JP6367842B2 - Stripper composition for removing photoresist and photoresist stripping method using the same - Google Patents

Description

  The present invention provides a stripper composition for removing a photoresist that can effectively suppress the occurrence or residue of stains or foreign matters on a lower film containing copper and the like, while exhibiting excellent removal and stripping performance for a photoresist. The present invention relates to a photoresist peeling method using the same.

  A fine circuit process of a liquid crystal display element or a semiconductor direct circuit manufacturing process is carried out on a substrate by a conductive metal film such as aluminum, aluminum alloy, copper, copper alloy, molybdenum, molybdenum alloy, or silicon oxide film, silicon nitride film, fork. Various lower films such as an insulating film such as an acrylic insulating film are formed, a photoresist is uniformly coated on the lower film, and selectively exposed and developed to form a photoresist pattern. And various processes for patterning the lower film using as a mask. After such a patterning step, a step of removing the photoresist remaining on the lower film is performed. For this purpose, a stripper composition for removing the photoresist is used.

  A stripper composition containing an amine compound, a protic polar solvent, an aprotic polar solvent and the like has been widely known, and in particular, an alkylene glycol monoalkyl ether solvent as a polar protic solvent is mainly used. Have been used. Such stripper compositions are known to exhibit some degree of removal and stripping power to the photoresist.

  On the other hand, recently, as the TFT-LCD has been increased in area, ultra-miniaturized and increased in resolution, an attempt has been made to use a wiring pattern containing copper as a gate electrode or a signal electrode. However, due to the characteristics of copper, after patterning the copper-containing film by a photolithography process using a photoresist pattern, the remaining photoresist pattern on the copper-containing film is stripped and stripped using a known stripper composition. When removed, fine stains or foreign matters are often generated and remain on the copper-containing film. This is expected due to the hydrophobicity of copper.

  Such fine stains or foreign substances may deteriorate the display characteristics of the TFT-LCD, and in particular, the resolution is very high, and it is regarded as a larger problem in the recent TFT-LCD in which the pixels are miniaturized. It is coming.

  Accordingly, there is a continuing demand for the development of a stripper composition or related technology having an excellent peeling force for a photoresist without generating and remaining a stain or a foreign substance on the lower film containing copper.

  The present invention provides a stripper composition for removing a photoresist that can effectively suppress the occurrence or residue of stains or foreign matters on a lower film containing copper and the like, while exhibiting excellent removal and stripping performance for a photoresist. A method for removing a photoresist using the same is provided.

  The present invention provides a stripper composition for removing a photoresist comprising one or more amine compounds; a polar organic solvent; an alkylene glycol solvent; and a corrosion inhibitor.

  The present invention also includes a step of forming a photoresist pattern on a substrate on which a lower film containing copper is formed, patterning the lower film with the photoresist pattern, and using the stripper composition. And a method for stripping the photoresist.

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

  According to one embodiment of the invention, a stripper composition for removing a photoresist is provided that includes one or more amine compounds; a polar organic solvent; an alkylene glycol solvent; and a corrosion inhibitor.

  As a result of the experiments by the present inventors, a photocatalyst using an alkylene glycol solvent such as bis (2-hydroxyethyl) ether together with a polar organic solvent such as an amine compound, a protic polar solvent and / or an aprotic polar solvent is used. It was confirmed that substantially no stain or foreign matter was generated and remained on the lower film containing copper or the like while exhibiting excellent peeling and removing power with respect to the resist, and completed the invention.

  More specifically, the alkylene glycol-based solvent can basically lower the surface tension of the stripper composition to improve the wettability (wetability) with respect to the photoresist, and has excellent dissolution in the photoresist. Can show gender. Moreover, such an alkylene glycol solvent can exhibit excellent compatibility with other organic substances forming the stripper composition. Accordingly, the stripper composition according to an embodiment including such an alkylene glycol-based solvent can exhibit excellent peeling and removing power for a photoresist.

  In addition, the alkylene glycol solvent can improve the wettability of the stripper composition even for a hydrophobic lower film containing copper or the like. Therefore, the stripper composition of one embodiment including the same exhibits excellent rinsing power with respect to the copper-containing lower film, and hardly generates or remains a stain or foreign matter on the lower film even after the stripper composition is processed. Such stains and foreign matters can be effectively removed.

  Accordingly, the stripper composition of one embodiment solves the problems of existing stripper compositions and provides excellent stripping to the photoresist without substantially generating and leaving stains or foreign matter on the copper-containing lower film. Can show power.

  In addition, the stripper composition of the embodiment includes a corrosion inhibitor together with the above-described components, and in the process of stripping the photoresist using the same, the stripper composition, for example, an amine compound, Corrosion can be prevented from occurring in the lower film containing copper or the like. As a result, it is possible to suppress deterioration of electrical characteristics such as a copper wiring pattern and to provide an element having improved characteristics.

  Hereinafter, the stripper composition of one embodiment will be described in detail by each component.

  The stripper composition according to the embodiment basically includes an amine compound as a component that exhibits a peeling force against a photoresist. Such amine compounds can serve to dissolve and remove the photoresist.

  In view of the excellent peeling force of the stripper composition of one embodiment, the amine compound may include one or more selected from the group consisting of a chain amine compound and a cyclic amine compound. More specifically, examples of the chain amine compound include (2-aminoethoxy) -1-ethanol [(2-aminoethoxy) -1-ethanol; AEE], aminoethylethanolamine (AEEA), Monomethanolamine, monoethanolamine, N-methylethylamine (N-MEA), 1-aminoisopropanol (AIP), methyldimethylamine (MDEA), diethylenetriamine TA ), And triethylenetetraamine (TET) One or a mixture of two or more selected from the group consisting of A) can be used, among which (2-aminoethoxy) -1-ethanol or aminoethylethanolamine can be used appropriately . The cyclic amine compound is selected from the group consisting of imidazolyl-4-ethanol (IME), aminoethyl piperazine (AEP), and hydroxyethyl piperazine (HEP). One or a mixture of two or more of the above can be used, and imidazolyl-4-ethanol can be suitably used.

  Among such amine compounds, the cyclic amine compound can exhibit a better peeling force for the photoresist, and the chain amine compound has a peeling force for the photoresist, along with a lower film such as a copper-containing film. A natural oxide film (such as a copper oxide film) can be appropriately removed to further improve the adhesive force between the copper-containing film and the insulating film above it, for example, a silicon nitride film.

  In consideration of the superior peeling force and the removal performance of the natural oxide film exhibited by the stripper composition of one embodiment, the mixing ratio of the chain amine compound and the cyclic amine compound is determined as follows: chain amine compound: cyclic amine compound The weight ratio may be about 5: 1 to 1: 5, or about 3: 1 to 1: 3.

  The amine compound described above is about 0.1 to 10%, alternatively about 0.5 to 7%, alternatively about 1 to 5%, alternatively about 1.5 to 3% by weight of the total composition. It may be included by content. The content range of such an amine compound can reduce the reduction in economic efficiency and efficiency of the process due to excess amine while the stripper composition of one embodiment can exhibit excellent peeling force and the like. Generation of waste liquid and the like can be reduced. If an amine compound is contained in an excessively large content, this may cause corrosion of the lower film, for example, a copper-containing lower film, and it may be necessary to use a large amount of a corrosion inhibitor to suppress this. In this case, a large amount of the corrosion inhibitor may cause a considerable amount of the corrosion inhibitor to be adsorbed and remain on the surface of the lower film, thereby reducing the electrical characteristics of the copper-containing lower film.

  Meanwhile, the stripper composition of one embodiment includes a polar organic solvent. The polar organic solvent can dissolve the amine compound satisfactorily, but allows the stripper composition of one embodiment to appropriately permeate the photoresist pattern to be removed and the lower film thereof, thereby removing the stripper. The excellent peeling force and rinsing force of the composition can be ensured.

  More specifically, the polar organic solvent may include an aprotic polar solvent, a protic polar solvent such as an alkylene glycol monoalkyl ether solvent, or a mixture thereof.

  Of these, N-methylformamide (NMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), dipropylene glycol monomethyl ether (DPM), diethyl sulfoxide, dipropyl sulfoxide (dipropyl sulfoxide) dipropylsulfoxide, sulfolane, N-methylpyrrolidone (N-methyl-2-pyrrolidone, NMP), pyrrolidone, N-ethylpyrrolidone, dipropylene glycol monoethyl ether (PE) And one or more solvents selected from the group consisting of N, N′-dialkylcarboxamides It is possible, a variety of aprotic polar solvents which are known to be used in other stripping composition can be used.

  However, among them, N, N′-dialkylcarboxamide such as N, N′-diethylcarboxamide or N-methylformamide can be preferably used, and N, N′-diethylcarboxamide is most preferably used. be able to.

  By using the N, N′-dialkylcarboxamide, N-methylformamide, or the like, the stripper composition of one embodiment is better soaked on the lower film, and the stripper composition of one embodiment is more excellent in photo. The resist peeling force, the rinsing force, and the like can be shown.

  However, among them, N-methylformamide and N, N′-dimethylcarboxamide are known to be toxic to the living body, and also induce amine degradation over time, so that the stripper composition of one embodiment The peeling force and rinsing force of an object may be reduced over time. On the other hand, the stripper composition containing the N, N′-diethylcarboxamide conforms to the composition containing the N-methylformamide or N, N′-dimethylcarboxamide or has a photoresist stripping force superior to this. Although it can show rinsing power, it is not substantially biotoxic.

  Further, the N, N'-diethylcarboxamide hardly induces decomposition of the amine compound, and substantially does not cause decomposition of the amine compound even when the residual photoresist is dissolved in the stripper composition. Therefore, since the stripper composition containing this can reduce a drop in peel strength with time, such N, N′-diethylcarboxamide can be most preferably used as an aprotic polar solvent.

  Compared to such N, N′-diethylcarboxamide, other aprotic polarities such as N-methylformamide, N, N′-dimethylcarboxamide, and dimethylacetamide, which have been widely used in stripper compositions in the past In the case of solvents, reproductive or biotoxicity issues have restricted their use during display or device processes, and in particular, N, N′-dimethylcarboxamide is a reproductive toxicity and specific target organ toxicant that is associated with leukemia It has been confirmed that its use is regulated. In addition, the aprotic polar solvent of N-methylpyrrolidone (NMP), which has been conventionally used in stripper compositions, is also used in Europe with SVHC (high risk) together with N, N′-dimethylcarboxamide and dimethylacetamide. Substance), and a review for use restrictions is underway. In addition, in Korea, N-methylformamide, N, N′-dimethylcarboxamide, dimethylacetamide, N-methylpyrrolidone, and the like are classified and managed as Category 1B (GHS standard) substances exhibiting reproductive toxicity. . In contrast, the aprotic organic solvent of N, N′-diethylcarboxamide makes it possible to achieve excellent physical properties such as excellent stripping force of the stripper composition while not exhibiting such reproduction and biotoxicity. .

  On the other hand, the polar organic solvent may include a protic polar solvent such as an alkylene glycol monoalkyl ether solvent, but such a protic polar solvent soaks the stripper composition of one embodiment better on the lower membrane. Thus, the excellent peeling force of the stripper composition can be assisted. However, such a protic polar solvent may be a different type of solvent from an alkylene glycol solvent described later.

  Such protic polar solvents 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, 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 Use of an alkylene glycol monoalkyl ether solvent, such as monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, or tripropylene glycol monobutyl ether Two or more selected from these may be used. In consideration of the excellent wettability of the stripper composition according to an embodiment and the improved peeling force associated therewith, the protic polar solvent includes diethylene glycol monomethyl ether (MDG) or diethylene glycol monobutyl ether (BDG). Can be used appropriately.

  The polar organic solvent including the aprotic polar solvent or the protic polar solvent described above may be included in a content of about 20 to 80% by weight with respect to the entire composition. And when both the aprotic polar solvent and the protic polar organic solvent are included, the aprotic polar solvent may be included in a content of about 10 to 65% by weight, or about 15 to 60% by weight, Protic polar solvents may be included at a content of about 5 to 60 wt%, alternatively about 10 to 55 wt%. By such a content range of the polar solvent, the excellent peeling force of the stripper composition of one embodiment can be secured.

  On the other hand, the stripper composition of one embodiment may be used as an aqueous stripper composition by further containing water in addition to the polar organic solvent described above, and when such water is selectively contained, The amount can be determined within an appropriate range in the content range of the polar organic solvent.

  In addition, the stripper composition of one embodiment further includes an alkylene glycol solvent in addition to the above-described amine compound and polar organic solvent. Such an alkylene glycol solvent is a kind of protic organic solvent, but is included as a kind different from the above-mentioned protic polar solvent such as alkylene glycol monoalkyl ether. As already described above, the alkylene glycol solvent is included in the stripper composition of one embodiment, so that the surface tension of the stripper composition is lowered and the wettability to the lower film containing the photoresist and copper to be removed is reduced. And wettability can be improved. Further, such an alkylene glycol solvent can exhibit excellent solubility in a photoresist, and can exhibit excellent compatibility with other organic substances forming the stripper composition. Therefore, the stripper composition of one embodiment including such an alkylene glycol-based solvent can exhibit an excellent peeling and removing power for a photoresist, and at the same time, an excellent rinsing power for the lower film. As shown, even after the stripper composition is processed, almost no stains or foreign matters are generated and remain on the lower film, and such stains and foreign matters can be effectively removed.

  Such an alkylene glycol solvent includes a protic organic compound selected from the group consisting of bis (2-hydroxyethyl) ether, glycol bis (hydroxyethyl) ether, and [2- (2-hydroxyethoxy) ethoxy] ethanol. A solvent or a mixture of two or more types can be used, and various other alkylene glycol solvents may be used. Among these, the bis (2-hydroxyethyl) ether can be preferably used in consideration of better wettability with respect to the photoresist and the lower film, and excellent peeling force and rinsing force of the stripper composition to be developed.

  The above-described alkylene glycol-based solvent may be contained in a content of about 10 to 70% by weight, alternatively about 20 to 60% by weight, alternatively about 30 to 50% by weight, based on the total composition. By such a content range, it is possible to ensure excellent peeling force and rinsing force of the stripper composition of one embodiment, particularly excellent stain and foreign matter removal performance on the lower film containing copper and the like.

  Meanwhile, the stripper composition of one embodiment described above further includes a corrosion inhibitor. Such a corrosion inhibitor may be used to remove a metal-containing lower part such as a copper-containing film when removing a photoresist pattern using the stripper composition. It is possible to effectively suppress the corrosion of the film, and to suppress the lowering of the electrical characteristics of the lower film due to the stripper composition, in particular, the amine compound contained therein.

  In order to effectively suppress the corrosion of the lower film, a triazole compound, a tetrazole compound, a compound represented by the following chemical formula 1 or 2 can be used as the corrosion inhibitor.

In the formula, R9 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
R10 and R11 are the same or different from each other, and are each a hydroxyalkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 4,

In the formula, R12 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
b is an integer of 1-4.

  More specific examples of such a corrosion inhibitor include triazole compounds such as benzotriazole or tetrahydrotolyltriazole, tetrazole compounds such as 5-aminotetrazole or hydrates thereof, and in Formula 1, R9 is methyl. A compound in which R10 and R11 are each hydroxyethyl and a is 1, or a compound in which R12 is a methyl group and b is 1 in the chemical formula 2, and these compounds are used. Thus, the stripping composition can be kept excellent in peeling force while effectively suppressing the corrosion of the metal-containing lower film.

  Also, such a corrosion inhibitor is about 0.01 to 0.5 wt%, alternatively about 0.05 to 0.3 wt%, alternatively about 0.1 to 0.2 wt%, relative to the total composition. % May be included. While such a content range can effectively suppress corrosion on the lower film, it can suppress the physical properties of the stripper composition from being deteriorated due to excessive inclusion of such a corrosion inhibitor. . If such a corrosion inhibitor is excessively contained, a considerable amount of the corrosion inhibitor may be adsorbed and remain on the lower film, thereby reducing the electrical characteristics of the copper-containing lower film.

  In addition, the stripper composition of the above-described embodiment may additionally include a surfactant to enhance cleaning characteristics.

  As such a surfactant, a silicone-based nonionic surfactant can be used, but such a silicone-based nonionic surfactant includes an amine compound and the like, and has a strong basicity. It can be stably maintained without causing chemical change, modification or decomposition in the composition, and has excellent compatibility with the aprotic polar solvent, the protic polar solvent, or the alkylene glycol solvent described above. Can be a thing. As a result, the silicone-based nonionic surfactant is well mixed with other components to lower the surface tension of the stripper composition, so that the stripper composition is removed from the photoresist and its underlying film. Better wettability and wettability can be exhibited. As a result, the stripper composition according to an embodiment including the same can exhibit a superior photoresist stripping force and also exhibits an excellent rinsing force with respect to the lower film. Almost no stain or foreign matter is generated or left on the film, and such stain and foreign matter can be effectively removed.

  In addition, the silicone-based nonionic surfactant can exhibit the above-described effects even when added in a very low content, and the generation of by-products due to its modification or decomposition can be minimized.

  As such surfactants, conventional silicone-containing nonionic surfactants that have been known or commercially available, for example, surfactants including polysiloxane polymers are all used without any particular limitation. be able to. Specific examples of such surfactants include polyether modified acrylic functional polydimethylsiloxane, polyether modified siloxane, polyether modified polydimethylsiloxane, polyethylalkylsiloxane, aralkyl modified polymethylalkylsiloxane, polyether modified hydroxy. Examples include functional polydimethylsiloxane, polyether-modified dimethylpolysiloxane, modified acrylic-functional polydimethylsiloxane, and solutions thereof. In addition, such a surfactant reduces the surface tension of the stripper and increases the surface energy of the lower film so that the wettability of the stripper composition to the photoresist and the lower film can be further improved. Can be shown.

  The silicone-based nonionic surfactant is about 0.0005 to 0.1% by weight, or about 0.001 to 0.09% by weight, or about 0.001 to 0%, based on the entire composition. It may be included at a content of 0.01% by weight. If the surfactant content is excessively low, the effect of improving the stripping force and rinsing power of the stripper composition due to the addition of the surfactant may not be sufficient, and the surfactant content is too high. When the stripping process using the stripper composition proceeds, bubbles may be generated at a high pressure to cause a stain on the lower film, or the equipment sensor may malfunction.

  Furthermore, the stripper composition of one embodiment may additionally contain conventional additives as required, and the types and contents thereof are well known to those skilled in the art.

  And the stripper composition of one Embodiment mentioned above can be manufactured with the general method which mixes each component mentioned above, The manufacturing method in particular is not restrict | limited. Such a stripper composition can substantially prevent the stain and / or foreign matter from being generated and remaining on the copper-containing lower film while exhibiting an excellent peeling force with respect to the photoresist. Accordingly, it is possible to suppress deterioration of display characteristics of an element such as a high-resolution TFT-LCD due to the stain and / or foreign matter.

  Thus, according to another embodiment of the invention, there is provided a method for removing a photoresist using the above-described stripper composition. Such a peeling method includes a step of forming a photoresist pattern on a substrate on which a lower film containing copper is formed, a step of patterning the lower film with the photoresist pattern, and the method of the embodiment. Stripping the photoresist with a stripper composition.

  In such a peeling method, first, a photoresist pattern can be formed by a photolithography process on a substrate on which a copper-containing lower film to be patterned is formed. At this time, the copper-containing lower film may be a single film of a copper film or may have a multilayer structure including other metal films such as a copper film and a molybdenum film. Thereafter, after patterning the lower film using such a photoresist pattern as a mask, the photoresist can be peeled off using the above-described stripper composition or the like. In the process described above, the formation of the photoresist pattern and the patterning process of the lower film can follow a normal element manufacturing process.

  On the other hand, when the photoresist is stripped using the stripper composition, fine foreign matters and / or stains are not substantially generated and remain on the lower film, and corrosion is generated on the lower film in such a stripping process. Can be suppressed.

ADVANTAGE OF THE INVENTION According to this invention, the stripper composition for a photoresist removal which does not generate | occur | produce and remain a stain | stain or a foreign material on the lower film | membrane containing copper etc. can be provided, showing the outstanding peeling and removal power with respect to a photoresist. That is, using such a stripper composition, while effectively removing the photoresist on the lower film containing copper or the like, it exhibits an excellent rinsing force, and after the stripper composition is processed, Such stains and foreign matters can be effectively removed without generating and remaining almost no stains or foreign matters.
Moreover, the occurrence of corrosion of the lower film can be effectively suppressed during the treatment using the stripper composition.

It is a FE-SEM photograph which shows the surface shape after processing a copper gate pattern using the stripper composition of Example 2. FIG. It is a FE-SEM photograph which shows the surface shape after processing a copper gate pattern using the stripper composition of Example 9.

  Hereinafter, with reference to the Example of an invention and a comparative example, the operation and effect of the invention are explained more concretely. However, such Examples and Comparative Examples are merely examples of the invention, and the scope of rights of the invention is not limited thereto.

<Example and Comparative Example> Manufacture of Stripper Composition for Removing Photoresist Stripper Composition for Removing Photoresist according to Examples 1 to 11 and Comparative Examples 1 and 2 by mixing each component according to the compositions shown in Tables 1 and 2 below Each thing was manufactured.

[Experimental example] Evaluation of physical properties of stripper composition Stripping Composition Evaluation of Stripper Composition The peeling force of the stripper compositions of Examples and Comparative Examples was evaluated by the following method.
First, 3.5 ml of a photoresist composition (product name: JC-800; known to enable the formation of a photoresist having a relatively strong strength) is dropped on a glass substrate of 100 mm × 100 mm. The photoresist composition was applied at a speed of 400 rpm for 10 seconds. Such a glass substrate was mounted on a hot plate and hard baked at a temperature of 165 ° C. for 10 minutes to form a photoresist.

  The glass substrate on which the photoresist was formed was air-cooled at room temperature and then cut into a size of 30 mm × 30 mm to prepare a peel strength evaluation sample.

  500 g of the stripper composition obtained in the examples and comparative examples were prepared, and the photoresist on the glass substrate was treated with the stripper composition in a state where the temperature was raised to 50 ° C. The peel time was evaluated by measuring the time during which the photoresist was completely peeled and removed. At this time, the presence or absence of peeling of the photoresist was confirmed by observing whether or not the photoresist remained by irradiating the glass substrate with ultraviolet rays.

  The peel strengths of the stripper compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated by the above method and are shown in Table 3 below. Such evaluation results were evaluated and shown for each hard baking condition of the photoresist.

  Referring to Table 3, it was confirmed that the stripper compositions of the examples exhibited superior photoresist stripping power (fast stripping time) compared to the stripper compositions of the comparative examples.

2. Evaluation of Rinsing Power of Stripper Composition The rinsing power of the stripper compositions of Examples and Comparative Examples was evaluated by the following method.
500 g of the stripper composition was prepared, heated to a temperature of 50 ° C., and photoresist powder hard-baked at 150 ° C. for 4 hours was dissolved in 0 to 5% by weight. A single copper film was formed on an insulating glass substrate made of silicon nitride to form a photoresist pattern, which was then treated with the stripper composition. Thereafter, the glass substrate was drained, a few drops of ultrapure water were dropped, and the system was on standby for 30 to 90 seconds. After washing again with ultrapure water, the stain and foreign matter on the copper single film were observed with an optical microscope, and the concentration of the photoresist in which the stain within the area of 3 × ³ cm ² and the foreign matter derived from the photoresist were generated was measured.

  The rinsing power of the stripper compositions of Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated by the above method, and the results are shown in Table 4 below.

  Referring to Table 4, when the stripper composition of the example is used, the rinsing power is improved by generating and remaining a very small number of stains and foreign matters on the copper single film as compared with the comparative example. It was confirmed that In particular, it was confirmed that the use of an alkylene glycol solvent and a protic polar solvent such as BDG in an amount of 20 to 30% by weight improved the rinsing power more conspicuously. And it was confirmed that the rinse power in the case where content of the whole alkylene glycol solvent and the protic polar solvent is 45 to 55% by weight becomes more excellent.

3. Evaluation of presence or absence of corrosion on copper film surface The stripper compositions of Examples 2 and 9 were treated at a temperature of 70 ° C. for 10 minutes on a glass substrate on which a copper gate pattern was formed. After the treatment, the surface shape was analyzed with a scanning electron microscope (FE-SEM). Together with the analysis of the surface shape, the roughness of the copper gate pattern surface was measured to determine the presence or absence of corrosion. The surface shape analysis and roughness measurement method and specific evaluation criteria are as follows.

(1) Analysis of the roughness of the copper gate surface The roughness of the copper gate surface was measured using AFM to determine the presence or absence of corrosion. The gate surface before and after the stripper composition treatment was subjected to AFM measurement, and the measurement conditions were set to a measurement area of 5 × ⁵ cm ² and a scan speed of 1 Hz. After the treatment, when the surface roughness is within 2.3 nm, it is evaluated that there is no corrosion. When the surface roughness is 2.3 to 3.0 nm, it is evaluated that low level corrosion has occurred, and 3.0 to 4.0 nm. In the case of the case, it is evaluated that the intermediate level of corrosion has occurred, in the case of 4.0 to 5.0 nm, it is evaluated that the high level of corrosion has occurred, and in the case of 5.0 nm or more, it is evaluated that the serious corrosion has occurred. did. Such evaluation results are summarized in Table 5 below.

(2) Analysis of copper gate surface shape An FE-SEM photograph was observed with the naked eye to confirm whether surface damage was generated. As shown in the following figure, the presence or absence of surface damage was visually checked, and the presence or absence of surface corrosion was evaluated. The FE-SEM photographs after treatment of the stripper compositions of Examples 2 and 9 are as shown in FIGS. 1 and 2, respectively.

  The result of (1) was mainly considered, and the result of (2) was supplementarily considered to determine whether or not corrosion occurred.

  As can be seen from Table 5 and FIGS. 1 and 2, it was confirmed that the stripper compositions of the examples did not substantially cause corrosion during the processing of the copper gate pattern.

Claims (14)

One or more amine compounds;
Aprotic polar solvents, alkylene glycol monoalkyl ether solvents, or mixtures thereof;
One or more solvents selected from the group consisting of bis (2-hydroxyethyl) ether, alkylene glycol bis (hydroxyethyl) ether, and [2- (2-hydroxyethoxy) ethoxy] ethanol; and triazole compounds, tetrazole Compounds, or
Including a corrosion inhibitor comprising a compound of formula 1 or 2 below:
The stripper composition for removing a photoresist, wherein the amine compound comprises one or more chain amine compounds and one or more cyclic amine compounds:
In the formula, R9 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
R10 and R11 are the same or different from each other, and are each a hydroxyalkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 4,
In formula, R12 is hydrogen or a C1-C4 alkyl group, b is an integer of 1-4.   The chain amine compound includes (2-aminoethoxy) -1-ethanol [(2-aminoethoxy) -1-ethanol; AEE], aminoethylethanolamine (AEEA), monomethanolamine, monoethanolamine. N-methylethylamine (N-MEA), 1-aminoisopropanol (AIP), methyl dimethylamine (MDEA), diethylenetriamine (DETA), and triethylenetetraamine Selected from the group consisting of (Triethylene tetraamine; TETA) The stripper composition for removing a photoresist according to claim 1, wherein the stripper composition comprises one or more of the above.   The cyclic amine compound is selected from the group consisting of imidazolyl-4-ethanol (IME), aminoethylpiperazine (AEP), and hydroxyethylpiperazine (HEP). The stripper composition for removing a photoresist according to claim 1, comprising at least a seed.   The stripper composition for removing a photoresist according to claim 1, wherein the amine compound is contained in an amount of 0.1 to 10% by weight based on the total composition.   Aprotic polar solvents are N-methylformamide (NMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), diethyl sulfoxide, dipropylsulfoxide, sulfolane, N-methylpyrrolidone ( Including one or more solvents selected from the group consisting of N-methyl-2-pyrrolidone (NMP), pyrrolidone, N-ethylpyrrolidone, and N, N-diethylformamide. The stripper composition for removing a photoresist according to claim 1, wherein the stripper composition is a photoresist strip.   The alkylene glycol monoalkyl ether solvent is diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl 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, One or more selected from the group consisting of reethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, and tripropylene glycol monobutyl ether The stripper composition for removing a photoresist according to claim 1. The aprotic polar solvent, the alkylene glycol monoalkyl ether solvent, or a mixture thereof is included in a total content of 20 to 80% by weight based on the total composition. Stripper composition for removing photoresist as described in 1. One or more solvents selected from the group consisting of the bis (2-hydroxyethyl) ether, alkylene glycol bis (hydroxyethyl) ether, and [2- (2-hydroxyethoxy) ethoxy] ethanol are included in the overall composition. On the other hand, the stripper composition for removing a photoresist according to claim 1, wherein the total content is 10 to 70% by weight.   The stripper composition for removing a photoresist according to claim 1, wherein the corrosion inhibitor is included in an amount of 0.01 to 0.5% by weight based on the total composition.   The stripper composition for removing a photoresist according to claim 1, further comprising a silicone-based nonionic surfactant.   The stripper composition for removing a photoresist according to claim 10, wherein the silicone-based nonionic surfactant contains a polysiloxane-based polymer.   The silicone-based nonionic surfactant includes polyether-modified acrylic functional polydimethylsiloxane, polyether-modified siloxane, polyether-modified polydimethylsiloxane, polyethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified hydroxy-functional The stripper composition for removing a photoresist according to claim 10, comprising at least one selected from the group consisting of a functional polydimethylsiloxane and a modified acrylic functional polydimethylsiloxane.   The stripper composition for removing a photoresist according to claim 10, wherein the silicone-based nonionic surfactant is contained in an amount of 0.0005 to 0.1% by weight based on the total composition. Forming a photoresist pattern on a substrate on which a lower film containing copper is formed;
Patterning the lower film with the photoresist pattern;
A method for stripping a photoresist, comprising stripping the photoresist using the stripper composition according to claim 1.