JP3377938B2 - Cleaning composition and cleaning method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is effective in removing fine organic or inorganic foreign matter and oil used for forming a semiconductor element on a semiconductor substrate such as a silicon wafer, and has low foaming property. The present invention relates to a cleaning composition and a cleaning method using the same.

[0002]

2. Description of the Related Art A semiconductor element typified by a silicon semiconductor is highly integrated to meet market needs such as higher performance, higher sensitivity, smaller size, and the like, and the minimum dimension of its circuit pattern is 1KDRAM. It is predicted that the miniaturization will be reduced from 10 micron meter to 4 micron DRAM to 0.8 micron meter, and further 1 giga DRAM to 0.15 micron meter. These semiconductor elements include resist coating, exposure, development, etching, resist removal, after smoothing and cleaning of a substrate such as a silicon wafer.
It is manufactured by repeating a process such as semiconductor formation by ion doping a plurality of times.

In each of these processes, the semiconductor substrate or the semiconductor element surface is formed of an inorganic material such as
It is exposed to various kinds of foreign substances, such as organic solid fine particles or oily dirt, either alone or in combination. For example, abrasive grains used in smoothing processes such as lapping or polishing of substrates such as silicon wafers, wax or resin as a fixing agent, resist decomposition products generated during dry ashing of resist in the semiconductor device manufacturing process, and scattering during dry etching Inorganic substances and resists that are reattached or remain when the resist is removed. Further, during these steps, skin powder, sebum, abrasion powder generated from a machine, machine oil mist, etc. may adhere to the treatment liquid or the element surface from a person, an apparatus, or the atmosphere working.

Further, in recent years, in manufacturing a semiconductor device, a CMP method of polishing the device surface with fine particles has been adopted in order to secure the smoothness of the device surface. In this process, fibrous buff-derived fine powder, abrasive particles, and element-derived inorganic powder may adhere and remain on the element.

In this semiconductor element manufacturing process, if the above-mentioned foreign matter remains on the substrate or the element when working,
Problems such as substrate lattice defects, oxide film insulation defects, epitaxial film abnormal protrusions and stacking faults, wiring breaks, and shorts and leaks of fine particles entering between the wirings may occur. It causes a decrease in production yield. This tendency becomes more pronounced as the degree of integration of semiconductor elements increases and the circuit pattern becomes finer. Therefore, it has been strongly desired to develop a new method for removing the above-mentioned fine foreign matter in order to suppress the deterioration of product quality and the reduction in yield due to the miniaturization of circuit patterns.

Various foreign matter removing methods have been proposed to cope with such a situation. The typical method is 197
There is a cleaning method proposed by RCA Company for 0 years. The outline is to first immerse the wafer in a mixed solution of ammonia water and hydrogen peroxide, and then dip the wafer in a mixed solution of hydrochloric acid and hydrogen peroxide. If necessary, hydrofluoric acid is used before and after these treatments. It is to add aqueous solution treatment or pure water treatment.

In addition, a method of treating with a mixed aqueous solution of hydrofluoric acid and nitric acid, an aqueous solution of hydrofluoric acid and hydrogen peroxide, an aqueous solution of sulfuric acid and hydrogen peroxide, and the like have been proposed and carried out while utilizing their characteristics. These treatments include partial etching of the wafer surface to remove organic and inorganic foreign substances remaining on the surface, dissolution of adhering metals with acid, or oxidation of adhering substances such as organic substances with hydrogen peroxide. It is intended to clean the surface by decomposing it with decomposing power and removing it.

However, although these methods can remove various kinds of fine particles from the surface of the wafer by a force such as etching, they have a weak force for preventing the reattachment of the separated fine particles, so that a sufficient removability is not always obtained. It may not be possible. Therefore, there has been an attempt to obtain a target cleanliness by performing cleaning treatment, post-treatment, or rinsing using a plurality of treatment tanks, but sufficient detergency has not always been obtained. In particular, when a composite contaminant of oily stains and fine particles adheres, the oil film impedes the etching ability, so that it is extremely difficult to remove the complex contaminant.

Various methods have been proposed in order to solve such problems. For example, in JP-A-6-41770, a surfactant is added to a treatment liquid as a cleaning liquid,
A method of maintaining the zeta potential of fine particles in the treatment liquid at a certain value or less, JP-A-6-216098 discloses EDTA.
Cleaning method using chelating agent such as JP-A-7-62
Japanese Patent Publication No. 386 discloses a detergent composition containing a tertiary ammonium salt of fluoroalkylsulfonic acid.

[0010]

However, even if these cleaning agents and cleaning methods are carried out, the removal of fine particles, especially the removal of dirt when oily dirt adheres or is mixed, is not sufficient, and the surfactant Utilization has caused a new problem that foaming occurs during cleaning work and wastewater treatment, which lowers workability. For this reason, the problems of increased cost for cleaning in the manufacture of semiconductor devices, decreased production yield, and decreased productivity remain major problems. Therefore, an object of the present invention is to provide a cleaning composition which is excellent in cleaning properties of a semiconductor substrate or a semiconductor element on which solid fine particles or oily stains are adhered and which has less foaming. A further object of the present invention is to provide a cleaning method which is excellent in the cleaning property of a semiconductor substrate or a semiconductor element on which solid fine particles or oily stains are adhered and which has less foaming.

[0011]

Therefore, the present inventors have found that the cleaning composition has excellent removability and detergency of solid fine particles or solid fine particles having oily stains attached, and does not easily foam in the washing or draining process. As a result of investigations to find out a cleaning method, a highly effective cleaning composition and a cleaning method were invented.

That is, the gist of the present invention is [1] a compound having two or more phosphonic acid groups in a molecule, and a compound represented by the general formula (1):

[0013]

[Chemical 2]

(In the formula, R ¹ is a hydrogen atom or a carbon atom number of 1 to 1.
5 represents an alkyl group having 5 or an alkenyl group having 2 to 5 carbon atoms. AO represents ethylene oxide and / or propylene oxide. X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms. n
Represents an integer of 0 to 2. m shows the integer of 1-8. ) And / or general formula (2) R ² —O— (AO) m—X (2) (In the formula, R ² is an alkyl group having 1 to 6 carbon atoms, and 2 to 6 carbon atoms. Represents an alkenyl group or an acyl group having 1 to 6 carbon atoms, AO represents ethylene oxide and / or propylene oxide, X represents a hydrogen atom and 1 carbon atom.
Is an alkyl group having 4 to 4 or an acyl group having 1 to 4 carbon atoms. m shows the integer of 1-8. Comprising a compound <br/> contain represented by), the cleaning compositions for semiconductor substrate or a semiconductor element, (2) washing of the nonionic surfactant further comprising the (1) Symbol placement Agent composition, [ 3 ] The nonionic surfactant has 7 to 22 carbon atoms.
A compound obtained by adding ethylene oxide and / or propylene oxide to a linear or branched saturated or unsaturated alcohol having a hydrocarbon group of 1 to 22 carbon atoms
A straight-chain or branched-chain saturated or unsaturated amine having a hydrocarbon group of ethylene oxide and / or propylene oxide added thereto, a straight-chain or branched-chain compound having a hydrocarbon group having 1 to 22 carbon atoms Compounds obtained by adding ethylene oxide and / or propylene oxide to saturated or unsaturated fatty acids, compounds obtained by adding ethylene oxide and / or propylene oxide to polyhydric alcohols having 2 to 10 carbon atoms, and 2 to 10 carbon atoms. , A compound obtained by adding ethylene oxide and / or propylene oxide to the polyamine, a compound obtained by adding ethylene oxide and / or propylene oxide to a polyhydric fatty acid having 2 to 10 carbon atoms, alkylphenol (however, the number of carbon atoms in the alkyl group Is 6 or more.) To ethylene oxide and / Or compound of propylene oxide is added, ethylene oxide styrenated phenol and / or compounds which propylene oxide is added, ethylene oxide benzylated phenol and /
Or a compound having propylene oxide added, and one or more compounds selected from a compound having ethylene oxide and / or propylene oxide added to naphthol, the cleaning composition according to [ 2 ],

[ 4 ] The nonionic surfactant has the general formula (3) R ³ —O— (AO) z—X (3) (wherein R ³ is an alkyl group having 8 to 18 carbon atoms, or a carbon atom). Represents an alkenyl group having 8 to 18 atoms, an acyl group having 8 to 18 carbon atoms, or an alkylphenol group having 14 to 18 carbon atoms, AO represents ethylene oxide and / or propylene oxide, and X represents a hydrogen atom or a carbon atom. Number 1
Is an alkyl group having 4 to 4 or an acyl group having 1 to 4 carbon atoms. z represents an integer of 3 to 35. [ 5 ] The detergent composition according to the above [ 2 ], which is a compound represented by the formula [ 5 ], further comprising at least one selected from hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, formic acid and acetic acid, and having a pH of 6 or less. [ 6 ] The cleaning composition according to any one of [1] to [ 4 ], further comprising one or more selected from [ 6 ] ammonia, amino alcohol, tetramethylammonium hydroxide, choline and potassium hydroxide,
The cleaning composition according to any one of [1] to [ 4 ], which has a pH of 8 to 14, and [ 7 ] a semiconductor substrate cleaned using the cleaning composition according to any one of [1] to [ 6 ]. Or a method for cleaning a semiconductor device, [ 8 ] 1) a compound having two or more phosphonic acid groups in a molecule, 2) a compound represented by the general formula (1), 3) a compound represented by the general formula (2), And 4) the nonionic surfactant, wherein the total content of the nonionic surfactant is 0.001 to 20% by weight, and the cleaning method according to the above [ 7 ].

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The cleaning composition and the cleaning method of the present invention are applied to a semiconductor substrate such as a silicon wafer, a wafer of a chemical semiconductor, a glass panel in a liquid crystal panel, and a semiconductor device formed on the substrate. Applied to.

1. Cleaning Agent Composition The cleaning agent composition of the present invention is used for cleaning a semiconductor substrate or a semiconductor element. A specific example of such a detergent composition is a composition containing a compound having two or more phosphonic acid groups in the molecule.

When a compound having one phosphonic acid group in the molecule is used as the compound containing a phosphonic acid group used in the detergent composition, the resulting detergent composition has fine particle removability, dispersibility, and The anti-redeposition ability tends to be poor, and good detergency may not be obtained. Therefore, the number of phosphonic acid groups in the molecule in the compound having a phosphonic acid group in the molecule that can be used in the present invention is 2 or more, preferably 2 to 7, and more preferably 2 to 5. From the viewpoint of availability of the compound, the number of phosphonic acid groups in the molecule is preferably 7 or less. The number of carbon atoms in the compound having a phosphonic acid group in the molecule is preferably 1 to 13 from the viewpoint of detergency and production and purification of the compound, and particularly preferably 2 to 10.

The compound having two or more phosphonic acid groups in the molecule includes not only phosphonic acid but also phosphonate. Examples of the phosphonic acid include 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and triethylenetetraaminehexamethylenephosphonic acid. Further, as the phosphonate, ammonium salts of phosphonic acid, salts of amino alcohols, salts with choline, salts with tetramethylammonium hydroxide, various primary to quaternary organic amine salts, sodium salts, potassium salts and the like. Examples thereof include alkaline earth metal salts such as alkali metal salts and calcium salts.

The phosphonic acid group-containing compound may be used alone or in combination of two or more kinds.

From the viewpoint of the influence on the semiconductor element and the like,
When used as a phosphonate, an ammonium salt, an amino alcohol salt, a choline salt, or a tetramethylammonium hydroxide salt is preferable.

When phosphonate is obtained from amino alcohol, the amino alcohol used is, for example,
Examples thereof include alkylene oxide adducts of alkylamines and polyalkylpolyamines. Specific examples of amino alcohols include monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, monopropanolamine, dipropanolamine, tripropanolamine,
Methyl propanol amine, methyl di propanol amine, amino ethyl ethanol amine etc. are mentioned.

The detergent composition of the present invention containing a compound having two or more phosphonic acid groups in the molecule is particularly excellent in the effect of removing fine particles and preventing redeposition, and the washing of the compound is performed. The content in the agent composition is not particularly limited. Further, the detergent composition can be appropriately diluted before use.

Further, the detergent composition of the present invention may contain a compound represented by the general formula (1) and / or a compound represented by the general formula (2). A detergent composition containing such a compound has a better permeability of a cleaning component to a semiconductor substrate or a semiconductor element and a better cleaning ability to oily stains, and as a result, the fine particle removability is improved. Further, since such a detergent composition has less foaming, it is possible to reduce troubles caused by foaming during cleaning work or wastewater treatment, which contributes to improvement in productivity and workability. It is a thing.

The compound represented by the general formula (1) is

[0026]

[Chemical 3]

(In the formula, R ¹ is a hydrogen atom, and the number of carbon atoms is 1 to
5 represents an alkyl group having 5 or an alkenyl group having 2 to 5 carbon atoms. AO represents ethylene oxide and / or propylene oxide. X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms. n
Represents an integer of 0 to 2. m shows the integer of 1-8. ) Is a compound represented by.

In the general formula (1), R ¹ is a hydrogen atom,
An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, which is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms has detergency. It is preferable from the viewpoint. Further, when R ¹ is an alkyl group or an alkenyl group and the number of carbon atoms is 6 or more, the compound represented by the general formula (1) easily foams, which is not preferable. AO is ethylene oxide and / or propylene oxide. Ethylene oxide and propylene oxide may be used alone or in combination. When mixed and used, the (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain them in blocks.

X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and when X is an alkyl group or an acyl group from the viewpoint of solubility in water and rinsability. The number of carbon atoms is preferably 4 or less. X
Is more preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or an acyl group having 1 to 2 carbon atoms from the viewpoint of detergency. n is an integer of 0-2. m is an integer of 1 to 8, and from the viewpoint of detergency against oily stains, m is preferably an integer of 8 or less, more preferably an integer of 2 to 6.

As the compound represented by the general formula (1),
Specifically, phenol, alcohol such as phenol, methylphenol, isopropylphenol, isobutylphenol, ethylphenol, vinylphenol, benzyl alcohol, methylbenzyl alcohol, ethylbenzyl alcohol, isopropylbenzyl alcohol, and phenylethyl alcohol are added to ethylene oxide. And / or an alkylene oxide adduct in which propylene oxide is added. Ethylene oxide and propylene oxide may be used alone,
You may mix and use it. When mixed and used (AO)
The portion may contain ethylene oxide and propylene oxide at random, or may contain as a block. Furthermore, in such alkylene oxide adduct,
For example, a compound in which alkylene chloride such as methylene chloride is reacted with acetic acid and the like, and X is an alkyl group or an acyl group is also included in the compound represented by the general formula (1).

The compound represented by the general formula (2) means R ² —O— (AO) m—X (2) (wherein R ² is an alkyl group having 1 to 6 carbon atoms, and ² carbon atoms). To A6 represent an alkenyl group or an C1 to C6 acyl group, AO represents ethylene oxide and / or propylene oxide, X represents a hydrogen atom and 1 carbon atom.
Is an alkyl group having 4 to 4 or an acyl group having 1 to 4 carbon atoms. m shows the integer of 1-8. ) Is a compound represented by.

In the general formula (2), R ² is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an acyl group having 1 to 6 carbon atoms, which suppresses foamability. From this viewpoint, the number of carbon atoms of R ² is preferably 6 or less. Further, R ² is more preferably an alkyl group having 3 to 6 carbon atoms or an alkenyl group having 3 to 6 carbon atoms from the viewpoint of detergency. AO is ethylene oxide and / or propylene oxide. Ethylene oxide and propylene oxide may be used alone or in combination. When mixed and used, the (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain them in blocks.

X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and when X is an alkyl group or an acyl group from the viewpoint of solubility in water and rinsability. The number of carbon atoms is preferably 4 or less. X
Is more preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or an acyl group having 1 to 2 carbon atoms from the viewpoint of detergency. m is an integer of 1 to 8, and an integer of 2 to 6 is preferable.

As the compound represented by the general formula (2),
Specifically, an alkylene oxide adduct obtained by adding ethylene oxide and / or propylene oxide to an alcohol such as methanol, ethanol, isopropanol, butanol, amyl alcohol, hexanol, vinyl alcohol, 1-propenyl alcohol, 1-butenyl alcohol. Etc. Ethylene oxide and propylene oxide may be used alone or in combination. When mixed and used, the (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain them in blocks. Further, the compound represented by the general formula (2) also includes a compound in which the alkylene oxide adduct is reacted with an alkylene chloride such as methylene chloride, acetic acid, or the like to form X as an alkyl group or an acyl group.

Since the compound represented by the general formula (1) and the compound represented by the general formula (2) have a low foaming property, the foaming of the resulting detergent composition during use can be suppressed.
Therefore, the cleaning composition of the present invention is preferable because it has good workability and wastewater treatment property.

When a compound having two or more phosphonic acid groups in the molecule is used in combination with a compound represented by the general formula (1) and / or a compound represented by the general formula (2), the characteristics of each compound Appear synergistically and exhibit better cleaning properties.

Here, the ratio of the compound represented by the general formula (1) to the compound represented by the general formula (2) is not particularly limited, but in terms of weight ratio, [the compound represented by the general formula (1)].
/ [Compound represented by general formula (2)] is 8/2 to 2/8
Is preferred.

Further, the detergent composition of the present invention may contain a nonionic surfactant. The detergent composition containing such a nonionic surfactant has a better permeability of the cleaning component to the semiconductor substrate or the semiconductor element and a better cleaning ability to oily stains, and as a result, the removability of fine particles, the dispersibility, etc. Is an improved one.

Examples of such nonionic surfactants include compounds contained in the following groups (a), (b) and (c), and further compounds represented by the general formula (3). Can be mentioned. As the nonionic surfactant, one kind may be used alone, or two or more kinds may be mixed and used. Next, specific examples of the groups (a), (b) and (c) will be shown.

Group (a): A compound obtained by adding ethylene oxide and / or propylene oxide to a linear or branched saturated or unsaturated alcohol having a hydrocarbon group having 7 to 22 carbon atoms, and having 1 carbon atom. A compound obtained by adding ethylene oxide and / or propylene oxide to a linear or branched saturated or unsaturated amine having a hydrocarbon group of 22 to 22 and a straight chain having a hydrocarbon group of 1 to 22 carbon atoms or A compound in which ethylene oxide and / or propylene oxide is added to a branched or saturated fatty acid.

Group (b): a compound obtained by adding ethylene oxide and / or propylene oxide to a polyhydric alcohol having 2 to 10 carbon atoms, and an ethylene oxide and / or propylene oxide addition to a polyamine having 2 to 10 carbon atoms. Compounds, as well as having 2 to 10 carbon atoms
A compound obtained by adding ethylene oxide and / or propylene oxide to the polyvalent fatty acid of.

Group (c): a compound obtained by adding ethylene oxide and / or propylene oxide to alkylphenol (wherein the alkyl group has 6 or more carbon atoms), ethylene oxide and / or propylene oxide to styrenated phenol. A compound having ethylene oxide and / or propylene oxide added to benzylated phenol, and a compound having ethylene oxide and / or propylene oxide added to naphthol.

In the compounds included in the groups (a), (b) and (c), ethylene oxide and propylene oxide may be used alone or in combination. Furthermore, the compounds contained in the groups (a), (b) and (c) are reacted with, for example, an alkylene chloride having 1 to 4 carbon atoms or a fatty acid having 1 to 4 carbon atoms, and the end portion thereof is A compound having an alkyl group or an acyl group is also included in the nonionic surfactant referred to herein.

The detergent composition of the present invention containing the compound represented by the general formula (3) has excellent removability of oily stains, and particularly good removal of fine particles having oily stains. It is a thing.

The compound represented by the general formula (3) means R ³ —O— (AO) z—X (3) (wherein R ³ is an alkyl group having 8 to 18 carbon atoms, and 8 carbon atoms). To 18 alkenyl groups, C 8 to C 18 acyl groups or C 14 to C 18 alkylphenol groups, AO represents ethylene oxide and / or propylene oxide, X represents a hydrogen atom and 1 carbon atom.
Is an alkyl group having 4 to 4 or an acyl group having 1 to 4 carbon atoms. z represents an integer of 3 to 35. ) Is a compound represented by.

In the general formula (3), R ³ is an alkyl group having 8 to 18 carbon atoms, an alkenyl group having 8 to 18 carbon atoms, an acyl group having 8 to 18 carbon atoms, or 1 carbon atom.
It is an alkylphenol group having 4 to 18 carbon atoms.
To 14 alkyl groups, 8 to 14 carbon alkenyl groups, 8 to 14 carbon acyl groups or 14 carbon atoms
From the viewpoint of detergency, an alkylphenol group of 16 is preferable. AO is ethylene oxide and / or propylene oxide. Ethylene oxide and propylene oxide may be used alone or in combination. When mixed and used, the (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain them in blocks.

X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or 1 to 4 carbon atoms.
An acyl group of 2 is preferred. z is an integer of 3 to 35,
From the viewpoint of detergency, an integer of 6 to 25 is more preferable. Further, the (AO) portion contains ethylene oxide and propylene oxide in a random or block manner, and the ratio of ethylene oxide and propylene oxide is 9 / molar.
Those in the range of 1 to 5/5 are preferable because they have less foaming.

Specific examples of the nonionic surfactant represented by the general formula (3) include 2-ethylhexanol, octanol, decanol, isodecyl alcohol, tridecyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, Examples thereof include alcohols such as oleyl alcohol, octylphenol, nonylphenol and dodecylphenol, and compounds obtained by adding ethylene oxide and / or propylene oxide to phenols and the like. Ethylene oxide and propylene oxide may be used alone or in combination. Furthermore, a compound in which an alkylene chloride such as methylene chloride or acetic acid is reacted with such an alkylene oxide adduct to form an alkyl group or an acyl group at the X portion is also a nonionic surfactant represented by the general formula (3). include.

When the cleaning composition contains components such as the compound represented by the general formula (1), the compound represented by the general formula (2), and a nonionic surfactant, the composition of the cleaning composition contains The total content of such components is not particularly limited, and the cleaning composition of the present invention can be appropriately diluted and used when cleaning the object to be cleaned.

In the detergent composition of the present invention, the pH of the detergent composition may be appropriately adjusted depending on the purpose of washing. From the viewpoint of more effectively removing metal impurities, the detergent composition of the present invention is preferably acidic. Specifically, a detergent composition having a pH of 6 or less, further containing one or more selected from hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, formic acid and acetic acid is preferable. In this case, the pH of the detergent composition is more preferably 3 or less.

From the viewpoint of more effectively removing fine particles, the detergent composition of the present invention is preferably alkaline. Specifically, ammonia, amino alcohol,
A detergent composition which further contains one or more selected from tetramethylammonium hydroxide, choline and potassium hydroxide and has a pH in the range of 8 to 14 is preferable. In this case, the pH of the detergent composition is more preferably 10-13.

Examples of amino alcohols include monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylpropanolamine, methyldipropanolamine and aminoethyl. Examples include ethanolamine and the like. Such amino alcohols may be used alone or in combination of two or more.

The detergent composition of the present invention contains a silicone type defoaming agent, a chelating agent such as EDTA, alcohols, glycol ethers, etc. within the range of not impairing the characteristics of the present invention.
Preservatives, antioxidants and the like can be added.

The cleaning composition of the present invention may be used in any step of manufacturing a semiconductor element or a semiconductor substrate. For example, a cleaning process after a silicon wafer lapping or polishing process; a cleaning process before a semiconductor device manufacturing process; a semiconductor device manufacturing process, for example, after resist development, dry etching, wet etching, dry ashing,
After the resist is peeled off, it can be used in a cleaning process such as before and after CMP treatment and before and after CVD treatment.

The detergent composition of the present invention can be easily prepared by mixing the above components.

2. Cleaning Method The cleaning method of the present invention uses the cleaning composition of the present invention,
It is a method of cleaning a semiconductor substrate or a semiconductor element. When washing with the detergent composition of the present invention, 1) 2 in the molecule
The compound having two or more phosphonic acid groups, 2) the compound represented by the general formula (1), 3) the compound represented by the general formula (2), and 4) the total content of the nonionic surfactant is fine particle removal. From the viewpoint of cleaning properties, detergency, etc., it is preferable to perform cleaning at 0.001 to 20% by weight, and 0.01 to 20% by weight.
It is more preferable to carry out washing with 0.05 to 10% by weight, and it is further preferable to carry out washing with 0.1 to 5.0% by weight.
It is particularly preferred to perform the washing at a weight percentage.

The cleaning means that can be used in the present invention is not particularly limited, and includes immersion cleaning, rocking cleaning, cleaning using rotation such as spinner, paddle cleaning, air or liquid spray cleaning. Also, known means such as ultrasonic cleaning and brush cleaning can be used. Such cleaning means may be implemented alone or in combination. Further, the semiconductor substrates or semiconductor elements may be washed one by one by one washing operation, or a plurality of sheets may be washed. The number of cleaning tanks used for cleaning may be one or more. The temperature of the detergent composition at the time of washing is not particularly limited, but a temperature range of 20 to 100 ° C. is preferable in terms of safety and operability.

The cleaning method of the present invention can be carried out in any step of manufacturing a semiconductor element or a semiconductor substrate. For example, a cleaning process after the lapping or polishing process of a silicon wafer; a cleaning process before the semiconductor device manufacturing; a semiconductor device manufacturing process, for example, after resist development, dry etching, wet etching, dry ashing, and resist stripping. , Before and after CMP treatment, before and after CVD treatment, and the like.

[0059]

EXAMPLES Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples. However, the products 1, 2 and 6, 7 of the present invention
This is a reference example.

Example 1 1. Preparation of contaminated liquid Silica particles (particle size 0.5 to 2 μm) assuming abrasive particles and wear particles of silicon wafer in a 2 liter beaker
Was dispersed in 1500 mL of ultrapure water in an amount of 1% by weight to prepare a contaminated liquid (A). Next, 1.0% of lauric acid butyl ester was added to the contaminated liquid (A), assuming a mechanical oil mist.
g was added to prepare a contaminated liquid (B).

2. Preparation of Cleaning Agent Composition / Cleaning Solution A cleaning agent composition having the composition (numerical values are% by weight) shown in Tables 1 and 2 was prepared.

[0062]

[Table 1]

[0063]

[Table 2]

Then, the cleaning composition was diluted to prepare a cleaning liquid (1), a cleaning liquid (2), and a cleaning liquid (3).
Specifically, it is as follows.

(1): The cleaning composition was diluted with pure water and then adjusted to pH 7.5 with aqueous ammonia or hydrochloric acid to obtain a cleaning liquid. The total content (% by weight) of each component constituting the cleaning composition in the obtained cleaning liquid is as shown in Table 3, Table 4, Table 5, Table 6 and Table 7. Here, the cleaning liquid having a total content of 0% by weight was prepared by adjusting the pH to 7.5 with pure water and ammonia water without using the cleaning composition. The cleaning liquid thus prepared was used as the cleaning liquid (1) in the cleaning method.

(2): A cleaning composition was obtained by adding the detergent composition to aqueous ammonia having a pH of 11. The total content (% by weight) of each component constituting the cleaning composition in the obtained cleaning liquid is as shown in Table 3, Table 4, Table 5, Table 6 and Table 7. The cleaning liquid thus prepared was used as the cleaning liquid (2) in the cleaning method.

(3): A detergent composition was added to a hydrochloric acid aqueous solution having a pH of 2 to obtain a detergent solution. The total content (% by weight) of each component constituting the cleaning composition in the obtained cleaning liquid is as shown in Table 3, Table 4, Table 5, Table 6 and Table 7. The cleaning liquid thus prepared was used as the cleaning liquid (3) in the cleaning method.

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

[Table 6]

[0072]

[Table 7]

The compounds used in the preparation of the detergent composition are shown in Tables 8 and 9.

[0074]

[Table 8]

[0075]

[Table 9]

3. Preparation of rinse liquid Ultrapure water was used as the rinse liquid. Ultra pure water 1500m
Two beakers containing L were prepared.

4. Detergency evaluation method (1) A detergency magnetic stirrer for the test piece 1 was used, in which the silica particles were uniformly dispersed and the contaminated liquid (A) kept at 50 ° C. had a diameter of 10 cm.
The silicon wafer of 1 was soaked for 5 minutes to contaminate the wafer.

The contaminated wafer is cleaned by the following cleaning method,
It was washed by either the washing method or the washing method.

Cleaning method: The contaminated wafer is treated at 60 ° C.
Immersion in cleaning solution (1) kept at
After irradiating with 8 KHz), it was washed for 3 minutes while oscillating up and down once / second.

Cleaning method: The contaminated wafer is treated at 60 ° C.
Immersion in cleaning solution (2) kept at
After irradiating with 8 KHz), it was washed for 3 minutes while oscillating up and down once / second.

Cleaning method: The contaminated wafer is kept at 30 ° C.
Immersion in cleaning solution (3) kept at
After irradiating with 8 KHz), it was washed for 3 minutes while oscillating up and down once / second.

The wafer thus washed is kept at 60 ° C.
The sample was immersed in the rinse solution kept for 2 minutes and rinsed for 3 minutes while rocking up and down once / second. This operation was repeated once with the beaker changed.

The cleanability of the test piece 1 was evaluated as follows.

After the rinsed wafer was dried, the number of particles remaining on the surface of the wafer was observed with a microscope and counted, and the relative particle removal rate (cleanability) was determined from the following equation.

Relative particle removal rate (%) = [(number of particles when using control cleaning solution-number of particles when using cleaning solution) / (number of particles when using control cleaning solution)] × 100 The results are shown in Tables 3 and 4. .

(2) Cleaning Property for Test Piece 2 In the same manner as the cleaning property test for the test piece 1, the silicon wafer is contaminated with the contaminated liquid (B), the contaminated wafer is cleaned, and the cleaned wafer is rinsed. I went.

After the rinsed wafer was dried, the number of particles remaining on the surface of the wafer was observed under a microscope and counted, and the relative particle removal rate (cleanability) was determined from the following equation.

Relative particle removal rate (%) = [(number of particles when using control cleaning solution-number of particles when using cleaning solution) / (number of particles when using control cleaning solution)] × 100

After drying the rinsed wafer, the organic substances remaining on the surface of the wafer are extracted with a solvent, and HORIBA OCM is used.
The amount of organic matter was measured with an oil content analyzer A, and the relative oil content removal rate (detergency) was determined from the following equation.

Relative oil removal rate (%) = [(Amount of organic substance when using control cleaning liquid-Amount of organic substance when using cleaning liquid) / (Amount of organic substance when using control cleaning liquid)] × 100

Here, the “control cleaning liquid” is a liquid of pure water and ammonia water having a pH of 7.5 in the cleaning method, is ammonia water having a pH of 11 in the cleaning method, and is a liquid in the cleaning method. , An aqueous solution of hydrochloric acid having a pH of 2.

Further, in the cleaning property test of the test piece 2, the foaming property of the cleaning liquid was also tested as follows.

20 mL of the cleaning composition used as a cleaning solution in the cleaning method was placed in a 50 mL graduated cylinder, kept warm at 30 ° C., shaken up and down 10 times, and allowed to stand for 10 seconds, and the volume of foam was measured. .

The results are shown in Tables 5, 6 and 7.

The detergent composition of the present invention exhibited excellent detergency against oily stains and fine particles. On the other hand, the detergent composition containing a compound having one phosphonic acid group in the molecule had low detergency (Comparative Product 1). Further, a detergent composition containing the compound represented by the general formula (1) and / or the compound represented by the general formula (2) has very little foaming property, and has a detergency for oily stains and a fine particle removability. Was excellent (the present invention product 3,
Inventive product 4, Inventive product 5, Inventive product 13, Inventive product 1
4). In addition, although cleaning with only a nonionic surfactant was insufficient in removing fine particles (Comparative Product 2), it was necessary to use a compound having two or more phosphonic acid groups in the molecule in combination with a nonionic surfactant. As a result, very good fine particle removability was exhibited. Particularly, a system in which oily dirt and fine particle dirt are mixed (Examples 6 to 12 and Example 1 in Tables 5 to 7).
In 5), the effect was remarkable.

From this, by appropriately adjusting the composition of the detergent composition of the present invention, a detergent composition having a balance between the washing property and the foaming property during washing can be obtained.

[0097]

EFFECTS OF THE INVENTION A detergent composition containing a compound having two or more phosphonic acid groups in the molecule has good detergency and low foamability. Further, by the cleaning method using such a detergent composition, foreign matters such as oily dirt and fine particles adhered to the element surface in the manufacturing process of the semiconductor element are efficiently removed, and the yield and quality of the manufactured semiconductor element are improved. . In addition, since the cleaning composition has a low foaming property, the operability in cleaning and the wastewater treatment property are not impaired.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-259140 (JP, A) JP-A-6-116770 (JP, A) JP-A-6-41773 (JP, A) JP-A-5- 275405 (JP, A) JP 7-173655 (JP, A) JP 63-211724 (JP, A) JP 9-263792 (JP, A) JP 6-136396 (JP, A) JP-A 5-179289 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) H01L 21/304 647 C11D 1/00-17/08 H05K 3/26

Claims (8)

(57) [Claims] 1. A compound having two or more phosphonic acid groups in a molecule and a compound represented by the general formula (1) : (In the formula, R ¹ is a hydrogen atom or an alkyl having 1 to 5 carbon atoms.
A group or an alkenyl group having 2 to 5 carbon atoms is shown. AO
Ethylene oxide and / or propylene oxide
Show. X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or
Represents an acyl group having 1 to 4 carbon atoms. n is an integer from 0 to 2
Indicates a number. m shows the integer of 1-8. ) Compounds
And / or general formula (2) R ² —O— (AO) m—X (2) (wherein R ² is an alkyl group having 1 to 6 carbon atoms, carbon atom
An alkenyl group having 2 to 6 carbon atoms or an acyl group having 1 to 6 carbon atoms
Represents a radical. AO is ethylene oxide and / or pro
Indicates pyrene oxide. X is a hydrogen atom, 1 carbon atom
~ 4 alkyl groups or C1-4 acyl groups are shown.
You m shows the integer of 1-8. ) A cleaning composition for a semiconductor substrate or a semiconductor element, which comprises: 2. A nonionic surfactant further comprising Claim 1 Symbol placement detergent composition. 3. The nonionic surfactant has 7 to 7 carbon atoms.
A compound in which ethylene oxide and / or propylene oxide is added to a linear or branched saturated or unsaturated alcohol having 22 hydrocarbon groups, having 1 to 1 carbon atoms
A compound obtained by adding ethylene oxide and / or propylene oxide to a linear or branched saturated or unsaturated amine having 22 hydrocarbon groups, and having 1 to 22 carbon atoms.
A compound obtained by adding ethylene oxide and / or propylene oxide to a linear or branched saturated or unsaturated fatty acid having a hydrocarbon group, ethylene oxide and / or propylene oxide to a polyhydric alcohol having 2 to 10 carbon atoms. Compounds with the addition of 2 to 10 carbon atoms
A compound obtained by adding ethylene oxide and / or propylene oxide to the polyamine, the number of carbon atoms is 2 to 10
A compound obtained by adding ethylene oxide and / or propylene oxide to the polyhydric fatty acid, a compound obtained by adding ethylene oxide and / or propylene oxide to an alkylphenol (wherein the alkyl group has 6 or more carbon atoms), styrene Selected from a compound obtained by adding ethylene oxide and / or propylene oxide to benzylated phenol, a compound obtained by adding ethylene oxide and / or propylene oxide to benzylated phenol, and a compound obtained by adding ethylene oxide and / or propylene oxide to naphthol The cleaning composition according to claim 2 , wherein the cleaning composition is one or more compounds. 4. The nonionic surfactant has the general formula (3) R ³ —O— (AO) z—X (3) (wherein R ³ is an alkyl group having 8 to 18 carbon atoms, or a carbon atom). Represents an alkenyl group having 8 to 18 carbon atoms, an acyl group having 8 to 18 carbon atoms, or an alkylphenol group having 14 to 18 carbon atoms, AO represents ethylene oxide and / or propylene oxide, and X represents a hydrogen atom or carbon atom number. 1
Is an alkyl group having 4 to 4 or an acyl group having 1 to 4 carbon atoms. z represents an integer of 3 to 35. The cleaning composition according to claim 2 , which is a compound represented by the formula (1). 5. A hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, further and also contains the one or more kinds selected from formic acid and acetic acid, according to claim 1-4 detergent composition according to any one of a pH of 6 or less. 6. ammonia, amino alcohols, tetramethylammonium hydroxide, choline and further it contains one or more kinds selected from potassium hydroxide, claim 1-4 cleaning according any pH is 8 to 14 Agent composition. 7. The method for cleaning a semiconductor substrate or a semiconductor device washing with detergent composition according to any one of claims 1-6. 8. A compound having 2 or more phosphonic acid groups in the molecule, 2) a compound represented by the general formula (1), and 3) a general formula (2).
The cleaning method according to claim 7 , wherein the cleaning is carried out at a total content of 0.001 to 20% by weight of the compound represented by 4) and 4) a nonionic surfactant.