KR101522903B1 - Thinner composition and method of forming a photosensitive film using the same - Google Patents

Abstract

A thinner composition having improved solubility for various photosensitive materials and applicable to various process steps in the manufacture of a photoresist, and a method for forming a photoresist using the same, wherein the thinner composition comprises 50 to 90% by weight of propylene glycol monomethyl ether acetate, propylene glycol monomethyl 1 to 20% by weight of ether, 1 to 10% by weight of gamma-butyrolactone and 1 to 20% by weight of n-butyl acetate. The thinner composition has excellent solubility and appropriate volatility for various photosensitive materials and can be usefully used for an edge bead removing process, a rework process, or a process for pre-wetting a substrate before forming a photoresist film.

Description

Thinner composition and method for forming a photosensitive film using the same

The present invention relates to a thinner composition and a method for forming a photoresist film using the same. More particularly, the present invention relates to a thinner composition that can be used in various process steps in the manufacture of a photoresist, and a method of forming a photoresist using the same.

The photo lithography process refers to a process of transferring a previously designed pattern to a photoresist film on a wafer using a photomask, and then etching the underlying film according to the transferred pattern. Such a photolithography process is a key process for determining circuit miniaturization and integration in a process for manufacturing an electronic device such as a semiconductor memory device, an integrated circuit device, and a thin film transistor liquid crystal display device.

In the photolithography process, a photosensitive material is coated on a wafer to form a photosensitive film. A photomask or a pattern on a reticle is projected using exposure equipment to expose the photoresist film, and then a photoresist pattern of a desired shape is manufactured through a development process. The wafer substrate or the lower film is etched using a photoresist pattern as a mask, or a process such as ion implantation is performed. Thereafter, the photoresist pattern that is no longer needed is removed from the substrate through an ashing process or a stripping process.

Various kinds of light sources are used in the photolithography process in consideration of the line width of the pattern in the process of manufacturing an integrated circuit device composed of various pattern structures. Examples of the light source used in the photolithography process include G-line, I-line, KrF, ArF, ultraviolet ray, e-beam and X-ray. Among these, the wavelength of the G-line is the longest and the wavelength of the X-ray is the shortest.

The photoresist used for the formation of the photoresist film is a photosensitive material sensitive to light and reacts to light of a specific wavelength. Therefore, various kinds of photoresists containing components capable of responding to each light source are used. In other words, the photoresist includes various kinds of main component resins, photosensitizers, and the like depending on the type of the light source. Various physical properties such as chemical or physical properties of the photoresist, for example, sensitivity to a light source, corrosion resistance, stripping properties, and solubility in solvents vary greatly depending on the chemical structure of the resin or photosensitive agent.

In a photolithography process, a thinner composition refers to a material that has solubility in the photoresist described above and is used as a diluent for removing 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, commercially available thinner compositions generally have a problem in that the solubility is not constant for various photoresists because the chemical composition differs greatly depending on the kind of the photoresist.

2. Description of the Related Art In recent years, semiconductor wafers having a large diameter have been increasingly used due to high integration and high density of semiconductor integrated circuits. The case where the rinsing process is performed under the condition that the rotation speed of the substrate is relatively slow due to the large-scale curing of the substrate is increasing. If the thinner composition does not have a proper dissolution rate with respect to the photoresist, uniform removal of the photoresist may be difficult because the substrate swings at relatively slow rotational speeds. Therefore, in the low rotation rinse process due to the large-scale curing of the substrate, the thinner rinse process requires a further improved thinning capability of the thinner composition.

Accordingly, one embodiment of the present invention provides a thinner composition having improved solubility for various photosensitive materials and which can be usefully applied to various process steps of photoresist film production.

Another embodiment of the present invention provides a method of forming a photosensitive film using the above-described thinner composition.

The thinner composition according to one embodiment of the present invention comprises 50 to 90 wt% propylene glycol monomethyl ether acetate, 1 to 20 wt% propylene glycol monomethyl ether, 1 to 10 wt% gamma butyrolactone, and 1 to 20 % ≪ / RTI > by weight.

In one embodiment, the thinner composition comprises 55 to 80% by weight of propylene glycol monomethyl ether acetate, 5 to 20% by weight of propylene glycol monomethyl ether, 3 to 8% by weight of gamma butyrolactone and 5 to 20% by weight of n-butyl acetate %. ≪ / RTI > In another embodiment, the thinner composition comprises 60 to 80% by weight of propylene glycol monomethyl ether acetate, 5 to 20% by weight of propylene glycol monomethyl ether, 3 to 8% by weight of gamma butyrolactone and 5 to 15% by weight of n-butyl acetate %. ≪ / RTI >

In one embodiment, the thinner composition may have a relative volatility in the range of 0.2 to 0.8 based on the volatility of n-butyl acetate.

In the method of forming a photoresist film according to another embodiment of the present invention, a photosensitive resin composition is coated on a substrate, and then 50 to 90% by weight of propylene glycol monomethyl ether acetate, 1 to 20% by weight of propylene glycol monomethyl ether, 1 to 10% by weight of gamma-butyrolactone and 1 to 20% by weight of n-butyl acetate may be applied to remove at least a part of the photosensitive resin composition from the substrate.

In one embodiment, the thinner composition may be applied to an edge portion of the substrate to selectively remove the photosensitive resin composition applied to the edge portion. The application of the thinner composition to the edge portion of the substrate may be performed by spraying the thinner composition under pressure at the edge portion of the substrate while rotating the substrate. For example, the substrate may be rotated at a speed of 300 to 3,000 rpm, and the thinner composition may be sprayed at a flow rate of 5 to 50 mL / min.

In one embodiment, the thinner composition may be sprayed onto the backside of the substrate to remove the photosensitive resin composition from the substrate.

In one embodiment, it is possible to pre-wet the substrate by applying the thinner composition to the substrate before applying the photosensitive resin composition.

In one embodiment, the photosensitive resin composition comprises an i-line photoresist containing a novolac resin, a KrF photoresist containing hydrogen hydrogens partially blocked with an acetal group, a hydrogen atom of a hydroxyl group A photoresist for KrF containing polyhydroxystyrene partially blocked with a tert-butyl carbonate group, a photoresist for ArF containing a methacrylate resin, a lower antireflection coating for KrF including a triazine-based resin, and a polyester Antireflective coating for ArF containing a fluorocarbon-based resin.

In one embodiment, after removing at least a part of the photosensitive resin composition from the substrate, the photosensitive resin composition coated on the substrate may be baked to form a photosensitive film. After detecting defects existing in the photoresist layer, the photoresist layer having defects may be removed from the substrate by applying the thinner composition.

According to another embodiment of the present invention, there is provided a method for forming a photoresist film, comprising the steps of: preparing a substrate comprising 50 to 90 wt% of propylene glycol monomethyl ether acetate, 1 to 20 wt% of propylene glycol monomethyl ether, 1 to 10 wt% of gamma-butyrolactone, And 1 to 20% by weight of n-butyl acetate in order to increase the wettability of the substrate, and then to apply the photosensitive resin composition on the substrate.

The thinner composition according to the embodiments of the present invention described above has an improved solubility in a photosensitive resin composition such as I-line, KrF or ArF photoresist and KrF or ArF bottom anti-reflective coating. In addition, the thinner composition has physical properties such as volatility, viscosity and surface tension in an appropriate range. Therefore, the thinner composition can cleanly remove the edge beads attached to the edge or the rear surface of the substrate without damaging the photoresist film applied on the entire surface of the substrate, and can also be applied to a rework process for removing the photoresist film from the front surface of the substrate have. In addition, the thinner composition can be applied to a substrate before applying the photosensitive resin composition to a substrate, thereby improving the wetting performance of the substrate and remarkably improving the applicability of the photosensitive resin composition.

Hereinafter, a thinner composition according to embodiments of the present invention and a method for forming a photoresist using the same will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the following embodiments, and various modifications may be made without departing from the technical idea of the present invention.

The terms used in the embodiments of the present invention are used to describe only specific embodiments and are not intended to limit the present invention. The singular forms "a," "an", "the", and "the" include plural referents unless the context clearly dictates otherwise, and the terms "comprise" or "comprise" It is to be understood that the combination is intended to specify that it is present and not to preclude the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Thinner composition

Embodiments of the present invention provide a thinner composition having improved solubility for various photosensitive materials and which can be usefully applied to various process steps of photoresist film fabrication. Embodiments of the present invention provide a thinner composition that can improve work stability and is less corrosive because it is not toxic to the human body and has no discomfort due to odor. The thinner composition according to embodiments of the present invention may include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, gamma butyrolactone, and n-butyl acetate.

The thinner composition has excellent solubility and sensitivity to EBR (Egde Bead Removal) for photosensitive materials such as various photoresists including I-line, KrF or ArF photoresists and Bottom Anti-Reflective Coating (BARC) ). Therefore, in the process of forming a photoresist using the photosensitive material, the thinner composition may be formed by an edge bead removing process for removing a photosensitive material applied or attached to an edge or a rear surface of a substrate or an edge bead removing process for removing a photosensitive film, And can be applied to a rework process. The thinner composition may also be used in a stripping process for removing the photoresist pattern after the development and etching process.

In addition, the thinner composition has physical properties such as volatility, surface tension and viscosity in addition to solubility in the photosensitive material. Therefore, by pre-wetting the substrate with the thinner composition before applying the photosensitive material on the substrate, the wetting performance of the substrate is improved to improve the thickness uniformity of the photoresist film and to provide a defect such as tearing of the photoresist film formed on the wafer edge portion The occurrence can be reduced.

The term "edge bead" refers to a state in which a photosensitive material is aggregated in a spherical shape at an edge portion and a rear surface of a substrate by a centrifugal force in a process of forming a photosensitive film by spin coating. The edge beads can act as a source of contamination causing malfunction of the semiconductor device or manufacturing equipment, and can also cause defocusing in the exposure process. The excellent edge bead removal characteristic means that the edge beads attached to the edge or the rear surface of the substrate can be easily removed without damaging the photosensitive film formed on the front surface of the substrate and the boundary line of the photosensitive film in the edge portion of the substrate can be clearly And is uniformly produced.

Ethylene glycol monoethyl ether acetate, which has been used in conventional thinner compositions, 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. Further, in the case of ethyl lactate, since the viscosity is high and the dissolution rate is relatively low, it is difficult to sufficiently improve the cleaning power of the thinner composition. When a mixed solvent composed of pyruvic acid alkyls and methyl ethyl ketone is used as the thinner composition, the solubility in 1,2-naphthaquinone diazide-based photosensitizer in the photosensitive agent, which is one of the important components of the photosensitive film, may be lowered. When a substrate having a high volatility such as a mixed solvent of propylene glycol alkyl ether propionate and butyl acetate is used as a thinner composition and the rear surface of the substrate is cleaned, a thickness variation of the photoresist film may be increased as the substrate is cooled. 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. Further, 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.

Propylene Glycol Monomethyl Ether Acetate (PGMEA) used in the thinner composition according to embodiments of the present invention has excellent solubility for various types of photoresist, and has appropriate volatility, not too high or low, Tension and viscosity. However, propylene glycol monomethyl ether acetate has low solubility in some photoresists, for example, methacrylate-based ArF photoresists. Therefore, as the amount of propylene glycol monomethyl ether acetate is increased, the ability to remove edge beads from the photoresist for ArF may be lowered, or the uniformity of application of the photoresist film formed through prewetting may be lowered.

In some embodiments, when the content of propylene glycol monomethyl ether acetate is more than about 90% by weight, the solubility in the methacrylate-based ArF photoresist is low so that the edge bead removal property and the coating uniformity of the photoresist film are lowered . Further, when the content of propylene glycol monomethyl ether acetate is less than about 50% by weight, the volatility of the thinner composition becomes relatively high, so that the photosensitive resin composition spreads evenly on the substrate in the step of applying the photosensitive resin composition after pre- Failure to do so may result in tearing of the photoresist or cracking of the edges. When the propylene glycol monomethyl ether acetate is used in an amount of less than 50% by weight, the volatility of the thinner composition is increased because the content of propylene glycol monomethyl ether and n-butyl acetate, which are highly volatile, is relatively increased.

In one embodiment, the content of propylene glycol monomethyl ether acetate contained in the thinner composition may range from about 50 to about 90 weight percent. In another embodiment, the content of propylene glycol monomethyl ether acetate may range from about 55 to about 80 weight percent. In yet another embodiment, the content of propylene glycol monomethyl ether acetate may range from about 60 to about 80 weight percent.

The propylene glycol monomethyl ether (PGME) contained in the thinner composition has excellent solubility in various types of photoresist including methacrylate-based photoresist for ArF. Therefore, as the content of propylene glycol monomethyl ether increases, the solubility of the photoresist for ArF can be improved. However, since propylene glycol monomethyl ether has relatively high volatility, when a relatively large amount is used in prewetting the substrate before the application of the photoresist, thickness variation or lifting of the photoresist may occur.

For example, if the content of propylene glycol monomethyl ether is less than about 1% by weight, the solubility of the thinner composition in the ArF photoresist is lowered, and the edge bead removing property of the photoresist using the ArF photoresist may be lowered And the photoresist film may not be easily removed during the rework process due to the occurrence of defects. If the content of propylene glycol monomethyl ether exceeds about 20% by weight, the volatility of the thinner composition increases, and the thickness of the photoresist film formed after prewetting may be large and non-uniformly coated.

In one embodiment, the content of propylene glycol monomethyl ether in the thinner composition may range from about 1 to about 20 weight percent. In another embodiment, the amount of propylene glycol monomethyl ether may range from about 5 to about 20 weight percent. In yet another embodiment, the amount of propylene glycol monomethyl ether may range from about 5 to about 15 weight percent.

The gamma-butyrolactone contained in the thinner composition has excellent solubility in various types of photoresist. For example, gamma-butyrolactone has excellent solubility in a polyhydroxystyrene-based KrF photoresist blocked with a t-butyl carbonate group. Accordingly, as the content of gamma-butyrolactone increases, the solubility of various photosensitive materials including KrF photoresist can be improved. However, gamma butyrolactone has a relatively high surface tension and viscosity. Therefore, as the content of gamma-butyrolactone increases, the uniform spreading property on the entire surface of the substrate in the pre-wetting process may be deteriorated. In addition, gamma-butyrolactone may cause damage or defects of the photoresist film by dissolving the photoresist in the process of applying the photoresist film after prewetting due to the relatively low volatility, and may remain on the substrate and may act as a contaminant in a subsequent process have.

For example, if the content of gamma-butyrolactone is greater than about 10% by weight, the thinner composition may be rounded in the edge bead removal experiment due to the relatively high viscosity and surface tension, or tailing may occur at the edge of the photoresist have. Also, when the content of gamma-butyrolactone is less than about 1% by weight, solubility in a specific photosensitive material such as a polyhydroxystyrene-based KrF photoresist blocked with a t-butyl carbonate group may be lowered.

In one embodiment, the gamma butyrolactone content may range from about 1 to about 10 weight percent. In another embodiment, the gamma butyrolactone content may range from about 3 to about 8 weight percent.

The n-butyl acetate (nBA) contained in the thinner composition is excellent in solubility in a KrF photoresist containing a specific photosensitive material, for example, polyhydroxystyrene blocked with a tert-butyl carbonate group. In addition, since n-butyl acetate has high volatility and relatively low surface tension and viscosity, it can contribute to improving edge bead removal characteristics and coating uniformity of prewetted photoresist by adjusting these properties to an appropriate range . However, n-butyl acetate has a relatively low solubility in a photosensitive material such as a methacrylate-based ArF photoresist. In addition, since n-butyl acetate has a relatively high volatility, when the content thereof is increased to a certain level or more, the overall volatility of the thinner composition is increased, and the wettability to the substrate is lowered, and the thickness of the photoresist film formed after pre- Or lifting of the photoresist film may occur.

For example, when the content of normal butyl acetate is more than about 20% by weight, the volatility of the thinner composition becomes high, and the applicability or wettability of the thinner composition to the substrate may be lowered. In addition, when the content of normal butyl acetate is less than about 1% by weight, solubility in KrF photoresist containing polyhydroxystyrene blocked with a tert-butyl carbonate group is lowered, and the edge bead removing ability can be reduced.

In one embodiment, the content of normal butyl acetate may range from about 1 to about 20 weight percent. In another embodiment, the content of normal butyl acetate may range from about 5 to about 20 weight percent. In yet another embodiment, the content of normal butyl isethate may range from about 5 to about 15 weight percent.

If the volatility of the thinner composition is excessively high, the substrate may rapidly cool at the time of applying the thinner composition, and the thickness variation of the photoresist film may remarkably increase. If the volatility of the thinner composition is excessively low, the thinner composition may remain on the substrate at the time of prewetting to dissolve the photoresist film or cause defects such as distortion of the photoresist film. After the edge bead is removed, And may act as a source of contaminants in subsequent processes. In one embodiment, the thinner composition may have a relative volatility in the range of 0.2 to 0.8 based on the volatility of n-butyl acetate.

In some embodiments of the present invention, the thinner composition may further comprise a surfactant. The surfactant can improve the detergency or the ability to remove edge beads of the thinner composition. Examples of the surfactant include a fluorine surfactant, a nonionic surfactant, and an ionic surfactant. The content of the surfactant may range from about 10 to about 500 ppm based on the total weight of the thinner composition.

Method of forming photoresist film

FIG. 1 is a process flow chart for explaining a method of forming a photoresist film according to embodiments of the present invention.

Referring to FIG. 1, a substrate may be prewetted by applying a thinner composition according to embodiments of the present invention described above to a substrate on which a photoresist layer is to be formed (step S110). The thinner composition according to embodiments of the present invention may include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, gamma butyrolactone, and n-butyl acetate. By applying the substrate with the above-described thinner composition, it is possible to improve the wetting performance such as the wettability of the substrate before applying the photosensitive resin composition to the substrate.

The substrate may be a substrate used for manufacturing an electronic device such as a semiconductor memory device, an integrated circuit device, or a thin film transistor liquid crystal display device. A plurality of structures, for example, an insulating film, a conductive film, a wiring, a hole, a plug, a pad, a gate, a capacitor, and a conductive region may be formed on the substrate. In addition, a step may exist on the upper surface of the substrate due to the structures.

The prewetting process may be performed by spin-coating the substrate with a thinner composition. In one embodiment, after applying the thinner composition on the substrate, the thinner composition may be dispensed onto the entire surface of the substrate by rotating the substrate. In another embodiment, the thinner composition can be applied to the entire substrate by dropping the thinner composition while rotating the substrate. For example, during application of the thinner composition, the substrate may be rotated at a speed of from about 300 to about 3,000 rpm.

If the volatility of the thinner composition used in the pre-wetting process is excessively high, the substrate may rapidly cool during application of the thinner composition, and the thickness variation of the photoresist film may significantly increase. When the volatility of the thinner composition is excessively low, the thinner composition may remain on the substrate excessively, causing the photoresist film to dissolve or cause defects such as distortion of the photoresist film. In one embodiment, the thinner composition may have a relative volatility in the range of 0.2 to 0.8 based on the volatility of n-butyl acetate.

Also, the thinner composition used in the pre-wetting process may increase the thickness deviation of the subsequently formed photoresist film even when the surface tension or viscosity is excessively high or the solubility to the photosensitive resin composition is low.

In one embodiment, the thinner composition used in the pre-wetting process comprises 50 to 90 wt% propylene glycol monomethyl ether acetate, 1 to 20 wt% propylene glycol monomethyl ether, 1 to 10 wt% gamma butyrolactone, 1 to 20% by weight of butyl acetate. In another embodiment, the thinner composition comprises 60 to 80% by weight of propylene glycol monomethyl ether acetate, 5 to 20% by weight of propylene glycol monomethyl ether, 3 to 8% by weight of gamma butyrolactone and 5 to 15% by weight of n-butyl acetate %. ≪ / RTI >

When the content of propylene glycol monomethyl ether acetate (PGMEA) exceeds about 90% by weight, for example, the solubility in the methacrylate-based ArF photoresist is low, and the coating uniformity of the photoresist formed by the photoresist Can be lowered. Further, when the content of propylene glycol monomethyl ether acetate is less than about 50 wt%, the volatility of the thinner composition becomes excessively high due to an increase in other highly volatile components, so that the photosensitive resin composition does not spread evenly on the substrate and tearing of the photoresist film occurs A defect may occur.

If the content of propylene glycol monomethyl ether (PGME) is less than 1% by weight, solubility in various types of photoresist films including methacrylate-based ArF photoresist may be lowered. If the content of propylene glycol monomethyl ether exceeds about 20% by weight, for example, wettability to the substrate may be reduced due to the relatively high volatility, resulting in a severe step difference in the photosensitive film.

Since gamma-butyrolactone has a relatively high surface tension and viscosity and has a very low volatility, the thickness variation of the photoresist film may increase as the gamma-butyrolactone content increases. In one embodiment, when the content of gamma butyrolactone is greater than about 10% by weight, for example, about 20% by weight, the thickness variation of the photoresist film formed after prewetting can be significantly increased. When the content of gamma-butyrolactone (GBL) is less than about 1 wt%, the solubility of the photoresist for KrF in the polyhydroxystyrene series blocked with a t-butyl carbonate group is lowered and a thickness variation of the photoresist film may occur have

N-butyl acetate has a relatively high degree of volatility, and if its content exceeds, for example, about 20% by weight, it may volatize too quickly to reduce the applicability or wettability of the thinner composition to the substrate.

Referring again to FIG. 1, a photosensitive resin composition may be coated on the substrate to which the thinner composition has been applied to form a pre-photosensitive film (step S120). By the above-described thinner composition increasing the wettability of the substrate, the subsequently applied photosensitive resin composition can be more uniformly applied to the substrate. In addition, a thin film can be formed using a relatively small amount of the photosensitive resin composition. The photosensitive resin composition can be uniformly applied to the edge portion of the substrate by prewetting the thinner composition and the occurrence of defective coating of the photosensitive film at the edge portion of the substrate can be reduced and the step due to the fine pattern on the substrate can be easily overcome, Can be reduced.

Examples of the photosensitive resin composition include photoresists for I-line including novolac resin, KrF photoresists containing polyhydroxystyrene in which hydrogen of the hydroxyl group is partially blocked with an acetal group, - a photoresist for KrF containing a polyhydroxystyrene blocked with a butylcarbonate group, a photoresist for ArF including a methacrylate resin, a bottom antireflection coating for KrF containing a triazine-based resin, an ArF And a bottom anti-reflection coating for use.

For example, the I-line photoresist may comprise 2,4-dinitroquinone as a novolak 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.

In one embodiment, the application of the photosensitive resin composition may be performed by spin coating. When the photosensitive resin composition is applied by spin coating, the photosensitive resin composition may be squeezed to form edge beads on the edge portion and the rear surface of the substrate by centrifugal force. The edge beads can act as a source of contamination leading to defects in electronic devices or malfunctioning of manufacturing equipment, and can also cause defocusing in the exposure process.

Referring to FIG. 1, at least a part of the photosensitive resin composition, for example, the photosensitive resin composition adhered to the edge or the rear surface of the substrate, can be removed from the substrate using the thinner composition according to the embodiments of the present invention S130). The thinner composition used for removing the photosensitive resin composition may include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, gamma butyrolactone, and n-butyl acetate.

In one embodiment, the step of removing the photosensitive resin composition from the edge or the rear surface of the substrate may be performed by spraying the thinner composition under a pressurizing condition while rotating the substrate. For example, the thinner composition may be sprayed at a flow rate of from about 5 to about 50 mL / min. The thinner composition may be injected in a pressurized container having a pressure of from about 0.5 to about 3 kgf. Also, in the edge bead removal step, the substrate may be rotated at a speed of from about 300 to about 3,000 rpm.

FIGS. 2A to 2D are schematic views for explaining a boundary portion of a pre-photosensitive film on which an edge bead removal process is performed. FIG.

2A is a schematic diagram for explaining a case where a boundary line of the preliminary photoresist film is clearly and uniformly formed in an edge bead removing process. FIGS. 2B and 2C are schematic views for explaining a case in which the edge shape of the preliminary photoresist layer is distorted or irregular by the edge bead removal process, thereby failing to maintain the line shape. FIG. 2D is a schematic view for explaining a case where tailing occurs at a boundary portion of a pre-photoresist film by an edge bead removing process. FIG.

The thinner composition according to the embodiments of the present invention can be used for various photosensitive resin compositions such as I-line, KrF or ArF photoresist and antireflective coating for KrF or ArF, and has excellent solubility and good physical properties such as viscosity, surface tension, So that only the edge beads can be cleanly removed while sharpening the boundary line as shown in FIG. 2A. If the solubility of the thinner composition is low or the viscosity or surface tension is excessively high, the boundary line may not be maintained in a line shape as shown in FIG. 2B or FIG. 2C, May result in tailing.

If the volatility of the thinner composition used in the edge bead removal process is excessively high, the thinner composition may easily volatilize into the work space, resulting in deterioration of the cleanliness of the semiconductor manufacturing facility or increased hazard to the human body. If the volatility of the thinner composition is too low, the thinner composition may remain on the substrate without being volatilized after edge bead removal, and may act as a source of contamination of the substrate or manufacturing facility in subsequent processes.

In one embodiment, the thinner composition used in the edge bead removal process comprises 50 to 90% by weight of propylene glycol monomethyl ether acetate, 1 to 20% by weight of propylene glycol monomethyl ether, 1 to 10% by weight of gamma butyrolactone, And 1 to 20% by weight of normal butyl acetate. In another embodiment, the thinner composition comprises 60 to 80% by weight of propylene glycol monomethyl ether acetate, 5 to 20% by weight of propylene glycol monomethyl ether, 3 to 8% by weight of gamma butyrolactone and 5 to 15% by weight of n-butyl acetate %. ≪ / RTI >

When the content of propylene glycol monomethyl ether acetate (PGMEA) is more than about 90% by weight, for example, the solubility in the methacrylate-based ArF photoresist is low and the boundary line of the preliminary photoresist film is distorted, Lt; / RTI > In addition, when the content of propylene glycol monomethyl ether acetate is less than about 50 wt%, the volatility of the thinner composition may become excessively high due to an increase in other highly volatile components.

When the content of propylene glycol monomethyl ether (PGME) is less than about 1% by weight, the solubility of various types of photoresist films including the methacrylate-based photoresist for ArF is lowered, and the edge line of the pre- Distortion or tailing may occur. If the content of propylene glycol monomethyl ether is, for example, more than about 20% by weight, the volatility of the thinner composition can be remarkably increased.

If the content of gamma-butyrolactone exceeds about 10% by weight, tailing may occur at the boundary of the pre-photoresist film due to high viscosity and surface tension and low volatility. When the content of gamma-butyrolactone (GBL) is less than about 1% by weight, the solubility of the photoresist for KrF for polyhydroxystyrene series blocked with a t-butyl carbonate group is decreased and the preliminary photoresist The boundary of

When the content of n-butyl acetate exceeds about 20 wt%, the volatility of the thinner composition may be excessively increased. When the content of n-butyl acetate is less than about 1 wt%, the polyhydroxystyrene series blocked with a t- The solubility in a specific photosensitive resin composition such as KrF photoresist may be lowered.

In one embodiment, the thinner composition used in the edge bead removal process may be the same as the thinner composition used in the pre-wetting process. In another embodiment, the thinner composition used in the edge bead removal process may not be the same as the thinner composition used in the pre-wetting process.

Referring to FIG. 1 again, after removing the edge beads attached to the edge or rear surface of the substrate, the photosensitive film may be formed by soft-baking the pre-photosensitive film (step S140). During the soft-baking, the solvent or moisture remaining in the pre-photoresist can be removed.

Thereafter, the substrate on which the photoresist layer is formed is checked for the occurrence of a defect in the photoresist layer using a defect detecting device (step S150). If no defect is found in the photoresist, a photoresist pattern may be formed by performing exposure and development processes on the photoresist (steps S180 and S190).

If defects such as tearing, tailing, distortion of a boundary line, and thickness deviation occur in the photoresist film, a photoresist film formed on the entire surface of the substrate is removed by performing a rework process (step S160). The removal of the photoresist layer may be performed using a thinner composition according to embodiments of the present invention. The thinner composition used in the rework process may include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, gamma butyrolactone, and n-butyl acetate. The thinner composition has a good solubility with respect to the photoresist film on which baking has been performed, so that the photoresist film can be removed from the substrate in a short period of time.

In one embodiment, the thinner composition used in the rework process may be the same as the thinner composition used in the pre-wetting process and / or the edge bead removal process. In another embodiment, the thinner composition used in the edge bead removal process may not be the same as the thinner composition used in the pre-wetting process and / or the edge bead removal process.

After the rework process is performed, the substrate on which the photoresist layer is removed is dried (step S170). Thereafter, the steps such as the pre-wetting step (step S110), the application of the photosensitive resin composition (step S120), the edge bead removing step (step S130), the soft baking (step S140), the exposure and development Thereby forming a defect-free photosensitive film.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples are provided for illustrating the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made.

Preparation of thinner composition

Example 1

55% by weight of propylene glycol monomethyl ether acetate (PGMEA), 20% by weight of propylene glycol monomethyl ether (PGME), 5% by weight of gamma-butylolactone (GBL) By weight, and the mixture was stirred at room temperature for 1 hour at a speed of 500 rpm to prepare a thinner composition.

Examples 2 to 5 and Comparative Examples 1 to 11

A thinner composition was prepared in substantially the same manner as in Example 1, except that the ingredients and the content thereof used in the preparation of the thinner composition were varied. The components used in the preparation of each of the thinner compositions and their contents are shown in Table 1 below. In Table 1, the unit of the content is% by weight.

Table 1

On the other hand, the boiling points of the propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), gamma butyrolactone (GBL) and normal butyl acetate (nBA) used in Comparative Examples 8 to 11, The surface tension, the vapor pressure and the viscosity are shown in Table 2 below.

Table 2

Experimental Example  1: Edge according to the type of photosensitive film Bead  remove( EBR ) Ability assessment

A photosensitive resin composition was applied to an oxidized 4-inch silicon substrate to form a photoresist film. As the photosensitive resin composition, a photoresist for I-line, a photoresist for KrF, a photoresist for ArF, a bottom antireflective coating (BARC) for KrF, and a bottom antireflection coating for ArF were used. The photoresist film was formed by spin coating. Table 3 shows the kinds of the main component resin of the photosensitive resin composition used in the production of the photoresist film and the thickness of the photoresist film thus produced.

Table 3

In Table 3, a photoresist containing a novolac resin was used as the I-line photoresist (PR 1), and a photoresist (PR 2) used as the KrF photoresist was a polyhydroxy resin in which hydrogen of the hydroxyl group was partially blocked with an acetal group A photoresist containing rxstyrene was used. As another KrF photoresist (PR 3), a photoresist containing polyhydroxystyrene (PHS) in which hydrogen of a hydroxyl group was partially blocked with a tert-butylcarbonate group was used As the photoresist (PR 4) for ArF, a photoresist including a methacrylate resin blocked with adamantaldehyde was used. As the BARC (PR 5) for KrF, a lower antireflection coating containing a triazine-based resin was used, and a BARC (PR 6) for ArF was a lower antireflection coating containing a polyester-based resin.

The photosensitive resin composition as described above was spin-coated to form a photoresist layer on the substrate, and then the unnecessary photoresist layer was removed from the edges of the substrate using the thinner compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 11 Edge bead removal (EBR). Each thinner composition was supplied in a pressure vessel equipped with a pressure gauge, and the pressure in the pressure vessel was adjusted to about 1 kgf. The flow rate of the thinner composition from the EBR nozzle was 10 to 30 cc / min, and the thinner composition was sprayed to the edge portion of the substrate for about 20 seconds while rotating the substrate at a speed of about 2,000 rpm. Thereafter, the substrate was dried for about 6 seconds while rotating at a speed of about 1,300 rpm. Thus, after performing the EBR process using each of the thinner compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 11, it was confirmed whether unnecessary photoresist films of edge portions were removed using an optical microscope and a scanning electron microscope And the EBR characteristics were evaluated. The evaluation results of the EBR characteristics are shown in Table 4 below.

Table 4

In Table 4, "?" Means that edge beads are cleanly removed by the EBR process, and the edge partial lines of the photoresist film are uniform and constant, and "? &Quot; means that after the EBR process, To maintain a good line form. &Quot; X "means that the edge bead can not be removed by the EBR process, and the edge portion of the photoresist film is tailed to the edge portion of the photoresist film. &Quot; DELTA" means that the edge portion of the photoresist film is distorted without maintaining the line shape after the EBR process. .

Referring to Table 4, the thinner compositions prepared in Examples 1 to 5 were found to have excellent or good level of edge bead removal ability for various kinds of photoresist films.

Specifically, the thinner compositions prepared in Examples 1 to 4 were prepared by uniformly laminating edges of the four types of photoresist films (PR 1 to PR 4) and the lower antireflection coating layer of PR 5 while keeping the edge beads clean It can be removed. Also, for the lower antireflective coating layer of the PR 6, it was found that the edge bead could be removed while maintaining the line shape of the photoresist film of the edge portion at 75% or more. The thinner composition prepared in Example 5 showed that the edge beads could be removed cleanly while the lines of the edge portions were made uniform for the PR 1 and PR 2 photoresist films, and the thin film of PR-3 to PR-6 The edge portion of the photoresist film was found to be capable of removing edge beads while maintaining a line shape of 75% or more. On the other hand, the thinner compositions prepared in Comparative Examples 1 to 11 showed that the edge portions were distorted due to the dissolving action of the thinner composition, and tailing phenomenon occurred in at least one of the six types of photoresist films.

Compared with the thinner compositions prepared in Comparative Examples in which the composition and content were different from each other, the thinner compositions prepared in Examples 1 to 5 exhibited better edge bead removal characteristics, that is, superior EBR characteristics without damaging the edge portions of the photoresist Able to know. Further, the thinner compositions of Examples 1 to 4, in which the content of PGMEA was in the range of 55 to 80% by weight, were superior to the thinner compositions of Example 5 in which the content of PGMEA was 85% by weight, .

On the other hand, in the composition of Comparative Example 1 in which the content of PGMEA was less than 50% by weight, a distortion of the boundary line was observed with respect to some photoresist films (PR 1 and PR 4). In the thinner compositions of Comparative Examples 3 and 4 which did not contain PGME or nBA, the boundary line distortion was observed in a plurality of photoresist films.

The thinner composition of Comparative Example 2, which does not contain GBL, showed a marked decrease in the edge bead removal force for the polyhydroxystyrene-based KrF photoresist (PR 3) blocked with the t-butyl carbonate group. As in the thinner compositions of Comparative Examples 7 and 10, when the GBL was used in an amount of about 20 wt% or more, it was found that the thinner composition was rounded in the edge bead removal test due to the high surface tension or tailing occurred at the edge portion of the photoresist.

Experimental Example 2: Evaluation of dissolution rate according to the type of photoresist

The dissolution rates of various types of photoresist films were evaluated using the thinner compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 11. Six photosensitive resin compositions shown in Table 3 were each applied to an oxidized 6-inch silicon substrate to prepare a photoresist film. The photoresists PR 1 to PR 4 were soft baked after application and the bottom antireflective coatings of PR 5 and PR 5 were not heat treated after application. The dissolution rate of the photoresist film was measured using a development rate monitor (DRM) apparatus while developing the photoresist film on each thinner composition without exposure. The dissolution rate was measured and the results are shown in Table 5.

Table 5

In Table 5, "" means a case where the dissolution rate is 700 nm / sec or more, "o" means a case where the dissolution rate is 400 nm / sec or more and less than 700 nm / / sec to less than 400 nm / sec, and "X" means a case where the dissolution rate is less than 100 nm / sec.

Referring to Table 5, the thinner compositions prepared in Examples 1 to 5 showed excellent dissolution rates of 700 nm / sec or more or at least 400 nm / sec or more for various types of photoresist films. In particular, the thinner compositions prepared in Examples 3 and 4 were found to have a fast dissolution rate of more than 700 nm / sec for all six types of photosensitive films.

The compositions of Comparative Examples 8 and 11 were each a thinner composition containing propylene glycol monomethyl ether acetate (PGMEA) or n-butyl acetate (nBA) as a single component. These compositions were solubility in a specific photoresist, that is, Respectively.

The compositions of Comparative Examples 9 and 10 are each a thinner composition containing propylene glycol monomethyl ether (PGME) or gamma butyrolactone (GBL) as a single component, and have excellent overall dissolution rates for the photoresist used in the experiment appear. However, as shown in Table 4, the thinner compositions were evaluated as having a tailing phenomenon in the photosensitive film adjacent to the edge portion of the substrate or a distortion of the photosensitive film boundary in the EBR characteristic evaluation. Therefore, although the photoresist dissolution rate of the thinner composition is a factor affecting the EBR characteristics, it can be seen that excellent dissolution rate does not guarantee excellent EBR characteristics.

FIG. 3 is a graph showing the results of evaluating the change of the dissolution rate of the photoresist and the EBR characteristics according to the content of gamma-butyrolactone (GBL). 3, the content of PGME was fixed to about 10% by weight, the content of nBA was fixed to about 10% by weight, and the content of GBL and PGMEA was varied under the condition that the total weight was 100% And EBR experiments were conducted. PR-1, PR-2 and PR-3 were used as the photoresist. In the evaluation of the EBR characteristics, "?" Means that the edge beads are cleanly removed by the EBR process, and the edge partial lines of the photoresist film are uniform and constant, and "DELTA" means that, after the EBR process, However, it means maintaining a good line form with more than 75%. Also, "X" means that after the EBR process, the edge portion of the photoresist film fails to maintain a line shape and is distorted or tailing occurs at the edge portion.

Referring to FIG. 3, as the content of GBL contained in the thinner composition increased from 0 wt% to about 20 wt%, the dissolution rate for PR-1, PR-2 and PR-3 gradually increased. However, when the content of GBL is more than about 10% by weight, edge beads of the PR-1, PR-2 and PR-3 photosensitive films subjected to the EBR process are partially distorted or can not maintain the line shape, It was confirmed that the removal ability was decreased. Thus, it can be seen that by adjusting the content of GBL to greater than 0 wt% (e.g., greater than about 1 wt%) and less than about 10 wt%, the EBR characteristics of the thinner composition can be improved.

Experimental Example 3: Coating uniformity evaluation according to the type of photoresist

The coating uniformity was evaluated according to the type of the photoresist using the thinner compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 11. The coating uniformity was evaluated as to whether or not the photoresist film was uniformly coated on the entire surface of the substrate. The thinner composition was applied to the substrate before application of the photosensitive resin composition, and the thickness deviation of the photoresist film formed thereon was measured and evaluated.

A thinner composition was applied to a 6-inch silicon substrate which had been oxidized on a substrate, and each of the six photosensitive resin compositions of Table 3 was spin-coated on a substrate to which a thinner composition was applied to form a photoresist film. The uniformity of the photoresist film was evaluated by measuring the thickness of the photoresist film at nine points in total on the photoresist-coated substrate, that is, the center point and eight points located one inch and two inches from the center point in an X shape Respectively. Table 6 shows the process conditions for the application of the thinner composition and the formation of the photoresist film. Table 7 shows the evaluation results of the coating uniformity of the photosensitive film.

Table 6

Table 7

In Table 7, "" means the case where the standard deviation of the film thickness is 1% or less, "o" means the case where the standard deviation of the film thickness exceeds 1% to 2% Means a case where the standard deviation of the film thickness is more than 2% but not more than 3%, and "X" means the case where the standard deviation of the film thickness exceeds 3%.

As shown in Table 7, when pre-wetting with the thinner compositions prepared in Examples 1 to 6, very low levels of less than 1% or 2% for various types of photoresist and antireflective coatings The standard deviation of the thickness was generated. On the other hand, the photosensor films formed on the prewetted substrates with the thinner compositions prepared in Comparative Examples 1 to 11 had a thickness standard deviation exceeding 2% or exceeding 3%. Therefore, it can be seen that when the photoresist film is applied to the substrate prewetted with the thinner compositions of Examples 1 to 6, uniformity of application of the photoresist film is greatly improved.

EXPERIMENTAL EXAMPLE 4 Evaluation of Coating Performance of Photoresist According to Volatility of Thinner Composition

Relative volatilities of the thinner compositions prepared in Examples 1, 4 and 5 and Comparative Examples 1, 10 and 11 were measured. The coating uniformity of the photoresist film formed on the substrate pretreated with the thinner composition was evaluated, and the relationship between the volatility and the coating uniformity was analyzed.

Two grams (g) of the sample of the thinner composition was sampled, placed in a round silver plate, allowed to stand at room temperature, and the change in the amount of the sample with time was measured. The volatilized amount of normal butyl acetate was defined as a reference value 1, and the volatilization amounts of the other compositions were compared to evaluate relative volatilities. Further, the substrate was pretreated with the thinner composition prepared in Examples 1, 4 and 5 and Comparative Examples 1, 10 and 11 according to the process conditions shown in Table 6, and then a photoresist was formed using PR 1 photoresist Respectively. Table 8 shows the results of evaluation of relative volatility and coating property of the photoresist film.

Table 8

Referring to Table 8, it was confirmed that the thinner composition of Example 1 had a relative volatility of about 0.800, and a faint comb pattern was observed in the photoresist film, resulting in slight step differences. Relative volatilities of the thinner compositions of Examples 4 and 5 were measured to be 0.494 and 0.312, respectively, and the volatility was appropriate. Thus, the photoresist film was formed to have a uniform thickness without a difference in step or thickness. On the other hand, the relative volatilities of the thinner compositions of Comparative Example 1 and Comparative Example 11 were measured to be 0.924 and 1.000, respectively. These compositions were found to have too high volatility, so that a step with a very large thickness deviation in the photoresist film occurred, and the photoresist film did not adhere to the substrate, resulting in lifting. The relative volatility of the thinner composition of Comparative Example 10 was measured to be 0.005. The composition of Comparative Example 10 was found to have a too low volatility so that the amount of the remaining thinner composition was large during the application of the photoresist, resulting in a portion where the photoresist dissolved in the center of the wafer.

FIG. 4 is a graph showing a change in relative volatilization rate according to the content of gamma-butyrolactone (GBL), and FIG. 5 is a graph showing a change in relative volatilization rate according to the content of n-butyl acetate (nBA). In FIGS. 4 and 5, the relative volatilization rate refers to the volatilization rate of the composition when the volatility rate of nBA is 1.

4, the content of propylene glycol monomethyl ether (PGME) was maintained at about 10% by weight, the content of nBA was kept at about 10% by weight, and the content of GBL Relative volatilization rates were evaluated by varying the content of propylene glycol monomethyl ether acetate (PGMEA). 5, the content of propylene glycol monomethyl ether (PGME) was maintained at about 10% by weight, the content of GBL was kept at about 5% by weight, and the content of nBA The relative volatilization rate was evaluated by varying the content of PGMEA.

Referring to FIG. 4, when the content of GBL was 0 wt%, the relative volatilization rate of the composition was about 0.56. As the content of GBL increased, the relative volatilization rate gradually decreased. When the content of GBL was about 20 wt% The relative volatilization rate was measured to be about 0.30.

Referring to FIG. 5, the relative volatilization rate of the composition was about 0.42 when the content of nBA was 0 wt%, and gradually increased with the content of nBA. When the content of nBA is about 25% by weight or more, the relative volatilization rate becomes 0.8 or more. It has been confirmed that when the photoresist film is formed on the prewetted substrate with such a thinner composition, a step is generated on the wafer surface. When the content of nBA is 30 wt% or more, a severe step is generated in the photoresist film, and when the subsequent etching process is performed using the photoresist film, lifting or peeling of the photoresist occurs.

Therefore, when the content of nBA contained in the thinner composition is about 20% by weight or less, or the relative vortexing speed is about 0.8 or less, the wettability of the thinner composition to the substrate can be improved and a more uniform and improved It can be seen that a resist film can be formed.

The thinner composition according to the embodiments of the present invention described above has an improved solubility in a photosensitive resin composition such as I-line, KrF or ArF photoresist and KrF or ArF bottom anti-reflective coating. In addition, the thinner composition has physical properties such as volatility, viscosity and surface tension in an appropriate range. Therefore, the thinner composition can cleanly remove the edge beads attached to the edge or the rear surface of the substrate without damaging the photoresist film applied on the entire surface of the substrate, and can also be applied to a rework process for removing the photoresist film from the front surface of the substrate have. In addition, the thinner composition can be applied to a substrate before applying the photosensitive resin composition to a substrate, thereby improving the wetting performance of the substrate, and remarkably improving the applicability of the photosensitive resin composition.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. And changes may be made without departing from the spirit and scope of the invention.

FIG. 1 is a process flow chart for explaining a method of forming a photoresist film according to embodiments of the present invention.

FIGS. 2A to 2D are schematic views for explaining a boundary portion of a pre-photosensitive film on which an edge bead removal process is performed. FIG.

FIG. 3 is a graph showing the results of evaluating the change of the dissolution rate of the photoresist and the EBR characteristics according to the content of gamma-butyrolactone (GBL).

4 is a graph showing the relative volatilization rate change of the thinner composition according to the content of gamma-butyrolactone (GBL).

5 is a graph showing the relative volatilization rate change of the thinner composition according to the content of n-butyl acetate (nBA).

Claims (16)

50 to 90% by weight of propylene glycol monomethyl ether acetate; 1 to 20% by weight of propylene glycol monomethyl ether; 1 to 10% by weight of gamma-butyrolactone; And 1 to 20% by weight of normal butyl acetate. The thinner composition of claim 1, 55 to 80% by weight of propylene glycol monomethyl ether acetate; 5 to 20% by weight of propylene glycol monomethyl ether; 3 to 8% by weight gamma-butyrolactone; And And 5 to 20% by weight of normal butyl acetate. The thinner composition of claim 1, 60 to 80% by weight of propylene glycol monomethyl ether acetate; 5 to 20% by weight of propylene glycol monomethyl ether; 3 to 8% by weight gamma-butyrolactone; And And 5 to 15% by weight of normal butyl acetate. The thinner composition according to claim 1, wherein the thinner composition has a relative volatility of 0.2 to 0.8 based on the volatility of normal butyl acetate. Applying a photosensitive resin composition on a substrate; And A thinner composition comprising 50 to 90% by weight of propylene glycol monomethyl ether acetate, 1 to 20% by weight of propylene glycol monomethyl ether, 1 to 10% by weight of gamma butyrolactone and 1 to 20% by weight of n-butyl acetate, And removing at least a part of the photosensitive resin composition from the substrate. 6. The method of claim 5, wherein the step of removing at least a part of the photosensitive resin composition comprises the step of selectively applying the thinner composition to the edge portion of the substrate to selectively remove the photosensitive resin composition applied to the edge portion ≪ / RTI > delete delete 6. The method according to claim 5, wherein the step of removing at least a part of the photosensitive resin composition includes the step of spraying the thinner composition on the rear surface portion of the substrate to remove the photosensitive resin composition adhering to the rear surface portion from the substrate ≪ / RTI > 6. The method according to claim 5, wherein, before applying the photosensitive resin composition, Further comprising the step of pre-wetting the substrate by applying the thinner composition to the substrate. delete The method for forming a photoresist film according to claim 5, further comprising a step of removing at least a part of the photosensitive resin composition from the substrate and then baking the photosensitive resin composition coated on the substrate to form a photoresist film . The method of claim 12, further comprising: detecting a defect existing in the photoresist layer; And Further comprising the step of removing the photoresist film having the defect from the substrate by applying the thinner composition. delete delete delete

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