KR20050028380A - Composition for removing a (photo)resist - Google Patents

Abstract

A composition is provided to remove a photoresist for patterning a copper membrane used as a metal wire of an electronic circuit or a display device, which is excellent in a removing ability and can minimize corrosion of a patterned copper membrane. The composition comprises: 10-30wt% of an alkyl alkanol amine compound selected from N-methylethanol amine, N-ethylethanol amine, diethyl ethanol amine, and dimethyl ethanol amine; 10-80wt% of a glycol ether or ethylene glycol compound selected from ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol, and etc.; 9.5-80pts.wt. of a polar solvent selected from N-methyl-2-pyrrolidone, N,N-dimethyl acetamide, N,N-dimethyl formamide, and etc.; 0.5-10pts.wt. of an anticorrosive agent selected from tolyltriazole, benzotriazole, mercapto benzodiazole, and etc.

Description

Composition for removing a resist {Composition for removing a (photo) resist}

The present invention relates to a removal solution for removing the resist (resist) used in the photo-lithography process, in particular, when removing the resist patterning the copper film can minimize the corrosion of the copper film, The present invention relates to a resist removal solution having excellent removal ability.

Resist (photo-resist) is an essential material for photolithography process, which is integrated circuit (IC), large scale integration (LSI), very large integrated circuit (very large) One of the processes generally used to fabricate semiconductor devices such as scale integration (VLSI), and image display devices such as liquid crystal display (LCD) and plasma display devices (PDP).

In order to explain the photolithography process, the manufacturing process of the array substrate of the liquid crystal display device will be described by way of example.

The liquid crystal display device can be divided into passive matrix type and active matrix type according to its driving method, and as the display device becomes larger, it is being manufactured into active matrix type.

Hereinafter, the configuration of an array substrate of an active matrix liquid crystal display device will be briefly described with reference to FIG. 1 (a plan view showing an enlarged configuration of one pixel).

As shown in the drawing, the array substrate 10 for a liquid crystal display device includes a plurality of illustrated pixels P. The switching elements T are configured for each pixel P, and the switching elements T are shown in FIG. Array wiring for transmitting different signals is configured.

Hereinafter, the configuration of the array substrate for the liquid crystal display device will be described.

As shown in the drawing, the gate wiring 14 is formed on the insulating substrate 10 in one direction, and the data wiring 26 defining the pixel region P is formed by crossing the gate wiring 14 perpendicularly. .

At the intersection of the two wirings 14 and 26, a gate electrode 12 connected to the gate wiring 14, a semiconductor layer 18 on the gate electrode 12, and an upper portion of the semiconductor layer 18. The thin film transistor T includes a source electrode 22 connected to the data line 26 and a drain electrode 24 spaced apart from the data line 26.

The pixel region P includes a transparent pixel electrode 30 in contact with the drain electrode 24.

Hereinafter, with reference to FIG. 2, the planar configuration of FIG.

FIG. 2 is a cross-sectional view taken along the line II-II of FIG. 1.

As shown in the drawing, the gate electrode 12 and the gate wiring 14 are first formed on the substrate 10.

Next, the first insulating film 16 is formed on the entire surface of the substrate 10 having the gate electrode 12 and the gate wiring 14 formed thereon.

Semiconductor layers (active layer and ohmic contact layer) 18 and 20 are formed on the gate electrode 12 above the first insulating layer 16 and spaced apart on the semiconductor layers 18 and 20. The source electrode 22 and the drain electrode 24 are comprised. Although not shown, the data line 26 connected to the source electrode 22 crosses the gate line 14 to define the pixel region P. Referring to FIG.

As a result, the thin film transistor T and the array wiring are completed on the substrate.

A second insulating film 28 is formed on the entire surface of the substrate 10 including the source and drain electrodes 22 and 24, and the transparent pixel electrode 30 is in contact with the drain electrode 24 on the second insulating film. ) Is configured.

In general, the configuration of the array substrate for a liquid crystal display device is formed in the cross-sectional configuration as described above.

In the above-described configuration, however, the gate wiring 14, the data wiring 26, and each electrode of the thin film transistor (T) may be made of a conductive metal, and a metal having a low back resistance is preferably used.

In the case of a display device, such a resistance characteristic is urgently required as the display area increases, and accordingly, studies on metal materials for making low resistance wiring or electrodes have been actively conducted.

A representative material of these metals is copper (Cu).

However, the disadvantage of copper is that some oxidation occurs in the air, and the initial copper itself is made pure by 99.9999%, which is easily oxidized when exposed to air, and oxidized copper is also exposed to air (photo resist). Corrosion may occur at a faster rate due to the vapor of the removal solution.

That is, a problem of rapid corrosion may occur due to the removal solution of the resist used during photo-lithography processing.

To understand this, a photolithography process and an etching process will be described below with reference to FIGS. 3A to 3C.

In general, the configuration of each wire and the thin film transistor described above is generally made in a predetermined pattern through a photolithography process.

Hereinafter, the part to describe is a photolithography process for forming a gate wiring and a gate electrode among the structures mentioned above.

3A to 3C are cross-sectional views of the photolithography process taken along the II-II of FIG. 1 according to the process sequence.

As shown, copper (Cu) is deposited on the substrate 10 to form the first metal layer 11.

A photoresist film 40 is formed by applying photoresist on the first metal layer 11.

A mask M including a transmissive part E for transmitting light and a blocking part F for blocking light is positioned on the photoresist layer 40.

Next, the photoresist film 40 corresponding to the transmission portion E of the mask M is exposed by irradiating high energy active rays such as ultraviolet rays or transfer rays or X-rays to the upper portion of the mask M. Proceed with the process.

In more detail, the high energy active line passing through the transmissive portion E of the mask M pattern reaches the photoresist layer 40 below.

The high energy active line reaching the photoresist film 40 deforms the physical properties of the photoresist film 40. As described above, when the irradiation of the high energy active line is finished, the photoresist film 40 has a region maintained in the same physical properties as before the irradiation of the high energy active line, and the properties of the inside thereof by irradiation of the high energy active line It is divided into deformed areas.

The pattern formed by the deformation of the physical property of the photoresist film 40 as described above is usually referred to as the "latent image" of the mask pattern because it is determined later to the pattern of the mask.

When the exposure process as described above is completed, the development process for the photoresist film is performed.

As shown in FIG. 3B, when the developing process is performed, a predetermined photoresist pattern 42 formed by transferring the transmission portion E of the mask (M in FIG. 3A) is formed.

The process of etching the exposed first metal layer using the photoresist pattern 42 as an etch stop layer is performed.

In this case, as shown in FIG. 3C, a metal pattern is formed below the photoresist pattern.

Some of these metal patterns are used as the gate electrode 12 and some are used as the gate wiring 14.

As described above, when the process of patterning the metal layer into the gate electrode 12 and the gate wiring 14 is completed, the process of removing the photoresist pattern remaining on the upper portion of the structure is performed.

The photolithography process proceeds as described above, and such a process is an essential process for forming the above-described thin film transistor and array wiring.

However, as mentioned earlier, when the metal layer is formed of copper, a problem due to oxidation of copper occurs.

That is, there is a problem that the oxidized copper is accelerated in its corrosion degree by the resist removal solution. A resist removal solution for preventing such copper corrosion problems has been presented in US Pat. Nos. 5,417,877 and 5,556,482.

This is to prevent the corrosion of copper by using a resist removal solution in which a corrosion inhibitor is added to the mixture of the amide material and the organic amine. In this case, as the organic amine, monoethanolamine is specified as the preferred amine.

In addition, it is recommended to use an appropriate amount of corrosion inhibitor, and when the amount exceeds the appropriate amount, the removal force of the photoresist film is poor.

An object of the present invention is to propose a resist removal solution which is excellent in removing ability of a resist film without corrosion of the copper film during removal of the resist film for copper film pattern.

To this end, the work of selecting the composition contained in the resist removal solution was carried out as follows.

4 and 5, when the composition of the resist removal solution is changed, the surface characteristics of the copper film will be examined.

4 is a SEM photograph showing the surface of the copper film when the resist removal solution containing monoethanol amine is used, and FIG. 5 is a SEM photograph showing the surface of the copper film when the resist removal solution containing N-methanol amine is used. to be.

As shown in FIG. 4, when the monoethanolamine was contained in the resist removal solution, the corrosion of the copper film was very severe. As shown in FIG. 5, when the N-methyl ethanol was contained, The surface is very smooth, showing very little corrosion.

By selecting the amine and the solvent itself does not affect the corrosion of the copper as a resist removal solution according to the present invention through the photos of Figures 4 and 5 described above, there is no excess residue of the corrosion inhibitor which causes problems in the removal power during evaporation of the solvent, corrosion The resist can be removed without.

Accordingly, the present invention is based on the above-described results, 10% to 30% by weight of at least one material selected from N-methylethanolamine, N-ethylethanolamine, diethylethanolamine, dimethylethanolamine, 10% by weight ~ 80% by weight of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, ethylene glycol, diethylene One or more substances selected from the group consisting of glycols, triethylene glycol, tetraethylene glycol, glycol ether or ethylene glycol solvent, 9.5% by weight to 80% by weight of N-methyl-2-pyridone, N, N -At least one polar solvent selected from the group consisting of dimethylacetamide, N, N-dimethylformamide and N, N-dimethylimidazole, 0.5 wt% to 10 Substances comprising wt% tolytriazole, benzotriazole, aminotriazole, carboxybenzotriazole, mercaptobenzodiazole, mecaptoethanol, mecaptopropanediol, succinic acid, benzoic acid, citric acid in antioxidants A resist removal solvent for a copper film pattern including at least one corrosion inhibitor selected from the group is proposed.

The above-mentioned resist removal solvent can minimize the corrosion of the copper film and has the advantage of excellent resist removal ability.

The resist removal solvent for a copper film pattern according to the present invention for achieving the above object, in the resist removal solvent for a copper film pattern, 10 wt% to 30 wt% alkylalkanol amine compound; 10% to 80% by weight glycol ether compound; 9.5% to 80% by weight of a polar solvent; 0.5 wt% to 10 wt% of a corrosion inhibitor.

The alkyl alkanol amine compound is characterized in that at least one selected from N-mailethanolamine, N-ethylethanolamine, diethylethanolamine, dimethylethanolamine.

The glycol ether or ethylene glycol compound is ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, ethylene glycol, At least one selected from diethylene glycol, triethylene glycol and tetraethylene glycol.

The polar solvent may be selected from one or more of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and N, N-dimethylimidazole.

The preservative is at least one of tolytriazole, benzotriazole, aminotriazole, carboxybenzotriazole, mercaptobenzodiazole, mecaptoethanol, mecaptopropanediol, succinic acid, benzoic acid, citric acid It is characterized by being selected.

Hereinafter, with reference to the accompanying drawings, an embodiment of the present invention will be described.

Example

The main components of the resist removal solvent for copper film patterns according to the present invention are an amine compound, a glycol ether solvent, a polar solvent, and a corrosion inhibitor.

Hereinafter, the composition and the characteristic of each component are demonstrated.

First, the amine compound in the resist removing composition is a strongly alkaline material and is modified or crosslinked under various process conditions such as dry etching or wet etching, ashing or ion implant processing. It penetrates strongly into the polymer matrix of the resist and breaks the attraction force between molecules.

This action of the amine compound makes it easier to remove the resist attached to the top of the substrate by forming a void in the structurally weak portion of the resist remaining on the substrate to transform the resist into an amorphous polymer gel mass. .

In this case, when the amine having an alkyl group attached to -N (nitrogen) is contained in the remover, corrosion is weakened, and in order to increase the activity of the non-covalent electron pair of -N-, the secondary amine compound is superior to the tertiary.

The basicity of such an amine compound is as follows in Table 1 below.

Corrosion of copper among the amine compounds described in Table 1 is irrelevant to the basicity, and the corrosion occurs severely only for amines in which both remaining hydrogens attached to the nitrogen of the amino alkanol are unsubstituted.

If the content of the amine exceeds 30%, the corrosion may be severe and the composition ratio cannot be controlled because evaporation is easy at 70 ° C.

Therefore, the present invention uses at least one material selected from 10 wt% to 30 wt% of N-methylethanolamine, N-ethylethanolamine, diethylethanolamine, dimethylethanolamine. In this case, the most preferred material is N-methylethanolamine.

Next, the glycol ether or ethylene glycol-based solvent according to the present invention is 10% to 80% by weight of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, It is characterized by using at least one material selected from the group consisting of diethylene glycol propyl ether, diethylene glycol butyl ether, ethylene glycol, diethylene glycol, triethylene glycol, tetra ethylene glycol.

Since the amine compound is used as the secondary, when the movement of the glycol ether solvent decreases, the activity of the amine itself decreases.

Compounds lacking ether-based bonds, ie simple alkylene glycol systems, cause corrosion that results in tight holes in the copper surface. However, the addition of corrosion inhibitors can prevent corrosion that is tight enough to puncture.

The most preferable effect can be obtained when using diethylene glycol methyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether which have a boiling point of 180 degreeC or more and water and solubility of the glycol ether are almost infinite.

When the resist removal process is performed under high temperature conditions, when the glycol ether solvent having a high boiling point is higher than 180 ° C., volatilization does not occur easily, and thus the composition ratio of the initial use of the resist remover may be kept constant.

Therefore, the removal performance of the resist remover can be continuously expressed throughout the resist removal process cycle.

In addition, the use of a glycol ether solvent having a boiling point of 180 ° C. or higher can improve the resist removal efficiency due to the low surface force in the resist and the lower metal film layer, and is advantageous in terms of storage stability due to the low freezing point and high flash point. Can work.

Next, in the present invention, as the polar solvent, 10% to 80% by weight of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and N, N It is characterized by using at least one substance selected from the group of substances containing dimethylimidazole.

Such polar solvent functions to dissolve the polymer gel lumps peeled off by the amine compound at a level of unit molecules.

In particular, it is possible to prevent the resist re-adhesiveness mainly caused in the cleaning process. Polar solvents such as N-methyl-2-pyrrolidone containing an amine as an intramolecular functional group serve to assist the function of penetrating into and removing the resist of the amine compound.

The corrosion inhibitor comprises 0.5 wt% to 10 wt% of tolytriazole, carboxybenzotriazole, mercaptobenzodiazole, mecaptoethanol, mecaptopropanediol, and succinic acid, benzoic acid, citric acid in the demulsifier. It characterized in that it comprises at least one corrosion inhibitor selected from the group of materials.

The above-mentioned corrosion inhibitor is effective in a reaction in which oxygen is reduced on the surface of copper (Cu) or aluminum (Al), that is, a reaction in which an oxide film is formed, and remains as a copper complex in the resist removal solution by reacting with the copper oxide or aluminum oxide film. It creates electrical and physical barriers to prevent surface corrosion and galvanic corrosion of copper and aluminum.

When summarized once again for the composition contained in the resist removal solvent in the present invention described as described above is as follows.

1. Amine compound: 10% to 30% by weight of one or more selected from N-methylethanolamine, N-ethylethanolamine, dietinethanolamine, dimethylethanolamine.

2. Glycol ether solvent: 10 wt% to 80 wt% ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene Use of at least one material selected from the group of glycols including butyl ether, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol.

3. Polar solvent: 9.5% to 80% by weight of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and N, N-dimethylimidazole Use of one or more substances selected from the group of substances.

4. Preservatives: One or more substances selected from the group consisting of tolytriazole, carboxyl benzotriazole, mercaptobenzodiazole, mecaptoethanol, mecaptopropanediol, succinic acid, benzoic acid and citric acid among antioxidants use.

Hereinafter, a number of experimental condition processes and processes that have been performed to obtain the composition as described above will be described with reference.

Experiment 1 and Experiment 2 are to select the amine and glycol ether solvents, and the test specimens, first, to evaluate the corrosion of the solvent to the copper, after depositing about 2000Å copper on the glass surface After applying the resist, use the finished specimen until development.

Secondly, to evaluate the removal ability of the resist, after forming chromium (Cr) on the glass, the resist is applied and wet etching is used. The adhesion of the resist in chromium is maximized, and when subjected to dry etching gas, it can be used as a suitable specimen for testing resist removal ability because the resist is deformed and not easy to remove with a remover.

<Experiment 1>

Table 2 shows the results of evaluating resist removal and copper corrosion on the single raw material.

Copper corrosion Resist removal 70 ℃ 20 minutes sleep 70 ℃ one minute sleep Monoethanolamine Corrosion Complete removal 10 N-methylethanolamine Front corrosion Complete removal 10 N-methyl-2-pyrrolidone No corrosion Not removed at all 0 N, N-dimethylacetamide No corrosion Stay thin 5 Diethylene glycol ethyl ether No corrosion Stay thin 5 Diethylene glycol butyl ether No corrosion Stay thin 5 Triethylene glycol There is a regular small pit. Stay thin 5

(Table 2) * 0 (no control at all) → 10 (completely remove)

As shown in Table 2, in the case of amines, the corrosion of the surface is possible but the partial pitting does not occur, which shows the possibility of corrosion control.

In the case of triethylene glycol, surface corrosion did not occur while small pores appeared on the surface.

<Experiment 2>

Table 3 is a table showing the degree of copper corrosion according to the amine type.

Copper corrosion 70 ℃ 400 seconds sleep Monoethanolamine 0 Monoisopropanolamine 3 N-methylethanolamine 10 Dimethylethanolamine 10 Diethylethanolamine 10

Table 3 * 0 (complete corrosion) → 10 (no corrosion at all)

Table 3 shows the result of using a dilution solution of 45% by weight of glycol ether and 45% by weight of polar solvent that does not cause corrosion of copper because the entire surface corrosion of copper occurs in the previous evaluation alone. As shown in Table 3, N In the case of -methylethanolamine, dimethylethanolamine, and diethylethanolamine , it can be seen that no corrosion of copper occurs.

Hereinafter, Experiment 3 and Experiment 4 were conducted to evaluate the removal force of the resist and the corrosion force of copper in the composition of the resist removal solution.

The specimens to be used in Experiments 3 and 4 were made of four specimens as follows.

<Specimens to be used in Experiment 3>

(1) After dry etching the active film (n + a-Si: H) / a-Si: H), the resist remaining on n + a-Si: H is removed and the specimen size is 1 cm * 4 cm. .

(2) Specimens exposed to dry etching gas after chromium (Cr) on glass was wet etched, and the resist on chromium (Cr) was removed. (Chromium was used as source and drain before copper film. ), The specimen size should be 1 cm * 4 cm.

(3) Apply DTFR-3650B (Dongjin Semichem, Positive Resist) on glass, remove resist baked at 170 ° C for 25 minutes, and make specimen 2cm * 4cm.

Specimens to be used in Experiment 4

(4) Specimens obtained by wet etching the lower film and copper double layer, and the size of the specimen shall be 2cm * 4cm.

Using the specimen described above, the experiment was performed using a resist removal solvent prepared under 22 conditions as shown in Table 4.

division Amine compound Glycol ether solvent Polar solvent additive Kinds Content (wt%) Kinds Content (wt%) Kinds Content (wt%) Kinds Content (wt%) Example 1 NMEA 10 DEGEE 80 NMP 10 TT 0.5 Example 2 NMEA 10 DEGEE 60 NMP 30 TT 0.5 Example 3 NMEA 10 DEGEE 40 NMP 50 TT 0.5 Example 4 NMEA 10 DEGBE 80 NMP 10 TT 0.5 Example 5 NMEA 10 DEGBE 60 NMP 30 TT 0.5 Example 6 NMEA 10 DEGBE 40 NMP 50 TT 0.5 Example 7 NMEA 20 DEGEE 50 NMP 30 TT 0.5 Example 8 NMEA 20 DEGBE 50 NMP 30 TT 0.5 Example 9 NMEA 30 DEGEE 40 NMP 30 TT 0.5 Example 10 NMEA 30 DEGBE 40 NMP 30 TT 0.5 Example 11 NMEA 10 DEGEE 60 NMP 30 CBT 0.5 Example 12 NMEA 10 TEG 55 NMP 30 TT 5 Example 13 NMEA 10 TEG 55 NMP 30 Succinicacid 2 Comparative Example 1 MEA 10 DEGEE 60 NMP 30 Comparative Example 2 nMEA 10 DEGEE 60 DMAc 30 Comparative Example 3 nMEA 10 TEG 60 NMP 30 Comparative Example 4 MEA 10 DEGEE 60 NMP 30 TT 0.5 Comparative Example 5 NMEA 10 DEGEE 60 NMP 30 BT 0.5 Comparative Example 6 NMEA 10 DEGEE 60 NMP 30 8-HQ 0.5 Comparative Example 7 NMEA 10 DEGEE 60 NMP 30 MBT 0.5 Comparative Example 8 NMEA 10 DEGEE 60 NMP 30 Succinicacid 0.5 Comparative Example 9 NMEA 10 DEGEE 90 TT 0.5 NMEA: N-methylethanolamine DEGEE: diethylene glycol ethyl ether DEGBE: diethylene glycol butyl ether TEG: triethylene glycol NMP: N-methyl-2-pyrrolidone DMAc: N, N-diethyl acetamide BT: benzo Triazole 8-HQ: 8-hydroxyquinoline TT: tolytriazole CBT: carboxybenzotriazole MBT: mercaptobenzodiazole

Table 4

<Experiment 3>

Hereinafter, Table 5 is a result of evaluating the removal force for the film quality of the first to third specimens.

After removing the solution at 70 ° C, the specimen (1) (2) (3) was immersed in the specimen, and (1) (2) was observed by scanning electron micrograph, and (3) was visually observed.

(1) 200 seconds sleep (2) 60 seconds sleep (3) 50 seconds sleep Example 1 10 10 7 Example 2 10 10 8 Example 3 10 10 8 Example 4 10 10 7 Example 5 10 10 8 Example 6 10 10 8 Example 7 10 10 10 Example 8 10 10 10 Example 9 10 10 10 Example 10 10 10 10 Example 11 10 10 7 Example 12 10 9 6 Example 13 10 9 5 Comparative Example 1 10 10 7 Comparative Example 2 10 10 7 Comparative Example 3 10 10 6 Comparative Example 4 10 10 8 Comparative Example 5 10 10 8 Comparative Example 6 10 10 7 Comparative Example 7 10 10 7 Comparative Example 8 10 10 7 Comparative Example 9 10 10 One

(Table 5) * 0 (not removed) → 10 (completely removed)

The characteristic of Table 5 is that as the amine compound is added, the removal of the resist which has undergone dry etching is excellent, whereas when the polar solvent is excluded as in Comparative Example 9, it is hardly removed at 50 seconds subsidence. I can see that it does not.

<Experiment 4>

Experiment 4 evaluates the corrosion on copper using Specimen 4.

(4) 400 seconds sleep Example 1 10 Example 2 10 Example 3 10 Example 4 10 Example 5 10 Example 6 10 Example 7 10 Example 8 10 Example 9 10 Example 10 10 Example 11 10 Example 12 10 Example 13 8 (weak pitting) Comparative Example 1 2 Comparative Example 2 2 Comparative Example 3 3 (deep pitting) Comparative Example 4 7 (weak pitting) Comparative Example 5 5 Comparative Example 6 5 (severe pitting) Comparative Example 7 7 Comparative Example 8 3 Comparative Example 9 10

(Table 6) * 0 (complete corrosion) → 10 (no corrosion)

As in Examples 1 to 13 of Table 6, the corrosion inhibitors of copper include tolytriazole, carboxyl benzotriazole, succinic acid, and the like. In the case of succinic acid, glycol ether is added to the composition. If included, it does not function and only has a corrosion inhibitor effect in the glycol series.

In Comparative Examples 1 to 3 where no corrosion inhibitor was added, copper was severely corroded, and in Comparative Example 5, a BT similar to TT forming a complex with copper (Cu) due to a non-covalent electron pair of nitrogen was corroded. Although it is used as an inhibitor, it is insufficient as an additive to suppress copper corrosion.

In Comparative Examples 6 to 8, the corrosion inhibitor 8-HQ was added, but the unshared electron pair of nitrogen also caused copper fitting without forming a complex with copper.

Hereinafter, Experiment 5 is an evaluation of copper corrosion through water absorption.

The solution containing the secondary amine absorbs moisture to more than 3% when left for one day at room temperature, and less than 2% when heated to 70 ℃. In fact, moisture absorption or mixing of 2% ~ 3% or more in the LCD manufacturing process can be confirmed as a general case.

When water is contained, amines are activated by water to generate aluminum ions and hydroxide ions, creating an oxidizing atmosphere.

Copper is vulnerable in an oxidizing atmosphere, so it is easily corroded under high temperature and moisture absorption.

Hereinafter, the mode example of Table 7 was evaluated by adding artificially 3wt% ultrapure water (water with metal ions removed).

(4) 30 minutes sleep Example 1 10 Example 2 10 Example 3 10 Example 4 10 Example 5 10 Example 6 10 Example 7 10 Example 8 10 Example 9 10 Example 10 10 Example 11 10 Example 12 10 Example 13 10 Comparative Example 1 0 Comparative Example 2 0 Comparative Example 3 0 Comparative Example 4 5 (severe fitting, pitting) Comparative Example 5 5 Comparative Example 6 2 (severe fitting, pitting) Comparative Example 7 7 Comparative Example 8 0 Comparative Example 9 10

Table 7 0 (complete corrosion) → 10 (no corrosion)

As shown in Table 7, tolitriazole, benzotriazole, aminotriazole, carboxybenzotriazole, mercaptobenzodiazole, mecaptoethanol, and mecapto to prevent corrosion of copper due to moisture absorption in question Propanediol and succinic acid, benzoic acid and citric acid in antioxidants were added to evaluate copper corrosion.

As in Examples 1 to 13, corrosion inhibitors of copper include tolytriazole, carboxyl benzotriazole, succinic acid, and the like, and in the case of succinic acid as in Comparative Example 8, when glycol ether is included in the composition, Corrosion occurs completely, and only the glycol series has a corrosion inhibitor effect.

Copper is completely corroded when moisture is mixed in Comparative Examples 1 to 3 without the addition of corrosion inhibitors. BT, which is similar to TT, which forms a complex with copper due to the unshared electron pair of nitrogen in Comparative Example 5, is used as a corrosion inhibitor. However, it is insufficient as an additive for inhibiting copper corrosion. In Comparative Examples 6-8, corrosion inhibitor 8-HQ was added, but the unshared electron pair of nitrogen also caused a copper fitting which did not form a complex with copper.

The corrosion inhibitor is effective in a reaction in which oxygen is reduced on the surface of copper or aluminum, that is, a reaction in which an oxide film is formed. It prevents the surface corrosion and galvanic of aluminum.

The above examples and comparative examples are illustrative for the purpose of understanding the present invention and do not limit the technical scope of the present invention.

Accordingly, the present invention can be variously modified by those skilled in the art other than the above embodiments, and these also belong to the technical scope of the present invention.

Therefore, the resist removal solution for a copper film pattern according to the present invention minimizes the corrosion of the copper film under the resist, and has an excellent effect of removing the resist.

Therefore, it is possible to fabricate electrodes and wiring of an electronic circuit or a display element with copper, thereby improving the operating characteristics of such a product, and in the case of the display element, it is possible to increase the display area.

1 is an enlarged plan view of an enlarged single pixel of an array substrate for a liquid crystal display device;

2 is a cross-sectional view taken along the line II-II of FIG. 1,

3A to 3C are process cross-sectional views illustrating a photolithography process according to a process sequence;

4 is a SEM photograph showing the surface of a copper film immersed for 20 minutes at 70 ℃ in a composition containing monoethanol amine,

5 is a SEM photograph showing the surface of a copper film submerged in a composition containing N-methanol amine.

<Brief description of the main parts of the drawings>

5

Claims (5)

In the resist removal solvent for copper film patterns, 10 wt% to 30 wt% alkylalkanol amine compound; 10% to 80% by weight glycol ether compound; 9.5% to 80% by weight of a polar solvent; 0.5 wt% to 10 wt% corrosion inhibitor A resist removal solvent comprising a. The method of claim 1, The alkyl alkanol amine compound is a resist removal solvent, characterized in that at least one selected from N-mailethanolamine, N-ethylethanolamine, diethylethanolamine, dimethylethanolamine. The method of claim 1, The glycol ether or ethylene glycol compound is ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, ethylene glycol, A resist removal solvent, characterized in that at least one selected from diethylene glycol, triethylene glycol, tetraethylene glycol. The method of claim 1, The polar solvent is at least one selected from N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazole . The method of claim 1, The preservative is at least one of tolytriazole, benzotriazole, aminotriazole, carboxybenzotriazole, mercaptobenzodiazole, mecaptoethanol, mecaptopropanediol, succinic acid, benzoic acid, citric acid A resist removal solvent, characterized in that selected.