JP5236217B2 - Resist removing composition - Google Patents

Description

  The present invention relates to a resist removing composition used in a photolithography process. More specifically, when removing a resist for patterning a metal wiring, the corrosion of the metal wiring can be minimized, and the resist removing power can be reduced. The present invention relates to a resist removing composition that is excellent in.

  A resist (photoresist) is a substance that is essential for a photolithography process. This photolithography process is a semiconductor device such as an integrated circuit (IC), a highly integrated circuit (LSI), or a very high integrated circuit (VLSI). This is one of the processes generally performed for manufacturing image display devices such as liquid crystal display devices (LCD) and flat panel display devices (PDP).

  However, the resist is removed at a high temperature by the removing solution after the photolithography process. If the resist is removed at the high temperature as described above, there is a problem that the lower metal film is rapidly corroded by the removing solution.

  That is, there is a problem that the degree of corrosion of the metal wiring is accelerated by the resist removal solution. A resist removal solution for preventing such corrosion problem of metal wiring is disclosed in Patent Document 1, Patent Document 2, and Patent Document 3.

  In the above method, there is disclosed a method for preventing corrosion of a wiring metal used for a metal wiring by using a resist removing solution obtained by adding a corrosion inhibitor to a mixture of amide and organic amine. As monoethanolamine is clearly preferred. In addition, an appropriate amount of the corrosion inhibitor is disclosed, and when the appropriate amount is exceeded, it is clearly stated that the resist removing ability is reduced.

  In general, primary or secondary amines such as monoethanolamine and methylethanolamine have been mainly used as the amine in the constituents of the resist removal solution.

  However, such a primary or secondary amine has a low boiling point and a serious change in composition. After a certain period of time, all removal solutions are removed during the process due to changes in weight and composition due to volatilization. There is a problem that must be replaced. In addition, when such a primary or secondary amine does not contain a corrosion inhibitor, there is a problem that the metal wiring is significantly corroded even if a small amount of water is mixed.

US Pat. No. 5,417,877 US Pat. No. 5,556,482 JP 2001-188363 A

  In order to solve such a problem in the prior art, an object of the present invention is to remove metal wiring patterning resist film for embodying an electronic circuit or a display element, in particular, metal wiring, particularly aluminum, molybdenum. An object of the present invention is to provide a resist removing composition that does not corrode copper, titanium, etc. and has excellent resist removing power.

In order to achieve the above object, the present invention includes a) 1 to 20% by weight of one or more diamine compounds selected from compounds represented by the following chemical formula 1, and b) a glycol ether compound in the balance. A component-based resist removal composition is provided.
[Chemical Formula 1]

In the above formula, R and R ′ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ″ is hydrogen, an alkanol having 1 to 10 carbon atoms, or an alkyl having 1 to 10 carbon atoms. It is a group.

  The composition of the present invention can also be a three-component composition further comprising at least one polar solvent, wherein the composition comprises a) a diamine compound in an amount of 1 to 20% by weight, and b) a glycol ether compound in an amount of 10 to 90%. % By weight and c) at least one polar solvent may be included in the balance.

  The composition for removing a resist according to the present invention has an effect that the resist can be completely removed and washed by minimizing the corrosion of the lower metal film of the resist.

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

  The cyclic amine used in the present invention is less affected by corrosion on the metal wiring, but has a lower removing power than a chain amine on a resist whose composition has been significantly changed by a dry etching process. Therefore, in the present invention, in order to increase the resist removal power when a cyclic amine having a low removal power against a resist whose composition has changed remarkably but has little influence of corrosion on such metal wiring, diamine is used as an amine compound. And devised a method of using cyclic amines or chain amines with diamines. Although the diamine has the same resist removing ability as that of the chain amine, the influence of corrosion on the metal wiring is smaller than that of the chain amine, the boiling point is high, and the composition of two types of amines even when used with a cyclic amine. There is no need to worry about performance changes due to changes in performance.

  In the present invention, when an amine and a solvent that hardly affect the metal wiring are used in the resist removal composition, the lower film is prevented from being corroded by a galvanic phenomenon with the upper metal film. , Found that there is a possibility to remove the resist. However, even in the case of amines that do not have the influence of corrosion on ordinary metal wiring, when about 0.1 to 3% of water is mixed, the corrosion proceeds remarkably in the case of a single film, and the double film Even in this case, the upper film and the lower film are corroded by the galvanic phenomenon. Further, even if water is not mixed in the resist removal composition, if an intermediate cleaning step with alcohols such as isopropyl alcohol is not performed after the stripping step, corrosion due to galvanic phenomenon proceeds. Therefore, in this case, a small amount of a corrosion inhibitor is added to prevent corrosion.

  Therefore, the composition for removing a resist according to the present invention has an advantage that the metal wiring is not corroded in the step of removing the resist for patterning the metal wiring, and at the same time, the resist removing power is excellent.

  Such a resist removal composition of the present invention is a two-component composition that uses at least one selected from the group consisting of diamine compounds as an amine compound, and uses a glycol ether compound in the concept of a solvent. It can also be a ternary composition that additionally uses one or more polar solvents. In addition, the composition of the present invention further includes one or more anticorrosive agents to prevent corrosion due to water contained in a small amount. The resist removal composition of the present invention further contains a cyclic amine compound or a chain amine compound as the amine compound.

  Hereinafter, each component used for the composition for resist removal of this invention is demonstrated concretely.

  In general, the corrosion of the metal wiring is not related to the basicity, and corrosion occurs remarkably only in the amine in which the remaining two hydrogen atoms attached to the nitrogen of the cyclic amine or the chain amine are not substituted. However, when the resist removal process proceeds under high temperature conditions, if a diamine compound is used as in the present invention, the volatilization phenomenon does not occur so much, so that the initial composition ratio of the resist removal composition is maintained constant, Changes in removal force due to changes in composition can be minimized. In the present invention, such an effect can be increased by additionally using a chain amine or one or more compounds selected from the group consisting of cyclic amines having a boiling point of 200 ° C. or higher. .

  The amine compound is a strong alkaline substance, and is modified under various process conditions such as dry or wet etching, ashing, or ion implant processing to form a crosslinked resist polymer matrix. It acts as a powerful intruder and destroys the attractive forces that exist within or between molecules. Such an amine compound acts on the top of the substrate by forming a space in a structurally weak portion of the resist remaining on the substrate and transforming the resist into a lump of amorphous polymer gel. The attached resist can be easily removed.

The diamine compound is one or more selected from compounds represented by the following chemical formula 1.
[Chemical Formula 1]

In the above formula, R and R ′ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, R ″ is hydrogen, an alkanol having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. It is an alkyl group.

Representative examples of the diamine compound include 2-[(2-aminoethyl) amino] ethanol , 1 -[(2-aminoethyl) amino] -2-propanol, 2-{[2- (methylamino) One or more selected from the group consisting of ethyl] amino} ethanol, 2-[(2-amino-2-methylpropyl) amino] ethanol, and 2-{[2- (dimethylamino) ethyl] methylamino} ethanol More preferably, one compound selected from the group consisting of 2-[(2-aminoethyl) amino] ethanol and 1-[(2-aminoethyl) amino] -2-propanol The above compounds can be used.

  The content of the diamine compound is preferably 1 to 20% by weight with respect to the entire composition in consideration of the decrease in resist removing ability and the significant corrosion.

  In addition, the cyclic amine that can be additionally used in the present invention has a high boiling point, changes in weight and composition due to volatilization are not serious, and can be applied to a process for a longer time than a chain amine. Examples of the cyclic amine compound include 1- (2-hydroxyethyl) piperazine, N- (3-aminopropyl) morpholine, 1- (2-aminoethyl) piperazine, and 1- (2-hydroxyethyl) -4-ethyl. One or more selected from the group consisting of piperazine, 4-amino-1-methylpiperazine, 1-methylpiperazine, 2-methylpiperazine, 1-benzylpiperazine, and 2-phenylpiperazine can be used. Examples of the chain amine compound include monoethanolamine, monoisopropanolamine, diethanolamine, triethanolamine, n-methylethanolamine, n-ethylethanolamine, dimethylethanolamine, diethylethanolamine, aminoethoxyethanol, and amino One or more selected from the group consisting of methoxyethanol can be used. When the cyclic amine or the chain amine compound is used, it is additionally contained in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the composition.

  The glycol ether compounds include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol propyl ether, triethylene glycol butyl ether, triethylene glycol ethyl ether, and triethylene glycol. One or more selected from the group consisting of methyl ether can be used.

  However, among the glycol ether compounds, those having a low boiling point are toxic and have a problem that they are difficult to apply because the composition change due to volatilization is serious.

  Therefore, in the present invention, it is preferable to use a compound having a boiling point of 180 ° C. or higher and having almost infinite solubility in water among the glycol ether solvents so as not to cause the above problem. In other words, when the resist removal process proceeds under high temperature conditions, if a glycol ether solvent having a boiling point of 180 ° C. or higher is used, the volatilization phenomenon does not occur so much, so that the composition ratio of the resist removal composition at the initial stage of use is constant. Maintained.

  In addition, when a glycol ether solvent having a boiling point of 180 ° C. or higher is used, the removal power of the resist removal composition is continuously expressed throughout the resist removal process, and the surface strength of the resist and the lower metal film is low. Therefore, not only the resist removal efficiency is improved, but also the melting point is low and the ignition point is high.

  Such a glycol ether compound having a boiling point of 180 ° C. or higher, for example, selected from the group consisting of diethylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether, triethylene glycol butyl ether, triethylene glycol ethyl ether, and triethylene glycol methyl ether If one or more are used, the most preferable effect can be obtained.

  In addition, when the content of glycol ether compound is too small, corrosion of metal wiring becomes significant due to the relatively increasing polar solvent and amine compound, and the polymer gelled by the amine compound and polar solvent is insufficient in solubility. As a result, the resist removing ability is reduced, and when the amount is too large, the content of the polar solvent is reduced and the resist removing ability may be lowered. Therefore, in consideration of the above points, the content of the glycol ether compound can be included in the remainder excluding the diamine in the case of a two-component composition, and the composition in the case of a three-component composition including a solvent. It is preferable to use 10 to 90% by weight based on the whole product.

  In particular, the resist removing composition of the present invention acts to dissolve a lump of a polymer gel peeled by an amine compound to a unit molecule level by further using at least one polar solvent. Therefore, the polar solvent according to the present invention has a feature that can prevent the resist re-adhesion failure phenomenon mainly generated in the cleaning process. In addition, a polar solvent such as N-methyl-2-pyrrolidone containing amine as a functional group in the molecule serves to assist the function of the amine compound entering the resist and removing the resist.

  Examples of the polar solvent include N-methyl-2-pyrrolidone (NMP), N-methylacetamide, N, N-dimethylacetamide, acetamide, N-ethylacetamide, N, N-diethylacetamide, formamide, N-methylformamide, One or more selected from the group consisting of N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, and N, N-dimethylimidazole can be used, and more preferably N-methyl One or more selected from the group consisting of 2-pyrrolidone (NMP), N-methylformamide, N-methylacetamide, and N, N-dimethylacetamide can be used.

  The content of the polar solvent is used in the remaining amount with respect to the entire composition of the ternary composition in consideration of the resist removing power, the degree of corrosion of the metal wiring, and the cleaning power, and more preferably 9 to 70 weights. Used in%.

  In addition, the composition of the present invention further includes one or more corrosion inhibitors to prevent corrosion due to water contained in a small amount.

  As the corrosion inhibitor, a compound containing an element such as —N—, —S—, —O— or the like having an unshared electron pair is effective. In particular, in the case of an —OH group or —SH group, the physical properties of the metal Excellent anti-corrosion performance due to chemical and chemical adsorption.

  The corrosion inhibitor is selected from the group consisting of mercaptobenzimidazole, mercaptomethylbenzimidazole, mercaptomethylimidazole, hydroxypyridine, dihydroxypyridine, methyltrihydroxybenzoate, pyrocatechol, catechol, L-ascorbic acid, and D-isoascorbic acid. One or more selected can be used. More preferably, the corrosion inhibitor may be one or more selected from the group consisting of mercaptomethylimidazole, methyltrihydroxybenzoate, pyrocatechol, L-ascorbic acid, and D-isoascorbic acid.

  If the content of the corrosion inhibitor is too small, the corrosion cannot be prevented and the metal wiring is corroded, and if it is too much, the resist removing power is affected to reduce the resist removing power. , It may be adsorbed significantly on the substrate and may not be cleaned properly in the subsequent cleaning step. Therefore, in view of the above points, the corrosion inhibitor is contained in an amount of 0.01 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the composition.

  Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, an Example is for demonstrating this invention and is not limited to this. On the other hand, in the following examples, unless otherwise noted, the percentage and the mixing ratio are based on weight.

  In order to select amines and corrosion inhibitors, Experimental Examples 1 and 2 were carried out, and the test specimens used here are as follows.

Specimens used in Experimental Examples 1 and 2 (Specimen 1, Specimen 2)
First, in order to evaluate the corrosion with respect to a metal, the specimen which formed the film of about 2000 mm of aluminum, molybdenum, and copper on the surface of glass, apply | coated the resist, and was developed (development 1) was used.

  Next, in order to evaluate the resist removing power, a chromium film is formed on the surface of the glass, a resist is applied, wet etching is performed, and then an n + a-Si: H active film specimen supplied with a dry etching gas is used. (Specimen 2). In addition, in order to form a resist whose composition was changed by more remarkable dry etching, a test piece obtained by repeatedly performing the dry etching process was used (Sample 3). Since the adhesion of the resist is maximized with chromium and the supply of a dry etching gas is applied, the resist composition changes and it is difficult to remove with a removal composition. Used as a piece.

Experimental example 1
In order to evaluate the resist removal power for single raw materials (Sample 2 and Sample 3), and the degree of corrosion on Aluminum, Molybdenum, and Copper (Sample 1), each prepared sample was used and the result was The results are shown in Table 1 below.

Note) In Table 1 above,
1) Corrosion: ◎ (not corroded at all), ○ (slightly corroded), △ (significantly corroded), × (completely corroded)
2) Resist removing power: ◎ (complete resist removal), ○ (there is some resist residue), Δ (resist residue is remarkable), × (resist is not removed at all)
As shown in Table 1, in the case of a chain amine such as monoethanolamine, the degree of corrosion is remarkable, but in the case of a cyclic amine, the resist removing power is excellent and the metal is not significantly corroded. Further, when all the hydrogen attached to nitrogen in the structure of the cyclic amine was substituted with an alkyl group, a benzene group, or an alcohol group, the corrosion prevention performance was excellent, but there was no removal power.

  It can be seen from Table 1 that the resist removing power with respect to each raw material varies depending on the degree of change in the composition of the resist film. In the case of a resist film having a remarkably changed composition, the removing power may be gradually reduced as compared with the chain amine. I understand. However, it can be seen that, for chain amines and diamines, the removal power is not greatly reduced by the degree of change in the composition of the resist film. From the above results, diamine is not lower in resist removal power than chain amines, and metal It can be seen that the influence of corrosion on the wiring is less than that of the chain amine.

Experimental example 2
As shown in Table 2 below, the degree of metal corrosion was evaluated using specimen 1 for monoethanolamine and the amine used in the present invention. In the case of an amine that has a problem in resist removal ability in a single evaluation, the evaluation was performed using two types of amines. Further, in the single evaluation, there is a little corrosion for each metal, so that 45% by weight of glycol ether and 45% by weight of diethylene glycol butyl ether which is a polar solvent are used, and two or one type excluding the solvent is used. Evaluation was made using a solution in which the total amount of amine was 10% by weight, and the results are shown in Table 2.

Note) In Table 2 above, corrosion: ◎ (not corroded at all), ○ (slightly corroded), △ (significantly corroded), × (completely corroded)
Referring to Table 2, the cyclic amine showed favorable results in terms of corrosion with respect to aluminum and molybdenum as compared with monoethanolamine. In addition, the more functional groups substituted in place of the hydrogen attached to the nitrogen in the structure of the cyclic amine, the more advantageous the corrosion to copper.

  In addition, when a diamine or monoethanolamine having no other functional group substituted in place of hydrogen attached to nitrogen is used together with a cyclic amine, it has an improved effect in terms of corrosion.

Examples 1 to 8, Reference Examples 1 to 12, and Comparative Examples 1 and 2
The compositions of Examples and Comparative Examples were produced with the compositions shown in Table 3 below.
The following Experimental Examples 3 and 4 were advanced in order to evaluate the resist removing power and the corrosion of each metal wiring in the resist removing composition. The target specimens used in Experimental Examples 3 and 4 were specimen 1 for evaluation of corrosion prevention and specimen 3 for evaluation of resist removal power. Using the specimen, the resist removal composition manufactured under the conditions shown in Table 3 below was evaluated.

Note) In Table 3 above,
HEP: 1- (2-hydroxyethyl) piperazine APM: N- (3-aminopropyl) morpholine AEAE: 2-[(2-aminoethyl) amino] ethanol AEAP: 1-[(2-aminoethyl) amino] 2 -Propanol MAEAE: 2- [2- (methylamino) ethyl] aminoethanol MEA: monoethanolamine DEA: diethanolamine MMI: mercaptomethylimidazole MTHB: methyltrihydroxybenzoate Pyro: pyrocatechol L-AA: L-ascorbic acid NMP: N-methyl-2-pyrrolidone DMAc: dimethylacetamide MMAc: monomethylacetamide MMF: N-methylformamide DEGME: diethylene glycol methyl ether DEGBE: diethylene glycol butyl ether

Experimental example 3
Using Examples 1 to 8, Reference Examples 1 to 12, and Comparative Examples 1 and 2, the removal power of the specimen 3 on the resist film was evaluated. In particular, in order to evaluate the change in resist removing power due to volatilization, each removing composition was maintained at 70 ° C. for 48 hours in a forced exhaust state, and the removing power for the specimen 3 was evaluated. Table 4 shows the results obtained by heating the removal composition to 70 ° C. and then submerging the specimen 3 and observing it with the naked eye.

Note) In Table 4 above, removal power: ◎ (complete resist removal), ○ (there is some resist residue), Δ (resist residue is remarkable), × (resist is not removed at all)
From the comparative example, it was found that when an amine having a low boiling point is used alone, the removal power is remarkably lowered when maintained at 70 ° C. for 48 hours. Each corrosion inhibitor does not significantly affect the stripping performance. In all examples, the boiling point of the cyclic amine is 200 ° C. or higher, so that the composition does not change greatly even after volatilization for 48 hours, and the stripping performance is low. It can be seen that the composition does not change, and that the composition that greatly affects the peeling performance is amine. In addition, it can be seen that the examples have superior peeling performance as compared with Comparative Example 2, and the peeling performance changes when a different polar solvent is added. Further, in Examples 1 and 2 using both diamine and chain amine and Examples 3 to 8 using both diamine and cyclic amine, an effect of increasing the peeling performance was observed. In particular, since the boiling point of diamine exceeds 200 ° C., it can be seen that the peeling performance is not greatly affected even after 48 hours. Therefore, when a diamine is used together with a cyclic amine that reduces the peeling performance for a resist film whose composition has changed significantly, an increase effect on the peeling performance can be observed.

Experimental Example 4
The degree of corrosion of each of the metal films of Examples 1 to 8, Reference Examples 1 to 12, and Comparative Examples 1 and 2 was evaluated with the specimen 1. Moreover, in order to make the difference of each example remarkable, it evaluated by adding 3% of water, and the result was shown in Table 5.

Note) In Table 5, the degree of corrosion: ◎ (not corroded at all), ○ (slightly corroded), △ (considerably corroded), × (completely corroded)
From the results of Table 5 above, the corrosion of each metal film of the examples of the present invention shows a result superior to that of the comparative example due to the use of the diamine compound, and the cyclic amine or chain is more than when the diamine is used alone. When both the amine and the diamine were used, more excellent corrosion prevention performance was shown.

  In addition, even when diamine or the like was added to assist some resist removing power, the corrosion prevention performance was not affected, and all showed excellent results. That is, even if only one type of corrosion inhibitor is used, all the metal films have excellent results, and even when two types of amines are added, an increase effect that can take advantage of each advantage is observed.

  In addition, hydroxyl phenolic antioxidants selected as corrosion inhibitors show excellent corrosion inhibition performance against aluminum or molybdenum, which is selectively adsorbed on aluminum or molybdenum by physicochemical adsorption. It is presumed to obstruct the flow of electrons. Similarly, mercapto corrosion inhibitors not only chemically adsorb to the copper surface, but also suppress the galvanic phenomenon by overcoming the potential difference with the underlying film by lowering the redox potential. To do.

Claims (7)

a) 1 to 20% by weight of one or more diamine compounds selected from compounds represented by the following chemical formula 1,
b) 10 to 90% by weight of a glycol ether compound, and c) a polar solvent in the balance,
The polar solvent is N-methyl-2-pyrrolidone (NMP), N-methylacetamide, N, N-dimethylacetamide, acetamide, N-ethylacetamide, N, N-diethylacetamide, formamide, N-methylformamide, N , N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, and one or more selected from the group consisting of N, N-dimethylimidazole,
The composition comprises 1- (2-hydroxyethyl) piperazine, N- (3-aminopropyl) morpholine, 1- (2-aminoethyl) piperazine, and 1- (2-hydroxyethyl) -4-ethylpiperazine, One or more cyclic amine compounds selected from the group consisting of 4-amino-1-methylpiperazine, 1-methylpiperazine, 2-methylpiperazine, 1-benzylpiperazine, and 2-phenylpiperazine, or monoethanolamine, One or more chains selected from the group consisting of monoisopropanolamine, diethanolamine, triethanolamine, n-methylethanolamine, n-ethylethanolamine, dimethylethanolamine, diethylethanolamine, aminoethoxyethanol, and aminomethoxyethanol State The emission compound, resist removing composition characterized in that it further comprises 0.5 to 20 parts by weight per 100 parts by weight of the composition.
[Chemical Formula 1]

In the above formula, R and R ′ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ″ is hydrogen, an alkanol having 1 to 10 carbon atoms, or an alkyl having 1 to 10 carbon atoms. It is a group. The diamine compound includes 2-[(2-aminoethyl) amino] ethanol , 1 -[(2-aminoethyl) amino] -2-propanol, 2-{[2- (methylamino) ethyl] amino} ethanol, It is at least one selected from the group consisting of 2-[(2-amino-2-methylpropyl) amino] ethanol and 2-{[2- (dimethylamino) ethyl] methylamino} ethanol. The composition for removing a resist according to claim 1.   The glycol ether compounds include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol propyl ether, triethylene glycol butyl ether, triethylene glycol ethyl ether, and triethylene glycol. The resist removal composition according to claim 1, wherein the composition is one or more selected from the group consisting of methyl ether.   The polar solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-methylformamide, N-methylacetamide, and N, N-dimethylacetamide. The resist removal composition according to claim 1.   The resist removal composition according to claim 1, wherein the composition further comprises a corrosion inhibitor in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the composition.   The corrosion inhibitor is selected from the group consisting of mercaptobenzimidazole, mercaptomethylbenzimidazole, mercaptomethylimidazole, hydroxypyridine, dihydroxypyridine, methyltrihydroxybenzoate, pyrocatechol, catechol, L-ascorbic acid, and D-isoascorbic acid. The resist removal composition according to claim 5, wherein the composition is one or more selected.   The said corrosion inhibitor is at least one selected from the group consisting of mercaptomethylimidazole, methyltrihydroxybenzoate, pyrocatechol, L-ascorbic acid, and D-isoascorbic acid. A composition for removing a resist as described in 1.