JPH11116984A - Cleaning composition and cleaning method - Google Patents

Abstract

(57) [Problem] To provide a detergent composition which is excellent in cleaning properties of a semiconductor substrate or a semiconductor element to which solid fine particles or oily dirt is adhered and which has less foaming, and solid fine particles or oily dirt. Provided is a cleaning method which is excellent in the cleaning property of a semiconductor substrate or a semiconductor element to which is adhered and has less foaming. A cleaning composition for a semiconductor substrate or a semiconductor element, comprising a compound having two or more phosphonic acid groups in a molecule, and a semiconductor substrate or a semiconductor to be cleaned using the cleaning composition Element cleaning method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a semiconductor element on a semiconductor substrate such as a silicon wafer or the like, which is effective for removing fine organic or inorganic foreign matter and oil and has a 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 Semiconductor devices typified by silicon semiconductors are highly integrated to meet market needs such as higher speed, higher sensitivity, and smaller size, and the minimum size of the circuit pattern is 1K DRAM. It is expected that the size will be reduced from 10 micron meters to 0.8 micrometer for 4 mega DRAMs, and further to 0.15 micrometer for 1 giga DRAMs. These semiconductor elements, after smoothing and cleaning of a substrate such as a silicon wafer, resist coating, exposure, development, etching, resist removal,
It is manufactured by repeating a process such as semiconductor formation by ion doping a plurality of times.

In each of these steps, the surface of a semiconductor substrate or semiconductor element is made of an inorganic or
It is exposed to various kinds of single or combined foreign substances such as organic solid fine particles or oily dirt. For example, abrasive grains used in a smoothing process such as lapping or polishing of a substrate such as a silicon wafer, wax or resin as a fixing agent, resist decomposed products generated during dry ashing of a resist in a semiconductor device manufacturing process, and scattered during dry etching. Inorganic material and resist that re-adheres or remains when the resist is removed. Further, during these steps, skin powder, sebum, abrasion powder generated from a machine, a machine oil mist, or the like may adhere to the processing liquid or the element surface from a worker, a device, or the atmosphere.

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

In the semiconductor device manufacturing process, if the above-mentioned foreign matter is left on the substrate or the device, the work is performed.
Troubles such as lattice defects on the substrate, defective insulation of the oxide film, abnormal protrusions and stacking faults of the epitaxial film, disconnection of the wiring, and short-circuiting or leaking of fine particles between the wirings occur. This causes a decrease in production yield. This tendency appears more strongly as the degree of integration of the semiconductor element increases and the circuit pattern becomes finer. Therefore, there has been a strong demand for the development of a new method for removing fine foreign matter as described above in order to suppress the deterioration of product quality and the decrease in yield due to the miniaturization of circuit patterns.

In order to cope with such a situation, various foreign matter removing methods have been proposed. A typical method is 197
There is a cleaning method proposed by RCA for 0 years. The outline is that the wafer is first immersed in a mixed solution of ammonia water and hydrogen peroxide, and then the wafer is immersed in a mixed solution of hydrochloric acid and hydrogen peroxide. That is, an aqueous solution treatment or a pure water treatment is added.

[0007] 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, or a method of treating with sulfuric acid and an aqueous solution of hydrogen peroxide, and the like have been proposed, and are carried out by utilizing the characteristics. In these processes, the wafer surface is partially etched to remove organic and inorganic foreign substances remaining on the surface, to dissolve the adhering metal with an acid, or to oxidize organic substances and the like to oxidize hydrogen peroxide. It is intended to be decomposed or removed by a decomposing force to clean its surface.

However, these methods can release various fine particles from the surface of the wafer by the force of etching or the like. However, since the power of preventing the separated fine particles from re-adhering is weak, sufficient removability is not necessarily obtained. May not be possible. Therefore, there has been an attempt to obtain a target cleanliness by performing a cleaning treatment, a post-treatment, or a rinsing by using a plurality of treatment tanks, but sufficient cleaning properties have not always been obtained. In particular, when a composite contaminant of oily dirt and fine particles adheres, it is extremely difficult to remove the composite contaminant since the etching ability is hindered by the oil film.

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

[0010]

However, even if these cleaning agents and cleaning methods are carried out, the removal of fine particles, particularly the removal of dirt when oily dirt is adhered or mixed, is not sufficient. Utilization has created a new problem of foaming during washing and wastewater treatment, which reduces workability. For this reason, the problems of an increase in cost for cleaning, a decrease in production yield, and a decrease in productivity in the manufacture of semiconductor elements have been still serious 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 to which solid fine particles or oily dirt is attached, and which has less foaming. It is a further object of the present invention to provide a cleaning method which is excellent in cleanability of a semiconductor substrate or a semiconductor element to which solid fine particles or oily dirt is attached, and which has less foaming.

[0011]

SUMMARY OF THE INVENTION Accordingly, the present inventors have developed a detergent composition which is excellent in the removability and detergency of solid fine particles or solid fine particles to which oily dirt is adhered, and which causes less foaming in the washing or draining process. As a result of investigations to find a cleaning method, a very effective cleaning composition and a cleaning method were invented.

That is, the gist of the present invention is: [1] A cleaning composition for a semiconductor substrate or a semiconductor element, comprising a compound having two or more phosphonic acid groups in a molecule;
[2] General formula (1)

[0013]

Embedded image

(Wherein R ¹ is a hydrogen atom and has 1 to 1 carbon atoms)
5 represents an alkyl group 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 a compound represented by the general formula (2): R ² —O— (AO) m−X (2) (wherein, R ² is an alkyl group having 1 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
Represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms. m shows the integer of 1-8. The cleaning composition according to the above [1], which further contains one or more compounds selected from the compounds represented by the following [3], [3] or [1], which further contains a nonionic surfactant. The cleaning composition according to 2), wherein the nonionic surfactant is a straight-chain or branched-chain saturated or unsaturated alcohol having a hydrocarbon group having 7 to 22 carbon atoms, and ethylene oxide and / or propylene. Compounds in which oxides are added, compounds in which ethylene oxide and / or propylene oxide are added to a linear or branched saturated or unsaturated amine having a hydrocarbon group having 1 to 22 carbon atoms, Compound in which ethylene oxide and / or propylene oxide is added to a linear or branched saturated or unsaturated fatty acid having 22 hydrocarbon groups, having 2 carbon atoms
A compound in which ethylene oxide and / or propylene oxide is added to a polyhydric alcohol having 10 to 10 carbon atoms; a compound in which ethylene oxide and / or propylene oxide is added to a polyamine having 2 to 10 carbon atoms; A compound in which ethylene oxide and / or propylene oxide is added to a polyvalent fatty acid; a compound in which ethylene oxide and / or propylene oxide is added to an alkylphenol (provided that the alkyl group has 6 or more carbon atoms); a styrenated phenol A compound in which ethylene oxide and / or propylene oxide is added to phenol, a compound in which ethylene oxide and / or propylene oxide is added to benzylated phenol, and an ethylene oxide and / or naphthol to naphthol.
Or the cleaning composition according to the above [3], which is one or more compounds selected from compounds to which propylene oxide has been added,

[5] The nonionic surfactant is represented by the general formula (3) R ³ -O- (AO) z-X (3) (wherein R ³ is an alkyl group having 8 to 18 carbon atoms, It 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
Represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms. z shows the integer of 3-35. The cleaning composition according to the above [3], which is a compound represented by:
The cleaning composition according to any one of the above [1] to [5], further comprising at least one selected from sulfuric acid, nitric acid, hydrofluoric acid, formic acid and acetic acid, and having a pH of 6 or less, [7]
It further contains at least one selected from ammonia, amino alcohol, tetramethylammonium hydroxide, choline and potassium hydroxide, and has a pH of 8
The cleaning composition according to any one of the above [1] to [5], [8] a semiconductor substrate or a semiconductor element to be cleaned using the cleaning composition according to any one of the above [1] to [7]. Washing method,

[9] 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) nonionic surface activity The cleaning method according to [8], wherein the cleaning is performed at a total content of the agent of 0.001 to 20% by weight.

[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 element formed on such a substrate. Applied to

1. Detergent composition The detergent 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 a 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 a property of removing and dispersing fine particles. There is a tendency that the re-adhesion preventing power is inferior, and good cleaning properties may not be obtained. Therefore, the number of phosphonic acid groups in the molecule of the compound having a phosphonic acid group in the molecule which can be used in the present invention is 2 or more, preferably 2 to 7, 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 of the compound having a phosphonic acid group in the molecule is preferably from 1 to 13 in view of detergency and production and purification of the compound, and particularly preferably from 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. Examples of the phosphonate include ammonium salts of phosphonic acids, 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. And alkaline earth metal salts such as alkali metal salts and calcium salts.

Such phosphonic acid group-containing compounds may be used alone or in combination of two or more.

From the viewpoint of the influence on the semiconductor element and the like,
When used as a phosphonate, ammonium salts, salts of amino alcohols, salts with choline, and salts with tetramethylammonium hydroxide are preferred.

When a phosphonate is obtained using an amino alcohol, the amino alcohol to be used includes, for example,
Alkylene oxide adducts of alkylamines and polyalkylpolyamines are exemplified. Specific examples of amino alcohols include monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, monopropanolamine, dipropanolamine, tripropanolamine,
Methylpropanolamine, methyldipropanolamine, aminoethylethanolamine and the like can be mentioned.

The cleaning composition of the present invention comprising a compound having two or more phosphonic acid groups in the molecule is particularly excellent in the effect of removing fine particles and preventing re-adhesion, and is effective in cleaning the compound. The content in the agent composition is not particularly limited. Further, at the time of washing, the detergent composition can be appropriately diluted and used.

Further, the cleaning 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). The detergent composition containing such a compound has better permeability of a cleaning component to a semiconductor substrate or a semiconductor element, and better cleaning of oily stains, and as a result, improved removability of fine particles. In addition, since such a detergent composition has less foaming, it is possible to reduce troubles caused by foaming during washing operation and wastewater treatment, thereby contributing to improvement in productivity and workability. Things.

The compound represented by the general formula (1) is

[0026]

Embedded image

(Wherein R ¹ is a hydrogen atom, having 1 to 1 carbon atoms)
5 represents an alkyl group 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. ).

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, wherein a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms has detergency. Preferred from a viewpoint. Further, when R ¹ is an alkyl group or an alkenyl group, if the number of carbon atoms is 6 or more, the compound represented by the general formula (1) is not preferable because it easily foams. AO is ethylene oxide and / or propylene oxide. Ethylene oxide and propylene oxide may be used alone or as a mixture. When used as a mixture, the (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain 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. From the viewpoint of solubility in water and rinsing properties, when X is an alkyl group or an acyl group, The number of carbon atoms is preferably 4 or less. X
Is 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 to 2. m is an integer of 1 to 8, and m is preferably an integer of 8 or less, and more preferably an integer of 2 to 6, from the viewpoint of detergency against oily stains.

The compound represented by the general formula (1) includes
Specifically, phenols and alcohols such as phenol, methyl phenol, isopropyl phenol, isobutyl phenol, ethyl phenol, vinyl phenol, benzyl alcohol, methyl benzyl alcohol, ethyl benzyl alcohol, isopropyl benzyl alcohol, and phenyl ethyl alcohol are used as ethylene oxide. And / or an alkylene oxide adduct to which propylene oxide has been added. Ethylene oxide and propylene oxide may be used alone,
You may mix and use. When used as a mixture, (AO)
May contain ethylene oxide and propylene oxide at random, or may contain blocks. Further, to such an alkylene oxide adduct,
For example, a compound in which X is converted to an alkyl group or an acyl group by reacting an alkylene chloride such as methylene chloride or acetic acid is also included in the compound represented by the general formula (1).

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

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 foaming. In view of the above, the number of carbon atoms of R ² is preferably 6 or less. 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 as a mixture. When used as a mixture, the (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain 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. From the viewpoint of solubility in water and rinsing properties, when X is an alkyl group or an acyl group, The number of carbon atoms is preferably 4 or less. X
Is 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, preferably 2 to 6.

The compound represented by the general formula (2) includes
Specifically, alkylene oxide adducts obtained by adding ethylene oxide and / or propylene oxide to alcohols such as methanol, ethanol, isopropanol, butanol, amyl alcohol, hexanol, vinyl alcohol, 1-propenyl alcohol, and 1-butenyl alcohol And the like. Ethylene oxide and propylene oxide may be used alone or as a mixture. When used as a mixture, the (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain blocks. Further, the compound represented by the general formula (2) includes a compound in which X is converted to an alkyl group or an acyl group by reacting the alkylene oxide adduct with, for example, an alkylene chloride such as methylene chloride or acetic acid.

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

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

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 the weight ratio of the compound represented by the general formula (1)
/ [Compound represented by general formula (2)] is 8/2 to 2/8
Is preferable.

Further, the cleaning composition of the present invention may contain a nonionic surfactant. The cleaning composition containing such a nonionic surfactant has better permeability of the cleaning component to the semiconductor substrate or the semiconductor element and better cleaning of oily dirt, and as a result, the removal properties of fine particles, the dispersibility and the like. Has been improved.

Examples of such nonionic surfactants include compounds included in the following groups (a), (b) and (c), and compounds represented by the general formula (3). No. As the nonionic surfactant, one type may be used alone, or two or more types may be used in combination. Next, specific examples of the groups (a), (b) and (c) will be described.

Group (a): a compound in which ethylene oxide and / or propylene oxide is added to a linear or branched saturated or unsaturated alcohol having a hydrocarbon group having 7 to 22 carbon atoms, A compound in which ethylene oxide and / or propylene oxide is added to a linear or branched saturated or unsaturated amine having a hydrocarbon group of from 22 to 22; Compounds in which ethylene oxide and / or propylene oxide are 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 adding ethylene oxide and / or propylene oxide to a polyamine having 2 to 10 carbon atoms. Compound, and 2 to 10 carbon atoms
The compound which added ethylene oxide and / or propylene oxide to the polyvalent fatty acid of the above.

Group (c): a compound in which ethylene oxide and / or propylene oxide is added to an alkyl phenol (the alkyl group has 6 or more carbon atoms); ethylene oxide and / or propylene oxide to a styrenated 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.

In the compounds included in the groups (a), (b) and (c), ethylene oxide and propylene oxide may be used alone or as a mixture. Further, 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 terminal portion thereof is Compounds converted into an alkyl group or an acyl group are also included in the nonionic surfactant herein.

The cleaning composition of the present invention containing the compound represented by the general formula (3) is excellent in the removability of oily dirt, and particularly good in the removability of fine particles to which oily dirt is adhered. Things.

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

In the general formula (3), R ³ represents 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.
4 to 18 alkylphenol groups having 8 carbon atoms
An alkyl group having 14 to 14 carbon atoms, an alkenyl group having 8 to 14 carbon atoms, an acyl group having 8 to 14 carbon atoms or 14 carbon atoms.
~ 16 alkylphenol groups are preferred from the viewpoint of detergency. AO is ethylene oxide and / or propylene oxide. Ethylene oxide and propylene oxide may be used alone or as a mixture. When used as a mixture, the (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain 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 is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or 1 to 2 carbon atoms.
Two acyl groups are preferred. z is an integer of 3-35,
From the viewpoint of detergency, an integer of 6 to 25 is more preferable. The (AO) portion contains ethylene oxide and propylene oxide in random or block form, and the ratio of ethylene oxide to propylene oxide is 9 / molar.
Those having a ratio of 1/5 to 5/5 are preferable because they have less foaming.

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. Ethylene oxide and propylene oxide may be used alone or as a mixture. Further, a compound in which X is converted to an alkyl group or an acyl group by reacting the alkylene oxide adduct with an alkylene chloride such as methylene chloride or acetic acid is also used as the nonionic surfactant represented by the general formula (3). include.

When components such as the compound represented by the general formula (1), the compound represented by the general formula (2), and the nonionic surfactant are contained in the cleaning composition, 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 an object to be cleaned.

In the cleaning composition of the present invention, the pH of the cleaning composition may be appropriately adjusted according to the purpose of cleaning. From the viewpoint of more effectively removing metal impurities, the cleaning composition of the present invention is preferably acidic. Specifically, a detergent composition further containing 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 is preferable. In this case, the pH of the detergent composition is more preferably 3 or less.

From the viewpoint of more effectively removing the fine particles, the detergent composition of the present invention is preferably alkaline. Specifically, ammonia, amino alcohol,
A detergent composition further containing at least one selected from tetramethylammonium hydroxide, choline and potassium hydroxide and having a pH in the range of 8 to 14 is preferred. In this case, the pH of the cleaning composition is more preferably from 10 to 13.

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

The cleaning composition of the present invention may contain a silicone-based antifoaming agent, a chelating agent such as EDTA, alcohols, glycol ethers, or the like as long as the properties of the present invention are not impaired.
Preservatives, antioxidants and the like can be added.

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

The cleaning composition of the present invention can be easily prepared by mixing the above-mentioned components.

2. Cleaning method The cleaning method of the present invention uses the cleaning composition of the present invention,
This is a method for cleaning a semiconductor substrate or a semiconductor element. When washing with the detergent composition of the present invention, 1) 2 in the molecule
A compound having two or more phosphonic acid groups, 2) a compound represented by the general formula (1), 3) a compound represented by the general formula (2), and 4) the total content of the nonionic surfactant is such that fine particles are removed. It is preferable to perform the washing at 0.001 to 20% by weight from the viewpoints of the properties and washing properties, and 0.01 to 20% by weight.
More preferably, the washing is performed at 0.05 to 10% by weight, and more preferably, 0.1 to 5.0% by weight.
It is particularly preferred to carry out the washing in weight%.

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 a spinner, paddle cleaning, air or liquid spray cleaning. 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 substrate or the semiconductor element may be washed one by one in one washing operation, or a plurality of semiconductor substrates or semiconductor elements may be washed. Further, the number of washing tanks used for washing may be one or more. The temperature of the detergent composition at the time of washing is not particularly limited, but is preferably in the range of 20 to 100 ° C. in terms of safety and operability.

The cleaning method of the present invention can be carried out in any of the steps of manufacturing semiconductor devices and semiconductor substrates. For example, a cleaning process after a lapping or polishing process of a silicon wafer; a cleaning process before manufacturing a semiconductor device; a semiconductor device manufacturing process, for example, after resist development, after dry etching, after wet etching, after dry ashing, after resist removal , And before and after the CMP process and before and after the CVD process.

[0059]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Embodiment 1 1. Preparation of contaminated liquid Silica particles (particle size 0.5 to 2 μm) assuming abrasive particles and silicon wafer wear particles 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, butyl laurate, which is assumed to be a machine oil mist, was added to the contaminated liquid (A) for 1.0 hour.
g was added to prepare a contaminated liquid (B).

[0061] 2. Preparation of Detergent Composition / Cleaning Solution Detergent compositions having the compositions shown in Tables 1 and 2 (the numerical values are% by weight) were prepared.

[0062]

[Table 1]

[0063]

[Table 2]

Next, 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 the pH was adjusted to 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 Tables 3, 4, 4, 5, 6, and 7. Here, the cleaning liquid having a total content of 0% by weight is obtained by adjusting the pH to 7.5 with pure water and aqueous ammonia without using the cleaning composition. The cleaning solution thus prepared was used as the cleaning solution (1) by the cleaning method.

(2): A cleaning solution was obtained by adding the cleaning 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 Tables 3, 4, 4, 5, 6, and 7. The cleaning solution thus prepared was used as the cleaning solution (2) by the cleaning method.

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

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

[Table 6]

[0072]

[Table 7]

Tables 8 and 9 show the compounds used for preparing the detergent composition.

[0074]

[Table 8]

[0075]

[Table 9]

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

4. Detergency Evaluation Method (1) Detergency for Test Piece 1 A magnetic stirrer was used to uniformly disperse silica particles and uniformly maintain a diameter of 10 cm in a contaminated liquid (A) maintained at 50 ° C.
Was soaked for 5 minutes to contaminate the wafer.

The contaminated wafer is cleaned by the following cleaning method:
Washing was performed by either a washing method or a washing method.

Cleaning method: The contaminated wafer is cleaned at 60 ° C.
Immersed in the cleaning solution (1) kept in
After washing while irradiating (8 KHz), washing was performed for 3 minutes while rocking up and down at a rate of once / second.

Cleaning method: A contaminated wafer is cleaned at 60 ° C.
Immersed in the cleaning solution (2) kept in
After washing while irradiating (8 KHz), washing was performed for 3 minutes while rocking up and down at a rate of once / second.

Cleaning method: The contaminated wafer is kept at 30 ° C.
Immersed in the cleaning solution (3) kept in
After washing while irradiating (8 KHz), washing was performed for 3 minutes while rocking up and down at a rate of once / second.

The wafer thus cleaned is kept at 60 ° C.
And rinsed for 3 minutes while swinging up and down at a rate of once every 2 seconds. This operation was performed once again while changing the beaker.

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

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

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

(2) Cleaning Property for Test Piece 2 A silicon wafer is contaminated with the contaminant (B) in the same manner as in the cleaning property test for the test piece 1 to clean the contaminated wafer and rinse the cleaned wafer. Was done.

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

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

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

Relative oil removal rate (%) = [(amount of organic substance when using control washing liquid−amount of organic substance when using washing liquid) / (amount of organic substance when using control washing liquid)] × 100

Here, the "control cleaning solution" is a liquid having a pH of 7.5 consisting of pure water and aqueous ammonia in the cleaning method, is an aqueous ammonia having a pH of 11 in the cleaning method, and is a aqueous solution of ammonia in the cleaning method. , A hydrochloric acid aqueous solution having a pH of 2.

In the test of the test piece 2 for cleaning properties, the foaming property of the cleaning liquid was also tested as follows.

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

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

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

Thus, by appropriately adjusting the composition of the cleaning composition of the present invention, it is possible to obtain a cleaning composition that is compatible with the detergency and the foaming property during cleaning.

[0097]

According to the present invention, a detergent composition containing a compound having two or more phosphonic acid groups in a molecule has good detergency and low foamability. Further, by the cleaning method using such a detergent composition, foreign substances such as oily dirt and fine particles adhered to the element surface in the semiconductor element manufacturing process are efficiently removed, and the yield and quality of the manufactured semiconductor element are improved. . In addition, since the foaming property of the detergent composition is low, operability in washing and drainage treatment properties are not impaired.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1:66 7:26)

Claims (9)

[Claims] 1. A cleaning composition for a semiconductor substrate or a semiconductor element, comprising a compound having two or more phosphonic acid groups in a molecule. 2. A compound of the general formula (1) (Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. AO represents ethylene oxide and / or propylene oxide. X represents a hydrogen atom, carbon atom A alkyl group having 1 to 4 atoms or an acyl group having 1 to 4 carbon atoms; n represents an integer of 0 to 2; m represents an integer of 1 to 8); (2) R ² —O— (AO) mx (2) (wherein, R ² is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 to 6 carbon atoms) AO represents ethylene oxide and / or propylene oxide, X represents a hydrogen atom, and has 1 carbon atom.
Represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms. m shows the integer of 1-8. 2. The cleaning composition according to claim 1, further comprising one or more compounds selected from the compounds represented by the formula (1). 3. The cleaning composition according to claim 1, further comprising a nonionic surfactant. 4. The method according to claim 1, wherein the nonionic surfactant has 7 to 7 carbon atoms.
Compounds in which ethylene oxide and / or propylene oxide are added to a linear or branched saturated or unsaturated alcohol having a hydrocarbon group of 22 and has 1 to 1 carbon atoms
Compounds 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.
Compounds obtained by adding ethylene oxide and / or propylene oxide to a linear or branched saturated or unsaturated fatty acid having a hydrocarbon group of the formula: and ethylene oxide and / or propylene oxide to a polyhydric alcohol having 2 to 10 carbon atoms , A compound having 2 to 10 carbon atoms
A compound in which ethylene oxide and / or propylene oxide is added to a polyamine having 2 to 10 carbon atoms
A compound in which ethylene oxide and / or propylene oxide is added to a polyvalent fatty acid of the above, a compound in which ethylene oxide and / or propylene oxide is added to an alkylphenol (provided that the alkyl group has 6 or more carbon atoms), and styrene Selected from compounds obtained by adding ethylene oxide and / or propylene oxide to phenol phenol, compounds obtained by adding ethylene oxide and / or propylene oxide to benzylated phenol, and compounds obtained by adding ethylene oxide and / or propylene oxide to naphthol 4. The cleaning composition according to claim 3, which is one or more compounds. 5. A nonionic surfactant represented by the general formula (3): R ³ —O— (AO) z—X (3) (wherein, R ³ is an alkyl group having 8 to 18 carbon atoms, a carbon atom It 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. 1
Represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms. z shows the integer of 3-35. The cleaning composition according to claim 3, which is a compound represented by the formula: 6. The cleaning composition according to claim 1, 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. 7. The cleaning method according to claim 1, further comprising at least one selected from ammonia, amino alcohol, tetramethyl ammonium hydroxide, choline and potassium hydroxide, and having a pH of 8 to 14. Composition. 8. A method for cleaning a semiconductor substrate or a semiconductor element using the cleaning composition according to claim 1. 9. 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) a nonionic compound. The cleaning method according to claim 8, wherein the cleaning is performed when the total content of the surfactant is 0.001 to 20% by weight.