JP2012216690A - Cleaning agent for copper wiring semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleaning agent for copper and copper alloy wiring semiconductor which exhibits excellent removability of organic residue, e.g. an anticorrosive agent added for the purpose of corrosion inhibition of a wiring metal, and residue of copper of a polished copper wiring metal without causing corrosion of the copper wiring.SOLUTION: The cleaning agent for copper wiring semiconductor used in the cleaning step following the chemical mechanical polishing step in a semiconductor production process for forming copper or copper alloy wiring contains, as essential components, an amine (A) having HLB of 15-35 and at least one hydroxyl in the molecule, an amine (B) having HLB of 10-30 and at least one tertiary amino group but not having hydroxyl in the molecule, and water, and the pH is 7.5-13.0 during use.

Description

The present invention relates to a cleaning agent (hereinafter referred to as a post-CMP cleaning agent) used in a cleaning step after a chemical mechanical polishing (hereinafter, “chemical mechanical polishing” is abbreviated as CMP) step in a semiconductor manufacturing process. And a post-CMP cleaning agent for a semiconductor having a copper or copper alloy wiring on its surface.

Semiconductor elements typified by silicon semiconductors have been miniaturized and highly integrated in response to market needs such as higher performance and smaller size. Along with this, an advanced planarization technique for creating a fine wiring pattern is essential, and a polishing slurry (hereinafter abbreviated as CMP slurry) containing fine particles of alumina or silica on the wafer surface in a semiconductor manufacturing process. A CMP process that uses and polishes is introduced.

However, in this CMP process, abrasive fine particles such as alumina and silica in the CMP slurry (hereinafter, “abrasive fine particles” are abbreviated as abrasive grains), an iron nitrate aqueous solution added to promote polishing, and metal corrosion suppression purposes. The anticorrosive agent added in step 1 and the polished copper wiring metal are likely to remain on the polished wafer. Since these residues adversely affect the electrical characteristics of the semiconductor such as a short circuit between wirings, it is necessary to remove these residues and clean the wafer surface.

  As a cleaning agent used in the cleaning step after the CMP step, an alkaline cleaning agent mainly composed of a polyalkylene polyamine (Patent Document 1) and an alkaline cleaning agent mainly composed of a chain alkanolamine are known ( Patent Document 2).

However, the cleaning agents of Patent Document 1 and Patent Document 2 are excellent in removability of metal residues, removability of abrasive grains added to the CMP slurry, and corrosion resistance, but low removability of organic residues. There is a problem.

No. 2001-71789 Japanese Patent Laid-Open No. 11-74243

Accordingly, the present invention provides an organic residue such as an anticorrosive added for the purpose of inhibiting corrosion of the wiring metal without corroding the copper wiring, and copper having excellent removability of the copper residue of the polished copper wiring metal and It aims at providing the cleaning agent for copper alloy wiring semiconductors.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention is a cleaning agent used in a cleaning process subsequent to a chemical mechanical polishing process in a semiconductor manufacturing process for forming a copper or copper alloy wiring, and has an HLB of 15 to 35 and in the molecule. An amine (A) having at least one hydroxyl group, an amine (B) having an HLB of 10 to 30 and having at least one tertiary amino group in the molecule and no hydroxyl group, and water are essential components. A cleaning agent for copper wiring semiconductors, wherein the pH during use is 7.5 to 13.0; and a semiconductor substrate or a semiconductor element manufactured using this cleaning agent.

The cleaning agent of the present invention is excellent in removing organic residues and metal residues without corroding the copper wiring.
Further, when a nonionic surfactant having a cloud point of 2% aqueous solution having a cloud point of 40 ° C. or higher is used in combination, the wettability of the cleaning agent with respect to the wafer surface is improved, and the metal residue removability is further improved.

The copper wiring semiconductor cleaning agent of the present invention is a cleaning agent used in a cleaning step after the CMP step, and has a specific HLB and at least one hydroxyl group in the molecule (A), a specific The amine (B) which has HLB, has at least one tertiary amino group in the molecule and does not contain a hydroxyl group, and water are essential components, and the pH during use is 7.5 to 13.0. It is characterized by.
Furthermore, it is also a requirement that the amine (A) has an HLB of 15 to 35 and the amine (B) has an HLB of 10 to 30.

Here, “HLB” is an index indicating a balance between hydrophilicity and lipophilicity, and is described in, for example, “Introduction to Surfactants” (published by Sanyo Chemical Industries, Ltd., 2007, Takehiko Fujimoto), page 212. It is known as the calculated value by the Oda method, not the calculated value by the Griffin method.
The HLB value can be calculated from the ratio between the organic value and the inorganic value of the organic compound.
The organic value and the inorganic value for deriving HLB≈10 × inorganic / organic HLB can be calculated using the values in the table described in “Introduction of Surfactant” on page 213.

In the present invention, the amine (A) having an HLB of 15 to 35 as the first essential component and having at least one hydroxyl group in the molecule is, for example, an aliphatic amine (A1) having one or more hydroxyl groups. And alicyclic amine (A2) having one or more hydroxyl groups, aralkylamine (A3) having one or more hydroxyl groups, and heterocyclic amine (A4) having one or more hydroxyl groups.

Specific examples of the aliphatic amine (A1) having an HLB of 15 to 35 and having at least one hydroxyl group in the molecule include diethanolamine (HLB = 33), triethanolamine (HLB = 31), dimethylaminoethanol ( HLB = 22), 2-amino-2-methyl-1-propanol (HLB = 28), 2-[(aminoethyl) amino] ethanol, (HLB = 30) and the like.
A monoamine or polyamine may be used as long as it contains at least one hydroxyl group.

Specific examples of the alicyclic amine (A2) having an HLB of 15 to 35 and having at least one hydroxyl group in the molecule include monohydroxyethyl substituted products (HLB) of 1,3- and 1,4-diaminocyclohexane. = 18) and the like.

Specific examples of aralkylamines (A3) having an HLB of 15 to 35 and having at least one hydroxyl group in the molecule include aromatic fats such as metaxylylenediamine ethylene oxide 2-mol adduct (HLB = 16). Group amines.

Specific examples of the heterocyclic amine (A4) having an HLB of 15 to 35 and having at least one hydroxyl group in the molecule include 1- (2-hydroxyethyl) piperazine (HLB = 20), morpholine-4- Ethanol (HLB = 17) etc. are mentioned.

Of these amines (A), from the viewpoint of copper wiring corrosion resistance and removability of organic residues remaining on the wafer after the CMP step, the above-mentioned aliphatic amine (A1) and heterocyclic amine (A4) are preferable. ).
Further, from the viewpoint of removal of abrasive grains remaining on the wafer after the CMP process, triethanolamine, 2-[(aminoethyl) amino] ethanol, and 1- (2-hydroxyethyl) piperazine are particularly preferable. 2-[(Aminoethyl) amino] ethanol is preferred.

The content of the amine (A) is usually 0.001 to 10 based on the total weight when the amine (A), the amine (B) and water are used from the viewpoint of copper wiring corrosion resistance and organic residue removal. % By weight, preferably 0.005 to 5% by weight, more preferably 0.01 to 2% by weight, and particularly preferably 0.01 to 1% by weight.

In the present invention, the amine (B) having a HLB of 10 to 30 as the second essential component and having at least one tertiary amino group in the molecule and not containing a hydroxyl group includes, for example, a tertiary amino group. And an aliphatic amine having a group (B1), an alicyclic amine having a tertiary amino group (B2), and a heterocyclic amine having a tertiary amino group (B3).

Specific examples of the aliphatic amine (B1) having an HLB of 10 to 30 and having at least one tertiary amino group in the molecule include N, N′-dimethylaminodiethyl ether (HLB = 11), tetramethyl And ethylenediamine (HLB = 13), N-methyl-N, N-bis (2-dimethylaminoethyl) amine (HLB = 26), and the like. In addition, as long as HLB is 10-30 and it contains at least one tertiary amino group in the molecule, it may be a monoamine or a polyamine.

Specific examples of the alicyclic amine (B2) having an HLB of 10 to 30 and having at least one tertiary amino group in the molecule include N, N-dimethyl-1,4-diaminocyclohexane (HLB = 11 ) And the like.

Specific examples of the heterocyclic amine (B3) having an HLB of 10 to 30 and having at least one tertiary amino group in the molecule include N- (2-aminoethyl) piperidine (HLB = 11), N -(2-aminoethyl) piperazine (HLB = 18), 1,4-bis (3-aminopropyl) piperazine (HLB = 15), 1-methyl-4- [2- (dimethylamino) ethyl] piperazine (HLB) = 12) and the like.

Of these amines (B), the above-mentioned aliphatic amines (B1) and heterocyclic amines (B3) are preferable from the viewpoint of removability of organic residues remaining on the wafer after the CMP process.
Further, from the viewpoint of corrosiveness of copper wiring, N-methyl-N, N-bis (2-dimethylaminoethyl) amine, 1,4-bis (3-aminopropyl) piperazine, 1-methyl-4- [ 2- (dimethylamino) ethyl] piperazine, particularly preferably N-methyl-N, N-bis (2-dimethylaminoethyl) amine.

The content of the amine (B) is usually 0.001 to 10 based on the total weight when the amine (A), the amine (B) and water are used from the viewpoint of copper wiring corrosion resistance and organic residue removal. % By weight, preferably 0.005 to 5% by weight, more preferably 0.01 to 2% by weight, and particularly preferably 0.01 to 1% by weight.

In the present invention, the ratio of amine (A) to amine (B) is preferably (A) / (B) = 0.5 to 0.5 in terms of a molar ratio from the viewpoint of coexistence of copper wiring corrosivity and organic residue removability. 10.0, more preferably (A) / (B) = 0.7 to 5.0, and particularly preferably (A) / (B) = 0.8 to 1.5. When the molar ratio of (A) and (B) is within this range, the balance between copper wiring corrosivity and organic residue removability is good.

The cleaning agent for a copper wiring semiconductor of the present invention contains water as an essential component, and specifically includes those having a low electrical conductivity (μS / cm; 25 ° C.). Specifically, the electrical conductivity is usually from the viewpoint of removability of organic residues and metal residues, availability, and prevention of re-contamination of copper wiring (re-adhesion of metal ions in water to copper wiring). It is 0.055 to 0.2, preferably 0.056 to 0.1, and more preferably 0.057 to 0.08. As such water with low electrical conductivity, ultrapure water is preferable.
In addition, electrical conductivity is measured based on JIS K0400-13-10: 1999.

The pH when the cleaning agent for copper wiring semiconductor of the present invention is actually used as it is or after further dilution is usually 7.5 to 13.0, preferably 8.5 to 13.0, more preferably 9.5 to 13.0.
If the pH is too low, the organic residue removability deteriorates, and if it is too high, the copper wiring corrosion resistance deteriorates.

In addition to the essential components amine (A), amine (B), and water, the copper wiring semiconductor cleaning agent should be used in combination with a nonionic surfactant (C) having a cloud point of 2% aqueous solution of 40 ° C or higher. As a result, the wettability of the cleaning agent to the wafer is improved, and in addition to the copper wiring corrosion resistance and organic residue removability, the metal residue removability can also be satisfied.
The cloud point of a 2% aqueous solution of the nonionic surfactant (C) is preferably 50 ° C. or higher, more preferably 70 ° C. or higher.

Specific examples of such nonionic surfactant (C) include cocoamine ethylene oxide (5 to 10 mol) adduct (cloud point of 50 ° C. or higher), lauryl alcohol ethylene oxide (8 to 12 mol) adduct ( Cloud point of 40 ° C. or higher).

The content of the nonionic surfactant (C) may be an amount necessary to reduce the surface tension of the cleaning agent, and is usually 0.0001 to 1 based on the weight of the cleaning agent for copper wiring semiconductor of the present invention. % By weight, preferably 0.0005 to 0.3% by weight, particularly preferably 0.001 to 0.1% by weight.

The cleaning agent for a copper wiring semiconductor according to the present invention contains the essential component amine (A), amine (B), water, and nonionic surfactant (C) added as necessary. A corrosion inhibitor (D), a reducing agent (E), a complexing agent (F) and the like may be added as long as the performance of the semiconductor cleaning agent is not impaired.

Examples of the corrosion inhibitor (D) include quaternary ammonium hydroxides and guanidine compounds.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and benzyltrimethylammonium hydroxide. Examples of the guanidine compound include guanidine carbonate and guanidine sulfamate.

Of these corrosion inhibitors (D), quaternary ammonium hydroxide is preferred, and tetramethylammonium hydroxide is more preferred from the viewpoint of water solubility and copper wiring corrosion resistance.

The content of the corrosion inhibitor (D) is usually 0.001 to 1.0% by weight, more preferably, based on the weight of the cleaning agent for copper wiring semiconductor of the present invention, from the viewpoint of improving copper wiring corrosion inhibition. 0.01 to 0.5% by weight.

Examples of the reducing agent (E) include organic reducing agents and inorganic reducing agents.
Examples of the organic reducing agent include polyphenol compounds, oxalic acid or salts thereof, aliphatic aldehydes having 6 to 9 carbon atoms, and benzaldehyde. Examples of inorganic reducing agents include sulfurous acid or salts thereof, thiosulfuric acid or salts thereof, and the like. It is done.

Among these reducing agents (E), an organic reducing agent is preferable from the viewpoint of organic residue removability, and more preferably a polyphenol compound, oxalic acid or a salt thereof. Furthermore, from the viewpoint of complexing action, a polyphenol compound is preferable, and gallic acid is particularly preferable.

When these reducing agents are added, the content of the reducing agent (E) is usually 0.001 to 1.0 based on the weight of the cleaning agent for copper wiring semiconductor of the present invention from the viewpoint of organic residue removal. % By weight, more preferably 0.01 to 0.5% by weight, particularly preferably 0.05 to 0.1% by weight. When these reducing agents are more than 1.0% by weight, the copper wiring corrosion resistance is lowered.

Examples of the complexing agent (F) include aromatic or aliphatic hydroxycarboxylic acids (or salts thereof), heterocyclic compounds having at least one of a hydroxyl group and a carboxyl group, and phosphonic acids (or salts thereof).

Of these complexing agents (F), aliphatic hydroxycarboxylic acid (or a salt thereof) and polycarboxylic acid (or a salt thereof) are preferable from the viewpoint of organic residue removal, and an aliphatic hydroxycarboxylic acid (or a salt thereof). Is particularly preferred.

In the case of adding a complexing agent, the content of the complexing agent (F) is usually 0.001 to 0 based on the weight of the cleaning agent for a copper wiring semiconductor of the present invention, from the viewpoint of improving organic residue removability. 0.5 wt%, preferably 0.01 to 0.3 wt%, particularly preferably 0.05 to 0.1 wt%. If the content of the complexing agent (F) is more than 0.5% by weight, the organic residue removing effect is adversely affected.

The cleaning agent for a copper wiring semiconductor of the present invention can be produced by mixing the amine (A), the amine (B), and other components as necessary with water.
The method of mixing is not particularly limited, but water, amine (A) and amine (B) are mixed from the viewpoint of easy and uniform mixing in a short time, and then other components are mixed as necessary. The method is preferred.

As the mixing device, a stirrer or a disperser can be used. Examples of the stirrer include a mechanical stirrer and a magnetic stirrer. Examples of the disperser include a homogenizer, an ultrasonic disperser, a ball mill, and a bead mill.

The cleaning agent for copper wiring semiconductor of the present invention includes a semiconductor substrate having copper wiring, a semiconductor element, a copper plating substrate for semiconductor cleaning property evaluation, an aluminum substrate for a recording medium magnetic disk, a glassy carbon substrate, a glass substrate, It can be used in a cleaning method for cleaning a ceramic substrate, a glass substrate for liquid crystal, a glass substrate for solar cell, and the like.

As a cleaning method for cleaning a semiconductor substrate or a semiconductor element having a copper wiring, a single wafer method and a batch method can be given. The single wafer method is a method in which a semiconductor substrate or a semiconductor element is rotated one by one, and a cleaning is performed using a brush while injecting a cleaning agent for a copper wiring semiconductor. The batch method is a plurality of semiconductor substrates or semiconductor elements. Is cleaned by immersing it in a cleaning agent for copper wiring semiconductors.

The copper wiring semiconductor cleaning agent of the present invention is a process for producing a semiconductor substrate or a semiconductor element having copper wiring, after resist development, after dry etching, after wet etching, after dry ashing, after resist stripping, before and after CMP treatment, and It can be used for cleaning processes before and after CVD processing. In particular, from the viewpoint of organic residue removability and metal impurity removability, it is preferably used in the cleaning step after CMP treatment.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Examples 1-7 and Comparative Examples 1-5
The composition shown in Table 1 was carried out in a polyethylene container to obtain a cleaning agent for copper wiring semiconductor of the present invention and a cleaning agent for comparison.

In addition, the cloud points of 2% aqueous solution of (C-1) and (C-2) in Table 1 are 100 degreeC and 52 degreeC, respectively.

About the cleaning agent for semiconductors for copper wiring of this invention, and the cleaning agent for copper wiring semiconductors for comparison, organic residue removal property, metal residue removal property, and copper wiring corrosion resistance were measured and evaluated by the following methods.
The evaluation results are shown in Table 1.

<Evaluation method of organic residue removability>
The organic residue removal property was evaluated according to the following procedure.

(1) Cleaning of a copper-plated silicon wafer A wafer obtained by subjecting a silicon wafer to copper plating (manufactured by Advanced Material Technology, “Cu plating 10000A Wafer”, copper plating film thickness = 1.0 μm) is longitudinally 1. The sample was cut into 5 cm × 1.5 cm, immersed in a 10% aqueous acetic acid solution for 1 minute, and then washed with ultrapure water.

(2) Preparation of organic residue liquid 0.4 g of benzotriazole (BTA), 0.6 g of 30% hydrogen peroxide water, and 200 g of ultrapure water are mixed and adjusted to a pH of 3.0 with hydrochloric acid. An organic residue liquid was prepared.

(3) Preparation of copper-plated wafer to which organic residue was adhered After immersing the copper-plated wafer in the organic residue liquid prepared in (2) for 60 seconds, it was immersed in ultrapure water for 60 seconds, and the wafer surface was dried with a nitrogen stream. A copper-plated wafer with an organic residue attached was prepared.

(4) Measurement of amount of organic residue adhered to copper-plated wafer Using an X-ray photoelectron spectroscopy (XPS) device (ESCA-5400, manufactured by ULVAC-PHI), the amount of nitrogen derived from benzotriazole, which is an organic residue, was used. The amount of organic residue adhering to the copper-plated wafer prepared in (3) was measured.
Specifically, using XPS, the number of photoelectrons was measured within a binding energy range of 397 eV to 399 eV, and a peak area value within a range of 397.5 to 398.4 eV derived from nitrogen was determined. As the soft X-ray, MgKα ray (1253.6 eV) was used.

(5) Removal of organic residue adhered to copper-plated wafer The copper-plated wafer with the organic residue prepared in (3) was immersed in 50 g each of the present invention and the comparative copper wiring semiconductor cleaning agent for 3 minutes to obtain copper. Organic residues were removed from the plated wafer. Thereafter, the wafer surface was immersed in 1 L of ultrapure water for 60 seconds, and the wafer surface was dried with a nitrogen stream.

(6) Measurement of amount of organic residue remaining on copper-plated wafer Organic residue remaining on copper-plated wafer by measuring the amount of nitrogen derived from benzotriazole, which is an organic residue, using XPS as in (4) The amount was measured.

(7) Evaluation and Evaluation of Organic Residue Removability The respective peak area values measured by XPS in (4) and (6) were substituted into the following formula (1) to calculate the BTA residue removal rate.

Xa: Peak area value of nitrogen derived from benzotriazole before organic residue removal Xb: Peak area value of nitrogen derived from benzotriazole after organic residue removal

From the calculated organic residue removal rate, organic residue removability was determined according to the following criteria.
○: Organic residue removal rate is 90% or more Δ: Organic residue removal rate is 80 to 90%
X: Organic residue removal rate is less than 80%

<Evaluation method of metal residue removability>
The metal residue removal property was evaluated according to the following procedure.
(1) Pretreatment of wafer having a silicon oxide single layer film A silicon wafer having a silicon oxide single layer film (manufactured by Advantech, “P-TEOS 1.5 μ”, silicon oxide film thickness = 1.5 μm) is vertically 1 A section of 0.0 cm × 2.0 cm was cut, immersed in a 10% aqueous acetic acid solution for 1 minute, and then washed with ultrapure water.

(2) Preparation of aqueous solution containing metal ions To 0.1 part of zinc nitrate, 0.1 part of iron nitrate and 0.1 part of magnesium nitrate, water is added so that the total amount becomes 100 g. An aqueous solution containing 0.1% by weight of metal ions was prepared.

(3) Contamination treatment of wafer with aqueous metal ion solution
The slice of the pretreated wafer was immersed in 10 g of an aqueous solution containing metal ions for 1 minute, and then dried by nitrogen blowing, thereby attaching metal ions to the surface of the wafer.

(4) Cleaning of wafer The section of the wafer subjected to the contamination treatment was immersed in 10 g of cleaning agent for copper wiring semiconductor. After leaving still at 25 degreeC for 3 minutes, it took out from the washing | cleaning agent.

(5) Measurement of the concentration of metal ions eluted from the wafer surface into the cleaning agent
5 g of the copper wiring semiconductor cleaning agent after the immersion was taken out, and the pH was adjusted to 3.0 with an aqueous nitric acid solution.
Thereafter, ultrapure water was added until the total amount became 10 g to prepare a measuring solution. The concentrations of zinc, iron, and magnesium metal ions contained in the measurement liquid were measured using an ICP-MS analyzer (inductively coupled plasma mass spectrometer) (manufactured by Agilent Technologies, Agilent 7500cs type).

(6) Calculation of the elution amount of metal ions eluted from the wafer surface into the cleaning agent The elution amount of each metal ion was calculated using the following mathematical formula (2).

Metal _con : each metal ion concentration (ppb (ng / g)) in the measurement solution quantified by ICP-MS analysis
G1: Liquid amount (g) of the cleaning agent for copper wiring semiconductor in which the test piece is immersed
G2: Liquid amount (g) of cleaning agent for copper wiring semiconductor taken out before pH adjustment
G3: Amount of measurement liquid (g)
S _SiO2 : Area of the silicon oxide film (cm 2) in the wafer having a single layer film of silicon oxide

(7) Evaluation of metal residue removability The metal residue removability is evaluated from the calculated total amount of elution of each metal ion. The greater the amount of metal ion elution per wafer unit area, the greater the metal residue removability. Judged to be excellent.
Specifically, metal residue removability was determined according to the following criteria.
○: 15 ng / cm ² or more Δ: 5 to 15 ng / cm ²
X: Less than 5 ng / cm ²

<Copper wiring corrosion resistance evaluation method>
The corrosion resistance of the copper wiring was evaluated according to the following procedure.
(1) Pretreatment of a wafer having a copper single layer film A wafer on which a copper single layer film is deposited (manufactured by Adbas Materials Technology, copper metal is deposited on a silicon substrate with a film thickness of 2 μm) is 1.0 cm in length and width It was cut into 2.0 cm sections, immersed in a 10% aqueous acetic acid solution for 1 minute, and then washed with ultrapure water.

(2) A section of a wafer having a copper monolayer film pretreated by copper extraction was immersed in 10 g each of a cleaning agent for copper wiring semiconductors, allowed to stand at 25 ° C. for 3 minutes, and then taken out from the cleaning agent.

(3) Measurement of copper ion concentration
After removing the section, 5 g of the copper wiring semiconductor cleaning agent was weighed, and 0.1% nitric acid aqueous solution was added to adjust the pH to 3.0. Thereafter, ultrapure water was added until the total amount became 10 g to obtain a sample solution for measurement.
The copper ion concentration in the measurement sample solution was measured using an ICP-MS analyzer (inductively coupled plasma mass spectrometer) (Agilent Technology, Agilent 7500cs type).

(4) Calculation of copper ion elution amount The copper ion concentration was substituted into the following mathematical formula (3) to calculate the copper ion elution amount (ng / cm2).

Cu _con : Copper ion concentration (ppb (ng / g)) in the measurement liquid quantified by ICP-MS analysis
H1: Liquid amount (g) of the cleaning agent for copper wiring semiconductor in which the test piece is immersed
H2: Liquid amount (g) of cleaning agent for copper wiring semiconductor taken out before pH adjustment
H3: Amount of measuring solution (g)
S _CU : Area of the copper single layer film in the wafer having the copper single layer film (cm ² )

(5) Evaluation and judgment of copper wiring corrosion resistance From the calculated copper ion elution amount, the copper wiring corrosion resistance is evaluated. The smaller the copper ion elution amount per unit area of the wafer having a copper single layer film, the more copper The wiring corrosion resistance was judged to be excellent. Specifically, the copper wiring corrosion resistance was determined according to the following criteria.
○: Less than 15 ng / cm ² Δ: 15-20 ng / cm ²
×: 20 ng / cm ² or more

As shown in Table 1, the cleaning agents for copper wiring semiconductors of the present invention of Examples 1 to 7 have good results in both the metal residue removing property on the organic residue removing insulating film and the copper wiring corrosion resistance. Obtained.
On the other hand, an amine (A′-1) having a hydroxyl group but not having an HLB of 15 to 35 and an amine (A′-2) having an HLB of 15 to 35 but having no hydroxyl group were used in place of (A). Example 1 and Comparative Example 2, and amines (B′-1) and (B′-2) each containing at least one tertiary amino group and no hydroxyl group but HLB of 10 to 30 (B) Comparative Example 3 and Comparative Example 4 used in place of No. were poor in organic residue removability.
Further, Comparative Example 5, which does not contain any of the amines (A) and (B), which are essential components of the present invention, had insufficient copper wiring corrosivity and metal residue removability.

The cleaning agent for copper wiring semiconductor of the present invention is excellent in organic residue removing property, copper wiring corrosiveness, and excellent metal residue removing property. Therefore, in the CMP process in the semiconductor manufacturing process for forming copper or copper alloy wiring. It can be suitably used as a cleaning agent used in subsequent steps.

Claims (4)

A cleaning agent used in a cleaning process following a chemical mechanical polishing process in a semiconductor manufacturing process for forming a copper or copper alloy wiring, wherein HLB is 15 to 35, and at least one hydroxyl group is formed in the molecule. Having amine (A), HLB of 10-30, amine (B) having at least one tertiary amino group in the molecule and no hydroxyl group, and water as essential components; It is 7.5-13.0, The cleaning agent for copper wiring semiconductors characterized by the above-mentioned.   The cleaning agent for a copper wiring semiconductor according to claim 1, wherein a molar ratio (A) / (B) of the amine (A) to the amine (B) is 0.1 to 2.0.   The cleaning agent for a copper wiring semiconductor according to claim 1 or 2, further comprising 1% by weight or less of a nonionic surfactant (C) having a clouding point of 2% aqueous solution of 40 ° C or higher with respect to the total cleaning agent in use. The semiconductor substrate or semiconductor element manufactured using the cleaning agent in any one of Claims 1-3 in the process following the chemical mechanical polishing in the semiconductor manufacturing process which forms copper or copper alloy wiring.