TW200844689A - Photoresist stripper composition - Google Patents

Abstract

Disclosed is a photoresist remover composition which enables to remove a photoresist without corroding Cu or Cu alloy wiring formed on a substrate during a wiring board manufacturing process for FPD. The composition contains 0.05-10% by weight of at least one heterocyclic compound selected from the group consisting of maltol, 2,6-dimethylgammapyrone, 4-hydroxy-6-methyl-2- pyrone, 4-hydroxycoumarin, 2,4-dihydroxyquinoline, 2-amino- 4,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, 4,6-dimethyl-2- hydroxypyrimidine, uracil and 6-methyluracil, 5-45% by weight of a primary or secondary alkanol amine, and 50-94.95% by weight of a polar organic solvent and/or water.

Description

[Technical Field] The present invention relates to a photoresist stripper composition, and more particularly to a flat panel which is suitable for use in a liquid crystal display (hereinafter referred to as lcd). A resist release agent composition excellent in anti-money property and releasability of the Cu alloy wiring board produced by the present invention (also referred to as FpD). [Prior Art] The FPD is based on various display principles such as LCD, LED, EL, VFD, FED, SED, and PDP, and H & For example, in a liquid crystal display, a photoresist is applied to an insulating film such as an A1, Al alloy, Cu, Cu alloy or the like which is formed on a substrate, or an insulating film such as a Si〇2 film, and exposure and development are performed thereon. The resist pattern is formed, and the patterned photoresist is used as a mask. The conductive metal film or the insulating film is subjected to (4), and fine wiring is formed, and then the unnecessary photoresist layer is removed by a stripping liquid. Conventionally, as the photoresist release agent composition, a single solvent such as an organic base, an inorganic base, an organic acid, an inorganic acid or a polar solvent, or a mixed solution thereof is used. Further, in order to improve the repellent property, it is also known to use a mixture of an amine and water. For example, in the liquid crystal display, 帛ai has been widely used as a wiring material. In the patent literature! A photoresist stripper is disclosed, the main component of which is: mercaptoamine or prealcoholamine, and polar organic (tetra) fluorene, and the element constituting the ring is a compound containing a heterocyclic ring composed of a rat and a carbon (4) to prevent Or significantly inhibit the corrosion of A1. 200844689 However, in recent years, in response to the increase in the size of substrates, attempts have been made to use Cu, which has a lower resistivity than A1, and to enter into the Rongshen method as a wiring material. Patent Document 2 discloses that a heterocyclic compound having a five-membered or six-membered heterocyclic ring containing an atomic group consisting of a C(〇H)=N- or -c〇nh-, and a kind of alkoxylated amine Anti-etching 丨 丨 to prevent corrosion of a metal film such as a formed on a semiconductor wafer. The A1 wiring formation step is used for the external corpse/T and the IX or CU or Cu alloy wiring is used in the forming step. > loyalty Kn + t a is used in the first resistance, the photoresist itself is almost the same. However, in the stage where the patterned photoresist is etched as a mask to form fine wiring, since the rot behavior of A1 and CU is completely different, it is necessary to use the Cu or Cu alloy wiring forming step. It is different from the remainder of the μ wiring forming step. In general, an oxidizing agent-based etching solution is used in the step of forming a Cu or Cu alloy wiring. In order to be used as a mask, w„ after the patterning of the light is blocked by the wet engraving, it will be changed due to the residual engraving. Xiang # & —, u , , , and the quality of the k-level or deterioration Depending on the money engraving or the remaining conditions used, the phase μ and + phase are etched into the photoresist layer caused by the etching solution for the A1 wiring forming step, and the oxidizing agent used for the Cu or Cu alloy wiring forming step is produced. It is difficult to peel off the metamorphic film which is very difficult to peel off. Therefore, the peeling liquid used in the wiring forming step is difficult to wire the Cu or Cii alloy without the wiring material. In the above-mentioned Patent Document 1, the yak is removed. The state in which the Cu or Cu alloy wiring is not formed is formed, and the system is difficult to ^^r 乂The Cu or Cu alloy wire is formed in the step of forming the resistive stripping. In addition, the anti-corrosion agent of the manuscript 2 has been considered to be harmful to the Cu corrosion-resistant or low-dielectric film, and the mouth is limited to Semi-conductive 200844689 metal film on the body wafer, Tian μ self-guided...Γ The steps cause the metamorphic film to be caused by the V-body remnant method (such as dry or ashing), and the photoresist required for the FPD process,

^ Even if the ruthenium contains a heterocyclic compound consisting of a C(OH)=N fruit: a group of atoms, it is impossible to exert a c-effect. Patent Document 1: Japanese Patent Laid-Open No. 2 〇〇 1_3 No. 6 Patent Document 2. Japanese Laid-Open Patent Publication No. 2002-97584. SUMMARY OF THE INVENTION This invention is based on the above-mentioned circumstances, and aims to provide a photoresist stripper composition which is not rotted in the wiring substrate process of the coffee. A Cu or Cu alloy wiring on the substrate and capable of stripping the photoresist. As a result of an effort to review the above-mentioned problems, the results show that a heterocyclic compound having a structure of 4 inches of ruthenium and containing an alkanolamine and a polar organic solvent and/or water is used as a photoresist stripper composition. In the Cu or Cu bonding wire forming step, the wiring material is not corroded, and the photoresist layer which is deteriorated by the etching liquid for the Cu or Cl! alloy wiring forming step can be peeled off, and the present invention has been completed. That is, the present invention is a photoresist stripper composition which is used in the CU or Cii alloy wiring forming step of the FPD, and is characterized in that: έ has % maltol, 2,6 dioxin y -π-pyrone, 4_ylamino 6-methylpyranone, 4-hydroxycoumalin, 2,4-one to phthalocyanine, 2-amino-4,6-dihydroxy Pyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2-amino-aminomethylpyrimidine, 4,6-dimethyl-2-hydroxypyrimidine, uracil, 200844689 and 6-methyluracil At least! The heterocyclic compound 〇〇5~ι〇 is a solvent %, a primary or secondary alkanolamine 5 to 45 wt%, and a polar organic and/or water 50 to 94.95 wt%. In the form of the present invention, the -, or a secondary alkoxylated amine is selected from the group consisting of free ethanolamine, diethanolamine, n-propanolamine, monoisopropanolamine, monoethylethanolamine, aminoethoxyethanol, and single At least one of the group consisting of methylethanolamine. In another aspect of the invention, the polar organic solvent is selected from the group consisting of diethylene glycol monobutyl ether, hydrazine-methylpyrrolidone, and dimethyl ethanoamine. According to the present invention, in the wiring board process of the FPD, the photoresist layer which is modified by the etching liquid for the Cumu alloy wiring forming step has excellent photoresist properties. 2) Excellent corrosion resistance to wiring materials, that is, Cu or Cu alloy. Hereinafter, the present invention will be described in detail. [Embodiment] The photoresist stripper composition of the present invention is a step of forming a ruthenium alloy wiring in an FPD. The FPD is not particularly limited, and examples thereof include displays of various principles, and can be suitably applied to, for example, lcd, pDp, VFD, and SED. Examples of the Cu alloy of the Cu or Cu alloy wiring include a low-oxygen Cu alloy, a Cu-X (X is Sn, Zr, Be, pb, M〇, Run, and Bu, etc.) 200844689 alloy, and Cu. 3-Cr alloy such as -Cr_Zr.

The heterocyclic compound used in the present invention is selected from the group of free maltitol, U-diyl-r-r-r-, 4, yl-methyl-2-denyl, 4, coumarin, 6 2, 4_2啥 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 4. More preferably, 2,4_dihydroxyquinoline, 2_amino quinone 6_2%

Pyrimidine, 2,4-diamino -6-hydroxypyrimidine <, and uridine. In this case, only one type of these may be used, or two or more types may be used in combination. The amount of the heterocyclic compound added is 〇5 重 5 % to 10% by weight in the release agent composition. If the amount is less than this range, the effect of prevention is not fully realized. If the addition exceeds this range, the amount of other components added will be reduced, and the corrosion resistance will not be particularly improved. It is preferably 〇 · i by weight % to 5% by weight. The primary or secondary alkanolamines used in the present invention are dry G alcohol amines (MEA), diethanolamine (DEA), n-propanolamine (NpA), monoisopropanol (MIPA), monoethylethanolamine (MEEA). The β-alkanolamines such as the amine ethoxyethanol oxime and the monomercaptoethanolamine (MMEA) may be used singly or in combination of two or more. Among these, at least one selected from the group consisting of amine, n-propanolamine, monoisopropanolamine, and monodecylethanolamine is preferred. The amount of the calcining alcohol fe added is 5% by weight to % by weight of the stripper composition. If the amount is less than this range, the deteriorated photoresist layer cannot be sufficiently peeled off. If it is added beyond this range, the wiring material may be corroded.妒 preferably 10% by weight to 30% by weight. 9 200844689 The polar organic solvent used in the present invention may, for example, be diethylene glycol monobutyl scale (BDG), N-methylpyrrolidone (NMp), dimethylacetamide (DMAC), propylene glycol (PG), Dimethyl sulphate (dms 〇) and so on. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of free diethylene glycol monobutyl sulphate N-methyl σ-succinone and dimethylethenol is preferred. In the present invention, only a polar organic solvent, water alone, or hydrazine may be used in any of a polar organic solvent and water. The amount of the organic solvent and water added is the total amount of 50% by weight to 94.95% by weight of the composition of the peeling sword. If it is less than this range, the wiring material may be corroded or the deteriorated photoresist layer may be peeled off. If it is added beyond this range, the deteriorated photoresist layer may not be sufficiently peeled off. It is preferably from 6% by weight to 90% by weight. The composition of the photoresist stripper of the present invention can be prepared by mixing the amounts of the above components in a usual manner. The photoresist peeling step of the Cii or Cu alloy wiring forming step of the FPD is for peeling off the photoresist after the oxidizing agent-based etching liquid for Cu or Cu alloy wiring formation, according to the wiring formation step of the LCD, and other types of FPD. 'Industry people can also do it properly. The photoresist stripper composition of the present invention can be used (e.g., 30 ° C to 7 Torr). The time required for peeling varies depending on the degree of change of the photoresist, and is generally about 3 sec. to about 1 〇 minutes. Further, the photoresist release agent composition of the present invention can be washed directly without washing with a solvent such as propanol after the release treatment. 200844689 Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to the examples. In addition, in the abbreviations in the table, the following abbreviations are as follows. Other abbreviations are as described above. MDEA · N-methyl-N,N,-diethanolamine EDG: diethylene glycol monoethyl ether Examples 1 to 27, Comparative Examples 1 to 7 According to Table 1, the components were separately mixed to obtain Stripper composition. With respect to each of the obtained release agent compositions, the corrosion state of the wiring material at the time of the photoresist removal step and the corrosion state of the wiring material at the time of water washing were evaluated in the following manner for the corrosion state of the wiring material of the photoresist peeling step and the case of direct water washing after the peeling treatment. Table 2 shows the results of the evaluation. 200844689 Table 1

Amine (% by weight) Solvent (% by weight) Water (% by weight) Heterocyclic compound (% by weight) Example 1 MEA30 BDG69 - Urine 1 Example 2 MIPA30 BDG 69 - urination bit 1 Example 3 NPA30 BDG 69 - Urine 0 close bit 1 Example 4 MMEA 10 BDG 89 - ash feed bit 1 Example 5 MMEA30 BDG 69.9 - Urine VJ Marina 0.1 Example 6 MMEA30 BDG 65 - Urine. dense. Example 5 Example 7 MMEA5 BDG 94.95 - Urine η σ 0.05 0.05 Example 8 MMEA45 BDG 54 - urinary 0 dense.例 1 Example 9 MMEA30 - 69 urinary σ dense TJ fixed 1 Example 10 MEA30 NMP 69 - urine 5 close bit 1 Example 1] i MEA30 DMAC 69 - urinary σ dense 定 1 Example 12 MEA30 BDG 39 30 urine, Bit 1 Example 13 MEA30 BDG 69 - Protol 1 Example 14 MEA30 BDG 69 - 2,6-Dimethyl 7-σ ratio I 1 Example 15 MEA 30 BDG 69 - 4-Phase-6- Methyl-2-12 is the same as 1 and Example 1 MEA30 BDG 69-4 4-Coumarin 1 Example 17 MEA30 BDG 69-2,4-Dihydroxyquinoline 1 Example 18 MEA30 BDG 69 — 2- Amino-4,6-dihydroxypyrimidine 1 Example 19 MEA30 BDG 69-2,4-Diamino-6--mouth bit 1 Example 20 MEA30 BDG 69-2-Amino-4-hydroxy-6- Mercaptopyrimidine 1 Example 21 'MEA 30 BDG 69 — 4,6-Dimethyl-2-borrowed 1 Example 22 MEA30 BDG 69 — 6-曱Urine, 唆1 Example 23 DEA30 BDG 60 — Urine σ密密〇1 Example 24 MEEA30 BDG 69 - Urine 17 Bite 1 Example 25 EEA30 BDG 69 - Urine.密|1定1 Example 26 MEA30 PG 69 - uracil 1 Example 27 MEA30 DMSO 69 - urinary tract 1 Comparative Example 1 MEA5 BDG 95 - - Comparative Example 2 MEA30 BDG 40 30 - Comparative Example 3 ME A 2 BDG 97 - Pee. dense. 1 Comparative Example 4 MEA 50 BDG 49 - urinary thief 1 Comparative Example 5 MEA 30 BDG 69 - 4-amino-6 via 2-thiol 1 Comparative Example 6 MDEA20 EDG 69 50 4,6-di 1 Comparative Example 7 — BDG 100 — — Evaluation 1. Evaluation of the corrosion condition of the wiring material in the Cu corrosion photoresist stripping step during photoresist stripping. When the composition of the stripping agent 12 200844689 is water, the Cu film substrate is attached. Time immersion; The stripping agent of c, when the stripper composition is not containing water, is obtained by immersing the Cu film substrate with a stripping agent for a predetermined period of time, and determining the Cii according to the film thickness reduction of the film. The etching rate (A/min) was evaluated by the following criteria. The evaluation of the corrosion condition of the wiring material in the water washing step after the Cu etching photoresist peeling at the time of washing was performed by immersing the Cu film substrate in water for a predetermined period of time. The peeling agent composition was diluted to a normal temperature test liquid of 10 times, and the etching rate (A/min) of Cu was determined from the amount of decrease in the film thickness of the cu film, and was evaluated by the following criteria. Further, the reason why the agent was diluted 10 times with water was that the peeling agent: water ratio was 1:9, and the corrosion rate of the wiring material was the maximum. The evaluation criteria for the etch rate measurement are as follows. The above is acceptable. The unit is A/min. When peeling, it is less than 2 when it is washed, less than 80 〇: 2 or more, less than 5 80 or more, less than 100 Δ : 5 or more, less than 10 100 or more, less than 120 X : 10 or more 120 or more 3 · Photoresist peeling property The following trace method evaluates the peeling state of the photoresist layer which is deteriorated by the oxidizing agent etching solution. Further, the oblique + h b is not evaluated for the corrosion condition of the wiring material. (1) Method for producing metamorphic film for evaluation 13 200844689 A positive photoresist (NPR3510S1 lOmPa.s, manufactured by Nagase ChemteX Corporation) was coated with 15,000 A on a Shihwa wafer by a spin coater, and prebaked at 100 C for 2 minutes. This is passed through a reticle and exposed and developed to form a resist pattern. The tantalum wafer which had been formed into a photoresist pattern was immersed in an oxidizing agent-based etching solution at 40 ° C for 1 minute to prepare a metamorphic film for evaluation. After washing with water and drying with nitrogen, this was subdivided into evaluation pieces. (2) Peeling evaluation method

The peeling treatment is carried out when the stripper composition contains water, and the stripper composition is in the case where water is not contained, and the sample sheet is immersed for 2 minutes, and the mixture is gently stirred for treatment. After the completion of the routine, the sample was taken out and immediately washed under the microscope. After the 丨 丨 & amp amp amp Λ虱 Λ虱 Λ虱 Λ虱 后 。 。 。 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光The evaluation criteria for peelability are as follows. The above is acceptable. ◎: no photoresist residue

〇 △ X Although the photoresist pattern cannot be seen, the photoresist pattern can be seen faintly. The photoresist pattern can be clearly seen but there is a trace of photoresist residue. 14 200844689 Table 2

Cu etching during peeling peeling Cu etching during water washing Example 1 〇〇 ◎ Example 2 〇〇 ◎ Example 3 〇〇 ◎ Example 4 〇 ◎ ◎ Example 5 〇 ◎ ◎ Example 6 〇 ◎ ◎ Example 7 〇 ◎ 例 Example 8 〇 ◎ ◎ Example 9 〇〇 ◎ Example 10 ◎ 〇 ◎ Example 11 ◎ 〇 ◎ Example 12 ◎ 〇 ◎ Example 13 〇 ◎ ◎ Example 14 〇 ◎ ◎ Example 15 〇 ◎ ◎ Example 16 〇〇 ◎ Example 17 δ ◎ ◎ Example 18 〇 ◎ ◎ Example 19 〇 ◎ ◎ Example 20 〇 ◎ ◎ Example 21 〇〇 ◎ Example 22 〇〇 ◎ Example 23 〇 ◎ ◎ Example 24 〇 ◎ ◎ Example 25 〇 ◎ ◎ Example 26 〇 ◎ ◎ Example 27 ◎ 〇〇 Comparative Example 1 〇 X △ Comparative Example 2 ◎ X △ Comparative Example 3 X -- Comparative Example 4 〇 Δ Δ Comparative Example 5 〇 X △ Comparative Example 6 X - Comparative Example 7 X - - As is clear from Table 2, Examples 1 to 25 were excellent in Cu corrosion resistance, and the peeling property of the photoresist layer which was deteriorated by the oxidizing agent etching liquid was also good. On the other hand, in Comparative Examples 1 and 2 which did not contain the heterocyclic compound used in the present invention, Cu corrosion was observed. Comparative Example 3, in which the content of the alkanolamine was less than the range of the present invention, 15 200844689, the peeling property was poor, and the addition was over the slanting angle. In the case of the human and female a 丄々 之 4 4 4 4 4 4 4 Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu In Comparative Example 5 of the heterocyclic compound of the atomic group, the anti-reduction effect of Cu and the conversion of 5丨丨η α " τ 砚 observed Cu corrosion. Further, in Comparative Example 6 using a tertiary alkanolamine, The peeling property was not good. 1 Further, Comparative Example 7 in which the composition of the solvent was added without adding an amine was also inferior in peelability. The example "having a high viscosity" may cause a liquid feed pump load of the peeling device in practice. It becomes larger, but it has excellent corrosion resistance at Cii, and the peelability of #九阻层 is also good. In Example 27, although there was a solvent odor, the Cu layer was excellent in corrosion resistance and the peeling property of the photoresist layer was also excellent. [Simple diagram description] None [Main component symbol description] None 16

Claims (1)

200844689 X. Application for Patent Park: i A photoresist stripper composition for the Cu or Cu alloy wiring forming step of a flat panel display, characterized in that it comprises: I select free wheat, 2, 6- A fluorenyl gamma quinone, 4-carbyl-6-methyl-2-nonanone, 4-hydroxycoumarin, coix seed bishydroxyquinoline, amine group & bis, 2, 4 _ A group consisting of amino-hydroxypyrimidine, aminohydroxy-6-methylpyrimidine, 4,6-dimercapto-2-hydroxypyrimidine, uracil, and &methyluracil = at least one heterocyclic compound 0 05~10% by weight, primary or secondary alkanol female 45 heavy /. And a polar organic solvent and/or water 5〇~94·95% by weight 〇 _ _ / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / Ethanolamine, diethanolamine, n-propanolamine, monoisopropanolamine, . ^ At least one of the group consisting of early ethylethanolamine, aminoethoxyethanol, and monomethylethanolamine! Kind. Shenyue q dry cocoon 1 or 2 of the photoresist stripping agent composition, Bingzhong, polar organic solvent # 剜 k select free diethylene glycol monobutyl ether, N-methyl pyrrolidone, and second trial IT At least one of the group consisting of ethylethylamine. Eleven, circle: 17