TWI713459B - Etching residue removal composition, etching residue removal method, etching residue removal kit, and manufacturing method of magnetoresistive memory - Google Patents

Abstract

The present invention is an etching residue removal composition that contains an oxidizing agent, a glycol compound, and an amine compound, and has a moisture content of 30% by mass or less based on the total composition.

Description

Etching residue removal composition, etching residue removal method And etching residue removal kit and manufacturing method of magnetoresistive memory

The present invention relates to an etching residue removal composition, a method for removing etching residue using the same, an etching residue removal kit, and a method for manufacturing a magnetoresistive memory.

The processing of semiconductor substrates consists of various processing steps in multiple stages. In its manufacturing process, the process of patterning semiconductor layers or electrodes by dry etching occupies an important position. In dry etching, plasma (discharge) is generated in a chamber, and the processed object is processed using ions or radicals generated in the chamber.

On the other hand, in many cases, the processed object cannot be completely removed in the dry etching, and the residue usually remains on the processed substrate. In addition, in ashing performed when the resist and the like are removed, residues remain on the substrate similarly. These residues are required to be effectively removed without damaging the processed substrate (Patent Document 1 and Patent Document 2). The size of wiring or integrated circuit in a semiconductor substrate is becoming smaller, and the importance of accurately removing residues without corroding components that should remain is increasing.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Korean Patent Publication No. 10-20130049500

[Patent Document 2] Korean Patent Publication No. 10-20130049502

Regarding the constituent material of the semiconductor substrate in the process and the residue remaining on the semiconductor substrate by dry etching or the like, the constituent elements are generally the same. Therefore, it is not easy to reliably remove only the residue of the semiconductor substrate without damaging it.

An object of the present invention is to provide an etching residue removal composition, an etching residue removal method, an etching residue removal kit, and a manufacturing method of a magnetoresistive memory that can remove residues containing a specific metal while suppressing damage to a specific metal layer.

The problem was solved by the following means.

[1] An etching residue removal composition containing an oxidizing agent, a glycol compound, and an amine compound, and having a moisture content of 30% by mass or less based on the total composition.

[2] The etching residue removal composition according to [1], wherein the oxidizing agent is hydrogen peroxide.

[3] The etching residue removal composition according to [1] or [2], wherein the diol compound is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and ethylene glycol. Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, three Ethylene Glycol Mono B One or more of the group consisting of ether, triethylene glycol monobutyl ether, and diethylene glycol dimethyl ether.

[4] The etching residue removal composition according to any one of [1] to [3], wherein the diol compound is diethylene glycol monobutyl ether.

[5] The etching residue removal composition according to any one of [1] to [4], wherein the amine compound comprises a compound selected from the group consisting of monoethanolamine, diglycolamine, monoisopropanolamine, and isopropanolamine. Butanolamine, C ₂ ~C ₈ alkanolamine, methylethanolamine, N-methylaminoethanol, diethanolamine, triethanolamine, methyldiethanolamine, triethylamine, pentamethyldiethylenetriamine , N-methylmorpholine-N-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorpholine Lin-N-oxide, N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide, substituted derivatives of these, and combinations of these Amine type.

[6] The etching residue removal composition according to any one of [1] to [5], wherein the amine compound is at least any one selected from monoethanolamine and diglycolamine.

[7] The etching residue removal composition according to any one of [1] to [6], wherein the moisture content based on the total amount of the composition is 0.5% by mass or more and less than 15% by mass.

[8] The etching residue removal composition according to any one of [1] to [7], wherein the content of the amine compound based on the total amount of the composition is 5% by mass or more and 50% by mass or less.

[9] The etching residue removal composition according to any one of [1] to [8], which is used for Removal of hard mask.

[10] The etching residue removal composition according to any one of [1] to [9], which is applied to a substrate containing CoFeB, CoFe, MgO, or Al ₂ O ₃ , and has a dissolution rate of 1 Å/min or less .

[11] A method for removing etching residues, comprising applying the etching residue removing composition according to any one of [1] to [10] to a ferromagnetic layer to which any one of CoFeB and CoFe is attached Etching residue and the substrate of the etching residue of the insulator layer containing either MgO and Al ₂ O ₃ .

[12] The etching residue removal method according to [11], which is further applied to a substrate having a hard mask.

[13] The etching residue removal method according to [11] or [12], which suppresses or prevents damage to at least any one of the ferromagnetic layer and the insulator layer, and simultaneously removes the ferromagnetic layer and the insulator layer. The residues generated during the etching of at least any of the layers are removed.

[14] A method of manufacturing a magnetoresistive memory, which is manufactured by the method described in any one of [11] to [13].

[15] An etching residue removal kit comprising a first liquid containing an oxidizing agent, and a second liquid containing a glycol compound and an amine compound.

[16] The etching residue removal kit according to [15], wherein the total amount of water in the first liquid and the second liquid is 30% by mass or less.

[17] A method for removing etching residues, using the etching residue removal method of the etching residue removal kit as described in [15] or [16], and combining the first liquid with the etching residue The second liquid is mixed and used at an appropriate time before the residue removal treatment.

[18] An etching residue removal composition containing only an oxidizing agent, a glycol compound, an amine compound, and water.

According to the etching residue removal composition, the etching residue removal method using the same, and the etching residue removal kit of the present invention, it is possible to remove the residue containing the specific metal while suppressing damage to the specific metal layer.

In addition, according to the manufacturing method of the present invention, a magnetoresistive memory can be preferably manufactured using the etching residue removal composition.

The above and other features and advantages of the present invention will become more clarified from the following description with reference to the attached drawings.

1: Hard mask

2: free layer

3: The second ferromagnetic layer

4: Insulator layer

5: The first ferromagnetic layer

6: Base electrode

7: Residue

d: Damaged part

H: Hole

Fig. 1 (a), Fig. 1 (b), and Fig. 1 (c) are diagrams schematically showing an example of the manufacturing procedure of the semiconductor substrate of the present invention.

FIG. 2 is a diagram schematically showing an example of a semiconductor substrate (comparative example) damaged by a residue removal process.

The etching residue removal composition of the present invention and the etching residue removal method using the same will be described with the processing of a magnetoresistive random access memory (MRAM) as a preferred embodiment thereof as an example. However, the present invention is not limited to this and will be interpreted.

[Removal step of residue]

Fig. 1(a) is a diagram showing a semiconductor substrate before dry etching is performed. If the multilayer structure of the MRAM of this embodiment is described from the lower layer, it is composed of a base electrode 6, a first ferromagnetic layer 5, an insulator layer 4, a second ferromagnetic layer 3, and a free layer 2. In the processing step at this stage, a pattern is formed by the hard mask 1 for the next dry etching. The material of the hard mask 1 is not particularly limited, and any material can be appropriately selected and used. In addition, although not shown, there is a silicon wafer below the laminated body shown in the figure. The material of the silicon wafer is not particularly limited, and a substrate made of Si, SiO ₂ or the like can be suitably used. Commercially available silicon wafers can also be used.

The material of the base electrode 6 is not particularly limited, and common electrode materials such as copper, aluminum, and titanium nitride (TiN) can be used. The material constituting the first ferromagnetic layer 5 and the second ferromagnetic layer 3 is not particularly limited, and examples thereof include Fe, CoFe, CoFeB, and the like. The material of the insulator layer 4 may be aluminum oxide (AlO _x ) or magnesium oxide (MgO _x ). Examples of the material of the free layer 2 include permalloy (Py) (alloy of Fe-Ni), Co-Fe, and the like. The materials of these layers can be appropriately selected and used for each material applied to MRAM. The method of forming each layer is not particularly limited, and it can be appropriately formed by MBE (Molecular Beam Epitaxy) or the like.

MRAM is a memory using ferromagnetic tunnel junctions (MTJ) with a ferromagnetic body/insulator/ferromagnetic body as a basic structure. According to its operating principle, it can be roughly divided into those using the Giant magnetoresistance effect (GMR effect) and those using the tunneling magnetoresistance effect. Should (Tunnel magnetoresistance effect, referred to as TMR effect), use CMR (Colossal magnetoresistance) effect, etc. The examples in Fig. 1(a), Fig. 1(b), and Fig. 1(c) are elements that utilize the TMR effect, but the present invention is not limited to this.

In the case of a device (device), the MTJ is arranged at the intersection of a bit line with a matrix-like wiring and a write word line. When a current flows through the bit line and the write word line, a composite magnetic field of the magnetic field induced by each wire is applied at the intersection of the bit line and the write word line. If the magnetic field generated by the bit line or the written word line alone does not exceed the magnetic field necessary to invert the free layer (switching magnetic field) and the combined magnetic field exceeds the switching magnetic field, it can only The write control is located at the cell at the intersection of the two wires. If the reversal of the magnetization is caused by the simultaneous rotation, the magnetic field required for the reversal is applied in an astroid curve.

The structure of the MTJ element of MRAM proposed before can be listed: (Co ₇₅ Fe ₂₅ ) ₈₀ B ₂₀ /AlOx/CoFe/Ru/CoFe/PtMn, Fe/MgO/Fe, Co ₂ MnAl/Al-O _X /CoFe, Co ₂ (Crl-xFex)Al(CCFA) CCFA/Al-O _X /Co-Fe, Fe/MgO/Fe, CoFe/MgO/CoFe, CoFeB/MgO/CoFeB, etc.

For technical details related to this type of MRAM, please refer to "MRAM/Rotating Memory Technology", Japanese Patent Laid-Open No. 2014-22730, and the "Standard Technology Collection (MRAM.)" posted on the home page of the Japan Patent Office. Rotating memory)" http://www.jpo.go.jp/shiryou/s_sonota/hyoujun_gijutsu/mram/mokuj i.htm (content disclosed on May 3, 2014), etc.

Fig. 1(b) shows a state after dry etching is performed on the laminate of Fig. 1(a). In this state, the substrate material in the portion not provided with the hard mask 1 is removed, and a hole H is formed in this portion. The method of dry etching is not particularly limited, and may be according to a usual method. For example, it can be performed by a dry etching method using a mixed gas of fluorine-based gas (gas) and O ₂ (fluorine-based gas/O ₂ ) in a flow ratio of 4/1 to 1/5 (fluorine-based gas) The ratio of gas to oxygen depends on the C content of the fluorine-based gas). Representative examples of the dry etching method are known as Japanese Patent Laid-Open No. 59-126506, Japanese Patent Laid-Open No. 59-46628, Japanese Patent Laid-Open No. 58-9108, Japanese Patent Laid-Open No. 58-2809, Japan The method described in Japanese Patent Laid-Open No. 57-148706 and Japanese Patent Laid-Open No. 61-41102.

At the same time, in this step, residue 7 remains inside the hole H formed. If the residue is supplied to the next step in a state where it remains as it is, it may cause poor conduction or material deterioration in the part when the device is manufactured, so it is preferable to completely remove it as much as possible. In addition, the hard mask 1 may be etched to a considerable extent in this step.

Preferred examples of dry etching conditions include the following.

Processing parameters (parameter)

Pressure: 0.5Pa~5Pa

Use gas: Ar/C ₄ F ₆ /O ₂ =500~1000/5~50/20~100mL/min

Processing temperature: 5℃~50℃

Power source: 100W~1000W

Upper bias (bias)/electrode bias = 100W~1000W/100W~1000W

Processing time: 50sec~1000sec

Fig. 1(c) shows an example of the form of the semiconductor substrate after the residue has been removed. In the present invention, as shown in the figure, it is preferable to maintain a good shape after etching without damaging or corroding the materials of each layer constituting the substrate. Fig. 2 shows a comparative example for comparison. In this example, erosion occurs in the ferromagnetic layer 3, the ferromagnetic layer 5, and the insulator layer 4 in the semiconductor substrate, and a damaged portion d where the material is shaved off occurs in the lateral direction. It is preferable to treat such damage d to be as small as possible so that such damage d does not occur if possible. However, the present invention is not limited by the embodiments and comparative examples shown in the drawings for explanation.

In addition, the figure shown in the figure shows the form in which the hard mask 1 remains even after the residue is removed, and the hard mask 1 may be removed simultaneously by the removal process of the residue.

The thickness of each layer is not particularly limited, but from the viewpoint that the effect of the present invention becomes significant, the ferromagnetic layer preferably has a thickness of 5 nm or more and 20 nm or less. From the viewpoint that the effect of the present invention becomes remarkable, the insulator layer preferably has a thickness of 10 nm or more and 20 nm or less. In terms of the function of the element, the free layer preferably has a thickness of 10 nm or more and 20 nm or less. In terms of the function of the element, the base electrode preferably has a thickness of 10 nm or more and 20 nm or less. In terms of the suitability for etching, the hard mask preferably has a thickness of 10 nm or more and 20 nm or less. In addition, unless otherwise specified, the thickness of each layer in the semiconductor substrate and the size of the member are evaluated by an average value of 10 arbitrary points observed with a transmission electron microscope (TEM).

[Etching residue removal composition]

The etching residue removal composition of the present invention contains an oxidizing agent, a glycol compound, and an amine compound. Hereinafter, each component including other components will be described.

(Oxidant)

Examples of the oxidizing agent include nitric acid, hydrogen peroxide, ammonium persulfate, perboric acid, peracetic acid, periodic acid, perchloric acid, or combinations thereof. In the present invention, hydrogen peroxide is particularly preferred.

The oxidizing agent is preferably contained at least 0.05% by mass relative to the total mass of the etching residue removal composition of this embodiment, more preferably at least 0.1% by mass, and particularly preferably at least 0.3% by mass. The upper limit is preferably 10% by mass or less, more preferably 7.5% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. From the viewpoint of obtaining good protective properties of the insulator layer, the ferromagnetic layer, etc., it is preferably set to the upper limit or less. By setting it as the above-mentioned lower limit or more, the sufficient removal rate of a residue can be ensured, and it is preferable.

The oxidizing agent may be used alone or in combination of two or more. When two or more types are used in combination, the combined use ratio is not particularly limited, and the total amount used is preferably the sum of two or more types as the concentration range. The concentration of each component should just be the said concentration at the time of use.

It can be understood that the oxidant plays a role of dissolving metal components (metal) in the system. It is difficult to predict what chemical state of the residue of the elements of each layer will be in the dry etching step. Therefore, it is difficult to specify how the etching residue removal composition of the present invention and the oxidizing agent contained therein act on which metal components. however, In this embodiment, it can be understood that by using an oxidizing agent to impart the removability of the metal component (metal), efficient residue removal can be achieved, and each layer of the substrate (especially strong (Magnetic layer, insulator layer) protection.

(Diol compound)

The diol compound means a compound having a site represented by the following formula (G) in the structure. The diol compound is preferably a compound containing a carbon atom, an oxygen atom, and a hydrogen atom. The diol compound preferably has a carbon number of 2 to 32, more preferably a carbon number of 4 to 24, and particularly preferably a carbon number of 4 to 18.

*-(OR ^G -O)-* (G)

* Indicates the bonding position. R ^G represents an alkylene group (the carbon number is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3).

The diol compound is preferably a compound represented by the following formula (O-1).

R ^O1 -(-OR ^O2 -) _n -OR ^O3 (O-1)

. R ^O1

R ^O1 is a hydrogen atom or an alkyl group with 1 to 12 carbons (preferably 1 to 6, more preferably 1 to 3), an aryl group with 6 to 14 carbons (preferably 6 to 10), or a carbon number 7-15 (preferably 7-11) aralkyl group. Among them, an alkyl group is preferred.

. R ^O2

R ^O2 is a linear or branched alkylene chain having 1 to 12 carbon atoms. When there are multiple RO ² , each of them may be different. R ^O2 preferably has a carbon number of 2-10, more preferably 2-6.

. n

n represents an integer of 0 or more and 8 or less, preferably an integer of 1 or more and 6 or less. When n is 2 or more, a plurality of ^RO2 may be different from each other. Among them, when R ^O1 and R ^O3 are both hydrogen atoms, there is no case where n is 0 (the case where there is no water molecule).

. R ^O3

R ^O3 is a hydrogen atom or an alkyl group having 1 to 12 carbons (preferably 1 to 6), an aryl group having 6 to 14 carbons (preferably 6 to 10), or 7 to 15 carbons (preferably 7~11) aralkyl group. Among them, a hydrogen atom or an alkyl group is preferred.

In addition, the diol compound is preferably selected according to the structure, which is easy to decompose, and is particularly difficult to decompose in combination with an oxidant.

The glycol compound is preferably selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and diethylene glycol. Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (2-(2-butoxyethoxy) ethanol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, One or more of the group consisting of triethylene glycol monobutyl ether and diethylene glycol dimethyl ether. Among them, alkanediol monoalkyl ether is more preferred, and diethylene glycol monobutyl ether is particularly preferred.

The concentration of the glycol compound is preferably 10% by mass in the total amount of the composition Above, it is more preferably 20% by mass or more. The upper limit is preferably 98% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass or less.

If compared with an oxidant, relative to 100 parts by mass of the oxidant, it is preferable to apply the diol compound at 100 parts by mass or more, more preferably at 500 parts by mass or more, and particularly preferably at 1000 parts by mass or more. The upper limit is preferably used below 100,000 parts by mass, more preferably used below 50,000 parts by mass, and particularly preferably used below 2000 parts by mass.

It can be understood that the diol compound exhibits a function of protecting the layer (ferromagnetic layer, insulator layer, etc.) on the semiconductor substrate side. The mechanism of action is not clear, but it can be understood that the amount of water in the system can be relatively reduced and the elution of the materials constituting the layer can be prevented. From this point of view, it is preferable to blend at the lower limit or more. The upper limit is preferably set to the upper limit or less in consideration of the amounts of other components.

In addition, in the present invention, only one kind of the diol compound may be used, or two or more kinds may be used in combination. When two or more types are used in combination, the combined use ratio is not particularly limited, and the total amount used is preferably the sum of two or more types as the concentration range. The concentration of each component should just be the said concentration at the time of use.

(Amine compound)

The term “amine compound” is a general term for compounds having any one of primary, secondary, and tertiary amine groups in the molecule. Here, the amine oxide compound has the meaning included therein. The amine compound is preferably a compound having carbon atoms, nitrogen atoms, and hydrogen atoms as essential constituent elements, and optionally containing oxygen atoms.

The amine compound can be any of the following formula (P-1) ~ formula (P-5) Represents the compound.

R ^P1 ~R ^P9 each independently represent an alkyl group (preferably carbon number 1 to 6), alkenyl group (preferably carbon number 2 to 6), alkynyl group (preferably carbon number 2 to 6), aryl group (Preferably carbon number 6 to 10), or heterocyclic group (preferably carbon number 2 to 6), acyl group (preferably carbon number 1 to 6), aryl acyl group (preferably carbon number 7 to 15), alkoxy group (preferably carbon number 1~6), aryloxy group (preferably carbon number 6-14), alkoxycarbonyl group (preferably carbon number 2-6), alkoxycarbonyl group Amino group (preferably carbon number 2-6) or a group represented by the following formula (x).

Among them, R ^P1 to R ^P9 are each independently preferably an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, or a group represented by the following formula (x), and an alkyl group and an alkane group are particularly preferred. An oxy group or a group represented by the following formula (x).

These groups may further have a substituent T. The optional substituent added therein is preferably a hydroxyl group (OH), a carboxyl group (COOH), a thio group (SH), an alkoxy group, or a thioalkoxy group. In addition, an alkyl group, an alkenyl group, and an alkynyl group may respectively intervene, for example, 1 to 4 O, S, CO, NR ^N (R ^N is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms).

X1-(Rx1-X2)mx-Rx2-* (x)

X1 represents a hydroxyl group, a thio group, an alkoxy group having 1 to 4 carbons, or a thioalkoxy group having 1 to 4 carbons. Among them, a hydroxyl group is preferred.

Rx1 and Rx2 each independently represent an alkylene group with 1 to 6 carbons, an alkenylene group with 2 to 6 carbons, an alkynylene group with 2 to 6 carbons, an arylalkylene group with 6 to 10 carbons, or these The combination. Among them, an alkylene group having 1 to 6 carbon atoms is preferred.

X2 represents O, S, CO, NR ^N. Among them, O is preferred.

mx represents an integer from 0 to 6. When mx is 2 or more, a plurality of Rx1 and X2 may be different. Rx1 and Rx2 may further have a substituent T.

* Is the bonding bond with the nitrogen atom.

R ^P10 has the same meaning as the substituent T described later. np is an integer from 0 to 5.

The amine compound is preferably selected from monoethanolamine, diglycolamine (aminoethoxyethanol), monoisopropanolamine, isobutanolamine, C ₂ ~C ₈ alkanolamine, methylethanolamine, N-methyl Alcohol, Diethanolamine, Triethanolamine, Methyldiethanolamine, Triethylamine, Pentamethyldiethylenetriamine, N-Methylmorphine-N-oxide (NMMO), Trimethyl Amine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorphine-N-oxide, N-methylpyrrolidine-N-oxide, N -Ethylpyrrolidine-N-oxide, these substituted derivatives, and the group consisting of these combinations. Among them, alkanolamine is preferred, and monoethanolamine or diglycolamine is particularly preferred. In addition, the term "substituent derivative" is a general term for compounds having a substituent (for example, substituent T described later) in each compound.

From the above viewpoint, the concentration of the amine compound in the etching residue removal composition is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10 Mass% or more, and more preferably 20 mass% or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

If compared with the oxidant, relative to 100 parts by mass of the oxidant, it is preferable to apply the amine compound in 100 parts by mass or more, more preferably 200 parts by mass or more, and particularly preferably 300 parts by mass or more. The upper limit is preferably used below 20,000 parts by mass, more preferably used below 10,000 parts by mass, and particularly preferably used below 8,000 parts by mass.

In addition, in the present invention, only one kind of the amine compound may be used, or two or more kinds may be used in combination. When two or more types are used in combination, the combined use ratio is not particularly limited, and the total amount used is preferably the sum of two or more types as the concentration range. The concentration of each component should just be the said concentration at the time of use.

It can be understood that the amine compound functions to protect a layer (for example, a ferromagnetic layer, an insulator layer, etc.) in the semiconductor substrate. For example, it can be considered that a protective film is formed on the surface of the layer to suppress its dissolution. From this viewpoint, it is preferable to apply above the lower limit. On the other hand, it is preferably applied below the upper limit so as not to hinder its performance due to the relationship with other components.

In this specification, in the compound or substituent. The linking group and the like include an alkyl group. Alkylene, alkenyl. Alkenylene, alkynyl. In the case of an alkynylene group, these may be cyclic or chain-like, and may be linear or branched, and may be substituted or unsubstituted with any group. At this time, the alkyl group. Alkylene, alkenyl. Alkenylene, alkynyl. The alkynylene group may interpose a heteroatom-containing group (for example, O, S, CO, NR ^N, etc.), and may form a ring structure along with it. In addition, when an aryl group, a heterocyclic group, etc. are contained, these may be a monocyclic ring or a condensed ring, and similarly may be substituted or unsubstituted.

In this specification, adjacent substituents may be linked to form a ring within the range where the effect of the present invention is exhibited. In this case, it may be connected via the heteroatom-containing group.

In this specification, each technical item such as temperature and thickness represented by the options of the substituents of the compound or the linking group may be combined with each other even if the respective technical items such as temperature and thickness are separately described in their respective lists.

In the present specification, when a compound is attached to the end and a compound is specified, it is within the scope that the effect of the present invention is exhibited, and the ion and salt are included in addition to the compound. In addition, the meaning includes the derivatives in the same way.

(water)

It is preferable that the etching residue removal composition of the present invention contains water (aqueous medium). Water (aqueous medium) may be an aqueous medium containing dissolved components within a range that does not impair the effects of the present invention, or may contain unavoidable trace amounts of mixed components. Among them, distilled water, ion-exchanged water, or ultrapure water is preferably purified water, and ultrapure water used in semiconductor manufacturing is particularly preferred. The concentration of water is not particularly limited, but is preferably more than 0% by mass, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is controlled to 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

In the etching residue removal composition of the present invention, in the absence of water, the residue removability may not be sufficiently exhibited. In this respect, it is preferable to use water. By suppressing the amount to a predetermined amount, the damage of the metal layer to be protected can be suppressed. Injury, so better.

The etching residue removal composition of the present invention may further contain optional components. Examples include: paragraph [0026] of Japanese Patent Application Publication No. 2014-093407, paragraph [0024] to paragraph [0027] of Japanese Patent Application Publication No. 2013-055087, paragraph of Japanese Patent Application Publication No. 2013-012614 [0024] ~ Each of the surfactants described in paragraph [0027] and the like. Alternatively, it may include: paragraph [0017] ~ paragraph [0038] of Japanese Patent Laid-open No. 2014-107434, paragraph [0033] ~ paragraph [0047] of Japanese Patent Laid-open No. 2014-103179, Japanese Patent Laid-open 2014- The additives (corrosion inhibitors, etc.) disclosed in paragraph [0017] to paragraph [0049] of the 093407 publication. However, in the present invention, a composition that does not contain these optional components is preferable, and it is particularly preferable to be an etching residue removal composition containing only an oxidizing agent, a glycol compound, an amine compound, and water. However, even in this case, it is impossible to prevent the inevitable impurities from being contained in the composition.

[pH value]

In the present invention, the pH of the etching residue removal composition is preferably an alkaline region. Specifically, the pH is preferably 9 or more and 14 or less, more preferably 11 or more and 14 or less. The pH value is preferably high within the above range, but if it is too high, the surface of the membrane may be deteriorated.

(Method of measuring pH value)

The pH value is a value measured with F-51 (trade name) manufactured by HORIBA Corporation at room temperature (25°C).

In addition, regarding the representation of the compound in this specification (for example, at the end When referred to as a compound), it is used in addition to the compound itself, but also includes the meaning of its salt and its ion. In addition, in the range where the desired effect is exhibited, the meaning includes a derivative obtained by introducing a substituent or the like and partially changing it.

In this manual, the unclear record has been replaced. The unsubstituted substituent (the same applies to the linking group) means that the group may have any substituent. Its unclear record has been replaced. The unsubstituted compound also has the same meaning. Preferable substituents include the following substituent T.

Examples of the substituent T include the following substituents.

Examples include alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, tertiary butyl, pentyl, heptyl, 1-ethylpentyl, benzyl , 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl (preferably an alkenyl with 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl ( Preferably they are alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopropyl Group, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), aryl (preferably an aryl group with 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl , 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (preferably a heterocyclic group with 2 to 20 carbon atoms, preferably having at least one oxygen atom, sulfur atom, or nitrogen atom Five-membered or six-membered heterocyclic groups, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), alkoxy Group (preferably an alkoxy group with 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropoxy, benzyloxy, etc.), aryloxy (preferably one with 6 to 26 carbon atoms) Aryloxy, such as phenoxy, 1-naphthoxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkane An oxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), an amine group (preferably containing 0 to 20 carbon atoms) Amino, alkylamino, arylamino, such as amino, N,N-dimethylamino, N,N-diethylamino, N-ethylamino, anilino, etc.), amine Sulfonyl (preferably a sulfasulfonyl with 0 to 20 carbon atoms, such as N,N-dimethylsulfasulfonyl, N-phenylsulfasulfonyl, etc.), sulfonyl (preferably carbon An acyl group having 1 to 20 atoms, such as acetyl, propionyl, butyryl, benzyl, etc.), acyloxy (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetoxy) , Benzoyloxy group, etc.), carbamate (preferably a carbamate with 1 to 20 carbon atoms, such as N,N-dimethylaminomethanoyl, N-phenylaminomethanoyl Etc.), an amide group (preferably an amide group with 1 to 20 carbon atoms, such as acetamido, benzamide, etc.), an alkylthio group (preferably an alkane with 1 to 20 carbon atoms) Thio groups, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio) Group, 3-methylphenylthio, 4-methoxyphenylthio, etc.), alkyl or arylsulfonyl (preferably an alkyl or arylsulfonyl having 1 to 20 carbon atoms, such as Methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc.), hydroxyl group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.).

In addition, each of the groups listed in these substituents T may further substitute the substituent T.

In the compound or substituent. The linking group and the like include an alkyl group. Alkylene, alkenyl. Alkenylene, alkynyl. In the case of an alkynylene group, these may be cyclic or chain-like, and may be linear or branched, and may be substituted or unsubstituted as described above.

Each substituent specified in this specification may be substituted by interposing the following linking group L within the range in which the effect of the present invention is exerted. For example, alkyl. Alkylene, alkenyl. The alkenylene group and the like may further include the following heterolinking group in the structure.

The linking group L is preferably a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably a carbon number 1 to 6, and more preferably 1 to 3), an alkenylene group having 2 to 10 carbon atoms (more preferably Is carbon number 2~6, more preferably 2~4), carbon number 6~22 arylene group (more preferably carbon number 6~10)], heterolinking group [carbonyl (-CO-), ether group (-O-), thioether group (-S-), imine group (-NR ^N -), imine linking group (R ^N -N=C<,-N=C(R ^N )-)], Or a linking base formed by combining these. In addition, when condensed to form a ring, the hydrocarbon linking group may form a double bond or a triple bond as appropriate to link. The formed ring is preferably a five-membered ring or a six-membered ring. The five-membered ring is preferably a nitrogen-containing five-membered ring. If the compound forming the ring is exemplified, pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazoline, and pyrazoline , Indoline, carbazole, or derivatives of these. Examples of the six-membered ring include piperidine, mopholine, piperazine, or derivatives of these. In addition, when an aryl group, a heterocyclic group, etc. are contained, these may be a monocyclic ring or a condensed ring, and similarly may be substituted or unsubstituted.

In this specification, the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, still more preferably 1 to 12, and particularly preferably 1 to 6. The number of linking atoms of the linking group is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more, preferably 2 or more. The number of connecting atoms refers to the minimum number of atoms that participate in the connection on the path between the structural parts scheduled for connection. For example, in the case of -CH ₂ -C(=O)-O-, the number of atoms constituting the linking group becomes 6, and the number of linking atoms becomes 3.

Specifically, the following combinations of linking groups can be cited. It is an oxycarbonyl group, a carbonyloxy group, a carbonate group, an amido group, a urethane group, a (oligomeric) alkoxy group (-(Lr-O-)x-: x is Integers above 1, and the same below), carbonyl (oligo)oxyalkylene groups (-CO-(O-Lr)x-) with 2-20 carbons, carbonyloxy with 2-20 carbons (oligo) Alkylene group (-COO-(Lr-O-)x-), (oligomeric) alkyleneimino group (-(Lr-NR ^N -)x) with carbon number 1-20, carbon number 2~ 20 alkylene (oligomeric) iminoalkylene (-Lr-(NR ^N -Lr-)x-), carbon 2-20 carbonyl (oligomeric) iminoalkylene (-CO-( NR ^N -Lr-)x-) etc.

Lr is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. The multiple Lr or R ^N , x, etc. need not be the same.

(Set)

The etching residue removal composition in the present invention may also be a set in which the raw material is divided into multiple parts. For example, an embodiment in which a composition containing the diol compound and an amine compound is prepared as the first liquid, and a composition containing an oxidizing agent and, if necessary, water is prepared as the second liquid. In this case, components such as other compounds may be separately separated or contained in the first liquid, the second liquid, or the other third liquids in advance. The ratio of each component of the set is such that the concentration of each component in the composition is appropriate relative to the total amount of the set.

The use example of the kit is preferably a state in which the two components are mixed to prepare a residue removal composition, and then applied to the treatment in a timely manner. Thereby, deterioration of performance due to decomposition of each component is not caused, and the desired residue removal effect can be effectively exhibited. Here, "just in time" after mixing refers to the period after mixing until the desired effect is lost. Specifically, it is preferably within 60 minutes, more preferably within 30 minutes, and even more preferably within 10 minutes, particularly preferably Within 1 minute. The lower limit is not particularly limited, but actually More than 1 second.

(container)

As long as the etching residue removal composition of the present invention (whether it is a kit or not) is not a problem, it can be filled in any container, stored and transported, and then used. In addition, for semiconductor applications, a container with high cleanliness and less elution of impurities is preferable. Examples of containers that can be used include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd., and the "Pure Bottle" manufactured by Kodama Resin Industries Co., Ltd. Etc., but not limited to these.

[Conditions for residue removal]

The residue removal process of the present invention can be carried out using a batch-wise device or a piece-by-piece device. The treatment temperature is preferably 10°C or higher, more preferably 30°C or higher, and particularly preferably 40°C or higher. The upper limit is preferably 100°C or lower, more preferably 80°C or lower, and still more preferably 70°C or lower. By setting it as the above-mentioned lower limit or more, the sufficient removal rate of a residue can be ensured, and it is preferable. By setting it below the upper limit value, the stability of the processing speed over time can be maintained, which is preferable. In addition, it will also reduce energy consumption.

The metal layer to be protected preferably has a low etching rate. For example, the etching rate [R1] of the ferromagnetic layer or insulating layer (specifically, COFe, CoFeB, MgO, Al ₂ O _3, etc.) in MRAM is preferably 10 Å/min or less, more preferably 50 Å/min or less, It is particularly preferably less than 1Å/min. The lower limit is not particularly limited, and the lower the speed, the better.

The exposed width of the metal layer (the thickness of each layer) is not particularly limited. From the viewpoint that the advantages of the invention become more pronounced, it is preferably 2 nm or more, and more preferably 4 nm or more. Similarly, from the viewpoint of the significance of the effect, the upper limit is actually 1000 nm or less, preferably 100 nm or less, and more preferably 20 nm or less.

[Manufacturing of Magnetoresistive Memory]

In the present embodiment, it is preferable to manufacture a magnetoresistive memory (semiconductor substrate product) having a desired structure through the following steps: a step of preparing a silicon wafer, and making the silicon wafer formed on the silicon wafer A step of a semiconductor substrate of a metal or metal compound layer, a step of dry etching the semiconductor substrate, a step of applying a residue removal composition to the semiconductor substrate to remove an etching residue. The order of the steps is not limitedly interpreted, and other steps may be included between each step.

The wafer size is not particularly limited, and a diameter of 8 inches, a diameter of 12 inches, or a diameter of 14 inches (1 inch = 25.4 mm) can be preferably used.

In addition, when it is described as "preparation" in this manual, in addition to preparing for synthesizing or preparing specific materials, it also includes the meaning of preparing a reservation through purchase, etc. In addition, in this specification, the case where the composition (chemical solution) is used for the treatment of each material of the semiconductor substrate is referred to as "application", and the embodiment is not particularly limited. For example, it is widely included that the composition is brought into contact with the substrate, and specifically, it may be immersed and etched in a batch type, or it may be etched by spitting out a piece by piece.

In this specification, the term “semiconductor substrate” is used to include not only the wafer but also the entire substrate structure on which the circuit structure is applied. The term “semiconductor substrate member” refers to a member constituting the semiconductor substrate defined above, and may include one material or multiple materials. In addition, there is a semiconductor substrate area that will be processed In the case of nicknamed a semiconductor substrate product, it is further distinguished if necessary, and the chip and the processed product thereof which are diced and taken out are called a semiconductor element. That is, in a broad sense, semiconductor elements or semiconductor products incorporating semiconductor elements are semiconductor substrate products.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to the following examples. In addition, the% and the part shown as a formula or a compounding amount in an Example are a mass standard unless otherwise specified.

(Production of test board)

On a commercially available silicon substrate (diameter: 12 inches), each layer is formed by MBE (Molecular Beam Epitaxy) or Chemical Vapor Deposition (Chemical Vapor Deposition, CVD) in a manner as shown in FIG. 1(a). The thickness of each layer is set to 500Å. The predetermined part patterned by the hard mask is subjected to dry etching under normal conditions and processed so as to have the structure of FIG. 1(b).

(Preparation of residue removal composition)

The residue removal composition (removal liquid) used in each test was prepared according to the composition described in the following Table 1-1. At this time, the components 1 to 3 in the table were mixed to prepare the first liquid. On the other hand, a second liquid (hydrogen peroxide water) prepared by mixing component 4 and component 5 in the table is prepared. The first liquid and the second liquid were mixed, and thereafter (within 2 minutes), each residue removal test was performed immediately. The test results are shown in the table.

(Residue removal test)

Put the test substrate into a container filled with removal liquid, and feed it at 250 rpm Line stirring. The treatment temperature was set to 60°C, and the treatment time was set to 10 minutes. The treated test substrate was taken out and rinsed with isopropanol.

(Etching speed [ER])

Regarding the etching rate (ER), instead of using a patterned substrate with the hard mask added, a substrate in which each layer of Table 1 was exposed was used. Specifically, a substrate in which a CoFeB layer is formed on a commercially available silicon wafer and a substrate in which a MgO layer is formed are separately prepared. The thickness of each layer is set to 500Å. In the same manner as described above, the substrate was put into a container filled with the removal liquid and stirred. The stirring conditions, temperature, etc. were set to be the same as the above-mentioned residue removal test. It is calculated by measuring the film thickness before and after the etching process using an ellipsometry (spectroscopic ellipsometry, using Vase of J.A. Woollam Japan Co., Ltd.). The average value of 5 points is used (measurement condition measurement range: 1.2eV-2.5eV, measurement angle: 70 degrees, 75 degrees).

(Residue removability, damage)

The evaluation of the residue removability and damage of the test substrate was performed by observing the substrate after the treatment with a transmission electron microscope (TEM) and using the imaging image (photograph) thereof. The observation field was set to 5 locations in the cross section of Fig. 1(a), Fig. 1(b), and Fig. 1(c), and the results were evaluated by averaging. The evaluation criteria are as follows.

. Residue removal

C: The residue remains so as to cover the entire wall surface

B: The residue remains to cover more than one third of the wall surface

A: No residues are seen on the wall, or remain with less than one-third coverage, or no residue at all

. damage

C: A lot of tiny holes are visible on the wall (damage d)

B: Many tiny holes are visible on the wall (damage d)

A: No tiny holes are seen on the wall (damage d)

Notes to the table:

DEGMBE: Diethylene glycol monobutyl ether

(2-(2-Butoxyethoxy)ethanol)

TEGDME: Triethylene glycol dimethyl ether

MEA: Monoethanolamine (2-aminoethanol)

DGA: Diglycolamine (2-(2-aminoethoxy)ethanol)

1Å=0.1nm

The present invention and its implementation are described above, but as long as we do not specify it, it is not intended to limit our invention in any details of the description. It can be considered that it should not violate the scope of the attached patent application. The spirit and scope of the invention are explained extensively.

This application is an application claiming priority based on Japanese Patent Application No. 2014-139864 filed in Japan on July 7, 2014, and these are all incorporated herein by reference and their contents are incorporated into this specification Part of the record.

1: Hard mask

2: free layer

3: The second ferromagnetic layer

4: Insulator layer

5: The first ferromagnetic layer

6: Base electrode

7: Residue

H: Hole

Claims (29)

An etching residue removal composition containing an oxidizing agent, a glycol compound, and two or more amine compounds, and having a moisture content of 0.5% by mass or more and less than 15% by mass based on the total composition. The content of the two or more amine compounds when the amount is used as a reference is 5% by mass or more and 90% by mass or less. The etching residue removal composition described in the first item of the patent application, wherein the oxidizing agent is hydrogen peroxide. The etching residue removal composition described in item 1 or item 2 of the scope of patent application, wherein the diol compound is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and ethylene glycol. Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, three One or more of the group consisting of ethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and diethylene glycol dimethyl ether. The etching residue removal composition according to item 1 or item 2 of the scope of patent application, wherein the two or more amine compounds are selected from the group consisting of monoethanolamine, diglycolamine, monoisopropanolamine, and isobutanolamine , C ₂ ~C ₈ alkanolamine, methylethanolamine, N-methylaminoethanol, diethanolamine, triethanolamine, methyldiethanolamine, triethylamine, pentamethyldiethylenetriamine, N- Methylmorphine-N-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorphine-N-oxide , N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide, substituted derivatives of these, and amine species in the group consisting of combinations of these. The etching residue removal composition described in item 1 or item 2 of the scope of the patent application, wherein the content of the two or more amine compounds based on the total composition is 5 mass% or more and 50 mass% or less . The etching residue removal composition described in item 1 or item 2 of the scope of patent application is used for the removal of hard masks. The etching residue removal composition described in item 1 or item 2 of the scope of patent application is applied to a substrate containing CoFeB, CoFe, MgO, or Al ₂ O ₃ , and its dissolution rate is 1 Å/min or less. An etching residue removal method, which is to apply the etching residue removal composition as described in any one of the 1st to 7th items of the scope of the patent application to a ferromagnetic layer to which any one of CoFeB and CoFe is attached Etching residue and the substrate of the etching residue of the insulator layer containing either MgO and Al ₂ O ₃ . The etching residue removal method as described in item 8 of the scope of patent application is further applied to a substrate with a hard mask. The method for removing etching residues described in the scope of the patent application, which suppresses or prevents damage to at least any one of the ferromagnetic layer and the insulator layer, while removing at least any one of the ferromagnetic layer and the insulator layer The residue generated in the etching is removed. A method for manufacturing a magnetoresistive memory is to manufacture a magnetoresistive memory through the method described in item 8 of the scope of the patent application. An etching residue removal kit comprising a first liquid containing an oxidizing agent, and a second liquid containing a diol compound and two or more amine compounds. The total amount of moisture in the first liquid and the second liquid is 0.5% by mass or more and less than 15% by mass, and the content of the two or more amine compounds is 5% by mass or more and 90% by mass or less. An etching residue removal method, which uses the etching residue removal method of the etching residue removal kit as described in the 12th patent application, and the first liquid and the second liquid are before the residue removal process Mix and use when appropriate. An etching residue removal composition containing an oxidizing agent, a glycol compound, and two or more amine compounds, and having a moisture content of 30% by mass or less based on the total amount of the composition, with respect to 100 parts by mass of the oxidizing agent , The diol compound is 100 parts by mass or more and 100,000 parts by mass or less. The etching residue removal composition according to the 14th patent application, wherein the oxidizing agent is hydrogen peroxide. The etching residue removal composition according to item 14 of the scope of patent application, wherein the glycol compound is selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol mono One or more of the group consisting of diethyl ether, triethylene glycol monobutyl ether, and diethylene glycol dimethyl ether. The etching residue removal composition according to item 14 of the scope of patent application, wherein the amine compound comprises selected from the group consisting of monoethanolamine, diglycolamine, monoisopropanolamine, isobutanolamine, and C ₂ ~C ₈ alkanol Amine, methylethanolamine, N-methylaminoethanol, diethanolamine, triethanolamine, methyldiethanolamine, triethylamine, pentamethyldiethylenetriamine, N-methylmorphine-N- Oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorphine-N-oxide, N-methylpyrrolidine- The amine species in the group consisting of N-oxide, N-ethylpyrrolidine-N-oxide, substituted derivatives of these, and combinations of these. The etching residue removal composition described in claim 14 has a moisture content of 0.5% by mass or more and less than 15% by mass based on the total amount of the composition. The etching residue removal composition according to the 14th patent application, wherein the content of the amine compound based on the total composition is 5 mass% or more and 50 mass% or less. The etching residue removal composition as described in item 14 of the scope of the patent application is used for the removal of hard masks. The etching residue removal composition described in item 14 of the scope of patent application is applied to a substrate containing CoFeB, CoFe, MgO, or Al ₂ O ₃ , and its dissolution rate is 1 Å/min or less. An etching residue removal composition containing an oxidizing agent, a glycol compound, and two or more amine compounds, and having a moisture content of 30% by mass or less based on the total amount of the composition, with respect to 100 parts by mass of the oxidizing agent The amine compound is 100 parts by mass or more and 10,000 parts by mass or less. The etching residue removal composition described in item 22 of the scope of patent application, The oxidant is hydrogen peroxide. The etching residue removal composition according to item 22 of the scope of patent application, wherein the glycol compound is selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol mono One or more of the group consisting of diethyl ether, triethylene glycol monobutyl ether, and diethylene glycol dimethyl ether. The etching residue removal composition according to item 22 of the scope of patent application, wherein the amine compound comprises selected from monoethanolamine, diglycolamine, monoisopropanolamine, isobutanolamine, and C ₂ ~C ₈ alkanol Amine, methylethanolamine, N-methylaminoethanol, diethanolamine, triethanolamine, methyldiethanolamine, triethylamine, pentamethyldiethylenetriamine, N-methylmorphine-N- Oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, N-ethylmorphine-N-oxide, N-methylpyrrolidine- The amine species in the group consisting of N-oxide, N-ethylpyrrolidine-N-oxide, substituted derivatives of these, and combinations of these. The etching residue removal composition described in the scope of patent application item 22 has a moisture content of 0.5% by mass or more and less than 15% by mass based on the total amount of the composition. The etching residue removal composition as described in claim 22, wherein the content of the amine compound based on the total composition is 5% by mass or more and 50% by mass or less. The etching residue removal composition described in item 22 of the scope of patent application, It is used for the removal of hard masks. The etching residue removal composition described in the 22nd scope of the patent application is applied to a substrate containing CoFeB, CoFe, MgO, or Al ₂ O ₃ , and its dissolution rate is 1 Å/min or less.

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