KR101191731B1 - Stripper composition for photo-resist - Google Patents

Abstract

PURPOSE: A photoresist stripping composition is provided to effectively implement a stripping process by preventing the corrosion of an aluminum, molybdenum, or copper-based metal film. CONSTITUTION: A photoresist stripping composition includes 25.0-65.0 weight% of diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, or the mixture of the same, 5.0-15.0 weight% of aminoethylethanolamine, 0.1-1.0 weight% of monoethanolamine, 0.1-10.0 weight% of fatty acid alcohol polyglycol ether, and remaining amount of water. The content of the fatty acid alcohol polyglycol ether is in a range between 3.5 and 5.5 weight%. The composition further includes 3.5-5.5 weight% of diethylene glycol and triisobutyl phosphate.

Description

Photoresist stripper composition {Stripper Composition For Photo-Resist}

The present invention relates to a photoresist stripper composition, wherein a photoresist stripper composition capable of effectively removing a photoresist without using an aprotic polar organic solvent without affecting a metal film such as aluminum, molybdenum, and copper. It is about.

Photolithography (Rhoto-Lithography) processes are widely used to form certain patterns (circuits) in the semiconductor device and electronic device manufacturing sectors, such as LCD, PDP and OLED. The composition of the photolithographic process consists of the application of resist, exposure, development, etching and exfoliation of the remaining resist. After forming a certain pattern by etching, the resist material present on the metal pattern is removed using a release agent.

U.S. Patent No. 4,904,571 discloses solvents (water, alcohols, ethers, ketones, etc.), alkaline compounds dissolved in the solvent (primary, secondary, tertiary amines, quaternary amines, cyclic amines, polyamines, quaternary ammonium amines). , A sulfonium hydroxide, an alkali hydroxide, and the like) and a borohydride compound (sodium borohydride, pyridine boron) dissolved in the solvent is disclosed. U.S. Patent No. 5,478,443 and U.S. Patent No. 5,320,709 use certain organic corrosion inhibitors (glycol and dimethyl sulfoxide) and fluorine-containing compounds (ammonium fluoride, hydrofluoric acid, perfluoric acid, etc.) to address metal corrosion problems. It is suggested to solve. However, these compositions have a disadvantage of requiring a large amount of organic solvent and thus treating a large amount of waste.

Korean Patent Publication No. 2000-8103 discloses a photoresist stripper composition consisting of alkanolamine + sulfoxide + glycol ether + pyrrolidone. The patent describes that if the alkanolamine is more than 15% by weight, or the sulfoxide or sulfone compound is less than 35% by weight, the absorbency with the LCD film is reduced, and the contact angle is increased, thereby degrading peeling performance by the air knife. . Japanese Laid-Open Patent Publication No. 64-42653 contains more than 50% by weight, or more than 70% by weight of dimethyl sulfoxide, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, 1,3-dimethyl-2-imida. A peeling liquid composition for photoresists comprising 1 to 50% by weight of at least one solvent selected from zolidinone and gamma-butyrolactone and 0.1 to 5% by weight of a nitrogen-containing organic hydroxyl compound such as monoethanolamine is proposed. . This patent describes that when the dimethyl sulfoxide is less than 50% by weight, the peelability is significantly lowered, and when the nitrogen-containing organic hydroxyl compound solvent is more than 5% by weight, metal layers such as aluminum corrode. These patents use aprotic polar organic solvents of sulfoxides and nitrogen-based cyclic compounds.

These aprotic polar organic solvents are not only very expensive but also harmful to the environment, they do not have sufficient reactivity and dissolvability for high molecular materials, and thus have insufficient peeling ability for organic membranes including overcoats. A washing process with a solvent is necessary.

Korean Patent Laid-Open No. 2001-65038 discloses tetramethylammonium hydroxide ("TMAH") as a fine aid before removing a photoresist with a stripper and washing in distilled water when forming a wiring film of a TFT-LCD lower plate. In the above patents, KOH and TMAH each illustrate the use of a photoresist stripper and a post-split cleaning aid, but they are not efficient enough and not stable enough to be used to remove all laminated layers of defective TFT-LCD tops. .

The above prior arts are problematic in that economical factors are employed in important regeneration treatments by using expensive chemicals, and these are themselves environmentally hazardous substances, and additional costs are added to the disposal treatments. In addition, if a separate solvent is introduced into the intermediate cleaning step to prevent corrosion of the regenerated glass plate by the residual stripping liquid composition after the peeling step, there is a possibility that additional cost is incurred and remains a variable in the process operation.

Korean Unexamined Patent Publication Nos. 2007-0111870, 2009-0078867, and 2010-0122001 disclose a photoresist stripper composition comprising water. However, in order to prevent corrosion of the metal film, the above release agents must necessarily use a corrosion inhibitor and a polar organic solvent as an essential component.

The present invention is to provide a water-based photoresist stripper composition containing a large amount of water without using a polar organic solvent, having a peeling ability and can prevent metal film corrosion.

According to the present invention, 25.0 to 65.0 wt% of diethylene glycol monoethyl ether, ethylene glycol monomethyl ether or a mixture thereof; 5.0-15.0 wt% aminoethylethanolamine; 0.1 to 1.0 wt% monoethanolamine; There is provided a photoresist stripper composition comprising a fatty acid alcohol polyglycol ether 0.1 to 10.0% by weight; and a residual amount of water.

In the present invention, diethylene glycol monoethyl ether is preferably 15.0 to 35.0% by weight, most preferably 15.0 to 20.0% by weight, and ethylene glycol monomethyl ether is preferably 10.0 to 30.0% by weight and most preferably , 15.0 to 20.0 wt% and aminoethylethanolamine (“AEEA”) is preferably 7.0 to 13.0 wt%, and monoethanolamine (“MEA”) is preferably 0.25 to 0.35 wt% and diethylene glycol , Fatty acid alcohol polyglycol ether and triisobutyl phosphate are preferably 2.0 to 7.0% by weight, respectively. Diethylene glycol and triisobutyl phosphate are most preferably approximately 1: 1 by weight.

In the present invention, the 'peel composition' is also simply referred to as 'peeling agent'.

In the photoresist stripper composition of the present invention, diethylene glycol monoethyl ether (EDG) and ethylene glycol monomethyl ether (Ethyleneglycolmonomethylether or 2-methoxyethanol, or Methyl cellosolve) stably dissolve the resin of the resist in the release agent and reprecipitate. It plays the main role of preventing the ethylene glycol monoethyl ether [Diethylenglycolmonoethylether, EDG] and ethylene glycol monomethyl ether can be used in combination, in the case of using only one, diethylene glycol monoethyl ether [Diethylenglycolmonoethylether, EDG] is preferred. Do.

Alkanolamine plays a major role of swelling (swelling) to the photoresist layer, it can be maximized by using a primary amine and a tertiary amine. As the primary amine, alkanolamine acts as a swelling initiation for the photoresist layer, and aminoethylethanolamine, the tertiary amine, serves to further advance swelling. Monoethanolamine is essential for initiating swelling by breaking the novolak structure of the resist, but when used in an amount of 1.0% by weight or more, the Ph is high and causes corrosion of the metal film. In the present invention, aminoethylethanolamine is used in an amount of 5.0 to 15.0% by weight to promote novolak chain breakage and maintain a release agent pH of 12.6 or less to induce passivation of a metal film, for example, a Cu film, to prevent corrosion.

The fatty acid alcohol polyglycol ether used as a stabilizer may be composed of the combination A with three compounds of diethylene glycol and triisobutyl phosphate. In this case, it is most preferable to use 1: 1: 1 in approximately weight ratio.

The peeling liquid composition of this invention is applicable at room temperature of about 30 degrees C or less, and can obtain the more excellent effect at the time of temperature rising. More preferable temperature of peeling is 35-50 degreeC, More preferably, it is 37-45 degreeC.

The photoresist stripper composition of the present invention can realize effective peeling while containing a large amount of water without using an aprotic polar organic solvent and preventing corrosion of Al or Mo and Cu metal films.

FIG. 1 is a SEM photograph of a specimen before application of a release agent after completion of etching of soft baking and hard baking after developing a Cu film formed on a glass substrate with a Posi-photoresist in a specimen preparation step of an embodiment of the present invention.
FIG. 2 is a cross-sectional SEM photograph of the specimen of FIG. 1. FIG.
3 is a SEM photograph of the Cu surface of a specimen peeled with 99% acetone, a standard laboratory release agent.
4 is a cross-sectional SEM photograph of the specimen of FIG.
FIG. 5 is a SEM photograph of the Cu surface of the specimen with peeling completed using the composition of Example 4. FIG.
6 is a SEM cross-sectional SEM photograph of the specimen of FIG.

Hereinafter, the present invention will be described in detail by way of examples. These examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention to these examples.

Psalm Formation

Soda-lime glass is used as the support, and the molybdenum layer is 200 ungerstrong chemically deposited, and the copper layer is chemically deposited to a thickness of 1500-2000 ungerstrong. The photoresist is prepared by using AZ 1512 and developing the sample with a TMAH 2.38% solution, followed by soft baking and hard baking. Cu was deposited on the glass substrate as a support in FIG. 1, and the Posi-photoresist was patterned on the Cu film, and then the Posi-photoresist was developed, and the specimens were prepared by etching through soft baking and hard baking.

Comparative Example 1 Example  1 to Example  21

In Control Example 1, 99% of acetone, a standard laboratory release agent, was used.

In Example 1 to Example 21 was prepared a photoresist stripper composition in the ratio shown in Table 1. Combination A used as a stabilizer (anticorrosive) is diethylene glycol; Fatty acid alcohol polyglycol ether; Three compounds of triisobutyl phosphate were used at a weight ratio of 1: 1: 1.

Application of Release Agent

The prepared specimens were cut into 40 mm * 40 mm size to prepare a sample amount so that each Example can be repeated 10 times. As a control example, a metal film immersed for 2 minutes under the same conditions using 99% acetone as a standard laboratory release agent for corrosion and peeling was used.

Using a thermostat in which the volume of the chemical solution was 1000ml, the temperature of the chemical solution was increased to 40 degrees before the experiment, and then maintained for 15 minutes. In order to keep the degree of locking uniformly, the height of the test piece was fixed on the specimen fixing frame so that the test piece was positioned at the center of the thermostat in a state of being locked about 5 mm with respect to the release agent. In each example, the peeling time was fixed at 120 sec. After the peeling test, the specimens were washed with ultrapure water for 10 seconds, dried with N2 gas, and placed in a sample storage box to prevent surface corrosion by external factors.

Evaluation

Each specimen was immersed for 2 minutes while circulating the prepared specimen in a thermostat maintained at a temperature of 40 degrees to evaluate the peeling and corrosion of the metal film.

Evaluation of the degree of peeling is evaluated by classifying the peeling degree by making the state in which the resist does not exist completely, giving a number of "3" and giving a number of "3" abnormally, and giving a number of "0".

FIG. 3 is a SEM photograph obtained by immersing the specimen for 2 minutes in 99% acetone of Comparative Example 1. FIG. 4 is a cross-sectional SEM photograph of Comparative Example 1. FIG. 99% of acetone, a standard laboratory releasing agent, had a degree of delamination of "3" in which the resist was not completely present, and no corrosion was found. Acetone 99% is a laboratory standard releasing agent that, in practice, is highly volatile and flammable and rapidly deteriorates and cannot be used on an industrial scale.

In Example 15, it can be seen that the metal film is not affected even when 1.0% of MEA is contained, and in Example 19, 20 and 21, where the content of the combination is 7.0% or more, the peeling is normal, but the chemical liquid Changes over time have been found. The change over time means that the transparency in the liquid is not maintained even after the chemical liquid combination is opaque.

Example 4 is the most effective in view of the cumulative number of sheets and the retention and efficiency of the liquid and the economic part based on the experiments from Examples 1 to 21.

SEM images of the specimens calculated by the experiment through Example 4 can be confirmed with the data of FIGS. 5 and 6. The SEM photograph in FIG. 5 shows the part covered with Posi-PR removed by the release agent. The metal film deposited by the CVD process has a smooth surface. Even after removing the PR film using a release agent, the surface state was smooth and no damage traces were found on the SEM photograph. In addition to visual inspection through SEM scanning, the thickness of the metal film can be measured. To be sure, it is more accurate to check the surface condition.

Figure 6 is a photograph confirming the damage of the metal film on the etching surface. Even in the metal part affected by the etchant, the metal film was maintained without damaging the release agent.

Example Methyl Cellosolve EDG AEEA MEA Combination A water Peeling time Peeling state Surface damage One 10% 20% 9.70% 0.30% 5.00% 55.00% 120 sec One none 2 15% 20% 9.70% 0.30% 5.00% 50.00% 120 sec 2 none 3 20% 20% 9.70% 0.30% 5.00% 45.00% 120 sec 2 none 4 20% 25% 9.70% 0.30% 5.00% 40.00% 120 sec 3 none 5 25% 25% 9.70% 0.30% 5.00% 35.00% 120 sec 3 none 6 25% 30% 9.70% 0.30% 5.00% 30.00% 120 sec 2 none 7 20% 25% 5.00% 0.30% 5.00% 44.70% 120 sec 2 none 8 20% 25% 7.00% 0.30% 5.00% 42.70% 120 sec 3 none 9 20% 25% 11.00% 0.30% 5.00% 38.70% 120 sec 3 none 10 20% 25% 13.00% 0.30% 5.00% 36.70% 120 sec 2 none 11 20% 25% 15.00% 0.30% 5.00% 34.70% 120 sec One none 12 20% 25% 9.70% 0.10% 5.00% 40.20% 120 sec 2 none 13 20% 25% 9.70% 0.50% 5.00% 39.80% 120 sec 3 none 14 20% 25% 9.70% 0.70% 5.00% 39.60% 120 sec 3 none 15 20% 25% 9.70% 1.00% 5.00% 39.30% 120 sec 3 none 16 20% 25% 9.70% 0.30% 0.10% 44.90% 120 sec 2 none 17 20% 25% 9.70% 0.30% 1.00% 44.00% 120 sec 2 none 18 20% 25% 9.70% 0.30% 3.00% 42.00% 120 sec 2 none 19 20% 25% 9.70% 0.30% 7.00% 38.00% 120 sec 3 none 20 20% 25% 9.70% 0.30% 9.00% 36.00% 120 sec 3 none 21 20% 25% 9.70% 0.30% 10.00% 35.00% 120 sec 3 none Control Example 1 Acetone 99% 120SEC 3 none

Claims (4)

Diethylene glycol monoethyl ether, ethylene glycol monomethyl ether or a mixture thereof 25.0 to 65.0 wt%, aminoethylethanolamine 5.0 to 15.0 wt%; 0.1 to 1.0 wt% monoethanolamine; Fatty acid alcohol polyglycol ether 0.1 to 10.0% by weight; and a photoresist stripper composition comprising a residual amount of water. The method according to claim 1, wherein the diethylene glycol monoethyl ether is 15.0 to 35.0 wt%, the ethylene glycol monomethyl ether is 10.0 to 30.0 wt%, the aminoethylethanolamine is 5.0 to 15.0 wt%, and the monoethanolamine is 0.2 to 0.5. A photoresist stripper composition in weight percent. The method according to claim 2, wherein the diethylene glycol monoethyl ether is 20.0 to 30.0 wt%, the ethylene glycol monomethyl ether is 15.0 to 20.0 wt%, the aminoethylethanolamine is 7.0 to 13.0 wt%, and the monoethanolamine is 0.25 to 0.35 A photoresist stripper composition having a weight percent and fatty acid alcohol polyglycol ether of 2.0 to 7.0 weight percent. The photoresist stripper composition according to claim 3, wherein the fatty acid alcohol polyglycol ether is 3.5 to 5.5 wt% and further comprises 3.5 to 5.5 wt% of diethylene glycol and triisobutyl phosphate.

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