TWI677437B - Phase shift mask base, manufacturing method of phase shift mask, and display device manufacturing method - Google Patents

Abstract

The present invention provides a phase shift mask substrate, which is used to form a phase shift mask for a display device having excellent pattern cross-sectional shape and excellent CD uniformity and forming a fine pattern. . A phase shift film containing a chromium-based material provided on a transparent substrate has a phase shift layer, a reflectance reduction layer, and a wavelength region between 350 nm and 436 nm, which is provided between the phase shift layer and the reflectance reduction layer. A metal layer having a higher extinction coefficient than a reflectance-reduced layer, and the phase shift film's transmittance and phase difference for exposure light satisfy specific optical characteristics necessary as a phase shift film, and The film surface reflectance of the offset film is 10% or less in a wavelength region of 350 nm to 436 nm.

Description

Phase shift mask base, manufacturing method of phase shift mask, and display device manufacturing method

The present invention relates to a method for manufacturing a phase shift mask substrate, a phase shift mask using the same, and a method for manufacturing a display device.

In recent years, as display devices such as FPD (Flat Panel Display, flat panel display) have become high-resolution and high-definition, an excellent pattern cross-sectional shape and excellent CD (crystal display) uniformity and Phase shift masks for display devices with fine patterns. In addition, affected by the lower cost of display devices such as FPDs, it is necessary to reduce the manufacturing cost of phase shift masks. In the case of the previous phase shift mask substrate on which the light-shielding film was formed on the phase shift film, the light-shielding film was etched by using the resist film pattern as a mask to form a light-shielding film pattern. The phase shift film is etched with the protective film pattern as a mask to form a phase shift film pattern. Thereafter, the resist film pattern is peeled off, and the light-shielding film pattern is peeled off to produce a phase shift film having the phase shift film pattern. Shift the hood. On the other hand, in the case where the phase shift mask substrate on which the light-shielding film is not formed on the phase shift film, the step of forming the light-shielding film pattern on the phase shift film and the step of peeling are not necessary, thereby reducing the manufacturing cost. . Corresponding to such a situation in recent years, a phase shift mask substrate without a light-shielding film formed on the phase shift film is required to have an excellent pattern cross-sectional shape and excellent CD uniformity, and a fine pattern is formed. Phase shift masks for display devices. For example, Patent Document 1 proposes a phase shift mask substrate for a display device including a phase shift film having a structure in which two or more thin films are laminated on a transparent substrate. Although the thin films constituting the phase shift film have different compositions from each other, they include substances that can be etched by the same etching solution, and have different etching rates due to different compositions. In Patent Document 1, when the phase shift film is patterned, the etching rate of each thin film constituting the phase shift film is adjusted so that the cross section of the edge portion of the phase shift film pattern is formed steeply. Furthermore, Patent Document 1 proposes a method for disposing a pattern including a light-shielding film, a semi-transmissive film, an etching stopper film, and a hard mask film above or below the phase inversion film. A phase shift mask substrate for a display device of a functional film with one or more of the films. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2014-26281

[Problems to be Solved by the Invention] The phase shift film used in the phase shift mask for display devices previously proposed does not take into consideration the pattern of the resist film used for forming the phase shift film pattern during patterning. The laser used is designed to describe the effect on the resist film caused by the reflection of light. Therefore, the phase-reflection film has a film surface reflectance of more than 20% for laser drawing light. As a result, standing waves are generated in the resist film, and the CD uniformity of the resist film pattern is deteriorated. Even the phase uniformity of the phase shift film pattern formed by patterning the resist film pattern as a mask cannot satisfy the recent years. Situation of required value. Therefore, the present invention has been made in view of the above problems, and an object thereof is to provide a phase for reducing the reflectance of the film surface of light in a wavelength range of 350 nm to 436 nm used as laser drawing light. Shift film to form a phase shift mask base for a phase shift mask for a display device having excellent pattern cross-sectional shape and excellent CD uniformity and forming a fine pattern, and phase shift light using the same Manufacturing method of the cover. Furthermore, an object of the present invention is to provide a high-resolution, high-definition display device by using a phase shift mask for a display device having excellent pattern cross-sectional shape and excellent CD uniformity and forming a fine pattern. Production method. [Technical means to solve the problem] The present inventors conducted diligent research in order to achieve the above-mentioned object, and obtained the following insight: The phase shift film can be composed of at least three layers, and the composition or film of each layer constituting the phase shift film can be designed. Thick, while making the phase shift film transmittance and phase difference to the exposure light satisfy the specific optical characteristics required as a phase shift film, while making the phase shift film to light in the wavelength range of 350 nm to 436 nm The film surface reflectance decreases. This invention is based on this knowledge, and has the following structures. (Composition 1) A phase shift mask substrate characterized in that it is provided on a transparent substrate with a phase shift film containing a chrome-based material, and the phase shift film has: a phase shift layer, which mainly has The function of adjusting the transmittance and phase difference of the exposure light; the reflectance reducing layer is arranged on the upper side of the phase shift layer and has the function of reducing the reflectance of the light incident from the phase shift film side; The metal layer is disposed between the phase shift layer and the reflectance reducing layer, and has a higher extinction coefficient than the reflectance reducing layer in a wavelength region of 350 nm to 436 nm; The phase shift layer, the metal layer, and the reflectance reduction layer have a laminated structure. The phase shift film has specific optical characteristics with respect to transmittance and phase difference of the exposure light. The film surface reflectance of the light incident on the shift film side is 10% or less in a wavelength region of 350 nm to 436 nm. (Composition 2) A phase shift mask substrate characterized in that it is provided on a transparent substrate with a phase shift film containing a chrome-based material, and the phase shift film has: a phase shift layer, which mainly has The function of adjusting the transmittance and phase difference of the exposure light; the reflectance reducing layer is arranged on the upper side of the phase shift layer and has the function of reducing the reflectance of the light incident from the phase shift film side; The metal layer is disposed between the phase shift layer and the reflectance reducing layer, and has a chromium content higher than the chromium content of the reflectance reducing layer. With the phase shift layer and the metal, Layer and the reflectance reducing layer, the phase shift film has specific optical characteristics for the transmittance and phase difference of the exposure light, and the phase shift film is a film for light incident from the phase shift film side The surface reflectance is 10% or less in a wavelength range of 350 nm to 436 nm. (Structure 3) The phase shift mask base according to Structure 1 or 2 is characterized in that the fluctuation range of the film surface reflectance of the phase shift film is 5% or less in a wavelength region of 350 nm to 436 nm. (Structure 4) The phase shift mask base according to Structure 1 or 2, characterized in that the film surface reflectance of the phase shift film is 13% or less in a wavelength region of 313 nm to 436 nm. (Structure 5) The phase shift mask base according to Structure 4, characterized in that the fluctuation range of the film surface reflectance of the phase shift film is 10% or less in a wavelength range of 313 nm to 436 nm. (Structure 6) The phase shift mask base according to any one of Structures 1 to 5, wherein a light-shielding film pattern is provided between the transparent substrate and the phase shift film. (Composition 7) A method for manufacturing a phase shift mask, which is characterized by having the following steps: on the above-mentioned phase shift film of the phase shift mask base described in any one of 1 to 6, by using Forming a resist film pattern with a drawing process and a development process of laser light having a wavelength selected from a wavelength region of 350 nm to 436 nm; and performing the phase shift film with the resist film pattern as a mask Etching forms a phase shift film pattern on the transparent substrate. (Structure 8) A method for manufacturing a display device, which comprises the following steps: placing a phase shift mask manufactured by the manufacturing method described in Structure 7 on a mask stage of an exposure device; The light shifting cover irradiates the exposure light, and transfers the phase shift film pattern to a resist film formed on a display device substrate. (Structure 9) The manufacturing method of the display device according to Structure 8, wherein the exposure light is a composite light including light having a plurality of wavelengths selected from a wavelength range of 313 nm to 436 nm. [Effects of the Invention] As described above, the phase shift mask base of the present invention is a phase shift film containing a chromium-based material provided on a transparent substrate, and has a phase shift layer, a reflectance reduction layer, and a phase shift layer. A metal layer having a higher extinction coefficient than the reflectance-reduced layer in the wavelength region of 350 nm to 436 nm between the transfer layer and the reflectivity-reduced layer, and the phase shift film's transmittance and The phase difference satisfies specific optical characteristics required as a phase shift film, and the film surface reflectance of the phase shift film is 10% or less in a wavelength region of 350 nm to 436 nm. Therefore, the phase shift mask substrate can be used to manufacture a phase shift mask having excellent pattern cross-sectional shape and excellent CD uniformity and having a fine pattern formed. In addition, the phase shift mask can be used to manufacture a high-resolution and high-definition display device. In addition, another phase shift mask base of the present invention is a phase shift film containing a chromium-based material provided on a transparent substrate, and includes a phase shift layer, a reflectance reducing layer, and a phase shift layer and a reflectance. A metal layer having a higher chromium content than the reduced reflectance layer between the reduced layers, and the transmittance and phase difference of the phase shift film with respect to the exposure light satisfy the specific requirements for a phase shift film The optical characteristics of the phase shift film are 10% or less in the wavelength region of 350 nm to 436 nm. Therefore, the phase shift mask substrate can be used to manufacture a phase shift mask having excellent pattern cross-sectional shape and excellent CD uniformity and having a fine pattern formed. In addition, the phase shift mask can be used to manufacture a high-resolution and high-definition display device.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, the following embodiment is a form which embodies this invention, and does not limit this invention to this range. Furthermore, the same or equivalent parts may be denoted by the same symbols in the drawings, and the description thereof may be simplified or omitted. Embodiment 1. Embodiment 1 describes a phase shift mask base. FIG. 1 is a schematic view showing a film configuration of a phase shift mask substrate 10. The phase shift mask base 10 includes a transparent substrate 20 that is transparent to exposure light, and a phase shift film 30 made of a chromium-based material and disposed on the transparent substrate 20. When the transparent substrate 20 is set to have no surface reflection loss, it has a transmittance of 85% or more for the exposure light, and preferably a transmittance of 90% or more. The phase shift film 30 includes a phase shift layer 31, a metal layer 33, and a reflectance reduction layer 32 which are sequentially arranged from the transparent substrate 20 side. The phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 are each formed of a chromium-based material containing chromium (Cr). Therefore, the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 can be etched by the same etching solution. The phase shift layer 31 is disposed on the main surface of the transparent substrate 20. The phase shift layer 31 has a function of adjusting transmittance and phase difference with respect to exposure light. The phase shift layer 31 is formed of a chromium compound containing at least one of chromium (Cr), oxygen (O), and nitrogen (N). The phase shift layer 31 may be formed of a chromium compound containing at least one of chromium (Cr), oxygen (O), and nitrogen (N) and further containing at least one of carbon (C) and fluorine (F). . For example, examples of the material for forming the phase shift layer 31 include CrO, CrN, CrOFCrNF, CrON, CrCO, CrCN, CrOCN, CrFCO, and CrFCON. The phase shift layer 31 can be formed by sputtering. The reflectance reduction layer 32 is disposed on the upper side of the phase shift layer 31. The reflectance reduction layer 32 has a function of reducing the reflectance of light incident on the phase shift film 30 side (that is, the side of the reflectance reduction layer 32 opposite to the transparent substrate 20 side). The reflectance reduction layer 32 is formed of a chromium compound containing chromium (Cr) and oxygen (O). The reflectance reducing layer 32 may be formed of a chromium compound containing chromium (Cr) and oxygen (O) and further containing at least one of nitrogen (N), carbon (C), and fluorine (F). Examples of the material for forming the reflectance-reducing layer 32 include CrO, CrON, CrCO, CrOF, CrOCN, and CrFON. The reflectance reduction layer 32 can be formed by sputtering. The metal layer 33 is disposed between the phase shift layer 31 and the reflectance reduction layer 32. The metal layer 33 has a function of adjusting the transmittance with respect to the exposure light, and in combination with the reflectance reducing layer 32 has a function of reducing the reflectance with respect to light incident from the phase shift film 30 side. The metal layer 33 is formed of chromium (Cr) or a chromium compound containing at least one of chromium (Cr), carbon (C), and nitrogen (N). The metal layer 33 may be formed of a chromium compound containing at least one of chromium (Cr), carbon (C), and nitrogen (N), and further containing at least one of oxygen (O) and fluorine (F). Examples of the material for forming the metal layer 33 include Cr, CrC, CrN, CrCN, CrCO, and CrCF. Since the metal layer 33 is provided, the sheet resistance of the phase shift film is reduced, so that it is possible to prevent the phase shift mask base and the phase shift mask from being charged. When the metal layer 33 is not provided, the phase shift mask base and the electricity generated when the phase shift mask comes in and out of the housing will not escape, and the phase shift mask base and the phase shift mask will not escape. Medium power storage makes it easy for foreign matter to adhere. In addition, when a relatively small pattern is formed in the phase shift mask, it is easy for electricity to enter the pattern from the pattern and cause static electricity damage. The metal layer 33 can be formed by sputtering. The metal layer 33 has a higher extinction coefficient in the wavelength region of 350 nm to 436 nm than the extinction coefficient of the reflectance reduction layer 32. Moreover, it is preferable to have an extinction coefficient higher in the wavelength range of 313 nm-436 nm than the extinction coefficient of the reflectance reduction layer 32. The difference between the extinction coefficient of the metal layer 33 and the extinction coefficient of the reflectance reduction layer 32 is preferably 1.5 to 3.5, and more preferably 1.8 to 3.5. If the difference in extinction coefficient is 1.5 to 3.5, it is possible to increase the wavelength range of the interface between the metal layer 33 and the reflectance reduction layer 32 (the wavelength range of 350 nm to 436 nm or the wavelength range of 313 nm to 436 nm). The reflectance is more preferable because it can further exert the effect of reducing the reflectance. Furthermore, the metal layer 33 has a higher extinction coefficient in the wavelength region of 350 nm to 436 nm than the extinction coefficient of the offset layer 31. In addition, it is preferable that the wavelength range of 313 nm to 436 nm has an extinction coefficient higher than that of the offset layer 31. The extinction coefficient can be measured using an n & k analyzer, an ellipsometer, or the like. The metal layer 33 has a chromium (Cr) content rate (atomic%) higher than the chromium (Cr) content rate (atomic%) of the reflectance reduction layer 32. The difference between the Cr content rate of the metal layer 33 and the Cr content rate of the reflectance reduction layer 32 is preferably 10 to 80 atomic%, more preferably 15 to 80 atomic%. If the difference in Cr content is 10 to 80 atomic%, the above-mentioned wavelength region (a wavelength region of 350 nm to 436 nm or a wavelength region of 313 nm to 436 nm) of the interface between the metal layer 33 and the reflectance reduction layer 32 can be increased. ), It is preferable because the reflectance reduction effect can be further exerted. In addition, the etching rate of the metal layer 33 can be adjusted by making nitrogen (N), oxygen (O), carbon (C), and fluorine (F) contained in chromium (Cr) into a chromium compound. For example, the wet etching rate can be slowed by containing carbon (C) or fluorine (F) in chromium (Cr), and the nitrogen (N) or oxygen (O) can be contained in chromium (Cr) Speed up wet etching. The phase of the etched phase can be shifted by considering the wet etching speed of the phase shift layer 31 and the reflectance reduction layer 32 formed on the metal layer 33 and the reflectance reduction layer 32. The cross-sectional shape of the film 30 becomes favorable. In addition, the metal layer 33 has a chromium (Cr) content rate higher than that of the offset layer 31. The Cr content can be measured using an Auje electronic spectrometer, an X-ray photoelectron spectrometer (XPS), or the like. Each of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 preferably has a refractive index of 2.0 or more in a wavelength region of 350 nm to 436 nm. If it has a refractive index of 2.0 or more, the film thickness of the phase shift film 30 required for obtaining the required optical characteristics (transmittance and retardation) can be made thin. Therefore, a phase shift mask produced using the phase shift mask substrate 10 provided with the phase shift film 30 can have a phase shift film pattern having an excellent pattern cross-sectional shape and excellent CD uniformity. The refractive index can be measured using an n & k analyzer or an ellipsometer. With the laminated structure of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32, the phase shift film 30 has specific optical characteristics with respect to the transmittance and phase difference of the exposure light. The transmittance of the phase shift film 30 to the exposure light satisfies a value required as the phase shift film 30. The transmittance of the phase shift film 30 is preferably 1% to 20%, and more preferably 3% to 10% with respect to light of a specific wavelength (hereinafter, referred to as a representative wavelength) included in the exposure light. That is, when the exposure light is a composite light including light in a wavelength range of 313 nm to 436 nm, the phase shift film 30 has the above-mentioned transmittance for light of a representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i-line, h-line, and g-line, the phase shift film 30 has the above-mentioned transmittance for any of the i-line, h-line, and g-line. The phase difference of the phase shift film 30 with respect to the exposure light satisfies a value required as the phase shift film 30. The phase difference of the phase shift film 30 is preferably 160 ° to 200 °, and more preferably 170 ° to 190 ° with respect to light having a representative wavelength included in the exposure light. By this property, the phase of light having a representative wavelength included in the exposure light can be changed by 160 ° to 200 °. Therefore, a phase difference of 160 to 200 ° occurs between light having a representative wavelength transmitted through the phase shift film 30 and light having a representative wavelength transmitted through the transparent substrate 20 only. That is, when the exposure light is a composite light including light in a wavelength range of 313 nm to 436 nm, the phase shift film 30 has the above-mentioned phase difference with respect to light of a representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i-line, h-line, and g-line, the phase shift film 30 has the above-mentioned phase difference for any of the i-line, h-line, and g-line. The transmittance and phase difference of the phase shift film 30 can be controlled by adjusting the composition and thickness of each of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 constituting the phase shift film 30. Therefore, in this embodiment, the composition and thickness of each of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 are adjusted so that the transmittance and phase difference of the phase shift film 30 have the above-mentioned specific optical characteristics. . Moreover, the transmittance of the phase shift film 30 is mainly affected by the composition and thickness of the phase shift layer 31 and the metal layer 33. The refractive index of the phase shift film 30 is mainly affected by the composition and thickness of the phase shift layer 31. The transmittance and phase difference can be measured using a phase shift amount measuring device or the like. The film surface reflectance of the phase shift film 30 with respect to light incident from the side of the phase shift film 30 is 10% or less in a wavelength region of 350 nm to 436 nm. The wavelength range of 313 nm to 436 nm is preferably 13% or less. That is, it is preferable that the film surface reflectance of the phase shift film 30 with respect to light incident from the phase shift film 30 side is 10% or less in a wavelength range of 350 nm to 436 nm, and even if the wavelength range is expanded to 313 nm ～ 436 nm is also less than 13%. If the film surface reflectance of the phase shift film 30 is 10% or less in the wavelength range of 350 nm to 436 nm, the film surface reflectance of the laser drawing light is reduced, so that a phase having excellent CD uniformity can be formed. Offset mask. In addition, if the film surface reflectance of the phase shift film 30 is 13% or less in the wavelength region of 313 nm to 436 nm, the film surface reflectance with respect to the exposure light is reduced, and therefore the film formed in the phase shift mask During pattern transfer, it is possible to prevent blurring (flashing) of the transferred pattern due to reflected light from the display device substrate. The fluctuation range of the film surface reflectance of the phase shift film 30 is preferably 9% or less in the wavelength region of 350 nm to 436 nm, and more preferably 8.5% or less. The wavelength range of 313 nm to 436 nm is preferably 12.5% or less, and more preferably 12%. That is, it is preferable that the variation range of the film surface reflectance of the phase shift film 30 is 9% or less, and further 8.5% or less in the wavelength range of 350 nm to 436 nm, and it is preferable that the wavelength range is enlarged even if the wavelength range is enlarged. It is also 12.5% to 313 nm to 436 nm, and further to 12%. The film surface reflectance of the phase shift film 30 and its fluctuation range can be determined by the respective refractive indices, extinction coefficients, and thicknesses of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 constituting the phase shift film 30. Adjust and control. The extinction coefficient and refractive index can be controlled by adjusting the composition. Therefore, in this embodiment, the phase shift layer 31, the film surface reflectance of the phase shift film 30, and the variation range thereof are adjusted to have the specific physical properties described above. The composition and thickness of each of the metal layer 33 and the reflectance reduction layer 32. In addition, the film surface reflectance of the phase shift film 30 and its fluctuation range are mainly affected by the composition and thickness of each of the metal layer 33 and the reflectance reduction layer 32. The film surface reflectance can be measured using a spectrophotometer or the like. The variation range of the reflectance of the film surface can be obtained from the difference between the maximum reflectance and the minimum reflectance in the wavelength region of 350 nm to 436 nm or 313 nm to 436 nm. The phase shift layer 31 may be a case where a single film having a uniform composition is included, a case where a plurality of films having different compositions are included, or a case where a single film whose composition is continuously changed in the thickness direction is included. The same applies to the metal layer 33 and the reflectance reduction layer 32. FIG. 2 is a schematic view showing another film configuration of the phase shift mask base 10. As shown in FIG. 2, the phase shift mask base 10 may be one having a light-shielding film pattern 40 between the transparent substrate 20 and the phase shift film 30. When the phase shift mask base 10 includes a light-shielding film pattern 40, the light-shielding film pattern 40 is disposed on the main surface of the transparent substrate 20. The light-shielding film pattern 40 has a function of blocking the transmission of the exposure light. The material for forming the light-shielding film pattern 40 is not particularly limited as long as it has a function of blocking the transmission of exposure light. Examples include chromium-based materials. Examples of the chromium-based material include chromium (Cr) or a chromium compound containing at least one of chromium (Cr), carbon (C), and nitrogen (N). In addition, examples include a chromium compound containing at least one of chromium (Cr), oxygen (O), and fluorine (F), or at least one of chromium (Cr), carbon (C), and nitrogen (N) and further including A chromium compound of at least one of oxygen (O) and fluorine (F). Examples of the material for forming the light-shielding film pattern 40 include Cr, CrC, CrN, and CrCN. The light-shielding film pattern 40 can be formed by patterning a light-shielding film formed by sputtering by etching. In a portion where the phase shift film 30 and the light-shielding film pattern 40 are laminated, the optical density with respect to the exposure light is preferably 3 or more, and more preferably 3.5 or more. The optical density can be measured using a spectrophotometer or an OD (Optical Densitometer). The light-shielding film pattern 40 may be a case including a single film having a uniform composition, a case including a plurality of films having different compositions, or a case including a single film having a composition that continuously changes in thickness direction. In addition, the phase shift mask base 10 may be one having a resist film on the phase shift film 30. Next, a method for manufacturing the phase shift mask base 10 according to this embodiment will be described. The phase shift mask substrate 10 can be manufactured by performing the following preparation steps and a phase shift film formation step. Hereinafter, each step will be described in detail. 1. Preparation Step In the preparation step, first, the transparent substrate 20 is prepared. The material of the transparent substrate 20 is not particularly limited as long as the material is transparent to the exposure light used. Examples include synthetic quartz glass, soda lime glass, and alkali-free glass. When the phase shift mask base 10 provided with the light-shielding film pattern 40 is manufactured, thereafter, a light-shielding film containing a chromium-based material is formed on the transparent substrate 20 by sputtering, for example. Thereafter, a resist film pattern is formed on the light-shielding film, and the light-shielding film is etched using the resist film pattern as a mask to form a light-shielding film pattern 40. Thereafter, the resist film pattern is peeled. 2. Phase shift film forming step In the phase shift film forming step, a phase shift film 30 containing a chromium-based material is formed on the transparent substrate 20 by sputtering. Here, when the light-shielding film pattern 40 is formed on the transparent substrate 20, the phase shift film 30 is formed so as to cover the light-shielding film pattern 40. The phase shift film 30 is formed by forming a phase shift layer 31 on the main surface of the transparent substrate 20, a metal layer 33 on the phase shift layer 31, and a reflectance reduction layer 32 on the metal layer 33. form. The film formation of the phase shift layer 31 is performed using a sputtering target containing chromium or a chromium compound, for example, under a sputtering gas atmosphere containing a mixed gas of an inert gas and an active gas. The inert gas contains a material selected from the group consisting of helium and neon. At least one of the group consisting of argon, argon, krypton, and xenon, and the active gas includes a gas selected from the group consisting of oxygen, nitrogen, nitrogen monoxide, nitrogen dioxide, carbon dioxide, hydrocarbon, and fluorine. At least one of the group. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas. Similarly, the metal layer 33 is formed using a sputtering target containing chromium or a chromium compound, for example, an inert gas containing at least one selected from the group consisting of helium, neon, argon, krypton, and xenon. Performed under a sputtering gas atmosphere or a sputtering gas atmosphere containing a mixed gas of an inert gas and an active gas. The inert gas includes a gas selected from the group consisting of helium, neon, argon, krypton, and xenon. At least one of a group, the active gas contains at least one selected from the group consisting of oxygen, nitrogen, nitrogen monoxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon-based gas, and fluorine-based gas. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas. Similarly, the film formation of the reflectance reduction layer 32 is performed using a sputtering target containing chromium or a chromium compound, for example, under a sputtering gas atmosphere containing a mixed gas of an inert gas and an active gas, the inert gas containing At least one of the group consisting of: neon, argon, krypton, and xenon; the active gas includes a gas selected from the group consisting of oxygen, nitrogen, nitrogen monoxide, nitrogen dioxide, carbon dioxide, hydrocarbon, and fluorine At least one of the groups formed. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas. When the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 are formed, the composition and thickness of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 are based on the transmittance of the phase shift film 30. The phase difference and the phase difference have the specific optical characteristics described above, and the film surface reflectance of the phase shift film 30 and the variation range thereof are adjusted in such a manner as to have the specific physical properties described above. The composition of each of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 can be controlled by the composition and flow rate of the sputtering gas. The thickness of each of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 can be controlled by sputtering power, sputtering time, and the like. When the sputtering apparatus is a continuous sputtering apparatus, the thickness of each of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 can be controlled by the substrate transfer speed. When the phase shift layer 31 includes a single film having a uniform composition, the above-described film formation process is performed only once without changing the composition and flow rate of the sputtering gas. In the case where the phase shift layer 31 includes a plurality of films having different compositions, the composition and flow rate of the sputtering gas are changed at each film formation process to perform the above-mentioned film formation process a plurality of times. When the phase shift layer 31 includes a single film whose composition continuously changes in the thickness direction, the above-described film formation process is performed only while changing the composition and flow rate of the sputtering gas. The same applies to the film formation of the metal layer 33 and the film formation of the reflectance reduction layer 32. In the case of performing a plurality of film formation processes, the sputtering power applied to the sputtering target can be reduced. The phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 are preferably formed continuously using a continuous sputtering device without being exposed to the atmosphere by taking the transparent substrate 20 out of the device. Film formation can be continuously performed without taking it out of the device to prevent accidental surface oxidation or surface carbonization of each layer. Unexpected surface oxidation or surface carbonization of each layer causes laser light used for drawing a resist film formed on the phase shift film 30 or transfers a phase shift film pattern onto a display device substrate The reflectance of the exposure light used in the resist film may change, and the etching rate of the oxidized portion or the carbonized portion may change. When a phase shift mask substrate 10 including a resist film is manufactured, a resist film is then formed on the phase shift film. The phase shift mask base 10 of the first embodiment is a phase shift film 30 made of a chrome-based material provided on a transparent substrate 20, and includes a phase shift layer 31, a reflectance reduction layer 32, and a phase shift layer. The metal layer 33 having a higher extinction coefficient than the reflectance reduction layer 32 in a wavelength region between 350 nm and 436 nm between the 31 and the reflectance reduction layer 32, and the phase shift film 30 is The transmittance and phase difference of the exposure light satisfy specific optical characteristics required as the phase shift film 30. On the one hand, the film surface reflectance of the phase shift film 30 is 10% or less in a wavelength region of 350 nm to 436 nm. Therefore, the phase shift mask substrate 10 can be used to manufacture a phase shift mask having excellent pattern cross-sectional shape and excellent CD uniformity and having a fine pattern formed. The phase shift mask base 10 of the first embodiment is a phase shift film 30 containing a chrome-based material provided on a transparent substrate 20, and includes a phase shift layer 31, a reflectance reduction layer 32, and a phase shift layer. The metal layer 33 having a higher chromium content than the reflectance-reducing layer 32 between the shift layer 31 and the reflectance-reducing layer 32, and on the one hand the phase shift film 30's transmittance and The phase difference satisfies specific optical characteristics required as the phase shift film 30. On the one hand, the film surface reflectance of the phase shift film 30 is 10% or less in a wavelength region of 350 nm to 436 nm. Therefore, the phase shift mask substrate 10 can be used to manufacture a phase shift mask having excellent pattern cross-sectional shape and excellent CD uniformity and having a fine pattern formed. Embodiment 2. Embodiment 2 describes a method for manufacturing a phase shift mask. The phase shift mask substrate can be manufactured by performing the following resist film pattern formation steps and phase shift film pattern formation steps. Hereinafter, each step will be described in detail. 1. Resist film pattern forming step In the resist film pattern forming step, first, a resist film is formed on the phase shift film 30 of the phase shift mask base 10 of Embodiment 1. However, in the case where the phase shift mask substrate 10 is provided with a resist film on the phase shift film 30, the formation of the resist film is not performed. The material of the resist film is not particularly limited. It suffices to be a person who is sensitive to laser light having a wavelength selected from a wavelength range of 350 nm to 436 nm described later. The resist film may be either a positive type or a negative type. Thereafter, a specific pattern is drawn on the resist film using laser light having any wavelength selected from a wavelength range of 350 nm to 436 nm. Examples of the pattern drawn on the resist film include a line and gap pattern or a contact hole pattern. After that, the resist film is developed using a specific developing solution to form a resist film pattern on the phase shift film 30. 2. Phase shift film pattern forming step In the phase shift film pattern forming step, first, the phase shift film 30 is etched using the resist film pattern as a mask to form a phase shift film pattern. Each of the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 constituting the phase shift film 30 is formed of a chromium-based material containing chromium (Cr). Therefore, the phase shift layer 31, the metal layer 33, and the reflectance reduction layer 32 can be etched by using the same etching medium (etching solution, etching gas). The etching medium (etching solution, etching gas) for etching the phase shift film 30 is not particularly limited as long as it can selectively etch the phase shift film 30. Specific examples include an etching solution containing cerium ammonium nitrate and perchloric acid, or an etching gas containing a mixed gas of chlorine gas and oxygen. Thereafter, the resist film pattern is peeled using a resist stripping solution or by ashing. According to the manufacturing method of the phase shift mask of the second embodiment, a phase shift mask having excellent pattern cross-sectional shape and excellent CD uniformity and having a fine pattern formed can be manufactured. Embodiment 3. In Embodiment 3, the manufacturing method of a display device is demonstrated. The display device can be manufactured by performing the following mask mounting steps and pattern transfer steps. Hereinafter, each step will be described in detail. 1. Mounting step The mounting step is to place the phase shift mask manufactured in Embodiment 2 on a mask stage of an exposure device. Here, the phase shift mask is disposed so as to face the resist film formed on the display device substrate through the projection optical system of the exposure device. 2. Pattern transfer step The pattern transfer step irradiates the phase shift mask with exposure light, and transfers the phase shift film pattern to a resist film formed on a display device substrate. The exposure light is a composite light including a plurality of wavelengths of light selected from a wavelength range of 313 nm to 436 nm, or a single wavelength region selected by using a filter or the like from a wavelength range of 313 nm to 436 nm. Shade. For example, the exposure light is a composite light including i-line, h-line, and g-line, or a mixed light including j-ray, i-line, h-line, and g-line, or a monochromatic light of i-line. If composite light is used as the exposure light, the intensity of the exposure light can be increased to increase the output, so the manufacturing cost of the display device can be reduced. According to the method for manufacturing a display device according to the third embodiment, a high-resolution and high-definition display device can be manufactured. [Examples] Hereinafter, the present invention will be described more specifically based on examples and comparative examples. In addition, the following embodiment is an example of the present invention, and the present invention is not limited thereto. The phase shift mask bases of Examples 1 to 4 and Comparative Examples 1 to 3 are provided with a transparent substrate and a phase shift film containing a chromium-based material disposed on the transparent substrate. As the transparent substrate, a synthetic quartz glass substrate having a size of 800 mm × 920 mm and a thickness of 10 mm was used. FIG. 3 shows the film surface reflectance spectrum of the phase shift film of the phase shift mask substrates of Examples 1, 3, and 4. FIG. 4 shows the phase shift of the phase shift mask substrates of Comparative Examples 1 and 2. The film surface reflectance spectrum of the film. FIG. 5 shows the film surface reflectance spectrum of the phase shift film of the phase shift mask base of Comparative Examples 1 and 3. Hereinafter, Examples 1 to 4 and Comparative Examples 1 to 3 will be described in detail. Example 1. The phase shift film of the phase shift mask base of Example 1 includes a phase shift layer (CrOCN, film thickness 89 nm), a metal layer (CrC, film thickness 10 nm) sequentially arranged from the transparent substrate side. ), And a reflectance reduction layer (CrOCN, film thickness 30 nm). The phase shift layer (CrOCN) has a refractive index of 2.44 and an extinction coefficient of 0.71 at a wavelength of 313 nm, a refractive index of 2.51 and an extinction coefficient of 0.59 at a wavelength of 350 nm, and a refractive index of 2.52 and an extinction coefficient at a wavelength of 365 nm. Is 0.55, the refractive index is 2.54 and the extinction coefficient is 0.44 at a wavelength of 413 nm, and the refractive index is 2.54 and the extinction coefficient is 0.40 at a wavelength of 436 nm. The metal layer (CrC) has a refractive index of 2.14 at a wavelength of 313 nm and an extinction coefficient of 2.61, a refractive index of 2.24 at a wavelength of 350 nm and an extinction coefficient of 2.85, a refractive index at a wavelength of 365 nm of 2.29 and an extinction coefficient of 2.94 The refractive index at a wavelength of 413 nm is 2.52 and the extinction coefficient is 3.20, and the refractive index at a wavelength of 436 nm is 2.65 and the extinction coefficient is 3.3. The refractive index reduction layer (CrOCN) has a refractive index of 2.46 and an extinction coefficient of 0.47 at a wavelength of 313 nm, a refractive index of 2.47 and an extinction coefficient of 0.37 at a wavelength of 350 nm, and a refractive index of 2.47 and an extinction coefficient at a wavelength of 365 nm. It is 0.33, the refractive index at a wavelength of 413 nm is 2.43 and the extinction coefficient is 0.23, and the refractive index at a wavelength of 436 nm is 2.41 and the extinction coefficient is 0.20. The refractive index and extinction coefficient of the phase shift layer were measured using n & k Analyzer 1280 (trade name) manufactured by n & k Technology. The measurement of the refractive index and the extinction coefficient of the phase shift layer was performed on a synthetic quartz glass substrate with a sample formed under the same conditions as the film formation conditions of the phase shift layer shown below. The measurement of the refractive index and the extinction coefficient of the metal layer and the measurement of the refractive index and the extinction coefficient of the reflectance-reducing layer were performed in the same manner. The measurement was performed in the same manner in Examples 2 to 4 and Comparative Examples 1 to 3. The Cr content of the phase shift layer (CrOCN) was 32 atomic%, the Cr content of the metal layer (CrC) was 46 atomic%, and the Cr content of the reflectance reduction layer (CrOCN) was 28 atomic%. In addition, the Cr content was measured using a SAM670 scanning-type Ogilvy electronic spectrometer (trade name) manufactured by ULVAC-PHI. The measurement was performed in the same manner in Examples 2 to 4 and Comparative Examples 1 to 3. The phase shift film has a transmittance of 5.98% for a light of 365 nm and a phase difference of 178.66 ° by the above-mentioned three-layer structure. The transmittance and phase difference are measured using MPM-100 (trade name) manufactured by Japan Lasertec Corporation. The measurement was performed in the same manner in Examples 2 to 4 and Comparative Examples 1 to 3. The phase reflectance of the phase shift film is 12.0% at a wavelength of 313 nm, 8.3% at 350 nm, 7.3% at a wavelength of 365 nm, 6.6% at a wavelength of 405 nm, and 413 It has a wavelength of 6.6% in nm and 6.8% in a wavelength of 436 nm. In addition, the variation range of the film surface reflectance of the phase shift film is 1.7% in a wavelength region of 350 nm to 436 nm, 0.7% in a wavelength region of 365 nm to 436 nm, and a wavelength of 313 nm to 436 nm. In the region it is 5.5%. Curve a in FIG. 3 shows the film surface reflectance spectrum of the phase shift film of the phase shift mask substrate of Example 1. The film surface reflectance was measured using SolidSpec-3700 (trade name) manufactured by Shimadzu Corporation. The measurement was performed in the same manner in Examples 2 to 4 and Comparative Examples 1 to 3. The sheet resistance of the phase shift film is 508 Ω / □. Therefore, the phase shift mask substrate of Embodiment 1 can prevent charging. The sheet resistance was measured using K-705RM (trade name) manufactured by Kyowa Riken Co., Ltd. The measurement was performed in the same manner in Examples 2 to 4 and Comparative Examples 1 to 3. The phase shift mask substrate of Example 1 was manufactured by the following method. First, a synthetic quartz glass substrate is prepared as a transparent substrate. Mirror-polishing both major surfaces of the transparent substrate. The two main surfaces of the transparent substrates prepared in Examples 2 to 4 and Comparative Examples 1 to 3 were also mirror-polished in the same manner. Thereafter, the transparent substrate was carried into a continuous sputtering apparatus. A sputtering chamber is provided in the continuous sputtering device. After that, a sputtering power of 2.7 kW was applied to the chromium target disposed in the sputtering chamber, and Ar gas, N ₂ Gas and CO ₂ The mixed gas of the gas is introduced into the sputtering chamber, and the transparent substrate is conveyed at a speed of 200 mm / min. When the transparent substrate passed near the chromium target, a phase shift layer including CrOCN with a film thickness of 89 nm was formed on the main surface of the transparent substrate. Here, the mixed gas system has a flow rate of Ar of 35 sccm, N ₂ Becomes a flow of 35 sccm, CO ₂ A flow rate of 14.5 sccm was introduced into the sputtering chamber. After that, a sputtering power of 0.4 kW was applied to the chromium target, and Ar gas and CH ₄ Gas mixture (contains CH at 8% concentration in Ar gas) ₄ The gas mixture is introduced into the sputtering chamber at a flow rate of 100 sccm, and the transparent substrate is conveyed at a speed of 400 mm / min. When the transparent substrate passes near the chromium target, a metal layer with a thickness of 10 nm including CrC is formed on the phase shift layer. Thereafter, a sputtering power of 2.0 kW was applied to the chromium target, and Ar gas and N ₂ Gas and CO ₂ The mixed gas of the gas is introduced into the sputtering chamber, and the transparent substrate is conveyed at a speed of 200 mm / min. When the transparent substrate passes near the chromium target, a reflectance-reducing layer having a thickness of 30 nm including CrOCN is formed on the metal layer. Here, the mixed gas system has a flow rate of Ar of 35 sccm, N ₂ Becomes a flow of 35 sccm, CO ₂ It was introduced into the sputtering chamber at a flow rate of 18.2 sccm. Thereafter, a phase shift film including a phase shift layer (CrOCN, film thickness 89 nm), a metal layer (CrC, film thickness 10 nm), and a reflectance reduction layer (CrOCN, film thickness 30 nm) will be formed. The transparent substrate was taken out from the continuous sputtering apparatus and cleaned. Furthermore, the film formation of the phase shift layer, the film formation of the metal layer, and the film formation of the reflectance reduction layer are continuously performed in the continuous sputtering device without taking out the transparent substrate to the continuous sputtering. Outside the unit leads to exposure to the atmosphere. Using the phase shift mask substrate described above, a phase shift mask is manufactured by the following method. First, a resist film including a novolac-type positive photoresist is formed on the phase shift film of the phase shift mask substrate. Thereafter, a specific pattern is drawn on the resist film using laser light with a wavelength of 413 nm by a laser drawing machine. After that, the resist film is developed with a specific developing solution to form a resist film pattern on the phase shift film. Thereafter, the phase shift film is etched using the resist film pattern as a mask to form a phase shift film pattern. Each of the phase shift layer, the metal layer, and the reflectance reduction layer constituting the phase shift film is formed of a chromium-based material containing chromium (Cr). Therefore, the phase shift layer, the metal layer, and the reflectance reduction layer can be etched by the same etching solution. Here, as an etching solution for etching the phase shift film, an etching solution containing ceric ammonium nitrate and perchloric acid was used. After that, the resist film pattern was peeled using a resist stripping solution. The phase shift film pattern cross-section of the phase shift mask manufactured using the phase shift mask substrate described above has some corrosion in the metal layer located in the center portion of the film thickness direction of the phase shift film pattern, but it The extent to which the mask characteristics are affected. The phase shift film pattern cross section of the phase shift mask was observed using an electron microscope (JSM7401F (trade name) manufactured by Japan Electronics Co., Ltd.). The measurement was performed in the same manner in Examples 2 to 4 and Comparative Examples 1 to 3. The CD unevenness of the phase shift film pattern of the phase shift mask manufactured using the above phase shift mask substrate is relatively good and is 70 nm. The CD unevenness is an offset width from the target line and gap pattern (width of line pattern: 2.0 μm, width of gap pattern: 2.0 μm). The CD unevenness of the phase shift film pattern of the phase shift mask was measured using SIR8000 manufactured by Seiko Instruments Nano Technologies. The measurement was performed in the same manner in Examples 2 to 4 and Comparative Examples 1 to 3. The phase shift mask described above has excellent pattern cross-sectional shape and excellent CD uniformity, and the phase shift film pattern has a low reflectance to the film surface of the exposed light. Therefore, the phase shift mask can be used to manufacture a high resolution And high-definition display device. In addition, the phase shift mask can be manufactured using a phase shift mask substrate provided with a phase shift film having a small sheet resistance, so even when a small pattern is formed, it is difficult for electricity to enter the pattern from the pattern. It is not easy to cause static damage. Example 2. The phase shift film of the phase shift mask base of Example 2 includes a phase shift layer (CrOCN, film thickness 89 nm), a metal layer (CrC, film thickness 20 nm) sequentially arranged from the transparent substrate side. ), And a reflectance reducing layer (CrOCN, film thickness 30 nm). Only the metal layer is different from the phase shift mask substrate of Example 1. The values of the refractive index and the extinction coefficient of the phase shift layer (CrOCN) are the same as those of the first embodiment. The metal layer (CrC) has a refractive index of 2.09 and an extinction coefficient of 2.05 at a wavelength of 313 nm, a refractive index of 2.08 and an extinction coefficient of 2.18 at a wavelength of 350 nm, and a refractive index of 2.08 and an extinction coefficient of 2.24 at a wavelength of 365 nm. The refractive index at a wavelength of 413 nm is 2.11 and the extinction coefficient is 2.45, and the refractive index at a wavelength of 436 nm is 2.15 and the extinction coefficient is 2.55. The values of the refractive index and the extinction coefficient of the reflectance reduction layer (CrOCN) are the same as those of the first embodiment. The Cr content of the phase shift layer (CrOCN) and the reflectance reduction layer (CrOCN) are the same as those in Example 1. The Cr content of the metal layer (CrC) was 43 atomic%. The phase shift film has a transmittance of 5.78% for a light of 365 nm and a phase difference of 179.02 ° by the above three-layer structure. The phase shift film surface reflectance is 12.0% at a wavelength of 313 nm, 8.4% at 350 nm, 8.4% at a wavelength of 365 nm, 8.2% at a wavelength of 405 nm, and 413 nm. It was 8.4% in wavelength and 8.7% in 436 nm. In addition, the variation range of the reflectance of the phase shift film surface is 1.0% in a wavelength range of 350 nm to 436 nm, 0.6% in a wavelength range of 365 nm to 436 nm, and a wavelength of 313 nm to 436 nm. In the region it was 3.8%. The sheet resistance of the phase shift film is 560 Ω / □. Therefore, the phase shift mask substrate of Embodiment 2 can prevent charging. In Example 2, when forming a metal layer, a sputtering power of 0.33 kW was applied to a chromium target, and Ar gas and CH ₄ Gas mixture (containing 15% CH in Ar gas) ₄ The gas mixture is introduced into the sputtering chamber at a flow rate of 100 sccm, and the transparent substrate is conveyed at a speed of 400 mm / min. When the transparent substrate passes near the chromium target, a metal layer with a thickness of 20 nm including CrC is formed on the phase shift layer. Otherwise, the phase shift mask substrate of Example 2 was manufactured by the same method as that of Example 1. Using the phase shift mask substrate described above, a phase shift mask was manufactured by the same method as in Example 1. The phase shift film pattern cross-section of the phase shift mask manufactured using the phase shift mask substrate is vertical, and no corrosion occurs in the metal layer. The CD unevenness of the phase shift film pattern of the phase shift mask manufactured using the above phase shift mask substrate is relatively good and is 50 nm. The phase shift mask described above has excellent pattern cross-sectional shape and excellent CD uniformity, and the phase shift film pattern has a low reflectance to the film surface of the exposed light. Therefore, the phase shift mask can be used to manufacture a high resolution And high-definition display device. In addition, the phase shift mask can be manufactured using a phase shift mask substrate provided with a phase shift film having a small sheet resistance, so even when a small pattern is formed, it is difficult for electricity to enter the pattern from the pattern. It is not easy to cause static damage. Example 3. The phase shift film of the phase shift mask base of Example 3 includes a phase shift layer (CrOCN, film thickness 89 nm), a metal layer (CrCN, film thickness 22) sequentially arranged from the transparent substrate side. nm), and a reflectance reduction layer (CrOCN, film thickness 30 nm). Only the metal layer is different from the phase shift mask substrate of Example 1. The values of the refractive index and the extinction coefficient of the phase shift layer (CrOCN) are the same as those of the first embodiment. The metal layer (CrCN) has a refractive index of 2.07 and an extinction coefficient of 2.14 at a wavelength of 313 nm, a refractive index of 2.12 and an extinction coefficient of 2.28 at a wavelength of 350 nm, a refractive index of 2.14 and an extinction coefficient of 2.35 at a wavelength of 365 nm The refractive index at a wavelength of 413 nm is 2.26 and the extinction coefficient is 2.55, and the refractive index at a wavelength of 436 nm is 2.33 and the extinction coefficient is 2.64. The values of the refractive index and the extinction coefficient of the reflectance reduction layer (CrOCN) are the same as those of the first embodiment. The Cr content of the phase shift layer (CrOCN) and the reflectance reduction layer (CrOCN) are the same as those in Example 1. The Cr content of the metal layer (CrCN) is 40 atomic%. The phase shift film has a transmittance of 6.00% for a light of 365 nm and a phase difference of 176.78 ° by the above three-layer structure. The phase reflectance of the film surface is 13.0% at a wavelength of 313 nm, 9.5% at 350 nm, 8.4% at a wavelength of 365 nm, 7.6% at a wavelength of 405 nm, and 413 nm. The wavelength is 7.6% and the wavelength at 436 nm is 7.6%. The variation range of the phase shift film surface reflectance is 1.9% in a wavelength region of 350 nm to 436 nm, 0.8% in a wavelength region of 365 nm to 436 nm, and a wavelength of 313 nm to 436 nm. In the region it is 5.6%. Curve b in FIG. 3 shows the film surface reflectance spectrum of the phase shift film of the phase shift mask substrate of Example 3. The sheet resistance of the phase shift film is 800 Ω / □. Therefore, the phase shift mask substrate of Embodiment 3 can prevent charging. In Example 3, when a metal layer was formed, a sputtering power of 0.42 kW was applied to a chromium target, and Ar gas and CH ₄ Gas and N ₂ The mixed gas of the gas is introduced into the sputtering chamber, and the transparent substrate is conveyed at a speed of 400 mm / min. When the transparent substrate passed near the chromium target, a metal layer with a thickness of 22 nm including CrCN was formed on the phase shift layer. Here, the mixed gas system uses Ar gas and CH ₄ Gas mixture (containing 8% CH in Ar gas) ₄ Gas mixture) becomes 100 sccm, and N ₂ A flow rate of 30 sccm was introduced into the sputtering chamber. Otherwise, the phase shift mask substrate of Example 3 was manufactured by the same method as that of Example 1. The phase shift mask substrate was used, and a phase shift mask was manufactured by the same method as in Example 1. The phase shift film pattern section of the phase shift mask manufactured using the above phase shift mask substrate has some corrosion in the metal layer located at the center portion of the film thickness direction of the phase shift film pattern, but it does not affect The extent of the mask characteristics. The CD unevenness of the phase shift film pattern of the phase shift mask manufactured using the above phase shift mask substrate is relatively good and is 75 nm. The phase shift mask described above has excellent pattern cross-sectional shape and excellent CD uniformity, and the phase shift film pattern has a low reflectance on the film surface of the exposed light. Therefore, the phase shift mask can be used to manufacture a high resolution And high-definition display device. In addition, the phase shift mask can be manufactured using a phase shift mask substrate provided with a phase shift film having a small sheet resistance, so even when a small pattern is formed, it is difficult for electricity to enter the pattern from the pattern. It is not easy to cause static damage. Example 4. The phase shift film of the phase shift mask base of Example 4 includes a phase shift layer (CrOCN, film thickness 91.5 nm), a metal layer (CrC, film thickness 10) sequentially arranged from the transparent substrate side. nm), and a reflectance reduction layer (CrOCN, film thickness 28 nm). The values of the refractive index and the extinction coefficient of the phase shift layer (CrOCN), the metal layer (CrN), and the reflectance reduction layer (CrOCN) are the same as those of the first embodiment. The Cr content of each of the phase shift layer (CrOCN), the metal layer (CrN), and the reflectance reduction layer (CrOCN) is the same as that of Example 1. The phase shift film has a transmittance of 5.55% and a phase difference of 182.30 ° for 365 nm light by the above-mentioned three-layer structure. The phase shift film surface reflectance is 12.3% at a wavelength of 313 nm, 9.2% at 350 nm, 8.5% at a wavelength of 365 nm, 8.3% at a wavelength of 405 nm, and 413 nm The wavelength was 8.5% and the wavelength at 436 nm was 8.8%. In addition, the variation range of the reflectance of the phase shift film surface is 1.0% in a wavelength range of 350 nm to 436 nm, 0.6% in a wavelength range of 365 nm to 436 nm, and a wavelength of 313 nm to 436 nm. In the region it was 4.2%. Curve c in FIG. 3 shows the film surface reflectance spectrum of the phase shift film of the phase shift mask substrate of Example 4. The sheet resistance of the phase shift film is 510 Ω / □. Therefore, the phase shift mask substrate of Embodiment 4 can prevent charging. In Example 4, the transparent substrate was transported at a speed of 205 mm / min when the phase shift layer was formed. When forming the metal layer, Ar gas and CH ₄ Gas mixture (containing 15% CH in Ar gas) ₄ A mixed gas of gases) was introduced into the sputtering chamber at a flow rate of 200 sccm. When forming the reflectance-reducing layer, the transparent substrate was transported at a speed of 215 mm / min. Otherwise, the phase shift mask substrate of Example 4 was manufactured by the same method as that of Example 1. The phase shift mask substrate was used, and a phase shift mask was manufactured by the same method as in Example 1. The phase shift film pattern cross-section of the phase shift mask manufactured using the phase shift mask substrate described above has extremely slight corrosion in the metal layer located at the center portion of the phase shift film pattern in the film thickness direction, but Not to the extent that the characteristics of the mask are affected. The CD unevenness of the phase shift film pattern of the phase shift mask manufactured using the above phase shift mask substrate is relatively good and is 55 nm. The above-mentioned phase shift mask has excellent pattern cross-sectional shape and excellent CD uniformity, and the film surface reflectance for exposure light is low. Therefore, the above-mentioned phase shift mask can be used to produce a high-resolution and high-definition display. Device. In addition, the phase shift mask can be manufactured using a phase shift mask substrate provided with a phase shift film having a small sheet resistance, so even when a small pattern is formed, it is difficult for electricity to enter the pattern from the pattern. It is not easy to cause static damage. Comparative Example 1. The phase shift film of the phase shift mask substrate of Comparative Example 1 contained only a phase shift layer (CrOCN, film thickness 122 nm). The phase shift mask substrate of Comparative Example 1 is different from the phase shift mask substrate of the Example in that the phase shift film does not include a metal layer and a reflectance reduction layer. The phase shift layer (CrOCN) has a refractive index of 2.36 and an extinction coefficient of 0.74 at a wavelength of 313 nm, a refractive index of 2.43 and an extinction coefficient of 0.66 at a wavelength of 350 nm, and a refractive index of 2.45 and an extinction coefficient at a wavelength of 365 nm. It is 0.62, the refractive index at a wavelength of 413 nm is 2.49 and the extinction coefficient is 0.53, and the refractive index at a wavelength of 436 nm is 2.50 and the extinction coefficient is 0.49. The Cr content of the phase shift layer (CrOCN) was 32 atomic%. The phase shift film has a transmittance of 5.20% for a light of 365 nm and a phase difference of 179.60 ° by the above-mentioned one-layer structure. The phase reflectance of the film is 19.9% at a wavelength of 313 nm, 20.3% at 350 nm, 20.7% at a wavelength of 365 nm, 22.0% at a wavelength of 405 nm, and 413 nm The wavelength was 22.1%, and the wavelength at 436 nm was 22.2%. In addition, the variation range of the reflectance of the phase shift film surface is 1.9% in the wavelength region of 350 nm to 436 nm, 1.6% in the wavelength region of 365 nm to 436 nm, and the wavelength of 313 nm to 436 nm. In the region it was 2.4%. Curves d in FIGS. 4 and 5 show the film surface reflectance spectrum of the phase shift film of the phase shift mask base of Comparative Example 1. The sheet resistance of the phase shift film cannot be measured (∞). Therefore, the phase shift mask substrate of Comparative Example 1 is more likely to cause charging than the phase shift mask substrate of Example. The phase shift mask base of Comparative Example 1 was manufactured by the following method. First, a synthetic quartz glass substrate is prepared as a transparent substrate. After that, the transparent substrate was carried into a continuous sputtering apparatus. Thereafter, a sputtering power of 3.5 kW was applied to the chromium target disposed in the sputtering chamber, and Ar gas and N ₂ Gas and CO ₂ The mixed gas of the gas is introduced into the sputtering chamber, and the transparent substrate is conveyed at a speed of 200 mm / min. When the transparent substrate passed near the chromium target, a phase shift layer including CrOCN with a thickness of 122 nm was formed on the main surface of the transparent substrate. Here, the mixed gas system is 46 sccm, N with Ar ₂ Becomes 46 sccm, and CO ₂ A flow rate of 18.5 sccm was introduced into the sputtering chamber. Thereafter, the transparent substrate on which the phase shift film including the phase shift layer (CrOCN, film thickness: 122 nm) was formed was taken out from the continuous sputtering apparatus and washed. The phase shift mask substrate was used, and a phase shift mask was manufactured by the same method as in Example 1. The phase shift film pattern section of the phase shift mask manufactured using the phase shift mask substrate is vertical. The CDs of the phase shift film patterns of the phase shift masks manufactured using the above phase shift mask substrates are not all 90 nm, and do not reach the phase shift masks used for the manufacture of high-resolution and high-definition display devices. Required level. Although the above phase shift mask has an excellent pattern cross-sectional shape, the phase shift film pattern has a large CD unevenness, and the film reflectance of the phase shift film pattern to the exposure light is high, so the phase shift mask cannot be used. Manufacture of high-resolution and high-definition display devices. In addition, the phase shift mask can be manufactured by using a phase shift mask base having a phase shift film with a large sheet resistance, so even when a small pattern is formed, electricity is easy to enter the pattern from the pattern. It is easy to cause electrostatic damage. Comparative Example 2. The phase shift film of the phase shift mask base of Comparative Example 2 includes a phase shift layer (CrOCN, film thickness: 113.4 nm) and a reflectance reduction layer (CrOCN, Film thickness 7 nm). The phase shift mask substrate of Comparative Example 2 is different from the phase shift mask substrate of the Example in that the phase shift film does not have a metal layer. The phase shift layer (CrOCN) has a refractive index of 2.37 at a wavelength of 313 nm and an extinction coefficient of 0.72, a refractive index of 2.45 at a wavelength of 350 nm and an extinction coefficient of 0.64, and a refractive index at a wavelength of 365 nm of 2.48 and an extinction coefficient. It is 0.60, the refractive index at a wavelength of 413 nm is 2.52 and the extinction coefficient is 0.48, and the refractive index at a wavelength of 436 nm is 2.53 and the extinction coefficient is 0.44. The reflectance reduction layer (CrOCN) has a refractive index of 2.24 and an extinction coefficient of 0.36 at a wavelength of 313 nm, a refractive index of 2.20 and an extinction coefficient of 0.28 at a wavelength of 350 nm, and a refractive index of 2.18 and an extinction coefficient at a wavelength of 365 nm. It is 0.26, the refractive index is 2.13 and the extinction coefficient is 0.20 at a wavelength of 413 nm, and the refractive index is 2.11 and the extinction coefficient is 0.17 at a wavelength of 436 nm. The Cr content of the phase shift layer (CrOCN) was 33 atomic%, and the Cr content of the reflectance reduction layer (CrOCN) was 26 atomic%. The phase shift film has a transmittance of 8.40% for a light of 365 nm and a phase difference of 172.50 ° by the above two-layer structure. The phase shift film surface reflectance is 16.2% at a wavelength of 313 nm, 17.9% at 350 nm, 18.9% at a wavelength of 365 nm, 20.4% at a wavelength of 405 nm, and 413 nm. The wavelength was 20.4%, and the wavelength at 436 nm was 19.7%. In addition, the variation range of the phase reflectance film surface reflectance is 2.5% in a wavelength range of 350 nm to 436 nm, 1.5% in a wavelength range of 365 nm to 436 nm, and a wavelength of 313 nm to 436 nm. In the region it was 4.2%. The curve e in FIG. 4 represents the film surface reflectance spectrum of the phase shift film of the phase shift mask base of Comparative Example 2. The sheet resistance of the phase shift film cannot be measured (∞). Therefore, the phase shift mask substrate of Comparative Example 2 is more likely to cause charging than the phase shift mask substrate of Example. The phase shift mask base of Comparative Example 2 was manufactured by the following method. First, a synthetic quartz glass substrate is prepared as a transparent substrate. After that, the transparent substrate was carried into a continuous sputtering apparatus. After that, a sputtering power of 3.4 kW was applied to the chromium target disposed in the sputtering chamber, while Ar gas, N ₂ Gas and CO ₂ The mixed gas of the gas is introduced into the sputtering chamber, and the transparent substrate is conveyed at a speed of 200 mm / min. When the transparent substrate passed near the chromium target, a phase shift layer including CrOCN with a film thickness of 113.4 nm was formed on the main surface of the transparent substrate. Here, the mixed gas system uses Ar as 35 sccm, N ₂ Becomes 35 sccm, and CO ₂ A flow rate of 19.8 sccm was introduced into the sputtering chamber. After that, a sputtering power of 0.5 kW was applied to the chromium target disposed in the sputtering chamber, and Ar gas, N ₂ Gas and CO ₂ The mixed gas of the gas is introduced into the sputtering chamber, and the transparent substrate is conveyed at a speed of 200 mm / min. When the transparent substrate passed near the chromium target, a 7 nm-thickness reflectance-reducing layer including CrOCN was formed on the phase shift layer. Here, the mixed gas system uses Ar as 35 sccm, N ₂ Becomes 35 sccm, and CO ₂ A flow rate of 19.8 sccm was introduced into the sputtering chamber. Thereafter, the transparent substrate on which the phase shift film including the phase shift layer (CrOCN, film thickness of 113.4 nm) and the reflectance reduction layer (CrOCN, film 7 nm) was formed was taken out from the continuous sputtering apparatus and washed. . Furthermore, the film formation of the phase shift layer and the film formation of the reflectance reduction layer are continuously performed in the continuous sputtering apparatus, without having to take out the transparent substrate to the outside of the continuous sputtering apparatus and expose it to the atmosphere. The phase shift mask substrate was used, and a phase shift mask was manufactured by the same method as in Example 1. The phase shift film pattern cross section of the phase shift mask manufactured using the phase shift mask substrate described above is in a shape where an etching solution is immersed in the interface with the resist film. The CDs of the phase shift film patterns of the phase shift masks manufactured using the above phase shift mask substrates are not all 200 nm, and do not reach the phase shift masks used for the manufacture of high resolution and high definition display devices Required level. The phase shift mask is formed in a cross-sectional shape of a pattern with immersion at the interface with the resist film, and the CD unevenness is large. Furthermore, the phase shift film pattern has a high reflectance to the film surface of the exposure light, so it cannot be used. The phase shift mask is used to manufacture a high-resolution and high-definition display device. In addition, the phase shift mask can be manufactured by using a phase shift mask base having a phase shift film with a large sheet resistance, so even when a small pattern is formed, electricity is easy to enter the pattern from the pattern. It is easy to cause electrostatic damage. Comparative Example 3. The phase shift film of the phase shift mask base of Comparative Example 3 includes a phase shift layer (CrOCN, film thickness: 113.4 nm) and a first reflectance reduction layer (CrOCN) which are sequentially arranged from the transparent substrate side. , Film thickness 7 nm), and a second reflectance reduction layer (CrOCN, film thickness 13.6 nm). The phase shift film of the phase shift mask base of Comparative Example 3 corresponds to a case where a second reflectance reduction layer (CrOCN) is provided on the reflectance reduction layer of the phase shift mask base of Comparative Example 2. The values of the refractive index and the extinction coefficient of the phase shift layer (CrOCN) are the same as the values of the refractive index and the extinction coefficient of the phase shift layer (CrOCN) of Comparative Example 2. The values of the refractive index and the extinction coefficient of the first reflectance-reducing layer (CrOCN) are the same as the values of the refractive index and the extinction coefficient of the reflectance-reducing layer (CrOCN) of Comparative Example 2. The second reflectance reduction layer (CrOCN) has a refractive index of 2.41 and an extinction coefficient of 0.41 at a wavelength of 313 nm, a refractive index of 2.40 and an extinction coefficient of 0.32 at a wavelength of 350 nm, and a refractive index of 2.39 and 365 nm. The extinction coefficient is 0.29, the refractive index at a wavelength of 413 nm is 2.35 and the extinction coefficient is 0.21, the refractive index at a wavelength of 436 nm is 2.33, and the extinction coefficient is 0.19. The Cr content of the phase shift layer (CrOCN) and the first reflectance reduction layer (CrOCN) are the same as those of the phase shift layer (CrOCN) and the reflectance reduction layer (CrOCN) of Comparative Example 2. The Cr content of the second reflectance reduction layer (CrOCN) was 29 atomic%. The phase shift film has a transmittance of 8.00% for a light of 365 nm and a phase difference of 190.00 ° by the above three-layer structure. The phase reflectance of the film is 12.9% at a wavelength of 313 nm, 12.2% at 350 nm, 12.8% at a wavelength of 365 nm, 15.7% at a wavelength of 405 nm, and 413 nm The wavelength was 16.3%, and the wavelength at 436 nm was 17.5%. The variation range of the phase shift film surface reflectance is 5.2% in a wavelength region of 350 nm to 436 nm, 4.6% in a wavelength region of 365 nm to 436 nm, and a wavelength of 313 nm to 436 nm. In the region it was 5.4%. The curve f in FIG. 5 represents the film surface reflectance spectrum of the phase shift film of the phase shift mask base of Comparative Example 3. The sheet resistance of the phase shift film cannot be measured (∞). Therefore, the phase shift mask substrate of Comparative Example 3 is more likely to cause charging than the phase shift mask substrate of Example. In Comparative Example 3, after forming the reflectance-reducing layer of Comparative Example 2, a sputtering power of 1.0 kW was applied to a chromium target disposed in a sputtering chamber, and Ar gas, N ₂ Gas and CO ₂ The mixed gas of the gas is introduced into the sputtering chamber, and the transparent substrate is conveyed at a speed of 200 mm / min. When the transparent substrate passed near the chromium target, a second reflectance-reducing layer having a thickness of 13.6 nm including CrOCN was formed on the first reflectance-reducing layer. Here, the mixed gas system uses Ar as 35 sccm, N ₂ Becomes 35 sccm, and CO ₂ A flow rate of 19.8 sccm was introduced into the sputtering chamber. Otherwise, the phase shift mask substrate of Comparative Example 3 was manufactured by the same method as that of Comparative Example 2. The phase shift mask substrate was used, and a phase shift mask was manufactured by the same method as in Example 1. The phase shift film pattern cross section of the phase shift mask manufactured using the phase shift mask substrate is vertical, but it is in a shape where an etching solution is immersed at the interface with the resist film. The CDs of the phase shift film patterns of the phase shift masks manufactured using the above phase shift mask substrates are not all 180 nm, and do not reach the phase shift masks used for the manufacture of high resolution and high definition display devices Required level. The phase shift mask is formed in a cross-sectional shape of a pattern with immersion at the interface with the resist film, and the CD unevenness is large. Furthermore, the phase shift film pattern has a high reflectance to the film surface of the exposure light, so it cannot Using the phase shift mask described above, a high-resolution and high-definition display device is manufactured. In addition, the phase shift mask can be manufactured by using a phase shift mask base having a phase shift film with a large sheet resistance, so even when a small pattern is formed, electricity is easy to enter the pattern from the pattern. It is easy to cause electrostatic damage. As mentioned above, although this invention was demonstrated in detail based on embodiment and an Example, this invention is not limited to this. As long as they have general knowledge in the field, they will understand that changes or improvements can be made within the technical idea of the present invention.

10‧‧‧phase shift mask base

20‧‧‧ transparent substrate

30‧‧‧phase shift film

31‧‧‧phase offset layer

32‧‧‧Reflectivity reduction layer

33‧‧‧metal layer

40‧‧‧Light-shielding film pattern

FIG. 1 is a schematic view showing a film configuration of a phase shift mask base. FIG. 2 is a schematic view showing the structure of another film of the phase shift mask base. FIG. 3 is a film surface reflectance spectrum of the phase shift film of the phase shift mask substrate of Examples 1, 3, and 4. FIG. 4 is a film surface reflectance spectrum of the phase shift film of the phase shift mask base of Comparative Examples 1 and 2. FIG. FIG. 5 is a film surface reflectance spectrum of the phase shift film of the phase shift mask base of Comparative Examples 1 and 3. FIG.

Claims (10)

A phase shift mask base is characterized in that it is a phase shift mask base for manufacturing a display device, which is provided with a phase shift film formed of a chrome-based material on a transparent substrate, and the phase shift film has: The phase shift layer mainly has the function of adjusting the transmittance and phase difference with respect to the exposure light; the reflectance reducing layer is arranged on the upper side of the phase shift layer, and has a function to make the phase shift layer incident on the phase shift film side A function of reducing the reflectance of light; and a metal layer disposed between the phase shift layer and the reflectance reducing layer, and having a chromium content higher than the chromium content of the reflectance reducing layer; The phase shift film has a laminated structure of the phase shift layer, the metal layer, and the reflectance reducing layer. By adjusting the composition and thickness of each of the phase shift layer, the metal layer, and the reflectance reducing layer, the phase The transmittance of the shift film to the exposure light is 1% to 20%, the phase difference of the phase shift film to the exposure light is 160 ° to 200 °, and the phase shift film is suitable for the light incident from the phase shift film side. Film reflectance of light - the entire wavelength region of 313nm 436nm is 13% or less. For example, the phase shift mask substrate of claim 1, wherein the difference between the Cr content rate of the metal layer and the Cr content rate of the reflectance reduction layer is 10 to 80 atomic%. A phase shift mask base is characterized in that it is a phase shift mask base for manufacturing a display device, which is provided with a phase shift film formed of a chrome-based material on a transparent substrate, and the phase shift film has: The phase shift layer mainly has the function of adjusting the transmittance and phase difference with respect to the exposure light; the reflectance reducing layer is arranged on the upper side of the phase shift layer, and has a function to make the phase shift layer incident on the phase shift film side A function of reducing the reflectance of light; and a metal layer disposed between the phase shift layer and the reflectance reducing layer, and having an extinction coefficient compared to the reflectance reducing layer in a wavelength range of 313 nm to 436 nm Higher extinction coefficient; the phase shift film is a laminated structure of the phase shift layer, the metal layer, and the reflectance reduction layer, and each of the phase shift layer, the metal layer, and the reflectance reduction layer is adjusted by adjusting In terms of composition and thickness, the transmittance of the phase shift film to the exposure light is 1% to 20%, the phase difference of the phase shift film to the exposure light is 160 ° to 200 °, and the phase shift film is Phase shift film The film surface reflectance of the side incident light is 13% or less in the entire wavelength range of 313nm to 436nm. For example, the phase shift mask substrate of claim 3, wherein the difference between the extinction coefficient of the metal layer and the extinction coefficient of the reflectance reduction layer is 1.5 to 3.5. For example, the phase shift mask substrate according to any one of claims 1 to 4, wherein the variation range of the film surface reflectance of the phase shift film is 10% or less in a wavelength range of 313 nm to 436 nm. The phase shift mask substrate according to any one of claims 1 to 4, wherein the phase shift layer is a chromium compound containing chromium, at least one of oxygen and nitrogen, and the metal layer is chromium, or contains chromium, and A chromium compound of at least one of carbon and nitrogen, and the reflectance reducing layer is composed of a chromium compound containing chromium and oxygen. The phase shift mask substrate according to any one of claims 1 to 4, which has a resist film on the phase shift film. A method for manufacturing a phase shift mask, comprising the steps of: performing a drawing process using laser light on the above-mentioned resist film of the phase shift mask base as claimed in claim 7, and a development process, whereby Forming a resist film pattern on the phase shift film; and etching the phase shift film using the resist film pattern as a mask to form a phase shift film pattern on the transparent substrate. A method for manufacturing a display device is characterized by having the steps of: placing a phase shift mask manufactured by the manufacturing method as claimed in claim 8 on a mask stage of an exposure device; and the phase shift mask described above. The exposure light is irradiated to transfer the phase shift film pattern to a resist film formed on a display device substrate. The method for manufacturing a display device according to claim 9, wherein the exposure light is a composite light including a plurality of wavelengths of light selected from a wavelength range of 313 nm to 436 nm.