KR20160074396A - Thinner compositoin - Google Patents

Abstract

The present invention relates to a thinner composition having excellent solvency and proper volatility with respect to a poorly soluble resist for a spin-on hard mask, thereby effectively removing an unnecessarily adhered photoresist or the spin-on hard mask in an edge bead removal process or the like within a short time, and is applied to a pre-wetting process of a semiconductor substrate or the like, thereby enabling a photosensitive film to be effectively formed with a small amount of photoresist or the spin-on hard mask.

Description

THINNER COMPOSITOIN

The present invention relates to a thinner composition, and more particularly, to a thinner composition which can be used in various steps of a photolithography process during a semiconductor manufacturing process, and a method of forming a photoresist or a spin-on hard mask film using the same.

This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0183528 dated December 18, 2014, the entire contents of which are incorporated herein by reference.

The photolithography process refers to a process of transferring a previously designed pattern to a photoresist film on a semiconductor substrate using a photomask, and then etching the substrate or the underlying film according to the transferred pattern.

In the photolithography step, a photoresist is coated on a semiconductor substrate to form a photoresist film. Then, a photomask pattern is projected by using an exposure apparatus to expose the photoresist film, and then a photoresist pattern having a desired shape is manufactured through a development process. Subsequently, after the substrate is etched using the photoresist pattern as a mask, the photoresist pattern that is no longer needed is removed from the substrate by a stripping process or the like. Various kinds of light sources such as G-line, I-line, KrF, ArF, ultraviolet ray, e-beam, and X-ray are used depending on the line width of a pattern to be formed in this process. The photoresist used for the formation of the photoresist film includes various kinds of main component resins and photoresists depending on the type of the light source, the performance of the photoresist, and the like.

On the other hand, in a photolithography process, a thinner composition refers to a material having solubility in a photoresist and used as a diluent for removing a photoresist.

The solubility of the thinner composition on the photoresist depends on the chemical composition of the thinner composition and on the chemical composition of the photoresist to be dissolved. However, since the chemical composition varies greatly depending on the kind of the photoresist, commercially available thinner compositions generally have a problem that the solubility of the various photoresists is not constant.

Particularly, when the solubility of the thinner composition on the photoresist is insufficient, the edge bead removing process to remove the photoresist that is unnecessarily adhered to the substrate or the pre-wetting of the thinner composition for the reducing resist consumption (RRC) pre-wetting process or the like may occur, which may lead to a reduction in the yield of the photolithography process.

U.S. Patent Publication No. 4983490 (1991.01.08) Japanese Patent Application Laid-Open No. 1995-128867 (1995.05.19)

The present invention is to provide a thinner composition having an excellent solubility to a weakly soluble resist for a spin-on hard mask and the like, which can be applied to various processes of forming a photoresist film.

The present invention also provides a method for forming a photosensitive film using the thinner composition.

According to the present invention,

1-methoxy-2-propanol acetate;

Methyl 3-methoxypropionate;

Gamma-butyrolactone;

Ketocyclopentane; And

One or more of the components of 2-methoxy-1-propyl acetate, propylene glycol monomethyl ether and butylated hydroxytoluene,

≪ / RTI > is provided.

Hereinafter, the thinner composition according to embodiments of the present invention and its use will be described in more detail.

Prior to that, unless explicitly stated throughout the present specification, the terminology is for reference only, and is not intended to limit the invention.

And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning.

Also, as used herein, the term " comprises " embodies specific features, regions, integers, steps, operations, elements or components, and does not exclude the presence of other specified features, regions, integers, steps, operations, elements, It does not.

On the other hand, as a result of continuous research by the inventors of the present invention, it has been found that when a composition including the above-described components simultaneously is applied to a semiconductor manufacturing process using a thinner composition, excellent solubility And it was confirmed that the edge bead removal process and the pre-wetting process of the semiconductor substrate can be performed with higher efficiency. Further, the thinner composition according to the present invention is excellent in handling and storage stability and can provide improved reliability.

Particularly, the thinner composition according to the present invention exhibits excellent solubility for photoresists applied to light source processes such as G-line and I-line as well as high-polarity photoresists applied to light source processes such as KrF and ArF . Furthermore, the thinner composition according to the present invention can exhibit excellent solubility even for resists for a spin-on hardmask process which are poorly soluble in common organic solvents.

Accordingly, in the step of forming a photoresist film using a photoresist, the thinner composition may be applied to an edge or rear surface of a substrate, or an edge bead removing step of removing the attached photoresist, And a rework process for removing the film from the film.

The thinner composition can also be applied to a stripping process for removing a photoresist pattern after development and etching and is applied to a pre-wetting process of a thinner composition for a reducing resist consumption (RRC) coating to produce a more uniform thickness To form a photoresist film.

I. Thinner  Composition

According to one embodiment of the invention,

1-methoxy-2-propanol acetate;

Methyl 3-methoxypropionate;

Gamma-butyrolactone;

Ketocyclopentane; And

At least one of 2-methoxy-1-propyl acetate, propylene glycol monomethyl ether and butylated hydroxytoluene

≪ / RTI > is provided.

Generally, in a process of forming a photoresist film by a spin coating method, edge beads in which a photoresist is aggregated in a spherical shape on the edge portion and the rear surface of the substrate by centrifugal force may be formed. Such edge beads can act as a source of contamination leading to defects in the semiconductor device or malfunction of the manufacturing equipment, and can also cause defocusing in the exposure process.

However, when the thinner composition according to the embodiment of the present invention is applied to the edge bead removal process, the beads attached to the edge or rear surface of the substrate can be easily removed without damaging the photosensitive film formed on the front surface of the substrate, So that the boundary line of the photoresist film can be obtained more clearly and uniformly at the edge portion of the photoresist film.

In the case of ethyl lactate which has been applied to conventional thinner compositions, it is difficult to sufficiently improve the cleaning power of the thinner composition because the viscosity is high and the dissolution rate is relatively low.

In addition, ethylene glycol monoethyl ether acetate has excellent solubility in photoresist, but has high volatility and flammability, and has a problem of reproductive toxicity such as leukopenia and fetal lactic acid induction.

When a mixed solvent composed of pyruvic acid alkyls and methyl ethyl ketone is used as the thinner composition, the solubility of 1,2-naphthaquinone diazide type photosensitive agent in the photosensitive agent, which is one of the important components of the photosensitive film, may be deteriorated.

In addition, when a solvent such as methyl pyruvate or ethyl pyruvate is used as the thinner composition, the metal parts in the photosensitive waste solution reservoir attached to the photoresist film rotator can be corroded for a long period of time.

When the rear surface of the substrate is cleaned using a solvent having a high volatility such as a mixed solvent of propylene glycol alkyl ether propionate and butyl acetate as a thinner composition, the substrate may be cooled and the thickness variation of the photosensitive film may be increased have.

In addition, when a solvent having a low volatility such as a mixed solvent of ethyl lactate and methyl ethyl ketone is used as the thinner composition, the cleaning ability of the substrate edge portion may be deteriorated.

Compared to these prior thinner compositions, the 1-methoxy-2-propanol acetate included in the thinner composition according to the embodiment of the invention exhibits good solubility for various types of photoresists, but also exhibits good volatility, .

According to an embodiment of the invention, the 1-methoxy-2-propanol acetate is present in an amount of from 45 to 95% by weight, or from 50 to 95% by weight, or from 55 to 95% by weight, or from 55 to 90% by weight, Or 59 to 90% by weight.

That is, in order to exhibit an excellent dissolving power even for a photoresist having a high polarity and a resist for a spin-on hard mask process, the 1-methoxy-2-propanol acetate is contained in an amount of 45 wt% .

However, when the 1-methoxy-2-propanol acetate is added in an excessive amount, the volatility of the thinner composition is increased, so that the thickness of the photoresist film formed after prewetting may be varied or the edge may be cracked. Therefore, in order to prevent such a phenomenon, it is preferable that the 1-methoxy-2-propanol acetate is contained in an amount of 95% by weight or less of the entire thinner composition.

On the other hand, methyl 3-methoxypropionate contained in the thinner composition according to the embodiment of the present invention may exhibit excellent characteristics in the solubility of the photoresist in the photosensitizer component compared to other solvents.

In particular, the methyl 3-methoxypropionate can be used in the resist for spin-on hard mask processes, such as fluorene, carbazole, naphthole, anthracene, pyrene ) And the like can be exhibited.

According to an embodiment of the present invention, the methyl 3-methoxypropionate may be included in an amount of 1 to 100 parts by weight based on 100 parts by weight of the 1-methoxy-2-propanol acetate. Preferably, the content of the methyl 3-methoxypropionate is 1 part by weight or more, or 3 parts by weight or more, or 5 parts by weight or more, or 7 parts by weight or more per 100 parts by weight of the 1-methoxy- Parts by weight or more. The content of the methyl 3-methoxypropionate is 100 parts by weight or less, or 98 parts by weight or less, or 96 parts by weight or less based on 100 parts by weight of the 1-methoxy-2-propanol acetate.

That is, in order to secure the effect of improving the solubility of the photoresist to the photosensitizer component and the pyrene structure polymer, the methyl 3-methoxypropionate is added in an amount of 1 part by weight based on 100 parts by weight of the 1-methoxy- Or more, or 3 parts by weight or more, or 5 parts by weight or more, or 7 parts by weight or more.

However, when the methyl 3-methoxypropionate is added in an excess amount, the volatility of the thinner composition is increased, so that the thickness of the photoresist film formed after prewetting may be varied or the edge may be cracked. Therefore, in order to prevent this phenomenon, the methyl 3-methoxypropionate is added in an amount of 100 parts by weight or less, or 98 parts by weight or less, or 96 parts by weight or less with respect to 100 parts by weight of the 1-methoxy- .

According to embodiments of the present invention, when the volatility of the thinner composition is excessively high, the substrate may be rapidly cooled during application of the thinner composition, and the thickness variation of the photoresist layer may significantly increase. If the volatility of the thinner composition is excessively low, the thinner composition may exist excessively on the substrate at the time of prewetting, resulting in the dissolution of the photoresist film or the occurrence of defects such as distortion of the photoresist film, It may remain on the substrate and may act as a source of contamination in subsequent processes.

Meanwhile, the thinner composition according to the embodiment of the present invention includes gamma-butyrolactone and keto cyclopentane as ketone compounds.

As the thinner composition simultaneously contains gamma-butyrolactone and keto cyclopentane, synergism with the 1-methoxy-2-propanol acetate and methyl 3-methoxypropionate can be obtained. In particular, the gamma-butyrolactone and keto cyclopentane enable the provision of a thinner composition having improved solubility for sparingly soluble resist for spin-on hardmask.

According to an embodiment of the present invention, the gamma-butyrolactone may be contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the 1-methoxy-2-propanol acetate. Preferably, the content of gamma-butyrolactone is 0.1 parts by weight or more, or 0.5 parts by weight or more, or 1 part by weight or more based on 100 parts by weight of the 1-methoxy-2-propanol acetate. The content of the gamma-butyrolactone is 50 parts by weight or less, or 35 parts by weight or less, or 25 parts by weight or less, or 20 parts by weight or less based on 100 parts by weight of the 1-methoxy-2-propanol acetate.

The keto cyclopentane may be contained in an amount of 0.1 to 70 parts by weight based on 100 parts by weight of the 1-methoxy-2-propanol acetate. Preferably, the content of keto cyclopentane is 0.1 parts by weight or more, or 0.5 parts by weight or more, or 1 part by weight or more based on 100 parts by weight of the 1-methoxy-2-propanol acetate. The keto cyclopentane content is 70 parts by weight or less, or 50 parts by weight or less, or 40 parts by weight or less, or 35 parts by weight or less based on 100 parts by weight of the 1-methoxy-2-propanol acetate.

That is, in order to exhibit the synergistic effect with the 1-methoxy-2-propanol acetate and methyl 3-methoxypropionate and the solubility enhancement effect on the resist which is poorly soluble for the spin-on hard mask, -Butyrolactone and keto cyclopentane are preferably contained in an amount of 0.1 part by weight or more, or 0.5 parts by weight or more, or 1 part by weight or more, based on 100 parts by weight of the 1-methoxy-2-propanol acetate.

However, when the gamma-butyrolactone and keto cyclopentane are contained in an excessive amount, the solubility in some photoresists may be lowered. Therefore, in order to prevent such a phenomenon, the gamma-butyrolactone is added in an amount of 50 parts by weight or less, or 35 parts by weight or less, or 25 parts by weight or less, or 20 parts by weight or less, based on 100 parts by weight of the 1-methoxy- By weight or less. The keto cyclopentane is preferably contained in an amount of 70 parts by weight or less, or 50 parts by weight or less, or 40 parts by weight or less, or 35 parts by weight or less, based on 100 parts by weight of the 1-methoxy- .

Meanwhile, the thinner composition according to the embodiment of the present invention includes 2-methoxy-1-propyl acetate, propylene glycol monomethyl ether and butylated hydroxytoluene ( butylated hydroxytoluene).

Wherein the 2-methoxy-1-propyl acetate is a beta isomer of 1-methoxy-2-propanol acetate which has a lower polarity than the propylene glycol monomethyl ether and does not contain a hydroxyl group, Especially for spin-on hard masks with hydrophobic properties.

According to an embodiment of the present invention, the 2-methoxy-1-propyl acetate may be included in an amount of 0.001 to 30 parts by weight based on 100 parts by weight of the 1-methoxy-2-propanol acetate. Preferably, the content of the 2-methoxy-1-propyl acetate is 0.001 parts by weight or more, or 0.01 parts by weight or more, or 0.03 parts by weight or more based on 100 parts by weight of the 1-methoxy-2-propanol acetate. The content of the 2-methoxy-1-propyl acetate is 30 parts by weight or less, or 25 parts by weight or less, 20 parts by weight or less, or 18 parts by weight or less based on 100 parts by weight of the 1-methoxy- Or less.

The 2-methoxy-1-propyl acetate can be used as a beta isomer of 1-methoxy-2-propanol acetate in an amount of about 100 ppm of 2-methoxy-1-propyl acetate Can be included by natural formation. However, in order to sufficiently manifest the effect of the addition of 2-methoxy-1-propyl acetate in the thinner composition of the present invention, the content of 2-methoxy-1-propyl acetate is required to satisfy the above- Artificial conditioning is required. In one example, the content of the 2-methoxy-1-propyl acetate is reduced to within the above-mentioned range by fractional distillation under reduced pressure for 1-methoxy-2-propanol acetate (preferably 1-methoxy- Or more than the amount that can be contained by the natural formation in the body.

The propylene glycol monomethyl ether has a hydroxyl group in the molecule to allow an excellent wetting property to be exhibited on a semiconductor substrate and to reduce the use amount of a spin-on hard mask composition.

However, in the case of the thinner composition in which the propylene glycol monomethyl ether is excessively added, it is necessary to contain the propylene glycol monomethyl ether in a proper amount as it may cause pipe clogging or failure in the EBR process.

Also, as the content of the propylene glycol monomethyl ether in the thinner composition increases, the hydrogen bonding force of the thinner composition tends to increase. Therefore, it is preferable to determine the content of the propylene glycol monomethyl ether in consideration of the characteristics of the process to which the thinner composition is applied and the characteristics of the photoresist composition or the spin-on hard mask composition.

According to an embodiment of the present invention, the propylene glycol monomethyl ether may be contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the 1-methoxy-2-propanol acetate. Preferably, the content of the propylene glycol monomethyl ether is 0.01 parts by weight or more, or 0.05 parts by weight or more, or 0.1 parts by weight, or 0.5 parts by weight or more based on 100 parts by weight of the 1-methoxy-2-propanol acetate . The content of the propylene glycol monomethyl ether is 20 parts by weight or less, or 15 parts by weight or less, or 10 parts by weight or less, or 6.5 parts by weight or less based on 100 parts by weight of the 1-methoxy-2-propanol acetate.

The butylated hydroxytoluene suppresses the formation of by-products by photodegradation of the 1-methoxy-2-propanol acetate and / or 2-methoxy-1-propyl acetate, . ≪ / RTI >

According to an embodiment of the present invention, the butylated hydroxytoluene may be included in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the 1-methoxy-2-propanol acetate. Preferably, the content of butylated hydroxytoluene is 0.0001 parts by weight or more, or 0.0005 parts by weight or more, or 0.001 parts by weight or more based on 100 parts by weight of the 1-methoxy-2-propanol acetate. The content of butylated hydroxytoluene is 10 parts by weight or less, or 5 parts by weight or less, or 1 part by weight or less, or 0.5 parts by weight or less based on 100 parts by weight of the 1-methoxy-2-propanol acetate .

In short, in order to enable the above-described effect of each component to be exhibited, the thinner composition contains 0.001 parts by weight or more of 2-methoxy-1-propyl acetate , 0.01 parts by weight or more of propylene glycol monomethyl ether, and 0.0001 parts by weight or more of butylated hydroxytoluene.

However, when one or more of the components of the 2-methoxy-1-propyl acetate, propylene glycol monomethyl ether, and butylated hydroxytoluene are added to the thinner composition in excess, the clogging of the pipe with the thinner composition or the Defects may occur or the solubility of the thinner composition may not be sufficiently expressed.

In particular, when the 2-methoxy-1-propyl acetate is added to the thinner composition in an excess amount, the volatility of the thinner composition may be reduced and the coating uniformity of the resist after the reducing resist consumption (RRC) process may decrease .

Accordingly, in order to prevent such a phenomenon, the thinner composition contains 30 parts by weight or less of 2-methoxy-1-propyl acetate, 20 parts by weight or less of propylene Glycol monomethyl ether, and up to 10 parts by weight of butylated hydroxytoluene.

According to an embodiment of the invention, the 2-methoxy-1-propyl acetate, propylene glycol monomethyl ether and butylated hydroxytoluene may be included in various combinations depending on the characteristics of the desired thinner composition.

Specifically, the 2-methoxy-1-propyl acetate, the propylene glycol monomethyl ether, and the butylated hydroxytoluene may be contained individually in the thinner composition; Two or more components may be included together; Three components can be included at the same time.

Preferably, the thinner composition is comprised of 1-methoxy-2-propanol acetate, methyl 3-methoxypropionate, gamma-butyrolactone, ketocyclopentane, and 2- have.

Also preferably, the thinner composition may comprise 1-methoxy-2-propanol acetate, methyl 3-methoxypropionate, gamma-butyrolactone, ketocyclopentane, and propylene glycol monomethyl ether.

Also preferably, the thinner composition may comprise 1-methoxy-2-propanol acetate, methyl 3-methoxypropionate, gamma-butyrolactone, ketocyclopentane, and butylated hydroxytoluene .

Also preferably, the thinner composition is selected from the group consisting of 1-methoxy-2-propanol acetate, methyl 3-methoxypropionate, gamma-butyrolactone, ketocyclopentane, 2-methoxy- Propylene glycol monomethyl ether.

Also preferably, the thinner composition is selected from the group consisting of 1-methoxy-2-propanol acetate, methyl 3-methoxypropionate, gamma-butyrolactone, ketocyclopentane, 2-methoxy- Butylated hydroxytoluene.

Also preferably, the thinner composition is selected from the group consisting of 1-methoxy-2-propanol acetate, methyl 3-methoxypropionate, gamma-butyrolactone, ketocyclopentane, propylene glycol monomethyl ether, Lt; / RTI > toluene.

Also preferably, the thinner composition is selected from the group consisting of 1-methoxy-2-propanol acetate, methyl 3-methoxypropionate, gamma-butyrolactone, ketocyclopentane, 2-methoxy- Glycol monomethyl ether, and butylated hydroxytoluene.

In addition, the thinner composition according to the embodiment of the present invention may further include a surfactant.

Due to the nature of the photoresist-forming process, the surfactant is preferably a non-ionic surfactant. The nonionic surfactant may be any surfactant that is conventional in the art to which the present invention pertains, and therefore the constitution thereof is not particularly limited.

The surfactant may be included in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of the thinner composition.

That is, the surfactant may be included in an amount of 0.001 part by weight or more based on 100 parts by weight of the thinner composition in order to ensure a better profile in the edge bead removing step.

However, when the surfactant is contained in an excess amount, bubbles may be generated in the thinner composition severely, thereby causing a malfunction of the sensor to detect the amount of liquid when the thinner composition is used. Therefore, in order to prevent such a phenomenon, the surfactant is preferably included in an amount of 0.1 part by weight or less based on 100 parts by weight of the thinner composition.

II. Thinner  Use of composition

According to another embodiment of the invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: applying the above-described thinner composition onto a semiconductor substrate to pre-wet the semiconductor substrate; And applying a photoresist composition or a spin-on hard mask composition on the prewetted semiconductor substrate.

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a photoresist or a spin-on hard mask on a semiconductor substrate; And applying the thinner composition to the semiconductor substrate to remove at least a portion of the photoresist or spin-on hard mask from the semiconductor substrate.

In the method of forming the photoresist film, the semiconductor substrate may be a substrate used for manufacturing an electronic device such as a semiconductor memory device, an integrated circuit device, or a liquid crystal display device.

A plurality of structures, for example, an insulating film, a conductive film, a wiring, a hole, a gate, and the like may be formed on the semiconductor substrate, and a step may exist on the upper surface of the substrate due to the structures. have.

On the other hand, the pre-wetting process is a process for improving the wettability of the semiconductor substrate before applying the photoresist by applying the thinner composition to the semiconductor substrate on which the photoresist film is to be formed.

Since the thinner composition according to the present invention exhibits a higher solubility for various kinds of photoresists (particularly, a weakly soluble resist for a spin-on hard mask), the thinner composition of the present invention, Thereby making it possible to form a photoresist film having a thickness.

That is, when the prewetting process is performed using the above-described thinner composition, a thin film having a uniform thickness can be formed using a relatively small amount of photoresist. In addition, it is possible to minimize the defective coating of the photoresist film on the edge portion of the substrate, easily overcome the step that may exist in the substrate, and reduce the thickness variation of the photoresist film.

Such a pre-wetting process may be performed by a method using a conventional spin coating, for example, a method of coating the thinner composition on the entire surface of the substrate by rotating the substrate after applying the thinner composition on the substrate, Coating the thinner composition on the entire surface of the substrate by applying the composition, and the like.

In the method of forming the photoresist film, the photoresist composition may vary depending on the line width of a pattern to be formed, the type of a light source applied thereto, and the composition is not particularly limited.

However, according to the present invention, examples of the resin included in the photoresist composition include an I-line photoresist containing a novolak resin, a KrF containing a polyhydroxystyrene in which hydrogen of the hydroxyl group is partially blocked with an acetal group A photo-resist for KrF, a photo-resist for ArF including a methacrylate resin, a KrF-containing lower part including a triazine-based resin, Antireflection coatings, and bottom antireflection coatings for ArF including ester-based resins.

The photoresist for the I-line may include 2,4-dinitroquinone as a novolac resin and a photosensitizer.

The photoresist for KrF may include a polyhydroxystyrene in which hydrogen of the hydroxyl group is partially blocked with an acetal group or a tert-butylcarbonate group, and a triphenylsulfonium salt as a photosensitizer.

The photoresist for ArF is prepared by reacting an adamantyl group and / or 4-oxa- tricyclo (4.2.1.0 (3,7)) nonan-5-one (4-oxa-tricyclo (4.2.1.0 5-one-blocked polymethacrylate and a triphenylsulfonium salt as a photosensitizer.

The step of applying the photoresist on the prewetted substrate may be performed using spin coating. When the photoresist is applied by spin coating, edge beads can be formed by the centrifugal force so that the photoresist is agglomerated in a spherical shape on the edge portion and the rear surface of the substrate. The edge beads can act as a source of contamination leading to defects in the electronic device or malfunction of the manufacturing equipment, and can also cause fogging in the exposure process.

Thus, the thinner composition of the present invention can be used to remove at least a portion of the photoresist from the substrate, for example, the photoresist deposited on the edge or backside of the substrate. In this case, the thinner can be performed by pressurizing the thinner composition while rotating the substrate.

As described above, since the thinner composition of the present invention has properties such as good solubility, appropriate viscosity and volatility for various photoresists, it is possible to remove only the edge beads while keeping the boundary line of the photosensitive film clear, So that the process can be efficiently performed in a shorter time.

The thinner composition applied to the step of removing at least a part of the photoresist (edge bead removing step) may or may not be the same as the thinner composition applied to the above-described pre-wetting step.

That is, different compositions of the thinner composition may be used depending on the conditions of the respective steps and the required characteristics. However, since the thinner composition according to the present invention can satisfy physical properties suitable for both the edge bead removing step and the pre-wetting step, it may be preferable to use a thinner composition having an equivalent range of composition to improve the efficiency of the entire process .

After removing the edge beads attached to the edge or backside of the substrate, a photoresist layer can be formed through a soft bake process. After the defect is detected in the photoresist layer using a defect detection device, A photoresist pattern may be formed.

If there is a defect such as tearing, tailing, thickness variation or the like in the photoresist film, a photoresist film formed on the entire surface of the substrate is removed by performing a rework process. In this case, the thinner composition of the present invention can also be used.

The thinner composition according to the present invention has excellent solubility and appropriate volatility for various kinds of photoresists (especially, a weakly soluble resist for a spin-on hard mask), so that the photoresist unnecessarily adhered in the edge bead removal process or the like can be efficiently And it is also applicable to a pre-wetting process or the like of a semiconductor substrate, so that it is possible to form an effective photosensitive film even with a small amount of photoresist.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. It is to be understood, however, that the following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example  And Comparative Example

In the mixing tank equipped with the stirrer, the components shown in the following Tables were compounded in the respective amounts (weight%) to prepare respective thinner compositions. At this time, the content of 2-methoxy-1-propyl acetate was artificially controlled by fractional distillation under reduced pressure to 1-methoxy-2-propanol acetate.

The ingredients listed in the following Tables are as follows.

[A] 1-methoxy-2-propanol acetate

[B] methyl 3-methoxypropionate

[C] gamma-butyrolactone

[D] keto cyclopentane

[E] 2-Methoxy-1-propyl acetate

[F] propylene glycol monomethyl ether

[G] Butylated hydroxytoluene

[P] n-butyl acetate

[Q] Ethyl lactate

[R] cyclohexanone

Example A B C D E F P Q 1-01 59.97 35 3 2 0.03 - - - 1-02 69 10 10 10 One - - - 1-03 67 10 10 10 3 - - - 1-04 65 10 10 10 5 - - - 1-05 63 10 10 10 7 - - - 1-06 60 5 5 20 10 - - - 1-07 79.97 18 One One 0.03 - - - 1-08 79 10 5 5 One - - - 1-09 77 10 5 5 3 - - - 1-10 75 10 5 5 5 - - - 1-11 73 10 5 5 7 - - - 1-12 80 6 3 One 10 - - -

Comparative Example A B C D E F P Q 1-01 60 35 3 3 - - - - 1-02 60 30 5 5 - - - - 1-03 70 10 10 10 - - - - 1-04 80 10 5 5 - - - - 1-05 - 30 20 - - 50 - - 1-06 50 30 - - - 20 - - 1-07 50 25 5 - - - 20 - 1-08 50 30 - - - - 10 10 1-09 - 50 20 - - - 30 - 1-10 - 40 10 - - 50 - 1-11 - - - 50 - - 30 20 1-12 50 - 10 - - 40 - - 1-13 - - 10 10 - 80 - - 1-14 - - - 10 - 40 - 50

Example A B C D E G 2-01 59.969 35 3 2 0.03 0.001 2-02 69.95 10 10 10 One 0.05 2-03 66.95 10 10 10 3 0.05 2-04 64.95 10 10 10 5 0.05 2-05 59.95 10 10 10 10 0.05 2-06 59.8 5 5 20 10 0.2 2-07 79.969 18 One One 0.03 0.001 2-08 78.95 10 5 5 One 0.05 2-09 66.95 10 10 10 3 0.05 2-10 64.95 10 10 10 5 0.05 2-11 59.95 10 10 10 10 0.05 2-12 79.8 6 3 One 10 0.2

Comparative Example A B C D E G 2-01 59 35 3 3 - - 2-02 60 30 5 5 - - 2-03 70 10 10 10 - - 2-04 80 10 5 5 - -

Example A B C D F P Q 3-01 47 45 3 2 3 - - 3-02 49 45 3 2 One - - 3-03 49.5 45 3 2 0.5 - - 3-04 70 20 2 5 3 - - 3-05 72 20 2 5 One - - 3-06 72.5 20 2 5 0.5 - - 3-07 82 10 3 2 3 - - 3-08 84 10 3 2 One - - 3-09 84.5 10 3 2 0.5 - -

Comparative Example A B C D F P Q 3-01 50 45 3 2 - - - 3-02 73 20 2 5 - - - 3-03 82 13 3 2 - - - 3-04 50 30 - 20 - - - 3-05 50 30 - - 20 - - 3-06 50 25 5 - - 20 - 3-07 50 30 - - - 10 10 3-08 - 50 20 - - 30 - 3-09 - 40 10 - - 50 - 3-10 - - - 50 - 30 20 3-11 50 - 10 - 40 - - 3-12 - - 10 10 80 - - 3-13 - - - 10 40 - 50

Example A B C D E F 4-01 47 44.97 3 2 0.03 3 4-02 49 44 3 2 One One 4-03 49.5 35 3 2 10 0.5 4-04 69.97 20 2 5 0.03 3 4-05 71 20 2 5 One One 4-06 62.5 20 2 5 10 0.5 4-07 81.97 10 3 2 0.03 3 4-08 83 10 3 2 One One 4-09 74.5 10 3 2 10 0.5

Comparative Example A B C D E F 4-01 50 45 3 2 - - 4-02 73 20 2 5 - - 4-03 82 13 3 2 - - 4-04 50 30 - 20 - - 4-05 50 30 - - - 20

Example A B C D G 5-01 49.999 45 3 2 0.001 5-02 49.95 45 3 2 0.05 5-03 49.8 45 3 2 0.2 5-04 72,999 20 2 5 0.001 5-05 72.95 20 2 5 0.05 5-06 72.8 20 2 5 0.2 5-07 84.999 10 3 2 0.001 5-08 84.95 10 3 2 0.05 5-09 84.8 10 3 2 0.2

Comparative Example A B C D G 5-01 50 45 3 2 - 5-02 73 20 2 5 - 5-03 82 13 3 2 -

Test Example

(1) Edge Bead  Removal performance evaluation ( EBR  evaluation)

: The oxidized 8-inch silicon substrate was immersed in two baths containing hydrogen peroxide / sulfuric acid mixture for 5 minutes each, and then rinsed with ultra-pure water. Subsequently, the substrate was spin-dried in a spin dryer, and then the thinner composition according to each of Examples and Comparative Examples was spin-coated (about 1500 to 2500 rpm) to perform a pre-wetting process for RRC coating.

Subsequently, each of the spin-on hard mask resist shown in the following Table 11 was spin-coated on the prewetted substrate by spin coating (about 300 rpm for about 3 seconds, then about 1000 to 2000 rpm for about 20 to 30 seconds To adjust the thickness to a predetermined thickness) to form a photosensitive film having the corresponding thickness. Tests were conducted to remove edge beads unnecessarily adhered to the edge portions of the substrate using the thinner compositions according to each of the Examples and Comparative Examples.

At this time, each of the thinner compositions was supplied (pressurized pressure: about 1.0 kgf) in a pressurized vessel equipped with a pressure gauge and injected through an EBR nozzle (composition flow rate 10 to 20 cc / min) The injection time of the composition according to the rotational speed was controlled.

In the evaluation of the edge bead removal performance, the EBR line uniformity after the edge bead removal was uniform and constant [⊚]; [○] EBR line uniformity after edge bead removal is in good line form over 80%; [?] That EBR line uniformity after edge bead removal is in good line form with 50% or more and less than 80%; [X] indicates that EBR line uniformity after edge bead removal is 20% or more and less than 50% is good, and tailing phenomenon occurs at an edge portion.

Type of Resist Usage Curing temperature Film thickness SOCA (C-hardmask) Normal, Gap-fill High temperature hardening 0.15 탆 SOC B (C-hardmask) Normal High temperature hardening 0.30 탆 SOC C (C-hardmask) Normal, Gap-fill Low temperature hardening 0.15 탆 SOC D (C-hardmask) Normal High temperature hardening 0.30 탆 SOC E (C-hardmask) Normal High temperature hardening 0.35 탆 SOC F (C-hardmask) Normal High temperature hardening 0.30 탆

division Substrate rotation speed (rpm) Spray time (sec) Dispense condition 300 3 Spin coating Adjustable according to resist thickness EBR condition 1000 10 1500 10 2000 10

(2) Evaluation of storage stability

: The time required for decomposing the thinner composition to produce 2,5-dimethyl-4-hydroxy-3-hexanone was measured by storing the thinner composition in a transparent container at a temperature of 20 ° C. Here, the formation of 2,5-dimethyl-4-hydroxy-3-hexanone was confirmed by gas chromatography (GC).

In the storage stability evaluation, [○] indicates that the storable time is 3 months or longer; [DELTA] that the storable time is from 1 month to less than 3 months; [X] indicating that the storable time is less than one month.

(3) Resist  Evaluation of coating uniformity (RRC evaluation)

: Whether the photoresist film was uniformly coated on the entire surface of the substrate was evaluated in the following manner. The oxidized 8-inch silicon substrate was immersed in two baths containing a hydrogen peroxide solution / sulfuric acid mixture for 5 minutes each, and rinsed with ultra-pure water. Then, the substrate was spin-dried in a spin dryer, and then the thinner compositions of Examples and Comparative Examples were spin-coated (about 1500 to 2500 rpm) on each substrate to perform a prewetting process for RRC coating. At this time, each of the thinner compositions was fed through a nozzle (composition flow rate: 10 to 20 cc / min) in a pressurization cylinder equipped with a pressure gauge and pressurized The injection time of the composition according to the speed was controlled.

Subsequently, each of the spin-on hard mask resist shown in Table 11 above was spin-coated on the prewetted substrate by spinning at about 300 rpm for about 3 seconds, then about 1000 to 2000 rpm for about 20 to 30 seconds To adjust the thickness to a predetermined thickness) to form a photosensitive film having the corresponding thickness.

In the evaluation of the coating uniformity of the resist, the coating uniformity of the photoresist film was uniform and constant [O]; [?] Indicating that the coating uniformity of the photoresist film is 90% or better; [X] indicates that a coating failure phenomenon occurred at the edge portion of the photoresist film.

division Substrate rotation speed (rpm) Spray time (sec) Thinner condition jet 0 One rotation 2000 One Spin coating Adjusted according to photoresist thickness EBR condition 1000 10 1500 10 2000 10

Test result

Example EBR Save
stability RRC
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 1-01 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-02 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-03 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-04 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-05 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-06 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-07 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-08 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-09 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-10 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-11 ◎ ◎ ◎ ◎ ◎ ◎ X ○ 1-12 ◎ ◎ ◎ ◎ ◎ ◎ X ○

Comparative Example EBR Save
stability RRC
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 1-01 ○ ○ ○ ○ ○ ○ X ○ 1-02 ○ ○ ○ ○ ○ ○ X ○ 1-03 ○ ○ △ △ △ △ X ○ 1-04 ○ ○ ○ △ △ △ X ○ 1-05 ○ ○ ○ ○ ○ ○ X X 1-06 ○ △ ○ X ○ X X X 1-07 ○ ○ ○ X X X X △ 1-08 ○ ○ ○ X X X X X 1-09 ○ △ △ X X X X X 1-10 ○ ○ △ X X X X X 1-11 ○ △ △ X X X X X 1-12 ○ ○ ○ X X X X X 1-13 △ △ △ X X X X X 1-14 △ △ △ △ X X X X

Example EBR Save
stability RRC
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 2-01 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-02 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-03 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-04 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-05 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-06 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-07 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-08 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-09 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-10 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-11 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ 2-12 ◎ ◎ ◎ ◎ ◎ ◎ ○ ○

Comparative Example EBR Save
stability RRC
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 2-01 ○ ○ ○ ○ ○ ○ X ○ 2-02 ○ ○ ○ ○ ○ ○ X ○ 2-03 ○ ○ △ △ △ △ X ○ 2-04 ○ ○ ○ △ △ △ X ○

RRC Storage stability EBR
(SOCA) Example SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 3-01 ○ ○ ○ ○ ○ ○ X ◎ 3-02 ○ ○ ○ ○ ○ ○ X ◎ 3-03 ○ ○ ○ ○ ○ ○ X ◎ 3-04 ○ ○ ○ ○ ○ ○ X ◎ 3-05 ○ ○ ○ ○ ○ ○ X ◎ 3-06 ○ ○ ○ ○ ○ ○ X ◎ 3-07 ○ ○ ○ ○ ○ ○ X ◎ 3-08 ○ ○ ○ ○ ○ ○ X ◎ 3-09 ○ ○ ○ ○ ○ ○ X ◎

Comparative Example RRC Save
stability EBR
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 3-01 △ △ △ △ △ △ X ◎ 3-02 △ △ △ △ △ △ X ◎ 3-03 △ △ △ △ △ △ X ◎ 3-04 X X X X X X X ○ 3-05 X X X X X X X X 3-06 △ △ △ △ △ △ X △ 3-07 X X X X X X X △ 3-08 △ △ △ △ △ △ X X 3-09 X X X X X X X X 3-10 △ △ △ △ △ △ X △ 3-11 X X X X X X X X 3-12 X X X X X X X X 3-13 X X X X X X X X

Example RRC Save
stability EBR
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 4-01 ○ ○ ○ ○ ○ ○ X ◎ 4-02 ○ ○ ○ ○ ○ ○ X ◎ 4-03 ○ ○ ○ ○ ○ ○ X ◎ 4-04 ○ ○ ○ ○ ○ ○ X ◎ 4-05 ○ ○ ○ ○ ○ ○ X ◎ 4-06 ○ ○ ○ ○ ○ ○ X ◎ 4-07 ○ ○ ○ ○ ○ ○ X ◎ 4-08 ○ ○ ○ ○ ○ ○ X ◎ 4-09 ○ ○ ○ ○ ○ ○ X ◎

Comparative Example RRC Save
stability EBR
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 4-01 △ △ △ △ △ △ ○ X 4-02 △ △ △ △ △ △ ○ X 4-03 △ △ △ △ △ △ ○ X 4-04 X X X X X X ○ X 4-05 X X X X X X X X

Example RRC Save
stability EBR
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 5-01 ○ ○ ○ ○ ○ ○ ○ ◎ 5-02 ○ ○ ○ ○ ○ ○ ○ ◎ 5-03 ○ ○ ○ ○ ○ ○ ○ ◎ 5-04 ○ ○ ○ ○ ○ ○ ○ ◎ 5-05 ○ ○ ○ ○ ○ ○ ○ ◎ 5-06 ○ ○ ○ ○ ○ ○ ○ ◎ 5-07 ○ ○ ○ ○ ○ ○ ○ ◎ 5-08 ○ ○ ○ ○ ○ ○ ○ ◎ 5-09 ○ ○ ○ ○ ○ ○ ○ ◎

Comparative Example RRC Save
stability EBR
(SOCA) SOC
A SOC
B SOC
C SOC
D SOC
E SOC
F 5-01 ○ ○ ○ ○ ○ ○ X ◎ 5-02 ○ ○ ○ ○ ○ ○ X ◎ 5-03 ○ ○ ○ ○ ○ ○ X ◎

Referring to the results of the test examples, the thinner compositions according to the Examples show superior solubility to the weakly soluble resist for spin-on hard mask as compared with the thinner compositions of the comparative examples, and the edge bead removing step and the substrate pre- So that it can be performed more effectively.

In addition, it has been found that the thinner compositions according to the examples exhibit excellent storage stability compared to the thinner compositions of the comparative examples.

Claims (8)

1-methoxy-2-propanol acetate;
Methyl 3-methoxypropionate;
Gamma-butyrolactone;
Ketocyclopentane; And
At least one of 2-methoxy-1-propyl acetate, propylene glycol monomethyl ether and butylated hydroxytoluene
≪ / RTI >
The method according to claim 1,
100 parts by weight of 1-methoxy-2-propanol acetate;
1 to 100 parts by weight of methyl 3-methoxypropionate;
0.1 to 50 parts by weight of gamma-butyrolactone;
0.1 to 70 parts by weight of keto cyclopentane; And
From 0.001 to 30 parts by weight of 2-methoxy-1-propyl acetate, from 0.01 to 20 parts by weight of propylene glycol monomethyl ether and from 0.0001 to 10 parts by weight of butylated hydroxytoluene
≪ / RTI >
3. The method of claim 2,
The 2-methoxy-1-propyl acetate is prepared by fractional distillation under reduced pressure to 1-methoxy-2-propanol acetate so as to obtain a thinner, which is adjusted to 0.001 to 30 parts by weight relative to 100 parts by weight of 1-methoxy- Composition.
The method according to claim 1,
1-methoxy-2-propanol acetate;
Methyl 3-methoxypropionate;
Gamma-butyrolactone;
Ketocyclopentane; And
Methoxy-1-propyl acetate, propylene glycol monomethyl ether, and butylated hydroxytoluene.
≪ / RTI >
The method according to claim 1,
1-methoxy-2-propanol acetate;
Methyl 3-methoxypropionate;
Gamma-butyrolactone;
Ketocyclopentane;
2-methoxy-1-propyl acetate; And
Butylated hydroxytoluene
≪ / RTI >
The method according to claim 1,
1-methoxy-2-propanol acetate;
Methyl 3-methoxypropionate;
Gamma-butyrolactone;
Ketocyclopentane;
2-methoxy-1-propyl acetate; And
Propylene glycol monomethyl ether
≪ / RTI >
The method according to claim 1,
1-methoxy-2-propanol acetate;
Methyl 3-methoxypropionate;
Gamma-butyrolactone;
Ketocyclopentane;
Propylene glycol monomethyl ether; And
Butylated hydroxytoluene
≪ / RTI >
The method according to claim 1,
1-methoxy-2-propanol acetate;
Methyl 3-methoxypropionate;
Gamma-butyrolactone;
Ketocyclopentane;
2-methoxy-1-propyl acetate;
Propylene glycol monomethyl ether; And
Butylated hydroxytoluene
≪ / RTI >