KR20070013777A - Thinner composition for removing photoresist - Google Patents

Abstract

A thinner composition for removing photoresist used in manufacturing semiconductor or liquid crystal display is provided to efficiently and rapidly remove photoresist adhered in undesired portions of a substrate regardless of kinds of photoresist by comprising alkyl ethanoate and fluorinated acrylic copolymer. The composition principally comprises (a) alkyl ethanoate and (b) fluorinated acrylic copolymer in amount of 0.001 to 1.0wt. parts relative to 100wt. parts of alkyl ethanoate. The fluorinated acrylic copolymer has weight average molecular weight of 1,000 to 10,000. The alkyl ethanoate is selected from a group consisting of methyl ethanoate, ethyl ethanoate, isopropyl ethanoate, normal propyl ethanoate and butyl ethanoate.

Description

Thinner composition for removing photoresist {THINNER COMPOSITION FOR REMOVING PHOTORESIST}

[Industrial use]

The present invention relates to a thinner composition for removing a photoresist, and more particularly, to a thinner composition capable of effectively removing unnecessary photoresist during a manufacturing process of a semiconductor device or a liquid crystal display device.

[Prior art]

The TFT-array process of the thin film transistor-liquid crystal display (TFT-LCD) manufacturing process is similar to the silicon semiconductor manufacturing process using the photolithography process. The photolithography step is a step of forming an electronic circuit by applying a photosensitive film to a substrate, transferring and developing the pattern of the photomask, and etching appropriately according to the transferred pattern.

The photolithography process ultimately forms a TFT-array on the substrate to fabricate the TFT-LCD. In such a process, the thinner composition penetrates between the photoresist interfaces and may cause various defects in subsequent processes such as etching or ion implantation, thereby causing a decrease in yield of the entire process.

As described above, the phenomenon in which the thinner composition penetrates between the photoresist interfaces causes defocus during exposure after the baking process and reduces the yield of the TFT-LCD manufacturing process.

Unlike the edge portion rinse of the silicon wafer where centrifugal force acts, the glass substrate of the TFT-LCD is square, so that rotation EBR (edge bead removing) operation is not possible. In addition, since the glass substrate is fixed and the injection hole moves linearly along the four sides of the glass substrate, when the photoresist is applied, the interface at the end portion of the photoresist even after removing the photoresist formed at the edge portion when the volatilization rate decreases. Penetration into the cell occurs. This is different from the rotating EBR operation, when rotating at high speed on a silicon wafer, even thinner thinner reduces penetration into the interface at the photoresist tip. That is, since the LCD glass substrate is fixed and only the thinner injection hole is moved, when a thinner having a conventional dissolution rate is used, penetration of photoresist interface occurs during rinsing of the edge portion, thereby reducing the yield of the entire process.

Looking at the conventional thinner compositions having the above problems as follows.

Japanese Laid-Open Patent Publication No. 63-69563 discloses a method of removing a thinner by contacting an unnecessary photoresist with a lead portion, a flue portion, and a back portion of a substrate. Ethers such as acetates, propylene glycol ethers, propylene glycol ether acetates and ether acetates, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate Ester, such as butyl acetate, is used as a thinner. Japanese Unexamined Patent Application Publication No. Hei 4-49938 discloses the use of propylene glycol methyl ether acetate as a thinner, and Japanese Laid-Open Patent Publication No. 4-42523 discloses a method of using alkylalkoxy propionate as a thinner. have.

That is, these solvents may be used alone as above, or a mixture of single solvents may be used for physical property improvement and safety reasons. Such solvents have been used to increase the rotational speed in the process of manufacturing semiconductor devices that perform EBR while rotating the substrate even though the initial volatilization speed is not high, unlike the manufacturing process of the TFT-LCD, in which the substrate is fixed and the straight EBR.

However, conventionally, there was a problem that the glass substrate EBR does not cope with the penetration phenomenon between the photoresist interface.

In view of the problems of the prior art as described above, the object of the present invention is not only used for the substrate used for the manufacture of the display device irrespective of the type of photoresist, but also used for the edge and the rear portion of the large glass substrate for the organic EL, which is unnecessary. It is to provide a thinner composition for removing a photoresist capable of efficiently removing the attached photoresist in a short time.

In order to achieve the above object, the present invention

a) alkyl ethanoate; And b) a fluorinated acrylic copolymer.

Preferably, the thinner composition comprises a) 100 parts by weight of alkyl ethanoate; b) 0.001 to 1.0 parts by weight of fluorinated acrylic copolymer.

Hereinafter, the present invention will be described in detail.

The thinner composition for removing a photoresist according to the present invention includes a glass substrate used in a photolithography process of a liquid crystal display and a display device such as an organic EL, including a specific surfactant, and an edge and a rear portion of a wafer used during a semiconductor manufacturing process. Compared to the conventional single organic solvent, unnecessary unnecessary photoresist can be removed in a short time, can be applied to various processes, can be economically used, and can simplify the manufacturing process and improve the production yield. It can be effective. The thinner composition of the present invention can preferably be used in the photolithography process of organic EL or LCD.

The thinner composition for removing photoresist of the present invention comprises a) alkyl ethanoate; And b) fluorinated acrylic copolymers.

The alkyl ethanoate used in the thinner composition for removing the photoresist of the present invention may be selected to use a pure grade of semiconductor grade, and it is preferable to use a filtration of 0.1 μm in the VLSI grade.

In the thinner composition of the present invention, a) the alkyl ethanoate preferably has 1 to 4 carbon atoms in the alkyl group, and specific examples thereof include methyl ethanoate, ethyl ethanoate, isopropyl ethanoate and normal propyl eta. It is preferable to select at least one from the group consisting of noate and butyl ethanoate. Of these, it is preferable to use a solvent such as isopropyl ethanoate, normal propyl ethanoate, or butyl ethanoate, which have a relatively low viscosity and have a moderate volatility. In particular, the alkyl ethanoate is preferably used normal butyl ethanoate.

In addition, b) fluorinated acrylic copolymers used in the thinner compositions of the present invention act as nonionic surfactants. The content of the fluorinated acrylic copolymer is preferably 0.001 to 1.0 parts by weight based on 100 parts by weight of the alkyl ethanoate. When the content of the fluorinated acrylic copolymer is between 0.001 and 1.0 parts by weight, it may exhibit excellent removal performance by lowering the dynamic surface tension at the interface to the photoresist. When the content of the copolymer is less than 0.001 parts by weight, the volatility and the cleaning power of the thinner at the end of the substrate is significantly reduced, and when exceeding 1.0 parts by weight, bubbles are severely generated, making it inconvenient to use.

The fluorinated acrylic copolymer has a weight average molecular weight of 1000 to 10000, the flash point (measured by the open cup method) 200 ℃, specific gravity 1.10 g / ml (25 ℃), viscosity (20 ℃) 2100 cst, surface The tension is 24.0 mN / m (Wilhermy method) on ethyl lactate and it is preferable to dilute and mix with ethyl lactate. The fluorinated acrylic copolymer may be selected and used according to the purpose from commercially available megaface series.

The manufacturing method of the thinner composition for photoresist removal according to the present invention is not particularly limited, and may be prepared by mixing the above components by a conventional method. Then, the present invention is applied to the photoresist using an applicator, and removes unnecessary photoresist generated on the edge and the rear portion of the substrate by dropping 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.

Hereinafter, the present invention will be described in more detail with reference to 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 8 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 photoresist was coated with a predetermined thickness on the upper surface of the substrate. A spin coater (Korea Semiconductor, Model EBR TRACK) was used to apply the photoresist. In the rotation coating operation, 10 cc of photoresist was added dropwise to the center of the stationary substrate. The photoresist was then distributed for 3 seconds at 300 rpm using a rotating coater. Thereafter, the substrate was accelerated at a rotational speed of about 1000 to 2000 rpm to adjust each photoresist to a predetermined thickness. The rotation time at this speed is about 20-30 seconds.

(Examples 1-3 and Comparative Examples 1-4)

The thinner compositions of Examples 1 to 3 and Comparative Examples 1 to 4 having the compositions and contents shown in Table 1 below were prepared, respectively.

Classification (part by weight) nBA ¹ PGMEA ² PGME ³ Acetone ⁴ Sur. ⁵ Example One 100 - - - 0.01 2 100 - - - 0.05 3 100 - - - 0.1 Comparative example One 100 - - - - 2 - 100 - - - 3 - - 100 - - 4 - - - 100 -

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1.nBA: n-Buthyl acetate,

2.PGMEA: Propyleneglycol monomethyl ether acetate,

3. PGME: Propyleneglycol monomethyl ether,

4. Acetone: Acetone,

5. Sur. : Fluorinated acrylic copolymer (Surfactant), Megaface R-08

Photoresist  About Thinner  No need of composition Photoresist  Removal experiment

Each photoresist was applied to an 8-inch silicon oxide substrate, and then the thinner compositions of Examples 1 to 3 and Comparative Examples 1 to 4 were used to remove unnecessary photoresist at the edge portion. Proceeds). EBR experiments also used the same spin coater used to apply the photoresist to the substrate.

Each thinner composition shown in Table 1 was sprayed onto the photoresist-coated substrate through an EBR nozzle to remove the photoresist under the conditions of Table 2 below. Each thinner composition was supplied from a pressure vessel equipped with a pressure gauge, the pressurization pressure was 1.0 kgf, and the flow rate of the thinner composition from the EBR nozzle was 10 to 20 cc / min.

The EBR experimental evaluation for each photoresist is shown in Table 3 below.

EBR  Experimental conditions division Rotation speed (rpm) Time (sec) Distribution conditions 300 3 Spin coating Adjusted according to photoresist thickness  EBR condition 1000 10 1500 10 2000 10

Photoresist  About EBR  Experimental evaluation division EBR condition Example Comparative Example One 2 3 One 2 3 4    Positive type 1000 rpm 10sec ◎ ◎ ◎ × ○ △ × 1500 rpm 10sec ◎ ◎ ◎ × ○ △ × 2000 rpm 10sec ◎ ◎ ◎ × ○ △ ×    Negative 1000 rpm 10sec ◎ ◎ ◎ × ○ △ × 1500 rpm 10sec ◎ ◎ ◎ × ○ △ × 2000 rpm 10sec ◎ ◎ ◎ × ○ △ ×

In Table 3, the evaluation symbol '◎' indicates that the EBR line uniformity for the photoresist after EBR is constant, and '○' indicates that the EBR line uniformity for the photoresist after EBR is more than 80% good. The evaluation symbol '△' indicates that the EBR line uniformity for the photoresist after EBR is more than 50% good, and the evaluation symbol '×' indicates that the EBR line uniformity is more than 20% good and the tailing of the photoresist on the edge part ( tailing).

As shown in Table 3, the thinner compositions according to the preferred embodiment of the present invention showed excellent EBR performance (good EBR line uniformity) for all photoresists. On the other hand, the thinner compositions of Comparative Examples 1, 3, and 4 consisted only of a single general organic solvent different from the present, and showed poor results for all photoresists, and Comparative Example 2 showed good results, but compared to the present invention. It can be seen that it is insufficient.

As described above, the thinner composition for removing a photoresist according to the present invention is not necessary because it is used not only on the substrate used for the manufacture of the liquid crystal display device, but also on the edge and the rear portion of the large glass substrate for organic EL regardless of the photoresist type. The photoresist can be effectively removed in a short time, can be applied to a variety of processes, there is an effect that can simplify the manufacturing process and improve the production yield.

Claims (4)

a) alkyl ethanoate; And b) fluorinated acrylic copolymers Thinner composition for removing photoresist comprising a. The method of claim 1, a) based on 100 parts by weight of alkyl ethanoate; b) 0.001 to 1.0 parts by weight of fluorinated acrylic copolymer Thinner composition for removing photoresist comprising a. The method of claim 1, The alkyl ethanoate may be one or more selected from the group consisting of methyl ethanoate, ethyl ethanoate, isopropyl ethanoate, normal propyl ethanoate, and butyl ethanoate. . The method of claim 1, The fluorinated acrylic copolymer has a weight average molecular weight of 1000 to 10000 thinner composition for removing the photoresist.