Thinner composition

Abstract

Disclosed is a thinner composition having an improved edge bead removal (EBR) effect. According to an aspect, provided is a thinner composition comprising: an ester-based compound having a solubility parameter due to dipol-dipol forces (δP) of at least 3 MPa1 / 2; a hydrocarbon-based compound having a solubility parameter due to hydrogen bonding forces (δH) of at least 9 MPa1 / 2 and containing at least one hydroxyl group; and a ketone having a solubility parameter due to dipol-dipol forces (δP) of at least 9 MPa1 / 2.

Description

Thinner composition

[0001] The present disclosure relates to a thinner composition, and more specifically, to a thinner composition and a method for removing a resist using the same.

[0002] A fine circuit pattern, such as a semiconductor integrated circuit, can be manufactured by uniformly applying a resist composition containing a resist compound and a solvent to a conductive metal film or oxide film formed on a substrate using a spin coating method, and then sequentially performing exposure, development, etching, and stripping processes.

[0003] The above exposure process utilizes short-wavelength ultraviolet light to finely expose the desired pattern to the coating, making it highly susceptible to external and internal contamination. Unnecessary resist residue and other contaminants left on the edges or back of the substrate can become a critical source of contamination in subsequent exposure processes.

[0004] Therefore, an edge bead removal (EBR) process or back rinse process is proposed to remove unnecessary resist residue and contaminants applied to the edge or back surface of the substrate before performing the exposure process.

[0005] Typically, the edge bead removal process or backside rinse process can be performed using a thinner composition for resist removal. Research is continuously being conducted to improve the performance of such thinner compositions.

[0006] According to one aspect of the present invention, a thinner composition having improved RRC (Reduced resist coating) and EBR (Edge bead removal) performance is provided.

[0007] According to another aspect of the present invention, a thinner composition having excellent pipe cleaning ability is provided.

[0008] According to another aspect of the present invention, there is provided a thinner composition capable of effectively removing not only KrF and ArF resists but also EUV (Extreme ultraviolet) resists.

[0009] According to another aspect of the present invention, a thinner composition is provided that improves solubility and compatibility with EUV resist.

[0010] According to another aspect of the present invention, a thinner composition is provided that can achieve a small dispersion effect by uniformly coating the resist over the entire area of ​​a substrate even when coating is performed using a small amount of resist.

[0011] The purposes of the present invention are not limited to those mentioned above, and other unmentioned purposes and advantages of the present invention can be understood through the following description and will be more clearly understood through the embodiments of the present invention. Furthermore, it will be readily apparent that the purposes and advantages of the present invention can be realized by the means and combinations thereof described in the specification.

[0012] [1] According to one aspect of the present invention, the solubility parameter due to dipol-dipol forces (δP) is 3 MPa. 1 / 2 An ester compound having a solubility parameter due to hydrogen bonding forces (δH) of 9 MPa 1 / 2 A hydrocarbon compound containing at least one hydroxyl group; and a polarity (δP) of 9 MPa. 1 / 2 A thinner composition comprising an ideal ketone is provided.

[0013] [2] In the above [1], the content of the ester compound may be 15 to 80 wt% based on the total weight of the thinner composition.

[0014] [3] In the above [1] or [2], the ester compound may include at least one selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether propionate, and propylene glycol monomethyl ether acetate.

[0015] [4] In any one of the above [1] to [3], the content of the hydrocarbon compound may be 15 to 80 wt% based on the total weight of the thinner composition.

[0016] [5] In any one of the above [1] to [4], the hydrocarbon compound may further include one or more ether groups.

[0017] [6] In any one of the above [1] to [5], the hydrocarbon compound may include at least one selected from the group consisting of propylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether.

[0018] [7] In any one of the above [1] to [6], the content of the ketone may be 0.3 to 40 wt% based on the total weight of the thinner composition.

[0019] [8] In any one of the above [1] to [7], the ketone may be any one selected from the group consisting of cyclopentanone, cycloheptanone, and combinations thereof.

[0020] [9] In any one of the above [1] to [8], the weight ratio of the hydrocarbon compound and the ester compound may be 1:0.1 to 1:6.

[0021]

[0010] In any one of the above [1] to [9], the weight ratio of the ketone and the ester compound may be 1:3 to 1:16.

[0022]

[0011] In any one of the above [1] to

[0010] , the weight ratio of the ketone and the hydrocarbon compound may be 1:3 to 1:16.

[0023]

[0012] In any one of the above [1] to

[0011] , the thinner composition may further include a surfactant.

[0024]

[0013] In the above

[0012] , the content of the surfactant may be 0.0001 to 1.0 wt% based on the total weight of the thinner composition.

[0025]

[0014] In any one of the above [1] to

[0013] , the ester compound may include methyl 3-methoxypropionate, the hydrocarbon compound may include propylene glycol monomethyl ether, and the ketone may include cyclopentanone.

[0026]

[0015] In any one of the above [1] to

[0014] , the content of the methyl-3-methoxypropionate may be 60 to 70 wt%, the content of the propylene glycol monomethyl ether may be 25 to 35 wt%, and the content of the cyclopentanone may be 1 to 5 wt% based on the total weight of the thinner composition.

[0027]

[0016] In the above

[0015] , the surfactant includes a silicone-based surfactant, and the content of the silicone-based surfactant may be 0.0001 to 1.0 wt% based on the total weight of the thinner composition.

[0028] The solutions to the above problems are not exhaustive and may be combined with several embodiments of the present disclosure. The various features of the present invention and their corresponding advantages and effects can be understood in more detail by referring to the detailed description below.

[0029] According to one aspect of the present invention, a thinner composition can be provided that improves RRC (Reduced resist coating) and EBR (Edge bead removal) performance and enhances solubility and compatibility with EUV photoresists.

[0030] According to another aspect of the present invention, a thinner composition having excellent pipe cleaning ability and effectively removing not only KrF and ArF resists but also EUV (Extreme ultraviolet) resists can be provided.

[0031] According to another aspect of the present invention, a thinner composition can be provided that can achieve a small dispersion effect by uniformly coating the resist over the entire area of ​​the substrate even when coating is performed using a small amount of resist.

[0032] In addition to the aforementioned effects, specific effects of the present invention are described below along with specific details for implementing the invention. Furthermore, the effects of the present invention are not limited to the effects described above and can be readily achieved using the means and combinations thereof described in the specification.

[0033] Figure 1 shows the experimental results for the contact angle and the EBR performance evaluation results of the thinner compositions according to Examples 6, 11 and Comparative Example 7.

[0034] FIG. 2 is an image of an EBR profile of a photoresist for EUV after performing an RRC process using the thinner compositions of Example 11, Comparative Example 1, and Comparative Example 6.

[0035] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0036] The terms "comprise" and / or "comprising" in this specification specify the presence of stated features, steps, numbers, operations, elements, elements and / or groups thereof, but do not preclude the presence or addition of one or more other features, steps, numbers, operations, elements, elements and / or groups thereof.

[0037] In this specification, expressions such as "first," "second," "first," "second," "(S1)", "(S2)", etc. may describe various components, regardless of order and / or importance, and do not limit the components. These expressions may be used to distinguish one component from another. For example, without departing from the scope of the present disclosure, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.

[0038] In this specification, “At least one of a, b and c” may include a, b or c alone, or a combination of two or more selected from the group consisting of a, b and c.

[0039] If multiple embodiments are described in this specification, the embodiments may be combined unless specifically stated otherwise. In this case, the effects of the present invention may be defined as including the effects derived from each embodiment and the effects resulting from the organic combination of the embodiments. For example, even if Embodiments 1 and 2 are described independently in this specification, Embodiments 1 and 2 may be organically combined with each other, unless the context clearly indicates otherwise, and the effects of the present invention may include the effects resulting from the combination of Embodiments 1 and 2.

[0040] The numerical range indicated by the term "to" in this specification refers to a numerical range that includes the values ​​described before and after the term as the lower limit and the upper limit, respectively. When multiple numerical values ​​are disclosed as the upper and lower limits of an arbitrary numerical range, the numerical range disclosed in this specification can be understood as any numerical range that has any one of the multiple lower limit values ​​and any one of the multiple upper limit values ​​as the lower limit and the upper limit, respectively. For example, when a to b, or c to d is described in the specification, it can be understood that a or more and b or less, a or more and d or less, c or more and d or less, or c or more and b or less is described.

[0041] In this specification, “composition” may mean a mixture of materials including the composition, a reaction product formed from the materials of the composition, or a decomposition product. For example, the content of the material in the composition may be measured using gas chromatography. Specifically, the content of the material may be analyzed using a gas chromatography device from Agilent (Product name: Agilent 7890 GC, Column: HP-5, Carrier gas: Helium (flow rate 2.4 mL / min), Detector: FID, Injection volume: 1 uL, Initial value: 70°C / 4.2 min, Final value: 280°C / 7.8 min, Program rate: 15°C / min).

[0042] In the present specification, the polarity force and hydrogen bonding force may be Hansen solubility parameters according to the Stefanis-Panayiotou method. For example, the polarity force and hydrogen bonding force may be measured at about 25°C with reference to Ref 1 (Stefanis, Emmanuel, and Costas Panayiotou. "Prediction of Hansen solubility parameters with a new group-contribution method." International Journal of Thermophysics 29 (2008): 568-585) or Ref 2 (Bertouche, S., et al. "Determining Hansen solubility parameters by Stefanis Panayiotou method for fatty acids extraction by petrochemical and green solvents." Int. J. Sci. Res. Eng. Technol 6 (2018): 14-20).

[0043] According to one aspect of the present invention, the solubility parameter due to dipol-dipol forces (δP) is 3 MPa 1 / 2 An ester compound having a solubility parameter due to hydrogen bonding forces (δH) of 9 MPa 1 / 2 A hydrocarbon compound containing at least one hydroxyl group; and a polarity (δP) of 9 MPa. 1 / 2 A thinner composition comprising an ideal ketone is provided.

[0044] According to one aspect of the present invention, by satisfying the combination relationship of the ester compound, hydrocarbon compound, and ketone, the reduced resist coating (RRC) and edge bead removal (EBR) performances are improved, and the solubility and compatibility with EUV photoresists can be enhanced. According to another aspect of the present invention, by satisfying the combination relationship, the pipe cleaning ability is excellent, and not only KrF and ArF resists but also EUV (Extreme ultraviolet) resists can be effectively removed. According to still another aspect of the present invention, by satisfying the combination relationship, even when coating is performed using a small amount of resist, the resist can be uniformly coated over the entire area of ​​the substrate, thereby achieving the effect of low dispersion. If the thinner composition does not satisfy the combination relationship, not only the coating property of the resist on the substrate may be deteriorated under conditions where the amount of resist applied is low, but also the resist removal ability may be deteriorated.

[0045] Below, the configuration of the present invention is described in more detail.

[0046] 1. Thinner composition

[0047] ester compounds

[0048] In this specification, an ester compound may be defined as a chain or cyclic compound having at least one ester group in the molecule.

[0049] The ester compound according to the present invention has excellent solubility in all types of resists and can provide uniform coating ability to the resist.

[0050] Meanwhile, the solubility parameter due to dipol-dipol forces (δP) is the energy derived from the polar forces between molecules. For example, the polarity parameter can be the Hansen solubility parameter.

[0051] The polarity (Solubility parameter due to dipol-dipol forces, δP) of the ester compound according to the present invention is 3 MPa 1 / 2 Above, 4 MPa 1 / 2 Above, 5 MPa 1 / 2 Above, 6 MPa 1 / 2 or more than 6.6 MPa 1 / 2 It may be any one of the multiple lower limits and 8 MPa in particular. 1 / 2 It can be as follows. By controlling the polarity of the ester compound within the above numerical range, excellent solubility can be achieved for all types of resists and uniform coating ability can be achieved for the resist.

[0052] In some embodiments of the present invention, the content of the ester compound may be 15 to 80 wt%, 20 to 80 wt%, 20 to 75 wt%, 45 to 75 wt%, 50 to 75 wt%, or 60 to 70 wt%, based on the total weight of the thinner composition, and specifically may be 60 to 65 wt% or 65 to 70 wt%. According to some embodiments of the present invention, by adjusting the content of the ester compound within the above numerical range, even when the RRC (Reduced resist coating) process is performed under conditions where the coating amount of the EUV resist is low, a more excellent coatability effect can be realized.

[0053] In some embodiments of the present invention, the ester compound may include at least one selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether propionate, and propylene glycol monomethyl ether acetate, and specifically may include methyl 3-methoxypropionate. According to some embodiments of the present invention, since the ester compound includes methyl 3-methoxypropionate, even when the RRC process is performed under conditions where the coating amount of the EUV resist is low, a more excellent coating effect can be achieved.

[0054] Hydrocarbon compound containing one or more hydroxyl groups

[0055] In this specification, a “hydrocarbon compound containing at least one hydroxyl group” may be defined as a compound in which at least one hydrogen atom in a chain or ring composed of carbon and hydrogen is replaced with a hydroxyl group.

[0056] For convenience of explanation below, “hydrocarbon compound containing one or more hydroxyl groups” is referred to as “hydrocarbon compound.”

[0057] The hydrocarbon compound according to the present invention can provide an effect of easily removing not only KrF and ArF resists, but also EUV resists. Specifically, in order to stably proceed with the EBR process, development of a thinner composition that can easily remove not only KrF and ArF resists, but also EUV resists may be required. EUV photons with a wavelength of 13.5 nm have a wavelength 14 times shorter than ArF photons with a wavelength of 193 nm, and thus have 14 times more energy. This means that the number of photons required for exposure with the same energy is 14 times fewer. Therefore, a non-uniform spatial distribution of photons occurs, resulting in a stochastic effect that prevents the formation of a pattern evenly. To improve this problem, EUV resists have been developed in the direction of increasing the content of a photoacid generator (PAG) to increase the production of acid per photon. Since these photoacid generators have polar and hydrophilic properties, a thinner composition suitable for an EUV resist can be implemented by simultaneously controlling the molecular structure of the hydrocarbon compound included in the thinner composition suitable for an EUV resist and the hydrogen bonding strength of the compound.

[0058] Meanwhile, hydrogen bonding strength is the energy derived from intermolecular hydrogen bonding. For example, hydrogen bonding strength can be a Hansen solubility parameter.

[0059] The hydrogen bonding force (Solubility parameter due to hydrogen bonding forces, δH) of the hydrocarbon compound according to the present invention is 9 MPa 1 / 2 Above, 10 MPa 1 / 2 Above, 11 MPa 1 / 2 or more than 11.6 MPa 1 / 2 It may be more than, and specifically, any one of the multiple lower limits above and 14 MPa 1 / 2 It may be as follows. By controlling the hydrogen bonding strength of the hydrocarbon compound within the above numerical range, the polarity and hydrophilicity of the thinner composition are further increased, so that the effect of easily removing not only KrF and ArF resists but also EUV resists can be realized.

[0060] The hydrocarbon compound according to the present invention contains at least one hydroxyl group. Specifically, by containing at least one hydroxyl group, the hydrocarbon compound can further increase the polarity and hydrophilicity of the thinner composition. Accordingly, it can effectively remove EUV resists with high photoacid generator content.

[0061] In some embodiments of the present invention, the content of the hydrocarbon-based compound based on the total weight of the thinner composition may be 15 to 80 wt%, 20 to 80 wt%, 20 to 75 wt%, 20 to 50 wt%, 25 to 45 wt%, or 25 to 35 wt%, and specifically may be 25 to 30 wt% or 30 to 35 wt%. According to some embodiments of the present invention, by adjusting the content of the hydrocarbon-based compound within the above numerical range, the polarity and hydrophilicity of the thinner composition are controlled to an appropriate level, so that the effect of easily removing not only KrF and ArF resists but also EUV resists can be implemented.

[0062] In some embodiments of the present invention, the hydrocarbon compound may include at least one of primary, secondary, and tertiary alcohols, specifically, may include primary or secondary alcohols, and more specifically, may include secondary alcohols. The hydrogen bonding strength of the hydrocarbon compound may vary depending on the alcohol order. According to some embodiments of the present invention, by adjusting the alcohol order of the hydrocarbon compound within the above numerical range, the hydrogen bonding strength and volatility of the hydrocarbon compound can be controlled to an appropriate level. Accordingly, the polarity and hydrophilicity of the thinner composition can be controlled to an appropriate level.

[0063] In some embodiments of the present invention, the hydrocarbon-based compound may further comprise one or more ether groups. According to some embodiments of the present invention, by comprising one or more ether groups in the hydrocarbon-based compound, the polarity of the thinner composition can be controlled to an appropriate level, thereby effectively removing resists for various purposes while effectively preventing defects in the resist pattern.

[0064] In some embodiments of the present invention, the hydrocarbon-based compound may include at least one of the compounds represented by the following general formulae 1 and 2. In some embodiments of the present invention, by including at least one of the compounds represented by the following general formulae 1 and 2, the polarity of the thinner composition can be controlled to an appropriate level, thereby effectively removing resists for various purposes and effectively preventing defects in the resist pattern from occurring.

[0065] [General Formula 1]

[0066] HO-R1-O-R2

[0067] In the above general formula 1, R1 is an alkylene group having 1 to 3 carbon atoms, and R2 is a chain-like or branched alkyl group having 1 to 5 carbon atoms.

[0068] [General Formula 2]

[0069] R3-OLC(OH)H-R4

[0070] In the above general formula 2, R3 is a chain-like or branched alkyl group having 1 to 3 carbon atoms, L is a direct bond; or an alkylene group having 1 to 3 carbon atoms; and R4 is a chain-like or branched alkyl group having 1 to 3 carbon atoms.

[0071] In some examples, the hydrocarbon compound may be the same as or different from the ester compound, and may be specifically different.

[0072] In some embodiments of the present invention, the hydrocarbon-based compound may include at least one selected from the group consisting of propylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether, and specifically may include propylene glycol monomethyl ether. According to some embodiments of the present invention, since the hydrocarbon-based compound includes propylene glycol monomethyl ether, the polarity and hydrophilicity of the thinner composition are controlled to an appropriate level, so that the effect of easily removing not only KrF and ArF resists but also EUV resists can be implemented.

[0073] ketones

[0074] In this specification, “ketone” may be defined as a chain or cyclic compound having at least one ketone functional group (C=O).

[0075] The ketone according to the present invention can improve excellent RRC (Reduced resist coating) and EBR (Edge bead removal) performance by increasing the solubility of the thinner composition for all types of resists and controlling the surface tension of the thinner composition.

[0076] The polarity (δP) of the ketone according to the present invention is 9 MPa 1 / 2 Above, 10 MPa 1 / 2 Above, 11 MPa 1 / 2 or more than 11.9 MPa 1 / 2 This may be ideal. Specifically, by controlling the polarity of the ketone within the above numerical range, the solubility of the thinner composition for all types of resists can be increased, while simultaneously controlling the surface tension of the thinner composition, thereby further improving excellent RRC (Reduced resist coating) and EBR (Edge bead removal) performance.

[0077] In some embodiments of the present invention, the content of the ketone may be 0.3 to 40 wt%, 0.5 to 30 wt%, 0.5 to 15 wt%, 0.5 to 10 wt%, 0.5 to 5 wt%, 1 to 5 wt%, 2 to 5 wt%, 3 to 5 wt%, or 4 to 5 wt%, based on the total weight of the thinner composition. According to some embodiments of the present invention, by adjusting the content of the ketone within the above numerical range, the solubility of the thinner composition for all types of resists can be increased, while at the same time controlling the surface tension of the thinner composition, thereby further improving excellent reduced resist coating (RRC) and edge bead removal (EBR) performances.

[0078] In some embodiments of the present invention, the ketone may be a cyclic compound. Cyclic compounds can further improve compatibility with resist materials compared to chain compounds.

[0079] In some embodiments of the present invention, the ketone may be any one selected from the group consisting of cyclopentanone, cycloheptanone, and combinations thereof, and may specifically include cyclopentanone. According to some embodiments of the present invention, cyclopentanone can increase the polarity of the thinner composition compared to other types of compounds, thereby improving the solubility for highly polar resists such as KrF and ArF. In addition, the cyclopentanone has high volatility and excellent solubility, so that it can further improve EBR or RRC performance, and it is less harmful to the human body when inhaled or in contact with the skin, and has no unpleasant odor, so that work safety can be greatly improved.

[0080] Relationships between components

[0081] In some embodiments of the present invention, the weight ratio (hydrocarbon compound: ester compound) of the hydrocarbon compound and the ester compound may be 1:0.1 to 1:6, 1:0.19 to 1:5.33, 1:0.27 to 1:3.75, 1:1.11 to 1:3.75, 1:1.71 to 1:2.80, or 1:2 to 1:2.17. According to some embodiments of the present invention, by adjusting the weight ratio of the hydrocarbon compound and the ester compound within the above numerical range, the solubility and compatibility for various resists are excellent, and the coatability can be further improved under conditions where the amount of resist applied after the RRC process is low.

[0082] In some embodiments of the present invention, the weight ratio of the ketone and the ester compound (ketone: ester compound) may be 1:3 to 1:16, 1:4 to 1:15, 1:9 to 1:16, 1:10 to 1:15, or 1:12 to 1:14. According to some embodiments of the present invention, by adjusting the weight ratio of the ketone and the ester compound within the above numerical range, the solubility and compatibility for various resists are excellent, and the coatability can be further improved under conditions where the amount of resist applied after the RRC process is low.

[0083] In some embodiments of the present invention, the weight ratio of the ketone and the hydrocarbon compound (ketone:hydrocarbon compound) may be 1:3 to 1:16, 1:4 to 1:15, 1:5 to 1:10, 1:5 to 1:9, or 1:5 to 1:7. According to some embodiments of the present invention, by adjusting the weight ratio of the ketone and the hydrocarbon compound within the above numerical range, the solubility and compatibility for various resists are excellent, and the coatability can be further improved under conditions of a low coating amount of the resist after performing the RRC process.

[0084] additives

[0085] In some embodiments of the present invention, the thinner composition may further include a surfactant. Specifically, the surfactant can lower the surface tension of the thinner composition, improve the coatability of the resist on the substrate, and effectively prevent the formation of defects such as distortion of the resist pattern.

[0086] In some embodiments of the present invention, the surfactant may include at least one of an ionic surfactant and a nonionic surfactant, and specifically may include a nonionic surfactant. According to some embodiments of the present invention, when a nonionic surfactant is used rather than an ionic surfactant, the generation of hydrogen ions by a photoacid generator included in a resist material can be effectively prevented, thereby improving the LWR (line width roughness) of the resist pattern and effectively preventing the generation of defects.

[0087] In some embodiments of the present invention, the surfactant may include at least one selected from the group consisting of silicone-based surfactants, fluorinated surfactants, and polyoxyethylene-based surfactants, and specifically may include a silicone-based surfactant or a fluorinated surfactant. According to some embodiments of the present invention, when a silicone-based surfactant or a fluorinated surfactant is used rather than other types of surfactants, the effect of lowering the surface tension of the thinner composition may be further improved due to its high diffusivity for hydrophobic substrates.

[0088] In some embodiments of the present invention, the content of the surfactant may be more than 0 and less than or equal to 1.0 wt%, 0.0001 to 1.0 wt%, 0.0001 to 0.13 wt%, or 0.0001 to 0.10 wt%, based on the total weight of the thinner composition. According to some embodiments of the present invention, by adjusting the content of the surfactant within the above numerical range, bubbles can be effectively prevented from occurring and a tailing phenomenon can be effectively prevented from occurring.

[0089] 2. Application of thinner composition

[0090] According to another aspect of the present invention, a method of removing a resist using a thinner composition of some embodiments may be provided.

[0091] According to another aspect of the present invention, the thinner composition can be used in the RRC process to reduce the amount of resist and bottom anti-reflective coating (BARC) used, while facilitating uniform application. In addition, the thinner composition provides excellent performance even when removing unnecessary resist or bottom anti-reflective coating after resist application, and can contribute to the efficient execution of rework processes, wafer bottom surface cleaning processes, etc.

[0092] In some examples, the above thinner composition can be applied to a photosensitive resin that uses high-energy rays, X-rays, and electron rays of 500 nm or less as a light source, and in this case, the photosensitive resin can be, for example, a KrF photoresist or an ArF photoresist.

[0093] In some other examples, the above thinner composition can also be used in processes using EUV photoresists.

[0094] According to another aspect of the present invention, a method for manufacturing a semiconductor device or a thin film transistor liquid crystal display device may be provided, wherein the thinner composition is sprayed onto the edge and rear surfaces of a substrate on which a photosensitive resin composition is applied to remove an unnecessary photosensitive film. Subsequent processes may be applied to the manufacturing of semiconductor devices and thin film transistor liquid crystal display devices, using general processes known in the relevant technical field.

[0095] A thinner composition according to some embodiments of the present invention can uniformly and quickly remove unnecessary resist from the edge or back surface of a substrate generated due to curing of the substrate used in the manufacture of a semiconductor device. In addition, the thinner composition according to some embodiments of the present invention has excellent solubility for various resists and lower anti-reflection films, and can improve EBR characteristics, rework characteristics, and coating performance of photoresists. In particular, in the case of KrF photoresists, ArF photoresists, and EUV photoresists, since the basic structures of the constituent resins are different from each other, it is necessary to control the composition content of the organic solvent to improve the solubility and coating performance of all of them, but the thinner composition according to some embodiments of the present invention can satisfy all of these.

[0096] In addition, the thinner composition of some embodiments of the present invention has excellent solubility for major components of resists and antireflection films having a highly polar structure, and thus does not cause a phenomenon of blocking the outlet after the EBR process, the wafer lower cleaning process, and the wafer upper pretreatment process prior to photoresist application, thereby helping to improve productivity.

[0097] In some embodiments of the present invention, the thinner composition can be more preferably used in the RRC process, EBR process, rework process, and wafer lower surface cleaning process according to the EUV photoresist.

[0098] According to another aspect of the present invention, a method for forming a photosensitive film can be provided, comprising the steps of applying a thinner composition of several embodiments onto a semiconductor substrate to pre-wet the semiconductor substrate; and applying a resist composition or a spin-on hardmask composition onto the pre-wetted semiconductor substrate.

[0099] According to another aspect of the present invention, a method for forming a photosensitive film may be provided, comprising: forming a resist or spin-on hardmask on a semiconductor substrate; and removing at least a portion of the formed resist or spin-on hardmask on the semiconductor substrate with a thinner composition of some embodiments.

[0100] According to another aspect of the present invention, a method for removing a resist attached to an edge or back surface of a substrate using a thinner composition of some embodiments may be provided. In this case, the method may be performed by pressurizing and spraying the thinner composition while rotating the substrate.

[0101] For example, the substrate may be a substrate used for manufacturing electronic devices such as semiconductor memory devices, integrated circuit devices, and liquid crystal display devices.

[0102] For example, various structures constituting an electronic device, such as an insulating film, a conductive film, wiring, holes, and gates, may be formed on the substrate, and a step may exist on the upper surface of the substrate due to the structures.

[0103] For example, the resin included in the resist composition may include an I-line photoresist including a novolak resin, a KrF photoresist including polyhydroxystyrene in which hydrogens of hydroxyl groups are partially blocked with acetal groups, a KrF photoresist including polyhydroxystyrene in which hydrogens of hydroxyl groups are partially blocked with tert-butylcarbonate groups, an ArF photoresist including a methacrylate resin, a KrF lower antireflection coating including a triazine-based resin, an ArF lower antireflection coating including an ester-based resin, and an I-line photoresist including a novolak resin and 2,4-dinitroquinone as a photosensitizer, or a resist material for EUV.

[0104] For example, a resist for KrF may contain polyhydroxystyrene in which the hydrogens of the hydroxyl groups are partially blocked with acetal groups or tert-butyl carbonate groups and a triphenylsulfonium salt as a photosensitizer.

[0105] For example, a resist for ArF may include a polymethacrylate blocked with adamantyl groups and / or 4-oxa-tricyclo(4.2.1.0(3,7))nonan-5-one and a triphenylsulfonium salt as the photosensitizer.

[0106] For example, a resist for EUV may include a polymer matrix and a photoacid generator commonly used in the art. In some examples, the polymer matrix may include a polyvinylphenol-based polymer, and the photoacid generator may include triphenylsulfonium triflate.

[0107] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, this is merely an example, and the scope of the present invention is not limited by the following contents.

[0108] As used herein, terms such as "about" or "substantially" mean a reasonable amount of variation from the term that does not significantly alter the final result. These terms may be interpreted to include a variation of at least ±5% or at least ±10%, provided that such variation does not alter the meaning of the term and render it invalid.

[0109] [Manufacturing Preparation Example: Compound Parameter Information]

[0110] Compounds were prepared according to Table 1 below. Specifically, in Table 1 below, the polar force (Solubility parameter due to dipol-dipol forces, δP) of each compound is the energy derived from the polar force between molecules, and the hydrogen bond force (Solubility parameter due to hydrogen bonding forces, δH) means the energy derived from the hydrogen bonding force between molecules.

[0111] The above polarity and hydrogen bonding forces may be Hansen solubility parameters.

[0112] Classification δP (MPa) 1 / 2 )δH(MPa 1 / 2 )MMP(Methyl 3-methoxypropionate)6.610.3PGME(Propylene glycol monomethyl ether)6.311.6PGMEP(Propylene glycol methyl ether propionate)6.27.2CPN(Cyclopentanone)11.95.2EEP(Ethyl 3-ethoxypropionate)3.38.8PGMEA(Propylene glycol monomethyl ether) acetate)5.69.8CHN(Cyclohexanone)6.35.1EGPE(Ethylene glycol monopropyl ether)8.713.5Cycloheptanone10.64.8EL(Ethyl lactate)7.612.5

[0113] [Manufacturing Example 1: Manufacturing of a thinner composition with controlled content of ester compound or hydrocarbon compound]

[0114] A thinner composition having a composition according to Table 2 below was prepared.

[0115] Classification MMP (A) PGME (B) CPN (C) C: A (w / w) C: B (w / w) B: A (w / w) Example 1 1580 51: 31: 16 1: 0. 19 Example 2 207 551: 41: 15 1: 0. 27 Example 3 4550 51: 91: 101: 0. 90 Example 4 504 551: 101: 91: 1. 11 Example 5 603 551: 12 1: 7 1: 1. 71 Example 6 653 0 51: 13 1: 6 1: 2. 17 Example 7 702 551: 14 1: 5 1: 2. 80 Example 8 752 0 51: 15 1: 41: 3. 75 Example 9801551:161:31:5.33

[0116] [Manufacturing Example 2: Preparation of a thinner composition containing a surfactant]

[0117] A thinner composition having a composition according to Table 3 below was prepared. Specifically, in Table 3 below, the surfactant is a silicone-based nonionic surfactant or an acetylenediol-based nonionic surfactant.

[0118] Classification MMP (A) PGME (B) CPN (C) Surfactant Example 10653050.0001 (silicone-based) Example 11653050.003 (silicone-based) Example 12653050.1 (silicone-based) Example 13653050.13 (silicone-based) Example 14653050.003 (acetylene-diol-based) Example 15653050.13 (acetylene-diol-based)

[0119] [Manufacturing Example 3: Manufacturing of a thinner composition with controlled ketone content]

[0120] A thinner composition having a composition according to Table 4 below was prepared.

[0121] Classification MMP (A) PGME (B) CPN (C) Example 16 40 30 30 Example 17 30 30 40 Example 18 70 20 10 Example 19 60 30 10 Example 20 60 25 15 Example 21 60 39.5 0.5 Example 22 65 34.7 0.3

[0122] [Manufacturing Example 4: Preparation of Thinner Composition]

[0123] A thinner composition having a composition according to Table 5 below was prepared.

[0124] ClassificationEster compoundsHydrocarbon compoundsKetoneExample 2365(EEP)30(PGME)5(CPN)Example 2465(PGMEP)30(PGME)5(CPN)Example 2565(MMP)30(EGPE)5(CPN)Example 2665(MMP)30(PGME)5(Cycloheptanone)Example 2784(MMP)15.7(PGME)0.3(CPN)

[0125] [Manufacturing Example 5: Preparation of Thinner Composition]

[0126] A thinner composition having a composition according to Table 6 below was prepared.

[0127] ClassificationEster compoundHydrocarbon compoundKetoneComparative example 160(MMP)40(PGME)-Comparative example 2-70(PGME)30(CPN)Comparative example 370(MMP)-30(CPN)Comparative example 430(MMP)30(EEP)10(EL)30(CHN)Comparative example 575(MMP)10(EL)15(CHN)Comparative example 655(PGMEA)15(PGME)15(CPN)15(CHN)Comparative example 765(PGMEA)30(PGME)5(CPN)Comparative example 860(MMP)10(EL)30(CHN)

[0128] [Experimental Example 1: Contact Angle Measurement and EBR Performance Evaluation]

[0129] Contact angle measurement evaluation:

[0130] An experiment was conducted to check the contact angle at approximately 23°C by coating a thinner composition using an RRC coating process on a substrate (silicon oxide film) of approximately 12 inches and then dropping an EUV photoresist on the coated substrate. The contact angle at this time indicates the wetting between two substances, and a smaller contact angle may indicate a higher compatibility between the two substances.

[0131] Contact angle (°) Example 6: about 21.9 Example 11: about 20.5 Comparative example 7: about 24.6

[0132] EBR Performance Evaluation:

[0133] After applying EUV photoresist to a substrate (silicon oxide film) of approximately 12 inches, an EBR (Edge bead removal) experiment was conducted to remove unnecessary photoresist from the edge of the substrate for Examples 6 and 11 and Comparative Example 7.

[0134] Height of the protrusion (Hump, Å) Example 6: Approximately 757 Example 11: Approximately 548 Comparative Example 7: Approximately 2137

[0135] Figure 1 shows the experimental results for the contact angle and the EBR performance evaluation results of the thinner compositions according to Examples 6, 11 and Comparative Example 7.

[0136] Referring to FIG. 1, Table 7, and Table 8, it was confirmed that the contact angle of the EUV photoresist for the substrate coated with the compositions of Examples 6 and 11 was significantly lowered compared to Comparative Example 7. Through this, it was confirmed that when the compositions of Examples 6 and 11 were used compared to Comparative Example 7, the wettability for the EUV photoresist was implemented excellently, and the compatibility between the two materials was increased. Specifically, it can be inferred that the RRC performance can be improved when the thinner composition of Example 11 was used. In addition, when the EBR profiles were compared, no photoresist tailing was found at the edge of the substrate with the naked eye, so it seemed that there was no uneven application part, but when the height of the EBR hump was measured, the hump height in Example 6 was 757Å, the hump height in Example 11 was 548Å, and the hump height in Comparative Example 7 was 2137Å. Through this, it was confirmed that Examples 6 and 11 had superior solubility and compatibility for EUV photoresists compared to Comparative Example 7.

[0137] FIG. 2 is an image of an EBR profile of a photoresist for EUV after performing an RRC process using the thinner compositions of Example 11, Comparative Example 1, and Comparative Example 6.

[0138] Referring to Figure 2, it was confirmed that the EBR performance was excellent in the order of Example 11, Comparative Example 1, and Comparative Example 6.

[0139] [Experimental Example 2: Evaluation of EUV PR Usage Reduction]

[0140] After performing the RRC (Reduced resist coating) process on the substrate (silicon oxide film) with the thinner compositions of the examples and comparative examples, the coating amount of the EUV photoresist was adjusted to 0.4 cc, 0.5 cc, 0.6 cc, 0.7 cc, or 0.8 cc, and it was confirmed whether the EUV photoresist was coated on the entire surface of the substrate. If 99% or more of the substrate area was coated, it was evaluated as ◎, if 90% or more but less than 99% was coated, it was evaluated as ○, if 80% or more but less than 90% was coated, it was evaluated as △, and if less than 80% was coated, it was evaluated as X.

[0141] Classification 0.4cc 0.5cc 0.6cc 0.7cc 0.8cc Example 1 △△○◎◎ Example 2 △△○◎◎ Example 3 △△○◎◎ Example 4 △△○◎◎ Example 5 △○◎◎◎ Example 6 △○◎◎◎ Example 7 △○◎◎◎ Example 8 △△○◎◎ Example 9 △△○◎◎ Example 10 △◎◎◎◎ Example 11 △◎◎◎◎ Example 12 △◎◎◎◎ Example 13 △△○◎◎ Example 14 △○○◎◎ Example 15 △○○◎◎ Example 16 △△○◎◎ Example 17 △△○◎◎ Example 18 △△○◎◎ Example 19 △△○◎◎ Example 20 △△○◎◎ Example 21△△○◎◎Example 22△△○◎◎Example 23X△○○◎Example 24X△○○◎Example 25X△○○◎Example 26X△○○◎Example 27X△△○◎

[0142] Classification 0.4cc 0.5cc 0.6cc 0.7cc 0.8cc Comparison Example 1XX△○○ Comparison Example 2XX△○○ Comparison Example 3XX△○○ Comparison Example 4XX△○○ Comparison Example 5XX△○○ Comparison Example 6XX△○○ Comparison Example 7XX△○○ Comparison Example 8XX△○○

[0143] Referring to Tables 9 and 10 above, comparing Examples 1 to 22 with Comparative Examples 1 to 3, the solubility parameter due to dipol-dipol forces (δP) is 3 MPa. 1 / 2 An ester compound having a solubility parameter due to hydrogen bonding forces (δH) of 9 MPa 1 / 2 A hydrocarbon compound containing at least one hydroxyl group; and a polarity (δP) of 9 MPa. 1 / 2 It was confirmed that when the combination relationship of the above ketones is satisfied, the coatability is excellent even when the RRC process is performed under the condition of a low coating amount of EUV photoresist of 0.4 cc. It was confirmed that when at least one of the above combination relationships is not satisfied, the coatability is deteriorated under the condition of a low coating amount of EUV photoresist of 0.4 cc.

[0144] When comparing Examples 1 to 9 in terms of coatability according to the content of ester compound (MMP), Examples 5 to 7, in which the content of ester compound satisfies about 60 to 70 wt%, showed excellent coatability even when the RRC process was performed under the condition of 0.4 cc, which is a low coating amount of EUV photoresist compared to other examples.

[0145] Comparing Examples 10 to 15 with other examples in terms of coatability according to the use of a surfactant, it was confirmed that the overall coatability was improved under conditions where the amount of EUV photoresist applied was low due to the inclusion of a surfactant in the thinner composition.

[0146] Meanwhile, in the following experimental examples 3 to 6, EUV PR1 is a PTD (Positive Tone Development) composition, EUV PR2 is a NTD (Negative Tone Development) composition, and EUV PR3 is a PTD (Positive Tone Development) composition having a photoacid generator different from EUV PR1.

[0147] [Experimental Example 3: Rework Performance Evaluation]

[0148] About 20 cc of the thinner compositions of the above examples and comparative examples were applied to a 12-inch substrate (silicon oxide film) coated with EUV photoresist, and after rotating, whether the photoresist was completely removed was evaluated, and the results are shown in Tables 11 and 12 below. At this time, in Tables 11 and 12 below, '◎' means that 95% or more of the photoresist was removed after the rework experiment, '○' means that 80% or more but less than 95% of the photoresist was removed after the rework experiment, '△' means that 60% or more but less than 80% of the photoresist was removed after the rework experiment, and 'X' means that less than 60% of the photoresist was removed after the rework experiment.

[0149] Classification EUV PR1 EUV PR2 EUV PR3 Embodiment 1 ○○○ Embodiment 2 ○○○ Embodiment 3 ○○○ Embodiment 4 ○○○ Embodiment 5 ○○◎ Embodiment 6 ○○◎ Embodiment 7 ○◎○ Embodiment 8 ○○○ Embodiment 9 ○○○ Embodiment 10 ○◎◎ Embodiment 11 ○◎◎ Embodiment 12 ○◎◎ Embodiment 13 ○○○ Embodiment 14 ○○○ Embodiment 15 ○○○ Embodiment 16 ○○○ Embodiment 17 ○○○ Embodiment 18 ○○○ Embodiment 19 ○○○ Embodiment 20 ○○○ Embodiment 21 ○○○ Embodiment 22 ○○○ Embodiment 23 ○○○ Embodiment 24 ○○△ Embodiment 25 ○△○ Embodiment 26 ○△○ Embodiment 27△○△

[0150] Classification EUV PR1 EUV PR2 EUV PR3 Comparative Example 1 ○X△Comparative Example 2 X△△Comparative Example 3 ○△△Comparative Example 4△△○Comparative Example 5△△△Comparative Example 6△△△Comparative Example 7△△○Comparative Example 8△○△

[0151] [Experimental Example 4: EBR Experimental Evaluation]

[0152] After applying EUV photoresist to a 12-inch substrate (silicon oxide film), an EBR experiment was conducted to remove unnecessary photoresist at the edge of the substrate using the thinner compositions of the above examples and comparative examples. In Tables 13 and 14 below, when the EBR uniformity of the substrate edge after EBR was measured, '◎' means that the edge area was in a good straight state of 90% or more, '○' means that the edge area was in a good straight state of 80% or more but less than 90%, '△' means that the edge area was in a good straight state of 50% or more but less than 80%, and 'X' means that a photoresist tailing phenomenon occurred at the edge area.

[0153] Classification EUV PR1 EUV PR2 EUV PR3 Example 1 ○○△ Example 2 ○○△ Example 3 ○○△ Example 4 ○△○ Example 5 ○○◎ Example 6 ○○◎ Example 7 ○◎○ Example 8 ○△○ Example 9 ○△○ Example 10 ○◎◎ Example 11 ○◎◎ Example 12 ○◎◎ Example 13 ○△○ Example 14 ○△○ Example 15 ○△△ Example 16 ○△○ Example 17 ○△○ Example 18 ○△○ Example 19 ○△○ Example 20 ○△○ Example 21 ○△○ Example 22 ○△○ Example 23 ○△△ Example 24 ○△△ Example 25 ○△△ Example 26 ○△○ Example 27X△○

[0154] Classification EUV PR1 EUV PR2 EUV PR3 Comparative Example 1△X△Comparative Example 2△X△Comparative Example 3△△△Comparative Example 4△△△Comparative Example 5△X△Comparative Example 6△X△Comparative Example 7X△XComparative Example 8△△△

[0155] [Experimental Example 5: RRC Performance Evaluation]

[0156] After performing the RRC process on a 12-inch substrate (silicon oxide film) with the thinner compositions of the above examples and comparative examples, an experiment was conducted to see if the EUV photoresist was coated on the entire substrate. At this time, in Tables 15 and 16 below, '◎' means that more than 99% was coated when visually confirmed, indicating that the coating degree of the photoresist was very excellent, '○' means that more than 90% and less than 99% of the substrate area was coated when visually confirmed, '△' means that more than 80% and less than 90% of the substrate area was coated when visually confirmed, and 'X' means that the coating degree of the photoresist was incomplete, and that the coating was not completed at the outer part of the substrate, resulting in tearing.

[0157] Classification EUV PR1 EUV PR2 EUV PR3 Embodiment 1 ○△○ Embodiment 2 △○○ Embodiment 3 ○○△ Embodiment 4 △○○ Embodiment 5 ◎○◎ Embodiment 6 ◎○◎ Embodiment 7 ◎◎○ Embodiment 8 △○○ Embodiment 9 ○△○ Embodiment 10 ◎◎◎ Embodiment 11 ◎◎◎ Embodiment 12 ◎◎◎ Embodiment 13 ○○○ Embodiment 14 ○○○ Embodiment 15 ○○○ Embodiment 16 ○△○ Embodiment 17 △○○ Embodiment 18 ○○○ Embodiment 19 ○○○ Embodiment 20 ○○○ Embodiment 21 ○○△ Embodiment 22 ○○△ Embodiment 23 ○○○ Embodiment 24 △△○ Embodiment 25 ○△○ Embodiment 26 ○△○ Embodiment 27△△X

[0158] Classification EUV PR1 EUV PR2 EUV PR3 Comparative Example 1 X△X Comparative Example 2 XX△ Comparative Example 3 X△△ Comparative Example 4 X△X Comparative Example 5 △X△ Comparative Example 6 △X△ Comparative Example 7 X△X Comparative Example 8 X△△

[0159] [Experimental Example 6: Coating Uniformity Evaluation]

[0160] After performing the RRC process on a 12-inch substrate (silicon oxide film) with the thinner compositions of the above examples and comparative examples, the coating uniformity of the EUV photoresist was measured. In each experiment, the same amount of EUV PR 1, EUV PR 2, and EUV PR 3 was applied, and the coating uniformity was measured using a film thickness measuring device (KLA SFX Series) as a linear 29 point thickness. In addition, the maximum and minimum values ​​of the coated substrate thickness measured in the above experiment were measured.

[0161] In Tables 17 and 18 below, '◎' means that the difference between the maximum and minimum values ​​of the coated substrate thickness is within 1% of the substrate thickness, which means that the coating uniformity for the substrate is the best; '○' means that the difference between the maximum and minimum values ​​is more than 1% and less than 2% of the substrate thickness, which means that the coating uniformity for the substrate is excellent; '△' means that the difference between the maximum and minimum values ​​is more than 2% and less than 5% of the substrate thickness, which means that the coating uniformity for the substrate is good; and 'X' means that the difference between the maximum and minimum values ​​is more than 5% of the substrate thickness, which means that the photoresist is not applied well at the edge of the substrate, which means that the coating uniformity is poor.

[0162] Classification EUV PR1 EUV PR2 EUV PR3 Embodiment 1△△○ Embodiment 2○△△ Embodiment 3○△○ Embodiment 4○○△ Embodiment 5◎○◎ Embodiment 6○◎◎ Embodiment 7◎◎○ Embodiment 8○△△ Embodiment 9△○△ Embodiment 10◎◎◎ Embodiment 11◎◎◎ Embodiment 12◎◎◎ Embodiment 13○○○ Embodiment 14○○○ Embodiment 15○○○ Embodiment 16○○△ Embodiment 17○△○ Embodiment 18○△○ Embodiment 19○○△ Embodiment 20△○○ Embodiment 21○○△ Embodiment 22○△○ Embodiment 23○○○ Embodiment 24△△△ Embodiment 25△△△ Embodiment 26△△△ Embodiment 27△△△

[0163] Classification EUV PR1 EUV PR2 EUV PR3 Comparative Example 1 X△X Comparative Example 2 △△X Comparative Example 3 △X△ Comparative Example 4 XX△ Comparative Example 5 △△X Comparative Example 6 △△X Comparative Example 7 △△X Comparative Example 8 △X△

[0164] The features described in the above-described embodiment may be combined with other embodiments unless explicitly stated otherwise. Furthermore, while the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto. Various modifications and improvements made by those skilled in the art utilizing the basic concepts of the present invention defined in the following claims also fall within the scope of the present invention.

Claims

1. Solubility parameter due to dipol-dipol forces, δP is 3 MPa 1 / 2 Ideal ester compound; Hydrogen bonding strength (Solubility parameter due to hydrogen bonding forces, δH) is 9 MPa 1 / 2 and a hydrocarbon compound containing at least one hydroxyl group; and Polar force (δP) is 9 MPa 1 / 2 Containing abnormal ketones; Thinner composition.

2. In paragraph 1, The content of the ester compound is 15 to 80 wt% based on the total weight of the thinner composition. Thinner composition.

3. In paragraph 1, The above ester compound is, Comprising at least one selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether propionate, and propylene glycol monomethyl ether acetate. Thinner composition.

4. In paragraph 1, The content of the hydrocarbon compound is 15 to 80 wt% based on the total weight of the thinner composition. Thinner composition.

5. In paragraph 1, The above hydrocarbon compound further comprises one or more ether groups. Thinner composition.

6. In paragraph 1, The above hydrocarbon compound is, Comprising at least one selected from the group consisting of propylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether. Thinner composition.

7. In paragraph 1, The content of the ketone is 0.3 to 40 wt% based on the total weight of the thinner composition. Thinner composition.

8. In paragraph 1, The above ketones are, Any one selected from the group consisting of cyclopentanone, cycloheptanone, and combinations thereof; Thinner composition.

9. In paragraph 1, The weight ratio of the hydrocarbon compound and the ester compound is 1:0.1 to 1:6, Thinner composition.

10. In paragraph 1, The weight ratio of the above ketone and the above ester compound is 1:3 to 1:16, Thinner composition.

11. In paragraph 1, The weight ratio of the above ketone and the above hydrocarbon compound is 1:3 to 1:16, Thinner composition.

12. In paragraph 1, further comprising a surfactant; Thinner composition.

13. In paragraph 12, The content of the surfactant is 0.0001 to 1.0 wt% based on the total weight of the thinner composition. Thinner composition.

14. In paragraph 1, The above ester compound includes methyl 3-methoxypropionate, The above hydrocarbon compound includes propylene glycol monomethyl ether, The above ketone includes cyclopentanone, Thinner composition.

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