KR101016724B1 - Thinner composition for removing photosensitive resin - Google Patents

Abstract

The present invention relates to a thinner composition for removing the photosensitive resin composition used in the manufacturing process of the semiconductor device and the liquid crystal display device, more specifically, a) alkyl amide; And b) a ketone. The thinner composition of the present invention may further comprise c) perfluoroalkyl amine oxide.

The thinner composition for removing the photosensitive resin composition according to the present invention can efficiently remove unnecessarily attached color resists in a short time by being used at the edges and the rear portions of substrates, particularly color large glass substrates, used in the manufacture of liquid crystal display devices. In addition, by removing the thin film and reducing the level of the interface, it is possible to clean the clean substrate after development, so that it can be applied to various processes, which is economical as well as the effect of simplifying the manufacturing process and improving the production yield. .

Thinner composition for removing photosensitive resin, alkyl amide, ketone, perfluoroalkyl amine oxide

Description

Thinner composition for removing photosensitive resin composition {THINNER COMPOSITION FOR REMOVING PHOTOSENSITIVE RESIN}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist cleaning liquid composition in a semiconductor device and a liquid crystal display device manufacturing process, and more particularly, to a cleaning liquid thinner composition capable of effectively cleaning unnecessary resist after applying a resist in a liquid crystal display device manufacturing process.

In the case of manufacturing by lithography to form a fine circuit pattern such as a semiconductor integrated circuit or a TFT-LCD circuit, a thin film such as an oxide film is generally formed on a substrate, and then a resist is uniformly applied on the surface thereof. A resist pattern is formed by exposure and development, and a pattern is formed by selectively etching a thin film in the lower layer using the resist pattern as a mask, and then a series of processes of completely removing the resist on the substrate are performed. . In the case of manufacturing a semiconductor device or a TFT-LCD by such a lithography method, after the resist is applied to a glass or a silicon wafer substrate, it is necessary to remove the resist and the unnecessary film that may be formed on the lower portion of the substrate. Before the development process, a process of cleaning the substrate with a thinner is required.

Conventional thinner compositions include ether and ether acetates such as cellosolve, cellosolve acetate, propylene glycol ether, propylene glycol ether acetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; And esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate are used as thinners.

Japanese Patent Laid-Open Publication No. Hei 4-49938 discloses a method using propyleneglycol monomethylether acetate (PGMEA) as a thinner in the prior art for the thinner composition. In addition, Japanese Patent Laid-Open No. 4-42523 discloses a method of using alkyl alkoxy propionate as a thinner. However, the conventional methods use a single solvent such as ethyleneglycol monoethylether acetate (EGMEA), propyleneglycol monomethylether acetate (PGMEA) and ethyl lactate (EL). However, it has a problem with the following limitations.

In other words, ethylene glycol monoethyl ether acetate has excellent dissolution rate but high volatility and flammability, and in particular, has reproductive toxicity such as leukopenia and induction of fetal abortion. The propylene glycol monomethyl ether acetate contains a material of beta (β) form in the manufacturing process, which also has a problem of causing teratogenicity and maternal toxicity. In addition, since ethyl lactate has a high viscosity and a low dissolution rate, a sufficient cleaning effect cannot be obtained by itself, and solvents such as acetone and methyl ethyl ketone have a low flash point, thereby degrading work safety.

In order to solve this problem, a method of mixing and using conventional single solvents has been researched and developed.

Japanese Patent Application Laid-Open No. Hei 4-130715 describes a method of using a mixed solvent consisting of an alkyl pyrufinic acid solvent and methyl ethyl ketone as a thinner. Japanese Patent Application Laid-Open No. 7-146562 uses a thinner composition composed of a mixture of propylene glycol alkyl ether and alkyl 3-alkoxypropionic acid. Japanese Patent Application Laid-Open No. 7-128867 describes a method using a thinner composition composed of a mixture of propylene glycol alkyl ether and butyl acetate and ethyl lactate, or a mixture of butyl acetate and ethyl lactate, and propylene glycol alkyl ether acetate. have. Japanese Patent Application Laid-Open No. 7-160008 uses a thinner composition composed of a mixture of propylene glycol alkyl ether propionate and methyl ethyl ketone, or a mixture of propylene glycol alkyl ether propionate and butyl acetate. U.S. Patent No. 4,983,490 uses a mixed solvent consisting of propylene glycol alkyl ether acetate and propylene glycol alkyl ether as a thinner composition.

However, the above-described mixed solvents also have many difficulties in application to the manufacture of semiconductor devices and liquid crystal display devices, which are gradually becoming highly integrated and large diameters.                         

For example, a mixed solvent consisting of an alkyl pyrupin acid solvent and methyl ethyl ketone has poor solubility in 1,2-naphthoquinonediazide-based photosensitizer having a high esterification rate among the photosensitive agents which are important components of the photoresist film. When a highly volatile solvent, such as a mixed solvent of propylene glycol alkyl ether propionate and butyl acetate, is applied to the rear surface cleaning, the thickness of the photoresist film becomes severe as the substrate is cooled. In addition, when a low volatility solvent, such as a mixed solvent of ethyl lactate and methyl ethyl ketone, is used, the cleaning performance of the substrate edge region is poor. In particular, solvents such as methyl pyruvate and ethyl pyruvate are known to corrode metal parts in the photosensitive waste solution reservoir attached to the photosensitive film rotating coater for long term use.

In addition, when such a mixed solution is applied to a color large glass substrate used in a liquid crystal display device manufacturing process, there is a problem in that a resist which is not removed in black is not removed and a thin residual film is left. There is also a problem in that the interface between the remaining resist and the resist which is removed unnecessarily forms a band after development. That is, the interface between the remaining resist and the resist that is removed unnecessarily becomes thicker than the thickness of the actual resist and is not easily removed.

SUMMARY OF THE INVENTION In view of the problems of the prior art as described above, the present invention can efficiently remove unnecessarily attached color resists used in the edges and rear portions of substrates, particularly color large glass substrates, for use in the manufacture of liquid crystal display devices in a short time. It is an object to provide a thinner composition for removing the photosensitive resin composition.

Another object of the present invention is to provide a thinner composition for removing a photosensitive resin composition having excellent cleaning property capable of cleanly cleaning a clean substrate after development by reducing the step difference of the interface.

In order to achieve the above object, the present invention

a) alkyl amides; And b) provides a thinner composition for removing a photosensitive resin composition comprising a ketone.

The thinner composition may further comprise c) perfluoroalkyl amine oxide.

Preferably, the thinner composition for removing the photosensitive resin composition of the present invention comprises a) 10 to 90 parts by weight of an alkyl amide; b) 10 to 90 parts by weight of the ketone; And c) 0.001 to 1 part by weight of perfluoroalkyl amine oxide.

Hereinafter, the present invention will be described in detail.

The present invention is a thinner for removing the photosensitive resin composition effective to be used in the manufacturing process of semiconductor devices and liquid crystal display devices because it is possible to efficiently remove unnecessary color resist attached to the edge and the back portion of the color large glass substrate in a short time. There is a characteristic of providing a composition.

In the thinner composition of the present invention, a) alkyl amide, b) ketone, and c) perfluoroalkyl amine oxide, which are used as solvents, can be selected from the most pure semiconductor grades, respectively, and 0.1 μm level in the VLSI grade. The filtrate was used.

The a) alkyl amide is used to improve the dissolution rate of the composition, it is possible to use an alkyl group of at least 1 or more, preferably 2 to 5 carbon atoms. Specific examples of the alkyl amide may be selected from one or more selected from the group consisting of N-methyl acetamide, dimethyl formamide, and dimethyl acetamide, and more preferably, the dissolution rate of dimethyl acetamide is the fastest.

The content of the alkyl amide is preferably used in 10 to 90 parts by weight based on the total composition. When the content of the alkyl amide is less than 10 parts by weight, there is a problem in that the color resist dissolving ability is reduced, resulting in residue at the end of the substrate. When the content of the alkyl amide is more than 90 parts by weight, the volatilization is reduced, so that the EBR line is uneven. There is a problem that occurs.

In addition, in the thinner composition of the present invention, b) ketone may be a cyclo ketone and a C1 alkyl group of R1 and R2 at least 1, preferably 1 to 5 carbon atoms in the R1COR2 structural formula. Specific examples of the ketones include acetone, methyl isopropyl ketone, methyl normal propyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and cycloheptanone. It is preferable to be selected more than.

The content of the ketone is preferably used in 10 to 90 parts by weight based on the total composition. If the content of the ketone is less than 10 parts by weight, there is a problem in that the EBR line is uneven because the volatilization is lowered.

In addition, the thinner composition of the present invention may further comprise c) perfluoroalkyl amine oxide. The perfluoroalkyl amine oxide has excellent solubility in water and various solvents, and the alkyl group of the perfluoroalkyl amine oxide preferably has 5 to 30 carbon atoms.

The commercialized product of the perfluoroalkyl amine oxide may include S-141 manufactured by Asahi Glass.

The content of the perfluoroalkyl amine oxide is preferably used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the total thinner composition. If the content of the perfloolalkyl amine oxide is less than 0.001 parts by weight, there is a problem in that the dye cleaning effect of the color filter is inferior, and if it exceeds 1 part by weight, there is a problem in that the removal power is reduced without improving the performance.

In addition, the present invention can remove the photoresist using the thinner composition. That is, in the present invention, the photoresist is applied using an applicator, and unnecessary photoresist generated at edges and rear surfaces of the substrate is dropped into the thinner composition by spraying or spraying through a nozzle. The dropping or spraying amount of the thinner composition of the present invention can be adjusted according to the kind of the photosensitive resin to be used and the thickness of the film, and the appropriate amount is preferably selected from the range of 5 to 100 cc / min. The present invention may spray the thinner composition as described above and then form a fine circuit pattern through a subsequent photolithography process.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

[Example]

The substrate specimens used in this example were prepared as follows.

A silicon oxide substrate 5 inches in diameter was used. These substrates were first washed in two baths, each containing a hydrogen peroxide / sulfuric acid mixture (soaked for 5 minutes in each bath) and then rinsed with ultrapure water. This process was carried out in a customized cleaning facility. These substrates were then spin-dried in a spin dryer (VERTEQ, model SRD 1800-6). Subsequently, each photosensitive film was coated with a predetermined thickness on the upper surface of the substrate. A rotary coating machine (Korea Semiconductor Co., Model EBR TRACK) was used to apply the photosensitive film.

In the rotation coating operation, 10 cc of the photosensitive film composition was added dropwise to the center of the stationary substrate. The photosensitive film was then distributed for 3 seconds at 300 rpm using a rotating coater. Subsequently, the substrate was accelerated at a rotational speed of about 500 rpm to adjust each photosensitive film to a predetermined thickness. At this speed, the rotation time is about 25 seconds.

Examples 1-4 and Comparative Examples 1-5

Each of the thinner compositions having the composition and content as shown in Table 1 was prepared. (Unit: parts by weight)                     

division DMAc Acetone CXN PGME PGMEA nBA S Example One 70 30 - - - - - 2 70 30 - - - - 0.5 3 10 - 90 - - - - 4 10 - 90 - - - 0.5 Comparative example One - - - 50 - 50 - 2 - - - 70 30 - - 3 - - - - 50 50 - 4 - 50 - 50 - - - 5 50 - - - - 50 -

week)

DMAc (Dimethylacetamide)

2.CXN: cyclohexanone

3. PGME: Propyleneglycol monomethyl ether

4.PGMEA: Monomethyl ether acetate (PGMEA; propyleneglycol monomethylether acetate)

5. nBA: Butyl ethanoate,

6. S: Perfluoroalkyl aminoxide; S-141 'from Ashahi Glass

Unnecessary photoresist removal experiment of thinner composition with respect to photosensitive resin composition

After applying each photosensitive film composition to a 5 inch silicon oxide substrate experiment to remove the unnecessary photosensitive film of the edge portion with the thinner composition of Examples 1 to 4 and the thinner composition of Comparative Examples 5 to 9 (Edge Bead Removing Experiment: EBR Experiments). EBR experiments also used the same spin coater that was used to apply the photoresist to the substrate.

Each thinner composition shown in Table 1 was sprayed onto the photosensitive film-coated substrate of the photosensitive resin composition shown in Table 2 through an EBR nozzle to remove the spherical photosensitive material in the edge portion under the conditions shown in Table 3 below. Each thinner composition was supplied from a pressure vessel equipped with a pressure gauge at a pressure of 1.0 kgf and a flow rate of the thinner composition from the EBR nozzle was 10 to 20 cc / min.

The EBR experimental evaluation for each photosensitive resin composition is shown in Table 4 below.

Photosensitive resin composition type and film thickness division Composition type Composition product name Film thickness (㎛) Photosensitive resin
Composition Resin black matrix FFO Corp 2 Red JSR Corporation 2 Green 2 Blue 2

EBR experimental conditions division Rotation speed (rpm) Time (sec) Distribution conditions 300 3 Spin coating 500 25 EBR Condition 1 150 13 EBR Condition 2 150 15 Dry condition 700 7 Developing condition Determined by photoresist

Evaluation of EBR Experiments on Photosensitive Resin Compositions division Example Comparative Example One 2 3 4 One 2 3 4 5 Suzy
Black matrix Tail after EBR ○ ◎ ○ ○ × × × △ △ Uniformity after EBR ◎ ◎ ○ ○ × × × △ △ With or without EBR assay ◎ ◎ △ ○ × × × × × After the phenomenon ○ ◎ △ ○ × × × × × Red Tail after EBR ○ ◎ ○ ○ × × × △ △ Uniformity after EBR ◎ ◎ ○ ○ × × × △ △ With or without EBR assay ◎ ◎ △ ○ × × × × △ After the phenomenon ○ ◎ △ ○ × × × × △ Green Tail after EBR ○ ◎ ○ ○ × × × △ △ Uniformity after EBR ◎ ◎ ○ ○ × × × △ △ With or without EBR assay ◎ ◎ △ ○ × × × × △ After the phenomenon ○ ◎ △ ○ × × × × △ Blue Tail after EBR ○ ◎ ○ ○ × × × △ △ Uniformity after EBR ◎ ◎ ○ ○ × × × △ △ With or without EBR assay ◎ ◎ △ ○ × × × × △ After the phenomenon ○ ◎ △ ○ × × × × △

In Table 4, the development means that the substrate after finishing the resist coating and thinner process and finished until the bake is sprinkled with 100 dilutions of JSR developer for 60 seconds by spin method.

Evaluation symbol '◎' indicates that the shape of the edge area after EBR is clear, and '○' indicates that the shape of the edge area after EBR is more than 80% good, and evaluation symbol '△' indicates the edge area after EBR. The shape of is shown to be distorted by the dissolution of the thinner, 'x' indicates that the tailing of the film occurs in the edge portion after the EBR.

In the results of Table 4, the thinner compositions of Examples 1 to 4 according to the present invention showed excellent EBR performance (clean edge shape) for all photoresist films, and the stripping of color resist after development was completely removed. In addition, no residual film was formed on the substrate to which the thinner liquid was introduced. In particular, in the case of Examples 2 and 4 containing a perfluoroalkyl amine oxide, the residual film and the band were further improved than those of Examples 1 and 3. As a result, when the perfluoroalkyl amine oxide is included as in the present invention, it can be seen that the photoresist removal performance is improved.

In addition, the thinner compositions according to the invention maintained an equally good cross-sectional shape even when changing the EBR rpm conditions. This means that the thinner composition according to the present invention exhibits the same performance under various conditions, not only in specific conditions, but is more stable than a conventional thinner composition against changes in process conditions.

As described above, the thinner composition for removing the photosensitive resin composition according to the present invention is a short-time use of the color resist, which is unnecessarily attached to the edges and rear surfaces of substrates used in the manufacture of liquid crystal display devices, in particular, color large glass substrates. It can be removed efficiently, removes thin film, reduces the level of interface, and cleans the substrate after development, so that it can be applied to various processes, making it economical to use, simplifying the manufacturing process, and improving production yield. It can be effected.

Claims (7)

a) 10 to 90 parts by weight of dimethyl acetamide; And b) 10 to 90 parts by weight of acetone, Thinner composition for photosensitive resin composition removal of the board | substrate used for manufacture of a liquid crystal display element. The method of claim 1, a) 10 to 70 parts by weight of dimethyl acetamide; And b) 30 to 90 parts by weight of acetone, The thinner composition for removing the photosensitive resin composition used for removing the color resist of the edge and back part of the color glass substrate of a liquid crystal display element. The thinner composition of claim 1, wherein the thinner composition further comprises c) perfluoroalkyl amine oxide. The method of claim 3, wherein a) 10 to 90 parts by weight of dimethyl acetamide; b) 10 to 90 parts by weight of acetone; And c) 0.001 to 1 part by weight of perfluoroalkyl amine oxide Thinner composition for removing the photosensitive resin composition comprising a. delete delete The method according to claim 3 or 4, The alkyl group of the perfluoroalkyl amine oxide is a thinner composition for removing a photosensitive resin composition having 5 to 30 carbon atoms.