2-4), (B2-5), (B2-7), (B2-8) and (B2- 9).
Examples of the counter ion when (B2) is a salt include the same cations as in the case of (B1) above, and preferred ones are also the same.

  As water (C) contained in the cleaning agent of the present invention, tap water, industrial water, ground water, distilled water, ion-exchanged water (conductivity 0.2 μS / cm or less) and ultrapure water (specific resistance value 18 MΩ) Cm or more), preferably ion-exchanged water and ultrapure water, more preferably ultrapure water.

  Each content of (A), (B) and (C) based on the total weight of (A) to (C) in the present invention is preferably (A) 0.1 to 20%, (B ) Is 0.1-10% and (C) is 70-99.5%, more preferably (A) is 0.5-10%, (B) is 0.2-6.5% and (C) is 85 to 99.3%, particularly preferably (A) is 2 to 10%, (B) is 0.5 to 2%, and (C) is 88 to 97%.

  If (A) is 0.1% or more, the surface tension of the cleaning agent will be low, and it will be easy to penetrate into the details. Therefore, it is easy to exert the desired cleaning effect. It is suppressed and preferable.

  The weight ratio [(B) / (A)] of (B) to (A) is preferably 0.05 to 3, more preferably 0.07 to 2, and particularly preferably 0.1 to 1. When the weight ratio of (B) to (A) is 0.05 to 3, the removability of the finely divided particles is easily exhibited.

  In addition to the above (A) to (C), the cleaning agent of the present invention may further contain the following alkaline component (D), chelating agent (E), and other interfaces within the range not impairing the effects of the cleaning agent of the present invention. One or more optional components selected from the group consisting of activator (F), dispersant (G), trihydric or higher polyhydric alcohol (H), water-soluble organic solvent (I) and other additives (J) May also be included.

By containing the alkali component (D) [hereinafter, it may be simply expressed as (D)], the detergency with respect to particles or wax stains is further improved.
(D) includes a quaternary ammonium salt (D1) represented by the general formula (3), ammonia (D2), an alkanolamine (D3) having 2 to 14 carbon atoms, hydroxylamine (D4) and (D1). (D4) can be used in combination.

In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrocarbon group having 1 to 24 carbon atoms or a group represented by — (R ⁹ O) r—H, and R ⁹ O is a carbon number. 2 to 4 oxyalkylene groups, r represents an integer of 1 to 6;
Examples of the hydrocarbon group having 1 to 24 carbon atoms include the same groups as those exemplified for the aforementioned R ² and R ³ .
Examples of the oxyalkylene group having 2 to 4 carbon atoms include the same groups as those exemplified above for AO.
r is preferably 1 to 3.

Specific examples of (D1) include salts composed of the following cations (D11) to (D15) and hydroxide anions.
(D11) C1-C6 tetraalkylammonium cation of alkyl group:
Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, trimethylethylammonium and the like.

(D12) Ammonium cation comprising three alkyl groups having 1 to 6 carbon atoms and one hydrocarbon group having 7 to 24 carbon atoms:
Trimethyl heptyl ammonium, trimethyl octyl ammonium, trimethyl decyl ammonium, trimethyl dodecyl ammonium, trimethyl stearyl ammonium, trimethyl benzyl ammonium, triethyl octyl ammonium, triethyl stearyl ammonium, triethyl benzyl ammonium, tributyl octyl ammonium, tributyl octyl ammonium and trihexyl stearyl ammonium Such.

(D13) Ammonium cation comprising two alkyl groups having 1 to 6 carbon atoms and two hydrocarbon groups having 7 to 24 carbon atoms:
Dimethyl dioctyl ammonium, diethyl dioctyl ammonium and dimethyl dibenzyl ammonium and the like.

(D14) Ammonium cation comprising one alkyl group having 1 to 6 carbon atoms and three hydrocarbon groups having 7 to 24 carbon atoms:
Such as methyltrioctylammonium, ethyltrioctylammonium and methyloctyldibenzylammonium.

(D15) Ammonium cation having an oxyalkylene group:
(I) a cation having one oxyalkylene group [hydroxyethyltrimethylamine cation, hydroxyethyltriethylamine cation, hydroxypropyltrimethylamine cation, hydroxypropyltriethylamine cation, hydroxyethyldimethylethylamine cation, hydroxyethyldimethyloctylamine cation, etc.];
(Ii) cations having two oxyalkylene groups [dihydroxyethyldimethylamine cation, dihydroxyethyldiethylamine cation, dihydroxypropyldimethylamine cation, dihydroxypropyldiethylamine cation, dihydroxyethylmethylethylamine cation, dihydroxyethylmethyloctylamine cation and bis (2 -Hydroxyethoxyethyl) octylamine cation and the like];
(Iii) Cations having three oxyalkylene groups [trihydroxyethylmethylamine cation, trihydroxyethylethylamine cation, trihydroxyethylbutylamine cation, trihydroxypropylmethylamine cation, trihydroxypropylethylamine cation and trihydroxyethyloctylamine cation Such].

  Examples of the alkanolamine (D3) having 2 to 14 carbon atoms include monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine. Preferred among (D3) are monoethanolamine, diethanolamine and triethanolamine.

  Among (D), from the viewpoint of detergency, a quaternary ammonium salt (D1), an alkanolamine (D3) having 2 to 14 carbon atoms and hydroxylamine (D4) are preferable. More preferably (D1), particularly preferably (D11) to (D14), particularly preferably (D11) and (D12), most preferably a hydroxide anion salt of a tetramethylammonium cation, a tetraethylammonium cation. These hydroxide anion salts and combinations thereof.

  When using the alkali component (D), from the viewpoint of detergency, the content of (D) is usually 10% or less, preferably 0.1 to 10% based on the weight of the cleaning agent of the present invention, Preferably it is 0.3-8%, Most preferably, it is 0.5-5%.

  The pH of the cleaning agent when the alkaline component (D) is used in the cleaning agent of the present invention is preferably 9 to 14, more preferably 10 to 13.5, and particularly preferably 11 to 13. If pH is 9-14, it will be easy to exhibit the effect of particle removal further.

As the chelating agent (E), aminopolycarboxylic acid (salt) {ethylenediaminetetraacetic acid (salt) (EDTA), diethylenetriaminepentaacetic acid (salt) (DTPA), triethylenetetraminehexaacetic acid (salt) (TTHA), hydroxyethyl Ethylenediaminetriacetic acid (salt) (HEDTA), dihydroxyethylethylenediaminetetraacetic acid (salt) (DHEDDA), nitrilolic acid acetic acid (salt) (NTA), hydroxyethyliminodiacetic acid (salt) (HIDA), β-alanine diacetate (salt) ), Aspartic acid diacetate (salt), methylglycine diacetate (salt), iminodisuccinic acid (salt), serine diacetate (salt), hydroxyiminodisuccinic acid (salt), dihydroxyethylglycine (salt), aspartic acid (salt) ) And glutamic acid (salts, etc.); Acid (salt) {hydroxyacetic acid (salt), tartaric acid (salt), citric acid (salt) and gluconic acid (salt)}; cyclocarboxylic acid (salt) {pyromellitic acid (salt), benzopolycarboxylic acid ( Salt) and cyclopentanetetracarboxylic acid (salt), etc .; ether carboxylic acid (salt) (carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid monosuccinate and tartaric acid disuccinate); Acid (salt) (maleic acid derivative and oxalic acid (salt), etc.); phosphonic acid (salt) {methyldiphosphonic acid (salt), aminotri (methylenephosphonic acid) (salt), 1-hydroxyethylidene-1, 1- Diphosphonic acid (salt), ethylenediaminetetra (methylenephosphonic acid) (salt), hexamethylenediamine Tetra (methylenephosphonic acid) (salt), propylenediaminetetra (methylenephosphonic acid) (salt), diethylenetriaminepenta (methylenephosphonic acid) (salt), triethylenetetramine hexa (methylenephosphonic acid) (salt), triaminotriethylamine hexa (Methylene phosphonic acid) (salt), trans-1,2-cyclohexanediamine tetra (methylene phosphonic acid) (salt), glycol ether diamine tetra (methylene phosphonic acid) (salt) and tetraethylenepentamine hepta (methylene phosphonic acid) (Salt), etc.};
In addition, as a counter ion in case (E) is a salt, the same cation as the case of the above-mentioned polymeric anionic surfactant (B1) is mentioned, A preferable thing is also the same. These may be used alone or in combination of two or more.

  Of these, aminopolycarboxylic acid (salt), hydroxycarboxylic acid (salt), and phosphonic acid (salt) are preferred from the viewpoint of metal-supplementability, and more preferably aminopolycarboxylic acid (salt) and phosphonic acid. (Salt), particularly preferably ethylenediaminetetraacetic acid (salt) (EDTA), dihydroxyethylethylenediaminetetraacetic acid (salt) (DHEDDA), aspartic acid diacetic acid (salt), aspartic acid (salt), glutamic acid (salt), 1- Hydroxyethylidene-1,1-diphosphonic acid (salt) and ethylenediaminetetra (methylenephosphonic acid) (salt), most preferably ethylenediaminetetraacetic acid (salt) (EDTA), 1-hydroxyethylidene-1 and 1-diphosphonic acid (salt) ).

  When the chelating agent (E) is used, the content of (E) is usually 10% or less based on the weight of the cleaning agent of the present invention, from the viewpoint of preventing metal diffusion to the substrate, etc. 01 to 5%, more preferably 0.05 to 3%, and particularly preferably 0.1 to 1%.

  Examples of the other surfactant (F) include one or more surfactants selected from the group consisting of nonionic surfactants other than (A), cationic surfactants, and amphoteric surfactants.

  Nonionic surfactants other than (A) include alkylene oxide addition-type nonionic surfactants [higher alcohols (8 to 18 carbon atoms), alkyl (however, having no aromatic ring) phenol (10 to 10 carbon atoms). 24), higher fatty acids (12 to 24 carbon atoms), aliphatic primary or secondary amines (6 to 36 carbon atoms), alkylene oxides {2 to 4 carbon atoms such as EO, PO, 1,2-butylene Oxide, THF, etc., which are the same below (Mn158-200,000); Polyoxyalkylene glycol (Mn150-6,000) reacted with higher fatty acid (C12-24), etc .; Diol Alternatively, an esterified product obtained by reacting a higher fatty acid (having 12 to 24 carbon atoms) with a hydroxyl group-containing compound such as a tri- to octavalent polyhydric alcohol is used as an alkyl compound. Nmoxide added (Mn 250 to 30,000), higher fatty acid (8 to 24 carbon atoms) amide added with alkylene oxide (Mn 200 to 30,000), polyhydric alcohol {(H) below } Alkyl (carbon number 8 to 60) ether added with alkylene oxide (Mn 120 to 30,000), etc.], polyhydric alcohol (carbon number 3 to 20) type nonionic surfactant [polyhydric alcohol fatty acid ( Pluronic or polyoxyethylene and polyoxypropylene obtained by random or block condensation of carbon number 8-60) ester, polyhydric alcohol alkyl (carbon number 8-60) ether, fatty acid (carbon number 8-60) alkanolamide, etc.] Tetronic type.

  As the cationic surfactant, a quaternary ammonium salt type surfactant {for example, alkyl (C1-30) trimethylammonium salt, dialkyl (C1-30) dimethylammonium salt, nitrogen ring-containing quaternary Ammonium salt, poly (addition mole number 2 to 15) oxyalkylene (carbon number 2 to 4) chain-containing quaternary ammonium salt and alkyl (carbon number 1 to 30) amidoalkyl (carbon number 1 to 10) dialkyl (carbon number) 1-4) methylammonium salt} and amine surfactant {for example, aliphatic tertiary amine having 3 to 90 carbon atoms, alicyclic (including nitrogen-containing heterocycle) tertiary amine having 3 to 90 carbon atoms, and Inorganic acid salt or organic acid salt of a tertiary amine having a hydroxyalkyl group having 3 to 90 carbon atoms} and the like.

  Examples of amphoteric surfactants include betaine-type amphoteric surfactants [for example, alkyl (1 to 30 carbon atoms) dimethyl betaine, alkyl (1 to 30 carbon atoms) amide alkyl (1 to 4 carbon atoms) dimethyl betaine, alkyl (carbon Number 1-30) dihydroxyalkyl (carbon number 1-30) betaine and sulfobetaine type amphoteric surfactant}, amino acid type amphoteric surfactant {for example, alanine type [alkyl (carbon number 1-30) aminopropionic acid type And alkyl (carbon number 1-30) iminodipropionic acid type] amphoteric surfactant and glycine type [alkyl (carbon number 1-30) aminoacetic acid type] amphoteric surfactant} and aminosulfonate type amphoteric surfactant Agent {for example, alkyl (C1-C30) taurine type amphoteric surfactant} etc. are mentioned.

  When using these other surfactants (F), the content of (F) is usually 10% or less, preferably 0.0001 to 10%, based on the weight of the cleaning agent of the present invention.

Examples of the dispersant (G) include those conventionally used as fine particle dispersants such as polysaccharides and derivatives thereof (hydroxyethylcellulose, cationized cellulose, hydroxymethylcellulose, hydroxypropylcellulose, guar gum, cationized guar gum, xanthan gum). , Alginate and cationized starch); poval; condensed phosphoric acid (such as metaphosphoric acid and pyrophosphoric acid) and phosphoric acid esters {phytic acid, di (polyoxyethylene) alkyl ether phosphoric acid and tri (polyoxyethylene) alkyl ether Phosphoric acid etc.} and the like (B) also has a dispersing action, but is not included in the dispersant (G) in the present invention.
When these dispersants (G) are used, the content of the dispersant (G) is usually 10% or less, preferably 0.0001 to 10, based on the weight of the cleaning agent of the present invention.

  Of the other components, the total content of the alkaline component (D), chelating agent (E), other surfactant (F) and dispersant (G) is usually 50 based on the weight of the cleaning agent. % Or less, preferably 1 to 30%.

Among the optional components, a trihydric or higher polyhydric alcohol (H) [hereinafter sometimes simply referred to as (H)] is particularly useful when cleaning electronic parts to which metal (such as aluminum wiring) is applied. You may add from a viewpoint of preventing metal corrosion.
(H)
(H1) aliphatic polyhydric alcohols (such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol);
(H2) dehydration condensate of (H1) (such as diglycerin, triglycerin, tetraglycerin and pentaglycerin);
(H3) saccharides such as monosaccharides {pentose (such as arabinose, xylose, ribose, xylulose and ribulose), hexose (such as glucose, mannose, galactose, fructose, sorbose and tagatose) and heptose (such as cedoheptulose)}, disaccharide (trehalose) , Sucrose, maltose, cellobiose, gentiobiose and lactose) and trisaccharides (such as raffinose and maltotriose);
(H4) sugar alcohols (such as arabitol, adonitol, xylitol, sorbitol, mannitol and dulcitol);
(H5) Trisphenol (such as Trisphenol PA);
These alkylene oxides (2 to 4 carbon atoms) adducts (1 to 7 moles of added moles) and the like are also included.
(H) may be used alone or in combination of two or more.

  Among (H), (H1), (H2), (H3) and (H4) are preferable, and glycerin, saccharose and sorbitol are more preferable because they are highly effective in preventing metal corrosion.

  When (H) is used, the content of (H) is usually 20% or less, preferably 1 to 20%, more preferably 2 to 10%, particularly preferably 3 to 7 based on the weight of the cleaning agent. %.

(H) can exhibit a particularly excellent metal corrosion prevention effect for a substrate having metal wiring (aluminum or the like) when the cleaning agent of the present invention contains an alkali component (D).
In this case, the content of (D) relative to the total weight of (D) and water (C) is preferably 0.1 to 50%, more preferably 0.5 to 40%, particularly from the viewpoint of detergency. Preferably it is 1-35%. Further, the content of (H) with respect to the total weight of (D) and (H) is preferably 10 to 90%, more preferably 20 to 80%, particularly preferably 30 to 90% from the viewpoint of preventing metal corrosion. 75%.

The water-soluble organic solvent (I) [hereinafter sometimes simply referred to as (I)] is an organic solvent having a solubility in water (g / 100 gH ₂ O) at 20 ° C. of 3 or more, preferably 10 or more. Can be mentioned.
For example, sulfoxide {dimethyl sulfoxide, sulfolane, butyl sulfone, 3-methyl sulfolane, 2,4-dimethyl sulfolane, etc.}; sulfone {dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, etc.}; amide {N, N -Dimethylformamide, N-methylformamide, N, N-dimethylacetamide and N, N-dimethylpropionamide and the like}; lactam {N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-hydroxymethyl-2 -Pyrrolidone and the like}; lactones {β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone and δ-valerolactone, etc.}; alcohols {such as methanol, ethanol and isopropanol}; And glycol ether {ethylene glycol, ethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monophenyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol, diethylene glycol dimethyl ether, diethylene glycol Ethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether}; oxazolidinones (such as N-methyl-2-oxazolidinone and 3,5-dimethyl-2-oxazolidinone); nitriles (acetonitrile, propionitrile, butyronitrile, acrylonitrile, Carbonate (such as ethylene carbonate and propionate carbonate); ketone (such as acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone, cyclopentanone and diacetone alcohol); cyclic ether (such as tetrahydrofuran and tetrahydropyran) Is mentioned.
(I) may be used alone or in combination of two or more.

  Among (I), glycol and glycol ether are preferable from the viewpoint of detergency, and ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol and propylene glycol are more preferable.

When (I) is used, the total content of (I) and water (C) contained in the cleaning agent is usually 90% or less, preferably 10 to 90%, based on the weight of the cleaning agent. Preferably it is 30 to 80%.
Further, the weight ratio {(I) / (C)} of (I) to water (C) is preferably less than 1 from the viewpoint of detergency against particles and oil stains, more preferably 0.5 or less, particularly preferably. Is 0.2 or less.

  Examples of other additives (J) include antioxidants, chelating agents, rust inhibitors, pH adjusters, buffers, antifoaming agents, reducing agents, hydrotropes, and preservatives.

  Antioxidants include phenolic antioxidants {2,6-di-t-butylphenol, 2-t-butyl-4-methoxyphenol and 2,4-dimethyl-6-t-butylphenol}; amine-based oxidation Inhibitors {monoalkyldiphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamines such as 4,4'-dibutyldiphenylamine and 4,4'-dipentyldiphenylamine; polyalkyldiphenylamines such as tetrabutyldiphenylamine and tetrahexyldiphenylamine; -Naphtylamine such as naphthylamine and phenyl-α-naphthylamine}; sulfur compounds {phenothiazine, pentaerythritol-tetrakis- (3-laurylthiopropio Nate) and bis (3,5-tert-butyl-4-hydroxybenzyl) sulfide, etc.]; Phosphorus antioxidant {bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, phenyldiisodecylphos Phyte, diphenyl diisooctyl phosphite and triphenyl phosphite}; and the like.

  Examples of the rust preventive include benzotriazole, tolyltriazole, benzotriazole having 2 to 10 carbon atoms, benzimidazole, imidazole having 2 to 20 carbon atoms, and 2 to 20 hydrocarbon groups. Nitrogen-containing organic rust preventives such as thiazole and 2-mercaptobenzothiazole; alkyl or alkenyl succinic acids such as dodecenyl succinic acid half ester, octadecenyl succinic anhydride and dodecenyl succinic acid amide; sorbitan monooleate, glycerin monoole And polyhydric alcohol partial esters such as acrylate and pentaerythritol monooleate. These may be used alone or in combination of two or more.

  Examples of pH adjusters include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, alkanolamines such as monoethanolamine and triethanolamine, and water-soluble amines such as ammonia, which are substantially free of impurities such as metal ions. Any one can be used, and one or more of these may be used in combination.

  Examples of the buffer include organic acids, inorganic acids and salts thereof having a buffering action. Examples of organic acids include acetic acid, formic acid, gluconic acid, glycolic acid, tartaric acid, fumaric acid, levulinic acid, valeric acid, maleic acid and mandelic acid, and inorganic acids include, for example, phosphoric acid and boric acid. . Examples of these acid salts include those whose cation is the cation exemplified in the above-mentioned polymer type anionic surfactant (B1). These may be used alone or in combination of two or more.

  Examples of the antifoaming agent include silicone antifoaming agents {antifoaming agents containing dimethyl silicone, fluorosilicone, polyether silicone, and the like}. These may be used alone or in combination of two or more.

Reducing agents include sulfites (eg, sodium sulfite and ammonium sulfite), thiosulfates (eg, sodium thiosulfate and ammonium thiosulfate), phosphites (eg, sodium phosphite and ammonium phosphite), Phosphites (eg sodium hypophosphite and ammonium hypophosphite), aldehydes (eg formaldehyde and acetaldehyde), phosphorus reducing agents (eg tris-2-carboxyethylphosphine), other organic reductions Agents (for example, formic acid, oxalic acid, succinic acid, lactic acid, malic acid, butyric acid, pyruvic acid, citric acid, 1,4-naphthoquinone-2-sulfonic acid, ascorbic acid, isoascorbic acid, gallic acid, hydroxylamine, Diethylhydroxylamine, cysteine, amino Tanchioru, pyrocatechol, resorcinol, hydroquinone, etc. naphthoquinone Torre sol maytansinol and pyrogallol) and derivatives thereof.
These may be used alone or in combination of two or more.

  Examples of the hydrotrope include toluene sulfonic acid (salt), xylene sulfonic acid (salt), cumene sulfonic acid (salt), and the like. These may be used alone or in combination of two or more.

  Examples of preservatives include triazine derivatives {hexahydro-1,3,5-tris (2-hydroxyethyl) -S-triazine, etc.}, isothiazoline derivatives {1,2-benzisothiazolin-3-one, 2-methyl-4- Isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one}, pyridine derivatives {pyridine 2-pyridinethiol-1-oxide (salts)}, morpholine derivatives {4- (2- Nitrobutyl) morpholine and 4,4- (2-ethyl-2-nitrotrimethylene) -dimorpholine etc.}, benzimidazole derivatives {2- (4-thiazolyl) benzimidazole etc.}, other preservatives {poly [oxyethylene ( Dimethylimino) ethylene (dimethylimino) ethylene] dichloride, p-c Rho-m-xylenol, phenoxyethanol, phenoxypropanol, acetoxydimethyldioxane, isopropylmethylphenol, tetrachloroisophthalonitrile, bisbromoacetoxyethane, 3-iodo-2-propynylbutylcarbamate and 2-bromo-2-nitropropane-1 , 3-diol, etc.}. These may be used alone or in combination of two or more.

When other additives (J) are used, the amount of each additive added is antioxidant, chelating agent, rust inhibitor, pH adjuster, buffer, reducing agent, hydrotrope and preservative, Based on the weight of the cleaning agent, it is usually 10% or less, preferably 0.001 to 10%. Moreover, the addition amount of an antifoamer is 1% or less normally, Preferably it is 0.0001 to 1%.
The total content of other additives (J) is usually 30% or less, preferably 0.001 to 30%, based on the weight of the cleaning agent.

As the product shape of the cleaning agent of the present invention, any shape such as liquid and solid can be applied. Among these shapes, liquid is preferable from the viewpoint of handling during use, and the like is particularly preferable.
As the solvent in the case of a solution, only water (C) used in the cleaning agent of the present invention or a mixed solvent of water and a water-soluble organic solvent (I) can be used. Preference is given to aqueous solutions with water alone.

The cleaning agent of the present invention can be produced by mixing the essential components (A) to (C) and optional components at normal temperature to 80 ° C.
The order of charging at the time of mixing is not particularly limited. Usually, a liquid component having a low viscosity and a relatively high content (for example, water) is initially charged, and other liquid components are contained therein. Or a solid component is added with heating if necessary. Although it does not specifically limit as a mixing apparatus, The stirring mixing apparatus equipped with the saddle-type blade | wing, the stirring mixing apparatus equipped with the helical blade | wing, etc. can be used.

When the electronic material is cleaned using the cleaning agent of the present invention, the cleaning agent may be further diluted with water if necessary. As water used at that time, the same water as exemplified in the above water (C) can be used, but preferably ion-exchanged water (conductivity: 0.2 μS / cm or less) or ultrapure water (specific resistance value). 18 MΩ · cm or more), more preferably ultrapure water.
The dilution ratio when used after dilution is preferably 2 to 500 times, more preferably 5 to 200 times, and particularly preferably 10 to 100 times.

  The pH when the detergent of the present invention is diluted with a stock solution or water is preferably 1 to 13, more preferably 4 to 12.5, and particularly preferably 8 to 12.

The total content of Na, K, Ca, Fe, Cu, Al, Pb, Ni and Zn atoms in the cleaning agent of the present invention is 100 ppb or less based on the weight of the cleaning agent from the viewpoint of preventing metal contamination of the semiconductor substrate. Is more preferably 50 ppb or less, and particularly preferably 20 ppb or less.
As a method for measuring the content of these metal atoms, known methods such as atomic absorption spectrometry, ICP emission spectrometry, and ICP mass spectrometry can be used. From the viewpoint of analysis accuracy, ICP mass spectrometry is preferable. .

  Objects to be cleaned (dirt) of the cleaning agent of the present invention include oil, dirt from human bodies (fingerprints, etc.), resins (resist resin and wax, etc.), plasticizers (dioctyl phthalate, etc.), organic substances such as organic particles, and inorganic particles. Inorganic substances such as (abrasives and polishing scraps) can be mentioned.

The foaming power of a 2% aqueous solution of the cleaning agent of the present invention is preferably 200 mm or less, more preferably 120 mm or less, particularly preferably 80 mm or less, from the viewpoint of suppressing foaming during use. Moreover, the lower limit of said foaming power is 0 mm.
From the same viewpoint as described above, the stability of the foam is preferably 180 mm or less, more preferably 100 mm or less, and particularly preferably 50 mm or less. Moreover, the lower limit of the stability of the foam is 0 mm.
Here, the foaming power and the foam stability of the cleaning agent of the present invention can be measured in accordance with the Ross Miles test {JIS K3362 (1998)}. In a test using a 2% aqueous solution of a cleaning agent prepared with ultrapure water, the foam height immediately after flowing out all the test solutions was taken as the foaming power, and the foam height after 5 minutes was taken as the foam height. Expressed as the stability of. In addition, a measured value points out the value measured visually.

  The cloud point of the cleaning agent of the present invention is preferably 20 ° C. or higher, more preferably 40 to 95 ° C., and particularly preferably 45 to 90 ° C. from the viewpoint of detergency. When the cloud point is within this range, the components in the cleaning agent do not separate even during long-term storage, which is stable and preferable.

The surface tension (dyn / cm) at 25 ° C. of the cleaning agent of the present invention is preferably 10 to 65, more preferably 15 to 40, and particularly preferably 20 to 40.
The surface tension can be measured in accordance with JIS K3362: 1998 Annulus Method: Corresponding ISO 304.

  The method for producing a semiconductor substrate of the present invention is one type selected from the group consisting of ultrasonic cleaning, shower cleaning, spray cleaning, brush cleaning, immersion cleaning, immersion oscillation, and single wafer cleaning, using the above-described cleaning agent. An electronic material manufacturing method including a step of cleaning by the above-described cleaning method. In particular, the cleaning effect can be satisfactorily exhibited in a cleaning method including an ultrasonic cleaning method.

  The washing temperature when using the cleaning agent of the present invention is preferably 10 to 80 ° C., more preferably 15 to 70 ° C., and particularly preferably 20 to 60 ° C. from the viewpoint of detergency.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “parts” means “parts by weight” below. The molecular weight of the polymer by GPC was measured under the aforementioned measurement conditions. The ultrapure water used in the examples and comparative examples had a specific resistance value of 18 MΩ · cm or more.

[Production Example 1]
A 1 liter stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 212 g (1.0 mol) of cumylphenol and 10 g (2.6 mol%) of a 25% aqueous solution of tetramethylammonium hydroxide. It dehydrated for 30 minutes under reduced pressure of 4 kPa or less. After dropwise addition of 440 g (10.0 mol) of ethylene oxide over 3 hours while controlling the reaction temperature at 100 ° C., the mixture was aged for about 3 hours at 100 ° C. until the internal pressure of the autoclave showed the same pressure as when the addition was started. The crude product was obtained. In order to decompose and remove the remaining tetramethylammonium hydroxide, the crude product was kept at a temperature of 150 ° C. for 2 hours under a reduced pressure of 2.6 kPa or less for the nonionic surfactant of the present invention. 640 g of a certain cumylphenol ethylene oxide 10 mol adduct (A-1) was obtained. The HLB value of (A-1) was 12.6, and the cloud point was 80 ° C.

[Production Example 2]
A 1 liter stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 144 g (1.0 mol) of 2-naphthol and 10 g (2.6 mol%) of a 25% aqueous solution of tetramethylammonium hydroxide at 100 ° C. It dehydrated for 30 minutes under reduced pressure of 4 kPa or less. 352 g (8.0 mol) of ethylene oxide was added dropwise over 3 hours while controlling the reaction temperature at 100 ° C., and then aged for about 3 hours at 100 ° C. until the internal pressure of the autoclave showed the same pressure as when the addition was started. The crude product was obtained. In order to decompose and remove the remaining tetramethylammonium hydroxide, the crude product was kept at a temperature of 150 ° C. for 2 hours under a reduced pressure of 2.6 kPa or less for the nonionic surfactant of the present invention. 490 g of a certain 2-naphthol ethylene oxide 8 mol adduct (A-2) was obtained. The HLB value of (A-2) was 13.0, and the cloud point was 95 ° C.

[Production Example 3]
A 1 liter stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 42 g (0.2 mol) of cumylphenol and 2 g (2.6 mol%) of a 25% aqueous solution of tetramethylammonium hydroxide at 100 ° C. It dehydrated for 30 minutes under reduced pressure of 4 kPa or less. A mixture of 440 g (10.0 mol) of ethylene oxide and 290 g (5.0 mol) of propylene oxide was added dropwise over 10 hours while controlling the reaction temperature at 100 ° C., and then the internal pressure of the autoclave started dropping at 100 ° C. Aging was carried out for about 3 hours until the same pressure as the time was obtained, and a crude product was obtained. In order to decompose and remove the remaining tetramethylammonium hydroxide, the crude product was maintained at 150 ° C. for 2 hours under a reduced pressure of 2.6 kPa or less, and the nonionic surfactant of the present invention Thus, 770 g of 75 mol random adduct (A-3) of cumylphenol ethylene oxide / propylene oxide was obtained. The HLB value of (A-3) was 12.3, and the cloud point was 80 ° C.

[Production Example 4]
136 parts of octylbenzenesulfonic acid and 245 parts of ultrapure water were charged into a beaker and dissolved until uniform. By neutralizing the obtained octylbenzenesulfonic acid aqueous solution with a 25% tetramethylammonium hydroxide (hereinafter abbreviated as TMAH) aqueous solution (about 180 parts) until the pH becomes 7, and adjusting the concentration with ultrapure water. A 40% aqueous solution of octylbenzenesulfonic acid TMAH salt (B-1) was obtained.

[Production Example 5]
144 parts of octanoic acid and 300 parts of ultrapure water were charged into a beaker and dissolved until uniform. The obtained octanoic acid aqueous solution was neutralized with diethanolamine (about 100 parts) until the pH became 7, and the concentration was adjusted with ultrapure water to obtain a 40% aqueous solution of octanoic acid diethanolamine salt (B-2).

[Production Example 6]
A reaction vessel capable of temperature control and stirring was charged with 300 parts of isopropyl alcohol and 100 parts of ultrapure water, and the temperature was raised to 75 ° C. after purging with nitrogen. Under stirring, 407 parts of a 75% aqueous solution of acrylic acid and 95 parts of a 15% isopropyl alcohol solution of dimethyl-2,2′-azobisisobutyrate were added over 3.5 hours while maintaining the system temperature at 75 ° C. The solution was added dropwise (at the same time starting to be suitable) After completion of the dropwise addition, after stirring at 75 ° C. for 5 hours, about 900 ultrapure water is intermittently added so that the system does not solidify, and the mixture of water and isopropyl alcohol is distilled off until no isopropyl alcohol can be detected. A polyacrylic acid aqueous solution was obtained. The obtained polyacrylic acid aqueous solution is neutralized with diethanolamine (about 450 parts) until the pH becomes 7, and the concentration is adjusted with ultrapure water to obtain a 40% aqueous solution of polyacrylic acid diethanolamine salt (B-3). It was. In addition, Mw of (B-3) was 10,000.

[Production Example 7]
100 parts of ethylene dichloride was charged into a stirred reaction vessel capable of temperature control and refluxing, and after purging with nitrogen under stirring, the temperature was raised to 90 ° C. to reflux ethylene dichloride. An initiator solution prepared by dissolving 120 parts of styrene and 1.7 parts of 2,2′-azobisisobutyronitrile in 20 parts of ethylene dichloride in advance over 6 hours while maintaining the system temperature at 90 ° C. separately The solution was dropped into the reaction vessel, and after completion of the dropping, polymerization was further performed at 90 ° C. for 1 hour. After the polymerization, the mixture was cooled to 20 ° C. under a nitrogen seal, 105 parts of anhydrous sulfuric acid was added dropwise over 10 hours while controlling the temperature at 20 ° C., and the sulfonation reaction was further carried out at 20 ° C. for 3 hours. After the reaction, the solvent was distilled off and solidified, and then 345 parts of ultrapure water was added and dissolved to obtain a polystyrenesulfonic acid aqueous solution. The obtained polystyrene sulfonic acid aqueous solution was neutralized with 25% TMAH aqueous solution (about 400 parts) until the pH became 7, and the concentration was adjusted with ultrapure water to adjust the concentration of polystyrene sulfonic acid TMAH salt (B-4) to 40%. An aqueous solution was obtained. In addition, Mw of (B-4) was 40,000, and the sulfonation rate was 97%.

[Production Example 8]
A reaction vessel with stirring was charged with 21 parts of naphthalenesulfonic acid and 10 parts of ultrapure water, and 8 parts of a 37% formaldehyde aqueous solution was added dropwise at 80 ° C. over 3 hours. After completion of the dropwise addition, the temperature was raised to 105 ° C. and reacted for 25 hours, then cooled to room temperature (about 25 ° C.), and DBU was gradually added while adjusting to 25 ° C. in a water bath to adjust the pH to 6.5 ( Use about 15 parts of DBU). Ultrapure water was added to adjust the solid content to 40% to obtain a 40% aqueous solution of a DBU salt (B-5) of a naphthalenesulfonic acid formalin condensate. In addition, Mw of (B-5) was 5,000.

[Production Example 9]
Production Example except that 407 parts of 70% monomer aqueous solution consisting of 227 parts of acrylamido-2-methylpropanesulfonic acid, 78 parts of acrylic acid and 131 parts of ultrapure water was used instead of 407 parts of 75% aqueous solution of acrylic acid. Polymerization was conducted in the same manner as in Example 6 to obtain an aqueous solution of an acrylamide-2-methylpropanesulfonic acid / acrylic acid copolymer. DBU was gradually added to the obtained aqueous solution of acrylamide-2-methylpropanesulfonic acid / acrylic acid copolymer while adjusting the temperature to 25 ° C. to adjust the pH to 6.5 (using about 280 parts of DBU). A 40% aqueous solution of acrylamide-2-methylpropanesulfonic acid / acrylic acid copolymer DBU salt (B-6) was obtained by adjusting the concentration with water. In addition, Mw of (B-6) was 8,000.

[Production Example 10]
Instead of 407 parts of 75% aqueous solution of acrylic acid, 65% consisting of 320 parts of 50% aqueous solution of methacryloyloxypolyoxyalkylenesulfate sodium salt [manufactured by Sanyo Chemical Co., Ltd., Eleminol RS-30] and 145 parts of acrylic acid Polymerization was conducted in the same manner as in Production Example 6 except that 465 parts of the monomer aqueous solution was used to obtain an aqueous solution of methacryloyloxypolyoxyalkylene sulfate sodium salt / acrylic acid copolymer. After diluting the aqueous solution of the obtained copolymer with ultrapure water so that the solid content concentration becomes 10%, using a cation exchange resin “Amberlite IR-120B” (manufactured by Organo Corporation), Sodium ions were removed until the concentration became 1 ppm or less. The sodium content was measured using an ICP emission analyzer (ICPS-8000, manufactured by Shimadzu Corporation). The resulting aqueous solution of methacryloyloxypolyoxyalkylene sulfate / acrylic acid copolymer was neutralized with a 25% aqueous TMAH solution (about 600 parts) while adjusting the temperature to 25 ° C. until the pH reached 7; By adjusting the concentration with water, a 10% aqueous solution of methacryloyloxypolyoxyalkylene sulfate / acrylic acid copolymer TMAH salt (B-7) was obtained. In addition, Mw of (B-7) was 9,000.

[Production Example 11]
173 parts of n-butanol was charged into a glass reactor equipped with a stirrer and a temperature controller, and the temperature was adjusted to 70 ° C. with stirring. 135 parts of phosphoric anhydride was added dropwise over 2 hours while maintaining the internal temperature at 70 ° C., and stirring was further continued at 70 ° C. for 3 hours to obtain n-butanol phosphate. The obtained n-butanol phosphate was cooled to 30 ° C., and 25% TMAH aqueous solution (about 520 parts) was gradually added to this while stirring at 25 ° C. with stirring until the pH reached 7. A 47% aqueous solution of butanol phosphate TMAH salt (B-8) was obtained.

[Production Example 12]
A glass reactor equipped with a stirrer and a temperature controller was charged with 26 parts of 2-ethylhexanol and cooled to 0 ° C. with stirring. Here, 23 parts of chlorosulfonic acid was added dropwise over 3 hours while maintaining the system temperature at 0 ° C. to obtain 2-ethylhexanol sulfate. The obtained 2-ethylhexanol sulfate was adjusted with ultrapure water so that the concentration was 10%. From the top of a chromatographic tube having a diameter of 3 cm and a length of 50 cm, which is vertically filled with an anion exchange resin “Amberlite IRA400J” (manufactured by Organo Corporation) that has been adjusted to an OH form with a regenerant (NaOH aqueous solution) in advance. At 25 ° C., a 10% aqueous solution of 2-ethylhexanol sulfate was gradually passed little by little. The operation of passing the effluent again from the top of the column was repeated until the chloride content of the effluent using ICP (ICPS-8000, manufactured by Shimadzu Corporation) was less than 1 ppm to remove chloride in the aqueous solution.
DBU (about 30 parts) was gradually added at 25 ° C. while cooling with stirring until pH became 7, to obtain a 16% aqueous solution of 2-ethylhexanol sulfate DBU salt (B-9).

[Production Example 13]
116 parts of 2-ethylbutyric acid and 350 parts of ion-exchanged water were charged into a beaker and dissolved until uniform. The 2-ethylbutyric acid aqueous solution is neutralized by adding N-methyldiethanolamine (about 120 parts) to 25 at 25 ° C. under cooling to give 2-ethylbutyric acid N-methyldiethanolamine salt (B-10). A 40% aqueous solution of was obtained.

[Comparative Production Example 1]
An autoclave capable of stirring and temperature adjustment was charged with 186 parts (1.0 mol) of lauryl alcohol and 0.5 part of potassium hydroxide, and dehydrated at 100 ° C. under a reduced pressure of 30 mmHg or less for 30 minutes. 440 parts (10.0 mol) of ethylene oxide was added dropwise over 3 hours while maintaining the reaction temperature at 160 ° C., and then aged at 160 ° C. for 2 hours to obtain a liquid crude polyether. This crude polyether is cooled to about 80 ° C., 6 parts of ultrapure water and 100 parts of cation exchange resin {manufactured by Organo Corporation, Amberlite IR120B (H)} are added and stirred at room temperature (about 20 ° C.) for 30 minutes. Then, filtration under reduced pressure and dehydration were performed to obtain a comparative nonionic surfactant (ethylene oxide 10 mol adduct of lauryl alcohol, HLB value 13.2, cloud point 85 ° C.) (S-1).

[Examples 1 to 21] and [Comparative Examples 1 to 4]
Ingredients listed in Tables 1 and 2 were uniformly stirred at room temperature (about 20 ° C.) in a beaker with the blending amounts listed in Tables 1 and 2 (indicated by solid content in Tables 1 and 2). The detergents of Examples 1 to 21 and Comparative Examples 1 to 4 were prepared by mixing. The abbreviations of alkali component (D) and chelating agent (E) in Tables 1 and 2 are as follows.
TMAH: tetramethylammonium hydroxide DEA: diethanolamine DBU: 1,8-diazabicyclo [5.4.0] -7-undecene EDTA: ethylenediaminetetraacetic acid diammonium of the obtained Examples 1-21 and Comparative Examples 1-4 The pH of the cleaning agent was measured at 25 ° C. using a pH meter (H-12, M-12).
Moreover, what diluted the cleaning agent of Examples 1-21 and Comparative Examples 1-4 with the 20 times amount of ultrapure water beforehand was used for the test liquid, and the fine particle adhesion number and surface flatness were measured with the following method.
Furthermore, the foaming power and foam stability of the cleaning agents of Examples 1 to 21 and Comparative Examples 1 to 4 were measured according to JIS K3362 (1998).
These measurement results are shown in Tables 1 and 2.

<Number of fine particles attached>
A dispersion was prepared by diluting 1,000 parts of a colloidal silica (average particle diameter 50 nm) 40% aqueous dispersion (KEMIRA, VI-80) 10 times with ultra pure water.
An 8-inch blanket TEOS wafer (manufactured by Advantech Co., Ltd., film thickness: 15,000 mm) was immersed in the dispersion at 25 ° C. for 1 minute at 25 ° C., then the wafer was taken out and washed with running water. By cleaning for 2 seconds and spin drying, a wafer having a surface contaminated with colloidal silica was produced. Using a single wafer cleaning apparatus equipped with a PVA brush, scrub cleaning was performed for 20 seconds at room temperature (23 ° C.) while supplying the test solution onto the contaminated wafer at a rate of about 25 ml / s. Thereafter, rinsing was performed with ultrapure water for 30 seconds, followed by spin drying, and the number of particles of 0.14 μm or more adhering to the silicon wafer surface was measured using a laser surface inspection apparatus (WM-2500, manufactured by Topcon Corporation).
This evaluation was performed in a class 1 (FED-STD-209D, US Federal Standard, 1988) clean room in order to prevent contamination from the atmosphere.

<Surface flatness>
The bare silicon wafer was cut into a size of 1 cm × 1 cm, 10 ml of each test solution was taken in a 20 ml glass container, the temperature was adjusted to 50 ° C., the wafer was placed, and immersed at 50 ° C. for 10 minutes. After immersion, the wafer was taken out using tweezers, rinsed in running water for 30 seconds to flow the test solution, and then blown with nitrogen at room temperature (25 ° C.) to dry the wafer. The surface roughness (Ra) of the dried wafer was measured using an atomic force microscope (S-I Nano Technology Co., Ltd., E-Sweep) to evaluate the surface flatness. In addition, the surface roughness (Ra) of the wafer before the test was 0.050 nm.

Furthermore, what diluted the washing | cleaning agent of Examples 9-21 and Comparative Examples 3-4 with the 20 times amount of ultrapure water previously was used for the test liquid, and the wax removability was evaluated with the following method. The results are shown in Table 3.
<Wax detergency>
5 ml of a commercially available wax (Nikka Seiko Co., Ltd., Sky Liquid) was dropped on an 8-inch silicon wafer, and uniformly applied by rotating at 1000 rpm for 3 seconds. The coated wafer was heated on a hot plate adjusted to 100 ° C. for 5 minutes, and then cut into a size of 2 cm × 5 cm to prepare a test wafer. 100 ml of each test solution was taken in a 100 ml glass beaker and the temperature was adjusted to 40 ° C., and then the test wafer was placed and immersed for 5 minutes. After immersion, the wafer was taken out using tweezers, rinsed in running water for 30 seconds to flow the test solution, and then blown with nitrogen at room temperature (25 ° C.) to dry the wafer. The state of wax remaining on the dried wafer surface was visually evaluated according to the following rating.
○: No wax remains on the surface.
Δ: A trace of wax is observed.
X: Dirt clearly remains.

From the results of Tables 1 and 2, it was found that the cleaning agent of the present invention can greatly reduce the number of adhered particles per wafer. It was also found that since there was almost no change in the flatness of the wafer surface after cleaning, there was no fear of causing wafer surface roughness during cleaning. Furthermore, it has been found that the cleaning agent of the present invention is very excellent in low-foaming properties and has an effect that there is no trouble due to foaming which becomes a problem during cleaning.
Moreover, it turned out that the cleaning agent (Examples 9-21) of this invention which added the alkali component (D) shows high detergency with respect to wax from the result of Table 3.

  Since the cleaning agent of the present invention is excellent in the cleaning property of particles on a semiconductor substrate and the permeability to organic dirt, it is effectively used as a cleaning agent in the process of manufacturing a semiconductor substrate (such as a semiconductor element and a silicon wafer). be able to.

Claims (10)

One or more nonionic surfactants (A) selected from the group consisting of nonionic surfactants represented by general formula (1) and nonionic surfactants represented by general formula (2), anionic surfactant A cleaning agent for a semiconductor substrate comprising an agent (B) and water (C).

[Wherein R ¹ is an aromatic ring-containing hydrocarbon group having 6 to 24 carbon atoms, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, and AO is a carbon group having 2 to 4 carbon atoms. An oxyalkylene group, n is an integer of 1 to 5, m is an integer of 1 to 100, n (R ¹ R ² R ³ C—) may be the same or different, and m AO May be the same or different. ]

[Wherein, R ⁴ represents a hydrocarbon group having 1 to 24 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, p represents an integer of 1 to 7, k represents an integer of 1 to 100, The p R ^{4 s} may be the same or different, and the k AOs may be the same or different. ]   The detergent according to claim 1, wherein the nonionic surfactant (A) is a nonionic surfactant represented by the general formula (1), and is an alkylene oxide adduct of cumylphenol.   The cleaning agent according to claim 1 or 2, wherein the nonionic surfactant (A) has an HLB value of 10 to 16.   The anionic surfactant (B) is a polymer type anionic surfactant (B1) and / or a low molecular type anionic surfactant (B2), and (B1) and (B2) are sulfonic acids ( 1) one or more groups selected from the group consisting of a salt) group, a sulfate ester (salt) group, a phosphate ester (salt) group, a phosphonate ester (salt) group, and a carboxylic acid (salt) group. 4. The cleaning agent according to any one of 3.   The cleaning agent according to claim 4, wherein the polymer type anionic surfactant (B1) has a weight average molecular weight of 300 to 800,000.   The low-molecular-weight anionic surfactant (B2) is a sulfuric acid ester of an aliphatic alcohol having 3 to 8 carbon atoms (salt), an ethylene oxide 1 to 10 mol adduct of an aliphatic alcohol having 3 to 8 carbon atoms. Esters (salts), ether carboxylic acids (salts) of aliphatic alcohols having 3 to 8 carbon atoms, phosphoric acid (mono or di) esters (salts) of aliphatic alcohols having 3 to 8 carbon atoms and fats having 3 to 8 carbon atoms The cleaning agent according to claim 4 or 5, which is at least one member selected from the group consisting of phosphoric acid (mono or di) esters (salts) of alkylene oxide adducts of aliphatic alcohols.   The detergent according to any one of claims 1 to 6, further comprising an alkali component (D) and having a pH of 9 to 14. The cleaning agent according to claim 7, wherein the alkali component (D) is an organic alkali (D1) represented by the general formula (3), an alkanolamine (D3) having 2 to 14 carbon atoms, and / or a hydroxylamine (D4). .

[Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrocarbon group having 1 to 24 carbon atoms or a group represented by — (R ⁹ O) q—H, and R ⁹ is a carbon number. 2 to 4 alkylene groups, q represents an integer of 1 to 6, and q (R ⁹ O) may be the same or different. ]   The cleaning agent according to any one of claims 1 to 8, wherein a weight ratio of the anionic surfactant (B) to the nonionic surfactant (A) is 0.05 to 3.   One or more types selected from the group consisting of ultrasonic cleaning, shower cleaning, spray cleaning, brush cleaning, immersion cleaning, immersion rocking cleaning, and single wafer cleaning, using the cleaning agent according to claim 1. The manufacturing method of the semiconductor substrate including the process wash | cleaned by this washing | cleaning method.