KR20130049502A - Composition for removing magnetic membrane and magnetic membrane residues - Google Patents
Composition for removing magnetic membrane and magnetic membrane residues Download PDFInfo
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- KR20130049502A KR20130049502A KR1020110114579A KR20110114579A KR20130049502A KR 20130049502 A KR20130049502 A KR 20130049502A KR 1020110114579 A KR1020110114579 A KR 1020110114579A KR 20110114579 A KR20110114579 A KR 20110114579A KR 20130049502 A KR20130049502 A KR 20130049502A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
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Abstract
Description
The present invention relates to a magnetic film and a composition for removing magnetic film residue.
Magnetic Random Access Memory (MRAM) is a memory device capable of storing nonvolatile data at low power consumption. The magnetic random access memory (MRAM) is a nonvolatile data storage device using a plurality of thin film magnetic bodies formed in a semiconductor integrated circuit. And a random access to each of the plurality of thin film magnetic bodies. The performance of the magnetic memory device was improved by using a thin film magnetic material using a magnetic tunnel junction as a memory cell. In particular, Korean Patent Registration No. 10-0512180 describes the magnetoresistance ratio and resistance of a magnetic tunnel junction (MTJ). In order to form a magnetic tunnel junction of a magnetic memory device having excellent characteristics, an oxide film is formed on a lower electrode as shown in FIG. 1, and the fixed layer including at least a seed layer, an antiferromagnetic layer, and a first ferromagnetic layer on the oxide film. Provided are a tunneling barrier oriented in the same crystal direction as the maximum dense surface direction of a layer and crystal grown in the largest dense surface, a magnetic tunnel junction in which a free layer including at least a second ferromagnetic layer is sequentially stacked and a method of forming the same.
In more detail with respect to the specific stacked structure of the MRAM, as shown in FIG. 1, the magnetic film (100, 120) and the
In the case of dry etching the stacked MRAM, the structure of FIG. 2 is ideal. However, in the case of the actual dry etching, the
Therefore, it is necessary to remove the
By such a need, Korean Patent Laid-Open Publication No. 10-2003-0092310 provides a dry etching method using a carbonyl group-containing gas and a halogen element-containing gas as a dry etching method of a multilayer film material including a metal thin film. The etching method is dry etching using gas, and thus is not suitable when a wet etching method is required. In addition, Korean Patent Laid-Open Publication No. 10-2004-0061227 provides an etching solution containing an organic acid as an etching solution for etching a magnetic film of a magnetic memory device, but the organic acid is limited to an organic acid having a carboxyl group and a hydroxyl group. The scope of use is narrow. U.S. Patent No. 6426012 also provides a composition for use in magnetic film laser etching, but this also limits the organic acid to a composition containing dicarboxylic acid.
The present invention is to solve the problems of the prior art as described above, the magnetic film and the magnetic film excellent in the ability to remove the magnetic components remaining in the process of etching the magnetic layer, tunneling barrier, etc. during the manufacture of the magnetic memory device It is an object to provide a composition for removing residues.
The present invention provides a composition for removing magnetic film and magnetic film residue comprising (a) at least one of aliphatic or aromatic amines and (b) at least one of alcohols or glycol ethers.
In another aspect, the present invention, after immersing the substrate in which the magnetic residue is present in the composition for removing the magnetic film residue, the magnetic film and the magnetic film residual comprising a step of immersing for 10 to 30 minutes at a temperature of 30 ~ 80 ℃ Provide a method for removing water.
Magnetic film residue removal composition comprising at least one of the aliphatic or aromatic amines of the present invention and at least one of alcohols or glycol ethers is excellent in the ability to remove the magnetic components, magnetic film used during the manufacturing process of the magnetic memory device And magnetic film residues can be effectively removed.
1 is a diagram illustrating a basic stacked structure of a magnetic random access memory.
2 is a diagram illustrating an ideal structure after dry etching of a magnetic random access memory.
3 is a diagram illustrating a structure in which residues appear around a stacked layer after dry etching of a magnetic random access memory.
4 is a diagram showing an ideal structure after the residue around the magnetic random access memory laminate is removed using a wet process.
The composition for removing magnetic film residues of the present invention comprises one or more of (a) aliphatic or aromatic amines and (b) one or more of alcohols, glycols, or glycol ethers. Each component is described below.
(a) aliphatic or aromatic amines
The (a) aliphatic or aromatic amine is a compound containing a nitrogen (N) atom, has a strong basic properties, it is easy to exchange electrons with surrounding elements by the unshared electron pair in the nitrogen atom, the movement of electrons By reacting with the metal component it can exhibit the effect of oxidizing or reducing the metal, and due to this redox effect has the effect of corroding metals such as aluminum and the like. As described above, in the case of the amine, the magnetic film and the magnetic film residue may be etched by using the property of transmitting and receiving electrons by the unshared electron pair of the nitrogen atom included in the amine. In the present invention, it was confirmed that the etching effect of the magnetic film can be realized by adding the magnetic film and the magnetic film residue removal composition.
As the aliphatic amine included in the composition, an alkyl amine or an alkanol amine can be used. Specific examples of the alkyl amine include methylamine, propylamine, dimethylamine, trimethylamine, ethylenediamine, and the like. Specific examples include monoethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, butanolamine, butyl monoethanolamine, N-methylethanolamine And ethyl diethanolamine; these may be used alone or in combination of two or more thereof.
Specific examples of the aromatic amine included in the composition include aniline, o-toluidine, 2,4,6-trimethylaniline, anisidine, N-methylaniline, and the like, which may be used alone or in combination of two or more thereof. Can be.
The content of one or more of the (a) aliphatic amine or aromatic amine is not particularly limited, and may be adjusted by varying the content according to the process conditions, but preferably 5 to 40 wt% based on the total amount of the composition. More preferably 20% to 30% by weight. In case of less than 5 wt%, it is difficult to obtain the desired etching amount of the magnetic film due to the lack of etching ability of the magnetic film.In the case of more than 40% by weight, the etching amount of the magnetic film increases due to the increase in the amount of amine due to the increase of the amine content. It is undesirable in terms of cost of the contrast composition.
(b) alcohols, glycols or glycol ethers
The alcohol (b), glycol or glycol ether has the effect of preventing the etching of the barrier oxide. There is a problem that the oxide is corroded by the water contained in the composition, by using one or more of alcohol, glycol or glycol ether as a solvent to prevent the possibility of etching of the barrier oxide that may occur by contact with water.
The alcohol contained in the composition may be a high boiling point alcohols, preferably tetrahydrofurfuryl alcohol (THFA; tetrahydrofurfuryl alcohol), furfuryl alcohol and the like, these may be used alone or two or more It can be mixed and used.
The glycol included in the composition is ethylene glycol,Trimethylene glycol,Tetramethylene glycol, 1,3-butanediol, propylene glycol, butylene glycol, dimethylene glycol, pentylene glycol, These can be used individually or in mixture of 2 or more types.
The glycol ethers contained in the composition include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, triethylene glycol monomethyl ether It is mentioned, and these may be used individually or in combination of two or more.
At least one of (b) alcohol, glycol, or glycol ether is a solvent, which is not particularly limited with respect to the total weight of the composition. However, when the amount of the solvent is small, the viscosity of the composition is high, so that it is difficult to apply the process, or sulfonic acid is dissolved. The problem may not occur, it is preferable to include from 60% to 95% by weight.
The above-mentioned magnetic film removing method may be performed by a method commonly known in the art. For example, deposition, spraying, or a method using deposition and spraying may be used, in which case, the temperature conditions are usually 30 to 80 ° C., preferably 50 to 70 ° C., and deposition, spray, or deposition and spraying The time is usually 5 seconds to 30 minutes, preferably 5 minutes to 20 minutes. However, these conditions are not strictly applied and can be selected as easy or suitable conditions by those skilled in the art.
In addition, in the case of washing after removing the magnetic body film, it is preferable to use alcohol or the like as the cleaning solution, since it is possible to remove the barrier film such as aluminum oxide when washing with water, and in this case, washing with isopropanol is particularly preferable. .
Hereinafter, the present invention will be described in more detail using examples, comparative examples, and experimental examples. However, the following Examples, Comparative Examples and Experimental Examples are for illustrating the present invention, the present invention is not limited to the following Examples, Comparative Examples and Experimental Examples can be variously modified and changed.
Examples 1-9 and Comparative Examples 1-3: Preparation of magnetic film and composition for removing magnetic film residue
By mixing the components and contents shown in Table 1 below to prepare a magnetic film and a composition for removing the magnetic film residue. All of the units of content in Table 1 are by weight.
THFA: tetrahydrofurfuryl alcohol
MTG: triethylene glycol monomethyl ether
MIPA: Monoisopropanolamine
DETA: diethanolamine
Experimental Example 1 Evaluation of Etching Ability of Magnetic Film and Magnetic Film Residue
The evaluation of the etching ability of the magnetic film and the composition for removing the magnetic film residue on the magnetic film was performed using a substrate in which CoFe was laminated to a thickness of 200 GPa. First, the CoFe-laminated substrate was immersed for 10 minutes at 60 ° C. in the magnetic film residue removal composition prepared in Examples 1 to 9 and Comparative Examples 1 to 3, followed by washing and drying with isopropanol. The substrate was etched. The thickness of the CoFe layer etched on the substrate was evaluated using a 4-point probe (Changmin Tech, CMT series). The results are shown in the etching amount of CoFe in Table 2 below.
(Å for 10min)
As confirmed in Table 2 above, the composition for removing the magnetic body film and the magnetic film residue of Examples 1 to 9 containing 5% to 40% by weight of at least one of aliphatic or aromatic amines based on the total weight of the composition While exhibiting excellent etching performance for the magnetic film, the composition for removing the magnetic film and the magnetic film residue of Comparative Examples 1 to 3 that do not satisfy the above range shows poor etching performance. Etching effects on barrier oxides were not found in all compositions.
From these results, it can be seen that the magnetic film and the composition for removing the magnetic film residue of the present invention not only have excellent etching ability of the magnetic film but also no etching effect of the barrier oxide.
Claims (10)
In the total amount of the composition,
5% to 40% by weight of at least one of the above (a) aliphatic or aromatic amines; And
(B) at least one of alcohol, glycol, or glycol ether, 60 to 95% by weight of the magnetic film and the composition for removing the magnetic film residues, characterized in that it comprises.
Wherein said aliphatic amine is any one of alkyl amines or alkanol amines or mixtures thereof.
The alkyl amine is a composition for removing the magnetic film and magnetic film residues, characterized in that any one or a mixture thereof selected from the group consisting of methylamine, propylamine, dimethylamine, trimethylamine, ethylenediamine.
The alkanol amines are monoethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, butanolamine, butyl monoethanolamine, N -methyl A composition for removing a magnetic film and magnetic film residues, characterized in that any one or a mixture thereof selected from the group consisting of ethanolamine, ethyl diethanolamine.
The aromatic amine may be any one selected from the group consisting of aniline, o-toluidine, 2,4,6-trimethylaniline, anisidine, and N-methylaniline or mixtures thereof. Removal composition.
The (b) the alcohol is a composition for removing magnetic film and magnetic film residues, characterized in that any one or a mixture of tetrahydrofurfuryl alcohol and furfuryl alcohol.
(B) glycol is any one selected from the group consisting of ethylene glycol , trimethylene glycol , tetramethylene glycol, 1,3-butanediol, propylene glycol, butylene glycol, dimethylene glycol, pentylene glycol, or a mixture thereof The magnetic film and the composition for removing the magnetic film residues, characterized in that.
(B) the glycol ether is ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol dipropyl In the group consisting of ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, triethylene glycol monomethyl ether Magnetic film, characterized in that any one or a mixture thereof is chosen and magnetic films, the residue removal composition.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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KR1020110114579A KR20130049502A (en) | 2011-11-04 | 2011-11-04 | Composition for removing magnetic membrane and magnetic membrane residues |
PCT/KR2012/009093 WO2013066058A2 (en) | 2011-11-04 | 2012-11-01 | Magnetic substance layer and composition for removing residue from a magnetic substance layer |
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KR1020110114579A KR20130049502A (en) | 2011-11-04 | 2011-11-04 | Composition for removing magnetic membrane and magnetic membrane residues |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10049883B2 (en) | 2014-10-31 | 2018-08-14 | Fujifilm Corporation | MRAM dry etching residue removal composition, method of producing magnetoresistive random access memory, and cobalt removal composition |
US10062837B2 (en) | 2015-11-25 | 2018-08-28 | Samsung Electronics Co., Ltd. | Method of forming magnetic patterns, and method of manufacturing magnetic memory devices |
-
2011
- 2011-11-04 KR KR1020110114579A patent/KR20130049502A/en not_active Application Discontinuation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10049883B2 (en) | 2014-10-31 | 2018-08-14 | Fujifilm Corporation | MRAM dry etching residue removal composition, method of producing magnetoresistive random access memory, and cobalt removal composition |
US10062837B2 (en) | 2015-11-25 | 2018-08-28 | Samsung Electronics Co., Ltd. | Method of forming magnetic patterns, and method of manufacturing magnetic memory devices |
US10833251B2 (en) | 2015-11-25 | 2020-11-10 | Samsung Electronics Co., Ltd. | Composition for cleaning magnetic patterns |
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