Stripper composition for removing photoresist and photoresist stripping method using the same

Abstract

The present invention relates to a stripper composition for removing photoresist in a process for manufacturing FPD (LCD, OLED) and a method using the same. Specifically, the stripper composition for removing photoresist according to the present invention can not only strip the photoresist in a short time at a low temperature, but also can strip without damaging the surface of the underlying film, and does not leave photoresist residues on the substrate after cleaning.

Description

Technical Field

[0001] The present invention relates to a stripper composition for removing a photoresist and a method for stripping a photoresist using the same. Background Art

[0002] Generally, the fine circuits of flat panel display (FPD) devices such as LEDs and OLEDs are realized by photolithography. The photolithography process 1) uniformly coats a photoresist on a conductive metal film or insulating film formed on a substrate, 2) selectively exposes and develops them to form a photoresist pattern, 3) wet or dry etches the conductive metal film or insulating film using the patterned photoresist film as a mask to transfer the fine circuit pattern to the photoresist lower layer, and 4) removes unnecessary photoresist layers with a stripper composition.

[0003] The photoresist stripper composition needs to strip the photoresist in a short time even at low temperatures, needs to minimize damage to the insulating layer and the metal layer during the stripping process, and needs to ensure that no residues of the stripped photoresist and the stripper composition remain on the substrate after cleaning.

[0004] In addition, recently, with the demand for large-area, ultra-fine, and high-resolution displays, it is actively proposed not to use copper (Cu) wiring patterns with excellent resistivity and electromigration characteristics. However, since conventional stripper compositions severely corrode copper, when used as strippers for copper wiring, fine stains and residues are generated due to damage to the copper-containing lower film.

[0005] Therefore, attempts have been made to develop stripper compositions with low corrosion to copper, such as by adding anti-corrosion additives, but there are limitations such as little effect in preventing copper damage and a decrease in photoresist stripping performance or difficulty in cleaning from the substrate surface even after cleaning.

[0006] That is, there is an urgent need to develop a stripper composition that has excellent stripping power and cleaning power for photoresists and excellent anticorrosion effect for copper-containing underlying films.

[0007] Prior art literature

[0008] Patent Literature

[0009] KR 10-2016-0114360A

[0010] KR 10-2017-0029285A Summary of the invention

[0011] Technical issues

[0012] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a stripper composition for removing a photoresist which has excellent corrosion protection for an underlying film and excellent stripping power for a photoresist.

[0013] Furthermore, the present invention provides a method for stripping a photoresist using the stripper composition for removing a photoresist.

[0014] Solutions to technical problems

[0015] For the above purpose, the present invention provides a stripper composition for removing a photoresist, the stripper composition for removing a photoresist comprising an amine compound represented by the following Chemical Formula 1.

[0016] [Chemical formula 1]

[0017]

[0018] (In the chemical formula 1,

[0019] R1 and R2 are independently hydrogen, (C1-C10)alkyl or hydroxy(C1-C10)alkyl,

[0020] L1 and L2 are each independently (C1-C12) alkylene, and the -CH2- of the alkylene of L1 and L2 may be substituted with -O-.

[0021] The amine compound represented by Chemical Formula 1 according to an embodiment of the present invention may be represented by the following Chemical Formula 2, Chemical Formula 3 or Chemical Formula 4.

[0022] [Chemical formula 2]

[0023]

[0024] [Chemical formula 3]

[0025]

[0026] [Chemical formula 4]

[0027]

[0028] (In the chemical formulas 2 to 4,

[0029] a, b, c, d, e and f are each independently an integer of 1 or 2.

[0030] The stripper composition for removing a photoresist according to an embodiment of the present invention may include the amine compound of Chemical Formula 1, an aprotic polar organic solvent, and a glycol-based compound.

[0031] According to one embodiment of the present invention, the aprotic polar organic solvent may include one or more selected from the group consisting of N,N-dimethylpropionamide, N-methylformamide, dimethyl sulfoxide, dimethylacetamide, diethyl sulfoxide, dipropyl sulfoxide, cyclopentane, N-methylpyrrolidone, pyrrolidone, N-ethylpyrrolidone, dipropylene glycol monoethyl ether and N,N'-dialkylformamide.

[0032] According to an embodiment of the present invention, the glycol-based compound may be an alkylene glycol monoalkyl ether.

[0033] According to one embodiment of the present invention, the alkylene glycol monoalkyl ether may include one or more selected from the group consisting of ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, 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 and tripropylene glycol monobutyl ether.

[0034] The stripper composition for removing a photoresist according to an embodiment of the present invention may further include an anticorrosive agent.

[0035] The anticorrosive agent according to an embodiment of the present invention may include one or more selected from the group consisting of benzimidazole-based compounds, triazole-based compounds, and tetrazolyl-based compounds.

[0036] The triazole-based compound according to an embodiment of the present invention may include a compound of the following Chemical Formula 5.

[0037] [Chemical formula 5]

[0038]

[0039] The benzimidazole-based compound according to an embodiment of the present invention may include a compound of the following Chemical Formula 6.

[0040] [Chemical formula 6]

[0041]

[0042] The stripper composition for removing photoresist according to one embodiment of the present invention may include 30 to 60 wt % of aprotic polar organic solvent, 20 to 60 wt % of glycol-based compound, 0.1 to 10 wt % of the compound of Chemical Formula 1, and 0.005 to 0.6 wt % of anticorrosive agent, based on the total weight of the stripper composition for removing photoresist.

[0043] In addition, the present invention provides a photoresist stripping method, which includes: forming a photoresist pattern on a substrate on which a lower film is formed; patterning the lower film with the photoresist pattern; and stripping the photoresist using the stripper composition for removing the photoresist.

[0044] The lower film according to an embodiment of the present invention may include a metal film including aluminum (Al), copper (Cu), molybdenum (Mo), titanium (Ti) or an alloy thereof, an insulating film of a silicon oxide film or a silicon nitride film, or a combination thereof.

[0045] Effects of the Invention

[0046] The stripper composition according to the present invention has excellent anti-corrosion capability for the underlying film and excellent stripping power for the photoresist, so that no stains and residues remain on the substrate after cleaning.

[0047] Specifically, the photoresist can be stripped in a short time even at low temperature, so the stripping speed can be further increased, and the dissolving power of the stripped photoresist is also excellent, so no photoresist residue remains on the substrate after cleaning. At the same time, due to the excellent corrosion resistance to the insulating film and metal film as the underlying film, only the photoresist can be selectively stripped quickly without causing stains and damage on the underlying film.

[0048] Furthermore, the stripping force of the stripper composition according to the present invention can be maintained for a long time as time passes, and due to its excellent solubility for the stripped photoresist, defects such as filter clogging in the process can be minimized. In addition, the stripper composition according to the present invention can be perfectly removed only by a cleaning process using ultrapure water, so it does not remain on the substrate after cleaning.

[0049] In this regard, the economy and efficiency of the process can be improved, and a semiconductor device with high reliability can be provided by a very economical method. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is a scanning electron microscope (SEM) photograph of a cross section of a sample for evaluation of photoresist peeling strength according to Example 1.

[0051] Figure 2 This is a scanning electron microscope (SEM) photograph of the surface of the sample evaluated for the lower film corrosion protection according to Example 1. DETAILED DESCRIPTION

[0052] The present invention will be described in more detail below. For the technical terms and scientific terms used here, unless otherwise defined, they have the meanings commonly understood by those of ordinary skill in the art to which the present invention belongs, and the description of the well-known functions and configurations that may confuse the gist of the present invention is omitted in the following description.

[0053] Unless the context specifically indicates otherwise, the singular forms used in the present specification may be intended to include the plural forms as well.

[0054] Units used in this specification unless otherwise specified are based on weight. For example, % or ratio units mean weight % or weight ratio, and unless otherwise defined, weight % means the weight % of any one component in the entire composition.

[0055] The wording “comprising” in this specification is an open description having a meaning equivalent to expressions such as “provided with,” “containing,” “having,” or “characterized by,” and does not exclude elements, materials, or processes that are not further listed.

[0056] The term “residue” of the present specification may be a byproduct generated from a substrate used in the semiconductor industry after etching or ashing, and may mean contamination particles or a contamination layer including an organic material or an inorganic material that may exist on the substrate after the process.

[0057] Conventional stripper compositions have the problem of unnecessary etching of the metal layer or the insulating layer or causing surface damage to the metal layer. In order to solve this problem, compositions using various anticorrosive additives have been proposed, but these additives have limitations such as reducing the stripping performance for the photoresist or not being easily cleaned off from the substrate surface after cleaning.

[0058] To this end, the present invention provides a stripper composition for removing photoresist, the stripper composition for removing photoresist comprising a novel amine compound having excellent stripping power for photoresist, an aprotic polar organic solvent, a glycol compound and an anticorrosive agent. The stripper composition according to the present invention has the advantages of excellent anticorrosion ability for the underlying film and excellent stripping power and cleaning power for the photoresist by adopting the above-mentioned configuration combination.

[0059] Hereinafter, the present invention will be described in detail.

[0060] The stripper composition for removing a photoresist according to the present invention may include an amine compound represented by Chemical Formula 1 below.

[0061] [Chemical formula 1]

[0062]

[0063] (In the chemical formula 1,

[0064] R1 and R2 are independently hydrogen, (C1-C10)alkyl or hydroxy(C1-C10)alkyl,

[0065] L1 and L2 are each independently (C1-C12) alkylene, and the -CH2- of the alkylene of L1 and L2 may be substituted with -O-.

[0066] Preferably, the R1 and R2 according to one embodiment of the present invention are the same as each other and are hydrogen or hydroxy (C1-C10) alkyl. More specifically, the amine compound represented by the chemical formula 1 according to one embodiment of the present invention can be represented by the following chemical formula 2, chemical formula 3 or chemical formula 4.

[0067] [Chemical formula 2]

[0068]

[0069] [Chemical formula 3]

[0070]

[0071] [Chemical formula 4]

[0072]

[0073] (In the chemical formulas 2 to 4,

[0074] a, b, c and d are each independently an integer from 1 to 5, and e and f are each independently an integer from 1 to 3.)

[0075] As an example, in the chemical formula 2, a to d may be independently integers of 1 to 3, and specifically may be 1 or 2.

[0076] As an example, in the chemical formula 3, a and b may be independently integers of 1 to 3, and specifically may be 1 or 2.

[0077] As an example, in the chemical formula 4, e and f may be 1 or 2, respectively and independently.

[0078] As an example, in the Chemical Formula 2, a to d may be identical to each other, in the Chemical Formula 3, a and b may be identical to each other, and in the Chemical Formula 4, e and f may be identical to each other.

[0079] More preferably, the amine compound according to an embodiment of the present invention may be selected from the following Chemical Formula 2-1, Chemical Formula 3-1 or Chemical Formula 4-1, but is not limited thereto.

[0080] [Chemical formula 2-1]

[0081]

[0082] [Chemical formula 3-1]

[0083]

[0084] [Chemical formula 4-1]

[0085]

[0086] The amine compound according to one embodiment of the present invention can melt and remove the bonding structure of the photoresist with the structural characteristics as described above, and can achieve very excellent stripping force for the photoresist. As a result, it is possible to prevent the reduction in the economy and efficiency of the process caused by using excessive amines in the conventional stripper composition, and can significantly reduce the amount of waste liquid, etc. In addition, the photoresist can be perfectly stripped in a short time at low temperature, thereby minimizing the surface damage of the lower film containing copper, etc.

[0087] The amine compound according to an embodiment of the present invention may include 0.1 to 10 wt % with respect to the total weight of the entire stripper composition, and preferably may include 1 to 6 wt %, and more preferably may include 2 to 5.5 wt %.

[0088] In the above numerical range, the effect to be achieved by the present invention is exhibited without affecting the stability of the composition, that is, the anticorrosion effect on the copper-containing lower film is remarkable while the stripping force and cleaning force on the photoresist are excellent, so it is preferred.

[0089] In addition, the amine compound can be mixed with an amine compound commonly used in this field as needed. As non-limiting examples, it can be selected from chain amine compounds such as diethanolamine, 2-aminoethoxy)-1-ethanol, aminoethylethanolamine, monomethanolamine, monoethanolamine, N-methylethylamine, 1-aminoisopropanol, methyldimethylamine, diethylenetriamine and triethylenetetramine, and cyclic amine compounds such as 1-imidazolidinylethanol, aminoethylpiperazine and hydroxyethylpiperazine.

[0090] According to one embodiment of the present invention, the aprotic polar organic solvent can be listed as N,N-dimethylpropionamide, N-methylformamide, dimethyl sulfoxide, dimethylacetamide, diethyl sulfoxide, dipropyl sulfoxide, cyclopentane, N-methylpyrrolidone, pyrrolidone, N-ethylpyrrolidone, dipropylene glycol monoethyl ether and N,N'-dialkylformamide, etc., and can be one or a mixed solvent of more than two selected from them, and more preferably, N,N-dimethylpropionamide or N-methylformamide can be used without limitation.

[0091] The aprotic polar organic solvent according to an embodiment of the present invention may include 30 to 60 wt %, preferably 35 to 60 wt %, and more preferably 40 to 58 wt % based on the total weight of the entire composition.

[0092] The aprotic polar organic solvent satisfies the aforementioned numerical range when mixed with the amine compound, thereby achieving a more significant effect. Specifically, the amine compound can be easily dissolved in the stripper composition, and the stripper composition can be properly impregnated into the photoresist pattern and the lower film. In this regard, the excellent stripping force and cleaning power of the stripper composition according to the present invention can be maximized.

[0093] In addition, in addition to the above-mentioned aprotic polar organic solvent, the stripper composition for removing photoresist according to one embodiment of the present invention may also contain water and use it as a water-based demolding composition. In the case of selectively containing water, its content can be determined within an appropriate range within the content range of the aprotic organic solvent.

[0094] The glycol-based compound according to one embodiment of the present invention may be an alkylene glycol monoalkyl ether, and as a non-limiting example, the alkylene glycol monoalkyl ether may be ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, 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 and tripropylene glycol monobutyl ether, and may be one or more selected from them, and more preferably, diethylene glycol monomethyl ether or diethylene glycol monobutyl ether may be used without limitation.

[0095] The one or more glycol-based compounds according to an embodiment of the present invention may include 20 to 60 wt %, preferably 30 to 60 wt %, and more preferably 35 to 55 wt % based on the total weight of the composition.

[0096] When the glycol-based compound satisfies the above-mentioned numerical range, the wettability (humidity) of the photoresist can be improved by reducing the surface tension of the stripper composition, and the excellent stripping force for the hardened or deteriorated photoresist can also play a role in improving the solubility of the stripped photoresist. In addition, it is possible to impart excellent compatibility between the various organic substances present in the stripper composition according to the present invention. In this regard, the stripping force and cleaning power of the stripper composition according to the present invention can be maintained for a long time as time passes.

[0097] The anticorrosive agent according to an embodiment of the present invention may be selected from the group consisting of benzimidazole-based compounds, triazole-based compounds and tetrazolyl-based compounds.

[0098] More preferably, the triazole-based compound according to an embodiment of the present invention may include a compound of the following Chemical Formula 5.

[0099] [Chemical formula 5]

[0100]

[0101] More preferably, the benzimidazole-based compound according to an embodiment of the present invention may include a compound of the following Chemical Formula 6.

[0102] [Chemical formula 6]

[0103]

[0104] By using the anticorrosive agent as described above, the stripping force of the stripper composition can be kept excellent while effectively suppressing the corrosion of the underlying film, and a synergistic effect with the amine compound (Chemical Formula 1) according to the present invention is exhibited, thereby achieving a maximized corrosion inhibition effect.

[0105] The anticorrosive agent according to an embodiment of the present invention may include 0.005 to 0.6 wt %, preferably 0.1 to 0.5 wt %, and more preferably 0.2 to 0.4 wt % with respect to the total weight of the composition.

[0106] When the anticorrosive agent satisfies the above numerical range, it can exhibit a maximized corrosion inhibition effect and can be perfectly removed only by a cleaning process using ultrapure water, thereby not being adsorbed and remaining on the substrate after cleaning.

[0107] In this regard, the stripper composition for removing the photoresist according to the present invention is mixed with the amine compound, aprotic polar organic solvent, glycol compound and anticorrosive as described above in a specific ratio, which can further improve the stripping force, cleaning power and anticorrosive power. Specifically, the photoresist can be perfectly removed in a short time at low temperature, and the dissolving power for the stripped photoresist is also excellent, so that the photoresist residue is not left on the substrate after cleaning. At the same time, due to the excellent anticorrosive power for the insulating film and metal film as the lower film, the photoresist can only be selectively stripped quickly without residual stains and damage on the lower film. Further, the stripping force of the stripper composition according to the present invention can be maintained for a long time as time passes, and due to the excellent dissolving power for the stripped photoresist, the defects of filter clogging, etc. can be minimized in the process. In addition, the stripper composition according to the present invention can also be perfectly removed only by the cleaning process of ultrapure water, so it is not adsorbed and remains on the substrate after cleaning.

[0108] In this regard, the economy and efficiency of the process can be improved, and a highly reliable FPD (LCD, OLED) device can be provided through a very economical method.

[0109] Furthermore, the present invention provides a method for stripping a photoresist using the above-mentioned stripper composition for removing a photoresist.

[0110] According to an embodiment of the present invention, a method for stripping a photoresist may include: forming a photoresist pattern on a substrate having an underlying film formed thereon; patterning the underlying film with the photoresist pattern; and stripping the photoresist using the stripper composition for removing the photoresist.

[0111] Specifically, the photoresist stripping method may include using a photoresist pattern formed on a substrate including an insulating film, a metal film or a combination thereof as a mask to etch the substrate, and performing a stripping step of stripping the photoresist using the stripper composition for removing the photoresist.

[0112] The insulating film according to an embodiment of the present invention may be any commonly used one, and non-limiting examples thereof include a silicon oxide film and a silicon nitride film.

[0113] The metal film according to one embodiment of the present invention may be any commonly used one, and non-limiting examples thereof include metal films or alloy films containing a metal selected from aluminum (Al), copper (Cu), and molybdenum (Mo).

[0114] In a method for stripping a photoresist according to an embodiment of the present invention, a photoresist pattern may first be formed on a substrate on which a lower film to be patterned is formed by a photolithography process. Subsequently, after the lower film is patterned using the photoresist pattern as a mask, the photoresist may be stripped using the stripper composition for removing the photoresist or the like. In the above process, the formation of the photoresist pattern and the patterning process of the lower film may follow a conventional semiconductor device manufacturing method, and thus additional description thereof will be omitted.

[0115] In addition, when the photoresist is stripped using the stripper composition for removing the photoresist, the stripper composition may be first processed on a substrate with a photoresist pattern remaining thereon, and a process of cleaning with ultrapure water and a process of drying may be performed. In addition, after processing the stripper composition, a process of cleaning with an alkaline buffer solution may also be included.

[0116] The step of stripping photoresist from a substrate engraved with a fine circuit pattern using a stripper composition for removing photoresist according to an embodiment of the present invention can use an immersion method of simultaneously immersing (dipping) multiple substrates to be stripped in a large amount of stripper composition and a single-sheet method of spraying the stripper composition onto the substrate one by one to remove the photoresist, etc., and the method is not limited.

[0117] In a method for stripping a photoresist according to an embodiment of the present invention, when the stripper composition is used in an immersion manner, the step of stripping the photoresist can be performed in a range of 25 to 70°C. Specifically, the step can be performed in a range of 30 to 65°C or in a range of 40 to 60°C. That is, according to the present invention, excellent photoresist stripping force and cleaning force can be achieved under mild temperature conditions without damaging the lower film. In addition, the step can be performed under the above-mentioned temperature conditions for 30 seconds to 10 minutes, or for 30 seconds to 5 minutes, or for 30 seconds to 1 minute. That is, according to the present invention, excellent stripping performance can be achieved in a very fast time under mild temperature conditions as described above.

[0118] Hereinafter, the present invention will be described in more detail based on the examples and comparative examples. However, the following examples and comparative examples are only an example for describing the present invention in more detail, and the present invention is not limited to the following examples and comparative examples.

[0119] [Manufacturing example]

[0120] Production of amine compounds (WJEA)

[0121]

[0122] Under a nitrogen atmosphere, after diethanolamine (20 g, 0.19 mol) and 200 ml of methanol were put into a three-necked flask and stirred at room temperature (25° C.) to melt, 7.7 g (0.095 mol) of formaldehyde solution (37 wt % in H2O) was slowly dripped over 30 minutes. After the dripping was completed, the mixed solution was further stirred for 4 hours under a temperature condition of 50° C. and a nitrogen atmosphere reflux condition. After the reaction was completed, after washing with distilled water and ethyl acetate, the organic layer was dried with MgSO4 and the solvent was removed by reduced pressure distillation. Subsequently, it was refined under the conditions of silica gel column chromatography hexane / ethyl acetate = 3:1 (vol:vol) to obtain 52% of the amine compound (WJEA), and by 1 H-NMR confirmed the production of WJEA.

[0123] HRMS (EI): m / z calculated for C9H22N2O4 222.16

[0124] Production of amine compounds (MNA)

[0125]

[0126] In the production example of the amine compound (WJEA), the amine compound (MNA) was obtained in the same manner except that 2-aminoethanol was used instead of 2-aminoethanol, and 37% of the amine compound (MNA) was obtained by 1 H-NMR confirmed the fabrication of MNAs.

[0127] HRMS (EI): m / z calculated for C5H14N2O2 134.11

[0128] Production of amine compounds (WJEA300)

[0129]

[0130] In the production example of the amine compound (WJEA), the amine compound (MNA) was obtained by the same method except that 2,2-(aminoethoxy)ethanol was used instead of diethanolamine, and 37% of the amine compound (MNA) was obtained by 1 H-NMR confirmed the manufacture of WJEA300.

[0131] HRMS (EI): m / z calculated for C9H22N2O4 222.16

[0132] [Example 1 to Example 12 and Comparative Example 1 and Comparative Example 2]

[0133] After mixing the components in the ratio described in Table 1 below, the mixture was stirred at a speed of 500 rpm for 30 minutes at normal temperature (25° C.) to prepare a stripper composition for removing a photoresist.

[0134] [Table 1]

[0135]

[0136]

[0137] Photoresist stripping strength evaluation

[0138] For the stripper compositions manufactured in the embodiments and comparative examples, the photoresist stripping performance was evaluated. After floating the photoresist on the silicon wafer deposited with the Cu / Ti double film using a spin coater, hard bake for 100 seconds to 150 seconds at 110°C, 120°C, 130°C, 140°C, and 150°C, respectively, to form a photoresist film with a thickness of about 1.2 to 2.1um. Next, the wafer formed with the photoresist was cut into a size of 10mm x 150mm x 150mm to manufacture a sample. The sample was immersed in the corresponding stripper composition at 50°C for 1 minute to remove the photoresist. After the evaluation sample with the photoresist removed was washed with ultrapure water, it was dried with nitrogen.

[0139] Subsequently, whether or not the photoresist was removed was confirmed for the dried sample by EDS (surface qualitative analysis) of FE-SEM, and the results of the evaluation were recorded in Table 2 below based on the following evaluation.

[0140] ◎: Photoresist is removed 100% without residue

[0141] ○: The photoresist is removed by more than 80% and less than 100% with almost no residue

[0142] △: Photoresist is removed by more than 50% and less than 80%, and a considerable amount remains.

[0143] X: Less than 50% of the photoresist is removed and a small amount of photoresist remains

[0144] Evaluation of the corrosion resistance of the lower film

[0145] For the stripper compositions prepared in the examples and comparative examples, in order to evaluate the copper film corrosion resistance, a sample of a silicon wafer having a Cu / Ti double film deposited thereon cut into a size of 10 mm x 150 mm x 150 mm was immersed in a corresponding stripper at 50° C. for 18 hours. The sample was washed with ultrapure water and then dried with nitrogen.

[0146] Subsequently, the change in the copper ion concentration present in the stripper composition was measured by ICP-MS, and the degree of copper damage of the dried sample was confirmed by FE-SEM, and the results are shown in the following Tables 2 and Figure 2 middle.

[0147] Evaluation of peel force over time

[0148] For the stripper compositions manufactured in the embodiments and comparative examples, stripping performance according to the photoresist concentration was evaluated. The photoresist was heat-treated at 150° C. for 24 hours to remove all solvents, thereby preparing a photoresist solid powder. The photoresist coated was immersed in a stripper composition in which the photoresist solid powder was dissolved from 1 wt % to 5 wt % at 50° C. for 1 minute to manufacture a photoresist. After the evaluation sample from which the photoresist was removed was washed with ultrapure water, it was dried with nitrogen.

[0149] Subsequently, whether or not the photoresist was removed was confirmed with FE-SEM for the dried sample, and the results of the evaluation were recorded in Table 2 below based on the following evaluation.

[0150] ◎: Photoresist is removed 100% without residue

[0151] ○: The photoresist is removed by more than 80% and less than 100% with almost no residue

[0152] △: Photoresist is removed by more than 50% and less than 80%, and a considerable amount remains.

[0153] X: Less than 50% of the photoresist is removed and a small amount of photoresist remains

[0154] [Table 2]

[0155]

[0156] As shown in Table 2, it was observed that the stripper composition for removing photoresist according to the present invention had excellent stripping power for photoresist and remarkable anticorrosion power for the lower film containing copper. In addition, the stripper composition according to the present invention can be perfectly removed only by a cleaning process with ultrapure water, so that no residue remains on the substrate after cleaning.

[0157] Specifically, the photoresist stripping force evaluation results of Examples 1 to 12 show that the photoresist was removed 100% in a very short time, and the residue was not left on the substrate and was perfectly cleaned. Figure 1 As shown, when the photoresist was removed using the stripper composition of Example 1 of the present invention, it was confirmed that no undercut occurred and the inclinations of the two metal layers were appropriate, so that an excellent tapered shape could be obtained.

[0158] In addition, the evaluation results of the lower film corrosion resistance of Examples 1 to 12 show that there are almost no dissolved copper ions in the stripper composition, and Figure 2 As shown in , no damage to the copper film was observed in the SEM measurement results. In addition, it was confirmed that excellent peeling strength for the photoresist was maintained even when the photoresist solid powder was dissolved to 3 wt%.

[0159] That is, it can be known that the stripper composition for removing a photoresist according to the present invention is excellent in stripping power, cleaning power, anticorrosive power, and stripping power over time.

[0160] On the contrary, in the case of Comparative Examples 1 and 2 which are stripper compositions not containing the amine compound (WJEA or MNA) according to the present invention, the stripping force for the photoresist was low, and the evaluation results of the lower film corrosion resistance observed a considerable amount of copper ions in the stripper composition, and a significant difference was also observed in the corrosion resistance for the lower film.

Claims

1. A stripper composition for removing a photoresist, comprising an amine compound of the following chemical formula 4; and an anticorrosive agent comprising a triazole-based compound of the following chemical formula 5 and a benzimidazole-based compound of the following chemical formula 6, [Chemical formula 4] [Chemical formula 5] [Chemical formula 6] In the chemical formula 4, e and f are each independently an integer of 1 or 2. 2 . The stripper composition for removing a photoresist according to claim 1 , further comprising an aprotic polar organic solvent and a glycol-based compound.

3. The stripper composition for removing photoresist as claimed in claim 2, wherein the aprotic polar organic solvent comprises one or more selected from the group consisting of N,N-dimethylpropionamide, N-methylformamide, dimethyl sulfoxide, dimethylacetamide, diethyl sulfoxide, dipropyl sulfoxide, cyclopentane, N-methylpyrrolidone, pyrrolidone, N-ethylpyrrolidone, dipropylene glycol monoethyl ether and N,N'-dialkylformamide. 4 . The stripper composition for removing a photoresist according to claim 2 , wherein the glycol-based compound is an alkylene glycol monoalkyl ether.

5. The stripper composition for removing photoresist according to claim 4, wherein the alkylene glycol monoalkyl ether comprises one or more selected from the group consisting of ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, 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 and tripropylene glycol monobutyl ether.

6. The stripper composition for removing photoresist as claimed in claim 2, comprising 30 to 60 wt% of aprotic polar organic solvent, 20 to 60 wt% of glycol-based compound, 0.1 to 10 wt% of the amine compound, and 0.005 to 0.6 wt% of anti-corrosion agent, relative to the total weight of the stripper composition for removing photoresist.

7. A photoresist stripping method comprising: forming a photoresist pattern on the substrate on which the lower film is formed; patterning a lower film using the photoresist pattern; as well as The photoresist is stripped using the stripper composition for removing the photoresist according to any one of claims 1 to 6.

8. The photoresist stripping method according to claim 7, wherein the lower film comprises a metal film containing aluminum (Al), copper (Cu), molybdenum (Mo), titanium (Ti) or an alloy thereof, an insulating film of a silicon oxide film or a silicon nitride film, or a combination thereof.

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