JPH09111224A - Surface treatment composition and substrate surface treatment method using the same - Google Patents

Abstract

(57) [Abstract] [Objective] A surface treatment composition capable of preventing a metal impurity from contaminating a surface treatment composition on a substrate surface and stably achieving an extremely clean substrate surface, and a substrate using the same. The surface treatment method is provided. In a surface treatment composition containing a complexing agent as a metal adhesion preventing agent in a liquid medium, the complexing agent is (A
Group) A complexing agent having a cyclic skeleton in its molecular structure and having at least one OH group and / or O ⁻ group bonded to a carbon atom constituting the ring (for example, Tyrone, catechol), and (B Group) Complexing agents having at least one donor nitrogen atom in their molecular structure (eg, quinolinol, EDTA)
A surface treatment composition comprising at least one complexing agent selected from each group and a method for surface treatment of a substrate using the surface treatment composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface treatment composition and a method for treating a surface of a substrate using the same. More specifically, when performing surface treatment of a substrate using a surface treatment composition mainly composed of a liquid medium, contamination of the surface of the substrate by metal impurities from the surface treatment composition is prevented, and extremely stable and extremely clean. The present invention relates to a surface treatment composition capable of achieving a stable substrate surface and a method for treating a substrate surface using the same.

[0002]

2. Description of the Related Art With the high integration of various devices represented by ultra LSIs and TFT liquid crystals, the demand for cleaning the surface of a substrate used in the devices has become increasingly severe. Contamination by various substances is one of the obstacles to cleaning, and among these, the contamination by metal particularly deteriorates the electrical characteristics of the device.To prevent such degradation, the metal on the substrate surface on which the device is formed is to be prevented. It is necessary to reduce the concentration of impurities as much as possible. Therefore, it is common practice to clean the substrate surface with a cleaning agent.

Conventionally, water, electrolytic ionized water, aqueous solutions of acids, alkalis, oxidizing agents, surfactants, etc., or organic solvents have been generally used for this type of cleaning agent. In addition to excellent cleaning performance, the cleaning agent is required to have an extremely low impurity concentration in the cleaning agent in order to prevent reverse contamination of the substrate from the cleaning agent by metal impurities. In order to satisfy such demands, purification of semiconductor chemicals used for cleaning has been promoted, and the concentration of metal impurities contained in the chemicals immediately after purification has reached a level that is difficult to detect with current analysis techniques. In this way, it is still difficult to achieve a highly clean substrate surface even if the impurities in the cleaning agent have reached a level that is difficult to detect. This is because it is inevitable to contaminate the cleaning agent itself. That is, the metal impurities once detached from the surface of the base are mixed in the cleaning agent to contaminate the cleaning agent, and the metal impurities from the contaminated cleaning agent adhere to the substrate (reverse contamination).

In the semiconductor cleaning process, cleaning with an [ammonia + hydrogen peroxide + water] solution (SC-1 cleaning)
(RCA Review, p.187-206, June (1970), etc.) is widely used. The main cleaning is usually performed at 40 to 90 ° C.
The composition ratio in the solution is usually (30% by weight aqueous ammonia): (31% by weight aqueous hydrogen peroxide): (water) = 0.0.
It has been used for about 5: 1: 5 to 1: 1: 5. However, this cleaning method has high particle removal ability and organic matter removal ability, but when a very small amount of metal such as Fe, Al, Zn, and Ni is present in the solution, it adheres to the substrate surface and causes reverse contamination. There is. Therefore, in the semiconductor cleaning process, [ammonia + hydrogen peroxide + water] is usually used.
After the solution cleaning, cleaning with an acidic cleaning agent such as [hydrochloric acid + hydrogen peroxide + water] solution cleaning (SC-2 cleaning) is performed to remove metal contamination on the substrate surface. Therefore, in the cleaning process, a technique for preventing such reverse contamination has been required in order to efficiently and stably obtain a highly clean surface.

Further, the problem that the metal impurities in the liquid adhere to the surface of the substrate is not limited to the cleaning step, but the substrate using the solution is not only the cleaning step but also the alkali etching of the silicon substrate and the etching step of the silicon oxide film with dilute hydrofluoric acid. It is a big problem in the overall surface treatment process. In the diluted hydrofluoric acid etching step, if there is a noble metal impurity such as Cu or Au in the liquid, it adheres to the silicon surface and significantly degrades the electrical characteristics of the device such as carrier lifetime. Further, in the alkali etching step, if trace amounts of metallic impurities such as Fe and Al are present in the liquid, these easily adhere to the surface of the substrate, which adversely affects the quality. Therefore, a technique for preventing such contamination in a surface treatment step using a solution is also strongly demanded.

In order to solve these problems, a complexing agent such as a chelating agent is added to the surface treatment agent to capture metal impurities in the solution as a stable water-soluble complex and prevent adhesion to the substrate surface. A method has been proposed. For example, Japanese Patent Application Laid-Open
In 158281, ammonium cyanide or ethylenediamine 4 was added to an aqueous solution of tetraalkyl ammonium hydroxide.
It has been proposed to add a complexing agent such as acetic acid (EDTA) to prevent metal impurities from adhering to the surface of the semiconductor substrate. In JP-A-3-219000, chelating agents such as catechol and Tyrone, in JP-A-5-275405, phosphonic acid-based chelating agents or complexing agents such as condensed phosphoric acid, and JP-A-6-16.
In 3495, a complexing agent such as a hydrazone derivative is added to an alkaline cleaning liquid such as [ammonia + hydrogen peroxide + water] to prevent metal impurities from adhering to the substrate, and thereby to prevent metal contamination with particles and organic substances. It is proposed to achieve a substrate surface without any.

However, when these complexing agents are added, the effect of preventing or removing specific metals (for example, Fe) is observed, but metals other than Fe (which are likely to contaminate the processing liquid or the substrate) ( For example, with respect to Al), the effect of the complexing agent is extremely small, and there is a problem that a sufficient effect cannot be obtained even if a large amount of complexing agent is added. To solve this problem, JP-A-6-216098
Proposes a method of cleaning the substrate with a cleaning solution [ammonia + hydrogen peroxide + water] to which a chelating agent such as a phosphonic acid chelating agent is added, and then rinsing with a hydrofluoric acid aqueous solution of 1 ppm or more. Since a cleaning liquid containing a phosphonic acid-based chelating agent cannot sufficiently reduce Al contamination on the substrate surface, it is intended to remove Al by etching using a hydrofluoric acid aqueous solution of 1 ppm or more in a subsequent step. As described above, the conventional metal adhesion preventing method is not effective enough, and when the substrate needs to be cleaned, the metal contamination must be removed in a later process, thereby increasing the number of processes. Therefore, this has caused an increase in production costs. As described above, in order to prevent the contamination of metal impurities from the surface treatment composition to the surface of the substrate, the addition of various complexing agents has been attempted to prevent the adhesion, but no sufficient improvement has been made yet.
Pollution control technology has not been achieved yet.

[0008]

The present invention has been made to solve the above problems, and prevents contamination of metal impurities from the surface treatment composition to the surface of the substrate, and provides a stable and extremely clean substrate surface. It is an object of the present invention to provide a surface treatment composition capable of achieving the above and a method for surface treatment of a substrate using the same.

[0009]

According to the present invention, when two or more specific complexing agents are added as a metal adhesion preventive agent in a surface treatment composition, compared with the case where there is one complexing agent, This has been achieved based on the new finding that the effect of preventing the adhesion of metal impurities from the treatment liquid to the substrate is significantly improved.
That is, the gist of the present invention is a surface treatment composition containing a complexing agent as a metal adhesion inhibitor in a liquid medium, wherein the complexing agent has a cyclic skeleton in the (A group) molecular structure, and A complexing agent having one or more OH groups and / or O ⁻ groups bonded to carbon atoms constituting a ring, and (Group B) a complexing agent having one or more nitrogen atoms as donor atoms in the molecular structure A surface treatment composition comprising at least one complexing agent selected from each group, and a substrate surface treatment method using this surface treatment composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The surface treatment composition of the present invention is characterized by containing therein two or more specific complexing agents as metal adhesion preventing agents. The specific two or more complexing agents are composed of one or more complexing agents selected from the group A and one or more complexing agents selected from the group B defined below. Incidentally, the surface treatment composition in the present invention means a substrate cleaning,
It is a general term for surface treatment agents used for the purpose of etching, polishing, film formation and the like.

The group A complexing agent is a complexing agent having a cyclic skeleton in its molecular structure and having at least one OH group and / or O ⁻ group bonded to the carbon atoms constituting the ring. is there. The cyclic skeleton in the molecular structure may be any of cyclic skeletons corresponding to an alicyclic compound, an aromatic compound or a heterocyclic compound, and one or more of these cyclic skeletons are present in the molecular structure. O bound to the carbon atoms that make up
It has at least one H group and / or O ⁻ group. Specific examples of such a complexing agent include the following, but are not particularly limited thereto. Also,
Specific examples are illustrated as compounds having an OH group, but also include corresponding salts such as ammonium salts and alkali metal salts thereof.

(1) Phenols having only one OH group and derivatives thereof Phenol, cresol, ethylphenol, t-butylphenol, methoxyphenol, salicyl alcohol, chlorophenol, aminophenol, aminocresol, amidole, p- (2 -Aminoethyl) phenol, salicylic acid, o-salicylanilide, naphthol, naphtholsulfonic acid, 7-amino-4-hydroxy-2-naphthalenedisulfonic acid and the like.

(2) Phenols having two or more OH groups and derivatives thereof Catechol, resorcinol, hydroquinone, 4-methylpyrocatechol, 2-methylhydroquinone, pyrogallol, 1,2,5-benzenetriol, 1,3,3. 5-
Benzenetriol, 2-methylphloroglucinol,
2,4,6-trimethylphloroglucinol, 1,2,2
3,5-benzenetetraol, benzenehexaol, Tyrone, aminoresorcinol, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, dihydroxyacetophenone, 3,4-dihydroxybenzoic acid, gallic acid, 2,3,4 -Trihydroxybenzoic acid, 2,4-dihydroxy-6-methylbenzoic acid, naphthalenediol, naphthalenetriol,
Nitronaphthol, naphthalenetetraol, binaphthyldiol, 4,5-dihydroxy-2,7-naphthalenedisulfonic acid, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid, 1,2,3-anthracentriol, 1,3 , 5-Tris [((2,3-dihydroxybenzoyl) amino) methyl) benzene] [MECA
M], 1,5,10-tris (2,3-dihydroxybenzoyl) -1,5,10-triazadecane [3,4-
LICAM], 1,5,9-tris (2,3-dihydroxybenzoyl) -1,5,9-cyclotriazatridecane [commonly known as 3,3,4-CYCAM], 1,3,5-
Tris [(2,3-dihydroxybenzoyl) carbamide] benzene [TRIMCAM], enterobactin,
Enanthus enterobactin etc.

(3) Hydroxybenzophenones Dihydroxybenzophenones, 2,3,4-trihydroxybenzophenones, 2,6-dihydroxy-4-methoxybenzophenones, 2,2 ', 5,6'-tetrahydroxybenzophenones, 2,3 ', 4,4', 6-pentahydroxybenzophenone and the like.

(4) Hydroxybenzanilide O-hydroxybenzanilide and the like. (5) Hydroxyanil Glyoxal bis (2-hydroxyanyl) and the like. (6) Hydroxybiphenyls Biphenyltetraol and the like.

(7) Hydroxyquinones and derivatives thereof 2,3-dihydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, dihydroxyanthraquinone, 1,2-dihydroxy-3- (aminomethyl) anthraquinone -N, N'-2 acetic acid [alizarin complexan], trihydroxy anthraquinone, etc.

(8) Diphenyl or triphenylalkane derivative Diphenylmethane-2,2'-diol, 4,4 ',
4 "-triphenylmethanetriol, 4,4'-dihydroxyfuchsone, 4,4'-dihydroxy-3-methylfuchsone, pyrocatechol violet [PV] and the like.

(9) Phenol derivative of alkylamine Ethylenediaminedioltohydroxyphenylacetic acid [E
DDHA], N, N-bis (2-hydroxybenzyl)
Ethylenediamine-N, N-2acetic acid [HBED], ethylenediaminedihydroxymethylphenylacetic acid [EDD
HMA] etc.

(10) Phenol derivative of alkyl ether 3,3'-ethylenedioxydiphenol and the like.

(11) Phenols having an azo group and derivatives thereof 4,4'-bis (3,4-dihydroxyphenylazo)
-Diammonium 2,2'-stilbene disulfonic acid [stilbazo], 2,8-dihydroxy-1- (8-hydroxy-3,6-disulfo-1-naphthylazo)-
3,6-naphthalenedisulfonic acid, o, o'-dihydroxyazobenzene, 2-hydroxy-1- (2-hydroxy-5-methylphenylazo) -4-naphthalenesulfonic acid [calmagite], chlorohydroxyphenylazonaphthol, 1 '2-dihydroxy-6-nitro-
1,2′-azonaphthalene-4-sulfonic acid [Eriochrome Black T], 2-hydroxy-1- (2-hydroxy-4-sulfo-1-naphthylazo) -3,6-
Naphthalenedisulfonic acid, 5-chloro-2-hydroxy-3- (2,4-dihydroxyphenylazo) benzenesulfonic acid [lumogallion], 2-hydroxy-1
-(2-hydroxy-4-sulfo-1-naphthylazo)
-3-Naphthalene acid [NN], 1,8-dihydroxy-
2- (4-sulfophenylazo) -3,6-naphthalenedisulfonic acid, 1,8-dihydroxy-2,7-bis (5-chloro-2-hydroxy-3-sulfophenylazo) -3,6-naphthalene Disulfonic acid, 1,8-dihydroxy-2,7-bis (2-sulfophenylazo)-
3,6-naphthalenedisulfonic acid, 2- [3- (2,
4, -Dimethylphenylaminocarboxy) -2-hydroxy-1-naphthylazo] -3-hydroxybenzenesulfonic acid, 2- [3- (2,4, -dimethylphenylaminocarboxy) -2-hydroxy-1-naphthylazo] Such as phenol.

(12) Heterocyclic compounds having an OH group and derivatives thereof 8-quinolinol, 2-methyl-8-quinolinol, quinolinediol, 1- (2-pyridylazo) -2-naphthol, 2-amino-4 , 6,7-Pteridinetriol, 5,7,3′4′-tetrahydroxyflavone [luteolin], 3,3′-bis [N, N-bis (carboxymethyl) aminomethyl] fluorescein [calcein], 2, 3-hydroxypyridine and the like.

(13) Cycloaliphatic compounds having OH group and derivatives thereof, cyclopentanol, croconic acid, cyclohexanol, cyclohexanediol, dihydroxydiquinoyl, tropolone, 6-isopropyltropolone and the like.

The surface treatment composition of the present invention must contain at least one complexing agent selected from the above-mentioned group A as a metal adhesion preventing agent. When selecting a complexing agent, it is necessary to make a comprehensive judgment based on the level of cleanliness required for the substrate surface, the cost of the complexing agent, the chemical stability in the surface treatment composition to be added, and so on. Although it cannot be said that any of the complexing agents is the best, ethylenediamine diorthohydroxyphenylacetic acid [EDDH] is particularly preferable in terms of the effect of preventing metal adhesion when the content in the surface treatment composition is constant.
Phenol derivatives of alkylamines such as A] and phenols having two or more OH groups such as catechol and Tyrone and their derivatives are excellent and are preferably used. In addition, in terms of chemical stability, phenol derivatives of alkylamines such as ethylenediaminedioltohydroxyphenylacetic acid [EDDHA] are excellent, and in terms of production cost of complexing agents, 8-quinolinol, catechol, Tyrone, etc. are each It is excellent and is preferably used when these are important. Furthermore, it is preferable that the complexing agent has a sulfonic acid group and a carboxyl group in addition to the OH group, because both the metal adhesion preventing effect and the chemical stability are excellent.

The group B complexing agent is a complexing agent having at least one nitrogen atom which is a donor atom in its molecular structure. In the present invention, the nitrogen atom that is a donor atom refers to a nitrogen atom that can supply electrons necessary for coordination bond with a metal. Examples of such a coordination group having a nitrogen atom include an amino group, an imino group, a nitrilo group (third nitrogen atom), a thiocyanate group, a hydroxyamino group, a hydroxyimino group, a nitro group, a nitroso group, a hydrazino group and a hydrazono group. , A hydrazo group, an azo group, an azoxy group, a diazonium group, an azido group and the like. Specific examples of the complexing agent having such a coordination group include those shown below, but the complexing agent is not particularly limited thereto.

(1) Monoamines Ethylamine, isopropylamine, vinylamine, diethylamine, dipropylamine, N-methylethylamine, triethylamine, benzylamine, aniline,
Toluidine, ethylaniline, xylidine, thymilamine, 2,4,6-trimethylaniline, diphenylamine, N-methyldiphenylamine, biphenylylamine, benzidine, chloroaniline, nitrosoaniline,
Aminobenzenesulfonic acid, aminobenzoic acid and the like.

(2) Diamines and polyamines Ethylenediamine, propylenediamine, trimethylenediamine, hexamethylenediamine, diethylenetriamine, diaminobenzene, toluenediamine, N-methylphenylenediamine, triaminobenzene, aminodiphenylamine, diaminophenylamine and the like.

(3) Amino alcohols Ethanolamine, 2-amino-1-butanol, 2-
Amino-2-methyl-1-propanol, 2-amino-
2-ethyl-1,3-propanediol, 2- (ethylamino) ethanol, 2,2′-iminodiethanol,
Dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, 3-diethylamino-
1,2-propanediol, triethanolamine and the like.

(4) Aminophenols Aminophenol, p-aminophenol sulfate, (methylamino) phenol, aminoresorcinol and the like.

(5) Amino acids Glycine, glycine ethyl ester, sarcosine, alanine, aminobutyric acid, norvaline, valine, isovaline,
Norleucine, leucine, isoleucine, serine, L-
Threonine, cysteine, cystine, methionine, ornithine, lysine, arginine, citrulline, aspartic acid, asparagine, glutamic acid, glutamine, β-
Hydroxyglutamic acid, N-acetylglycine, glycylglycine, diglycylglycine, phenylalanine, tyrosine, L-thyroxine, N-phenylglycine, N-benzoylglycine and the like.

(6) Iminocarboxylic acids Imino diacetic acid, nitrilo triacetic acid, nitrilo 3 propionic acid, ethylenediamine diacetic acid [EDDA], ethylenediamine tetraacetic acid [EDTA], hydroxyethylethylenediamine tetraacetic acid [EDTA-OH], trans-1 , 2
-Diaminocyclohexane tetraacetic acid [CyDTA], dihydroxyethylglycine [DHGE], diaminopropanol tetraacetic acid [DPTA-OH], diethylenetriamine pentaacetic acid [DTPA], ethylenediamine dipropion diacetic acid [EDDP], glycol ether diamine tetraacetic acid [GEDTA] 1,6-hexamethylenediamine 4
Acetic acid [HDTA], hydroxyethyl imino diacetic acid [H
IDA], methyl EDTA (diaminopropane tetraacetic acid), triethylenetetramine hexaacetic acid [TTHA],
3,3'-dimethoxybenzidine-N, N, N ', N'
-4 acetic acid and the like.

(7) Iminophosphonic acids ethylenediamine-N, N'-bis (methylenephosphonic acid) [EDDPO], ethylenediaminetetrakis (methylenephosphonic acid) [EDTPO], nitrilotris (methylenephosphonic acid) [NTPO], diethylenetriaminepenta ( Methylene phosphonic acid) [ETTPO],
Propylenediaminetetra (methylenephosphonic acid) [P
DTMP].

(8) Heterocyclic amines pyridine, coniline, lutidine, picoline, 3-pyridinol, isonicotinic acid, picolinic acid, acetylpyridine, nitropyridine, 4-pyridone, bipyridyl, 2,
4,6-tris (2-pyridyl) -1,3,5-triazine [TPTZ], 3- (2-pyridyl) -5,6-bis (4-sulfonyl) -1,2,4-triazine [P
Pyridines such as DTS], syn-phenyl-2-pyridylketoxime [PPKS], quinoline, quinaldine, lepidine, dimethylquinoline, 8-quinolinol,
Quinolines such as 2-methyl-8-quinolinol, methoxyquinoline, chloroquinoline, quinoline diol, quinaldic acid, quinic acid, nitroquinoline, quinulin, kynurenic acid, 8-acetoxyquinoline and bicinchoninic acid;
Isoquinolines, acridine, 9-acridone, phenanthridine, benzoquinoline, benzoquinolines such as benzoisoquinoline, naphthoquinolines such as naphthoquinoline, o-phenanthroline, 2,9-dimethyl-
1,10-phenanthroline, bathocuproine, bathocuproine sulfonic acid, bathophenanthroline, bathophenanthroline sulfonic acid, 2,9-dimethyl-4,7-
Phenanthrolines such as diphenyl-1,10-phenanthroline.

Further, pyrazoles such as pyrazole and 5-pyrrolozone, imidazoles such as imidazole and methylimidazole, imidazolines and imidazolidines such as 2-imidazoline, imidazolidine and ethylene urea, benzimidazoles such as benzimidazole and diazines , Pyrimidines, diazines such as pyrazine, uracil, hydropyrimidines such as thymine, piperazines such as piperazine, benzodiazines and dibenzodiazines such as cinnoline and phenazine, triazines, purines, oxazole, 4-oxazolone,
Oxazoles and isoxazoles such as isoxazole and azoxime, oxazines such as 4H-1,4-oxazine and morpholine, thiazoles and benzothiazoles, isothiazoles, thiazines, pyrroles, pyrrolines and pyrrolidines, indoles ,
Indolines, isoindoles, carbazoles, indigo, porphyrins and the like.

(9) Amides and imides Carbamic acid, ammonium carbamate, oxamic acid, ethyl oxamate, ethyl N-nitrocarbamate, carbanilic acid, carbanilonitrile, oxanilic acid, formamide, diacetamide, hexaneamide,
Acrylamide, lactamide, cyanoacetamide, oxamide, succinamide, salicylamide, nitrobenzamide, succinimide, maleimide, phthalimide, and the like.

(10) Anilides Formanilide, acetanilide, hydroxyanilide, chloroanilide, methoxyacetanilide, oxanilide and the like.

(11) Urea, thiourea and its derivatives Urea, N-methylurea, N, N'-ethylidene urea, alophanic acid, glycolic acid, oxalic acid, biuret, N-nitrourea, azodicarbonamide, thiourea , Methylthiourea, dimethylthiourea, etc.

(12) Oximes Formaldoxime, p-benzoquinonedioxime, benzaldoxime, benzyldioxime and the like.

(13) Having a coordination group in which nitrogen atoms are bonded to each other: As hydrazines and hydrazides such as azobenzene, azotoluene, methyl red, azobenzene dicarboxylic acid, hydroxyazobenzene and azoxybenzene, phenylhydrazine and p-bromophenylhydrazine. , P
Azo and azoxy compounds such as -nitrophenylhydrazine, N ',-phenylacetohydrazide, hydrazobenzenes, hydrazo compounds such as hydrazo-2-benzoic acid, oxalic bis (salicylidene hydrazide), salicylaldehyde (2- (Carboxyphenyl) hydrazone, benzaldehyde hydrazone, acetaldehyde phenylhydrazone and other hydrazones, benzylidene azine and other azines, benzoyl azide and other azides, benzenediazonium chloride and other diazonium salts, benzenediazohydroxide and other diazo compounds, semicarbazide, etc. And other thiosemicarbazides such as thiosemicarbazides.

(14) Others Ammonium azide, azides such as sodium azide, nitriles such as acetonitrile, amide sulfuric acid, imide disulfuric acid, nitride 3 sulfuric acid, thiocyanic acid, ammonium thiocyanate and the like.

Among the above-mentioned Group B, in terms of the effect of preventing metal adhesion when the content in the surface treatment composition is constant, amino acids such as glycine, iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid [EDTA] And the like, and heterocyclic polycyclic amines such as 8-quinolinol and o-phenanthroline are excellent and are preferably used.

The amount of the complexing agent added as the metal anti-adhesion agent varies depending on the type and amount of metal impurities in the liquid which is the object of anti-adhesion and the level of cleanliness required on the substrate surface, and therefore is determined in a general manner. However, the total amount added in the surface treatment composition is usually 10 ⁻⁷ to 2% by weight, preferably 10
^Over a 6 to 0.1% by weight. If the addition amount is too small, the effect of preventing metal adhesion, which is the object of the present invention, is difficult to be exhibited.On the other hand, even if the amount is too large, not only no further effect is obtained, but also, in some cases, a metal adhesion inhibitor is applied to the surface of the substrate. It is not preferable because the risk of attaching a certain complexing agent increases.

The liquid medium as the main component in the surface treatment composition of the present invention is not particularly limited, but usually water, electrolytic ion water, acid, alkali, oxidizing agent, reducing agent, surfactant, etc. are dissolved. An aqueous solution, an organic solvent, or a mixed solution thereof is used. In particular, in the case of an alkaline aqueous solution or a diluted hydrofluoric acid solution used for cleaning or etching of a semiconductor substrate, since a metal impurity in the solution is very easily attached to the substrate surface, a complexing agent is added to these solutions according to the present invention. It is preferable to use it.

The alkaline aqueous solution used in the present invention is a general term for aqueous solutions having a pH of more than 7. The alkaline component of this aqueous solution is not particularly limited, but a typical one is ammonia. Further, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkaline salts such as sodium hydrogencarbonate and ammonium hydrogencarbonate, or tetramethylammonium hydroxide (TMAM), trimethyl. 2-Hydroxyethylammonium hydroxide, quaternary ammonium salt hydroxides such as choline, etc. are also used. It is safe to add two or more of these alkalis,
Usually, the total concentration in the total solution of the surface treatment composition is 0.01
It is used so as to be ˜30% by weight. Further, alkaline electrolytic ionic water obtained by electrolysis of water is also preferably used. Further, an oxidizing agent such as hydrogen peroxide may be appropriately compounded in such an alkaline aqueous solution. When cleaning bare (no oxide film) silicon in the semiconductor wafer cleaning process, the mixing of the oxidizing agent can suppress the etching and surface roughness of the wafer. When hydrogen peroxide is added to the alkaline aqueous solution of the present invention, the concentration of hydrogen peroxide in the total solution of the surface treatment composition is usually 0.01 to
It is used in a concentration range of 30% by weight.

The method of adding the complexing agent according to the present invention to the surface treatment composition is not particularly limited. Of the components constituting the surface treatment composition (for example, aqueous ammonia, aqueous hydrogen peroxide, water, etc.), any one or more of the components are preliminarily blended, and then these components are mixed and used. Alternatively, the components may be mixed and then mixed with the mixture before use. When acids such as phenols, amino acids and iminocarboxylic acids are added, they may be added in the form of acid or in the form of salt such as ammonium salt.

The surface treatment composition of the present invention is for cleaning, etching, polishing, film-forming, etc. of substrates such as semiconductors, metals, glass, ceramics, plastics, magnetic materials, and superconductors, in which contamination of the substrate with metal impurities is a problem. It is used for the surface treatment of. In particular, the present invention is suitably used for cleaning and etching of a semiconductor substrate requiring a highly clean substrate surface. Among the cleaning of semiconductor substrates, in particular, [ammonia + hydrogen peroxide +
When the present invention is applied to the alkaline cleaning using a cleaning solution comprising water, the problem of the metal impurities adhering to the substrate, which was a problem of the cleaning method, is improved. It is very suitable because a clean and clean substrate surface is achieved.

The reason why the surface-treating composition of the present invention exerts an extremely good effect in preventing the adhesion of metal impurities is not yet clear, but it is not possible to clarify the reason why two or more specific complexing agents and metal ions are added. It is presumed that some kind of mixing effect occurs during this period and a stable water-soluble metal complex is formed extremely effectively.

When the surface treatment composition of the present invention is used as a cleaning liquid for cleaning a substrate, a method of directly contacting the liquid with the substrate is used. Such cleaning methods include dip-type cleaning in which a cleaning tank is filled with a cleaning liquid to immerse the substrate, spray-type cleaning in which the liquid is sprayed on the substrate to clean the substrate, and spin-type cleaning in which the cleaning liquid is dropped on the substrate and rotated at high speed. And the like. In the present invention, among the above-mentioned cleaning methods, an appropriate one is adopted depending on the purpose, but dip type cleaning is preferably used. Regarding the washing time, the washing is carried out for an appropriate time, preferably 10 seconds to 30 minutes, more preferably 30 seconds to 15
Minutes. If the time is too short, the cleaning effect will not be sufficient, and if it is too long, the throughput will only be deteriorated, and the cleaning effect will not increase and is meaningless. The washing may be performed at room temperature, but may be performed with heating for the purpose of improving the washing effect. Further, at the time of cleaning, a cleaning method using physical force may be used in combination. Examples of such a cleaning method using physical force include ultrasonic cleaning and mechanical cleaning using a cleaning brush.

[0048]

EXAMPLES Next, specific embodiments of the present invention will be described with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Examples 1 to 15 and Comparative Examples 1 to 12 Ammonia water (30% by weight), hydrogen peroxide water (31% by weight) and water were mixed at a volume ratio of 0.25: 1: 5, and the obtained mixture was obtained. A solution is used as a main component of an aqueous solvent, and a predetermined amount of two or more specific complexing agents of the present invention shown in Table 1 as metal adhesion inhibitors are added to the aqueous solvent in a predetermined amount, and the surface treatment composition of the present invention is added. The thing was prepared. For comparison, one of the complexing agents used in the examples was added to the aqueous solvent, and the complexing agents catechol, tyron, and catechol + described in JP-A-3-2199000. ED containing citric acid, which is the complexing agent described in JP-A-5-275405
Addition of TPO [ethylenediaminetetrakis (methylphosphonic acid)], addition of oxalic bis (salicylidene hydrazide) which is a complexing agent described in JP-A-6-163495, and addition of no complexing agent Also prepared.

After adding 10 ppb each of Al and Fe as chlorides to the surface treatment solution thus prepared,
Clean silicon wafer (p-type, CZ, plane orientation (10
0)) was soaked for 10 minutes. During the immersion, the temperature of the surface treatment liquid was maintained at 40 to 50 ° C. by heating. The silicon wafer after the immersion was subjected to overflow rinse with ultrapure water for 10 minutes and then dried by nitrogen blowing to quantify Al and Fe adhering to the wafer surface. Al and Fe adhering to the silicon wafer are recovered with a mixed solution of 0.1% by weight of hydrofluoric acid and 1% by weight of hydrogen peroxide, and the amount of the metal is measured by a flameless atomic absorption method to determine the substrate surface concentration (atoms / It was converted to cm ² ). Table 1 shows the results.

[0050]

[Table 1]

Example 16 and Comparative Example 13 A mixed solution obtained by mixing ammonia water (30% by weight), hydrogen peroxide solution (31% by weight) and water in a volume ratio of 1: 1 was the main component. Was added to the aqueous solvent as a metal adhesion inhibitor, and a predetermined amount of each of the two specific complexing agents of the present invention shown in Table 2 was added to the aqueous solvent to prepare the surface treatment composition of the present invention. For comparison, a solution was also prepared in which no complexing agent was added to the aqueous solvent.

A silicon wafer (p-type, CZ, plane orientation (100)) whose surface was contaminated with metal was immersed in the surface treatment solution thus prepared for 10 minutes to wash the metal-contaminated surface. During the immersion, the temperature of the surface treatment liquid is heated to 40 to 5
It was kept at 0 ° C. The silicon wafer after the immersion was subjected to overflow rinse with ultrapure water for 10 minutes and then dried by nitrogen blowing to quantify the metal on the wafer surface. The metal on the surface of the silicon wafer is 0.1% by weight of hydrofluoric acid and 1 of hydrogen peroxide.
The amount of the metal was measured by a flameless atomic absorption method and was converted into a substrate surface concentration (atoms / cm ² ). Table 2 shows the results.

[0053]

[Table 2]

As shown in Table 2, when the substrate is treated with the surface treatment liquid of the present invention, not only the metal is prevented from adhering to the substrate surface from the liquid, but the substrate surface is contaminated with the metal. In some cases, contaminant metals can also be removed.

[0055]

The surface treatment composition of the present invention contains two or more specific complexing agents as a metal adhesion preventive agent, so that metal impurities such as Al and Fe from the surface treatment composition to the surface of the substrate can be contained. It is possible to prevent contamination and stably achieve an extremely clean substrate surface. In particular, when the present invention is applied to alkali cleaning of a semiconductor substrate represented by [ammonia + hydrogen peroxide + water] cleaning, the problem of metal impurities adhering to the substrate, which is a problem of the cleaning method, is improved, As a result, the cleaning achieves a highly clean substrate surface free from metal contamination as well as particles and organic substances. Therefore, acid cleaning such as [hydrochloric acid + hydrogen peroxide + water] cleaning conventionally used after the cleaning can be omitted, and the cleaning cost and the cost of the clean room such as exhaust equipment can be significantly reduced. Therefore, it is a great advantage for industrial production of semiconductor integrated circuits.

When manufacturing devices such as semiconductors and liquid crystals,
In a wet process such as etching and cleaning, ultrapure water and ultrahigh-purity chemicals having a metal impurity concentration of 0.1 ppb or less are used to prevent metal impurities from adhering to the substrate surface. Furthermore, these chemicals need to be replaced frequently because metal impurities are mixed during use. However, if the surface treatment composition of the present invention is used, it is possible to prevent adhesion even if a large amount of metal impurities are present in the liquid, so there is no need to use an ultra-high purity chemical liquid, and the chemical liquid is used. Even if it is contaminated with metal impurities, it does not need to be replaced frequently, so the cost of the chemical solution and its management can be greatly reduced.

When etching or cleaning a substrate having a metal on the surface, if a metal having a higher ionization tendency than the metal to be treated is present as an impurity in the cleaning liquid, it is electrochemically attached to the substrate surface. When the composition of the present invention is used, metal impurities become a stable water-soluble metal complex, which can be prevented. Further, when the composition of the present invention is applied to an abrasive slurry for polishing a substrate, it is possible to prevent metal impurities, which are present in a large amount in the abrasive slurry and are concentrated in the slurry as the substrate is polished, from adhering to the substrate. As described above, the ripple effect of the surface treatment agent of the present invention is tremendous,
Very useful industrially.

Claims (8)

[Claims] 1. In a surface treatment composition containing a complexing agent as a metal adhesion preventing agent in a liquid medium, the complexing agent comprises (A)
(Group) A complexing agent having a cyclic skeleton in the molecular structure and having at least one OH group and / or O ⁻ group bonded to carbon atoms constituting the ring, and (Group B) a donor in the molecular structure A surface treatment composition comprising at least one complexing agent selected from each group of complexing agents having at least one nitrogen atom as an atom. 2. The complexing agent having at least one nitrogen atom as a donor atom in the group B is an amino group, an imino group, a nitrilo group (third nitrogen atom), a thiocyanate group, a hydroxyamino group or a hydroxyimino group. 2. A nitro group, a nitroso group, a hydrazino group, a hydrazono group, a hydrazo group, an azo group, an azoxy group, a diazonium group, and an azido group, and at least one kind of coordination group is selected from the above-mentioned. Surface treatment composition. 3. The group A complexing agent is an OH group and / or O ^−.
3. The surface treatment composition according to claim 1, which has at least two groups and the complexing agent of Group B has an iminocarboxylic acid group or a heterocyclic polycyclic amino group. 4. The surface treatment composition according to claim 1, wherein the content of the metal adhesion inhibitor is 10 ⁻⁷ to 2% by weight. 5. The surface treatment composition according to claim 1, wherein the liquid medium is an alkaline aqueous solution. 6. The surface treatment composition according to claim 5, wherein the alkaline aqueous solution contains ammonia and hydrogen peroxide. 7. A method for treating the surface of a substrate, which comprises subjecting the substrate to the surface treatment using the surface treatment composition according to claim 1. 8. The method for surface treatment of a substrate according to claim 7, wherein the substrate is a semiconductor substrate.