JP2005260213A - Cleaning liquid for substrate for semiconductor device and cleaning method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide cleaning liquid for a substrate for a semiconductor device capable of simultaneously removing particle contaminants, organic contaminants and metal contaminants without corroding any surface of the substrate and capable of highly cleaning the surface of the substrate in a short time wherein water rinse nature is also good, and a cleaning method. <P>SOLUTION: The cleaning liquid for the substrate for the semiconductor device includes component (a): organic acid, component (b): organic alkali component, component (c): surfactant, and component (d): water, wherein pH is 1.5 or more and less than 6.5. The cleaning method of the substrate for the semiconductor device comprises the step of cleaning the substrate for the semiconductor device after chemical mechanical polishing treatment which is provided with a Cu film and a low dielectric constant insulating film on a surface thereof, by using this cleaning liquid for the substrate for the semiconductor device. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a semiconductor device substrate and a cleaning method thereof, and in particular, fine particles (particles) adhering to a semiconductor device substrate having a metal wiring, a low dielectric constant (Low-k) insulating film or the like on a part of or the entire surface. ), Organic contamination, and metal contamination in a short time without corroding the metal wiring, and a cleaning method using this cleaning solution.

In the manufacturing process of semiconductor devices such as microprocessors, memories, and CCDs, and flat panel display devices such as TFT liquid crystals, submicron to sub0.1 micron dimensions on the substrate surface of silicon, silicon oxide (SiO ₂ ), glass, etc. Thus, pattern formation and thin film formation are carried out, and it is an extremely important issue to reduce a small amount of contamination on the surface of the substrate in each manufacturing process. Among contaminations on the substrate surface, particle contamination, organic contamination, and metal contamination reduce the electrical characteristics and yield of the device, so it is necessary to reduce them as much as possible before bringing them into the next process. In order to remove such contamination, the substrate surface is generally cleaned with a cleaning liquid. For this cleaning, it is required to clean a highly clean surface at a low cost in a short time with good reproducibility without any side effects. This required level is becoming stricter with the recent high integration and low cost of devices.

  In recent semiconductor device manufacturing processes, a new metal material (Cu, etc.) having a low resistance value is introduced as a wiring and a low dielectric constant (Low-k) material is introduced as an interlayer insulating film in order to increase the speed and integration of the device. It is coming. In addition, in order to form a wiring, application of CMP (Chemical Mechanical Polishing) technology is progressing. For cleaning between processes, the conventional RCA cleaning in which an acidic or alkaline solution and hydrogen peroxide are mixed cannot corrode the wiring material because it corrodes. Further, many of the low dielectric constant insulating films have a hydrophobic surface, and thus repel the cleaning liquid, and are difficult to clean. Further, in the cleaning after the CMP process, there is a problem that the slurry (abrasive particles) used for CMP contaminates the surface of the wiring and the low dielectric constant insulating film. In order to solve these problems, adaptation of various cleaning techniques has been attempted conventionally.

For example, there has been proposed a cleaning liquid containing a surfactant having a specific structure that can remove particle contamination and metal contamination without corroding the surface transition metal (Japanese Patent Laid-Open No. 2001-284308).
In addition, a cleaning liquid in which an organic acid compound is added to a dispersant and / or a surfactant has been proposed to remove metal impurities and particles adsorbed on a substrate having metal wiring (Japanese Patent Laid-Open No. 2001-007071).
In addition, a cleaning liquid containing an aliphatic polycarboxylic acid and a surfactant that makes a contact angle of a substrate having a surface contact angle of 70 degrees or more when water is dropped to 50 degrees or less has been proposed (Japanese Patent Laid-Open No. 2003-2003). No. 318150).
In addition, a cleaning liquid containing an organic acid and a complexing agent that can remove particles and metal contamination without corroding the metal wiring has been proposed (Japanese Patent No. 3219020).
Furthermore, an efficient method for flattening Cu and a Cu alloy in which surface defects are greatly reduced has been proposed (Japanese Patent Laid-Open No. 2001-156029).
In addition, a cleaning solution in which an alkali or an organic acid is added to a specific surfactant and water has been proposed in order to remove fine particles and organic contamination adhering to the substrate without corroding the substrate surface (Japanese Patent Laid-Open No. 2003-2003). 289060).
JP 2001-284308 A JP 2001-007071 A JP 2003-318150 A Japanese Patent No. 3219020 Japanese Patent Laid-Open No. 2001-156029 JP 2003-289060 A

  In order to further increase the speed and integration of semiconductor devices, new materials such as low resistance metal wiring materials such as Cu and low dielectric constant materials have been introduced rapidly in recent years. In order to solve various problems of substrate cleaning in the semiconductor device manufacturing process using these, the above-described cleaning methods have been proposed, but on the surface of a hydrophobic low dielectric constant insulating film or a corrosive Cu film. There is no technology that can sufficiently remove the various contaminations in a short time, and its establishment has been demanded.

  In order to effectively clean the surface of the hydrophobic low dielectric constant insulating film, it is important to improve the wettability of the hydrophobic surface by using a surfactant. However, in the prior art, since this surfactant is difficult to be removed in the rinsing process using ultrapure water (especially on the Cu surface), long-time rinsing is required, which hinders shortening of cleaning time. there were.

  The present invention has been made to solve the above problems, and can simultaneously remove particle contamination, organic contamination and metal contamination without corroding the substrate surface, and also has good water rinsing properties in a short time. An object of the present invention is to provide a semiconductor device substrate and a cleaning method capable of highly cleaning the substrate surface.

  As a result of intensive studies in order to solve the above problems, the inventors of the present invention have found that a cleaning solution having a specific pH value containing an organic acid, an organic alkali component, and a surfactant is not contaminated with the substrate surface, but is contaminated with particles and organic substances. In addition to the simultaneous removal of metal contamination and metal contamination, it has been found that the water rinsability can be improved and the surface of the substrate can be highly purified in a short time, and the present invention has been completed.

The substrate cleaning liquid for semiconductor devices of the present invention contains the following components (a), (b), (c), and (d) in the cleaning liquid for semiconductor device substrates, and has a pH of 1.5 or more and 6.5. It is characterized by being less than.
Component (a): Organic acid Component (b): Organic alkali component Component (c): Surfactant Component (d): Water

  This semiconductor device substrate cleaning solution is particularly suitable for cleaning a semiconductor device substrate having a metal wiring or a low dielectric constant insulating film on its surface.

  In this invention, as a component (a), a C1-C10 organic compound which has 1 or more of carboxyl groups is preferable. More preferably, it is C1-C8, More preferably, it is C1-C6. Any carboxylic acid may be used as long as it has one or more carboxyl groups, and monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, and the like can be used as appropriate. However, usually the carboxyl group is 5 or less. Particularly preferred is at least one organic acid selected from the group consisting of acetic acid, propionic acid, succinic acid, succinic acid, malonic acid, citric acid, tartaric acid and malic acid.

Further, as the component (b), an organic alkali represented by the following general formula (I), in particular, a hydroxyl group having an alkyl group having 1 to 4 carbon atoms and / or a hydroxyalkyl group having 1 to 4 carbon atoms. Quaternary ammonium is preferred.
(R ¹ ) ₄ N ⁺ OH ⁻ (I)
(However, R ¹ represents a hydrogen atom, a hydroxyl group, an alkoxy group, or an alkyl group which may be substituted with a halogen, and all four R ^{1 s} may be the same or different from each other. (Except when all are hydrogen atoms at the same time.)

Component (c) includes an anionic surfactant, particularly alkyl sulfonic acid and its salt, alkyl benzene sulfonic acid and its salt, alkyl diphenyl ether disulfonic acid and its salt, alkyl methyl tauric acid and its salt, alkyl sulfate ester And at least one anionic surfactant selected from the group consisting of a salt thereof, an alkyl ether sulfate ester and a salt thereof, and a sulfosuccinic acid diester and a salt thereof.

  The content of component (a) is 0.05 to 10% by weight, the content of component (b) is 0.01 to 10% by weight, and the content of component (c) is 0.0003 to 0.1% by weight. The weight ratio of components (a) and (b) [component (a) / component (b)] is 0.8 or more and 5 or less, and the weight ratio of components (c) and (b). [Component (c) / Component (b)] is preferably 0.01 or more and 0.2 or less.

  The method for cleaning a substrate for a semiconductor device of the present invention comprises a substrate for a semiconductor device, particularly a Cu film and a low dielectric constant insulating film on the surface, using such a substrate cleaning solution for a semiconductor device of the present invention, and The semiconductor device substrate after the CMP process is washed.

  This method is particularly effective for cleaning a semiconductor device substrate after CMP using an abrasive containing an azole anticorrosive.

  According to the present invention, in a semiconductor device substrate having a semiconductor material such as silicon, an insulating material such as silicon nitride, silicon oxide, glass, or a low dielectric constant material, a transition metal or a transition metal compound on a part of or the entire surface. It is possible to simultaneously remove fine particles (particles) adhering to the substrate, organic contamination, and metal contamination without corroding the substrate surface. In addition, since the water rinsing property is also good, the substrate surface can be highly cleaned in a short time. Therefore, the present invention is an industrial cleaning technology for contaminated semiconductor device substrates in the manufacturing process of semiconductor devices and display devices. Very useful. Note that the water rinsability is good means that when the substrate after cleaning is rinsed with water, the cleaning liquid, fine particles, organic contamination, and metal contamination are easily removed from the substrate surface.

  Hereinafter, embodiments of the present invention will be described in detail.

  The cleaning liquid of the present invention contains an organic acid as component (a), an organic alkali component as component (b), a surfactant as component (c), and water as component (d), and has a pH of 1.5 or higher. Less than 5.

In the present invention, the organic acid of component (a) is a general term for organic compounds that exhibit acidity (pH <7) in water, and includes a carboxyl group (—COOH), a sulfo group (—SO ₃ H), and a phenolic hydroxyl group. (ArOH: Ar represents an aryl group such as a phenyl group) and an acid functional group such as a mercapto group (-SH). The organic acid used is not particularly limited, but a carboxylic acid having a carboxyl group as a functional group is preferable. More preferably, it is a C1-C10 organic compound which has 1 or more of carboxyl groups, More preferably, it is a C1-C8 organic compound, Especially preferably, it is a C1-C6 organic compound.

  Any carboxylic acid may be used as long as it has one or more carboxyl groups, and monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, and the like can be used as appropriate. However, usually the carboxyl group is 5 or less. Specific examples include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, ethylmethylacetic acid, trimethylacetic acid, succinic acid, succinic acid, malonic acid, citric acid, tartaric acid, malic acid and the like. Preferred are acetic acid, propionic acid, succinic acid, succinic acid, malonic acid, citric acid, tartaric acid and malic acid, and more preferred are acetic acid, succinic acid and citric acid. These organic acid components may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios.

  The content of the component (a) in the cleaning liquid of the present invention is usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably, based on the cleaning liquid in order to sufficiently remove contamination. 0.1 wt% or more. However, if importance is attached to not corroding the substrate surface and being economical, the content of the component (a) is usually 30% by weight or less, preferably 10% by weight or less, more preferably 2% by weight or less. If the concentration of the component (a) is too high, no further effect can be obtained.

In the present invention, the organic alkali component of component (b) is a general term for organic compounds that exhibit alkalinity (pH> 7) in water. The organic alkali component to be used is not particularly limited, and examples thereof include quaternary ammonium hydroxide, amines and amino alcohols represented by the following general formula (I).
(R ¹ ) ₄ N ⁺ OH ⁻ (I)
(However, R ¹ represents a hydrogen atom, a hydroxyl group, an alkoxy group, or an alkyl group which may be substituted with a halogen, and all four R ^{1 s} may be the same or different from each other. (Except when all are hydrogen atoms at the same time.)

As the quaternary ammonium hydroxide, in the above general formula (I), R ¹ may be substituted with a hydroxyl group, an alkoxy group, or a halogen, an alkyl group having 1 to 4 carbon atoms, particularly 1 to 4 carbon atoms. Are preferably alkyl groups and / or hydroxyalkyl groups having 1 to 4 carbon atoms. The alkyl group of R ¹ is a lower alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, and the hydroxyalkyl group is a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxybutyl group. And a lower hydroxyalkyl group having 1 to 4 carbon atoms such as a group.

  Examples of amines include triethylamine and ethylenediamine, and examples of amino alcohols include monoethanolamine, diethanolamine, and trimethanolamine.

  The component (b) is preferably quaternary ammonium hydroxide represented by the general formula (I). Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide (TMAH), tetraethyl Ammonium hydroxide, trimethyl (hydroxyethyl) ammonium hydroxide (common name: choline), triethyl (hydroxyethyl) ammonium hydroxide, and the like can be given.

  Among the organic alkali components described above, tetramethylammonium hydroxide (TMAH), trimethyl (hydroxyethyl) ammonium hydroxide are used as the organic alkali component because of the cleaning effect, low metal residue, economy, and stability of the cleaning solution. (Common name: Choline) and the like are particularly preferable. These organic alkali components may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios.

  Ammonia is not preferable because it easily forms a complex with copper used for metal wiring and causes corrosion.

  The content of the component (b) in the cleaning liquid of the present invention is usually 0.001% by weight or more, preferably 0.01% by weight or more, more preferably, based on the cleaning liquid in order to sufficiently improve the water rinsing property. Is 0.05% by weight or more. However, if importance is attached to the high decontamination effect and economic efficiency, the content of the component (b) is usually 30% by weight or less, preferably 10% by weight or less, more preferably 2% by weight or less. . If the concentration of component (b) is too high, the decontamination effect may be reduced.

  In the present invention, the surfactant used as the component (c) is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of the anionic surfactant include alkyl sulfonic acid and its salt, alkyl benzene sulfonic acid and its salt, alkyl diphenyl ether disulfonic acid and its salt, alkyl methyl tauric acid and its salt, alkyl sulfate and its salt, alkyl ether sulfate and The salt, sulfosuccinic acid diester, its salt, etc. are mentioned. Examples of nonionic surfactants include alkylene oxide surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene fatty acid esters. Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type surfactants. Examples of amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants. Among these, it is preferable to use an anionic surfactant. More preferably, the alkylbenzene sulfonic acid having 8 to 12 carbon atoms and a salt thereof, an alkyl diphenyl ether disulfonic acid having 8 to 12 carbon atoms and a salt thereof, an alkylmethyl tauric acid having 8 to 12 carbon atoms and a salt thereof, and 8 to 12 carbon atoms. Examples thereof include alkyl sulfates and salts thereof, alkyl ether sulfates having 8 to 12 carbon atoms and salts thereof, and sulfosuccinic acid diesters having 8 to 12 carbon atoms and salts thereof. These surfactant components may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios.

  The content of the component (c) in the cleaning liquid of the present invention is usually 0.0001% by weight or more, preferably 0.0003% by weight or more, more preferably, based on the cleaning liquid in order to obtain sufficient particle contamination removal performance. 0.001% by weight or more. However, if importance is placed on suppressing excessive foaming and reducing the load of waste liquid treatment, the content of the component (c) is usually 1% by weight or less, preferably 0.1% by weight or less, more preferably 0.8%. 05 wt% or less. If the concentration of component (c) is too high, no further effect can be obtained.

  In addition, the surfactant as the component (c) may contain metal impurities such as Na, K, and Fe of about 1 to several thousand ppm by weight in the form that is usually on the market. Component (c) becomes a metal contamination source. Therefore, when the surfactant used as component (c) contains metal impurities, the content of each metal impurity is usually 10 ppm or less, preferably 1 ppm or less, more preferably 0.3 ppm or less. In addition, it is preferable to use the surfactant after purification. As this purification method, for example, a method in which a surfactant is dissolved in water and then passed through an ion exchange resin to capture metal impurities in the resin is suitable. By using the component (c) thus purified, it is possible to obtain a cleaning liquid in which the metal impurity content is extremely reduced.

  In the present invention, water is used as the component (d). As water, in order to obtain a highly clean substrate surface, deionized water, preferably ultrapure water is usually used. Moreover, electrolytic ionic water obtained by electrolysis of water, hydrogen water in which hydrogen gas is dissolved in water, or the like can also be used.

  The pH of the cleaning liquid of the present invention is 1.5 or more, preferably 2 or more, more preferably 3 or more, in order to suppress corrosion of the substrate surface. However, in order to sufficiently remove metal contamination, the pH is less than 6.5, preferably 6 or less, more preferably 5 or less.

  In the cleaning liquid of the present invention, the weight ratio [component (a) / component (b)] of the organic acid of component (a) and the organic alkali component of component (b) is sufficient to obtain a metal contamination removal effect. Is preferably 0.8 or more, more preferably 1 or more. However, if importance is placed on suppressing corrosion of the substrate surface, the weight ratio is preferably 5 or less, more preferably 4 or less. If the weight ratio is too large, no further effect can be obtained.

  Further, in the cleaning liquid of the present invention, the organic alkali has an effect of accelerating the desorption of the surfactant on the surface of the substrate, and contains a larger amount of the organic alkali component than the surfactant in order to obtain a sufficient effect of improving the water rinsing property. It is preferable. Therefore, the weight ratio [component (c) / component (b)] between the surfactant of component (c) and the organic alkali component of component (b) is preferably 0.2 or less, more preferably 0.15 or less. And However, even if there is too much organic alkali, the effect does not change. Therefore, if importance is attached to the economy, the important ratio is preferably 0.01 or more, and more preferably 0.05 or more.

  The cleaning liquid of the present invention containing such components (a) to (d) includes at least each of Na, Mg, Al, K, Ca, Fe, Cu, Pb, and Zn among the metal impurities in the cleaning liquid. Is preferably 20 ppb or less, more preferably 5 ppb or less, and particularly preferably 0.1 ppb or less, in order to prevent metal contamination of the semiconductor device substrate due to cleaning. In particular, the total content of these metal impurities is preferably 20 ppb or less, more preferably 5 ppb or less, and particularly preferably 0.1 ppb or less.

In the cleaning liquid of the present invention, in addition to the components (a) to (d), a complexing agent may be further contained as necessary. The complexing agent has an effect of reducing metal contamination on the substrate surface. Any conventionally known complexing agent can be used. The type of complexing agent may be selected based on comprehensive judgment from the contamination level of the substrate surface, the type of metal, the level of cleanliness required for the substrate surface, the cost of the complexing agent, chemical stability, etc. The following (1) to (4) are exemplified.

(1) Compounds having nitrogen as a donor atom and a carboxyl group and / or phosphonic acid group: for example, amino acids such as glycine; iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid [EDTA], trans-1,2- Nitrogen-containing carboxylic acids such as diaminocyclohexane tetraacetic acid [CyDTA], diethylenetriaminepentaacetic acid [DTPA], triethylenetetramine hexaacetic acid [TTHA]; ethylenediaminetetrakis (methylenephosphonic acid) [EDTPO], nitrilotris (methylenephosphonic acid) [NTPO And nitrogen-containing phosphonic acids such as propylenediaminetetra (methylenephosphonic acid) [PDTMP].

(2) A compound having an aromatic hydrocarbon ring and having two or more OH groups and / or O-groups directly bonded to carbon atoms constituting the aromatic hydrocarbon ring: for example, catechol, resorcinol, tyrone, etc. Examples thereof include phenols and derivatives thereof.

(3) Compounds having the above structures (1) and (2): For example, the following (3-1) and (3-2) may be mentioned.
(3-1) Ethylenediamine diorthydroxyphenylacetic acid [EDDHA] and its derivatives: For example, ethylenediaminediorthydroxyphenylacetic acid [EDDHA], ethylenediamine-N, N′-bis [(2-hydroxy-5-methylphenyl) acetic acid ] [EDDHMA], ethylenediamine-N, N′-bis [(2-hydroxy-5-chlorophenyl) acetic acid] [EDDHCA], ethylenediamine-N, N′-bis [(2-hydroxy-5-sulfophenyl) acetic acid Aromatic nitrogen-containing carboxylic acids such as [EDDHSA]; ethylenediamine-N, N′-bis [(2-hydroxy-5-methylphenyl) phosphonic acid], ethylenediamine-N, N′-bis [(2-hydroxy- Aromatic nitrogen-containing phosphonic acids such as 5-phosphophenyl) phosphonic acid] It is below.
(3-2) N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-2 acetic acid [HBED] and its derivatives: for example, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N , N′-2 acetic acid [HBED], N, N′-bis (2-hydroxy-5-methylbenzyl) ethylenediamine-N, N′-2 acetic acid [HMBED], N, N′-bis (2-hydroxy-) 5-chlorobenzyl) ethylenediamine-N, N′-2 acetic acid and the like.

(4) Others: For example, amines such as ethylenediamine, 8-quinolinol, o-phenanthroline; carboxylic acids such as formic acid, acetic acid, oxalic acid, tartaric acid; hydrofluoric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, etc. Examples thereof include hydrogen halides and salts thereof; oxo acids such as phosphoric acid and condensed phosphoric acid, and salts thereof.

  The complexing agent may be in the form of an acid, or may be in the form of a salt such as an ammonium salt.

  Among the complexing agents described above, nitrogen-containing carboxylic acids such as ethylenediaminetetraacetic acid [EDTA] and diethylenetriaminepentaacetic acid [DTPA]; ethylenediaminetetrakis (methylenephosphonic acid) [EDTPO] for reasons of cleaning effect, chemical stability, etc. , Nitrogen-containing phosphonic acids such as propylenediaminetetra (methylenephosphonic acid) [PDTMP]; ethylenediaminedioltohydroxyphenylacetic acid [EDDDHA] and its derivatives; N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N ′ -2 acetic acid [HBED] is preferred. Among them, from the viewpoint of the cleaning effect, enediaminediolhydroxyhydroxyacetic acid [EDDHA], ethylenediamine-N, N′-bis [(2-hydroxy-5-methylphenyl) acetic acid] [EDDHMA], diethylenetriaminepentaacetic acid [DTPA], ethylenediamine Tetraacetic acid [EDTA] and propylenediaminetetra (methylenephosphonic acid) [PDTMP] are preferred.

  The above complexing agents may be used alone or in combination of two or more in any proportion.

  The concentration of the complexing agent in the cleaning liquid of the present invention may be arbitrarily selected depending on the type and amount of contaminating metal impurities on the semiconductor device substrate to be cleaned, and the cleanliness level required for the substrate surface. In order to obtain a sufficient adhesion preventing effect, it is generally 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more. However, the concentration of the complexing agent is usually 10000 ppm or less, preferably 1000 ppm or less, if importance is attached to reducing the possibility that the complexing agent adheres to the substrate surface and remains after the surface treatment or is economical. Preferably it is 200 ppm or less.

  In addition, since the complexing agent contains about 1 to several thousand ppm of metal impurities such as Fe, Al, and Zn in reagents that are usually sold, the complexing agent used may be a source of metal contamination. It is done. These metals initially exist in the form of a stable complex with the complexing agent. However, if the complexing agent decomposes during long-term use as a cleaning solution, it is released from the complexing agent. And adheres to the surface of the substrate to be cleaned. Therefore, the complexing agent used in the present invention is preferably used after being purified, and the content of each metal impurity by purification is usually 5 ppm or less, preferably 1 ppm or less, more preferably 0.1 ppm or less. It is preferable that As the purification method, for example, a method in which the complexing agent is dissolved in an acidic or alkaline solution, insoluble impurities are removed by filtration, neutralized again to precipitate crystals, and the crystals are separated from the liquid is preferable. It is.

The cleaning liquid of the present invention may also contain other components in any proportion within a range not impairing its performance. Other components include sulfur-containing organic compounds (2-mercaptothiazoline, 2-mercaptoimidazoline, 2-mercaptoethanol, thioglycerol, etc.), nitrogen-containing organic compounds (benzotriazole, 3-aminotriazole, N (R ² ) ₃ (R ² may be the same or different from each other and may be different from each other, and may be different from each other, alkyl group having 1 to 4 carbon atoms and / or hydroxyalkyl group having 1 to 4 carbon atoms), urea, thiourea, etc.), water-soluble polymer (polyethylene glycol, Polyvinyl alcohol, etc.), anticorrosives such as alkyl alcohol compounds (R ³ OH (R ³ is an alkyl group having 1 to 4 carbon atoms)), acids such as sulfuric acid, hydrochloric acid and methanesulfonic acid, reducing agents such as hydrazine, hydrogen , Dissolved gases such as argon and nitrogen, hydrofluoric acid, ammonium fluoride, BHF (buffered hydrofluoric acid), etc. Removal effect of polymers which firmly adhered after dry etching and the like etching accelerator can be expected.

  As other components to be contained in the cleaning liquid of the present invention, oxidizing agents such as hydrogen peroxide, ozone and oxygen can be mentioned. In the step of cleaning a semiconductor device substrate, when the surface of a silicon (bare silicon) substrate without an oxide film is cleaned, it is preferable because the surface roughness due to etching on the substrate surface can be suppressed by adding an oxidizing agent. When the cleaning liquid of the present invention contains hydrogen peroxide or the like, the concentration of hydrogen peroxide in the cleaning liquid is usually 0.01% by weight or more, preferably 0.1% by weight or more, and usually 5% by weight or less, preferably Is 1% by weight or less.

By the way, the wiring of a semiconductor device and device element electrodes made of a metal material that reacts and dissolves with hydrogen peroxide may be exposed on the surface of the substrate to be cleaned. Examples of such a metal material include transition metals or transition metal compounds such as Cu and W. At this time, it is preferable that the cleaning liquid used for cleaning does not substantially contain hydrogen peroxide. Unlike the conventional APM cleaning liquid, the cleaning liquid of the present invention exhibits sufficient cleaning performance without adversely affecting such a metal material even if it does not substantially contain hydrogen peroxide.

  In the cleaning liquid of the present invention, “substantially does not contain hydrogen peroxide” means that the material on the substrate to be cleaned, for example, the wiring material such as Cu and W, the electrode material, and the low dielectric constant film is excessive. This means that there is no adverse effect such as corrosion or alteration due to hydrogen oxide. That is, when these materials are used as semiconductor devices, it means that they function sufficiently as wirings or electrodes. For that purpose, hydrogen peroxide is not contained in the cleaning liquid of the present invention, and even if it is contained, the content is preferably reduced. The content is, for example, 10 ppm or less, preferably 1 ppm, more preferably 10 ppb or less.

  The method for preparing the cleaning liquid of the present invention may be a conventionally known method. Among the components of the cleaning liquid (organic acid, organic alkali component, surfactant, water, other components such as a complexing agent as required), any two components or three or more components are blended in advance, and then the rest These components may be mixed or all at once.

The cleaning liquid of the present invention is used for cleaning the surface of a semiconductor device substrate such as a semiconductor, glass, metal, ceramics, resin, magnetic material, and superconductor in which metal contamination or particle contamination is a problem. In particular, it is suitably used for cleaning a semiconductor device substrate surface in a process of manufacturing a substrate for a semiconductor device such as a semiconductor element or a display device, which requires a highly clean substrate surface. Wirings, electrodes, and the like may be present on the surfaces of these substrates. Wiring and electrode materials include semiconductor materials such as Si, Ge, and GaAs; SiO ₂ , silicon nitride, glass, low dielectric constant materials, aluminum oxide, transition metal oxides (titanium oxide, tantalum oxide, hafnium oxide, zirconium oxide) Etc.), (Ba, Sr) TiO ₂ (BST), polyimide, organic thermosetting resin and other insulating materials; metals such as W, Cu, Al, or alloys thereof, silicide, nitride, and the like. Here, the low dielectric constant material is a general term for materials having a relative dielectric constant of 3.5 or less. The relative dielectric constant of SiO ₂ is 3.8 to 3.9.

  In particular, the cleaning liquid of the present invention can remove the surfactant that does not corrode the metal surface and remains on the metal surface with a short rinse, and can improve the throughput. It is suitably used for cleaning a semiconductor device substrate having a metal compound. Examples of transition metals include W, Cu, Ti, Cr, Co, Zr, Hf, Mo, Ru, Au, Pt, and Ag. Transition metal compounds include nitrides, oxidations of these transition metals. Material, silicide and the like. In these, W and / or Cu are preferable.

  The cleaning liquid of the present invention is also suitably used for cleaning a semiconductor device substrate having a low dielectric constant interlayer insulating film on the surface. Examples of the low dielectric constant material include organic polymer materials such as Polyimide, BCB (Benzocyclobutylene), Flare (Honeywell), SiLK (Dow Chemical), FSG (Fluorinated Silicate Glass), and BLACKDIAMD ), SiOC-based materials such as Aurora (ASM Japan). In particular, the use of the present cleaning liquid can remove contamination of the substrate surface in a short time even with a strong hydrophobic low dielectric constant insulating film such as Flare, SiLK, BLACK DIAMOND, or Aurora.

  As a process for cleaning a substrate having Cu or a low dielectric constant insulating film on the surface, in particular, a cleaning process after performing CMP (Chemical Mechanical Polishing) on the Cu film, or dry etching the interlayer insulating film on the wiring The cleaning process after opening a hole is mentioned, The cleaning liquid of this invention which has said effect is used suitably.

In the CMP process, polishing is performed by rubbing the substrate against the pad using an abrasive. As an abrasive | polishing agent component, an abrasive particle, an oxidizing agent, a dispersing agent, and another additive are contained. Examples of the abrasive particles include colloidal silica (SiO ₂ ), fumed silica (SiO ₂ ), alumina (Al ₂ O ₃ ), and ceria (CeO ₂ ). Examples of the oxidizing agent include hydrogen peroxide, ammonium persulfate, iron nitrate, and potassium iodate. Examples of the dispersant include a surfactant, KOH, ammonia, and amine. Other additives include organic acids (such as citric acid and quinaldic acid) and anticorrosives. In particular, in CMP polishing of a Cu film, it is important that a Cu film is easily corroded and an anticorrosive agent is added. Among the anticorrosive agents, an azole anticorrosive agent having a high anticorrosive effect is preferably used. An azole is a general term for a 5-membered aromatic compound containing two or more heteroatoms, and at least one heteroatom is a nitrogen atom. As heteroatoms other than nitrogen, oxygen and sulfur are well known. Examples of the nitrogen-only heterocycle include diazole, triazole, and tetrazole. Examples of nitrogen and oxygen heterocycles include oxazole, isoxazole, and oxadiazole. Examples of nitrogen and sulfur heterocycles include thiazole, isothiazole, and thiadiazole. Among them, a benzotriazole (BTA) type anticorrosive having an excellent anticorrosive effect is particularly preferably used. Moreover, there are abrasives having various pH such as acidic, neutral and alkaline depending on the composition, and can be selected according to the purpose.

  When the cleaning liquid of the present invention is applied to the surface after polishing with an abrasive containing such an anticorrosive, it is excellent in that it can very effectively remove contamination derived from these anticorrosive. That is, when these anticorrosives are present in the polishing agent, while suppressing the corrosion of the Cu film surface, it reacts with Cu ions eluted during polishing to produce a large amount of insoluble precipitates. The cleaning solution of the present invention can efficiently dissolve and remove such insoluble precipitates. Furthermore, the surfactant that tends to remain on the metal surface can be removed by rinsing in a short time, and throughput can be improved. is there. In particular, it is preferably used for cleaning a semiconductor device substrate after a CMP treatment is performed on a surface on which a Cu film and a low dielectric constant insulating film coexist with an abrasive containing an azole anticorrosive.

  The cleaning method of the present invention is performed by a method in which the cleaning liquid of the present invention is brought into direct contact with the substrate. The contact method of the cleaning liquid to the substrate is a dip type in which the cleaning tank is filled with the cleaning liquid and the substrate is immersed, a spin type in which the substrate is rotated at high speed while flowing the cleaning liquid from the nozzle onto the substrate, and the substrate is cleaned by spraying the liquid on the substrate. A spray type etc. are mentioned. As an apparatus for performing such cleaning, there are a batch-type cleaning apparatus that simultaneously cleans a plurality of substrates housed in a cassette, a single-wafer cleaning apparatus that mounts and cleans a single substrate in a holder, and the like. .

  Although the cleaning liquid of the present invention can be applied to any of the above methods, it is preferably used for spin-type or spray-type cleaning because it allows more efficient decontamination in a short time. And if it applies to the single-wafer | sheet-fed washing | cleaning apparatus in which shortening of washing | cleaning time and the reduction of the usage-amount of washing | cleaning liquid are desired, since these problems are eliminated, it is preferable.

  In addition, the cleaning method of the present invention further improves the removability of particle contamination if a cleaning method using physical force, particularly scrub cleaning using a cleaning brush or ultrasonic cleaning with a frequency of 0.5 MHz or higher is used in combination. This is preferable because it also shortens the cleaning time. In particular, in the cleaning after CMP, it is preferable to perform scrub cleaning using a resin brush. The material of the resin brush can be arbitrarily selected, but for example, PVA (polyvinyl alcohol) is preferably used.

  Furthermore, before and / or after washing according to the present invention, washing with electrolytic ionic water obtained by electrolysis of water or hydrogen water in which hydrogen gas is dissolved in water may be combined.

  The temperature of the cleaning liquid is usually room temperature, but may be heated to about 40 to 70 ° C. within a range that does not impair the performance.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited by the following Examples, unless the summary is exceeded.

<Examples 1-12 and Comparative Examples 1-6>
(Evaluation of cleanability of particle contamination by scrub cleaning)
An 8-inch silicon substrate with a Cu film was polished with a slurry for CMP containing a benzotriazole-based anticorrosive agent (acidic, containing SiO ₂ particles) for 1 minute, followed by water polishing for 17 seconds. The substrate after the CMP polishing is subjected to brush scrub cleaning using a PVA brush by a multi-spinner (“KSSP-201” manufactured by Kaijo Co., Ltd.) using a cleaning liquid having the composition shown in Table 1 to remove particles. did. The cleaning with the cleaning liquid was performed at room temperature for 30 seconds, and then the substrate was rinsed with ultrapure water for 10 seconds or 30 seconds and spin-dried to obtain a cleaned substrate.

  Thereafter, the number of particles (particle size of 0.35 μm or more) adhering to the substrate surface was measured using a laser surface inspection device (“LS-6600” manufactured by Hitachi Electronics Engineering Co., Ltd.). The results are shown in Table 1.

In Table 1, the abbreviations of the components in the cleaning liquid are as follows. The same applies to Tables 2 to 6 below.
TMAH: Tetramethylammonium hydroxide N (Et) 3: Triethylamine Choline: Trimethyl (hydroxyethyl) ammonium hydroxide NH3: Ammonia DBS: Dodecylbenzenesulfonic acid DPDSA: Dodecyldiphenyl ether disulfonic acid diammonium salt MMTA: N-myristoylmethyltauronium ammonium MSA: Methanesulfonic acid IPA: Isopropyl alcohol In Table 1, the concentration of metal impurities in the cleaning solution represents the concentration of Na, Mg, Al, K, Ca, Fe, Cu, Pb, and Zn contained in the cleaning solution. . The same applies to Tables 2 to 6 below.

From Table 1, according to the substrate cleaning solution for a semiconductor device of the present invention, particle contamination on the Cu film after polishing with a slurry for CMP (acid, containing SiO ₂ particles) containing a benzotriazole anticorrosive is prevented. It can be seen that it can be cleaned cleanly and the rinsing time can be as short as 10 seconds.

  Even when acetic acid or succinic acid was used instead of citric acid as the organic acid of component (a), it was confirmed that the rinsing property was improved and the same effect was obtained.

<Examples 13 to 14>
(Evaluation of cleanability of particle contamination by scrub cleaning)
An 8-inch silicon substrate with a Cu film was polished with a slurry for CMP containing an anticorrosive agent (alkaline, containing SiO ₂ particles) for 1 minute, followed by water polishing for 17 seconds. The substrate after CMP polishing is subjected to brush scrub cleaning with a multi-spinner (“KSSP-201” manufactured by Kaijo Co., Ltd.) using a cleaning liquid having the composition shown in Table 2 to remove particles. did. The cleaning with the cleaning liquid was performed at room temperature for 30 seconds, and then the substrate was rinsed with ultrapure water for 30 seconds and spin-dried to obtain a cleaned substrate.

  Thereafter, the number of particles (particle size of 0.35 μm or more) adhering to the substrate surface was measured using a laser surface inspection device (“LS-6600” manufactured by Hitachi Electronics Engineering), and the results are shown in Table 2.

As is clear from Table 2, the number of remaining particles on the Cu film is very small, and according to the semiconductor device substrate cleaning liquid of the present invention, an anticorrosive-containing CMP slurry (alkaline, containing SiO ₂ particles) is used. It can be seen that particle contamination on the Cu film after polishing can be prevented and cleaning can be performed highly cleanly.

<Examples 15 to 16>
(Evaluation of cleanability of particle contamination by scrub cleaning)
An 8-inch silicon substrate with a Cu film was polished for 1 minute with a CMP slurry (acidic, containing SiO ₂ particles) containing a benzotriazole anticorrosive, and then the polishing was terminated without water polishing, and the substrate was removed. In a state where Cu contamination remains on the polishing pad, an 8-inch silicon substrate with a low-k film (BLACK DIAMOND) film is continuously placed in a CMP slurry (acidic, SiO ₂ particles) containing a benzotriazole anticorrosive for 1 minute. After polishing, water polishing was performed for 17 seconds. The substrate with the low-k film (BLACK DIAMOND) film after the CMP polishing is subjected to a PVA brush by a multi-spinner (“KSSP-201” manufactured by Kaijo Co., Ltd.) using a cleaning liquid having the composition shown in Table 3. Using brush scrub cleaning, particles were removed. The cleaning with the cleaning liquid was performed at room temperature for 30 seconds, and then the substrate was rinsed with ultrapure water for 30 seconds or 60 seconds and spin-dried to obtain a cleaned substrate.

  Thereafter, the number of particles (particle size of 0.2 μm or more) adhering to the substrate surface was measured using a laser surface inspection device (“LS-6600” manufactured by Hitachi Electronics Engineering Co., Ltd.), and the results are shown in Table 3.

From Table 3, according to the substrate cleaning solution for semiconductor devices of the present invention, even a substrate with a low-k film which is usually difficult to clean is a CMP slurry (acidic, containing SiO ₂ particles) containing a benzotriazole anticorrosive. It can be seen that particle contamination after polishing can be prevented and cleaning can be performed with high cleanliness.

<Examples 17-18>
(Evaluation of cleanability of particle contamination by scrub cleaning)
An 8-inch silicon substrate with a Cu film was polished with a slurry for CMP containing an anticorrosive agent (alkaline, containing SiO ₂ particles) for 1 minute, and was then polished without water polishing, and the substrate was removed. With the Cu contamination remaining on the polishing pad, the 8-inch silicon substrate with the Low-k film (BLACK DIAMOND) film is polished for 1 minute with a slurry for CMP (alkaline, SiO ₂ particles) containing an anticorrosive agent, Water polishing was performed for 17 seconds. The substrate with the low-k film (BLACK DIAMOND) film after the CMP polishing is subjected to a PVA brush by a multi-spinner (“KSSP-201” manufactured by Kaijo Co., Ltd.) using a cleaning liquid having the composition shown in Table 4. Using brush scrub cleaning, particles were removed. The cleaning with the cleaning liquid was performed at room temperature for 30 seconds, and then the substrate was rinsed with ultrapure water for 30 seconds and spin-dried to obtain a cleaned substrate.

  Thereafter, the number of particles (particle size of 0.2 μm or more) adhering to the substrate surface was measured using a laser surface inspection apparatus (“LS-6600” manufactured by Hitachi Electronics Engineering Co., Ltd.). The results are shown in Table 4.

From Table 4, according to the semiconductor device substrate cleaning liquid of the present invention, even a substrate with a low-k film that is usually difficult to clean is polished with an anticorrosive-containing CMP slurry (alkaline, containing SiO ₂ particles). It can be seen that it is possible to prevent the contamination of the particles and clean the surface with high cleanliness.

From Tables 1 to 4, according to the semiconductor device substrate cleaning liquid of the present invention, both the Cu film and the Low-k film, CMP slurry containing benzotriazole-based anticorrosive agent (acidic, containing SiO ₂ particles) It can be seen that even after polishing with any slurry of anti-corrosion agent-containing CMP slurry (alkaline, containing SiO ₂ particles), particle contamination can be prevented and cleaning can be performed with high cleanliness. Moreover, it turns out that the rinse time for the substrate cleaning solution for semiconductor devices of the present invention can be shortened as compared with the conventional case.

<Example 19>
(Evaluation of cleanability of metal contamination by scrub cleaning)
An 8-inch silicon substrate with a Cu film was polished for 1 minute with a CMP slurry (acidic, containing SiO ₂ particles) containing a benzotriazole anticorrosive, and then the polishing was terminated without water polishing, and the substrate was removed. After the Cu contamination remains on the polishing pad, an 8-inch silicon substrate with a TEOS (tetraethoxysilane) film is polished for 1 minute with CMP slurry (acidic, SiO ₂ particles) containing a benzotriazole anticorrosive. Then, water polishing was performed for 17 seconds. The substrate with the TEOS film after polishing is subjected to brush scrub cleaning using a PVA brush with a multi-spinner (“KSSP-201” manufactured by Kaijo Co., Ltd.) using the cleaning liquid shown in Table 5 to remove metal contamination. Removed. The cleaning with the cleaning liquid was performed at room temperature for 30 seconds, and then the substrate was rinsed with ultrapure water for 60 seconds and spin-dried to obtain a cleaned substrate.

  Residual contaminating metals (Fe, Cu) on this substrate were analyzed by the following method, and the results are shown in Table 5.

(Analyzing method for residual contaminated metals)
The metal on the surface of the substrate was recovered by treating the substrate with an aqueous solution containing 0.1% by weight of hydrofluoric acid and 1% by weight of hydrogen peroxide, and the inductively coupled plasma mass spectrometer (ICP-MS) was used to recover the metal. The amount of metal was measured and converted to a metal concentration (× 10 ¹⁰ atoms / cm ² ) on the substrate surface.

  From Table 5, it can be seen that the semiconductor device substrate cleaning liquid of the present invention can prevent metal contamination and can be cleaned with high cleanliness.

<Example 20 and Comparative Example 7>
(Cu film etching rate evaluation)
An 8-inch silicon substrate piece (1.5 cm × 2 cm) with a Cu film was immersed in the cleaning liquid shown in Table 6 for 3 hours. The Cu concentration (ppb) of the cleaning liquid after immersion was measured using an inductively coupled plasma mass spectrometer (ICP-MS), and the Cu etching rate (nm / min) of the cleaning liquid was calculated by the following formula.
Cu etching rate (nm / min) = C × L / G / S / 100 / H
C: Cu concentration (ppb) of the cleaning solution
L: Amount of cleaning liquid (cm ³ )
G: Cu density (8.95 g / cm ³ )
S: Area of the Cu substrate piece (cm ² )
H: Immersion time (180 min)

  From Table 6, it can be seen that the substrate cleaning solution for semiconductor devices of the present invention has a very low Cu etching rate, and can be cleaned highly clean while preventing corrosion of metal wiring on the substrate.

  From the above results, it is clear that the cleaning liquid of the present invention is excellent in removal of fine particles (particles) after being polished with a slurry for CMP containing an anticorrosive agent, and is excellent in cleaning properties by rinsing for a short time. . In addition, it is clear that the excellent cleaning effect is similarly exhibited in terms of metal contamination removability and metal wiring corrosion prevention.

Claims (28)

A semiconductor device comprising a semiconductor device substrate cleaning liquid comprising the following components (a), (b), (c), and (d), and having a pH of 1.5 or more and less than 6.5: Substrate cleaning solution.
Component (a): Organic acid Component (b): Organic alkali component Component (c): Surfactant Component (d): Water   2. The semiconductor device substrate cleaning solution according to claim 1, wherein the semiconductor device substrate has a metal wiring on a surface thereof.   3. The semiconductor device substrate cleaning solution according to claim 1, wherein the semiconductor device substrate has a low dielectric constant insulating film on a surface thereof.   4. The substrate cleaning solution for a semiconductor device according to any one of claims 1 to 3, wherein the component (a) is an organic compound having 1 to 10 carbon atoms having at least one carboxyl group.   5. The component (a) according to claim 4, wherein the component (a) is at least one organic acid selected from the group consisting of acetic acid, propionic acid, succinic acid, succinic acid, malonic acid, citric acid, tartaric acid, and malic acid. Substrate cleaning solution for semiconductor devices. 6. The substrate cleaning liquid for a semiconductor device according to claim 1, wherein the component (b) is represented by the following general formula (I).
(R ¹ ) ₄ N ⁺ OH ⁻ (I)
(However, R ¹ represents a hydrogen atom, a hydroxyl group, an alkoxy group, or an alkyl group which may be substituted with a halogen, and all four R ^{1 s} may be the same or different from each other. (Except when all are hydrogen atoms at the same time.)   7. The semiconductor device substrate according to claim 6, wherein the component (b) is a quaternary ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms and / or a hydroxyalkyl group having 1 to 4 carbon atoms. Cleaning liquid.   8. The semiconductor device substrate cleaning liquid according to claim 1, wherein the component (c) is an anionic surfactant.   9. The anionic surfactant according to claim 8, wherein the anionic surfactant is an alkyl sulfonic acid and a salt thereof, an alkyl benzene sulfonic acid and a salt thereof, an alkyl diphenyl ether disulfonic acid and a salt thereof, an alkyl methyl tauric acid and a salt thereof, an alkyl sulfate ester and a salt thereof, an alkyl A substrate cleaning solution for a semiconductor device, which is at least one anionic surfactant selected from the group consisting of ether sulfates and salts thereof, and sulfosuccinic acid diesters and salts thereof.   The substrate cleaning solution for a semiconductor device according to any one of claims 1 to 9, wherein the content of the component (a) is 0.05 to 10% by weight.   11. The substrate cleaning solution for a semiconductor device according to claim 1, wherein the content of the component (b) is 0.01 to 10% by weight.   12. The substrate cleaning liquid for a semiconductor device according to claim 1, wherein the content of the component (c) is 0.0003 to 0.1% by weight.   The weight ratio [component (a) / component (b)] of the components (a) and (b) is 0.8 or more and 5 or less according to any one of claims 1 to 12. Substrate cleaning solution for semiconductor devices.   14. The weight ratio [component (c) / component (b)] between the components (c) and (b) according to any one of claims 1 to 13 is 0.01 or more and 0.2 or less. A substrate cleaning solution for semiconductor devices. A semiconductor device substrate is cleaned using a liquid containing the following components (a), (b), (c), and (d) and having a pH of 1.5 or more and less than 6.5: A method for cleaning a semiconductor device substrate.
Component (a): Organic acid Component (b): Organic alkali component Component (c): Surfactant Component (d): Water   16. The method of cleaning a semiconductor device substrate according to claim 15, wherein the semiconductor device substrate has a Cu film and a low dielectric constant insulating film on the substrate surface, and the substrate is cleaned after the CMP process.   17. The method for cleaning a substrate for a semiconductor device according to claim 16, wherein the CMP treatment is performed with an abrasive containing an azole anticorrosive.   18. The method for cleaning a substrate for a semiconductor device according to claim 15, wherein the component (a) is an organic compound having 1 to 10 carbon atoms having at least one carboxyl group.   19. The component (a) according to claim 18, wherein the component (a) is at least one organic acid selected from the group consisting of acetic acid, propionic acid, succinic acid, succinic acid, malonic acid, citric acid, tartaric acid, and malic acid. A method for cleaning a substrate for a semiconductor device. 20. The method for cleaning a semiconductor device substrate according to any one of claims 15 to 19, wherein the component (b) is represented by the following general formula (I).
(R ¹ ) ₄ N ⁺ OH ⁻ (I)
(However, R ¹ represents a hydrogen atom, a hydroxyl group, an alkoxy group, or an alkyl group which may be substituted with a halogen, and all four R ^{1 s} may be the same or different from each other. (Except when all are hydrogen atoms at the same time.)   21. The substrate for a semiconductor device according to claim 20, wherein the component (b) is a quaternary ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms and / or a hydroxyalkyl group having 1 to 4 carbon atoms. Cleaning method.   The method for cleaning a substrate for a semiconductor device according to any one of claims 15 to 21, wherein the component (c) is an anionic surfactant.   23. The anionic surfactant according to claim 22, wherein the anionic surfactant is an alkyl sulfonic acid and a salt thereof, an alkyl benzene sulfonic acid and a salt thereof, an alkyl diphenyl ether disulfonic acid and a salt thereof, an alkyl methyl tauric acid and a salt thereof, an alkyl sulfate ester and a salt thereof, an alkyl A method for cleaning a substrate for a semiconductor device, which is at least one anionic surfactant selected from the group consisting of ether sulfates and salts thereof, and sulfosuccinic acid diesters and salts thereof.   The method for cleaning a semiconductor device substrate according to any one of claims 15 to 23, wherein the content of the component (a) is 0.05 to 10% by weight.   25. The method for cleaning a substrate for a semiconductor device according to any one of claims 15 to 24, wherein the content of the component (b) is 0.01 to 10% by weight.   26. The method for cleaning a substrate for a semiconductor device according to any one of claims 15 to 25, wherein the content of the component (c) is 0.0003 to 0.1% by weight.   27. The weight ratio [component (a) / component (b)] between the components (a) and (b) according to any one of claims 15 to 26 is 0.8 or more and 5 or less. A method for cleaning a substrate for a semiconductor device.   28. The weight ratio [component (c) / component (b)] between the components (c) and (b) according to any one of claims 15 to 27 is 0.01 or more and 0.2 or less. A method for cleaning a semiconductor device substrate.