KR100536044B1 - Thinner composition and method for stripping a photoresist using the same - Google Patents

Abstract

A novel thinner composition and a method of stripping a photoresist applied onto a substrate using the thinner composition are disclosed. The thinner composition consists of 8 to 95% by weight of normal butyl acetate, 0.1 to 13% by weight of gamma-butyrolactone and 3 to 80% by weight of nonacetic acid ester compound. In addition, the thinner composition may be composed of 42 to 90% by weight of normal butyl acetate, 1 to 13% by weight of gamma-butyrolactone and 5 to 45% by weight of a polyhydric alcohol derivative. In addition, the thinner composition may be used to selectively strip the photoresist applied to the substrate edge and the back surface portion. In addition, the thinner composition may be used to strip the photoresist applied to the entire surface of the substrate. Low cost thinner compositions can be used to strip various types of photoresist.

Description

Thinner composition and method for stripping a photoresist using the same}

The present invention relates to a novel thinner composition and a method of stripping a photoresist using the same. More particularly, the present invention relates to novel thinner compositions that can be manufactured at low cost and to methods of stripping photoresist applied onto a substrate using the thinner compositions.

In order to manufacture a fine circuit, impurities must be precisely controlled and injected into a small area of a silicon substrate, and these areas are interconnected to form a device and a VLSI circuit. A pattern defining these areas is formed by a photolithography process. . That is, by applying a photoresist polymer film on the wafer substrate, it is selectively exposed by irradiating ultraviolet rays, electron beams or X-rays, and then developed. The remaining photoresist protects the applied substrate, and the portion where the photoresist is removed is used as a pattern to perform various additional or extractive processes on the substrate surface.

When performing the photolithography, defects in the application of the photoresist often occur. If such a defect occurs, the substrate on which the photoresist is applied is stripped to remove the photoresist, and the substrate is reused. This process is called a rework process of the wafer.

In addition, when forming the photoresist layer, the photoresist is applied onto the substrate while mainly rotating the substrate. Then, the photoresist is also applied to the substrate edge and the back side. However, the photoresist applied to the substrate edge and the back surface may cause particles or the like in a subsequent process such as an etching or ion implantation process or cause pattern defects. Therefore, a process of stripping and removing the photoresist applied to the edge and the back surface of the substrate using the thinner composition (hereinafter referred to as an 'EBR process') is performed.

The photoresist used in the prior art is too slow or incompletely dissolved so that residual contaminants of the photoresist component on the substrate after stripping have not been removed in a subsequent process. In such a case, the yield of the apparatus is lowered, which adversely affects reliability.

On the other hand, as the degree of integration of semiconductor devices increases, photoresist compositions used in I-line and G-line have been developed, and these photoresist compositions have novolac resin as a main component. In addition, amplified photoresists that respond to excimer laser wavelengths or far ultraviolet rays have also been used. Therefore, there is a need for a stripping thinner composition of photoresist that exhibits excellent solubility in common with these various photoresists.

Recently presented thinner compositions are disclosed, for example, in US Pat. No. 5,866,305 (issued to Chon et al.) And US Pat. No. 6,159,646 (issued to Jeon et al.).

U.S. Patent No. 5,866,305 discloses a thinner composition consisting of ethyl lactate and ethyl-3-ethoxy propionate, or ethyl lactate and ethyl-3-ethoxy propionate. Thinner compositions are disclosed that consist of nate and gamma-butyro lactone. Although the thinner composition disclosed in the above-mentioned US Patent No. 5,866,305 is currently used a lot, it is expensive because ethyl-3-ethoxy propionate is a main component. In addition, the thinner composition disclosed in the above-mentioned US Pat. No. 5,866,305 has a disadvantage in that it has a poor solubility in stripping of a specific photoresist, for example, an amplified photoresist.

According to US Pat. No. 6,159,646, a thinner composition consisting of ethyl lactate and gamma butyrolactone, a thinner composition consisting of ethyl lactate and ethyl-3-ethoxy propionate and gamma butyrolactone, or ethyl lactate and ethyl A thinner composition consisting of -3-ethoxy propionate is disclosed. However, since the thinner composition is an expensive EEP, GBL, etc. as a main component, the manufacturing cost of the thinner composition is high.

In addition, Korean Patent Application Publication No. 2001-36461, filed Oct. 8, 1999 (Application No. 1999-43486) and published on May 7, 2001, by Applicant (assignee), includes acetone, gamma-butiro, A stripping composition based on lactones and ester compounds is disclosed. However, acetone, which is the main component of the thinner, has a strong penetration property, so that the edge profile of the photoresist is poor, especially in the EBR process. This is especially true for certain photoresists such as DUV photoresists. In addition, acetone has a very high volatilization degree, and thus generates residues, for example, when the EBR process is performed using a thinner made of NBA + GBL + acetone.

The thinner compositions may be commonly used for stripping the photoresist for reuse (rework process) and stripping the photoresist applied to the substrate edge and backside (EBR process), but thinners having the same effect on the two processes may be used. Desperately needed.

The thinner compositions also have the disadvantage of being expensive on the ingredients. This acts as a fatal defect in the manufacture of recent semiconductor devices requiring cost reduction.

Therefore, in recent years, there is a need for developing low-cost thinner compositions that do not interfere with stripping properties.

It is a first object of the present invention to provide a novel thinner composition at low cost having excellent stripping characteristics common to all REWORK processes and EBR processes for all currently used photoresists.

It is a second object of the present invention to provide a method for stripping a photoresist using the thinner composition.

The present invention provides a thinner for photoresist strips, which is generally effective in various photoresist and EBR / REWORK processes while increasing the content of NBA, which is inexpensive, and reducing the content of relatively expensive EEP, GBL, etc., compared to conventional thinners, and It relates to the strip method used.

In order to achieve the first object of the present invention described above, the present invention is an acetic acid ester compound, gamma-butyro lactone and non-acetate type ester compound Provided is a thinner composition for a photoresist strip comprising a).

In addition, the first object of the present invention described above may be achieved in a thinner composition for a photoresist strip composed of an acetic acid ester compound, gamma-butyrolactone, and poly alkyl alcohol derivatives. .

In order to achieve the above-mentioned second object of the present invention, the present invention provides a thinner composition for a photoresist strip or an acetate ester compound, a gamma-butyrol lactone, and an acetate ester compound, a gamma-butyrolactone and a nonacetic acid ester compound. Preparing a photoresist strip thinner composition composed of a polyhydric alcohol derivative; And contacting the thinner composition to the substrate on which the photoresist is applied to strip the photoresist. As the acetic acid ester compound, it is preferable to use normal butyl acetate.

According to the present invention, a low-cost compound such as the acetic acid ester compound, particularly the normal butyl acetate, can be used as a main component or a compound having a high composition ratio of the thinner composition. Although the thinner compositions can be manufactured at a low price, the same or better photoresist stripping characteristics can be obtained as in the conventional thinner compositions. Therefore, the thinner compositions are economically very advantageous when used in the semiconductor industry that requires a recent cost reduction. Further, since the compounds constituting the thinner composition are environmentally friendly, they can actively cope with recent environmental problems.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, a first group thinner composition composed of an acetic acid ester compound, gamma-butyro lactone and a nonacetic acid ester compound will be described.

Examples of the acetic acid ester compound that can be used in the present invention include normal butyl acetate, amyl acetate, ethyl acetoacetate, isopropyl acetate, and the like. These can be used individually or in mixture. Preferred acetic acid ester compounds usable in the present invention include normal butyl acetate (hereinafter often referred to as 'NBA').

Here, the NBA is known to have a good dissolving ability with respect to resins. The NBA has a specific gravity of 0.882 at 20 ° C, a viscosity of 0.693 cps at 25 ° C, a boiling point of 126.5 ° C at atmospheric pressure, a flash point of 38 ° C, and a burning point of 421 ° C. Has characteristics. In particular, NBA is cheap and has good WETTABILITY characteristics, but when used alone, the photoresist edge profile is poor, especially in the EBR process.

In the first group of thinner compositions, when the content of acetic acid ester (specific content may vary depending on the type of acetic acid ester) is less than 8% by weight or more than 95% by weight, the stripping characteristics of the photoresist decrease. It is not preferable because it becomes. Therefore, the content of acetic acid ester is 8 to 95% by weight, preferably 50 to 90% by weight. In particular, when the acetic acid ester is NBA, the content of NBA is 20 to 90% by weight, preferably 30 to 89% by weight.

In addition, examples of the non-acetic acid ester compound that can be used in the present invention include ethyl lactate (hereinafter sometimes referred to as 'EL') and ethyl-3-ethoxy propionate (hereinafter often referred to as 'EL'). And Methyl-3-methoxy propionate (hereinafter sometimes referred to as MMP). These may be used alone or in combination of two or more components. The materials have a property of inhibiting penetration characteristics, for example, serves to suppress photoresist residues generated when only NBA and GBL are used as the thinner composition.

If the content of the non-acetic acid ester compound is less than 3% by weight or more than 80% by weight, the stripping property of the photoresist is lowered, which is not preferable. Therefore, the content of the non-acetic acid ester compound is 3 to 80% by weight, preferably 10 to 70% by weight.

In particular, in the case of using EEP as the nonacetic acid ester compound, the content of EEP is 10 to 70% by weight, preferably 10 to 65% by weight.

The thinner composition of the first group of the present invention contains gamma-butyro lactone (hereinafter sometimes referred to as 'GBL') as a main component.

GBL is known as a solvent of synthetic resin, has a high flash point, and is relatively stable as a solvent. In addition, the GBL is safe for the human body to be used as a food additive. The GBL has physical properties of specific gravity at 25 DEG C, 1.1254, viscosity at 25 DEG C, 1.7 cps, boiling point 204 DEG C, flash point 98.3 DEG C, and flash point 457 DEG C at atmospheric pressure. The GBL has a very good photoresist dissolving ability, but the price is high. Therefore, if the GBL content is low, the dissolving ability is low. More specifically, GBL plays a role in improving edge profile due to good solubility, but if a thinner composed of NBA + GBL only causes residue, a nonacetic acid ester such as EEP is required.

If the content of the GBL is less than 0.1% by weight, it is not preferable because the production of the thinner composition is not easy. In addition, when the content of the GBL exceeds 13%, it is not preferable because the manufacturing price of the thinner composition is increased. Therefore, the content of the GBL is 0.1 to 13% by weight, preferably 0.1 to 7% by weight, more preferably 0.5 to 5% by weight.

Preferred thinner compositions of the present invention include thinner compositions composed of NBA, GBL and EL, thinner compositions composed of NBA, GBL and EEP, thinner compositions composed of NBA, GBL and MMP.

In the thinner composition consisting of NBA, GBL and EL, the content of NBA is 50 to 85% by weight, the content of GBL is 1 to 13% by weight, and the content of EL is preferably 10 to 40% by weight. And, in a more preferred thinner composition, the content of the NBA is 55 to 85% by weight, the content of the GBL is 1 to 7% by weight, and the content of the EL is 10 to 40% by weight.

In the thinner composition consisting of NBA, GBL and EEP, the content of the NBA is 20 to 90% by weight, the content of the GBL is 0.1 to 13% by weight, and the content of the EEP is preferably 10 to 70% by weight. In a more preferred thinner composition, the content of NBA is 30 to 89% by weight, the content of GBL is 0.1 to 7% by weight, and the content of EEP is 20 to 70% by weight. And, in the most preferred thinner composition, the content of NBA is 30 to 89% by weight, the content of the GBL is 0.5 to 5% by weight, and the content of the EEP is 10 to 65% by weight.

In the thinner composition consisting of NBA, GBL and MMP, the content of NBA is 50 to 90% by weight, the content of GBL is 1 to 13% by weight, and the content of MMP is preferably 5 to 40% by weight. In a more preferred thinner composition, the NBA content is 55 to 90% by weight, the GBL content is 1 to 7% by weight, and the MMP content is 5 to 40% by weight.

The thinner composition may further include a trace amount of a surfactant as necessary. Surfactants usable in the present invention include alkylbenzenesulfonates and alkali metal salts thereof, alkylated diphenyl disulfonates and alkali metal salts thereof, alkyl aryl sulfonates, alkali metal fluoroalkaline carboxylate salts, ammonium perfluoroalkyl Sulfonates, and the like. The role of the surfactant is to improve the wettability (WETTABILITY) and to mix each component of the thinner evenly. The content of the surfactant is preferably 1% by weight or less.

Next, a thinner composition for stripping photoresist according to a second embodiment group consisting of an acetic acid ester compound, gamma-butyrolactone, and a polyhydric alcohol derivative will be described.

The thinner composition according to the second embodiment of the present invention contains an acetic acid ester compound. The description of the acetic acid ester compound is as described above.

In the thinner composition, when the content of the acetic acid ester compound is less than 42% by weight or more than 90% by weight, the stripping characteristics of the photoresist are lowered, which is not preferable. Therefore, the content of acetic acid ester in the thinner composition is 42 to 90% by weight, preferably 50 to 85% by weight.

The thinner composition according to the second group of embodiments of the present invention includes GBL. The description in GBL is as described above.

If the content of the GBL is less than 1% by weight, it is not preferable because the production of the thinner composition is not easy. In addition, when the content of the GBL exceeds 13%, it is not preferable because the manufacturing price of the thinner composition is increased. The content of the GBL is 1 to 13% by weight, preferably 1 to 7% by weight.

The thinner composition according to the second embodiment of the present invention includes a polyhydric alcohol derivative. Polyhydric alcohol derivatives that can be used in the present invention include propylene glycol monomethyl ether (hereinafter sometimes referred to as 'PGME'), propylene glycol monomethyl ether acetate (hereinafter referred to as 'PGMEA') Etc. can be mentioned. These can be used individually or in mixture. Like the thinner compositions of the first group described above, thinners consisting solely of NBA + GBL cause residues and therefore require the polyhydric alcohol derivatives.

If the content of the polyhydric alcohol derivative is less than 5 wt% or more than 45 wt%, the stripping characteristics of the photoresist are deteriorated, which is not preferable. Therefore, the content of the polyhydric alcohol derivative is 5 to 45% by weight, preferably 10 to 40% by weight.

Preferred examples of the thinner compositions according to the second embodiment of the present invention include a thinner composition composed of the NBA, GBL, and PGME, a thinner composition composed of the NBA, GBL, and PGMEA.

In the case of the thinner composition consisting of the NBA, GBL and PGME, the content of the NBA is 50 to 85% by weight, preferably 55 to 85% by weight, and the content of the GBL is 1 to 13% by weight, preferably 1 to 1%. 7% by weight, and the content of PGME is 5 to 40% by weight, preferably 10 to 30% by weight.

In the thinner composition consisting of the NBA, GBL and PGMEA, the content of the NBA is 50 to 85% by weight, preferably 55 to 85% by weight, the content of the GBL is 1 to 13% by weight, preferably 1 to 7 wt% and the content of PGMEA is 10-40 wt%.

And, the thinner composition according to the second embodiment group preferably further comprises a surfactant. The surfactant is the same as described above. The content of the surfactant is preferably 1% by weight or less.

The stripping method of the photoresist using the thinner compositions will be described.

EBR process

1 is a process diagram illustrating a method for stripping photoresist applied to a substrate edge and a back surface area using a thinner composition according to an embodiment of the present invention.

Referring to FIG. 1, a thinner composition composed of the NBA, GBL and nonacetic acid ester compounds or a thinner composition composed of the NBA, GBL and a polyhydric alcohol derivative is prepared. (Step S10)

Next, a photoresist is applied onto the substrate. (Step S12) The application of the photoresist mainly uses a spin-coater. Thus, photoresist is applied to the substrate to be rotated by the spin-coater. Accordingly, the photoresist sprayed on the substrate is pushed to the edge of the substrate by centrifugal force and applied to the entire region of the substrate with a uniform thickness.

The photoresist pushes not only the edge portion of the substrate but also the back portion portion of the substrate by the centrifugal force. As such, the photoresist that is pushed to the edge and backside portions of the substrate and applied to the edges and backside of the substrate acts as a defect in subsequent processes.

Therefore, the thinner composition is brought into contact with the edge and the back surface of the substrate to which the photoresist is applied to strip the photoresist. (Step S14) The contact of the thinner composition may include a method of spraying the thinner composition on the substrate.

The method of spraying the thinner composition may be performed using a spin-chuck for rotating the substrate, a nozzle for spraying the thinner composition, or the like.

In this embodiment, a method of spraying the thinner composition using the rotary chuck and the nozzle will be described.

When spraying the thinner composition, the substrate is preferably subjected to a low speed rotation and a high speed rotation sequentially by the rotation-chuck.

First, the thinner composition is sprayed while rotating the photoresist-coated substrate at a relatively low speed. The thinner composition is sprayed to the edge and backside of the substrate for about 5-10 seconds, preferably 6 seconds, through the nozzle while rotating the substrate at a speed of, for example, 800 to 2,000 rpm. Then, the thinner composition sprayed on the rotating substrate strips and removes the photoresist unnecessarily applied to the edge and the backside of the substrate by centrifugal force.

Next, the substrate is spin-dried by rotating the substrate at a relatively high speed of 2,000 to 2,500 rpm. (Step S16) This spin dry step can be omitted if necessary.

In addition, other methods of spraying the thinner composition are as follows. After fixing the nozzle, there is a method of spraying the thinner composition to the edge of the substrate while rotating the substrate, and after fixing the substrate, spraying the thinner composition while moving the nozzle along the edge portion of the substrate There is a way. The method of spraying the thinner composition on the back surface of the substrate is also similar to the method of spraying the thinner composition on the edge of the substrate using another nozzle. After that, the usual photo process, that is, photoresist baking, exposure and development process are performed.

Rework process

2 is a flowchart illustrating a method for stripping a photoresist applied to the entire surface of a substrate using a thinner composition according to an embodiment of the present invention.

First, if a defect occurs in a state in which the normal photo process, that is, the development process is completed, the rework process is performed.

2, a thinner composition composed of the NBA, GBL and non-acetic acid ester compounds or a thinner composition composed of the NBA, GBL and polyhydric alcohol derivatives is prepared. (Step S20)

Then, the thinner composition is contacted with a substrate on which the photoresist is applied, that is, a substrate for reworking for reuse, to strip the photoresist. The method of contacting the thinner composition may include dipping the substrate into the thinner composition contained in the bath, or spraying the thinner composition on the substrate using a spin-chuck and a nozzle.

This embodiment describes a method of spraying thinner composition onto a substrate using the rotation-chuck and nozzle.

First, the thinner composition is sprayed onto the substrate while rotating the substrate on which the photoresist is applied at a relatively low speed. (Step S22) Specifically, the thinner composition is sprayed on the substrate for about 10 to 20 seconds through the nozzle while rotating the substrate at a speed of 800 to 2,000 rpm. Then, the thinner composition sprayed on the rotating substrate is uniformly provided on the substrate by centrifugal force.

Then, the rotation of the substrate is temporarily stopped. (Step S24) The stop of the substrate is held for about 10 to 30 seconds. Then, the photoresist applied on the substrate is dissolved by the thinner composition sprayed on the substrate.

Next, the wafer is optionally spin-dried by rotating the substrate at a high speed of about 2,000 to 2,500 rpm. The spin dry may be omitted.

The substrate is then rotated at a relatively high speed to remove photoresist residue remaining on the substrate. Specifically, the thinner composition is sprayed on the substrate rotating at high speed while rotating the substrate at a speed of about 2000 to 2500 rpm for about 10 to 20 seconds. (Step S26) Then, the photoresist residue remaining on the said board | substrate is removed.

Then, the injection of the thinner composition to the substrate rotating at a high speed is stopped. Then, only the substrate continues to rotate at a high speed of 2000-2500 rpm. As a result, spin dry of the thinner composition injected onto the substrate is performed. (Step S28)

Subsequently, pure water is sprayed onto the substrate to clean the substrate, and the substrate is continuously rotated to spin dry. (Step S30)

Here, the steps S24, S26 and S30 may be omitted by the operator as an additional process.

Therefore, when stripping of the photoresist is performed through the above method, the substrate can be reused.

As such, when stripping the various photoresists, excellent stripping characteristics may be obtained even by using the thinner compositions. That is, the present invention does not affect the stripping properties of the photoresist despite the use of the low cost thinner composition.

Hereinafter, embodiments of the present invention will be described in detail.

Example 1

The NBA, GBL, and EL were put in a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted such that the NBA content was 85% by weight, the GBL content was 5% by weight, and the EL content was 10% by weight. The viscosity of the obtained thinner composition was 0.79 cps (measured in a 25 ° C thermostat).

Example 2

The NBA, GBL, and EL were put in a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted so that the content of NBA was 75% by weight, the content of GBL was 5% by weight, and the content of EL was 20% by weight. The viscosity of the thinner composition obtained was 0.88cp (measured in a 25 degreeC thermostat).

Example 3

The NBA, GBL and EEP were put into a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted such that the NBA content was 85 wt%, the GBL content was 5 wt%, and the EEP content was 10 wt%. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Example 4

The NBA, GBL and EEP were put into a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted so that the content of NBA was 75% by weight, the content of GBL was 5% by weight, and the content of EEP was 20% by weight. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Example 5

The NBA, GBL and EEP were put into a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted such that the NBA content was 35% by weight, the GBL content was 5% by weight, and the EEP content was 60% by weight. The viscosity of the obtained thinner composition was 0.78 cps (measured in a 25 ° C thermostat).

Example 6

The NBA, GBL and PGMEA were put in a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted so that the NBA content was 85% by weight, the GBL content was 5% by weight, and the PGMEA content was 10% by weight. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Example 7

The NBA, GBL and PGMEA were put in a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted so that the content of NBA was 75% by weight, the content of GBL was 5% by weight, and the content of PGMEA was 20% by weight. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Example 8

The NBA, GBL and PGME were put in a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted so that the NBA content was 85 wt%, the GBL content was 5 wt%, and the PGME content was 10 wt%. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Example 9

The NBA, GBL and PGME were put in a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted so that the content of NBA was 75% by weight, the content of GBL was 5% by weight, and the content of PGME was 20% by weight. The viscosity of the obtained thinner composition was 0.78 cps (measured in a 25 ° C thermostat).

Example 10

The NBA, GBL and MMP were put into a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted such that the NBA content was 90% by weight, the GBL content was 5% by weight, and the MMP content was 5% by weight. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Example 11

The NBA, GBL and EEP were put into a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted so that the NBA content was 87% by weight, the GBL content was 1% by weight, and the EEP content was 12% by weight. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Comparative Example 1

EEP, EL, and GBL were put into a container, and these were mixed, and the thinner composition was prepared. The thinner composition was adjusted so that the content of the EEP was 75% by weight, the content of the EL was 20% by weight, and the content of the GBL was 5% by weight. The viscosity of the thinner composition obtained was 1.30 cps (measured in a 25 ° C thermostat).

Comparative Example 2

The thinner composition disclosed in Korean Patent Laid-Open No. 2001-0036461 was prepared.

NBA, GBL, and acetone were put into a container, and these were mixed to prepare a thinner composition. The thinner composition was adjusted so that the NBA content was 85% by weight, the GBL content was 5% by weight, and the acetone content was 10% by weight. The viscosity of the obtained thinner composition was 0.66 cps (measured in a 25 ° C thermostat).

Comparative Example 3

GBL and EL were put into the container, and these were mixed, and the thinner composition was prepared. The thinner composition was adjusted so that the content of GBL was 20% by weight and the content of EL was 80% by weight. The viscosity of the obtained thinner composition was 2.40 cps (measured in a 25 ° C thermostat).

Comparative Example 4

NBA and EL were put into a container, and these were mixed to prepare a thinner composition. The ratio of NBA: EL in the thinner composition was adjusted to 85: 5. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Comparative Example 5

NBA and GBL were put into a container, and these were mixed, and the thinner composition was prepared. The ratio of NBA: GBL in the thinner composition was adjusted to 85: 5. The viscosity of the obtained thinner composition was 0.74 cps (measured in a 25 ° C thermostat).

Dissolution rate test by type of photoresist

The dissolution rate for the photoresist currently in use was tested using the thinner composition prepared in Example 8.

Test Example 1

After spin-coating AZ1520HS (product name) of Clariant Company (USA), an i-line photoresist, on a substrate in an amount of about 1.5 cc, soft baking (heating to 110 ° C.) was performed. The thickness of the formed photoresist film was 42,000 kPa.

Then, the substrate was dipped into the thinner composition at 25 ° C. to strip the photoresist, and then the dissolution rate was observed. The dissolution rate observed was 5,000 kPa / sec.

Test Example 2

After spreading the MCPR-4100H (product name) of the Shipley Korea company (hingeuk), i-line photoresist, in an amount of about 1.5 cc, soft baking (heating at 90 ° C.) was performed. . The thickness of the formed photoresist film was 11,900 GPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 3,000 Pa / sec.

Test Example 3

After spin-coating SAT-701 (product name) of a Tiokei Co., Ltd. (TOK company: Japan), which is an i-line photoresist, on a substrate, soft baking (heating at 90 ° C.) was performed. The thickness of the formed photoresist film was 9,700 GPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 9,700 kPa / sec.

Test Example 4

After spin-coating SAT-668 (product name) of an i-line photoresist (TOK company (Japan)) as an amount of about 1.5 cc, soft baking (heating to 90 ° C.) was performed. The thickness of the formed photoresist film was 19,700 GPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 19,000 kPa / sec.

Test Example 5

After spin-coating the MCPR-i7010N (product name), which is an i-line photoresist, on the substrate in an amount of about 1.5 cc, soft baking (heating at 110 ° C.) was performed. The thickness of the formed photoresist film was 35,000 kPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 20,000 kPa / sec.

Test Example 6

PFI-58A (product name) of Dongwoo Company (Korea), an i-line photoresist, was spin-coated on the substrate in an amount of about 1.5 cc, followed by soft baking (heating to 110 ° C.). The thickness of the formed photoresist film was 12,300 GPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 12,200 kPa / sec.

Test Example 7

After spin-coating THMR-ip3100 (product name) of thiokei, i-line photoresist, on the substrate in an amount of about 1.5 cc, soft baking (heating to 110 ° C.) was performed. The thickness of the formed photoresist film was 14,400 GPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 14,400 kPa / sec.

Test Example 8

After spin-coating the GS111M (product name) of Shipley Korea, a g-line photoresist, on an amount of about 1.5 cc, soft baking (heating at 90 ° C.) was performed. The thickness of the formed photoresist film was 12,200 GPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The dissolution rate observed was over 12,000 kPa / sec.

Test Example 9

After spin-coating SEPR-402 (product name) of Shin-Etsu Co., Ltd. (Shinetsu company, Japan), which is an ultraviolet photoresist, on a substrate, soft baking (heating at 100 ° C.) was performed. The thickness of the formed photoresist film was 10,300 GPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 7,000 kPa / sec.

Test Example 10

After spin-coating SEPR-430 (product name) of Shin-Etsu Co., Ltd. (Shinetsu company, Japan), which is an ultraviolet photoresist, on a substrate, soft baking (heating at 100 ° C.) was performed. The thickness of the formed photoresist film was 5,700 GPa.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 5,700 kPa / sec.

Test Example 11

SSK-500MA (product name) of Sumitomo company (Japan), an ultraviolet photoresist, was spin-coated on the substrate in an amount of about 1.5 cc, followed by soft baking (heating at 100 ° C.). The formed photoresist film was 16,000 GPa thick.

The substrate was then immersed in the thinner composition to strip the photoresist, and then the dissolution rate was observed. The observed dissolution rate was over 7,000 kPa / sec.

In Test Examples 1 to 11, by using the thinner composition prepared in Example 8, the dissolution rates of various photoresists were observed, indicating that the dissolution rates were excellent for most photoresists. In addition, thinner compositions according to other examples showed similar results. Therefore, it can be seen that the thinner composition according to the present invention can be used to dissolve the photoresist applied on the wafer.

Residue evaluation test according to the type of photoresist

After dissolving the photoresist using the thinner compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 5, the presence of a residue, which is a remaining photoresist, was examined. Specifically, the same photoresist as used in Test Examples 1 to 11 was applied onto the substrate in the same manner as in Test Examples 1 to 11. After the applied substrate was immersed in the thinner composition obtained in Examples 1 to 10 and Comparative Examples 1 to 5 for 120 seconds, the substrate was naturally dried. The naturally dried substrate was observed under a microscope to assess the presence of residues remaining on the substrate. The evaluation results are shown in Table 1 below.

Photoresist Type PR 1 PR 2 PR 3 PR 4 PR 5 PR 6 PR 7 PR 8 PR 9 PR 10 PR 11 Example 1 0 △ △ △ △ 0 0 0 △ 0 0 Example 2 △ △ 0 △ 0 0 0 0 0 0 0 Example 3 0 △ △ △ △ 0 0 △ △ △ △ Example 4 △ △ △ △ △ △ △ 0 △ △ △ Example 5 △ △ △ △ △ △ △ △ △ △ △ Example 6 △ △ △ △ △ △ 0 △ △ △ △ Example 7 △ △ △ △ △ △ △ △ △ △ △ Example 8 0 0 △ △ 0 0 0 0 0 0 0 Example 9 △ 0 △ △ △ 0 △ 0 △ △ 0 Example 10 0 △ 0 0 0 0 0 0 0 △ △ Example 11 0 △ △ 0 △ 0 0 △ △ △ △ Comparative Example 1 △ △ △ 0 △ 0 0 △ △ 0 △ Comparative Example 2 0 △ △ △ △ △ △ △ 0 × 0 Comparative Example 3 0 0 0 △ △ 0 △ △ 0 △ △ Comparative Example 4 △ X △ △ 0 △ △ △ △ △ △ Comparative Example 5 0 △ △ △ △ 0 △ △ △ △ 0

Legend: 0 Good, △ Normal, × Bad

O: Good condition in which no residue remains on the substrate

△: Residual residue on substrate

X: When residue remains on the substrate to a certain extent and stripping is not good (residue occupies more than 10% of the substrate area)

* PR 1 to 11 are the same photoresist as the photoresist used in Test Examples 1 to 11, respectively.

As can be seen from Table 1, even when the photoresist is stripped by the immersion method using the thinner composition obtained in Examples 1 to 11 of the present invention, good stripping properties are obtained as in the previously used thinner composition. It can be seen that.

Therefore, it can be seen that the thinner composition of the present invention can be used as a photoresist stripping thinner composition by dipping.

Evaluation of the EBR Process According to the Type of Photoresist

The thinner compositions obtained in Example 11 and Comparative Examples 1, 2, 3, and 5 were subjected to the above-described EBR process for each type of photoresist, and then the degree of stripping of the photoresist was evaluated (EBR evaluation). In this EBR evaluation, photoresist contact was made by spraying a thinner composition onto the substrate. The injection was performed using DNS nitrogen (N2) pressurized coater (Coater). At this time, the nitrogen pressure was 0.7 Kg / Cm 2, and the thinner composition was supplied for 4 seconds at a flow rate of 13 cc / min. The evaluation results are shown in Table 2 below.

Photoresist Type PR 3 PR 4 PR 5 PR 6 PR 7 PR 9 PR 10 PR 11 Example 11 0 0 0 0 0 0 0 0 Comparative Example 1 △ 0 0 0 △ 0 0 0 Comparative Example 2 △ △ △ △ △ △ △ △ Comparative Example 3 X X X X X X X X Comparative Example 5 △ △ △ △ △ X X X

Legend: 0 Good, △ Normal, × Bad

O: Residue is not present at the site where the EBR process is performed, and the boundary line of the photoresist after performing the EBR process (the boundary between the site where the EBR process is performed and the area where the process is not performed) is neatly formed.

(Triangle | delta): There is no residue in the site which performed the EBR process, but the photoresist boundary after the EBR process is dirty.

X: Residue at the site where the EB process was performed, and the photoresist boundary after the EBR process was dirty

* PR 3 to 7 and 9 to 11 denote the same photoresist as those used in Test Examples 3 to 7 and 9 to 11, respectively.

As can be seen from Table 2, when the EBR process is performed using the thinner composition obtained in Example 11 of the present invention, it can be seen that good stripping characteristics can be obtained.

Although the thinner composition of Comparative Example 1 exhibited almost the same stripping characteristics as Example 11 of the present invention, the EBR boundary line was not neat for some i-Line PRs, and in particular, it was expensive. In addition, the thinner composition of Comparative Example 2 did not leave a residue after the EBR process, while containing the acetone as an additive component, it was found that the EBR boundary is not neat. The composition of Comparative Example 3 was found to have good solubility in photoresist but high viscosity (2.40 cps) and poor EBR characteristics.In the thinner composition of Comparative Example 5, after the EBR process, a few photoresists were used. Leave residue on the composition.

Good stripping properties have been shown for various photoresist and EBR / REWORK processes using the novel thinner compositions according to the present invention. In particular, an inexpensive acetic acid ester compound such as normal butyl acetate is included as a main component of the stripper, and this component can make it possible to increase the component content of the stripper. Therefore, the stripper composition can be produced at low cost, and excellent stripping properties can be secured for various photoresists. Since the stripper composition is environmentally friendly, it can be confirmed that it does not cause an environmental problem, thereby actively coping with an environmental problem to be caused later, and does not interfere with the lower layer.

 The thinner composition of the present invention can obtain good stripping properties despite the low price, and thus can be widely used in the semiconductor industry.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the present invention without departing from the spirit and scope of the invention described in the claims below. I can understand that you can.

1 is a process diagram illustrating a method for stripping photoresist applied to a substrate edge and a back surface area using a thinner composition according to an embodiment of the present invention.

2 is a flowchart illustrating a method for stripping a photoresist applied to the entire surface of a substrate using a thinner composition according to an embodiment of the present invention.

Claims (38)

Acetic acid ester compound 8 to 95% by weight; 0.1 to 13% by weight of gamma-butyro lactone; And A thinner composition comprising 3 to 80% by weight of a nonacetic acid ester compound. The thinner composition of claim 1, wherein the acetic acid ester compound is at least one selected from the group consisting of normal butyl acetate, amyl acetate, ethyl acetoacetate, and isopropyl acetate. According to claim 1, wherein the non-acetic acid ester compound is ethyl lactate (ethly lactate), ethyl-3-ethoxy propionate (ethly-3-ethoxy propionate) and methyl-3-methoxy propionate (methyl Thinner composition, characterized in that at least one selected from the group consisting of -3-methoxy propionate). delete According to claim 1, wherein the content of the acetic acid ester compound is 50 to 90% by weight, the content of the gamma-butyro lactone is 0.1 to 7% by weight, the non-acetic acid ester compound (ester compound) content of 10 to 70% by weight of the thinner composition. The thinner composition according to claim 1, wherein the acetic acid ester compound is normal butyl acetate. According to claim 6, wherein the non-acetic acid ester compound is ethyl lactate, the content of the normal butyl acetate is 50 to 85% by weight, the content of the gamma-butyro lactone is 1 to 13% by weight %, Wherein the content of the ethyl lactate is 10 to 40% by weight of the thinner composition. According to claim 6, wherein the non-acetic acid ester compound is ethyl lactate, the content of the normal butyl acetate is 55 to 85% by weight, the content of the gamma-butyro lactone is 1 to 7% by weight %, Wherein the content of the ethyl lactate is 10 to 40% by weight of the thinner composition. The non-acetic acid ester compound is ethyl-3-ethoxy propionate, the content of the normal butyl acetate is 20 to 90% by weight, and the content of the gamma-butyrolactone is 0.1 to 13% by weight. %, Wherein the content of ethyl-3-ethoxy propionate is 10 to 70% by weight. The non-acetic acid ester compound is ethyl-3-ethoxy propionate, the content of the normal butyl acetate is 30 to 89% by weight, and the content of the gamma-butyrolactone is 0.1 to 7%. %, The content of the ethyl-3-ethoxy propionate is a thinner composition, characterized in that 20 to 70% by weight. The method of claim 10, wherein the content of the normal butyl acetate is 30 to 89% by weight, the content of the gamma-butyrolactone is 0.5 to 5% by weight, the content of the ethyl-3-ethoxy propionate is 10 To 65% by weight of the thinner composition. The non-acetic acid ester compound is methyl-3-methoxy propionate, the content of the normal butyl acetate is 50 to 90% by weight, the content of the gamma-butyrolactone is 1 to 13% %, And the content of the methyl-3-methoxy propionate is 5 to 40% by weight of the thinner composition. The non-acetic acid ester compound is methyl-3-methoxy propionate, the content of the normal butyl acetate is 55 to 90% by weight, the content of the gamma-butyrolactone is 1 to 7% %, And the content of the methyl-3-methoxy propionate is 5 to 40% by weight of the thinner composition. The thinner composition according to claim 1, wherein the thinner composition further comprises a surfactant. The thinner composition according to claim 14, wherein the amount of the surfactant is 1 wt% or less. delete delete delete delete delete delete delete delete delete delete delete delete Preparing a thinner composition for a photoresist strip comprising an acetic acid ester compound, gamma-butyrolactone, and a nonacetic acid ester compound; Stripping the photoresist by contacting the thinner composition to the edge and / or backside of the substrate on which the photoresist is applied; And drying the thinner composition in contact with the substrate. delete delete delete         29. The method of claim 28, wherein the acetic acid ester compound is at least one selected from the group consisting of normal butyl acetate, amyl acetate, ethyl acetoacetate and isopropyl acetate. The method of claim 28, wherein the non-acetic acid ester compound is ethyl lactate, ethyl-3-ethoxy propionate and methyl-3-methoxy propionate. Stripping method of photoresist, characterized in that at least one selected from the group consisting of -3-methoxy propionate). 29. The method of claim 28, wherein the content of the acetic acid ester compound is 8 to 95% by weight, the content of the gamma-butyro lactone is 0.1 to 13% by weight, the non-acetic acid ester compound (ester compound) ) Content of 3 to 80% by weight of the stripping method of the photoresist, characterized in that. 29. The method of claim 28, wherein the acetic acid ester compound is normal butyl acetate. 36. The method of claim 35, wherein the non-acetic acid ester compound is ethyl lactate, the content of the normal butyl acetate is 50 to 85% by weight, and the content of the gamma-butyro lactone is 1 to 13% by weight. %, Wherein the content of the ethyl lactate is 10 to 40% by weight. 36. The method of claim 35, wherein the non-acetic acid ester compound is ethyl-3-ethoxy propionate, the content of normal butyl acetate is 20 to 90 wt%, and the content of gamma-butyrolactone is 0.1 to 13 wt%. %, Wherein the content of ethyl-3-ethoxy propionate is 10 to 70% by weight. 36. The method of claim 35, wherein the non-acetic acid ester compound is methyl-3-methoxy propionate, the content of normal butyl acetate is 50 to 90% by weight, and the content of gamma-butyrolactone is 1 to 13 weight. %, And the methyl-3-methoxy propionate content is 5 to 40% by weight.