STRIPPER COMPOSITION FOR REMOVING PHOTORESIST AND STRIPPING METHOD OF PHOTORESIST USING THE SAME

Abstract

This invention relates to a stripper composition for removing photoresist that may have excellent photoresist stripping force, inhibit corrosion of the under metal film in the stripping process, and effectively remove oxide, and a method for stripping photoresist using the same.

Claims

1. A stripper composition for removing photoresist comprising at least two amine compounds; an aprotic solvent selected from the group consisting of an amide compound in which nitrogen is substituted with one or two C1-5 linear or branched alkyl groups, a sulfone compound, a sulfoxide compound; and a combination thereof; a protic solvent; and a corrosion inhibitor, wherein the at least two amine compounds comprise a) a tertiary amine compound; and b) one or more amine compounds selected from the group consisting of a cyclic amine compound, a primary amine compound and a secondary amine compound, and a weight ratio of a) the tertiary amine compound and b) the one or more amine compounds is 1:0.05 to 1:0.8.

2. The stripper composition for removing photoresist according to claim 1, wherein the at least two amine compounds comprise a) the tertiary amine compound and b) the secondary amine compound; a) the tertiary amine compound, and b) the cyclic amine compound and the primary amine compound; or a) the tertiary amine compound, and b) the cyclic amine compound and the secondary amine compound.

3. The stripper composition for removing photoresist according to claim 2, wherein a weight ratio of the cyclic amine compound and the primary amine compound is 1:1 to 1:10; or a weight ratio of the cyclic amine compound and the secondary amine compound is 1:1 to 1:10.

4. The stripper composition for removing photoresist according to claim 1, wherein the stripper composition has copper oxide removal force of a cleaned substrate surface of 0.35 or less, and wherein the copper oxide removal force is measured by the following Formula 1 using XPS(X-ray photoelectron spectroscopy), after dipping the substrate on which copper is deposited with the stripper composition and cleaning the substrate with distilled water:
Cu Oxide removal force=Quantified number of XPS narrow scan O(Oxygen)after stripping a substrate with the stripper composition for removing photoresist/Quantified number of XPS narrow scan Cu(copper)after stripping a substrate with the stripper composition for removing photoresist  [Formula 1].

5. The stripper composition for removing photoresist according to claim 1, wherein the at least two amine compounds are included in the amount of 0.1 to 10 wt %, based on the total weight of the stripper composition.

6. The stripper composition for removing photoresist according to claim 1, wherein the tertiary amine compound comprises one or more compounds selected from the group consisting of methyl diethanolamine(MDEA), N-butyldiethanolamine(BDEA), diethylaminoethanol(DEEA), and triethanolamine(TEA).

7. The stripper composition for removing photoresist according to claim 1, wherein the primary amine comprises one or more compounds selected from the group consisting of (2-aminoethoxy)-1-ethanol(AEE), aminoethyl ethanol amine(AEEA), isopropanolamine(MIPA) and ethanolamine(MEA).

8. The stripper composition for removing photoresist according to claim 1, wherein the secondary amine comprises one or more compounds selected from the group consisting of diethanolamine(DEA), triethylene tetraamine(TETA), N-methylethanloamine(N-MEA), and diethylene triamine(DETA).

9. The stripper composition for removing photoresist according to claim 1, wherein the cyclic amine comprises one or more compounds selected from the group consisting of 1-imidazolidine ethanol, 4-imidazolidine ethanol, hydroxyethylpiperazine(HEP) and aminoethylpiperazine.

10. The stripper composition for removing photoresist according to claim 1, wherein the amide compound comprises a compound of the following Chemical Formula 1: ##STR00002## in the Chemical Formula 1, R.sub.1 is hydrogen, a methyl group, an ethyl group, or a propyl group, R.sub.2 is a methyl group or an ethyl group, R.sub.3 is hydrogen or a C1 to 5 linear or branched alkyl group, and optionally R.sub.1 and R.sub.3 is may be linked with each other to form a ring.

11. The stripper composition for removing photoresist according to claim 1, wherein the amide compound comprises N,N-diethylformamide, N,N-dimethylacetamide, N-methylformamide, 1-methyl-2-pyrrolidinone, N-formylethylamine, or a mixture thereof.

12. The stripper composition for removing photoresist according to claim 1, wherein the amide compound comprises N-methylformamide or 1-methyl-2-pyrrolidinone.

13. The stripper composition for removing photoresist according to claim 1, wherein the protic solvent comprises one or more selected from the group consisting of alkyleneglycol monoalkylether-based compounds.

14. The stripper composition for removing photoresist according to claim 1, wherein the composition comprises 0.1 to 10 wt % of the at least two amine compounds; 10 to 80 wt % of the aprotic solvent; 10 to 80 wt % of the protic solvent; and 0.01 to 10 wt % of the corrosion inhibitor.

15. A method for stripping a photoresist, comprising a step of applying the stripper composition for removing photoresist of claim 1 to a photoresist formed on a substrate and step for stripping the photoresist from the substrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0101] FIG. 1 is a schematic diagram for explaining film lifting in an insulator film, after stripping and annealing in the previous display manufacturing process.

[0102] FIG. 2 shows (a) FE-SEM image and (b) FIB image regarding film lifting after annealing of an insulator film.

[0103] Hereinafter, the invention will be explained in more detail in the following Examples. However, these examples are presented only as illustrations of the invention, and the invention is not limited thereby.

Example and Reference Example: Preparation of Stripper Composition for Removing Photoresist

[0104] According to the compositions of the following Table 1, components were mixed to prepare each stripper composition for removing photoresist of Examples and Reference Examples. Specific compositions of the prepared stripper compositions for removing photoresist are as described in the following Tables 1 and 2.

[0105] Specifically, the components described in the following Tables 1 and 2 were mixed in a 500 ml beaker to prepare 300 g of a mixture. It was stirred and heated on a hot plate to prepare liquid chemical (stripper composition) under 50° C. temperature condition.

TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 8 9 tertiary MDEA 3 3 3 amine TEA 3 3 3 BDEA 3 3 3 cyclic IDE 0.5 0.5 0.5 amine HEP 0.5 0.5 0.5 AEP 0.5 0.5 0.5 primary AEEA 0.5 0.5 0.5 amine AEE 0.5 0.5 0.5 secondary N- 0.5 0.5 0.5 amine MEA Aprotic NMF 55.00 55.00 55.00 50.00 50.00 50.00 solvent NMP 55.00 55.00 55.00 5.00 5.00 5.00 Protic EDG 40.70 40.70 40.70 solvent MDG 40.70 40.70 40.70 BDG 40.70 40.70 40.70 Corrosion inhibitor 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30

TABLE-US-00002 TABLE 2 Reference Example 1 2 3 4 5 6 tertiary MDEA 3 3 amine TEA 3 3 BDEA 3 3 cyclic IDE 0.5 amine HEP 0.5 AEP 0.5 primary AEEA 0.5 amine AEE 0.5 secondary N-MEA 0.5 amine Aprotic NMF 55.00 55.00 55.00 55.00 55.00 55.00 solvent NMP Protic EDG 41.20 41.20 solvent MDG 41.20 41.20 BDG 41.20 41.20 Corrosion inhibitor 0.30 0.30 0.30 0.30 0.30 0.30 [0106] MDEA: N-methyldiethanolamine (CAS: 150-59-9) [0107] TEA: triethanolamine (CAS: 102-71-6) [0108] BDEA: N-butyldiethanolamine (CAS: 102-79-4) [0109] IDE: 1-imidazolidine ethanol (CAS: 77215-47-5) [0110] HEP: hrdoxyethyl-piperazine (CAS: 103-76-4) [0111] AEP: N-aminoethylpiperazine (CAS: 140-31-8) [0112] AEEA: aminoethylethanolamine (CAS: 111-41-1) [0113] AEE: 2-(2-amino ethoxy) ethanol (CAS: 929-06-6) [0114] N-MEA: N-methylethanolamine (CAS: 109-83-1) [0115] NMF: N-methylformamide (CAS: 123-39-7) [0116] NMP: N-methyl-2-pyrrolidone (CAS: 872-50-4) [0117] EDG: ethyl digylcol (CAS: 111-90-0) [0118] MDG: methyl digylcol (CAS: 111-77-3) [0119] BDG: diethyleneglycol monobutylether (CAS: 112-34-5) [0120] corrosion inhibitor:

[0121] 2,21[(methyl-1H-benzotriazole-1-yl)methyl]imino]bisethanol(2,21[(Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, CAS: 88477-37-6), (DEATTA, IR-42)

Comparative Examples 1 to 15: Preparation of Stripper Composition for Removing Photoresist

[0122] According to the compositions of the following Tables 3 and 4, components were mixed to prepare each stripper composition for removing photoresist of Comparative Examples. Specific compositions of the prepared stripper compositions for removing photoresist are as described in the following Tables 3 and 4.

[0123] Specifically, the components as described in the following Tables 3 and 4 were mixed in a 500 ml beaker to prepare 300 g of a mixture. It was stirred and heated in a hot plate to prepare liquid chemical (stripper composition) under 50° C. temperature condition.

TABLE-US-00003 TABLE 3 Comparative Example 1 2 3 4 5 6 7 8 9 tertiary MDEA 3.5 amine TEA 3.5 BDEA 3.5 cyclic IDE 3.5 amine HEP 3.5 AEP 3.5 primary AEEA 3.5 amine AEE 3.5 secondary N- 3.5 amine MEA Aprotic NMF 55.00 55.00 55.00 55.00 55.00 55.00 55.00 55.00 55.00 solvent NMP Protic EDG 41.20 41.20 41.20 solvent MDG 41.20 41.20 41.20 BDG 41.20 41.20 41.20 Corrosion 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 inhibitor

TABLE-US-00004 TABLE 4 Comparative Example 10 11 12 13 14 15 Tertiary MDEA 3 3 3 5 3 amine TEA 3 BDEA cyclic IDE 0.5 3 amine HEP 0.05 AEP primary AEEA amine AEE 5.5 1 1 secondary N-MEA 3 0.04 amine Aprotic NMF 55.00 55.00 55.00 solvent NMP 55.00 33.99 35.98 Protic EDG 50 30 solvent MDG 35.7 BDG 43.7 41.20 43.7 Corrosion inhibitor 0.3 0.30 0.30 0.30 0.01 MTBT 0.01 0.01 HMDM 10 Deionized water 30 [0124] MDEA: N-methyldiethanolamine (CAS: 150-59-9) [0125] TEA: triethanolamine (CAS: 102-71-6) [0126] BDEA: N-butyldiethanolamine (CAS: 102-79-4) [0127] IDE: 1-imidazolidine ethanol (CAS: 77215-47-5) [0128] HEP: hydroxyethyl-piperazine (CAS: 103-76-4) [0129] AEP: N-aminoethylpiperazine (CAS: 140-31-8) [0130] AEEA: aminoethylethanolamine (CAS: 111-41-1) [0131] AEE: 2-(2-amino ethoxy) ethanol (CAS: 929-06-6) [0132] N-MEA: N-methylethanolamine (CAS: 109-83-1) [0133] NMF: N-methylformamide (CAS: 123-39-7) [0134] NMP: N-methyl-2-pyrrolidone (CAS: 872-50-4) [0135] EDG: ethyl diglycol (CAS: 111-90-0) [0136] MDG: methyldiglycol (CAS: 111-77-3) [0137] BDG: diethyleneglycol monobutylether (CAS: 112-34-5) [0138] corrosion inhibitor: 2,21[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, CAS: 88477-37-6), (DEATTA, IR-42) [0139] MTBT: 4-methyl-4,5,6,7-tetrahydro-1H-benzo[1,2,3]triazole [0140] HMDM: 4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane

Experimental Example: Measurement of Properties of Stripper Compositions for Removing Photoresist Obtained Examples and Comparative Examples

[0141] The properties of the stripper compositions obtained in Examples and Comparative Examples were measured as follows, and the results were shown in Tables.

[0142] 1. Evaluation of Stripping Force [0143] (1) Preparation of Substrate for Evaluation

[0144] First, on a 100 mm×100 mm glass substrate on which a copper-containing thin film was formed, 3.5 m of a photoresist composition(product name: JC-800) was dropped, and the photoresist composition was coated at 400 rpm for 10 seconds in a spin coater. The glass substrate was mounted on a hot plate, and hard-baked under very serious conditions of temperature of 170° C. for 20 minutes to form photoresist. The glass substrate on which the photoresist was formed was air cooled at room temperature, and then, cut to a size of 50 mm×50 mm, thus preparing a sample for the evaluation of stripping force.

[0145] (2) Evaluation of Stripping

[0146] 300 g of each stripper composition obtained in Examples and Comparative Examples was prepared, and while raising the temperature to 50° C., the above prepared substrate was dipped with the stripper composition for 60 to 600 seconds.

[0147] After the dipping, the substrate was taken out and cleaned with tertiary distilled water for 30 seconds, which process was repeated three times, and dried with air gun.

[0148] Using an optical microscope, a time when the residual photoresist disappeared in the cleaned sample was confirmed to evaluate stripping force (unit: sec).

[0149] The stripping force of each stripper composition of Examples and Comparative Examples was evaluated as explained above, and the results were shown in the following Tables 5 to 7.

TABLE-US-00005 TABLE 5 Example Reference Example 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 Stripping 240 240 240 240 240 240 240 240 240 240 240 240 300 300 300 time (sec)

TABLE-US-00006 TABLE 6 Comparative Example 1 2 3 4 5 6 7 8 9 Strip- 420 420 420 240 240 240 300 300 300 ping time (sec)

TABLE-US-00007 TABLE 7 Comparative Example 10 11 12 14 15 Striping time 300 360 240 360 420 (sec)

[0150] As shown in the Tables 5 to 7, it was confirmed that the stripper compositions of Examples comprising two or more kinds of amine compounds with specific combinations and ratios exhibit stripping forces equivalent to or more excellent than those of stripper compositions of Comparative Examples and Reference Examples.

[0151] Namely, it was confirmed that in Examples 1 to 9 and Reference Examples 1 to 3, since a tertiary amine is basically included, and a cyclic amine is included together, or a cyclic amine and a primary or a secondary linear amine are included together, stripping forces were improved compared to Comparative Examples. And, in Reference Examples 4 to 6, a small amount of a primary linear amine or secondary linear amine was included together with a tertiary amine, thus exhibiting stripping forces equivalent to those of Comparative Examples.

[0152] However, although the results of Reference Examples 1 to 6 were better than the results of Comparative Examples, striping forces were inferior compared to Examples 1 to 9. Namely, even if a tertiary amine and other kinds of amines are included, unless the specific combination and ratio of amines as disclosed herein are satisfied, stripping force of the photoresist composition cannot be improved.

[0153] On the other hand, Examples 1 to 9 generally exhibit stripping forces equivalent to or more excellent than those of Comparative Examples and Reference Examples.

[0154] 2. Evaluation of Cu Oxide Removal

[0155] (1) Preparation of substrate for evaluation

[0156] A glass substrate on which copper (no pattern) was deposited was prepared with a size of 5 cm×5 cm.

[0157] (2) Evaluation of copper oxide removal

[0158] 300 g of each stripper composition obtained in Examples and Comparative Examples was prepared, and while raising the temperature to 50° C., the above prepared substrate was dipped with the stripper composition for 60 seconds.

[0159] After the dipping, the substrate was taken out and cleaned with tertiary distilled water for 30 seconds, and then, dried with air gun.

[0160] Using XPS(X-ray photoelectron spectroscopy), copper oxide removal force on the copper surface of the cleaned sample was evaluated.

[0161] Specifically, C, Cu, 0 were XPS narrow scanned to quantify the elements, and then, 0/Cu was calculated, and it was compared with 0/Cu ratio after photoresist strip in the specimen. (The smaller the 0/Cu ratio, the better the Cu oxide removal rate.)

Cu Oxide removal force=quantified number of XPS narrow scan O(Oxygen)after stripping the sample with the stripper composition for removing photoresist/quantified number of XPS narrow scan Cu(copper)after stripping the sample with the stripper composition for removing photoresist  [Formula 1-1]

[0162] As explained above, copper oxide removal force of each stripper composition of Examples and Comparative Examples was evaluated, and the results were shown in the following Tables 8 to 10.

TABLE-US-00008 TABLE 8 Example Reference Example 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 O/Cu 0.23 0.22 0.23 0.23 0.23 0.22 0.23 0.22 0.23 0.55 0.56 0.54 0.35 0.37 0.34 Ratio

TABLE-US-00009 TABLE 9 Comparative Example 1 2 3 4 5 6 7 8 9 O/Cu 0.61 0.62 0.61 0.55 0.56 0.54 0.41 0.39 0.40 Ratio

TABLE-US-00010 TABLE 10 Comparative Example 10 11 12 14 15 O/Cu 0.42 0.53 0.40 0.62 0.64 Ratio

[0163] As shown in the Tables 8 to 10, the stripper compositions of Examples comprising two or more kinds of amine compounds with specific combinations and ratios exhibited excellent Cu oxide removal rate, compared to the stripper compositions of Comparative Examples and Reference Examples.

[0164] Namely, in the case of Comparative Examples 1 to 9 wherein a primary, secondary or tertiary amine or a cyclic amine is included alone, Cu oxide removal rates were generally inferior to Examples. And, in the case of Comparative Examples 10 to 12 wherein a primary, secondary amine or a cyclic amine is additionally included together with a tertiary amine but the specific content ratio as disclosed herein is not satisfied, Cu oxide removal rates were inferior to Examples. And, in the case of Comparative Examples 14 to 15 wherein deionized water or oxolane compound is included, Cu oxide removal rates were inferior and metal corrosion was caused.

[0165] Particularly, it was confirmed that compared to the stripper compositions of Comparative Examples 1 to 3 wherein only a tertiary amine is included, in the case of Examples 1 to 9 wherein a tertiary amine is basically included and a cyclic and linear amine are included together, Cu oxide removal rates were further improved. And, in the case of Reference Examples 1 to 6 wherein a tertiary amine and a cyclic amine or a linear amine are included at a specific content ratio, the effects were equivalent to or better than the effects of Comparative Examples 4 to 9, but excellent compared to Comparative Examples 1 to 3. However, although Reference Examples 1 to 6 have better results than Comparative Examples, Cu oxide removal rates were inferior compared to Examples 1 to 9. That is, even if a tertiary amine and other kinds of amines are included, unless the specific combination and ratio of amines as disclosed herein are satisfied, Cu oxide removal rate cannot be improved.

[0166] On the other hand, in the case of Examples 1 to 9, compared to Reference Examples as well as to Comparative Examples, equivalent or more excellent stripping forces were generally exhibited.

[0167] Thus, it was confirmed that in the case of Examples 1 to 9 wherein a mixture of a cyclic amine and a primary or secondary amine of specific contents are included together with a tertiary amine, Cu oxide removal rate was very excellent.

[0168] Therefore, the stripper composition of Examples have excellent Cu oxide removal rate, and thus, can solve film lifting defect between Cu/ITO when annealing ITO wiring.

[0169] 3. Evaluation of Corrosion of Copper(Cu)/Molybdenum(Mo) Metal Under Film (Evaluation of Cu/Mo Under-Cut Damage)

[0170] (1) Preparation of substrate for evaluation

[0171] A glass substrate on which copper/molybdenum pattern was formed was prepared with the size of 5 cm×5 cm.

[0172] (2) Evaluation of corrosion of copper/molybdenum metal under film

[0173] 300 g of each stripper composition obtained Examples and Comparative Examples was prepared, and while raising the temperature to 50° C., the substrate was dipped with the stripper composition for 10 minutes.

[0174] After the dipping, the substrate was taken out and cleaned with tertiary distilled water for 30 seconds, and then, dried with air gun.

[0175] Using transmission electron microscope(Helios NanoLab650), the cross-sections of the samples for evaluating corrosion of under films, obtained in Examples, Reference Examples and Comparative Examples, were observed. Specifically, using FIB(Focused Ion Beam), thin specimens of the samples for evaluating corrosion of under film were manufactured, and then, observed at the acceleration voltage of 2 kV, and in order to prevent surface damage of the sample by ion beam during the specimen manufacturing process, TEM thin specimens were manufactured after forming a Pt(platinum) protection layer on the surface of the specimen (Cu layer). As explained above, corrosion of the stripper compositions of Examples,

[0176] Reference Examples and Comparative Examples were evaluated, and the results were shown in the following Tables 11 to 13.

TABLE-US-00011 TABLE 11 Example Reference Example 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 Size <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 (nm) nm nm nm nm nm nm nm nm nm nm nm nm nm nm nm

TABLE-US-00012 TABLE 12 Comparative Example 1 2 3 4 5 6 7 8 9 Size(nm) <20 nm <20 nm <20 nm 280 nm 252 nm 182 nm 312 nm 151 nm 211 nm

TABLE-US-00013 TABLE 13 Comparative Example 10 11 12 14 15 Size(nm) 208 125 186 301 412

[0177] As shown in the Tables 11 to 13, it was confirmed that in the case of the stripper composition of Examples wherein two or more kinds of amine compounds are included with specific combinations and ratios, compared to the stripper compositions of Comparative Examples and Reference Examples, corrosion of Cu/Mo metal under film was decreased, and thus, excellent Cu/Mo under-cut damage evaluation results were confirmed.

[0178] Namely, the stripper compositions of Examples satisfying the weight ratio of a tertiary amine:one or more kinds of amine compounds in the range of 1:0.1 to 1:0.5 comprise relatively small amounts of other amines(a cyclic amine and a primary or secondary linear amine) compared to a tertiary amine, thereby preventing corrosion of Cu/Mo metal under film. And, in the case of Reference Examples, a cyclic amine, and primary or secondary amine are used at a specific ratio in smaller amounts compared to a tertiary amine, thereby improving corrosion of Cu/Mo metal under film compared to Comparative Examples.

[0179] Specifically, in the case of Examples 1 to 9 and Reference Examples 1 to 3, since a tertiary amine is basically included, and a cyclic amine is included together, or a cyclic amine and a primary or secondary linear amine are included together, stripping forces were improved. And, in the case of Reference Examples 4 to 6, since a secondary linear amine or primary linear amine is included together with a tertiary amine, stripping forces equivalent to those of Comparative Examples were exhibited.

[0180] However, although Reference Examples 1 to 6 exhibited equivalent corrosion compared to Examples 1 to 9, stripping force and Cu oxide removal rate of the photoresist composition could not be improved as explained above.

[0181] And, the stripper compositions of Comparative Examples 4 to 9 have increased contents of a primary, secondary amine or cyclic amine, and thus, Cu/Mo under-cut size increased, and corrosion was inferior. Wherein, in the case of Comparative Examples 1 to 3 wherein only a tertiary amine is included in the stripper composition, Cu/Mo under-cut size was similar to those of Examples, but stripping force and Cu oxide removal rate were inferior. And, in the case of Comparative Examples 10 to 12 wherein, a primary, secondary amine or cyclic amine is additionally included together with a tertiary amine, but the specific content ratio as disclosed herein is not satisfied, the results were inferior. And, in Comparative Examples 14 to 15 wherein deionized water or oxolane compound is included, corrosion of Cu/Mo metal under film was caused to the contrary.

[0182] From these results, it can be confirmed that the stripper compositions of Examples have very excellent capability of preventing corrosion of Cu/Mo metal under film.