KR20130085729A

KR20130085729A - A thinner composition for removing photosensitive resin

Info

Publication number: KR20130085729A
Application number: KR1020120006743A
Authority: KR
Inventors: 신성건; 김병욱; 권오환; 조태표; 정종현; 윤석일
Original assignee: 주식회사 동진쎄미켐
Priority date: 2012-01-20
Filing date: 2012-01-20
Publication date: 2013-07-30

Abstract

The present invention relates to a thinner composition for removing photoresist, in particular a) ethyl 3-ethoxypropionic acid; b) propylene glycol monomethyl ether acetate; c) gamma butyrolactone; And d) relates to a thinner composition for removing a photoresist comprising methyl lactate.
The thinner composition for removing photoresist of the present invention can not only efficiently remove photoresist unnecessarily applied to the edge part or the back side of a wafer during the photoresist application during semiconductor manufacturing or display manufacturing process, High stability to human body, economical production yield can be improved economically by simplifying semiconductor manufacturing process and display device, especially suitable for Reduce Resist Coating (RRC) process.

Description

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

The present invention not only efficiently removes unnecessary photoresist applied to the edge portion or the back side of the wafer during the photoresist application during semiconductor manufacturing or display manufacturing process, but also has high stability to the human body. The present invention relates to a thinner composition for removing photoresist suitable for RRC (Reduce Resist Coating) process, which can economically improve production yield by simplifying a semiconductor manufacturing process and a display device.

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.

After the photoresist is uniformly applied to the surface of the wafer during the photolithography process, an operation of removing unnecessarily applied photoresist on the edge portion or the back side of the wafer is required. In the case where photoresist is present, various defects may occur in subsequent processes such as etching and ion implantation due to their presence, thereby resulting in a decrease in yield of the entire semiconductor device.

Conventionally, in order to remove photoresist existing on the edge or backside of the 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 a photoresist conventionally used, Japanese Patent Laid-Open No. 63-69563 discloses a thinner composition as an edge upside part, an edge side part, and a back back part of a substrate. A method of removing contact with unnecessary photoresist film is proposed. Examples of the solvent for removing the photoresist film include ethers and ether acetates such as cellosolve acetate, propylene glycol ether, and propylene glycol ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and methyl. Ester, such as lactate, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate, is used. The solvent is used as a thinner composition, and a method of removing the thinner composition by contacting the photosensitive film of the substrate, the flue part, and the back part of the substrate is unnecessary. Japanese Unexamined Patent Application Publication No. Hei 4-42523 is a thinner composition. A method of using alkoxy propionate is disclosed.

As the integration of semiconductor devices increases, photoresist compositions for I-line and G-line have been developed, and since the main components of i-Line, KrF, and ArF are all different from each other, sufficient removal effect is obtained alone. There is a problem that can not be.

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

Japanese Patent Application Laid-Open No. Hei 4-130715 uses a thinner composition composed of a mixed solvent consisting of an alkyl pyrupinic acid solvent and methyl ethyl ketone. Japanese Laid-Open Patent Publication No. 7-146562 uses a thinner composition composed of a mixture of propylene glycol alkyl ether and 3-alkoxy propionic acid alkyls. Japanese Patent Application Laid-Open No. 7-128867 uses a thinner composition composed of a mixture of propylene glycol alkyl ether and butyl acetate and ethyl lactate or a mixture of butyl acetate, ethyl lactate and propylene glycol alkyl ether acetate. U.S. Patent No. 4,983,490 uses a mixed solvent of propylene glycol alkyl ether acetate and propylene glycol alkyl ether as a thinner composition.

However, there are many difficulties in the application of the semiconductor device and the thin film transistor liquid crystal display device, which have been increasingly integrated and large diameter even with the above-described mixed solvents. In addition, particles may be generated when they do not have sufficient solubility as in the thinner composition. Therefore, there is a need for further research on thinner compositions that can efficiently remove unnecessarily attached photoresist that is used at edges and rear surfaces of the wafer in a short time.

Meanwhile, RRC (Reduce Resist Coating) process is also being studied. In the process of uniformly applying the photosensitive resin composition to the wafer surface, the thinner is first applied before the photoresist is applied to the wafer surface to enhance the advice of the thinner and the photoresist to apply a small amount of photoresist. ought. However, in this case, the photoresist composition of KrF and ArF, which realizes the micropattern as compared to the i-line, also uses a resin having high polarity, which causes the photoresist to not spread evenly with respect to the existing thinner composition. In some cases, more studies on thinner compositions satisfying all of these conditions are required.

In order to solve the problems of the prior art as described above, the present invention can efficiently remove unnecessarily applied photoresist on the edge portion or the back of the wafer in a short time during the photoresist coating during semiconductor manufacturing or display manufacturing process. In addition, it has high stability to the human body, can simplify the semiconductor manufacturing process and display device, and can economically improve the production yield. Especially, a thinner composition for removing photoresist suitable for RRC (Reduce Resist Coating) process and a device using the same An object of the present invention is to provide a pattern forming method.

In order to achieve the above object,

a) ethyl 3-ethoxypropionic acid;

b) propylene glycol monomethyl ether acetate;

c) gamma butyrolactone; And

d) methyl lactate

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

In another aspect, the present invention provides a method for forming a pattern of a semiconductor or display device using the thinner composition for removing the photoresist.

The thinner composition for removing a photoresist according to the present invention can efficiently remove unnecessarily applied photoresist on an edge portion or a back side of a wafer in a short time during photoresist application during semiconductor manufacturing or display manufacturing process. In addition, it has high stability to human body and can improve production yield economically by simplifying semiconductor manufacturing process and display device. Especially, it is suitable for RRC (Reduce Resist Coating) process.

Hereinafter, the present invention will be described in detail.

The present invention is to study the thinner composition in which ethyl 3-ethoxypropionic acid, propylene glycol monomethyl ether acetate and gamma butyrolactone are harmless to human body and can remove photoresist efficiently in a short time. As a result of preparing the thinner composition, the photoresist used on the edge and backside of the wafer used for semiconductor manufacturing can be removed efficiently in a short time, as well as high stability to the human body, It was confirmed that the step can be applied to various processes by reducing the step, and the semiconductor manufacturing process can be simplified to economically improve the production yield.

The thinner composition for removing a photoresist of the present invention is characterized by comprising a) ethyl 3-ethoxypropionic acid, b) propylene glycol monomethyl ether acetate, c) gamma butyrolactone, and d) methyl lactate.

In the present invention, the a) ethyl 3-ethoxypropionic acid is preferably included in an amount of 20-70 parts by weight, more preferably 30-60 parts by weight, based on 100 parts by weight of the thinner composition. When a) the content of ethyl 3-ethoxypropionic acid is included in 20 to 70 parts by weight, it is effective to remove the photoresist by having a proper volatilization and dissolving power for the photoresist, in particular can be applied uniformly when applied to the RRC process have. However, if the content is out of the range, the volatilization and dissolving power for the photoresist may fall, and when applied to the RRC process, the photoresist may not evenly spread when the photoresist is applied, so that the edge may be cracked.

In the present invention, the propylene glycol monomethyl ether acetate of b) is excellent in the solubility of the photosensitive component of the photosensitive resin compared to other solvents, it is preferably included in 20 to 60 parts by weight based on 100 parts by weight of the thinner composition, in particular 30- It is preferably included in 50 parts by weight. When the content of the propylene glycol monomethyl ether acetate of b) is included in 20 to 60 parts by weight, solubility can be increased, so that the photoresist can be removed in a short time by showing excellent dissolving power when used as a thinner.

In the present invention, the gamma butyrolactone of c) has a very excellent dissolving ability with respect to the resin of the photoresist, so that it is preferably included in an amount of 1-20 parts by weight based on 100 parts by weight of the thinner composition, and particularly, 1-10 parts by weight. It is preferable. C) When the content of gamma butyrolactone is less than 1 part by weight, there is a problem in that the EBR performance is lowered. When the content of the gamma butyrolactone is less than 1 part by weight, it may cause a residue problem due to volatilization, in particular the gamma butyrolactone 1 to 10 When included in parts by weight, excellent EBR performance can be obtained.

In addition, in the present invention, the d) methyl lactate is preferably included in an amount of 1-20 parts by weight, particularly 1-10 parts by weight based on 100 parts by weight of the thinner composition. Recently, the photoresist composition of KrF and ArF, which implements micropatterns, may use a resin having high polarity. In particular, when d) methyl lactate is contained in 1-10 parts by weight, the thinner composition of the present invention increases the polarity of the thinner composition, thereby providing excellent EBR performance. When applied to the RRC process, the photoresist leveling (PR LEVELING) can be improved.

In addition, the thinner composition of the present invention may further include a surfactant that can be used in the thinner composition. As a specific example, the surfactant may be a fluorine-based or nonionic surfactant. The surfactant may be included in an amount of 0.001-0.1 parts by weight based on 100 parts by weight of the thinner composition. Including the surfactant in an amount of 0.001-0.1 parts by weight may improve the EBR Profile, and if it exceeds 0.1 parts by weight, bubbles may be severely generated, which may cause a malfunction of the sensor that detects the amount of liquid.

The thinner composition for removing photoresist of the present invention comprising the above components may be sprayed by dropping or spraying through a nozzle to remove unnecessary photoresist generated at edges and rear portions of the substrate, and in particular, the photoresist of the present invention. The removal thinner composition shows an excellent effect even when applied to the RRC process.

In addition, the amount of the thinner composition for removing the photoresist may be used according to the kind of the photoresist and the thickness of the film, and may form a fine circuit pattern through a subsequent photolithography process.

The thinner composition for photoresist removal of the present invention as described above can efficiently remove unnecessarily attached photoresist in a short time by being used at the edge and the rear portion of the glass substrate used in the wafer or display device used in semiconductor manufacturing. At the same time, it is safer for workers due to its high stability to the human body, and it is possible to economically improve the production yield by simplifying the manufacturing process of liquid crystal display devices and semiconductors. Suitable for coating process.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Example 1-7 and Comparative Example 1-10

The thinner composition was prepared with the components and composition ratios shown in Table 1 below. At this time, the unit of Table 1 is a weight part.

Example EEP PGMEA GBL ML nBA PGME MEK One 50 34 8 8 2 40 44 8 8 3 30 54 8 8 4 40 35 15 10 5 37 40 8 15 6 45 32 15 8 7 40 37 8 15

Comparative Example One 60 40 2 50 40 10 3 50 40 10 4 50 40 10 5 40 40 10 10 6 40 40 10 10 7 40 40 10 10 8 45 45 5 5 9 50 40 10 10 50 10 40

1.EEP: ethyl 3-ethoxypropionic acid (ETHYL 3-ETHOXYPROPIONATE)

2.PGMEA: Propyleneglycol monomethyl ether acetate,

3.GBL: gamma-butyrolactone,

4. ML: Methyl lactate,

5. nBA: n-Buthyl acetate,

6 PGME: Propyleneglycol monomethyl ether,

7.MEK: METHYL ETHYL KETONE

Experiment 1: Unnecessary Photoresist Removal Experiment of Thinner Composition to Photoresist

Each photoresist was applied to an 8-inch silicon oxide substrate, and then an experiment was performed to remove unnecessary photoresist at the edge portion using the thinner compositions of Examples 1-7 and Comparative Examples 1-5. 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 apply the photosensitive resin composition shown in Table 2, and then the photoresist was removed under the conditions of Table 3 below. Each thinner composition was supplied from a pressure vessel equipped with a pressure gauge, and the pressurized pressure was 1.0 kgf, and the flow rate of the thinner composition from the EBR nozzle was 10-20 cc / min. EBR experimental evaluations for each photoresist are shown in Table 4 below.

EBR experimental conditions division PR type Film thickness
(탆) PRE i-line PR 1.0 PR B i-line PR 1.5 PR C KrF PR 0.8 PR D KrF PR 0.3 PR E ArF PR 0.3 PR F ArF PR 0.2 PR G ArF PR 0.1

EBR experimental conditions division Rotational speed (rpm) Time (sec) Dispense condition 300 3 Spin coating Adjusted according to photoresist thickness EBR condition 1000 10 1500 10 2000 10

division PRE PR B PR C PR D PR E PR F PR G Example 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ○ ◎ ○ ○ Example 5 ◎ ◎ ◎ ○ ◎ ○ ◎ Example 6 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ ○ ◎ Comparative Example 1 ○ ○ △ △ △ × × Comparative Example 2 ○ ○ △ △ △ × × Comparative Example 3 ○ ○ △ △ △ × × Comparative Example 4 ○ ○ △ △ △ × × Comparative Example 5 ○ ○ △ △ △ × × Comparative Example 6 ○ ○ △ △ △ × × Comparative Example 7 △ △ △ △ △ △ △ Comparative Example 8 ○ ○ △ △ × × × Comparative Example 9 △ △ △ △ × × × Comparative Example 10 △ △ △ △ × × ×

In Table 4 above,

'◎' indicates that the EBR line uniformity for the photoresist after EBR is constant, '○' indicates that the EBR line uniformity for the photoresist after EBR is more than 80% good, and '△' indicates after EBR. The EBR line uniformity of the photoresist is 50% or more in a good linear state, and '×' indicates that the EBR line uniformity is more than 20% in good condition and the tailing of the photoresist occurs at the edge portion.

Experiment 2: Coating Uniformity Test of Thinner Composition on Photoresist

Each thinner composition was applied to an 8-inch silicon oxide substrate to apply the photoresist shown in Table 2, and the coating ability was then applied to the thinner compositions of Examples 1-7 and Comparative Examples 1-10. Each thinner composition shown in Table 1 was sprayed onto the photoresist-coated substrate through an EBR nozzle to apply a photoresist under the conditions shown in Table 5 below. The applicability test evaluation for each photoresist is shown in Table 6 below.

division Rotational speed (rpm) Time (sec) Thinner condition Thinner spray 0 One Thinner rotation 2000 One Spin coating Adjusted according to photoresist thickness EBR condition 1000 10 1500 10 2000 10

division PRE PR B PR C PR D PR E PR F PR G Example 1 ○ ○ ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ ○ ○ Example 4 ○ ○ ○ △ ○ △ ○ Example 5 ○ ○ ○ ○ △ ○ ○ Example 6 ○ ○ ○ ○ ○ ○ ○ Example 7 ○ ○ ○ ○ ○ ○ △ Comparative Example 1 △ ○ △ × △ × △ Comparative Example 2 △ ○ △ × △ × △ Comparative Example 3 △ ○ △ × △ × △ Comparative Example 4 △ ○ △ △ △ × × Comparative Example 5 ○ ○ △ △ △ × × Comparative Example 6 ○ ○ × △ △ × × Comparative Example 7 △ △ × △ △ × △ Comparative Example 8 ○ ○ × △ × × × Comparative Example 9 △ △ × △ × × × Comparative Example 10 △ △ × △ × × ×

In Table 6, the evaluation symbol '○' indicates that the coating uniformity on the substrate after coating is constant, '△' indicates that the coating uniformity on the substrate after coating is more than 90% good, and '×' after coating The coating uniformity on the substrate indicates that the photoresist coating defect occurred at the edge portion.

As shown in Table 4 and Table 6, the thinner compositions according to the present invention was confirmed to exhibit excellent EBR performance and coating properties for all photoresists than the thinner composition of the comparative examples.

Claims

a) ethyl 3-ethoxypropionic acid;
b) propylene glycol monomethyl ether acetate;
c) gamma butyrolactone; And
d) methyl lactate
Thinner composition for removing photoresist comprising a.

The method of claim 1,
a) 20-70 parts by weight of ethyl3-ethoxypropionic acid;
b) 20-60 parts by weight of propylene glycol monomethyl ether acetate;
c) 1-20 parts by weight of gamma butyrolactone; And
d) 1-20 parts by weight of methyl lactate
Thinner composition for removing photoresist comprising a.

The method of claim 1,
a) 30-60 parts by weight of ethyl3-ethoxypropionic acid;
b) 30-50 parts by weight of propylene glycol monomethyl ether acetate;
c) 1-10 parts by weight of gamma butyrolactone; And
d) 1-10 parts by weight of methyl lactate
Thinner composition for removing photoresist comprising a.

The method of claim 1,
The thinner composition for removing a photoresist, further comprising 0.001-0.1 parts by weight of surfactant based on 100 parts by weight of the thinner composition.

The pattern formation method of the semiconductor or display element using the thinner composition for photoresist removal of any one of the thinner compositions for photoresist removal of Claims 1-4.

The method of claim 5,
The pattern forming method comprises a Reduce Resist Coating (RRC) process.