JP2007188077A - Resist removing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist removing composition which has excellent power to remove a resist film and ensures a low fatigue degree of the liquid chemicals. <P>SOLUTION: The resist removing composition uses a compound selected from the group consisting of a cyclic compound having an oxygen double bond, a glycol compound and a carbonate compound. The resist removing composition may further contain a lactone compound, an amine, an organic acid, an oxidizing agent or a mixture of these. The resist removing composition is used to remove resist for patterning of a metal film for an electronic circuit or metal wiring of a display device, has excellent power to remove resist remaining on a patterned metal film, ensures a slight composition change due to volatilization at high temperature and a low fatigue degree of the liquid chemicals, and minimizes corrosion of the patterned metal film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composition for removing a resist used in a photolithography process, and more particularly, when removing a resist patterning a metal film, corrosion of the metal film can be minimized, The present invention relates to a resist removal composition having excellent removal power.

  Resist (photoresist) is a substance used indispensable for the photolithography process. Such a photolithography process is used for integrated circuits (IC), highly integrated circuits (LSI), ultra-high integrated circuits (VLSI), etc. This is one of the processes generally used for manufacturing a semiconductor device and an image realization device such as a liquid crystal display (LCD) and a flat panel display (PDP).

  Hereinafter, the photolithography process will be briefly described.

  First, a resist film is formed on a predetermined substrate such as a semiconductor substrate or a glass substrate. The substrate may not go through any process before forming the resist film, but usually, before the resist film is formed, various pre-processes have already been performed to form the substructure such as metal wiring. Generally, it is formed. Accordingly, the resist film is generally formed on the substrate or on the substrate where a predetermined lower structure is already provided. The resist film is formed on the front surface of the substrate or a selective region, but is more generally applied to the front surface of the substrate. By proceeding with the subsequent pattern formation process, the resist film in a predetermined area is removed, the upper part of the substrate is exposed, and the resist film in other areas is continuously left to protect the upper part of the substrate with the remaining resist film. To come. There are various methods of applying a resist film on the front surface of the upper part of the substrate, but the most common is a spin coating method.

  Next, an exposure mask on which a desired predetermined pattern is formed is placed in close contact with the upper portion of the resist formed on the front surface of the substrate, or is placed at a predetermined distance from the upper portion of the resist. Thereafter, an exposure process of irradiating the front surface of the mask with high energy active rays such as ultraviolet rays, electron beams or X-rays is performed. The pattern of the mask is formed so as to be divided into a region that transmits the irradiated high-energy active rays and a region that blocks light. Therefore, the high-energy active line that has passed through the transmission region of the mask pattern reaches the resist film below it. The high energy active rays that reach the resist film deform the physical properties of the resist film. When the irradiation with the high energy actinic radiation is completed, the resist film is divided into a region where the resist film is maintained with the same physical properties as before the high energy irradiation and a region where the internal physical properties are deformed by the irradiation. It is formed. As described above, the pattern formed according to whether or not the physical properties of the resist film need to be deformed is tentatively determined by the mask pattern, and is therefore referred to as a “latent” of the normal mask pattern.

  A phenomenon process is performed on the latent phase formed on the resist film to form a resist pattern to which the mask pattern is transferred. Next, a predetermined pattern is finally formed inside the substrate by etching the lower substrate using the resist pattern as an etching mask. Thereafter, a series of photolithography steps are completed by removing the resist pattern remaining on the upper part of the substrate on which the predetermined pattern is formed.

  At this time, Korean Published Patent No. 2003-0033988 discloses a method for producing an organic film on a substrate surface using a treatment liquid containing ethylene carbonate, propylene carbonate, or a mixture thereof as a resist removal composition already used. ing. US Pat. No. 6,403,544 discloses a regeneration method for ethylene carbonate, propylene carbonate, and the like.

  In the above method, a carbonate compound is used, but in the case of ethylene carbonate, the melting point is higher than room temperature and it is difficult to handle as a release solvent, and in the case of propylene carbonate, the release performance is lower than other release solvents. Further, the method is a method in which lactone is fractionally distilled to separate and regenerate from impurities, and unlike the case of decomposition in real time as in the present invention, a solvent containing a certain amount of resist after use is removed. Since it is collected and a separate fractional distillation step is provided, there is a disadvantage that additional cost is required.

  An object of the present invention is to provide a resist removal composition that has excellent resist film removal power and low chemical fatigue.

  In order to achieve the above object, the present invention provides at least one compound selected from the group consisting of a compound represented by the following chemical formula 1, a cyclic compound represented by the chemical formula 2, the chemical formula 3 or the chemical formula 4, and a glycol compound represented by the chemical formula 5. A resist removal composition comprising the above is provided.

[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

(In the above formula, R, R ′, R ″, and R ′ ″ are hydrogen, hydroxyl group, alkyl group having 1 to 10 carbon atoms, alkanol group having 1 to 10 carbon atoms, or alkyl group having 1 to 10 carbon atoms, respectively. An acetate group, R ₃ is a hydroxyl group, an alkyl having 1 to 10 carbon atoms, or an alkyl acetate group having 1 to 10 carbon atoms, and n is an integer of 1 to 12.)
The composition may further include an amine, an organic acid, an oxidizing agent, a lactone solvent represented by Formula 6 or 7 below, or a mixture thereof.

[Chemical formula 6]

[Chemical formula 7]

(In the above formula, each R is hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkanol group having 1 to 10 carbon atoms, or an alkyl acetate group having 1 to 10 carbon atoms.)
The present invention also provides a resist removal composition comprising a carbonate compound represented by the following chemical formula 8, and an amine or organic acid, an oxidizing agent, a lactone solvent represented by the chemical formula 6 or the chemical formula 7, or a mixture thereof. I will provide a.

[Chemical formula 8]

(In the above formula, R ₁ is alkyl having 1 to 10 carbon atoms, benzyl, phenyl, or alkyl acetate having 1 to 10 carbon atoms, and R ₂ is alkyl having 1 to 10 carbon atoms, benzyl, phenyl, carbon number. 1 to 10 alkyl acetates or alkyl carbonates having 1 to 10 carbon atoms.)

  The resist removing composition according to the present invention is excellent in resist removing ability, resist decomposing ability, and substrate cleaning ability during the process.

  Hereinafter, the present invention will be described in more detail.

  The present invention provides a composition for removing a resist remaining on a substrate after a resist pattern is formed by a photolithography process.

  In the present invention, a resist removing composition composed of various components is used as a single solvent having a high boiling point in order to reduce chemical fatigue. As the single solvent having a high boiling point in the present invention, polar and nonpolar solvents are most desirable. Among them, polar solvents can reduce the decomposition efficiency because they cannot decompose or stabilize the oxidizing agents such as ozone and hydrogen peroxide water that can be added during the process of decomposing the resist due to its unique characteristics. Excellent removal performance. In the case of a non-polar solvent, the resist removing ability is lower than that of a polar solvent, but it can stabilize an oxidizing agent such as ozone or hydrogen peroxide. In order to compensate for the shortcomings of such solvents, the present invention adds catalyst agents and additives to promote the generation of radicals necessary for decomposition while stabilizing oxidants such as ozone and hydrogen peroxide, Add amines, organic acids or other additives to aid in removal capacity.

  Specifically, the components used in the single solvent of the resist removal composition according to the present invention are composed of a compound of the following chemical formula 1, a cyclic compound of the chemical formula 2, chemical formula 3 or chemical formula 4, and a glycol compound of the chemical formula 5. These compounds must be selected from the group described above, and must not be decomposed by an oxidant such as ozone or hydrogen peroxide solution, and should have a small decrease in chemical solution at a high boiling point of 120 ° C. or higher. While these compounds of the present invention are contained in 100 parts by weight of a resist removing composition, they serve as a solvent in the composition.

[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

(In the above formula, R, R ′, R ″, and R ′ ″ are hydrogen, hydroxyl group, alkyl group having 1 to 10 carbon atoms, alkanol group having 1 to 10 carbon atoms, or alkyl group having 1 to 10 carbon atoms, respectively. An acetate group, R ₃ is a hydroxyl group, an alkyl having 1 to 10 carbon atoms, or an alkyl acetate group having 1 to 10 carbon atoms, and n is an integer of 1 to 12.)
At this time, according to the present invention, the compound selected from the group consisting of the carbonate compound of Formula 8 can satisfy the above properties and can be used as a single solvent.

  In addition, the present invention provides a catalyst agent, an additive, and the like that can decompose the resist component resin and the photosensitive agent component during the resist removal process in order to prevent the removal performance from deteriorating due to the resist being contained in the chemical solution. While applying, a specific additive or the like is added in order to supplement the removal performance deteriorated by a single solvent.

  Preferably, the resist removal composition of the present invention is represented by an amine or organic acid, an oxidizing agent, the chemical formula 6 or 7 selected from the group consisting of the cyclic compound and the glycol compound or a carbonate compound. A lactone compound, or a mixture thereof.

  The main object of the present invention is to provide a resist contained in a solvent by adding an oxidizing agent to a compound selected from the group consisting of the cyclic compound and glycol-based compound serving as a solvent or a carbonate-based compound. Is to decompose. Another object of the present invention is to increase the efficiency of the oxidizing agent by further adding an amine or an organic acid to improve the resist stripping ability that is insufficient for the solvent itself. At this time, even if an amine, an organic acid, or an oxidizing agent is used, in order to increase the efficiency in the process, the generated radical is further activated by the amine, the organic acid in the solvent, or through the oxidizing agent by heat. It is necessary to make it. Of course, amine or organic acid plays a role of a kind of catalyst that increases the efficiency of radical generation, but the function is combined with the environment of the solvent that generates radicals to meet the conditions and the resist stripping performance improvement. There is a need for catalysts, additives, and equipment compatible with ozone, hydrogen peroxide, and oxidizing agents that increase the efficiency of radical generation.

  Also, according to the present invention, when an amine, an organic acid, or a lactone compound is added to the composition of the compound or carbonate compound selected from the group consisting of the cyclic compound and the glycol compound, and the oxidizing agent, the resist is peeled off. The performance and resist decomposition performance can be further improved.

  Such a composition for removing a resist of the present invention comprises 70 to 99.9 parts by weight of a compound selected from the group consisting of the cyclic compound and the glycol compound, and 0.1 to 30 parts by weight of an amine or an organic acid. A two-component composition may be included. In addition, the resist composition of the present invention may be a two-component composition containing 70 to 99.9 parts by weight of the carbonate compound of Formula 3 and 0.1 to 30 parts by weight of an amine or an organic acid.

  Further, the resist removing composition of the present invention is 90 to 99.99 parts by weight of a compound or carbonate compound selected from the group consisting of the cyclic compound and the glycol compound, and 0.01 to 10 parts by weight of an oxidizing agent. A two-component composition may be included. At this time, the resist removing composition of the present invention is composed of 70 to 99.499 parts by weight of a compound selected from the group consisting of the cyclic compound and glycol compound, or a carbonate compound, and 0.001 to 1 in ozone. It is preferable to contain 0.5 to 10 parts by weight of an oxidizing agent excluding parts by weight and ozone.

  The resist removing composition of the present invention is a compound selected from the group consisting of the cyclic compound and glycol compound or a carbonate compound of 70 to 89.9 parts by weight, a lactone compound of 10 to 50 parts by weight, And a three-component composition containing 0.1 to 30 parts by weight of an amine or an organic acid.

  The resist removing composition of the present invention is a compound selected from the group consisting of the cyclic compound and the glycol compound or a carbonate compound of 90 to 89.99 parts by weight, a lactone compound of 10 to 50 parts by weight, And a three-component composition containing 0.01 to 10 parts by weight of an oxidizing agent. At this time, the resist removing composition of the present invention is 70 to 89.899 parts by weight of a compound or carbonate compound selected from the group consisting of the cyclic compound and glycol compound, and 10 to 50 parts by weight of lactone compound. It is preferable to contain 0.001 to 1 part by weight of ozone and 0.1 to 10 parts by weight of an oxidizing agent.

  The resist removing composition of the present invention is a compound selected from the group consisting of the cyclic compound and glycol compound or a carbonate compound of 70 to 99.99 parts by weight, and an amine or organic acid of 1 to 30 parts by weight. And a three-component composition containing 0.01 to 10 parts by weight of an oxidizing agent.

  Further, the resist removing composition of the present invention is a compound selected from the group consisting of the cyclic compound and the glycol compound or a carbonate compound of 70 to 88.9 parts by weight, a lactone compound of 10 to 50 parts by weight, It may be a four-component composition containing 1 to 30 parts by weight of an amine or organic acid and 0.01 to 10 parts by weight of an oxidizing agent.

  The cyclic compounds that can be used in a single component composition in the present invention include cyclopentanone, methylcyclopentanone, tetrahydrofurfuryl acetate, tetrahydro-4H-pyran-4-one, and tetrahydropyran-2-methanol. It is preferable to use one or more selected from the group consisting of: The glycol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether. , Triethylene glycol ethyl ether, triethylene glycol butyl ether, and diethylene glycol dimethyl ether can be selected from one or more types.

  The carbonate compound is preferably one or more selected from the group consisting of dibenzyl carbonate, diethyl carbonate, and diethyl dicarbonate.

  In the case of 2 to 4 component system in the present invention, the content of the compound or carbonate compound selected from the group consisting of the cyclic compound and the glycol compound can be changed depending on the compound added together. Preferably, in the case of a two-component composition containing an amine or an organic acid, the compound selected from the group consisting of the cyclic compound and the glycol compound, or the carbonate compound is 70 to 99.9 parts by weight based on the total composition Can be used in In the case of a two-component composition containing an oxidizing agent, a compound selected from the group consisting of a cyclic compound and a glycol compound, or a carbonate compound is used in an amount of 90 to 99.99 parts by weight based on the entire composition. In addition, when ozone and an oxidizing agent excluding ozone are included, the compound selected from the group consisting of cyclic compounds and glycol compounds, or the carbonate compound is 70 to 99.499 parts by weight with respect to the entire composition. use. In the case of a three-component composition containing a lactone compound and an amine or organic acid, a compound selected from the group consisting of a cyclic compound and a glycol compound, or a carbonate compound is 70 to 89.9 based on the total composition. Used in parts by weight. In the case of a three-component composition containing a lactone and an oxidizing agent, the compound selected from the group consisting of a cyclic compound and a glycol compound, or a carbonate compound is 90 to 89.99 parts by weight based on the entire composition. Used in. When ozone and an oxidizing agent excluding ozone and a lactone compound are included, the compound selected from the group consisting of a cyclic compound and a glycol compound, or a carbonate compound is 70 to 89.899 wt. Used in the department. At this time, if the content of the compound selected from the group consisting of the cyclic amine compound and the glycol compound or the carbonate-based compound is less than the lower limit in each case, the weight of the oxidizing agent and the amine or organic acid is relatively However, when the upper limit is exceeded in each case, the oxidizing agent and amine or organic acid parts by weight are separated and radical generation is insufficient. Thus, there is a problem that resist decomposition in the solvent is difficult.

  The amine or organic acid used in the present invention itself can assist in resist stripping, and it reacts with a photosensitive compound (PAC) in the resist composition to oxidize the photosensitive compound. Since the photosensitive compound is present between the polymers, the oxidized photosensitive compound is dissolved in a compound selected from the group consisting of the cyclic compound and glycol compound of the present invention or a carbonate compound while being dissolved in a polymer chain. Becomes loose and easily dissolved. The amine or organic acid not only serves to assist the removal performance of a resist that is not a single solvent, but also adjusts the pH of the solvent to adjust the alkalinity and the oxidant easily generates radicals in the solvent It creates a condition that can be controlled and plays a role in regulating the activity of the oxidant. For example, when the pH is 7.5 or higher, the conditions are such that hydroxy radicals are likely to be generated, and when the pH is 7.5 or lower, the conditions are such that the oxidizing agent can be stably present in the solvent.

  At this time, in the case of amine, in the state in which an oxidizing agent such as ozone or hydrogen peroxide water is continuously supplied at a high pH by increasing the pH of the solvent, the reactive efficiency is increased while increasing the decomposition efficiency of the oxidizing agent. Create conditions that can easily generate high hydroxyl radicals. Such hydroxyl radicals can react with the constituent components of the resist contained in the solvent to be decomposed, and at the same time, assist the peeling of the resist applied to the substrate. The amine is preferably a primary, secondary, tertiary chain amine or cyclic amine, specifically, monoethanolamine, monoisopropylamine, aminoethoxyethanol, methylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine. , Diethylmethanolamine, methyldiethanolamine, 1- (2-hydroxyethyl) -4-methylpiperazine, N-methyl-N- (N, N-dimethylaminoethyl) -aminoethanol, N-methyl-N- (N, Select one or more of N-dimethylaminoethyl) -aminobutanol, 1- (N, N-dimethyl) 2- (2-hydroxyethoxy) ethylamine, hydroxyethylpiperazine, aminoethylpiperazine, and aminopropylmorphine. Can do.

  The organic acid is constant in hydroxyl radical or oxygen radical while reducing the pH of the solvent so that the solvent is stably contained in the solvent in a state where the oxidizing agent such as ozone or hydrogen peroxide is limited to a certain amount. To be disassembled. The organic acid is preferably selected from the group consisting of carboxylic acids, dicarboxylic acids, and anhydrides thereof. Specifically, benzoic acid, methylbenzoic acid, hydroxybenzoic acid, aminobenzic acid, citric acid, succinic acid, malic acid, maleic acid, salicylic acid, succinic acid, phthalic acid, itaconic acid, succinic anhydride, phthalic anhydride , And one or more of itaconic anhydride.

  In the case of the two-component composition and the three-component composition in the present invention, the amine or organic acid is preferably used in an amount of 0.1 to 30 parts by weight based on the entire composition. If the content of the amine or organic acid is less than 0.1 parts by weight, there is a problem that the modified resist removal performance is lowered by dry etching or the like, and the pH of the solvent is adjusted to make it difficult to create a radical generation environment. When the amount exceeds 30 parts by weight, there is a problem that the ability to dissolve the gelled polymer is lowered and the resist removal performance is lowered as a whole.

  The oxidizing agent used in the composition of the present invention is ozone, aqueous hydrogen peroxide, tert-butyl hydrogen peroxide, benzoyl hydrogen peroxide, urea-hydrogen peroxide adduct, ammonium nitrate, ammonium formate, ammonium carbonate, hydrogen carbonate. It is preferably at least one selected from the group consisting of ammonium, ammonium acetate, ammonium difluoride, ammonium thiocyanate, ammonium sulfate, ammonium sulfide, ammonium oxalate, and ammonium thiosulfate, and ozone is particularly desirable.

  When ozone is included, it is better to include it together with one or more oxidizing agents excluding ozone. In such a case, it is most preferable that the oxidizing agent is selected from among hydrogen peroxide solution and ammonium salt. When an oxidizing agent such as hydrogen peroxide solution and ammonium salt is added to the solvent, water is always used. The effect can be expected only when it is added in a dissolved state. When used with ozone and hydrogen peroxide, the resist decomposing ability is doubled, and when ozone and ammonium salt are used together, the resist decomposing ability is increased and the function of easily removing the modified resist that appears after the ashing process is also performed. it can. The resist decomposition ability can be confirmed even when hydrogen peroxide solution or ammonium salt is used together with the compound selected from the cyclic compounds, glycol compounds, and carbonate compounds without containing ozone. It can be observed that the ability to decompose the resin decreases and the ability to decompose the photosensitizer (PAC) is the same. Therefore, in the present invention, it is more preferable to use one or more oxidizers in combination and ozone alone, and the type of oxidizer may differ depending on the required process.

  Hydrogen peroxide water, ozone, ammonium salts, etc. used as oxidizing agents generate hydroxy radicals, oxygen radicals, and ammonium radicals under specific conditions to decompose photosensitive compounds (PAC: Photo active compound) in resist components. In addition to the role of directly reducing the content of the resist contained in the solvent, it also plays the role of enhancing the resist removal performance that is insufficient for the solvent itself.

  At this time, ozone that can be used as an oxidizing agent should be supplied in real time using an ozone generator, and is used to decompose or remove the resist contained in the solvent and the resist applied to the substrate. From about 100 ppm of ozone must be dissolved in the solvent, and the resist removal capability can only be helped if it is present in the resist removal composition of at least 30 ppm or more. In order for ozone to dissolve efficiently in the solvent, a contactor between the generator and the tank containing the solvent is required. The higher the decomposition efficiency of such ozone in the solvent, the higher the resist stripping efficiency, and the higher the temperature and the more hydroxy oxide, the faster the decomposition rate.

  In the two- to four-component composition of the present invention, the oxidant content may be 0.01 to 10 parts by weight with respect to the total composition. If the content of the oxidizing agent is less than 0.01 parts by weight, there is a problem that the amount of radical generation is insufficient and the resist decomposition is difficult, and if it exceeds 10 parts by weight, there is a problem that the metal wiring is corroded. When ozone is contained in the composition of the present invention, the content of ozone can be 0.001 to 1 part by weight, and in the case of an oxidizing agent excluding ozone, 0.1 to 10 parts by weight can be used.

  Examples of the lactone compounds represented by the chemical formula 6 or 7 include gamma butyrolactone, gamma methylene gamma butyrolactone, alphamethyl gamma butyrolactone, alpha methylene gamma butyrolactone, 2-acetylbutyrolactone, gamma hexanolactone, gamma nonanol lactone, tertaocta One or more selected from the group consisting of lolactone, gamma valerolactone, deltavalerolactone, and deltahexanone lactone can be used.

  In the case of a three-component or four-component composition in the present invention, the lactone compound is preferably used in an amount of 10 to 50 parts by weight relative to the total composition, and if the content is less than 10 parts by weight, There is a problem in that the weight of the oxidizer and amine or organic acid is increased to reduce the corrosion of the metal wiring and the ability to remove the resist. There is a problem that it is difficult to decompose the resist in the solvent because the part is separated and radical generation is insufficient.

  The method for producing the resist removing composition of the present invention as described above is not particularly limited, and can be used for removing a resist patterning a metal wiring of an electronic circuit or a display element in combination with a normal method.

  Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, an Example illustrates this invention and does not limit these. On the other hand, in the following examples, percentages and mixing ratios are based on weight unless otherwise stated.

  Examples 1 to 7 are experiments for examining the resist removal performance and resist decomposition performance of each composition.

  Specimens for investigating resist removal performance were DTFR-3650B (Toshin Semichem, positive resist) coated on glass, then 10 minutes at 140 ° C. (Sample 1) and 10 minutes at 150 ° C. (Sample 2) ), The baking resist removal time was measured, and the size of the specimen was 2 cm × 4 cm.

  In order to investigate the resist decomposition performance, 3 parts by weight of DTFR-3650B (Toshin Semichem, positive resist) is forcibly added to each composition, and when ozone is used, ozone is maintained at 60 ppm or higher in the solvent using an ozone generator. And the presence or absence of resist decomposition was observed through reaction with ozone for 6 hours or more. The ozone generator is widely known for the discharge method, photochemical reaction method, electrolysis method, etc. In this experiment, a dielectric method is used to convert oxygen with ozone in the discharge space by inserting a dielectric between two or more electrodes. Then, ozone was dissolved in the form of fine bubbles by bringing it into contact with a sealed container having a large surface area in the solvent.

  The necessity of resist decomposition was observed through UV absorbance measurement, and the absorbance at 280 nm, 350 nm, and 550 nm was observed, respectively, and the presence or absence of reference contrast decomposition was shown in (%).

  At the time of application of the process, as a test piece for examining the presence or absence of corrosion on the wiring metal, molybdenum and aluminum were sequentially deposited in a thin film of 200 mm and 2000 mm on a glass substrate, and the wiring was shaped into DTFR-3650B, and then wet. Etching was performed by an etching method (Sample 3).

  The size of the specimen was 2 cm × 4 cm, each composition was induced at 70 ° C., washed for 30 minutes with pure water, and then, through SEM, the necessity of corrosion of the lower film quality was observed. .

<Example 1>
The resist removal performance of the glycol compound or the carbonate compound itself was evaluated.

  Using the respective solvents shown in Table 1 below, the removal power of the first specimen on the film quality was evaluated.

  In particular, in order to see the change in resist removal performance according to volatilization, each removal solution is maintained at 70 ° C. in a forced exhaust state, the removal performance of each specimen is evaluated, and the time required to completely remove the resist As shown in Table 1.

  In Table 1, DEC: diethyl carbonate, THFA: tetrahydropropylene acetate, TEG: triethylene glycol, BDG: diethylene glycol butyl ether, DMDG: diethylene glycol dimethyl ether.

  From the results of Table 1, the glycol compounds or carbonate compounds according to the present invention (Experiments 1 to 5) all showed similar ability in resist removal power. At this time, when the thermosetting is 150 ° C. or higher, or when the resist is modified by dry etching, the above solvent cannot be simply applied. It can be used effectively during the process.

<Example 2>
The removal performance of the resist and the presence or absence of corrosion in the two-component system in which the cyclic compound, glycol system, or carbonate compound of the present invention and an amine or organic acid were mixed were evaluated.

  Using the compositions of Experiments 1 to 7 shown in Table 2 below, the removal power for the film quality of the first specimen, the second specimen, and the third specimen, and Psychobuul were evaluated. In particular, in order to see the change in resist removal performance according to volatilization, each removal solution is kept at 70 ° C. in a forced exhaust state, the removal performance of each specimen is evaluated, and with time to completely remove the resist, The results are shown in Table 2.

  In Table 2 above, DEC: diethyl carbonate, THFA: tetrahydropopulare acetate, TEG: triethylene glycol, BDG: diethylene glycol butyl ether, DMDG: diethylene glycol dimethyl ether, PhAA: phthalic anhydride, SAA: succinic anhydride, MEA: Monoethanolamine, MDAEAE: N-methyl-N- (N, N-dimethylaminoethyl) aminoethanol.

  It can be seen that when an amine or an organic acid is added to each solvent, the resist removal performance increases as compared to a single solvent, and a slight difference occurs depending on the type of solvent. It can also be seen that the addition of amine or organic acid does not affect the corrosion of the lower film quality.

<Example 3>
The removal performance of a resist in a three-component system in which a cyclic compound, a glycol-based compound, a lactone-based compound, and an amine or an organic acid are mixed was compared with the presence or absence of corrosion.

  Using the compositions of Experiments 1 to 6 shown in Table 3 below, the removal ability and corrosion propriety on the film quality of the first specimen, the second specimen, and the third specimen were evaluated. In particular, in order to examine the change in resist removal performance according to volatilization, each removal solution is maintained at 70 ° C. in a forced exhaust state, the removal performance of each specimen is evaluated, and with time to completely remove the resist, The results are shown in Table 3.

  In Table 3 above, DEC: diethyl carbonate, THFA: tetrahydropopulare acetate, BDG: diethylene glycol butyl ether, DMDG: diethylene glycol dimethyl ether, PhAA: phthalic anhydride, SAA: succinic anhydride, GBL: gamma butyrolactone, ABL: 2 -Acetylbutyrolactone, MDAEAE: N-methyl-N- (N, N-dimethylaminoethyl) aminoethanol.

  It can be seen that when a lactone solvent and an amine or organic acid are added to each solvent, the resist removal performance increases as compared to a single solvent, and a slight difference occurs depending on the type of solvent. It can also be seen that the addition of amine or organic acid does not affect the corrosion of the lower film quality. The reason why the resist removal performance is increased by the lactone compound in the present invention is that the lactone compound is a highly polar solvent in which the polarity is gathered where there are oxygen double bonds.

  Such a polar solvent not only helps resist removal performance but also serves to lower the viscosity of the removal solvent.

<Example 4>
The removal performance of the resist, the presence or absence of corrosion, and the resist decomposition performance were compared in a three-component system in which a glycol-based or carbonate compound and an oxidizing agent such as hydrogen peroxide, ozone, or ammonium salt as an oxidizing agent were mixed.

  Using the compositions of Experiments 1 to 11 in Table 4 below, the removal power for the film quality of the first, second, and third specimens was evaluated. In order to investigate the change in the resist removal performance, each removal solution was kept at 70 ° C. in a forced exhaust state, and the removal performance of each specimen was evaluated to show the time for completely removing the resist. In addition, in order to investigate the resist decomposition performance, each removal solution was kept at 70 ° C. in a forced exhaust state, and after the initial and 6 hours passed, each removal solution was sampled and measured for UV absorbance. The results are shown in Table 4.

In Table 4 above, DEC: diethyl carbonate, THFA: tetrahydropropylene acetate, TEG: triethylene glycol, BDG: diethylene glycol butyl ether, DMDG: diethylene glycol dimethyl ether, hydrogen peroxide solution: 35% H ₂ O ₂ aqueous solution, ammonium carbonate: 10% aqueous ammonium carbonate solution.

  In this experiment, ozone was continuously supplied by the ozone generator and the experiment was conducted in a state where the solvent was maintained at a concentration of 60 ppm. In the case of hydrogen peroxide solution and ammonium salt, it was not continuously supplied and was consumed by heat. Or proceeded in a disassembled state.

  As a result, since ozone is continuously supplied, the decomposition efficiency is better than that of other oxidizing agents, and an excellent effect is shown in a specific solvent. Such ozone, hydrogen peroxide solution, and ammonium salt generated radicals in the solvent, and mainly decomposed the photosensitizer (PAC), and the resin in the resist component was less decomposed than the photosensitizer. Therefore, over time, it was observed that the color of the composition changed to a transparent yellow while the opaque red color was lightened by the photosensitizer.

  Like amines or organic acids, ozone also has the effect of improving the resist stripping ability, but is not as effective as amines or organic acids. It is judged that the ozone that was continuously supplied hits the substrate and helped to improve the resist stripping ability through the reaction with the photosensitizing agent in the thermally denatured resist components.

<Example 5>
The resist removal performance and the presence or absence of corrosion were compared in a three-component system in which a cyclic compound containing an oxygen double bond, a glycol compound, or a carbonate compound and a lactone compound, and an oxidizing agent were mixed.

  Using the compositions of Experiments 1 to 13 shown in Table 5 below, the removal power for the film quality of the first specimen, the second specimen, and the third specimen, and Psychobuul were evaluated. In particular, in order to see the change in resist removal performance according to volatilization, each removal solution is kept at 70 ° C. in a forced exhaust state, the removal performance of each specimen is evaluated, and with time to completely remove the resist, The results are shown in Table 5.

In Table 5 above, THFA: tetrahydropopulare acetate, BDG: diethylene glycol butyl ether, DMDG: diethylene glycol dimethyl ether, GBL: gamma butyrolactone, ABL: 2-acetylbutyrolactone, aqueous hydrogen peroxide: 35% H ₂ O ₂ aqueous solution, ammonium carbonate : 10% ammonium carbonate aqueous solution.

  From the above results, it has been clarified that the lactone compound is mixed with the solvent and improves the efficiency of resist stripping performance and decomposition performance.

<Example 6>
Resist in a three-component system in which a cyclic compound containing an oxygen double bond, glycol system, or carbonate system, an amine or organic acid, and an oxidizing agent such as hydrogen peroxide, ozone, or ammonium salt as an oxidizing agent are mixed. Removal performance, presence of corrosion, and resist decomposition performance were compared.

  Using the compositions of Experiments 1 to 12 in Table 6 below, the removal power for the film quality of the first, second, and third specimens was evaluated. In order to see the change in the resist removal performance, each removal solution was kept at 70 ° C. in the forced exhaust state, and the removal performance of each specimen was evaluated to show the time for completely removing the resist. In order to investigate the resist decomposition performance, each removal solution was kept at 70 ° C. in a forced exhaust state, and after the initial and 6 hours passage, each removal solution was collected and measured for UV absorbance to show the decomposition ratio. The results are shown in Table 6.

In Table 6 above, DEC: diethyl carbonate, THFA: tetrahydropopulare acetate, TEG: triethylene glycol, BDG: diethylene glycol butyl ether, DMDG: diethylene glycol dimethyl ether, hydrogen peroxide solution: 35% H ₂ O ₂ aqueous solution, ammonium carbonate: 10% ammonium carbonate aqueous solution, MDAEAE: N-methyl-N- (N, N-dimethylaminoethyl) aminoethanol.

  It can be seen that each amine or organic acid improves the conditions for generating radicals, such as the pH of the solvent, to improve the decomposition efficiency of the resist by about 15 to 20%, and in particular, the resist stripping performance is also greatly improved.

  Except for amines or organic acids, when used with ozone and hydrogen peroxide, it showed higher decomposition efficiency than amines or organic acids. In addition, it can be seen that the effect of rising by the interaction between hydrogen peroxide and ozone is large.

<Example 7>
4 components in which cyclic compounds, glycol-based or carbonate-based compounds containing oxygen double bonds are mixed with lactone compounds, amines or organic acids, and oxidizing agents such as hydrogen peroxide, ozone, ammonium salts as oxidizing agents. The resist removal performance, the presence or absence of corrosion, and the resist decomposition performance in the system were compared.

  Using the compositions of Experiments 1 to 12 in Table 7 below, the removal power for the film quality of the first specimen, the second specimen, and the third specimen was evaluated, and each removal solution was used to see the change in resist removal performance. Was maintained at 70 ° C. in a forced exhaust state, and the removal performance of each specimen was evaluated to show the time for completely removing the resist. In order to investigate the resist decomposition performance, each removal solution was kept at 70 ° C. in a forced exhaust state. After the initial and 6 hours, each removal solution was sampled and measured for UV absorbance. Table 8 shows.

In Table 7, THFA: Tetrahydropopulare acetate, BDG: Diethylene glycol butyl ether, DMDG: Diethylene glycol dimethyl ether, GBL: Gamma butyrolactone, ABL: 2-acetylbutyrolactone, hydrogen peroxide solution: 35% H ₂ O ₂ aqueous solution, ammonium carbonate : 10% ammonium carbonate aqueous solution.

  The resist removing composition according to the present invention is excellent in resist removal ability, resist decomposition ability and substrate cleaning ability in the process.

Claims (30)

A resist removal comprising at least one compound selected from the group consisting of a compound of the following chemical formula 1, a cyclic compound of the chemical formula 2, chemical formula 3 or chemical formula 4, and a glycol compound of the chemical formula 5 Composition.
[Chemical formula 1]


[Chemical formula 2]


[Chemical formula 3]


[Chemical formula 4]


[Chemical formula 5]


(In the above formula, R, R ′, R ″, and R ′ ″ are hydrogen, hydroxyl group, alkyl group having 1 to 10 carbon atoms, alkanol group having 1 to 10 carbon atoms, or alkyl group having 1 to 10 carbon atoms, respectively. An acetate group, R ₃ is a hydroxyl group, an alkyl having 1 to 10 carbon atoms, or an alkyl acetate group having 1 to 10 carbon atoms, and n is an integer of 1 to 12.)   The cyclic compound is at least one selected from the group consisting of cyclopentanone, methylcyclopentanone, tetrahydrofurfuryl acetate, tetrahydro-4H-pyran-4-one, tetrahydropyran 2-methanol. The composition for removing a resist according to claim 1.   The glycol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene. The resist removal composition according to claim 1, wherein the composition is one or more selected from the group consisting of glycol ethyl ether, triethylene glycol butyl ether, and diethylene glycol dimethyl ether. The resist removal composition according to claim 1, wherein the composition further comprises an amine, an organic acid, an oxidizing agent, a lactone solvent represented by the following chemical formula 6 or chemical formula 7, or a mixture thereof. .
[Chemical formula 6]


[Chemical formula 7]


(In the above formula, each R is hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkanol group having 1 to 10 carbon atoms, or an alkyl acetate group having 1 to 10 carbon atoms.)   The composition includes 70 to 99.9 parts by weight of a compound selected from the group consisting of a cyclic compound and a glycol compound, and 0.1 to 30 parts by weight of an amine or an organic acid with respect to the entire composition. The resist removing composition according to claim 4.   The composition includes 90 to 99.99 parts by weight of a compound selected from the group consisting of a cyclic compound and a glycol compound, and 0.01 to 10 parts by weight of an oxidizing agent, based on the total composition. The composition for removing a resist according to claim 1.   90 to 99.499 parts by weight of a compound selected from the group consisting of a cyclic compound and a glycol compound, 0.001 to 1 part by weight of ozone, and ozone are excluded from the total composition. The resist removing composition according to claim 6, further comprising 0.5 to 10 parts by weight of an oxidizing agent.   The composition comprises 70 to 99.99 parts by weight of a compound selected from the group consisting of a cyclic compound and a glycol compound, 1 to 30 parts by weight of an amine or an organic acid, and an oxidizing agent based on the total composition. The resist removing composition according to claim 4, comprising 0.01 to 10 parts by weight.   The composition comprises 70 to 89.9 wt. Of a compound selected from the group consisting of a cyclic compound and a glycol compound, 10 to 50 wt. Parts of a lactone compound, and 0 of an amine or an organic acid. The composition for removing a resist according to claim 4, comprising 1 to 30 parts by weight.   The composition comprises 70 to 89.99 parts by weight of a compound selected from the group consisting of a cyclic compound and a glycol compound, 10 to 50 parts by weight of a lactone compound, and 0 to 0 parts of an oxidizing agent. The resist removing composition according to claim 4, comprising 0.01 to 10 parts by weight.   The composition comprises 70 to 88.9 parts by weight of a compound selected from the group consisting of a cyclic compound and a glycol compound, 10 to 50 parts by weight of a lactone compound, an amine or an organic acid, based on the total composition. The resist removing composition according to claim 4, comprising 1 to 30 parts by weight and 0.01 to 10 parts by weight of an oxidizing agent.   The composition comprises 70 to 89.899 parts by weight of a compound selected from the group consisting of a cyclic compound and a glycol compound, 10 to 50 parts by weight of a lactone compound, and 0.01 to ozone with respect to the total composition. The resist removing composition according to claim 11, further comprising 0.5 to 10 parts by weight of an oxidizing agent excluding ozone and 1 part by weight of ozone.   The amine is monoethanolamine, monoisopropylamine, aminoethoxyethanol, methylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylmethanolamine, methyldiethanolamine, 1- (2-hydroxyethyl) -4-methylpiperazine, N-methyl-N- (N, N-dimethylaminoethyl) -aminoethanol, N-methyl-N- (N, N-dimethylaminoethyl) -aminobutanol, 1- (N, N-dimethyl) 2- ( The resist removing composition according to claim 4, wherein the composition is one or more selected from the group consisting of 2-hydroxyethoxy) ethylamine, hydroxyethylpiperazine, aminoethylpiperazine, and aminopropylmorphine.   The organic acid is benzoic acid, methylbenzoic acid, hydroxylbenzoic acid, aminobenzoic acid, citric acid, succinic acid, malic acid, maleic acid, salicylic acid, succinic acid, phthalic acid, itaconic acid, succinic anhydride, phthalic anhydride And the composition for removing a resist according to claim 4, wherein the composition is one or more selected from the group consisting of itaconic anhydride.   The oxidizing agent is ozone, hydrogen peroxide, tert-butyl hydrogen peroxide, benzoyl hydrogen peroxide, urea-hydrogen peroxide adduct, ammonium nitrate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, ammonium hydrogen fluoride The resist removal composition according to claim 4, wherein the composition is one or more selected from the group consisting of ammonium thiocyanate, ammonium sulfate, ammonium sulfide, ammonium oxalate, and ammonium thiosulfate.   The lactone compounds are gamma butyrolactone, gamma methylene gamma butyrolactone, alphamethyl gamma butyrolactone, alpha methylene gamma butyrolactone, 2-acetylbutyrolactone, gamma hexanolactone, gamma nonanol lactone, delta octanolactone, gamma valerolactone, delta valerolactone. And at least one selected from the group consisting of deltahexanone lactone. A resist removing composition comprising: a carbonate compound represented by the following chemical formula 8; and an amine, an organic acid, an oxidant, a lactone solvent represented by the following chemical formula 6 or the chemical formula 7, or a mixture thereof. object.
[Chemical formula 8]


(In the above formula, R ₁ is alkyl having 1 to 10 carbons, benzyl, phenyl, or alkyl acetate having 1 to 10 carbons;
R ₂ is alkyl having 1 to 10 carbons, benzyl, phenyl, alkyl acetate having 1 to 10 carbons or alkyl carbonate having 1 to 10 carbons. )
[Chemical formula 6]


[Chemical formula 7]


(In the above formula, each R is hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkanol group having 1 to 10 carbon atoms, or an alkyl acetate group having 1 to 10 carbon atoms.)   18. The resist removing composition according to claim 17, wherein the composition comprises 70 to 99.9 parts by weight of a carbonate compound and 0.1 to 30 parts by weight of an amine or an organic acid with respect to the entire composition. object.   18. The resist removing composition according to claim 17, wherein the composition comprises 90 to 99.99 parts by weight of a carbonate compound and 0.01 to 10 parts by weight of an oxidizing agent with respect to the entire composition.   The composition includes 90 to 99.499 parts by weight of a carbonate compound, 0.001 to 1 part by weight of ozone, and 0.5 to 10 parts by weight of an oxidant excluding ozone based on the total composition. The composition for removing a resist according to claim 19.   The composition comprises 70 to 99.99 parts by weight of a carbonate compound, 1 to 30 parts by weight of an amine or an organic acid, and 0.01 to 10 parts by weight of an oxidant based on the total composition. Item 18. The resist removal composition according to Item 17.   The composition comprises 70 to 89.9 wt.% Of a carbonate compound, 10 to 50 wt.% Of a lactone compound, and 0.1 to 30 wt.% Of an amine or organic acid based on the total composition. Item 18. The resist removal composition according to Item 17.   The composition comprises 70 to 89.99 parts by weight of a compound selected from the group consisting of a cyclic compound and a glycol compound, 10 to 50 parts by weight of a lactone compound, and 0 to 0 parts of an oxidizing agent. The resist removing composition according to claim 17, comprising 0.01 to 10 parts by weight.   The composition is composed of 70 to 88.9 parts by weight of carbonate, 10 to 50 parts by weight of lactone compound, 1 to 30 parts by weight of amine or organic acid, and 0.01 to 30 parts of oxidant based on the total composition. The resist removing composition according to claim 17, comprising 10 parts by weight.   The composition is composed of 70 to 89.899 parts by weight of carbonate compound, 10 to 50 parts by weight of lactone compound, 0.01 to 1 part by weight of ozone, and 0 oxidizer excluding ozone. The resist removing composition according to claim 17, comprising .5 to 10 parts by weight.   The resist removal composition according to claim 17, wherein the carbonate compound is at least one selected from the group consisting of dibenzyl carbonate, diethyl carbonate, and diethyl dicarbonate.   The amine is monoethanolamine, monoisopropylamine, aminoethoxyethanol, methylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylmethanolamine, methyldiethanolamine, 1- (2-hydroxyethyl) -4-methylpiperazine, It is one or more selected from the group consisting of N-methyl-N (n, n-dimethylaminoethyl) -aminoethanol, hydroxyethylpiperazine, aminoethylpiperazine, and aminopropylmorphine. Item 18. The resist removal composition according to Item 17.   The organic acid is benzoic acid, methylbenzoic acid, hydroxylbenzoic acid, aminobenzoic acid, citric acid, succinic acid, malic acid, maleic acid, salicylic acid, succinic acid, phthalic acid, itaconic acid, succinic anhydride, phthalic anhydride And a composition for removing a resist according to claim 17, wherein the composition is one or more selected from the group consisting of itaconic anhydride.   The oxidizing agent is ozone, hydrogen peroxide, tert-butyl hydrogen peroxide, benzoyl hydrogen peroxide, urea-hydrogen peroxide adduct, ammonium nitrate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, ammonium hydrogen fluoride The resist removal composition according to claim 17, wherein the composition is one or more selected from the group consisting of ammonium thiocyanate, ammonium sulfate, ammonium sulfide, ammonium oxalate, and ammonium thiosulfate.   The lactone compounds include gamma butyrolactone, gamma methylene gamma butyrolactone, alphamethyl gamma butyrolactone, alpha methylene gamma butyrolactone, 2-acetylbutyrolactone, delta hexanolactone, delta nonanool lactone, delta octanolactone (delta- The resist removal composition according to claim 17, wherein the composition is one or more selected from the group consisting of octanolactone), gamma valerolactone, deltavalerolactone, and deltahexanone lactone.