JP2014170927A - Substrate cleaning solvent for semiconductor devices, and method for cleaning semiconductor device substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleaning solvent which is used for a cleaning process after CMP process on a semiconductor device substrate, especially a semiconductor device substrate with a metal wiring line on its surface, and which has an anticorrosion property adequate for the metal wiring line, and can suppress the production of residue, and the attachment of residue to a substrate surface.SOLUTION: A substrate cleaning solvent for semiconductor devices comprises components (A) to (C), and has pH 8-14. The component (A) is a chelating agent. The component (B) is a compound expressed by the general formula (1): NH-R-NH(1), where the coupling group R is an aliphatic hydrocarbon group expressed by the general formula (2): -(CXX)- (2), where n is an integer of 3 or larger, and Xand Xare independently a hydrogen atom or an alkyl group. The component (C) is water.

Description

  The present invention relates to a semiconductor device substrate cleaning liquid and a method for cleaning a semiconductor device substrate, and more particularly, after a chemical mechanical polishing, an effective surface of a semiconductor device substrate having a metal such as Cu exposed on the surface. The present invention relates to a cleaning liquid for cleaning and a cleaning method using the cleaning liquid.

  A semiconductor device substrate is a chemical mechanical polishing (chemical) that uses a polishing slurry made of a water-based slurry containing abrasive fine particles after forming a metal film or interlayer insulating film deposition layer on a silicon wafer substrate. The surface is flattened by Mechanical Polishing (hereinafter referred to as “CMP”), and a new layer is stacked on the flattened surface. In microfabrication of a substrate for a semiconductor device, high-precision flatness in each layer is required, and the importance of planarization by CMP is increasing.

In recent semiconductor device manufacturing processes, wiring (Cu wiring) made of a copper (Cu) film having a low resistance value has been introduced in order to increase the speed and integration of devices.
Cu is suitable for microfabrication because of its good workability, but it is prone to oxidative degradation in water and easily corroded by acid and alkali components, so oxidation and corrosion of Cu wiring are problematic in the CMP process. .
Therefore, conventionally, in CMP of a semiconductor device substrate having Cu wiring, an anticorrosive agent such as benzotriazole, tolyltriazole or a derivative thereof is added to the polishing agent, and this anticorrosive agent is strongly adsorbed on the Cu surface. By forming a protective film, corrosion of Cu wiring in CMP is suppressed.

  The semiconductor device substrate surface after the CMP process has abrasive grains such as colloidal silica used in the CMP process, fine particles derived from the Cu wiring and interlayer insulating film generated by the CMP, and the anticorrosive contained in the slurry. In order to remove these organic residues and the like in large quantities, the semiconductor device substrate after the CMP process is subjected to a cleaning process.

As a cleaning liquid in the cleaning process after CMP, an acidic cleaning liquid and an alkaline cleaning liquid are mainly used. In an acidic aqueous solution, colloidal silica is positively charged, the substrate surface is negatively charged, and an electric attractive force acts, making it difficult to remove the colloidal silica. On the other hand, since OH ⁻ is abundant in the alkaline aqueous solution, both the colloidal silica and the substrate surface are negatively charged, an electric repulsive force works, and the colloidal silica can be easily removed.

On the other hand, Cu is oxidized to Cu ²⁺ in an acidic aqueous solution and dissolved in the liquid, but a passive film such as Cu ₂ O or CuO is formed on the surface in an alkaline aqueous solution. For this reason, the use of an alkaline cleaning solution compared to an acidic cleaning solution can reduce corrosion in the cleaning process to some extent. However, the uniformity of the oxide film on the Cu surface is low, and the cleaning conditions and fine processing of the substrate (Cu Corrosion may occur depending on the wiring conditions.

  Various methods for adding an anticorrosive to the cleaning liquid used in the cleaning process have been proposed in order to prevent Cu oxidation deterioration and corrosion in the cleaning process after CMP of the substrate having the Cu wiring.

  For example, Patent Document 1 describes a cleaning liquid containing a benzotriazole derivative having a specific structure as an anticorrosive as a cleaning liquid used in a cleaning process after CMP. Among them, an organic acid is mainly used. It is described that an acidic cleaning liquid containing an organic alkali component typified by quaternary ammonium hydroxide or amines or a sulfonic acid type anionic surfactant is preferably used as a component.

  Patent Document 2 discloses a cleaning agent containing a solvent and an amine typified by ethylenediamine or alkanolamine, and as a corrosion inhibitor, cyanuric acid; barbituric acid and its derivatives; glucuronic acid; squaric acid; alpha-keto acid; Adenosine and derivatives thereof; purine compounds and derivatives thereof; phosphonic acid derivatives; phenanthroline / ascorbic acid; glycine / ascorbic acid; nicotinamide and derivatives thereof; flavonol and derivatives thereof; anthocyanins and derivatives thereof; A cleaning composition comprising a chemical species selected from the group is described, and these corrosion inhibitors are contained in a basic solution comprising trimethylammonium hydroxide (TMAH) and 1-amino-2-propanol. Example of calculation of corrosion rate of Cu in the case of using by changing the type and content are described.

  In Patent Document 3, as a cleaning agent, a compound selected from the group of ammonium hydroxide and tetraalkylammonium hydroxide, as a chelating agent, a compound selected from the group consisting of ammonium citrate, ammonium oxalate, etc., as a corrosion inhibiting compound In addition, a composition for cleaning a semiconductor workpiece containing a compound selected from the group consisting of acetamidophenol, aminophenol, benzotriazole and the like is disclosed.

JP2012-44118A Special table 2010-527405 gazette Special table 2007-525836 gazette

  Conventionally, an anticorrosive agent used in a cleaning solution used for cleaning after CMP has a problem that it forms a complex with Cu ions eluted from a Cu wiring to generate a residue having adhesion to a substrate. Moreover, when the anticorrosive agent with little residue production | generation known until now is used, the above-mentioned residue is not produced | generated, but there existed a problem that suppression of oxidation deterioration and corrosion of Cu wiring became inadequate.

  Under such circumstances, an object of the present invention is to be used in a cleaning process after a CMP process in a semiconductor device substrate, particularly a semiconductor device substrate having a metal wiring on the surface, and has sufficient anticorrosive properties against the metal wiring, It is an object of the present invention to provide a cleaning liquid and a cleaning method capable of suppressing generation and adhesion of residues to the substrate surface.

  As a result of intensive studies to solve the above problems, the present inventors combined use of a compound having a specific structure with a chelating agent to suppress the occurrence of corrosion without adding a conventional anticorrosive, Further, the inventors have found that the progress of corrosion can be reduced, and therefore the problem of generation of residue and adhesion of residue on the substrate surface by using an anticorrosive agent can be solved, and the present invention has been achieved. That is, the present invention relates to the following inventions.

[1] A substrate cleaning solution for a semiconductor device having a pH of 8 to 14, comprising the following components (A) to (C).
(A) Chelating agent (B) Compound represented by the following general formula (1) NH ₂ —R—NH ₂ (1)
(The linking group R in the general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX ¹ X ² ) _n- (2)
(In the general formula (2), n is an integer of 3 or more, and X ¹ and X ² each independently represent a hydrogen atom or an alkyl group. The n CX ¹ X ² may be the same or different from each other. Good.)
(C) Water

[2] The component (B) is a compound in which n in the general formula (1) is an integer of 3 to 10 and X ¹ and X ² are both hydrogen atoms [1] The board | substrate washing | cleaning liquid for semiconductor devices of description.

[3] The substrate cleaning liquid for a semiconductor device according to [1] or [2], further comprising a component (D) a surfactant.

[4] The semiconductor device substrate cleaning solution according to any one of [1] to [3], further comprising a component (E) pH adjuster.

[5] The substrate cleaning liquid for a semiconductor device according to [3], wherein the component (D) is an anionic surfactant.

[6] The group (D) is composed of alkylsulfonic acid and its salt, alkylbenzenesulfonic acid and its salt, alkyldiphenyl ether disulfonic acid and its salt, alkylmethyl tauric acid and its salt, and sulfosuccinic acid diester and its salt The substrate cleaning liquid for a semiconductor device according to [5], which is at least one selected from the group consisting of:

[7] The component (A) is at least one selected from the group consisting of oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, ethylenediamine, 1,2-diaminopropane, glycine and iminodiacetic acid. The substrate cleaning liquid for a semiconductor device according to any one of [1] to [6], which is characterized.

[8] A method for cleaning a semiconductor device substrate, comprising: cleaning a semiconductor device substrate using the semiconductor device substrate cleaning liquid according to any one of [1] to [7].

[9] The semiconductor device substrate according to [8], wherein the substrate has a Cu wiring and a low dielectric constant insulating film on the substrate surface, and is a substrate after chemical mechanical polishing. A method for cleaning a substrate for a semiconductor device.

  By using the semiconductor device substrate cleaning solution of the present invention, in the semiconductor device substrate cleaning process after the CMP process, the corrosion of metal wiring is prevented and the generation of residues and the adhesion of residues to the substrate surface are suppressed. Efficient cleaning.

It is a SEM photograph of the pattern substrate after being immersed in the cleaning liquid (dilution liquid) of Example 1 for 30 minutes. It is a SEM photograph of the pattern substrate after being immersed in the cleaning liquid (dilution liquid) of Example 2 for 30 minutes. It is a SEM photograph of the pattern substrate after being immersed in the cleaning liquid (dilution liquid) of Example 3 for 30 minutes. It is a SEM photograph of the pattern substrate after being immersed in the washing | cleaning liquid (dilution liquid) of Example 4 for 30 minutes. It is a SEM photograph of the pattern substrate after being immersed in the washing | cleaning liquid (dilution liquid) of the comparative example 1 for 30 minutes. It is a SEM photograph of the pattern substrate after being immersed in the washing | cleaning liquid (dilution liquid) of the comparative example 2 for 30 minutes. It is a SEM photograph of a pattern board after being immersed in a washing liquid (dilution liquid) of comparative example 3 for 30 minutes. It is a SEM photograph of the pattern substrate after being immersed in the washing | cleaning liquid (dilution liquid) of the comparative example 4 for 30 minutes.

  Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

[Substrate cleaning solution for semiconductor devices]
The substrate cleaning solution for semiconductor devices of the present invention (hereinafter sometimes referred to as “the cleaning solution of the present invention”) is used for cleaning a substrate for semiconductor devices, preferably a chemical mechanical polishing (CMP) step in semiconductor device manufacturing. A cleaning liquid used in a semiconductor device substrate cleaning step performed later, wherein the cleaning liquid contains the following components (A) to (C) as essential components and has a pH of 8 to 14: .
(A) Chelating agent (B) Compound represented by the following general formula (1) NH ₂ —R—NH ₂ (1)
(The linking group R in the general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX ¹ X ² ) _n- (2)
(In the general formula (2), n is an integer of 3 or more, and X ¹ and X ² each independently represent a hydrogen atom or an alkyl group. The n CX ¹ X ² may be the same or different from each other. Good.)
(C) Water

  In this invention, a component (B) functions as an anticorrosive agent by using the compound of the said component (B) with a component (A) chelating agent, and can improve the anticorrosion performance of a washing | cleaning liquid. The details of the mechanism of action are not clear, but the following is presumed.

  For example, in order for an anticorrosive to exhibit anticorrosion performance with respect to copper, generally, a film of a copper-anticorrosive complex is formed on the wiring surface, and the water solubility of the film is required to be low. However, when the solubility of the copper-corrosion inhibitor complex is too low, it cannot be removed in the washing step, and there is a problem that it remains as a crystal or an organic residue on the copper wiring.

Since the compound represented by the general formula (1) of the component (B) in the present invention has two amino groups in the molecule, the two amino groups each coordinate to copper to form a copper complex. . Here, it is presumed that due to the difference in water solubility of the formed copper complex, this compound exhibits different functions such as exhibiting the ability as a chelating agent and the ability as a corrosion inhibitor.
Based on this assumption, ethylenediamine (that is, the structural formula represented by the general formula (1) widely used in conventional detergents is used, and in the case where R as a cross-linking group is —CH ₂ CH ₂ — (that is, In the general formula (2), n is 2, and X ¹ and X ² are hydrogen atoms)) acts as a chelating agent. In the invention, it has been found that the bridging group R is sometimes referred to as "linking group R"), which is related to the water solubility of the complex.
That is, when the linking group R itself has low hydrophobicity, the formed copper complex has high water solubility, and it is assumed that the compound functions as a chelating agent. On the other hand, when the hydrophobicity of the linking group R itself is high, the water solubility of the formed copper complex is reduced, so that this complex covers the copper surface, and the compound is presumed to function as an anticorrosive.

Moreover, although the distance between two amino groups is adjusted with the kind of coupling group R, when the coupling group R is too short, copper wiring will be corroded. On the other hand, when the linking group R is too long, a large amount of the compound remains on the copper surface, so that a sufficient cleaning effect is not exhibited.
Therefore, in order for the compound represented by the general formula (1) to achieve both anticorrosion and detergency, it is preferable to select a cross-linked structure that can keep the distance between two amino groups at an appropriate length. It is done.
Furthermore, since the chelating agent is also present as the component (A) in the cleaning liquid of the present invention, the compound of the component (B) exhibiting an appropriate anticorrosive effect is selected in consideration of the dissolving action of copper by the chelating agent. It is considered preferable to do so.

  Therefore, in the present invention, as the component (B), a compound in which the linking group R in the general formula (1) is an aliphatic hydrocarbon group represented by the general formula (2) is used. Coexistence of the chelating agent of (A) and the compound of component (B) makes it possible to achieve both sufficient cleaning properties and sufficient anticorrosion properties for metal wiring, and suppress the generation of residues and the adhesion of residues to the substrate surface. Make it possible.

<PH>
The cleaning liquid of the present invention has a pH of 8-14. When the pH of the cleaning liquid is 8 or more, the zeta potential of colloidal silica or the like in the liquid is reduced, and the removal of fine particles can be facilitated by increasing the electrical repulsion with the substrate, and The removed fine particles can be prevented from reattaching to the surface of the substrate to be cleaned.

  Here, in order to further reduce the zeta potential, the cleaning liquid of the present invention preferably has a pH of 9 or more, and more preferably has a pH of 10 or more. The upper limit of the pH of the cleaning liquid of the present invention is preferably 13 or less.

  In addition, pH in the washing | cleaning liquid of this invention can be adjusted to the above-mentioned pH range with the addition amount etc. of the below-mentioned component (E) pH adjuster and another component.

  Hereinafter, each component contained in the cleaning liquid of the present invention will be described in detail together with its action.

<Component (A): Chelating agent>
The component (A) chelating agent contained in the cleaning liquid of the present invention is insoluble in copper and impurity metals contained in the metal wiring on the surface of the substrate and in the anticorrosive agent present in the barrier slurry used in the CMP process and copper. It has a function of dissolving and removing metal complexes and alkali metals such as sodium and potassium by chelating action.

  As the chelating agent, organic acids having the above action, amines and salts thereof or derivatives thereof can be used, one kind may be used alone, or two or more kinds may be used in combination at an arbitrary ratio. Also good.

As the component (A), particularly a group consisting of oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, ethylenediamine, 1,2-diaminopropane, ethylenediaminetetraacetic acid, glycine, aspartic acid, iminodiacetic acid, alanine and β-alanine It is preferably at least one selected from the group consisting of Moreover, these salts can also be used suitably.
Among these, it consists of oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, ethylenediamine, 1,2-diaminopropane, glycine and iminodiacetic acid in terms of chelate effect strength, quality stability and availability. At least one selected from the group can be preferably used, and in particular, at least one selected from the group consisting of oxalic acid, citric acid, tartaric acid, picolinic acid, ethylenediamine, 1,2-diaminopropane, glycine and iminodiacetic acid. Species can be suitably used.

In addition, the component (A) chelating agent contained in the washing | cleaning liquid of this invention remove | excludes the compound represented by the compound represented by following General formula (1).
NH ₂ —R—NH ₂ (1)
(The linking group R in the general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX ¹ X ² ) _n- (2)
(In the general formula (2), n is an integer of 3 or more, and X ¹ and X ² each independently represent a hydrogen atom or an alkyl group. The n CX ¹ X ² may be the same or different from each other. Good.)

<Component (B): Compound represented by Formula (1)>
The component (B) contained in the cleaning liquid of the present invention is a compound represented by the following general formula (1), but this component (B) is a fat whose linking group R is represented by the following general formula (2). By being a group hydrocarbon group, it has a low hydrophilicity and functions as an anticorrosive agent mainly exhibiting a Cu corrosion inhibition effect.
(B) Compound represented by the following general formula (1) NH ₂ —R—NH ₂ (1)
(The linking group R in the general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX ¹ X ² ) _n- (2)
(In the general formula (2), n is an integer of 3 or more, and X ¹ and X ² each independently represent a hydrogen atom or an alkyl group. The n CX ¹ X ² may be the same or different from each other. Good.)

In the general formula (2), the alkyl group represented by X ¹ and X ² may be linear, branched or cyclic, but a linear chain having 1 to 12 carbon atoms. Alkyl groups are preferred. Moreover, n is an integer greater than or equal to 3, Preferably n is an integer of 3-10, More preferably, n is an integer of 3-8, Most preferably, n is an integer of 3-6.

When the number of carbon atoms in the alkyl group of X ¹ and X ² is too large, or when n is too large, the water solubility is lowered and the component (B) is precipitated, so that the cleaning effect cannot be exhibited. Therefore, in the general formula (2), X ¹ and X ² are preferably both hydrogen atoms, n is more preferably 3 to 8, and n is particularly preferably 3 to 6. .

  Specific examples of the compound represented by the general formula (1) include 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, 8-Diaminooctane is a preferred example.

  Among these, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane are preferably used as the component (B) from the viewpoint of stability of quality and availability.

  As the component (B), one type of the compound represented by the general formula (1) may be used alone, or two or more types may be used in combination at any ratio.

<Ingredient (C): Water>
As the component (C) water contained in the cleaning liquid of the present invention, it is preferable to use deionized water or ultrapure water in which impurities are reduced as much as possible.

<Component (D): Surfactant>
The cleaning liquid of the present invention preferably further contains a component (D) surfactant in addition to the components (A) to (C) for the following reasons.
When a hydrophobic material is used for the interlayer insulating film, cleaning becomes difficult with a cleaning liquid having a water-based composition. The surfactant of component (D) has an action of improving the affinity between the hydrophobic substrate surface and the cleaning liquid. By adding the surfactant of the component (D) to the cleaning liquid of the present invention to improve the affinity with the substrate surface, the cleaning liquid can also act on particles existing on the substrate, When cleaning highly hydrophobic substrate surfaces that can contribute to the removal of residues, the cleaning solution that does not contain a surfactant does not have a sufficient cleaning effect because the affinity between the cleaning solution and the substrate surface is low. There is a risk of becoming.

  There is no restriction | limiting in particular as surfactant of a component (D), Any of anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.

  As the surfactant of component (D) that can be suitably used in the cleaning liquid of the present invention, there is an anionic surfactant. Examples of anionic surfactants include alkyl sulfonic acids and salts thereof, alkyl benzene sulfonic acids and salts thereof, alkyl diphenyl ether disulfonic acids and salts thereof, alkyl methyl tauric acids and salts thereof, and sulfosuccinic acid diesters and salts thereof. Particularly preferred sulfonic acid type anionic surfactants include dodecylbenzenesulfonic acid (DBS), dodecanesulfonic acid, and alkali metal salts thereof. Among these, dodecylbenzenesulfonic acid and its alkali metal salt are particularly preferable in terms of quality stability and availability.

Another example of the anionic surfactant is a carboxylic acid type anionic surfactant. The carboxylic acid type anionic surfactant is an anionic surfactant containing a carboxyl group in the molecule, and among them, a compound represented by the following general formula (4) is preferable.
R ² —O— (AO) _a — (CH ₂ ) _b —COOH (4)

In the general formula (4), ^{R 2} is an alkyl group of straight or branched chain, the number of carbon atoms is 8-15, preferably 10-13. AO is an oxyethylene group and / or oxypropylene group, and a is 3 to 30, preferably 4 to 20, and more preferably 4.5 to 10. B is 1 to 6, preferably 1 to 3.

  Specific examples of the carboxylic acid type anionic surfactant represented by the general formula (4) include polyoxyethylene lauryl ether acetic acid, polyoxyethylene tridecyl ether acetic acid, polyoxyethylene alkyl ether acetic acid and the like. Can do.

  These surfactants such as anionic surfactants may be used alone or in combination of two or more at any ratio.

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

<Component (E): pH adjuster>
In the cleaning liquid of the present invention, in addition to the above components (A) to (C), it is preferable to further contain a pH adjuster as the component (E). As a pH adjuster, if it is a component which can be adjusted to the target pH, it will not specifically limit, An acid compound or an alkali compound can be used.

  Preferable examples of the acid compound include inorganic acids such as sulfuric acid and nitric acid and salts thereof, or organic acids such as acetic acid, lactic acid, oxalic acid, tartaric acid and citric acid and salts thereof.

  As the alkali compound, an organic alkali compound and an inorganic alkali compound can be used. Examples of the organic alkali compound include quaternary ammonium such as organic quaternary ammonium hydroxide and salts thereof, trimethylamine, Suitable examples include salts of alkylamines such as triethylamine and derivatives thereof, and alkanolamines such as monoethanolamine and derivatives thereof.

Examples of the organic quaternary ammonium hydroxide as the organic alkali compound include those represented by the following general formula (3).
(R ¹ ) ₄ N ⁺ OH ⁻ (3)
(In the general formula (3), R ¹ represents 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. .)

As the organic quaternary ammonium hydroxide, in the above general formula (3), R ¹ may be a linear or branched chain which may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or a halogen. What is a C1-C4 alkyl group, especially a linear C1-C4 alkyl group and / or a linear C1-C4 hydroxyalkyl group is preferable. Examples of the alkyl group for R ¹ include lower alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. As a hydroxyalkyl group, C1-C4 lower hydroxyalkyl groups, such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, are mentioned, for example.

  Specific examples of the organic quaternary ammonium hydroxide include bis (2-hydroxyethyl) dimethylammonium hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and methyltriethyl. Ammonium hydroxide, trimethyl (hydroxyethyl) ammonium hydroxide (common name: choline), triethyl (hydroxyethyl) ammonium hydroxide, and the like can be given.

  Among the organic quaternary ammonium hydroxides described above, bis (2-hydroxyethyl) dimethylammonium hydroxide, trimethyl (hydroxy) are used for reasons such as cleaning effect, low metal residue, economy, and stability of the cleaning solution. Particularly preferred are ethyl) ammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like.

  An inorganic alkali compound is an inorganic compound containing an alkali or mainly an alkali metal or an alkaline earth metal and a salt thereof among those exhibiting alkalinity in an aqueous solution, and among these, a hydroxide containing an alkali metal as an inorganic alkali. It is preferable to use a product in terms of safety and cost. Specific examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.

  When these acid compounds or alkali compounds are used for the purpose of adjusting the pH of the cleaning liquid of the present invention, one kind may be used alone, or two or more kinds may be used in combination at an arbitrary ratio. Also good.

  Particularly preferred acid compounds or alkali compounds include organic acids such as acetic acid, oxalic acid, tartaric acid and citric acid and salts thereof, inorganic alkali compounds such as sodium hydroxide and potassium hydroxide and salts thereof, tetramethylammonium hydroxide, tetraethyl Examples thereof include salts of quaternary ammonium such as ammonium hydroxide and choline and derivatives thereof.

<Other ingredients>
The cleaning liquid of the present invention may contain components other than the above components (A) to (E) in any ratio within a range not impairing the performance.

Examples of other components include the following.
Benzotriazole, 3-aminotriazole, N (R ³ ) ₃ (R ³ may be the same or different from each other, and may be the same or different from each other) Nitrogen-containing organic compounds such as ammonia, urea and thiourea; water-soluble polymers such as polyethylene glycol and polyvinyl alcohol; alkyl alcohol compounds such as R ⁴ OH (R ⁴ is an alkyl group having 1 to ⁴ carbon atoms); Agent: Hydrogen, Argon, Nitrogen, Carbon dioxide, Ammonia, etc. Dissolved gas: Acceleration of etching that can be expected to remove polymer attached firmly after dry etching such as hydrofluoric acid, ammonium fluoride, BHF (buffered hydrofluoric acid) Agents: Ascorbic acid, gallic acid, hydrazine and other reducing agents: acids such as hydrogen peroxide, ozone and oxygen Agent: monoethanolamine: amino acids such as arginine.
Moreover, components other than water, such as ethanol, may be included as a solvent.

<Manufacturing method of cleaning liquid>
The method for producing the cleaning liquid of the present invention is not particularly limited, and may be a conventionally known method. For example, constituents of the cleaning liquid (components (A) to (C), and in addition to these, preferably component (D) and (Or component (E), and other components used as necessary)). Usually, component (A) to (B), preferably component (D) and / or component (E), and other components used as needed are added to component (C) water as a solvent. Manufactured by.

  The mixing order is arbitrary as long as there is no particular problem such as reaction or precipitation, and any two or more components among the components of the cleaning liquid are blended in advance, and then the remaining components are mixed. You may mix and a component may be mixed at once.

  The cleaning liquid of the present invention can be manufactured by adjusting the concentration of each component so that the concentration is suitable for cleaning. However, from the viewpoint of reducing the cost during transportation and storage, each component is highly concentrated. In many cases, it is diluted with water after it has been produced (hereinafter sometimes referred to as “cleaning stock solution”).

  The concentration of each component in the washing stock solution is not particularly limited, but it is preferably components (A) to (C), and in addition to these, preferably component (D) and / or component (E), and used as necessary. It is preferable that other components to be obtained and these reactants are in a range in which they are not separated or precipitated in the washing stock solution.

  Specifically, the concentration range of the cleaning stock solution is 0.01 to 10% by mass for component (A), 0.01 to 10% by mass for component (B), and 0.01 to 10% for component (D). The concentration range is preferably 10% by mass.

  When the concentration is within the above-mentioned range, separation of contained components hardly occurs during transportation and storage, and it can be suitably used as a cleaning solution having a concentration suitable for easy cleaning by adding component (C) water. it can.

The concentration of each component of the cleaning liquid when cleaning the semiconductor device substrate is appropriately determined according to the semiconductor device substrate to be cleaned.
The cleaning solution used for cleaning may be manufactured by diluting the cleaning stock solution so that the concentration of each component is appropriate with respect to the semiconductor device substrate to be cleaned. You may adjust and manufacture each component directly.

<Concentration of each component of cleaning liquid>
The concentration of each component of the cleaning liquid of the present invention, that is, the concentration of each component in the cleaning liquid of the present invention when used as a cleaning liquid is as follows.

  The concentration of the component (A) in the cleaning liquid is preferably 0.0001 to 1% by mass, more preferably 0.001 to 1% by mass. If the concentration of the component (A) is too low, the removal of contamination of the substrate for semiconductor devices may be insufficient. If the concentration exceeds 1% by mass, no further effect can be obtained, and the cost of the cleaning liquid Will take more. Further, when the concentration of the component (A) exceeds 1% by mass, a problem such as corrosion of metal wiring such as Cu may be caused.

  The concentration of the component (B) in the cleaning liquid is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.5% by mass. When the concentration of the component (B) is less than 0.001% by mass, the anticorrosion property is not sufficiently exhibited. If the concentration of the component (B) exceeds 1% by mass, a large amount of the insoluble complex of the component (B) and Cu may be generated as a residue, and the substrate surface may not be cleaned. Moreover, there is a possibility of causing problems such as corrosion of metal wiring such as Cu.

  In the cleaning liquid of the present invention, the component (A) and the component (B) are used in order to more effectively exhibit the effects of anticorrosion and detergency by coexisting the chelating agent of the component (A) and the component (B). ) Is preferably used in a mass ratio of component (A): component (B) = 1: 0.01 to 100, particularly 1: 0.1 to 50.

  The concentration of the component (D) surfactant in the cleaning liquid is preferably 0.0001 to 1% by mass, more preferably 0.0003 to 0.1% by mass, and still more preferably 0.001 to 0.1% by mass. It is. If the concentration of the component (D) is too low, the effect of adding the surfactant may be insufficient, but if the concentration of the component (D) is too high, no further effect can be obtained and excessive foaming occurs. May occur or the load of waste liquid treatment may increase.

<Cleaning method of semiconductor device substrate>
The method for cleaning a semiconductor device substrate of the present invention (hereinafter sometimes referred to as “the cleaning method of the present invention”) is as follows.

  The cleaning method of the present invention is carried out by a method in which the above-described cleaning liquid of the present invention is brought into direct contact with a semiconductor device substrate.

Examples of the semiconductor device substrate to be cleaned include various semiconductor device substrates such as a semiconductor, glass, metal, ceramics, resin, magnetic material, and superconductor.
When the cleaning liquid of the present invention is used, cleaning can be performed with a short time rinse, and therefore, it is particularly suitable for a substrate for a semiconductor device having a metal or a metal compound on the surface as a wiring, and particularly a semiconductor device having a Cu wiring on the surface. It is suitable for a substrate for use.

  Here, examples of the metal used for the semiconductor device substrate include W, Cu, Ti, Cr, Co, Zr, Hf, Mo, Ru, Au, Pt, and Ag. Examples thereof include nitrides, oxides, silicides, and the like of these metals. In these, Cu and the compound containing these are suitable washing | cleaning objects.

Further, the cleaning method of the present invention is suitable for a semiconductor device substrate having a low dielectric constant insulating material because the cleaning effect is high even for a low dielectric constant insulating material having strong hydrophobicity.
Examples of such a low dielectric constant material include organic polymer materials such as Polyimide, BCB (Benzocyclobutylene), Flare (Honeywell), SiLK (Dow Chemical), and inorganic polymer materials such as FSG (Fluorinated silicate glass) and BLACK. Examples thereof include SiOC-based materials such as DIAMOND (Applied Materials) and Aurora (Japan ASM).

  Here, the cleaning method of the present invention is particularly preferably applied when the substrate for a semiconductor device has Cu wiring and a low dielectric constant insulating film on the substrate surface and the substrate is cleaned after the CMP process.

In the CMP process, for example, polishing is performed by rubbing the substrate against the pad using an abrasive.
The abrasive includes abrasive particles such as colloidal silica (SiO ₂ ), fumed silica (SiO ₂ ), alumina (Al ₂ O ₃ ), and ceria (CeO ₂ ). Such abrasive particles are a major cause of particulate contamination of the substrate for semiconductor devices. However, the cleaning liquid of the present invention has an action of removing the fine particles adhering to the substrate and dispersing them in the cleaning liquid and preventing re-adhesion. Therefore, it has a high effect on removing fine particle contamination.

Further, the abrasive may contain additives other than abrasive particles such as an oxidizing agent and a dispersant.
In particular, in CMP polishing on a semiconductor device substrate having a Cu film as a metal wiring on its surface, an anticorrosive agent is often added because the Cu film tends to corrode.
As the anticorrosive, an azole anticorrosive having a high anticorrosive effect is preferably used. More specifically, examples of the hetero atom containing a heterocyclic ring containing only a nitrogen atom include a diazole type, a triazole type, and a tetrazole type, and those containing a heterocyclic ring of a nitrogen atom and an oxygen atom, An oxazole type and an oxadiazole type are mentioned, As a thing containing the heterocyclic ring of a nitrogen atom and a sulfur atom, a thiazole type, an isothiazole type, and a thiadiazole type are mentioned. Among these, a benzotriazole (BTA) anticorrosive having an excellent anticorrosive effect is particularly preferable.

When the cleaning liquid of the present invention is applied to the surface of a substrate after being polished with an abrasive containing the above-described anticorrosive, it is excellent in that the contamination derived from the anticorrosive can be removed extremely effectively.
That is, when these anticorrosives are present in the abrasive, the corrosion of the surface of the Cu film is suppressed, but on the other hand, 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 the insoluble precipitates described above, and can remove the surfactant that tends to remain on the metal surface with a short rinse, thereby improving the throughput. It is.

  Therefore, the cleaning method of the present invention is suitable for cleaning a substrate for a semiconductor device after performing CMP treatment on the surface on which the Cu film and the low dielectric constant insulating film coexist, and in particular, using a polishing agent containing an azole anticorrosive agent for CMP. It is suitable for cleaning the treated substrate.

  As described above, 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 semiconductor device substrate. A cleaning liquid having a suitable component concentration is selected according to the type of the semiconductor device substrate to be cleaned.

  Examples of the method of contacting the cleaning liquid with the substrate include 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 a high speed while flowing the cleaning liquid from the nozzle, and the liquid is sprayed on the substrate. The spray type etc. which wash is mentioned. As an apparatus for performing such cleaning, for example, a batch cleaning apparatus that simultaneously cleans a plurality of substrates accommodated in a cassette, a single wafer cleaning apparatus that mounts and cleans a single substrate in a holder, and the like There is.

  The cleaning liquid of the present invention can be applied to any of the above-described methods, but is preferably used for spin-type or spray-type cleaning because it allows more efficient decontamination in a short time. In this case, if the present invention is applied to a single wafer cleaning apparatus in which a reduction in cleaning time and a reduction in the amount of cleaning liquid used are desired, the above problem is solved, which is preferable.

  In addition, the cleaning method of the present invention can remove contamination caused by fine particles adhering to the substrate when used in combination with a cleaning method based on physical force, particularly scrub cleaning using a cleaning brush or ultrasonic cleaning with a frequency of 0.5 MHz or higher. This is preferable because it further improves and 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, you may perform the washing | cleaning by water before and / or after the washing | cleaning by the washing | cleaning method of this invention.

  In the cleaning method of the present invention, the temperature of the cleaning liquid is usually room temperature, but may be heated to about 40 to 70 ° C. within a range not impairing the performance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is changed.

[Example 1]
<Preparation of washing solution stock solution>
As component (A) chelating agent, 0.5% by mass of citric acid, as compound of component (B), 0.5% by mass of 1,3-diaminopropane, water of component (C), component (D) interface 0.5% by mass of dodecylbenzenesulfonic acid (DBS) as an activator, and 5% by mass of bis (2-hydroxyethyl) dimethylammonium hydroxide (AH212, Yokkaichi Synthesis Co., Ltd.) as a component (E) pH adjuster ) Were mixed to prepare a stock solution of the semiconductor device substrate cleaning liquid of Example 1 having the composition shown in Table 1A. Subsequently, the washing | cleaning liquid (dilution liquid) of Example 1 was prepared by adding water to this washing | cleaning-solution stock solution and diluting 40 times.

<PH measurement>
While the cleaning liquid diluted 40 times was stirred using a magnetic stirrer, the pH was measured with a pH meter (Horiba, Ltd. “D-24”). The measurement sample kept the liquid temperature at 25 degreeC in the thermostat. The measurement results are shown in Table 1A.

<Evaluation of corrosion resistance>
A pattern substrate (SEMATECH 854) including a comb pattern of Cu wiring of line / space = 180 nm / 180 nm was prepared by cutting it into 1 cm square, and immersed in a cleaning solution diluted 40 times at 40 ° C. for 30 minutes. The substrate after immersion was taken out and immediately washed with ultrapure water and dried by air blow.
The substrate after the immersion was observed with an electrolytic emission scanning electron microscope (“JSM-6320F” manufactured by JEOL Ltd.) to evaluate the corrosion resistance. In addition, anticorrosion was judged by the progress of the corrosion of the Cu wiring pattern, and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1A.
○: Corrosion was not confirmed.
X: Corrosion was confirmed.
Moreover, the SEM photograph of the pattern board | substrate after being immersed in FIG. 1 for 30 minutes in the washing | cleaning liquid (dilution liquid) of Example 1 is shown.

<Measurement of etch rate>
A copper seed substrate (commercially available) formed by PVD (physical vapor deposition) was cut into 2.5 cm square. The copper film thickness (nm) of the cut substrate was measured with a fluorescent X-ray analyzer (XRF) (JEOL Co., Ltd. RIX-3000). The copper substrate was immersed in the cleaning solution diluted 40 times as described above for 120 minutes. After rinsing the substrate after immersion with ultrapure water and drying with air blow. Again, the film thickness (nm) of copper was measured by XRF. The etch rate was calculated by the following equation (5).
((Film thickness before immersion (nm)) − (film thickness after immersion (nm))) / 120 minutes (5)
The evaluation results are shown in Table 1A.

<Cleaning experiment>
200 mL of 0.1% by mass benzotriazole aqueous solution was poured onto a silicon substrate (Advantech Co., Ltd.) on which a Cu film was formed by PVD method, and then 0.01% by mass colloidal silica aqueous solution (Fuso Chemical Co., Ltd. “ PL-10H ") was poured in, then 1 L of ultrapure water was poured, and the substrate was washed with" Multispinner KSSP-201 "(Caijo Co., Ltd.) using the washing solution diluted 40 times as described above. The number of defects of 0.23 μm or more was examined by a wafer surface inspection device “LS-6600” (Hitachi High-Tech Co., Ltd.). The evaluation results are shown in Table 1A.

[Example 2]
As component (A) chelating agent, 0.05% by mass of ethylenediamine, as component (B), 0.5% by mass of 1,3-diaminopropane, water of component (C), as component (D) surfactant As a pH adjuster, 0.5% by mass of dodecylbenzenesulfonic acid (DBS), 8% by mass of tetraethylammonium hydroxide (TEAH) are mixed, and the composition of Example 2 having the composition shown in Table 1A is mixed. A stock solution of a substrate cleaning solution for a semiconductor device was prepared. Subsequently, the washing | cleaning liquid (dilution liquid) of Example 2 was prepared by adding water to this washing | cleaning-solution stock solution and diluting 40 times.
The cleaning liquid was evaluated in the same manner as in Example 1 and the results are shown in Table 1A.
Moreover, the SEM photograph of the pattern board | substrate after being immersed in the washing | cleaning liquid (dilution liquid) of Example 2 for 30 minutes in FIG.

[Example 3]
As component (A) chelating agent, 0.5% by mass of citric acid, as component (B), 0.5% by mass of 1,3-diaminobutane, water of component (C), component (D) surfactant As an example of the composition shown in Table 1A, 0.5% by mass of dodecylbenzenesulfonic acid (DBS) and 8% by mass of tetraethylammonium hydroxide (TEAH) as a component (E) pH adjuster were mixed. A stock solution of the semiconductor device substrate cleaning solution 3 was prepared. Subsequently, the washing | cleaning liquid (dilution liquid) of Example 3 was prepared by adding water to this washing | cleaning-solution stock solution and diluting 40 times.
The cleaning liquid was evaluated in the same manner as in Example 1 and the results are shown in Table 1A.
Moreover, the SEM photograph of the pattern board | substrate after being immersed in the washing | cleaning liquid (dilution liquid) of Example 3 for 30 minutes in FIG.

[Example 4]
As component (A) chelating agent, 0.05% by mass of ethylenediamine, as component (B), 0.5% by mass of 1,3-diaminopentane, as component (C) water, as component (D) surfactant As a pH adjuster, 0.5% by mass of dodecylbenzenesulfonic acid (DBS) and 8% by mass of tetraethylammonium hydroxide (TEAH) were mixed, and Example 4 having the composition shown in Table 1A was mixed. A stock solution of a substrate cleaning solution for a semiconductor device was prepared. Subsequently, the washing | cleaning liquid (dilution liquid) of Example 4 was prepared by adding water to this washing | cleaning-solution stock solution and diluting 40 times.
The cleaning liquid was evaluated in the same manner as in Example 1 and the results are shown in Table 1A.
FIG. 4 shows an SEM photograph of the pattern substrate after being immersed in the cleaning liquid (diluent) of Example 4 for 30 minutes.

[Comparative Example 1]
As component (D) surfactant, 0.5% by mass of dodecylbenzenesulfonic acid (DBS), as component (E) pH adjuster, 8% by mass of tetraethylammonium hydroxide (TEAH) and water of component (C) Were mixed to prepare a stock solution of the substrate cleaning liquid for semiconductor devices of Comparative Example 1 having the composition shown in Table 1B. Next, water was added to the cleaning solution stock solution to dilute it 40 times to prepare a cleaning solution (diluted solution) of Comparative Example 1.
The results of evaluating this cleaning solution in the same manner as in Example 1 are shown in Table 1B.
FIG. 5 shows an SEM photograph of the pattern substrate after being immersed in the cleaning liquid (diluent) of Comparative Example 1 for 30 minutes.

[Comparative Example 2]
As component (A) chelating agent, 0.05% by mass of ethylenediamine, component (C) water, as component (D) surfactant, 0.5% by mass of dodecylbenzenesulfonic acid (DBS) and component (E) As a pH adjusting agent, 8% by mass of tetraethylammonium hydroxide (TEAH) was mixed to prepare a stock solution of the semiconductor device substrate cleaning liquid of Comparative Example 2 having the composition shown in Table 1B. Subsequently, the washing | cleaning liquid (dilution liquid) of the comparative example 2 was prepared by adding water to this washing | cleaning-solution stock solution and diluting 40 times.
The results of evaluating this cleaning solution in the same manner as in Example 1 are shown in Table 1B.
Moreover, the SEM photograph of the pattern board | substrate after being immersed in the washing | cleaning liquid (dilution liquid) of the comparative example 2 for 30 minutes in FIG.

[Comparative Example 3]
As component (A) chelating agent, 0.05% by weight of ethylenediamine, water of component (C), as component (D) surfactant, 0.5% by weight of dodecylbenzenesulfonic acid (DBS), component (E) As a pH adjuster, 8% by mass of tetraethylammonium hydroxide (TEAH) and 0.5% by mass of 1,2-diaminopropane were mixed, and the substrate cleaning solution for semiconductor devices of Comparative Example 3 having the composition shown in Table 1B. A stock solution of was prepared. Next, water was added to the cleaning solution stock solution to dilute it 40 times to prepare a cleaning solution (diluted solution) of Comparative Example 3.
The results of evaluating this cleaning solution in the same manner as in Example 1 are shown in Table 1B.
Moreover, the SEM photograph of the pattern board | substrate after being immersed in the washing | cleaning liquid (dilution liquid) of the comparative example 3 for 30 minutes in FIG.

[Comparative Example 4]
As component (B), 0.5% by mass of 1,3-diaminopropane, water of component (C), as component (D) surfactant, 0.5% by mass of dodecylbenzenesulfonic acid (DBS), component (E) As a pH adjuster, 5% by mass of bis (2-hydroxyethyl) dimethylammonium hydroxide (AH212, Yokkaichi Gosei Co., Ltd.) is mixed, and the substrate for semiconductor devices of Comparative Example 4 having the composition shown in Table 1B A stock solution of the cleaning solution was prepared. Next, water was added to the cleaning solution stock solution to dilute it 40 times to prepare a cleaning solution (diluted solution) of Comparative Example 4.
The results of evaluating this cleaning solution in the same manner as in Example 1 are shown in Table 1B.
Moreover, the SEM photograph of the pattern board | substrate after being immersed in the washing | cleaning liquid (dilution liquid) of the comparative example 4 for 30 minutes in FIG.

[Discussion]
In the cleaning liquids of Examples 1 to 4, no diaminoalkane remained on the substrate due to the blending of component (A) and component (B), and no corrosion was observed on the Cu wiring. From these results, in Example 1 to Example 4, the chelating agent having the appropriate strength and amount of the component (A) and the compound of the component (B) showing the appropriate strength of the anticorrosive property are selected. It was confirmed that the effect of the invention was appropriately exhibited. In the cleaning liquids of Examples 1 to 4, a high cleaning effect can be obtained by suppressing dissolution and defects of copper.

On the other hand, in Comparative Example 1, the chelating agent of component (A) and the diaminoalkane of component (B) are not included, and it can be seen that the Cu wiring surface is rough.
In Comparative Example 2, the compound of component (B) is not included, the Cu wiring is dissolved by the action of the chelating agent of component (A), significant corrosion is confirmed, and there are many defects after cleaning.
In Comparative Example 3, as a comparison of the component (B), in the general formula NH _2- (CX ¹ X ² ) _n -NH ₂ , n = 2 and one of X ¹ and X ² is a hydrogen atom and the other However, although 1,2-diaminopropane having a methyl group was used, sufficient corrosion resistance was not exhibited, the copper wiring was significantly corroded, and defects after cleaning were also remarkable.
In Comparative Example 4, the component (A) was not included, and sufficient corrosion resistance was not exhibited, and the copper wiring was significantly corroded.

  From the above results, it is clear that by using the cleaning liquid of the present invention, effective cleaning can be performed without causing corrosion of the Cu wiring, and by preventing corrosion of the surface of the Cu wiring, It is clear that an excellent cleaning effect is achieved.

  The semiconductor device substrate cleaning liquid of the present invention can be efficiently cleaned without causing corrosion on the surface of the semiconductor device substrate, and the water rinsing property is also good. As a cleaning technology for contaminated semiconductor device substrates in the manufacturing process of display devices and display devices, it is very useful industrially.

Claims (9)

A substrate cleaning solution for a semiconductor device having a pH of 8 to 14, comprising the following components (A) to (C).
(A) Chelating agent (B) Compound represented by the following general formula (1) NH ₂ —R—NH ₂ (1)
(The linking group R in the general formula (1) represents an aliphatic hydrocarbon group represented by the following general formula (2).)
-(CX ¹ X ² ) _n- (2)
(In the general formula (2), n is an integer of 3 or more, and X ¹ and X ² each independently represent a hydrogen atom or an alkyl group. The n CX ¹ X ² may be the same or different from each other. Good.)
(C) Water The component (B) is a compound in which n in the general formula (1) is an integer of 3 to 10 and X ¹ and X ² are both hydrogen atoms. Substrate cleaning solution for semiconductor devices.   Furthermore, component (D) surfactant is contained, The board | substrate washing | cleaning liquid for semiconductor devices of Claim 1 or 2 characterized by the above-mentioned.   Furthermore, component (E) pH adjuster is contained, The board | substrate washing | cleaning liquid for semiconductor devices of any one of Claims 1-3 characterized by the above-mentioned.   The substrate cleaning liquid for a semiconductor device according to claim 3, wherein the component (D) is an anionic surfactant.   The component (D) is selected from the group consisting of alkyl sulfonic acids and salts thereof, alkyl benzene sulfonic acids and salts thereof, alkyl diphenyl ether disulfonic acids and salts thereof, alkyl methyl tauric acids and salts thereof, and sulfosuccinic acid diesters and salts thereof. 6. The semiconductor device substrate cleaning liquid according to claim 5, wherein the substrate cleaning liquid is at least one kind.   The component (A) is at least one selected from the group consisting of oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, ethylenediamine, 1,2-diaminopropane, glycine and iminodiacetic acid. The substrate cleaning liquid for a semiconductor device according to any one of claims 1 to 6.   A semiconductor device substrate cleaning method, comprising: cleaning a semiconductor device substrate using the semiconductor device substrate cleaning liquid according to claim 1.   9. The semiconductor device substrate according to claim 8, wherein the substrate for a semiconductor device has a Cu wiring and a low dielectric constant insulating film on the substrate surface, and is a substrate after chemical mechanical polishing. Substrate cleaning method.

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