KR20070052943A - Thinner composition for removing photoresist - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to thinner compositions for removing photoresists used in the manufacturing process of semiconductor devices, liquid crystal display devices, and organic light emitting devices, more particularly thinner compositions comprising glycol ethers, more preferably fluorinated acrylics. A composition further comprising a copolymer, an organic solvent or a mixture thereof.

The thinner composition of the present invention is a glass substrate used for manufacturing a liquid crystal display device and an organic light emitting device, and a photo used unnecessarily attached to an edge and a rear portion of a wafer used for manufacturing a semiconductor, regardless of the type of photoresist. The resist can be removed efficiently in a short time.

Glycol ethers, thinners, photoresists

Description

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

1 to 3 is a photograph showing the results of the edge bead photoresist removal (EBR) experimental evaluation (surface treatment characteristics) of the thinner composition of Examples 1 to 11 of the present invention,

Figure 4 shows a photograph of the results of the experimental evaluation of the edge bead (Edge Bead Removing, EBR) for the thinner composition of Comparative Examples 1 to 4.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thinner composition for removing photoresist, and more particularly, to a glass substrate used in the manufacture of a liquid crystal display device, and to a photoresist unnecessarily attached to edges and rear surfaces of a semiconductor wafer. The present invention relates to a thinner composition for removing a photoresist that can be efficiently removed in a short time and can be applied to various processes, and can be economically used as well as to simplify the manufacturing process and improve the production yield.

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.

The phenomenon that the thinner composition penetrates between the photoresist interfaces as described above causes defocus during exposure after the bake process, and reduces the yield of the TFT-LCD manufacturing process.

In addition, the thinner should consider both economic and performance aspects at the same time, when considering only the performance aspect, there was a problem of deteriorating EBR performance when applying a conventional thinner to the wafer due to the difference in the components of the PR.

In particular, unlike the rinse of the edge portion of the silicon wafer where the centrifugal force acts, the glass substrate of the TFT-LCD is square, so that the edge bead removing (EBR) operation of the rotating edge portion in the LCD is impossible. 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 volatilization rate is lowered, and even after the photoresist formed at the edge portion is removed, Penetration between interfaces occurs. This is different from a rotating EBR operation in which a silicon wafer is rotated at high speed, and even a thinner thinner reduces penetration into the interface at the end of the photoresist. 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. Examples of organic solvents for cleaning removal include cellosolves and cellosolves. 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, in the above method, 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 manufacturing process of semiconductor devices that perform EBR operations while rotating even though the initial volatilization speed is not high, unlike the manufacturing process of TFT-LCD with straight substrate EBR with a fixed substrate.

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

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

In order to achieve the above object, the present invention provides a thinner composition for removing a photoresist comprising a glycol ether.

Preferably, the thinner composition of the present invention may comprise a fluorinated acrylic copolymer, an organic solvent, or a mixture thereof as a surfactant.

Hereinafter, the present invention will be described in more detail.

The thinner composition for removing a photoresist of the present invention is used on edges and rear portions of wafers and glass substrates used in photolithography processes such as semiconductors, LCDs, and PDPs, so that unnecessary photoresist can be efficiently removed in a short time. .

In addition, the thinner composition of the present invention can be applied to various processes and economical, as well as the effect of simplifying the manufacturing process and improving the production yield. The thinner composition of the present invention can preferably be used in the photolithography process of the organic insulating film or LCD.

The thinner composition of the present invention includes a glycol ether compound, which may be selected from the group consisting of alkylene glycol alkyl ethers having an alkyl group having 1 to 6 carbon atoms. In this case, the alkylene glycol alkyl ether is one having an alkylene having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, and PGME: propylene. It is preferably selected from the group consisting of glycol monomethyl ether, and mixtures thereof. The content of the glycol ether compound may be included in 100% by weight in the thinner composition.

In addition, the thinner composition of the present invention may further include a fluorinated acrylic copolymer, an organic solvent, or a mixture thereof as a surfactant.

In the thinner composition of the present invention, it is preferable that the nonionic surfactant uses fluorinated acrylic copolymer. 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 Preference is given to using a tension exhibiting 24.0 mN / m (Wilhermy method) on ethyl lactate. The fluorinated acrylic copolymer may be selected and used as a commercially available product, by using the Megaface series of Dainippon Ink and Chemicals. The content of the fluorinated acrylic copolymer is preferably 0.001 to 1 parts by weight, and more preferably 0.01 to 0.3 parts by weight based on 100 parts by weight of glycol ether. When the content of the fluorinated acrylic copolymer is less than 0.001 parts by weight, the dissolving power to the photoresist is significantly lowered. When the content of the fluorinated acrylic copolymer is more than 1 part by weight, the dynamic surface tension is lowered at the interface to show excellent removal performance, but bubbles are severely generated. In use, it may cause malfunction of the sensor to detect the liquid level.

The organic solvent is N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), methyl isobutyl ketone (MIBK), gamma butyrolactone (GBL), ethyl lactate (EL ), Propylene glycol monomethyl ether acetate (PGMEA), and ethyl-3-ethoxypropionate (EEP). The amount of the organic solvent is preferably used in an amount of 20 to 50 parts by weight based on 100 parts by weight of the glycol ether compound. If the content is less than 20 parts by weight, thinner performance is not exerted. There is a problem that does not express.

When using a nonionic surfactant and an organic solvent in this invention, the weight ratio is not specifically limited.

The present invention is applied to the photoresist using an applicator and removed by removing the unnecessary photoresist generated on the edge and the rear surface of the substrate by dropping or spraying through a nozzle to the thinner composition. The dropping or spraying amount of the thinner composition of the present invention can be adjusted according to the kind of 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 the following examples. These examples are only for illustrating the present invention, of course, the scope of the present invention is not limited to the following examples.

Example

Example  1 to 11 and Comparative example  1 to 4

The thinner compositions of Examples 1 to 11 and Comparative Examples 1 to 4 having the compositions and contents shown in Table 1 below were prepared, respectively.

Classification (part by weight) EGME ¹ nBA ² PGMEA ³ PGME ⁴ Acetone MIBK ⁵ DMAc ⁶ NMP ⁷ Sur. ⁸ Example 1 100 - - - - - - - 0.01 Example 2 100 - - - - - - - 0.05 Example 3 100 - - - - - - - 0.1 Example 4 100 - - - - - - - - Example 5 50 - - - - 50 - - - Example 6 70 - - - - - 30 - 0.01 Example 7 70 - 30 - - - - 0.05 Example 8 70 - - 30 - - - - 0.1 Example 9 80 - - - - - 20 - - Example 10 70 - - - - - - 30 - Example 11 - - - 100 - - - - - Comparative Example 1 - 100 - - - - - - - Comparative Example 2 - - 100 - - - - - - Comparative Example 3 - - - - 100 - - - - Comparative Example 4 - 100 - - - - - - 0.01

Note) In Table 1 above,

1.EGME: Ethylene glycol monomethyl ether,

2.nBA: n-Buthyl acetate,

3. PGMEA: Propyleneglycol monomethyl ether acetate,

4. PGME: Propyleneglycol monomethyl ether,

5. MIBK: Methyl isobutyl ketone

6. DMAc: Dimethylacetamide

7.NMP: N-methylpyrrolidone

8. Sur. (Surfactant): Fluorinated acrylic copolymer (Megaface series of Dainippon Ink and Chemicals)

Photoresist  About Thinner  No need of composition Photoresist  Removal experiment

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 (organic insulating film) 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 700 to 1000 rpm to adjust each photoresist to a predetermined thickness. The rotation time at this speed is about 20 seconds.

Then, after applying each photoresist to the 8-inch silicon oxide substrate as described above, the experiment to remove the unnecessary photoresist of the edge region with the thinner composition of Examples 1 to 11 and Comparative Examples 1 to 4 (Edge Bead Removing experiment (Hereinafter referred to as EBR experiment). 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 following conditions. 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 coming out of the EBR nozzle was 10 cc / min. EBR experimental evaluations for each photoresist are shown in Figures 1-4 and Table 2.

(Exam conditions)

1) dispense: 300rpm / 3sec

2) coating: PR target thickness rpm / sec (700 ~ 1000rpm / 20sec)

3) EBR: 200rpm / 10, 15 sec (low rpm process for LCD scan EBR simulation)

4) Dry: 600rpm, 10sec

1 is an EBR photograph after applying the thinner compositions of Examples 1 to 4 of the present invention to an organic EL, and FIG. 2 is an EBR photograph after applying the thinner compositions of Examples 5 to 7 of the present invention to an organic insulating film. 3 is an EBR photograph after applying the thinner composition of Example 8-9 of the present invention to the positive type. 4 is an EBR photograph after applying the thinner compositions of Comparative Examples 1 to 4 to the organic insulating film. EBR photographs were measured with an Olympus 2D instrument.

1 to 4, it can be seen that the thinner composition of Examples 1-11 according to the present invention has better EBR surface treatment characteristics than the thinner composition of Comparative Examples 1-4.

In addition, the EBR experiments were performed on the thinner compositions of Examples 1 to 11 and Comparative Examples 1 to 4 under the same conditions as above, and the results of the EBR experiment evaluation are shown in Table 2.

Positive type Organic insulating film For organic EL EBR condition 200 rpm, 10 sec 200 rpm, 15 sec 200 rpm, 10 sec 200 rpm, 15 sec 200 rpm, 10 sec 200 rpm, 15 sec Example 1 ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ ◎ Example 5 ○ ◎ ○ ◎ ○ ◎ Example 6 ○ ◎ ○ ◎ ○ ◎ Example 7 ○ ◎ ○ ◎ ○ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ ◎ Example 9 ○ ◎ ○ ◎ ○ ◎ Example 10 ○ ◎ ○ ◎ ○ ◎ Example 11 △ ○ △ ○ △ ○ Comparative Example 1 △ △ × × × × Comparative Example 2 △ △ △ △ △ △ Comparative Example 3 × × × × × × Comparative Example 4 ○ ○ × × △ △

In Table 2, 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 2, the thinner compositions according to the present invention showed excellent EBR performance (good EBR line uniformity) for all photoresists.

The thinner composition for removing a photoresist according to the present invention can efficiently remove unnecessarily attached photoresist in a short time by being used at the edges and the back side of a glass substrate used in a liquid crystal display device and a semiconductor manufacturing and a PDP. It can be applied to various processes, economical use, as well as the effect of simplifying the manufacturing process and improving the production yield.

Claims (8)

Thinner composition for removing photoresist comprising a glycol ether. The thinner composition of claim 1, wherein the composition further comprises a fluorinated acrylic copolymer, an organic solvent, or a mixture thereof. The thinner composition of claim 1, wherein the glycol ether compound is selected from the group consisting of alkylene glycol alkyl ethers having an alkyl group having 1 to 6 carbon atoms.  The thinner composition of claim 2, wherein the fluorinated acrylic copolymer has a weight average molecular weight of 1000 to 10000. The method of claim 2, wherein the organic solvent is N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl acetamide (DMAc), methyl isobutyl ketone (MIBK), gamma butyrolactone (GBL) At least one selected from the group consisting of ethyl lactate (EL), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and ethyl-3-ethoxypropionate (EEP). Phosphorus thinner composition. 3. The thinner composition according to claim 2, wherein the composition comprises 0.001 to 1 parts by weight of fluorinated acrylic copolymer with respect to 100 parts by weight of glycol ether. The thinner composition according to claim 2, wherein the composition comprises 20 to 50 parts by weight of an organic solvent based on 100 parts by weight of a glycol ether. The thinner composition according to claim 2, wherein the composition comprises 0.001 to 1 parts by weight of fluorinated acrylic copolymer, and 20 to 50 parts by weight of an organic solvent, based on 100 parts by weight of glycol ether.

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