JP6532919B2 - Phase shift mask blank for manufacturing display device, phase shift mask for manufacturing display device, and method of manufacturing display device - Google Patents

Description

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

  At present, there are VA (Vertical alignment) method and IPS (In Plane Switching) method as methods adopted in liquid crystal display devices. By these methods, a liquid crystal display device with high definition, high-speed display performance, and a wide viewing angle is realized. In the liquid crystal display device to which these methods are applied, the response speed and the viewing angle can be improved by forming the pixel electrode of the line and space pattern by patterning the transparent conductive film by a photolithography process, for example. . Recently, from the viewpoint of further improvement of response speed and viewing angle and improvement of light utilization efficiency of liquid crystal display, that is, reduction of power consumption of liquid crystal display and improvement of contrast, fineness of pitch width of line and space pattern Needs to be For example, it is desired to narrow the pitch width of the line and space pattern from 6 μm to 5 μm and further from 5 μm to 4 μm.

  Further, in the case of manufacturing a liquid crystal display device or an organic EL display device, a semiconductor element such as a transistor is formed by laminating a plurality of conductive films and insulating films subjected to necessary patterning. At that time, a photolithography process is often used also for patterning of individual films to be laminated. For example, some thin film transistors and LSIs used in these display devices have a structure in which a contact hole is formed in an insulating layer by a photolithography process, and a pattern of an upper layer and a pattern of a lower layer are connected. Recently, in such a display device, there is a growing need to display a bright and fine image with a sufficient operating speed and to reduce power consumption. In order to satisfy such a demand, it is required to miniaturize and highly integrate components of a display device. 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.

  From such a background, a photomask for manufacturing a display device that can cope with the miniaturization of line and space patterns and contact holes is desired.

  In realizing the miniaturization of line and space patterns and contact holes, the resolution limit of an exposure machine for manufacturing a display device is 3 μm in a conventional photomask, so there is no sufficient process margin (Process Margin). Products with a minimum line width close to the resolution limit must be produced. Therefore, there has been a problem that the defect rate of the display device becomes high.

  For example, in the case of using a photomask having a hole pattern for forming a contact hole and transferring it to a transfer target, if it is a hole pattern having a diameter exceeding 3 μm, transfer is performed using a conventional photomask I was able to. However, it has been very difficult to transfer hole patterns having a diameter of 3 μm or less, in particular, those 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, for example, conversion to an exposure machine having a high NA is considered, but a large investment is required.

  Then, in order to improve resolution and correspond to miniaturization of line and space patterns and contact holes, a phase shift mask attracts attention as a photomask for manufacturing a display device.

Recently, a phase shift mask provided with a chromium-based phase shift film has been developed as a photomask for manufacturing a liquid crystal display device.
In Patent Document 1, a transparent substrate, a light shielding layer formed on the transparent substrate, and a light shielding layer formed around the light shielding layer, which has a phase difference of 180 degrees with respect to light in any wavelength region of 300 nm to 500 nm. A halftone phase shift mask has been described that includes a single layer phase shift layer of a chromium oxynitride-based material that can be added. In this phase shift mask, a light shielding layer on a transparent substrate is patterned, a phase shift layer is formed on the transparent substrate so as to cover the light shielding layer, a photoresist layer is formed on the phase shift layer, and a photoresist layer is formed. It is manufactured by forming a resist pattern by exposing and developing in a photolithography process, and patterning the phase shift layer using the resist pattern as an etching mask.
The single-layer chromium phase shift layer is formed in a sputtering gas atmosphere composed of a mixed gas containing nitrogen (N ₂ ) gas and carbon dioxide (CO ₂ ) gas (see FIG. 2 of Patent Document 1). See sample Nos. 1 to 5). Therefore, it is presumed that the phase shift layer may be formed not only from chromium oxynitride (CrON) but also from chromium oxycarbonitride (CrOCN).

  Such phase shift masks receive exposure light of various 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 unit used in a photolithography process, for example, it has peak intensities at i line (365 nm), h line (405 nm) and g line (436 nm). There is known one provided with a light source (ultra-high pressure UV lamp) that outputs composite light. For example, if the compound light is used as the exposure light when transferring the mask pattern of the phase shift mask onto the main surface of the mother glass substrate whose size is increasing with the recent increase in size of liquid crystal display devices, The tact time can be shortened.

Also, in general, it is known that a film showing a certain degree of transmittance in light of a certain wavelength has optical characteristics including the transmittance changing depending on the wavelength, that is, has wavelength dependency.
The phase shift film is a film having the property of changing the phase of the exposure light, and thus exhibits a certain degree of transmissivity in the exposure light by its nature. Therefore, according to the above findings, in the phase shift film, the transmittance, the reflectance, and the phase difference in the exposure light have wavelength dependency.
And in patent document 2, the photomask which has the phase shift film which suppressed the phase difference deviation and the transmittance | permeability deviation is described.

JP, 2011-13283, A JP 2012-230379

However, the phase shift films specifically described in the above-mentioned Patent Documents 1 and 2 were all single-layer chromium phase shift films. Therefore, in the case of transferring a fine pattern having a contact hole diameter of 2.5 μm or 2 μm, for example, by using a phase shift mask obtained from such a phase shift film material, the wavelength dependency such as the transmittance of exposure light Or the cross-sectional shape of the phase shift film pattern can not be made perpendicular, resulting in a problem that sufficient resolution can not be obtained.
In addition, a drawing machine for producing a mask and an exposure machine used at the time of manufacturing a display device are provided with a light source for alignment in order to recognize an alignment mark provided on the mask. For example, light of a wavelength of 365 to 700 nm is used as alignment light, and the alignment mark is detected using the difference in transmittance between the transparent substrate and the alignment mark in the alignment light. As the difference in transmittance in the alignment light (wavelength 365 to 700 nm) is larger, the recognition of alignment becomes easier, and the alignment accuracy is improved, so that the handleability of the phase shift mask can be improved. However, it can not be said that the phase shift masks of Patent Documents 1 and 2 described above have sufficient characteristics in handling.
Further, as a mask inspection apparatus, for example, one provided with a light source that outputs light having a wavelength of 365 nm or 546 nm is known. It is known that a mask pattern can be identified by using a difference in reflectance or a difference in transmittance between a transparent substrate and a mask pattern in inspection light of the mask inspection apparatus. When such a mask inspection apparatus is used, for example, it becomes possible to grasp the presence or absence of a shape defect of a mask pattern or an attached foreign substance on the mask pattern. However, it can not be said that the phase shift masks of Patent Documents 1 and 2 described above have sufficient characteristics as the optical properties of the phase shift film in mask inspection.

  Therefore, the present invention has been made in view of the above-described problems, and is provided for the manufacture of a display device including a phase shift film exhibiting optical characteristics in which the wavelength dependency of each optical characteristic with respect to exposure light is suppressed. It is an object of the present invention to provide a phase shift mask blank, a phase shift mask using the phase shift mask blank, a method of manufacturing the same, and a method of manufacturing a display device using the phase shift mask.

  In order to solve the problems described above, the present invention has the following configuration.

(Configuration 1) In a phase shift mask blank for manufacturing a display device,
A transparent substrate,
A phase shift film formed on the transparent substrate;
The phase shift film is a single layer film or a laminated film having at least one metal silicide material layer containing metal, silicon, and any one element of nitrogen and / or oxygen,
The phase shift film is
The transmittance for light with a wavelength of 365 nm is in the range of 3.5% to 8%,
The phase difference of light with a wavelength of 365 nm is in the range of 160 degrees to 200 degrees,
A phase shift mask blank characterized in that a wavelength-dependent change amount of transmittance in a wavelength range of 365 nm to 436 nm is within 5.5%.

(Configuration 2) The phase shift film is
The phase shift mask blank according to Configuration 1, wherein the wavelength dependent variation of the transmittance in the wavelength range of 365 nm to 700 nm is within 20%.

(Configuration 3) The phase shift film is
The phase shift mask blank according to Configuration 1 or 2, wherein a difference between a retardation applied at a wavelength of 365 nm and a retardation applied at a wavelength of 436 nm is 30 degrees or less.

(Configuration 4) The phase shift film is
The phase shift mask blank according to any one of the configurations 1 to 3, wherein a reflectance in a wavelength range of 365 nm to 700 nm is 5% to 45%.

(Structure 5) The phase shift mask blank according to structure 4, wherein the phase shift film has a wavelength dependent change amount of reflectance in a wavelength range of 365 nm to 700 nm within 5%.

(Structure 6) The phase described in any one of the structures 1 to 5 characterized in that the phase shift film is composed of at least one metal silicide-based material layer and at least one chromium-based material layer. Shift mask blank.

(Structure 7) The metal silicide-based material layer is a metal silicide nitride, a metal silicide oxide, a metal silicide oxynitride, a metal silicide carbonitride, a metal silicide oxide carbide, and a metal silicide oxide. The phase shift mask blank according to any one of the configurations 1 to 6, characterized in that it is composed of at least one material of carbonitrides.

(Structure 8) The chromium-based material layer is a nitride of chromium, an oxide of chromium, a carbide of chromium, an oxynitride of chromium, an carbonitride of chromium, an oxide carbide of chromium, and an oxycarbonitride of chromium 7. The phase shift mask blank according to claim 6, wherein the phase shift mask blank is made of at least one material.

(Structure 9) The phase shift mask blank according to Structure 6, wherein the film thickness of the metal silicide-based material layer is larger than the film thickness of the chromium-based material layer.

(Structure 10) The phase shift mask blank according to any one of structures 1 to 9, further comprising a light shielding film formed on the phase shift film.

(Structure 11) In a phase shift mask for manufacturing a display device,
A transparent substrate,
A phase shift film pattern formed on the transparent substrate;
The phase shift film pattern is composed of a single layer film or a laminated film having at least one metal silicide material layer containing metal, silicon, and any one element of nitrogen and / or oxygen,
The phase shift film pattern is
The transmittance for light with a wavelength of 365 nm is in the range of 3.5% to 8%,
The phase difference in wavelength light of wavelength 365 nm is in the range of not less than 160 degrees and not more than 200 degrees,
A phase shift mask characterized in that a wavelength-dependent change amount of transmittance in a wavelength range of 365 nm to 436 nm is within 5.5%.

(Structure 12) The phase shift film pattern is
11. The phase shift mask according to configuration 11, wherein the wavelength dependent variation of the transmittance in the wavelength range of 365 nm to 700 nm is within 20%.

(Structure 13) The phase shift film pattern is
11. The phase shift mask according to configuration 11 or 12, wherein a difference between the phase difference given at a wavelength of 365 nm and the phase difference given at a wavelength of 436 nm is 30 degrees or less.

(Structure 14) The phase shift film pattern is
11. The phase shift mask according to any one of the configurations 11 to 13, wherein a reflectance in a wavelength range of 365 nm to 700 nm is 15% to 30%.

(Structure 15) The phase shift film pattern is
The phase shift mask according to Configuration 14, wherein a wavelength-dependent change amount of reflectance in a wavelength range of 365 nm to 700 nm is within 5%.

(Structure 16) The phase shift mask according to any one of structures 11 to 15, comprising a light shielding film pattern formed on the phase shift film pattern.

(Structure 17) The phase shift mask according to any one of structures 11 to 16, comprising a light shielding film pattern formed under the phase shift film pattern.

(Structure 18) In a method of manufacturing a phase shift mask for manufacturing a display device,
A resist pattern forming step of forming a resist pattern on the phase shift film of the phase shift mask blank according to any one of constitutions 1 to 9;
A phase shift film pattern forming step of wet etching the phase shift film using the resist pattern as a mask to form a phase shift film pattern.

(Structure 19) In a method of manufacturing a phase shift mask for manufacturing a display device,
A resist pattern forming step of forming a resist pattern on the light shielding film of the phase shift mask blank according to Configuration 10;
A light shielding film pattern forming step of forming the light shielding film pattern by wet etching the light shielding film using the resist pattern as a mask;
A phase shift film pattern forming step of wet etching the phase shift film using the light shielding film pattern as a mask to form a phase shift film pattern.

(Configuration 20) In a method of manufacturing a display device,
Obtained by the phase shift mask according to any one of the constitutions 11 to 17 or the method for producing a phase shift mask according to the constitution 18 or 19, for a resist film-coated substrate having a resist film formed on a substrate Placing a phase shift mask in opposition to the resist film;
and a resist film exposure step of exposing the resist film by irradiating the phase shift mask with composite exposure light including i-line, h-line and g-line.

As described above, according to the phase shift mask blank for manufacturing the display device of the present invention, the transparent substrate and the phase shift film formed on the transparent substrate are provided. The phase shift film is composed of a single layer film or a laminated film having at least one metal silicide material layer containing metal, silicon, and any one element of nitrogen and / or oxygen. The phase shift film has a transmittance of 3.5% to 8% for light with a wavelength of 365 nm, a phase difference of 160 degrees to 200 degrees for light with a wavelength of 365 nm, and a wavelength of 365 nm to 436 nm or less The wavelength dependent variation of the transmittance in the range of is within 5.5%. Such a phase shift film exhibits optical characteristics in which the wavelength dependency of the transmittance for light in the wavelength range of 365 nm to 436 nm is suppressed.
For this reason, when receiving the exposure light of the said wavelength range, the phase shift effect can fully be exhibited and it can obtain the phase shift mask blank provided with the phase shift film which can aim at the improvement of resolution. In addition, it has a phase shift film that can be patterned into a phase shift film pattern that can strengthen the light intensity gradient at pattern boundaries, improve resolution, and obtain a desired transfer pattern shape with good CD characteristics. A phase shift mask blank can be obtained.

Further, according to the phase shift mask for manufacturing a display device of the present invention, a transparent substrate and a phase shift film pattern formed on the transparent substrate are provided. The phase shift film pattern is composed of a single layer film or a laminated film having at least one metal silicide material layer containing metal, silicon, and any one element of nitrogen and / or oxygen. The phase shift film pattern has a transmittance of 3.5% to 8% for light of wavelength 365 nm, a phase difference of 160 degrees to 200 degrees for light of wavelength 365 nm, and a wavelength of 365 nm to 436 nm. The wavelength dependent variation of the transmittance in the following range is within 5.5%. Such a phase shift film pattern exhibits optical characteristics in which the wavelength dependency of the transmittance of light in the wavelength range of 365 nm to 436 nm is suppressed.
Therefore, when exposure light in the wavelength range is received, the phase shift effect can be sufficiently exhibited, the light intensity inclination at the pattern boundary can be strengthened, and a desired transfer pattern shape having good CD characteristics can be obtained. A phase shift mask provided with a phase shift film pattern that can be obtained can be obtained. This phase shift mask can cope with the miniaturization of line and space patterns and contact holes.

  Further, according to the method of manufacturing a phase shift mask for manufacturing a display device according to the present invention, a phase shift mask is manufactured using the above-described phase shift mask blank. For this reason, it is possible to manufacture a phase shift mask provided with a phase shift film pattern exhibiting optical characteristics in which the wavelength dependency with respect to exposure light is suppressed. According to this phase shift mask, the phase shift effect can be sufficiently exerted, the light intensity gradient at the pattern boundary can be strengthened, and a desired transfer pattern shape having good CD characteristics can be obtained.

  Further, according to the method of manufacturing a phase shift mask for manufacturing a display device according to the present invention, the phase shift mask blank provided with the light shielding film formed on the phase shift film of the above-described phase shift mask blank is used. A phase shift mask provided with a light shielding film pattern formed on the shift film pattern is manufactured. For this reason, it is possible to manufacture a phase shift mask provided with a phase shift film pattern exhibiting optical characteristics in which the wavelength dependency with respect to exposure light is suppressed. According to this phase shift mask, the phase shift effect can be sufficiently exhibited, the light intensity inclination of the pattern boundary portion of the phase shift film pattern where the light shielding film pattern is not stacked can be strengthened, and the CD characteristic is excellent. A desired transfer pattern shape can be obtained.

  Further, according to the method of manufacturing a display device according to the present invention, a fine line can be obtained by manufacturing a display device using the phase shift mask described above or the phase shift mask obtained by the method of manufacturing the phase shift mask described above. A display device having an and space pattern and a contact hole can be manufactured. Furthermore, accurate alignment of the line and space pattern of the display device and the contact holes can be performed, and the manufacturing yield of the display device can also be improved.

It is sectional drawing which shows a structure of the phase shift mask blank for display apparatus manufacture by Embodiment 1 of this invention. It is sectional drawing for demonstrating the structure of the phase shift mask for display apparatus manufacture by Embodiment 2 of this invention. It is process drawing for demonstrating the manufacturing method of the phase shift mask using a phase shift mask blank. It is a transmittance | permeability spectrum of each phase shift film | membrane of phase shift mask blank (Example 1, 2, 5, 6 and 9, Comparative example 1 and 2). It is a transmittance | permeability spectrum of each phase shift film | membrane of phase shift mask blank (Example 3, 4, 7, 8 and 9, Comparative example 1 and 2). It is a reflectance spectrum which shows the reflectance of each phase shift film of a phase shift mask blank (Examples 1, 2, 5, 6 and 9, comparative examples 1 and 2). It is a reflectance spectrum which shows each phase shift film reflectance of a phase shift mask blank (Example 3, 4, 7, 8 and 9, the comparative examples 1 and 2). It is a table | surface which shows the optical characteristic of the phase shift film of a phase shift mask blank. It is a simulation result (light intensity distribution) of the spatial image of the light which passed the phase shift mask (Example 1, 3, 7 and 9, Comparative example 2). It is a simulation result (light intensity distribution) of the spatial image of the light which passed the phase shift mask (Example 2, 4, 6 and 8 and the comparative example 1).

  Hereinafter, a phase shift mask blank for display device manufacture according to an embodiment of the present invention, a phase shift mask for display device manufacture using this phase shift mask blank, a method for manufacturing the same, and a display using this phase shift mask The method of manufacturing the device will be described in detail.

Embodiment 1
In the first embodiment, a phase shift mask blank for manufacturing a display device and a method for manufacturing the same will be described.

First, a phase shift mask blank for manufacturing a display device of Embodiment 1 will be described.
FIG. 1 is a cross-sectional view showing a configuration of a phase shift mask blank for manufacturing a display device according to Embodiment 1 of the present invention.
The phase shift mask blank 1 according to Embodiment 1 includes a transparent substrate 2 and a phase shift film 3 formed on the transparent substrate 2. The light shielding film 4 may be formed on the phase shift film 3. Alternatively, the resist film 5 may be formed on the phase shift film 3 or the light shielding film 4.

  The transparent substrate 2 is translucent to the exposure light to be used. The material of the transparent substrate 2 is not particularly limited as long as it is a material having transparency to the exposure light to be used. As a material which has translucency, synthetic quartz glass, soda lime glass, an alkali free glass is mentioned, for example.

The phase shift film 3 is formed of a single layer film or a laminated film having at least one metal silicide material layer containing metal, silicon, and any one of nitrogen and / or oxygen. When the phase shift film 3 is a single layer film, the optical characteristics of the entire phase shift film 3 are determined by, for example, the type and thickness of the material constituting the material layer constituting the phase shift film 3, for example Determined by optical characteristics such as refractive index, transmittance, and reflectance, and when the phase shift film 3 is a laminated film, it is determined by the type and film thickness of the materials constituting the plurality of material layers constituting the phase shift film 3 It is determined by the combination of the optical characteristics and the configuration such as the stacking order and the number of layers of each material layer. Here, when the phase shift film 3 is a single layer film, the single layer film is a film formed of a single material. Therefore, the film of the laminated structure made of a single material is also a single layer film. Further, in the case where the phase shift film 3 is a laminated film, the laminated film is a combination of a film formed of a single material or the same material and a film formed of a material different from this film. It is a constructed membrane.
In such a phase shift film 3, the transmittance of light of a specific wavelength is controlled in the following range by the selection of the material layer constituting the phase shift film 3, and the transmittance and position of light of a specific wavelength are The phase difference is controlled in the following range, and the wavelength-dependent variation of the transmittance, phase difference and reflectance of light in a specific wavelength range is further suppressed in the following range.

Specifically, the phase shift film 3 has a transmittance at a wavelength of 365 nm (hereinafter, may be referred to as T% (365)) in a range of 3.5% to 8%. For this reason, the light intensity inclination of the pattern boundary portion becomes strong, and the resolution can be improved. If T% (365) is less than 3.5%, it will be difficult to obtain the amount of transmitted light necessary to sufficiently exhibit the desired phase shift effect. If T% (365) exceeds 8%, the light intensity inclination at the pattern boundary becomes weak, making it difficult to improve the resolution.
Further, the phase shift film 3 has a wavelength-dependent variation (hereinafter may be referred to as ΔT% (436-365)) of the transmittance in the wavelength range of 365 nm to 436 nm, which is within 5.5%. Since the wavelength dependency of the transmittance in the wavelength range is suppressed, the light intensity inclination of the pattern boundary portion becomes strong, and the resolution can be improved. When ΔT% (436-365) exceeds 5.5%, it is affected by transmitted light of h-line (405 nm) and g-line (436 nm) having peak intensity other than i-line (365 nm), and pattern boundary part The light intensity inclination becomes weak, and it becomes difficult to improve the resolution. The phase shift film 3 is desirable because the resolution is particularly improved when the transmittance of g-line (436 nm) is less than 10%.
The phase shift film 3 has a phase difference (hereinafter, also referred to as P (365)) at a wavelength of 365 nm in the range of 160 degrees or more and 200 degrees or less. For this reason, it is possible to obtain a phase difference of approximately 180 degrees, and it is possible to sufficiently exhibit the phase shift effect. When P (365) is less than 160 degrees or exceeds 200 degrees, a phase difference of about 180 degrees can not be obtained, and it becomes difficult to exhibit the phase shift effect.

In addition, it is preferable that the phase shift film 3 have a wavelength dependent variation (hereinafter, sometimes referred to as ΔT% (700-365)) of the transmittance in the wavelength range of 365 nm to 700 nm within 20%. . In this case, since the phase shift film 3 suppresses the wavelength dependency of the transmittance also in the wavelength range, in the exposure machine at the time of manufacturing the display device, the recognition of the alignment mark provided on the mask becomes easy. Alignment accuracy is improved. Further, in the case of an inspection apparatus for identifying a mask pattern by using a difference in transmittance between a transparent substrate and a mask pattern in a mask inspection apparatus, it is preferable because defects such as shape defect of the mask pattern can be easily recognized.
Further, in the phase shift film 3, the difference (ΔP (365-436)) between the phase difference given at a wavelength of 365 nm and the phase difference given at a wavelength of 436 nm is 30 degrees or less. Since the wavelength dependency of the phase difference in the wavelength range is suppressed, the phase shift effect can be sufficiently exhibited, the light intensity inclination of the pattern boundary portion becomes strong, and the resolution can be improved. Become.

  The phase shift film 3 preferably has a reflectance (hereinafter sometimes referred to as R% (700 to 365)) in a wavelength range of 365 nm to 700 nm in a range of 5% to 45%. Furthermore, the phase shift film 3 has a reflectance (R% (700-365)) of 5% to 45% in a wavelength range of 365 nm to 700 nm, and a reflectance of a wavelength range of 365 nm to 700 nm. It is preferable that the variation depending on the wavelength (hereinafter sometimes referred to as ΔR% (700-365)) be within 5%. In this case, the phase shift film 3 forms a resist film on the phase shift film 3, and when drawing a pattern by a laser drawing machine or the like, a standing wave generated by the light used for drawing overlapping the reflected light. Less affected by Therefore, at the time of pattern writing, 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. In addition, since acquisition of alignment at the time of pattern drawing becomes easy and mask pattern measurement by long dimension (MMS) measurement becomes easy, it becomes possible to recognize a mask pattern with high accuracy. In addition, in the case of manufacturing a display device by performing pattern transfer using a phase shift mask, in the case of detecting the alignment mark using the difference in reflectance between the transparent substrate and the alignment mark, the mask alignment is recognized. This facilitates the process and improves the alignment accuracy. In addition, when a display device is manufactured by performing pattern transfer using a phase shift mask, the influence of the flare phenomenon can be suppressed, so that good CD characteristics can be obtained, and resolution can be improved. Can be obtained.

As described above, the phase shift film 3 exhibiting such optical properties is a single-layer film or a laminate having at least one metal silicide-based material layer containing metal, silicon, and any one element of nitrogen and / or oxygen. It is composed of a membrane.
In order to suppress the wavelength dependency of the transmittance, phase difference and reflectance of the phase shift film 3 in a predetermined wavelength range, it is more preferable to use a laminated film composed of a plurality of material layers having different optical characteristics. good. The plurality of material layers having different optical properties are preferably composed of at least one metal silicide-based material layer and at least one chromium-based material layer. In this case, the optical characteristics of the entire phase shift film 3 depend on, for example, the refractive index and transmittance of each material layer determined by the type and film thickness of the material forming the metal silicide material layer or the chromium material layer. And the combination of optical characteristics such as reflectance, and the configuration such as the stacking order and the number of layers of each material layer.

Specifically, the phase shift film 3 has a two-layer structure including a metal silicide-based material layer formed on the transparent substrate 2 and a chromium-based material layer formed on the metal silicide-based material layer. It can be made into the lamination film which it has. Moreover, it can be set as the laminated film which has a three-layer structure comprised from the 2nd-layer metal silicide type-material layer formed on the chromium-type material layer. In this case, the phase shift film 3 may have four or more layers by further laminating a chromium-based material layer or a metal silicide-based material layer.
In addition, the phase shift film 3 is a laminated film having a two-layer structure including a chromium-based material layer formed on the transparent substrate 2 and a metal silicide-based material layer formed on the chromium-based material layer. can do. In addition, it is possible to obtain a laminated film having a three-layer structure configured of the second chromium-based material layer formed on the metal silicide-based material layer. In this case, the phase shift film 3 may have four or more layers by further laminating a metal silicide-based material layer or a chromium-based material layer.
The phase shift film 3 having such a configuration exhibits optical characteristics in which the wavelength dependency of the transmittance, the phase difference, and the reflectance in a predetermined wavelength range is suppressed. For this reason, when receiving the exposure light of the said wavelength range, a phase shift effect can fully be exhibited and resolution improvement can be aimed at.
Further, each of the metal silicide-based material layer and the chromium-based material layer constituting the phase shift film 3 may be formed of one layer, or may be formed of a plurality of layers. When the metal silicide-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 for each layer, or each layer may be the same. .
When the phase shift film 3 is composed of at least one metal silicide material layer and at least one chromium material layer, the lowermost layer of the phase shift film 3 formed on the transparent substrate 2 side is a chromium material. It is preferable to use a material layer from the viewpoint of suppressing the wavelength dependency of transmittance, phase difference and reflectance, and suppressing damage to the transparent substrate 2 when patterning the phase shift film 3. When the resist film 5 is formed on the phase shift film 3, the adhesion of the resist film is improved by using a chromium-based material layer as the top layer of the phase shift film 3. It is preferable in that the pattern shape can be made vertical.

The film thickness of such a phase shift film 3 is to obtain the desired phase difference to be imparted to the exposure light, and the desired transmittance and reflectance of the exposure light, which are required to exhibit the phase shift effect. The phase shift film 3 is appropriately determined depending on the materials for forming the metal silicide-based material layer and the chromium-based material layer that constitute the phase shift film 3, the stacking order, the film thickness, and the like.
Further, the thickness of the metal silicide-based material layer constituting the phase shift film 3 is a combination of the metal silicide-based material layer or the metal silicide-based material layer and the chromium-based material layer formed thereunder or above The phase shift film 3 is appropriately determined in consideration of showing a desired phase difference and transmittance. The thickness of the metal silicide-based material layer in the phase shift film 3 is preferably, for example, in the range of 90 nm or more and 140 nm or less, but is not limited thereto.
In the case where the phase shift film 3 includes at least a metal silicide-based material layer and a chromium-based material layer, the thickness of the chromium-based material layer is the metal formed under or over the chromium-based material layer. In combination with the silicide-based material layer, it is appropriately determined in consideration of the desired phase difference and transmittance of the phase shift film 3. For example, the range of 2.5 nm or more and 15 nm or less is preferable. It is not limited to It is substantially difficult to deposit a chromium-based material layer with a thickness of less than 2.5 nm. In addition, when the chromium-based material layer is formed to a thickness of more than 15 nm, the transmittance decreases, and for example, the transmittance of the phase shift film 3 at a wavelength of 365 nm may fall below 3.5%.

The metal silicide-based material that constitutes the metal silicide-based material layer is not particularly limited as long as it contains a metal and silicon (Si). The composition of the metal and silicon (Si) constituting the metal silicide-based material layer is adjusted from the viewpoint of the optical characteristics of the phase shift film 3 as a whole. The ratio of metal to silicon is appropriately selected according to the type of metal and the optical properties required of the metal silicide material layer, and metal: silicon = 1: 1 or more and 1: 9 or less is preferable.
Examples of the metal include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), and titanium (Ti). Examples of the metal silicide-based material constituting the metal silicide-based material layer include nitride of metal silicide, oxide of metal silicide, oxynitride of metal silicide, carbonitride of metal silicide, oxide carbide of metal silicide, At least one material of oxycarbonitrides of metal silicides may be mentioned.
Since a phase shift mask blank used for manufacturing a display device like the present invention is generally a large phase shift mask blank having a side of 350 mm or more, wet etching is adopted in the production of the phase shift mask. Further, also from the viewpoint of defect correction in a large phase shift mask, the defect quality of the phase shift film in the phase shift mask blank is required to have a certain quality or more. From the viewpoint of defect quality of the phase shift film, controllability of the cross-sectional shape of the phase shift film pattern by wet etching, transmittance of the phase shift film, and controllability of the phase difference, the metal silicide material is a material containing nitrogen. Is preferred. The metal silicide-based material is preferably a nitride of metal silicide, an oxynitride of metal silicide, or an oxycarbonitride of metal silicide, and particularly preferably a nitride of metal silicide.
If the cross-sectional shape of the phase shift film pattern is controlled to be vertical, sufficient contrast can be obtained at the pattern boundary portion between the phase shift film pattern and the transparent substrate, so that the light intensity inclination of the pattern boundary portion can be easily strengthened. Become.

The metal silicide-based material is specifically mentioned below.
In the case of molybdenum silicide (MoSi), nitride of molybdenum silicide (MoSi), oxide of molybdenum silicide (MoSi), oxynitride of molybdenum silicide (MoSi), carbonitride of molybdenum silicide (MoSi), molybdenum silicide Examples thereof include oxidized carbides of (MoSi) and oxidized carbonitrides of molybdenum silicide (MoSi).
In the case of tantalum silicide (TaSi), nitride of tantalum silicide (TaSi), oxide of tantalum silicide (TaSi), oxynitride of tantalum silicide (TaSi), carbonitride of tantalum silicide (TaSi), tantalum silicide Examples thereof include oxidized carbides of (TaSi) and oxidized carbonitrides of tantalum silicide (TaSi).
In the case of tungsten silicide (WSi), nitride of tungsten silicide (WSi), oxide of tungsten silicide (WSi), oxynitride of tungsten silicide (WSi), carbonitride of tungsten silicide (WSi), tungsten silicide Examples include oxidized carbides of (WSi) and oxidized carbonitrides of tungsten silicide (WSi).
In the case of titanium silicide (TiSi), nitride of titanium silicide (TiSi), oxide of titanium silicide (TiSi), oxynitride of titanium silicide (TiSi), carbonitride of titanium silicide (TiSi), titanium silicide Examples include oxidized carbides of (TiSi) and oxidized carbonitrides of titanium silicide (TiSi).

  As described above, such a metal silicide-based material includes a component that reduces the wet etching rate of the metal silicide-based material layer from the viewpoint of controllability of the cross-sectional shape of the phase shift film pattern by wet etching. Is preferred. As a component for reducing the wet etching rate of the metal silicide-based material layer, for example, nitrogen (N) described above can be mentioned. In this case, the composition of the metal, silicon (Si) and nitrogen constituting the metal silicide-based material layer is adjusted from the viewpoint of the optical characteristics of the phase shift film 3 as a whole. When nitrogen is included, the nitrogen content is preferably 25 atomic percent or more and 55 atomic percent or less, more preferably 30 atomic percent or more and 50 atomic percent or less. In addition, elements other than those listed above may be contained in the metal silicide material without departing from the effects of the present invention.

A chromium compound containing chromium (Cr) and at least one selected from oxygen (O), nitrogen (N), and carbon (C) is used as the chromium-based material constituting the chromium-based material layer. As a chromium compound, for example, nitride of chromium (Cr), oxide of chromium, carbide of chromium, chromium oxynitride, chromium carbonitride, chromium oxide carbide, chromium oxycarbonitride At least one kind of material is mentioned.
Among such chromium-based materials, nitrides of chromium or oxynitrides of chromium are preferable in that the wavelength dependency of the transmittance can be easily controlled.
In addition, elements other than those listed above may be contained in the chromium-based material without departing from the effects of the present invention.

Further, as described above, the phase shift mask blank 1 according to Embodiment 1 includes the transparent substrate 2, the phase shift film 3 formed on the transparent substrate 2, and the light shielding film on the phase shift film 3. 4 may be formed.
The light shielding film 4 may be either a single layer or a plurality of layers.
In the case where the light shielding film 4 is composed of a plurality of layers, for example, in the case where it has 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. Alternatively, it may have a three-layer structure formed of an insulating layer formed in contact with the phase shift film 3, a light shielding layer formed on the insulating layer, and an antireflective layer formed on the light shielding layer.
The light shielding layer may be either a single layer or a plurality of layers. Examples of the light shielding layer include a chromium nitride film (CrN), a chromium carbonized film (CrC), a chromium carbonitrided film (CrCN), a molybdenum silicide film (MoSi), and a molybdenum silicide nitride film (MoSiN).
The antireflective layer may be either of a single layer or a plurality of layers. Examples of the antireflection layer include a chromium oxynitride film (CrON), a molybdenum silicide oxide film (MoSiO), and a molybdenum silicide oxynitride film (MoSiON).
The insulating layer is made of, for example, CrCO or CrOCN containing less than 50 atomic percent of Cr, and has a thickness of 10 nm to 50 nm. In the case of a phase shift mask blank in which a light shielding film 4 made of a chromium material is formed on the phase shift film 3 having a metal silicide material layer on the outermost layer, the light shielding film 4 made of a chromium material is wetted When etching is performed, metal ions dissolve from the phase shift film 3 having the metal silicide material layer on the outermost layer. At that time, electrons are generated. When the insulating layer is formed to be in contact with the phase shift film 3, it is possible to prevent the electrons generated when the metal ions are melted out of the phase shift film 3 from being supplied to the light shielding film. For this reason, the etching rate in the surface at the time of wet-etching the light shielding film 4 can be made uniform. In addition, as the light shielding film 4, a combination of a light shielding layer of a chromium carbonized film (CrC) and an antireflection layer of a chromium oxynitride film (CrON), or a light shielding layer of a molybdenum silicide film (MoSi) and a molybdenum silicide oxynitride film ( Combinations of anti-reflective layers of MoSiON) are preferred, but not limiting.

The phase shift film 3 and the light shielding film 4 in the phase shift mask blank 1 having the above-described configuration can be formed by a known film forming method. Generally as a film-forming method, sputtering method is mentioned. As a sputtering apparatus, any of a cluster type sputtering apparatus and an in-line type sputtering apparatus may be used.
The metal silicide-based material layer and the chromium-based material layer constituting the phase shift film 3 and the light shielding film 4 can be formed, for example, by the following sputtering target or sputtering gas atmosphere.
When manufacturing a phase shift mask using the phase shift mask blank 1 including the phase shift film 3 and the light shielding film 4 described above, the light shielding film pattern narrower than the phase shift film pattern is provided on the phase shift film pattern. For example, a phase shift portion that changes the phase of exposure light by approximately 180 degrees is configured by a portion of the phase shift film pattern where the light shielding film pattern is not stacked, and the light shielding portion is formed by stacking the phase shift film pattern and the light shielding film pattern. Thus, it is possible to obtain a phase shift mask constituted by the portion where the light transmitting portion is constituted by the portion where the transparent substrate 2 is exposed.

As a sputtering target used to form the metal silicide-based material layer, one containing a metal and silicon (Si) is selected. Specifically, metal silicide, nitride of metal silicide, oxide of metal silicide, carbide of metal silicide, oxynitride of metal silicide, carbonitride of metal silicide, oxide carbide of metal silicide, and metal silicide Oxidized carbonitrides may be mentioned.
The sputtering gas atmosphere at the time of film formation of the metal silicide type material layer is nitrogen (N ₂ ) gas, nitrogen monoxide (NO) gas, nitrogen dioxide (NO ₂ ) gas, nitrous oxide (N ₂ O) gas, and monoxide An active gas containing at least one selected from the group consisting of carbon (CO) gas, carbon dioxide (CO ₂ ) gas and oxygen (O ₂ ) gas, helium (He) gas, neon (Ne) gas, argon (Ar) A mixed gas of an inert gas containing at least one selected from the group consisting of a gas, krypton (Kr) gas and xenon (Xe) gas.
The combination of the material for forming the sputtering target and the type of gas in the sputtering gas atmosphere, and the mixing ratio of the active gas and the inert gas in the sputtering gas atmosphere are the same as that of the metal silicide-based material constituting the metal silicide-based material layer. It is decided appropriately according to the kind and composition.

As a sputtering target used to form the chromium-based material layer, one containing chromium (Cr) or a chromium compound is selected. Specifically, chromium (Cr), chromium nitride, chromium oxide, chromium carbide, chromium oxynitride, chromium carbonitride, chromium oxide carbide, and chromium oxycarbonitride It can be mentioned.
The sputtering gas atmosphere at the time of film formation of the chromium-based material layer is nitrogen (N ₂ ) gas, nitrogen monoxide (NO) gas, nitrogen dioxide (NO ₂ ) gas, nitrous oxide (N ₂ O) gas, carbon monoxide (CO) gas, carbon dioxide (CO ₂ ) gas, oxygen (O ₂ ) gas, hydrocarbon-based gas and fluorine-based gas, an active gas containing at least one selected from the group consisting of helium (He) gas, neon ( Ne) A mixed gas of an inert gas including at least one selected from the group consisting of a gas, an argon (Ar) gas, a krypton (Kr) gas and a xenon (Xe) gas. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas and styrene gas.
The combination of the above-described sputtering target forming material and the type of gas in the sputtering gas atmosphere, and the mixing ratio of the active gas and the inert gas in the sputtering gas atmosphere may be selected depending on the type of chromium material constituting the chromium material layer or It can be determined appropriately according to the composition.

The phase shift mask blank 1 for manufacturing the display device according to the first embodiment described above is any of the transparent substrate 2 and any of metal, silicon, nitrogen and / or oxygen formed on the main surface of the transparent substrate 2. And a phase shift film 3 composed of a single layer film or a laminated film having at least one metal silicide material layer containing one element. As described above, the phase shift film 3 has a transmittance of 3.5% to 8% for light of wavelength 365 nm, and a phase difference of 160 degrees to 200 degrees for light of wavelength 365 nm. The variation of the transmittance in the wavelength range of 365 nm to 436 nm, which depends on the wavelength, is within 5.5%. The phase shift film 3 exhibits optical characteristics in which the wavelength dependency of the transmittance of light in the wavelength range of 365 nm to 436 nm is suppressed.
For this reason, when receiving the exposure light of the said wavelength range, the phase shift effect can fully be exhibited and it can obtain the phase shift mask blank provided with the phase shift film which can aim at the improvement of resolution. In addition, the phase shift film 3 is provided which can be patterned into a phase shift film pattern which can strengthen the light intensity gradient at the pattern boundary portion, improve the resolution, and obtain a desired transfer pattern shape having good CD characteristics. Phase shift mask blank can be obtained.

In the phase shift mask blank 1 for manufacturing the display device of the first embodiment, when the transmittance of the phase shift film 3 in the wavelength range of 365 nm to 700 nm is within 20%, Even in the above wavelength range, the wavelength dependency of the transmittance of the phase shift film 3 is suppressed, so that the alignment mark provided on the mask can be easily recognized in the exposure device at the time of manufacturing the display device, and the alignment accuracy is improved. Do. Further, in the case of an inspection apparatus for identifying a mask pattern by using a difference in transmittance between a transparent substrate and a mask pattern in a mask inspection apparatus, it becomes easy to recognize defects such as shape defect of the mask pattern.
Further, in the phase shift mask blank 1 for manufacturing the display device of the first embodiment, when the difference between the retardation applied at the wavelength 365 nm and the retardation applied at the wavelength 436 nm is 30 degrees or less, the wavelength range Since the wavelength dependency of the phase difference in is suppressed, the phase shift effect can be sufficiently exhibited, the light intensity inclination of the pattern boundary portion becomes strong, and the resolution can be improved.

In the phase shift mask blank 1 for manufacturing the display device of the first embodiment, the reflectance of the phase shift film 3 in the wavelength range of 365 nm to 700 nm is 5% to 45%, which is more preferable. In the phase shift mask blank 1 for manufacturing a display device, the reflectance of the phase shift film 3 in the wavelength range of 365 nm to 700 nm is 5% to 45%, and reflection in the wavelength range of 365 nm to 700 nm is The resist film is formed on the phase shift film 3 when the variation depending on the wavelength is within 5%, and the light used for drawing and its reflected light when drawing a pattern with a laser drawing machine etc. It is less likely to be affected by standing waves caused by the overlapping of Therefore, at the time of pattern writing, 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. In addition, since acquisition of alignment at the time of pattern drawing becomes easy and mask pattern measurement by long dimension (MMS) measurement becomes easy, it becomes possible to recognize a mask pattern with high accuracy. In addition, in the case of manufacturing a display device by performing pattern transfer using a phase shift mask, in the case of detecting the alignment mark using the difference in reflectance between the transparent substrate and the alignment mark, the mask alignment is recognized. This facilitates the process and improves the alignment accuracy. In addition, when a display device is manufactured by performing pattern transfer using a phase shift mask, the influence of the flare phenomenon can be suppressed, so that excellent CD characteristics can be obtained, and resolution can be improved. A desired transfer pattern shape can be obtained.
Further, the phase shift mask blank 1 for manufacturing the display device of the first embodiment and the phase shift mask 30 for manufacturing the display device of the second embodiment described later are phase shift masks used for projection exposure of equal magnification exposure. Particularly effective for blanks and phase shift masks. In particular, as the exposure environment, the numerical aperture (NA) is preferably 0.06 to 0.15, more preferably 0.08 to 0.10, and the coherence factor (σ) is preferably 0.5 to 0.5. It is 1.0.

Second Embodiment
In the second embodiment, a phase shift mask for manufacturing a display device and a method of manufacturing the same will be described with reference to FIGS. FIG. 2 is a cross-sectional view showing the configuration of a phase shift mask for manufacturing a display according to a second embodiment of the present invention. FIG. 3 is a process diagram for explaining a method of manufacturing a phase shift mask using a phase shift mask blank in which the light shielding film 4 is formed on the phase shift film 3. In FIGS. 2 and 3, the same components as in FIG.

The phase shift mask 30 according to the second embodiment includes the transparent substrate 2 and the phase shift film pattern 3 'formed on the transparent substrate 2 (FIG. 2A, hereinafter, the first type). Sometimes called a phase shift mask). The light shielding film pattern 4 'may be formed on the phase shift film pattern 3' (FIG. 2B, hereinafter, it may be referred to as a second type phase shift mask). Further, the light shielding film pattern 4 'may be formed under the phase shift film pattern 3' (FIG. 2 (c), hereinafter, it may be referred to as a third type phase shift mask).
The phase shift mask 30 of the first type is composed of a phase shift portion composed of a phase shift film pattern 3 'and a light transmission portion composed of a portion where the transparent substrate 2 is exposed.
The phase shift mask 30 of the second and third types is a phase shift portion of a portion of the phase shift film pattern 3 'where the light shielding film pattern 4' is not formed above or below the phase shift film pattern 3 ', The light shielding portion of the laminated portion in which the light shielding film pattern 4 'is formed on or under the phase shift film pattern 3', and the portion where the transparent substrate 2 is exposed is a light transmitting portion. The phase shift mask 30 of the second and third types can prevent the film reduction of the resist film formed on the transfer target by the exposure light transmitted through the phase shift portion.

In the first type, second type or third type phase shift mask 30 described above, the phase shift film pattern 3 'includes a metal, silicon, and a metal containing any one of nitrogen and / or oxygen. It is formed of a single layer film or a laminated film having at least one silicide material layer. The optical characteristics of the entire phase shift film pattern 3 'are determined by the type and thickness of the material constituting the material layer constituting the phase shift film pattern 3' when the phase shift film pattern 3 'is formed of a single layer film. For example, when the phase shift film pattern 3 'is formed of a laminated film, the plurality of material layers constituting the phase shift film pattern 3' are determined according to optical properties such as refractive index, transmittance and reflectance of each material layer. It is determined by the combination of the optical characteristics, which is determined by the type and thickness of the material to be configured, and the configuration such as the stacking order and the number of layers of each material layer.
In such a phase shift film pattern 3 ', the transmittance of light of a specific wavelength is controlled within the following range by the combination of material layers constituting the phase shift film pattern 3', and the light of the specific wavelength is also controlled. The transmittance and the phase difference are controlled in the following range, and further, the wavelength dependent variation of the transmittance, the phase difference and the reflectance in the light of the specific wavelength range is suppressed in the following range.

Specifically, the phase shift film pattern 3 'has a transmittance of 3.5% to 8% at a wavelength of 365 nm, and a phase difference of 160 degrees to 200 degrees at a wavelength of 365 nm. The wavelength-dependent variation of the transmittance in the wavelength range of 365 nm to 436 nm is within 5.5%. Such a phase shift film pattern 3 'exhibits optical characteristics in which the wavelength dependency of the transmittance of light in the wavelength range of 365 nm to 436 nm is suppressed.
Therefore, when the phase shift film pattern 3 'receives the light of the wavelength and the wavelength range, the phase shift effect can be sufficiently exhibited, and the light intensity inclination of the pattern boundary portion can be strengthened. It is possible to obtain the phase shift mask 30 provided with the phase shift film pattern 3 'which can obtain a desired transfer pattern shape having various CD characteristics. The phase shift mask 30 can cope with the miniaturization of line and space patterns and contact holes.

  Further, in the first type, second type or third type phase shift mask 30 described above, the wavelength shift of the transmittance of the phase shift film pattern 3 'in the wavelength range of 365 nm to 700 nm depends on the wavelength. When the amount is within 20%, the wavelength dependency of the transmittance is suppressed even in the relevant wavelength range, so that in the exposure machine at the time of manufacturing the display device, recognition of the alignment mark provided on the mask becomes easy. Alignment accuracy is improved. Further, in the case of an inspection apparatus for identifying a mask pattern by using a difference in transmittance between a transparent substrate and a mask pattern in a mask inspection apparatus, it becomes easy to recognize defects such as shape defect of the mask pattern.

  Further, in the first type, second type or third type phase shift mask 30 described above, the phase shift film pattern 3 'has a phase difference given at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm. When the difference (.DELTA.P (365-436)) with the above is 30 degrees or less, the wavelength dependency of the phase difference in the wavelength range is suppressed, so that the phase shift effect can be sufficiently exhibited, and the pattern The light intensity inclination at the boundary portion becomes strong, and the resolution can be improved.

  In the first type, second type, or third type phase shift mask 30, the reflectance of the phase shift film pattern 3 'in the wavelength range of 365 nm to 700 nm is 5% to 45%. Further, the phase shift film pattern 3 'has a reflectance of 5% to 45% in a wavelength range of 365 nm to 700 nm and a wavelength-dependent change of the reflectance in a wavelength range of 365 nm to 700 nm. When the amount (ΔR% (700-365)) is within 5%, the mask pattern measurement by the long dimension (MMS) measurement becomes easy, so that the mask pattern can be recognized with high accuracy. In addition, in the case of manufacturing a display device by performing pattern transfer using a phase shift mask, in the case of detecting the alignment mark using the difference in reflectance between the transparent substrate and the alignment mark, the mask alignment is recognized. This facilitates the process and improves the alignment accuracy. In addition, when a display device is manufactured by performing pattern transfer using a phase shift mask, the influence of the flare phenomenon can be suppressed, so that good CD characteristics can be obtained, and resolution can be improved. Can be obtained.

Next, a method of manufacturing a phase shift mask for manufacturing a display device 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 the phase shift mask for manufacturing the first type and the second type of display, first, a resist pattern is formed on the light shielding film 4 of the phase shift mask blank 1 for manufacturing the display according to the first embodiment. To form a resist pattern.
Specifically, in the resist pattern forming step, first, as shown in FIG. 3A, the resist film 5 is formed on the light shielding film 4. Thereafter, a pattern of a predetermined size is drawn on the resist film 5. Thereafter, the resist film 5 is developed with a predetermined developing solution to form a resist pattern 5 'as shown in FIG. 3 (b).
Examples of the pattern to be drawn on the resist film 5 include a line and space pattern and a hole pattern.

Next, as shown in FIG. 3C, a light shielding film pattern forming step is performed in which the light shielding film 4 is wet etched using the resist pattern 5 'as a mask to form a light shielding film pattern 4'.
The etching solution for wet-etching the light shielding film 4 is not particularly limited as long as it can selectively etch the chromium-based material or the metal silicide-based material forming the light shielding film 4. When the material for forming the light shielding film 4 is a chromium-based material, for example, an etching solution containing ceric ammonium nitrate and perchloric acid can be mentioned. When the light shielding film 4 is formed of a metal silicide material, for example, at least one fluorine compound selected from hydrofluoric acid, silicohydrofluoric acid, and ammonium hydrogen fluoride, and hydrogen peroxide And an etchant containing at least one oxidizing agent selected from nitric acid and sulfuric acid. Specifically, an etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water may be mentioned.

Next, as shown in FIG. 3D, the resist pattern 5 'is peeled off, and then, as shown in FIG. 3E, the phase shift film 3 is wet etched using the light shielding film pattern 4' as a mask. A phase shift film pattern formation step of forming a phase shift film pattern 3 'is performed.
The etching solution 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 silicide-based material layer constituting the phase shift film 3. For example, as an etching solution for wet etching a chromium-based material layer, an etching solution containing cerium nitrate ammonium and perchloric acid can be mentioned. Further, as an etching solution for wet etching the metal silicide-based material layer, at least one fluorine compound selected from hydrofluoric acid, silicohydrofluoric acid, and ammonium hydrogen fluoride, hydrogen peroxide, nitric acid, and sulfuric acid And an etchant containing at least one oxidizing agent selected from
In the case of the phase shift film 3 in which the chromium-based material layer is formed on the metal silicide-based material layer, when the chromium-based material layer is wet-etched, metal ions are dissolved out from the metal silicide-based material layer therebelow, Is supplied to the chromium-based material layer, causing a phenomenon that the wet etching of the chromium-based material layer is delayed. However, in the case of the phase shift film 3 in which the metal silicide based material layer is formed on the chromium based material layer, such a phenomenon does not occur. For this reason, the etching rate in the surface at the time of wet-etching the phase shift film 3 can be made uniform.

Next, a phase shift mask 30 (first type phase shift) of a type having a phase shift portion configured of the phase shift film pattern 3 'and a light transmission portion configured of a portion where the transparent substrate 2 is exposed. In the case of manufacturing the mask), as shown in FIG. 3F, the light shielding film pattern 4 'is peeled off after the phase shift film pattern forming step.
In addition, a light shielding film pattern 4 'narrower than the phase shift film pattern 3' is provided on the phase shift film pattern 3 ', and the phase is formed of the portion of the phase shift film pattern 3' where the light shielding film pattern 4 'is not stacked. A type having a light transmitting portion constituted of a shift portion, a light shielding portion constituted of a laminated portion of a phase shift film pattern 3 'and a light shielding film pattern 4', and a portion exposed with the transparent substrate 2 In the case of manufacturing the phase shift mask 30 (second type phase shift mask), after the phase shift film pattern forming step, as shown in FIG. It is patterned into a predetermined pattern narrower than the pattern 3 '.

The phase shift mask 30 for manufacturing a display device is manufactured by such a resist pattern forming process, a light shielding film pattern forming process, and a phase shift film pattern forming process.
The method of manufacturing the phase shift mask 30 of the first type and the second type described above is not limited to the method described above. In the phase shift mask 30 of the first type, as the phase shift mask blank 1 for manufacturing the display device according to the first embodiment, one having a configuration in which the light shielding film 4 is not formed is used. A resist pattern forming step of forming a resist pattern 5 'is performed, and then a phase shift film pattern forming step of forming a phase shift film pattern 3' by wet etching the phase shift film 3 using the resist pattern 5 'as a mask Finally, the resist pattern 5 'is peeled off to obtain the phase shift mask 30 of the first type.

  Further, according to the method of manufacturing a phase shift mask for manufacturing a display device of Embodiment 2, a phase shift mask is manufactured using the phase shift mask blank 1 of Embodiment 1. Therefore, the phase shift film pattern 3 'can be provided which can sufficiently exhibit the phase shift effect, strengthen the light intensity gradient at the pattern boundary portion, and obtain a desired transfer pattern shape having good CD characteristics. The phase shift mask 30 can be manufactured.

In the above, the manufacturing method of the phase shift mask 30 of the first type and the second type has been described, but on the main surface of the transparent substrate 2 on which the light shielding film pattern is already formed on a part of the main surface. The present invention is also applicable to the phase shift mask 30 (third type phase shift mask) in which the phase shift film pattern 3 'is formed. In this case, the phase shift film pattern 3 'is formed to cover the light shielding film pattern 4' already formed on a part of the main surface, or on the main surface where the light shielding film pattern 4 'is not formed. Thus, a portion where the light shielding film pattern and the phase shift film pattern 3 'are not stacked can be used as a phase shift portion, and a phase shift effect can be exhibited in the phase shift portion.
Such a third type phase shift mask 30 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' is already formed on a part of the main surface is, for example, A light shielding film forming step of forming a light shielding film by sputtering on the main surface of the transparent substrate 2 and a light shielding film forming a light shielding film pattern by patterning the light shielding film by wet etching after the light shielding film forming step; A pattern forming step; a phase shift film forming step of forming a phase shift film 3 so as to cover the light shielding film pattern on the main surface of the transparent substrate 2 after the light shielding film pattern forming step; Later, the phase shift film 3 is patterned by wet etching to form a phase shift film pattern 3 'and manufactured by a phase shift film pattern forming step. It is.

Third Embodiment
In the third embodiment, a method of manufacturing a display device using the phase shift mask according to the second embodiment will be described.

In the method of manufacturing a display device according to the third embodiment, first, the method for manufacturing a phase shift mask for manufacturing a display device described in the second embodiment is applied to a substrate with a resist film having a resist film formed on a substrate. The phase shift mask disposing step is performed in which the obtained phase shift mask 30 or the phase shift mask 30 for manufacturing a display device described in the second embodiment is disposed to face the resist film.
Next, the phase shift mask 30 is irradiated with exposure light to perform a resist film exposure step of exposing the resist film.

  The exposure light is, for example, composite light including light in a wavelength range of 300 nm to 700 nm. Specifically, it is a composite light including i-line, h-line and g-line. The intensity ratio of i-line, h-line and g-line in the composite light used for the exposure light has an intensity ratio of i-line: h-line: g-line 1: 1: 1 or 2, depending on the manufacture of the display device. : 1: 1 etc. can be changed suitably.

  According to the method of manufacturing the display device of the third embodiment, the phase shift mask 30 obtained by the method of manufacturing the phase shift mask for manufacturing the display device described in the second embodiment or the second embodiment will be described. The display device is manufactured using the phase shift mask 30 for manufacturing the display device. Therefore, a display device having a fine line and space pattern and a contact hole can be manufactured.

Hereinafter, the present invention will be more specifically described based on examples.
In the following, the abbreviation of synthetic quartz glass substrate is referred to as QZ. Moreover, when it describes with QZ / A / B / C, it shows that it is the structure which A layer, B layer, and C layer were formed into a film in this order on QZ.

Example 1
In Example 1, a phase shift mask blank having a QZ / CrON / MoSiN configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same In order to manufacture the phase shift mask blank 1 having the above-described configuration, first, a synthetic quartz glass substrate of 3345 size (330 mm × 450 mm × 5 mm) was prepared as the transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputter target made of chromium and a sputter target made of molybdenum silicide (Mo: Si = 1: 4) are disposed, A chromium-based material layer (film thickness: 10 nm) composed of chromium oxynitride (CrON) on the surface, and a metal silicide-based material layer (film thickness: 120 nm) composed of molybdenum silicide nitride (MoSiN) on the chromium-based material layer To form a phase shift mask blank 1 having a phase shift film 3 (total film thickness: 130 nm) formed thereon.
The chromium-based material layer introduces a mixed gas (Ar: 30 sccm, NO: 30 sccm) containing argon (Ar) gas and nitrogen monoxide (NO) gas near the chromium target, and has a sputtering power of 4.0 kW, and is transparent. The film was formed on the main surface of the transparent substrate 2 by reactive sputtering at a transfer speed of the substrate 2 of 400 mm / min.
In the metal silicide material layer, a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced near the molybdenum silicide target, and the sputtering power is 8.0 kW. The transparent substrate 2 was deposited on the chromium-based material layer by reactive sputtering at a transfer speed of 400 mm / min. The metal silicide material layer was laminated a plurality of times under the same conditions in order to obtain a desired film thickness of 120 nm.

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation, and the phase difference was measured by MPM-100 manufactured by Lasertec Corporation. In the following examples and comparative examples, the same devices were used for measurement of transmittance and phase difference. In addition, the value of the transmittance | permeability in a following example and a comparative example is a value of Air standard in all.
In order to measure the transmittance of the phase shift film 3 and the phase difference, chromium oxynitride (on a main surface of the 6025 size (152 mm × 152 mm) transparent substrate 2 set in the same substrate holder (not shown) With phase shift film formed of phase shift film 3 (total film thickness 130 nm) of laminated structure composed of chromium material layer of CrON and metal silicide material layer of molybdenum silicide nitride (MoSiN) A substrate (dummy substrate) was used.
As a result, as shown in FIG. 4, the transmittance spectrum of Example 1 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than in Comparative Examples 1 and 2 described later. The specific measurement result of the transmittance | permeability 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 was found that the phase shift film 3 of Example 1 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm is suppressed.
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 13.35%. Therefore, it was found that the phase shift film 3 of Example 1 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm was suppressed.
The measurement results of the phase difference are shown in FIG. The phase difference (hereinafter, sometimes referred to as P (365)) given at a wavelength of 365 nm was 181.7 degrees, and ΔP (365-436) was 28.7 degrees. Therefore, it was found that the phase shift film 3 of Example 1 exhibited optical characteristics in which the wavelength dependency of the retardation was suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured using a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. In the following examples, comparative examples, and reference examples, the same device was used to measure the reflectance.
As a result, as shown in FIG. 6, the reflectance spectrum of Example 1 at a wavelength of 200 nm to 800 nm has a characteristic that the change in reflectance is smaller than that of Comparative Examples 1 and 2 described later. Specific reflectance measurement results of Example 1 are shown in FIG. The reflectance in the wavelength range of 365 nm to 700 nm (hereinafter sometimes referred to as R% (700-365)) is 17.9% to 22.4%, and the range in the range of 700 nm to 365 nm (maximum value and The difference between the minimum values was 4.5%. Therefore, it was found that the phase shift film 3 of Example 1 exhibited optical characteristics in which the wavelength dependency of the reflectance in the wavelength range of 365 nm to 700 nm was suppressed.

B. Phase Shift Mask and Method of Manufacturing the Same In order to manufacture the phase shift mask 30 using the phase shift mask blank 1 manufactured as described above, first, a resist coating device is applied on the phase shift film 3 of the phase shift mask blank 1 The resist material was applied using
Thereafter, through a heating and cooling process, a resist film 5 with a film thickness of 1000 nm was formed.
Thereafter, the resist film 5 is drawn using a laser drawing apparatus, and through the development and rinse steps, a resist pattern 5 'having a 2.5 μm square contact hole pattern (not shown) is formed on the phase shift film 3. did.

  Thereafter, a metal silicide made of molybdenum silicide nitride (MoSiN) of the phase shift film 3 with a molybdenum silicide etching solution in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water using the resist pattern 5 'as a mask The base material layer was wet etched.

Thereafter, using the resist pattern 5 'as a mask, the chromium-based material layer made of chromium oxynitride (CrON) of the phase shift film 3 is wet-etched with a chromium etching solution containing ceric ammonium nitrate and perchloric acid. A phase shift film pattern 3 'was formed.
Thereafter, the resist pattern 5 'was peeled off.

  Thus, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on the transparent substrate 2.

A simulation was performed on the phase shift effect of the phase shift mask having the above-described phase shift film pattern. The simulation includes numerical aperture (NA) = 0.1, coherence factor (σ) = 0.5, exposure light includes i-line (365 nm), h-line (405 nm) and g-line (436 nm), i-line: The composite light has a light intensity ratio of h-line: g-line = 2: 1: 1.
A simulation result (light intensity distribution) of a spatial image of light having passed through a phase shift mask on which a phase shift film pattern having a 2.5 μm square contact hole pattern is formed is shown in FIG.
The horizontal axis in FIG. 9 is the position (μm) from the contact hole center of the contact hole pattern to be transferred to the resist film on the transfer target, and the vertical axis is the intensity ratio (maximum light amount transmitted from the phase shift mask Ratio when 1 is 1). In the light intensity distribution curve of FIG. 9, the light intensity of the transmitted light peaks at the center of the contact hole, and the light intensity of the transmitted light gradually decreases as the distance from the center thereof increases. In the light intensity distribution curve of FIG. 9, the position of ± 1 μm from the center of the contact hole showing the peak intensity is the boundary portion of the 2.0 μm square contact hole pattern formed on the resist film on the transfer target (contact hole pattern Corresponds to the straight part). The light intensity inclination at the pattern boundary portion can be obtained from the difference in light intensity in the vicinity of the pattern boundary portion.
As shown in FIG. 9, the light intensity distribution curve of Example 1 has a sharp peak intensity at the center of the contact hole, a large change in light intensity at the pattern boundary portion, and a large portion at the pattern boundary portion. In the outer peripheral area, it is shown that the light intensity change is small.
The light intensity slope (resolution) of the pattern boundary was 0.446. For this reason, it was found that the phase shift mask of Example 1 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Example 2
In Example 2, a phase shift mask blank having a QZ / CrN / MoSiN configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.
Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputter target made of chromium and a sputter target made of molybdenum silicide (Mo: Si = 1: 4) are disposed, A chromium-based material layer (film thickness: 10 nm) made of chromium nitride (CrN) on the surface, and a metal silicide-based material layer (film thickness: 120 nm) made of molybdenum silicide nitride (MoSiN) on the chromium-based material layer It formed into a film and obtained phase shift mask blank 1 in which phase shift film 3 (total film thickness: 130 nm) was formed.

In addition, the chromium-based material layer introduces a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) containing argon (Ar) gas and nitrogen (N ₂ ) gas near the chromium target, and has a sputtering power of 4.0 kW and is transparent. The film was formed on the main surface of the transparent substrate 2 by reactive sputtering at a transfer speed of the substrate 2 of 400 mm / min.
In addition, the metal silicide-based material layer was formed under the same conditions as Example 1 (laminated several times under the same conditions to obtain a desired film thickness of 120 nm).

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (total film thickness 130 nm) of QZ / CrN / MoSiN configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 4, the transmittance spectrum of Example 2 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than that of Comparative Examples 1 and 2 described later. The specific measurement result of the transmittance | permeability of Example 2 is shown in FIG. T% (365) was 3.34% and ΔT% (436-365) was 3.28%. Therefore, it was found that the phase shift film 3 of Example 2 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm is suppressed.
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 12.68%. Therefore, it was found that the phase shift film 3 of Example 2 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm was suppressed.
The measurement results of the phase difference are shown in FIG. P (365) was 182.7 degrees and ΔP (365-436) was 27.7 degrees. Therefore, it was found that the phase shift film 3 of Example 2 exhibits optical characteristics in which the wavelength dependency of the retardation is suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
As a result, as shown in FIG. 6, the reflectance spectrum of Example 2 at a wavelength of 200 nm to 800 nm has a characteristic that the change in reflectance is smaller than that of Comparative Examples 1 and 2 described later. The measurement result of the concrete reflectance of Example 2 is shown in FIG. R% (700-365) was 16.6% or more and 24.8% or less, and the range (the difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 8.2%. Therefore, it was found that the phase shift film 3 of Example 2 exhibited optical characteristics in which the wavelength dependency of the reflectance in the wavelength range of 365 nm to 700 nm was suppressed.

B. Phase Shift Mask and Method of Manufacturing the Same In the same manner as in Example 1, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on a transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 10, the light intensity distribution curve of Example 2 has a sharp peak intensity at the center of the contact hole, a large change in light intensity at the pattern boundary portion, and the pattern boundary portion In the outer peripheral area, it is shown that the light intensity change is small.
The light intensity slope at the pattern boundary was 0.447. For this reason, it was found that the phase shift mask of Example 2 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Example 3
In the third embodiment, a phase shift mask blank of the QZ / CrON / MoSiN / CrON configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputter target made of chromium and a sputter target made of molybdenum silicide (Mo: Si = 1: 4) are disposed, A chromium-based material layer (film thickness: 5 nm) composed of chromium oxynitride (CrON) on the surface, and a metal silicide-based material layer (film thickness: 120 nm) composed of molybdenum silicide nitride (MoSiN) on the chromium-based material layer And forming a chromium-based material layer (film thickness: 5 nm) made of chromium oxynitride (CrON) on the metal silicide-based material layer, and forming a phase shift film 3 (total film thickness: 130 nm) A shift mask blank 1 was obtained.
The chromium-based material layer was formed under the same conditions as in Example 1 except that the transfer speed of the transparent substrate 2 was 800 mm / min. In addition, a metal silicide-based material layer was also formed under the same conditions as Example 1 (laminated several times under the same conditions to obtain a desired film thickness of 120 nm).

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (total film thickness 130 nm) of QZ / CrON / MoSiN / CrON configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 5, the transmittance spectrum of Example 3 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than in Comparative Examples 1 and 2 described later. The specific measurement result of the transmittance | permeability of Example 3 is shown in FIG. T% (365) was 4.03% and ΔT% (436-365) was 3.32%. Therefore, it was found that the phase shift film 3 of Example 3 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm is suppressed.
Moreover, as shown in FIG. 7, (DELTA) T% (700-365) was 12.49%. Therefore, it was found that the phase shift film 3 of Example 3 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.
The measurement results of the phase difference are shown in FIG. P (365) was 181.0 degrees and ΔP (365-436) was 28.3 degrees. Therefore, it was found that the phase shift film 3 of Example 3 exhibits optical characteristics in which the wavelength dependency of the retardation is suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
As a result, as shown in FIG. 7, the reflectance spectrum of Example 3 at a wavelength of 200 nm to 800 nm has a characteristic that the change in reflectance is smaller than that of Comparative Examples 1 and 2 described later. The measurement result of the concrete reflectance of Example 3 is shown in FIG. R% (700-365) was 26.4% or more and 30.0% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 3.5%. Therefore, it was found that the phase shift film 3 of Example 3 exhibits optical characteristics in which the wavelength dependency of the reflectance is suppressed in the wavelength range of 365 nm to 700 nm.

B. Phase Shift Mask and Method of Manufacturing the Same In order to manufacture the phase shift mask 30 using the phase shift mask blank 1 manufactured as described above by the same method as in Example 1, first, the phase of the phase shift mask blank 1 On the shift film 3, a resist pattern 5 ′ having a 2.5 μm square contact hole pattern was formed.

  Thereafter, using the resist pattern 5 'as a mask, a chromium-based material layer composed of the second layer chromium oxynitride (CrON) of the phase shift film 3 is formed by a chromium etching solution containing ceric ammonium nitrate and perchloric acid. Wet etched.

  Thereafter, a metal silicide made of molybdenum silicide nitride (MoSiN) of the phase shift film 3 with a molybdenum silicide etching solution in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water using the resist pattern 5 'as a mask The base material layer was wet etched.

Thereafter, using the resist pattern 5 'as a mask, a chromium-based material layer composed of the first chromium oxynitride (CrON) of the phase shift film 3 is wetted with a chromium etching solution containing cerium nitrate ammonium and perchloric acid. Etching was performed to form a phase shift film pattern 3 '.
Thereafter, the resist pattern 5 'was peeled off.

  Thus, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on the transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 9, the light intensity distribution curve of Example 3 has a sharp peak intensity at the center of the contact hole, a large change in light intensity at the pattern boundary portion, and the pattern boundary portion In the outer peripheral area, it is shown that the light intensity change is small.
The light intensity slope at the pattern boundary was 0.447. For this reason, it was found that the phase shift mask of Example 3 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Example 4
In the fourth embodiment, a phase shift mask blank having a QZ / CrN / MoSiN / CrN configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputter target made of chromium and a sputter target made of molybdenum silicide (Mo: Si = 1: 4) are disposed, A chromium-based material layer (film thickness: 5 nm) made of chromium nitride (CrN) on the surface, and a metal silicide-based material layer (film thickness: 120 nm) made of molybdenum silicide nitride (MoSiN) on the chromium-based material layer A phase shift film in which a chromium-based material layer (film thickness: 5 nm) made of chromium nitride (CrN) is formed on a metal silicide-based material layer and a phase shift film 3 (total film thickness: 130 nm) is formed I got a blank 1.
The chromium-based material layer was formed under the same conditions as in Example 1 except that the transfer speed of the transparent substrate 2 was 800 mm / min. In addition, a metal silicide-based material layer was also formed under the same conditions as Example 1 (laminated several times under the same conditions to obtain a desired film thickness of 120 nm).

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (total film thickness 130 nm) of QZ / CrN / MoSiN / CrN configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 5, the transmittance spectrum of Example 4 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than in Comparative Examples 1 and 2 described later. The specific measurement result of the transmittance | permeability of Example 4 is shown in FIG. T% (365) was 3.82% and ΔT% (436-365) was 3.33%. Therefore, it was found that the phase shift film 3 of Example 4 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm was suppressed.
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 14.64%. Therefore, it was found that the phase shift film 3 of Example 4 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.
The measurement results of the phase difference are shown in FIG. P (365) was 180.2 degrees and ΔP (365-436) was 26.8 degrees. Therefore, it was found that the phase shift film 3 of Example 4 exhibited optical characteristics in which the wavelength dependency of the retardation was suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
As a result, as shown in FIG. 7, the reflectance spectrum of Example 4 at a wavelength of 200 nm to 800 nm has a characteristic that the change in reflectance is smaller than that of Comparative Examples 1 and 2 described later. The measurement result of the concrete reflectance of Example 4 is shown in FIG. R% (700-365) was 22.4% or more and 27.5% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 5.0%. Therefore, it was found that the phase shift film 3 of Example 4 exhibits optical characteristics in which the wavelength dependency of the reflectance is suppressed in the wavelength range of 365 nm to 700 nm.

B. Phase Shift Mask and Method of Manufacturing the Same In the same manner as in Example 3, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on the transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment. The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 10, the light intensity distribution curve of Example 4 has a sharp peak intensity at the center of the contact hole, a large change in light intensity at the pattern boundary portion, and the pattern boundary portion In the outer peripheral area, it is shown that the light intensity change is small.
The light intensity slope at the pattern boundary was 0.447. For this reason, it was found that the phase shift mask of Example 4 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Example 5
In the fifth embodiment, a phase shift mask blank of the QZ / MoSiN / CrN configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into a sputtering target made of molybdenum silicide (Mo: Si = 1: 4) and an in-line type sputtering apparatus (not shown) in which a sputtering target made of chromium is arranged. A metal silicide material layer (film thickness: 120 nm) made of molybdenum silicide nitride (MoSiN) on the surface, and a chromium material layer (film thickness: 10 nm) made of chromium nitride (CrN) on the metal silicide material layer To form a phase shift mask blank 1 having a phase shift film 3 (total film thickness: 130 nm) formed thereon.
In the metal silicide material layer, a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced near the molybdenum silicide target, and the sputtering power is 8.0 kW. The transparent substrate 2 was formed on the main surface of the transparent substrate 2 by reactive sputtering at a transfer speed of 400 mm / min. In order to obtain a desired film thickness of 120 nm, lamination was performed multiple times under the same conditions.
Further, the chromium-based material layer introduces mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) containing argon (Ar) gas and nitrogen (N ₂ ) gas in the vicinity of the chromium target, and has a sputtering power of 4.0 kW The film was formed on the metal silicide-based material layer by reactive sputtering at a transfer speed of the substrate 2 of 800 mm / min.

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (total film thickness 130 nm) of QZ / MoSiN / CrN configuration was formed was used for measurement of transmittance and phase difference.
As a result, as shown in FIG. 4, the transmittance spectrum of Example 5 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than in Comparative Examples 1 and 2 described later. The specific measurement result of the transmittance | permeability of Example 5 is shown in FIG. T% (365) was 3.16% and ΔT% (436-365) was 2.88%. Therefore, it was found that the phase shift film 3 of Example 5 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm is suppressed.
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 12.21%. Therefore, it was found that the phase shift film 3 of Example 5 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.
The measurement results of the phase difference are shown in FIG. P (365) was 178.4 degrees and ΔP (365-436) was 26.6 degrees. Therefore, it was found that the phase shift film 3 of Example 5 exhibits optical characteristics in which the wavelength dependency of the retardation is suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
As a result, as shown in FIG. 6, the reflectance spectrum of Example 5 at a wavelength of 200 nm to 800 nm has a characteristic that the change in reflectance is smaller than in Comparative Examples 1 and 2 described later. The measurement result of the concrete reflectance of Example 5 is shown in FIG. R% (700-365) was 33.6% or more and 44.6% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 11.0%. Therefore, it was found that the phase shift film 3 of Example 5 exhibited optical characteristics in which the wavelength dependency of the reflectance in the range of wavelength 365 nm or more and 700 nm or less was suppressed as compared with Comparative Examples 1 and 2 described later .

B. Phase Shift Mask and Method of Manufacturing the Same In the same manner as in Example 5, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on the transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 10, the light intensity distribution curve of Example 5 has a sharp peak intensity at the center of the contact hole, a large change in light intensity at the pattern boundary portion, and the pattern boundary portion In the outer peripheral area, it is shown that the light intensity change is small.
The light intensity slope at the pattern boundary was 0.448. For this reason, it was found that the phase shift mask of Example 5 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Example 6
In the sixth embodiment, a phase shift mask blank of the QZ / MoSiN / CrON configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into a sputtering target made of molybdenum silicide (Mo: Si = 1: 4) and an in-line type sputtering apparatus (not shown) in which a sputtering target made of chromium is arranged. A metal silicide material layer (film thickness: 120 nm) made of molybdenum silicide nitride (MoSiN) on the surface, and a chromium material layer (film thickness: 10 nm) made of chromium oxynitride (CrON) on the metal silicide material layer ) Was formed to obtain a phase shift mask blank 1 in which a phase shift film 3 (total film thickness: 130 nm) was formed.
The metal silicide material layer was formed under the same conditions as in Example 5.
In addition, the chromium-based material layer introduces a mixed gas (Ar: 30 sccm, NO: 30 sccm) containing argon (Ar) gas and nitrogen monoxide (NO) gas near the chromium target, and has a sputtering power of 4.0 kW, transparent. The film was formed on the metal silicide-based material layer by reactive sputtering at a transfer speed of the substrate 2 of 800 mm / min.

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (total film thickness 130 nm) of QZ / MoSiN / CrON configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 4, the transmittance spectrum of Example 6 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than in Comparative Examples 1 and 2 described later. The specific measurement result of the transmittance | permeability of Example 6 is shown in FIG. T% (365) was 4.21% and ΔT% (436-365) was 3.5%. Therefore, it was found that the phase shift film 3 of Example 6 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm is suppressed.
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 12.88%. Therefore, it was found that the phase shift film 3 of Example 6 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.
The measurement results of the phase difference are shown in FIG. P (365) was 178.8 degrees and ΔP (365-436) was 28 degrees. Therefore, it was found that the phase shift film 3 of Example 6 exhibits optical characteristics in which the wavelength dependency of the retardation is suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
As a result, as shown in FIG. 6, the reflectance spectrum of Example 6 at a wavelength of 200 nm to 800 nm has a characteristic that the change in reflectance is smaller than in Comparative Examples 1 and 2 described later. The measurement result of the concrete reflectance of Example 6 is shown in FIG. R% (700-365) was 30.7% or more and 39.4% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 8.7%. For this reason, it was found that the phase shift film 3 of Example 6 exhibited optical characteristics in which the wavelength dependency of the reflectance in the wavelength range of 365 nm to 700 nm was suppressed as compared with Comparative Examples 1 and 2 described later. .

B. Phase Shift Mask and Method of Manufacturing the Same In order to manufacture the phase shift mask 30 using the phase shift mask blank 1 manufactured as described above, first, a resist coating device is applied on the phase shift film 3 of the phase shift mask blank 1 The resist material was applied using
Thereafter, through a heating and cooling process, a resist film 5 with a film thickness of 1000 nm was formed.
Thereafter, the resist film 5 is drawn using a laser drawing apparatus, and through the development and rinse steps, a resist pattern 5 'having a 2.5 μm square contact hole pattern (not shown) is formed on the phase shift film 3. did.
Thereafter, using the resist pattern 5 'as a mask, the chromium-based material layer made of chromium oxynitride (CrON) of the phase shift film 3 was wet-etched with a chromium etching solution containing ceric ammonium nitrate and perchloric acid.
Thereafter, a metal silicide made of molybdenum silicide nitride (MoSiN) of the phase shift film 3 with a molybdenum silicide etching solution in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water using the resist pattern 5 'as a mask The base material layer was wet etched to form a phase shift film pattern 3 '.
Thereafter, the resist pattern 5 'was peeled off.

  Thus, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on the transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
As a result, the light intensity inclination at the pattern boundary portion was equivalent to that of Example 5. For this reason, it was found that the phase shift mask of Example 6 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Example 7
In Example 7, a phase shift mask blank of the QZ / MoSiN / CrON / MoSiN configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into an in-line type sputtering apparatus (not shown) in which a sputter target made of molybdenum silicide (Mo: Si = 1: 4) and a sputter target made of chromium are arranged. A metal silicide material layer (film thickness: 60 nm) made of molybdenum silicide nitride (MoSiN) and a chromium material layer (film thickness: 10 nm) made of chromium oxynitride (CrON) on the metal silicide material layer And a metal silicide-based material layer (film thickness: 60 nm) made of molybdenum silicide nitride (MoSiN) on the chromium-based material layer, and a phase shift film 3 (total film thickness: 130 nm) is formed. A shift mask blank 1 was obtained.
The metal silicide-based material layer was formed under the same conditions as in Example 6 except that the transfer speed of the transparent substrate 2 was set to about 800 mm / min. In addition, a chromium-based material layer was also formed under the same conditions as in Example 6.

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (total film thickness 130 nm) of QZ / MoSiN / CrON / MoSiN configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 5, the transmittance spectrum of Example 7 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than in Comparative Examples 1 and 2 described later. The concrete measurement result of the transmittance | permeability of Example 7 is shown in FIG. T% (365) was 4.49% and ΔT% (436-365) was 3.92%. Therefore, it was found that the phase shift film 3 of Example 7 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm was suppressed.
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 23.78%. Therefore, it was found that the phase shift film 3 of Example 7 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.
The measurement results of the phase difference are shown in FIG. P (365) was 178.8 degrees and ΔP (365-436) was 24 degrees. Therefore, it was found that the phase shift film 3 of Example 7 exhibited optical characteristics in which the wavelength dependency of the retardation was suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
The results are shown in FIG. Moreover, the measurement result of the concrete reflectance of Example 7 is shown in FIG. R% (700-365) was 5.4% or more and 24.4% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 19.0%.

B. Phase Shift Mask and Method of Manufacturing the Same In order to manufacture the phase shift mask 30 using the phase shift mask blank 1 manufactured as described above by the same method as in Example 1, first, the phase of the phase shift mask blank 1 On the shift film 3, a resist pattern 5 ′ having a 2.5 μm square contact hole pattern was formed.
Thereafter, a metal silicide made of molybdenum silicide nitride (MoSiN) of the phase shift film 3 with a molybdenum silicide etching solution in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water using the resist pattern 5 'as a mask The base material layer was wet etched.
Thereafter, using the resist pattern 5 'as a mask, a chromium-based material layer composed of the first chromium oxynitride (CrON) of the phase shift film 3 is wetted with a chromium etching solution containing cerium nitrate ammonium and perchloric acid. It was etched.
Thereafter, a metal silicide made of molybdenum silicide nitride (MoSiN) of the phase shift film 3 with a molybdenum silicide etching solution in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water using the resist pattern 5 'as a mask The base material layer was wet etched to form a phase shift film pattern 3 '.
Thereafter, the resist pattern 5 'was peeled off.

  Thus, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on the transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 9, the light intensity distribution curve of Example 7 has a sharp peak intensity at the center of the contact hole, a large change in light intensity at the pattern boundary portion, and the pattern boundary portion In the outer peripheral area, it is shown that the light intensity change is small.
The light intensity slope at the pattern boundary was 0.446. For this reason, it was found that the phase shift mask of Example 7 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Example 8
In Example 8, a phase shift mask blank of the QZ / MoSiN / CrN / MoSiN configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into an in-line type sputtering apparatus (not shown) in which a sputter target made of molybdenum silicide (Mo: Si = 1: 4) and a sputter target made of chromium are arranged. A metal silicide type material layer (film thickness: 59 nm) made of molybdenum silicide nitride (MoSiN) and a chromium type material layer (film thickness: 10 nm) made of chromium nitride (CrN) on the metal silicide type material layer And a metal silicide-based material layer (film thickness: 59 nm) made of molybdenum silicide nitride (MoSiN) on the chromium-based material layer, and phase shift film 3 (total film thickness: 128 nm) is formed. Mask blank 1 was obtained.
The metal silicide layer was formed under the same conditions as in Example 5 except that the transfer speed of the transparent substrate 2 was set to about 800 mm / min. In addition, a chromium-based material layer was also formed under the same conditions as in Example 5.

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (total film thickness 128 nm) of QZ / MoSiN / CrN / MoSiN configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 5, the transmittance spectrum of Example 8 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than in Comparative Examples 1 and 2 described later. The concrete measurement result of the transmittance | permeability of Example 8 is shown in FIG. T% (365) was 3.55% and ΔT% (436-365) was 3.65%. Therefore, it was found that the phase shift film 3 of Example 8 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm was suppressed.
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 23.62%. Therefore, it was found that the phase shift film 3 of Example 8 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm was suppressed.
The measurement results of the phase difference are shown in FIG. P (365) was 178.3 degrees and ΔP (365-436) was 22 degrees. Therefore, it was found that the phase shift film 3 of Example 8 exhibited optical characteristics in which the wavelength dependency of the retardation was suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
The result is shown in FIG. Moreover, the measurement result of the concrete reflectance of Example 8 is shown in FIG. R% (700-365) was 5.1% or more and 24.8% or less, and the range (the difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 19.7%.

B. Phase Shift Mask and Method of Manufacturing the Same In the same manner as in Example 7, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on the transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 10, the light intensity distribution curve of Example 8 has a sharp peak intensity at the center of the contact hole, a large change in light intensity at the pattern boundary portion, and the pattern boundary portion In the outer peripheral area, it is shown that the light intensity change is small.
The light intensity slope at the pattern boundary was 0.447. For this reason, it was found that the phase shift mask of Example 8 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Example 9
In Example 9, a phase shift mask blank of QZ / MoSiN configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputter target consisting of molybdenum silicide (Mo: Si = 1: 4) is disposed, and molybdenum silicide nitride is formed on the main surface of transparent substrate 2 A phase shift mask blank 1 was obtained by forming a metal silicide-based material layer (film thickness: 120 nm) made of (MoSiN).
In the metal silicide material layer, a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced near the molybdenum silicide target, and the sputtering power is 8.0 kW. The transparent substrate 2 was formed on the transparent substrate 2 by reactive sputtering at a conveyance speed of 400 mm / min. In order to obtain a desired film thickness of 120 nm, lamination was performed multiple times under the same conditions.

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (film thickness 110 nm) of QZ / MoSiN configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 4, the transmittance spectrum of Example 9 at a wavelength of 200 nm to 800 nm has a characteristic that the change in transmittance is smaller than in Comparative Examples 1 and 2 described later. The concrete measurement result of the transmittance | permeability of Example 9 is shown in FIG. T% (365) was 4.36% and ΔT% (436-365) was 3.97%. Therefore, it was found that the phase shift film 3 of Example 9 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm was suppressed.
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 21.60%. Therefore, it was found that the phase shift film 3 of Example 9 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm was suppressed.
The measurement results of the phase difference are shown in FIG. P (365) was 180.00 degrees and ΔP (365-436) was 24.00 degrees. Therefore, it was found that the phase shift film 3 of Example 9 exhibited optical characteristics in which the wavelength dependency of the retardation was suppressed in the wavelength range of 365 nm to 436 nm.

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
As a result, as shown in FIG. 6, the reflectance spectrum of Example 9 at a wavelength of 200 nm to 800 nm has a characteristic that the change in reflectance is smaller than in Comparative Examples 1 and 2 described later. The measurement result of the concrete reflectance of Example 9 is shown in FIG. R% (700-365) was 18.0% or more and 28.3% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 10.4%. Therefore, it was found that the phase shift film 3 of Example 9 exhibits optical characteristics in which the wavelength dependency of the reflectance in the wavelength range of 365 nm to 700 nm is suppressed.

B. Phase Shift Mask and Method of Manufacturing the Same In the same manner as in Example 1, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on a transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 9, the light intensity distribution curve of Example 9 has a sharp peak intensity at the center of the contact hole, a large change in light intensity at the pattern boundary portion, and the pattern boundary portion In the outer peripheral area, it is shown that the light intensity change is small.
The light intensity slope at the pattern boundary was 0.444. For this reason, it was found that the phase shift mask of Example 9 exhibits a strong light intensity inclination and improves the resolution as compared with a comparative example described later.

Comparative Example 1
In Comparative Example 1, a phase shift mask blank of the CrON configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputter target made of chromium is disposed, and a chromium-based material layer (chromic oxynitride) (CrON) is formed on the main surface of the transparent substrate 2 A film thickness of 157 nm was deposited to obtain a phase shift mask blank 1.
The chromium-based material layer is a mixture of argon (Ar) gas and nitrogen monoxide (NO) gas (Ar: 46 sccm, NO: 70 sccm) introduced near the chromium target, and the sputtering power is 8.0 kw, transparent. The film was formed on the transparent substrate 2 by reactive sputtering at a transfer speed of the substrate 2 of about 400 mm / min. In order to obtain a desired film thickness of 157 nm, lamination was performed multiple times under the same conditions.

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (film thickness: 157 nm) of QZ / CrON configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 4 and FIG. 5, in the transmittance spectrum of Comparative Example 1 at a wavelength of 200 nm to 800 nm, the transmittance change rapidly increases from around the wavelength of 300 nm and around 700 nm. The curve shows a substantially S-shaped curve in which the change in transmittance decreases. The specific measurement result of the transmittance | permeability of the comparative example 1 is shown in FIG. T% (365) is 7.73% and ΔT% (436-365) is 9.82%. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 does not exhibit optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm is suppressed, as compared with the above-described example. The
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 48.00%. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 does not exhibit optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed, as compared with the above-described example. The
The measurement results of the phase difference are shown in FIG. P (365) was 181.3 degrees and ΔP (365-436) was 32.5 degrees. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 does not exhibit optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm to 436 nm is suppressed, as compared with the above-described example. The

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
As a result, as shown in FIG. 6 and FIG. 7 and the measurement results of specific reflectance in FIG. 8, R% (700-365) is 7.60% or more and 18.45% or less, and 700 nm to 365 nm. The range (difference between the maximum value and the minimum value) in the range of is 10.8%, which is as good as that of the above-mentioned Example 6.

B. Phase Shift Mask and Method of Manufacturing the Same In the same manner as in Example 1, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on a transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 10, in the light intensity distribution curve of Comparative Example 1, the peak of the light intensity at the center of the contact hole is not so sharp as compared with the above example, and the light intensity change is not so large at the pattern boundary portion. In the peripheral region outside the pattern boundary portion, it is shown that the light intensity change is large.
The light intensity slope at the pattern boundary was 0.432. For this reason, it was found that the phase shift mask of Comparative Example 1 exhibits a weak light intensity inclination as compared with the above-described example.

Comparative Example 2
In Comparative Example 2, a phase shift mask blank having a CrOCN configuration will be described.

A. Phase Shift Mask Blank and Method of Manufacturing the Same A transparent substrate 2 having the same size as in Example 1 was prepared as a transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputter target made of chromium is disposed, and a chromium-based material layer made of chromium oxycarbonitride (CrOCN) on the main surface of the transparent substrate 2 A film thickness of 117 nm was formed to obtain a phase shift mask blank 1.
Incidentally, the chromium-based material layer in the vicinity of chromium target, argon (Ar) gas and carbon dioxide (CO ₂₎ gas and nitrogen _{(N 2)} gas mixture containing a gas _{(Ar: 46sccm, CO 2:} 35sccm, N 2: 46 sccm), and a sputtering power of 8.0 kw and a transfer speed of the transparent substrate 2 of about 400 mm / min were used to form a film on the transparent substrate 2 by reactive sputtering. In order to obtain a desired film thickness of 117 nm, lamination was performed multiple times under the same conditions.

  Thus, the phase shift mask blank 1 in which the phase shift film 3 was formed on the transparent substrate 2 was obtained.

The transmittance and the phase difference of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.
A substrate with a phase shift film (dummy substrate) on which the phase shift film 3 (film thickness 117 nm) of QZ / CrOCN configuration was formed was used for measurement of transmittance and retardation.
As a result, as shown in FIG. 4 and FIG. 5, in the transmittance spectrum of Comparative Example 2 at a wavelength of 200 nm to 800 nm, the transmittance change rapidly increases from around the wavelength of 300 nm and around 600 nm. The curve shows a substantially S-shaped curve in which the change in transmittance decreases. The specific measurement result of the transmittance | permeability of the comparative example 2 is 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 does not exhibit optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm is suppressed, as compared with the above-described example. The
Moreover, as shown in FIG. 8, (DELTA) T% (700-365) was 50.63%. Therefore, it is understood that the phase shift film 3 of Comparative Example 2 can not be said to exhibit optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed as compared with the above example. The
The measurement results of the phase difference are shown in FIG. P (365) was 182.1 degrees and ΔP (365-436) was 31.0 degrees. Therefore, it is understood that the phase shift film 3 of Comparative Example 2 does not exhibit optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described example. The

The reflectance of the phase shift film 3 of the obtained phase shift mask blank 1 was measured in the same manner as in Example 1.
As a result, R% (700-365) is 11.4% or more and 28.7% or less, as shown in FIGS. 6 and 7 and the specific measurement results of reflectance in FIG. 8, and 700 nm to 365 nm. The range (the difference between the maximum value and the minimum value) in the range of is 17.3%, which is as good as Example 5 described above.

B. Phase Shift Mask and Method of Manufacturing the Same In the same manner as in Example 1, a phase shift mask 30 was obtained in which a phase shift film pattern 3 'having a 2.5 μm square contact hole pattern was formed on a transparent substrate 2.

The simulation was performed on the phase shift effect of the phase shift mask 30 in the same manner as in the first embodiment.
The light intensity distribution curve which simulated the spatial image of the light which passed the phase shift mask in which the phase shift film pattern which has a 2.5 micrometer square contact hole pattern was formed is shown in FIG.
As shown in FIG. 9, in the light intensity distribution curve of Comparative Example 2, the peak of the light intensity at the center of the contact hole is not so sharp as compared with the above-described example, and the light intensity change is not so large at the pattern boundary portion. In the peripheral region outside the pattern boundary portion, it is shown that the light intensity change is large.
The light intensity slope at the pattern boundary was 0.440. Therefore, it was found that the phase shift mask of Comparative Example 2 exhibits a weak light intensity inclination as compared with the above-described example.

In the above-described embodiment, an example of molybdenum silicide nitride (MoSiN) has been described as the material of the metal silicide-based material layer constituting the phase shift film 3, but the invention is not limited thereto. The material of the metal silicide-based material layer may be molybdenum silicide oxide (MoSiO), molybdenum silicide carbonitride (MoSiCN), or molybdenum silicide carbide oxide carbide (MoSiOC). Also in the case of a metal silicide based material other than molybdenum silicide, the same effect as described above can be obtained.
Further, in the above-described embodiment, although examples of chromium nitride (CrN) and chromium oxynitride (CrON) as materials of the chromium-based material layer constituting the phase shift film 3 have been described, the present invention is not limited thereto. The material of the chromium-based material layer may be chromium oxide (CrO), chromium carbide (CrC), chromium carbonitride (CrCN), chromium oxycarbide (CrCO), chromium oxycarbonitride (CrOCN).

Further, in the above embodiment, an example of the phase shift mask blank 1 in which only the phase shift film 3 is formed on the transparent substrate 2 and the phase shift mask 30 in which only the phase shift film pattern 3 'is formed on the transparent substrate 2 is described. Although explained, it is not limited to this. It may be a phase shift mask blank having the phase shift film 3 and the light shielding film 4 on the transparent substrate 2, and a phase shift having the phase shift film pattern 3 'and the light shielding film pattern 4' on the transparent substrate 2. Even if it is a mask, the same effect as the above embodiment can be obtained.
In the phase shift mask blank having the phase shift film 3 and the light shielding film 4 on the transparent substrate 2 described above, the light shielding film formed on the phase shift film 3 includes a light shielding layer, a light shielding layer and an antireflection layer. It is good also as laminated structure of these, an insulating layer, a light shielding layer, and a reflection prevention layer.
Moreover, although the above-mentioned Example demonstrated the manufacturing method which produces the phase shift mask 30 by wet etching, it is not restricted to this. In the case of a metal silicide-based material layer as a material constituting phase shift mask blank 1, a fluorine-based gas (for example, CF ₄ gas, CHF ₃ gas, SF ₆ gas, or a mixture of these gases with O ₂ gas) In the case of a chromium-based material layer, patterning can be performed by dry etching using a chlorine-based gas (for example, a mixed gas of Cl ₂ gas and O ₂ gas).

1 phase shift mask blank, 2 transparent substrate, 3 phase shift film,
4 light shielding film, 5 resist film, 3 'phase shift film pattern,
4 'shading film pattern, 5' resist film pattern,
30 phase shift mask.

Claims (19)

In order to apply and expose an exposure apparatus having an exposure environment having an optical system having a numerical aperture (NA) of 0.06 to 0.15 and using a complex light including light in a wavelength range of 300 nm to 700 nm as a light source A phase shift mask blank for producing a phase shift mask for manufacturing a display device of
A transparent substrate,
A phase shift film formed on the transparent substrate;
The phase shift film is a single layer film or a laminated film having at least one metal silicide material layer containing metal, silicon and nitrogen,
The phase shift film is
The transmittance at a wavelength of 365 nm is in the range of 3.5% to 8%,
The phase difference at a wavelength of 365 nm is in the range of 160 degrees to 200 degrees,
Of transmittance in the range of less than the wavelength 365nm or more 436 nm, the amount of change depends on the wavelength state, and are within 5.5%,
The phase shift mask blank characterized in that the metal silicide-based material layer has a nitrogen content of 25 atomic% or more and 55 atomic% or less . The phase shift film is
2. The phase shift mask blank according to claim 1, wherein the change depending on the wavelength of the transmittance in the wavelength range of 365 nm to 700 nm is within 20%. The phase shift film is
The phase shift mask blank according to claim 1 or 2, wherein a difference between a retardation applied at a wavelength of 365 nm and a retardation applied at a wavelength of 436 nm is 30 degrees or less. The phase shift film is
The phase shift mask blank according to any one of claims 1 to 3, wherein a reflectance in a wavelength range of 365 nm to 700 nm is 5% to 45%.   The phase shift mask blank according to any one of claims 1 to 4, wherein the metal silicide-based material layer is composed of a nitride of a metal silicide composed of a metal, silicon and nitrogen.   The phase shift mask blank according to any one of claims 1 to 5, wherein a metal: silicon ratio in the metal silicide-based material layer is metal: silicon = 1: 1 or more and 1: 9 or less. . The phase shift film is composed of at least one metal silicide based material layer and at least one chromium based material layer,
The phase shift mask blank according to any one of claims 1 to 6 , wherein the chromium-based material layer is composed of a nitride of chromium or an oxynitride of chromium. The phase shift mask blank according to any one of claims 1 to 7 , further comprising a light shielding film formed on the phase shift film. In order to apply and expose an exposure apparatus having an exposure environment having an optical system having a numerical aperture (NA) of 0.06 to 0.15 and using a complex light including light in a wavelength range of 300 nm to 700 nm as a light source A phase shift mask for manufacturing a display device of
A transparent substrate,
A phase shift film pattern formed on the transparent substrate;
The phase shift film pattern is formed of a single layer film or a laminated film having at least one metal silicide material layer containing metal, silicon and nitrogen,
The phase shift film pattern is
The transmittance at a wavelength of 365 nm is in the range of 3.5% to 8%,
The phase difference at a wavelength of 365 nm is in the range of 160 degrees to 200 degrees,
Of transmittance in the range of less than the wavelength 365nm or more 436 nm, the amount of change depends on the wavelength state, and are within 5.5%,
The phase shift mask characterized in that the metal silicide-based material layer has a nitrogen content of 25 atomic% or more and 55 atomic% or less . The phase shift film pattern is
10. The phase shift mask according to claim 9 , wherein a wavelength dependent change amount of the transmittance in the wavelength range of 365 nm to 700 nm is within 20%. The phase shift film pattern is
A phase difference given at a wavelength 365 nm, the difference in the phase difference given at a wavelength 436nm is claim 9 or 10 phase shift mask according to equal to or less than 30 degrees. The phase shift film pattern is
The phase shift mask according to any one of claims 9 to 11, wherein a reflectance in a wavelength range of 365 nm to 700 nm is 5% to 45%. The metal silicide-based material layer, phase Shifutomasu click according to any one of claims 9 to 12, characterized in that they are composed of a nitride of the metal silicide comprising a metal, silicon and nitrogen. The phase shift mask according to any one of claims 9 to 13 , wherein a ratio of metal to silicon in the metal silicide-based material layer is metal: silicon = 1: 1 or more and 1: 9 or less. The phase shift film pattern is composed of at least one metal silicide-based material layer and at least one chromium-based material layer,
The phase shift mask according to any one of claims 9 to 14 , wherein the chromium-based material layer is composed of nitride of chromium or oxynitride of chromium. The phase shift mask according to any one of claims 9 to 15 , further comprising a light shielding film pattern formed on the phase shift film pattern. In a method of manufacturing a display device,
And a phase shift mask disposing step of disposing the phase shift mask according to any one of claims 9 to 16 to the resist film coated substrate having a resist film formed on the substrate, ,
An exposure apparatus having an optical system having a numerical aperture (NA) of 0.06 to 0.15 and using compound light including light in a wavelength range of 300 nm to 700 nm as a light source is used to form the phase shift mask A resist film exposure step of exposing the resist film by irradiating light;
A method of manufacturing a display device, comprising: The method according to claim 17 , wherein the composite light is composite light including i-line, h-line and g-line. The method according to claim 17 or 18 , wherein the exposure environment has a coherence factor (σ) of 0.5 to 1.0.

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