JP2023076384A - Stripper composition for photoresist removal, and photoresist peeling method using the same - Google Patents

Abstract

To provide a stripper composition for photoresist removal which has excellent peeling force against a photoresist, suppresses corrosion on a lower metal film in a peeling step, and has improved photoresist solubility.SOLUTION: A stripper composition for photoresist removal contains a primary or secondary linear amine compound, a cyclic amine compound, an amide compound which has a boiling point of 180°C or higher and one to two 1-5C straight-chain or branched-chain alkyl groups substituted with nitrogen, a protonic solvent, and a corrosion inhibitor, wherein 60-90 wt.% of the amide compound has the boiling point of 180°C or higher and the one to two 1-5C straight-chain or branched-chain alkyl groups substituted with nitrogen is contained with respect to the total weight of the stripper composition, and a weight ratio of the primary or secondary linear amine compound and the cyclic amine compound is 100:1 to 1:1 in a weight ratio.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a stripper composition for removing photoresist and a method of stripping photoresist using the same, and more particularly, it has excellent stripping power against photoresist and suppresses corrosion of the underlying metal film during the stripping process. and a photoresist removal stripper composition having improved photoresist solubility and a photoresist stripping method using the same.

In the fine circuit process of liquid crystal display elements or the manufacturing process of semiconductor integrated circuits, conductive metal films such as aluminum, aluminum alloys, copper, copper alloys, molybdenum, molybdenum alloys, silicon oxide films, silicon nitride films, and acrylic insulating films are formed on substrates. Various lower layers such as insulating layers are formed, and a photoresist is evenly coated on the lower layers, selectively exposed and developed to form a photoresist pattern, and then removed. It includes various steps of patterning the underlying film as a mask. After the patterning process, the photoresist remaining on the underlying layer is removed, and a stripper composition for removing the photoresist is used for this purpose.

Stripper compositions containing amine compounds, protic polar solvents and aprotic polar solvents have long been widely known and mainly used. Such stripper compositions are known to exhibit some degree of removal and stripping power for photoresist.

However, such a conventional stripper composition has a problem in that when a large amount of photoresist is stripped, the decomposition of the amine compound is accelerated over time, resulting in a decrease in stripping power and rinsing power over time. In particular, such problems can be exacerbated when a portion of the residual photoresist dissolves into the stripper composition upon use and recycling of the stripper composition.

In addition, if the photoresist denatured by dry etching remains on the substrate, a film floating phenomenon or a wiring disconnection phenomenon occurs during the post-process, which affects the TFT yield.

Therefore, there is a demand for the development of a new stripper composition that has excellent stripping power even under strong hard baking conditions, suppresses corrosion of the underlying metal film, and has improved photoresist solubility.

SUMMARY OF THE INVENTION The present invention provides a stripper composition for removing photoresist that has excellent stripping power for photoresist, inhibits corrosion of the underlying metal film during the stripping process, and has improved photoresist solubility.

The present invention also provides a method for stripping photoresist using the stripper composition for removing photoresist.

In the present specification, a primary or secondary chain amine compound; a cyclic amine compound; a linear or branched alkyl group having a boiling point (bp) of 180° C. or higher and having 1 to 5 carbon atoms on the nitrogen is 1 to 1 A disubstituted amide compound; a protic solvent; and a corrosion inhibitor, wherein the boiling point (bp) is 180° C. or higher, and one straight or branched chain alkyl group having 1 to 5 carbon atoms is present on the nitrogen. The disubstituted amide compound is present in an amount of 60 to 90% by weight based on the total weight of the stripper composition, and the weight ratio of the primary or secondary linear amine compound to the cyclic amine compound is 100:1 to 1. : 1 is provided.

Also provided herein is a method of stripping a photoresist, comprising stripping the photoresist using the stripper composition for removing photoresist.

Hereinafter, a stripper composition for removing photoresist and a method for stripping photoresist using the same according to specific embodiments of the present invention will be described in more detail.

The terminology used herein is merely used to describe exemplary embodiments and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates a different meaning. As used herein, terms such as "include," "comprise," or "have" are intended to specify the presence of embodied features, numbers, steps, components, or combinations thereof, and or the presence or addition of other features, figures, steps, components, or combinations thereof, etc., are not to be precluded.

Since the present invention is susceptible to various modifications and may have various forms, specific embodiments will be illustrated and described in detail below. However, it is not intended to limit the invention to the particular disclosed forms, but should be construed to include all modifications, equivalents or alternatives falling within the spirit and scope of the foregoing.

According to one embodiment of the invention, the primary or secondary chain amine compound; the cyclic amine compound; a protic solvent; and a corrosion inhibitor, wherein the linear or branched alkyl group having 1 to 5 carbon atoms and having a boiling point (bp) of 180° C. or higher is The amide compound substituted with 1 to 2 nitrogen atoms is contained in an amount of 60 to 90% by weight based on the total weight of the stripper composition, and the weight ratio of the primary or secondary linear amine compound to the cyclic amine compound is 100. :1 to 1:1.

The inventors of the present invention conducted research on a stripper composition for removing photoresist and found that a stripper composition for removing photoresist containing all of the above components had excellent stripping power for the photoresist, and the underlying metal was removed during the stripping process. The invention was completed by confirming experimentally that it inhibits corrosion to the film and has improved photoresist solubility.

As described above, the stripper composition for removing photoresist of the above embodiment has 1 to 2 linear or branched alkyl groups having 1 to 5 carbon atoms and a boiling point (bp) of 180° C. or higher on nitrogen. The amide compound having a boiling point (bp) of 180° C. or higher and having 1 to 2 C 1-5 linear or branched alkyl groups substituted on nitrogen is a stripper. It is 60 to 90% by weight based on the total weight of the composition, and the weight ratio of the primary or secondary chain amine compound and the cyclic amine compound is 100:1 to 1:1, so that the can have improved strength and improved photoresist solubility.

The amide compound having a boiling point (bp) of 180° C. or higher and having 1 to 2 linear or branched alkyl groups of 1 to 5 carbon atoms substituted on the nitrogen is an aprotic polar organic solvent that dissolves the amine compound. Since the stripper composition for removing the photoresist can be dissolved well, the stripper composition for removing the photoresist can be effectively impregnated on the underlying layer, thereby improving the stripping force and the rinsing force of the stripper composition.

The amide compound in which nitrogen is substituted with 1 to 2 linear or branched alkyl groups having 1 to 5 carbon atoms has a boiling point (bp) of 180°C or higher, or 182°C or higher, or 185°C. or higher, or 190°C or higher, or 250°C or lower, or 210°C or lower, or 180°C to 250°C, or 180°C to 210°C, or 182°C to 250°C, or 182°C to 210°C, or 185°C to 250°C ° C., or 185° C. to 210° C., or 190° C. to 250° C., or 190° C. to 210° C., and when stripping the photoresist using a stripper composition containing an amide compound having the predetermined boiling point, the amide compound can reduce loss due to volatilization of amine compounds, hardly induces decomposition of amine compounds over time, and the stripper composition of the embodiment maintains excellent physical properties such as stripping power and rinsing power for a long period of time. can be made to

The boiling point can be applied without limitation to a commonly known organic solvent measurement method (e.g., Simple Distillation apparatus, etc.), normal temperature (20 ° C. to 30 ° C. temperature) and atmospheric pressure (1 atm pressure).

On the other hand, if the boiling point (bp) of the amide compound in which 1 to 2 straight or branched alkyl groups having 1 to 5 carbon atoms are substituted on nitrogen is excessively high, the waste liquid can be subsequently distilled under reduced pressure. It is preferable to have a boiling point of 250° C. or less because the recovery efficiency becomes low.

On the other hand, the amide compound having a boiling point (bp) of 180° C. or higher and having 1 to 2 straight or branched alkyl groups of 1 to 5 carbon atoms substituted on the nitrogen is added to the total weight of the stripper composition. In contrast, more specifically, based on 100% by weight of the total weight of the stripper composition, 60% by weight or more, or 65% by weight or more, or 70% by weight or more, and 90% by weight or less, or 85% by weight or less , or up to 80% by weight.

In the stripper composition for removing photoresist according to one embodiment, nitrogen is substituted with 1 to 2 linear or branched alkyl groups having 1 to 5 carbon atoms and having a boiling point (bp) of 180° C. or higher. When the amide compound is included in the above content, the solubility of the photoresist is increased, excellent stripping force is ensured, and the stripping force and rinse force can be maintained for a long period of time.

In addition, if the used photoresist remains on the substrate, a film floating phenomenon or a wiring disconnection phenomenon occurs during the post-process, which affects the process yield. The product contains an amide compound having a boiling point (bp) of 180° C. or higher and having 1 to 2 straight- or branched-chain alkyl groups of 1 to 5 carbon atoms substituted on nitrogen in the above-mentioned content. By increasing the photoresist solubility, the probability of photoresist residue remaining on the substrate after the stripping process is reduced, which can increase the economics and efficiency of the process.

On the other hand, the amide compound having a boiling point (bp) of 180° C. or higher and having 1 to 2 straight or branched alkyl groups of 1 to 5 carbon atoms substituted on the nitrogen is added to the total weight of the stripper composition. On the other hand, if it is less than 60% by weight, the peeling force may be lowered and the photoresist may remain on the substrate. there can be problems.

前記化学式１において、
Ｒ_１は水素、メチル基、エチル基またはプロピル基であり、
Ｒ_２はメチル基またはエチル基であり、
Ｒ_３は水素または前記炭素数１～５の直鎖または分枝鎖のアルキル基であり、
Ｒ_１およびＲ_３は互いに結合して環を形成することができる。 Specifically, the amide compound having a boiling point (bp) of 180° C. or higher and having 1 to 2 linear or branched alkyl groups of 1 to 5 carbon atoms substituted on nitrogen has the structure of the following chemical formula 1 can have
[Chemical Formula 1]

In the chemical formula 1,
R ₁ is hydrogen, a methyl group, an ethyl group or a propyl group,
_R2 is a methyl group or an ethyl group,
R ₃ is hydrogen or the linear or branched alkyl group having 1 to 5 carbon atoms,
R ₁ and R ₃ can be combined with each other to form a ring.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms are not limited, and examples thereof include methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, and the like. be able to.

For example, an amide compound having a boiling point (bp) of 180° C. or higher and having 1 to 2 straight or branched alkyl groups of 1 to 5 carbon atoms substituted on nitrogen is N-methylformamide (N- Methylformamide (NMF), N-Ethylformamide (NEF), N-Methyl-2-pyrrolidone (NMP) and N-ethyl-2-pyrrolidone (N-ethyl-2- pyrrolidone, NEP).

Meanwhile, the stripper composition for removing photoresist may include a primary or secondary chain amine compound and a cyclic amine compound.

The amine compound including the primary or secondary chain amine compound and the cyclic amine compound enables the stripper composition for removing photoresist to have stripping power against the photoresist, and dissolves the photoresist to remove it. It can act as a remover. Specifically, the primary or secondary chain amine compound may play a role in improving the peel strength, and the cyclic amine compound may play a role in improving the peel strength and minimizing metal wiring damage. can be done.

In particular, the stripper composition for removing photoresist of the above embodiments comprises one primary or secondary chained amine compound and one cyclic amine compound to improve the removal rate for Cu Oxide and conventionally After the insulating film is stripped, no photoresist remains on the insulating film, metal oxides that may be generated on the lower metal film (for example, lower Cu wiring) are easily removed, and when forming a transparent conductive film such as ITO, A film floating phenomenon between the insulating film and the lower metal film can be prevented.

On the other hand, the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is 100:1 to 1:1, or 80:1 to 1:1, or 50:1 to 1:1, or 10:1. 1 to 1:1, or 100:1 to 1.5:1, or 80:1 to 1.5:1, or 50:1 to 1.5:1, or 10:1 to 1.5:1 could be. Specifically, it means the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound in the proportional formula. For example, the weight ratio of the primary or secondary chain amine compound to 1 part by weight of the cyclic amine compound is 1 part by weight to 100 parts by weight, or 1 part by weight to 80 parts by weight, or 1 part by weight to 50 parts by weight. parts by weight, or 1 part to 10 parts by weight, or 1.5 parts to 100 parts by weight, or 1.5 parts to 80 parts by weight, or 1.5 parts to 50 parts by weight, or 1.5 parts by weight parts to 10 parts by weight.

At this time, if the weight ratio of the primary or secondary chain amine compound and the cyclic amine compound exceeds 100:1, corrosion occurs in Cu or the metal of the TFT, resulting in poor adhesion to the next insulating film or metal. If the ratio is less than 1:1, the decomposability of the photoresist is lowered and remains on the substrate, which may cause problems such as film floating.

That is, the stripper composition for removing photoresist of the above embodiment contains a primary or secondary chain amine compound and a cyclic amine compound, and the content of the cyclic amine compound is the content of the primary or secondary chain amine compound. A more equal or relatively less content can improve the peeling force and the ability to remove the metal oxide of the metal-containing underlayer.

On the other hand, the total content of the primary or secondary linear amine compound and the cyclic amine compound is 1 based on the total weight of the stripper composition, more specifically 100% by weight of the total weight of the stripper composition. % by weight or more, or 3% by weight or more, or 5% by weight or more, and may be included at 20% by weight or less, or 15% by weight or less, or 10% by weight or less.

Within such a range of the content of the amine compound, the stripper composition of one embodiment can exhibit excellent stripping force and the like, while the excessive amount of amine reduces the economics and efficiency of the process. can be reduced, and the generation of waste liquid and the like can be reduced.

If an excessively large content of the amine compound is included, it may lead to corrosion of the underlying film, for example, a copper-containing underlying film, and it may be necessary to use a large amount of corrosion inhibitor to suppress this. In this case, a large amount of the corrosion inhibitor adsorbs and remains on the surface of the lower layer, thereby deteriorating the electrical properties of the copper-containing lower layer.

Specifically, if the total content of the primary or secondary chain amine compound and the cyclic amine compound is less than 1% by weight with respect to the total weight of the stripper composition, the stripper composition for removing photoresist The release force of the compound decreases, and above 20% by weight based on the total weight of the composition, the inclusion of excessive amounts of amine compound can reduce process economics and efficiency.

Also, the weight ratio between the primary or secondary chain amine compound and the cyclic amine compound can be adjusted within the range of the content of the amine compound.

The primary or secondary chain amine compounds include 2-(2-aminoethoxy)ethanol (2-(2-Aminoethoxy)ethanol, 1-amino-2-propanol, monoethanol It may include, but is not limited to, one or more compounds selected from the group consisting of Monoethanolamine, Aminoethylethanolamine, N-methylethanolamine and Diethylolamine.

The cyclic amine compound may contain a tertiary amine structure in its molecule. The tertiary amine means a structure in which three organic functional groups (excluding hydrogen) are bonded to one nitrogen atom, and the cyclic amine compound may include at least one tertiary amine nitrogen atom. As a specific example, in the case of 1-imidazolidineethanol, the nitrogen atom in the ring bonded to ethanol corresponds to the nitrogen atom of the tertiary amine.

Also, the cyclic amine compound may be a saturated amine compound. The saturated amine compound means a compound consisting only of single bonds without intramolecular unsaturated bonds (double bonds or triple bonds).

The cyclic amine compounds include 1-imidazolidine ethanol, 1-(2-hydroxyethyl)piperazine (1-(2-Hydroxyethyl)piperazine) and N-(2-aminoethyl)piperazine (N- (2-Amonoethyl)piperazine), but not limited thereto.

Meanwhile, the stripper composition for removing photoresist may include a protic solvent. The protic solvent, as a polar organic solvent, allows the stripper composition for removing photoresist to be better soaked into the underlying film, thereby supporting excellent stripping power of the stripper composition for removing photoresist, and a copper-containing film. It is possible to effectively remove stains on the underlying film such as , and improve the rinsing power of the stripper composition for removing photoresist.

The protic solvent may include an alkylene glycol monoalkyl ether-based compound. More specifically, the alkylene glycol monoalkyl ether compounds include diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and diethylene glycol monoethyl. ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether or mixtures of two or more thereof. can.

In consideration of the excellent wettability of the stripper composition for removing photoresist and the accompanying improved peeling force and rinsing force, diethylene glycol monomethyl ether (MDG) and diethylene glycol are used as the alkylene glycol monoalkyl ether compounds. Monoethyl ether (EDG), diethylene glycol monobutyl ether (BDG) or diethylene glycol mono-tert-butyl ether (DGtB) and the like can be used.

The protic solvent is a primary or secondary chain amine compound, a cyclic amine compound, or a linear or branched alkyl group having a boiling point (bp) of 180° C. or higher and having 1 to 5 carbon atoms, relative to the total weight of the composition. can be included in the remaining content excluding amide compounds with 1 to 2 substitutions on nitrogen, corrosion inhibitors, and the like.

For example, 1% to 50%, or 5% to 45%, or 10% to 10% by weight, based on the total weight of the composition, and more specifically based on 100% by weight of the total weight of the stripper composition. It may be included at a content of 40% by weight. By satisfying the content range, the stripper composition for removing photoresist can have excellent peeling force, etc., and the peeling force and rinsing force can be maintained for a long period of time. can be done.

Meanwhile, the stripper composition for removing photoresist may contain a corrosion inhibitor. Such a corrosion inhibitor can inhibit corrosion of a metal-containing underlying layer such as a copper-containing layer during removal of a photoresist pattern using the stripper composition for removing photoresist.

The corrosion inhibitor may include one or more selected from the group consisting of triazole compounds and imidazole compounds.

At this time, examples of the triazole compound are not particularly limited, but for example, (2,2'[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol and 4,5 It may be one or more selected from the group consisting of 6,7-tetrahydro-1H-benzotriazole.

Examples of the imidazole compound are not particularly limited, but may be, for example, 2-mercapto-1-methylimidazole.

Alternatively, the corrosion inhibitor may be from 0.01% to 10% by weight, or 0.01% by weight, based on the total weight of the stripper composition, more specifically based on 100% by weight of the total weight of the stripper composition. -5.0% by weight, or from 0.01% to 1.0% by weight. If the content of the corrosion inhibitor is less than 0.01% by weight based on the total weight of the composition, it is difficult to effectively suppress corrosion on the lower layer. In addition, when the content of the corrosion inhibitor exceeds 10% by weight based on the total weight of the composition, a considerable amount of the corrosion inhibitor adsorbs and remains on the lower layer, resulting in a copper-containing lower layer, especially copper/molybdenum. The electrical properties of metal films and the like can be reduced.

In addition, the photoresist removing stripper composition contains 0.001 silicon-based nonionic surfactant based on the total weight of the stripper composition, more specifically based on 100% by weight of the total weight of the stripper composition. It may be included at a content of less than 0.0001% by weight. More preferably, the photoresist removal stripper composition may contain substantially no or only a very small amount of silicon-based nonionic surfactant.

When the content of the silicon-based nonionic surfactant increases to 0.001% by weight or more than 0.0001% by weight based on the total weight of the composition, a metal contact resistance change problem may occur.

Specifically, the silicon-based nonionic surfactant may include a polysiloxane-based polymer. More specifically, examples of the polysiloxane-based polymer are not greatly limited. Siloxanes, aralkyl-modified polymethylalkylsiloxanes, polyether-modified hydroxy-functional polydimethylsiloxanes, polyether-modified dimethylpolysiloxanes, modified acrylic-functional polydimethylsiloxanes, or mixtures of two or more of these, and the like, can be used.

If necessary, the stripper composition for removing photoresist may further contain conventional additives, and the specific type and content of the additives are not particularly limited.

In addition, the stripper composition for removing photoresist can be prepared by a general method of mixing each component described above, and the specific method for preparing the stripper composition for removing photoresist is not particularly limited. do not have.

Meanwhile, according to another embodiment of the present invention, there may be provided a method of stripping a photoresist, including stripping the photoresist using the stripper composition for removing photoresist of the embodiment.

According to one embodiment, a photoresist stripping method includes forming a photoresist pattern on a substrate having a lower layer formed thereon; patterning the lower layer with the photoresist pattern; and applying the stripper composition for removing the photoresist. stripping the photoresist using.

The content regarding the stripper composition for removing photoresist includes the content described above for the embodiment.

Specifically, the method of stripping the photoresist includes forming a photoresist pattern on a substrate having a patterned lower layer formed thereon by a photolithography process, and then removing the lower layer using the photoresist pattern as a mask. and stripping the photoresist using the stripper composition described above.

In the photoresist stripping method, the step of forming a photoresist pattern and the step of patterning an underlying layer can be performed using a general device manufacturing process, and the specific manufacturing method is not particularly limited.

On the other hand, an example of the step of stripping the photoresist using the stripper composition for removing photoresist is not particularly limited. is treated, washed with an alkaline buffer solution, washed with ultrapure water, and dried. The stripper composition exhibits excellent stripping power, rinsing power for effectively removing stains on the underlying film, and ability to remove natural oxide film, thereby effectively removing the photoresist pattern remaining on the underlying film, In addition, the surface condition of the underlying film can be maintained in good condition. Therefore, subsequent processes can be properly performed on the patterned lower layer to form a device.

Specific examples of the lower film formed on the substrate are not particularly limited, but aluminum or aluminum alloys, copper or copper alloys, molybdenum or molybdenum alloys, mixtures thereof, composite alloys thereof, these Composite laminates and the like can be included.

The type, composition, or physical properties of the photoresist to be subjected to the stripping method are also not greatly limited. It can be a photoresist known as a More specifically, the photoresist may contain a photosensitive resin component such as a novolac resin, a resole resin, or an epoxy resin.

INDUSTRIAL APPLICABILITY According to the present invention, a stripper composition for removing photoresist having excellent stripping force for photoresist, suppressing corrosion of an underlying metal film during the stripping process, and having improved solubility in photoresist, and a photoresist using the same A resist stripping method can be provided.

FIG. 2 is a scanning electron microscope (FE-SEM) photograph showing the results of evaluating the damage of Ti/Al/Ti cross sections with the stripper compositions for removing photoresist according to Examples 1 to 6, 9 and 11 of the present invention; FIG. 4 is a scanning electron microscope (FE-SEM) photograph showing the results of evaluation of damage on a Cu surface with the stripper compositions for removing photoresist according to Examples 1 to 6, 9 and 11 of the present invention;

The invention is explained in more detail in the following examples. However, the following examples merely illustrate the present invention, and the content of the present invention is not limited by the following examples.

<Examples 1 to 16: Production of stripper composition for removing photoresist>
Each component was mixed according to the compositions in Tables 1 and 2 below to prepare stripper compositions for removing photoresist of Examples 1 to 16, respectively. Specific compositions of the prepared photoresist removing stripper composition are as shown in Tables 1 and 2 below.

ＡＥＥ：２－（２－アミノエトキシ）エタノール（２－（２－Ａｍｉｎｏ Ｅｔｈｏｘｙ） Ｅｔｈａｎｏｌ，ＣＡＳ：９２９－０６－６）
ＭＩＰＡ：１－アミノ－２－プロパノール（１－Ａｍｉｎｏ－２－Ｐｒｏｐａｎｏｌ，ＣＡＳ：７８－９６－６）
ＭＥＡ：モノエタノールアミン（Ｍｏｎｏｅｔｈａｎｏｌａｍｉｎｅ，ＣＡＳ：１４１－４３－５）
ＡＥＥＡ：アミノエチルエタノールアミン（Ａｍｉｎｏｅｔｈｙｌｅｔｈａｎｏｌａｍｉｎｅ，ＣＡＳ：１１１－４１－１）
Ｎ－ＭＥＡ：Ｎ－メチルエタノールアミン（Ｎ－ｍｅｔｈｙｌｅｔｈａｎｏｌａｍｉｎｅ，ＣＡＳ：１０９－８３－１）
ＤＥＡ：ジエタノールアミン（Ｄｉｅｔｈａｎｏｌａｍｉｎｅ，ＣＡＳ：１５０－５９－９）
ＩＭＥ：１－イミダゾリジンエタノール（１－Ｉｍｉｄａｚｏｌｉｄｉｎｅ ｅｔｈａｎｏｌ，ＣＡＳ：７７２１５－４７－５）
ＨＥＰ：１－（２－ヒドロキシエチル）ピペラジン（Ｈｙｄｒｏｘｙｅｔｈｙｌ－ｐｉｐｅｒａｚｉｎｅ，ＣＡＳ：１０３－７６－４）
ＡＥＰ：Ｎ－（２－アミノエチル）ピペラジン（Ｎ－Ａｍｉｎｏｅｔｈｙｌｐｉｐｅｒａｚｉｎｅ，ＣＡＳ：１４０－３１－８）
ＮＭＦ：Ｎ－メチルホルムアミド（Ｎ－Ｍｅｔｈｙｌｆｏｒｍａｍｉｄｅ，ＣＡＳ：１２３－３９－７，沸点１８２．５℃）
ＮＭＰ：Ｎ－メチル－２－ピロリドン（Ｎ－Ｍｅｔｈｙｌ－２－ｐｙｒｒｏｌｉｄｏｎｅ，ＣＡＳ：８７２－５０－４．沸点２０２℃）
ＮＥＦ：Ｎ－エチルホルムアミド（Ｎ－Ｅｔｈｙｌｆｏｒｍａｍｉｄｅ，ＣＡＳ：６２７－４５－２，沸点２０２～２０４℃）
ＤＥＦ：Ｎ，Ｎ－ジエチルホルムアミド（Ｎ，Ｎ－Ｄｉｅｔｈｙｌｆｏｒｍａｍｉｄｅ，ＣＡＳ：６１７－８４－５，沸点１７８．３℃）
ＭＤＧ：ジエチレングリコールモノメチルエーテル（Ｄｉｅｔｈｙｌｅｎｅ ｇｌｙｃｏｌ ｍｅｔｈｙｌ ｅｔｈｅｒ，ＣＡＳ：１１１－７７－３）
ＥＤＧ：ジエチレングリコールモノエチルエーテル（Ｄｉｅｔｈｙｌｅｎｅ Ｇｌｙｃｏｌ Ｍｏｎｏｅｔｈｙｌ Ｅｔｈｅｒ，ＣＡＳ：１１１－９０－０）
ＢＤＧ：ジエチレングリコールモノブチルエーテル（Ｄｉｅｔｈｙｌｅｎｅ Ｇｌｙｃｏｌ Ｍｏｎｏｂｕｔｙｌ Ｅｔｈｅｒ，ＣＡＳ：１１２－３４－５）
ＤＧｔＢ：ジエチレングリコールモノ－ｔｅｒｔ－ブチルエーテル（Ｄｉｅｔｈｙｌｅｎｅ Ｇｌｙｃｏｌ Ｍｏｎｏ－ｔｅｒｔ－ｂｕｔｙｌ ｅｔｈｅｒ，ＣＡＳ：１１０－０９－８）
ＤＩＷ：蒸留水（ｄｅｉｏｎｉｚｅｄ ｗａｔｅｒ）
腐食防止剤１：（２，２'［［（メチル－１Ｈ－ベンゾトリアゾール－１－イル）メチル］イミノ］ビスエタノール（２，２'［［（Ｍｅｔｈｙｌ－１Ｈ－ｂｅｎｚｏｔｒｉａｚｏｌ－１－ｙｌ）ｍｅｔｈｙｌ］ｉｍｉｎｏ］ｂｉｓｅｔｈａｎｏｌ，ＣＡＳ：８８４７７－３７－６）
腐食防止剤２：４，５，６，７－テトラヒドロ－１Ｈ－ベンゾトリアゾール（４，５，６，７－ｔｅｔｒａｈｙｄｒｏｔｏｌｙｔｒｉａｚｏｌｅ，ＣＡＳ：６７８９－９９－７）
腐食防止剤３：２－メルカプト－１－メチルイミダゾール（２－Ｍｅｒｃａｐｔｏ－１－ｍｅｔｈｙｌｉｍｉｄａｚｏｌｅ，ＣＡＳ：６０－５６－０）

AEE: 2-(2-Aminoethoxy) Ethanol (CAS: 929-06-6)
MIPA: 1-Amino-2-Propanol (1-Amino-2-Propanol, CAS: 78-96-6)
MEA: Monoethanolamine (CAS: 141-43-5)
AEEA: Aminoethylethanolamine (CAS: 111-41-1)
N-MEA: N-methylethanolamine (N-methylethanolamine, CAS: 109-83-1)
DEA: Diethanolamine (CAS: 150-59-9)
IME: 1-imidazolidine ethanol (1-imidazolidine ethanol, CAS: 77215-47-5)
HEP: 1-(2-hydroxyethyl)piperazine (Hydroxyethyl-piperazine, CAS: 103-76-4)
AEP: N-(2-aminoethyl)piperazine (N-Aminoethylpiperazine, CAS: 140-31-8)
NMF: N-Methylformamide (N-Methylformamide, CAS: 123-39-7, boiling point 182.5°C)
NMP: N-Methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, CAS: 872-50-4. Boiling point 202°C)
NEF: N-ethylformamide (N-Ethylformamide, CAS: 627-45-2, boiling point 202-204°C)
DEF: N,N-diethylformamide (N,N-Diethylformamide, CAS: 617-84-5, boiling point 178.3°C)
MDG: Diethylene glycol methyl ether (CAS: 111-77-3)
EDG: Diethylene Glycol Monoethyl Ether (CAS: 111-90-0)
BDG: Diethylene Glycol Monobutyl Ether (CAS: 112-34-5)
DGtB: Diethylene Glycol Mono-tert-butyl ether (CAS: 110-09-8)
DIW: deionized water
Corrosion inhibitor 1: (2,2′[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol (2,2′[[(Methyl-1H-benzotriazol-1-yl)methyl] imino]bisethanol, CAS: 88477-37-6)
Corrosion inhibitor 2: 4,5,6,7-tetrahydro-1H-benzotriazole (4,5,6,7-tetrahydrotolytriazole, CAS: 6789-99-7)
Corrosion inhibitor 3: 2-Mercapto-1-methylimidazole (2-Mercapto-1-methylimidazole, CAS: 60-56-0)

<Comparative Examples 1 to 15: Production of stripper compositions for removing photoresist>
According to the compositions shown in Tables 3, 4 and 5 below, each component was mixed to prepare stripper compositions for removing photoresist of Comparative Examples 1 to 15, respectively. Specific compositions of the prepared photoresist removing stripper compositions are shown in Tables 3, 4 and 5 below.

<Experimental Example: Measurement of Physical Properties of Stripper Compositions for Removing Photoresist Obtained from Examples and Comparative Examples>
300 g of each composition shown in Tables 1 to 5 was prepared in a 500 ml beaker, stirred at 500 rpm on a hot plate, and heated to 60° C. to prepare a chemical solution (stripper composition).

The physical properties of the prepared chemical solutions were measured by the following methods, and the results are shown in each table.

1. Evaluation of Peeling Force A substrate having a size of 3 cm×3 cm and patterned with a photoresist after the photo process was prepared on a-Si and hard-baked at 170° C. for 20 minutes.

The substrate was dipped in the prepared chemical solution at 60° C. at intervals of 30 seconds, removed, washed in tertiary distilled water for 30 seconds, and dried in distilled water using an air gun.

The manufactured sample was analyzed with an optical microscope, and the peeling time was evaluated as the time when the residue of the photoresist disappeared.

The peel strength of the stripper compositions of Examples and Comparative Examples was evaluated by the method described above, and the results are shown in Tables 6 and 7 below.

As shown in Tables 6 and 7 above, the stripper compositions of Examples consisted of a primary or secondary chain amine compound, a cyclic amine compound, and a C 1-5 straight chain amine compound having a boiling point (bp) of 180° C. or higher. Alternatively, by including a predetermined content of an amide compound in which 1 to 2 branched alkyl groups are substituted on nitrogen, it is confirmed that superior stripping force is exhibited compared to the stripper composition of the comparative example. I was able to

Further, according to Table 7, the stripper compositions of Comparative Examples 1 to 6 containing one type of primary or secondary chain amine compound or one type of cyclic amine compound show a significant decrease in peel strength compared to the Examples. As a result, it was confirmed that there is a possibility that post-process defects may occur when the photoresist residue remains.

Also, the stripper composition of Comparative Example 15 containing an excessive amount of imidazolyl-4-ethanol, which is a cyclic amine, compared to (2-aminoethoxy)-1-ethanol, which is a chain amine, was also carried out. It was confirmed that there is a possibility that post-process defects may occur due to the fact that the peeling strength is significantly lower than that of the example, and that photoresist residue may occur.

2. Damage evaluation of Ti/Al/Ti cross section After preparing a substrate with a size of 3 cm × 3 cm on which photoresist was patterned after the photo process on Ti/Al/Ti, the substrate was placed in the prepared chemical solution at 60°C. After dipping for 120 seconds, the substrate was taken out, washed with tertiary distilled water for 30 seconds, and dried with an air gun.

After repeating the above process three times, the damage of the Ti/Al/Ti cross section was analyzed by FE-SEM.

As for the presence or absence of damage on the cross section, it was evaluated that there was damage on the cross section when there was damage on the Al layer compared to a test piece that was not chemically treated.

The Ti/Al/Ti cross-sectional damage of the stripper compositions of Examples and Comparative Examples was evaluated by the method described above, and the results are shown in Tables 8 and 9 below and FIG.

As shown in Tables 8 and 9 and FIG. 1, no damage was observed on the Ti/Al/Ti cross section in the examples of the present application, but damage on the Ti/Al/Ti cross section was observed in Comparative Examples 1 to 3. was done. As a result, 1 to 2 linear or branched alkyl groups of 1 to 5 carbon atoms having a primary or secondary chain amine compound, a cyclic amine compound and a boiling point (bp) of 180° C. or higher are substituted on nitrogen. It was confirmed that the stripper composition of the present application containing the above-mentioned amide compound in a predetermined content minimizes metal damage.

3. Damage evaluation of Cu surface After preparing a substrate having a size of 3 cm x 3 cm, on which Cu was deposited on the front surface, the substrate was dipped in the prepared chemical solution at 60°C for 120 seconds. was washed for 30 seconds and dried with distilled water using an air gun.

After repeating the above process three times, damage on the Cu surface was analyzed by FE-SEM.

The presence or absence of surface damage was evaluated as having surface damage when there was a change in morphology compared to a test piece that was not chemically treated.

The Cu surface damage of the stripper compositions of Examples and Comparative Examples was evaluated by the above method, and the results are shown in Tables 10 and 11 and FIG.

As shown in Tables 10 and 11 and FIG. 2, no damage on the Cu surface was observed in the examples of the present application, but damage on the Cu surface was observed in Comparative Examples 1 to 3. As a result, 1 to 2 linear or branched alkyl groups of 1 to 5 carbon atoms having a primary or secondary chain amine compound, a cyclic amine compound and a boiling point (bp) of 180° C. or higher are substituted on nitrogen. It was confirmed that the stripper composition of the present application containing the above-mentioned amide compound in a predetermined content minimizes metal damage.

4. Photoresist Solubility Evaluation A photoresist stock solution (CT-3813 from COTEM) was oven baked at 150° C. for 4 hours to prepare 3% photoresist powder.

After dissolving the PR Powder in the prepared chemical solution at 60° C. for 1 hour, the dissolved chemical solution was vacuum-filtered through a filter with a pore size of 1 μm and a diameter of 90 mm.

After drying in an oven at 100° C. for 1 hour, the weight of the filter was measured and compared with the weight before filtering to calculate the PR solubility. The results are shown in Table 12 below.
PR solubility = (filter weight before filtering/filter weight after drying) * 100%)

As shown in Table 12 above, the examples of the present application exhibited a total solubility of 95% or more, while the comparative examples exhibited a solubility of less than 95%.

Since the higher the photoresist solubility, the lower the probability that photoresist residues remain on the substrate after the stripping process, primary or secondary chain amine compounds, cyclic amine compounds, and carbon numbers with a boiling point (bp) of 180 ° C. or higher The stripper composition of the present application, which contains a predetermined content of an amide compound in which 1 to 2 straight or branched chain alkyl groups of 1 to 5 are substituted on nitrogen, is economical and efficient as compared with comparative examples. I was able to confirm that

5. Evaluation of Contact Angle A substrate having a size of 3 cm×3 cm, on which Cu was deposited on the front surface, was prepared, dipped in the prepared chemical solution at 60° C. for 120 seconds, and then taken out. Washing was performed in distilled water for 30 seconds, and the distilled water was dried using an air gun.

After dropping 3 μl of distilled water (DeIonized Water, DIW) on the prepared sample, the angle between the sample and the drop of distilled water was measured. The left and right angles of the sample were measured and the average value was calculated, using DSA100 from KRUSE. The degree of hydrophilization of the surface was evaluated by the average contact angle value, and the lower the contact angle value, the stronger the degree of hydrophilization.

The contact angles of the stripper compositions of Examples and Comparative Examples were evaluated by the method described above, and the results are shown in Table 13 below.

As shown in Table 13, the stripper composition of the example of the present application showed a contact angle distribution of 54°±2°, and the comparative example showed a value greatly deviating from 54°. As a result, it was found that the degree of hydrophilization of the surface is greatly affected by the content of the amide compound in the stripper composition.

In particular, in the case of Comparative Example 15, the hydrophilic surfactant remained in the stripper composition, and the contact angle was significantly decreased to 42°, which may cause a change in metal contact resistance.

Claims (16)

primary or secondary chain amine compound;
a cyclic amine compound;
An amide compound having a boiling point of 180° C. or higher and having 1 to 2 straight- or branched-chain alkyl groups of 1 to 5 carbon atoms substituted on nitrogen;
a protic solvent; and a corrosion inhibitor,
The amide compound having a boiling point of 180° C. or higher and having 1 to 2 straight-chain or branched-chain alkyl groups of 1 to 5 carbon atoms substituted on nitrogen is 60% by weight or more based on the total weight of the stripper composition. Contained at 90% by weight,
A stripper composition for removing photoresist, wherein the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is 100:1 to 1:1. The amide compound having a boiling point of 180° C. or higher and having 1 to 2 linear or branched alkyl groups of 1 to 5 carbon atoms substituted on the nitrogen atom according to claim 1, including a compound represented by the following chemical formula 1. stripper composition for removing photoresist of:
[Chemical Formula 1]

In the chemical formula 1,
R ₁ is hydrogen, a methyl group, an ethyl group or a propyl group,
_R2 is a methyl group or an ethyl group,
R ₃ is hydrogen or the linear or branched alkyl group having 1 to 5 carbon atoms,
R ₁ and R ₃ can be combined with each other to form a ring. The amide compound having a boiling point of 180° C. or higher and having 1 to 2 linear or branched alkyl groups of 1 to 5 carbon atoms substituted on nitrogen is N-methylformamide, N-ethylformamide, N-methyl 2. The stripper composition for removing photoresist according to claim 1, comprising at least one selected from the group consisting of -2-pyrrolidone and N-ethyl-2-pyrrolidone. 2. The stripper composition for removing photoresist according to claim 1, wherein the weight ratio of said primary or secondary linear amine compound and cyclic amine compound is 80:1 to 1.5:1. The stripper for removing photoresist according to claim 1, wherein the total content of the primary or secondary chain amine compound and the cyclic amine compound is 1 wt% to 20 wt% based on the total weight of the stripper composition. Composition. The primary or secondary linear amine compound is selected from the group consisting of 2-(2-aminoethoxy)ethanol, 1-amino-2-propanol, monoethanolamine, aminoethylethanolamine, N-methylethanolamine and diethanolamine. 2. The stripper composition for removing photoresist of claim 1, comprising one or more of: 2. The stripper composition for removing photoresist according to claim 1, wherein the cyclic amine compound contains a tertiary amine structure in its molecule. 2. The photoresist removal stripper composition of claim 1, wherein the cyclic amine compound is a saturated amine compound. The photo of claim 1, wherein the cyclic amine compound includes one or more selected from the group consisting of 1-imidazolidineethanol, 1-(2-hydroxyethyl)piperazine and N-(2-aminoethyl)piperazine. A stripper composition for removing resist. 2. The stripper composition for removing photoresist according to claim 1, wherein the protic solvent comprises an alkylene glycol monoalkyl ether compound. 2. The stripper composition for removing photoresist according to claim 1, wherein said corrosion inhibitor comprises one or more selected from the group consisting of triazole-based compounds and imidazole-based compounds. The triazole compound is selected from the group consisting of (2,2'[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol and 4,5,6,7-tetrahydro-1H-benzotriazole. 12. The photoresist removal stripper composition of claim 11, comprising one or more of: 12. The stripper composition for photoresist removal of claim 11, wherein the imidazole compound comprises 2-mercapto-1-methylimidazole. 1% to 20% by weight of the primary or secondary chain amine compound and the cyclic amine compound;
60% to 90% by weight of an amide compound having a boiling point of 180° C. or higher and having 1 to 2 linear or branched alkyl groups of 1 to 5 carbon atoms substituted on nitrogen.
The stripper composition for removing photoresist of claim 1, comprising 0.01% to 10% by weight of a corrosion inhibitor and a balance of a protic solvent. 2. The stripper composition for removing photoresist of claim 1, wherein the stripper composition for removing photoresist comprises a silicon-based nonionic surfactant in an amount of less than 0.001% by weight based on the total weight of the composition. thing. forming a photoresist pattern on the substrate on which the lower layer is formed;
A method for stripping a photoresist, comprising: patterning an underlying layer with the photoresist pattern; and stripping the photoresist using the stripper composition for removing photoresist according to any one of claims 1 to 15. .

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