TWI605299B - Phase-shift mask blank for display device manufacture, phase-shift mask for display device manufacture and its manufacturing method, and method for manufacturing display device - Google Patents

Description

Phase shift mask substrate for manufacturing display device, phase shift mask for manufacturing display device, method for manufacturing same, and method for manufacturing display device

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

At present, as a liquid crystal display device, there are a VA (Vertical Alignment) method or an IPS (In Plane Switching) method. According to these methods, a liquid crystal display device having high definition, high-speed display performance, and wide viewing angle can be realized. In the liquid crystal display device to which the above-described methods are applied, the transparent conductive film can be patterned by, for example, a photolithography step to form a pixel electrode of the line gap pattern, thereby improving the response speed and the viewing angle. Recently, the miniaturization of the width between the line gap patterns has been pursued from the viewpoint of further improvement in response speed and viewing angle, or improvement in light use efficiency of the liquid crystal display device, that is, improvement in power consumption and contrast of the liquid crystal display device. For example, it is desirable to narrow the width of the line gap pattern from 6 μm to 5 μm, and further narrow from 5 μm to 4 μm. Further, in the production of a liquid crystal display device or an organic EL display device, a plurality of conductive films or insulating films which have been subjected to necessary patterning are laminated to form a semiconductor element such as a transistor. At this time, the photolithography step is also often used for patterning the respective films of the deposited layers. For example, a thin film transistor or LSI used in such display devices has a structure in which a contact hole is formed in an insulating layer by a photolithography step, and an upper layer pattern and a lower layer pattern are connected. Recently, in such a display device, the demand for displaying a bright and fine image at a sufficiently fast moving speed and reducing power consumption has been increasing. In order to satisfy such a demand, it is desired to make the constituent elements of the display device finer and more integrated. For example, it is desirable to reduce the diameter of the contact hole from 3 μm to 2.5 μm, 2 μm, and 1.5 μm. According to such a background, a photomask for manufacturing a display device which can correspond to the miniaturization of a line gap pattern or a contact hole is desired. When the line gap pattern or the contact hole is miniaturized, since the resolution limit of the exposure machine for manufacturing the display device is 3 μm in the previous mask, there is not enough process margin (Process Margin), and it is necessary to produce close analysis. The product of the minimum line width of the limit. Therefore, there is a problem that the defective rate of the display device becomes high. For example, when a reticle having a hole pattern for forming a contact hole is used and transferred to a transfer target, if it is a hole pattern having a diameter of more than 3 μm, the transfer can be performed by the previous reticle. . However, it is very difficult to transfer a hole pattern having a diameter of 3 μm or less, particularly a hole pattern having a diameter of 2.5 μm or less. In order to transfer a hole pattern having a diameter of 2.5 μm or less, it is also conceivable to convert to, for example, an exposure machine having a high NA, but a large investment is required. Therefore, in order to improve the resolution and to correspond to the miniaturization of the line gap pattern or the contact hole, attention is paid to the phase shift mask as a photomask for manufacturing a display device. Recently, as a photomask for manufacturing a liquid crystal display device, a phase shift mask having a chromium phase shift film has been developed. Patent Document 1 describes a halftone phase shift mask including a transparent substrate, a light shielding layer formed on the transparent substrate, and a wavelength region of 300 nm or less and 500 nm or less formed around the light shielding layer. Any of the light may have a phase offset layer of a single layer of a chromium oxynitride-based material having a phase difference of 180 degrees. The phase shift mask is manufactured by patterning a light shielding layer on a transparent substrate, forming a phase shift layer on the transparent substrate by coating the light shielding layer, and forming a photoresist layer on the phase shift layer. Forming a resist pattern by exposing and developing the photoresist layer in the photolithography step; patterning the phase shift layer by using the resist pattern as an etch mask. Further, the single-layered chromium-based phase shifting layer is formed in a sputtering gas atmosphere containing a mixed gas containing a nitrogen (N ₂ ) gas and a carbon dioxide (CO ₂ ) gas (refer to the sample of FIG. 2 of Patent Document 1). No.1~5). Therefore, it is inferred that the phase offset layer is formed of chromium oxynitride (CrOCN) in addition to chromium oxynitride (CrON). Such phase shifting reticles receive exposure light of a plurality of wavelengths output from various exposure machines. For example, in the case of a phase shift mask for manufacturing a liquid crystal display device, as an exposure machine used in the photolithography step, for example, an output is provided on the i line (365 nm) and the h line (405 nm). And the g-line (436 nm) has a peak intensity composite light source (ultra-high pressure UV lamp). For example, as the exposure light in the case where the mask pattern of the phase shifting mask is transferred on the main surface of the mother glass substrate which is enlarged in size as the size of the liquid crystal display device has increased in recent years, if the composite light is used, The amount of light can be obtained, and the working time can be shortened. Further, it is known that a film which exhibits a certain degree of transmittance in light of a certain wavelength generally has an optical property depending on the wavelength, that is, has a wavelength dependency. The phase shifting film has a film that changes the properties of the phase of the exposure light, and thus exhibits a certain degree of transmittance in the exposure light. Therefore, according to the above findings, the phase shift film has wavelength dependence on the transmittance, reflectance, and phase difference of the exposure light. Further, in Patent Document 2, a photomask having a phase shift film that suppresses a phase difference variation or a transmittance deviation is described. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2011-13283 [Patent Document 2] JP-A-2012-230379

[Problems to be Solved by the Invention] However, any of the phase shifting films specifically described in Patent Documents 1 and 2 is a single-layered chromium-based phase shifting film. Therefore, when a phase shift mask obtained by such a phase shift film material is used to transfer a fine pattern such as a contact hole diameter of 2.5 μm or 2 μm, the wavelength dependence of the transmittance of the exposure light or the like is not The cross-sectional shape of the sufficient or phase-shifted film pattern cannot be perpendicularized, and there is a problem that sufficient resolution cannot be obtained. Further, in the image forming apparatus for mask production or the exposure machine used in the manufacture of the display device, an alignment light source is provided in order to recognize the alignment mark provided on the mask. As the alignment light, for example, light having a wavelength of 365 to 700 nm is used, and the alignment mark is detected by the difference in transmittance between the transparent substrate and the alignment mark in the alignment light. The greater the difference in transmittance between the alignment light (wavelength 365-700 nm), the simpler the alignment identification, and the higher the alignment accuracy, thus improving the rationality of the phase-shifting mask. However, the phase shift masks of the above Patent Documents 1 and 2 cannot be said to have sufficient characteristics in terms of handleability. Further, as a mask inspection device, it is known to provide, for example, a light source that outputs light having a wavelength of 365 nm or 546 nm. It is known that the difference between the reflectance of the transparent substrate and the reticle pattern in the inspection light by the reticle inspection device or the difference in transmittance is recognized, and the reticle pattern is recognized. When such a mask inspection apparatus is used, it is possible to grasp, for example, a defective shape of the mask pattern or the presence or absence of foreign matter adhering to the mask pattern. However, the phase shift masks of the above-mentioned Patent Documents 1 and 2 cannot be said to have sufficient characteristics as the optical characteristics of the phase shift film in the mask inspection. Therefore, the present invention has been made in view of the above problems, and an object of the invention is to provide phase-shifted light for manufacturing a display device including a phase shift film that exhibits optical characteristics in which wavelength dependence of optical characteristics of exposure light is suppressed. A cover substrate, a phase shift mask using the phase shift mask base, a method of manufacturing the same, and a method of manufacturing a display device using the phase shift mask. [Technical means for solving the problem] In order to solve the above problems, the present invention has the following configuration. (Configuration 1) A phase shift mask substrate, which is a phase shift mask substrate for manufacturing a display device, comprising: a transparent substrate; and a phase shift film formed on the transparent substrate; and the phase The offset film comprises a single layer film or a laminated film having at least one layer of a metal halide material layer containing a metal and any element of cerium, nitrogen and/or oxygen; the phase shifting film is as follows: light having a wavelength of 365 nm The transmittance is in the range of 3.5% or more and 8% or less; the phase difference of the light having a wavelength of 365 nm is in the range of 160 degrees or more and 200 degrees or less; and the transmittance in the range of 365 nm or more and 436 nm or less is dependent on the wavelength. Within 5.5%. (Configuration 2) The phase shift mask substrate of the first aspect, wherein the phase shift film is as follows: The transmittance in the range of 365 nm or more and 700 nm or less depends on the amount of change in wavelength of 20% or less. (Configuration 3) The phase shift mask substrate constituting 1 or 2, wherein the phase shift film is as follows: a difference between the phase difference given at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm is 30 degrees. the following. (Aspect 4) The phase shift mask substrate according to any one of the above 1 to 3, wherein the phase shift film is as follows: a reflectance of 5% or more and 45% or less in a wavelength range of 365 nm or more and 700 nm or less . (Configuration 5) The phase shift mask substrate of the fourth aspect, wherein the phase shift film has a reflectance in a range of 365 nm or more and 700 nm or less in a range of 5% or less depending on the wavelength. (Claim 6) The phase shift mask substrate according to any one of 1 to 5, wherein the phase shifting film is composed of at least one layer of a metal telluride-based material layer and at least one layer of a chromium-based material layer. (Structure 7) The phase shift mask substrate according to any one of 1 to 6, wherein the metal halide material layer is a nitride of a metal telluride, an oxide of a metal telluride, or a nitrogen of a metal telluride. The oxide, the metal halide, the carbon oxide of the metal halide, and the carbon oxynitride of the metal halide are at least one material. (Configuration 8) The phase shift mask substrate of the sixth aspect, wherein the chromium-based material layer is made of a nitride of chromium, an oxide of chromium, a carbide of chromium, a nitrogen oxide of chromium, a carbonitride of chromium, It is composed of at least one of chromium carbon oxide and chromium carbonitride. (Configuration 9) The phase shift mask substrate of the sixth aspect, wherein the metal telluride-based material layer has a film thickness larger than a film thickness of the chromium-based material layer. (Claim 10) The phase shift mask substrate according to any one of 1 to 9, which comprises a light-shielding film formed on the phase shift film. (Configuration 11) A phase shift mask which is a phase shift mask for manufacturing a display device, comprising: a transparent substrate; and a phase shift film pattern formed on the transparent substrate; The film pattern comprises a single layer film or a laminated film having at least one layer of a metal halide material layer containing a metal and any element of cerium, nitrogen and/or oxygen; the phase shifting film pattern is as follows: wavelength 365 nm The transmittance of light is in the range of 3.5% or more and 8% or less; the phase difference of light having a wavelength of 365 nm is in the range of 160 degrees or more and 200 degrees or less; and the transmittance in the range of 365 nm or more and 436 nm or less depends on the wavelength change. The amount is within 5.5%. (Structure 12) The phase shift mask of the configuration 11, wherein the phase shift film pattern is as follows: The transmittance in the range of 365 nm or more and 700 nm or less depends on the amount of change in wavelength within 20%. (Structure 13) The phase shift mask of the configuration 11 or 12, wherein the phase shift film pattern is as follows: a difference between the phase difference given at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm is 30 degrees. the following. (Aspect 14) The phase shift mask according to any one of the items 11 to 13, wherein the phase shift film pattern is as follows: a reflectance of 15% or more and 30% or less in a wavelength range of 365 nm or more and 700 nm or less . (Configuration 15) The phase shift mask of the configuration 14 is characterized in that the phase shift film pattern is as follows: The reflectance in the range of 365 nm or more and 700 nm or less depends on the amount of change in wavelength within 5%. (Structure 16) The phase shift mask of any one of Embodiments 11 to 15, comprising a light shielding film pattern formed on the phase shift film pattern. (Structure 17) The phase shift mask of any one of Embodiments 11 to 16, comprising a light shielding film pattern formed under the phase shift film pattern. (Configuration 18) A method of manufacturing a phase shift mask, which is a method of manufacturing a phase shift mask for manufacturing a display device, comprising: a resist pattern forming step, such as forming 1 to 9 Forming a resist pattern on the phase shift film of the phase shift mask substrate; and a phase shift film pattern forming step of masking the resist pattern and wet etching the phase shift The film forms a phase offset film pattern. (Configuration 19) A method of manufacturing a phase shift mask, which is a method of manufacturing a phase shift mask for manufacturing a display device, comprising: a resist pattern forming step of a phase such as composition 10. a resist pattern is formed on the light shielding film of the offset mask base; a light shielding film pattern forming step of masking the resist pattern, wet etching the light shielding film to form a light shielding film pattern; and a phase shift film A pattern forming step of forming the light shielding film pattern as a mask and wet etching the phase shift film to form a phase shift film pattern. (Configuration 20) A method of manufacturing a display device, which is characterized by comprising: a phase shift mask arrangement step for attaching a resist film substrate on which a resist film is formed on a substrate a phase shift mask obtained by any one of the structures 11 to 17 or a phase shift mask obtained by a method of manufacturing a phase shift mask of 18 or 19, which is opposed to the resist film And a resist film exposure step of irradiating the phase shift mask with composite exposure light including an i-line, an h-line, and a g-line to expose the resist film. [Effects of the Invention] As described above, the phase shift mask substrate for manufacturing a display device according to the present invention includes a transparent substrate and a phase shift film formed on the transparent substrate. The phase shifting film comprises a single layer film or a laminated film having at least one layer of a metal telluride-based material containing a metal and any element of cerium, nitrogen and/or oxygen. The phase shift film has a transmittance of light of 365 nm at a wavelength of 3.5% or more and 8% or less, and a phase difference of light of 365 nm is in a range of 160 degrees or more and 200 degrees or less, and a wavelength of 365 nm or more and 436 nm or less. The transmittance depends on the amount of change in wavelength within 5.5%. Such a phase shift film exhibits an optical property in which the wavelength dependence of the transmittance of light having a wavelength in the range of 365 nm or more and 436 nm or less is suppressed. Therefore, when the exposure light of the wavelength range is received, the phase shift effect can be sufficiently exhibited, and a phase shift mask substrate having a phase shift film capable of improving the resolution can be obtained. Further, a phase shift mask substrate having a phase shift film capable of obtaining a desired transfer of the light intensity of the boundary portion of the pattern, enhancing the resolution, and having good CD characteristics can be obtained. The phase-shifted film pattern of the pattern shape is patterned. Moreover, the phase shift mask for manufacturing a display device according to the present invention includes a transparent substrate and a phase shift film pattern formed on the transparent substrate. The phase shift film pattern comprises a single layer film or a laminate film having at least one layer of a metal halide material layer containing a metal and any element of cerium, nitrogen and/or oxygen. The phase shift film pattern has a transmittance of light of 365 nm at a wavelength of 3.5% or more and 8% or less, a phase difference of light of 365 nm and a range of 160 degrees or more and 200 degrees or less, and a wavelength of 365 nm or more and 436 nm or less. The internal transmittance depends on the amount of change in wavelength within 5.5%. Such a phase shift film pattern exhibits optical characteristics in which the wavelength dependence of the transmittance of light having a wavelength in the range of 365 nm or more and 436 nm or less is suppressed. Therefore, it is possible to obtain a phase shift which is capable of obtaining a desired transfer pattern shape in which the phase shift effect can be sufficiently exhibited when the exposure light of the wavelength range is received, and the light intensity of the pattern boundary portion is increased and the desired CD characteristic is obtained. The phase shifting mask of the film shifting pattern. The phase shift mask can correspond to the miniaturization of the line gap pattern or the contact hole. Further, according to the method of manufacturing a phase shift mask for manufacturing a display device of the present invention, a phase shift mask is manufactured using the phase shift mask substrate described above. Therefore, it is possible to manufacture a phase shift mask having a phase shift film pattern that exhibits optical characteristics in which the wavelength dependence of exposure light is suppressed. According to this phase shift mask, it is possible to obtain a desired transfer pattern shape which can sufficiently exhibit the phase shift effect and which can increase the light intensity of the boundary portion of the pattern and have a good CD characteristic. Further, according to the method for manufacturing a phase shift mask for manufacturing a display device of the present invention, a phase shift mask substrate having a light shielding film formed on the phase shift film of the phase shift mask substrate is used, and is manufactured. A phase shift mask having a light shielding film pattern formed on the phase shift film pattern. Therefore, it is possible to manufacture a phase shift mask having a phase shift film pattern that exhibits optical characteristics in which the wavelength dependence of exposure light is suppressed. According to the phase shift mask, it is possible to obtain a desired shift in the light intensity of the pattern boundary portion of the phase shift film pattern of the unstacked light-shielding film pattern, and to enhance the phase shift effect. Print pattern shape. Further, according to the method of manufacturing a display device of the present invention, the phase shift mask manufacturing display device obtained by using the phase shift mask described above or the method for manufacturing the phase shift mask described above can be manufactured to have fineness. A display device for a line gap pattern or contact hole. Further, the line gap pattern or the contact hole of the display device can be correctly aligned, and the manufacturing yield of the display device can be improved.

Hereinafter, a phase shift mask base for manufacturing a display device according to an embodiment of the present invention, a phase shift mask for manufacturing a display device using the phase shift mask base, a method for manufacturing the same, and a method for manufacturing the same, and a method for using the same A method of manufacturing a display device for an offset mask. Embodiment 1. In Embodiment 1, a phase shift mask base for manufacturing a display device and a method of manufacturing the same will be described. First, a phase shift mask substrate for manufacturing a display device according to the first embodiment will be described. Fig. 1 is a cross-sectional view showing the structure of a phase shift mask base for manufacturing a display device according to a first embodiment of the present invention. The phase shift mask substrate 1 of the first embodiment includes a transparent substrate 2 and a phase shift film 3 formed on the transparent substrate 2. Alternatively, a configuration in which the light shielding film 4 is formed on the phase shift film 3 may be employed. Further, a configuration in which the resist film 5 is formed on the phase shift film 3 or the light shielding film 4 can be employed. The transparent substrate 2 is translucent to the exposure light used. The material of the transparent substrate 2 is not particularly limited as long as it is a material that transmits light to the exposure light used. As a material having light transmissivity, synthetic quartz glass, soda lime glass, and alkali-free glass are exemplified. The phase shift film 3 is a single layer film or laminated film having at least one layer of a metal halide material layer containing a metal and an element of either of cerium, nitrogen and/or oxygen. The optical property of the phase shift film 3 as a whole is a material layer determined by the kind or film thickness of the material constituting the material layer of the phase shift film 3 when the phase shift film 3 includes a single layer film. The optical characteristics of the refractive index, the transmittance, the reflectance, and the like, for example, when the phase shift film 3 includes a laminated film, the type of material depending on the plurality of material layers constituting the phase shift film 3 or The combination of the optical characteristics determined by the film thickness and the like, and the order of the layers of the respective material layers and the number of layers are determined. Here, in the case where the phase shift film 3 includes a single layer film, the single layer film is a film formed of a single material. Therefore, a film comprising a laminate structure of a single material is also a single layer film. Further, when the phase shift film 3 includes a laminated film, the laminated film is a film formed by a combination of a film formed of a single material or the same material and a film formed of a material different from the film. The phase shifting film 3 controls the transmittance of light of a specific wavelength within a range as described below by selecting a material layer constituting the phase shift film 3, and the transmittance of light of a specific wavelength and The phase difference is controlled within the range as described below, and the amount of change in the transmittance, the phase difference, and the reflectance of the light in the specific wavelength range is suppressed within the range as described below. Specifically, the phase shift film 3 has a transmittance of 365 nm (hereinafter, sometimes referred to as T% (365)) in a range of 3.5% or more and 8% or less. Therefore, the light intensity of the boundary portion of the pattern becomes strong, and the resolution can be improved. When T% (365) is less than 3.5%, it is difficult to obtain the amount of transmitted light necessary to sufficiently exhibit the desired phase shift effect. Further, when T% (365) exceeds 8%, the light intensity at the boundary portion of the pattern is weakened, and it is difficult to achieve an improvement in resolution. Further, the phase shift film 3 has a transmittance (in some cases, ΔT% (436-365)) depending on the wavelength in the range of 365 nm or more and 436 nm or less, which is within 5.5%. Since the wavelength dependence of the transmittance in the wavelength range is suppressed, the light intensity at the boundary portion of the pattern becomes strong, and the resolution can be improved. If ΔT% (436-365) exceeds 5.5%, it is affected by the transmitted light of the h-line (405 nm) and the g-line (436 nm) having peak intensity other than the i-line (365 nm). The intensity tilt becomes weak, and it is difficult to achieve an improvement in resolution. Further, the phase shift film 3 is preferable because the reflectance is particularly improved when the transmittance of the g line (436 nm) is less than 10%. Further, the phase shift film 3 has a phase difference of 365 nm (hereinafter, sometimes referred to as P(365)) in a range of 160 degrees or more and 200 degrees or less. Therefore, a phase difference of approximately 180 degrees can be obtained, and the phase shift effect can be sufficiently exerted. When P (365) is less than 160 degrees or exceeds 200 degrees, a phase difference of approximately 180 degrees is not obtained, and it is difficult to exert a phase shift effect. Further, the phase shift film 3 preferably has a transmittance (in some cases, ΔT% (700-365)) depending on the wavelength in the range of 365 nm or more and 700 nm or less, which is within 20%. In this case, since the phase shift film 3 can suppress the wavelength dependency of the transmittance even in the wavelength range, it is easy to recognize the alignment mark provided in the mask in the exposure machine at the time of manufacture of the display device. Thereby the alignment accuracy is improved. Further, in the mask inspection apparatus, when the inspection apparatus of the mask pattern is recognized by the difference in transmittance between the transparent substrate and the mask pattern, it is preferable to easily recognize defects such as shape defects of the mask pattern. . Further, the difference (ΔP (365-436)) between the phase difference imparted by the phase shift film 3 at a wavelength of 365 nm and the wavelength given at 436 nm is 30 degrees or less. Since the wavelength dependence of the phase difference in the wavelength range is suppressed, the phase shift effect can be sufficiently exerted, and the light intensity at the boundary portion of the pattern can be made steeper, and the resolution can be improved. Further, the phase shift film 3 preferably has a reflectance (hereinafter, referred to as R% (700-365)) in a range of 365 nm or more and 700 nm or less of 5% or more and 45% or less. Further, the phase shift film 3 preferably has a reflectance (R% (700-365)) in a range of 365 nm or more and 700 nm or less of 5% or more and 45% or less, and a wavelength range of 365 nm or more and 700 nm or less. The internal reflectance depends on the amount of change in wavelength (hereinafter, sometimes referred to as ΔR% (700-365)) within 5%. In this case, the phase shift film 3 is formed by forming a resist film on the phase shift film 3, and when patterning is performed by a laser scanner or the like, it is less likely to be caused by the light used for drawing and the reflected light. The effect of the standing wave generated. Therefore, at the time of pattern drawing, the roughness of the edge portion of the resist pattern cross section on the phase shift film 3 can be suppressed, and the pattern accuracy can be improved. Moreover, since it is easy to obtain the alignment at the time of pattern drawing, it is easy to measure the mask pattern by the long-size (MMS) measurement, and the mask pattern can be recognized with high precision. Further, in the case of pattern transfer using a phase shift mask and manufacturing of a display device, when the alignment mark is detected by the difference in reflectance between the transparent substrate and the alignment mark, it is easy to recognize the mask alignment, thereby aligning Increased accuracy. Further, when a display device is manufactured by pattern transfer using a phase shift mask, since the influence of the glare phenomenon can be suppressed, good CD characteristics can be obtained, and the resolution can be improved, and desired. Transfer pattern shape. The phase shift film 3 exhibiting such optical characteristics is a single layer film or a laminated film having at least one metal halide material layer containing an element of either metal, neon, and/or oxygen as described above. Composition. In order to suppress the wavelength dependence of the transmittance, phase difference, and reflectance of the phase shift film 3 in a specific wavelength range, it is preferable to use a laminated film composed of a plurality of material layers having different optical characteristics. The plurality of material layers having different optical characteristics are preferably composed of at least one layer of a metal halide material layer and at least one layer of a chromium-based material layer. In this case, the optical characteristics of the entire phase-shifted film 3 are determined by, for example, refractive index and transmission depending on the kind or film thickness of the material constituting the metal halide-based material layer or the chromium-based material layer. The combination of the optical characteristics such as the ratio and the reflectance, and the order of the layers of the respective material layers and the number of layers are determined. Specifically, the phase shift film 3 may have a two-layer structure including a metal halide-based material layer formed on the transparent substrate 2 and a chromium-based material layer formed on the metal halide-based material layer. Laminated film. Further, a laminated film having a three-layer structure composed of a metal halide-based material layer formed on the second layer formed on the chromium-based material layer may be used. Further, in this case, a chromium-based material layer or a metal halide-based material layer may be further laminated, and the phase-shift film 3 may be formed in four or more layers. Further, the phase shift film 3 may be a laminated film having a two-layer structure composed of a chromium-based material layer formed on the transparent substrate 2 and a metal halide-based material layer formed on the chromium-based material layer. Further, a laminated film having a three-layer structure composed of a chromium-based material layer formed on the second layer of the metal halide-based material layer may be used. Further, in this case, a metal halide-based material layer or a chromium-based material layer may be laminated, and the phase-shift film 3 may be four or more layers. The phase shift film 3 having such a configuration exhibits optical characteristics in which the transmittance, phase difference, and reflectance of the specific wavelength range are suppressed in wavelength dependence. Therefore, when the exposure light of the wavelength range is received, the phase shift effect can be sufficiently exerted, and the resolution can be improved. Further, any of the metal halide material layer and the chromium material layer constituting the phase shift film 3 may be formed of one layer or a plurality of layers. When the metal telluride-based material layer and the chromium-based material layer are each formed of a plurality of layers, the materials constituting each layer of each material layer may be different from each other, or the layers may be the same. When the phase shift film 3 is composed of at least one layer of a metal halide-based material layer and at least one layer of a chromium-based material layer, as the lowermost layer of the phase-shift film 3 formed on the side of the transparent substrate 2, a chromium-based material is used. This layer is preferable in terms of the effect of suppressing the wavelength dependence of the transmittance, the phase difference, and the reflectance, and the suppression of damage to the transparent substrate 2 when the phase shift film 3 is patterned. Further, when the resist film 5 is formed on the phase shift film 3, a chromium-based material layer is used as the uppermost layer of the phase shift film 3, and the adhesion to the resist film is improved, and It is preferable to make the pattern shape of the phase shift film 3 vertical. The film thickness of the phase shift film 3 is required to obtain a desired phase difference in the exposure light and a desired transmittance or reflectance of the exposure light necessary for exhibiting the phase shift effect, and to form a phase shift according to the composition. The respective forming materials, the lamination order, and the film thickness of the metal telluride-based material layer or the chromium-based material layer of the transfer film 3 are appropriately determined. Further, the thickness of the metal halide-based material layer constituting the phase shift film 3 is considered in consideration of the metal telluride-based material layer, or the metal-telluride-based material layer, and a combination of the chromium-based material layer formed thereon or above. In the middle, the phase shift film 3 is appropriately determined by displaying a desired phase difference or transmittance. The thickness of the metal halide-based material layer of the phase shift film 3 is preferably in the range of, for example, 90 nm or more and 140 nm or less, but is not limited thereto. Further, when the phase shift film 3 is composed of at least a metal halide-based material layer and a chromium-based material layer, the thickness of the chromium-based material layer is considered in consideration of a metal formed under or on the chromium-based material layer. In the combination of the telluride-based material layers, the phase shift film 3 is appropriately determined by exhibiting a desired phase difference or transmittance. For example, it is preferably in the range of 2.5 nm or more and 15 nm or less, but is not limited thereto. It is substantially difficult to form a chromium-based material layer with a thickness of less than 2.5 nm. Further, when the chromium-based material layer is formed into a film with a thickness exceeding 15 nm, the transmittance is lowered. For example, the transmittance of the phase shift film 3 having a wavelength of 365 nm may be less than 3.5%. The metal halide-based material constituting the metal halide-based material layer is not particularly limited as long as it contains a metal or bismuth (Si). The composition of the metal and bismuth (Si) constituting the metal halide material layer is adjusted in accordance with the optical characteristics of the entire phase shift film 3. The ratio of the metal to the ruthenium is appropriately selected depending on the metal type or the optical characteristics required for the metal halide material layer, and is preferably metal: 矽 = 1:1 or more and 1:9 or less. As the metal, a transition metal such as molybdenum (Mo), tantalum (Ta), tungsten (W), or titanium (Ti) is exemplified. Examples of the metal telluride-based material constituting the metal halide-based material layer include a nitride of a metal telluride, an oxide of a metal telluride, a nitrogen oxide of a metal telluride, a carbonitride of a metal telluride, and a metal telluride. a material of at least one of a carbon oxide and a metal oxycarbide. The phase shift mask substrate used in the manufacture of the display device of the present invention is generally a large phase shift mask substrate having a side of 350 mm or more, and thus wet etching is employed in the fabrication of the phase shift mask. Further, according to the defect correction of the large phase shift mask, the defect quality of the phase shift film of the phase shift mask base is also required to be higher than or equal to a certain quality. The metal telluride-based material is preferably used in view of the defect quality of the phase-shift film, the controllability of the cross-sectional shape of the phase-shifted film pattern by wet etching, the transmittance of the phase-shift film, and the controllability of the phase difference. Nitrogen-containing material. The metal telluride-based material is preferably a nitride of a metal telluride, a nitrogen oxide of a metal telluride, or a carbonitride of a metal telluride, and particularly preferably a nitride of a metal telluride. If the cross-sectional shape of the phase shift film pattern is controlled to be vertical, since sufficient contrast can be obtained for the pattern boundary portion of the phase shift film pattern and the transparent substrate, it is easy to enhance the light intensity tilt of the pattern boundary portion. Hereinafter, a metal telluride-based material is specifically exemplified. In the case of molybdenum molybdenum (MoSi), a nitride of molybdenum molybdenum (MoSi), an oxide of molybdenum molybdenum (MoSi), a nitrogen oxide of molybdenum molybdenum (MoSi), a carbonitride of molybdenum molybdenum (MoSi), Carbon oxides of molybdenum molybdenum (MoSi) and carbon oxynitrides of molybdenum molybdenum (MoSi). In the case of TaSi, a nitride of tantalum (TaSi), an oxide of tantalum (TaSi), a nitrogen oxide of tantalum (TaSi), a carbonitride of tantalum (TaSi), Carbon oxides of tantalum (TaSi) and carbonitrides of tantalum telluride (TaSi). In the case of tungsten germanium (WSi), a nitride of tungsten telluride (WSi), an oxide of tungsten germanium (WSi), a nitrogen oxide of tungsten germanium (WSi), a carbonitride of tungsten germanium (WSi), Carbon oxides of tungsten (WSi) and carbonitrides of tungsten (WSi). In the case of titanium telluride (TiSi), a nitride of titanium telluride (TiSi), an oxide of titanium telluride (TiSi), a nitrogen oxide of titanium telluride (TiSi), a carbonitride of titanium telluride (TiSi), A carbon oxide of titanium telluride (TiSi) or a carbon oxynitride of titanium telluride (TiSi). Further, as described above, in view of the controllability of the cross-sectional shape of the phase-shifted film pattern by wet etching, it is preferable to include wet etching of the metal halide-based material layer. The component of speed. As a component which slows down the wet etching rate of the metal telluride-based material layer, the above-mentioned nitrogen (N) is exemplified. In this case, the metal constituting the metal halide-based material layer and the composition of cerium (Si) and nitrogen are adjusted in accordance with the optical characteristics of the entire phase shift film 3 as a whole. The nitrogen content in the case of containing nitrogen is preferably 25 atom% or more and 55 atom% or less, and more preferably 30 atom% or more and 50 atom% or less. Further, the metal halide-based material may contain elements other than the above-described examples without departing from the effects of the present invention. As the chromium-based material constituting the chromium-based material layer, a chromium compound containing at least one of chromium (Cr) and at least one selected from the group consisting of oxygen (O), nitrogen (N), and carbon (C) is used. As the chromium compound, a chromium (Cr) nitride, a chromium oxide, a chromium carbide, a chromium oxynitride, a chromium carbonitride, a chromium carbon oxide, and a chromium carbon oxynitride are exemplified. At least one material. Among such chromium-based materials, chromium nitride or chromium nitrogen oxide is preferred in terms of easily controlling the wavelength dependence of transmittance. Further, in the chromium-based material, elements other than the above-described examples may be included without departing from the effects of the present invention. Further, as described above, the phase shift mask substrate 1 of the first embodiment may have a transparent substrate 2, a phase shift film 3 formed on the transparent substrate 2, and a phase shift film 3 formed on the phase shift film 3. The structure of the light shielding film 4. The light shielding film 4 may be any one of a layered one and a plurality of layers. When the light shielding film 4 is composed of a plurality of layers, for example, a case having a two-layer structure composed of a light shielding layer formed on the phase shift film 3 side and an antireflection layer formed on the light shielding layer, or having a phase and a phase The case where the offset film 3 is connected to form an insulating layer, a light shielding layer formed on the insulating layer, and a three-layer structure formed of an antireflection layer formed on the light shielding layer. The light shielding layer may be any of a case composed of one layer and a case of a plurality of layers. Examples of the light shielding layer include a chromium nitride film (CrN), a chromium carbide film (CrC), a chromium carbonitride film (CrCN), a molybdenum telluride film (MoSi), and a molybdenum nitride nitride film (MoSiN). The antireflection layer may be either a case composed of one layer or a case composed of a plurality of layers. Examples of the antireflection layer include a chromium oxynitride film (CrON), a molybdenum oxide oxide film (MoSiO), and a molybdenum oxynitride oxynitride film (MoSiON). The insulating layer is made of, for example, CrCO or CrOCN containing less than 50 at% of Cr, and has a thickness of 10 nm or more and 50 nm or less. The phase shift film 3 having the metal telluride-based material layer on the outermost layer is formed on the light-shielding film 4 made of a chromium-based material in the case where the phase of the light-shielding film 4 made of the chromium-based material is offset from the mask base. At the time of wet etching, metal ions are melted from the phase shift film 3 having the metal telluride-based material layer on the outermost layer. At this time, electrons are generated. When the insulating layer is formed in such a manner as to be connected to the phase shift film 3, electrons generated when the metal ions are melted from the phase shift film 3 can be prevented from being supplied to the light shielding film. Therefore, the etching speed in the plane when the light-shielding film 4 is wet-etched can be made uniform. Further, as the light shielding film 4, a combination of a light shielding layer of a chromium carbide film (CrC) and an antireflection layer of a chromium oxynitride film (CrON), or a light shielding layer of a molybdenum oxide film (MoSi) and a molybdenum oxynitride oxynitride film are preferable. The combination of the antireflection layer of (MoSiON) is not limited thereto. The phase shift film 3 and the light shielding film 4 having the phase shift mask base 1 having the above configuration can be formed by a known film forming method. As a film formation method, a sputtering method is generally exemplified. The sputtering apparatus may be any of a cluster type sputtering apparatus and a series type sputtering apparatus. The metal halide material layer or the chromium material layer constituting the phase shift film 3 or the light shielding film 4 can be formed, for example, by a sputtering target or a sputtering gas atmosphere. When a phase shift mask is manufactured using the phase shift mask substrate 1 having such a phase shift film 3 or a light shielding film 4, the light is blocked by a phase shift film pattern on the phase shift film pattern. In the film pattern, for example, a phase shifting portion that changes the phase of the exposure light by substantially 180 degrees is formed by a portion of the phase shift film pattern of the unlaminated light-shielding film pattern, and the light-shielding portion is laminated with a phase-shifted film pattern and shading A portion of the film pattern is formed, and the light transmitting portion is made of a phase shift mask formed by a portion exposing the transparent substrate 2. As a sputtering target used for film formation of a metal telluride-based material layer, a metal or bismuth (Si) is selected. Specifically, a metal telluride, a nitride of a metal telluride, an oxide of a metal telluride, a carbide of a metal telluride, a nitrogen oxide of a metal telluride, a carbonitride of a metal telluride, a metal telluride Carbon oxides, and carbon oxynitrides of metal halides. The sputtering gas atmosphere at the time of film formation of the metal telluride-based material layer includes a gas selected from the group consisting of nitrogen (N ₂ ), nitrogen monoxide (NO) gas, nitrogen dioxide (NO ₂ ) gas, and nitrous oxide (N). ₂ O) an active gas of at least one of a group consisting of a gas, a carbon monoxide (CO) gas, a carbon dioxide (CO ₂ ) gas, and an oxygen gas (O ₂ ), and having an atmosphere selected from the group consisting of helium (He), helium (Ne), and argon. A mixed gas of at least one inert gas of at least one of a group of gas (Ar), helium (Kr), and xenon (Xe). The combination of the material for forming the sputtering target and the gas species of the sputtering gas atmosphere, or the mixing ratio of the reactive gas and the inert gas in the sputtering gas atmosphere is based on the metal halide material constituting the metal halide material layer. The type or composition is appropriately determined. As the sputtering target used for film formation of the chromium-based material layer, those containing chromium (Cr) or chromium compounds are selected. Specifically, chromium (Cr), chromium nitride, chromium oxide, chromium carbide, chromium nitrogen oxide, chromium carbonitride, chromium carbon oxide, and chromium carbonitride are exemplified. Things. The sputtering gas atmosphere during film formation of the chromium-based material layer comprises a gas selected from the group consisting of nitrogen (N ₂ ), nitrogen monoxide (NO) gas, nitrogen dioxide (NO ₂ ) gas, and nitrous oxide (N ₂ O). An active gas of at least one of a group consisting of a gas, a carbon monoxide (CO) gas, a carbon dioxide (CO ₂ ) gas, an oxygen gas (O ₂ ), a hydrocarbon gas, and a fluorine gas, and having a gas selected from the group consisting of helium (He) and helium A mixed gas of at least one inert gas of a group of gas (Ne), argon (Ar), helium (Kr), and xenon (Xe). Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas. The combination of the material for forming the sputtering target and the gas type of the sputtering gas atmosphere, or the mixing ratio of the reactive gas and the inert gas in the sputtering gas atmosphere is appropriately determined according to the type or composition of the chromium-based material constituting the chromium-based material layer. Decide. The phase shift mask substrate 1 for manufacturing a display device according to the first embodiment described above includes a transparent substrate 2 and a phase shift film 3 formed on the main surface of the transparent substrate 2 and having at least one layer A monolayer film or a laminate film comprising a layer of a metal halide material layer of a metal and an element of any of niobium, nitrogen, and/or oxygen. As described above, the phase shift film 3 has a transmittance of light of 365 nm at a wavelength of 3.5% or more and 8% or less, and a phase difference of light of 365 nm is in a range of 160 degrees or more and 200 degrees or less, and a wavelength of 365 nm or more 436. The transmittance in the range below nm is dependent on the change in wavelength within 5.5%. The phase shift film 3 exhibits optical characteristics in which the wavelength dependence of the transmittance of light having a wavelength of 365 nm or more and 436 nm or less is suppressed. Therefore, it is possible to obtain a phase shift mask substrate having a phase shift film which can sufficiently exhibit a phase shift effect when receiving exposure light in the wavelength range and which can improve the resolution. Further, a phase shift mask substrate having the phase shift film 3 can be obtained, and the phase shift film 3 can obtain a desired improvement in the light intensity of the boundary portion of the pattern, and the resolution is improved, and the CD characteristics are good. The phase shift film pattern of the transfer pattern shape is patterned. Further, in the phase shift mask substrate 1 for manufacturing a display device according to the first embodiment, the transmittance of the phase shift film 3 in the range of 365 nm or more and 700 nm or less depends on the amount of change in wavelength within 20%. In this case, in the wavelength range, the wavelength dependence of the transmittance of the phase shift film 3 can also be suppressed, so that the alignment mark provided in the mask can be easily recognized in the exposure machine at the time of manufacture of the display device, and the alignment precision is obtained. improve. Further, in the mask inspection apparatus, when the inspection apparatus of the mask pattern is recognized by the difference in transmittance between the transparent substrate and the mask pattern, it is easy to recognize defects such as defective shape defects of the mask pattern. Further, in the phase shift mask substrate 1 for manufacturing a display device according to the first embodiment, when the difference between the phase difference provided at a wavelength of 365 nm and the phase difference given at a wavelength of 436 nm is 30 degrees or less, the wavelength is suppressed. Since the wavelength dependence of the range is different, the phase shift effect can be sufficiently exerted, and the light intensity at the boundary portion of the pattern can be made steeper, and the resolution can be improved. Further, in the phase shift mask base 1 for manufacturing a display device according to the first embodiment, the reflectance of the phase shift film 3 in the range of 365 nm or more and 700 nm or less is 5% or more and 45% or less, and further preferred embodiment The phase shift mask base 1 for manufacturing a display device of the first embodiment has a reflectance of 5% or more and 45% or less in a range of 365 nm or more and 700 nm or less, and a wavelength of 365 nm or more and 700 nm or less. When the reflectance in the range depends on the amount of change in the wavelength within 5%, a resist film is formed on the phase shift film 3, and when the pattern is drawn by a laser scanner or the like, it is less likely to be drawn. The effect of standing waves generated by the light used to coincide with its reflected light. Therefore, at the time of pattern drawing, the roughness of the edge portion of the resist pattern cross section on the phase shift film 3 can be suppressed, and the pattern accuracy can be improved. Moreover, since the alignment at the time of pattern drawing can be easily acquired, and the mask pattern measurement can be easily performed by the long-size (MMS) measurement, the mask pattern can be recognized with high precision. Further, in the case where the phase shift mask is used for pattern transfer and the display device is manufactured, and the alignment mark is detected by the difference in reflectance between the transparent substrate and the alignment mark, the mask alignment is easily recognized, and the alignment is easy. Increased accuracy. Further, when pattern transfer is performed using a phase shift mask and a display device is manufactured, since the influence of the glare phenomenon can be suppressed, good CD characteristics can be obtained, and the resolution can be improved, and desired. Transfer pattern shape. Further, the phase shift mask base 1 for manufacturing a display device according to the first embodiment and the phase shift mask 30 for manufacturing a display device according to the second embodiment to be described later are used for the projection exposure of the double exposure. The shift mask substrate and the phase shift mask are particularly effective. In particular, as the exposure environment, the number of openings (NA) is preferably from 0.06 to 0.15, more preferably from 0.08 to 0.10, and the coherence coefficient (σ) is preferably from 0.5 to 1.0. Embodiment 2. In Embodiment 2, a phase shift mask for manufacturing a display device and a method of manufacturing the same will be described with reference to FIGS. 2 and 3. Fig. 2 is a cross-sectional view showing the configuration of a phase shift mask for manufacturing a display device according to a second embodiment of the present invention. 3 is a flow chart for explaining a method of manufacturing a phase shift mask for use in a phase shift mask substrate in which the light shielding film 4 is formed on the phase shift film 3. In FIG. 2 and FIG. 3, the same components as those in FIG. 1 are denoted by the same reference numerals and the description thereof will not be repeated. The phase shift mask 30 of the second embodiment includes a transparent substrate 2 and a phase shift film pattern 3' formed on the transparent substrate 2 (Fig. 2(a), hereinafter sometimes referred to as a first type of phase shift Shift cover). Further, a configuration in which the light shielding film pattern 4' is formed on the phase shift film pattern 3' may be employed (Fig. 2(b), hereinafter sometimes referred to as a second type of phase shift mask). Further, a configuration in which the light shielding film pattern 4' is formed under the phase shift film pattern 3' may be employed (Fig. 2(c), hereinafter sometimes referred to as a third type phase shift mask). The first type of phase shift mask 30 is composed of a phase shifting portion composed of a phase shift film pattern 3' and a light transmitting portion composed of a portion exposing the transparent substrate 2. The phase shifting masks 30 of the second and third types are caused by the phase shifting portion of the portion of the phase shifting film pattern 3' in which the light-shielding film pattern 4' is not formed on or under the phase-shifting film pattern 3'. The phase shift film pattern 3' is formed by a light-shielding portion in which a laminated portion of the light-shielding film pattern 4' is formed, or a light-transmitting portion in which a portion of the transparent substrate 2 is exposed. The phase shift mask 30 of the second and third types can prevent the film of the resist film formed on the transfer target from being reduced by the exposure light of the shifted portion of the transmission phase. In the phase shift mask 30 of the first type, the second type, or the third type described above, the phase shift film pattern 3' includes at least one layer having a metal and any element of germanium, nitrogen, and/or oxygen. A single layer film or laminated film of a metal halide material layer. The optical characteristics of the phase-shifted film pattern 3' as a whole are in the case where the phase-shifted film pattern 3' includes a single-layer film, depending on the kind or film thickness of the material constituting the material layer forming the phase-shifted film pattern 3'. The optical properties of the respective material layers determined, for example, such as the refractive index, the transmittance, and the reflectance, are such that when the phase-shifted film pattern 3' includes a laminated film, the phase-shifted film pattern 3' is formed according to the configuration. The combination of the material characteristics of the plurality of material layers, the combination of the optical characteristics determined by the film thickness, and the order of the layers of the respective material layers and the number of layers are determined. The phase shift film pattern 3' is controlled by a combination of material layers constituting the phase shift film pattern 3' to control the transmittance of light of a specific wavelength within a range as described below, and further, light of a specific wavelength The transmittance and the phase difference are controlled within the range described below, and the amount of change in the transmittance, the phase difference, and the reflectance of the light in the specific wavelength range is suppressed within the range as described below. Specifically, the phase shift film pattern 3' has a transmittance of 365 nm at a wavelength of 3.5% or more and 8% or less, a phase difference of 365 nm, a range of 160 degrees or more and 200 degrees or less, and a wavelength of 365 nm or more and 436 nm or less. The transmittance in the range depends on the amount of change in wavelength within 5.5%. The phase shift film pattern 3' is an optical characteristic in which the wavelength dependence of the transmittance of light having a wavelength of 365 nm or more and 436 nm or less is suppressed. Therefore, when the phase shift film pattern 3' receives light of the wavelength and the wavelength range, the phase shift effect can be sufficiently exerted, and the light intensity tilt of the boundary portion of the pattern can be enhanced, so that it is possible to obtain a film having good CD characteristics. The phase shifting film pattern 3' of the desired transfer pattern shape is offset from the mask 30. The phase shift mask 30 can correspond to the miniaturization of the line gap pattern or the contact hole. Further, in the phase shift mask 30 of the first type, the second type or the third type described above, the phase shift film pattern 3' is dependent on the wavelength in the range of 365 nm or more and 700 nm or less. When the amount of change is within 20%, the wavelength dependence of the transmittance can be suppressed in the wavelength range. Therefore, in the exposure machine at the time of manufacture of the display device, the alignment mark provided on the mask is easily recognized. The quasi-precision is improved. Further, in the mask inspection apparatus, when the inspection apparatus of the mask pattern is recognized by the difference in transmittance between the transparent substrate and the mask pattern, it is easy to recognize defects such as defective shape defects of the mask pattern. Further, in the phase shift mask 30 of the first type, the second type or the third type described above, the phase shift film pattern 3' is distinguished by a phase difference given at a wavelength of 365 nm and a wavelength difference of 436 nm. When the difference (ΔP (365-436)) is 30 degrees or less, the wavelength dependence of the phase difference in the wavelength range is suppressed, so that the phase shift effect can be sufficiently exerted, and the light intensity at the boundary portion of the pattern is made stronger. , can improve the resolution. Further, in the phase shift mask 30 of the first type, the second type, or the third type described above, the phase shift film pattern 3' has a reflectance of 5% or more in a range of 365 nm or more and 700 nm or less. % or less, and the reflectance of the phase shift film pattern 3' in the range of 365 nm or more and 700 nm or less is 5% or more and 45% or less, and the reflectance in the range of 365 nm or more and 700 nm or less depends on the reflectance. When the amount of change in wavelength (ΔR% (700-365)) is within 5%, the mask pattern measurement can be easily performed by the long-length (MMS) measurement, so that the mask pattern can be recognized with high precision. Further, in the case where the phase shift mask is used for pattern transfer and the display device is manufactured, and the alignment mark is detected by the difference in reflectance between the transparent substrate and the alignment mark, the mask alignment is easily recognized, and the alignment is easy. Increased accuracy. Further, when pattern transfer is performed using a phase shift mask and a display device is manufactured, since the influence of the glare phenomenon can be suppressed, good CD characteristics can be obtained, and the resolution can be improved, and desired. Transfer pattern shape. Next, a method of manufacturing a phase shift mask for manufacturing a display device to be implemented will be described with reference to FIG. The method of manufacturing the phase shift mask shown in FIG. 3 is a method of manufacturing the phase shift mask 30 of the first type and the second type described above. In the method of manufacturing a phase shift mask for manufacturing a display device of the first type and the second type, first, it is formed on the light shielding film 4 of the phase shift mask substrate 1 for manufacturing the display device according to the first embodiment. A resist pattern forming step of the resist pattern. Specifically, in the resist pattern forming step, first, as shown in FIG. 3(a), a resist film 5 is formed on the light shielding film 4. Thereafter, a pattern of a specific size is drawn to the resist film 5. Thereafter, the resist film 5 is developed with a specific developer, and as shown in FIG. 3(b), a resist pattern 5' is formed. As a pattern drawn to the resist film 5, a line gap pattern or a hole pattern is exemplified. Next, as shown in FIG. 3(c), a light-shielding film pattern forming step of wet etching the light-shielding film 4 with the resist pattern 5' as a mask and forming the light-shielding film pattern 4' is performed. The etching liquid for wet etching the light-shielding film 4 is not particularly limited as long as it is a chromium-based material or a metal halide-based material which can selectively etch the light-shielding film 4. When the material for forming the light-shielding film 4 is a chromium-based material, an etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate is exemplified. When the material for forming the light-shielding film 4 is a metal halide-based material, it is exemplified to include at least one fluoride selected from the group consisting of hydrofluoric acid, hydrofluoric acid hydrofluoric acid, and ammonium hydrogen fluoride, and hydrogen peroxide, and An etchant of at least one oxidizing agent of nitric acid and sulfuric acid. Specifically, an etching solution in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water is exemplified. Next, as shown in FIG. 3(d), after the resist pattern 5' is peeled off, as shown in FIG. 3(e), the light-shielding film pattern 4' is masked and the phase-shift film 3 is wet. The phase offset film pattern forming step of etching the phase shift film pattern 3' is formed. The etching liquid for wet etching the phase shift film 3 is not particularly limited as long as it can selectively etch the chromium-based material layer and the metal halide-based material layer constituting the phase shift film 3, respectively. For example, as an etching liquid for wet etching a chromium-based material layer, an etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate is exemplified. Further, the etching liquid for wet etching the metal telluride-based material layer includes at least one fluoride selected from the group consisting of hydrofluoric acid, hydrofluoric acid hydrofluoric acid, and ammonium hydrogen fluoride, and is selected from the group consisting of hydrogen peroxide and nitric acid. And an etchant of at least one oxidizing agent of sulfuric acid. Further, when the phase shift film 3 of the chromium-based material layer is formed on the metal halide-based material layer, when the chromium-based material layer is wet-etched, metal ions are melted from the metal halide-based material layer of the lower layer. Further, electrons are supplied to the chromium-based material layer, and the wet etching of the chromium-based material layer becomes slow. However, in the case where the phase shift film 3 of the metal halide-based material layer is formed on the chromium-based material layer, such a phenomenon does not occur. Therefore, the etching speed in the plane when the wet etching phase is shifted by the film 3 can be made uniform. Next, a phase shift mask 30 of the type having a phase shifting portion composed of the phase shift film pattern 3' and a light transmitting portion composed of a portion exposing the transparent substrate 2 is produced (phase shift of the first type) In the case of the photomask, after the phase shift film pattern forming step, as shown in FIG. 3(f), the light shielding film pattern 4' is peeled off. Further, a light-shielding film pattern 4' having a narrower phase-shifted film pattern 3' is provided on the phase-shifted film pattern 3', and has a portion of the phase-shifted film pattern 3' which is formed by the un-layered light-shielding film pattern 4'. The phase shifting portion of the type, the light-shielding portion formed by the portion in which the phase-shifted film pattern 3' and the light-shielding film pattern 4' are laminated, and the phase-shifted light of the type of the light-transmitting portion formed by the portion exposing the transparent substrate 2 In the case of the cover 30 (the phase shift mask of the second type), after the phase shift film pattern forming step, as shown in FIG. 3(g), the light shielding film pattern 4' is patterned into a phase shift film pattern. 3' narrower specific pattern. The phase shift mask 30 for manufacturing a display device is manufactured by the resist pattern forming step, the light shielding film pattern forming step, and the phase shift film pattern forming step. Further, the method of manufacturing the phase shift mask 30 of the first type and the second type described above is not limited to the above method. In the phase shift mask 30 of the first type, the phase shift mask substrate 1 for manufacturing the display device of the first embodiment is formed on the phase shift film 3 by using a structure in which the light shielding film 4 is not formed. A resist pattern forming step of forming the resist pattern 5', after which the phase shift of the phase shift film 3 is performed with the resist pattern 5' as a mask, and the phase shift film pattern 3' is formed. In the film pattern forming step, the resist pattern 5' is finally peeled off, and the phase shift mask 30 of the first type can be obtained. Further, according to the method of manufacturing a phase shift mask for manufacturing a display device according to the second embodiment, the phase shift mask is manufactured using the phase shift mask base 1 of the first embodiment. Therefore, it is possible to manufacture a phase shift of the phase shift film pattern 3' which is capable of obtaining a desired transfer pattern shape which can sufficiently exhibit the phase shift effect and which enhances the light intensity tilt of the pattern boundary portion and has good CD characteristics. Photomask 30. Further, a method of manufacturing the phase shift mask 30 of the first type and the second type will be described above, and a phase shift is formed on the main surface of the transparent substrate 2 on which a light shielding film pattern has been formed in one portion of the main surface. The present invention can also be applied to the phase shift mask 30 of the film shift pattern 3' (the phase shift mask of the third type). In this case, by covering the phase-shifting film pattern 3' with the light-shielding film pattern 4' which has been formed on one portion of the main surface, or on the main surface where the light-shielding film pattern 4' is not formed, the layer may be unlayered. The portion of the light-shielding film pattern and the phase-shift film pattern 3' is set as a phase shifting portion, and a phase shifting effect can be exerted in the phase shifting portion. The phase shift mask 30 of the third type in which the phase shift film pattern 3' is formed on the main surface of the transparent substrate 2 on which the light shielding film pattern 4' has been formed in one of the main surfaces is, for example, the following steps And manufacturing: a light-shielding film forming step on the main surface of the transparent substrate 2, forming a light-shielding film by sputtering; a light-shielding film pattern forming step, after the light-shielding film forming step, using the wet etching to make the light-shielding film pattern Forming a light-shielding film pattern; a phase-shifting film forming step of forming a phase-shift film 3 on the main surface of the transparent substrate 2 so as to cover the light-shielding film pattern after the light-shielding film pattern forming step; The offset film pattern forming step is performed by patterning the phase shift film 3 by wet etching after the phase shift film forming step to form the phase shift film pattern 3'. (Embodiment 3) In the third embodiment, a method of manufacturing a display device using the phase shift mask of the second embodiment will be described. In the method of manufacturing a display device according to the third embodiment, first, a resist film substrate on which a resist film is formed on a substrate, and a phase shift mask for manufacturing the display device described in the second embodiment are used. The phase shift mask 30 obtained by the manufacturing method or the phase shift mask 30 for manufacturing the display device described in the second embodiment is disposed in a phase shifting mask arrangement step opposite to the resist film. Next, a step of exposing the exposure film to the phase shift mask 30 and exposing the resist film to the resist film is performed. The exposure light system is, for example, a composite light containing light in a wavelength range of 300 nm or more and 700 nm or less. Specifically, it is a composite light including an i line, an h line, and a g line. The intensity ratio of the i-line, the h-line, and the g-line in the composite light used for the exposure light can be appropriately changed to 1:1:1 or 2 according to the manufacturing ratio of the i-line:h-line:g-line according to the manufacture of the display device: 1:1 and so on. According to the method of manufacturing the display device of the third embodiment, the phase shift mask 30 obtained by the method for manufacturing a phase shift mask for manufacturing a display device according to the second embodiment, or the second embodiment A phase shift mask 30 for manufacturing a display device manufactures a display device. Therefore, a display device having a fine line gap pattern or contact hole can be manufactured. [Examples] Hereinafter, the present invention will be more specifically described based on examples. In addition, the synthetic quartz glass substrate will be simply referred to as QZ hereinafter. Further, when expressed as QZ/A/B/C, it is shown that the A layer, the B layer, and the C layer are formed in this order on the QZ. Embodiment 1. In Embodiment 1, a phase shift mask substrate composed of QZ/CrON/MoSiN will be described. A. Phase-shifting reticle substrate and manufacturing method thereof for manufacturing the phase-shifting reticle substrate 1 of the above configuration, first, as a transparent substrate 2, preparing a synthetic quartz glass substrate of 3345 size (330 mm × 450 mm × 5 mm) . Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium and a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) are disposed, and A chromium-based material layer (film thickness: 10 nm) containing chromium oxynitride (CrON) is formed on the main surface of the transparent substrate 2, and a film containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer. A metal halide material layer (film thickness: 120 nm) was obtained, and a phase shift mask substrate 1 on which a phase shift film 3 (total film thickness: 130 nm) was formed was obtained. Further, the chromium-based material layer is placed in the vicinity of the chromium target, and a mixed gas containing Ar (30) and nitrogen monoxide (NO) gas (Ar: 30 sccm, NO: 30 sccm) is introduced to have a sputtering power of 4.0 kW. The transport speed of the transparent substrate 2 was 400 mm/min, and the film was formed on the main surface of the transparent substrate 2 by reactive sputtering. Further, the metal telluride-based material layer is in the vicinity of the molybdenum molybdenum target, and a mixed gas of Ar (Ar) and nitrogen (N ₂ ) (Ar: 30 sccm, N ₂ : 70 sccm) is introduced to have a sputtering power of 8.0 kW. The transfer speed of the transparent substrate 2 was 400 mm/min, and the film was formed on the chromium-based material layer by reactive sputtering. Further, the metal telluride-based material layer is laminated in plural times under the same conditions in order to obtain a desired film thickness of 120 nm. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. The phase shift film 3 of the obtained phase shift mask substrate 1 was measured for transmittance by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies, Japan, and the phase difference was measured by MPM-100 manufactured by Lasertec Corporation of Japan. . In the following examples and comparative examples, the same apparatus was used for the measurement of the transmittance or the phase difference. In addition, any of the transmittance values of the following examples and comparative examples are values based on the Air standard. When the transmittance and phase difference of the phase shift film 3 are measured, the film is formed on the main surface of the transparent substrate 2 of 6025 size (152 mm × 152 mm) fixed on the same substrate holder (not shown). A phase shifting film 3 (total film thickness: 130 nm) of a laminated structure comprising a chromium-based material layer of chromium oxide (CrON) and a metal halide-based material layer containing molybdenum nitride nitride (MoSiN) Offset film substrate (dummy substrate). As a result, as shown in FIG. 4, the transmittance spectrum of Example 1 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement result of the specific transmittance of Example 1 is shown in FIG. The transmittance at a wavelength of 365 nm (hereinafter sometimes referred to as T% (365)) was 4.41%, and ΔT% (436-365) was 3.91%. Therefore, it is understood that the phase shift film 3 of the first embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 13.35%. Therefore, it is understood that the phase shift film 3 of the first embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. The phase difference (hereinafter sometimes referred to as P(365)) at a wavelength of 365 nm is 181.7 degrees, and ΔP (365-436) is 28.7 degrees. Therefore, it is understood that the phase shift film 3 of the first embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, regarding the phase shift film 3 of the obtained phase shift mask substrate 1, the reflectance was measured by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. In the following examples, comparative examples, and reference examples, the same apparatus was used for the measurement of the reflectance. As a result, as shown in FIG. 6, the reflectance spectrum of Example 1 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 described below. The measurement results of the specific reflectance of Example 1 are shown in FIG. The reflectance in the range of 365 nm or more and 700 nm or less (hereinafter sometimes referred to as R% (700-365)) is 17.9% or more and 22.4% or less, and the range of values from 700 nm to 365 nm (maximum and minimum values) The difference) is 4.5%. Therefore, it is understood that the phase shift film 3 of the first embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and method of manufacturing the same for manufacturing phase-shifting reticle 30 using phase-shifting reticle substrate 1 manufactured in the above manner, first on phase-shifting film 3 of phase-shifting reticle substrate 1, The resist material is applied using a resist coating device. Thereafter, a resist film 5 having a film thickness of 1000 nm is formed by a heating and cooling step. Thereafter, the resist film 5 is drawn using a laser drawing device, and a resist pattern having a contact hole pattern (not shown) of 2.5 μm square is formed on the phase shift film 3 through development and cleaning steps. 5'. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched. Thereafter, the resist pattern 5' is used as a mask, and the chromium-containing oxynitride (CrON) chromium of the phase shift film 3 is obtained by a chromium etching solution containing cerium ammonium nitrate and ammonium peroxodisulfate. The material layer is wet etched to form a phase offset film pattern 3'. Thereafter, the resist pattern 5' is peeled off. Thus, a phase shift mask 30 having a phase shift film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained. The phase shift effect of the phase shift mask having the phase shift film pattern described above was simulated. The number of openings of the simulation system (NA) = 0.1, the coherence coefficient (σ) = 0.5, and as the exposure light, the i-line (365 nm), the h-line (405 nm), and the g-line (436 nm) are included, and the i-line is included: h line: g line = 2: 1:1 light intensity ratio composite light. The result of simulating the spatial image of the light by the phase shift mask formed with the phase shift film pattern having the contact hole pattern of 2.5 μm square is shown in Fig. 9 (light intensity distribution). The horizontal axis of Fig. 9 is the position (μm) of the contact hole pattern of the resist film transferred onto the transfer target from the center of the contact hole, and the vertical axis intensity ratio (the maximum amount of light transmitted from the phase shift mask) Set to 1 intensity ratio). The light intensity distribution curve of Fig. 9 is the peak intensity of the transmitted light when it is at the center of the contact hole, and the intensity of the transmitted light gradually decreases as it moves away from its center. In the light intensity distribution curve of FIG. 9, the distance from the center of the contact hole showing the peak intensity is ±1 μm, which corresponds to the boundary portion of the 2.0 μm square contact hole pattern of the resist film formed on the transfer target. (The straight line portion of the contact hole pattern). The light intensity tilt of the boundary portion of the pattern can be obtained from the difference in light intensity near the boundary portion of the pattern. As shown in FIG. 9, the light intensity distribution curve of Example 1 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity tilt (resolution) of the boundary portion of the pattern was 0.446. Therefore, it is understood that the phase shift mask of the first embodiment exhibits a stronger light intensity inclination and improves the resolution as compared with the comparative example described below. Embodiment 2. In Embodiment 2, a phase shift mask substrate composed of QZ/CrN/MoSiN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium and a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) are disposed, and A chromium-based material layer (film thickness: 10 nm) containing chromium nitride (CrN) is formed on the main surface of the transparent substrate 2, and a metal containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer. A vapor-based material layer (film thickness: 120 nm) was obtained, and a phase shift mask substrate 1 on which a phase shift film 3 (total film thickness: 130 nm) was formed was obtained. In addition, the chromium-based material layer is in the vicinity of the chromium target, and a mixed gas containing argon (Ar) and nitrogen (N ₂ ) (Ar: 30 sccm, N ₂ : 70 sccm) is introduced, and the sputtering power is 4.0 kW and transparent. The substrate 2 was transported at a speed of 400 mm/min, and was formed on the main surface of the transparent substrate 2 by reactive sputtering. Further, the metal telluride-based material layer was formed under the same conditions as in Example 1 (in order to obtain a desired film thickness of 120 nm and laminated under the same conditions). Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/CrN/MoSiN was formed was used for measurement of transmittance and phase difference. As a result, as shown in FIG. 4, the transmittance spectrum of Example 2 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 described below. The measurement results of the specific transmittance of Example 2 are shown in FIG. T% (365) was 3.34%, and ΔT% (436-365) was 3.28%. Therefore, it is understood that the phase shift film 3 of the second embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 12.68%. Therefore, it is understood that the phase shift film 3 of the second embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P(365) was 182.7 degrees and ΔP (365-436) was 27.7 degrees. Therefore, it is understood that the phase shift film 3 of the second embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 6, the reflectance spectrum of Example 2 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 described below. The measurement results of the specific reflectance of Example 2 are shown in FIG. R% (700-365) is 16.6% or more and 24.8% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 8.2%. Therefore, it is understood that the phase shift film 3 of the second embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the first embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Example 2 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.447. Therefore, in the phase shift mask of the second embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 3. In Embodiment 3, a phase shift mask substrate composed of QZ/CrON/MoSiN/CrON will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium and a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) are disposed, and A chromium-based material layer (film thickness: 5 nm) containing chromium oxynitride (CrON) is formed on the main surface of the transparent substrate 2, and a metal containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer. a germanide-based material layer (film thickness: 120 nm), and a chromium-based material layer (film thickness: 5 nm) containing chromium oxynitride (CrON) is formed on the metal telluride-based material layer to obtain a phase shift The phase shifting mask substrate 1 of the film 3 (total film thickness: 130 nm) was transferred. In addition, the chromium-based material layer was formed under the same conditions as in Example 1 except that the transport speed of the transparent substrate 2 was set to 800 mm/min. Further, the metal telluride-based material layer was also formed under the same conditions as in Example 1 (to obtain a desired film thickness of 120 nm and laminated in the same condition several times). Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/CrON/MoSiN/CrON was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 5, the transmittance spectrum of Example 3 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 described below. The measurement results of the specific transmittance of Example 3 are shown in FIG. T% (365) was 4.03%, and ΔT% (436-365) was 3.32%. Therefore, it is understood that the phase shift film 3 of the third embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 7, ΔT% (700-365) was 12.49%. Therefore, it is understood that the phase shift film 3 of the third embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) was 181.0 degrees and ΔP (365-436) was 28.3 degrees. Therefore, it is understood that the phase shift film 3 of the third embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 7, the reflectance spectrum of Example 3 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 3 are shown in FIG. R% (700-365) is 26.4% or more and 30.0% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 3.5%. Therefore, it is understood that the phase shift film 3 of the third embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and method of manufacturing the same, in order to manufacture the phase-shifting reticle 30 using the phase-shifting reticle substrate 1 manufactured in the above manner by the same method as in Embodiment 1, first, phase-shifted light On the phase shift film 3 of the cover substrate 1, a resist pattern 5' having a contact hole pattern of 2.5 μm square was formed. Thereafter, the resist pattern 5' is used as a mask, and the chromium oxide oxynitride of the second layer of the phase shift film 3 is replaced by a chromium etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate ( The chromium-based material layer of CrON) is subjected to wet etching. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched. Thereafter, the resist pattern 5' is used as a mask, and the first layer of the phase shift film 3 containing chromium oxynitride is contained by a chromium etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate ( The chromium-based material layer of CrON) is wet-etched to form a phase-shifted film pattern 3'. Thereafter, the resist pattern 5' is peeled off. Thus, a phase shift mask 30 having a phase shift film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 9, the light intensity distribution curve of Example 3 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity changes greatly at the boundary portion of the pattern, and is at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.447. Therefore, it is understood that the phase shift mask of the third embodiment exhibits a stronger light intensity inclination and improves the resolution as compared with the comparative example described below. Embodiment 4. In Embodiment 4, a phase shift mask substrate composed of QZ/CrN/MoSiN/CrN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium and a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) are disposed, and A chromium-based material layer (film thickness: 5 nm) containing chromium nitride (CrN) is formed on the main surface of the transparent substrate 2, and a metal telluride containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer. a material layer (film thickness: 120 nm), a chromium-based material layer (film thickness: 5 nm) containing chromium nitride (CrN) was formed on the metal telluride-based material layer to obtain a phase-shifted film. 3 (total film thickness: 130 nm) phase shift mask substrate 1. In addition, the chromium-based material layer was formed under the same conditions as in Example 1 except that the transport speed of the transparent substrate 2 was set to 800 mm/min. Further, the metal telluride-based material layer was also formed under the same conditions as in Example 1 (to obtain a desired film thickness of 120 nm and laminated in the same condition several times). Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. For the measurement of the transmittance and the phase difference, a phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/CrN/MoSiN/CrN was formed was used. As a result, as shown in FIG. 5, the transmittance spectrum of Example 4 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 4 are shown in FIG. T% (365) was 3.82%, and ΔT% (436-365) was 3.33%. Therefore, it is understood that the phase shift film 3 of the fourth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 14.64%. Therefore, it is understood that the phase shift film 3 of the fourth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P(365) was 180.2 degrees and ΔP (365-436) was 26.8 degrees. Therefore, it is understood that the phase shift film 3 of the fourth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 7, the reflectance spectrum of Example 4 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 4 are shown in FIG. R% (700-365) is 22.4% or more and 27.5% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 5.0%. Therefore, it is understood that the phase shift film 3 of the fourth embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the third embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Example 4 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, and is at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.447. Therefore, in the phase shift mask of the fourth embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 5. In Embodiment 5, a phase shift mask substrate composed of QZ/MoSiN/CrN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a sputtering device (not shown) in which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) and a sputtering target containing chromium are disposed, and A metal telluride-based material layer (film thickness: 120 nm) containing molybdenum nitride nitride (MoSiN) is formed on the main surface of the transparent substrate 2, and a chromium-containing nitride (CrN) is formed on the metal telluride-based material layer. A chromium-based material layer (film thickness: 10 nm) was obtained, and a phase shift mask substrate 1 on which a phase shift film 3 (total film thickness: 130 nm) was formed was obtained. In addition, the metal telluride-based material layer is in the vicinity of the molybdenum molybdenum target, and a mixed gas of argon (Ar) and nitrogen (N ₂ ) (Ar: 30 sccm, N ₂ : 70 sccm) is introduced to have a sputtering power of 8.0 kW. The transfer speed of the transparent substrate 2 was 400 mm/min, and the film was formed on the main surface of the transparent substrate 2 by reactive sputtering. In order to obtain a desired film thickness of 120 nm, the layers were laminated in the same conditions. Further, the chromium-based material layer was introduced in the vicinity of the chromium target, and a mixed gas containing argon (Ar) and nitrogen (N ₂ ) (Ar: 30 sccm, N ₂ : 70 sccm) was introduced, and the sputtering power was 4.0 kW and transparent. The substrate 2 was transported at a rate of 800 mm/min, and was deposited on the metal halide-based material layer by reactive sputtering. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. For the measurement of the transmittance and the phase difference, a phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/MoSiN/CrN was formed was used. As a result, as shown in FIG. 4, the transmittance spectrum of Example 5 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 5 are shown in FIG. T% (365) was 3.16% and ΔT% (436-365) was 2.88%. Therefore, it is understood that the phase shift film 3 of the fifth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 12.21%. Therefore, it is understood that the phase shift film 3 of the fifth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) was 178.4 degrees and ΔP (365-436) was 26.6 degrees. Therefore, it is understood that the phase shift film 3 of the fifth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 6, the reflectance spectrum of Example 5 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 5 are shown in FIG. R% (700-365) is 33.6% or more and 44.6% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 11.0%. Therefore, it is understood that the phase shift film 3 of the fifth embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed as compared with the comparative examples 1 and 2 described below. B. Phase-shifting reticle and manufacturing method thereof A phase-shifted light in which a phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square is formed on a transparent substrate 2 is obtained by the same method as in Embodiment 5. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Example 5 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, and is at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.448. Therefore, in the phase shift mask of the fifth embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 6. In Embodiment 6, a phase shift mask substrate composed of QZ/MoSiN/CrON will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a sputtering device (not shown) in which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) and a sputtering target containing chromium are disposed, and A metal telluride-based material layer (film thickness: 120 nm) containing molybdenum nitride nitride (MoSiN) is formed on the main surface of the transparent substrate 2, and oxynitride containing chromium is formed on the metal telluride-based material layer ( A Cr-based material layer (film thickness: 10 nm) of CrON) was obtained as a phase shift mask substrate 1 on which a phase shift film 3 (total film thickness: 130 nm) was formed. Further, a metal telluride-based material layer was formed into a film under the same conditions as in Example 5. Further, the chromium-based material layer is placed in the vicinity of the chromium target, and a mixed gas containing argon (Ar) and nitrogen monoxide (NO) (Ar: 30 sccm, NO: 30 sccm) is introduced, and the sputtering power is 4.0 kW and transparent. The substrate 2 was transported at a rate of 800 mm/min, and was deposited on the metal halide-based material layer by reactive sputtering. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. For the measurement of the transmittance and the phase difference, a phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/MoSiN/CrON was formed was used. As a result, as shown in FIG. 4, the transmittance spectrum of Example 6 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 6 are shown in FIG. T% (365) was 4.21%, and ΔT% (436-365) was 3.5%. Therefore, it is understood that the phase shift film 3 of the sixth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 12.88%. Therefore, it is understood that the phase shift film 3 of the sixth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) is 178.8 degrees and ΔP (365-436) is 28 degrees. Therefore, it is understood that the phase shift film 3 of the sixth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 6, the reflectance spectrum of Example 6 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 6 are shown in FIG. R% (700-365) is 30.7% or more and 39.4% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 8.7%. Therefore, it is understood that the phase shift film 3 of the sixth embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed as compared with the comparative examples 1 and 2 described below. B. Phase-shifting reticle and method of manufacturing the same for manufacturing phase-shifting reticle 30 using phase-shifting reticle substrate 1 manufactured in the above manner, first, on phase-shifting film 3 of phase-shifting reticle substrate 1 The resist material is applied using a resist coating device. Thereafter, a resist film 5 having a film thickness of 1000 nm is formed by a heating and cooling step. Thereafter, the resist film 5 is drawn using a laser drawing device, and a resist pattern 5 having a contact hole pattern (not shown) of 2.5 μm square is formed on the phase shift film 3 through development and cleaning steps. '. Thereafter, the resist pattern 5' is used as a mask, and the chromium-containing oxynitride (CrON) chromium of the phase shift film 3 is obtained by a chromium etching solution containing cerium ammonium nitrate and ammonium peroxodisulfate. The material layer is wet etched. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched to form a phase offset film pattern 3'. Thereafter, the resist pattern 5' is peeled off. Thus, a phase shift mask 30 having a phase shift film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. As a result, the light intensity inclination of the pattern boundary portion was the same as that of the fifth embodiment. Therefore, in the phase shift mask of the sixth embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 7. In Embodiment 7, a phase shift mask substrate composed of QZ/MoSiN/CrON/MoSiN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a sputtering device (not shown) in which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) and a sputtering target containing chromium are disposed, and A metal telluride-based material layer (film thickness: 60 nm) containing molybdenum nitride nitride (MoSiN) is formed on the main surface of the transparent substrate 2, and oxynitride containing chromium is formed on the metal telluride-based material layer ( CrON) chromium-based material layer (film thickness: 10 nm), and a metal telluride-based material layer (film thickness: 60 nm) containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer to obtain a phase The phase shifting mask substrate 1 of the offset film 3 (total film thickness: 130 nm). Further, the metal halide-based material layer was formed under the same conditions as in Example 6 except that the transport speed of the transparent substrate 2 was set to about 800 mm/min. Further, a chromium-based material layer was also formed under the same conditions as in Example 6. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/MoSiN/CrON/MoSiN was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 5, the transmittance spectrum of Example 7 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 7 are shown in FIG. T% (365) was 4.49% and ΔT% (436-365) was 3.92%. Therefore, it is understood that the phase shift film 3 of the seventh embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 23.78%. Therefore, it is understood that the phase shift film 3 of the seventh embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) is 178.8 degrees and ΔP (365-436) is 24 degrees. Therefore, it is understood that the phase shift film 3 of the seventh embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. The results are shown in Figure 7. Further, the measurement results of the specific reflectance of Example 7 are shown in Fig. 8. R% (700-365) is 5.4% or more and 24.4% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 19.0%. B. Phase-shifting reticle and method of manufacturing the same, in order to manufacture the phase-shifting reticle 30 using the phase-shifting reticle substrate 1 manufactured in the above manner by the same method as in Embodiment 1, first, phase-shifted light On the phase shift film 3 of the cover substrate 1, a resist pattern 5' having a contact hole pattern of 2.5 μm square was formed. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched. Thereafter, the resist pattern 5' is used as a mask, and the first layer of the phase shift film 3 containing chromium oxynitride is contained by a chromium etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate ( The chromium-based material layer of CrON) is subjected to wet etching. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched to form a phase offset film pattern 3'. Thereafter, the resist pattern 5' is peeled off. Thus, a phase shift mask 30 having a phase shift film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 9, the light intensity distribution curve of Example 7 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.446. Therefore, it is understood that the phase shift mask of the seventh embodiment exhibits a stronger light intensity inclination and improves the resolution as compared with the comparative example described below. Embodiment 8. In Embodiment 8, a phase shift mask substrate composed of QZ/MoSiN/CrN/MoSiN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a sputtering device (not shown) in which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) and a sputtering target containing chromium are disposed, and A metal telluride-based material layer (film thickness: 59 nm) containing molybdenum nitride nitride (MoSiN) is formed on the main surface of the transparent substrate 2, and a chromium-containing nitride (CrN) is formed on the metal telluride-based material layer. a chromium-based material layer (film thickness: 10 nm), and a metal telluride-based material layer (film thickness: 59 nm) containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer to obtain a phase shift The phase shifting mask substrate 1 of the film 3 (total film thickness: 128 nm) was transferred. Further, the metal telluride layer was formed under the same conditions as in Example 5 except that the transport speed of the transparent substrate 2 was set to about 800 mm/min. Further, a chromium-based material layer was also formed under the same conditions as in Example 5. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 128 nm) composed of QZ/MoSiN/CrN/MoSiN was formed was used for measurement of transmittance and phase difference. As a result, as shown in FIG. 5, the transmittance spectrum of Example 8 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 8 are shown in FIG. T% (365) was 3.55% and ΔT% (436-365) was 3.65%. Therefore, it is understood that the phase shift film 3 of the eighth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 23.62%. Therefore, it is understood that the phase shift film 3 of the eighth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) is 178.3 degrees and ΔP (365-436) is 22 degrees. Therefore, it is understood that the phase shift film 3 of the eighth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. The result is shown in FIG. Further, the measurement results of the specific reflectance of Example 8 are shown in Fig. 8. R% (700-365) is 5.1% or more and 24.8% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 19.7%. B. Phase-shifting reticle and manufacturing method thereof A phase-shifted light in which a phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square is formed on a transparent substrate 2 is obtained by the same method as in Embodiment 7. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Example 8 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.447. Therefore, in the phase shift mask of the eighth embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 9. In Embodiment 9, a phase shift mask substrate composed of QZ/MoSiN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) on which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) is disposed, and is formed on the main surface of the transparent substrate 2. The film contains a metal telluride-based material layer (film thickness: 120 nm) of molybdenum nitride nitride (MoSiN), and a phase shift mask substrate 1 was obtained. In addition, the metal telluride-based material layer is in the vicinity of the molybdenum molybdenum target, and a mixed gas of argon (Ar) and nitrogen (N ₂ ) (Ar: 30 sccm, N ₂ : 70 sccm) is introduced to have a sputtering power of 8.0 kW. The transfer speed of the transparent substrate 2 was 400 mm/min, and the film was formed on the transparent substrate 2 by reactive sputtering. In order to obtain a desired film thickness of 120 nm, the layers were laminated in the same conditions. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (film thickness: 110 nm) composed of QZ/MoSiN was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 4, the transmittance spectrum of Example 9 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 9 are shown in FIG. T% (365) was 4.36% and ΔT% (436-365) was 3.97%. Therefore, it is understood that the phase shift film 3 of the ninth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 21.60%. Therefore, it is understood that the phase shift film 3 of the ninth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) was 180.00 degrees and ΔP (365-436) was 24.00 degrees. Therefore, it is understood that the phase shift film 3 of the ninth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 6, the reflectance spectrum of Example 9 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 9 are shown in FIG. R% (700-365) is 18.0% or more and 28.3% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 10.4%. Therefore, it is understood that the phase shift film 3 of the ninth embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the first embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 9, the light intensity distribution curve of Example 9 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity changes greatly at the boundary portion of the pattern, and is at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.444. Therefore, it can be seen that in the phase shift mask of the ninth embodiment, the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Comparative Example 1. In Comparative Example 1, a phase shift mask substrate composed of CrON was described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium is disposed, and a chromium oxide (CrON) containing chromium is formed on the main surface of the transparent substrate 2. A chromium-based material layer (film thickness: 157 nm) was obtained to obtain a phase-shifted reticle substrate 1. In addition, the chromium-based material layer is in the vicinity of the chromium target, and a mixed gas containing argon (Ar) and nitrogen monoxide (NO) (Ar: 46 sccm, NO: 70 sccm) is introduced, and the sputtering power is 8.0 kW and transparent. The substrate 2 was transported at a speed of about 400 mm/min, and was formed on the transparent substrate 2 by reactive sputtering. In order to obtain a desired film thickness of 157 nm, the layers were laminated in the same conditions. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (film thickness: 157 nm) composed of QZ/CrON was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 4 and FIG. 5, the transmittance spectrum of Comparative Example 1 having a wavelength of 200 nm to 800 nm shows that the transmittance change sharply increases from the vicinity of the wavelength exceeding 300 nm, and is close to the wavelength exceeding 700 nm. A roughly S-shaped curve in which the change in transmittance becomes small. The measurement result of the specific transmittance of Comparative Example 1 is shown in FIG. T% (365) was 7.73%, and ΔT% (436-365) was 9.82%. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 cannot exhibit an optical characteristic in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment. Further, as shown in Fig. 8, ΔT% (700-365) was 48.00%. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 cannot exhibit an optical characteristic in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed as compared with the above-described embodiment. The measurement result of the phase difference is shown in FIG. P (365) is 181.3 degrees and ΔP (365-436) is 32.5 degrees. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 cannot exhibit an optical characteristic in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in the measurement results of the specific reflectances of FIG. 6 and FIG. 7 and FIG. 8, R% (700-365) is 7.60% or more and 18.45% or less, and the range of the range of 700 nm to 365 nm (maximum The difference between the value and the minimum value was 10.8%, which was not significantly different from the above-described Example 6, and was therefore good. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the first embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Comparative Example 1 shows that the peak of the light intensity at the center of the contact hole is not so sharp as compared with the above embodiment, and the light intensity does not change so much in the pattern boundary portion. In the peripheral region on the outer side of the boundary portion, the light intensity changes greatly. The light intensity of the boundary portion of the pattern is inclined to 0.432. Therefore, it is understood that the phase shift mask of Comparative Example 1 exhibits a weaker light intensity than the above-described embodiment. Comparative Example 2. In Comparative Example 2, a phase shift mask substrate composed of CrOCN was described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium is disposed, and a carbon oxynitride containing chromium (CrOCN) is formed on the main surface of the transparent substrate 2. A chromium-based material layer (film thickness: 117 nm) was obtained to obtain a phase-shifted mask substrate 1. Further, the chromium-based material layer is in the vicinity of the chromium target, and a mixed gas containing argon (Ar), carbon dioxide (CO ₂ ), and nitrogen (N ₂ ) is introduced (Ar: 46 sccm, CO ₂ : 35 sccm, N _{2 )} : 46 sccm), a sputtering power of 8.0 kW, a transfer speed of the transparent substrate 2 of about 400 mm/min, and a film formed on the transparent substrate 2 by reactive sputtering. In order to obtain a desired film thickness of 117 nm, the layers were laminated in the same conditions. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (thickness: 117 nm) composed of QZ/CrOCN was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 4 and FIG. 5, the transmittance spectrum of Comparative Example 2 having a wavelength of 200 nm to 800 nm shows that the transmittance change sharply increases from the vicinity of the wavelength exceeding 300 nm, and is close to the wavelength exceeding 600 nm. A roughly S-shaped curve in which the change in transmittance becomes small. The measurement results of the specific transmittance of Comparative Example 2 are shown in FIG. T% (365) was 5.10%, and ΔT% (436-365) was 7.58%. Therefore, it is understood that the phase shift film 3 of Comparative Example 2 cannot exhibit an optical characteristic in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment. Further, as shown in Fig. 8, ΔT% (700-365) was 50.63%. Therefore, it is understood that the phase shift film 3 of Comparative Example 2 cannot exhibit an optical characteristic in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed as compared with the above-described embodiment. The measurement result of the phase difference is shown in FIG. P (365) is 182.1 degrees and ΔP (365-436) is 31.0 degrees. Therefore, it is understood that the phase shift film 3 of Comparative Example 2 cannot exhibit an optical characteristic in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in the measurement results of the specific reflectances of FIG. 6 and FIG. 7 and FIG. 8, R% (700-365) is a range of 11.4% or more and 28.7% or less, and a range of 700 nm to 365 nm (maximum The difference between the value and the minimum value was 17.3%, which was not significantly different from the above-described Example 5, and was therefore good. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the first embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 9, the light intensity distribution curve of Comparative Example 2 shows that the peak of the light intensity at the center of the contact hole is not so sharp as compared with the above embodiment, and the light intensity does not change so much in the pattern boundary portion. In the peripheral region on the outer side of the boundary portion, the light intensity changes greatly. The light intensity of the boundary portion of the pattern is inclined to 0.440. Therefore, it is understood that the phase shift mask of Comparative Example 2 exhibits a weaker light intensity than the above-described embodiment. Further, in the above-described embodiment, an example of the molybdenum nitride nitride (MoSiN) is described as the material of the metal halide material layer constituting the phase shift film 3, but the invention is not limited thereto. The material of the metal halide material layer may be molybdenum oxide (MoSiO), molybdenum carbide (MoSiCN), or molybdenum carbide (MoSiOC). Further, in the case of a metal halide-based material other than molybdenum molybdenum, the same effects as described above can be obtained. Further, in the above-described embodiment, examples of the chromium-based material layer constituting the phase shift film 3 include chromium nitride (CrN) and chromium nitrogen oxide (CrON), but are not limited thereto. This is the case. As a material of the chromium-based material layer, it may also be chromium oxide (CrO), chromium carbide (CrC), chromium carbonitride (CrCN), chromium carbon oxide (CrCO), chromium carbonitride. (CrOCN). Further, in the above-described embodiment, the phase shift mask substrate 1 in which only the phase shift film 3 is formed on the transparent substrate 2, and the phase in which only the phase shift film pattern 3' is formed on the transparent substrate 2 have been described. The example of the offset mask 30 is not limited to this. The phase of the phase shift film 3 and the light shielding film 4 on the transparent substrate 2 may be offset from the mask substrate, and the phase of the phase shift film pattern 3 ′ and the light shielding film pattern 4 ′ may be formed on the transparent substrate 2 . The offset mask can also exert the same effects as the above embodiment. Further, in the phase shift mask substrate having the phase shift film 3 and the light shielding film 4 on the transparent substrate 2 described above, a light shielding layer or a light shielding layer may be used as the light shielding film formed on the phase shift film 3. And a laminated structure of the antireflection layer and a laminated structure of the insulating layer, the light shielding layer, and the antireflection layer. Further, in the above-described embodiment, a method of manufacturing the phase shift mask 30 by wet etching has been described, but the invention is not limited thereto. As a material constituting the phase shift mask substrate 1, in the case of a metal halide material layer, a fluorine-based gas (for example, CF ₄ gas, CHF ₃ gas, SF ₆ gas, or the like) may be used. Dry etching using a gas mixed with O ₂ gas for patterning, and in the case of a chromium-based material layer, by using a chlorine-based gas (for example, a mixed gas of Cl ₂ gas and O ₂ gas) Etching is patterned.

1‧‧‧phase offset mask base
2‧‧‧Transparent substrate
3‧‧‧ phase offset film
3'‧‧‧ phase offset film pattern
4‧‧‧Shade film
4'‧‧‧Shade film pattern
5‧‧‧resist film
5'‧‧‧resist film pattern
30‧‧‧phase offset mask

Fig. 1 is a cross-sectional view showing the structure of a phase shift mask base for manufacturing a display device according to a first embodiment of the present invention. 2(a) through 2(c) are cross-sectional views showing the configuration of a phase shift mask for manufacturing a display device according to a second embodiment of the present invention. 3(a)-(g) are process diagrams for explaining a method of manufacturing a phase shift mask using a phase shift mask base. Figure 4 is a transmission spectrum of each phase offset film of the phase shift mask substrate (Examples 1, 2, 5, 6 and 9, Comparative Examples 1 and 2). Figure 5 is a transmission spectrum of each phase offset film of the phase shift mask substrate (Examples 3, 4, 7, 8, and 9, and Comparative Examples 1 and 2). Fig. 6 is a graph showing the reflectance spectra of the reflectances of the phase shifting films of the phase shift mask substrates (Examples 1, 2, 5, 6 and 9, and Comparative Examples 1 and 2). Fig. 7 is a graph showing the reflectance spectra of the phase shift film reflectances of the phase-shifted mask substrates (Examples 3, 4, 7, 8, and 9, and Comparative Examples 1 and 2). Figure 8 is a table showing the optical characteristics of a phase shifting film of a phase shift mask substrate. Fig. 9 is a simulation result (light intensity distribution) of a spatial image of light passing through a phase shift mask (Examples 1, 3, 7 and 9, and Comparative Example 2). Fig. 10 is a simulation result (light intensity distribution) of a spatial image of light passing through a phase shift mask (Examples 2, 4, 6 and 8, and Comparative Example 1).

1‧‧‧phase offset mask base

2‧‧‧Transparent substrate

3‧‧‧ phase offset film

Claims (19)

A phase shift mask substrate, which is a phase shift mask substrate for manufacturing a display device, comprising: a transparent substrate; and a phase shift film formed on the transparent substrate; and the phase shift film comprises a single-layer film or a laminated film having at least one layer of a metal telluride-based material containing a metal and any element of cerium, nitrogen, and/or oxygen; the phase shifting film is as follows: a phase difference of 365 nm is 160 degrees or more and 200 The range below the wavelength; the transmittance at a wavelength of 365 nm is in the range of 3.5% or more and 8% or less; the transmittance in the range of 365 nm or more and 436 nm or less depends on the wavelength change within 5.5%; the wavelength is 365 nm or more and 700 or more The reflectance in the range of nm or less is 5% or more and 45% or less; and the reflectance in the range of 365 nm or more and 700 nm or less depends on the wavelength change amount within 5%. The phase shift mask substrate of claim 1, wherein the metal halide material layer is a nitride of a metal telluride, a nitrogen oxide of a metal telluride, a carbonitride of a metal telluride, and a metal telluride. It is composed of at least one material of carbon oxynitride. The phase shift mask substrate according to claim 1, wherein the metal halide-based material layer has a nitrogen content of 25 atom% or more and 55 atom% or less. The phase shift mask substrate of claim 1 wherein the phase shifting film is as follows: The transmittance in the range of 365 nm or more and 700 nm or less depends on the wavelength change amount within 20%. The phase shift mask substrate of claim 1 wherein the phase shifting film is as follows: a difference between the phase difference imparted at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm is 30 degrees or less. A phase shift mask substrate according to any one of claims 1 to 5, wherein said phase shifting film is composed of at least one layer of a metal halide material layer and at least one layer of a chromium-based material layer. The phase shift mask substrate of claim 6, wherein the lowermost layer of the phase shift film formed on the transparent substrate side is a chromium-based material layer. The phase shift mask substrate of claim 8, wherein the uppermost layer of the phase shifting film is a layer of a chromium-based material. The phase shift mask substrate of claim 6, wherein the chromium material layer is composed of chromium nitride, chromium oxide, chromium carbide, chromium oxynitride, chromium carbonitride, chromium carbon It is composed of at least one of an oxide and a carbon oxynitride of chromium. The phase shift mask substrate of claim 6, wherein the metal telluride material layer has a film thickness greater than a film thickness of the chromium material layer. A phase shift mask substrate according to any one of claims 1 to 5, comprising a light shielding film formed on said phase shift film. A phase shifting mask, which is a phase shifting mask for manufacturing a display device, comprising: a transparent substrate; and a phase shifting film pattern formed on the transparent substrate; a single layer film or a laminate film having at least one layer of a metal halide material layer containing a metal and any element of cerium, nitrogen and/or oxygen; the phase shifting film pattern is as follows: a phase difference of 365 nm is 160 degrees or more The range of 200 degrees or less; the transmittance of the wavelength of 365 nm is 3.5% or more and 8% or less; the transmittance of the wavelength of 365 nm or more and 436 nm or less depends on the wavelength change of 5.5%; the wavelength of 365 nm or more The reflectance in the range of 700 nm or less is 5% or more and 45% or less; and the reflectance in the range of 365 nm or more and 700 nm or less depends on the wavelength change amount within 5%. The phase shift mask of claim 12, wherein the phase shift film pattern is as follows: The transmittance in the range of 365 nm or more and 700 nm or less depends on the wavelength change amount within 20%. The phase shift mask of claim 12, wherein the phase shift film pattern is as follows: a difference between the phase difference given at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm is 30 degrees or less. A phase shift mask according to any one of claims 12 to 14, comprising a light shielding film pattern formed on said phase shift film pattern. The phase shift mask of any one of claims 12 to 14, comprising a light shielding film pattern formed under the phase shift film pattern. A method for manufacturing a phase shift mask, which is a method for manufacturing a phase shift mask for manufacturing a display device, comprising: a resist pattern forming step, which is in any one of claims 1 to 10 Forming a resist pattern on the phase shifting film of the phase shifting mask base; and forming a phase shifting film pattern forming step by using the resist pattern as a mask and wet etching the phase shifting film, A phase offset film pattern is formed. A method of manufacturing a phase shift mask, which is a method of manufacturing a phase shift mask for manufacturing a display device, comprising: a resist pattern forming step of phase shifting light as in claim 11 a resist pattern is formed on the light shielding film of the cover base; a light shielding film pattern forming step of forming the resist pattern as a mask, wet etching the light shielding film to form a light shielding film pattern, and forming a phase shift film pattern In the step of disposing the light-shielding film pattern as a mask, the phase-shift film is wet-etched to form a phase-shift film pattern. A manufacturing method of a display device, which is characterized by comprising: a phase shift mask arrangement step for attaching a resist film substrate on which a resist film is formed on a substrate, as requested a phase shift mask of item 12 is disposed opposite to the resist film; and a resist film exposing step of irradiating the phase shift mask with the composite exposure light including the i line, the h line, and the g line The above resist film is exposed.