KR20200037163A - Phase shift mask blank and manufacturing method therefor, phase shift mask and manufacturing method therefor, and display device manufacturing method - Google Patents

Abstract

The present invention relates to a phase shift mask blank which can be formed into a cross-sectional shape which effectively manifests a phase effect by wet etching. The phase shift mask blank comprises: a transparent substrate; a light semitransmissive film comprising a metal silicide-based material and formed on a main surface of the transparent substrate; and an etching mask film comprising a chromium-based material and formed on the light semitransmissive film, wherein a composition gradient region P is formed at the interface between the light semitransmissive film and the etching mask film. In the composition inclined region P, the proportion of components slowing the wet etching rate of the light semitransmissive film is gradually and/or continuously increasing toward the depth direction.

Description

Phase shift mask blank and manufacturing method thereof, phase shift mask and manufacturing method thereof, and manufacturing method of display device TECHNICAL FIELD

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

Currently, as a method employed in a liquid crystal display device, there are a VA (Vertical Alignment) method or an IPS (In Plane Switching) method. By these methods, realization of a high-precision, high-speed display performance and a wide viewing angle liquid crystal display device is achieved. In the liquid crystal display device to which these methods are applied, the response speed and viewing angle can be improved by forming the pixel electrode in a line and space pattern by a transparent conductive film. In recent years, it is required to refine the pitch width of the line and space pattern from the viewpoint of improving the response layer and viewing angle, and improving the light utilization efficiency of the liquid crystal display device, that is, reducing power consumption and improving contrast of the liquid crystal display device. have. For example, it is desired to narrow the pitch width of the line and space pattern from 6 μm to 5 μm and from 5 μm to 4 μm.

Further, when manufacturing a liquid crystal display device or an organic EL display device, elements such as transistors are formed by laminating a plurality of conductive films or insulating films, which are subjected to necessary patterning. In that case, a photolithography process is often used for patterning the individual films to be laminated. For example, some thin film transistors used in these display devices have a configuration in which a contact hole is formed in an insulating layer by a photolithography process, and a pattern of an upper layer and a pattern of a lower layer are connected. In recent years, in such a display device, there is an increasing demand to display bright, precise images with a sufficient operating speed and to reduce power consumption. In order to satisfy these demands, it is desired to make the components of the display device finer and more highly integrated. 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 capable of coping with the miniaturization of line and space patterns or contact holes is desired.

When realizing miniaturization of line and space patterns or contact holes, the conventional photomask produces a product with the minimum line width close to the resolution limit without sufficient process margin because the resolution limit of the exposure machine for display device manufacturing is 3 μm. must do it. For this reason, there is a problem that the defective rate of the display device increases.

For example, when considering using a photomask having a hole pattern for forming a contact hole and transferring it to an object to be transferred, a hole pattern having a diameter of more than 3 μm could be transferred to a conventional photomask. However, it has been very difficult to transfer hole patterns with a diameter of 3 µm or less, especially hole patterns with a diameter of 2.5 µm or less. In order to transfer a hole pattern having a diameter of 2.5 µm or less, it is also possible to switch to an exposure machine having a high NA, for example, but a large investment is required.

Therefore, a phase shift mask is attracting attention as a photomask for manufacturing display devices in order to improve resolution and cope with miniaturization of line and space patterns and contact holes.

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 a transparent substrate, and a light shielding layer are formed around, and it is possible to have a phase difference of 180 degrees with respect to any one of the wavelength regions of 300 nm or more and 500 nm or less. A halftone phase shift mask with a phase shift layer comprising a chromium oxynitride based material is described. This phase shift mask is patterned by patterning a light shielding layer on a transparent substrate, forming a phase shift layer on the transparent substrate to cover the light shielding layer, forming a photoresist layer on the phase shift layer, and exposing and developing the photoresist layer It is produced by forming a resist pattern and patterning the phase shift layer using the resist pattern as an etching mask.

Japanese Patent Publication No. 2011-13283

The present inventors have studied politely a phase shift mask provided with a chromium phase shift film. As a result, when the chromium-based phase shift film is patterned by wet etching using the resist pattern as a mask, wet etchant enters the interface between the resist film and the chromium-based phase shift film, and etching of the interface portion proceeds rapidly. Could know. The cross-sectional shape of the edge portion of the formed chromium-based phase shift film pattern generated an inclination and became a tapered shape where the lower end was drawn.

When the cross-sectional shape of the edge portion of the chromium-based phase shift film pattern is tapered, the phase shift effect is weakened as the film thickness of the edge portion of the chromium-based phase shift film pattern decreases. For this reason, the phase shift effect cannot be sufficiently exhibited. In addition, the intrusion of the wet etching solution into the interface between the resist film and the chromium phase shift film is due to 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 phase shift film pattern, and it is very difficult to control the line width (CD).

In addition, the present inventors have studied how to verticalize 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 making the film composition (for example, nitrogen content) of the phase shift film inclined and changing the etching rate in the film thickness direction, or adding additives (for example, Al, Ga) to the phase shift film Thus, a method of controlling the etching time has been developed. However, in these methods, it has been very difficult to realize uniformity of transmittance in the entire large-scale phase shift mask.

For this reason, the present invention has been made in view of the above-mentioned problems, and a phase shift mask blank capable of patterning a phase shift film into a cross-sectional shape capable of sufficiently exhibiting a phase shift effect by wet etching, a method of manufacturing the same, and a phase shift effect thereof A phase shift mask having a phase shift film pattern that can be sufficiently exhibited and a method for manufacturing the same, in particular, a phase shift mask blank for manufacturing a display device capable of patterning the phase shift film in a cross-sectional shape capable of sufficiently exhibiting a phase shift effect, and a manufacturing method and phase thereof An object of the present invention is to provide a phase shift mask for manufacturing a display device having a shift film pattern capable of sufficiently exhibiting a shift effect, a method for manufacturing the same, and a method for manufacturing a display device using the phase shift mask.

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

In addition, the present invention provides a phase shift mask blank having uniform optical properties and a method for manufacturing the same, a phase shift mask having uniform optical properties and a method for manufacturing the same, in particular, a phase shift mask blank for manufacturing a display device having uniform optical properties, and the same An object of the present invention is to provide a manufacturing method, a phase shift mask for manufacturing a display device having uniform optical characteristics, and a manufacturing method for the same, and a manufacturing method for a display device using the phase shift mask.

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

(Configuration 1)

In the phase shift mask blank,

Transparent substrate,

A light semitransmissive film formed on the main surface of the transparent substrate and having a property of changing the phase of exposure light, and further comprising a metal silicide-based material,

An etching mask film formed on the light semitransmissive film and comprising a chromium-based material

Equipped with,

A composition inclined region is formed at an interface between the light semitransmissive film and the etching mask film, and in the composition inclined region, a proportion of components that slow the wet etching rate of the light semitransmissive film is stepwise and / or continuous toward the depth direction. Phase shift mask blank characterized in that it is increasing.

(Configuration 2)

The phase shift according to Configuration 1, wherein the light semitransmissive film is substantially uniform in composition except for the interface between the light semitransmissive film and the etching mask film and the interface between the light semitransmissive film and the transparent substrate. Mask blank.

(Configuration 3)

The phase shift mask blank according to configuration 1 or 2, wherein the light semitransmissive film contains a plurality of layers.

(Configuration 4)

The metal silicide-based material is any one of nitrides of metal silicides, oxynitrides of metal silicides, oxides of metal silicides, carbon nitrides of metal silicides, and carbon oxynitrides of metal silicides. Phase shift mask blank.

(Configuration 5)

The phase shift mask blank according to configuration 1 or 2, wherein the component that slows the wet etching rate is nitrogen or carbon.

(Configuration 6)

When the component that slows the wet etching rate is nitrogen, the composition is measured under the condition of 0.5 minutes by X-ray photoelectron spectroscopy from the etching mask film side of the boundary with the etching mask film in the composition gradient region. When analysis is performed, the maximum value of the ratio (N / Si) of nitrogen (N) to silicon (Si) at a position where silicon (Si) of 1 atomic% or more is first detected is 3.0 to 30 The phase shift mask blank according to the configuration 5 described above.

(Configuration 7)

The phase shift mask blank according to configuration 1 or 2, wherein the etching mask film has light-shielding properties.

(Configuration 8)

The etching mask film comprises a light-shielding layer formed on the light semitransmissive film side and an anti-reflection layer formed on the light-shielding layer.

(Configuration 9)

The etching mask film, the phase shift mask blank according to the configuration 1 or 2, characterized in that it comprises an insulating layer formed to contact the light semitransmissive film.

(Configuration 10)

The insulating layer contains CrCO or CrCON containing less than 50 atomic% Cr, and has a thickness of 10 nm or more and 50 nm or less.

(Configuration 11)

The phase shift mask blank according to the configuration 1 or 2, wherein the phase shift mask blank is a phase shift mask blank for manufacturing a display device.

(Configuration 12)

In the manufacturing method of the phase shift mask blank,

Preparation process for preparing a transparent substrate,

A semi-transmissive film forming step of forming a light semi-transmissive film having a property of changing the phase of exposure light and sputtering on the main surface of the transparent substrate and including a metal silicide-based material,

On the light semitransmissive film, an etching mask film forming step of forming an etching mask film containing a chromium-based material by sputtering

Have

The semi-transmissive film forming process is performed by forming a light semitransmissive film containing a metal silicide-based material by applying sputter power in a sputter gas atmosphere, and a gas atmosphere containing a component that slows the wet etching rate of the light semitransmissive film. And a step of exposing the light semitransmissive film, wherein the exposing step is continuously performed after the film forming process without exposing the light semitransmissive film to the atmosphere.

(Configuration 13)

The film forming process, using a sputtering target containing a metal and silicon, and 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 , Nitrogen gas, nitrogen monoxide gas, dinitrogen monoxide gas, and an active gas containing nitrogen or nitrogen compounds containing at least one member selected from the group containing nitrogen dioxide gas, or a carbon compound comprising carbon dioxide gas or hydrocarbon gas A method for producing a phase shift mask blank according to Configuration 12, characterized in that it is carried out in a sputter gas atmosphere containing a mixed gas with an active gas.

(Configuration 14)

The said exposure process is a manufacturing method of the phase shift mask blank of the structure 12 or 13 characterized by being performed in a gas atmosphere containing nitrogen or a nitrogen compound.

(Configuration 15)

The said exposure process is a manufacturing method of the phase shift mask blank of the structure 12 or 13 characterized by being performed in a gas atmosphere containing carbon or a carbon compound.

(Configuration 16)

The said phase shift mask blank is the manufacturing method of the phase shift mask blank in the structure 12 or 13 characterized by the above-mentioned.

(Configuration 17)

Transparent substrate,

A light semitransmissive film pattern formed by wet etching on the main surface of the transparent substrate and having a property of changing the phase of exposure light and also comprising a metal silicide-based material

Equipped with,

In the light semitransmissive film pattern, the composition of the upper surface and a portion excluding the interface between the light semitransmissive film pattern and the transparent substrate is substantially uniform,

The cross section of the light semitransmissive film pattern includes upper, lower and side sides corresponding to the top, bottom, and side surfaces of the light semitransmissive film pattern, and a third of the film thickness from the contact point between the upper side and the lateral side and the upper side. 2 The angle formed between the straight line connecting the position of the side at the lowered position and the upper side is within a range of 85 degrees to 120 degrees, and furthermore, through the contact point between the upper side and the side, the transparent substrate The first imaginary line perpendicular to the main surface and the second imaginary line perpendicular to the main surface of the transparent substrate through the position of the lateral side at a position at a height of tenths of the film thickness from the bottom surface. A phase shift mask, characterized in that the width is 1/2 or less of the film thickness.

(Configuration 18)

In the phase shift mask for manufacturing a display device,

Transparent substrate,

A light semitransmissive film pattern formed on the main surface of the transparent substrate and having a property of changing the phase of exposure light and also comprising a metal silicide-based material

Equipped with,

In the light semitransmissive film pattern, the composition of the upper surface and a portion excluding the interface between the light semitransmissive film pattern and the transparent substrate is substantially uniform,

The cross section of the light semitransmissive film pattern includes upper, lower and side sides corresponding to the top, bottom, and side surfaces of the light semitransmissive film pattern, and a third of the film thickness from the contact point between the upper side and the lateral side and the upper side. 2 The angle formed between the straight line connecting the position of the side at the lowered position and the upper side is within a range of 85 degrees to 120 degrees, and furthermore, through the contact point between the upper side and the side, the transparent substrate The first imaginary line perpendicular to the main surface and the second imaginary line perpendicular to the main surface of the transparent substrate through the position of the lateral side at a position at a height of tenths of the film thickness from the bottom surface. A phase shift mask, characterized in that the width is 1/2 or less of the film thickness.

(Configuration 19)

The light-semitransmissive film pattern comprises a metal silicide nitride film, a metal silicide oxynitride film, a metal silicide oxide carbide, or a metal silicide carbide oxynitride phase shift mask described in 17 or 18.

(Configuration 20)

The phase shift mask according to configuration 17 or 18, wherein the light semitransmissive film pattern includes a line and space pattern.

(Configuration 21)

The phase shift mask according to configuration 17 or 18, wherein the light semitransmissive film pattern includes a hole pattern.

(Configuration 22)

In the manufacturing method of the phase shift mask,

A resist pattern is formed on the etching mask film of the phase shift mask blank of structure 1 or 2, or on the etching mask film of the phase shift mask blank obtained by the manufacturing method of the phase shift mask blank of structure 12 or 13. Resist pattern forming process,

An etching mask film pattern forming step of wet etching the etching mask film using the resist pattern as a mask to form an etching mask film pattern;

A semi-transmissive film pattern forming step of forming a light semitransmissive film pattern by wet etching the light semitransmissive film using the etching mask film pattern as a mask.

Method of manufacturing a phase shift mask, characterized in that it has a.

(Configuration 23)

In the semi-permeable layer pattern forming process, wet etching is performed using an etchant containing at least one fluorine compound selected from hydrofluoric acid, hydrofluoric acid and ammonium fluoride, and at least one oxidizing agent selected from hydrogen peroxide, nitric acid and sulfuric acid. The manufacturing method of the phase shift mask of the structure 22 characterized by the above-mentioned.

(Configuration 24)

The said phase shift mask is a manufacturing method of the phase shift mask in the structure 22 characterized by the above-mentioned.

(Configuration 25)

In the manufacturing method of the display device,

A phase shift mask arrangement step of arranging the phase shift mask described in Configurations 17 or 18 against the resist film with respect to the substrate provided with a resist film on which the resist film is formed;

A resist film exposure step of exposing the resist film by irradiating the exposure light to the phase shift mask

The manufacturing method of the display device characterized by having.

(Configuration 26)

The exposure light comprises a light in a wavelength range of 300 nm or more and 500 nm or less.

(Configuration 27)

The exposure light is a composite light comprising i-line, h-line and g-line, the manufacturing method of the display device according to configuration 25 or 26.

As described above, according to the phase shift mask blank according to the present invention, in particular, the phase shift mask blank for manufacturing a display device used for manufacturing a display device, a light semitransmissive film comprising a metal silicide-based material formed on a main surface of a transparent substrate And an etching mask film comprising a chromium-based material formed on the light semitransmissive film. In the composition gradient region formed at the interface between the light semitransmissive film and the etching mask film, the proportion of components that slow the wet etching rate of the light semitransmissive film is gradually and / or continuously increasing toward the depth direction. For this reason, the phase shift mask blank which can pattern the light semitransmissive film in the cross-sectional shape which can fully exhibit a phase shift effect by wet etching can be obtained. Further, by wet etching, a phase shift mask blank capable of patterning the light semitransmissive film in a cross-sectional shape with a small CD deviation can be obtained.

Further, according to the method of manufacturing a phase shift mask blank according to the present invention, in particular, a method of manufacturing a phase shift mask blank for manufacturing a display device used for manufacturing a display device, a light spot comprising a metal silicide-based material on a main surface of a transparent substrate A transmission film is formed, and an etching mask film containing a chromium-based material is formed on the light semitransmissive film. The light semitransmissive film is formed by forming the light semitransmissive film and exposing the light semitransmissive film to a gas atmosphere containing a component that slows the wet etching rate of the light semitransmissive film continuously after the film is formed without exposing the light semitransmissive film to the atmosphere. For this reason, the phase shift mask blank which can pattern the light semitransmissive film in the cross-sectional shape which can fully exhibit a phase shift effect by wet etching can be manufactured. Further, by wet etching, a phase shift mask blank capable of patterning the light semitransmissive film in a cross-sectional shape with a small CD deviation can be produced.

Further, according to the phase shift mask according to the present invention, in particular, the phase shift mask for manufacturing a display device used for manufacturing a display device is provided with a light semitransmissive film pattern comprising a metal silicide-based material formed on the main surface of the transparent substrate. .

The composition of the light semitransmissive film pattern is substantially uniform. For this reason, a phase shift mask with uniform optical characteristics can be obtained.

In addition, in the cross section of the light semitransmissive film pattern, the angle formed between the upper edge and the straight line connecting the position of the side edge at the position of the contact point between the upper side and the side edge and the height of two-thirds of the thickness of the film from the upper surface is 85. It is within the range of 120 degrees. In addition, in the cross section of the light semitransmissive film pattern, the position of the lateral side at the position of the first imaginary line perpendicular to the main surface of the transparent substrate through the contact point between the upper side and the lateral side, and a height raised by one tenth of the thickness of the film from the lower surface. Through the width of the second virtual line perpendicular to the main surface of the transparent substrate is less than half of the film thickness. For this reason, a phase shift mask having a light semitransmissive film pattern capable of sufficiently exhibiting a phase shift effect can be obtained. Further, a phase shift mask having a light semitransmissive film pattern with a small CD deviation can be obtained. This phase shift mask can cope with line and space patterns or miniaturization of contact holes.

Moreover, according to the manufacturing method of the phase shift mask which concerns on this invention, especially the manufacturing method of the phase shift mask for manufacture of a display device used for manufacture of a display device, the phase shift mask blank mentioned above or the manufacturing method of the phase shift mask blank mentioned above A phase shift mask is produced using the obtained phase shift mask blank. For this reason, a phase shift mask having a light semitransmissive film pattern capable of sufficiently exhibiting a phase shift effect can be produced. Further, a phase shift mask having a light semitransmissive film pattern with a small CD deviation can be produced. This phase shift mask can cope with line and space patterns or miniaturization of contact holes.

Moreover, according to the manufacturing method of the display device which concerns on this invention, the display device is manufactured using the phase shift mask mentioned above or the phase shift mask obtained by the manufacturing method of the phase shift mask mentioned above. For this reason, a display device having a fine line and space pattern or a contact hole can be manufactured.

1 is a schematic diagram of a line and space pattern used for simulation.
2 is a diagram showing the results of the first simulation.
3 is a view showing the results of the second simulation.
4 is a schematic diagram showing a sputtering device used for forming a light semitransmissive film and an etching mask film.
5 is a view showing the compositional analysis results in the depth direction for the phase shift mask blank of the first embodiment.
6 is a top view of the phase shift mask of the first embodiment.
7 is a cross-sectional photograph of the phase shift mask of the first embodiment.
8 is a cross-sectional photograph of the phase shift mask of the second embodiment.
9 is a cross-sectional photograph of the phase shift mask of the third embodiment.
10 is a cross-sectional photograph of the phase shift mask of the fourth embodiment.
11 is a plan view of the phase shift mask of the first reference example.
12 is a cross-sectional photograph of the phase shift mask of the first reference example.
13 is a cross-sectional photograph of the phase shift mask of the second reference example.
14 is a cross-sectional photograph of the phase shift mask of the third reference example.
15 is a cross-sectional photograph of the phase shift mask of the first comparative example.

Before explaining the embodiment of the present invention, the difference in the phase shift effect due to the difference in the cross-sectional shape of the phase shift film pattern will be described using simulation results.

In the simulation, the numerical aperture (NA) is 0.085, the coherence factor (σ) is 0.9, the exposure light is g-line, h-line, and i-line composite light (intensity ratio, g-line: h-line: i-line = 0.95: 0.8: 1.0). The simulation was performed twice.

In the first simulation, a phase shift mask (hereinafter, sometimes referred to as PSM (A)) having a phase shift film pattern in which the edge section has a vertical cross-sectional shape, and a phase shift film whose edge section has a tapered shape. A phase shift mask with a pattern (hereinafter, sometimes referred to as PSMTP (A)) and a binary mask (hereinafter, sometimes referred to as bin) were performed. Specifically, the phase shift masks PSM (A) and PSMTP (A) include a line pattern including a phase shift film pattern and a light-shielding film pattern formed on the phase shift film pattern, and a line pattern having a space pattern including a light transmitting portion It consists of an n-space pattern. The binary mask Bin has a line-and-space pattern having a line pattern including a light-shielding film pattern and a space pattern including a light transmitting portion. The width of the line pattern is 2.0 µm, and the width of the space pattern is 2.0 µm. The width of the edge portion of the phase shift film pattern is 0.5 µm. The width of the light-shielding film pattern is 1 µm. The light shielding film pattern is disposed on the phase shift film pattern excluding the edge portion.

In PSM (A), the transmittance of the edge portion of the phase shift film pattern is 6% with respect to i-line, and the phase difference between the light passing through the edge portion of the phase shift film pattern and the light passing through the light transmission portion is with respect to i-line. 180 degrees.

In the PSMTP (A), the edge portion of the phase shift film pattern is configured such that transmittance and phase difference are changed in steps of 10 at a width of 0.05 µm. The transmittance of the portion closest to the light-shielding film pattern of the edge portion composed of 10 steps is 6% with respect to the i-line, and the phase difference between the light transmitted through the light-transmitting portion and the light passing through the portion closest to the light-shielding film pattern is i-line. It is about 180 degrees. Among the edge parts composed of 10 steps, the transmittance of the portion closest to the light transmitting portion is 57.5% with respect to the i-line, and the phase difference between the light passing through the portion closest to the light transmitting portion and the light passing through the light transmitting portion is i-line. It is about 20.19 degrees. In addition, in the case of the molybdenum silicide nitride film (MoSiN) described in Examples described later, the angle of the virtual inclined surface of the edge portion composed of 10 steps is about 165 degrees.

1 is a schematic diagram of a line and space pattern used for simulation. Fig. 1 shows a part of the line and space pattern 1 in the PSM (A). In Fig. 1, the line pattern 2a positioned at the center and the space pattern 3a are interposed between the line pattern 2b located at the left side of the line pattern 2a, and the space pattern 3b is interposed. The line pattern 2c located on the right side of the line pattern 2a is shown. The line patterns 2b and 2c positioned to the left and right show only half the width of the line pattern. In Fig. 1, hatching is given to the edge portion 4 and the light-shielding film pattern 5 of the phase shift film pattern constituting the line patterns 2a, 2b, and 2c.

Table 1 and FIG. 2 show the results of the first simulation. In Fig. 2, curve a shows the result of PSM (A), curve b shows the result of PSMTP (A), and curve c shows the result of Bin. The horizontal axis in Fig. 2 represents the position (µm) when the center of the line pattern is zero, and the vertical axis represents light intensity.

As shown in Table 1 and FIG. 2, in PSM (A), the maximum light intensity is 0.43198, the minimum light intensity is 0.08452, and the contrast (the difference between the maximum light intensity and the minimum light intensity / the sum of the maximum light intensity and the minimum light intensity) ) Is 0.67273. In PSMTP (A), the maximum light intensity is 0.53064, the minimum light intensity is 0.13954, and the contrast is 0.58359. In the bin, the maximum light intensity is 0.49192, the minimum light intensity is 0.12254, and the contrast is 0.60114.

As shown in the simulation results shown in Tables 1 and 2, in the case of a phase shift mask (PSM (A)) in which the cross-sectional shape of the edge portion of the phase shift film pattern is vertical, the cross-sectional shape of the edge portion of the phase shift film pattern Compared to the case of the phase shift mask (PSMTP (A)) which is a taper shape or the case of the binary mask (Bin), contrast is high. Further, in the case of PSMTP (A), the contrast is lower than in the case of Bin. In the case of PSMTP (A), since the edge portion of the phase shift film pattern is tapered, the transmittance is high and the phase difference is small as it approaches the light transmitting portion. That is, as the amount of light leakage increases as the light transmitting portion approaches, the phase effect is lost. For this reason, in the case of PSMTP (A), contrast is low. In the case of PSM (A), since the edge portion of the phase shift film pattern is vertical, it has a constant transmittance (6%) and a phase difference (180 degrees) even when it is close to the light transmitting portion. That is, the transmittance and phase change directly at the boundary between the edge portion of the phase shift film pattern and the light transmission portion. For this reason, in the case of the PSM (A), there is leakage of light at the edge portion of the phase shift film pattern, but the contrast is higher than in the case of the bin. Therefore, it turns out that the phase shift effect can fully be exhibited by making the cross-sectional shape of the edge part of a phase shift film pattern perpendicular.

In the second simulation, a phase shift mask (hereinafter, sometimes referred to as PSM (B)) having a phase shift film pattern in which the edge section has a vertical cross-sectional shape, and a phase shift film in which the edge section has a tapered shape. A phase shift mask with a pattern (hereinafter, sometimes referred to as PSMTP (B)) and a binary mask (hereinafter, sometimes referred to as bin) were performed. The phase shift masks (PSM (B) and PSMTP (B)) used in the second simulation are obtained by removing the light-shielding film pattern from the PSM (A) and PSMTP (A) used in the first simulation. In detail, PSM (B) and PSMTP (B) have a line-and-space pattern having a line pattern including a phase shift film pattern and a space pattern including a light transmitting portion. The binary mask (Bin) used for the second simulation is the same as the bin used for the first simulation.

Table 2 and FIG. 3 show the results of the second simulation. In Fig. 3, curve d shows the result of PSM (B), curve e shows the result of PSMTP (B), and curve f shows the result of Bin. The horizontal axis in Fig. 3 represents the position (mu m) when the center of the line pattern is zero, and the vertical axis represents the light intensity.

As shown in Table 2 and FIG. 3, in PSM (B), the maximum light intensity is 0.40505, the minimum light intensity is 0.05855, and the contrast is 0.74743. In PSMTP (B), the maximum light intensity is 0.49925, the minimum light intensity is 0.09713, and the contrast is 0.67426. In the bin, the maximum light intensity is 0.49192, the minimum light intensity is 0.12254, and the contrast is 0.60114.

As shown in the simulation results shown in Table 2 and Fig. 3, in the case of a phase shift mask (PSM (B)) in which the cross-sectional shape of the edge portion of the phase shift film pattern is vertical, the cross-sectional shape of the edge portion of the phase shift film pattern The contrast is higher than in the case of the tapered phase shift mask (PSMTP (B)) or the binary mask (Bin). Therefore, it turns out that the phase shift effect can fully be exhibited by making the cross-sectional shape of the edge part of a phase shift film pattern perpendicular.

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 phase shift mask for manufacturing a display device using the phase shift mask blank, and a manufacturing method thereof and a display device using the phase shift mask The manufacturing method will be described in detail.

<First Embodiment>

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

In the manufacturing method of the phase shift mask blank for manufacture of the display device of 1st Embodiment, the preparation process of preparing a transparent substrate, and sputtering on the main surface of a transparent substrate are formed, and the light semitransmissive film containing a metal silicide type material is formed. The semi-transmissive film forming process is performed, and an etching mask film forming process is performed on the light semitransmissive film to form an etching mask film containing a chromium-based material by sputtering.

Hereinafter, each process is explained in full detail.

1. Preparation process

When manufacturing a phase shift mask blank for manufacturing a display device, first, a transparent substrate is prepared.

The material of the transparent substrate is not particularly limited as long as it is a material that has translucency with respect to the exposure light used. For example, synthetic quartz glass, soda-lime glass, and alkali-free glass are mentioned.

2. Semi-permeable film formation process

Next, a light semitransmissive film containing a metal silicide-based material is formed on the main surface of the transparent substrate by sputtering.

Specifically, in this semi-transmissive film forming step, first, a film forming step of applying a sputter power in a sputter gas atmosphere to form a light semitransmissive film containing a metal silicide-based material is performed. Subsequently, after exposing the light-semitransmissive film to the atmosphere, a process of exposing the light-semitransmissive film to a gas atmosphere containing a component that slows the wet etching rate of the light-semitransmissive film is performed continuously.

The light semitransmissive film has a property of changing the phase of exposure light. Due to this property, a predetermined phase difference occurs between the exposure light transmitted through the light semitransmissive film and the exposure light transmitted only through the transparent substrate. When the exposure light is a composite light containing light in a wavelength range of 300 nm or more and 500 nm or less, the light semitransmissive film is formed so as to generate a predetermined phase difference with respect to light having a representative wavelength. For example, when the exposure light is a composite light including i-line, h-line and g-line, the light semitransmissive film is formed to generate a phase difference of 180 degrees for any one of the i-line, h-line and g-line. In addition, in order to exert the phase shift effect described above, it is preferable to set the phase difference of the light semitransmissive film in a range of 180 degrees ± 20 degrees with respect to any representative wavelength of i-line, h-line, and g-line. More preferably, the phase difference of the light semitransmissive film is preferably set to a range of 180 degrees ± 10 degrees with respect to any one of i-ray, h-ray, and g-ray wavelengths. In addition, the transmittance of the light semitransmissive film is preferably 1% or more and 20% or less in any representative wavelength of i-line, h-line, and g-line. Particularly preferably, the transmittance of the light semitransmissive film is preferably 3% or more and 10% or less in any one of i-ray, h-ray, and g-ray wavelengths.

The metal silicide-based material constituting the light semitransmissive film may contain metal and silicon as long as it has a predetermined transmittance and phase difference with respect to exposure light, and may contain another element. As another element, an element which can control the refractive index (n) and extinction coefficient (k) in exposure light may be sufficient, and it is at least 1 selected from oxygen (O), nitrogen (N), carbon (C), and fluorine (F). It is selected from the elements of the species. For example, oxides of metal silicides, oxynitrides of metal silicides, nitrides of metal silicides, carbon nitrides of metal silicides, oxide oxides of metal silicides, carbon oxide oxynitrides of metal silicides, and the like. In addition, from the viewpoint of pattern controllability by wet etching, it is preferable that the metal silicide-based material constituting the light semitransmissive film is a material containing a metal, silicon, and a component that slows the wet etching rate of the light semitransmissive film. As a component for slowing the wet etching rate of the light semitransmissive film, nitrogen (N) and carbon (C) are exemplified. 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-based material constituting the light semitransmissive film include metal silicide nitrides, metal silicide oxide nitrides, metal silicide oxide carbides, metal silicide carbonitrides, and metal silicide carbonitride oxides. Specifically, nitride of molybdenum silicide (MoSi), nitride of tantalum silicide (TaSi), nitride of tungsten silicide (WSi), nitride of titanium silicide (TiSi), nitride of zirconium silicide (ZrSi), oxynitride of molybdenum silicide, Oxide nitride of tantalum silicide, oxide nitride of tungsten silicide, oxide nitride of titanium silicide, oxide nitride of zirconium silicide, oxide carbide of molybdenum silicide, oxide oxide of tantalum silicide, oxide oxide of titanium silicide, oxide carbide of tungsten silicide, zirconium silicide Oxide carbide, molybdenum silicide carbonitride, tantalum silicide carbonitride, titanium silicide carbonitride, zirconium silicide carbonitride, tungsten silicide carbonitride, molybdenum silicide carbon There may be mentioned oxy-nitride, tantalum silicide oxide nitride carbide, carbide oxide of titanium silicide nitride, carbide, oxynitride, oxynitride carbide of zirconium silicide of tungsten silicide.

The composition of the metal, silicon, and nitrogen constituting the light semitransmissive film includes a desired phase difference (180 ° ± 20 °) for exposure light, transmittance (1% or more and 20% or less), and wet etching characteristics (cross-sectional shape of the light semitransmissive film pattern or CD deviation). The ratio of metal to silicon is preferably metal: silicon = 1: 1 to 1: 9. The content of nitrogen is preferably 25 atomic% or more and 55 atomic% or less, more preferably 30 atomic% or more and 50 atomic% or less.

The light-semitransmissive film forming process was performed in a sputter gas atmosphere containing a gas having a component in which the refractive index (n) and extinction coefficient (k) in exposure light were controllable using a sputtering target containing metal and silicon. All. As such a gas, oxygen gas (O ₂ ), carbon monoxide gas (CO), carbon dioxide gas (CO ₂ ), nitrogen gas (N ₂ ), nitrogen monoxide gas (NO), nitrogen dioxide gas (NO ₂ ), nitrogen monoxide gas ( And active gases such as N ₂ O), hydrocarbon-based gases (such as CH ₄ ), fluorine-based gases (such as CF ₄ ), and fluorine-based gases (such as NF ₃ ). Further, from the viewpoint of pattern controllability by wet etching, a sputtering gas atmosphere comprising a gas having a component that slows the wet etching rate of the light semitransmissive film using a sputtering target containing metal and silicon in the film forming process of the light semitransmissive film. It is preferably done in. As a component which slows the wet etching rate of the light semitransmissive film, nitrogen (N) and carbon (C) are mentioned, for example, as described above. As a gas having a component that slows the wet etching rate of the light semitransmissive film, nitrogen gas, nitrogen monoxide gas, nitrogen dioxide gas, dinitrogen monoxide gas, carbon monoxide gas, carbon dioxide gas, hydrocarbon-based gas (CH _4, etc.), fluorocarbon gas (CF ₄ Etc.) and active gases, such as fluorine nitride gas (NF ₃ etc.). In the sputter gas atmosphere, helium gas, neon gas, argon gas, krypton gas, xenon gas, etc. may be included as an inert gas. The sputter gas atmosphere includes, for example, an inert gas containing at least one selected from the group comprising helium gas, neon gas, argon gas, krypton gas, and xenon gas, and nitrogen gas, nitrogen monoxide gas, and nitrogen dioxide gas. It contains the mixed gas with the active gas containing at least 1 sort (s) selected from the said group.

The exposure process after the light-semitransmissive film is formed is performed by exposing the light-semitransmissive film to a gas atmosphere for exposure including a gas having a component that slows the wet etching rate of the light semitransmissive film. As a component that slows the wet etching rate of the light semitransmissive film, nitrogen (N) is mentioned, for example, as described above. As a gas having a component that slows the wet etching rate of the light semitransmissive film, an active gas such as nitrogen gas can be mentioned. In the gas atmosphere for exposure, helium gas, neon gas, argon gas, krypton gas, xenon gas, etc. may be included as an inert gas. When the gas atmosphere for exposure includes a mixed gas atmosphere of nitrogen gas and inert gas, the ratio of nitrogen gas to nitrogen gas / inert gas to inert gas is 20% or more, preferably 30% or more.

The light-semitransmissive film may be either one of a layer or a plurality of layers. When the light semitransmissive film contains a plurality of layers, the film forming process of the light semitransmissive film and the exposing process after the film formation of the light semitransmissive film are performed multiple times. When the film forming step is performed multiple times, the sputter power applied to the sputtering target during film formation of the light semitransmissive film can be reduced.

3. Etching mask film forming process

Next, an etching mask film containing a chromium-based material is formed on the light semitransmissive film by sputtering.

The etching mask film may be either light-shielding or light-transmissive. The chromium-based material constituting the etching mask film is not particularly limited as long as it contains chromium (Cr). Examples of the chromium-based material constituting the etching mask film include chromium (Cr), chromium oxide, chromium nitride, chromium carbide, and chromium fluoride, and materials containing at least one of them.

This mask film forming process includes at least one selected from the group consisting of, for example, helium gas, neon gas, argon gas, krypton gas, and xenon gas, using a sputtering target containing a chromium or chromium compound. In a sputter gas atmosphere containing a mixed gas of an inert gas and at least one selected from the group consisting of oxygen gas, nitrogen gas, carbon dioxide gas, nitrogen oxide gas, hydrocarbon gas and fluorine gas. Is done.

The etching mask film may be either one of a layer or a plurality of layers. When the etching mask film includes a plurality of layers, for example, in the case of a laminated structure comprising a light-shielding layer formed on the light-semitransmissive film side and an anti-reflection layer formed on the light-shielding layer, or an insulating layer formed to contact the light-semitransmissive film There is a case of a laminated structure including a light blocking layer formed on an insulating layer and an antireflection layer formed on a light blocking layer. The light-shielding layer may be any one of a case including one layer and a case of including a plurality of layers. As a light shielding layer, a chromium nitride film (CrN), a chromium carbide film (CrC), and a chromium carbonitride film (CrCN) are mentioned, for example. The anti-reflection layer may be any one of a single layer and a plurality of layers. As an antireflection layer, a chromium oxynitride film (CrON) is mentioned, for example. The insulating layer contains, for example, CrCO or CrCON containing less than 50 atomic% Cr, and has a thickness of 10 nm or more and 50 nm or less. When wet etching the etching mask film containing the chromium-based material, metal ions begin to melt from the light semitransmissive film containing the metal silicide-based material. At that time, electrons are generated. When the insulating layer is formed to be in contact with the light semitransmissive film, it is possible to prevent electrons generated when metal ions begin to melt from the light semitransmissive film to be supplied to the etching mask film. For this reason, the etching rate in the surface when wet etching the etching mask film can be made uniform.

The phase shift mask blank for manufacturing the display device of the first embodiment is produced by such a preparatory step, a semi-transmissive film forming step, and an etching mask film forming step.

4 is a schematic view showing an example of a sputtering device used for forming a light semitransmissive film and an etching mask film.

The sputtering apparatus 11 shown in FIG. 4 is in-line, and 5 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 contains two chambers. These five chambers are sequentially arranged in sequence.

The transparent substrate 12 mounted on the tray (not shown), at a predetermined conveying speed, in the direction of the arrow S, is brought into the carry-in chamber LL, the first sputter chamber SP1, the buffer chamber BU, and the second. The sputtering chamber SP2 and the carrying-out chamber ULL may be transported in sequence. In addition, the transparent substrate 12 mounted on the tray (not shown), in the direction opposite to the arrow S, is taken out chamber ULL, second sputter chamber SP2, buffer chamber BU, first sputter chamber (SP1) and the return chamber LL may be sequentially returned.

The carrying-in chamber LL, the first sputtering chamber SP1, the second sputtering chamber SP2 and the carrying-out chamber ULL are partitioned 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 include a large container in which three chambers are connected.

Further, the carry-in chamber LL and the carry-out chamber ULL may be partitioned from the outside of the sputtering device 11 by a partition plate.

The carry-in chamber LL, the buffer chamber BU, and the carry-out chamber ULL are connected to an exhaust device (not shown) for performing exhaust.

In the first sputtering chamber SP1, a first sputtering target 13 including metal and silicon for forming a light semitransmissive film is disposed on the carrying chamber LL side, and in the vicinity of the first sputtering target 13, The first gas introduction port GA1 (not shown) is disposed. Further, in the first sputtering chamber SP1, a second sputtering target 14 containing chromium for forming an etching mask film is disposed on the buffer chamber BU side, and in the vicinity of the second sputtering target 14, A second gas introduction port GA2 (not shown) is provided.

In the second sputter chamber SP2, a third sputtering target 15 containing chromium for forming an etching mask film is disposed on the buffer chamber BU side, and in the vicinity of the third sputtering target 15, a third A gas introduction port GA31 (not shown) is provided. Further, in the second sputtering chamber SP2, a fourth sputtering target 16 containing chromium for forming an etching mask film is disposed on the discharge chamber ULL side, and in the vicinity of the fourth sputtering target, a fourth gas An introduction port GA4 (not shown) is provided.

In FIG. 4, hatching is given to the first sputtering target 13, the second sputtering target 14, the third sputtering target, and the fourth sputtering target 15.

When the light semitransmissive film and the etching mask film are formed using the inline sputtering device 11 shown in FIG. 4, first, to form the light semitransmissive film, a transparent substrate 12 mounted on a tray (not shown) ) Is carried into the transfer chamber LL.

After making the inside of the sputtering device 11 at a predetermined vacuum degree, a gas having a predetermined flow rate from the first gas inlet GA1, the active gas described above, specifically, a component that slows the wet etching rate of the light semitransmissive film. Introducing a sputtering gas containing, and further slowing the wet etching rate of the light semitransmissive film from at least one of the third gas inlet GA3 and the fourth gas inlet GA4 to the second sputter chamber SP2. A gas for exposure including a gas having a component is introduced, and a predetermined sputtering power is applied to the first sputtering target 13. The application of sputter power, introduction of sputtering gas, and introduction of gas for exposure continue until the transparent substrate 12 is conveyed to the discharge chamber ULL.

Thereafter, the transparent substrate 12 mounted on the tray (not shown), at a predetermined conveying speed, in the direction of the arrow S, is brought into the carry-in chamber LL, the first sputter chamber SP1, and the buffer chamber BU , The second sputter chamber (SP2) and the transfer chamber (ULL) in order. When the transparent substrate 12 passes around the first sputtering target 13 of the first sputtering chamber SP1, by reactive sputtering, metal silicide of a predetermined film thickness is formed on the main surface of the transparent substrate 12 A light semitransmissive film containing a system material is formed. Further, while the transparent substrate 12 passes through the second sputter chamber SP2, the light semitransmissive film is exposed to a gas atmosphere for exposure including a gas having a component that slows the wet etching rate of the light semitransmissive film.

In the case of forming the second layer of the light semitransmissive film, the transparent substrate 12 mounted on the tray (not shown), in the direction opposite to the arrow S, is carried out in the ejection chamber ULL, the second sputter chamber SP2, and the buffer. The chamber BU, the first sputtering chamber SP1, and the carrying-in chamber LL are returned in order, and the above-mentioned light semitransmissive film is formed again. When returning the transparent substrate 12 to the carry-in chamber LL, the first sputtering chamber SP1 and the second sputtering chamber SP2 are exposed with gas having a component that slows the wet etching rate of the light semitransmissive film. It is preferable to introduce a solvent gas. Thereby, while returning the transparent substrate 12 to the carrying-in chamber LL, the light semitransmissive film can be exposed to a gas atmosphere for exposure including a gas having a component that slows the wet etching rate of the light semitransmissive film.

In the case of forming the third and fourth layers of the light semitransmissive film, the same is done.

In this way, after the light semitransmissive film is formed on the main surface of the transparent substrate 12, the etching mask film is continuously formed without taking out the transparent substrate 12 on the outside of the sputtering device 11. The transparent substrate 12 mounted on the substrate is not carried in the direction opposite to the arrow S, and is carried out by the carrying-out chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, the first sputtering chamber SP1, and carrying in. The chamber LL is returned in turn. On the other hand, after forming the light semitransmissive film, once the transparent substrate 12 is taken out of the sputtering device 11, and when forming an etching mask film, the transparent substrate 12 mounted on a tray (not shown) is used. After carrying into the carrying-in chamber LL, as described above, the inside of the sputtering device 11 is set to a predetermined vacuum degree.

When forming an etching mask film of a laminated structure including a light-shielding layer and an anti-reflection layer, thereafter, while the inside of the sputtering device 11 is set to a predetermined vacuum, a predetermined flow rate from the second gas introduction port GA2 Sputtering gas is introduced, and a predetermined sputtering power is applied to the second sputtering target 14. Further, sputtering gas having a predetermined flow rate is introduced from the third gas introduction port GA3, and a predetermined sputtering power is applied to the third sputtering target 15. Further, sputtering gas having a predetermined flow rate is introduced from the fourth gas introduction port GA4, and a predetermined sputtering power is applied to the fourth sputtering target 16. The application of sputtering power and introduction of sputtering gas continue until the transparent substrate 12 is conveyed to the delivery chamber ULL.

Thereafter, the transparent substrate 12 mounted on the tray (not shown), at a predetermined conveying speed, in the direction of the arrow S, is brought into the carry-in chamber LL, the first sputter chamber SP1, and the buffer chamber BU , The second sputter chamber (SP2) and the transfer chamber (ULL) in order. When the transparent substrate 12 passes around the second sputtering target 14 of the first sputtering chamber SP1, light-shielding containing a chromium-based material of a predetermined film thickness on the light semitransmissive film by reactive sputtering The layer is formed. In addition, when the transparent substrate 12 passes around the third sputtering target 15 and the fourth sputtering target 16 of the second sputtering chamber SP2, by reactive sputtering, a predetermined film is formed on the light-shielding layer. A light-shielding layer or anti-reflection layer containing a thick chromium-based material is formed.

After forming the etching mask film of the laminated structure containing the light-shielding layer and the anti-reflection layer on the light semitransmissive film, the transparent substrate 12 is taken out of the sputtering device 11.

On the other hand, when forming an etching mask film having a laminated structure including an insulating layer, a light-blocking layer, and an anti-reflection layer, after forming a light semitransmissive film on the transparent substrate 12, the inside of the sputtering device 11 is set to a predetermined vacuum degree. In one state, sputtering gas having a predetermined flow rate is introduced from the second gas introduction port GA2, and a predetermined sputtering power is applied to the second sputtering target 14.

Thereafter, the transparent substrate 12 mounted on the tray (not shown), at a predetermined conveying speed, in the direction of the arrow S, is brought into the carry-in chamber LL, the first sputter chamber SP1, and the buffer chamber BU , The second sputter chamber (SP2) and the transfer chamber (ULL) in order. When the transparent substrate 12 passes around the second sputtering target 14 of the first sputtering chamber SP1, by reactive sputtering, insulation comprising a chromium-based material of a predetermined film thickness on the light semitransmissive film The layer is formed.

Thereafter, in order to form the light-shielding layer and the anti-reflection layer, the transparent substrate 12 mounted on the tray (not shown), in the direction opposite to the arrow S, is carried out in the discharge chamber ULL and the second sputter chamber ( SP2), the buffer chamber BU, the first sputter chamber SP1, and the return chamber LL are sequentially returned, and as described above, a light-shielding layer and an anti-reflection layer are formed.

After forming an etching mask film having a laminated structure including an insulating layer, a light-blocking layer, and an anti-reflection layer on the light semitransmissive film, the transparent substrate 12 is taken out of the sputtering device 11.

The phase shift mask blank for manufacturing the display device of the first embodiment manufactured as described above is formed on a transparent substrate, a light semitransmissive film comprising a metal silicide-based material formed on a main surface of the transparent substrate, and a light semitransmissive film. The formed etching mask film containing a chromium-based material is provided, and a composition gradient region is formed at the interface between the light semitransmissive film and the etching mask film.

Hereinafter, the phase shift mask blank of the first embodiment will be described with reference to FIG. 5 showing the result of compositional analysis in the depth direction by X-ray photoelectron spectroscopy (XPS).

The composition gradient region P is an etching mask film after the appearance of silicon (silicon: Si) peaks and molybdenum (Mo) peaks due to the light semitransmissive film in the composition analysis results in the depth direction by XPS with respect to the phase shift mask blank. This is the region until the chromium (Cr) peak due to disappears.

In the composition gradient region P, the proportion of the component (in FIG. 5, nitrogen (N)) that slows the wet etching rate of the light semitransmissive film is monotonically increasing stepwise and / or continuously toward the depth direction.

In addition, in the composition inclined region P, the proportion of oxygen hardly changes with the proportion of oxygen in the composition uniform region Q, and is contained substantially uniformly. The proportion (content) of oxygen in the composition gradient region P is 20 atomic% or less, preferably 10 atomic% or less, and more preferably 5 atomic% or less.

In addition, the maximum value of the ratio (N / Si) of nitrogen (N) to silicon (Si) at the boundary with the etching mask film in the composition gradient region P is 3.0 or more and 30 or less, preferably 3.5 or more and 25 Below, it is more preferably 4.0 or more and 20 or less. However, as for the boundary, when the phase shift mask blank was subjected to composition analysis under the condition of 0.5 min for the measurement step by X-ray photoelectron spectroscopy from the etching mask film side, silicon (Si) of 1 atomic% or more was initially found. Let it be the position to be detected.

The composition of the light semitransmissive film is substantially uniform. However, the above-mentioned composition gradient region P is formed at the interface between the light semitransmissive film and the etching mask film, and the region where the composition is inclined is also formed at the interface between the light semitransmissive film and the transparent substrate. Do not. In the composition uniformity region Q, in the composition analysis result in the depth direction by XPS of the phase shift mask blank, the chromium (Cr) peak due to the etching mask film disappeared, and then the oxygen (O) peak due to the transparent substrate appeared. This is the area until you do.

In the composition uniform region Q, the variation in the proportion of each of the components (slow in the nitrogen (N) in FIG. 5) that slows the wet etching rate of molybdenum (Mo), silicon (Si), and light semitransmissive film is preferably 5 atomic% or less, It is 3 atomic% or less.

When the light semitransmissive film includes a plurality of layers, the interface of each layer to the composition of a component (in FIG. 5, nitrogen (N)) that slows the wet etching rate of the light semitransmissive film near the center of the thickness direction of each layer ( In Fig. 5, the decrease in the composition of the component (in Fig. 5, nitrogen (N)) that slows the wet etching rate of the light semitransmissive film in the case of sputtering time of 25 minutes is 3 atomic% or less, preferably 2 atomic% Is below.

According to the manufacturing method of the phase shift mask blank for manufacturing the display device of this 1st Embodiment, the light semitransmissive film containing a metal silicide type material is formed on the main surface of a transparent substrate, and on the light semitransmissive film, a chromium type material An etching mask film is formed. The light semitransmissive film is formed by forming the light semitransmissive film and exposing the light semitransmissive film to a gas atmosphere containing a component that slows the wet etching rate of the light semitransmissive film continuously after the film is formed without exposing the light semitransmissive film to the atmosphere. By successively exposing the light-semitransmissive film to a gas atmosphere containing a component that slows the wet etching rate of the light-semitransmissive film after the film formation, it is possible to prevent separation of components that slow the wet etch rate from the surface of the light-semitransmissive film. For this reason, it is possible to manufacture a phase shift mask blank capable of patterning the light semitransmissive film in a cross-sectional shape close to vertically capable of sufficiently exhibiting a phase shift effect by wet etching. Further, by wet etching, a phase shift mask blank capable of patterning the light semitransmissive film in a cross-sectional shape with a small CD deviation can be produced.

Moreover, according to the phase shift mask blank for manufacture of the display device of this 1st Embodiment, the light semitransmissive film containing the metal silicide type material formed on the main surface of a transparent substrate, and the chrome type material formed on the light semitransmissive film are provided. It is equipped with the etching mask film containing. In the composition inclined region P formed at the interface between the light semitransmissive film and the etching mask film, the proportion of components that slow the wet etching rate of the light semitransmissive film is gradually and / or continuously increasing toward the depth direction. For this reason, a phase shift mask blank capable of patterning the light semitransmissive film in a cross-sectional shape close to vertically capable of sufficiently exhibiting a phase shift effect by wet etching can be obtained. Further, by wet etching, a phase shift mask blank capable of patterning the light semitransmissive film in a cross-sectional shape with a small CD deviation can be obtained.

<Second Embodiment>

In the second embodiment, a phase shift mask for manufacturing a display device and its manufacturing method will be described.

In the method of manufacturing the phase shift mask for manufacturing a display device of the second embodiment, first, on the etching mask film of the phase shift mask blank obtained by the method of manufacturing the phase shift mask blank for manufacturing the display device described in the first embodiment, Alternatively, a resist pattern forming step of forming a resist pattern is performed on the etching mask film of the phase shift mask blank for manufacturing the display device described in the first embodiment.

Specifically, in this resist pattern forming step, first, a resist film is formed on the etching mask film. Then, a pattern of a predetermined size is drawn on the resist film. Thereafter, the resist film is developed with a predetermined developer to form a resist pattern.

Examples of the pattern to be drawn on the resist film include a line and space pattern and a hole pattern.

Next, an etching mask film pattern forming step is performed by wet etching the etching mask film using a resist pattern as a mask to form an etching mask film pattern.

The etching solution for wet etching the etching mask film is not particularly limited as long as it can selectively etch the etching mask film. Specifically, an etchant containing cupric ammonium nitrate and perchloric acid is mentioned.

Next, a semi-transmissive film pattern forming process is performed by wet etching the light semitransmissive film using the etching mask film pattern as a mask to form the light semitransmissive film pattern.

The etching solution for wet etching the light semitransmissive film is not particularly limited as long as it can selectively etch the light semitransmissive film. For example, an etchant containing at least one fluorine compound selected from hydrofluoric acid, hydrofluoric acid and ammonium hydrogen fluoride, and at least one oxidizing agent selected from hydrogen peroxide, nitric acid and sulfuric acid. Specifically, an etchant obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water.

When a phase shift mask of a type having a light-shielding film pattern is produced on a semi-transmissive film pattern, after forming the semi-transmissive film pattern, the etching mask film pattern is patterned into a predetermined pattern narrower than the light semi-transmissive film pattern. In this case, the light semitransmissive film pattern has a property of changing the phase of the exposure light, and the etching mask film pattern has light blocking properties.

In the case of manufacturing a phase shift mask of a type having no light-shielding film pattern on a semi-transmissive film pattern, after forming the semi-transmissive film pattern, the etching mask film pattern is peeled off. In this case, the light semitransmissive film pattern has a property of changing the phase of exposure light.

A phase shift mask for manufacturing a display device is manufactured by such a resist pattern forming step, an etching mask film pattern forming step, and a semi-transmissive film pattern forming step.

The phase shift mask for manufacturing the display device of the second embodiment thus manufactured includes a transparent substrate and a light semitransmissive film pattern comprising a metal silicide-based material formed on a main surface of the transparent substrate. On the semi-transmissive film pattern, in the case of a type having a light-shielding film pattern, an etching mask film pattern comprising a chromium-based material is also provided on the light semi-transmissive film pattern. The portion where the light semitransmissive film pattern is disposed constitutes the phase shift portion, and the portion where the transparent substrate is exposed constitutes the light transmission portion.

As a light-semitransmissive film pattern, a line-and-space pattern or a hole pattern can be mentioned.

The light semitransmissive film pattern has a property of changing the phase of exposure light. Due to this property, a predetermined phase difference occurs between the exposure light transmitted through the phase shift portion where the light semitransmissive film pattern is disposed and the exposure light transmitted through the light transmission portion where the transparent substrate is exposed. When the exposure light is a composite light containing light in a wavelength range of 300 nm or more and 500 nm or less, the light semitransmissive film pattern generates a predetermined phase difference with respect to light having a representative wavelength. For example, when the exposure light is a composite light including i-line, h-line and g-line, the light semitransmissive film pattern generates a phase difference of 180 degrees with respect to any one of the i-line, h-line and g-line. As described above, it is preferable to set the phase difference of the light semitransmissive film pattern in a range of 180 degrees ± 20 degrees with respect to any one of i-ray, h-ray, and g-ray wavelengths. More preferably, the phase difference of the light semitransmissive film is preferably set to a range of 180 degrees ± 10 degrees with respect to any one of i-ray, h-ray, and g-ray wavelengths. In addition, the transmittance of the light semitransmissive film is preferably 1% or more and 20% or less in any representative wavelength of i-line, h-line, and g-line. Particularly preferably, the transmittance of the light semitransmissive film is preferably 3% or more and 10% or less in any one of i-ray, h-ray, and g-ray wavelengths.

In addition, the phase shift mask for manufacturing a display device of the present invention is used for projection exposure of equal magnification exposure to sufficiently exhibit the phase shift effect. In particular, as the exposure environment, the numerical aperture (NA) is preferably 0.06 to 0.15, more preferably 0.08 to 0.10, and the coherence factor (σ) is preferably 0.5 to 1.0.

The light semitransmissive film pattern may contain a metal and silicon as long as a predetermined transmittance and a phase difference are generated with respect to the exposure light, and may contain another element. As other elements, any element that can control the refractive index (n) and extinction coefficient (k) in exposure light may be used, and oxygen (O), nitrogen (N), carbon (C), and fluorine (F) It is selected from at least one element selected. For example, oxides of metal silicides, oxynitrides of metal silicides, nitrides of metal silicides, carbon nitrides of metal silicides, carbon oxynitrides of metal silicides, and the like. Further, from the viewpoint of pattern controllability by wet etching, it is preferable that the light semitransmissive film pattern includes a metal, a silicon, and a metal silicide-based material containing a component that slows the wet etching rate of the light semitransmissive film. As a component for slowing the wet etching rate of the light semitransmissive film, nitrogen (N) and carbon (C) are exemplified. Examples of the metal include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), and titanium (Ti). Examples of the metal silicide-based material constituting the semi-permeable layer pattern include metal silicide nitride, metal silicide oxynitride, metal silicide oxide carbide, metal silicide carbonitride, and metal silicide carbonitride oxynitride. The composition of the metal, silicon, and nitrogen constituting the light semitransmissive pattern includes a desired phase difference (180 ° ± 20 °) for exposure light, transmittance (1% or more and 20% or less), and wet etching characteristics (cross-sectional shape of the light semitransmissive film pattern) Or CD deviation). The ratio of metal to silicon is preferably metal: silicon = 1: 1 to 1: 9. The content of nitrogen is preferably 25 atomic% or more and 55 atomic% or less, more preferably 30 atomic% or more and 50 atomic% or less.

The composition of the light semitransmissive film pattern is substantially uniform toward the depth direction of the film. However, the above-described composition inclined region is formed on the upper surface of the light semitransmissive film pattern, and an area in which the composition is inclined is also formed at the interface between the light semitransmissive film pattern and the transparent substrate, so the composition of these parts is not uniform.

The etching mask film pattern contains a chromium-based material containing chromium (Cr). As a chromium-based material constituting the etching mask film pattern, for example, chromium nitride (CrN), chromium carbide (CrC), chromium carbide (CrCN), chromium oxynitride (CrON), chromium oxide (CrCO), chromic acid Picture quality carbide (CrCON) is mentioned.

It will be described below with reference to Fig. 7 showing a cross-sectional photograph of the phase shift mask of the first embodiment and Fig. 8 showing a cross-sectional photograph of the phase shift mask of the second embodiment.

The cross section of the light semitransmissive film pattern includes upper, lower and side sides 23 corresponding to the top, bottom, and side surfaces of the light semitransmissive film pattern. 7 and 8, the auxiliary line 21 represents the position of the upper side corresponding to the upper surface of the light semitransmissive film pattern, and the auxiliary line 22 represents the position of the lower side corresponding to the lower surface of the light semitransmissive film pattern. In this case, the angle θ between the straight line connecting the contact point 26 between the upper side and the lateral side and the position 27 of the lateral side at a height of two-thirds the thickness of the film from the upper surface, and the angle θ between the upper side is 85 degrees. To 120 degrees. In Fig. 7, the auxiliary line 24 indicates the position of a height that is two-thirds of the thickness of the film from the top surface. In addition, the first virtual line 29 perpendicular to the main surface of the transparent substrate through the contact 26 between the upper side and the side 23 and the side at a position at a height of one tenth of the thickness of the film from the bottom surface. The width of the second virtual line 30 perpendicular to the main surface of the transparent substrate through the position 28 of (hereinafter, sometimes referred to as the lower width) D is equal to or less than half of the film thickness. In Fig. 8, the auxiliary line 25 indicates the position of a height that is increased by one tenth of the thickness of the film from the lower surface.

The phase shift mask may have a light-shielding film pattern that shields the exposure light on the light semitransmissive film pattern. When the light-shielding film pattern has a light-shielding film pattern, it is easy to recognize the mask pattern by an exposure machine. Further, it is possible to prevent the resist film from being exposed to the light by passing through the light semitransmissive film pattern.

According to the manufacturing method of the phase shift mask for manufacture of the display apparatus of this 2nd embodiment, the phase shift mask blank obtained by the manufacturing method of the phase shift mask blank for manufacture of the display apparatus demonstrated in 1st Embodiment, or 1st Embodiment A phase shift mask is produced using the phase shift mask blank for manufacturing the display device described above. For this reason, it is possible to manufacture a phase shift mask having a light semitransmissive film pattern having a cross-sectional shape close to vertical that can sufficiently exhibit a phase shift effect. Further, a phase shift mask having a light semitransmissive film pattern with a small bottom width D and a small CD deviation can be manufactured. This phase shift mask can cope with line and space patterns or miniaturization of contact holes.

According to the phase shift mask for manufacturing a display device of this second embodiment, a light semitransmissive film pattern including a metal silicide-based material formed on a main surface of a transparent substrate is provided. The composition of the light semitransmissive film pattern is substantially uniform over the depth direction of the light semitransmissive film pattern. For this reason, a phase shift mask with uniform optical characteristics can be obtained. In addition, in the cross section of the light semitransmissive film pattern, a straight line connecting the contact point 26 between the upper side and the side edge and the position 27 of the side edge at a height of two-thirds the thickness of the film from the top surface, and the upper edge and The angle θ of is in the range of 85 degrees to 120 degrees. In addition, in the cross section of the light semitransmissive film pattern, the first virtual line 29 perpendicular to the main surface of the transparent substrate through the contact 26 between the upper side and the side side, and a height increased by one tenth of the film thickness from the lower surface. The width D of the second virtual line 30 perpendicular to the main surface of the transparent substrate through the position 28 on the side at the position of is less than half the film thickness. For this reason, it is possible to obtain a phase shift mask having a light semitransmissive film pattern having a cross-sectional shape close to vertical that can sufficiently exhibit a phase shift effect. Further, a phase shift mask having a light semitransmissive film pattern with a small bottom width D and a small CD deviation can be obtained. This phase shift mask can cope with line and space patterns or miniaturization of contact holes.

<Third embodiment>

In the third embodiment, a method of manufacturing the display device will be described.

In the method of manufacturing the display device of the third embodiment, first, a phase shift mask obtained by the method of manufacturing the phase shift mask for manufacturing the display device described in the second embodiment, for a substrate having a resist film on which a resist film is formed on a substrate, or A phase shift mask arrangement step for arranging the phase shift mask for manufacturing the display device described in the second embodiment to face the resist film is performed.

Next, a resist film exposure step of exposing the resist film by irradiating the exposure light with a phase shift mask is performed.

The exposure light is, for example, a composite light containing light in a wavelength range of 300 nm to 500 nm. Specifically, it is a composite light containing i-line, h-line and g-line. Moreover, as exposure at the time of manufacture of a display device, projection exposure of equal magnification exposure is preferable. In the exposure environment, the numerical aperture (NA) is preferably 0.06 to 0.15, more preferably 0.08 to 0.10, and the coherence factor (σ) is preferably 0.5 to 1.0.

According to the manufacturing method of the display apparatus of this 3rd embodiment, the phase shift mask obtained by the manufacturing method of the phase shift mask for manufacture of the display apparatus demonstrated in 2nd Embodiment, or the phase for manufacturing the display apparatus demonstrated in 2nd Embodiment A display device is manufactured using a shift mask. For this reason, a display device having a fine line and space pattern or a contact hole can be manufactured.

<Example>

Hereinafter, the present invention will be described in more detail based on examples.

<First Example>

A. Phase shift mask blank and manufacturing method thereof

To manufacture the phase shift mask blank of the first embodiment, first, as a transparent substrate 12, a 3345 size (330 mm × 450 mm × 5 mm) synthetic quartz glass substrate was prepared.

Thereafter, the synthetic quartz glass substrate was mounted on a tray (not shown) with the main surface facing downward, and was carried into the carrying chamber LL of the inline sputtering device 11 shown in FIG. 4. In the first sputtering chamber SP1, a sputtering target including molybdenum silicide (Mo: Si = 1: 4) is disposed as the first sputtering target 13 on the side of the transfer chamber LL. Further, a sputtering target containing chromium is disposed as a second sputtering target 14 on the buffer chamber BU side in the first sputtering chamber SP1. In addition, in the second sputtering chamber SP2, a sputtering target containing chromium is provided as a third sputtering target 15 on the buffer chamber BU side and the carrying-out chamber ULL side, respectively, and the fourth sputtering target 16 ), A sputtering target containing chromium is disposed.

In order to form a light semitransmissive film on the main surface of the synthetic quartz glass substrate, first, argon (Ar) from the first gas inlet GA1 disposed near the first sputtering target 13 of the first sputter chamber SP1. A mixed gas (Ar: 50 sccm, N ₂ : 90 sccm) of gas and nitrogen (N ₂ ) gas was introduced, and a sputter power of 8.0 kPa was applied to the first sputtering target 13. In addition, from the third gas inlet GA3 disposed near the third sputtering target 15 of the second sputtering chamber SP2 and the fourth gas inlet GA4 disposed near the fourth sputtering target 16. A mixed gas (Ar: 50 sccm, N ₂ : 90 sccm) of argon (Ar) gas and nitrogen (N ₂ ) gas was introduced. Applying sputter power to the first sputtering target 13, introducing a mixed gas of Ar gas and N ₂ gas from the first gas inlet GA1, and the third gas inlet GA3 and the fourth gas inlet The introduction of the mixed gas of Ar gas and N ₂ gas from (GA4) was continued until the synthetic quartz glass substrate was conveyed to the carrying-out chamber ULL.

Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown), in the direction of the arrow S, is brought into the carry-in chamber LL, the first sputter chamber SP1, the buffer chamber BU, and the second sputter chamber SP2. ) And the transfer chamber (ULL). In addition, the conveyance speed of the synthetic quartz glass substrate was 400 mm / min. When the synthetic quartz glass substrate passes near the first sputtering target 13 of the first sputtering chamber SP1, by reactive sputtering, a molybdenum silicide nitride film with a film thickness of 55.0 nm is formed on the main surface of the synthetic quartz glass substrate. A light-semitransmissive film on the first layer containing (MoSiN) was formed. While the synthetic quartz glass substrate passed through the second sputter chamber SP2, the light semitransmissive film on the first layer was exposed to a mixed gas atmosphere of Ar gas and N ₂ gas.

Subsequently, the synthetic quartz glass substrate mounted on the tray (not shown), in the direction opposite to the arrow S, is taken out (ULL), the second sputter chamber (SP2), the buffer chamber (BU), and the first sputter chamber (SP1) and the transfer chamber LL were sequentially returned, and returned to the transfer chamber LL. While returning the synthetic quartz glass substrate to the loading chamber LL, a mixed gas (Ar: 50 sccm, N ₂ : 90 sccm) of Ar gas and N ₂ gas is introduced from the first gas inlet GA1, and the third A mixed gas (Ar: 50 sccm, N ₂ : 90 sccm) of Ar gas and N ₂ gas is introduced from the gas inlet (GA3) and the fourth gas inlet (GA4), and the light semitransmissive film of the first layer is mixed with Ar gas. It was exposed to a mixed gas atmosphere with N ₂ gas.

Thereafter, application of sputter power to the first sputtering target 13, introduction of a mixture gas of Ar gas and N ₂ gas from the first gas introduction port GA1, and a third gas introduction port GA3 and fourth A mixed gas of Ar gas and N ₂ gas is introduced from the gas inlet (GA4), and a molybdenum silicide nitride film (with a thickness of 55.0 nm) is formed on the first light semitransmissive film by the same method as described above. MoSiN) -containing second-layer light-semitransmissive films were formed, and after the film formation, the second-layer light-semitransmissive films were exposed to a mixed gas atmosphere of Ar gas and N ₂ gas.

In this way, a light semitransmissive film having a total film thickness of 110 nm containing two layers of molybdenum silicide nitride films (MoSiN) 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 conveyed 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 light semitransmissive film on the second layer was exposed to a mixed gas atmosphere of Ar gas and N ₂ gas by the same method as described above.

Next, a light-blocking layer and an anti-reflection layer serving as an etching mask film were formed on the light semitransmissive film. The light-shielding layer and the anti-reflection layer have a second sputtering target 14 and a third sputtering target 15 such that the film surface reflectance for a specific wavelength (for example, g-line) is 15% or less and the optical density OD is 3.0 or more. , Type, flow rate and synthetic quartz of gas introduced into the second gas inlet (GA2), the third gas inlet (GA3), and the fourth gas inlet (4) near the chrome target of the fourth sputtering target (16) The conveyance speed of the glass substrate was adjusted, and the sputter power applied to each sputtering target was appropriately adjusted. A mixed gas of Ar gas and N ₂ gas from the second gas inlet GA2, a mixed gas of Ar gas and methane (CH ₄ ) gas from the third gas inlet GA3, and a fourth gas A mixed gas of Ar gas and nitrogen monoxide (NO) gas was introduced from the introduction port GA4. In addition, application of sputtering power to each sputtering target and introduction of a mixed gas from each gas introduction port continued until synthetic quartz glass was conveyed to the carrying-out chamber ULL. In addition, the conveyance speed of the synthetic quartz glass substrate was 400 mm / min.

As a result, on the light semitransmissive film, a light-shielding layer comprising a laminated film of a chromium nitride film (CrN) with a thickness of 25.0 nm and a chromium carbonitride film (CrCN) with a thickness of 70.0 nm, and a chromium oxide nitride film (CrON) having a film thickness of 20.0 nm ), A laminated film of the antireflection layer was formed.

In this way, on the light semitransmissive film, a light-blocking layer containing a laminated film of CrN and CrCN and an anti-reflective layer containing CrON were sequentially formed to form an etching mask film having a laminated structure.

Thereafter, after the second sputter chamber and the discharge chamber were completely partitioned by a partition plate, the discharge chamber was returned to an atmospheric pressure state, and a synthetic quartz glass substrate on which a light semitransmissive film and an etching mask film were formed was taken out from the sputtering device 11. .

In this way, a phase shift mask blank having a light semitransmissive film and an etching mask film formed on a synthetic quartz glass substrate was obtained.

About the light semitransmissive film of the obtained phase shift mask blank, the transmittance | permeability and phase difference were measured by MPM-100 by Lasertec Japan. For the measurement of transmittance and retardation of the light semitransmissive film, a light semitransmissive film having two layers of molybdenum silicide nitride film (MoSiN) (total film thickness of 110 nm) formed on a main surface of a synthetic quartz glass substrate produced by setting in the same tray was formed. The provided substrate (dummy substrate) was used. The transmittance and phase difference of the light semitransmissive film were measured by taking out the substrate (dummy substrate) provided with the light semitransmissive film from the carrying out chamber ULL before forming the etching mask film. As a result, the transmittance was 5.2% (wavelength: 365 nm) and the phase difference was 180 degrees (wavelength: 365 nm).

In addition, the obtained phase shift mask blank was measured for reflectance and optical density on the film surface by a spectrophotometer Solid Spec-3700 manufactured by Shimadzu Corporation. The phase shift mask blank (etching mask film) had a film surface reflectance of 10.0% (wavelength: 436 nm) and an optical density OD of 4.0 (wavelength: 436 nm). It has been found that this etching mask film functions as a light shielding film having a low reflectance at the film surface.

Further, the obtained phase shift mask blank was analyzed for composition in the depth direction by X-ray photoelectron spectroscopy (XPS). 5 shows the compositional analysis results in the depth direction by XPS for the phase shift mask blank of the first embodiment. The horizontal axis in Fig. 5 represents the sputtering time (minutes), and the vertical axis represents the content (atomic percent). In Fig. 5, curve a shows a change in content of silicon (Si), curve b shows a change in content of nitrogen (N), curve c shows a change in content of oxygen (O), and curve d shows carbon (C). Represents the change in content, curve e represents the change in content of chromium (Cr), and curve f represents the change in content of molybdenum (Mo).

As shown in Fig. 5, in the compositional analysis result in the depth direction by the XPS of the phase shift mask blank, after the appearance of the silicon (Si) peak and the molybdenum (Mo) peak due to the light semitransmissive film, the etching mask film In the composition gradient region P, which is the region until the chromium (Cr) peak due to the disappearance, the content of nitrogen (N) that slows the wet etching rate of the light semitransmissive film is in the depth direction of the light semitransmissive film (of a synthetic quartz glass substrate. Direction) and / or continuously.

In addition, in the composition gradient region P, the content of oxygen was 5 atomic% or less.

In addition, the maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 3.7.

In the composition uniform region Q from the disappearance of the chromium (Cr) peak attributable to the etching mask film to the appearance of the oxygen (O) peak attributable to the synthetic quartz glass substrate, the content of molybdenum (Mo) is an average of 15 atomic% , The content of silicon (Si) was 38 atomic% on average, the content of nitrogen (N) was 45 atomic% on average, the content of oxygen (O) was 2 atomic% or less, and the fluctuation of each content was 5 atomic% or less. .

In the manufacturing method of the phase shift mask blank mentioned above, the light semitransmissive film and the etching mask film were continuously formed in the state which maintained the predetermined vacuum degree. In order to reliably obtain the effects of the present invention, it is preferable to continuously form the light semitransmissive film and the etching mask film while maintaining a predetermined degree of vacuum. By forming the light semitransmissive film and the etching mask film while maintaining a predetermined degree of vacuum, it is possible to reduce variations in composition from the outermost surface of the light semitransmissive film to the synthetic quartz glass substrate.

Further, even if the light semitransmissive film is stored in the air after formation, or even if the light semitransmissive film is cleaned before forming the etching mask film, the same effect as in the first embodiment can be obtained if the composition is changed within a certain range.

B. Phase shift mask and its manufacturing method

In order to manufacture a phase shift mask using the phase shift mask blank manufactured as mentioned above, first, the photoresist film was apply | coated using the resist coating apparatus on the etching mask film of the phase shift mask blank.

Then, a photoresist film having a thickness of 1000 nm was formed through a heating and cooling process.

Thereafter, a photoresist film is drawn using a laser drawing apparatus, and after development and rinsing, a line-and-space pattern resist having a line pattern width of 2.0 µm and a space pattern width of 2.0 µm on the etching mask film. A pattern was formed.

Subsequently, an etching mask film was formed by wet etching the etching mask film with a chromium etching solution containing a second cerium ammonium nitrate and perchloric acid using the resist pattern as a mask.

Then, using the etching mask film pattern as a mask, the light semitransmissive film was wet-etched with a molybdenum silicide etching solution in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide was diluted with pure water to form a light semitransmissive film pattern.

Thereafter, the resist pattern was peeled off.

Thereafter, a photoresist film was applied to cover the etching mask film pattern using a resist coating device.

Then, a photoresist film having a thickness of 1000 nm was formed through a heating and cooling process.

Subsequently, a photoresist film was drawn using a laser writing apparatus, and after development and rinsing, a resist pattern having a line pattern width of 1.0 µm was formed on the etching mask film pattern.

Subsequently, using the resist pattern as a mask, the etching mask film pattern was wet-etched with a chromium etching solution containing ammonium cerium nitrate and perchloric acid to form an etching mask film pattern narrower than the width of the light semitransmissive film pattern.

Thereafter, the resist pattern was peeled off.

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

The plane and cross section of the obtained phase shift mask were observed with a scanning electron microscope. In the following examples and comparative examples, a scanning electron microscope was used for observation of the plane and cross-section of the phase shift mask. 6 is a top view of the phase shift mask of the first embodiment. 7 is a cross-sectional photograph of the phase shift mask of the first embodiment. 6 and 7, QZ represents a synthetic quartz glass substrate, PS represents a light semitransmissive film pattern, and Cr represents an etching mask film pattern.

As shown in FIG. 7, the cross-section of the light semitransmissive film pattern PS was dragged at the bottom of the portion in contact with the synthetic quartz glass substrate QZ, and almost vertical in the portion in contact with the etching mask film pattern Cr.

Specifically, the cross section of the light semitransmissive film pattern PS includes upper, lower and side sides 23 corresponding to the top, bottom, and side surfaces of the light semitransmissive film pattern PS. The auxiliary line 21 represents the position of the upper side corresponding to the upper surface of the light semitransmissive film pattern PS, and the auxiliary line 22 represents the position of the lower side corresponding to the lower surface of the light semitransmissive film pattern PS.

The angle θ between the straight line connecting the contact point 26 between the upper side and the lateral side and the position 27 of the lateral side at a height of 2/3 of the film thickness from the upper surface and the upper side was 105 degrees. The auxiliary line 24 represents the position of the height of two-thirds of the film thickness from the top surface.

In addition, at the position of the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ through the contact 26 between the upper side and the lateral side 23 and a height raised by one tenth of the film thickness from the lower surface. The width with the second virtual line perpendicular to the main surface of the synthetic quartz glass substrate QZ through the position of the side was 44 nm.

As described above, the cross-sectional shape of the light-semitransmissive film pattern has a good angle of θ of 105 degrees and a width of 44 nm (one-half to 2.5 of the film thickness of the light-semitransmissive film) of 300 nm to 500 nm. In exposure light containing light in the wavelength range of, more specifically, exposure light of composite light including i-line, h-line and g-line, has a phase shift effect equivalent to PSM (A) shown in Table 1 above. A phase shift mask was obtained.

The CD deviation of the light semitransmissive film pattern of the phase shift mask was measured by SIR8000 manufactured by Seiko Instruments Nano Technology. The CD deviation was measured at a point of 5 × 5 for an area of 270 mm × 390 mm excluding the peripheral region of the substrate. The CD deviation is the deviation width from the target line and space pattern (width of the line pattern: 2.0 µm, width of the space pattern: 2.0 µm). In the following Examples and Comparative Examples, the same apparatus was used for the measurement of CD deviation.

The CD deviation was good at 0.096 μm. As shown in Fig. 6, the edge E of the light semitransmissive film pattern PS is linear, suggesting that the CD deviation is good.

<Second Example>

In the second embodiment, a case where the light semitransmissive film includes a four-layer molybdenum silicide nitride film (MoSiN) will be described.

A. Phase shift mask blank and manufacturing method thereof

In the production of the phase shift mask blank of the second embodiment, a 3345 size synthetic quartz glass substrate was used as the transparent substrate 12.

By the same method as in the first embodiment, the synthetic quartz glass substrate was carried into the delivery chamber LL of the inline sputtering apparatus 11 shown in FIG. 4. As the first sputtering target 13, the second sputtering target 14, the third sputtering target 15, and the fourth sputtering target 16, the same sputtering target as in the first embodiment was used.

Thereafter, the inside of the sputtering apparatus 11 was set to a predetermined vacuum degree by the same method as in the first embodiment. Exhaust continued until the synthetic quartz glass substrate was taken out from the sputtering device 11.

Thereafter, a mixed gas of Ar gas and N ₂ gas (Ar: 30sccm, N ₂ : 30sccm) from the first gas inlet GA1 disposed near the first sputtering target 13 of the first sputter chamber SP1. ) Was introduced, and sputter power of 4.0 kW was applied to the first sputtering target 13. In addition, from the third gas inlet GA3 disposed near the third sputtering target 15 of the second sputtering chamber SP2 and the fourth gas inlet GA4 disposed near the fourth sputtering target 16. A mixed gas (Ar: 30 sccm, N ₂ : 30 sccm) of Ar gas and N ₂ gas was introduced. Application of sputter power to the first sputtering target 13, introduction of a mixed gas of Ar gas and N ₂ gas from the first gas inlet GA12 and third gas inlet GA3 and fourth gas inlet The introduction of the mixed gas of Ar gas and N ₂ gas from (GA4) was continued until the synthetic quartz glass substrate was conveyed to the carrying-out chamber ULL.

Then, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed to the carrying-out chamber ULL in the direction of the arrow S. In addition, the conveyance speed of the synthetic quartz glass substrate was 400 mm / min. When the synthetic quartz glass substrate passes near the first sputtering target 13 of the first sputtering chamber SP1, by reactive sputtering, a molybdenum silicide nitride film having a film thickness of 27.5 nm is formed on the main surface of the synthetic quartz glass substrate. A light-semitransmissive film on the first layer containing (MoSiN) was formed. While the synthetic quartz glass substrate passed through the second sputter chamber SP2, the light semitransmissive film on the first layer was exposed to a mixed gas atmosphere of Ar gas and N ₂ gas.

Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed 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 loading chamber LL, a mixed gas (Ar: 30 sccm, N ₂ : 30 sccm) of Ar gas and N ₂ gas is introduced from the first gas inlet GA1, and the third A mixed gas (Ar: 30 sccm, N ₂ : 30 sccm) of Ar gas and N ₂ gas is introduced from the gas inlet (GA3), and the light semitransmissive film of the first layer is introduced into a mixed gas atmosphere of Ar gas and N ₂ gas. Exposed.

Subsequently, the second-layer, third-layer, and fourth-layer light-semitransmissive films were formed by the same method as the first-layer light-semitransmissive films. After the formation of the second, third, and fourth light semitransmissive films, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed 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-, third-, and fourth-layer light semitransmissive films are exposed to a mixed gas atmosphere of Ar gas and N ₂ gas by the same method as described above. Ordered.

In this way, on the main surface of the synthetic quartz glass substrate, a light semitransmissive film having a total film thickness of 110 nm including four layers of molybdenum silicide nitride films (MoSiN) was formed.

Then, an etching mask film was formed on the light semitransmissive film by the same method as in the first embodiment, and a phase shift mask blank was formed on the synthetic quartz glass substrate, on which the light semitransmissive film and the etching mask film were formed.

Similar to the first embodiment, compositional analysis in the depth direction by XPS was performed on the obtained phase shift mask blank. As a result, in the composition gradient region P, the content of nitrogen (N), which slows wet etching of the light semitransmissive film, was continuously increasing toward the depth direction of the light semitransmissive film (in the direction of the synthetic quartz glass substrate).

In addition, the maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 3.6.

B. Phase shift mask and its manufacturing method

Using the phase shift mask blank prepared as described above, an etching mask film pattern and a light semitransmissive film pattern were formed in the same manner as in the first embodiment.

After formation of the light semitransmissive film pattern, the resist pattern was peeled off. Thereafter, the etching mask film pattern was removed with a chromium etchant containing cupric ammonium nitrate and perchloric acid.

In this way, a phase shift mask having a light semitransmissive film pattern formed on a synthetic quartz glass substrate was obtained.

8 is a cross-sectional photograph of the phase shift mask of the second embodiment. In Fig. 8, QZ represents a synthetic quartz glass substrate, and PS represents a light semitransmissive film pattern.

As shown in Fig. 8, the cross section of the light semitransmissive film pattern PS was drawn at a lower end in a portion in contact with the synthetic quartz glass substrate QZ, and almost vertical in a portion in contact with the etching mask film pattern.

Specifically, the cross section of the light semitransmissive film pattern PS includes upper, lower and side sides 23 corresponding to the top, bottom, and side surfaces of the light semitransmissive film pattern PS. The auxiliary line 21 represents the position of the upper side corresponding to the upper surface of the light semitransmissive film pattern PS, and the auxiliary line 22 represents the position of the lower side corresponding to the lower surface of the light semitransmissive film pattern PS.

The angle between the straight line connecting the contact point 26 at the height of the contact point 26 between the upper side and the lateral side and the upper side of the film thickness of 2/3 of the film thickness was 105 degrees.

In addition, the first virtual line 29 perpendicular to the main surface of the synthetic quartz glass substrate QZ through the contact 26 between the upper side and the side 23 is raised by a tenth of the film thickness from the lower surface. The width D of the second virtual line 30 perpendicular to the main surface of the synthetic quartz glass substrate QZ through the position 28 on the side at the position of was 48 nm. The auxiliary line 25 indicates a position at a height of tenths of the film thickness from the lower surface.

As described above, the cross-sectional shape of the light semitransmissive film pattern has a good angle of θ of 105 degrees and a width of 48 nm (approximately one-third of 2.3 with respect to the thickness of the light semitransmissive film of about 110 nm), 300 nm to 500 nm The phase shift effect equivalent to that of PSM (B) shown in Table 2 above is obtained in exposure light of exposure light including light in the following wavelength range, and more specifically, composite light including i-line, h-line and g-line. The phase shift mask to have was obtained.

<Third Example>

In the third embodiment, a case in which the light semitransmissive film includes a molybdenum silicide nitride film (MoSiN) of one layer will be described.

A. Phase shift mask blank and manufacturing method thereof

In the production of the phase shift mask blank of the third embodiment, as the transparent substrate 12, a synthetic quartz glass substrate having the same size of 3345 as the first and second embodiments described above was used.

By the same method as in the first embodiment, the synthetic quartz glass substrate was carried into the delivery chamber LL of the inline sputtering apparatus 11 shown in FIG. 4. As the first sputtering target 13, the second sputtering target 14, the third sputtering target 15, and the fourth sputtering target 16, the same sputtering target material as the first embodiment was used.

Sputter power of 10.0 kW was applied to the first sputtering target 13 of the first sputter chamber SP1. Further, a mixed gas (Ar: 50.0 sccm, N ₂ : 100.0 sccm) of Ar gas and N ₂ gas was introduced from the first gas introduction port GA1 disposed near the first sputtering target 13. In addition, from the third gas inlet GA3 disposed near the third sputtering target 15 of the second sputtering chamber SP2 and the fourth gas inlet GA4 disposed near the fourth sputtering target 16. A mixed gas (Ar: 50.0 sccm, N ₂ : 100.0 sccm) of Ar gas and N ₂ gas was introduced. Application of sputter power to the first sputtering target 13, introduction of a mixture gas of Ar gas and N ₂ gas from the first gas inlet GA1, and third gas inlet GA3 and fourth gas inlet The introduction of the mixed gas of Ar gas and N ₂ gas from (GA4) was continued until the synthetic quartz glass substrate was conveyed to the carrying-out chamber ULL.

Then, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed to the carrying-out chamber ULL in the direction of the arrow S. In addition, the conveyance speed of the synthetic quartz glass substrate was 350 mm / min. When the synthetic quartz glass substrate passes around the first sputtering target 13 of the first sputter chamber SP1, by reactive sputtering, a molybdenum silicide nitride film having a thickness of 110 nm is formed on the main surface of the synthetic quartz glass substrate. A light semitransmissive film containing (MoSiN) was formed. While the synthetic quartz glass substrate passed through the second sputter chamber SP2, the light semitransmissive film was exposed to a mixed gas atmosphere of Ar gas and N ₂ gas.

In this way, on the main surface of the synthetic quartz glass substrate, a light semitransmissive film having a thickness of 110 nm including a one-layer molybdenum silicide nitride film (MoSiN) was formed.

Thereafter, after the second sputtering chamber SP2 and the carrying-out chamber ULL are completely partitioned by a partition plate, the carrying-out chamber ULL is returned to the atmospheric pressure state, thereby sputtering the synthetic quartz glass substrate on which the light semitransmissive film is formed ( 11).

Thereafter, the synthetic quartz glass substrate on which the light semitransmissive film was formed was stored in the air for about 2 days.

Subsequently, the synthetic quartz glass substrate on which the light semitransmissive film was formed was carried into the delivery chamber LL of the inline sputtering apparatus 11 shown in FIG. 4.

Then, an etching mask film was formed on the light semitransmissive film by the same method as in the first embodiment, and a phase shift mask blank was formed on the synthetic quartz glass substrate, on which the light semitransmissive film and the etching mask film were formed.

Similar to the first embodiment, compositional analysis in the depth direction by XPS was performed on the obtained phase shift mask blank. As a result, in the composition gradient region P, the content of nitrogen (N), which slows wet etching of the light semitransmissive film, was continuously increasing toward the depth direction of the light semitransmissive film (in the direction of the synthetic quartz glass substrate).

In addition, the maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 8.2.

B. Phase shift mask and its manufacturing method

Using the phase shift mask blank produced as described above, a phase shift mask was produced in the same manner as in the first embodiment.

9 is a cross-sectional photograph of the phase shift mask of the third embodiment. In Fig. 9, QZ represents a synthetic quartz glass substrate, PS represents a light semitransmissive film pattern, and Cr represents an etching mask film pattern. Fig. 9 shows a cross-sectional photograph in a state before forming an etching mask film pattern narrower than the width of the light semitransmissive film pattern.

As shown in Fig. 9, the cross section of the light semitransmissive film pattern PS was dragged at the lower end in the portion in contact with the synthetic quartz glass substrate QZ, and almost vertical in the portion in contact with the etching mask film pattern Cr.

Specifically, the cross section of the light semitransmissive film pattern PS includes upper sides, lower sides and side sides corresponding to the top, bottom, and side surfaces of the light semitransmissive layer pattern PS.

The angle between the straight line connecting the position of the lateral side at the position of the height of the contact point between the upper side and the lateral side and the height down two-thirds of the film thickness from the upper surface, and the angle between the upper side and the upper side were 97 degrees.

In addition, it is synthesized through the first virtual line perpendicular to the main surface of the synthetic quartz glass substrate (QZ) through the contact point between the upper side and the side, and the position of the side at a height of one tenth of the film thickness from the bottom. The width with the second virtual line perpendicular to the main surface of the quartz glass substrate QZ was 20 nm.

In addition, the CD deviation was good at 0.098 µm.

As described above, in the cross-sectional shape of the light semitransmissive film pattern, the angle θ is 97 degrees and the width is good at 20 nm (1 / 5.5 of the film thickness of the light semitransmissive film is 1 / 5.5), 300 nm or more and 500 nm or less In the exposure light containing light in the wavelength range of, more specifically, the exposure light of the composite light containing i-line, h-line and g-line, has a phase shift effect equivalent to that of PSM (A) shown in Table 1 above. A phase shift mask was obtained.

<Fourth Example>

In the third embodiment, the synthetic quartz glass substrate on which the light semitransmissive film was formed was stored in the air for about 2 days.

In contrast, in the fourth embodiment, the synthetic quartz glass substrate on which the light semitransmissive film was formed was stored in the air for one week. Except for that, a phase shift mask blank and a phase shift mask were produced in the same manner as in the third embodiment.

Similar to the first embodiment, the compositional analysis of the obtained phase shift mask blank in the depth direction by XPS was performed. As a result, in the composition gradient region P, the content of nitrogen (N) that slows wet etching of the light semitransmissive film. It was continuously increasing toward the depth direction (the direction of the synthetic quartz glass substrate) of the light semitransmissive film.

In addition, the maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 3.2.

10 is a cross-sectional photograph of the phase shift mask of the fourth embodiment. In Fig. 10, QZ represents a synthetic quartz glass substrate, PS represents a light semitransmissive film pattern, and Cr represents an etching mask film pattern. Fig. 10 shows a cross-sectional photograph in a state before forming an etching mask film pattern narrower than the width of the light semitransmissive film pattern.

As shown in Fig. 10, the cross section of the light semitransmissive film pattern PS was a straight tapered shape.

Specifically, the cross section of the light semitransmissive film pattern PS includes upper sides, lower sides and side sides corresponding to the top, bottom, and side surfaces of the light semitransmissive layer pattern PS.

The angle formed by the straight line connecting the contact point between the upper side and the side edge and the position of the side edge at a height of two-thirds of the thickness of the film from the top surface, and the upper edge was 120 degrees.

In addition, it is synthesized through the first virtual line perpendicular to the main surface of the synthetic quartz glass substrate (QZ) through the contact point between the upper side and the side, and the position of the side at a height of one tenth of the film thickness from the bottom. The width with the second virtual line perpendicular to the main surface of the quartz glass substrate QZ was 42 nm.

In addition, the CD deviation was good at 0.105 μm.

As described above, the cross-sectional shape of the light semitransmissive film pattern has a good angle of θ of 120 degrees and a width of 42 nm (approximately 1 / 2.6 of the thickness of the light semitransmissive film of about 110 nm), 300 nm to 500 nm The phase shift effect equivalent to that of PSM (A) shown in Table 1 above is obtained in exposure light of the exposure light including light in the following wavelength range, and more specifically, composite light including i-line, h-line and g-line. The phase shift mask to have was obtained.

From the fourth example, it has been found that even if the light semitransmissive film is stored in the air for about a week, it is possible to maintain good CD deviation if the composition changes within a certain range.

<Example 5>

In the fifth embodiment, a case in which an insulating layer is formed on a light semitransmissive film will be described.

A. Phase shift mask blank and manufacturing method thereof

In the production of the phase shift mask blank of the fifth embodiment, a 3345 size synthetic quartz glass substrate was used as the transparent substrate 12.

In the same manner as in the first embodiment, a light semitransmissive film 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 conveyed 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 light semitransmissive film on the second layer was exposed to a mixed gas atmosphere of Ar gas and N ₂ gas by the same method as described above.

Thereafter, a mixed gas of Ar gas, N ₂ gas and CO ₂ gas (Ar: 55 sccm) from the _second gas inlet GA2 disposed near the second sputtering target 14 of the first sputter chamber SP1. N ₂ : 60 sccm, CO ₂ : 35 sccm) was introduced, and sputter power of 5.0 kW was applied to the second sputtering target 14. The application of sputter power to the second sputtering target 14 and the introduction of a mixed gas of Ar gas, N ₂ gas, and CO ₂ gas from the second gas inlet GA2 allow the synthetic quartz glass substrate to be carried out. ).

Then, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed to the carrying-out chamber ULL in the direction of the arrow S. In addition, the conveyance speed of the synthetic quartz glass substrate was 400 mm / min. When the synthetic quartz glass substrate passes around the second sputtering target 14 of the first sputtering chamber SP1, by reactive sputtering, a chromium oxynitride carbide film (CrCON) having a thickness of 200 nm is formed on the light semitransmissive film. An insulating layer containing) was formed.

Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed in the direction opposite to the arrow S, and returned to the carry-in chamber LL.

Thereafter, in the same manner as in the first embodiment, on the insulating layer, a laminated film of a light-blocking layer containing a chromium carbonitride film (CrCN) and an antireflective layer containing a chromium oxide nitride film (CrON) was formed.

In this way, on the light semitransmissive film, an etching mask film having a laminated structure in which an insulating layer containing CrCON, a light blocking layer containing CrCN, and an antireflection layer containing CrON were sequentially formed was formed.

Thereafter, after the second sputter chamber and the discharge chamber were completely partitioned by a partition plate, the discharge chamber was returned to an atmospheric pressure state, and a synthetic quartz glass substrate on which a light semitransmissive film and an etching mask film were formed was taken out from the sputtering device 11. .

In this way, a phase shift mask blank having a light semitransmissive film and an etching mask film formed on a synthetic quartz glass substrate was obtained.

Similar to the first embodiment, compositional analysis in the depth direction by XPS was performed on the obtained phase shift mask blank. As a result, in the composition gradient region P, the content of nitrogen (N), which slows wet etching of the light semitransmissive film, was continuously increasing toward the depth direction of the light semitransmissive film (in the direction of the synthetic quartz glass substrate).

In addition, the maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 3.7.

B. Phase shift mask and its manufacturing method

Using the phase shift mask blank produced as described above, a phase shift mask was produced in the same manner as in the first embodiment.

The cross section of the obtained phase shift mask was observed.

As in the first embodiment, the cross section of the light semitransmissive film pattern was drawn at a lower end in a portion in contact with the synthetic quartz glass substrate, and almost vertical in a portion in contact with the etching mask film pattern.

Specifically, the cross section of the light semitransmissive film pattern includes upper, lower and side sides corresponding to the upper, lower and side surfaces of the light semitransmissive film pattern.

The angle formed by the straight line connecting the position of the lateral side at the position of the height of the contact point between the upper side and the lateral side and the height of two-thirds the thickness of the film from the upper surface, and the angle between the upper side and the upper side were 105 degrees.

Further, the synthetic quartz glass substrate through the first virtual line perpendicular to the main surface of the synthetic quartz glass substrate through the contact point between the upper side and the side edge, and the position of the side edge at a height of one tenth of the film thickness from the lower surface. The width of the second virtual line perpendicular to the main surface of was 44 nm.

In addition, the angle of the light semitransmissive film pattern in contact with the synthetic quartz glass substrate was 60 degrees, and the angle of the light semitransmissive film pattern in contact with the etching mask film pattern was 75 degrees.

In addition, the CD deviation was very good at 0.060 µm.

As described above, the cross-sectional shape of the light-semitransmissive film pattern has a good angle of θ of 105 degrees and a width of 44 nm (one-half to 2.5 of the film thickness of the light-semitransmissive film) of 300 nm to 500 nm. In exposure light containing light in the wavelength range of, more specifically, exposure light of composite light including i-line, h-line and g-line, has a phase shift effect equivalent to PSM (A) shown in Table 1 above. A phase shift mask was obtained.

<First Reference Example>

In the first reference example, a case where the surface of the light semitransmissive film is not exposed to a gas atmosphere containing N ₂ after the light semitransmissive film is formed will be described.

A. Phase shift mask blank and manufacturing method thereof

In the production of the phase shift mask blank of the first reference example, a 3345 size synthetic quartz glass substrate was used as the transparent substrate 12.

By the same method as in the first embodiment, the synthetic quartz glass substrate was carried into the delivery chamber LL of the inline sputtering apparatus 11 shown in FIG. 4. As the first sputtering target 13, the second sputtering target 14, the third sputtering target 15, and the fourth sputtering target 16, the same sputtering target as in the first embodiment was used.

A mixed gas (Ar: 40 sccm, N ₂ : 90 sccm) of Ar gas and N ₂ gas is introduced from the first gas introduction port GA1 disposed near the first sputtering target 13 of the first sputter chamber SP1. Then, sputtering power of 8.5 kW was applied to the first sputtering target 13. In addition, from the third gas inlet GA3 disposed near the third sputtering target 15 of the second sputtering chamber SP2 and the fourth gas inlet GA4 disposed near the fourth sputtering target 16. Ar gas (130 sccm) was introduced. Application of sputter power to the first sputtering target 13, introduction of a mixture gas of Ar gas and N ₂ gas from the first gas inlet GA1, and third gas inlet GA3 and fourth gas inlet The introduction of Ar gas from (GA4) was continued until the synthetic quartz glass substrate was conveyed to the carrying out chamber ULL.

Then, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed to the carrying-out chamber ULL in the direction of the arrow S. In addition, the conveyance speed of the synthetic quartz glass substrate was 400 mm / min. When the synthetic quartz glass substrate passes near the first sputtering target 13 of the first sputtering chamber SP1, by reactive sputtering, a molybdenum silicide nitride film with a film thickness of 55.0 nm is formed on the main surface of the synthetic quartz glass substrate. A light-semitransmissive film on the first layer containing (MoSiN) was formed. While the synthetic quartz glass substrate passed through the second sputter chamber SP2, the light semitransmissive film of the first layer was exposed to an Ar gas atmosphere.

Thereafter, the synthetic quartz glass substrate mounted on the tray (not shown) was conveyed 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 formed first-layer light semitransmissive film was in a vacuum.

Subsequently, a light semitransmissive film of the second layer was formed by the same method as the light semitransmissive film of the first layer.

In this way, a light semitransmissive film having a total film thickness of 110 nm containing two layers of molybdenum silicide nitride films (MoSiN) 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 conveyed 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 formed second-layer light semitransmissive film was in a vacuum.

Then, an etching mask film was formed on the light semitransmissive film by the same method as in the first embodiment, and a phase shift mask blank was formed on the synthetic quartz glass substrate, on which the light semitransmissive film and the etching mask film were formed.

The obtained phase shift mask blank was analyzed for composition in the depth direction by XPS. As a result, in the vicinity of the center of each thickness direction of the two layers constituting the light semitransmissive film, the content of nitrogen (N) was 46-47 atomic%. On the other hand, in the vicinity of the interface of the two layers, the content of nitrogen (N) was 44 atomic%. A difference in the content of nitrogen (N) of 2-3 atomic% is seen between the vicinity of the center of each layer and the interface between the two layers. This difference is a slight difference as it approaches the detection limit, but after the light-semitransmissive film is formed, it passes through an Ar gas atmosphere, and then passes through a vacuum atmosphere while returning the tray to the LL chamber in full. It is assumed that nitrogen has escaped from the surface. Moreover, when the light semitransmissive film of the 2nd layer was formed, the content of nitrogen (N) became small in the vicinity of the interface between the 1st and 2nd layers. Further, in the composition inclined region P, the content of nitrogen (N), which slows wet etching of the light semitransmissive film, was continuously increasing toward the depth direction of the light semitransmissive film (in the direction of the synthetic quartz glass substrate).

B. Phase shift mask and its manufacturing method

Using the phase shift mask blank produced as described above, a phase shift mask was produced in the same manner as in the first embodiment.

11 is a plan view of the phase shift mask of the first reference example. 12 is a cross-sectional photograph of the phase shift mask of the first reference example. 11 and 12, QZ represents a synthetic quartz glass substrate, PS represents a light semitransmissive film pattern, and Cr represents an etching mask film pattern. Fig. 12 shows a cross-sectional photograph in a state before forming an etching mask film pattern narrower than the width of the light semitransmissive film pattern.

As shown in Fig. 12, a large bit was generated at the interface between the light semitransmissive film pattern on the first layer and the light semitransmissive film pattern on the second layer. As described above, near the interface between the light semitransmissive film on the first layer and the light semitransmissive film on the second layer, the content of nitrogen (N) is low. It is thought that the bite occurred because the vicinity of the interface with a small nitrogen content was etched faster.

Specifically, the cross section of the light semitransmissive film pattern PS includes upper sides, lower sides and side sides corresponding to the top, bottom, and side surfaces of the light semitransmissive layer pattern PS.

The angle formed by the straight line connecting the position of the lateral side at the position at a height of two-thirds of the thickness of the film from the contact point between the upper side and the lateral side was 80 degrees.

In addition, it is synthesized through the first virtual line perpendicular to the main surface of the synthetic quartz glass substrate (QZ) through the contact point between the upper side and the side, and the position of the side at a height of one tenth of the film thickness from the bottom. The width with the second virtual line perpendicular to the main surface of the quartz glass substrate QZ was 45 nm.

In addition, the CD deviation was 0.252 µm. As shown in Fig. 11, it is suggested that the edge E1 of the light semitransmissive film pattern PS is rough and the CD deviation is large. When the edge E1 of the light semitransmissive film pattern PS is rough, the edge E2 of the etching mask film pattern Cr is also rough. This is considered to be because, when forming the etching mask film pattern Cr, the etching solution enters along the shape of the edge E1 of the light semitransmissive film pattern PS. In order to control the shape of the etching mask film pattern Cr, the shape of the light semitransmissive film pattern PS is also important.

From the first reference example, when the light-semitransmissive film is repeatedly formed a plurality of times to form a light-semitransmissive film including a plurality of layers, between the film and the film, the light spot is in an N ₂ gas atmosphere having a component that slows the wet etching rate. When the transparent film was not exposed, it was found that the light semitransmissive film including a plurality of layers occurred at the interface between two adjacent layers. When the N ₂ gas is not contained in the gas atmosphere exposed after the film formation, it is presumed that the composition of the light semitransmissive film changes minutely by forming a small amount of nitrogen from the surface of the light semitransmissive film, and an easily etched portion is formed at this interface.

<Second Reference Example>

In the third embodiment, when forming the light semitransmissive film, a mixed gas of Ar gas and N ₂ gas is introduced from the third gas inlet GA3 and the fourth gas inlet GA4 of the second sputter chamber SP2. Did.

In contrast, in the second reference example, when forming the light semitransmissive film, no gas was introduced from the third gas inlet GA3 and the fourth gas inlet GA4 of the second sputter chamber SP2. Except for that, a phase shift mask blank and a phase shift mask were produced in the same manner as in the third embodiment.

Similar to the first embodiment, compositional analysis in the depth direction by XPS was performed on the obtained phase shift mask blank. As a result, in the composition inclined region P, the content of nitrogen (N), which slows wet etching of the light semitransmissive film, was gradually increased toward the depth direction of the light semitransmissive film (in the direction of the synthetic quartz glass substrate), but the composition inclined area The maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in P was 2.4.

13 is a cross-sectional photograph of the phase shift mask of the second reference example. In Fig. 13, QZ represents a synthetic quartz glass substrate, PS represents a light semitransmissive film pattern, and Cr represents an etching mask film pattern. 13 shows a cross-sectional photograph in a state before forming the light semitransmissive film pattern and before peeling the resist pattern.

As shown in Fig. 13, the cross section of the light semitransmissive film pattern PS was a straight tapered shape.

Specifically, the cross section of the light semitransmissive film pattern PS includes upper sides, lower sides and side sides corresponding to the top, bottom, and side surfaces of the light semitransmissive layer pattern PS.

The angle formed by the straight line connecting the contact point between the upper side and the side edge and the position of the side edge at a height of 2/3 of the thickness of the film from the top surface, and the upper edge was 135 degrees.

In addition, it is synthesized through the first virtual line perpendicular to the main surface of the synthetic quartz glass substrate (QZ) through the contact point between the upper side and the side, and the position of the side at a height of one tenth of the film thickness from the bottom. The width of the second virtual line perpendicular to the main surface of the quartz glass substrate QZ was 85 nm.

As described above, the cross-sectional shape of the light semitransmissive film pattern was tapered with the angle θ of 135 degrees and the width of 85 nm (approximately one-third with respect to the film thickness of the light semitransmissive film of 110 nm). Therefore, in the obtained phase shift mask, in the exposure light containing light in a wavelength range of 300 nm or more and 500 nm or less, and more specifically, in the exposure light of composite light containing i-line, h-line and g-line, the above table Until the phase shift effect equivalent to PSM (A) shown in 1 is not obtained.

<Example 3 Reference>

In the third embodiment, when forming the light semitransmissive film, a mixed gas of Ar gas and N ₂ gas was introduced from the gas inlet GA3 and the gas inlet GA4 of the second sputter chamber SP2.

In contrast, in the third reference example, when forming the light semitransmissive film, only Ar gas (150 sccm) was introduced from the third gas inlet GA3 and the fourth gas inlet GA4 of the second sputter chamber SP2. Except for that, a phase shift mask blank and a phase shift mask were produced in the same manner as in the third embodiment.

Similar to the first embodiment, compositional analysis in the depth direction by XPS was performed on the obtained phase shift mask blank. As a result, in the composition inclined region P, the content of nitrogen (N), which slows wet etching of the light semitransmissive film, was gradually increased toward the depth direction of the light semitransmissive film (in the direction of the synthetic quartz glass substrate), but the composition inclined area The maximum value of the ratio of nitrogen (N) to silicon (Si) in P was 2.6.

14 is a cross-sectional photograph of the phase shift mask of the third reference example. In Fig. 14, QZ represents a synthetic quartz glass substrate, PS represents a light semitransmissive film pattern, and Cr represents an etching mask film pattern. 14 shows a cross-sectional photograph in a state before wet etching the etching mask film pattern to form an etching mask film pattern narrower than the width of the light semitransmissive film pattern.

As shown in Fig. 14, the cross section of the light semitransmissive film pattern PS was a straight tapered shape.

Specifically, the cross section of the light semitransmissive film pattern PS includes upper sides, lower sides and side sides corresponding to the top, bottom, and side surfaces of the light semitransmissive layer pattern PS.

The angle formed by the straight line connecting the contact point between the upper side and the side edge and the position of the side edge at a height of 2/3 of the thickness of the film from the top surface, and the upper edge was 135 degrees.

In addition, it is synthesized through the first virtual line perpendicular to the main surface of the synthetic quartz glass substrate (QZ) through the contact point between the upper side and the side, and the position of the side at a height of one tenth of the film thickness from the bottom. The width with the second virtual line perpendicular to the main surface of the quartz glass substrate QZ was 89 nm.

As described above, the cross-sectional shape of the light semitransmissive film pattern was tapered at an angle of θ of 135 degrees and the width of 89 nm (approximately 1 / 1.2 of the film thickness of the light semitransmissive film of 110 nm). Therefore, in the obtained phase shift mask, in the exposure light containing light in a wavelength range of 300 nm or more and 500 nm or less, and more specifically, in the exposure light of composite light containing i-line, h-line and g-line, the above table Until the phase shift effect equivalent to PSM (A) shown in 1 is not obtained.

<First Comparative Example>

In the third embodiment, when the light semitransmissive film is formed, a mixed gas of Ar gas and N ₂ gas (Ar: 50.0 sccm, N ₂ : 100.0 sccm) from the first gas inlet (GA1) of the first sputter chamber (SP1) ) Is introduced, and a mixed gas (Ar: 50.0sccm, N ₂ ) of Ar gas and N ₂ gas from the third gas inlet GA3 and the fourth gas inlet GA4 of the second sputter chamber SP2: 100.0 sccm) was introduced. Further, a sputter power of 10.0 mW was applied to the first sputtering target 13 of the first sputter chamber SP1. In addition, the conveyance speed of the synthetic quartz glass substrate was 350 mm / min. In addition, the film thickness of the light semitransmissive film was 110 nm.

In contrast, in the first comparative example, a mixed gas (Ar: 65 sccm, N ₂ : 50 sccm) of Ar gas and N ₂ gas is introduced from the first gas inlet GA1 of the first sputter chamber SP1, Ar gas (120 sccm) was introduced from the third gas inlet GA3 and the fourth gas inlet GA4 of the second sputter chamber SP2. In addition, 6.3 kW of sputter power was applied to the first sputtering target 13 of the first sputter chamber SP1. In addition, the conveyance speed of the synthetic quartz glass substrate was 200 mm / min. Further, the film thickness of the light semitransmissive film was 115 nm. Moreover, after forming the light semitransmissive film, the surface of the light semitransmissive film was washed with ozone water. Except for that, a phase shift mask blank and a phase shift mask were produced in the same manner as in the third embodiment.

Similar to the first embodiment, compositional analysis in the depth direction by XPS was performed on the obtained phase shift mask blank. As a result, in the composition inclined region P, there existed a region in which the content of nitrogen (N), which slowed wet etching of the light semitransmissive film, was decreased toward the depth direction (the direction of the synthetic quartz glass substrate) of the light semitransmissive film.

In addition, the maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 2.0.

15 is a cross-sectional photograph of the phase shift mask of the first comparative example. In Fig. 15, QZ represents a synthetic quartz glass substrate, PS represents a light semitransmissive film pattern, and Cr represents an etching mask film pattern. 15 shows a cross-sectional photograph in a state before forming an etching mask film pattern narrower than the width of the light semitransmissive film pattern.

As shown in Fig. 15, the cross section of the light semitransmissive film pattern PS was a straight tapered shape.

Specifically, the cross section of the light semitransmissive film pattern PS includes upper sides, lower sides and side sides corresponding to the top, bottom, and side surfaces of the light semitransmissive layer pattern PS.

The angle formed by the straight line connecting the position of the lateral side at the position of the height of the contact point between the upper side and the lateral side and the height down two-thirds of the film thickness from the upper surface, and the angle between the upper side and the upper side were 160 degrees.

In addition, it is synthesized through the first virtual line perpendicular to the main surface of the synthetic quartz glass substrate (QZ) through the contact point between the upper side and the side, and the position of the side at a height of one tenth of the film thickness from the bottom. The width of the second virtual line perpendicular to the main surface of the quartz glass substrate QZ was 295 nm.

In addition, the angle of the light semitransmissive film pattern PS in contact with the synthetic quartz glass substrate QZ is 15 degrees, and the position of the side edge at the position of the contact point between the top side and the side edge and the height of two-thirds of the film thickness from the top side. The angle formed between the straight line connecting and the upper edge was 160 degrees.

In addition, it is synthesized through the first virtual line perpendicular to the main surface of the synthetic quartz glass substrate (QZ) through the contact point of the upper side and the side T, and the position of the side edge at a height of one tenth of the thickness of the film from the bottom surface. The width of the second virtual line perpendicular to the main surface of the quartz glass substrate QZ was 295 nm.

In addition, the angle of the light semitransmissive film pattern PS contacting the synthetic quartz glass substrate QZ was 15 degrees, and the angle of the light semitransmissive film pattern PS contacting the etching mask film pattern Cr was 165 degrees. Since the conveyance speed of the synthetic quartz glass substrate was slow and the exposure time to the Ar atmosphere was long after the light-semitransmissive film was formed, the nitrogen concentration at the interface between the light-semitransmissive film and the etching mask film was considered to be larger, resulting in a larger bite.

As described above, the cross-sectional shape of the light semitransmissive film pattern has a taper shape with a large angle of θ of 165 degrees and a width of 295 nm (approximately 3 times of 110 nm of the light semitransmissive film). Therefore, in the obtained phase shift mask, in the exposure light containing light in a wavelength range of 300 nm or more and 500 nm or less, and more specifically, in the exposure light of composite light containing i-line, h-line and g-line, the above table Only the phase shift effect equivalent to PSMTP (A) shown in 1 is obtained.

Further, the CD deviation was 0.230 µm.

Further, in the above-described embodiment, an example in which a molybdenum silicide nitride film is formed and then exposed under a mixed gas atmosphere of Ar gas and N ₂ gas has been described, but the same effect can be obtained even when exposed under an N ₂ gas atmosphere. Further, instead of nitrogen gas, even gas containing nitrogen compounds such as nitrogen monoxide gas, dinitrogen monoxide gas, and nitrogen dioxide gas exerts the same effects as the present invention. In addition, when carbon, which is a component that slows wet etching other than nitrogen, is included in the light semitransmissive film, a gas containing a carbon compound instead of nitrogen gas exhibits the same effects as the present invention.

In the above-described embodiment, an example of a molybdenum silicide nitride film has been described as a material for the light semitransmissive film, but is not limited thereto. As a material for the light semitransmissive film, a molybdenum silicide oxynitride film or a molybdenum silicide carbide oxynitride film may be used. Further, in the case of a metal silicide-based material other than molybdenum silicide, the same effect as described above is obtained.

Further, in the above-described embodiment, an example of a phase shift mask blank for manufacturing a display device or a phase shift mask for manufacturing a display device has been described, but is not limited thereto. The phase shift mask blank and phase shift mask of the present invention can also be applied to semiconductor device manufacturing, MEMS manufacturing, and printed circuit board use.

Further, in the above-described embodiment, the size of the transparent substrate has been described as an example of a size of 3345 (330 mm x 450 mm), 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 has a length of one side and 10 inches or more. The size of the transparent substrate used for the phase shift mask blank for manufacturing a display device is, for example, 330 mm x 450 mm or more and 2280 mm x 3130 mm or less.

In the case of a phase shift mask blank for semiconductor device manufacturing, MEMS manufacturing, and printed circuit boards, a small size transparent substrate is used, and the size of the transparent substrate has a length of one side of 9 inches or less. The size of the transparent substrate used for the phase shift mask blank for the above use is, for example, 63.1 mm × 63.1 mm or more and 228.6 mm × 228.6 mm or less. Typically, for semiconductor manufacturing and MEMS manufacturing, a size of 6025 (152 mm × 152 mm) or a size of 5009 (126.6 mm × 126.6 mm) is used, and for a printed circuit board, size 7012 (177.4 mm × 177.4 mm) or 9012 (228.6 mm) X 228.6 mm) is used.

1: Line and space pattern
2a, 2b, 2c: line pattern
3a, 3b: space pattern
4: Edge portion of the phase shift film pattern
5: shading film pattern
11: sputtering device
LL: Carrying chamber
SP1: 1st sputter chamber
BU: Buffer chamber
SP2: Second sputter chamber
ULL: take-out chamber
12: transparent substrate
13: first sputtering target
14: second sputtering target
15: third sputtering target
16: 4th sputtering target
21, 22: auxiliary line
23: side
24, 25: auxiliary line
26: contact
27, 28: side position
29: first virtual line
30: second virtual line
QZ: Synthetic quartz glass substrate
PS: light semitransmissive film pattern
Cr: etching mask film pattern

Claims (15)

In the phase shift mask blank for manufacturing a phase shift mask for manufacturing a display device in which a light semitransmissive film pattern is formed on a transparent substrate by wet etching,
The transparent substrate,
A light semitransmissive film formed on the main surface of the transparent substrate and having a property of changing the phase of exposure light,
An etching mask film made of a chromium-based material formed on the light semitransmissive film
Equipped with,
The light semitransmissive film is any one of nitrides of metal silicides, oxynitrides of metal silicides, oxides of metal silicides, carbon nitrides of metal silicides, and carbon oxynitrides of metal silicides, and is composed of a plurality of layers,
A composition gradient region is formed at the interface between the light semitransmissive film and the etching mask layer, and in the composition gradient region, the proportion of nitrogen or carbon is stepwise or continuously toward the depth direction, or some are stepwise and others are The phase shift mask blank characterized by increasing continuously. According to claim 1,
The light-semitransmissive film is a phase shift mask blank characterized in that the composition of the composition uniform region of the portion excluding the interface between the light-semitransmissive film and the etching mask film and the light semitransmissive film and the transparent substrate is substantially uniform. According to claim 2,
Phase shift mask blank, characterized in that the variation in the proportion of nitrogen in the composition uniform region is 5 atomic% or less. According to claim 1,
In the composition gradient region, the proportion of nitrogen is increasing stepwise or continuously toward the depth direction, or partly and other partly, continuously,
Among the boundaries with the etching mask film in the composition inclined region, when the compositional analysis is performed under the condition of 0.5 minutes for the measurement step by X-ray photoelectron spectroscopy from the etching mask film side, silicon at least 1 atomic% or more A phase shift mask blank characterized in that the ratio (N / Si) of nitrogen (N) to silicon (Si) at the position where (Si) is detected is 3.0 or more and 30 or less. According to claim 1,
A phase shift mask blank characterized in that the ratio of metal to silicon in the light semitransmissive film is metal: silicon = 1: 1 or more and 1: 9 or less. According to claim 1,
The metal is a phase shift mask blank, characterized in that any of molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), zirconium (Zr). The method of claim 6,
The metal is zirconium (Zr) phase shift mask blank, characterized in that. According to claim 1,
The said etching mask film has a light-shielding property, The phase shift mask blank characterized by the above-mentioned. As a phase shift mask,
A light-semitransmissive film pattern formed by wet etching the light-semitransmissive film of the phase shift mask blank according to any one of claims 1 to 8,
In the light semitransmissive film pattern, the composition of the upper surface and a portion excluding the interface between the light semitransmissive film pattern and the transparent substrate is substantially uniform,
A cross section of the light semitransmissive film pattern is composed of upper, lower and side sides corresponding to the upper, lower and side surfaces of the light semitransmissive film pattern, and a third of the film thickness from the contact point between the upper side and the lateral side and the upper side. 2 The angle formed between the straight side connecting the position of the side at the lowered position and the upper side is within a range of 85 degrees to 120 degrees, and the main side of the transparent substrate through a contact point between the upper side and the side. The width of the first imaginary line perpendicular to the surface and the second imaginary line perpendicular to the main surface of the transparent substrate through the position of the lateral side at a position at a height one tenth of the thickness of the film from the bottom surface , Wherein the phase shift mask is less than half of the film thickness. The method of claim 9,
The phase shift mask, characterized in that the light semitransmissive film pattern includes a line and space pattern. The method of claim 9,
The phase shift mask characterized in that the light semitransmissive layer pattern includes a hole pattern. In the manufacturing method of the phase shift mask,
A resist pattern forming step of forming a resist pattern on the etching mask film of the phase shift mask blank according to any one of claims 1 to 8,
An etching mask film pattern forming step of wet etching the etching mask film using the resist pattern as a mask to form an etching mask film pattern;
A semi-transmissive film pattern forming step of forming a light semitransmissive film pattern by wet etching the light semitransmissive film using the etching mask film pattern as a mask.
Method of manufacturing a phase shift mask, characterized in that it has a. In the manufacturing method of the display device,
A phase shift mask arrangement step of arranging the phase shift mask according to claim 9 opposite to the resist film with respect to the substrate having a resist film on which the resist film is formed;
A resist film exposure step of exposing the resist film by irradiating the exposure light to the phase shift mask
The manufacturing method of the display device characterized by having. The method of claim 13,
The exposure light comprises a light in the wavelength range of 300nm or more and 500nm or less. The method of claim 14,
The exposure light is a method of manufacturing a display device, characterized in that the composite light including i-line, h-line and g-line.

Images