Raw mask, photomask using this raw mask and manufacturing process of a semiconductor element

Abstract

Raw mask (100) comprising: a transparent substrate (10) and a light-shielding film (20) arranged on the transparent substrate (10), wherein the light-shielding film (20) comprises a transition metal and at least one of the elements oxygen and / or nitrogen, wherein the light-shielding film (20) comprises a first light-shielding layer (21) and a second light-shielding layer (22) arranged on the first light-shielding layer (21), and wherein the light-shielding film (20) has an Rd value according to Rd=er2er1, which is 0.4 to 0.8, wherein the er1 value is an etch rate of the first light-shielding layer (21) measured by etching with argon gas, and the er2 value is an etch rate of the second light-shielding layer (22) measured by etching with argon gas.

Description

1. Area The present invention relates to a raw mask and a photomask that uses this raw mask, and to a manufacturing process for a semiconductor element. 2. Description of the related prior art Due to the high integration of semiconductor devices and similar materials, miniaturization of the circuit patterns of semiconductor devices is necessary. For this reason, the importance of lithography, a technique for developing a circuit pattern on a wafer surface using a photomask, is further emphasized. For the development of a miniaturized circuit pattern, the exposure light used in an exposure process (photolithography) must have a shortened wavelength. Recently, an ArF excimer laser (wavelength 193 nm) or similar is being used as the exposure light. There is a binary mask and a phase-shift mask as photomasks. The binary mask has a structure in which a light-blocking pattern layer is formed on a transparent substrate. On a surface where a pattern is formed by the binary mask, a transparent area, which does not contain a light-blocking layer, allows exposure light to pass through, and a light-blocking area, which contains a light-blocking layer, blocks exposure light to transfer a pattern onto a photoresist film on the surface of a wafer. However, the binary mask can cause problems when developing a very small pattern because the light is diffracted at the edge of the transparent area when the pattern is reduced in size. There are Levenson-type, outrigger-type, and halftone-type phase-shift masks. The halftone phase-shift mask has a structure in which a pattern of semi-transparent layers is formed on a transparent substrate. On a surface where a pattern of the halftone phase-shift mask is formed, a transparent area that does not contain a semi-transparent layer allows the transmission of exposure light, and a semi-transparent area that contains a semi-transparent layer allows the transmission of attenuated exposure light. The attenuated exposure light may have a phase difference compared to the exposure light that penetrated the transparent area.Accordingly, the diffraction light that occurs at the edge of the transparent part is neutralized by the exposure light that has penetrated the semi-transparent part, and thus the phase-shift mask can form a further refined tiny pattern on the surface of a wafer. [Related state of the art] [Patent documents] Korean patent registration KR 10 1 579 843 B1, Korean patent registration KR 10 1 584 383 B1 and Korean patent registration KR 10 1 207 724 B1. US Patent 2017 / 0023854A1 discloses a raw mask and a photomask in which the composition of a light-shielding layer made of metals and light elements is controlled such that the light-shielding layer exhibits high light-shielding effectiveness, increased etching speed, reduced thickness, and minimal surface resistance. The disclosed raw mask comprises at least one light-shielding layer on a transparent substrate. This light-shielding layer includes a first layer adjacent to the transparent substrate and a second layer formed thereon. Both layers contain chromium (Cr) and molybdenum (Mo). According to US 2006 / 0088774A1, an opaque layer is deposited on a principal plane of an optically transparent substrate. This layer comprises a first and a second opaque layer. The first layer, which is practically unetchable by F-based dry etching, mainly comprises chromium oxide, chromium nitride, chromium oxynitride, or similar compounds. The second opaque layer mainly comprises a silicon-containing compound that is etchable by F-based dry etching, such as silicon oxide, silicon nitride, silicon oxynitride, silicon / transition metal oxide, silicon / transition metal nitride, or silicon / transition metal oxynitride. SUMMARY OF THE INVENTION A raw mask according to an embodiment of the present description comprises a transparent substrate and a light-shielding film arranged on the transparent substrate. The light-shielding film comprises a transition metal and at least one of the elements oxygen and / or nitrogen. The light-blocking film comprises a first light-blocking layer and a second light-blocking layer that is arranged on top of the first light-blocking layer. The light-blocking film has an Rd value according to equation 1 below, which is between 0.4 and 0.8. In equation 1, the er1 value is an etch rate of the first light-shielding layer, measured by etching with argon gas. The er2 value is an etch rate of the second light-shielding layer, measured by etching with argon gas. The er2 value can be between 0.4 and 0.5 Å / s. The er1 value can be 0.51 Å / s or more. A Do value of the light-blocking film according to equation 2 below can be less than 0.05. In equation 2, the Bo value is an optical density of the light-shielding film for light with a wavelength of 193 nm. When a light-shielding pattern film formed by structuring the light-shielding film is observed on a top surface, the Po value is an optical density for light with a wavelength of 193 nm of a measurement range corresponding to an area from an edge of the light-shielding pattern film to a position spaced 4 mm from the edge in the direction of the inside of the light-shielding pattern film. The transition metal can consist of Cr, Ta, Ti and Hf. An etch rate of the light-shielding film, measured with chlorine-based gas, can be 1.55 Å / s or more. A raw mask according to another embodiment of the present invention comprises a transparent substrate and a light-blocking film arranged on the transparent substrate. The light-shielding film comprises a transition metal and at least one of the elements oxygen and / or nitrogen. The light-blocking film comprises a first light-blocking layer and a second light-blocking layer that is arranged on top of the first light-blocking layer. A pattern edge loss area, measured by structuring the light-shielding film, is 10 nm2 or less. The pattern edge loss area is an area enclosed by a first line, a second line and a pattern edge profile of a structured light-shielding film when a TEM (transmission electron microscopy) image of the light-shielding pattern film is observed. The first line is an extended line connecting a first point placed at a height of 20% on a side surface profile of the structured light-blocking film and a second point placed at a height of 40% on the side surface, when a total height of the structured light-blocking film is set to 100%. The second line is an extended line that encompasses a pattern film intersection point and is arranged so that it is parallel to an upper boundary of the transparent substrate. The pattern film intersection point is a point where a pattern film center line and an upper surface profile of the light-shielding pattern film meet. The pattern film centerline is an extended line passing through the pattern film center point, which is the midpoint of a lower boundary of the light-blocking pattern film, and perpendicular to the upper boundary of the transparent substrate. A photomask according to another embodiment of the present invention comprises a transparent substrate and a light-blocking pattern film arranged on the transparent substrate. The light-shielding pattern film comprises a transition metal and at least one of the elements oxygen and / or nitrogen. The light-shielding pattern film comprises a first light-shielding layer and a second light-shielding layer arranged on top of the first light-shielding layer. The light-shielding pattern film has an Rd value according to equation 1 below, which is between 0.4 and 0.8. In equation 1, the er1 value is an etch rate of the first light-shielding layer, measured by etching with argon gas. The er2 value is an etch rate of the second light-shielding layer, measured by etching with argon gas. When the light-shielding pattern film is observed at the section, a pattern edge loss area of ​​the light-shielding pattern film can be 10 nm2 or less. A manufacturing process of a semiconductor element according to another embodiment of the present invention comprised a preparation process of arranging a light source, a photomask and a semiconductor wafer in which a resist film was applied; an exposure process of selectively transferring light incident from the light source onto the semiconductor wafer through the photomask; and a development process of developing a pattern on the semiconductor wafer. The photomask comprises a transparent substrate and a light-blocking pattern film arranged on the transparent substrate. The light-shielding pattern film comprises a transition metal and at least one of the elements oxygen and / or nitrogen. The light-shielding pattern film comprises a first light-shielding layer and a second light-shielding layer arranged on top of the first light-shielding layer. The Rd value according to equation 1 below for the light-shielding pattern film is 0.4 to 0.8. In equation 1, the er1 value is an etch rate of the first light-shielding layer, measured by etching with argon gas. The er2 value is an etch rate of the second light-shielding layer, measured by etching with argon gas. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual view illustrating a raw mask according to an embodiment disclosed in the present invention; Fig. 2 is a conceptual view illustrating a light-shielding pattern film formed by structuring a light-shielding film of a raw mask as a measurement target according to another embodiment; Fig. 3 is a top view observed on a top surface of a light-shielding pattern film formed by structuring a light-shielding film according to another embodiment; Fig. 4 is a conceptual view illustrating a method for measuring a pattern edge loss area of ​​a light-shielding pattern film formed by structuring a light-shielding film according to another embodiment; Fig. 5 is a conceptual view illustrating a raw mask according to another embodiment; and Fig.Figure 6 is a conceptual view to illustrate a photomask according to another embodiment. DETAILED DESCRIPTION Exemplary embodiments of the present invention are described in detail below with reference to the accompanying drawings, so that they can be easily implemented by those skilled in the field to which the present invention relates. However, the exemplary embodiments can be implemented in many different forms, and the invention should not be interpreted as being limited to the embodiments described herein. This application uses terms for degree such as "approximately," "essentially," and the like to indicate values ​​that are approximately within / to the specified range when a tolerance range exists due to manufacturing or compositional reasons. Furthermore, these terms for degree are used to facilitate the understanding of exemplary embodiments and to prevent an infringer from misusing the stated content, which specifies an exact or absolute number. In this application, the expression ‘combination(s) thereof’ contained in a Markush-like expression means one or more mixtures or combinations selected from the group consisting of components specified in the Markush-like expression; that is to say, one or more components selected from the group consisting of the components are included. In this application, the description of “A and / or B” means “A, B or A and B”. In this application, terms such as "first", "second", "A" or "B" are used to distinguish between identical terms, unless explicitly stated otherwise. In this application, “B is arranged on A” means that B is arranged in direct contact with A or is arranged above A with another layer or structure in between, and should therefore not be interpreted as being limited to “B arranged in direct contact with A”. In this application, a singular form is interpreted contextually as including a plural form as well as a singular form, unless explicitly stated otherwise. In this application, room temperature refers to 20 to 25 °C. In this application, a surface profile of a light-shielding pattern film means an outline of a light-shielding pattern film observed in the section when a section of the light-shielding pattern film is observed using TEM (Transmission Electron Microscopy) and the like. In this application, a side surface profile of a light-shielding pattern film means an outline of a side surface of a light-shielding pattern film observed in the section when a section of a light-shielding pattern film is observed using TEM (Transmission Electron Microscopy) and the like. In this application, a pattern edge profile of a light-shielding pattern film means an outline of an edge and the periphery of an upper boundary of a light-shielding pattern film when a section of the light-shielding pattern film is observed using TEM (Transmission Electron Microscopy) and the like. Due to the high integration of semiconductor devices, it is necessary to form increasingly miniaturized circuit patterns on semiconductor wafers. As the critical dimension (CD) of a pattern developed on a semiconductor wafer continues to decrease, problems related to photomask resolution increase. A light-blocking film contained in a raw mask can be formed into a light-blocking pattern film by etching or similar processes. The light-blocking pattern film can be formed by etching when a resist pattern or other thin-film pattern arranged on the light-blocking film is applied as a mask, and an etching gas is applied as an etchant. When a light-shielding film is patterned using a dry etching process with an etching gas as the etchant, the resulting patterned light-shielding film may exhibit inconsistent optical properties in one direction along the plane. Specifically, the etching gas may etch the light-shielding film along the resist pattern or etch mask in the direction of the lower portion of the film, away from the surface. During the etching process, within a given facet of the light-shielding film being formed, the upper region may be exposed to the etching gas for a relatively longer time compared to the lower region. This can lead to excessive etching in the upper region along the plane of the light-shielding film. This can contribute to the degradation of the resolution of a raw mask. The inventors of the present invention have verified that the deterioration of the resolution of a raw mask can be effectively suppressed by the methods for introducing a multilayer structure into a light-shielding film, thereby enabling an upper layer of the light-shielding layer to have a more resistant structure compared to a lower layer, and the like, and have thus completed the present invention. The present invention is described in detail below. Fig. 1 is a conceptual view illustrating a raw mask according to an embodiment disclosed in the present application. With reference to Fig. 1, the raw mask of the present invention is described. A raw mask 100 comprises a transparent substrate 10 and a light-shielding film 20 arranged on the transparent substrate 10. The material of the transparent substrate 10 is not limited if it has a light transmission property with respect to an exposure light and can be applied to a raw mask 100. In particular, the transmittance of the transparent substrate 10 with respect to an exposure light with a wavelength of 193 nm can be 85% or more. The transmittance can be 87% or more. The transmittance can be 99.99% or less. For example, the transparent substrate 10 can be applied using a synthetic quartz substrate. In such a case, the transparent substrate 10 can suppress attenuation of the light transmitted by the transparent substrate 10. Additionally, a surface characteristic, such as the smoothness and roughness of the transparent substrate 10, can be adjusted to suppress optical distortion. A light-blocking film 20 can be arranged on the top side of the transparent substrate 10. The light-blocking film 20 can have a characteristic of blocking at least a portion of the exposure light incident on the underside of the transparent substrate 10. Additionally, a phase-shifting film 30 (see Fig. 5) and the like can be arranged between the transparent substrate 10 and the light-blocking film 20. In such a case, the light-blocking film 20 can be used as an etching mask in a process of etching the phase-shifting film 30 to create a pattern. The light-shielding film 20 comprises a transition metal and at least one of the elements oxygen and / or nitrogen. The light-shielding film 20 comprises a first light-shielding layer 21 and a second light-shielding layer 22, which is arranged on the first light-shielding layer 21. Density of each layer of the light-blocking film A light-shielding film 20 has an Rd value of the equation 1 below, which is 0.4 to 0.8. In equation 1, one of the er1 values ​​is the etch rate of the first light-shielding layer 21, which is measured by etching with argon gas. The er2 value is an etch rate of the second light shielding layer 22, which is measured by etching with argon gas. In the process of structuring a light-shielding film 20, the upper surface of the light-shielding pattern film may be exposed to an etching gas for a relatively longer time compared to the lower surface. Furthermore, etching exceeding the necessary extent may occur within the upper region of a side surface of the structured light-shielding film in the direction along the plane of the light-shielding film 20. Because of this, it may be difficult to ensure that the side surface of the light-shielding pattern film is perpendicular to a surface of the transparent substrate 10. To solve problems like those described above, a method is employed to control the etch rate of a second light-shielding layer 22 so that it has a lower value compared to a first light-shielding layer 21, by adjusting the amount of a transition metal in the second light-shielding layer 22 so that it has a relatively higher value compared to a first light-shielding layer 22. However, although damage forming in the edge region of the second light-shielding layer 22 is reduced by applying such a method, the reduced damage forming in the edge region can still cause a problem related to the resolution of a photomask due to the trend toward miniaturization in a critical dimension (CD) of a desired pattern.Additionally, if the amount of a transition metal contained in the second light-shielding layer 22 is adjusted solely by considering the density of the side-surface profile of the light-shielding pattern film, a reduction in the etch rate of the light-shielding film and defects caused by chromium (Cr) migration may occur. That is, it is necessary to further adjust the side-surface profile of the light-shielding pattern film, which is formed by a structuring process, by adjusting other characteristics, such as the density of each layer, in addition to adjusting the composition quantity of the light-shielding film layer. Furthermore, an etching gas used in the structuring of a light-shielding film 20 undergoes a chemical reaction with the light-shielding film 20. Accordingly, the etch rate of each layer within the light-shielding film 20, as measured by the etching gas, can be strongly influenced by the elements present in each layer and by their reactivity with the etching gas. The inventors of the present invention found that an etch rate of each layer, as measured by the etching gas, cannot directly reflect the density of the layer. In contrast, etching with argon gas corresponds to a physical etching process that essentially does not involve any chemical reaction with the light-shielding film 20 as an etching target. Accordingly, the etch rate measured by etching with argon gas is assumed to be a parameter that can be independent of the composition and chemical reactivity of each layer within the light-shielding film 20 and can effectively reflect the degree of density of each layer within the light-shielding film. Accordingly, the inventors of the present invention found that the side surface profile of the light-shielding pattern film formed when the light-shielding film 20 is structured can be adjusted more precisely by controlling an Rd value than can be reflected by the degree of density of the first light-shielding layer 21 and the second light-shielding layer 22. The er1 value, er2 value, and Rd value can be adjusted depending on various factors. Specifically, these values ​​can be influenced by factors such as the density of a light-shielding layer, the crystallization of metallic elements, the quantity of non-metallic elements, the arrangement of each composite element within the light-shielding layer, and the like. In particular, the values ​​can vary depending on process conditions, such as the rotational speed of a magnet during the formation of each layer within the light-shielding film, or post-processing conditions, such as cooling after formation. The detailed description of the means of adjusting Rd values ​​is superseded by the content below and is therefore omitted. A method for measuring the Rd value of the light-shielding film 20 is the same as below. First, the thicknesses of the first light-shielding layer 21 and the second light-shielding layer 22 are measured using TEM (Transmission Electron Microscopy). An empty mask 100, serving as a measurement target, is machined to a size of 15 mm wide and 15 mm long, thus creating a sample. One surface of the sample is treated with FIB (Focused Ion Beam), then positioned in a TEM imaging device, and a TEM image of the sample is acquired. From this TEM image, the thicknesses of the first light-shielding layer 21 and the second light-shielding layer 22 are measured. For example, the TEM image can be measured using the JEM_2100F HR model, which is available from JEOL LTD Corporation. The sample is then etched with argon gas, and the etching times of the first light-shielding layer 21 and the second light-shielding layer 22 are measured. The sample is placed in XPS (X-ray Photoelectron Spectroscopy), and the 4 mm wide by 2 mm long area in the center of the sample is etched with argon gas to measure the etching time of each layer. While the etching time of each layer is being measured, a vacuum of 1.0 × 10⁻⁸ mbar is applied in a measuring device, an X-ray source is applied as a monochromator AI K α (1486.6 eV), an electrical anode power of 72 W is applied, an anode voltage of 12 kV is applied, and an argon ion beam voltage of 1 kV is applied. For example, the XPS measuring device can be created using a K-alpha model available from Thermo Scientific Corporation. The er1 value, the er2 value and the Rd value are calculated from the thicknesses and etch rates of the measured first light-shielding layer 21 and second light-shielding layer 22. The Rd value of the light-blocking film 20 can range from 0.4 to 0.8. The Rd value can range from 0.5 to 0.77. The Rd value can range from 0.6 to 0.8. The Rd value can range from 0.6 to 0.7. In such a case, the side surface profile of the structured light-blocking film can be controlled more precisely. The er2 value of the light-shielding film 20 can be 0.4 to 0.5 Å / s. The er2 value can be 0.4 to 0.47 Å / s. The er2 value can be 0.42 to 0.45 Å / s. In such a case, the Rd value of the light-shielding film 20 can be further easily controlled within a predetermined range in embodiments, and particle formation caused by the redeposition of sputter particles can be suppressed. The er1 value of the light-blocking film 20 can be 0.4 to 0.5 Å / s. The er1 value can be 0.55 Å / s or more. The er1 value can be 0.6 Å / s or more. The er1 value can be 1.0 Å / s or less. The er1 value can be 0.8 Å / s or less. The er1 value can be 0.7 Å / s or less. In such a case, the Rd value of the light-blocking film can be easily adjusted further, and etching of the light-blocking film can still be carried out efficiently. Optical properties of the light-blocking film A light-blocking film 20 can have a Do value according to equation 2 below that is less than 0.05. In equation 2, the Bo value is an optical density of the light-shielding film 20 for light with a wavelength of 193 nm. When a light-shielding pattern film formed by structuring the light-shielding film 20 is observed on a top surface, the Po value is an optical density for light with a wavelength of 193 nm of a measurement range corresponding to a region from an edge (Le) of the light-shielding pattern film to a position spaced 4 nm from the edge in the direction of the inside of the light-shielding pattern film (see Fig. 3 ). Fig. 2 is a conceptual view illustrating a light-shielding pattern film formed by structuring a light-shielding film of a raw mask as a measurement target. An embodiment is described below with reference to Fig. 2. The light-shielding pattern film 23 is formed by structuring a light-shielding film. One side face of the light-shielding pattern film 23 (the yz surface of the light-shielding pattern film) is normally formed by etching, unless it is a surface of a raw mask itself. An upper side of the side face formed by etching (the side located in a superior position in the z-axis direction from the yz surface of the light-shielding pattern film) is exposed to an etchant for a relatively long time, and more etching can occur compared to the lower side of the side face. Because of this, sections adjacent to both ends of the light-shielding pattern film 23 (the edge of the light-shielding pattern film located in the x-axis direction) can be formed to have a relatively thinner thickness compared to the central section of the light-shielding pattern film 23.As a result, a deviation in extinction characteristics in one direction along the plane of the light-screening pattern film 23 can be high. The present invention can provide a raw mask by controlling the Do value of the light-screening film, and thereby the degradation of resolution caused by structuring can be effectively suppressed. To control the Do value of a light-shielding film 20, it is necessary to control the durability of the layers themselves contained within the light-shielding film, in addition to controlling other conditions of each layer within the light-shielding film 20. Furthermore, the density can be influenced by the process conditions during sputtering, the condition of any post-processing, such as cooling after sputtering, and the composition of the film. The description of the control mechanism overlaps with the content below, and therefore further description is omitted. Fig. 3 is a top view of the upper surface of a light-blocking pattern film formed by structuring a light-blocking film. An embodiment is described below with reference to Fig. 3. The Bo value is measured by shining an exposure light with a wavelength of 193 nm onto a surface of the light-shielding film before it is patterned. If another thin film (a hard mask, for example) is formed on the light-shielding film, this other thin film is removed by etching, and the Bo value is then measured. When another thin film formed on the light-shielding film is removed, the difference in Bo value between the thickness of the light-shielding film before etching and the thickness of the light-shielding film after etching can be within 3 nm. Subsequently, Po is measured in a light-shielding pattern film 23, which is formed by structuring the light-shielding film. When the light-shielding pattern film 23 is observed at its upper surface, a region corresponding to an area from an edge of the light-shielding pattern film to a position spaced 4 nm from an edge (Le) formed by structuring in the direction of the inside of the light-shielding pattern film is defined as the measurement area (Am) (see Fig. 3). For the measurement area (Am), an exposure light with a wavelength of 193 nm is emitted to measure Po values. The Do value is calculated from the measured Bo value and Po value. The Bo and Po values ​​can be measured using ellipsometers. For example, the Bo and Po values ​​can be measured using the MG Pro model, available from Nano View Corporation. The Do value of the light-shielding film 20 can be less than 0.05. The Do value can be 0.04 or less. The Do value can be 0.03 or less. The Do value can be 0.02 or less. The Do value can be 0.01 or more. In such a case, a deterioration in the resolution of a raw mask 100 caused by structuring a light-shielding film 20 can be effectively suppressed. The Bo value of the light-blocking film 20 can be 1.8 or more. The Bo value can be 1.85 or more. The Bo value can be 3 or less. In such a case, laminated thin films comprising a light-blocking film 20 can effectively block transmitting exposure light. The Po value of the light-screening film 20 can be 1.8 or more. The Po value can be 1.82 or more. The Po value can be 3 or less. The Po value can be 2 or less. The Po value can be 1.9 or less. In such a case, it is possible to effectively suppress the degradation of the resolution of a raw mask 100. The transmittance of the light-blocking film 20 for light with a wavelength of 193 nm can be 1% or more. The transmittance can be 1.3% or more. The transmittance can be 1.4% or more. The transmittance can be 2% or less. In such a case, a thin film comprising a light-blocking film 20 can effectively suppress the transmission of an exposure light. Etching characteristics of the light-screening film An etch rate measured by etching with chlorine-based gas of the light shielding film 20 can be 1.55 Å / s or more. To improve the resolution of a raw mask 100, it may be necessary to make a resist film or an etch mask film arranged on a light-shielding film 20 into a thin film. If the light-shielding film 20 is textured, it is possible to allow the light-shielding film 20 to be textured by controlling the etch rate with respect to an etchant, even though a resist film of relatively thin thickness is formed on the light-shielding film 20. Chlorine-based gas may be present as an etching agent in the light-screening film 20. The chlorine-based gas may comprise chlorine gas (Cl2) and oxygen gas (O2). The etching characteristic of the light-shielding film 20 with respect to a chlorine-based gas can be controlled by controlling the durability of layers contained in the light-shielding film 20, the distribution of the amount by element in the thickness direction of the light-shielding film 20, the process condition when the light-shielding film 20 is formed, the cooling rate after it has been formed into a film, and the like. The procedure for measuring the etch rate of the light shielding film 20 with respect to chlorine-based gas is the same as below. First, a TEM image of the light-shielding film 20 is acquired to measure its thickness. A raw mask 100, serving as a measurement target, is prepared to measure 15 mm wide and 15 mm long, thus creating a sample. One surface of the sample is treated with FIB (Focused Ion Beam), then positioned in a TEM imaging device, and the TEM image of the sample is acquired. The thickness of the light-shielding film 20 is measured from the TEM image. For example, the TEM image can be acquired using the JEM-2199F HR model, which is available from JEOL LTD Corporation. The etching time of the light-shielding film 20 is then determined by etching with chlorine-based gas. The chlorine-based gas consists of chlorine gas at 90 to 95 vol% and oxygen gas at 5 to 10 vol%. The etching rate is calculated from the thickness of the light-shielding film 20 and the etching time of the light-shielding film 20. The etch rate of the light-shielding film 20, measured by etching with chlorine-based gas, can be 1.55 Å / s or more. The etch rate can be 1.6 Å / s or more. The etch rate can be 1.7 Å / s or more. The etch rate can be 3 Å / s or less. In such a case, a resist film placed on the light-shielding film 20 can be made into a thin film and can help to effectively suppress the degradation of the resolution of a raw mask 100. Pattern edge loss area of ​​the light-blocking film A raw mask according to another embodiment of the present invention comprises a transparent substrate and a light-blocking film arranged on the transparent substrate. The light-shielding film comprises a transition metal and at least one of the elements oxygen and / or nitrogen. The light-blocking film comprises a first light-blocking layer and a second light-blocking layer that is arranged on top of the first light-blocking layer. A pattern edge loss area, measured by structuring the light-shielding film, is 10 nm2 or less. The pattern edge loss area is an area enclosed by a first line, a second line and a pattern edge profile of a structured light shielding pattern film when a TEM (Transmission Electron Microscopy) image of the structured light shielding pattern film is observed. The first line is an extended line connecting a first point placed at a height of 20% on a side surface profile of the structured light-blocking film and a second point placed at a height of 40% on the side surface profile, when a total height of the structured light-blocking film is set to 100%. The second line is an extended line that encompasses a pattern film intersection point and is arranged so that it is parallel to an upper boundary of the transparent substrate. The pattern film intersection point is a point where a pattern film center line and an upper surface profile of the light-shielding pattern film are located. The pattern film centerline is an extended line passing through the pattern film center point, which is the midpoint of a lower boundary of the structured light-shielding film, and is perpendicular to an upper boundary of the transparent substrate. The light-shielding film 20 can be etched by means of a resist pattern or an etch mask film arranged on the light-shielding film 20. Since a side-face profile of the light-shielding pattern film formed after etching is such that it is closer to a surface of the transparent substrate 10, the resolution of a photomask 200 can be improved. Unless the side-face profile of the light-shielding pattern film is precisely controlled, the CD deviation (critical dimension) of a pattern developed on a semiconductor wafer may be larger. The present invention can precisely control the side surface profile of a light-shielding pattern film formed when it is structured by adjusting the pattern edge loss area of ​​the light-shielding film 20. Fig. 4 is a conceptual view illustrating a method for measuring the edge loss area of ​​a pattern shielding film. An embodiment is described below with reference to Fig. 4. A light-blocking film is structured, thereby forming a light-blocking pattern film 23. A raw mask comprising the light-shielding pattern film 23 is then processed to a size of 15 mm wide and 15 mm long, thus producing a sample. The surface of the sample is treated with FIB (Focused Ion Beam), then positioned in a TEM imaging device, and the TEM image of the sample is measured. For example, the TEM image can be measured using the JEM-2100F HR model, which is available from JEOL LTD Corporation. Subsequently, from a side surface profile of the light-shielding pattern film 23, which is observed in the TEM image when the total height of the light-shielding pattern film 23 is set to 100%, a first point (P1) located at a height of 20% on the side surface profile and a second point (P2) located at a height of 40% on the side surface are defined, and an extended line to connect both points is defined. The extended line is defined as a first line (L1). A pattern film intersection point (Pi), which is a point where a pattern film centerline (L0), forming an angle perpendicular to an upper boundary of a transparent substrate 10, and the upper surface profile of the light-shielding pattern film 23 intersect, in addition to passing through a pattern film centerline (Pc), which is the midpoint of a lower boundary of the light-shielding pattern film 23 observed by the TEM image. An extended line encompassing the pattern film intersection point (P1) and oriented perpendicular to the upper boundary of the transparent substrate 10 is defined as a second line (L2). A pattern edge loss area (Ap) is defined by the area enclosed by the first line (L1), the second line (L2), and the pattern edge profile of the light-shielding pattern film 23. A pattern edge loss area of ​​(Ap) is measured from the TEM image. The pattern edge loss area (Ap) of the light-shielding film 20 can be 10 nm² or less. The pattern edge loss area (Ap) of the light-shielding film 20 can be 8 nm² or less. The pattern edge loss area (Ap) of the light-shielding film 20 can be 6 nm² or less. The pattern edge loss area (Ap) of the light-shielding film 20 can be 0.5 nm² or more. In such a case, a degradation of the resolution can be effectively suppressed. The composition and film thickness of the light-blocking film The light-shielding film 20 can comprise a transition metal and at least one of the elements oxygen and / or nitrogen. The light-shielding film 20 can comprise a first light-shielding layer 21 and a second light-shielding layer 22 arranged on top of the first light-shielding layer 21. The present invention controls the quantity by means of an element that is included in the second light-shielding layer 22, and can thereby help the light-shielding film 20 to exhibit desired extinction characteristics, and if the light-shielding film 20 is structured, it can allow the side surface profile of the light-shielding pattern film 25 to form an angle close to that which is perpendicular to a surface of the transparent substrate. The second light-shielding layer 22 can comprise a transition metal and at least one of the elements oxygen and / or nitrogen. The second light-shielding layer 22 can comprise a transition metal in an amount of 50 to 80 at.%. The second light-shielding layer 22 can comprise a transition metal in an amount of 55 to 75 at.%. The second light-shielding layer 22 can comprise a transition metal in an amount of 60 to 70 at.%. The amount of oxygen or nitrogen in the second light-shielding layer 22 can be 10 to 35 at%. The amount of oxygen or nitrogen in the second light-shielding layer 22 can be 15 to 25 at%. The second light-shielding layer 22 can contain nitrogen in an amount of 5 to 20 at%. The second light-shielding layer 22 can contain nitrogen in an amount of 7 to 13 at%. In such a case, the second light-shielding layer 22 can help the light-shielding film 20 to exhibit excellent extinction characteristics. Furthermore, the side-surface profile of the light-shielding pattern film, which is formed by structuring the light-shielding film 20, can be controlled more precisely. The first light-shielding layer 21 can comprise a transition metal, oxygen, and nitrogen. The first light-shielding layer can comprise a transition metal in an amount of 30 to 60 at.%. The first light-shielding layer 21 can comprise a transition metal in an amount of 35 to 55 at.%. The first light-shielding layer 21 can comprise a transition metal in an amount of 40 to 50 at.%. The sum of the oxygen and nitrogen content of the first light-shielding layer 22 can be 40 to 70 at%. The sum of the oxygen and nitrogen content of the first light-shielding layer 22 can be 45 to 65 at%. The sum of the oxygen and nitrogen content of the first light-shielding layer 22 can be 50 to 60 at%. The first light-shielding layer 21 can contain oxygen in an amount of 20 to 40 at%. The first light-shielding layer 21 can contain oxygen in an amount of 23 to 33 at%. The first light-shielding layer 21 can contain oxygen in an amount of 25 to 30 at%. The first light-shielding layer 21 can contain nitrogen in an amount of 5 to 20 at%. The first light-shielding layer 21 can contain nitrogen in an amount of 7 to 17 at%. The first light-shielding layer 21 can contain nitrogen in an amount of 10 to 15 at%. In such a case, the first light-shielding layer 21 can help the light-shielding film 20 to exhibit excellent extinction characteristics and can help improve the etch rate of the light-shielding film 20. The transition metal can include at least one of Cr, Ta, Ti, and Hf. The transition metal can be Cr. The film thickness of the first light-blocking layer 21 can be 250 to 650 Å. The film thickness of the first light-blocking layer 21 can be 350 to 600 Å. The film thickness of the first light-blocking layer 21 can be 400 to 550 Å. In such a case, the first light-blocking layer 21 can help the light-blocking film 20 to effectively block exposure light. The film thickness of the second light-shielding layer 22 can be 30 to 200 Å. The film thickness of the second light-shielding layer 22 can be 30 to 100 Å. The film thickness of the second light-shielding layer 22 can be 40 to 80 Å. In such a case, the second light-shielding layer improves the extinction characteristics of the light-shielding film 20 and can help to control the shape of the side surface of the light-shielding pattern film more precisely. The film thickness ratio of the second light-shielding layer 22 to the film thickness of the first light-shielding layer 21 can be 0.05 to 0.3. The film thickness ratio can be 0.07 to 0.25. The film thickness ratio can be 0.1 to 0.2. In such a case, the light-shielding film 20 can form a side-surface profile that is perpendicular to the surface of a transparent substrate when structured, while exhibiting sufficient extinction characteristics. Other thin films Fig. 5 is a conceptual view illustrating a raw mask according to another embodiment of the present description. With reference to Fig. 5, the raw mask of one embodiment is described. A phase-shifting film 30 can be arranged between a transparent substrate 10 and a light-blocking film 20. The phase-shifting film 30 is a thin film that attenuates light transmitting through it, adjusts the phase delay of the light, and essentially suppresses diffraction light that occurs at the edge of a pattern. The phase-shift film 30 can exhibit a phase retardation of 170 to 190° for light with a wavelength of 193 nm. The phase-shift film 30 can exhibit a phase retardation of 175 to 185° for light with a wavelength of 193 nm. The phase-shift film 30 can exhibit a transmittance of 3 to 10% for light with a wavelength of 193 nm. The phase-shift film 30 can exhibit a transmittance of 4 to 8% for light with a wavelength of 193 nm. In such a case, the resolution of a photomask 200, which includes the phase-shift film 30, can be improved. The phase-shift film 30 can include a transition metal and silicon. The phase-shift film 30 can include a transition metal, silicon, oxygen, and nitrogen. The transition metal can be molybdenum. A description of the transparent substrate 10 and the light-shielding film 20 are each overlapped with the above description and therefore omitted. A hard mask (not shown) can be arranged on the light-shielding film 20. The hard mask can serve as an etching mask film when structuring the light-shielding film 20. The hard mask can comprise silicon, nitrogen, and oxygen. Photomask Fig. 6 is a conceptual view illustrating a photomask according to another embodiment. The photomask of one embodiment is described with reference to Fig. 6. A photomask 200 according to another embodiment of the present description comprises a transparent substrate 10 and a light-shielding pattern film 25 arranged on the transparent substrate 10. The light-shielding pattern film 25 comprises a transition metal and at least one of the elements oxygen and / or nitrogen. The light-shielding pattern film 25 comprises a first light-shielding layer 21 and a second light-shielding layer 22, which is arranged on the first light-shielding layer 21. The light-shielding pattern film 25 has an Rd value according to equation 1 below, which is 0.4 to 0.8. In equation 1, the er1 value is an etch rate of the first light-shielding layer 21, which is measured by etching with argon gas. The er2 value is an etch rate of the second light shielding layer 22, which is measured by etching with argon gas. The light-shielding pattern film 25 can be formed by structuring the light-shielding film 20 of the raw mask 100 described above. A method for measuring Rd values ​​of the light-shielding pattern film 25 is the same as the method for measuring Rd values ​​of the light-shielding film 20 in the raw mask 100. A pattern edge loss area of ​​the light shielding pattern film 25 can be 10 nm2 or less. A method for measuring the pattern edge loss area of ​​the light-shielding pattern film 25 is the same as a method for measuring the pattern edge loss area of ​​the light-shielding film 20 except for skipping a process for structuring the light-shielding film 20. The light-shielding pattern film 25 can have a PDo value according to equation 3 below, which is less than 0.05. In equation 3, the PBo value is an optical density for light with a wavelength of 193 nm of the light-shielding pattern film 25. When the light-shielding pattern film 25 is observed at the upper surface, the PPo value is an average value of the optical density for light with a wavelength of 193 nm of a measurement range corresponding to a range from an edge of the light-shielding pattern film 25 to a position spaced 4 nm away in the direction of the inside of the light-shielding pattern film 25. The edge refers to a section formed by etching within the edge of the light-shielding pattern film 25. The methods for measuring the PDo value, PBo value, and PPo value of the light-shielding pattern film 25 are the same as the methods for measuring the Do value, Bo value, and Po value. However, a process for structuring a light-shielding film is omitted when the PDo value, PBo value, and PPo value of the light-shielding pattern film 25 are not measured. Additionally, a surface of a measurement target is applied to the surface of the light-shielding pattern film 25, rather than being applied to the surface of the light-shielding film before structuring. Descriptions of the properties, composition and structure of the light-shielding pattern film 25 are overlapped with the description of the light-shielding film of a raw mask and are therefore omitted. Manufacturing process of a light-blocking film A manufacturing process for a raw mask according to an embodiment of the present description may include a preparation process of installing a transparent substrate, a sputtering target and a magnet within a sputtering chamber. A manufacturing process for a raw mask according to an embodiment of the present description may include a film formation process of injecting an atmospheric gas into a sputtering chamber, controlling the rotational speed of a magnet, supplying electrical power to the sputtering target and thereby forming a light-shielding film on the transparent substrate. A manufacturing process for a raw mask according to an embodiment of the present description may include a heat treatment process of thermal treatment for 5 to 30 minutes at 150 to 330°C. A manufacturing process for a raw mask according to an embodiment of the present description may include a cooling process of cooling the light-shielding film after passing through the heat treatment process. A manufacturing process for a raw mask according to an embodiment of the present description may include a stabilization process of stabilizing the raw mask after passing through the cooling process for 1 to 5 minutes at 30 to 50°C. The film formation process comprises a first light-shielding layer formation process to form a first light-shielding layer on a transparent substrate; and a second light-shielding layer formation process to form a second light-shielding layer on top of the first light-shielding layer. During the preparation process, when the light-shielding film is formed, a target can be selected based on the composition of the light-shielding film. A sputtering target containing a transition metal can be applied. The sputtering target can be applied by two or more targets, each containing a target containing a transition metal. The target containing a transition metal can contain 90 at% or more of the transition metal. The target containing a transition metal can contain 95 at% or more of the transition metal. The target containing a transition metal can contain 99 at% of the transition metal. The transition metal can include at least one of Cr, Ta, Ti, and Hf. The transition metal can include Cr. A description of the transparent substrate arranged in a sputtering chamber overlaps with the description above and is therefore omitted. During the preparation process, the magnet can be positioned in a sputtering chamber. The magnet can be placed on a surface opposite a surface of the sputtering target where sputtering occurs. In the light-shielding film formation process, the film formation process condition can be applied in such a way that it differs when each layer contained in the light-shielding film is formed into a film. This is particularly relevant when considering the extinction and etching properties of the light-shielding layers, and specific process conditions such as the composition of an atmospheric gas, the pressure in a chamber, the electrical power supplied to the sputtering target, the rotational speed of the magnet, the film formation time, the rotational speed of a substrate, and the like. The atmospheric gas can include an inert gas, a reactive gas, and a sputtering gas. The inert gas is a gas containing an element that does not form a thin film. The reactive gas is a gas containing an element that forms a thin film. The sputtering gas is a gas that is ionized in the plasma atmosphere and collides with a target. The inert gas can include helium. The reactive gas can include a gas containing nitrogen. The nitrogen-containing gas can be, for example, N₂, NO, NO₂, N₂O, N₂O₃, N₂O₄, N₂O₅, or the like. The reactive gas can include a gas containing oxygen. The oxygen-containing gas can be, for example, O₂, CO₂, or the like. The reactive gas can include a gas containing nitrogen and a gas containing oxygen. The reactive gas can include a gas containing both nitrogen and oxygen.The gas, which includes both nitrogen and oxygen, can be, for example, N2, NO, NO2, N2O, N2O3, N2O4, N2O5 or the like. The sputtering gas could be Ar gas. The power source that supplies electrical power to the sputtering target can be a DC power source or an RF power source. In the light-screening film formation process, the rotational speed of a magnet can be adjusted. This speed can influence the plasma distribution area formed within the sputtering chamber. Specifically, plasma tends to be closer to the sputtering target when the magnet's rotational speed is higher, and closer to the transparent substrate when the magnet's rotational speed is lower. Depending on the position where the plasma is generated in the sputtering chamber, the density of the resulting thin film can vary. Since plasma is generated closer to the sputtering target, the number of collisions between argon ions and the target surface is relatively increased, and the thin film tends to be denser. By controlling the rotational speed of a magnet while taking these plasma characteristics into account, the densities of the first and second light-shielding layers formed in the light-shielding film can be adjusted relatively easily. In the first light-shielding layer formation process, the electrical power supplied to a sputtering target can be set to 1.5 to 2.5 kW. In the first light-shielding layer formation process, the electrical power supplied to a sputtering target can be set to 1.6 to 2 kW. In the first light-shielding layer formation process, the ratio of the reactive gas flow rate to the inert gas flow rate in the atmospheric gas can be 1.5 to 3. The ratio can be 1.8 to 2.7. The ratio can be 2 to 2.5. The ratio of oxygen to nitrogen in the reactive gas can be 1.5 to 4. The ratio of oxygen to nitrogen in the reactive gas can be 2 to 3. The ratio of oxygen to nitrogen in the reactive gas can be 2.2 to 2.7. In such a case, the first light-blocking layer can help the light-blocking film exhibit sufficient extinction characteristics. Furthermore, the etching characteristics of the first light-blocking layer can be controlled, and the first light-blocking layer can, after being structured, help the side face of the light-blocking film pattern to have a shape that is nearly perpendicular to the surface of the transparent substrate. In the first light-shielding layer formation process, the rotation of a magnet can be applied at 90 to 140 rpm. Alternatively, in the first light-shielding layer formation process, the rotation of a magnet can be applied at 100 to 120 rpm. In such a case, the etch rate of the first light-shielding layer can be improved. The film formation time for the first light-blocking layer can be 200 to 300 seconds. The film formation time for the first light-blocking layer can be 210 to 240 seconds. In such a case, the first light-blocking layer can help the light-blocking film to exhibit sufficient extinction characteristics. In the second light-shielding layer formation process, the electrical power supplied to a sputtering target can be set to 1 to 2 kW. Alternatively, the electrical power supplied to a sputtering target can be set to 1.2 to 1.7 kW. In such a case, the electrical power of the second light-shielding layer can help to achieve a density within a predetermined range. In the second light-shielding layer formation process, the ratio of the flow rate of a reactive gas to the flow rate of an inert atmospheric gas can be 0.3 to 0.8. The ratio can be 0.4 to 0.6. In the second light-shielding layer formation process, the ratio of oxygen to nitrogen in the reactive gas can be 0.3 or less. The ratio of oxygen to nitrogen in the reactive gas can be 0.1 or less. The ratio of oxygen to nitrogen in the reactive gas can be 0.001 or more. In such a case, the density of a second light-shielding layer is set, and the side surface of the light-shielding pattern film formed by structuring can have a profile that is relatively perpendicular to the surface of the transparent substrate. In the second light-shielding layer formation process, the rotational speed of a magnet can be adjusted. If the rotational speed of the magnet is controlled solely with the aim of suppressing excessive etching that can occur on the side surface of the second light-shielding layer within the light-shielding pattern film during the film structuring process, sputter particles originating from the sputtering target will not be deposited on the surface of the film formation target and may instead be redeposited on the sputtering target surface. These redeposited sputter particles can act as a particle source and may induce a deterioration in the resolution of a raw mask.The present invention controls the rotational speed of a magnet within a predetermined range in the second light-shielding layer formation process, thereby precisely adjusting the shape of the side surface profile of the light-shielding pattern film and effectively suppressing particle formation. In the second light-shielding layer formation process, the rotational speed of a magnet can be set to 100 to 150 rpm. Alternatively, in the second light-shielding layer formation process, the rotational speed of a magnet can be set to 110 to 140 rpm. In such a case, if the light-shielding film is structured, the side-surface profile of the light-shielding pattern film can be precisely adjusted, and the degradation of pattern resolution caused by particles can be suppressed. The film formation time of the second light-blocking layer can be set for 10 to 30 seconds. Alternatively, the film formation time of the second light-blocking layer can be set for 15 to 25 seconds. In such a case, the second light-blocking layer can help the side surface of the structured light-blocking film form an angle close to that which is perpendicular to the surface of the transparent substrate. In the heat treatment process, the light-blocking film can be treated with heat after the film formation process. Specifically, after the light-blocking film has formed, the substrate is placed in a heat treatment chamber, and then the heat treatment can be carried out. During the heat treatment process, the atmospheric temperature can range from 150 to 300 °C. The atmospheric temperature can range from 170 to 280 °C. The atmospheric temperature can range from 200 to 250 °C. The heat treatment process can last from 5 to 25 minutes. Alternatively, it can last from 10 to 20 minutes. In such cases, the internal stress that forms in the light-blocking film can be effectively reduced. Cooling can be applied within 2 minutes of completing the heat treatment process. In such a case, the growth of transition metal particles contained in the light-blocking film, caused by heating, can be suppressed. During the cooling process, the light-blocking film can be cooled using a cooling plate. Specifically, a cooling plate, set to a predetermined cooling temperature, is positioned against the side of the transparent substrate of the raw mask after the heat treatment process to cool the raw mask. A gap can be created between the raw mask and the cooling plate to control the cooling rate of the raw mask. During the cooling process, the cooling temperature applied to the cooling plate can range from 10 to 40 °C. The cooling temperature can range from 20 to 30 °C. The cooling process can be carried out for 5 to 20 minutes. The cooling process can take 10 to 15 minutes. During the cooling process, the distance between the raw mask and the cooling plate can range from 0.01 to 30 mm. The distance can range from 0.05 to 5 mm. The distance can range from 0.1 to 2 mm. During the cooling process, the cooling rate of the raw mask can range from 0.45 to 1 °C / s. The cooling rate can range from 0.5 to 0.8 °C / s. In such a case, damage to the light-shielding film caused by cooling can be substantially suppressed, and deterioration of the durability of respective layers within the light-shielding film caused by the growth of particles of a transition metal contained in the light-shielding film after heat treatment can be effectively suppressed. The stabilization process stabilizes the raw mask after cooling. Significant damage can occur to the raw mask after cooling due to rapid temperature changes. To prevent this, a stabilization process may be necessary. The method for stabilizing the raw mask after cooling can vary. For example, the raw mask is removed from the cooling plate after cooling and then left at room temperature for a certain period. Alternatively, the raw mask is removed from the cooling plate after cooling and stabilized at 30 to 50 °C for 1 to 5 minutes. During this time, the raw mask can be rotated at 20 to 50 rpm. Another example is to inject a non-reactive gas into the raw mask at a flow rate of 5 to 10 L / min for 1 to 5 minutes after cooling. During this time, the non-reactive gas can reach a temperature of 20 to 40 °C. Manufacturing process of a semiconductor element A manufacturing process for a semiconductor element comprises a preparation process of arranging a light source, a photomask and a semiconductor wafer on which a resist film has been applied; an exposure process of selectively transferring light incident from the light source onto the semiconductor wafer through the photomask; and a development process of developing a pattern on the semiconductor wafer. The photomask comprises a transparent substrate and a light-blocking pattern film arranged on the transparent substrate. The light-shielding pattern film comprises a transition metal and at least one of the elements oxygen and / or nitrogen. The light-shielding pattern film comprises a first light-shielding film and a second light-shielding film arranged on top of the first light-shielding film. The light-shielding pattern film has an Rd value according to equation 1 below, which is between 0.4 and 0.8. In equation 1, the er1 value is an etch rate of the first light-shielding layer, measured by etching with argon gas. The er2 value is an etch rate of the second light-shielding layer, measured by etching with argon gas. In the preparation process, the light source is a device capable of generating exposure light with a short wavelength. This exposure light can have a wavelength of 200 nm or less. It can also be ArF light with a wavelength of 193 nm. A lens can be additionally positioned between a photomask and a semiconductor wafer. The lens serves to miniaturize the shape of a photomask circuit pattern and transfer it to the semiconductor wafer. The lens is not limited if it can be applied to a standard ArF semiconductor wafer during exposure. For example, the lens can be composed of calcium fluoride (CaF₂). During the exposure process, an exposure light can be transferred to the semiconductor wafer through a photomask. In such a case, a chemical transformation can occur in the section where the exposure light enters the resist film. In the development process, a pattern on the semiconductor wafer can be developed by treating the wafer with a developing solution after exposure. If the applied resist film is a positive resist, the area where exposure light falls within the resist film can be resolved by the developing solution. If the applied resist film is a negative resist, the area where exposure light does not fall can be resolved by the developing solution. The resist film is thus formed into a resist pattern by the developing solution treatment. A pattern can be created on the semiconductor wafer by using the resist pattern as a mask. The description of a photomask overlaps with the description above and is therefore omitted. The following section provides a more detailed description of specific exemplary embodiments. Manufacturing example: Formation of the light-blocking film Example 1: A transparent quartz substrate measuring 6 inches wide, 6 inches long, and 0.25 inches thick was placed in a chamber of a DC sputtering device. A chrome target was positioned in the chamber to establish a T / S distance of 255 mm and an angle of 25 degrees between the substrate and the target. A magnet was installed on the back of the chrome target. Then, an atmospheric gas in which Ar was mixed at 21 vol.%, N2 at 11 vol.%, CO2 at 32 vol.% and He at 36 vol.% was introduced into the chamber, electrical power supplied to the sputtering target was set to 1.85 kW, the rotational speed of the magnet was set to 113 rpm, and a sputtering process was carried out for 250 seconds, forming a first light-shielding layer. After the formation of the first light-shielding layer, an atmospheric gas in which Ar of 57 vol.% and N2 of 43 vol.% had been mixed was introduced into the chamber, electrical power supplied to a sputtering target was set to 1.5 kW, the rotational speed of a magnet was set to 113 rpm, a sputtering process was carried out for 25 seconds, and a raw mask sample in which a second light-shielding layer had been formed was produced. The sample, after the formation of the second light-shielding layer, was placed in a heat treatment chamber. The atmospheric temperature was then increased to 250 °C, and heat treatment was carried out for 15 minutes. After heat treatment, the raw mask was removed from the chamber and rotated for 2 minutes at an atmospheric temperature of 40 °C and a speed of 30 rpm. A cooling plate, pre-set to a temperature of 10 to 40 °C, was installed on the transparent substrate side of the raw mask. The gap between the transparent substrate and the cooling plate was set to 0.1 mm. The cooling process was carried out for 5 to 20 minutes. Example 2: A raw mask sample was prepared under the same conditions as Example 1. However, a gas in which Ar was mixed at 19 vol%, N2 at 11 vol%, CO2 at 36 vol% and He at 34 vol% was applied as the atmosphere when the first light-shielding layer was formed. Example 3: A raw mask sample was prepared under the same conditions as in Example 1. However, a gas mixture containing 17 vol% Ar, 24 vol% N₂, 29 vol% CO₂, and 30 vol% He was applied as the atmosphere when the first light-shielding layer was formed. Additionally, the distance between the substrate surface of the raw mask and the cooling plate was set to 2 mm when the raw mask sample was cooled. Example 4: A raw mask sample was produced under the same conditions as in Example 2. However, the rotational speed of a magnet was set to 127 rpm when a second light-shielding layer was formed. Additionally, the distance between the raw mask substrate and the cooling plate was set to 2 mm when the raw mask sample was cooled. Example 5: A raw mask sample was produced under the same conditions as Example 4. However, the rotational speed of a magnet was set to 131 rpm when a first light-shielding layer was formed. Example 6: A raw mask sample was prepared under the same conditions as Example 2. However, the distance between the substrate surface of the raw mask and the cooling plate was set to 5 mm when the raw mask sample was cooled. Comparative example 1: A raw mask sample was produced under the same conditions as Example 1. However, an atmospheric gas with Ar of 44 vol% and N2 of 56 vol% was used when the second light-shielding layer was formed. Comparative example 2: A raw mask sample was produced under the same conditions as example 2. However, the rotational speed of a magnet was set to 89 rpm when the second light-shielding layer was formed. Comparative example 3: A raw mask sample was produced under the same conditions as in example 2. However, when the raw mask sample was cooled, the distance between the substrate surface of the raw mask and the cooling plate was set to 10 mm. Comparative example 4: A raw mask sample was produced under the same conditions as in example 2. However, when the raw mask sample was cooled, the distance between the substrate surface of the raw mask and the cooling plate was set to 20 mm. The conditions for film formation, heat treatment and cooling of the respective examples and comparison examples are described in Table 1 below. Example of evaluation: Measurement of the Rd value of the light-blocking film Samples were prepared using examples and comparison samples to achieve a size of 15 mm vertically and horizontally. The surfaces of the prepared samples were treated with focused ion beam (FIB) irradiation, then mounted in a JEM-2100F HR model fixture (available from JEOL LTD Corporation), and thermal imaging (TEM) images of the samples were taken. The thicknesses of the first and second light-shielding layers were measured from the TEM images. The samples were then etched with argon gas, and the etching times of the first and second light-shielding layers were measured. The samples were arranged in the K-alpha model available from Thermo Scientific Corporation. The 4 mm wide by 2 mm long area placed in the center of each sample was etched with argon gas, and the etching time of each layer was measured. During the measurement of each layer's etching time, a vacuum of 1.0 × 10⁻⁸ mbar, an X-ray source from the AI ​​K α monochromator (1486.6 eV), an electrical anode power of 72 W, an anode voltage of 12 kV, and an argon ion beam voltage of 1 kV were applied. The er1 value, er2 value, and Rd value were calculated from the measured thicknesses and etching rates of the first and second light-shielding layers. Examples and comparisons of er1, er2, and Rd values ​​are described in Table 2 below. Evaluation example: Measurement of the optical properties of the light-blocking film The Bo value, as optical density and transmittance for an exposure light with a wavelength of 193 nm, was measured from the surface of the light-shielding film of the sample of each example or comparison example using the MG-Pro model available from Nano View Corporation. Subsequently, a light-shielding pattern film was formed by structuring the light-shielding film. The Po value was measured using an exposure light with a wavelength of 193 nm, employing the MG-Pro model available from Nano View Corporation, within a measurement range corresponding to an area from an edge formed by structuring to a position spaced 4 nm inward along the light-shielding pattern film when viewed from the top surface. The Do value was calculated from the Bo value and the Po value. The Do value, the Bo value, the Po value and the transmittance for light with a wavelength of 193 nm, measured according to examples and comparison examples, are described in Table 2 below. Example of evaluation: Measurement of the etching characteristics of the light-blocking film A TEM image of the light-shielding film contained in a sample of each example or comparison sample was acquired to measure the film thickness. The sample was prepared to measure 15 mm vertically and horizontally. One surface of the prepared sample was treated with FIB (Focused Ion Beam) irradiation and then placed in a JEM-2100F HR model fixture, available from JEOL LTD. A TEM image of the sample was then acquired, and the light-shielding film thickness was measured from the TEM image. The etching time of the light-blocking film, measured by etching with a chlorine-based gas, was then determined. The chlorine-based gas consisted of 90–95 vol% chlorine and 5–10 vol% oxygen. The etch rate of the light-blocking film, measured by etching with the chlorine-based gas, was calculated from the film's thickness and the etching time. The measured values ​​of the etching rates according to examples and comparison examples are described in Table 2 below. Evaluation example: Measurement of the pattern edge loss area of ​​the light-blocking film A light-shielding pattern film was formed by sampling the light-shielding film from each sample or reference sample. The substrate containing the light-shielding pattern film was then prepared to a size of 15 mm vertically and horizontally. The sample surface was treated with focused ion beam (FIB) irradiation, then mounted in a JEM-2100F HR model fixture available from JEOL LTD, and the TEM image of the sample was measured. Subsequently, in a side surface profile of the light shielding pattern film observed by the TEM image, when a total height of the light shielding pattern film was set to 100%, the point placed at a height of 20% on the side surface profile and the point placed at a height of 40% on the side surface profile were defined, and a first line, which was an extended line to connect both points, was defined. An intersection point of a line passing through a center of the light-shielding pattern film and an upper surface profile of the light-shielding pattern film observed by the TEM image was defined, and a second line encompassing the intersection point and positioned parallel to an upper boundary of the transparent substrate was defined. A pattern edge loss area, which was an area enclosed by the first line, the second line and a profile of the light-shielding pattern film, was measured from the TEM image. The sample edge loss areas, measured according to examples and comparison examples, are described in Table 2 below. [Table 1] [Table 1] Example 1: First light-shielding layer 250113211132360.10.6 Second light-shielding layer 25113574300 Example 2 First light-shielding layer 250113191136340,10,6 Second light-shielding layer 25113574300 Example 3 First light-shielding layer 2501131724293020.6 Second light-shielding layer 25113574300 Example 4 First light-shielding layer 2501131911363420.6 Second light-shielding layer 25127574300 Example 5 First light-shielding layer 2501131911363420.6 Second light-shielding layer 25131574300 Example 6 First light-shielding layer 2501131911363450.5 Second light-shielding layer 25113574300 Comparison example 1: First light-shielding layer 250113211132360.10.6 Second light-shielding layer 25113445600 Comparison example 2: First light-shielding layer 250113191136340.10.6 Second light-shielding layer 2589574300 Comparison example 3 First light-shielding layer 25011319113634100.4 Second light-shielding layer 25113574300 Comparison example 4: First light-shielding layer 25011319113634200.2 Second light-shielding layer 25113574300 [Table 2] [Table 2] Example 10,7670,4270,5570,041,881,841,3181,77,932 Example 20,6920,4300,6210,031,851,821,4121,76,680 Example 30,6500,4300,6610,021,821,801,5261,75,967 Example 40,6620,4110,6210,031,861,831,3781,66,162 Example 50,6500,4040,6220,031,871,841,3561,65,957 Example 60,6940,4300,6200,031,851,821,4111,77,566 Comparison example: 11,085, 0.602, 0.555, 0.091, 851, 761, 4131, 713, 318 Comparative example: 20,829, 518, 625, 051, 771, 721, 7121, 78, 988 Comparison example: 30.695, 30.43, 20.62, 20.07, 1.85, 1.78, 1.41, 61.71, 0.953 Comparison example: 40,700,4330,6190,081,851,771,4121,812,465 According to Table 2, the Rd values ​​of comparison examples 1 and 2 were shown as a value of less than 0.4 or more than 0.8, while the Rd values ​​of examples 1 to 6 were shown as a value of 0.4 to 0.8. For the Do value, all comparison examples showed a value of 0.05 or more, while examples 1 to 6 showed a value of less than 0.05. For permeability, comparative example 2 showed a value of 1.7% or more, while examples 1 to 6 showed a value of 1.55% or less. For etch rate, all example and comparison examples showed a value of 1.6 Å / s or more. For a sample edge loss area, all comparison examples showed a value of 8.5 nm2 or more, while examples 1 to 6 showed a value of 8 nm2 or less. REFERENCE MARK LIST 100 Raw mask 10 Transparent substrate 20 Light-shielding film 21 First light-shielding layer 22 Second light-shielding layer 30 Phase-shifting film 150 Mask formed by structuring a light-shielding film from a raw mask as a measurement target 23 Light-shielding pattern film obtained by structuring a light-shielding film from a raw mask as a measurement target 200 Photomask 25 Light-shielding pattern film Le An edge formed by structuring from the light-shielding pattern film L1 First line L2 Second line L0 Center line of the pattern film P1 First point P2 Second point Pc Center point of the pattern film Pi Intersection point of the pattern film Ap Loss area of ​​the pattern edge Am measuring area

Claims

Raw mask (100) comprising: a transparent substrate (10) and a light-shielding film (20) arranged on the transparent substrate (10), wherein the light-shielding film (20) comprises a transition metal and at least one of the elements oxygen and / or nitrogen, wherein the light-shielding film (20) comprises a first light-shielding layer (21) and a second light-shielding layer (22) arranged on the first light-shielding layer (21), and wherein the light-shielding film (20) has an Rd value according to Rd = er 2 er 1 exhibits a value of 0.4 to 0.8, whereby the 1 -value is an etch rate of the first light-shielding layer (21) measured by etching with argon gas, and he 2 -value is an etch rate of the second light shielding layer (22) which is measured by etching with argon gas. Raw mask (100) according to claim 1 , wherein the er2 value is 0.4 to 0.5 Å / s. Raw mask (100) according to claim 1, wherein the er1 value is 0.51 Å / s or more. Raw mask (100) according to claim 1, wherein the Do value of the light-shielding film (20) according to D o = B o − P o less than 0.05, where the Bo value is an optical density of the light-shielding film (20) for a light with a wavelength of 193 nm, and when a light-shielding pattern film (25) formed by structuring the light-shielding film (20) is observed on an upper surface, the Po value is an optical density for a light with a wavelength of 193 nm of a measurement area corresponding to a region from an edge of the light-shielding pattern film (25) to a position spaced 4 mm from the edge in the direction of the inside of the light-shielding pattern film (25). Raw mask (100) according to claim 1, wherein the transition metal comprises one of Cr, Ta, Ti and Hf. Raw mask (100) according to claim 1 or 4, wherein an etch rate of the light shielding film (20), measured with chlorine-based gas, is 1.55 Å / s or more. Photomask (200) comprising a transparent substrate (10) and a light-shielding pattern film (25) arranged on the transparent substrate (10), wherein the light-shielding pattern film (25) comprises a transition metal and at least one of the elements oxygen and / or nitrogen, wherein the light-shielding pattern film (25) comprises a first light-shielding layer (21) and a second light-shielding layer (22) arranged on the first light-shielding layer (21), and wherein the light-shielding pattern film (25) has an Rd value according to Rd = er 2 er 1 exhibits a value of 0.4 to 0.8, whereby the 1 -value is an etch rate of the first light-shielding layer (21) measured by etching with argon gas, and he 2 -value is an etch rate of the second light shielding layer (22) which is measured by etching with argon gas. Photomask (200) according to claim 7, wherein a pattern edge loss area of ​​the light-shielding pattern film (25) is 10 nm2 or less when the light-shielding pattern film (25) is observed at the section. Manufacturing process of a semiconductor element, comprising: a preparation process of arranging a light source, a photomask (200) and a semiconductor wafer in which a resist film has been applied; an exposure process of selectively transferring light incident from the light source onto the semiconductor wafer through the photomask (200);and a development process of developing a pattern on the semiconductor wafer, wherein the photomask (200) comprises a transparent substrate (10) and a light-shielding pattern film (25) arranged on the transparent substrate (10), wherein the light-shielding pattern film (25) comprises a transition metal and at least one of the elements oxygen and / or nitrogen, wherein the light-shielding pattern film (25) comprises a first light-shielding layer (21) and a second light-shielding layer (22) arranged on the first light-shielding layer (21), and wherein the light-shielding pattern film (25) has an Rd value according to R d = er 2 er 1; exhibits a value of 0.4 to 0.8, whereby the 1 -value is an etch rate of the first light-shielding layer (21) measured by etching with argon gas, and he 2 -value is an etch rate of the second light shielding layer (22) which is measured by etching with argon gas.

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