WO2005109108A1

WO2005109108A1 - Composition for removing a (photo) resist

Info

Publication number: WO2005109108A1
Application number: PCT/KR2005/001327
Authority: WO
Inventors: Byung-Uk Kim; Suk-Il Yoon; Seong-Bae Kim; Wy-Yong Kim; Suk-Chang Jang; Jong-Hyun Jeong
Original assignee: Dongjin Semichem Co., Ltd.
Priority date: 2004-05-07
Filing date: 2005-05-06
Publication date: 2005-11-17
Also published as: KR101167240B1; TW200536836A; CN1950755B; TWI385159B; CN1950755A; WO2005109108A8; JP2007536566A; KR20060045957A

Abstract

The present invention relates to a photoresist remover composition used in making circuit or display device patterns, more particularly to a photoresist remover composition containing amine, solvent and anticorrosive agent, the anticorrosive agent being at least one compound selected from a group consisting of triazole compounds, mercapto compounds, organic phenol compounds containing a hydroxyl group, and a mixture thereof. The photoresist remover composition of the present invention can easily and quickly remove a resist film and can minimize corrosion of the patterned metallic circuitry.

Description

DESCRIPTION Invention Title COMPOSITION FOR REMOVING A (PHOTO)RESIST

Technical Field The present invention relates to a removing composition for removing resists in a photo-lithography process. More particularly, the present invention relates to a removing composition which can minimize corrosion of the metallic circuitry during the resist removal process when it is used for the process of patterning the metallic circuitry and has an excellent ability to remove resist. Background Art Photo-resist is an essential material used in the photo-lithography process, and the photo-lithography process is one of the general processes used to manufacture semiconductor devices such as integrated circuits (IC), large scale integration (LSI), very large scale integration (VLSI) and image display devices such as liquid crystal displays (LCD) and plasma display devices (PDP). However, when resist is eliminated by removal solution at high temperatures after photo-lithography processing, problems can arise where the removal solution quickly corrodes the underlying metal substrate at high temperature. That is, the degree of corrosion of the metallic circuitry can be accelerated by the resist removal solution. A removal solution to avoid this problem has been suggested in USP No. 5,417,877 and USP No. 5,556,482. In the method previously proposed in those patents, a remover composition consisting of a mixture of amide compound and organic amine with added anti-corrosive agents was used to prevent the corrosion of copper on the metal wire, where the preferred amine is specified to be monoethanolamine as the organic amine. The appropriate dose of anticorrosive agents is also introduced where the capacity to remove the photo-resist film decreases when exceeding this dose. Primary or secondary amines such as monoethanolamine and methylethanolamine have conventionally been used as the amine component of the resist remover. However, because of the low boiling point of such open chain amines, their composition is unstable, so that there is the inconvenience of having to regularly replace the whole removal solution during the treatment process due to a change in weight and composition after a certain period of time caused by their volatility. DISCLOSURE Technical Problem It is an objective of the present invention to provide a resist remover composition that has an excellent ability to remove resist film, and that does not corrode the metallic circuitry when removing the resist film used in patterning process of metallic circuitry or displays. Technical Solution To attain this objective, the present invention provides a resist remover composition containing amine, solvent, and anticorrosive agent. The anticorrosive agent is one or more compounds selected from the group consisting of triazole group compounds, mercapto group compounds, benzens having a hydroxyl group, and a mixture thereof. Preferably, the amine is a cyclic amine compound and solvent is protonic polar solvent, aprotonic polar solvent, or a mixture thereof. Preferably, the resist remover composition contains 0.5 to 10 parts by weight of the anticorrosive agent based on 100 parts by weight of a mixture containing 5 to 30 wt% of the cyclic amine and 70 to 95 wt% of the protonic polar solvent. Also, the resist remover composition of the present invention can contain 0.5 to 10 parts by weight of the anticorrosive agent based on 100 parts by weight of a mixture containing 5 to 30 wt% of the cyclic amine and 70 to 95 wt% of an aprotonic polar solvent. Preferably, the resist remover composition contains 0.5 to 10 parts by weight of the anticorrosive agent based on 100 parts by weight of a mixture containing 5 to 30 wt% of the cyclic amine, 70 to 95 wt% of the protonic polar solvent, and 15 to 70 wt% of the aprotonic polar solvent. Advantageous Effects The resist remover composition of the present invention minimizes the corrosion of the metal layer under the resist, and has the effect of completely removing and washing away resist, while providing stability to the process due to little change in the composition by volatilization during heating. BEST MODE Hereinafter is given a detailed description of the present invention. It was discovered that utilization of amine and solvent which doesn't have an effect on corrosion of metal wire prevents corrosion of the bottom film due to Galvanic coupling with the upper metal film and eliminates resist effectively at the same time. However, amine which doesn't typically corrode metal wire acutely corrodes single film when mixed with 01. to 3 wt% water, and corrodes the upper and lower layers in double film layers through Galvanic coupling. And even when water is not mixed in the resist remover composition, corrosion by Galvanic coupling occurs if it is not washed after the exfoliation process with an alcohol such as isopropyl alcohol. Therefore, the present invention is characteristic in that a small amount of an anticorrosive agent. The resist remover composition can minimize corrosion of the metallic circuitry during the resist removal process when it is used for the process of patterning the metallic circuitry and has an excellent ability of resist removal. The resist remover composition of the present invention comprises amine, solvent, and anticorrosive agent for prevention of corrosion by the small amount of water contained therein. The anticorrosive agent that are compounds that contain -N-, -S-, -O- and other such elements which have a pair of non-covalent electrons are effective at prevention of corrosion, and in particular, ability of -OH, -SH groups in prevention of corrosion by physical or chemical adsorption to metals is excellent. The anticorrosive agent is one or more compounds selected from the group consisting of triazole group compounds, mercapto group compounds, benzenes having hydroxyl group, and a mixture thereof. As a preferable example, the anticorrosive agent can be one or more compounds selected from the group consisting of mercaptobenzimidazol, mercaptomethylimidazol, hydroxypyridine, dihydroxypyridine, methyl trihydroxybenzoate, tolyl triazole, benzotriazole, and carboxylic benzotriazole. Here, the present invention can maximise the efficacy of corrosion prevention by selectively using an anticorrosive agent for particular metal wire. The triazole group has a good ability of preventing corrosion for all metal wire, mercapto group has good ability for Cu, Mo, benzene group having hydroxyl group has good ability for Cu and Al. The anticorrosive agent of the triazole group is suitable for the formation of oxidation film, decreasing the oxygen at the surface of Cu or Al, and preventing transfer of proton by chemical adsorption to the oxidation film. In the case of mercapto group, the anticorrosive agent can prevent Galvanic coupling by lowering the oxidation-reduction potential, as well as chemically adsorb to the surface of Cu. The resist remover composition can contain 0.5 to 10 parts by weight of the anticorrosive agent based on100 parts by weight of a mixture of cyclic amine and solvent. If the content of the anticorrosive agent is below 0.1 parts by weight, the metal wire is corroded beyond control. Otherwise, if it exceeds 10 parts by weight, the ability of removal decreases and it is difficult to properly wash away due to strong adsorption of the anticorrosive agent to the substrate plate. Preferably, the composition of the present invention is a two or three- component composition of protonic polar solvent or aprotonic polar solvent individually or a mixture of one or more thereof. A preferable example is where resist removing composition of the present invention is a two-component compound containing the cyclic amine and protonic polar solvent, or it can be a two-component compound containing the cyclic amine and aprotonic polar solvent. It can also be a three-component compound containing the cyclic amine and both protonic polar and aprotonic polar solvents. Being strongly alkaline, this amine compound could cause to break the attractive force in intra or inter-molecules by penetrating the cross-linked resist polymer matrix transformed under various processes such as dry etching or wet etching, and ashing or ion implant processing. This reaction caused by amine compound helps to remove resist attached onto the substrate plate by transforming the remaining resist to an amorphous polymer gel mass by forming empty internal space in structurally weak areas of the resist. Preferably, the present invention uses cyclic amine which has high boiling point so that it does undergo significant changes in its weight or composition, and shows similar removal ability of previous open chain amines, and can be utilized for longer during the treatment process. The cyclic amine compounds can be one or more compound selected from the group consisting of in [Chemical formula 1] below. Chemical formula 1

(Wherein A is O or N, R₁ is C₁ to C₅alkyl, or C₁ to C₅allyl, R₂ and R₃ are each independently or simultaneously C-, to C₅alkyl, d to C₅ allyl, C-i to C₅ alkyl amino, C-i to C₅ hydroxyl alkyl (alkyl alcohol), or d to C₅ alkyl benzene.) Preferably, the cyclic amine is a piperazine group or a morpholine group compound. More preferably, the cyclic amine compounds is one or more compounds selected from the group consisting of 1-(2-hydroxyethyl)piperazine (1-1 ), 1-(2- aminoethy piperazine (1-2), 1-(2-hydroxyethyl)-4-methylpiperazine (1-3), and N-(3- aminopropyl)morpholine (1-4), 2-methylpiperazine (1-5), 1-methylpiperazine (1-6), 1-amin^'o-4-methylpiperazine (1-7), 1-benzylpiperazine (1-8), and 1- phenylpiperazine (1-9). The basicity of the compounds is as shown in table 1 below. Table 1

05/109108

We can predict the removal-ability of these cyclic amine compounds by its basicity. The corrosive property is significantly improved compared with open chain amines, although it varies depending on the substitution of the remaining two hydrogens bonded to nitrogen of the amine compound. 1(-2-aminoethyl)piperazine, a cyclic amine, contains primary, secondary, and tertiary amine in one structure, and the groups affecting corrosion and exfoliation are the primary and secondary amines. Thus 1 (-2-aminoethyl)piperazine is worse in terms of corrosion and exfoliation than other cyclic amines, but better than open chain amines. During the removal process at high temperature, using a cyclic amine with a boiling point above 200 °C can minimize the change in removal ability due to composition change. This cyclic amine does not volatilize much so that it maintains its initial composition. In the present invention, it is preferable for both two-component and three- component compositions to contain 5 to 30 wt% of the total composition, because if the content of amine is below 5 wt%, the resist-removal ability decreases. If the content of amine exceeds 30 wt%, the corrosion problem can become worse. The protonic polar solvent is preferably one or more glycolether compounds selected from the group consisting of ethyleneglycol methylether, ethyleneglycol ethylether, ethyleneglycol butylether, diethyleneglycol methylether, diethyleneglycol ethylether, diethyleneglycol butylether, and diethyleneglycol propylether. However, simple alkyleneglycol compound without ether bonds causes corrosion with tiny holes on the copper surface. To prevent this problem, it is best to use the glycolether solvent with boiling point above 180 ^°C and almost unlimited solubility in water. Diethyleneglycol methylether, diethyleneglycol butylether, and diethyleneglycol ethylether would be most appropriate. During the removal process at high temperature, using glycolether solvent with boiling point above 180 °C could minimize the change in removal ability due to change in composition. This glycolether solvent does not volatilize much so that it maintains its initial composition. Thus, it maintains the ability to remove resist throughout the whole process. Also, the glycolether solvent with boiling point above 180 ^°C can improve removal efficacy of resist because of its low surface force on metal film layer and resist, and due to its low freezing point and high combustion point, it is more stable during storage. In the case of two-component compositions, it is preferable to use the protonic polar solvent with 70 to 95 wt% of total composition. If the content is below

70 wt%, corrosion occurs excessively because of the increase of amine content, and removal performance declines if the content exceeds 95 wt%. For three-component compositions, it is preferable to use the protonic polar solvent at 10 to 80 wt%. Below 10 wt %, the weight percentage of aprotonic polar solvent and amine compound is relatively increased, which causes excessive corrosion of metal wire and decreases the resist removal ability because of the deficiency in ability to dissolve the polymer gel created by the amine compound and aprotonic polar solvent. Moreover, the present invention establishes the role of aprotonic polar solvent to dissolve exfoliated high polymer gel mass into unit molecules. Especially, it can prevent re-adhesion of removed resist that commonly occurs during the washing process. Polar solvent with amine as the functional group like N-methyl-2- pyrrolidone assists the amine compound penetrate and remove resist. The aprotonic polar solvent is one or more compounds selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- dimethyformamide, and N,N-dimethylimidazole. For the case of two-component composition, it is appropriate to have a content of protonic polar solvent that is 70 to 95 wt% of the total composition. If the content is below 70 wt%, corrosion occurs excessively because of the increase of amine constituent, and removal performance diminishes under the condition of its content over 95 wt%. Otherwise, for three component composition, the content of protonic polar solvent would preferably be 15 to 70 wt% of the total composition. Its content less than 15 wt% would decrease the resist removal ability. If it exceeds 70 wt%, metal wire is excessively corroded, and its potential to remove and wash resist decreases because of the relative decrease in weight % of glycolether, a protonic polar solvent. As described above, the present invention defines composition comprising cyclic amine for resist removal during use in photo-lithography, which shows excellent ability to remove resist and minimize the problem of patterned metal wire corrosion.

Mode for Invention The present invention is described in more detail through examples and comparisons that follow. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the Examples below, percentage or mixture ratio is weight based, unless otherwise noted. <Examples> The purpose of Experiment 1 and 2 is to select proper amine and glycolether solvent, a protonic polar solvent. The test sample is described below. First, to evaluate the corrosion of metal by the solvents, after coating with 2000 A aluminum, molybdenum, and copper, the developed glass after coating with resist was used as a specimen. Second, to estimate ability of resist removal, the specimen, n+a-Si:H active film, was prepared with glass coated with Chrome which after spreading resists underwent wet etching then treated with dry etching gas. Chrome maximizes adhesive strength of resist, and dry etching gas transforms resist into a form that is difficult to remove with removal solution. Thus, the specimen is suitable for testing the ability of resist removal. <Experiment 1> The result of testing resist removal and corrosion of aluminum, molybdenum, and copper for each solvent is described below in Table 2

Table 2

In Table 2 above, * resist removal © (complete removal of resist) O (low level of residual resist), Δ (a high level of residual resist), x (no removal of resist) *corrosion © (no corrosion), O (slight corrosion), Δ (severe corrosion), x (complete corrosion) As presented above in Table 2, monoethanol amine shows severe corrosion of metal while cyclic amines cause less corrosion of metal and removes resist just as well. Substitution of all hydrogens bonded to nitrogen of cyclic amine structures with alkyl, benzyl, or alcohol groups shows superior prevention of corrosion but lower removal ability. <Experiment 2> As shown in Table 3, typically-used monoethanol amine and amines used in this present invention were tested for corrosion rate of metal. As individual tests showed a small amount of corrosion of every metal, the same solution comprising 45 wt% of glycolether, 45 wt% of polar solvent and 10 wt% amine was used for all cases. Table 3

In Table 3 above, © (no corrosion), O (slight corrosion),

Δ (severe corrosion), x (complete corrosion) As shown in Table 3, compared to previously used monoethanal amine, cyclic amines were better in terms of corrosion for aluminum and molybdenum. For copper, the more substitution of the hydrogens bonded to nitrogen in cyclic amine structure for other functional group, the better it was in terms of corrosion. Experiment 3 and 4 were carried out to estimate which component of resist remover affects removal ability and corrosion of metal wire. The specimens for these experiments are prepared as follows. Specimen for Experiment 3 (1) Apply DTFR-3650B(Dongjin Semichem, positive resist) on glass, and then remove resist after baking at 170 °C, 25min. Size of specimen is 2cm X 4cm Specimen for Experiment 4 (2) Apply aluminum, molybdenum, and copper on the glass plate with 2000 A thickness. Size of specimen is 2cm x 4cm With the prepared specimen above, the experiment was performed with 31 different compositions of removal solution. Table 4

Note) In Table 4 above,

HEP : 1-(2-hydroxyethyl)piperazine, AEP: 1-(2-aminoethyl)piperazine

2-MP : 2-methylpiperazine, 1-MP : 1 -methylpiperazine

BP : benzylpiperazine, PP : phenylpiperazine

MMB : mercaptomethylbenzimidazole, MMI : mercaptoethylimidazole

TT : Tolyl triazole, BT : benzotriazole

CBT : Carboxylicbenzotriazole, NMP : n-methyl-2-pyrrolidone

DMAc : dimethylacetamide, DMSO : dimethylsulfoxide

DEGEE : diethyleneglycolethylether,

DEGBE : diethyleneglycolbutylether,

MTHB : methyltrihydroxybenzoate, HP : hydroxypyridine, DHP : dihydroxypyridine <Experiment 3> Examples 1 , 25 and comparative examples 1 , 6 were tests for resist layer removal of specimen 1. Particularly, to test any change in resist removal ability following volatilization, each removal solution was maintained under a condition of forced ventilation at 70 °C for 48 hrs. Table 5 shows the result of specimen (3).

The removal solution was boiled at 70 ^°C. Specimen (1) is soaked and observed visually.

Table 5 Evaluation of removal (1) Classification (1) Soaking for 200 sec Soaking for 200 sec after volatilization for 48hr

Example

10 11 12 13 14 15 16 17 18 19 20

Note) In Table 5, * © (complete removal of resist) O (a low level of residual resist), Δ (a high level of residual resist), x (no removal of resist) In comparative examples, when cyclic amines with low boiling point were kept for 24 hr at 70 ^°C, a significant fall in the ability of removal was observed.

Each anticorrosive does not greatly affect exfoliating performance, and since for all the examples, the boiling point of amine is over 200 ^°C , the exfoliating performance is not changed after volatilizing for 48 hr because the composition is not significantly changed. <Experiment 4> Using Specimen 2, examples 1 to 25 and comparative examples 1 to 6 was tested where 3 parts by weight of pure water was added to a 100 parts by weight of exfoliating solution and maintained at 70 ^°C . Corrosion of metal layer was measured and shown in Table 6 below. Table 6

(complete corrosion) According to the result in Table 6, in the Examples where 1-(2-aminoethyI) piperazine was used, slight corrosion of copper was observed. Although the results are slightly different depending on the type of amine, the results are generally superior in comparison to those of the Comparative Examples. Triazole is effective in preventing corrosion in all metal films according to the test result of Examples containing 1 -(2-hydroxyethyl)piperazine. The chemical structures containing a hydroxyl group such as methyltrihydroxylbenzoate, hydroxylpyridine, dihydroxypyridine give rise to poor results when using the molybdenum method. Anticorrosive agents with a mercapto group give rise to poor results when using the aluminum method. It can be concluded from this result that anticorrosive agents with particular functional groups are exceedingly effective in preventing corrosion of particular metal wires. In particular, even when open chain amines rather than cyclic amines are used, adding an anticorrosive agent improves anti-corrosiveness.. To summarize those test results, triazole such as benzotriazole, tolyl triazole, carboxylic benzotriazole shows good prevention of corrosion of any metal wires. Mercapto compounds such as mercaptomethylbenzimidazole and mercaptomethylimidazole show better corrosion prevention on copper and molybdenum, and benzene ring structures with hydroxyl group such as hydroxypyridine, dihydroxypyridine, methyltrihydroxybenzoate show superior corrosion prevention on copper and aluminum. Therefore, one can maximize the efficacy of the process by using particular anticorrosive agent for particular specific metal wires. While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

WHAT IS CLAIMED IS: 1. A resist remover composition comprising amine, solvent, and anticorrosive agent, wherein the anticorrosive agent is one or more compounds selected from the group consisting of triazole group compounds, mercapto group compounds, benzenes having a hydroxyl goup, and a mixture thereof.

2. The resist remover composition according to Claim 1 , wherein the resist remover composition comprises 0.5 to 10 parts by weight of the anticorrosive agent based on 100 parts by weight of a mixture of amine and solvent.

3. The resist remover composition according to Claim 1 , wherein the amine is one or more compounds selected from the group consisting of cyclic amine compounds having the following Chemical Formula 1 : Chemical Formula 1

Wherein A is O or N, R-i is to C₅ alkyl, or d to C₅ allyl, R₂ and R₃ are each independently or simultaneously C-, to C₅ alkyl, C-i to C₅ allyl, d to C₅ alkyl amino, d to C₅ hydroxyl alkyl (alkyl alcohol), or C-i to C₅ alkyl benzene. 4. The resist remover composition according to Claim 1 , wherein the amine is one or more cyclic amine compounds selected from the group consisting of 1-(2-hydroxyethyl)piperazine,

4-(3-aminopropyl)morpholine, 1- piperazinethanamine(1 -(2-aminoethyl)piperazine), and 1 -(2-hydroxyethyl)- 4-ethylpiperazine.

5. The resist remover composition according to Claim 1 , wherein the amine is 5 to 30 wt% of 100 parts by weight of a mixture of amine and solvent.

6. The resist remover composition according to Claim 1 , wherein the solvent is protonic polar solvent, aprotonic polar solvent, or a mixture thereof.

7. The resist remover composition according to Claim 6, wherein the protonic polar solvent is one or more compounds selected from the group consisting of ethyleneglycol methylether, ethyleneglycol ethylether, ethyleneglycol butylether, diethyleneglycol methylether, diethyleneglycol ethylether, diethyleneglycol butylether, and diethyleneglycol propylether.

8. The resist remover composition according to Claim 6, wherein the aprotonic polar solvent is N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- dimethylformamide, or N,N-dimethylimidazole.

9. The resist remover composition according to Claim 1 , wherein the composition comprises the anticorrosive agent in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of a mixture containing 5 to 30 wt% of cyclic amine and 70 to 95 wt% of protonic polar solvent.

10. The resist remover composition according to Claim 1 , wherein the composition comprises the anticorrosive agent in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of a mixture containing 5 to 30 wt% of cyclic amine and 70 to 95 wt% of aprotonic polar solvent.

11. The resist remover composition according to Claim 1 , wherein the composition comprises the anticorrosive agent in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of a mixture containing 5 to 30 wt% of cyclic amine, 10 to 80 wt% of protonic polar solvent and 15 to 70 wt% of aprotonic polar solvent.