KR20050037972A - Thinner composition for removing photosensitive resin - Google Patents

Abstract

The present invention relates to a thinner composition for removing photoresist, and more particularly, to a thinner composition for removing photoresist comprising a) 100 parts by weight of propylene glycol monoalkyl ether acetate and b) 0.001 to 1 part by weight of polyethylene oxide condensate.

The thinner composition for removing photoresist of the present invention can efficiently remove unnecessarily attached photoresist in a short time by being used at the edges and backside portions of the glass substrate used in the liquid crystal display device and the wafer used in semiconductor manufacturing. High stability to the human body, can be applied to a variety of processes by reducing the step of the interface, it is possible to simplify the liquid crystal display device and semiconductor manufacturing process to improve the production yield economically.

Description

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

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thinner composition for removing photoresist, and more particularly, a photoresist that is used unnecessarily to be attached to edges and backside portions of a glass substrate used in a liquid crystal display device and a semiconductor used in the manufacture of semiconductors in a short time. Not only can be removed, but also has high stability to the human body, can be applied to various processes by reducing the step difference of the interface, and for the photoresist removal that can economically improve the production yield by simplifying the liquid crystal display device and semiconductor manufacturing process It relates to a thinner composition.

The photolithography process in the semiconductor manufacturing process consists of applying a photoresist to a wafer, transferring the pattern as previously designed, and composing an electronic circuit through an etching process that appropriately scrapes according to the transferred pattern. Work is one of the very important work.

This photolithography process

(B) applying a photoresist uniformly to the surface of the wafer;

A soft baking process in which the solvent is evaporated from the applied photoresist to cause the photoresist to adhere to the surface of the wafer,

An exposure step of transferring the mask pattern onto the wafer by exposing the wafer while repeating and sequentially reducing and projecting the circuit pattern on the mask using a light source such as ultraviolet rays;

현상 a developing process for selectively removing parts with different physical properties such as solubility difference by exposure to light sources using a developer,

하드 a hard baking process for tighter adhesion of the photoresist remaining on the wafer to the wafer after development

An etching process for etching a predetermined portion to impart electrical characteristics according to the developed wafer pattern;

박리 a stripping process for removing unnecessary photoresist after the above step

Or the like.

In the photolithography process, after the soft baking process of the wafer, an operation of removing an unnecessarily applied photoresist on the edge part or the back side of the wafer is required, and when the photoresist exists on the edge or the back side of the wafer, Due to their presence, various defects may occur in subsequent processes such as etching, ion implantation, and the like, thereby causing a problem of lowering the yield of the entire semiconductor device.

Conventionally, in order to remove photoresist existing on the edge or backside of a wafer, a spray nozzle is provided above and below the wafer edge portion, and a thinner made of an organic solvent component is sprayed on the edge or backside through the nozzle.

As a thinner composition for removing photoresist used in the prior art, Japanese Patent Application Laid-Open No. 63-69563 discloses ether and ether acetates such as cellosolve, cellosolve acetate, propylene glycol ether, propylene glycol ether acetate, acetone, methyl ethyl ketone , Ketones such as methyl isobutyl ketone, cyclohexanone, and other esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate as thinner compositions. Disclosed is a method of contacting and removing unnecessary photoresist on the back portion. In addition, Japanese Patent Application Laid-open No. Hei 4-49938 discloses a method of using propylene glycol methyl ether acetate as the thinner composition, and Japanese Patent Laid-Open No. Hei 4-42523 uses an alkylalkoxy alkoxy propionate as the thinner composition. It discloses how to.

In the case of ethylene glycol monoethyl ether acetate, the dissolution rate is excellent, but there is a problem in that it exhibits reproductive toxicity, such as high volatility and flammability, in particular leukopenia and induction of fetal abortion. In addition, since ethyl lactate has a high viscosity and a low dissolution rate, there is a problem that a sufficient washing effect cannot be obtained alone.

Therefore, there is a need for further studies on thinner compositions capable of efficiently removing unnecessarily attached photoresist used at the edges and backsides of glass substrates used in liquid crystal display devices and wafers used in semiconductor manufacturing in a short time. .

In order to solve the problems of the prior art as described above, the present invention can efficiently remove unnecessarily attached photoresist in a short time to the glass substrate used in the liquid crystal display device and the wafer and used in the semiconductor manufacturing. An object of the present invention is to provide a thinner composition for removing photoresist.

It is another object of the present invention to provide a photoresist thinner composition for removing photoresist, which is safer for workers due to high stability to human body, can be applied to various processes, and can improve the production yield of liquid crystal display devices and semiconductor manufacturing processes. To provide.

In order to achieve the above object, the present invention

a) 100 parts by weight of propylene glycol monoalkyl ether acetate;

   And

b) 0.001 to 1 part by weight of polyethylene oxide condensate

It provides a thinner composition for removing a photoresist comprising a.

Hereinafter, the present invention will be described in detail.

The present inventors studied the thinner composition which is harmless to the human body and can efficiently remove the photoresist in a short time, and produced the thinner composition using propylene glycol monoalkyl ether acetate and polyethylene oxide-based condensate. It is not only able to efficiently remove unnecessary photoresist attached to the edges and the back side of the wafers used in the manufacturing of glass substrates and semiconductors used in display devices in a short time, but also has high stability to the human body. Applicable, it has been confirmed that it is possible to simplify the liquid crystal display device and semiconductor manufacturing process to improve the production yield economically, to complete the present invention based on this.

The thinner composition for removing photoresist of the present invention is characterized in that it comprises a) propylene glycol monoalkyl ether acetate, and c) polyethylene oxide-based condensate.

The propylene glycol monoalkyl ether acetate of a) used in the present invention is used as a solvent in the thinner composition, an extremely pure semiconductor grade can be used, and in the VLSI grade, it can be used filtered at a level of 0.1 μm.

The propylene glycol monoalkyl ether acetate is preferably used having an alkyl group having 1 to 5 carbon atoms, specifically, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, or propylene glycol mono Butyl ether acetate and the like are more preferable, and in particular, it is preferable to use propylene glycol monomethyl ether acetate having excellent solubility in polymers.

The propylene glycol monomethyl ether acetate has high safety for the human body when exposed to air, and in terms of metabolism, it is rapidly decomposed into propylene glycol and alcohol and is safe. In addition, the LD ₅₀ (mouse) showing a 50% lethal dose due to oral administration to mice in the toxicity test represents 8.5 g / kg and is rapidly degraded by hydrolysis. Its physical properties are boiling point 146 ℃, flash point (measured by closed cup method) 42 ℃, viscosity (25 ℃) 1.17 cps, surface tension 26 dyne / ㎠.

The b) polyethylene oxide-based condensate used in the present invention acts as a nonionic surfactant in the thinner composition, has excellent solubility in the propylene glycol monoalkyl ether acetate, and the step at the interface when the thinner meets the photoresist. It works effectively to reduce.

The polyethylene oxide-based condensate preferably includes a condensation product obtained by condensing an alkylphenol having a linear or branched alkyl group having 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of the alkylphenol. Alkyl substituents in such compounds include about 12 moles of ethylene oxide per mole of nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol derived from polymerized propylene, diisobutylene, octene, or nonene. Condensed dodecylphenol or diisooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol.

The polyethylene oxide-based condensate is preferably contained in an amount of 0.001 to 1 parts by weight based on 100 parts by weight of propylene glycol monoalkyl ether acetate, and when the content is in the above range, the effect of thinner volatility and cleaning power at the end of the substrate is sustained. It is maintained as, there is no foaming has the advantage that it is easy to use.

In addition, the thinner composition for removing a photoresist of the present invention may further include c) a fluorinated acrylic copolymer.

The fluorinated acrylic copolymer has good solubility in the propylene glycol monoalkyl ether acetate.

The fluorinated acrylic copolymer preferably has a weight average molecular weight of 3000 to 10000, the flash point (measured by the open cup method) 200 ℃, specific gravity 1.10 g / mL (25 ℃), viscosity (20 ℃) 2100 cst, surface tension (on ethyl lactate) It is desirable to have physical properties of 24.0 mN / m (Wilhermy method).

The fluorinated acrylic copolymer is preferably included in an amount of 0.001 to 0.1 parts by weight based on propylene glycol monoalkyl ether acetate, and when the content is in the above range, the surface of the fluorinated acrylic copolymer may be removed by lowering the dynamic surface tension at the interface to the photoresist. There is an advantage.

The thinner composition for removing photoresist of the present invention comprising the above components is sprayed by dropping or spraying through a nozzle to remove unnecessary photoresist generated at edges and rear surfaces of the substrate.

In addition, the dropping or spraying amount of the thinner composition for removing the photoresist can be used according to the kind of the photosensitive resin used and the thickness of the film, and it is preferable to select and use in 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.

As described above, the thinner composition for removing photoresist of the present invention can efficiently remove unnecessarily attached photoresist in a short time by being used at the edges and backside portions of the glass substrate used in the liquid crystal display device and the wafer used in semiconductor manufacturing. At the same time, the safety of the human body is high, which is safer for the worker, can be applied to various processes, and the liquid crystal display device and the semiconductor manufacturing process can be simplified to economically improve the production yield.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

A thinner composition was prepared by uniformly mixing 100 parts by weight of propylene glycol monoethyl ether acetate and 0.1 part by weight of polyethylene oxide-based condensate.

Examples 2-3 and Comparative Example 1

A thinner composition was prepared in the same manner as in Example 1, except that Example 1 was used as a component and a composition ratio shown in Table 1 below. At this time, the unit of Table 1 is a weight part.

division Example 1 Example 2 Example 3 Comparative Example 1 PGMEA 100 100 100 100 SUR.1 0.1 0.5 0.1 - SUR.2 - - 0.01 - PGMEA: Propylene glycol monoethyl ether acetate SUR.1: Polyethylene oxide-based condensate SUR.2: Fluorinated acrylic copolymer

In order to measure the degree of unnecessary photoresist removal of the thinner composition prepared in Examples 1 to 3 and Comparative Example 1, an EBR experiment was performed as follows, and the results are shown in Table 4 below.

The silicon oxide substrates, 8 inches in diameter, 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). Then, on the upper surface of the substrate, each photoresist shown in Table 2 was coated to a certain thickness using a rotating coater (EBR TRACK, Korea Semiconductor). In the rotation coating operation, 10 cc of photoresist was added dropwise to the center of the stationary substrate. Thereafter, the photoresist was distributed at 500 rpm for 3 seconds using a rotating coater, and then the substrate was accelerated at a rotational speed of about 2000 to 4000 rpm to adjust each photoresist to a predetermined thickness. At this time, the rotation time is about 20 to 30 seconds.

The photoresist was prepared by spraying the thinner composition prepared in Examples 1 to 3 and Comparative Example 1 onto the photoresist coated substrate prepared as described above, and removed the photoresist under the conditions shown in Table 3 below. At this time, each thinner composition was supplied from a pressure vessel equipped with a pressure gauge, the pressurization pressure at this time was 1.0 kgf, and the flow rate of the thinner composition coming out of the EBR nozzle was 10 to 20 cc / min.

division Composition type Composition Film thickness (㎛) Photoresist Positive type DTFR-2000 1.5 g-line positive DNR-H100PL 4 PI for organic EL DL-1003 1.5 ArF DHA-TG2 2

division Rotation speed (rpm) Time (sec) Distribution conditions 500 3 Spin coating Adjusted according to photoresist thickness EBR condition 400 7 400 10 500 7 500 10

division Example 1 Example 2 Example 3 Comparative Example 1  Positive type 400 rpm 7sec ○ ○ ◎ × 500 rpm 7sec ○ ○ ◎ △ 500 rpm 10sec ○ ○ ◎ △ g-line negative type 400 rpm 7sec ○ ○ ◎ × 500 rpm 7sec ○ ○ ◎ △ 500 rpm 10sec ○ ○ ◎ △ Organic EL type PI 400 rpm 7sec ○ ○ ◎ × 500 rpm 7sec ○ ○ ◎ × 500 rpm 10sec ○ ○ ◎ △ For ArF 400 rpm 7sec ○ ○ ◎ × 500 rpm 7sec ○ ○ ◎ × 500 rpm 10sec ○ ○ ◎ △ [Note] ◎: EBR line uniformity for photoresist after EBR is constant ○: EBR line uniformity for photoresist after EBR is more than 80% Good △: EBR line uniformity for photoresist after EBR is 50% Abnormal good linear state ×: EBR line uniformity for photoresist is less than 50% after EBR, and tailing of photoresist occurs at edges

Through the Table 4, the thinner compositions of Examples 1 to 3 according to the present invention showed excellent EBR performance (good EBR line uniformity) for all photoresists, and in particular, further comprising a fluorinated acrylic copolymer. 3 showed more excellent EBR performance, from which the thinner composition according to the present invention was found to have excellent photoresist removal performance.

On the other hand, Comparative Example 1, which does not include propylene glycol monoalkyl ether acetate and polyethylene oxide-based condensates, as shown in the present invention, was found to have significantly reduced performance compared to the examples in suppressing penetration into the photoresist. .

The thinner composition for removing photoresist according to the present invention can efficiently remove unnecessarily attached photoresist in a short time by being used at the edges and backside portions of a glass substrate used in a liquid crystal display device and a wafer used in semiconductor manufacturing. At the same time, the safety of the human body is high, which is safer for workers, can be applied to various processes, and the liquid crystal display device and the semiconductor manufacturing process can be simplified to economically improve the production yield.

Claims (5)

a) 100 parts by weight of propylene glycol monoalkyl ether acetate;    And b) 0.001 to 1 part by weight of polyethylene oxide condensate Thinner composition for removing photoresist comprising a. The method of claim 1, c) A thinner composition for removing photoresist, further comprising 0.001 to 0.1 parts by weight of fluorinated acrylic copolymer. The method of claim 1, The propylene glycol monoalkyl ether acetate of a) is a group consisting of propylene glycol monomethyl ether acetate having 1 to 5 carbon atoms of an alkyl group, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate Thinner composition for photoresist removal selected from one or more. The method of claim 1, Thinner for removing photoresist, wherein the polyethylene oxide condensate of b) is a condensation product of condensation of alkyl phenol having a linear or branched chain alkyl group having 6 to 12 carbon atoms and 5 to 25 moles of ethylene oxide per mole of the alkylphenol. Composition. The method of claim 2, C) Fluorinated acrylic copolymer has a weight average molecular weight of 3,000 to 10,000 of the thinner composition for removing a photoresist.