JP6324756B2 - Phase shift mask blank and method for manufacturing the same, method for manufacturing phase shift mask, and method for manufacturing display device - Google Patents

Description

  The present invention relates to a phase shift mask blank and a manufacturing method thereof in which a cross-sectional shape of a phase shift film pattern formed by wet etching is good, a phase shift mask using the phase shift mask blank, and a manufacturing method thereof. The present invention also relates to a phase shift mask blank for manufacturing a display device and a method for manufacturing the same, a method for manufacturing a phase shift mask for manufacturing a display device using the phase shift mask blank, and a display device using the phase shift mask. It relates to the manufacturing method.

  Currently, there are a VA (Vertical alignment) method and an IPS (In Plane Switching) method as a method adopted in a liquid crystal display device. By these methods, a high-definition, high-speed display performance and wide viewing angle liquid crystal display device 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 with a line and space pattern using a transparent conductive film. Recently, in order to further improve the response speed and viewing angle, improve the light utilization efficiency of the liquid crystal display device, that is, reduce the power consumption of the liquid crystal display device and improve the contrast, the pitch width of the line and space pattern is fine. Is required. For example, it is desired to reduce the pitch width of the line and space pattern from 6 μm to 5 μm, and further from 5 μm to 4 μm.

  In manufacturing a liquid crystal display device or an organic EL display device, an element such as a transistor is formed by stacking a plurality of conductive films and insulating films which have been subjected to necessary patterning. At that time, a photolithography process is often used for patterning of individual films to be stacked. For example, some thin film transistors used in these display devices have a structure in which a contact hole is formed in an insulating layer by a photolithography process and an upper layer pattern and a lower layer pattern are connected to each other. Recently, in such a display device, there is an increasing need to display a bright and fine image with sufficient operation speed and to reduce power consumption. In order to satisfy such a demand, it is required to miniaturize and highly integrate the constituent elements of the display device. For example, it is desired to reduce the diameter of the contact hole from 2 μm to 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.

Upon realizing the miniaturization of the line and space pattern or contact hole, in the conventional photomask, since the resolution limit of the exposure machine for display production is 3 [mu] m, without sufficient steps likelihood (Process Margin), Products with a minimum line width close to the resolution limit must be produced. For this reason, there has been a problem that the defect rate of the display device becomes high.

  For example, when a photomask having a hole pattern for forming contact holes is used and transferred to a transfer target, if the hole pattern has a diameter exceeding 3 μm, transfer is performed using a conventional photomask. I was able to. However, it has been very difficult to transfer a hole pattern having a diameter of 3 μm or less, particularly a hole pattern having a diameter of 2.5 μm or less. In order to transfer a hole pattern having a diameter of 2.5 μm or less, for example, it may be possible to switch to an exposure machine having a high NA, but a large investment is required.

  Therefore, in order to improve the resolution and cope with the miniaturization of the line and space pattern and the contact hole, a phase shift mask has attracted attention as a photomask for manufacturing a display device.

Recently, a phase shift mask having a chromium 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 phase difference of 180 degrees with respect to any light in a wavelength region of 300 nm to 500 nm formed around the light shielding layer. A halftone phase shift mask is described that includes a phase shift layer made of a chromium oxynitride-based material that can be provided. In this phase shift mask, the light shielding layer on the transparent substrate is patterned, the phase shift layer is formed on the transparent substrate so as to cover the light shielding layer, the photoresist layer is formed on the phase shift layer, and the photoresist layer is formed. A resist pattern is formed by exposure and development, and the phase shift layer is patterned using the resist pattern as an etching mask.

JP 2011-13283 A

  The present inventors diligently studied a phase shift mask provided with a chromium phase shift film. As a result, when the chromium phase shift film is patterned by wet etching using the resist pattern as a mask, the wet etching solution penetrates into the interface between the resist film and the chromium phase shift film, and the etching of the interface portion proceeds quickly. I understood. The cross-sectional shape of the edge portion of the formed chromium-based phase shift film pattern is a tapered shape with an inclination and a skirt.

  When the cross-sectional shape of the edge portion of the chromium-based phase shift film pattern is a taper shape, the phase shift effect is reduced as the film thickness of the edge portion of the chromium-based phase shift film pattern decreases. For this reason, a phase shift effect cannot fully be exhibited. The penetration of the wet etching solution into the interface between the resist film and the chromium phase shift film is caused by poor adhesion between the chromium phase shift film and the resist film. For this reason, it is difficult to strictly control the cross-sectional shape of the edge portion of the chromium-based phase shift film pattern, and it is very difficult to control the line width (CD).

  Furthermore, the present inventors diligently studied a method for verticalizing the cross-sectional shape of the edge portion of the phase shift film pattern in order to solve these problems. So far, a method of changing the etching rate in the film thickness direction by giving a gradient to the film composition (for example, nitrogen content) of the phase shift film, or adding an additive to the phase shift film to control the etching time. A method was developed. However, with these methods, it has been very difficult to realize the uniformity of transmittance over the entire large-area phase shift mask.

  For this reason, the present invention has been made in view of the above-described problems, and a phase shift mask blank capable of patterning a phase shift film into a cross-sectional shape that can sufficiently exhibit a phase shift effect by wet etching, and a method for manufacturing the same. A method of manufacturing a phase shift mask having a phase shift film pattern capable of sufficiently exhibiting the phase shift effect, particularly a phase shift mask for manufacturing a display device capable of patterning the phase shift film in a cross-sectional shape capable of sufficiently exhibiting the phase shift effect To provide a blank, a method for manufacturing the same, a method for manufacturing a phase shift mask for manufacturing a display device having a phase shift film pattern capable of sufficiently exhibiting the phase shift effect, and a method for manufacturing a display device using the phase shift mask. Objective.

  The present invention also provides a phase shift mask blank capable of patterning a phase shift film in a cross-sectional shape having a small CD variation by wet etching, a manufacturing method thereof, a method for manufacturing a phase shift mask having a phase shift film pattern having a small CD variation, In particular, a phase shift mask blank for manufacturing a display device capable of patterning a phase shift film in a cross-sectional shape having a small CD variation, and a manufacturing method thereof, and a manufacturing method of a phase shift mask for manufacturing a display device having a phase shift film pattern having a small CD variation. It is an object to provide a method and a manufacturing method of a display device using the phase shift mask.

  The present invention also relates to a phase shift mask blank having uniform optical characteristics and a method for manufacturing the same, a method for manufacturing a phase shift mask having uniform optical characteristics, and more particularly to a phase shift mask blank for manufacturing a display device having uniform optical characteristics and the same. It is an object of the present invention to provide a manufacturing method, a manufacturing method of a phase shift mask for manufacturing a display device having uniform optical characteristics, and a manufacturing method of a display device using the phase shift mask.

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

(Configuration 1) a transparent substrate;
A light semi-transmissive film formed on the main surface of the transparent substrate and having a property of changing the phase of light having a representative wavelength included in exposure light by approximately 180 degrees and made of a chromium-based material;
A phase shift mask blank comprising: an etching mask film made of a metal silicide material formed on the light semi-transmissive film.

(Structure 2) The phase shift mask blank according to Structure 1, wherein the etching mask film has a light shielding property.

(Configuration 3) In a phase shift mask blank for manufacturing a display device,
A transparent substrate;
A light semi-transmissive film formed on the main surface of the transparent substrate and having a property of changing the phase of light having a representative wavelength included in exposure light by a first angle and made of a chromium-based material;
An etching mask film formed on the light semi-transmissive film and having a property of changing the phase of light having a representative wavelength included in exposure light by a second angle and made of a metal silicide material;
The sum of the first angle and the second angle is approximately 180 degrees.

(Configuration 4) A composition gradient region is formed at the interface between the light semi-transmissive film and the etching mask film, and in the composition gradient region, the ratio of the component that slows the wet etching rate of the light semi-transmissive film is the depth. The phase shift mask blank according to any one of configurations 1 to 3, wherein the phase shift mask blank increases stepwise and / or continuously in the direction.

(Configuration 5) The light semi-transmissive film has a substantially uniform composition except for the interface between the light semi-transmissive film and the etching mask film and the interface between the light semi-transmissive film and the transparent substrate. The phase shift mask blank according to any one of configurations 1 to 4, wherein the phase shift mask blank is provided.

(Structure 6) The phase shift mask blank according to any one of structures 1 to 5, wherein the light semi-transmissive film is composed of a plurality of layers.

(Structure 7) The phase shift according to any one of Structures 1 to 6, wherein the chromium-based material is chromium carbide, chromium nitride carbide, chromium oxycarbide, or chromium oxynitride carbide. Mask blank.

(Arrangement 8) Any one of Arrangements 1 to 7, wherein the metal silicide-based material includes metal and silicon, and a ratio of metal to silicon is metal: silicon = 1: 1 or more and 1: 9 or less. A phase shift mask blank according to claim 1.

(Structure 9) The metal silicide material includes metal silicide, metal silicide nitride, metal silicide oxide, metal silicide carbide, metal silicide oxynitride, metal silicide carbonitride, metal silicide oxycarbide. Or a phase shift mask blank according to any one of Structures 1 to 8, wherein the phase shift mask blank is an oxycarbonitride of metal silicide.

(Structure 10) The metal silicide material is a metal silicide nitride, a metal silicide oxynitride, a metal silicide carbonitride, or a metal silicide oxycarbonitride, and a nitrogen content is 25 The phase shift mask blank according to Configuration 9, wherein the phase shift mask blank is an atomic% or more and 55 atomic% or less.

(Structure 11) The phase shift mask blank according to any one of Structures 1 to 10, further comprising a resist adhesion improving film made of a chromium-based material formed on the etching mask film.

(Structure 12) The phase shift mask blank according to any one of structures 1, 2, 4 to 11, wherein the phase shift mask blank is a phase shift mask blank for manufacturing a display device.

(Configuration 13)
A preparation step of preparing a transparent substrate;
A semi-transparent film is formed on the main surface of the transparent substrate by sputtering to form a light semi-transmissive film having a property of changing the phase of light having a representative wavelength included in exposure light by approximately 180 degrees and made of a chromium-based material. Forming process;
An etching mask film forming step of forming an etching mask film made of a metal silicide material on the light semi-transmissive film by sputtering. A method of manufacturing a phase shift mask blank, comprising:

(Configuration 14) In a method of manufacturing a phase shift mask blank for manufacturing a display device,
A preparation step of preparing a transparent substrate;
A semi-transmissive film is formed on the main surface of the transparent substrate by sputtering to form a light semi-transmissive film having a property of changing the phase of the light of the representative wavelength included in the exposure light by the first angle and made of a chromium-based material. A film forming step;
An etching mask film for forming an etching mask film having a property of changing the phase of light of a representative wavelength included in exposure light by a second angle and made of a metal silicide material on the light semi-transmissive film by sputtering. A forming process, and
The method of manufacturing a phase shift mask blank, wherein the sum of the first angle and the second angle is approximately 180 degrees.

(Structure 15) The semi-transmissive film forming step includes forming a light semi-transmissive film made of a chromium-based material by applying sputtering power in a sputtering gas atmosphere, and wet etching of the light semi-transmissive film. Exposing the light semi-transmissive film to a gas atmosphere containing a component that slows down the speed, and the exposing process is performed continuously after the film forming process without exposing the light semi-transmissive film to the atmosphere. A method of manufacturing a phase shift mask blank according to the structure 13 or 14, characterized in that:

(Structure 16) The film forming step uses an inert gas containing at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas using a sputtering target containing chromium or a chromium compound. The method for producing a phase shift mask blank according to the structure 15, wherein the method is performed in a sputtering gas atmosphere made of a mixed gas with an active gas containing carbon dioxide gas or hydrocarbon gas.

(Structure 17) The method of manufacturing a phase shift mask blank according to Structure 15 or 16, wherein the exposing step is performed in a gas atmosphere containing carbon.

(Configuration 18) The etching mask film forming step uses a sputtering target containing a metal and silicon, and contains at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas. Characterized in that it is performed in a sputtering gas atmosphere comprising a mixed gas of a gas and an active gas including at least one selected from the group consisting of oxygen gas, nitrogen gas, carbon dioxide gas, nitrogen oxide-based gas and hydrocarbon-based gas. The manufacturing method of the phase shift mask blank as described in any one of the structures 13 thru | or 17 to do.

(Structure 19) The method for manufacturing a phase shift mask blank according to any one of structures 13, 15 to 18, wherein the phase shift mask blank is a phase shift mask blank for manufacturing a display device.

(Configuration 20)
The phase shift mask obtained on the etching mask film of the phase shift mask blank according to any one of Configurations 1 to 10 and 12 or by the method of manufacturing the phase shift mask blank according to any one of Configurations 13 to 19 A resist pattern forming step of forming a resist pattern on a blank etching mask film;
Etching mask film pattern forming step of forming an etching mask film pattern by wet etching the etching mask film using the resist pattern as a mask;
And a semi-transmissive film pattern forming step of forming a light semi-transmissive film pattern by wet-etching the light semi-transmissive film using the etching mask film pattern as a mask.

(Configuration 21) In a method for manufacturing a phase shift mask for manufacturing a display device,
A resist pattern forming step of forming a resist pattern on the resist adhesion improving film of the phase shift mask blank according to Configuration 11,
Etching mask film pattern forming step of forming a resist adhesion improving film pattern and an etching mask film pattern by wet etching the resist adhesion improving film and the etching mask film using the resist pattern as a mask;
A semi-transmissive film pattern forming step of forming a light semi-transmissive film pattern by wet etching the light semi-transmissive film using the resist adhesion improving film pattern and the etching mask film pattern or the etching mask film pattern as a mask; A method of manufacturing a phase shift mask, comprising:

(Structure 22) The etching mask film pattern forming step is selected from at least one fluorine compound selected from hydrofluoric acid, silicohydrofluoric acid, and ammonium hydrogen fluoride, hydrogen peroxide, nitric acid, and sulfuric acid. 23. A method of manufacturing a phase shift mask according to Configuration 20 or 21, wherein wet etching is performed using an etching solution containing at least one oxidizing agent.

(Structure 23) The method for manufacturing a phase shift mask according to any one of structures 20 to 22, wherein the phase shift mask is a phase shift mask for manufacturing a display device.

(Configuration 24) In the display device manufacturing method,
Phase shift mask placement step of placing a phase shift mask obtained by the method of manufacturing a phase shift mask according to Configuration 23 on a substrate with a resist film on which a resist film is formed, facing the resist film When,
And a resist film exposure step of exposing the resist film by irradiating the phase shift mask with the exposure light.

(Structure 25) The method for manufacturing a display device according to structure 24, wherein the exposure light includes light having a wavelength range of 300 nm to 500 nm.

(Structure 26) A method of manufacturing a display device according to Structure 24 or 25, wherein the exposure light is composite light including i-line, h-line, and g-line.

  As described above, according to the phase shift mask blank according to the present invention, particularly according to the phase shift mask blank for display device manufacture used for display device manufacture, from the chromium-based material formed on the main surface of the transparent substrate. A light semi-transmissive film configured and an etching mask film formed on the light semi-transmissive film and made of a metal silicide material are provided. Adhesion between the light semi-transmissive film made of a chromium-based material and the etching mask film made of a metal silicide-based material is high. Therefore, when the light semi-transmissive film is patterned by wet etching using the etching mask film pattern as a mask, it is possible to prevent the wet etching liquid from entering the interface between the etching mask film pattern and the light semi-transmissive film. Therefore, it is possible to obtain a phase shift mask blank capable of patterning the light semitransmissive film into a cross-sectional shape that can sufficiently exhibit the phase shift effect by wet etching. In addition, a phase shift mask blank capable of patterning the light translucent film into a cross-sectional shape with small CD variation can be obtained by wet etching.

  Moreover, according to the manufacturing method of the phase shift mask blank which concerns on this invention, especially the manufacturing method of the phase shift mask blank for display apparatus manufacture used for display apparatus manufacture, from the chromium-type material on the main surface of a transparent substrate A configured light semi-transmissive film is formed, and an etching mask film made of a metal silicide material is formed on the light semi-transmissive film. As described above, the adhesion between the light semi-transmissive film made of a chromium-based material and the etching mask film made of a metal silicide-based material is high. Therefore, when the light semi-transmissive film is patterned by wet etching using the etching mask film pattern as a mask, it is possible to prevent the wet etching liquid from entering the interface between the etching mask film pattern and the light semi-transmissive film. Therefore, it is possible to manufacture a phase shift mask blank capable of patterning the light semitransmissive film into a cross-sectional shape that can sufficiently exhibit the phase shift effect by wet etching. In addition, a phase shift mask blank capable of patterning the light translucent film into a cross-sectional shape with small CD variation can be manufactured by wet etching.

  In addition, according to the method for manufacturing a phase shift mask according to the present invention, particularly the method for manufacturing a phase shift mask for manufacturing a display device used for manufacturing a display device, the phase shift mask blank described above or the phase shift mask blank described above A phase shift mask is manufactured using the phase shift mask blank obtained by the manufacturing method. For this reason, the phase shift mask which has the light semi-transmissive film | membrane pattern which can fully exhibit a phase shift effect can be manufactured. In addition, a phase shift mask having a light semi-transmissive film pattern with small CD variation can be manufactured. This phase shift mask can cope with the miniaturization of line and space patterns and contact holes.

  Further, according to the method for manufacturing a display device according to the present invention, the display device is manufactured using the phase shift mask obtained by the method for manufacturing the phase shift mask described above. For this reason, a display device having a fine line and space pattern or contact hole can be manufactured.

It is a schematic diagram which shows the film | membrane structure of the phase shift mask blank in which a resist adhesive improvement film | membrane is not formed. It is a schematic diagram which shows the film | membrane structure of the phase shift mask blank in which the resist adhesive improvement film | membrane is formed. It is a schematic diagram which shows the sputtering device used for formation of a light semipermeable film and an etching mask film | membrane. It is process drawing for demonstrating the manufacturing method of the phase shift mask using the phase shift mask blank in which the resist adhesive improvement film | membrane is not formed. It is process drawing for demonstrating the manufacturing method of the phase shift mask using the phase shift mask blank in which the resist adhesive improvement film | membrane is formed. It is process drawing for demonstrating the manufacturing method of the other phase shift mask using the phase shift mask blank in which the resist adhesive improvement film | membrane is formed.

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

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

FIG. 1 is a schematic diagram showing a film configuration of a phase shift mask blank 20 in which a resist adhesion improving film is not formed. In this phase shift mask blank 20, a light semi-transmissive film 22 and an etching mask film 23 are sequentially formed on the main surface of the transparent substrate 21. Note that a resist film 25 may be formed on the etching mask film 23. Further, the light semi-transmissive film 22 and the etching mask film 23 can be a single layer or a plurality of layers.
FIG. 2 is a schematic diagram showing the film configuration of the phase shift mask blank 20 on which the resist adhesion improving film 24 is formed. In this phase shift mask blank 20, a light semi-transmissive film 22, an etching mask film 23, and a resist adhesion improving film 24 are sequentially formed on the main surface of the transparent substrate 21. Note that a resist film 25 may be formed on the resist adhesion improving film 24. The resist adhesion improving film 24 may be a single layer or a plurality of layers.
In the method of manufacturing a phase shift mask blank for manufacturing a display device according to the first embodiment, a preparation process for preparing a transparent substrate 21 and an optical half composed of a chromium-based material by sputtering on the main surface of the transparent substrate 21. A semi-transmissive film forming step for forming the transmissive film 22 and an etching mask film forming step for forming an etching mask film 23 made of a metal silicide material on the light semi-transmissive film 22 by sputtering are performed.
Hereinafter, each process will be described in detail.

1. Preparation process When manufacturing the phase shift mask blank 20 for display apparatus manufacture, the transparent substrate 21 is prepared first.
The material of the transparent substrate 21 is not particularly limited as long as it is a material having translucency with respect to the exposure light to be used. Examples thereof include synthetic quartz glass, soda lime glass, and alkali-free glass.

2. Next, a light semi-transmissive film 22 made of a chromium-based material is formed on the main surface of the transparent substrate 21 by sputtering.
Specifically, in this semi-transmissive film forming step, first, a film forming step is performed in which sputtering power is applied in a sputtering gas atmosphere to form a light semi-transmissive film 22 made of a chromium-based material. Thereafter, preferably, the light semi-transmissive film 22 is exposed to a gas atmosphere containing a component that slows the wet etching rate of the light semi-transmissive film 22 continuously after the film forming step without exposing the light semi-transmissive film 22 to the atmosphere. Perform the process. Continuously after the formation of the light semi-transmissive film 22, the light semi-transmissive film 22 is exposed from the surface of the light semi-transmissive film 22 by exposing it to a gas atmosphere containing a component that slows the wet etching rate of the light semi-transmissive film 22. Separation of components that slow down the wet etching rate can be prevented.

  The light semi-transmissive film 22 has a property of changing the phase of light having a representative wavelength included in exposure light by approximately 180 degrees. Alternatively, the light semi-transmissive film 22 has a property of changing the phase of the light of the representative wavelength included in the exposure light by approximately 180 degrees by the laminated structure (for example, two layers) of the light semi-transmissive film 22 and the etching mask film 23. . Due to this property, the light having the representative wavelength transmitted through the light semi-transmissive film 22 or the laminated structure (for example, two layers) of the light semi-transmissive film 22 and the etching mask film 23 and the light having the representative wavelength transmitted through only the transparent substrate. A phase difference of about 180 degrees occurs between them. When the exposure light is composite light including light in the wavelength range of 300 nm to 500 nm, the light semi-transmissive film 22 or the laminated structure of the light semi-transmissive film 22 and the etching mask film 23 (for example, two layers) has the wavelength. It is formed so as to generate a phase difference of about 180 degrees with respect to light of a representative wavelength included in the range. For example, when the exposure light is composite light including i-line, h-line, and g-line, the light semi-transmissive film 22 or the two layers of the light semi-transmissive film 22 and the etching mask film 23 are i-line, h-line, and g. It is formed so as to generate a phase difference of about 180 degrees with respect to any of the lines. In order to exhibit the phase shift effect, the phase difference of the light semi-transmissive film 22 is preferably set to a range of 180 ° ± 20 ° with respect to any of the representative wavelengths of the i-line, h-line, and g-line. . More preferably, the phase difference of the light translucent film is desirably set to a range of 180 ° ± 10 ° with respect to any of the representative wavelengths of i-line, h-line, and g-line. The transmittance of the light semi-transmissive film 22 is preferably 1% or more and 20% or less at a representative wavelength of any of i-line, h-line, and g-line. Particularly preferably, the transmittance of the light semi-transmissive film is 3% or more and 10% or less with respect to the representative wavelength of any of i-line, h-line, and g-line.

As a chromium-based material constituting the light semi-transmissive film 22, chromium (Cr), oxygen (O), nitrogen (N), carbon (in order to change the phase of the light of the representative wavelength included in the exposure light by approximately 180 degrees A chromium compound containing at least one selected from C) is used. Examples of the chromium compound include chromium oxide, chromium nitride, chromium oxynitride, chromium carbide, chromium nitride carbide, chromium oxycarbide, or chromium oxynitride carbide. The composition of the chromium compound constituting the light semi-transmissive film 22 includes a desired phase difference (180 ° ± 20 °) with respect to exposure light, a transmittance (1% or more and 20% or less), wet etching characteristics (of the light semi-transmissive film pattern). Adjust from the viewpoint of cross-sectional shape and CD variation) and chemical resistance. In order to have the above-mentioned desired phase difference and transmittance, it is preferable to make the chromium compound less than 50 atomic% of chromium.
In order to pattern the light semi-transmissive film 22 by wet etching to obtain a light semi-transmissive film pattern having a cross-sectional shape that can sufficiently exhibit the phase shift effect, the above-described chromium compound increases the wet etching rate of the light semi-transmissive film 22. It is desirable to include a slowing component. Examples of the component that slows the wet etching rate of the light semitransmissive film 22 include fluorine (F) in addition to the carbon (C) mentioned above. Examples of desirable chromium-based materials constituting the light semi-transmissive film 22 include chromium carbide, chromium nitride carbide, chromium oxycarbide, chromium oxynitride carbide, and chromium fluoride.

  The light semi-transmissive film 22 is formed by using a sputtering target containing chromium or a chromium compound and containing, for example, at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas. Sputtering comprising a mixed gas of an active gas and an active gas containing at least one selected from the group consisting of oxygen gas, nitrogen gas, nitrogen monoxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon gas, and fluorine gas Performed in a gas atmosphere. Examples of the hydrocarbon gas include methane gas, butane gas, propane gas, and styrene gas. Preferably, it is desirable to perform in a sputtering gas atmosphere containing a gas having a component that slows the wet etching rate of the light semitransmissive film 22. Examples of the gas having a component that slows the wet etching rate of the light semitransmissive film 22 include active gases such as carbon dioxide gas, hydrocarbon gas, and fluorine gas.

After the light semi-transmissive film 22 is formed, an exposure step of exposing the light semi-transmissive film 22 to a gas atmosphere containing a component that slows the wet etching rate of the light semi-transmissive film 22 can be performed as necessary.
The exposure step after the formation of the light semi-transmissive film 22 is performed by exposing the light semi-transmissive film 22 to an exposure gas atmosphere containing a gas having a component that slows the wet etching rate of the light semi-transmissive film 22. Examples of the gas having a component that slows the wet etching rate of the light semitransmissive film 22 include active gases such as carbon dioxide gas, hydrocarbon gas, and fluorine gas. The exposure gas atmosphere may contain helium gas, neon gas, argon gas, krypton gas, xenon gas, etc. as the inert gas, and oxygen gas, nitrogen gas, etc. as the active gas. It may be. The content ratio of the gas having a component that slows the wet etching rate of the light semi-transmissive film 22 in the exposure gas atmosphere is the inclusion of the gas having a component that slows the wet etching rate of the light semi-transmissive film 22 in the sputtering gas atmosphere. The ratio is preferably the same as or higher than the content ratio of the gas having a component that slows the wet etching rate of the light semitransmissive film 22 in the sputtering gas atmosphere.

  The light semi-transmissive film 22 may be either a single layer or a plurality of layers. When the light semi-transmissive film 22 is composed of a plurality of layers, it is preferable that the light semi-transmissive film 22 and the exposure process after the light semi-transmissive film 22 are formed a plurality of times. When the film forming process is performed a plurality of times, it is possible to reduce the sputtering power applied to the sputter target when the light semitransmissive film 22 is formed. Therefore, it is preferable that the film forming process is performed a plurality of times because the number of defects in the light semitransmissive film 22 caused by the film forming process can be reduced. When the light semi-transmissive film 22 is composed of a plurality of layers, it is preferable to select the same material from the viewpoint of controllability of optical characteristics (transmittance and phase difference).

3. Etching Mask Film Formation Step Next, an etching mask film 23 made of a metal silicide material is formed on the light semi-transmissive film 22 by sputtering.

  The etching mask film 23 only needs to have etching selectivity with the light semitransmissive film 22. In addition to the etching selectivity with respect to the light semi-transmissive film 22, the etching mask film 23 is any of a case where it has a light shielding property with respect to exposure light and a case where it has a property of changing the phase of exposure light. Good. In the case where the etching mask film 23 has a light-shielding property, by providing an etching mask film pattern narrower than the light semi-transmissive film pattern on the light transmissive film pattern, the phase of the light of the representative wavelength included in the exposure light is approximately 180 degrees. The phase shift portion to be changed is constituted by a portion of the light semi-transmissive film pattern on which the etching mask film pattern is not laminated, and the light shielding portion is constituted by a portion on which the light semi-transmissive film pattern and the etching mask film pattern are laminated. The light transmission part can be constituted by a portion where the transparent substrate 21 is exposed. When the etching mask film 23 has a property of changing the phase of the exposure light, the laminated structure (for example, two layers) of the light semi-transmissive film 22 and the etching mask film 23 allows the light of the representative wavelength included in the exposure light to be reflected. A phase shift unit that changes the phase of the light of the representative wavelength included in the exposure light by about 180 degrees is configured on the light semi-transmissive film pattern and the light semi-transmissive film pattern by being configured to have the property of changing the phase by about 180 degrees. It can be constituted by a laminated structure (for example, two layers) with an etching mask film pattern provided.

  The metal silicide material constituting the etching mask film 23 is not particularly limited as long as it contains a metal and silicon. In order to improve the cross-sectional shape of the etching mask film pattern by wet etching, and to improve the cross-sectional shape of the light semi-transmissive film pattern by wet etching using the etching mask film pattern as a mask, the ratio of metal to silicon is metal : Silicon = 1: 1 or more and 1: 9 or less is preferable. Particularly preferably, the ratio of metal to silicon in the metal silicide material constituting the etching mask film 23 is desirably metal: silicon = 1: 2 or more and 1: 8 or less. Examples of the metal include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), and zirconium (Zr). Examples of the metal silicide material constituting the etching mask film include metal silicide, metal silicide nitride, metal silicide oxide, metal silicide carbide, metal silicide oxynitride, metal silicide carbonitride, and metal silicide. And oxycarbonitride of metal silicide. Specifically, molybdenum silicide (MoSi), its nitride, oxide, carbide, oxynitride, carbonitride, oxycarbide, and oxycarbonitride, tantalum silicide (TaSi), its nitride, oxide, Carbide, oxynitride, carbonitride, oxycarbide, and oxycarbonitride, tungsten silicide (WSi), its nitride, oxide, carbide, oxynitride, carbonitride, oxycarbide, and oxycarbonitride , Titanium silicide (TiSi), its nitride, oxide, carbide, oxynitride, carbonitride, oxycarbide, and oxycarbonitride, and zirconium silicide (ZrSi), its nitride, oxide, carbide, oxidation Examples include nitrides, carbonitrides, oxycarbides, and oxycarbonitrides. Among these, from the viewpoint of improving the adhesion with the light semi-transmissive film 22 and the cross-sectional controllability of the light semi-transmissive film 22 and the etching mask film, the metal silicide-based material is a metal silicide nitride, a metal silicide oxynitride, A metal silicide carbonitride is preferred. In this case, the nitrogen content is desirably 25 atomic% or more and 55 atomic% or less. In order to provide the etching mask film 23 with a reflectance reduction function, it is preferable that oxygen is further contained.

  The etching mask film forming step uses a sputtering target containing metal and silicon, an inert gas containing at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas, oxygen, It is performed in a sputtering gas atmosphere composed of a mixed gas with an active gas containing at least one selected from the group consisting of gas, nitrogen gas, carbon dioxide gas, nitrogen oxide-based gas and hydrocarbon-based gas. Examples of the nitrogen oxide-based gas include nitrogen monoxide gas, nitrogen dioxide gas, and dinitrogen monoxide gas.

The etching mask film 23 may be either a single layer or a plurality of layers. When the etching mask film 23 is composed of a plurality of layers, the sputtering power applied to the sputtering target when the etching mask film 23 is formed can be reduced. When the etching mask film 23 has only a mask function for patterning the light semi-transmissive film 22, the thickness of the etching mask film 23 is preferably as thin as possible. In this case, the thickness of the etching mask film 23 is preferably 5 nm or more and 75 nm or less. The size of the phase shift mask blank for manufacturing the display device is as large as 10 inches or more on one side, and it is difficult to form the etching mask film 23 uniformly over the surface. Therefore, in order to maintain the mask function of the etching mask film and to improve the cross-sectional shape of the light semi-transmissive film 22, it is desirable that the thickness of the etching mask film be 10 nm or more and 50 nm or less.
In addition, in addition to the etching selectivity with the light semi-transmissive film 22, the etching mask film 23 has a light shielding property with respect to the exposure light or a property to change the phase of the exposure light. In combination with the transmissive film 22, the material, composition, and film thickness of the etching mask film are adjusted so that desired optical characteristics can be obtained. When the etching mask film 23 is provided with a light-shielding property, the optical density (OD) is 2.5 or more in combination with the light semi-transmissive film 22, or the etching mask film 23 has a property of changing the phase. In consideration of the cross-sectional shape, the thickness of the etching mask film is desirably 75 nm to 150 nm, preferably 100 nm to 130 nm.

4). Next, a resist adhesion improving film 24 made of a chromium-based material is formed on the etching mask film 23 by sputtering as necessary.

  The resist adhesion improving film 24 has a property of improving the adhesion with the resist film 25. In addition to the property of improving the adhesion with the resist film 25, the resist adhesion improving film 24 may be any of a case of having a light shielding property and a case of having a light semi-transmitting property.

The chromium-based material constituting the resist adhesion improving film 24 is not particularly limited as long as it contains chromium (Cr). The chromium content of the chromium material constituting the resist adhesion improving film 24 is preferably larger than the chromium content of the chromium material constituting the light semi-transmissive film 22. Examples of the chromium-based material constituting the resist adhesion improving film 24 include, for example, chromium nitride, oxide, carbide, fluoride, oxynitride, carbonitride, fluorinated nitride, carbide oxide, and fluoride oxide. , Chromium compounds such as fluorinated carbides, oxycarbonitrides, oxyfluorinated nitrides, fluorinated fluorinated nitrides, fluorinated fluorinated oxides, and oxyfluorinated fluorinated nitrides can be used.
When the resist adhesion improving film 24 has only the property of improving the adhesion with the resist film 25, the resist adhesion improving film 24 is peeled off by the chromium wet etching solution in the manufacturing process of the phase shift mask 30. The In the process of peeling the resist adhesion improving film 24, the wet etching solution comes into contact with the side surface of the light semi-transmissive film pattern 22 ′. Therefore, it is preferable to shorten the peeling time of the resist adhesion improving film 24 as much as possible.
In addition, when the resist adhesion improving film 24 is formed into a desired pattern by wet etching, if the resist adhesion improving film pattern has a poor cross-sectional shape, etching is performed using the resist adhesion improving film pattern as a mask. The cross-sectional shape of each pattern of the mask film 23 and the light semi-transmissive film 22 is deteriorated.
From the above viewpoint, the film thickness of the resist adhesion improving film 24 is preferably thinner than the film thickness of the light semi-transmissive film 22. The film thickness of the resist adhesion improving film 24 is preferably 3 nm or more and 30 nm or less, and more preferably 5 nm or more and 25 nm or less.
Further, the wet etching rate of the resist adhesion improving film 24 in the wet etching solution of chromium is preferably higher than the wet etching rate of the light semi-transmissive film 22. The wet etching rate of the resist adhesion improving film 24 can be controlled by the chromium content of the chromium-based material. In order to increase the wet etching rate, the resist adhesion improving film 24 is preferably a film containing nitrogen. Specifically, it can be selected from chromium nitride, chromium oxynitride, chromium nitride carbide, and chromium oxynitride carbide chromium compound. The nitrogen content in the chromium compound is preferably 5 atom% or more and 45 atom% or less, more preferably 10 atom% or more and 40 atom% or less.
In addition, in addition to the property of improving the adhesion with the resist film 25, the resist adhesion improving film 24 has a light shielding property with respect to the exposure light or a property of changing the phase of the exposure light. In combination with the transmissive film 22 and the etching mask film 23, the material, composition, and film thickness of the resist adhesion improving film are adjusted so that desired optical characteristics can be obtained.

  This resist adhesion improving film forming step uses a sputtering target containing chromium or a chromium compound, for example, an inert containing at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas. It is carried out in a sputtering gas atmosphere consisting of a mixed gas of a gas and an active gas containing at least one selected from the group consisting of oxygen gas, nitrogen gas, carbon dioxide gas, nitrogen oxide gas, hydrocarbon gas and fluorine gas. . Examples of the nitrogen oxide-based gas include nitrogen monoxide gas, nitrogen dioxide gas, and dinitrogen monoxide gas.

  The phase shift mask blank 20 for manufacturing the display device according to the first embodiment includes such a preparation process, a semi-transmissive film forming process, an etching mask film forming process, and, if necessary, a resist adhesion improving film. Manufactured.

FIG. 3 is a schematic view showing an example of a sputtering apparatus used for forming the light semi-transmissive film 22, the etching mask film 23, and the resist adhesion improving film 24.
The sputtering apparatus 11 shown in FIG. 3 is an inline type, and includes five chambers: a carry-in chamber LL, a first sputter chamber SP1, a buffer chamber BU, a second sputter chamber SP2, and a carry-out chamber ULL. These five chambers are arranged sequentially in sequence.

  A transparent substrate 21 mounted on a tray (not shown) is loaded in the direction of arrow S at a predetermined transport speed in the direction of arrow S, a carry-in chamber LL, a first sputter chamber SP1, a buffer chamber BU, a second sputter chamber SP2, and a carry-out chamber. It can be transported in the ULL order. In addition, the transparent substrate 21 mounted on the tray (not shown) has a discharge chamber ULL, a second sputtering chamber SP2, a buffer chamber BU, a first sputtering chamber SP1, and a loading chamber LL in a direction opposite to the arrow S. Can be put back in order.

The carry-in chamber LL and the carry-out chamber ULL can be partitioned from the outside of the sputtering apparatus 11 by a partition plate. The first sputter chamber SP1, the buffer chamber BU, and the second sputter chamber SP2 are not partitioned by a GV (gate valve) and are configured by a large container in which three chambers are connected.
The carry-in chamber LL, the buffer chamber BU, and the carry-out chamber ULL are connected to an exhaust device (not shown) that performs exhaust.

In the first sputter chamber SP1, a first sputter target 13 containing chromium for forming the light semi-transmissive film 22 is disposed on the carry-in chamber LL side, and a first gas introduction port is provided in the vicinity of the first sputter target 13. GA1 (not shown) is arranged. In the first sputter chamber SP1, a second sputter target 14 containing a metal and silicon for forming the etching mask film 23 is disposed on the buffer chamber BU side. Two gas inlets GA2 (not shown) are arranged.
In the second sputter chamber SP2, a third sputter target 15 containing chromium for forming the resist adhesion improving film 24 is disposed on the buffer chamber BU side, and a third gas is introduced near the third sputter target 15. A mouth GA3 (not shown) is arranged.
In FIG. 3, the first sputter target 13, the second sputter target 14, and the third sputter target 15 are hatched.

  When forming the light semi-transmissive film 22, the etching mask film 23, and, if necessary, the resist adhesion improving film 24 using the in-line type sputtering apparatus 11 shown in FIG. 3, first, the light semi-transmissive film 22 is formed. Is formed, the transparent substrate 21 mounted on the tray (not shown) is loaded into the loading chamber LL.

After making the inside of the sputtering apparatus 11 have a predetermined degree of vacuum, a predetermined flow rate of sputtering gas is introduced from the first gas introduction port GA 1, and a predetermined sputtering power is applied to the first sputter target 13. When positively controlling the cross-sectional shape of the light semi-transmissive film pattern formed by wet etching, after the inside of the sputtering apparatus 11 is set to a predetermined degree of vacuum, the light semi-transmission at a predetermined flow rate from the first gas introduction port GA1. A sputtering gas containing a gas having a component that slows the wet etching rate of the transmissive film is introduced, and a component that slows the wet etching rate of the light semitransmissive film is introduced from the third gas introduction port GA3 to the second sputtering chamber SP2. An exposure gas containing the gas is introduced, and a predetermined sputtering power is applied to the first sputtering target 13. The application of the sputtering power, the introduction of the sputtering gas, and the introduction of the exposure gas are continued until the transparent substrate 21 is transferred to the carry-out chamber ULL.

Thereafter, the transparent substrate 21 mounted on the tray (not shown) is moved in the direction of the arrow S at a predetermined transport speed in the direction of the arrow S, the first sputtering chamber SP1, the buffer chamber BU, the second sputtering chamber SP2, and Transport in the order of the unloading chamber ULL. When the transparent substrate 21 passes through the vicinity of the first sputter target 13 in the first sputter chamber SP1, a light half composed of a chromium-based material having a predetermined film thickness is formed on the main surface of the transparent substrate 21 by reactive sputtering. A permeable film 22 is formed. Further, when actively controlling the cross-sectional shape of the light semi-transmissive film pattern formed by wet etching, the light semi-transmissive film 22 is light semi-transmissive while the transparent substrate 21 passes through the second sputtering chamber SP2. The film 22 is exposed to an exposure gas atmosphere containing a gas having a component that slows the wet etching rate.

When the second layer of light semi-transmissive film 22 is formed, the transparent substrate 21 mounted on the tray (not shown) is placed in the direction opposite to the arrow S in the carry-out chamber ULL, the second sputter chamber SP2, and the buffer. Returning to the order of the chamber BU, the first sputter chamber SP1, and the carry-in chamber LL, the above-described light semi-transmissive film 22 is formed again. When returning the transparent substrate 21 to the carry-in chamber LL, an exposure gas containing a gas having a component that slows the wet etching rate of the light semitransmissive film 22 may be introduced into the first sputter chamber SP1 and the second sputter chamber SP2. preferable. Thereby, while returning the transparent substrate 21 to the carry-in chamber LL, the light semi-transmissive film 22 can be exposed to an exposure gas atmosphere containing a gas having a component that slows the wet etching rate of the light semi-transmissive film 22.
The same process is performed when the third and fourth light semi-transmissive films 22 are formed.

  In the case where the light semi-transmissive film 22 is formed on the main surface of the transparent substrate 21 in this way and then the etching mask film 23 is continuously formed outside the sputtering apparatus 11 without taking out the transparent substrate 21, the tray The transparent substrate 21 mounted on (not shown) is returned in the order of the unloading chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, the first sputtering chamber SP1, and the loading chamber LL in the direction opposite to the arrow S. . On the other hand, when the etching mask film 23 is formed after the transparent substrate 21 is once taken out of the sputtering apparatus 11 after the light semi-transmissive film 22 is formed, the transparent substrate 21 mounted on a tray (not shown). Then, as described above, the inside of the sputtering apparatus 11 is set to a predetermined degree of vacuum.

Thereafter, a predetermined sputtering power is applied to the second sputtering target 14 and a sputtering gas is introduced from the second gas introduction port GA2. In this case, after the etching mask film 23 is formed, when the resist adhesion improving film 24 is not continuously formed in the second sputter chamber SP2, the pressure balance between the first sputter chamber SP1 and the second sputter chamber SP2. Therefore, pressure balancing gas is introduced from the third gas inlet GA3. When the resist adhesion improving film 24 is continuously formed in the second sputtering chamber SP2 after the etching mask film 23 is formed, a predetermined sputtering power is applied to the third sputtering target 15 to introduce a third gas. Sputtering gas is introduced from the opening GA3. The application of the sputtering power, the introduction of the sputtering gas, and the introduction of the pressure balancing gas are continued until the transparent substrate 21 is transferred to the carry-out chamber ULL.

  Thereafter, the transparent substrate 21 mounted on the tray (not shown) is moved in the direction of the arrow S at a predetermined transport speed in the direction of the arrow S, the first sputtering chamber SP1, the buffer chamber BU, the second sputtering chamber SP2, and Transport in the order of the unloading chamber ULL. When the transparent substrate 21 passes through the vicinity of the second sputter target 14 of the first sputter chamber SP1, an etching mask made of a metal silicide-based material having a predetermined thickness is formed on the light semitransmissive film 22 by reactive sputtering. A film 23 is formed. In addition, after the etching mask film 23 is formed, in order to continuously form the resist adhesion improving film 24 in the second sputtering chamber SP2, a sputtering power is applied to the third sputtering target 15, and the third gas inlet port is applied. When the sputtering gas is introduced from GA3, when the transparent substrate 21 passes near the third sputter target 15 in the second sputter chamber SP2, a predetermined film thickness is formed on the etching mask film 23 by reactive sputtering. A resist adhesion improving film 24 made of a chromium-based material is formed.

Thereafter, after forming only the etching mask film 23 on the light semi-transmissive film 22 in this manner and then not forming the resist adhesion improving film 24 on the etching mask film 23, the transparent substrate 21 of the sputtering apparatus 11 is used. Take it out.
In addition, even when the etching mask film 23 is formed on the light semi-transmissive film 22 and the resist adhesion improving film 24 is formed on the etching mask film 23 in this way, the transparent substrate 21 is attached to the outside of the sputtering apparatus 11. Take out.

Further, when only the etching mask film 23 is formed on the light semi-transmissive film 22 in this way, and then the resist adhesion improving film 24 is continuously formed without taking out the transparent substrate 21 outside the sputtering apparatus 11. Shows the transparent substrate 21 mounted on the tray (not shown) in the direction opposite to the arrow S in the carry-out chamber ULL, the second sputter chamber SP2, the buffer chamber BU, the first sputter chamber SP1, and the carry-in chamber LL. Return to order. On the other hand, when the resist adhesion improving film 24 is formed after the transparent substrate 21 is once taken out of the sputtering apparatus 11 after the etching mask film 23 is formed, the transparent substrate mounted on a tray (not shown). After loading 21 into the loading chamber LL, as described above, the inside of the sputtering apparatus 11 is set to a predetermined degree of vacuum.
Thereafter, a predetermined sputtering power is applied to the third sputtering target 15 and a sputtering gas is introduced from the third gas introduction port GA3. In this case, in order to balance the pressure between the first sputter chamber SP1 and the second sputter chamber SP2, a pressure balancing gas is introduced from at least one of the first gas introduction port GA1 and the second gas introduction port GA2. The application of the sputtering power, the introduction of the sputtering gas, and the introduction of the pressure balancing gas are continued until the transparent substrate 21 is transferred to the carry-out chamber ULL.
Thereafter, the transparent substrate 21 mounted on the tray (not shown) is moved in the direction of the arrow S at a predetermined transport speed in the direction of the arrow S, the first sputtering chamber SP1, the buffer chamber BU, the second sputtering chamber SP2, and Transport in the order of the unloading chamber ULL. When the transparent substrate 21 passes through the vicinity of the third sputter target 15 in the second sputter chamber SP2, the adhesion of the resist made of a chromium-based material having a predetermined thickness is formed on the etching mask film 23 by reactive sputtering. A film 24 is formed.
Thereafter, after the resist adhesion improving film 24 is formed on the etching mask film 23 in this manner, the transparent substrate 21 is taken out of the sputtering apparatus 11.

  The phase shift mask blank 20 for manufacturing a display device according to the first embodiment manufactured in this manner is a transparent substrate 21 and an optical half composed of a chromium-based material formed on the main surface of the transparent substrate 21. A transmissive film 22, an etching mask film 23 made of a metal silicide material formed on the light semi-transmissive film 22, and a resist adhesion improving film 24 as necessary are provided. Further, it is preferable that a composition gradient region is formed at the interface between the light semitransmissive film 22 and the etching mask film 23.

The composition gradient region is an etching mask film after a chromium (Cr) peak due to the light semi-transmissive film 22 appears in the composition analysis result in the depth direction by X-ray photoelectron spectroscopy (XPS) for the phase shift mask blank 20. This is a region until the silicon (silicon: Si) peak and the molybdenum (Mo) peak due to 23 disappear.
In the composition gradient region, the ratio of the component (for example, carbon (C)) that slows the wet etching rate of the light semitransmissive film 22 increases stepwise and / or continuously in the depth direction. preferable. This prevents the component (for example, carbon (C)) that slows the wet etching rate from coming off the surface of the light semi-transmissive film 22.

The composition of the light semi-transmissive film 22 is preferably substantially uniform. However, the composition gradient region described above is formed at the interface between the light semi-transmissive film 22 and the etching mask film 23, and the region where the composition is inclined is also formed at the interface between the light semi-transmissive film 22 and the transparent substrate 21. Therefore, the composition of these parts is not uniform. The composition uniform region in which the composition of the light semi-transmissive film 22 is substantially uniform is a result of the composition analysis in the depth direction by XPS for the phase shift mask blank. ) This is a region from when the peak disappears until the oxygen (O) peak due to the transparent substrate 21 appears.
In the uniform composition region, the variation in the proportion of each component (for example, carbon (C)) that slows the wet etching rate of chromium (Cr) and the light semi-transmissive film 22 is 5 atomic% or less, preferably 3 atomic%. It is as follows.

  When the light semi-transmissive film 22 is composed of a plurality of layers, the composition of each layer with respect to the composition of the component (for example, carbon (C)) that slows the wet etching rate of the light semi-transmissive film 22 near the center in the thickness direction of each layer. The decrease in the composition of the component (for example, carbon (C)) that slows the wet etching rate of the light semitransmissive film 22 at the interface is 5 atomic% or less, preferably 3 atomic% or less.

  According to the method of manufacturing the phase shift mask blank for manufacturing the display device of the first embodiment, the light semi-transmissive film 22 made of a chromium-based material is formed on the main surface of the transparent substrate 21, and the light semi-transmissive is formed. An etching mask film 23 made of a metal silicide material is formed on the film 22. The adhesion between the light semi-transmissive film 22 made of a chromium-based material and the etching mask film 23 made of a metal silicide-based material is high. For this reason, when the light semi-transmissive film 22 is patterned by wet etching using the etching mask film pattern as a mask, it is possible to prevent the wet etching solution from entering the interface between the etching mask film pattern and the light semi-transmissive film 22. . Therefore, the phase shift mask blank 20 capable of patterning the light semi-transmissive film 22 into a cross-sectional shape that can sufficiently exhibit the phase shift effect can be manufactured by wet etching. Further, the phase shift mask blank 20 capable of patterning the light translucent film into a cross-sectional shape with small CD variation can be manufactured by wet etching.

  Further, according to the phase shift mask blank 20 for manufacturing the display device of the first embodiment, the light semi-transmissive film 22 made of a chromium-based material formed on the main surface of the transparent substrate 21, and the light semi-mask And an etching mask film 23 formed on the transmissive film 22 and made of a metal silicide material. The adhesion between the light semi-transmissive film 22 made of a chromium-based material and the etching mask film 23 made of a metal silicide-based material is high. For this reason, when the light semi-transmissive film 22 is patterned by wet etching using the etching mask film pattern as a mask, it is possible to prevent the wet etching solution from entering the interface between the etching mask film pattern and the light semi-transmissive film 22. . Therefore, the phase shift mask blank 20 capable of patterning the light semitransmissive film 22 into a cross-sectional shape that can sufficiently exhibit the phase shift effect can be obtained by wet etching. Further, the phase shift mask blank 20 that can pattern the light semi-transmissive film 22 into a cross-sectional shape with small CD variation can be obtained by wet etching.

Embodiment 2. FIG.
In Embodiment 2, a method of manufacturing a phase shift mask for manufacturing a display device will be described with reference to FIGS. FIG. 4 is a process diagram for explaining a method of manufacturing a phase shift mask in which a phase shift mask is manufactured using a phase shift mask blank in which a resist adhesion improving film is not formed. 5 and 6 are process diagrams for explaining a method of manufacturing a phase shift mask in which a phase shift mask is manufactured using a phase shift mask blank on which a resist adhesion improving film is formed.

In the method for manufacturing a phase shift mask for manufacturing a display device according to the second embodiment, first, etching of the phase shift mask blank 20 obtained by the method for manufacturing the phase shift mask blank for manufacturing the display device described in the first embodiment. Resist on mask film 23 or resist adhesion improving film 24 or on etching mask film 23 or resist adhesion improving film 24 of phase shift mask blank 20 for manufacturing a display device described in the first embodiment. A resist pattern forming step for forming the pattern 25 ′ is performed.
Specifically, in this resist pattern forming step, first, a resist film 25 is formed on the etching mask film 23 or the resist adhesion improving film 24 (FIGS. 4A, 5A, 6A). )). Thereafter, a predetermined pattern is drawn on the resist film 25. Thereafter, the resist film 25 is developed with a predetermined developer to form a resist pattern 25 ′ (FIGS. 4B, 5B, and 6B).
Examples of the pattern drawn on the resist film 25 include a line and space pattern and a hole pattern.

Next, when the resist adhesion improving film 24 is not formed, the etching mask film pattern forming step of forming the etching mask film pattern 23 ′ by wet etching the etching mask film 23 using the resist pattern 25 ′ as a mask. (FIG. 4C). When the resist adhesion improving film 24 is formed, the resist adhesion improving film 24 is wet-etched using the resist pattern 25 ′ as a mask to form a resist adhesion improving film pattern 24 ′. Using the resist pattern 25 ′ and the resist adhesion improving film pattern 24 ′ as a mask, the etching mask film pattern 23 is wet etched to form an etching mask film pattern 23 ′ (FIG. 5C). FIG. 6 (c)).
The etchant for wet-etching the etching mask film 23 is not particularly limited as long as it can selectively etch the etching mask film 23. For example, etching including at least one fluorine compound selected from hydrofluoric acid, silicohydrofluoric acid, and ammonium hydrogen fluoride, and at least one oxidizing agent selected from hydrogen peroxide, nitric acid, and sulfuric acid Liquid. Specifically, an etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water can be used.
The etchant for wet etching the resist adhesion improving film 24 is not particularly limited as long as it can selectively etch the resist adhesion improving film 24. Specifically, an etching solution containing ceric ammonium nitrate and perchloric acid can be used.
When a metal silicide material film is provided under the chromium material film, when the chromium material film is wet-etched, metal ions are dissolved from the metal silicide material film and electrons are supplied to the chromium material film. This causes a phenomenon that the wet etching of the chromium-based material film is delayed. However, in the etching mask film pattern forming step described above, the etching mask film 23 is made of a metal silicide material, and the light semi-transmissive film 22 provided below the etching mask film is made of a chromium material. Therefore, such a phenomenon does not occur. For this reason, the in-plane etching rate when the etching mask film 23 is wet-etched can be made uniform.

Next, the light semi-transmissive film 22 is wet-etched using the etching mask film pattern 23 ′ or the resist adhesion improving film pattern 24 ′ and the etching mask film pattern 23 ′ as a mask to form the light semi-transmissive film pattern 22 ′. A semipermeable membrane pattern forming step is performed.
Specifically, when the resist adhesion improving film 24 is not formed, the resist pattern 25 ′ is peeled off (FIG. 4D), and then the light semitransmissive film 22 is used with the etching mask film pattern 23 ′ as a mask. A semi-transmissive film pattern forming step of forming a light semi-transmissive film pattern 22 ′ by performing wet etching is performed (FIG. 4E).
When the resist adhesion improving film 24 is formed, the resist pattern 25 ′ is peeled off (FIG. 5D), and then the light semitransmissive film 22 is wet using the etching mask film pattern 23 ′ as a mask. A semi-transmissive film pattern forming step of forming a light semi-transmissive film pattern 22 ′ by etching is performed (FIG. 5E). In this case, the resist adhesion improving film 24 is removed when the light semitransmissive film 22 is wet-etched. Alternatively, the semi-transmissive film pattern is formed by wet-etching the light semi-transmissive film 22 using the resist pattern 25 ′, the resist adhesion improving film pattern 24 ′ and the etching mask film pattern 23 ′ as a mask to form the light semi-transmissive film pattern 22 ′. After performing the formation process (FIG. 6D), the resist pattern 25 ′ and the resist adhesion improving film pattern 24 ′ are peeled off (FIG. 6E).
The etchant for wet-etching the light semi-transmissive film 22 is not particularly limited as long as it can selectively etch the light semi-transmissive film 22. Specifically, an etching solution containing ceric ammonium nitrate and perchloric acid can be used.

The phase shift part that changes the phase of the light of the representative wavelength included in the exposure light by approximately 180 degrees is constituted by the light semi-transmissive film pattern 22 ′, and the light transmissive part is constituted by a portion where the transparent substrate 21 is exposed. When manufacturing the type (hereinafter sometimes referred to as the first type) phase shift mask 30, the etching mask film pattern 23 ′ is peeled off after the semi-transmissive film pattern forming step (FIG. 4F). 5 (f), FIG. 6 (f)). In this case, the light semi-transmissive film pattern 22 ′ has a property of changing the phase of the light having the representative wavelength included in the exposure light by approximately 180 degrees.
Further, an etching mask film pattern 23 ′ narrower than the light semi-transmissive film pattern 22 ′ is provided on the light semi-transmissive film pattern 22 ′, and a phase shift unit that changes the phase of the light of the representative wavelength included in the exposure light by approximately 180 degrees. The light-transmitting film pattern 22 'is not laminated with the light semi-transmissive film pattern 22', and the light-shielding portion is formed with the light semi-transmissive film pattern 22 'with the etching mask film pattern 23'. In the case of manufacturing a phase shift mask 30 of a type (hereinafter sometimes referred to as a second type) in which the light transmission part is configured from a part where the transparent substrate 21 is exposed, the transflective film pattern After the formation process, the etching mask film pattern 23 ′ is patterned into a predetermined pattern narrower than the light semi-transmissive film pattern 22 ′ (FIGS. 4G, 5G, and 6G). In this case, the light semi-transmissive film pattern 22 ′ has a property of changing the phase of the light of the representative wavelength included in the exposure light by approximately 180 degrees, and the etching mask film pattern 23 ′ has a light shielding property.
Further, the phase shift portion that changes the phase of the light of the representative wavelength included in the exposure light by approximately 180 degrees is configured by a portion where the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′ are stacked, and transmits light. In the case of manufacturing a phase shift mask 30 of a type in which the portion is composed of a portion where the transparent substrate 21 is exposed (hereinafter sometimes referred to as a third type), the etching mask film pattern 23 ′ is left. (FIG. 4 (e), FIG. 5 (e), FIG. 6 (e)). In this case, the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′ are composed of two layers of the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′. Has a property of changing approximately 180 degrees.

  The phase shift mask 30 for manufacturing a display device is manufactured through such a resist pattern forming process, an etching mask film pattern forming process, and a semi-transmissive film pattern forming process.

In the case of the first type, the phase shift mask 30 for manufacturing a display device according to the second embodiment manufactured in this way is a transparent substrate 21 and a chromium-based material formed on the main surface of the transparent substrate 21. (Refer to FIG. 4 (f), FIG. 5 (f), and FIG. 6 (f)). The light semi-transmissive film pattern 22 ′ constitutes the phase shift portion, and the portion where the transparent substrate 21 is exposed constitutes the light transmissive portion.
In the case of the second type phase shift mask 30, the transparent substrate 21, the light semi-transmissive film pattern 22 ′ formed on the main surface of the transparent substrate 21 and made of a chromium-based material, and the light semi-transmissive film pattern And an etching mask film pattern 23 ′ made of a metal silicide material formed on 22 ′ (see FIGS. 4 (g), 5 (g), and 6 (g)). The portion of the light semi-transmissive film pattern 22 ′ where the etching mask film pattern 23 ′ is not stacked constitutes a phase shift portion, and the portion where the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′ are stacked is formed. The part which comprises a light shielding part and the transparent substrate 21 is exposed comprises a light transmission part. When the etching mask film pattern 23 ′ formed on the light semi-transmissive film pattern 22 ′ is provided, the mask pattern can be easily recognized by the exposure machine. Further, it is possible to prevent the resist film 25 from being reduced by the exposure light transmitted through the light semi-transmissive film pattern 22 ′.
In the case of the third type phase shift mask 30, a transparent substrate 21, a light semi-transmissive film pattern 22 ′ made of a chromium-based material formed on the main surface of the transparent substrate 21, and a light semi-transmissive film pattern And an etching mask film pattern 23 ′ made of a metal silicide material formed on 22 ′ (see FIGS. 4E, 5E, and 6E). A portion where the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′ are stacked constitutes a phase shift portion, and a portion where the transparent substrate 21 is exposed constitutes a light transmissive portion. When the phase shift portion is composed of the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′, the i-line and h-line can be obtained by adjusting the types of chromium-based materials and metal silicide-based materials and their compositions. Further, variation (variation) in the phase difference due to the g line can be reduced.
Examples of the light semi-transmissive film pattern 22 ′ include a line and space pattern and a hole pattern.

In the case of the first and second type phase shift masks 30, the light semi-transmissive film pattern 22 ′ has a property of changing the phase of the light of the representative wavelength included in the exposure light by approximately 180 degrees. Due to this property, a phase difference of about 180 degrees is generated between the exposure light transmitted through the light semi-transmissive film pattern 22 ′ constituting the phase shift portion and the exposure light transmitted through the transparent substrate 21 constituting the light transmission portion. The film thickness of the light semi-transmissive film pattern 22 ′ in the first and second types of phase shift mask 30 and the film thickness of the light semi-transmissive film in the phase shift mask blank 20 for producing the phase shift mask 30. Is appropriately adjusted in the range of 80 nm or more and 180 nm or less so as to obtain desired optical characteristics (transmittance, phase difference).
In the case of the third type phase shift mask 30, the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′ are composed of two layers of the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′. Has the property of changing the phase of the light of the representative wavelength included in the phase by approximately 180 degrees. Due to this property, the exposure light transmitted through the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′ constituting the phase shift portion and the exposure light transmitted through the transparent substrate 21 constituting the light transmission portion are substantially omitted. A phase difference of 180 degrees occurs. The film thickness of the light semi-transmissive film pattern 22 ′ in the third type phase shift mask 30 and the film thickness of the light semi-transmissive film in the phase shift mask blank 20 for producing the phase shift mask 30 are desired. The optical characteristics (transmittance, phase difference) are appropriately adjusted within a range of 75 nm to 200 nm.
When the exposure light is a composite light including light having a wavelength range of 300 nm to 500 nm, the light semi-transmissive film pattern 22 ′ or the two layers of the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′ are A phase difference of about 180 degrees is generated with respect to light having a representative wavelength included in the wavelength range. For example, when the exposure light is composite light including i-line, h-line, and g-line, the light semi-transmissive film pattern 22 ′ or the two layers of the light semi-transmissive film pattern 22 ′ and the etching mask film pattern 23 ′ are , I-line, h-line, and g-line, a phase difference of about 180 degrees is generated.

The light semi-transmissive film pattern 22 ′ is selected from chromium (Cr), oxygen (O), nitrogen (N), and carbon (C) in order to change the phase of the light of the representative wavelength included in the exposure light by approximately 180 degrees. It is comprised from the chromium-type material which consists of a chromium compound containing at least 1 type. Examples of the chromium compound include chromium oxide, chromium nitride, chromium oxynitride, chromium carbide, chromium nitride carbide, chromium oxycarbide, or chromium oxynitride carbide. The composition of the chromium compound constituting the light semi-transmissive film pattern 22 ′ includes a desired phase difference (180 ° ± 20 °) with respect to exposure light, transmittance (1% to 20%), wet etching characteristics (light semi-transmissive film) Adjustment is made from the viewpoint of the cross-sectional shape of the pattern 22 'and CD variation) and chemical resistance. In order to have the above-mentioned desired phase difference and transmittance, it is preferable to make the chromium compound less than 50 atomic% of chromium.
In order to pattern the light semi-transmissive film 22 by wet etching to obtain a light semi-transmissive film pattern 22 ′ having a cross-sectional shape that can sufficiently exhibit the phase shift effect, the above chromium compound is used for wet etching of the light semi-transmissive film 22. It is desirable to include a component that slows down the speed. Examples of a component that slows the wet etching rate of the light semitransmissive film 22 include fluorine (F) in addition to the carbon (C) mentioned above. Examples of a desirable chromium-based material film constituting the light semi-transmissive film pattern 22 'include, for example, a chromium carbide film, a chromium nitride carbonized film, a chromium oxycarbide film, a chromium oxynitride carbon film, and a chromium fluoride film.

  The composition of the light semitransmissive film pattern 22 'is preferably substantially uniform. However, the composition gradient region described above is formed on the upper surface of the light semi-transmissive film pattern 22 ′, and a region where the composition is inclined is also formed at the interface between the light semi-transmissive film pattern 22 ′ and the transparent substrate 21. The composition of these parts is not uniform.

  The etching mask film pattern 23 'is made of a metal silicide material containing metal and silicon. Examples of the metal include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), and zirconium (Zr). As the metal silicide material film constituting the etching mask film pattern 23 ′, for example, a metal silicide film, a metal silicide nitride film, a metal silicide oxide film, a metal silicide carbide film, a metal silicide oxynitride film, a metal silicide carbonitride film, a metal Examples thereof include a silicide oxycarbide film and a metal silicide oxycarbonitride film. Specifically, molybdenum silicide (MoSi) film, molybdenum silicide (MoSi) nitride film, oxide film, carbonized film, oxynitride film, carbonitride film, oxycarbide film, oxycarbonitride film, tantalum silicide (TaSi) Film, tantalum silicide (TaSi) nitride film, oxide film, carbonized film, oxynitride film, carbonitride film, oxycarbide film, oxycarbonitride film, tungsten silicide (WSi) film, tungsten silicide (WSi) nitride film , Oxide film, carbonized film, oxynitride film, carbonitride film, oxycarbide film, oxycarbonitride film, titanium silicide (TiSi) film, titanium silicide (TiSi) nitride film, oxide film, carbonized film, oxynitride film , Carbonitride film, oxycarbide film, oxycarbonitride film, zirconium silicide (ZrSi) film, zirconium Nitride film Risaido (ZrSi), oxide film, carbon film, oxynitride, carbonitride films include oxycarbide film, and oxycarbide nitride film.

  According to the method of manufacturing a phase shift mask for manufacturing a display device of the second embodiment, the phase shift mask blank obtained by the method of manufacturing the phase shift mask blank for manufacturing a display device described in the first embodiment, or A phase shift mask is manufactured using the phase shift mask blank for manufacturing a display device described in the first embodiment. Therefore, it is possible to manufacture the phase shift mask 30 having the light semi-transmissive film pattern 22 ′ having a nearly vertical cross-sectional shape that can sufficiently exhibit the phase shift effect. Further, the phase shift mask 30 having the light semi-transmissive film pattern 22 ′ with small CD variation can be manufactured. This phase shift mask 30 can cope with the miniaturization of line and space patterns and contact holes.

Embodiment 3 FIG.
In Embodiment 3, a method for manufacturing a display device will be described.

In the method for 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 on which a resist film is formed. A phase shift mask arrangement step is performed in which the obtained phase shift mask 30 is arranged to face the resist film.
Next, a resist film exposure process is performed in which the phase shift mask 30 is irradiated with exposure light to expose the resist film.

  The exposure light is, for example, composite light including light in a wavelength range of 300 nm to 500 nm. Specifically, it is composite light including i-line, h-line, and g-line.

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

Hereinafter, based on an Example, this invention is demonstrated more concretely.

Example 1.
A. Phase shift mask blank and manufacturing method thereof In order to manufacture the phase shift mask blank of Example 1, first, a 3045 size (330 mm × 450 mm × 5 mm) synthetic quartz glass substrate was prepared as the transparent substrate 21 .

  Thereafter, the synthetic quartz glass substrate was mounted on a tray (not shown) with the main surface facing downward, and was carried into the carry-in chamber LL of the inline-type sputtering apparatus 11 shown in FIG. In the first sputter chamber SP1, a sputter target made of chromium is disposed as the first sputter target 13 on the carry-in chamber LL side. In the first sputtering chamber SP1, a sputtering target made of molybdenum silicide (Mo: Si = 1: 4) is disposed as the second sputtering target 14 on the buffer chamber BU side. In the second sputter chamber SP2, a sputter target made of chromium is disposed as the third sputter target 15 on the buffer chamber BU side.

In order to form a light semi-transmissive film on the main surface of the synthetic quartz glass substrate, first, argon (Ar) gas and nitrogen are introduced from the first gas inlet GA1 disposed near the first sputter target 13 of the first sputter chamber SP1. A mixed gas (Ar: 50 sccm, N ₂ : 50 sccm, CO ₂ : 25 sccm) of (N ₂ ) gas and carbon dioxide (CO ₂ ) gas is introduced, and a sputtering power of 9.0 kW is applied to the first sputter target 13. did. Further, a mixed gas of argon (Ar) gas, nitrogen (N ₂ ) gas, and carbon dioxide (CO ₂ ) gas from a third gas introduction port GA3 disposed near the third sputter target 15 of the second sputter chamber SP2 ( Ar: 50 sccm, N ₂ : 50 sccm, CO ₂ : 25 sccm). Application of sputtering power to the first sputtering target 13 and introduction of a mixed gas of Ar gas, N ₂ gas, and CO ₂ gas from the first gas introduction port GA1 and the third gas introduction port GA3 are performed by a synthetic quartz glass substrate. This was continued until it was transferred to the unloading chamber ULL.

Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) is arranged in the direction of the arrow S in the order of the carry-in chamber LL, the first sputter chamber SP1, the buffer chamber BU, the second sputter chamber SP2, and the carry-out chamber ULL. It was conveyed to. When the synthetic quartz glass substrate passes through the vicinity of the first sputter target 13 of the first sputtering chamber SP1, a chromium oxynitride carbide film (CrCON) having a film thickness of 60 nm is formed on the main surface of the synthetic quartz glass substrate by reactive sputtering. The first layer of light semi-transmissive film was formed. In addition, the conveyance speed of the synthetic quartz glass substrate was performed with the predetermined | prescribed conveyance speed so that it might become the above-mentioned film thickness. While the synthetic quartz glass substrate passed through the second sputtering chamber SP2, the first light semi-transmissive film was exposed to a mixed gas atmosphere of Ar gas, N ₂ gas, and CO ₂ gas.

Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) is moved in the direction opposite to the arrow S in the carry-out chamber ULL, the second sputter chamber SP2, the buffer chamber BU, the first sputter chamber SP1, and the carry-in chamber LL. Were transferred in this order and returned to the loading chamber LL. While returning the synthetic quartz glass substrate to the loading chamber LL, a mixed gas of Ar gas, N ₂ gas and CO ₂ gas (Ar: 50 sccm, N ₂ : 50 sccm, CO ₂ : 25 sccm) is introduced from the third gas introduction port GA3. Then, the first light-semitransmissive film was exposed to a mixed gas atmosphere of Ar gas, N ₂ gas, and CO ₂ gas.

Thereafter, application of sputtering power to the first sputtering target 13 and introduction of a mixed gas of Ar gas, N ₂ gas, and CO ₂ gas from the first gas introduction port GA1 and the third gas introduction port GA3 were performed. A second light semi-transmissive film made of a chromium oxynitride carbide film (CrCON) having a film thickness of 60 nm is formed on the first light semi-transmissive film by the same method, and two layers are formed after the film formation. The light semi-transmissive film of the eye was exposed to a mixed gas atmosphere of Ar gas, N ₂ gas, and CO ₂ gas.

  In this manner, a light semi-transmissive film having a total film thickness of 120 nm made of two layers of chromium oxynitride and carbonized films (CrCON) was formed on the main surface of the synthetic quartz glass substrate.

Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) was transported in the direction opposite to the arrow S and returned to the carry-in chamber LL. While returning the synthetic quartz glass substrate to the carry-in chamber LL, the second-layer light semitransmissive film was exposed to a mixed gas atmosphere of Ar gas, N ₂ gas, and CO ₂ gas by the same method as described above.

  Thereafter, in order to form an etching mask film on the light semi-transmissive film, argon (Ar) gas and nitrogen monoxide (NO) are supplied from the second gas introduction port GA2 disposed near the second sputter target 14 of the first sputter chamber SP1. ) A mixed gas with gas (Ar: 60 sccm, NO: 45 sccm) was introduced, and a sputtering power of 8.0 kW was applied to the second sputtering target. In addition, argon (Ar) gas (115 sccm) was introduced from the third gas inlet GA3 disposed near the third sputter target 15 in the second sputter chamber SP2. Application of sputtering power to the second sputtering target 14, introduction of a mixed gas of Ar gas and NO gas from the second gas introduction port GA2, and introduction of Ar gas from the third gas introduction port GA3 are performed using synthetic quartz glass. This was continued until the substrate was transferred to the carry-out chamber ULL.

  Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed in the direction of arrow S to the carry-out chamber ULL. When the synthetic quartz glass substrate passes near the second sputter target 14 in the first sputter chamber SP2, it is made of a molybdenum silicide oxynitride film (MoSiON) having a thickness of 100 nm on the light semi-transmissive film by reactive sputtering. An etching mask film was formed. In addition, the conveyance speed of the synthetic quartz glass substrate was performed with the predetermined | prescribed conveyance speed so that it might become the above-mentioned film thickness.

  In this manner, an etching mask film having a thickness of 100 nm made of one layer of molybdenum silicide oxynitride film (MoSiON) was formed on the light semi-transmissive film.

Thereafter, the second sputtering chamber and the carry-out chamber are completely partitioned by the partition plate, and then the carry-out chamber is returned to the atmospheric pressure state, and the synthetic quartz glass substrate on which the light semi-transmissive film and the etching mask film are formed is sputtered. 11 was taken out.
In this way, a phase shift mask blank in which a light semi-transmissive film and an etching mask film were formed on a synthetic quartz glass substrate was obtained.

  The transmittance and the phase difference of the obtained light-transmissive film of the phase shift mask blank were measured by MPM-100 manufactured by Lasertec Japan. For the measurement of the transmittance and phase difference of the light semi-transmissive film, two layers of chromium oxynitride carbonized film (CrCON) (total film thickness) are formed on the main surface of the synthetic quartz glass substrate, which is set in the same tray. A substrate with a light translucent film (dummy substrate) on which 120 nm was formed was used. The transmittance and phase difference of the light semi-transmissive film were measured by taking out the substrate with the light semi-transmissive film (dummy substrate) from the carry-out chamber ULL before forming the etching mask film. As a result, the transmittance was 5.0% (wavelength: 365 nm), and the phase difference was 180 degrees (wavelength: 365 nm). Further, the fluctuation range of the phase difference at wavelengths of 365 nm to 436 nm was 25 degrees.

  Moreover, about the etching mask film | membrane of the obtained phase shift mask blank, the reflectance and the optical density were measured with the spectrophotometer SolidSpec-3700 by Shimadzu Corporation. The surface reflectance of the etching mask film was 12.0% (wavelength: 436 nm), and the optical density OD was 4.0. This etching mask film was found to function as a light shielding film having a low reflectance on the film surface.

  The obtained phase shift mask blank was subjected to composition analysis in the depth direction by X-ray photoelectron spectroscopy (XPS). As a result, in the composition gradient region, which is a region from the appearance of the chromium (Cr) peak due to the light semi-transmissive film to the disappearance of the silicon (Si) peak and molybdenum (Mo) peak due to the etching mask film, The content of carbon (C), which slows the wet etching rate of the light semitransmissive film, increased stepwise and / or continuously in the depth direction.

  In the uniform composition region from the disappearance of the silicon (Si) peak and molybdenum (Mo) peak due to the etching mask film to the appearance of the oxygen (O) peak due to the synthetic quartz glass substrate, the inclusion of chromium (Cr) The average amount was 47 atomic%, the carbon (C) content was 7 atomic% on average, the oxygen (O) content was average 32 atomic%, and the nitrogen (N) content was average 14 atomic%.

In the above-described method of manufacturing a phase shift mask blank, the light semitransmissive film and the etching mask film are continuously formed without breaking the vacuum. In order to reliably obtain the effects of the present invention, it is preferable that the light semitransmissive film and the etching mask film are continuously formed without breaking the vacuum. By continuously forming the light semi-transmissive film and the etching mask film without breaking the vacuum, the variation in composition from the outermost surface of the light semi-transmissive film to the synthetic quartz glass substrate can be reduced.
Even if the light semi-transmissive film is stored in the air after being formed, or the light semi-transmissive film is washed before forming the etching mask film, the same effect as in Example 1 can be obtained as long as the composition changes within a certain range. Can be obtained.

B. Phase shift mask and method for manufacturing the same In order to manufacture a phase shift mask using the phase shift mask blank manufactured as described above, first, a photo resist is applied to the etching mask film of the phase shift mask blank using a resist coating apparatus. A resist film was applied.
Thereafter, a 1000 nm-thick photoresist film was formed through a heating / cooling process (see FIG. 4A).
Thereafter, a photoresist film is drawn using a laser drawing apparatus, and after development and rinsing steps, a line and space pattern having a line pattern width of 2.0 μm and a space pattern width of 2.0 μm is formed on the etching mask film. A resist pattern was formed (see FIG. 4B).

  Thereafter, using the resist pattern as a mask, the etching mask film was wet-etched with a molybdenum silicide etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water to form an etching mask film pattern (FIG. 4 (c)).

Thereafter, the resist pattern was peeled off (see FIG. 4D).
Thereafter, using the etching mask film pattern as a mask, the light semi-transmissive film was wet etched with a chromium etching solution containing ceric ammonium nitrate and perchloric acid to form a light semi-transmissive film pattern (FIG. 4 (e)). )).
Thereafter, the etching mask film pattern was removed with a molybdenum silicide etchant obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water (see FIG. 4F).
In this way, a phase shift mask in which a light semitransmissive film pattern was formed on a synthetic quartz glass substrate was obtained.

The cross section of the obtained phase shift mask was observed with a scanning electron microscope JSM7401F manufactured by JEOL Ltd. In the following examples and comparative examples, the same apparatus was used to observe the cross section of the phase shift mask.
The cross section of the light translucent film pattern had a tail at the portion in contact with the synthetic quartz glass substrate, and the angle was 42 degrees. Further, the portion in contact with the etching mask film pattern had a substantially vertical shape, and the angle was 93 degrees.

The CD variation of the light translucent film pattern of the phase shift mask was measured by SIR8000 manufactured by Seiko Instruments Nano Technology. The CD variation was measured at 5 × 5 points in a 270 mm × 390 mm area excluding the peripheral area of the substrate. The CD variation is a deviation width from a target line and space pattern (line pattern width: 2.0 μm, space pattern width: 2.0 μm). In the following examples and comparative examples, the same apparatus was used to measure CD variation.
The CD variation was as good as 0.096 μm.

Example 2
In Example 2, a phase shift mask in which an etching mask film pattern narrower than the light semi-transmissive film pattern is provided on the light semi-transmissive film pattern and a phase shift mask blank used for producing the phase shift mask will be described. In this case, the etching mask film pattern narrower than the width of the light semi-transmissive film pattern on the light semi-transmissive film pattern functions as a light shielding film pattern.

A. Phase shift mask blank and manufacturing method thereof A phase shift mask blank was manufactured in the same manner as in Example 1.

B. Phase Shift Mask and Manufacturing Method Thereof An etching mask film pattern and a light semi-transmissive film pattern were formed by the same method as in Example 1 (see FIG. 4E).
Thereafter, a photoresist film was applied using a resist coating apparatus so as to cover the etching mask film pattern.
Thereafter, a photoresist film having a film thickness of 1000 nm was formed through a heating / cooling process.
Thereafter, a photoresist film was drawn using a laser drawing apparatus, and a resist pattern having a line pattern width of 1.0 μm was formed on the etching mask film pattern through a development and rinsing process.

Then, using the resist pattern as a mask, the etching mask film is wet-etched with a molybdenum silicide etchant obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water, so that the width of the translucent film pattern is larger A narrow etching mask film pattern was formed (see FIG. 4G).
Thereafter, the resist pattern was peeled off.

  In this way, a phase shift mask was obtained in which a light semi-transmissive film pattern and an etching mask film pattern narrower than the width of the light semi-transmissive film pattern were formed on a synthetic quartz glass substrate.

The cross section of the obtained phase shift mask was observed.
The cross section of the light translucent film pattern had a tail at the portion in contact with the synthetic quartz glass substrate, and the angle was 42 degrees. Further, the portion in contact with the etching mask film pattern had a substantially vertical shape, and the angle was 93 degrees.
Further, the CD variation of the light translucent film pattern was as good as 0.096 μm.

Example 3
In Example 3, a phase shift mask in which a phase shift portion is composed of a light semitransmissive film pattern and an etching mask film pattern, and a phase shift mask blank used for producing the phase shift mask will be described. In this case, the etching mask film pattern on the light semi-transmissive film pattern functions as a light semi-transmissive film pattern, and the two layers of the light semi-transmissive film pattern and the etching mask film pattern allow the light of the representative wavelength included in the exposure light to be reflected. The phase is changed by approximately 180 degrees.

A. Chromium oxynitride film (CrON) having a film thickness of 60 nm on the main surface of a 3345 size synthetic quartz glass substrate, using the same in-line type sputtering apparatus 11 as in Example 1 and the phase shift mask blank and its manufacturing method And an etching mask film made of molybdenum silicide oxynitride film (MoSiON).

First, in order to form a chromium oxynitride film (CrON) on the main surface of the synthetic quartz glass substrate, argon (Ar) is introduced from the first gas inlet GA1 disposed in the vicinity of the first sputter target 13 of the first sputter chamber SP1. A mixed gas of gas and nitrogen monoxide gas (NO) gas (Ar: 50 sccm, NO: 90 sccm) was introduced, and a sputtering power of 9.0 kW was applied to the first sputter target 13. Further, a mixed gas (Ar: 50 sccm, NO: 90 sccm) of argon (Ar) gas and nitrogen monoxide gas (NO) from a third gas inlet GA3 disposed near the third sputter target 15 of the second sputter chamber SP2. ) Was introduced. Application of sputtering power to the first sputter target 13 and introduction of a mixed gas of Ar gas and NO gas from the first gas introduction port GA1 and the third gas introduction port 3 are carried by the synthetic quartz glass substrate to the carry-out chamber ULL. Continued until allowed.
Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) is arranged in the direction of the arrow S in the order of the carry-in chamber LL, the first sputter chamber SP1, the buffer chamber BU, the second sputter chamber SP2, and the carry-out chamber ULL. It was conveyed to. In addition, the conveyance speed of the synthetic quartz glass substrate was performed with the predetermined | prescribed conveyance speed so that it might become the above-mentioned film thickness.

Thereafter, in order to form a molybdenum silicide oxynitride film (MoSiON) on the chromium oxynitride film (CrON), the synthetic quartz glass substrate mounted on the tray (not shown) is returned to the carry-in chamber LL, and then the first A mixed gas (Ar: 60 sccm, NO: 45 sccm) of argon (Ar) gas and nitrogen monoxide (NO) gas is introduced from the second gas introduction port GA2 disposed near the second sputter target 14 in the sputter chamber SP1. A sputtering power of 8.0 kW was applied to the second sputtering target. In addition, argon (Ar) gas (115 sccm) was introduced from the third gas inlet GA3 disposed near the third sputter target 15 in the second sputter chamber SP2. Application of sputtering power to the second sputtering target 14, introduction of a mixed gas of Ar gas and NO gas from the second gas introduction port GA2, and introduction of Ar gas from the third gas introduction port GA3 are performed using synthetic quartz glass. This was continued until the substrate was transferred to the carry-out chamber ULL.
Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed in the direction of arrow S to the carry-out chamber ULL. In addition, the conveyance speed of the synthetic quartz glass substrate was performed with the predetermined | prescribed conveyance speed so that it might become the above-mentioned film thickness.
Thereafter, the second sputter chamber and the carry-out chamber are completely partitioned by a partition plate, and then the carry-out chamber is returned to an atmospheric pressure state so that a light semi-transmissive film made of a chromium oxynitride film (CrON) and a molybdenum silicide oxynitride film ( The synthetic quartz glass substrate on which the etching mask film made of MoSiON) was formed was taken out from the sputtering apparatus 11.

In this way, a phase shift mask blank in which a light semi-transmissive film and an etching mask film were formed on a synthetic quartz glass substrate was obtained.
In the same manner as in Example 1, the transmittance and phase difference of the obtained phase shift mask blank were measured with MPM-100 manufactured by Japan Lasertec. As a result, the transmittance was 5.0% (wavelength: 365 nm), and the phase difference was 180 degrees (wavelength: 365 nm). Further, the fluctuation range of the phase difference at wavelengths of 365 nm to 436 nm was 20 degrees.

B. Phase shift mask and manufacturing method thereof Using the phase shift mask blank manufactured as described above, the process up to the step of wet-etching the light translucent film by the same method as in Example 1 (see FIG. 4E) And a phase shift mask was manufactured.

The cross section of the obtained phase shift mask was observed.
As in the first embodiment, the cross-section of the light translucent film pattern has a shape where the bottom is in contact with the synthetic quartz glass substrate, the angle is 35 degrees, and the part in contact with the etching mask film pattern is almost vertical. And the angle was 95 degrees.
The CD variation was as good as 0.098 μm.

Example 4
In Example 4, a case where an etching mask film and a resist adhesion improving film are formed on the light semi-transmissive film will be described.

A. Phase Shift Mask Blank and Method for Producing the Same By the same method as in Example 1, light semi-transmission with a total film thickness of 120 nm made of two layers of chromium oxynitride carbide film (CrCON) on the main surface of a 3345 size synthetic quartz glass substrate A film was formed.

Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) was transported in the direction opposite to the arrow S and returned to the carry-in chamber LL. While returning the synthetic quartz glass substrate to the carry-in chamber LL, the second light semi-transmissive film was exposed to a mixed gas atmosphere of Ar gas, N ₂ gas, and CO ₂ gas by the same method as in Example 1.
Thereafter, a mixed gas (Ar: 60 sccm, NO: 45 sccm) of argon (Ar) gas and nitrogen monoxide (NO) gas from the second gas introduction port GA2 disposed near the second sputter target 14 of the first sputter chamber SP1. ) And a sputtering power of 8.0 kW was applied to the second sputtering target. Further, a mixed gas (Ar: 50 sccm, N ₂ : 20 sccm) of argon (Ar) gas and nitrogen (N ₂ ) gas from a third gas introduction port GA3 disposed near the third sputter target 15 of the second sputter chamber SP2. ) And a sputtering power of 3.0 kW was applied to the third sputtering target. Application of sputtering power to the second sputtering target 14, introduction of a mixed gas of Ar gas and NO gas from the second gas introduction port GA2, application of sputtering power to the third sputtering target 15, and third gas introduction port The introduction of the mixed gas of Ar gas and N ₂ gas from GA 3 was continued until the synthetic quartz glass substrate was transported to the carry-out chamber ULL.

  Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed in the direction of arrow S to the carry-out chamber ULL. When the synthetic quartz glass substrate passes near the second sputter target 14 in the first sputter chamber SP1, it is made of a molybdenum silicide oxynitride film (MoSiON) having a film thickness of 60 nm on the light semi-transmissive film by reactive sputtering. An etching mask film was formed. Further, when the synthetic quartz glass substrate passes through the vicinity of the third sputter target 15 in the second sputter chamber SP2, the chromium nitride film (CrN, nitrogen (N ) Content of 15 atomic%) was formed. In addition, the conveyance speed of the synthetic quartz glass substrate was performed with the predetermined conveyance speed so that it might become the above-mentioned film thickness.

  In this manner, an etching mask film having a film thickness of 60 nm made of one layer of molybdenum silicide oxynitride film (MoSiON) is formed on the light translucent film, and one layer of chromium nitride film (CrN) is formed on the etching mask film. A resist adhesion improving film having a thickness of 20 nm is formed.

Thereafter, the second sputtering chamber and the carry-out chamber are completely partitioned by a partition plate, and then the carry-out chamber is returned to atmospheric pressure to form a light semi-transmissive film, an etching mask film, and a resist adhesion improving film. The quartz glass substrate was taken out from the sputtering apparatus 11.
In this way, a phase shift mask blank in which a light semi-transmissive film, an etching mask film, and a resist adhesion improving film were formed on a synthetic quartz glass substrate was obtained.

B. Phase shift mask and method for manufacturing the same In order to manufacture a phase shift mask using the phase shift mask blank manufactured as described above, first, a resist coating apparatus is used on the resist adhesion improving film of the phase shift mask blank. A photoresist film was applied.
Thereafter, a 1000 nm-thick photoresist film was formed through a heating / cooling process (see FIG. 6A).
Then, a photoresist film is drawn using a laser drawing apparatus, and after development and rinsing steps, a line and space having a line pattern width of 2.0 μm and a space pattern width of 2.0 μm on the resist adhesion improving film. A resist pattern of a pattern was formed (see FIG. 6B).

Thereafter, using the resist pattern as a mask, the resist adhesion improving film was wet etched with a chromium etching solution containing ceric ammonium nitrate and perchloric acid to form a resist adhesion improving film pattern.
Then, using the resist pattern and the resist adhesion improving film pattern as a mask, the etching mask film is wet-etched with a molybdenum silicide etchant obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water. A film pattern was formed (see FIG. 6C).

Thereafter, using the resist pattern, the resist adhesion improving film pattern, and the etching mask film pattern as a mask, the light translucent film is wet-etched with a chromium etching solution containing ceric ammonium nitrate and perchloric acid, and the light semi-transparent film is etched. A permeable membrane pattern was formed (see FIG. 6D).
Thereafter, the resist pattern was peeled off.
Thereafter, the resist adhesion improving film pattern is removed with a chromium etching solution containing ceric ammonium nitrate and perchloric acid (see FIG. 6 (e)), and a mixture of ammonium hydrogen fluoride and hydrogen peroxide is further removed. The etching mask film pattern was removed with a molybdenum silicide etching solution obtained by diluting the solution with pure water (see FIG. 6F).
In this way, a phase shift mask in which a light semitransmissive film pattern was formed on a synthetic quartz glass substrate was obtained.

The cross section of the obtained phase shift mask was observed.
As in the first embodiment, the cross-section of the light semi-transmissive film pattern has a skirt at the portion in contact with the synthetic quartz glass substrate, an angle of 30 degrees, and a shape that is substantially vertical at the portion in contact with the etching mask film pattern. And the angle was 98 degrees.
The CD variation was as good as 0.098 μm.

Comparative Example 1
In Comparative Example 1, a case where an etching mask film is not formed on the light semi-transmissive film will be described.

A. Phase Shift Mask Blank and Method for Producing the Same By the same method as in Example 1, light semi-transmission with a total film thickness of 120 nm made of two layers of chromium oxynitride carbide film (CrCON) on the main surface of a 3345 size synthetic quartz glass substrate A film was formed.

Thereafter, the second sputtering chamber and the carry-out chamber were completely partitioned by a partition plate, and then the carry-out chamber was returned to atmospheric pressure, and the synthetic quartz glass substrate on which the light semi-transmissive film was formed was taken out from the sputtering apparatus 11.
Thus, the phase shift mask blank in which the light semi-transmissive film was formed on the synthetic quartz glass substrate was obtained.

B. Phase shift mask and manufacturing method thereof In order to manufacture a phase shift mask using the phase shift mask blank manufactured as described above, first, a resist coating apparatus is used on the light semi-transmissive film of the phase shift mask blank. A photoresist film was applied.
Thereafter, a photoresist film having a film thickness of 1000 nm was formed through a heating / cooling process.
Thereafter, a photoresist film is drawn using a laser drawing apparatus, and after development and rinsing steps, a line and space pattern having a line pattern width of 2.0 μm and a space pattern width of 2.0 μm is formed on the light semi-transmissive film. The resist pattern was formed.

Thereafter, using the resist pattern as a mask, the light semitransmissive film was wet etched with a chromium etching solution containing ceric ammonium nitrate and perchloric acid to form a light semitransmissive film pattern.
Thereafter, the resist pattern was peeled off.
In this way, a phase shift mask in which a light semitransmissive film pattern was formed on a synthetic quartz glass substrate was obtained.

The cross section of the obtained phase shift mask was observed.
The cross section of the light translucent film pattern had a tail at the portion in contact with the synthetic quartz glass substrate, and the angle was 15 degrees. Further, the wet etching solution soaked in the portion in contact with the resist film pattern, and the angle was 160 degrees.
The CD variation was 0.251 μm.

Example 5 FIG.
A phase shift mask blank and a phase shift mask were manufactured in the same manner as in Example 1 except that the material of the etching mask film was a molybdenum silicide nitride film (MoSiN) and the film thickness was 25 nm. The etching mask film is formed by introducing a mixed gas (Ar: 50 sccm, N2: 90 sccm) of argon (Ar) gas and nitrogen (N2) gas from the second gas introduction port GA2 and applying it to the second sputtering target. The power to be used was 2.0 kW.
The composition of the obtained etching mask film was 15 atomic% for molybdenum (Mo), 40 atomic% for silicon (Si), and 45 atomic% for nitrogen (N).
The cross section of the obtained phase shift mask was observed.
The cross section of the light translucent film pattern had a tail at the portion in contact with the synthetic quartz glass substrate, and the angle was 50 degrees.
Further, the portion in contact with the etching mask film pattern had a substantially vertical shape, and the angle was 92 degrees.
Further, the CD variation of the light translucent film pattern was as good as 0.080 μm.
Compared with the phase shift mask obtained in Example 1, the CD variation of the light semi-transmissive film pattern was improved by 0.016 μm. This is because the etching mask film thickness is thinner than that of Example 1 and the etching mask film pattern has a good cross-sectional shape, and a light semi-transmissive film pattern is formed using the etching mask film pattern as a mask. It seems that it depends.

Example 6
In Example 5 above, the second sputter target 14 used when forming the etching mask film was changed to a sputter target made of molybdenum silicide (Mo: Si = 1: 2) in the same manner as in Example 5, A phase shift mask blank and a phase shift mask were manufactured.
The composition of the obtained etching mask film was 24 atomic% for molybdenum (Mo), 26 atomic% for silicon (Si), and 50 atomic% for nitrogen (N).
The cross section of the obtained phase shift mask was observed.
The cross section of the light translucent film pattern had a tail at the portion in contact with the synthetic quartz glass substrate, and the angle was 51 degrees.
Further, the portion in contact with the etching mask film pattern had a substantially vertical shape, and the angle was 92 degrees.
Further, the CD variation of the light semi-transmissive film pattern was as good as 0.076 μm.
Compared with the phase shift mask obtained in Example 5, the CD variation of the light semitransmissive film pattern was slightly better. This is because the etching mask film composition has a higher proportion of metal compared to Example 5, and the etching speed of the etching mask film is increased, so that the amount of side etching of the cross-sectional shape of the etching mask film pattern is reduced. This is probably because the light semi-transmissive film pattern was formed using the mask film pattern as a mask.

Example 7
In Example 1 described above, no gas was introduced from the third gas introduction port GA3 of the second sputtering chamber SP2 when the light semi-transmissive film was formed. Otherwise, a phase shift mask blank and a phase shift mask were produced in the same manner as in Example 1.
The cross section of the obtained phase shift mask was observed.
The cross section of the pattern of the light translucent film had a tail at the portion in contact with the synthetic quartz glass substrate, and the angle was 38 degrees.
Further, the portion in contact with the etching mask film pattern had a substantially vertical shape, and the angle was 97 degrees.
Further, the CD variation of the light translucent film pattern was as good as 0.105 μm.

In the above embodiment, after forming a chromium oxide nitride carbide film (CrCON), has been described an example in which exposure to a mixed gas atmosphere of Ar gas and N ₂ gas and CO ₂ gas, N ₂ gas and CO The same effect can be obtained even when exposed to a mixed gas with _two gases or a CO ₂ gas atmosphere.
Further, in the above-described embodiment, the example of the chromium oxynitride carbonized film (CrCON) is described as the material of the light semi-transmissive film, but it is not limited thereto. The material of the light semi-transmissive film may be a chromium carbide film (CrC), a chromium nitride carbonized film (CrCN), or a chromium oxide carbonized film (CrOC).
Further, in the above-described embodiment, a phase shift mask in which a light semi-transmissive film pattern is formed on a transparent substrate is used from a phase shift mask blank in which an etching mask film and a resist adhesion improving film are formed on the light semi-transmissive film. However, this is not a limitation. The resist adhesion improving film can have a function of shielding light from exposure light and a function of changing the phase of exposure light. The phase shift mask manufactured in that case may be a phase shift mask in which an etching mask film pattern narrower than the width of the light semi-transmissive film pattern or a resist adhesion improving film pattern is formed on the light semi-transmissive film pattern. I do not care.
In the above-described embodiment, an example of a phase shift mask for manufacturing a display device has been described. However, the present invention is not limited to this. The phase shift mask blank and phase shift mask of the present invention can also be applied to semiconductor device manufacturing, MEMS manufacturing, printed circuit boards, and the like.
Further, in the above-described embodiment, the example in which the size of the transparent substrate is 3345 size (330 mm × 450 mm) has been described, but is not limited thereto. In the case of a phase shift mask blank for manufacturing a display device, a large size transparent substrate is used, and the size of the transparent substrate is 10 inches or more on a side. The size of the transparent substrate used for the phase shift mask blank for manufacturing the display device is, for example, 330 mm × 450 mm or more and 2280 mm × 3130 mm or less.
In the case of phase shift mask blanks for semiconductor device manufacturing, MEMS manufacturing, and printed circuit boards, a small transparent substrate is used, and the size of the transparent substrate is 9 inches or less on a side. is there. The size of the transparent substrate used for the phase shift mask blank of the said use is 63.1 mm x 63.1 mm or more and 228.6 mm x 228.6 mm or less, for example. Normally, 6025 size (152 mm x 152 mm) and 5009 size (126.6 mm x 126.6 mm) are used for semiconductor manufacturing and MEMS manufacturing, and 7012 size (177.4 mm x 177.4 mm) for printed circuit boards. Alternatively, a 9012 size (228.6 mm × 228.6 mm) is used.

11 Sputtering device, LL carry-in chamber, SP1 first sputter chamber, BU buffer chamber, SP2 second sputter chamber, ULL carry-out chamber , 1 3 first sputter target, GA11 first gas inlet, GA12 second gas inlet, 14 Second Sputter Target, GA21 Third Gas Inlet, GA22 Fourth Gas Inlet, 15 Third Sputter Target, GA31 Fifth Gas Inlet, GA32 Sixth Gas Inlet, 20 Phase Shift Mask Blank, 21 Transparent Substrate, 22 Light semi-transmissive film, 22 ′ light semi-transmissive film pattern, 23 etching mask film, 23 ′ etching mask film pattern, 24 resist adhesion improving film, 24 ′ resist adhesion improving film pattern, 25 resist film, 25 ′ resist pattern, 30 phase shift Mask.

Claims (25)

A transparent substrate;
A light semi-transmissive film formed on the main surface of the transparent substrate and having a property of changing the phase of light having a representative wavelength included in exposure light by approximately 180 degrees and made of a chromium-based material;
An etching mask film made of a metal silicide material formed on the light semi-transmissive film ,
A composition gradient region is formed at the interface between the light semi-transmissive film and the etching mask film, and in the composition gradient region, the proportion of the component that slows the wet etching rate of the light semi-transmissive film is directed toward the depth direction. A phase shift mask blank characterized by increasing stepwise and / or continuously .   The phase shift mask blank according to claim 1, wherein the etching mask film has a light shielding property. In the phase shift mask blank for display device manufacture,
A transparent substrate;
A light semi-transmissive film formed on the main surface of the transparent substrate and having a property of changing the phase of light having a representative wavelength included in exposure light by a first angle and made of a chromium-based material;
An etching mask film formed on the light semi-transmissive film and having a property of changing the phase of light having a representative wavelength included in exposure light by a second angle and made of a metal silicide material;
The sum of the first angle and the second angle is approximately 180 degrees;
A composition gradient region is formed at the interface between the light semi-transmissive film and the etching mask film, and in the composition gradient region, the proportion of the component that slows the wet etching rate of the light semi-transmissive film is directed toward the depth direction. A phase shift mask blank characterized by increasing stepwise and / or continuously . The composition of the light semi-transmissive film is substantially uniform except for an interface between the light semi-transmissive film and the etching mask film and a portion excluding an interface between the light semi-transmissive film and the transparent substrate. A phase shift mask blank according to any one of claims 1 to 3 . The phase shift mask blank according to any one of claims 1 to 4 , wherein the light semi-transmissive film is composed of a plurality of layers. The chromium-based material, chromium carbide, carbide nitride, chromium oxide carbide chromium or chromium phase shift mask blank according to any one of claims 1 to 5 that wherein a oxynitride carbide.   The phase shift mask blank according to claim 1, wherein the component that slows down the wet etching rate is carbon.   The metal silicide-based material includes a metal and silicon, and a ratio of the metal to silicon is metal: silicon = 1: 1 or more and 1: 9 or less. The described phase shift mask blank.   The metal silicide material is metal silicide, metal silicide nitride, metal silicide oxide, metal silicide carbide, metal silicide oxynitride, metal silicide carbonitride, metal silicide oxycarbide, or metal silicide. The phase shift mask blank according to claim 1, wherein the phase shift mask blank is an oxycarbonitride.   The metal silicide-based material is a metal silicide nitride, a metal silicide oxynitride, a metal silicide carbonitride, or a metal silicide oxycarbonitride, and the nitrogen content is 25 atomic% or more 55 The phase shift mask blank according to claim 9, wherein the phase shift mask blank is at most atomic%.   The phase shift mask blank according to any one of claims 1 to 10, further comprising a resist adhesion improving film made of a chromium-based material formed on the etching mask film.   The phase shift mask blank according to claim 1, wherein the phase shift mask blank is a display device manufacturing phase shift mask blank. A preparation step of preparing a transparent substrate;
A semi-transparent film is formed on the main surface of the transparent substrate by sputtering to form a light semi-transmissive film having a property of changing the phase of light having a representative wavelength included in exposure light by approximately 180 degrees and made of a chromium-based material. Forming process;
On the light semi-transmitting film, by sputtering, and a etching mask film forming step of forming an etching mask film composed of a metal silicide-based material,
The semi-transmissive film forming step includes forming a light semi-transmissive film made of a chromium-based material by applying sputtering power in a sputtering gas atmosphere, and slowing a wet etching rate of the light semi-transmissive film. Exposing the light semi-transmissive film to a gas atmosphere containing a component, and the exposing process is performed continuously after the film forming process without exposing the light semi-transmissive film to the atmosphere. A method of manufacturing a phase shift mask blank. In the manufacturing method of the phase shift mask blank for display device manufacture,
A preparation step of preparing a transparent substrate;
A semi-transmissive film is formed on the main surface of the transparent substrate by sputtering to form a light semi-transmissive film having a property of changing the phase of the light of the representative wavelength included in the exposure light by the first angle and made of a chromium-based material. A film forming step;
An etching mask film for forming an etching mask film having a property of changing the phase of light of a representative wavelength included in exposure light by a second angle and made of a metal silicide material on the light semi-transmissive film by sputtering. A forming process, and
The sum of the first angle and the second angle is approximately 180 degrees;
The semi-transmissive film forming step includes forming a light semi-transmissive film made of a chromium-based material by applying sputtering power in a sputtering gas atmosphere, and slowing a wet etching rate of the light semi-transmissive film. Exposing the light semi-transmissive film to a gas atmosphere containing a component, and the exposing process is performed continuously after the film forming process without exposing the light semi-transmissive film to the atmosphere. A method of manufacturing a phase shift mask blank. The film forming step uses a sputtering target containing chromium or a chromium compound, an inert gas containing at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas, and carbon dioxide gas The method for producing a phase shift mask blank according to claim 13 or 14, wherein the method is performed in a sputtering gas atmosphere composed of a mixed gas with an active gas containing a hydrocarbon-based gas. The method of manufacturing a phase shift mask blank according to any one of claims 13 to 15, wherein the exposing step is performed in a gas atmosphere containing carbon. The etching mask film forming step uses a sputtering target containing a metal and silicon, an inert gas containing at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas, oxygen The sputtering is performed in a sputtering gas atmosphere composed of a mixed gas with an active gas containing at least one selected from the group consisting of gas, nitrogen gas, carbon dioxide gas, nitrogen oxide-based gas, and hydrocarbon-based gas. The manufacturing method of the phase shift mask blank as described in any one of thru | or 16 . The phase shift mask blank, method of manufacturing a phase shift mask blank according to any one of claims 13, 15 to 17, wherein the display device is manufactured for phase shift mask blank. A phase shift mask blank obtained by etching according to any one of claims 1 to 10 and 12 or a phase shift mask blank obtained by the method for producing a phase shift mask blank according to any one of claims 13 to 18. A resist pattern forming step of forming a resist pattern on the etching mask film of the shift mask blank;
Etching mask film pattern forming step of forming an etching mask film pattern by wet etching the etching mask film using the resist pattern as a mask;
And a semi-transmissive film pattern forming step of forming a light semi-transmissive film pattern by wet-etching the light semi-transmissive film using the etching mask film pattern as a mask. 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 resist adhesion improving film of the phase shift mask blank according to claim 11;
Etching mask film pattern forming step of forming a resist adhesion improving film pattern and an etching mask film pattern by wet etching the resist adhesion improving film and the etching mask film using the resist pattern as a mask;
A semi-transmissive film pattern forming step of forming a light semi-transmissive film pattern by wet etching the light semi-transmissive film using the resist adhesion improving film pattern and the etching mask film pattern or the etching mask film pattern as a mask; A method of manufacturing a phase shift mask, comprising: The etching mask film pattern forming step includes at least one fluorine compound selected from hydrofluoric acid, hydrofluoric acid, and ammonium hydrogen fluoride, and at least one selected from hydrogen peroxide, nitric acid, and sulfuric acid. One of the method of manufacturing a phase shift mask according to claim 19 or 20, wherein using an etchant containing an oxidizing agent and carrying out wet etching. The method of manufacturing a phase shift mask according to any one of claims 19 to 21 , wherein the phase shift mask is a phase shift mask for manufacturing a display device. In the manufacturing method of the display device,
23. A phase shift mask arrangement in which a phase shift mask obtained by the method of manufacturing a phase shift mask according to claim 22 is arranged opposite to the resist film with respect to a substrate with a resist film in which a resist film is formed on the substrate. Process,
And a resist film exposure step of exposing the resist film by irradiating the phase shift mask with the exposure light. 24. The method for manufacturing a display device according to claim 23 , wherein the exposure light includes light having a wavelength range of 300 nm to 500 nm. The exposure light, i-ray, a method of manufacturing a display device according to claim 23 or 24, wherein it is a composite light including the h-line and g-line.

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