Blank mask, photomask using the same, and method for manufacturing semiconductor element

Abstract

The present application relates to a blank mask including a light-transmissive substrate and a light-shielding film disposed on the light-transmissive substrate, a photomask using the same, and a method of manufacturing a semiconductor element. The light-shielding film contains at least any one of a transition metal, oxygen, and nitrogen. The SA1 value of the light-shielding film according to Formula 1-1 below is 60 mN / m to 90 mN / m. [Formula 1-1] SA1 = γ SL x tan θ. In the above Formula 1-1, the γ SL is the interfacial energy between the light-shielding film and pure water, and the θ is the contact angle of the light-shielding film measured with pure water. The blank mask or the like has an excellent cleaning effect when the light-shielding film is cleaned with a cleaning solution. In addition, damage to the light-shielding film by the cleaning solution remaining after cleaning can be effectively suppressed.

Description

TECHNICAL FIELD

[0001] The present embodiment relates to a blank mask, a photomask using the same, and a method of manufacturing a semiconductor element. BACKGROUND

[0002] With the high integration of semiconductor devices and the like, the refinement of the circuit pattern of the semiconductor device is required. Thus, the importance of the photolithography technology as a technology of developing the circuit pattern on the wafer surface using the photomask is further emphasized.

[0003] In order to develop the refined circuit pattern, it is required to realize the shortening of the wavelength of the exposure light source used in the exposure process. The exposure light sources used recently include an ArF excimer laser (wavelength of 193 nm) and the like.

[0004] On the other hand, the photomask includes a binary mask, a phase shift mask, and the like.

[0005] The binary mask has a structure in which a light-shielding layer pattern is formed on a light-transmissive substrate. In the surface of the binary mask on which the pattern is formed, the transmissive portion not including the light-shielding layer will transmit the exposure light, and the light-shielding portion including the light-shielding layer will block the exposure light, thereby exposing the pattern on the resist film on the wafer surface. However, in the binary mask, as the pattern becomes more refined, a problem can occur in the development of the refined pattern due to the diffraction of the light generated at the edge of the transmissive portion in the exposure process.

[0006] The phase shift mask includes a Levenson type mask, an outrigger type mask, and a half-tone type mask. Among them, the half-tone type phase shift mask has a structure in which a pattern formed of a semi-transmissive film is disposed on a light-transmissive substrate. On the surface of the half-tone type phase shift mask on which the pattern is disposed, the transmissive portion not including the semi-transmissive layer will transmit the exposure light, and the semi-transmissive portion including the semi-transmissive layer will transmit the exposure light attenuated. The above-mentioned exposure light attenuated has a phase difference compared to the exposure light transmitted through the transmissive portion. Thus, the diffracted light generated at the edge of the transmissive portion is canceled by the exposure light transmitted through the semi-transmissive portion, and thus the phase shift mask can form a more refined refined pattern on the surface of the wafer.

[0007] PRIOR ART DOCUMENT

[0008] PATENT DOCUMENT

[0009] Patent Document 1: Korean Patent Laid-Open No. 10-2011-0044123

[0010] Patent Document 2: Korean Patent Laid-Open No. 10-2007-0114025 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] An object of the present embodiment is to provide a blank mask having more excellent cleaning effect when cleaning is performed under the same conditions, and capable of effectively suppressing damage to the surface of a light-shielding film by cleaning solution remaining on the surface of the light-shielding film after cleaning, a photomask using the same, and a method for manufacturing a semiconductor element.

[0013] MEANS FOR SOLVING THE PROBLEMS

[0014] A blank mask according to an embodiment of the present specification includes a light-transmissive substrate and a light-shielding film disposed on the light-transmissive substrate.

[0015] The light-shielding film includes at least any one of a transition metal, oxygen, and nitrogen.

[0016] The SA1 value of the light-shielding film according to Formula 1-1 below is 60 mN / m to 90 mN / m.

[0017] [Formula 1-1]

[0018] SA1 = γ SL × tan θ

[0019] In the above Formula 1-1, the γ SL is an interfacial energy between the light-shielding film and pure water.

[0020] The θ is a contact angle of the light-shielding film measured with pure water.

[0021] The θ value can be 70° or more.

[0022] The γ SL value can be 22 mN / m or more.

[0023] The surface energy of the light-shielding film can be 42 mN / m to 47 mN / m.

[0024] The ratio of the polar component of the surface energy with respect to the surface energy of the light-shielding film can be 0.135 to 0.16.

[0025] The light-shielding film includes a first light-shielding layer and a second light-shielding layer disposed on the first light-shielding layer.

[0026] The content of the transition metal in the second light-shielding layer can be greater than the content of the transition metal in the first light-shielding layer.

[0027] The transition metal can include at least any one of Cr, Ta, Ti, and Hf.

[0028] The blank mask according to another embodiment of the present specification includes a light-transmissive substrate, a phase shift film disposed on the light-transmissive substrate, and a light-blocking film disposed on the phase shift film.

[0029] The phase shift film contains a transition metal and silicon.

[0030] The light-blocking film contains at least any one of a transition metal, oxygen, and nitrogen.

[0031] The contact angle of the light-blocking film measured with pure water is 70° or more.

[0032] The photomask according to still another embodiment of the present specification includes a light-transmissive substrate and a light-blocking pattern film disposed on the light-transmissive substrate.

[0033] The light-blocking pattern film contains at least any one of a transition metal, oxygen, and nitrogen.

[0034] The PSA1 value of the light-blocking pattern film according to the following Formula 3 is 60 mN / m to 90 mN / m.

[0035] [Formula 3]

[0036] PSA1 = γ PSL × tan θ P

[0037] In the above Formula 3, the γ PSL is an interfacial energy between the upper surface of the light-blocking pattern film and pure water.

[0038] The θ P is a contact angle of the upper surface of the light-blocking pattern film measured with pure water.

[0039] The method of manufacturing a semiconductor element according to still another embodiment of the present specification includes: a preparation step for disposing a light source, a photomask, and a semiconductor wafer on which a resist film is applied; an exposure step of selectively transmitting light incident from the light source on the semiconductor wafer through the photomask and making the light exit; and a development step of developing a pattern on the semiconductor wafer.

[0040] The photomask includes: a light-transmissive substrate; and a light-blocking pattern film disposed on the light-transmissive substrate,

[0041] The light-blocking pattern film contains at least any one of a transition metal, oxygen, and nitrogen.

[0042] The PSA1 value of the light-blocking pattern film according to the following Formula 3 is 60 mN / m to 90 mN / m.

[0043] [Formula 3]

[0044] PSA1 = γ PSL x tan θ P

[0045] In the above formula 3, the γ PSL is an interfacial energy between an upper surface of the light-shielding pattern film and pure water.

[0046] The θ P is a contact angle of the upper surface of the light-shielding pattern film measured with pure water.

[0047] A blank mask according to yet another embodiment of the present specification includes: a light-transmissive substrate; and a light-shielding film disposed on the light-transmissive substrate, the light-shielding film containing at least any one of a transition metal, oxygen, and nitrogen, a value of SA1 of the light-shielding film according to the following formula 1-1 is 60 mN / m to 90 mN / m:

[0048] [Formula 1-1]

[0049] SA1 = γ SL x tan θ

[0050] In the above formula 1-1, the γ SL is an interfacial energy between the light-shielding film and pure water, the θ is a contact angle of the light-shielding film measured with pure water, and a value of the θ is 70° or more.

[0051] A photomask according to yet another embodiment of the present specification includes: a light-transmissive substrate; and a light-shielding pattern film disposed on the light-transmissive substrate, the light-shielding pattern film containing at least any one of a transition metal, oxygen, and nitrogen, a value of PSA1 of the light-shielding pattern film according to the following formula 3 is 60 mN / m to 90 mN / m:

[0052] [Formula 3]

[0053] PSA1 = γ PSL x tan θ P

[0054] In the above formula 3, the γ PSL is an interfacial energy between an upper surface of the light-shielding pattern film and pure water, the θ P is a contact angle of the upper surface of the light-shielding pattern film measured with pure water, and a value of the θ P is 70° or more.

[0055] A method for manufacturing a semiconductor device according to another embodiment of this specification includes: a preparation step for configuring a light source, a photomask, and a semiconductor wafer coated with a resist film; an exposure step for selectively transmitting light incident from the light source through the photomask onto the semiconductor wafer and emitting the light; and a development step for developing a pattern on the semiconductor wafer, wherein the photomask includes: a light-transmitting substrate; and a light-shielding pattern film disposed on the light-transmitting substrate, the light-shielding pattern film comprising at least one of a transition metal, oxygen, and nitrogen, and the PSA1 value of the light-shielding pattern film according to Formula 3 below is 60 mN / m to 90 mN / m.

[0056] [Formula 3]

[0057] PSA1=γ PSL ×tanθ P

[0058] In Equation 3 above, the γ PSL The θ is the interfacial energy between the upper surface of the light-shielding patterned film and pure water. P The contact angle θ is the upper surface of the light-shielding patterned film measured with pure water. P The value is above 70°.

[0059] Invention Effects

[0060] The blank mask and the like according to this embodiment have the characteristic of excellent cleaning effect when cleaning the light-shielding film, and can effectively suppress the damage caused by cleaning solution remaining on the surface of the light-shielding film after cleaning. Attached Figure Description

[0061] Figure 1 This is a schematic diagram illustrating a blank mask according to an embodiment disclosed in this specification.

[0062] Figure 2 This is a schematic diagram illustrating a blank mask according to another embodiment disclosed in this specification.

[0063] Figure 3 This is a schematic diagram illustrating a blank mask according to another embodiment disclosed in this specification.

[0064] Figure 4 This is a schematic diagram illustrating a photomask according to another embodiment disclosed in this specification.

[0065] Explanation of reference numerals in the attached figures

[0066] 100: Blank Mask

[0067] 10: Transparent substrate

[0068] 20: Blackout film

[0069] 21: first light-blocking layer

[0070] 22: second light-blocking layer

[0071] 30: phase shift film

[0072] 200: photomask

[0073] 25: light-blocking pattern film DETAILED DESCRIPTION

[0074] Hereinafter, the embodiments will be described in detail so that those skilled in the art to which the present embodiments pertain can easily practice the embodiments. The present embodiments can be implemented in various ways, and are not limited to the embodiments described herein.

[0075] The term "about" or "substantially" and the like used in the present specification in connection with a degree means having a meaning close to a specified numerical value or range with an allowable error, and is intended to prevent the accurate or absolute numerical value disclosed in the present embodiments from being improperly or illegally used by any unreasonable third party.

[0076] In the present specification, the term "these combinations" included in the expression in Markush form means a mixture or combination of one or more selected from the group consisting of the plurality of structural elements described in the expression in Markush form, and means including one or more selected from the group consisting of the plurality of structural elements.

[0077] In the present specification, the description in the form of "A and / or B" means "A, B, or A and B".

[0078] In the present specification, unless otherwise specified, the terms such as "first", "second" or "A", "B" and the like are used to distinguish one entity from another entity, and do not limit the sequence or the order of the entities.

[0079] In the present specification, the meaning that B is on A means that B is on A or B is on A or can be on A with other layers therebetween, and should not be interpreted in the meaning that B is on the surface of A in a contact manner.

[0080] In the present specification, unless otherwise specified, the singular expression is interpreted to include the meaning of the singular or the plural as interpreted in the context.

[0081] In the present specification, room temperature means 20°C to 25°C.

[0082] In the present specification, the surface profile of the light-blocking film means the profile shape observed on the surface of the light-blocking film.

[0083] In the present specification, the side surface profile of the light shielding pattern film refers to a profile of the side surface of the light shielding pattern film observed from a cross section of the light shielding pattern film when the cross section is observed using a transmission electron microscope (TEM) measuring device or the like.

[0084] With the high integration of semiconductors, finer circuit patterns need to be formed on semiconductor wafers. As the line width of the patterns developed on semiconductor wafers is further reduced, resolution-related problems of photomasks also tend to increase.

[0085] After the light shielding film included in the blank mask is formed, a cleaning process using a cleaning solution having a relatively high polarity can be performed in order to remove particles and the like. Specifically, in order to temporarily increase the affinity between the surface of the light shielding film and the cleaning solution, ultraviolet light can be irradiated to the surface of the light shielding film. Thereafter, the cleaning solution can be sprayed to the surface of the light shielding film while the blank mask is rotated. In a case where particles and the like located on the surface of the light shielding film are not sufficiently removed by the cleaning process, the particles can become one of the factors that reduce the resolution of the blank mask. In addition, if the cleaning solution remaining on the surface of the light shielding film is not effectively removed after the cleaning process, the surface of the light shielding film can be damaged.

[0086] The inventors of the present embodiment have confirmed that the cleaning effect of the light shielding film can be improved and the light shielding film can be effectively inhibited from being damaged by the remaining cleaning solution by controlling the affinity between the surface of the light shielding film and the polar molecules, and the like, and thus the present embodiment has been completed.

[0087] Hereinafter, the present embodiment will be described in detail.

[0088] Figure 1 FIG. 1 is a schematic view for explaining a blank mask according to an embodiment disclosed in the present specification. The blank mask will be described with reference to FIG. 1. Figure 1 A blank mask according to the present embodiment will be described.

[0089] The blank mask 100 includes a light-transmissive substrate 10 and a light shielding film 20 disposed on the light-transmissive substrate 10.

[0090] As a material of the light-transmissive substrate 10, any material having light-transmissive properties with respect to exposure light and applicable to the blank mask 100 is acceptable. Specifically, the light-transmissive substrate 10 can have a transmittance of 85% or more with respect to exposure light having a wavelength of 193 nm. The transmittance can be 87% or more. The transmittance can be 99.99% or less. For example, a synthetic quartz substrate can be applied to the light-transmissive substrate 10. In this case, the light-transmissive substrate 10 can inhibit the attenuation of light transmitted through the light-transmissive substrate 10.

[0091] In addition, by adjusting the surface characteristics such as flatness and roughness of the light-transmitting substrate 10, the occurrence of optical distortion can be suppressed.

[0092] The light-shielding film 20 can be located on the top side of the light-transmitting substrate 10.

[0093] The light-shielding film 20 may have the property of blocking at least a portion of the exposure light incident from the bottom side of the light-transmitting substrate 10. Furthermore, when the phase-shifting film 30 (refer to...) Figure 3 When the light-transmitting substrate 10 and the light-shielding film 20 are located between the light-transmitting substrate 10 and the light-shielding film 20, the light-shielding film 20 can be used as an etching mask in the process of etching the phase-shifting film 30 and the like into a patterned shape.

[0094] The light-shielding film 20 contains at least one of a transition metal, oxygen, and nitrogen.

[0095] Properties related to surface energy of light shielding film

[0096] The SA1 value of the light-shielding film 20 according to Formula 1-1 below is 60mN / m to 90mN / m.

[0097] [Equation 1-1]

[0098] SA1=γ SL ×tanθ

[0099] In Equation 1-1 above, the above γ SL It is the interfacial energy between the aforementioned light-shielding film 20 and pure water, and θ is the contact angle of the light-shielding film 20 measured with pure water.

[0100] The affinity (cohesion) of the light-shielding film 20 to polar solutions is one of the important factors that may affect the cleaning effect of the light-shielding film. The cleaning solution used to clean the light-shielding film 20 is a solution made of ammonia, hydrogen peroxide, etc., mixed with water, which has high polarity. When the surface of the light-shielding film 20 is cleaned with the above-mentioned polar solution, the cleaning result may vary depending on the affinity of the light-shielding film 20 to the polar solution.

[0101] Before cleaning the light-shielding film 20, high-energy light, including ultraviolet light, can be irradiated onto the surface of the light-shielding film 20, thereby increasing the affinity of the light-shielding film 20 for polar solutions. Specifically, by irradiating the surface of the light-shielding film 20 with high-energy light, a portion of the interatomic bonds located on the surface of the light-shielding film 20 can be broken. On the other hand, high-energy light may cause the formation of hydroxyl radicals or the like, which are formed from oxygen or ozone contained in the atmosphere. When the surface of the light-shielding film 20 reacts with the free radicals or the like, polar functional groups can be formed on the surface of the light-shielding film 20, thereby increasing the affinity of the light-shielding film 20 for polar solutions. However, since the affinity enhancement effect of ultraviolet light irradiation is temporary and the degree of affinity enhancement is limited, there is a problem that it is difficult to remove the polar solutions or the like remaining on the surface of the light-shielding film 20 after the cleaning process. In order to solve the above problems, in this embodiment, the affinity of the light-shielding film 20 for polar solutions is controlled before irradiation.

[0102] Specifically, if the affinity of the light-shielding film 20 for the polar solution is not controlled before ultraviolet light irradiation, the surface of the light-shielding film 20 may still lack sufficient affinity for the polar solution even after ultraviolet light irradiation treatment. Furthermore, increased affinity between microparticles such as organic materials and the surface of the light-shielding film 20 may reduce the cleaning effect.

[0103] On the other hand, when adjusting the affinity of the light-shielding film 20 for polar materials solely considering its cleaning effect, the surface of the light-shielding film still exhibits a high affinity for polar solutions even after the affinity enhancement effect based on ultraviolet light irradiation disappears. This may result in difficulty in completely removing the polar solutions remaining on the surface of the light-shielding film 20 after the cleaning process. If the polar solutions remaining on the surface of the light-shielding film 20 cannot be effectively removed, the surface of the light-shielding film 20 may be damaged due to the reaction between the residual solutions and the surface of the light-shielding film 20.

[0104] This embodiment allows for control of the SA1 value, enabling the light-shielding film 20 to possess an affinity for polar materials adjusted before irradiation with ultraviolet light. Consequently, the light-shielding film 20, whose surface has been treated by ultraviolet light irradiation, exhibits excellent cleaning performance during the cleaning process. Simultaneously, it substantially suppresses damage to the surface of the light-shielding film caused by residual polar solutions.

[0105] The SA1 value of the light-shielding film 20 can be controlled based on various factors such as the process conditions in the heat treatment, cooling treatment, and stabilization steps after the formation of the light-shielding film 20, the composition of the light-shielding film 20, and the sputtering process conditions during the formation of the light-shielding film 20. Specific details regarding the method for controlling the SA1 value are repeated below and will therefore be omitted.

[0106] γ was measured using the goniometer method of a surface analyzer.SL The contact angles of the light-shielding film 20 and tanθ are calculated. Specifically, the surface of the film is divided into three equal parts horizontally and vertically, resulting in a total of nine regions. At approximately 2-second intervals, 0.8 μL to 1.2 μL (e.g., 1 μL) of pure water is dropped onto the center of each region, and the contact angle of the pure water in each region is measured using a surface analyzer. The average of the contact angle measurements for each region is used to calculate the contact angle of the light-shielding film 20 measured with pure water. Two seconds after the pure water drop, at approximately 2-second intervals, 0.8 μL to 1.2 μL (e.g., 1 μL) of diiodo-methane is dropped onto locations separated from the pure water drop location, and the contact angle of the diiodo-methane in each region is measured using a surface analyzer. The average of the contact angle measurements for each region is used to calculate the contact angle of the light-shielding film 20 measured with diiodo-methane. The surface energy and tanθ value of the light-shielding film were calculated from the contact angle between pure water and diiodomethane measured and calculated in the aforementioned light-shielding film 20.

[0107] Schematic, the surface energy γ of the light-shielding film can be measured using a double-type model of the Mobile Surface Analyzer (MSA) from KRUSS GmbH, Germany. SG and tanθ value.

[0108] The surface energy of the pure water used in the measurement is 72.8 mN / m, with the polar component of the surface energy being 51 mN / m and the dispersed component being 21.8 mN / m. The surface energy of the diiodomethane used in the measurement is 50.8 mN / m, with the polar component of the surface energy being 0 mN / m and the dispersed component being 50.8 mN / m.

[0109] From the surface energy γ of the light-shielding film SG The value of γ is calculated according to Equation 2-1 (Young's equation). SL Value, from the above γ SG The SA1 value is calculated from the tanθ value according to Equation 1-1 above.

[0110] [Equation 2-1]

[0111] γ SG =γ SL +γ LG ×cosθ

[0112] In Equation 2-1 above, the aforementioned γ SG The value is the surface energy of the light-shielding film, and the above γ SL The value is the interfacial energy between the light-shielding film and pure water, and the above γ LG The value is the surface energy of pure water.

[0113] The SA1 value of the light-shielding film 20 can be from 60 mN / m to 90 mN / m. The SA1 value of the light-shielding film 20 can be from 64 mN / m to 90 mN / m. The SA1 value of the light-shielding film 20 can be from 70 mN / m to 88 mN / m. The SA1 value of the light-shielding film 20 can be from 80 mN / m to 87 mN / m. In this case, the cleaning effect of the light-shielding film 20 after irradiation with ultraviolet light can be significantly improved. Furthermore, damage to the surface of the light-shielding film 20 that may occur after the cleaning process can be effectively suppressed.

[0114] The aforementioned θ value can be 70° or higher. The aforementioned θ value can be 72° or higher. The aforementioned θ value can be 74° or higher. The aforementioned θ value can be 85° or lower. The aforementioned θ value can be 75° or lower. The aforementioned θ value can be 74.5° or lower. In this case, the relatively polar solution remaining on the surface of the light-shielding film 20 after the cleaning process can be effectively removed.

[0115] The above γ SL The value can be above 22 mN / m. The aforementioned γ SL The value can be above 22.5 mN / m. The aforementioned γ SL The value can be above 23 mN / m. The aforementioned γ SL The value can be below 25 mN / m. The aforementioned γ SL The value can be below 24.5 mN / m. The aforementioned γ SL The value can be below 24 mN / m. In this case, the surface of the light-shielding film 20 can be effectively cleaned by the cleaning process, and damage to the light-shielding film 20 caused by the polar solution remaining on the surface of the light-shielding film after the cleaning process can be substantially prevented.

[0116] The surface energy of the light-shielding film 20 is calculated by adding the polar and dispersed components in the surface energy.

[0117] The surface energy of the light-shielding film 20 can be from 42mN / m to 47mN / m.

[0118] These light-shielding films 20 can be easily cleaned to remove particles from their surface. Furthermore, it is easier to remove polar solutions remaining on the surface of the light-shielding film 20 after the cleaning process is completed.

[0119] The surface energy of the light-shielding film 20 can be controlled based on its surface profile, the content of different elements contained in the film 20, and the post-processing conditions of the film 20 after film formation. The methods for controlling the surface energy of the light-shielding film 20 are repeated below and therefore omitted.

[0120] The method for measuring the surface energy of the light-shielding film 20 is the same as that described above, so its description is omitted.

[0121] The surface energy of the light-shielding film 20 can be from 42 mN / m to 47 mN / m. The surface energy of the light-shielding film 20 can be from 43 mN / m to 46 mN / m. The surface energy of the light-shielding film 20 can be from 43.2 mN / m to 44 mN / m. In this case, particles adhering to the surface of the light-shielding film 20 can be easily removed by a cleaning process, and damage to the light-shielding film 20 caused by polar solution residues on the surface of the light-shielding film 20 after cleaning can be suppressed.

[0122] The ratio of the polar component of the surface energy relative to the surface energy of the light-shielding film 20 can be from 0.135 to 0.16.

[0123] The affinity of a light-shielding film surface for a polar solution is influenced not only by the surface energy of the film but also by the ratio of the polar components that contribute to that surface energy. Specifically, even if two or more light-shielding films have the same surface energy, each film can have different affinities depending on the ratio of the polar components relative to the total surface energy. This embodiment allows for the control of both the surface energy and the ratio of the polar components relative to the total surface energy. Therefore, by employing a cleaning process using a polar solution, organic matter and other substances remaining on the surface of the light-shielding film can be effectively removed. Furthermore, it makes it easier to remove polar solution residues remaining on the surface of the light-shielding film after cleaning.

[0124] The ratio of the polar component of the surface energy relative to the surface energy of the light-shielding film 20 (polar component of the surface energy of the light-shielding film 20 / surface energy of the light-shielding film 20) can be 0.135 to 0.16. The ratio of the polar component of the surface energy relative to the surface energy of the light-shielding film 20 can be 0.137 to 0.155. The ratio of the polar component of the surface energy relative to the surface energy of the light-shielding film 20 can be 0.138 to 0.15. In this case, particles and the like formed on the surface of the light-shielding film can be effectively removed by cleaning, and the polar solution remaining on the surface of the light-shielding film 20 after cleaning can be easily removed.

[0125] The SA2 value of a light-shielding film is a parameter used to reflect the affinity of the film surface for hydrophobic substances.

[0126] The SA2 value of the light-shielding film according to the following formulas 1-2 can be 6.5 to 8.

[0127] [Equation 1-2]

[0128] SA2=γ SLd ×tanθ d

[0129] In equations 1-2 above, the aforementioned γ SLdIt is the interfacial energy between the aforementioned light-shielding film and diiodomethane, and the aforementioned θ d The contact angle of the light-shielding film was measured using diiodomethane.

[0130] From the surface energy γ of the light-shielding film SG and θ d The value is calculated according to the following equation 2-2 (Young's equation). SLd Value, and from the above γ SLd value and tanθ d The SA2 value is calculated according to Equation 1-2 above.

[0131] [Equation 2-2]

[0132] γ SG =γ SLd +γ LGd ×cosθ d

[0133] In Equation 2-2 above, the above γ SG The value is the surface energy of the light-shielding film, and the above γ SLd The value is the interfacial energy between the light-shielding film and diiodomethane, and the above γ LGd The value is the surface energy of diiodomethane.

[0134] The SA2 value of the light-shielding film can be between 6.5 and 8. Under these conditions, organic matter, i.e., non-polar particles, can be easily removed from the surface of the light-shielding film.

[0135] Layer structure and composition of light shielding film

[0136] Figure 2 This is a schematic diagram illustrating a blank mask 100 according to another embodiment of this specification. Referring to the above... Figure 2 This implementation method is described below.

[0137] The light-shielding film 20 may include: a first light-shielding layer 21; and a second light-shielding layer 22 disposed on the first light-shielding layer 21.

[0138] The second light-shielding layer 22 may contain at least one of a transition metal, oxygen, and nitrogen. The second light-shielding layer 22 may contain 50 atomic% (at%) to 80 atomic% of a transition metal. The second light-shielding layer 22 may contain 55 atomic% to 75 atomic% of a transition metal. The second light-shielding layer 22 may contain 60 atomic% to 70 atomic% of a transition metal.

[0139] The content of the element corresponding to oxygen or nitrogen in the second light-shielding layer 22 can be from 10 atomic% to 35 atomic%. The content of the element corresponding to oxygen or nitrogen in the second light-shielding layer 22 can be from 15 atomic% to 25 atomic.

[0140] The second light-shielding layer 22 may contain 5 atomic% to 20 atomic% nitrogen. The second light-shielding layer 22 may contain 7 atomic% to 13 atomic% nitrogen.

[0141] In this case, the light-blocking film 20 can be laminated together with the phase-shifting film 30, thereby helping to substantially block the exposure light.

[0142] The first light-shielding layer 21 may contain a transition metal, oxygen, and nitrogen. The first light-shielding layer 21 may contain 30 atomic% to 60 atomic% of a transition metal. The first light-shielding layer 21 may contain 35 atomic% to 55 atomic% of a transition metal. The first light-shielding layer 21 may contain 40 atomic% to 50 atomic% of a transition metal.

[0143] The total oxygen and nitrogen content of the first light-shielding layer 21 can be from 40 atomic% to 70 atomic%. The total oxygen and nitrogen content of the first light-shielding layer 21 can be from 45 atomic% to 65 atomic%. The total oxygen and nitrogen content of the first light-shielding layer 21 can be from 50 atomic% to 60 atomic.

[0144] The first light-shielding layer 21 may contain 20 atomic% to 40 atomic% oxygen. The first light-shielding layer 21 may contain 23 atomic% to 33 atomic% oxygen. The first light-shielding layer 21 may contain 25 atomic% to 30 atomic% oxygen.

[0145] The first light-shielding layer 21 may contain 5 atomic% to 20 atomic% of nitrogen. The first light-shielding layer 21 may contain 7 atomic% to 17 atomic% of nitrogen. The first light-shielding layer 21 may contain 10 atomic% to 15 atomic% of nitrogen.

[0146] In this case, the first light-shielding layer 21 can help give the light-shielding film 20 excellent light-absorbing properties.

[0147] The aforementioned transition metals may include at least one of Cr, Ta, Ti, and Hf. Cr may be one of the aforementioned transition metals.

[0148] The thickness of the first light-shielding layer 21 can be to The thickness of the first light-shielding layer 21 can be to The thickness of the first light-shielding layer 21 can be to In this case, the first light-shielding layer 21 can help the light-shielding film 20 effectively block the exposure light.

[0149] The thickness of the second light-shielding layer 22 can be to The thickness of the second light-shielding layer 22 can be to The thickness of the second light-shielding layer 22 can be to In this case, the second light-shielding layer 22 can help improve the light-shielding properties of the light-shielding film 20 and help to further precisely control the side shape of the light-shielding pattern film 25 formed by patterning.

[0150] The thickness ratio of the second light-shielding layer 22 to the thickness of the first light-shielding layer 21 can be from 0.05 to 0.3. Alternatively, the thickness ratio can be from 0.07 to 0.25. Or, the thickness ratio can be from 0.1 to 0.2. In this case, the light-shielding film 20 can have sufficient light-absorbing properties, and the side surface of the patterned light-shielding film can be formed to be nearly perpendicular to the surface of the light-transmitting substrate.

[0151] The content of transition metal in the second light-shielding layer 22 can be greater than the content of transition metal in the first light-shielding layer 21.

[0152] To precisely control the side surface profile of the patterned light-shielding film 25 formed through patterning, and to ensure the reflectivity required for defect inspection, the second light-shielding layer 22 needs to have a higher transition metal content compared to the first light-shielding layer 21. However, in this case, due to the heat treatment of the light-shielding film 20, the recovery, recrystallization, and grain growth of the transition metal may occur in the second light-shielding layer 22. When grain growth cannot be controlled in the second light-shielding layer 22 with a high transition metal content, the surface of the light-shielding film 20 may form a rougher profile than before the heat treatment due to the presence of overgrown transition metal particles. This surface may affect the affinity of the light-shielding film 20 for polar solutions, making it difficult to remove residual polar solutions from the surface of the light-shielding film 20 after the cleaning process.

[0153] In this embodiment, the transition metal content of the second light-shielding layer 22 is greater than that of the first light-shielding layer 21, and the SA1 value of the light-shielding film 20 is controlled within a preset range, thereby enabling the light-shielding film 20 to possess the desired optical and etching properties. Simultaneously, it effectively suppresses damage to the surface of the light-shielding film 20 caused by residual polar solution on the surface of the light-shielding film 20.

[0154] Optical properties of light shielding film

[0155] For light with a wavelength of 193 nm, the light-shielding film 20 can have a transmittance of more than 1%. For light with a wavelength of 193 nm, the light-shielding film 20 can have a transmittance of more than 1.3%. For light with a wavelength of 193 nm, the light-shielding film 20 can have a transmittance of more than 1.4%. For light with a wavelength of 193 nm, the light-shielding film 20 can have a transmittance of less than 2%.

[0156] For light with a wavelength of 193 nm, the light-shielding film 20 can have an optical density of 1.8 or higher. For light with a wavelength of 193 nm, the light-shielding film 20 can have an optical density of 1.9 or higher. For light with a wavelength of 193 nm, the light-shielding film 20 can have an optical density of 3 or lower.

[0157] In this case, the film including the light-shielding film 20 can effectively block the transmission of exposure light.

[0158] Other thin films

[0159] Figure 3 This is a schematic diagram illustrating a blank mask according to another embodiment disclosed in this specification. Referring to the above... Figure 3 This describes the blank mask used in this implementation method.

[0160] According to another embodiment of this specification, a blank mask 100 includes a light-transmitting substrate 10, a phase-shifting film 30 disposed on the light-transmitting substrate 10, and a light-shielding film 20 disposed on the phase-shifting film 30.

[0161] The phase-shifting film 30 may contain a transition metal and silicon.

[0162] The light-shielding film 20 contains at least one of a transition metal, oxygen, and nitrogen.

[0163] The contact angle of the light-shielding film 20, measured with pure water, is above 70°.

[0164] The phase shift film 30 can be located between the light-transmitting substrate 10 and the light-shielding film 20. The phase shift film 30 attenuates the intensity of the exposed light transmitted through the phase shift film 30 and substantially suppresses the diffraction light generated at the edge of the pattern by adjusting the phase difference.

[0165] For light with a wavelength of 193 nm, the phase shift film 30 can have a phase difference of 170° to 190°. For light with a wavelength of 193 nm, the phase shift film 30 can have a phase difference of 175° to 185°. For light with a wavelength of 193 nm, the phase shift film 30 can have a transmittance of 3% to 10%. For light with a wavelength of 193 nm, the phase shift film 30 can have a transmittance of 4% to 8%. In this case, the resolution of the photomask 200 including the aforementioned phase shift film 30 can be improved.

[0166] The phase-shifting film 30 may contain a transition metal and silicon. The phase-shifting film 30 may contain a transition metal, silicon, oxygen, and nitrogen. The aforementioned transition metal may be molybdenum.

[0167] The descriptions of the physical properties and composition of the light-transmitting substrate 10 and the light-shielding film 20 are repeated above, so their descriptions will be omitted.

[0168] A hard mask (not shown) may be located on the light-shielding film 20. The hard mask can be used as an etching mask film when patterning is performed on the light-shielding film 20. The hard mask may contain silicon, nitrogen, and oxygen.

[0169] Photomask

[0170] Figure 4 This is a schematic diagram illustrating a photomask according to another embodiment of this specification. Referring to the above... Figure 4 This describes the photomask used in this embodiment.

[0171] According to another embodiment of this specification, a photomask 200 includes: a light-transmitting substrate 10; and a light-shielding pattern film 25 disposed on the light-transmitting substrate 10.

[0172] The light-blocking patterned film 25 contains at least one of a transition metal, oxygen, and nitrogen.

[0173] The PSA1 value of the above-described light-shielding patterned film 25 according to Formula 3 below is 60mN / m to 90mN / m.

[0174] [Formula 3]

[0175] PSA1=γ PSL ×tanθ P

[0176] In Equation 3 above, the aforementioned γ PSL It is the interfacial energy between the upper surface of the aforementioned light-shielding patterned film 25 and pure water, the aforementioned θ P The contact angle of the upper surface of the light-blocking patterned film 25 is measured using pure water.

[0177] A light-shielding patterned film 25 can be formed by patterning the light-shielding film 20 of the blank mask 100 described above.

[0178] Except that the measurement target is the upper surface of the light-shielding pattern film 25 instead of the surface of the light-shielding film 20, the method for measuring the PSA1 value of the light-shielding pattern film 25 is the same as the method for measuring the SA1 value of the light-shielding film 20 in the blank mask 100.

[0179] When measuring the PSA1 value of the light-shielding pattern film 25, the pure water and diiodomethane are dripped in such a way that the entire area of ​​the bottom surface of the dripping pure water and diiodomethane droplets is in complete contact with the upper surface of the light-shielding pattern film.

[0180] When measuring the γ on the upper surface of the light-shielding pattern film 25 PSL value and θ PWhen the value is taken, if the upper surface of the light-shielding pattern film 25 is not located at the center of each region on the upper surface of the light-shielding film 20, then γ is measured on the upper surface of the light-shielding pattern film 25 located near the center. PSL value and θ P value.

[0181] The description of the physical properties, composition and structure of the light-shielding pattern film 25 is the same as the description of the light-shielding film 20 of the blank mask 100, so the description will be omitted.

[0182] Manufacturing method of light shielding film

[0183] A method for manufacturing a blank mask according to an embodiment of this specification may include a preparation step in which a light-transmitting substrate and a sputtering target are placed in a sputtering chamber.

[0184] A method for manufacturing a blank mask according to an embodiment of this specification may include a film-forming step in which an atmospheric gas is injected into a sputtering chamber and an electric current is applied to a sputtering target, thereby forming a light-shielding film on a light-transmitting substrate.

[0185] The film-forming steps may include: a first light-shielding layer film-forming process, forming a first light-shielding layer on a light-transmitting substrate; and a second light-shielding layer film-forming process, forming a second light-shielding layer on the first light-shielding layer.

[0186] A method for manufacturing a blank mask according to an embodiment of this specification may include a heat treatment step, in which the light-shielding film is subjected to heat treatment at a temperature of 150°C to 330°C for 5 to 30 minutes.

[0187] A method for manufacturing a blank mask according to an embodiment of this specification may include a cooling step of cooling the light-shielding film that has undergone the above-described heat treatment step.

[0188] A method for manufacturing a blank mask according to an embodiment of this specification may include a stabilization step, in which the light-shielding film that has undergone a cooling step is stabilized at a temperature of 15°C to 30°C.

[0189] In the preparation step, the target material used to form the light-shielding film can be selected based on the composition of the film. As a sputtering target, a target containing a transition metal can be used. The sputtering target can consist of two or more targets, including one target containing a transition metal. The target containing a transition metal can contain 90 atomic% or more of the transition metal. The target containing a transition metal can contain 95 atomic% or more of the transition metal. The target containing a transition metal can contain 99 atomic% of the transition metal.

[0190] Transition metals may include at least one of Cr, Ta, Ti, and Hf. Cr may be a transition metal.

[0191] The description of the light-transmitting substrate 10 disposed in the sputtering chamber is the same as the above description, so it will be omitted.

[0192] In the preparation step, a magnet can be placed in the sputtering chamber. The magnet can be placed on a surface opposite to the side of the sputtering target where sputtering will occur.

[0193] In the film formation process of the light-shielding film, different film formation process conditions can be used when forming each layer contained in the light-shielding film. In particular, considering the affinity of the light-shielding film for polar solutions, its extinction characteristics, and etching characteristics, different process conditions can be used for each layer, such as atmospheric gas composition, the electric current applied to the sputtering target, and the film formation time.

[0194] Atmosphere gases can include inactive gases, reactive gases, and sputtering gases. Inactive gases are gases containing elements that do not constitute the thin film to be formed. Reactive gases are gases containing elements that constitute the thin film to be formed. Sputtering gases are gases that are ionized in a plasma atmosphere and collide with the target material.

[0195] Inactive gases may include helium.

[0196] The reactant gas may include a nitrogen-containing gas. For example, the nitrogen-containing gas may be N2, NO, NO2, N2O, N2O3, N2O4, N2O5, etc. The reactant gas may also include an oxygen-containing gas. For example, the oxygen-containing gas may be O2, CO2, etc. The reactant gas may include both nitrogen-containing and oxygen-containing gases. The reactant gas may also include gases containing both nitrogen and oxygen. For example, gases containing both nitrogen and oxygen may be NO, NO2, N2O, N2O3, N2O4, N2O5, etc.

[0197] The sputtering gas can be Ar gas.

[0198] As the power source for applying power to the sputtering target, a DC power supply or an RF power supply can be used.

[0199] During the deposition of the first light-shielding layer, the power applied to the sputtering target can be from 1.5 kW to 2.5 kW. During the deposition of the first light-shielding layer, the power applied to the sputtering target can be from 1.6 kW to 2 kW.

[0200] During the film formation process of the first light-shielding layer, the flow rate ratio of the reactive gas to the inactive gas in the atmosphere can be 1.5 to 3. The aforementioned flow rate ratio can be 1.8 to 2.7. The aforementioned flow rate ratio can be 2 to 2.5.

[0201] In the reaction gas, the ratio of nitrogen content to oxygen content can be from 1.5 to 4. In the reaction gas, the ratio of oxygen content to nitrogen content can be from 2 to 3. In the reaction gas, the ratio of oxygen content to nitrogen content can be from 2.2 to 2.7.

[0202] In this case, the first light-shielding layer can help give the light-shielding film sufficient light-absorbing properties. By controlling the etching characteristics of the first light-shielding layer, it is possible to make the side of the patterned light-shielding film nearly perpendicular to the surface of the light-transmitting substrate.

[0203] The deposition time of the first light-shielding layer can be 200 to 300 seconds. Alternatively, the deposition time can be 210 to 240 seconds. In this case, the first light-shielding layer can help the light-shielding film 20 to have sufficient light-absorbing properties.

[0204] During the deposition of the second light-shielding layer, the power applied to the sputtering target can be from 1 kW to 2 kW. Alternatively, during the deposition of the second light-shielding layer, the power applied to the sputtering target can be from 1.2 kW to 1.7 kW.

[0205] During the film formation process of the second light-shielding layer, the flow ratio of the reactive gas to the inactive gas in the atmosphere can be 0.3 to 0.8. The aforementioned flow ratio can be 0.4 to 0.6.

[0206] During the film formation process of the second light-shielding layer, the oxygen content ratio relative to the nitrogen content in the reaction gas can be 0.3 or less. Alternatively, the oxygen content ratio relative to the nitrogen content in the reaction gas can be 0.1 or less. Or, the oxygen content ratio relative to the nitrogen content in the reaction gas can be 0.001 or more.

[0207] In this case, it can help control the affinity of the light-shielding film for polar solutions within the range desired in this embodiment. Furthermore, it can help give the light-shielding film stable extinction properties.

[0208] The deposition time of the second light-shielding layer can be from 10 to 30 seconds. Alternatively, the deposition time can be from 15 to 25 seconds. In this case, the second light-shielding layer is included within the light-shielding film, thereby helping to suppress the transmission of exposed light.

[0209] In the heat treatment step, the light-shielding film that has undergone the film formation step can be heat-treated. Specifically, the substrate on which the light-shielding film has been formed can be placed in a heat treatment chamber and then heat-treated.

[0210] In the cooling step, the light-shielding film that has undergone heat treatment can be cooled. A cooling plate adjusted to a preset cooling temperature in this embodiment can be placed on the substrate side of the blank mask that has undergone heat treatment, thereby cooling the blank mask. In the cooling step, the spacing between the blank mask and the cooling plate can be adjusted and an atmospheric gas can be introduced, thereby controlling the cooling rate of the blank mask.

[0211] To remove stress formed in the formed light-shielding film and to further increase its density, heat treatment is sometimes necessary. During heat treatment, the transition metals contained in the film undergo recovery and recrystallization, effectively removing the stress. However, if the heat treatment temperature and time are not controlled, grain growth will occur in the film, and the surface may become rougher than before heat treatment due to the presence of uncontrolled transition metal grains.

[0212] The affinity of a light-shielding film for polar solutions is influenced not only by its chemical properties, such as composition, but also by its physical properties, such as surface roughness. Therefore, deforming the surface contour of the light-shielding film after heat treatment can increase its affinity for polar solutions. Consequently, it may be difficult to remove residual cleaning solution from the surface of the light-shielding film after cleaning.

[0213] In this embodiment, the heat treatment time and temperature can be controlled during the heat treatment step, and the cooling rate, cooling time, and flow rate of the atmospheric gas during cooling can be controlled during the cooling step. This effectively removes the internal stress formed in the light-shielding film and allows control over changes in the film's affinity for polar solutions caused by heat treatment.

[0214] The heat treatment process can be performed at temperatures ranging from 150°C to 330°C. Alternatively, it can be performed at temperatures ranging from 180°C to 300°C.

[0215] The heat treatment step can be performed for 5 to 30 minutes. The heat treatment step can be performed for 10 to 20 minutes.

[0216] In this case, the internal stress formed in the light-shielding film can be effectively removed, and it can help suppress the excessive growth of transition metal particles in the light-shielding film caused by heat treatment.

[0217] The blank mask can be cooled within 2 minutes after the heat treatment step is completed. In this case, the growth of transition metal particles due to residual heat in the mask can be effectively prevented.

[0218] By providing fins of controlled length at each corner of the cooling plate and placing a blank mask on the fins such that the lower surface of the light-transmitting substrate faces the cooling plate, the cooling rate of the blank mask can be controlled.

[0219] Building upon the cooling plate, the cooling rate of the blank mask can be further increased by injecting an inert gas into the space where the cooling step is performed. The inert gas can more effectively remove residual heat generated within the light-shielding film.

[0220] In particular, in a blank mask, the cooling efficiency of the upper surface side of the light-shielding film, positioned facing the lower surface of the aforementioned light-transmitting substrate, via the cooling plate can be slightly lower than the cooling efficiency of the substrate. Residual heat on the upper surface side of the light-shielding film can be removed more effectively by injecting an inert gas. For example, the inert gas can be helium.

[0221] In the cooling step, the cooling temperature used on the cooling plate can be between 10°C and 30°C. The aforementioned cooling temperature can be between 15°C and 25°C.

[0222] During the cooling step, the spacing between the blank mask and the cooling plate can be from 0.01 mm to 30 mm. Alternatively, the spacing can be from 0.05 mm to 5 mm. Or, the spacing can be from 0.1 mm to 2 mm.

[0223] In the cooling step, the cooling rate of the blank mask can be from 10°C / min to 80°C / min. The aforementioned cooling rate can be from 20°C / min to 75°C / min. The aforementioned cooling rate can be from 40°C / min to 70°C / min.

[0224] In this case, the growth of transition metal grains caused by residual heat in the light-shielding film after heat treatment can be suppressed, and the polar solution remaining on the surface of the light-shielding film after the cleaning process can be easily removed.

[0225] The stabilization step can stabilize the blank mask that has undergone the cooling step. In the case of a blank mask that has undergone the cooling step, rapid temperature changes can cause significant damage. To prevent this, a stabilization step may be necessary.

[0226] Various methods can be used to stabilize a blank mask that has undergone a cooling step. For example, after separating the cooled blank mask from the cooling plate, it can be left in atmospheric air at room temperature for a predetermined time. Another example is to separate the cooled blank mask from the cooling plate and then stabilize it for 10 to 60 minutes by rotating the blank mask at a temperature of 15°C to 30°C. In this case, the blank mask can be rotated at a speed of 20 to 50 rpm. Yet another example is to inject a gas with low reactivity to the light-shielding film into the cooled blank mask at a flow rate of 5 L / min to 10 L / min for 1 to 5 minutes. In this case, the temperature of the gas with low reactivity to the light-shielding film can be 20°C to 40°C.

[0227] Manufacturing method of semiconductor element

[0228] A method for manufacturing a semiconductor device according to another embodiment of this specification includes: a preparation step for configuring a light source, a photomask, and a semiconductor wafer coated with a resist film; an exposure step for selectively transmitting light incident from the light source through the photomask onto the semiconductor wafer and emitting the light; and a development step for developing a pattern on the semiconductor wafer.

[0229] The photomask includes: a light-transmitting substrate; and a light-shielding pattern film disposed on the light-transmitting substrate.

[0230] The light-shielding patterned film contains at least one of transition metals, oxygen, and nitrogen.

[0231] The PSA1 value of the light-shielding patterned film according to Formula 3 below is 60mN / m to 90mN / m.

[0232] [Formula 3]

[0233] PSA1=γ PSL ×tanθ P

[0234] In Equation 3 above, the aforementioned γ PSL It is the interfacial energy between the upper surface of the aforementioned light-shielding patterned film and pure water, θ. P It is the contact angle of the upper surface of the light-blocking patterned film, measured with pure water.

[0235] In the preparation step, the light source is a device capable of generating exposure light with a short wavelength. The exposure light can be light with a wavelength below 200 nm. Alternatively, the exposure light can be ArF light with a wavelength of 193 nm.

[0236] A lens can be additionally placed between the photomask and the semiconductor wafer. The lens has the function of reducing the pattern shape within the photomask and transferring it onto the semiconductor wafer. As a lens, there are no limitations as long as it is a lens commonly used in ArF semiconductor wafer exposure processes. For example, the aforementioned lens could be a lens made of calcium fluoride (CaF2).

[0237] During the exposure step, exposure light can be selectively transmitted onto the semiconductor wafer using a photomask. In this case, the portions of the resist film that have been exposed to the exposure light may undergo chemical degradation.

[0238] In the development step, the semiconductor wafer that has already undergone exposure can be treated with a developing solution, thereby developing a pattern on the semiconductor wafer. When the applied resist film is a positive resist, the portions of the resist film exposed to the exposure light may be dissolved by the developing solution. When the applied resist film is a negative resist, the portions of the resist film not exposed to the exposure light may be dissolved by the developing solution. Through developing solution treatment, the resist film is formed into a resist pattern. This resist pattern can be used as a mask to form a pattern on the semiconductor wafer.

[0239] The explanation of photomasks is repeated from the previous content, so it will be omitted.

[0240] The specific embodiments will be described in more detail below.

[0241] Manufacturing example: Film formation of light-shielding film

[0242] Example 1: A transparent quartz substrate with a width of 6 inches, a length of 6 inches, and a thickness of 0.25 inches was placed inside the chamber of a DC sputtering apparatus. A chromium target was placed in the chamber such that the T / S distance was 255 mm, and the substrate and the target formed a 25-degree angle.

[0243] Subsequently, an atmosphere gas containing 21% by volume of Ar, 11% by volume of N2, 32% by volume of CO2, and 36% by volume of He was introduced into the chamber, and a sputtering process of 1.85 kW was applied to the sputtering target for 250 seconds to form the first light-shielding layer.

[0244] After the first light-shielding layer was formed, an atmosphere gas mixed with 57% by volume of Ar and 43% by volume of N2 was introduced into the first light-shielding layer in the chamber, and a sputtering process of 1.5 kW was applied to the sputtering target for 25 seconds to produce a blank mask sample with a second light-shielding layer.

[0245] The sample after the second light-shielding layer was formed was placed in a heat treatment chamber and heat-treated for 15 minutes at an atmospheric temperature of 200°C.

[0246] A cooling plate with a cooling temperature of 23°C was placed on the lower surface of the light-transmitting substrate of the heat-treated sample. The distance between the substrate and the cooling plate was adjusted so that the cooling rate measured on the upper surface of the light-shielding film of the sample was 36°C / min, and then a cooling step was performed for 5 minutes.

[0247] After cooling, the samples were placed in the atmosphere at 20°C to 25°C and stabilized for 15 minutes.

[0248] Example 2: A blank mask sample was fabricated under the same conditions as in Example 1. The difference was that after forming the light-shielding film, the sample was heat-treated at 250°C and cooled for 7 minutes, and the cooled sample was stabilized for 20 minutes.

[0249] Example 3: A blank mask sample was fabricated under the same conditions as in Example 1. The difference was that after forming the light-shielding film, the sample was heat-treated at 250°C and then cooled at a rate of 30°C / min for 8 minutes.

[0250] Example 4: A blank mask sample was manufactured under the same conditions as in Example 1. The difference was that after forming the light-shielding film, the sample was heat-treated at 300°C, and the heat-treated sample was cooled for 8 minutes and then stabilized for 30 minutes.

[0251] Example 5: A blank mask sample was fabricated under the same conditions as in Example 1. The difference was that after forming the light-shielding film, the sample was heat-treated at 300°C. During the cooling process, helium gas was injected onto the sample at a flow rate of 300 sccm, resulting in a cooling rate of 56°C / min. The cooled sample was then stabilized for 45 minutes.

[0252] Comparative Example 1: A blank mask sample was manufactured under the same conditions as in Example 1. The difference was that the film-formed sample was not subjected to heat treatment, cooling treatment, or stabilization.

[0253] Comparative Example 2: A blank mask sample was fabricated under the same conditions as in Example 1. The difference was that after forming the light-shielding film 20, the sample was heat-treated at 250°C, and instead of using a cooling plate, it was allowed to cool naturally in the atmosphere. During natural cooling, the atmosphere temperature was 23°C, the cooling time was 120 minutes, and the cooling rate measured on the sample was 2°C / minute. No stabilization was performed after the cooling treatment.

[0254] Comparative Example 3: A blank mask sample was fabricated under the same conditions as in Example 1. The difference was that the sample was heat-treated at 300°C, and during cooling, helium gas was injected onto the sample at a flow rate of 300 sccm, resulting in a cooling rate of 56°C / min. The cooled sample was not stabilized.

[0255] The heat treatment, cooling treatment, and stabilization conditions for each embodiment and comparative example are described in Table 1 below.

[0256] Evaluation example: Measurement of SA1 value, etc., of light-shielding film.

[0257] The surface of the light-shielding film of each embodiment and comparative example was divided into three equal parts horizontally and vertically, thus dividing it into a total of nine regions. At approximately 2-second intervals, 0.8 μL to 1.2 μL, for example 1 μL, of pure water was dropped onto the center of each region, and the contact angle of the pure water in each region was measured using a surface analyzer. The average of the contact angle measurements of each region was used to calculate the contact angle θ of the light-shielding film measured with pure water. At approximately 2-second intervals from the location where the pure water was dropped, 1 μL of diiodo-methane was dropped, and the contact angle of the diiodo-methane in each region was measured using a surface analyzer. The average of the contact angle measurements of each region was used to calculate the contact angle θ of the light-shielding film measured with diiodo-methane. d And calculated.

[0258] From the calculated contact angles, the surface energy γ of the light-shielding films in each embodiment and comparative example was measured and calculated using a surface analyzer. SG Value, surface energy γ of the light-shielding film SG The polar and dispersed components, the ratio of the polar component to the surface energy of the light-shielding film, and the tanθ value.

[0259] Then, the surface energy γ calculated from each of the above embodiments and comparative examples SG The values ​​of γ and tanθ were used to calculate γ according to Equation 2-1. SL value, and from γ SL The SA1 value was calculated from the tanθ value according to Equation 1-1.

[0260] Furthermore, the surface energy γ calculated from the various embodiments and comparative examples described above... SG value and tanθ d The value of γ was calculated according to Equation 2-2. SLd value, and from γ SLd value and tanθ d The SA2 value was calculated according to Equation 1-2.

[0261] As a surface analyzer, the double-type model of the Mobile Surface Analyzer (MSA) from KRUSS GmbH, Germany, was used.

[0262] The measured values ​​for each of the above embodiments and comparative examples are recorded in Tables 2 and 3 below.

[0263] Evaluation Example: Evaluation of the Cleaning Effect of Light-Shielding Film

[0264] Using an M6641S model inspection machine from Lasertec Corporation of Japan, it was checked whether microparticles were formed on the surface of the light-shielding film of each example and comparative example sample before cleaning.

[0265] After measurement, the surface of the sample's light-shielding film was irradiated with light at a wavelength of 172 nm for 120 seconds. Immediately after irradiation, the sample was rotated at 80 rpm, and simultaneously, SC-1 solution was sprayed onto the surface of the sample's light-shielding film at a flow rate of 600 ml / min for 8 to 10 minutes. The SC-1 solution contained 14.3 wt% NH4OH, 14.3 wt% H2O2, and 71.4 wt% H2O.

[0266] After cleaning, the surface of the light-shielding film of the sample was inspected using an M6641S model inspection machine from Lasertec Corporation of Japan to check whether microparticles had formed. Compared with before cleaning the light-shielding film, cases where no new microparticles were detected after cleaning were rated as O, and cases where new microparticles were detected after cleaning were rated as X.

[0267] The evaluation results for each embodiment and comparative example are recorded in Table 3 below.

[0268] [Table 1]

[0269]

[0270] [Table 2]

[0271]

[0272] [Table 3]

[0273]

[0274] In Table 2 above, the SA1 values ​​of Examples 1 to 5 are 60 mN / m to 90 mN / m, while the SA1 values ​​of Comparative Examples 1 to 3 are less than 60 mN / m or greater than 90 mN / m.

[0275] The θ values ​​of Examples 1 to 5 are 70° or higher, while the θ values ​​of Comparative Examples 1 and 2 are less than 70°.

[0276] γ in Examples 1 to 5 SL The value is above 22 mN / m. On the other hand, the γ values ​​of Comparative Examples 1 and 2 are... SL The value is less than 22 mN / m.

[0277] Regarding the surface energy of the light-shielding film, the surface energy values ​​of the light-shielding films 20 in Examples 1 to 5 are 42 mN / m to 47 mN / m. On the other hand, the surface energy of the light-shielding films 20 in Comparative Examples 1 and 2 is greater than 47 mN / m.

[0278] Regarding the ratio of the polar component relative to the surface energy of the light-shielding film, the ratio values ​​for Examples 1 to 5 were 0.135 to 0.16, while the ratio values ​​for Comparative Examples 1 to 3 were less than 0.135 or greater than 0.16.

[0279] Regarding the cleaning effect, the cleaning effect of Examples 1 to 5 was determined to be O, while the cleaning effect of Comparative Examples 1 to 3 was determined to be X.

[0280] The preferred embodiments of the present invention have been described in detail above, but the scope of the present invention is not limited thereto. Various modifications and improvements made by those skilled in the art based on the basic concepts of the embodiments as defined in the appended claims are also within the scope of the present invention.

Claims

1. A blank mask, wherein, include: Transparent substrate; as well as A light-shielding film is disposed on the light-transmitting substrate. The light-shielding film contains at least one of transition metals, oxygen, and nitrogen. The SA1 value of the light-shielding film according to the following formula 1-1 is 60mN / m to 90mN / m: [Equation 1-1] In Equation 1-1 above, The γ SL It is the interfacial energy between the light-shielding film and pure water. The θ is the contact angle of the light-shielding film measured with pure water. The value of θ is 70° or higher.

2. The blank mask according to claim 1, wherein, The γ SL The value is above 22mN / m.

3. The blank mask according to claim 1, wherein, The surface energy of the light-shielding film is 42 mN / m to 47 mN / m.

4. The blank mask according to claim 3, wherein, The ratio of the polar component of the surface energy relative to the surface energy of the light-shielding film is 0.135 to 0.

16.

5. The blank mask according to claim 1, wherein, The light-shielding film includes a first light-shielding layer and a second light-shielding layer disposed on the first light-shielding layer. The content of transition metal in the second light-shielding layer is greater than that in the first light-shielding layer.

6. The blank mask according to claim 1, wherein, The transition metal includes at least one of Cr, Ta, Ti, and Hf.

7. A blank mask, wherein, include: Transparent substrate; A phase-shifting film is disposed on the light-transmitting substrate; as well as A light-shielding film is disposed on the phase-shifting film. The phase-shifting film comprises a transition metal and silicon. The light-shielding film contains at least one of transition metals, oxygen, and nitrogen. The contact angle of the light-shielding film, measured with pure water, is greater than 70°. The SA1 value of the light-shielding film according to the following formula 1-1 is 60mN / m to 90mN / m: [Equation 1-1] In Equation 1-1 above, The γ SL It is the interfacial energy between the light-shielding film and pure water. θ is the contact angle of the light-shielding film measured with pure water.

8. A photomask, wherein, include: Transparent substrate; as well as A light-shielding patterned film is disposed on the light-transmitting substrate. The light-shielding patterned film contains at least one of transition metals, oxygen, and nitrogen. The PSA1 value of the light-shielding patterned film according to Formula 3 below is 60 mN / m to 90 mN / m: [Formula 3] In Equation 3 above, The γ PSL It is the interfacial energy between the upper surface of the light-shielding patterned film and pure water. The θ P The contact angle of the upper surface of the light-shielding patterned film was measured using pure water. The θ P The value is above 70°.

9. A method for manufacturing a semiconductor device, wherein, include: Preparation steps are used to configure the light source, photomask, and semiconductor wafer coated with resist film; The exposure step involves selectively transmitting light incident from the light source onto the semiconductor wafer via the photomask and causing the light to exit. as well as The development step involves developing a pattern on the semiconductor wafer. The photomask includes: a light-transmitting substrate; And a light-shielding pattern film, disposed on the light-transmitting substrate, The light-shielding patterned film contains at least one of transition metals, oxygen, and nitrogen. The PSA1 value of the light-shielding patterned film according to Formula 3 below is 60 mN / m to 90 mN / m: [Formula 3] In Equation 3 above, The γ PSL It is the interfacial energy between the upper surface of the light-shielding patterned film and pure water. The θ P The contact angle of the upper surface of the light-shielding patterned film was measured using pure water. The θ P The value is above 70°.

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