KR100306649B1 - Resist stripper, resist stripping method using the stripper, resist stripper recycling apparatus, and resist stripper controlling apparatus - Google Patents

Abstract

PURPOSE: Provided are a resist peeling liquid which can peel at a low temperature in a short time even resist film modified by etching, can be maximized in a replacement cycle, and can be easily recycled by distillation and compensation of components, and by which metallic wiring does not corrode, a method for peeling resist using the liquid, a device for recycling resist peeling, and a device for managing resist peeling liquid. CONSTITUTION: The resist peeling liquid comprises an organic amine compound, a protic glycol ether compound, an aprotic multipolar compound and an alkyl pyrrolidone compound. The content of the organic compound is 10-35 wt.%, and total content of the protic glycol ether compound and the aprotic multipolar compound is 60-85 wt.%. The content of the alkyl pyrrolidone is 0.1-5 wt.%. The alkyl pyrrolidone is at least one selected from the group consisting of N-cyclohexyl-2-pyrrolidone, N-octyl-2-pyrrolidone, and N-dodecyl-2-pyrrolidone. The method comprises contacting the peeling liquid with substrate coated with resist film. The recycling device comprises the first unit for removing water from wasted peeling liquid; the second unit for removing dissolved resist from the liquid(supplied from the first unit); and the diffusion unit for diffusing the first and second peeling components to wasted peeling liquid from the second unit and recycling them into a peeling liquid. The managing device comprises a unit for storing wasted peeling liquid; a unit for recycling wasted peeling liquid; a unit for storing peeling liquid; and a unit for mixing and supplying a peeling liquid, waste peeling liquid, and an organic compound.

Description

Resist stripper, resist stripping method, resist stripper regeneration apparatus, and resist stripper management apparatus {Resist stripper, resist stripping method using the stripper, resist stripper recycling apparatus, and resist stripper controlling apparatus}

The present invention relates to a resist stripping composition (hereinafter referred to as "peel"), a resist stripping method using the same, a resist stripper recycle apparatus, and a resist stripper contolling apparatus. More particularly, the present invention relates to a peeling liquid for peeling a resist from a substrate in a manufacturing process such as a semiconductor device and a liquid crystal display device, a resist peeling method using the same, a peeling liquid regeneration device, and a peeling liquid management device.

In order to manufacture semiconductor devices such as integrated circuits (ICs), high integrated circuits (LSI), ultra high integrated circuits (VLSI), and liquid crystal display devices, many steps of photoetching processes are repeatedly performed. The photoetching process is performed by the following steps.

First, a resist film is formed by spin coating a resist on a semiconductor substrate or a glass substrate having a substructure such as a metal layer. Subsequently, a latent image of the pattern is formed in the resist film by irradiating the resist film with active rays having high energy such as ultraviolet rays, electron beams, or X-rays through a mask having a predetermined pattern formed thereon. Subsequently, the resist film is developed to form the same resist pattern as the pattern. Subsequently, the pattern is transferred to the semiconductor substrate or the glass substrate by wet or dry etching the semiconductor substrate or the glass substrate using the resist pattern as an etching mask. Finally, the resist pattern is removed using a stripper composition.

By the way, as said peeling liquid, the inorganic acid aqueous solution, the inorganic base aqueous solution, or the organic solvent type peeling liquid which can melt | dissolve a resist has been used. For example, Japanese Laid-Open Patent No. 64-42653 has a stripping solution composed of a mixture of an aromatic hydrocarbon and an alkylbenzenesulfonic acid, and the like, and Japanese Laid-Open Patent Laid-Open No. 62-49355 adds ethylene oxide of alkanolamine and polyalkylene polyamine. The stripping solution consisting of water, sulfonate and glycol monoalkyl ether is disclosed in Japanese Laid-open Patent Application No. 64-81949 and Japanese Laid-open Patent Publication No. 64-81950 with a release liquid containing 50% or less amino alcohol.

However, since these are highly toxic to metal films and toxic, organic solvent-based stripping solutions are generally preferred. Examples of the stripping solution using such an organic solvent include stripping solutions disclosed in Japanese Patent Application Laid-Open No. Hei 4-124668, Japanese Patent Application Laid-Open No. Hei 4-350660, Japanese Patent Application Laid-Open No. Hei 5-273768, Japanese Patent Application Laid-Open No. Hei 5-281753 and the like. Can be. However, they have a problem in that the stripping capacity is weak in common.

On the other hand, the stripping liquid waste solution used in the resist stripping step contains a resist component and water in addition to the stripping liquid. As a method of discarding such a stripping liquid waste liquid, the method of incineration is common. However, such a method is not preferable in terms of economical efficiency because it not only adversely affects the environment by releasing incineration gas into the atmosphere but also discards components that can be recycled in the stripping liquid waste solution. Therefore, it is very useful to develop a peeling liquid and a peeling liquid management apparatus configured to separate and recycle useful peeling liquid components from the peeling liquid waste liquid. In particular, in the present situation where the amount of the stripping liquid is greatly increased due to the rapid enlargement of the substrate area for liquid crystal display elements.

In addition, the conventional resist stripping process is a batch method in which a stripping process is performed on a predetermined number of substrates based on experience using a predetermined amount of stripping solution, and then the stripping solution is discarded and replaced entirely with a new stripping solution. Taking shape. The replacement cycle of this stripping liquid is about 1 time / 12 hours, depending on the type and size of the substrate.

On the other hand, the organic amine compound in the stripping solution is reduced in concentration due to the reaction with acid in the resist, the evaporation loss due to heating, and the stripping reaction, thereby gradually reducing the stripping performance. Thus, as time passes, the dissolution rate of the resist decreases and the removal of the resist is incomplete, resulting in unstable product quality and lower yield. In addition, since the operation must be stopped in order to replace the stripping solution, there is a problem in that the production operation rate decreases and the product production cost increases due to an increase in the cost of the stripping solution.

Accordingly, an object of the present invention is to solve the above-mentioned problems of the conventional stripping liquid, and to deal with the harsh conditions of the dry etching, the wet etching and / or ashing process, and the metallic by-products etched from the lower metal film or the insulating film during the process. Can be easily peeled off at a low temperature in a short time, hardly corrodes the lower metal wiring, and the change of composition of the stripping solution due to heating can be minimized and the evaporation loss is small, maximizing the replacement cycle of the stripping solution. In the subsequent rinsing process, it is possible to rinse only with water without using organic solvents such as isopropyl alcohol and dimethyl sulfoxide, and to provide a stripping solution that can be easily regenerated through distillation.

Another object of the present invention is to provide a method for peeling a resist using the stripping solution.

Still another object of the present invention is to provide a stripping liquid regeneration apparatus capable of regenerating a stripping liquid from a stripping waste liquid.

It is still another object of the present invention to maintain the resist stripping performance in a certain range and to minimize the amount of the stripping solution and the downtime of the stripping solution. The present invention provides a peeling liquid management apparatus capable of automatically controlling the composition of the peeling liquid by automatically replenishing and supplying an organic amine compound and appropriately managing supplying the peeling liquid to the resist stripping apparatus.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the peeling liquid regeneration apparatus used for regenerating peeling liquid which concerns on this invention.

It is a schematic diagram which shows the peeling liquid management apparatus which concerns on this invention.

3 shows a calibration curve showing the correlation between the concentration of the dissolved resist and the absorbance in the stripping solution according to the present invention.

<Explanation of symbols for the main parts of the drawings>

One ; Peeling Waste Storage Tank

1 ', 6', 10, 21, 23: first load cell

2, 5 "', 8, 9, 16, 13"', 22 ", 23", 27 ": transfer pump

2 ', 5', 5 ", 8 ', 9', 13 ', 13", 16', 22 ', 23 ", 27': flow control valve

3: water distillation column 4, 12: condenser

4 ': organoamine titrator 4 ", 20,: controller

5, 13: reflux machine 6: water recovery tank

7, 15: decompression pump 11: stripping solution distillation column

14: stripping liquid recovery tank 18: resist discharge pump

18a: resist discharge valve 19: GC device

26: mixing tank 22: organic amine compound supplement tank

23: aprotic multipolar compound supplement tank

24: Feed Bag Pipeline 25: Feed Bag Pump

In order to achieve the above object, the present invention provides a stripping solution, characterized in that the stripping solution, consisting of an organic amine compound, a protic glycol ether compound, an aprotic multipolar compound and an alkylpyrrolidone compound.

In the stripper according to the present invention, the content of the organic amine compound is 10 to 35% by weight, the total content of the protic glycol ether compound and the aprotic polypolar compound is 60 to 85% by weight, and the alkylpy The content of the rollidone compound is preferably 0.1 to 5% by weight.

In the stripper according to the present invention, the content of the alkylpyrrolidone compound is preferably 0.3 to 1% by weight.

In the stripper according to the present invention, the organic amine compound is selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, cycloaliphatic amines, aromatic amines and heterocyclic amines, and hydroxyl amines. It is preferable that it is any one or more compounds.

In the stripper according to the present invention, the protic glycol ether compound is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol It is preferably at least one selected from the group consisting of monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. .

In the stripper according to the present invention, the aprotic multipolar compound is any one selected from the group consisting of dimethyl sulfoxide, dimethylacetamide, dimethylformamide, dimethylimidazolidinone, sulfolane, N-methyl pyrrolidone It is preferred that it is at least one compound.

In the stripper according to the present invention, the alkylpyrrolidone compound is composed of N-cyclohexyl-2-pyrrolidone, N-octyl-2-pyrrolidone, and N-dodecyl-2-pyrrolidone It is preferably a compound which is at least one selected from the group.

In order to achieve the above another object, the present invention provides a resist stripping method comprising contacting a substrate on which a resist film is applied and a stripping solution according to the present invention.

In order to achieve the above object, the present invention is also characterized in that a predetermined material film pattern and a substrate in which a resist pattern used as an etching mask for forming the material film pattern are sequentially stacked are brought into contact with the stripper according to the present invention. A resist stripping method is provided.

In the resist stripping method according to the present invention, the resist pattern may be ashed using plasma before contacting the substrate and the stripping liquid composition.

In the resist stripping method according to the invention, the material film is silicon, tantalum, titanium, chromium, molybdenum, tungsten, tin, nickel, aluminum, silicon oxide, silicon nitride, and indium tin oxide ( indium tinoxide) is preferably formed of one or more materials selected from the group consisting of.

The present invention in order to achieve the above another object is a first distillation apparatus for removing water from the peeling waste liquid; A second distillation apparatus for receiving a peeling waste liquid from which water is removed from the first distillation apparatus and removing the dissolved resist therefrom; And a replenishment device for replenishing the first stripping liquid component and the second stripping liquid component to the stripping waste liquid supplied from the second distillation apparatus to regenerate the stripping liquid.

In the stripping liquid regeneration apparatus according to the present invention, the first distillation apparatus includes a distillation column for distilling water from the stripping waste liquid, a condenser for condensing water vapor evaporated from the distillation column with water, and organic matter in the steam from the condenser. When the concentration of the amine compound is greater than a predetermined reference concentration in the distillation column to reduce the evaporation temperature of the reflux to return to the distillation column, the storage means for storing the water condensed in the condenser, and the water vapor evaporated in the distillation column It is preferable to include a pressure reducing pump for lowering the pressure.

In the stripping liquid regeneration apparatus according to the present invention, the second distillation apparatus receives a stripping waste liquid from which water is removed from the first distillation apparatus, a distillation column for distilling it, and a condenser for condensing the stripping waste liquid evaporated from the distillation column. A reflux condenser for returning the stripping waste condensed in the condenser to the distillation column, storage means for storing the stripping liquid condensed in the condenser, and a distillation column for reducing the evaporation temperature of the stripping waste liquid distilled in the distillation column. It is preferable to include a pressure reduction pump for lowering the internal pressure.

In the stripping liquid regeneration device according to the present invention, the replenishment device is an analysis means for analyzing the content of each component of the stripping waste liquid supplied from the second distillation apparatus, the first component and the second by detecting the analyzed content It is preferable to include replenishing means for replenishing the components, and mixing means for mixing the exfoliating waste liquid and the replenished first and second components.

In the stripping liquid regeneration apparatus according to the present invention, the first stripping liquid component and the second stripping liquid component are each preferably an organic amine compound and an aprotic polypolar compound.

In order to achieve the above another object, the present invention detects the dissolved resist concentration in the stripping waste liquid by an ultraviolet absorbance spectrometer, and transfers the stripping waste liquid to the stripping liquid supply means to reuse the stripping waste liquid as it is, if the dissolved resist concentration is below a predetermined reference value. Stripping waste storage means for transferring the stripping waste liquid to a stripping waste distillation apparatus for regeneration when the dissolved resist concentration exceeds the reference value; A peeling waste liquid regeneration device which receives the peeling waste liquid from the peeling waste liquid storage means, removes moisture and the dissolved resist therefrom, and replenishes the first peeling liquid component and the second peeling liquid component to regenerate the peeling liquid; Stripping liquid storage means for mixing and storing the stripping liquid recycled in the stripping waste liquid regeneration device and a new stripping liquid; And a stripping solution supply device for receiving the stripping solution transferred from the stripping solution storage means, the stripping waste solution transferred directly from the stripping waste storage means, and an organic amine compound, mixing them, and then supplying them to a resist stripping apparatus. A peeling liquid management apparatus is provided.

In the peeling liquid management apparatus which concerns on this invention, it is preferable that the said 1st peeling liquid component and the 2nd peeling liquid component are an organic amine compound and an aprotic polypolar compound, respectively.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

First, the peeling liquid which concerns on this invention is demonstrated. The stripper according to the present invention comprises an organic amine compound, a protic glycol ether compound, an aprotic multipolar compound and an alkylpyrrolidone compound, the content of the organic amine compound is 10 to 35% by weight, the protic glycol The total content of the ether compound and the aprotic polypolar compound is preferably 60 to 85% by weight, and the content of the alkylpyrrolidone compound is 0.1 to 5% by weight.

The organic amine compound is preferably a compound which is at least one selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, cycloaliphatic amines, aromatic amines and heterocyclic amines, and hydroxyl amines. Among them, the primary aliphatic amine compound, especially monoethanolamine, is more preferable because the molecular weight is small, so that it is easy to infiltrate the resist film in the peeling process to dissolve or swell it.

The content of the organic amine compound is preferably 10 to 35% by weight, more preferably 15 to 30% by weight. When the content of the organic amine compound is less than 10% by weight, the resist film which is deteriorated by the etching process cannot be severely peeled off, and when the content of the organic amine compound exceeds 35% by weight, corrosion resistance to metal wiring is increased. .

The second component of the stripper of the present invention is a protic glycol ether compound and an aprotic polypolar compound, which are neutral solvents well mixed with the organic amine compound.

The protic glycol ether compounds include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl It is preferably at least one selected from the group consisting of ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. Among them, diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether are particularly preferred, which have a low surface tension and a high flash point.

Although the examples of the protic glycol ethers may be used alone, it is preferable to use two or more kinds thereof. When two kinds of the protic glycol ethers are used in combination, the mixing ratio of the two kinds of protic glycol ethers is used. Is preferably from 5:95 to 95: 5. For example, when the diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether are mixed and used, it is preferable to mix and use in the ratio of 30: 70-70: 30.

The aprotic multipolar compound is preferably at least one compound selected from the group consisting of dimethyl sulfoxide, dimethylacetamide, dimethylformamide, dimethylimidazolidinone, sulfolane, and N-methyl pyrrolidone. Particularly preferred are dimethyl sulfoxide and N-methyl pyrrolidone having a solubility parameter of 10 or more and strong for breaking or modifying molecules due to heat during distillation and excellent in mixing with water.

The protic glycol ether compound and the aprotic polypolar compound added as a neutral solvent to the stripping solution according to the present invention exhibit performance even if added alone, but in order to obtain a better effect, they are preferably used in combination with each other. The total content of the neutral solvent is preferably 60 to 85% by weight, more preferably 65 to 80% by weight. The preferred total content of the neutral solvent is determined so that the degradation of the peeling performance can be minimized by the evaporation loss due to prolonged heating during the peeling process, and also the peeled resist film can be sufficiently peeled off by the etching process. Therefore, the use of the stripper according to the present invention can extend the use cycle of the stripper to maximize the number of treated substrates.

The alkylpyrrolidone compound, which is the last component of the stripper according to the present invention, is N-cyclohexyl-2-pyrrolidone (N-cyclohexyl-2-pyrrolidone), N-octyl-2-pyrrolidone (N-octy1- 2-pyrrolidone), and N-dodecyl-2-pyrrolidone (N-dodecyl-2-pyrrolidone) is preferably any one selected from the group consisting of. The alkylpyrrolidone compound may shorten the wetting time than the anionic or cationic surfactant as a nonionic surfactant. In addition, since the alkylpyrrolidone compound has a compact molecular structure, the alkylpyrrolidone compound moves easily in solution and rapidly decreases interfacial tension. Among the alkyl pyrrolidone compounds, N-octyl-2-pyrrolidone having the lowest dynamic surface tension is most effective because of the small hydrophilic group.

The content of the alkyl pyrrolidone compound is preferably 0.1 to 5% by weight, more preferably 0.3 to 1% by weight. If the content is less than 0.1% by weight, the effect as a surfactant is negligible when the resist film is deteriorated by the etching process. If the content is more than 5% by weight, the alkylpyrrolidone compound is expensive compared to the effect of lowering the interfacial tension. to be. The alkylpyrrolidone compound may be used alone, but may be used in combination of two or more.

Next, the method of peeling a resist from a board | substrate using the peeling liquid which concerns on this invention is demonstrated.

The method of peeling a resist from a substrate using the stripping solution according to the present invention is accomplished by contacting the stripping solution according to the present invention with a substrate coated with a resist film according to a conventional method. The contact is made by immersing the substrate in the stripping liquid or straying the stripping liquid onto the substrate. There is no restriction on the method of the above contact.

The stripper according to the present invention is particularly useful for stripping the resist which is deteriorated by the harsh conditions resulting from dry etching, wet etching and / or ashing processes and by-products etched from the metal film or insulating film during the etching process.

Examples of the metal film or insulating film include materials such as silicon, tantalum, titanium, chromium, molybdenum, tungsten, tin, nickel, aluminum, silicon oxide, silicon nitride, and indium tin oxide.

Next, with reference to FIG. 1, the peeling liquid regeneration apparatus 1-27 used to regenerate the peeling liquid which concerns on this invention is demonstrated.

Referring to FIG. 1, the stripper regenerating apparatuses 1 to 27 are largely composed of three parts. That is, the regeneration device receives the first distillation apparatus (2-9) for removing water from the stripping waste liquid and the stripping waste liquid from which the water is removed from the first distillation apparatus (2-8 '). The second distillation apparatus (11 to 18) for removing the water and the stripping waste liquid from which the water and the dissolving resist are removed from the second distillation apparatus (10 to 16) are supplied to supplement the organic amine compound and the aprotic polypolar compound. This is composed of a mixing device (19 to 27) for regenerating the peeling waste liquid to the peeling liquid having the same or similar composition as the original peeling liquid. In addition, the stripping liquid regeneration apparatus 1 to 27 according to the present invention is a stripping waste storage tank 1 for temporarily storing the stripping waste liquid recovered from the resist stripping apparatus (30 in FIG. 2) and the first and second distillation. A peeling waste liquid conveying pipe 10 for connecting the device is further provided.

Subsequently, the operation mechanism of the stripping liquid regeneration apparatus 1 to 27 according to the present invention shown in FIG. 1 will be described.

First, when the first load cell 1 'detects that the storage amount of the stripping waste liquid stored in the stripping waste liquid storage tank 1 exceeds a preset reference amount, a first controller (not shown) is connected to the first load cell 1'. (Omitted) generates an output signal to open the first flow control valve 2 'and operate the first transfer pump 2 to transfer the peeling waste liquid to the water distillation column 3. In the water distillation column 3, the stripping waste liquid is heated so that only the water having the lowest boiling point is evaporated. At this time, it is necessary to prevent the peeling liquid component from being decomposed or deformed by heat at a high temperature. To this end, the pressure reduction pump 7 lowers the pressure in the water distillation column 3 in order to lower the temperature at which the water is evaporated. Water vapor evaporated in the water distillation tower (3) is condensed into water in the condenser (4) and stored in the water recovery tank (6). When the second load cell 6 'detects that the amount of water recovered in the water recovery tank 6 exceeds a preset reference amount, a second controller (not shown) connected to the second load cell 6' is output. The signal is opened to open the second flow control valve 8 'and the second transfer pump 8 is operated to discharge to the outside. On the other hand, when the concentration of the organic amine compound in the distillate titrated by the organic amine titrator 4 'is greater than the predetermined reference concentration, the third controller 4 "outputs an output signal to generate the third flow control valve 5'. ) And at the same time open the fourth flow control valve (5 ") and operate the third transfer pump (5" ') to return the distillate to the water distillation column (3) through the reflux (5). When 3) reaches a steady state and the concentration of the organic amine compound in the distillate titrated by the organic amine titrator 4 'falls below a predetermined reference concentration, the third controller 4 " The flow rate control valve 5 'is opened and at the same time the fourth flow rate control valve 5 "is closed and the operation of the third transfer pump 5"' is stopped to send distilled water to the water recovery tank 6. On the other hand, in the apparatus shown in FIG. 1, it was determined by the organic amine titrator whether to return the distillate to the water distillation column through the reflux, but by experience, even if the first distillation apparatus is not provided with the organic amine titrator 4 ' By setting the conditions of the water distillation column (3), it is possible to determine whether to return the distillate through the reflux (5) or to the water recovery tank (6).

Subsequently, when it is detected that the amount of distillate flowing into the organic amine titrator 4 'is equal to or less than a predetermined reference amount, the third controller 4 " issues an output signal to close the decompression pump 7 and at the same time the fifth flow control valve. The separation waste distillation column 11 in the second distillation apparatus 11 to 18 is removed from the second distillation apparatus 11 to 18 by closing the 9 'and operating the fourth transfer pump 9 to remove the water from the first distillation apparatus 2 to 8'. Transfer to).

The stripping solution distillation column 11 distills the stripping solution component to separate the dissolved resist component from the stripping waste liquid and operates the resist discharge pump 18 with the dissolved resist component concentrated at the bottom through the resist discharge valve 18a. Dispose of it by hand. At this time, the pressure reduction pump 15 serves to lower the pressure in the stripper distillation column 11. The stripping solution evaporated in the stripping solution distillation column 11 is condensed in the condenser 12 and stored in the stripping solution recovery tank 14. When the third load cell 10 detects that the amount of the stripping liquid recovered in the stripping liquid recovery tank 14 exceeds a preset reference amount, a fourth controller (not shown) connected to the third load cell 10 The output signal is issued to open the sixth flow control valve 16 ′ and operate the fifth transfer pump 16 to transfer the distilled stripper to the mixing tank 26 via the GC device 19 of the mixing device. Meanwhile, if necessary, the seventh flow control valve 13 ′ is closed, and at the same time, the eighth flow control valve 13 ″ is opened, and the sixth transfer pump 13 ′ ′ is operated to return the distilled stripping liquid to the reflux machine 13. ) Can be returned to the stripping solution distillation column (11).

The GC device 19 in the mixing device analyzes the content of the components of the stripping solution introduced into it. The fifth controller 20 calculates the deficiency of the organic amine compound and the aprotic multipolar compound component (lack compared with the original stripping solution) based on the content of the component analyzed from the GC apparatus 19, The output signal is opened to open the ninth flow control valve 22 'and the tenth flow control valve 23', and operate the seventh transfer pump 2 "and the eighth transfer pump 23" to supply the organic amine compound supplement tank. The organic amine compound and the aprotic multipolar compound are respectively transferred from the 22 and the aprotic multipolar compound supplement tank 23 to the mixing tank to regenerate the stripping solution. When it is detected that the organic amine compound and the aprotic multipolar compound are supplied from the fourth load cell 21 and the fifth load cell 23 by the deficiency, the fifth controller 20 issues an output signal to generate a ninth flow rate control valve. Supplying the organic amine compound and the aprotic polypolar compound by closing the 22 'and the 10th flow regulating valve 23' and stopping the operation of the seventh transfer pump 22 "and the eighth transfer pump 23". To block.

Subsequently, the GC apparatus 19 takes some recycled stripping liquid from the mixing tank 26 by the feed bag pump 25 through the feed bag conduit 24 and analyzes the content of each component again. If it is confirmed from the analysis data that the content of the organic amine compound and the aprotic polypolar compound is within a predetermined content range, the fifth controller 20 issues an output signal to open the eleventh flow control valve 27 '. The ninth transfer pump 27 "is operated to discharge the regenerated peeling liquid to the outside.

Next, with reference to FIG. 2, the peeling liquid management apparatus which concerns on this invention which employ | adopted the said peeling liquid regeneration apparatus is demonstrated.

Referring to FIG. 2, the peeling process is performed by spraying the stripping solution onto the substrate 35 through the nozzle 33 in the resist stripping apparatus 30. When it is detected by the first load cell 36 that the amount of the stripping waste liquid 37 collected in the lower portion of the resist stripping apparatus 30 reaches a predetermined reference amount, the first material connected to the first load cell 36 is detected. A controller (not shown) outputs an output signal to operate the first transfer pump 39 to transfer the peeling waste liquid to the peeling waste liquid storage tank 43 through the first flow control valve 41. In the peeling waste liquid storage tank 43, the peeling waste liquid is stored until a predetermined reference amount is reached. Whether the storage amount of the peeling waste liquid has reached the reference amount is detected by the second load cell 45. When the second load cell 45 detects that the storage amount of the peeling waste liquid reaches a reference amount, a second controller (not shown) connected to the second load cell 45 issues an output signal to operate the first transfer pump 39. Stop and close the first flow control valve 41.

Subsequently, a part of the peeling waste liquid from the peeling waste liquid storage tank 43 is introduced into the ultraviolet absorbance photometer 49 through the conduit 47, and the absorbance of the peeling waste liquid is measured to detect the dissolved resist concentration in the peeling waste liquid.

At this time, in order to detect the dissolved resist concentration in the stripping waste liquid by the ultraviolet absorbance spectrometer 49, a calibration curve showing the correlation between the dissolved resist concentration in the stripping liquid and the absorbance should be prepared in advance. Fig. 3 shows the correlation between the absorbent resist concentration and the absorbance obtained by the inventors by measuring the absorbance while changing the concentration of the dissolved resist in the stripping solution. At this time, λ = 353 nm was used as the measurement wavelength.

When the dissolved resist concentration detected by the ultraviolet absorbance photometer 49 does not exceed a predetermined reference value, the third controller 51 issues an output signal to open the second flow control valve 53 to open the second transfer pump. By activating 55, the peeling waste liquid is supplied to the peeling liquid supply tank 57 to circulate the peeling waste liquid without regeneration treatment. When the fact that all the peeling waste liquid is discharged from the peeling waste liquid storage tank 43 is transmitted to the third controller 51 by the second load cell 45, the third controller 51 issues an output signal to generate the second flow control valve. Close 53 and stop the operation of the second transfer pump 55.

On the contrary, when the dissolved resist concentration detected by the ultraviolet absorbance photometer 49 exceeds a predetermined reference value and cannot be used again as it is, the third controller 51 issues an output signal to generate the third flow control valve 59. And the peeling waste liquid is transferred to the peeling waste liquid regeneration device 63 by operating the third transfer pump 61. The peeling waste liquid regeneration device 63 is the device described with reference to FIG. When the fact that all the peeling waste liquid is discharged from the peeling waste liquid storage tank 43 is transmitted to the third controller 51 by the second load cell 45, the third controller 51 issues an output signal to generate a third flow control valve. Close 59 and stop the operation of the third transfer pump 61.

In the stripping waste liquid regeneration device 63, the stripping waste liquid is regenerated into a stripping liquid having the same or similar composition as that of the original stripping liquid by removing water and the dissolving resist and supplementing the insufficient organic amine compound and aprotic multipolar compound component. The stripping liquid of the stripping waste liquid regeneration device 63 is transferred to the stripping liquid storage tank 69 by the fourth flow control valve 65 and the fourth transfer pump 67.

When the third load cell 70 detects that the amount of the stripping solution stored in the stripping solution storage tank 69 reaches a predetermined reference amount, a fourth controller (not shown) connected to the third load cell 70 generates an output signal. The operation of the fourth transfer pump 67 is stopped and the fourth flow control valve 65 is closed. On the other hand, the peeling liquid storage tank 69 is replenished with fresh peeling liquid from the outside whenever necessary.

The fourth load cell 75 detects the amount of the peeling liquid in the peeling liquid supply tank 57. When the amount is less than the reference amount, a fifth controller (not shown) connected to the fourth load cell 75 generates an output signal to operate the fifth transfer pump 73 and open the fifth flow control valve 71 to release the separation solution. The peeling liquid is supplied from the peeling liquid storage tank 69 to the peeling liquid supply tank 57 until the amount of the peeling liquid in the supply tank 57 reaches the reference amount. When the amount of the stripping solution in the stripping solution supply tank 57 reaches the reference amount, the fifth controller (not shown) issues an output signal to stop the operation of the fifth transfer pump 73 and the fifth flow control valve 71. To close it.

The organic amine compound, which greatly influences the peeling performance of the stripping solution, decreases in concentration due to reaction with acid in the resist, evaporation loss due to heating, and stripping reaction, so that the second flow control valve 53 is removed from the stripping waste storage tank 43. The stripping waste liquid supplied directly to the stripping solution supply tank 57 has a low concentration of the organic amine compound. Therefore, in order to maintain the peeling performance of the peeling liquid in the peeling liquid supply tank 57 at a constant level, the organic amine compound should be supplemented to maintain the content of the organic amine compound at a constant level.

For this purpose, a part of the stripping solution is introduced into the amine titrator 79 from the stripping solution supply tank 57 through the conduit 77 to titrate the content of the organic amine compound in the stripping solution in the stripping solution supply tank 57. When the appropriate concentration of the organic amine compound is lower than the predetermined reference concentration, the sixth controller 81 issues an output signal to open the sixth flow control valve 85 and operate the sixth transfer pump 83 to operate the organic amine compound. The organic amine compound is supplied from the supply tank 87 to the stripper supply tank 57. At this time, the supply amount of the organic amine compound required to maintain the content of the organic amine compound in the stripping solution in the stripping solution supply tank 57 at the reference concentration is calculated by the sixth controller 81. The fifth load cell 89 measures the supply amount of the organic amine compound supplied to the stripping solution supply tank 57 and transfers it to the sixth controller 81. The sixth controller 81 issues an output signal when the supply amount delivered from the fifth load cell 89 is equal to the calculated value, closes the sixth flow control valve 85 and stops the operation of the sixth transfer pump 83. Let's do it.

Subsequently, the sixth controller 81 issues an output signal to open the seventh flow control valve 93 and operate the seventh transfer pump 91 to supply the stripping liquid to the nozzle 33 of the resist stripping apparatus 30. do. On the other hand, the peeling liquid passes through the fine particle removal filtration device 95 before being supplied to the resist stripping device 30.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples. On the other hand, in the following examples, unless otherwise stated, percentages and mixing ratios are based on weight. In Examples and Comparative Examples of the present invention, performance evaluation of the peeling liquid composition was performed by the following method.

(1) Peeling performance of peeling liquid

Specimen Manufacturing

Positive type resist composition DTFR-1011SK (manufactured by Dongjin Chemical Industry Co., Ltd.), which is generally used on 1.1 mm × 60 mm × 70 mm sized glass substrates having Al or Cr formed at a thickness of 200 nm, is coated to have a thickness of 1.5 μm. Heat treatment was performed at 110 ° C. for 90 seconds on a hot plate.

After placing a mask having a predetermined pattern formed on the resist film, ultraviolet rays were irradiated, and the specimens were developed for 90 seconds at 21 ° C. with a 2.38% tetramethylammonium hardoxide (TMAH) developer DPD-100S (manufactured by Dongwha Chemical). And a hard bake at 120 ° C., 140 ° C., 160 ° C., or 180 ° C. for 15 minutes in a drying oven to form a predetermined resist pattern on the Al or Cr metal film.

The specimen was immersed in an etching solution containing cerium ammonium nitrate as a main component to etch a metal film not covered by the resist pattern to form a metal film pattern. The specimen was then washed with ultrapure water and dried over N2 gas.

Peel Test

The specimen was immersed in the stripping solution for 5 minutes while maintaining the temperature of 70 ℃. The specimen was removed from the stripping solution, washed with ultrapure water and dried with N2 gas, and then scanned with a scanning electron microscope to determine whether a resist residue was attached to the space between the lines in the metal film pattern and the surface of the metal film pattern. The peeling performance was evaluated as follows, and the results are shown in Table 2 below.

○: When the resist residue is completely removed from the surface of the metal film pattern and the space between the lines.

Δ: when the resist residue is partially removed from the surface of the metal film pattern and the space between the line and the line

X: When a resist residue remains in the form of a thin film on the entire surface of the metal film pattern

On the other hand, the positive photoresist composition DTFR-1011SK is an alkali soluble novolak resin as a film-forming component, a quinonediazide compound (quinonediazide) compound as a photosensitive compound and an organic solvent capable of dissolving them.

(2) Service life of peeling liquid

In order to evaluate the peeling performance of the peeling liquid after performing a long peeling process, the peeling performance test of (1) was performed with respect to the peeling liquid simulated in the state which peeled process with 2000 sheets or 4000 sheets of 8-inch semiconductor substrates. It was. The simulation is performed by adding resist and moisture having the same content as the content (concentration) of the resist and water contained in the stripping solution used to perform the stripping process on 2000 sheets or 4000 sheets of 8-inch semiconductor substrates to the stripping solution new liquid. It was done by. At this time, as described in the specimen (1), a Cr film was formed as the metal film, and the hard bake temperatures at the time of coating the resist film were 120 ° C, 140 ° C, 160 ° C, and 180 ° C, respectively. In addition, the peeling performance test was carried out by immersing the specimen in a peeling solution at 70 ℃ for 5 minutes and then taken out. On the other hand, the evaluation method of peeling performance is the same as the case of (1), and the result is shown in Table 3 below.

(3) Corrosion of metal wiring

10, 20, and 30 sheets of the film material prepared according to the method (1) were made of aluminum (Al) and chromium (Cr) at 20 ° C. in 20 L of stripping solution, respectively. Subsequently, after 10 minutes, the specimens were removed and the amount of Al and Cr ions eluted into the stripping solution was measured by ETV in ICP-MS (Inductively Coupled Plasma-Mass Spectroscopy) (model name: ELAN 6000, manufactured by PERKIN-ELMER, USA). (Electro Thermal Vaporizer) was measured and the results are shown in Table 4 in ppb units.

(4) change in weight due to evaporation loss

100 g of the stripping solution was put in a glass beaker having a diameter of 5 cm, and the weight change and composition change of the stripping solution due to evaporation were measured at intervals of 1, 2, 5, 10, and 20 hours while the stripping solution was heated at 70 ° C. The results are shown in Tables 5 and 6, respectively. In Table 5, the numerical values indicate the weight loss due to evaporation, and the (-) sign in front of the numerical value indicates that the stripper composition absorbed moisture in the air, thereby increasing the weight. The component change by evaporation of the stripping solution shown in Table 6 is the result of gas chromatography (model name; HP-5890 SERIES II, Mfg Co., manufactured by Hewlett-Packard Co., Ltd.) converted into percentage (%).

(5) Measurement of content change of organic amine compound

This test is to investigate whether the concentration decrease of the organic amine compound generated in the heating during the peeling process can be accurately confirmed by the amine titrator. First, the peeling solution was removed at intervals of 1, 2, 5, 10, 20, and 40 hours while heating the simulated stripping solution at a temperature of 70 ° C. in the state that the stripping process was performed on 2000 sheets and 8 000 semiconductor substrates. Sampling was carried out to measure the content of the organic amine compound in the stripping solution over time by measuring the content of the organic amine compound using an amine titrator (Model name; 682 Titroprocesser) of Metrohm AG, Switzerland. In addition, the amine content was measured by an amine titrator after 10 minutes after the spent organic amine compound was replenished to 20 wt%, which is the content of the initial organic amine compound after 20 hours and 40 hours, respectively.

The amine content measurement results are shown in Table 7, but the numerical values shown in Table 7 are the results in terms of percentages. The columns labeled 20-1 and 40-1 in Table 7 show the amine content measured 10 minutes after supplementing the consumed organic amine compound after 20 hours and 40 hours, respectively.

On the other hand, in order to confirm whether the result of measuring the content of the organic amine compound by the amine titrator is correct, the change of the composition of the stripping solution was analyzed by GC at 20 and 40 hours, respectively, and the results are shown in Table 8. . Here, the columns labeled 20-1 and 40-1 show the contents of the organic amine compound analyzed by GC after 10 minutes and supplemented with the consumed organic amine compound after 20 hours and 40 hours, respectively.

(6) distillation and regeneration of stripping waste liquid

This test is a test for investigating whether the stripping liquid used in the long time stripping process can be purified and regenerated by distillation. In the stripping liquid regeneration apparatus according to the present invention of FIG. 1, the stripping waste liquid containing the resist and water was distilled off to obtain a stripping liquid from which the dissolved resist and the moisture were removed. The composition of the stripping solution was analyzed by gas chromatography. Subsequently, the deficiency of each component was supplemented to the original component ratio shown in Table 1 with reference to the analysis result to complete the regeneration of the reusable stripping solution. Table 9 shows the results of analyzing the components of the stripping solution after distillation and regeneration by gas chromatography.

Subsequently, the resist stripping performance test of (1) was carried out using a stripped waste solution simulated in a state where 4000 sheets of the stripped stripping solution, the stripped stripping solution before regeneration and the 8-inch semiconductor substrate were treated, and the results are shown in Table 10.

(7) Peeling performance and interfacial tension change test by surfactant

This test is to compare the peeling performance and surface tension change of peeling solution according to the type and content of surfactant. The changes in resist stripping performance and dynamic surface tension described in (1) were investigated while varying the type and content of surfactant.

Nonionic surfactants include LP-100 (manufactured by ISP), an alkyl pyrrolidone derivative, and NOIGEN EA100 (manufactured by DKS International), a polyoxyethylene alkylphenyl ether derivative, and sodium dioctyl sulfosuccinate derivatives as anionic surfactants. Phosphorus Koremul 290 (manufactured by Hannong Thickening Co., Ltd.) was used as the cationic surfactant, ETHOQUAD C / 25 (manufactured by LION), which is a polyethoxylated quaternary ammonium salt.

Dynamic surface tension was measured according to a conventional method using PENANT DROP TENSIOMETER GPDA 10 from KRUSS GmbH, Germany.

The change of peeling performance according to the kind of surfactant is shown in Table 11. The result of Table 11 is the result of using the peeling liquid obtained by adding 0.1 weight% of surfactant shown in Table 11 to the peeling liquid which consists of 20 weight% of MEA, 25 weight% of EDG, and 54.9 weight% of DMSO.

The change in dynamic surface tension with the amount of surfactant is shown in Table 12, respectively. The result of Table 12 is the result of using the stripper obtained by adding 0-1.0 wt% of surfactants as shown in Table 12 to the stripper consisting of 20 wt% of MEA, 54 to 55 wt% of DMSO, and 25 wt% of EDG.

Examples 1-7. Comparative Examples 1 to 3

As in the composition ratio shown in Table 1, the content of the organic amine compound, the neutral solvent and the surfactant was mixed while changing within the claims of the present invention to prepare a peeling solution (Examples 1 to 7). In addition, the peeling solution (Comparative Examples 1 to 3) was prepared by mixing while changing the content of the organic amine compound, the neutral solvent and the surfactant in the range not included in the claims of the present invention.

Thus, the test of (1)-(7) demonstrated above was done about the peeling liquid obtained above, and the result was shown to Tables 2-12.

Component of the stripping solution Organoamine compounds Protic Glycol Ether Compound Aprotic Multipolar Compounds Kinds Content (wt%) Kinds Content (wt%) Kinds Content (wt%) Kinds Content (wt%) Example One MEA 20 EDG 25 DMSO 54.9 2 MEA 20 DPM 25 NMP 54.9 3 MEA 20 DPM 25 DMSO 54.9 4 MEA 30 BDG 25 NMP 44.9 5 MEA 30 DPM 25 DMSO 44.9 6 MIPA 20 EDG 25 DMI 54.9 7 MIPA 30 DPM 25 Sulfolane 44.9 Comparative example One MEA 5 BTG 15 PGME 30 GBL 49.9 2 DEA 9 BTG 10 PGMEA 40 DMAc 40.9 3 TEA 40 BTG 35 PGMEA 20 DMF 4.9 ※ MEA: monoethanolamine DEA: diethanolamine TEA: triethanolamine BDG: diethylene glycol monobutyl ether BTG: triethylene glycol monobutyl ether EDG: diethylene glycol monoethyl ether DPM: dipropylene glycol monomethyl ether PGME: propylene Glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate NMP: N-methyl pyrrolidone GBL: γ-butyrolactone DMSO: Dimethyl sulfoxide DMAc: Dimethyl acetamide DMF: Dimethyl formamide DMI: Dimethyl imidazolidinone * The exfoliating solutions of Examples 1 to 7 and Comparative Examples 1 to 3 each contained 0.1 wt% of N-octyl pyrrolidone as a surfactant.

Peeling performance test of peeling liquid Cr substrate Al substrate Hard Bake Temperature (℃) Hard Bake Temperature (℃) 120 140 160 180 120 140 160 180 Example One ○ ○ ○ ○ ○ ○ ○ ○ 2 ○ ○ ○ ○ ○ ○ ○ ○ 3 ○ ○ ○ ○ ○ ○ ○ ○ 4 ○ ○ ○ △ ○ ○ ○ △ 5 ○ ○ ○ ○ ○ ○ ○ △ 6 ○ ○ ○ ○ ○ ○ ○ △ 7 ○ ○ ○ △ ○ ○ ○ ○ Comparative example One ○ ○ △ × ○ ○ △ × 2 ○ ○ △ × ○ △ × × 3 ○ △ △ × ○ △ × ×

Referring to Table 2, it can be seen that the peeling solution of Examples 1 to 7 according to the present invention can peel off the resist film deteriorated by the etching process regardless of the film quality of the lower metal film and the hard bait temperature. However, it is understood that the peeling solution of Comparative Examples 1 to 3, which does not belong to the present invention, had excellent peeling performance when the hard bake temperature of the resist was 120 ° C., but poor peeling performance when the temperature of the hard bake increased to 140 ° C. or more. Can be.

Service life test of peeling solution Substrate Peeling Hard Bake Temperature (Cr Substrate / Deposition Temperature 70 ℃) 120 ℃ 140 ℃ 160 ℃ 180 ℃ Example 1 0 sheets ○ ○ ○ ○ 2000 sheets ○ ○ ○ △ 4000 sheets ○ ○ △ △ Example 2 0 sheets ○ ○ ○ ○ 2000 sheets ○ ○ ○ △ 4000 sheets ○ ○ △ △ Example 3 0 sheets ○ ○ ○ ○ 2000 sheets ○ ○ ○ ○ 4000 sheets ○ ○ △ △ Example 4 0 sheets ○ ○ ○ ○ 2000 sheets ○ ○ ○ △ 4000 sheets ○ ○ △ △ Example 5 0 sheets ○ ○ ○ ○ 2000 sheets ○ ○ ○ △ 4000 sheets ○ ○ ○ △ Example 6 0 sheets ○ ○ ○ ○ 2000 sheets ○ ○ ○ △ 4000 sheets ○ ○ △ × Example 7 0 sheets ○ ○ ○ ○ 2000 sheets ○ ○ ○ △ 4000 sheets ○ ○ △ △ Comparative Example 1 0 sheets ○ ○ △ × 2000 sheets ○ △ × × 4000 sheets ○ △ × × Comparative Example 2 0 sheets ○ △ × × 2000 sheets ○ △ × × 4000 sheets △ × × × Comparative Example 3 0 sheets ○ △ × × 2000 sheets ○ × × × 4000 sheets × × × ×

Referring to Table 3, the stripping solution of Examples 1 to 7 according to the present invention was subjected to the etching process to the same level as the initial stripping solution for the resist hard-baked at 120 ° C. even when 4000 sheets of 8-inch substrates were processed. It can be seen that even the deteriorated resist film can be peeled off well. In addition, the resist hard-baked at 160 ° C. was able to peel off the resist film deteriorated by the etching process at the same level as the initial stripping solution even when 2,000 sheets of 8-inch substrates were treated. In the treated state, the peeling performance began to decrease as compared with the initial stripping solution, but the peeling performance was still good. Therefore, it can be seen that the stripper according to the present invention has excellent service life.

On the other hand, in the case of the peeling solution of Comparative Examples 1 to 3 not belonging to the present invention, it can be seen that the peeling performance is poor with respect to the resist hard-baked at 140 ° C or higher even in the initial state in which the substrate was not previously treated at all. Peeling performance worsened in the state which processed 2000 sheets of 8-inch board | substrates. In addition, it can be seen that in the state where 4,000 sheets of 8-inch substrates are processed, the resist can hardly be peeled regardless of the hard bake temperature.

Elution amount of Al and Cr ions (unit: ppb) NO. Number of Cr substrates processed Al substrate processing sheets 0 sheets 10 sheets 20 sheets 30 sheets 0 sheets 10 sheets 20 sheets 30 sheets Example One 0 1.39 4.88 19.29 0 4.29 6.47 22.72 2 0 2.51 9.97 24.39 0 3.33 8.41 31.55 3 0 4.78 10.12 25.12 0 4.19 9.52 38.18 4 0 5.66 11.1 42.9 0 6.24 12.94 40.52 5 0 6.06 17.24 31.15 0 7.12 16.65 29.63 6 0 4.12 11.26 39.5 0 4.02 14.99 30.1 7 0 5.91 18.37 50.63 0 5.87 10.23 58.12 Comparative example One 0 5.99 21.98 101.3 0 7.95 25.83 145.62 2 0 3.84 15.6 95.25 0 8.61 19.21 181.14 3 0 4.20 18.51 74.9 0 5.89 21.68 85.37

Referring to Table 4, it can be seen that the peeling solutions of Examples 1 to 7 hardly corrode Al or Cr ions as compared to the peeling solutions of Comparative Examples 1 to 3. Therefore, it can be seen that the stripper according to the present invention hardly corrodes the underlying wiring material during the resist stripping process.

Weight change of stripping solution with evaporation time (unit: g) Elapsed time 0hr 1hr 2hr 5hr 10hr 20hr Example 2 0 -0.024 1.089 3.172 6.548 27.015 Example 3 0 0.065 1.315 3.749 6.295 19.144 Example 5 0 -0.265 1.531 4.764 7.970 31.426 Comparative Example 2 0 0.151 1.541 5.171 10.115 40.819

Change in composition with evaporation time (Unit:%) Elapsed time (hr) Organic amine compound (%) Protonic glycol ether compound (%) Aprotic Polypolar Compound (%) Example 1 0 20 25 54.9 10 19.1 24.2 56.6 20 18.1 23.6 58.2 Example 2 0 20 25 54.9 10 19.2 24.8 55.9 20 18.3 24.1 57.5 Example 5 0 30 25 44.9 10 27.7 24.5 47.7 20 26.4 23.8 49.7 Comparative Example 2 0 9 10 40 40.9 10 6.9 9.7 35.1 48.2 20 4.6 9.5 30.1 55.7

The peeling solution of Examples 1, 2, and 5 can be seen that the weight change and the component change is very small compared to the peeling solution of Comparative Example 2. Therefore, it can be seen that the stripper according to the present invention has a low component change due to heating even when the stripping process is performed for a long time so that the resist stripping performance can be maintained uniformly, and the stripping solution can be easily recycled through distillation and purification. In addition, it can be seen that the stripper according to the present invention has high economical efficiency and can prolong the exchange cycle of the stripper due to the small amount of evaporation due to heating even when the stripping process is performed for a long time, thereby improving productivity of semiconductor devices. . In addition, there is an advantage that can reduce the fire, deterioration of the working environment, damage to the exhaust duct filter caused by the evaporated stripping liquid.

Change in content of organic amine compound measured by amine titrator (Unit:%) Processing Elapsed time (hrs) One 2 5 10 20 20-1 40 40-1 Example 1 0 19.99 19.75 19.37 18.89 17.21 19.97 17.05 19.89 2000 19.98 19.78 19.31 18.86 17.18 19.99 17.11 19.91 4000 19.99 19.72 19.28 18.86 17.02 20.01 16.99 19.90 Example 2 0 19.98 19.99 19.65 18.62 17.01 19.95 16.89 20.01 2000 19.97 19.86 19.62 18.63 17.06 19.94 16.99 20.03 4000 19.96 19.89 19.65 18.62 17.04 19.95 16.98 20.04 Example 3 0 20.00 19.98 19.95 18.65 17.38 20.10 16.74 19.97 2000 20.02 19.95 19.95 18.63 17.54 20.03 16.79 19.96 4000 20.01 19.92 19.92 18.59 17.55 20.05 16.81 19.97

Referring to Table 7, it can be seen that the content of the organic amine compound decreases with time. However, it can be seen that the content of the organic amine compound in the stripping solution can be maintained at an initial level by additionally supplying the consumed organic amine compound after using the stripping solution for a long time (for example, 20 hours, 40 hours). Therefore, even after using the stripping solution for a long time, the peeling performance of the stripping solution can be restored by additionally supplying the organic amine compound as much as consumed after titrating the content of the organic amine compound by the amine titrator. Thereby, the use time of peeling liquid can be maximized. This is the basis of the peeling liquid management apparatus according to the present invention described above.

Change in content of organic amine compounds measured by GC (unit:%) Furtherance Elapsed time 0 20 20-1 40 40-1 Example 1 Organic Amine Compounds (MEA) 20 17.2 19.8 17.1 19.9 Protic Glycol Ether Compound (EDG) 25 24.1 24.4 24.1 24.6 Aprotic Multipolar Compounds (DMSO) 54.9 58.6 55.7 58.7 55.4 Example 2 Organic Amine Compounds (MEA) 20 17.05 19.9 16.8 19.8 Protonic Glycol Ether Compound (DPM) 25 24.6 24.2 24.1 24.85 Aprotic Multipolar (NMP) 54.9 58.25 55.8 59.0 55.25

In Table 8, the columns labeled 20-1 and 40-1 were analyzed by GC 10 minutes after 20 hours and 40 hours, respectively, were supplemented with the amount of organic amine compound measured by the amine titrator. Results are shown.

Referring to Table 7 and Table 8, it can be seen that comparing the content of the organic amine compound analyzed by the amine titrator with the content of the organic amine compound analyzed by GC, the two values are almost the same value. Therefore, it was found that a method of evaluating the component change of the peeling liquid by titrating the content of the organic amine compound by the amine titrator was useful.

Component analysis of peeling solution after distillation and regeneration (component supplement) (unit:%) ingredient Exfoliation Peeling Waste (After 4000 Sheets) Separation solution after distillation Peeling After Regeneration Example 1 Organic amine compound (MEA) 20 16.3 8.2 20 Protic Glycol Ether Compound (EDG) 25 24.1 23.6 25.1 Aprotic Multipolar Compounds (DMSO) 54.9 59.5 68.1 54.8 Example 2 Organic Amine Compounds (MEA) 20 16.1 8.3 19.9 Protonic Glycol Ether Compound (DPM) 25 24.2 23.8 24.9 Aprotic Multipolar Compounds (NMP) 54.9 59.6 67.8 55.1 Comparative Example 1 Organic Amine Compounds (MEA) 5 1.3 0.7 Not playable Protic Glycol Ether Compound BTG 15 15.1 18.1 PGME 30 29.2 81.1 ^# Aprotic Multipolar Compound (GBL) 49.9 54.3

#; Combined reaction product of MEA and GBL with PGME

Comparison of Peel Capacity of Peeling Solution, Peeling Waste Solution, and Peeling Solution Substrate film Cr substrate Al substrate Hard Bake Temperature (℃) 120 140 160 180 120 140 160 180 Example 1 Exfoliation ○ ○ ○ ○ ○ ○ ○ ○ Peeling Waste (After 4000 Sheets) ○ ○ △ △ ○ ○ △ △ Stripping solution after regeneration ○ ○ ○ ○ ○ ○ ○ ○ Example 2 Exfoliation ○ ○ ○ ○ ○ ○ ○ ○ Peeling Waste (After 4000 Sheets) ○ ○ △ △ ○ ○ △ △ Peeling After Regeneration ○ ○ ○ ○ ○ ○ ○ ○ Comparative Example 1 Exfoliation ○ ○ △ × ○ ○ △ × Peeling Waste (After 4000 Sheets) ○ △ × × ○ △ △ × Stripping solution after regeneration ○ △ × × ○ △ × ×

Referring to Table 9, in the case of the stripping solution (Examples 1 to 2) according to the present invention, it can be seen that the stripping solution regenerated by distillation and supplementation shows almost the same composition as the stripping solution. Referring to Table 10, in the case of the stripping solution (Examples 1 to 2) according to the present invention, it can be seen that the stripping solution regenerated by distillation and supplementation showed the same resist stripping performance as the stripping solution. Therefore, it was confirmed that the stripper according to the present invention can be regenerated by distillation and supplementation.

Change of Peeling Performance According to the Type of Surfactant Additive type Substrate film Hard Bake Temperature (℃) 160 180 200 220 LP-100 Cr ○ ○ ○ ○ Al ○ ○ ○ ○ Koremul 290 Cr ○ ○ △ × Al ○ △ △ × ETHOQUAD C / 25 Cr ○ △ △ × Al ○ △ × × NOIGEN EA 120 Cr ○ △ × × Al ○ ○ × ×

Referring to Table 11, it can be seen that the peeling performance of the peeling solution containing the alkylpyrrolidone compound which is a nonionic surfactant is the best.

Surface tension change according to surfactant content (unit: dynes / cm) Added amount of surfactant Surfactant Class LP-100 Koremul 290 ETHOQUAD C / 25 NOIGEN EA 120 0wt% 85 85 85 85 0.1wt% 21 72 72 64 0.5wt% <5 61 61 60 1wt% <5 48 48 49

Referring to Table 12, it can be seen that the dynamic surface tension of the stripping solution containing the alkylpyrrolidone compound which is a nonionic surfactant is the lowest. Therefore, it can be seen that the peeling solution containing the alkyl pyrrolidone compound as the surfactant has an excellent wetting effect and can improve the peeling performance.

The stripper according to the present invention can be easily peeled off at low temperatures in a short time even under the harsh conditions of the dry etching, wet etching and / or ashing process and the metal by-products etched from the lower metal film during the process. It is possible to minimize corrosion of the lower metal wiring during the peeling process, and it is possible to rinse only with water without using organic solvents such as isopropyl alcohol and dimethyl sulfoxide in the subsequent rinsing process. Even if it proceeds, the evaporation loss due to the heating is small to maximize the replacement cycle of the stripper composition, and can be easily regenerated by distillation and supplementation.

The peeling liquid regeneration apparatus of this invention can refine | purify a peeling waste liquid easily by distillation.

By using the peeling liquid management apparatus of this invention, control of the composition of a peeling liquid automatically and supplying a peeling liquid to a resist peeling apparatus can be managed suitably.

Claims (16)

In a photoresist stripper composed of an organic amine compound, a protic glycol ether compound, an aprotic multipolar compound, and an alkylpyrrolidone compound, the content of the organic amine compound is 10 to 35% by weight, and the protic glycol ether The total content of the compound and the aprotic multipolar compound is 60 to 85% by weight, and the content of the alkylpyrrolidone compound is 0.1 to 5% by weight, and the alkylpyrrolidone compound is N-cyclohexyl-2- A photoresist stripper, characterized in that any one or more compounds selected from the group consisting of pyrrolidone, N-octyl-2-pyrrolidone, and N-dodecyl-2-pyrrolidone. According to claim 1, wherein the content of the alkylpyrrolidone compound is stripping solution, characterized in that 0.3 to 1% by weight. The compound according to claim 1, wherein the organic amine compound is at least one selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, cycloaliphatic amines, aromatic amines and heterocyclic amines, and hydroxyl amines. It is a compound, The peeling liquid characterized by the above-mentioned. The method of claim 1, wherein the protic glycol ether compound is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether any one or more selected from the group consisting of . The compound of claim 1, wherein the aprotic multipolar compound is at least one selected from the group consisting of dimethyl sulfoxide, dimethylacetamide, dimethylformamide, dimethylimidazolidinone, sulfolane, and N-methyl pyrrolidone. A stripping liquid, characterized in that. A resist stripping method comprising contacting a substrate on which a resist film is applied and a stripping liquid composition according to any one of claims 1 to 7. A substrate in which a predetermined material film pattern and a resist pattern used as an etching mask for forming the material film pattern are sequentially stacked are contacted with the stripper composition of any one of claims 1 to 7. Resist stripping method. 8. The resist stripping method according to claim 7, wherein the resist pattern is ashed using plasma before contacting the substrate and the stripper composition. The method of claim 7 or 8, wherein the material film is silicon, tantalum, titanium, chromium, molybdenum, tungsten, tin, nickel, aluminum, silicon oxide, silicon nitride, and indium tin oxide ( indium tin oxide) resist stripping method characterized in that formed of one or more materials selected from the group consisting of. A first distillation apparatus for removing water from the stripping waste liquid; A second distillation apparatus for receiving a peeling waste liquid from which water is removed from the first distillation apparatus and removing the dissolved resist therefrom; And Claim 1 to 6 characterized in that it comprises a replenishment device for supplying the first peeling liquid component and the second peeling liquid component to the peeling waste liquid supplied from the second distillation apparatus to regenerate the peeling liquid. An apparatus for regenerating the peeling solution described. The method according to claim 10, wherein the first distillation apparatus comprises a distillation column for distilling water from the stripping waste liquid, a condenser for condensing water vapor evaporated from the distillation column with water, and a predetermined concentration of the organic amine compound in the water vapor from the condenser. A reflux pump for returning to the distillation column, a storage means for storing the water condensed in the condenser, and a decompression pump for lowering the pressure in the distillation column to lower the evaporation temperature of the water vapor evaporated from the distillation column when the concentration is higher than the reference concentration. An apparatus for regenerating a peeling liquid according to any one of claims 1 to 6, comprising: The method of claim 10, wherein the second distillation apparatus is a distillation column for receiving a stripping waste liquid from which water is removed from the first distillation apparatus, a condenser for condensing the stripping waste liquid evaporated from the distillation column, condensation in the condenser A reflux machine for returning the stripped waste liquid to the distillation column if necessary, a storage means for storing the stripped liquid condensed in the condenser, and a lowering pressure in the distillation column to lower the evaporation temperature of the stripped waste liquid distilled from the distillation column. An apparatus for regenerating the stripper according to any one of claims 1 to 6, comprising a pressure reducing pump. The method of claim 10, wherein the replenishment device is an analysis means for analyzing the content of each component of the stripping waste liquid supplied from the second distillation apparatus, for detecting the analyzed content to replenish the first component and the second component An apparatus for regenerating the peeling liquid according to any one of claims 1 to 6, comprising a replenishing means and mixing means for mixing the peeling waste liquid and the replenished first and second components. The said 1st peeling liquid component and the 2nd peeling liquid component are an organic amine compound and an aprotic multipolar compound, respectively, The regeneration liquid as described in any one of Claims 1-6 characterized by the above-mentioned. Device. When the dissolved resist concentration in the stripping waste liquid is detected by an ultraviolet absorbance photometer and the dissolved resist concentration is less than or equal to a predetermined reference value, the stripping waste liquid is transferred to the stripping solution supply means for reuse as it is, and when the dissolved resist concentration exceeds the above standard value. Stripping waste storage means for transferring the stripping waste liquid to a stripping waste distillation apparatus for regeneration; A peeling waste liquid regeneration device which receives the peeling waste liquid from the peeling waste liquid storage means, removes moisture and the dissolved resist therefrom, and replenishes the first peeling liquid component and the second peeling liquid component to regenerate the peeling liquid; Stripping liquid storage means for mixing and storing the stripping liquid recycled in the stripping waste liquid regeneration device and a new stripping liquid; And And a stripping solution supply device for receiving the stripping solution transferred from the stripping liquid storage means, the stripping waste liquid directly transferred from the stripping waste storage means, and an organic amine compound, mixing them, and then supplying them to a resist stripping apparatus. The apparatus which manages the peeling liquid as described in any one of Claims 1-6. The said 1st peeling liquid component and the 2nd peeling liquid component are each an organic amine compound and an aprotic multipolar compound, The management of the peeling liquid in any one of Claims 1-6 characterized by the above-mentioned. Device.