WO2014123126A1

WO2014123126A1 - Cleaning liquid for substrate for semiconductor devices and method for cleaning substrate for semiconductor devices

Info

Publication number: WO2014123126A1
Application number: PCT/JP2014/052587
Authority: WO
Inventors: 憲原田; 伊藤　篤史; 敏之鈴木
Original assignee: 三菱化学株式会社
Priority date: 2013-02-06
Filing date: 2014-02-04
Publication date: 2014-08-14
Also published as: JP2019208062A; JP2014170927A; TWI648430B; TW201831727A; TW201437432A; JP2018139307A

Abstract

The present invention provides a cleaning liquid which is used in a cleaning process after a CMP process for a substrate for semiconductor devices, in particular, for a substrate for semiconductor devices having a metal wiring line on the surface. This cleaning liquid has sufficient anti-corrosion properties with respect to metal wiring lines, and is capable of suppressing the occurrence of a residue and adhesion of the residue to the substrate surface.

Description

Semiconductor device substrate cleaning liquid and semiconductor device substrate cleaning method

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 abrasive, 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 an alkaline aqueous solution, both the colloidal silica and the substrate surface are negatively charged, and an electric repulsive force acts, making it easy to remove the colloidal silica.

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 agent to the cleaning liquid used in the cleaning process have been proposed in order to prevent oxidation degradation and corrosion of Cu in the cleaning process after CMP of the substrate having such 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, and among them, an organic acid is a main component. It is described that an acidic cleaning solution containing a quaternary ammonium hydroxide, an organic alkali component typified by amines or a sulfonic acid type anionic surfactant is preferably used.

Patent Document 2 discloses a detergent containing a solvent and an amine typified by ethylenediamine and alkanolamine, and as a corrosion inhibitor, cyanuric acid; barbituric acid and derivatives thereof; 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 is described comprising a chemical species selected from the group consisting of these 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 of the food inhibitor is 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, and the like, as a corrosion inhibiting compound A semiconductor workpiece cleaning composition containing a compound selected from the group consisting of acetamidophenol, aminophenol, benzotriazole and the like is disclosed.

Japanese Unexamined Patent Publication No. 2012-44118 Japanese National Table 2010-527405 Japan Special Table 2007-525836

Conventionally, the anticorrosive agent used in the cleaning solution used for cleaning after CMP has a problem that it forms a complex with Cu ions eluted from the Cu wiring to generate a residue having adhesion to the 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. In the component (B), the linking group R in the general formula (1) is an aliphatic hydrocarbon group represented by the general formula (2), n is an integer of 3 to 10, and X ¹ The substrate cleaning solution for a semiconductor device according to the above item 1, wherein X ² is a compound in which both are hydrogen atoms.
3. 3. The substrate cleaning liquid for a semiconductor device according to item 1 or 2, further comprising a component (D) a surfactant.
4). 4. The semiconductor device substrate cleaning solution according to any one of items 1 to 3, further comprising a component (E) pH adjuster.
5. 5. The substrate cleaning solution for a semiconductor device as described in 3 or 4 above, wherein the component (D) is an anionic surfactant.
6). 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 substrate cleaning solution for a semiconductor device according to any one of 3 to 5 above, which is at least one kind.
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. 7. The substrate cleaning solution for a semiconductor device according to any one of 1 to 6 above.
8). 8. A method for cleaning a semiconductor device substrate, comprising: cleaning the semiconductor device substrate using the semiconductor device substrate cleaning liquid according to any one of 1 to 7 above.
9. 9. The semiconductor device substrate according to the item 8, wherein the substrate for a semiconductor device has a Cu wiring and a low dielectric constant insulating film on the surface of the substrate and has been subjected to chemical mechanical polishing. Cleaning method.

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.

FIG. 1 is an SEM drawing (photograph) of a patterned substrate after being immersed in the cleaning liquid (diluent) of Example 1 for 30 minutes. FIG. 2 is an SEM drawing (photograph) of the pattern substrate after being immersed in the cleaning liquid (diluent) of Example 2 for 30 minutes. FIG. 3 is an SEM drawing (photograph) of the pattern substrate after being immersed in the cleaning liquid (diluent) of Example 3 for 30 minutes. FIG. 4 is an SEM drawing (photograph) of the pattern substrate after being immersed in the cleaning liquid (diluent) of Example 4 for 30 minutes. FIG. 5 is an SEM drawing (photograph) of the pattern substrate after being immersed in the cleaning liquid (diluent) of Comparative Example 1 for 30 minutes. FIG. 6 is an SEM drawing (photograph) of the pattern substrate after being immersed in the cleaning liquid (diluent) of Comparative Example 2 for 30 minutes. FIG. 7 is an SEM drawing (photograph) of the pattern substrate after being immersed in the cleaning liquid (dilution liquid) of Comparative Example 3 for 30 minutes. FIG. 8 is an SEM drawing (photograph) of the pattern substrate after being immersed in the cleaning liquid (diluent) of Comparative Example 4 for 30 minutes.

Hereinafter, embodiments of the present invention will be specifically described. However, 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 the present invention, by using the compound of the component (B) together with the component (A) chelating agent, the component (B) functions as an anticorrosive agent, and the anticorrosion performance of the cleaning liquid can be improved. The details of the mechanism of action are not clear, but the following is presumed.

For example, in order for an anticorrosion agent to exhibit anticorrosion performance with respect to copper, it is generally required that a film of a copper-anticorrosive complex is formed on the wiring surface and the water solubility of the film is low. However, when the solubility of the copper-corrosion inhibitor complex is too low, it cannot be removed by the cleaning process, 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 crosslinking 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 is highly water-soluble, and it is estimated 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), the linking group R in the general formula (1) is an aliphatic hydrocarbon group or an aromatic hydrocarbon group represented by the general formula (2). Using a certain compound, the coexistence of the chelating agent of component (A) and the compound of component (B) makes it possible to achieve both sufficient cleaning properties and sufficient anticorrosive properties for metal wiring, and generation of residues and residue on the substrate surface. It is possible to suppress adhesion.

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 lowered, and the electric repulsive force with the substrate is gained, whereby the removal of the fine particles can be facilitated. Furthermore, it is possible to suppress the removed fine particles 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 agent of the present invention comprises an impurity metal such as tungsten contained in the metal wiring on the surface of the substrate, and copper and an anticorrosive agent present in the barrier slurry used in the CMP process. It has an action of dissolving and removing insoluble 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.

Component (A) comprises in particular 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. Moreover, these salts can also be used suitably.

Of these, 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 suitably used, and in particular, at least selected from the group consisting of oxalic acid, citric acid, tartaric acid, picolinic acid, ethylenediamine, 1,2-diaminopropane, glycine and iminodiacetic acid One type can be suitably used.

In addition, the component (A) chelating agent contained in the cleaning agent of the present invention excludes a compound represented by a 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.)

<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.
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 (1), when the linking group R is an aliphatic hydrocarbon group represented by the general formula (2), the alkyl group of X ¹ and X ² may be a straight chain or a branched chain It may be cyclic or cyclic, but is preferably a linear alkyl group having 1 to 12 carbon atoms, and n is an integer of 3 or more, preferably n is an integer of 3 to 10. More preferably, n is an integer of 3 to 8, and particularly preferably, n is an integer of 3 to 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, the component (B) is precipitated, and a sufficient 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, and 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) because of the stability of quality and availability.
As the component (B), one type of compound of the formula (1) may be used alone, or two or more types may be used in combination at an arbitrary 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). When a hydrophobic material is used for the interlayer insulating film, the surfactant is difficult to clean with a cleaning solution 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 a surfactant to improve the affinity with the substrate surface, it is possible to act on the cleaning liquid between particles present on the substrate and contribute to the removal of residues. In particular, when cleaning a highly hydrophobic substrate surface, a cleaning liquid that does not contain a surfactant has a low affinity between the cleaning liquid and the substrate surface, so that the cleaning effect is insufficient.

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 component (D) surfactant 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 above general formula (4), R ² is a linear or branched alkyl group, and the carbon number thereof is 8 to 15, preferably 10 to 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 and polyoxyethylene alkyl ether acetic acid. 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, and examples of the organic alkali compound include salts of quaternary ammonium such as organic quaternary ammonium hydroxide and derivatives thereof, trimethylamine, and 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. Preferred are alkyl groups having 1 to 4 carbon atoms, particularly linear alkyl groups having 1 to 4 carbon atoms and / or linear hydroxyalkyl groups having 1 to 4 carbon atoms. 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. Examples of the hydroxyalkyl group include lower hydroxyalkyl groups having 1 to 4 carbon atoms such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.

Specific examples of the organic quaternary ammonium hydroxide include bis (2-hydroxyethyl) dimethylammonium hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Examples thereof include methyltriethylammonium hydroxide, trimethyl (hydroxyethyl) ammonium hydroxide (common name: choline), and triethyl (hydroxyethyl) ammonium hydroxide.

Among the organic quaternary ammonium hydroxides described above, bis (2-hydroxyethyl) dimethylammonium hydroxide, trimethyl (hydroxyl) 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 and tetrabutylammonium hydroxide.

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. Specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc. are mentioned, for example.

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 acids or alkalis include organic acids and salts thereof such as acetic acid, oxalic acid, tartaric acid and citric acid, inorganic alkalis and salts thereof such as sodium hydroxide and potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxy And salts of quaternary ammonium and its derivatives such as dodo and choline.

<Other ingredients>
The cleaning liquid of the present invention may contain components other than the above components (A) to (E) in any proportion 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 polymers attached firmly after dry etching such as hydrofluoric acid, ammonium fluoride and BHF (buffered hydrofluoric acid) Agents: Ascorbic acid, gallic acid, hydrazine and other reducing agents: hydrogen peroxide, ozone and Fine oxygen or the like of the oxidizing agent: monoethanolamine: amino acids such as arginine, also, such as ethanol as a solvent, may contain components other than water.

<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, the components of the cleaning liquid (components (A) to (C), and in addition to these, preferably the component (D) and / Or other components containing the component (E) and used as necessary). Usually, component (C), which is a solvent, is added with components (A) to (B), preferably including component (D) and / or component (E), and other components used as necessary. It is 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 preferably includes components (A) to (C), and in addition to these, preferably component (D) and / or component (E), and if necessary It is preferable that the other components used and these reactants are in a range that does not separate or precipitate in the cleaning 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). It is preferable that it is 10 mass%.

When the concentration is within the above 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 water of component (C). 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 on the semiconductor device substrate may be insufficient. Even if it exceeds 1% by mass, no further effect can be obtained, and the cost of the cleaning liquid is increased. Further, when the concentration of the component (A) exceeds 1% by mass, it may cause a problem such as corrosion of metal wiring such as Cu.

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 0.0001% by mass or more, the anticorrosive property is sufficiently exhibited. If the concentration of the component (B) is 1% by mass or less, it is possible to prevent a large amount of the insoluble complex between the component (B) and Cu from being generated as a residue, and to prevent the substrate surface from being washed. In addition, it is possible to prevent a problem 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 due to the coexistence of 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. 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 short-time rinsing, so that it is particularly suitable for a substrate for a semiconductor device having a metal or a metal compound on its surface as a wiring, and particularly a semiconductor device having a Cu wiring on its 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 of the metal compound include nitrides, oxides and silicides of the above metals. In particular, Cu and compounds containing these are suitable cleaning objects.

Also, 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 (Benzocycle), Flare (Honeywell) and SiLK (Dow Chemical), inorganic polymer materials such as FSG (Fluorinated silica glass), and ACK. 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 suitable when the semiconductor device substrate 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, polishing is performed by rubbing the substrate against the pad using an abrasive.
Examples of the abrasive include abrasive particles such as colloidal silica (SiO ₂ ), fumed silica (SiO ₂ ), alumina (Al ₂ O ₃ ), and ceria (CeO ₂ ). The abrasive particles are a major cause of contamination of the semiconductor device substrate, but 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 is highly effective for removing fine particle contamination.

In addition, the abrasive may contain additives other than abrasive particles, such as an oxidizing agent and a dispersing agent. In particular, in CMP polishing on a semiconductor device substrate having a Cu film as a metal wiring on the surface, an anticorrosive agent is often added because the Cu film is easily corroded.

What is used as an anticorrosive is preferably an azole anticorrosive having a high anticorrosive effect. More specifically, examples of the hetero atom containing a heterocycle containing only a nitrogen atom include diazole, triazole, and tetrazole, and examples containing a heterocycle of a nitrogen atom and an oxygen atom include, for example, Oxazole-based, isoxazole-based, and oxadiazole-based are included, and those containing a nitrogen atom and a sulfur atom heterocycle include, for example, thiazole-based, isothiazole-based, and thiadiazole-based. A benzotriazole (BTA) type anticorrosive having an excellent anticorrosive effect is particularly preferred.

When the cleaning liquid of the present invention is applied to the substrate surface after being polished with the above-mentioned abrasive containing an anticorrosive, it is excellent in that the contamination derived from the anticorrosive can be removed extremely effectively.

That is, when these anticorrosive agents 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 the polishing to produce a large amount of insoluble precipitates. The cleaning solution of the present invention can efficiently dissolve and remove the insoluble precipitates, and can remove the surfactant that tends to remain on the metal surface with a short rinse, thereby improving the throughput. is there.

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 a 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 high speed while flowing the cleaning liquid from the nozzle, and a liquid is sprayed on the substrate. And spray type to wash. Examples of the apparatus for performing the cleaning include a batch-type cleaning apparatus that simultaneously cleans a plurality of substrates housed in a cassette, and a single-wafer cleaning apparatus that mounts and cleans one substrate on a holder. .

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

In addition, the cleaning method of the present invention has the ability to remove contamination due to 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 solution is usually room temperature, but may be heated to about 40 to 70 ° C. within a range not impairing the performance.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless the gist thereof 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 Chemical Co., Ltd.) as a component (E) pH adjuster Were mixed to prepare a stock solution of a substrate cleaning solution for a semiconductor device of Example 1 having the composition shown in Table 1. 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>
The pH of the cleaning liquid diluted 40 times was measured with a pH meter (Horiba, Ltd. “D-24”) while stirring with a magnetic stirrer. The measurement sample kept the liquid temperature at 25 degreeC in the thermostat. The measurement results are shown in Table 1.

<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 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 1.
○: 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 was cut into 2.5 cm square. The film thickness (nm) of copper of the cut substrate was measured with a fluorescent X-ray analyzer (XRF) (JEOL Co., Ltd. RIX-3000). The copper substrate was immersed in a cleaning solution (diluted solution) 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 1.

<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, and 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. Then, the number of defects of 0.23 μm or more was examined by a wafer surface inspection apparatus “LS-6600” (Hitachi High-Tech Co., Ltd.). The evaluation results are shown in Table 1.

[Example 2]
As component (A) chelating agent, 0.05% by weight ethylenediamine, as component (B), 0.5% by weight 1,3-diaminopropane, as component (C) water, as component (D) surfactant 0.5% by mass of dodecylbenzenesulfonic acid (DBS), 8% by mass of tetraethylammonium hydroxide (TEAH) as a component (E) pH adjuster were mixed, and the composition of Example 2 having the composition shown in Table 1 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 2 was prepared by adding water to this washing | cleaning-solution stock solution and diluting 40 times.

Table 1 shows the results of evaluating the cleaning liquid in the same manner as in Example 1.
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]
Component (A) 0.5% by mass of citric acid as chelating agent, Component (B) as 0.5% by mass of 1,3-diaminobutane, water of component (C), component (D) surfactant Example 3 having the composition shown in Table 1 by mixing 0.5% by mass of dodecylbenzenesulfonic acid (DBS) and 8% by mass of tetraethylammonium hydroxide (TEAH) as a component (E) pH adjuster. A stock solution of the substrate cleaning solution for semiconductor devices 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.
Table 1 shows the results of evaluating the cleaning liquid in the same manner as in Example 1.
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 weight ethylenediamine, as component (B), 0.5% by weight 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 the composition of Example 4 having the composition shown in Table 1 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.
Table 1 shows the results of evaluating the cleaning liquid in the same manner as in Example 1.
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 1. 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.
Table 1 shows the results of evaluating the cleaning liquid in the same manner as in Example 1.
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 adjuster, 8% by mass of tetraethylammonium hydroxide (TEAH) was mixed to prepare a stock solution of the substrate cleaning liquid for semiconductor devices of Comparative Example 2 having the composition shown in Table 1. 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.
Table 1 shows the results of evaluating the cleaning liquid in the same manner as in Example 1.
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 semiconductor device substrate cleaning solution of Comparative Example 3 having the composition shown in Table 1 was mixed. Stock solutions were 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.
Table 1 shows the results of evaluating the cleaning liquid in the same manner as in Example 1.
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]
0.5% by weight of 1,3-diaminopropane as component (B), water of component (C), 0.5% by weight of dodecylbenzenesulfonic acid (DBS) as component (D) surfactant, component (E) 5% by mass of bis (2-hydroxyethyl) dimethylammonium hydroxide (AH212, Yokkaichi Gosei Co., Ltd.) as a pH adjusting agent was mixed, and the semiconductor device substrate of Comparative Example 4 having the composition shown in Table 1 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 3.
Table 1 shows the results of evaluating the cleaning liquid in the same manner as in Example 1.
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.

The amount of water of component (C) contained in each of the cleaning solution stock solutions of Examples 1 to 4 and Comparative Examples 1 to 4 is the component other than component (C) contained in each cleaning solution stock solution. The balance (mass%) of the content (mass%) of

[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.

On the other hand, it can be seen that Comparative Example 1 does not contain the chelating agent of component (A) and the diaminoalkane of component (B), and the Cu wiring surface is rough.

Comparative Example 2 did not contain the component (B) compound, and the Cu wiring was dissolved by the action of the chelating agent of the component (A), and significant corrosion was confirmed.

In Comparative Example 3, as a comparison with 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 methyl 1,2-diaminopropane was used, sufficient corrosion resistance was not exhibited, and significant corrosion was confirmed on the copper wiring.

In Comparative Example 4, the component (A) was not included, and sufficient corrosion resistance was not exhibited, and significant corrosion was confirmed in the copper wiring.

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.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on February 6, 2013 (Japanese Patent Application No. 2013-021241), which is incorporated by reference in its entirety.

Claims

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
In the component (B), the linking group R in the general formula (1) is an aliphatic hydrocarbon group represented by the general formula (2), n is an integer of 3 to 10, and X 1 The substrate cleaning solution for a semiconductor device according to claim 1, wherein X 2 and X 2 are both hydrogen atoms.
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.
4. The semiconductor device substrate cleaning liquid according to claim 1, further comprising a component (E) pH adjuster.
The substrate cleaning liquid for a semiconductor device according to claim 3 or 4, 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 substrate cleaning solution for a semiconductor device according to claim 3, wherein the substrate cleaning solution 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 solution for a semiconductor device according to any one of claims 1 to 6.
A method for cleaning a substrate for a semiconductor device, comprising: cleaning the substrate for a semiconductor device using the substrate cleaning liquid for a semiconductor device according to any one of claims 1 to 7.
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.