CN116500852A - Mask blank, mask for transfer, method for manufacturing same, method for manufacturing display device - Google Patents

Abstract

The invention provides a mask blank, a transfer mask, a manufacturing method thereof, and a display device manufacturing method. The mask blank has high light resistance to exposure light having wavelengths in the ultraviolet range and high chemical resistance, and can form a good transfer pattern. The mask blank has a light-transmitting substrate and a thin film for pattern formation provided on the main surface of the light-transmitting substrate. When the photoelectron intensity of Ti2p narrow spectrum with binding energy of 455eV is P _N and the photoelectron intensity of Si2p narrow spectrum with binding energy of 102eV is _PS , the relationship of P _N / _PS ratio of 1.18 is satisfied. The nitrogen content in the inner region of the thin film is 30 atomic % or more except for the vicinity region on the side of the light-transmitting substrate and the surface layer region on the side opposite to the light-transmitting substrate.

Description

Mask blank, mask for transfer, method for manufacturing same, method for manufacturing display device

technical field

The present invention relates to a mask blank, a transfer mask, a method for manufacturing a transfer mask, and a method for manufacturing a display device.

Background technique

In recent years, in display devices such as FPD (Flat Panel Display: flat panel display) represented by OLED (Organic Light Emitting Diode: Organic Light Emitting Diode), high-definition , High-speed display is also developing rapidly. One of the factors required for this high-definition and high-speed display is the ability to produce electronic circuit patterns such as elements and wiring that are fine and have high dimensional accuracy. Photolithography is often used in patterning electronic circuits for display devices. Therefore, there is a need for a transfer mask (photomask) such as a phase shift mask for display device manufacture and a binary mask in which a fine and high-precision pattern is formed.

For example, Patent Document 1 describes a photomask for exposing a fine pattern. In Patent Document 1, it has been described that the structure of the photomask is composed of a light-transmitting portion that actually transmits light whose intensity contributes to exposure, and a semi-transparent portion that actually transmits light whose intensity does not contribute to exposure. A mask pattern formed on a transparent substrate. In addition, Patent Document 1 describes that the contrast of the boundary portion is improved by making use of the phase shift effect to cancel out the light passing through the vicinity of the boundary portion between the semi-transparent portion and the light-transmitting portion. In addition, Patent Document 1 describes that the photomask comprises the semi-transparent portion with a thin film, the thin film is formed of a substance mainly composed of nitrogen, metal, and silicon, and that the composition of the substance constituting the thin film is Elemental silicon contains 34 to 60 atomic %.

Patent Document 2 describes a halftone type phase shift mask blank used in photolithography. Patent Document 2 describes that a mask blank has a substrate, an etch stop layer laminated on the substrate, and a phase shift layer laminated on the etch stop layer. In addition, Patent Document 2 describes that a photomask having a phase shift of approximately 180 degrees at a selected wavelength of less than 500 nm and a light transmittance of at least 0.001% can be produced using this mask blank.

Patent Document 3 describes a photomask blank having a thin film for pattern formation on a transparent substrate. Patent Document 3 describes that a photomask blank is an original plate for forming a photomask having a transferred pattern on a transparent substrate by wet etching a pattern-forming film. In addition, Patent Document 3 describes that a thin film for pattern formation of a photomask blank contains a transition metal and silicon and has a columnar structure.

prior art literature

patent documents

Patent Document 1: (Japanese) Patent No. 2966369

Patent Document 2: (Japanese) Special Publication No. 2005-522740

Patent Document 3: (Japanese) Unexamined Patent Publication No. 2020-95248

Contents of the invention

The technical problem to be solved by the invention

As a transfer mask used in the production of high-definition (1000ppi or more) flat panels in recent years, in order to be able to perform high-resolution pattern transfer, a transfer mask is required, and the transfer mask is formed There is a pattern for transfer including a thin film pattern for fine pattern formation with a pore size of 6 μm or less and a line width of 4 μm or less. Specifically, a transfer mask in which a transfer pattern including a fine pattern having a diameter or a width dimension of 1.5 μm is formed is required.

On the other hand, since the transfer mask obtained by patterning the pattern-forming film of the mask blank is repeatedly used in the transfer of the pattern to the object to be transferred, it is desirable that the actual pattern transfer is relatively The light resistance (ultraviolet light resistance) of the presumed ultraviolet rays is also high. In addition, since the transfer mask is repeatedly cleaned during its manufacture and use, it is also desired to improve the cleaning resistance (chemical resistance) of the mask.

However, the manufacture of mask blanks for pattern-forming films that satisfy the requirements for transmittance to exposure light of wavelengths including the ultraviolet region, and ultraviolet light resistance (hereinafter simply referred to as light resistance) and chemical resistance has traditionally been compared. difficulty.

The present invention was made in order to solve the above-mentioned problems. That is, an object of the present invention is to provide a mask blank that has high light resistance to exposure light of wavelengths including ultraviolet light and high chemical resistance, and can form a good transfer pattern.

In addition, an object of the present invention is to provide a transfer mask, a transfer mask having high light resistance to exposure light of a wavelength including an ultraviolet region, high chemical resistance, and a good transfer pattern. A method for manufacturing a mold, and a method for manufacturing a display device.

Technical solutions for solving technical problems

As technical means for solving the above-mentioned problems, the present invention has the following constitutions.

(Constitution 1) A mask blank comprising a light-transmitting substrate and a pattern-forming film provided on a main surface of the light-transmitting substrate, wherein the mask blank is characterized in that

The film contains titanium, silicon and nitrogen,

In the Ti2p narrow spectrum analyzed by X-ray photoelectron spectroscopy relative to the inner region of the thin film, the photoelectron intensity with binding energy of 455 eV is P _N , and the photoelectron intensity with binding energy of 102 eV in the Si2p narrow spectrum is When P _S is satisfied, the relationship that P _N / _PS is greater than 1.18 is satisfied,

The inner region is the region of the thin film except the vicinity of the light-transmitting substrate side and the surface layer region on the side opposite to the light-transmitting substrate,

The content of nitrogen in the inner region is 30 atomic % or more.

(Configuration 2) The mask blank according to Configuration 1, wherein

When the photoelectron intensity at which the binding energy is 461 eV in the Ti2p narrow spectrum is P _NU , the relationship that the P _NU /P _S ratio is greater than 1.05 is satisfied.

(Structure 3) The mask blank according to the structure 1 or 2, wherein

The ratio of the content of titanium to the total content of titanium and silicon in the inner region is 0.05 or more.

(Structure 4) The mask blank according to any one of the structures 1 to 3, wherein

The total content of titanium, silicon and nitrogen in the inner region is 90 atomic % or more.

(Structure 5) The mask blank according to any one of the structures 1 to 4, characterized in that

The oxygen content of the inner region is 7 atomic % or less.

(Structure 6) The mask blank according to any one of the structures 1 to 5, wherein

The surface region on the side opposite to the transparent substrate is a region extending from the surface opposite to the transparent substrate to the transparent substrate to a depth of 10 nm.

(Structure 7) The mask blank according to any one of the structures 1 to 6, wherein

The near region on the side of the light-transmitting substrate is a region extending from the surface on the side of the light-transmitting substrate to the side opposite to the light-transmitting substrate to a depth of 10 nm.

(Structure 8) The mask blank according to any one of the structures 1 to 7, wherein

The thin film is a phase shift film,

The phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365 nm, and a phase difference with respect to light having a wavelength of 365 nm of not less than 150 degrees and not more than 210 degrees.

(Structure 9) The mask blank according to any one of the structures 1 to 8, characterized in that

There is an etching mask film having an etching selectivity different from that of the thin film on the thin film.

(Configuration 10) The mask blank according to Configuration 9, wherein

The etching mask film contains chromium.

(Structure 11) A transfer mask comprising a light-transmitting substrate and a thin film having a transfer pattern provided on a main surface of the light-transmitting substrate, wherein the transfer mask is characterized in that

The film contains titanium, silicon and nitrogen,

In the Ti2p narrow spectrum analyzed by X-ray photoelectron spectroscopy relative to the inner region of the thin film, the photoelectron intensity with binding energy of 455 eV is P _N , and the photoelectron intensity with binding energy of 102 eV in the Si2p narrow spectrum is When P _S is satisfied, the relationship that P _N / _PS is greater than 1.18 is satisfied,

The inner region is the region of the thin film except the vicinity of the light-transmitting substrate side and the surface layer region on the side opposite to the light-transmitting substrate,

The content of nitrogen in the inner region is 30 atomic % or more.

(Configuration 12) The transfer mask according to Configuration 11, wherein:

When the photoelectron intensity at which the binding energy is 461 eV in the Ti2p narrow spectrum is P _NU , the relationship that the P _NU /P _S ratio is greater than 1.05 is satisfied.

(Structure 13) The transfer mask according to the structure 11 or 12, wherein

The ratio of the content of titanium to the total content of titanium and silicon in the inner region is 0.05 or more.

(Structure 14) The transfer mask according to any one of the structures 11 to 13, wherein

The total content of titanium, silicon and nitrogen in the inner region is 90 atomic % or more.

(Structure 15) The transfer mask according to any one of the structures 11 to 14, wherein

The oxygen content of the inner region is 7 atomic % or less.

(Structure 16) The transfer mask according to any one of Structures 11 to 15, wherein:

The surface region on the side opposite to the transparent substrate is a region extending from the surface opposite to the transparent substrate to the transparent substrate to a depth of 10 nm.

(Structure 17) The transfer mask according to any one of the structures 11 to 16, wherein

The near region on the side of the light-transmitting substrate is a region extending from the surface on the side of the light-transmitting substrate to the side opposite to the light-transmitting substrate to a depth of 10 nm.

(Structure 18) The transfer mask according to any one of the structures 11 to 17, characterized in that

The thin film is a phase shift film,

The phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365 nm, and a phase difference with respect to light having a wavelength of 365 nm of not less than 150 degrees and not more than 210 degrees.

(Structure 19) A method of manufacturing a transfer mask, comprising:

A process of preparing the mask stock material described in any one of 1 to 8;

A step of forming a resist film having a transferred pattern on the thin film;

A step of forming a transfer pattern on the thin film by performing wet etching using the resist film as a mask.

(Structure 20) A method of manufacturing a transfer mask, comprising:

The process of preparing the mask stock described in 9 or 10;

A step of forming a resist film having a transfer pattern on the etching mask film;

performing wet etching using the resist film as a mask, and forming a transfer pattern on the etching mask film;

A step of forming a transfer pattern on the thin film by performing wet etching using the etching mask film on which the transfer pattern is formed as a mask.

(Structure 21) A method of manufacturing a display device, comprising:

A step of placing the transfer mask described in any one of Configurations 11 to 18 on a mask stage of an exposure device;

A step of irradiating exposure light to the transfer mask to transfer a transfer pattern to the resist film provided on the display device substrate.

The effect of the invention

According to the present invention, it is possible to provide a mask blank which has high light resistance to exposure light of a wavelength including an ultraviolet range, high chemical resistance, and which can form a good transfer pattern.

In addition, according to the present invention, it is possible to provide a transfer mask, a method of manufacturing a transfer mask, and a method of manufacturing a display device, which have high light resistance to exposure light of wavelengths including the ultraviolet region, and have high Drug resistant, with good transfer pattern.

Description of drawings

FIG. 1 is a schematic cross-sectional view showing a film structure of a mask blank according to an embodiment of the present invention.

2 is a schematic cross-sectional view showing another film structure of a mask blank according to an embodiment of the present invention.

FIG. 3 is a schematic cross-sectional view illustrating a manufacturing process of the transfer mask according to the embodiment of the present invention.

4 is a schematic cross-sectional view showing another manufacturing process of the transfer mask according to the embodiment of the present invention.

5 is a graph showing the results of X-ray photoelectron spectroscopy analysis (Ti2p narrow spectrum) on the phase shift film of the mask blank of each Example of the present invention.

6 is a graph showing the results of X-ray photoelectron spectroscopy analysis (Si2p narrow spectrum) of the phase shift film of the mask blank of each Example of the present invention.

7 is a graph showing the results of X-ray photoelectron spectroscopy analysis (Ti2p narrow spectrum) on the phase shift film of the mask blank of each comparative example of the present invention.

8 is a graph showing the results of X-ray photoelectron spectroscopy analysis (Si2p narrow spectrum) on the phase shift film of the mask blank of each comparative example of the present invention.

Explanation of reference signs

10 mask blank; 20 light-transmitting substrate; 30 film for pattern formation; 30a film pattern; 40 etching mask film; 40a first etching mask film pattern; 40b second etching mask film pattern; 50 first resist Resist film pattern; 60 second resist film pattern; 100 transfer mask.

Detailed ways

First, the process of completing the present invention will be described. The inventors of the present invention have aimed at a mask blank that has high light resistance to exposure light of wavelengths including the ultraviolet region (hereinafter sometimes simply referred to as "exposure light"), has high chemical resistance, and can form a good transfer pattern. The structure of the material has been thoroughly studied. The inventors of the present invention conducted research on using a titanium silicide-based material as a material for a thin film pattern of a transfer mask used for manufacturing a display device such as an FPD (Flat Panel Display). The thin film of the titanium silicide-based material has good optical properties and chemical resistance. On the other hand, although it has been considered that a thin film of titanium silicide-based material has good properties in terms of resistance to exposure to exposure light (including exposure light of a wavelength in the ultraviolet region), it has been found that the light resistance to exposure light may be greatly improved. decline. Therefore, the inventors of the present invention conducted a multi-angle study on the difference between a thin film of a titanium silicide-based material with high light resistance to exposure light and a thin film of a titanium silicide-based material with low light resistance to exposure light. . First, the inventors of the present invention have studied the relationship between the composition of the thin film and the light resistance to exposure light by using analysis based on X-ray photoelectron spectroscopy (XPS: X-Ray Photoelectron Spectroscopy). A clear correlation was not obtained between the composition of the compound and the light fastness. In addition, observations of cross-sectional SEM images, planar STEM images, and electron diffraction images were performed, but no clear correlation with light resistance was obtained.

The inventors of the present invention conducted further intensive studies, and as a result, compared the Ti2p narrow spectrum and the Si2p narrow spectrum obtained by analyzing the inner region of the thin film for pattern formation based on X-ray photoelectron spectroscopy (XPS). Through observation, it has been found out that even if the overall behavior of the Ti2p narrow spectrum and the Si2p narrow spectrum are close, there are visible differences in its light fastness (refer to the third and fourth embodiments shown in Fig. 5 and Fig. 6, and Fig. 7 and Fig. 8 narrow spectrum of the first comparative example).

As a result of further research, when a thin film of titanium silicide-based material with a nitrogen content of 30 atomic % or more is in its internal region, the photoelectron intensity corresponding to the TiN bond of Ti2p 3/2 with a narrow Ti2p spectrum (binding energy of 455 eV When the ratio of the photoelectron intensity) P _N divided by the photoelectron intensity corresponding to the Si ₃ N ₄ bond with a Si2p narrow spectrum (the photoelectron intensity with a binding energy of 102 eV) P _S satisfies the condition that it is greater than 1.18, the obtained relative to the exposure light has Such a conclusion of high light fastness.

As a result of the intensive research described above, the mask blank of the present invention was obtained. That is, the mask blank of the present invention is a mask blank having a light-transmitting substrate and a thin film for pattern formation provided on the main surface of the light-transmitting substrate, and is characterized in that the thin film contains titanium, silicon, and nitrogen. With respect to the inner region of the thin film analyzed by X-ray photoelectron spectroscopy, when the photoelectron intensity of the binding energy of 455eV in the narrow Ti2p spectrum is P _N , and the photoelectron intensity of the binding energy of 102eV in the Si2p narrow spectrum is _PS , Satisfy the relationship that the P _N / _PS ratio is greater than 1.18, the inner region is the region of the film except the vicinity of the light-transmitting substrate side and the surface layer region on the side opposite to the light-transmitting substrate, and the content of nitrogen in the inner region is 30 atomic % above.

Next, embodiments of the present invention will be specifically described with reference to the drawings. It should be noted that the following embodiments are only modes for embodying the present invention, and are not intended to limit the scope of the present invention.

FIG. 1 is a schematic diagram showing a film structure of a mask blank 10 according to the present embodiment. The mask blank 10 shown in FIG. 1 has a light-transmitting substrate 20, a pattern-forming film 30 (for example, a phase shift film) formed on the light-transmitting substrate 20, and an etching mask formed on the pattern-forming film 30. film (eg light shielding film) 40 .

FIG. 2 is a schematic view showing a film structure of a mask blank 10 according to another embodiment. The mask blank 10 shown in FIG. 2 has a light-transmitting substrate 20 and a thin film 30 for pattern formation (for example, a phase shift film) formed on the light-transmitting substrate 20 .

In this specification, the "pattern-forming film 30" refers to a film in which a predetermined fine pattern is formed on a transfer mask 100 such as a light-shielding film or a phase shift film (hereinafter, may be simply referred to as "film 30"). It should be noted that, in the description of this embodiment, as a specific example of the pattern forming film 30, a phase shift film is sometimes used as an example for description, and as a pattern forming film pattern 30a (hereinafter sometimes simply referred to as "film pattern 30a") ) is sometimes described by taking a phase shift film pattern as an example. In other pattern forming films 30 and pattern forming film patterns 30 a such as light shielding films and light shielding film patterns, transmittance adjusting films and transmittance adjusting film patterns, the same applies to the phase shift film and phase shift film patterns.

Next, the light-transmitting substrate 20 , the thin film 30 for pattern formation (for example, a phase shift film), and the etching mask film 40 constituting the mask blank 10 for manufacturing a display device according to this embodiment will be specifically described.

<Light-transmitting substrate 20>

The light-transmitting substrate 20 is transparent to exposure light. The light-transmitting substrate 20 has a transmittance of 85% or more, preferably 90% or more, with respect to the exposure light when there is no surface reflection loss. The light-transmitting substrate 20 is made of a material containing silicon and oxygen, and can be made of glass materials such as synthetic quartz glass, quartz glass, aluminosilicate glass, soda lime glass, and low thermal expansion glass (SiO ₂ -TiO ₂ glass, etc.). In the case where the light-transmitting substrate 20 is made of low thermal expansion glass, it is possible to suppress the positional change of the thin film pattern 30 a due to thermal deformation of the light-transmitting substrate 20 . In addition, the light-transmitting substrate 20 used for a display device is generally a rectangular substrate. Specifically, a substrate having a short side length of 300 mm or more on the main surface (surface on which the pattern forming film 30 is formed) of the light-transmitting substrate 20 can be used. In the mask blank 10 of the present embodiment, a large-sized light-transmitting substrate 20 whose main surface has a shorter side length of 300 mm or more can be used. Using the mask blank 10 of the present embodiment, it is possible to manufacture a transfer mask having a transfer pattern including, for example, a thin film pattern 30a for forming a fine pattern with a width dimension and/or a diameter dimension of less than 2.0 μm on a light-transmitting substrate 20 . Die 100. By using the transfer mask 100 of the present embodiment described above, it is possible to stably transfer a transfer pattern including a predetermined fine pattern to a transfer target.

<Pattern Forming Film 30>

The pattern-forming film 30 (hereinafter sometimes simply referred to as the "pattern-forming film of the present embodiment") of the mask blank 10 for manufacturing a display device of the present embodiment (hereinafter sometimes simply referred to as "the mask blank 10 of the present embodiment") 30") is formed of a material containing titanium (Ti), silicon (Si), and nitrogen (N). The thin film 30 for pattern formation may be a phase shift film having a phase shift function.

The thin film 30 for pattern formation contains nitrogen. In the above-mentioned titanium silicide, nitrogen as a light element component has the effect of not lowering the refractive index as compared with oxygen, which is also a light element component. Therefore, the thin film 30 for pattern formation can reduce the film thickness for obtaining a desired retardation (also called a phase shift amount) by containing nitrogen. In addition, the content of nitrogen contained in the thin film 30 for pattern formation is preferably 30 atomic % or more, more preferably 40 atomic % or more. On the other hand, the nitrogen content is preferably 60 atomic % or less, more preferably 55 atomic % or less. Since the nitrogen content in the thin film 30 is large, excessive increase in transmittance with respect to exposure light can be suppressed.

The inside of the pattern-forming film 30 is divided into three regions, namely, the vicinity region, the inner region, and the surface layer region, sequentially from the light-transmitting substrate 20 side. The nearby region extends from the interface of the pattern-forming thin film 30 and the light-transmitting substrate 20 to the surface side opposite to the light-transmitting substrate 20 (i.e., the surface region side) to a depth of 10 nm (more preferably a depth of 5 nm, further preferably a depth of 4 nm). ) within the range of the area. When X-ray photoelectron spectroscopy is performed on this nearby area, it is easily affected by the light-transmitting substrate 20 existing therebelow, and the maximum peak of the photoelectron intensity of the Ti2p narrow spectrum and Si2p narrow spectrum obtained in the nearby area is The precision is lower.

The surface region is a region extending from the surface opposite to the transparent substrate 20 to the transparent substrate 20 to a depth of 10 nm (more preferably a depth of 5 nm, and a depth of preferably 4 nm). When another film such as the etching mask film 40 exists on the surface layer region, it is a region that is easily affected by the film. In addition, the surface layer region is a region containing oxygen taken in from the surface of the pattern forming thin film 30 when no other film exists thereon. Therefore, when X-ray photoelectron spectroscopy is performed on the surface region, the accuracy of the maximum peak of the photoelectron intensity of the Ti2p narrow spectrum and Si2p narrow spectrum obtained in the surface region is low.

The inner region is a region of the pattern-forming film 30 other than the vicinity region and the surface layer region. In the Ti2p narrow spectrum and Si2p narrow spectrum analyzed by X-ray photoelectron spectroscopy with respect to this inner region, when the photoelectron intensity with a binding energy of 455 eV is P _N and the photoelectron intensity with a binding energy of 102 eV is _PS , Satisfy the relationship that P _N / _PS is greater than 1.18.

Here, the binding energy of 455eV corresponds to the binding energy of TiN bonds in the Ti2p 3/2 peak, and the binding energy of 102eV corresponds to the binding energy of Si ₃ N ₄ bonds in the Si2p peak (see FIGS. 5 to 8 ).

The inventors of the present invention estimated the relationship between _PN / _PS and light resistance as follows.

In the case where the thin film 30 for pattern formation is made of a titanium silicide-based material containing titanium and silicon, the titanium (Ti) in the thin film 30 mainly includes titanium existing as Ti alone and titanium existing in a bonded state of TiN ( Refer to Figure 5, Figure 7). As shown in FIG. 5 and FIG. 7 , in the peak of Ti2p 3/2 , the binding energy of Ti existing in the bonded state of TiN is higher than that of titanium existing as a single Ti. Therefore, Ti existing in a bonded state of TiN is more resistant to changes in the state of Ti caused by irradiation of exposure light including ultraviolet rays, and it is less likely to cause a change in the transmittance due to a change in the state of Ti than Ti existing in a Ti monomer. changes, etc. On the other hand, since the nitrogen in the thin film 30 is also bonded to silicon (Si) in addition to titanium (Ti), it is considered that when the nitrogen content is small, the amount of nitrogen bonded to titanium is relatively large. The amount of titanium existing as a single Ti increases. When the nitrogen content is 30 atomic % or more, it is considered that Si exists in a stoichiometrically stable bonded state of Si ₃ N ₄ to some extent. In this situation, when the relationship of _PN / _PS ratio of 1.18 is satisfied, in the thin film 30, in the state where Si and nitrogen are bonded to a certain extent, it is considered that Ti exists in a certain ratio or more in TiN. In the bonded state, therefore, it is presumed to have high light resistance to exposure light including ultraviolet rays. However, this speculation is based on current knowledge and is not intended to limit the scope of rights of the present invention.

Even if composition analysis such as analysis based on X-ray photoelectron spectroscopy (XPS) is performed in the vicinity of the interface with the light-transmitting substrate 20, it is inevitably affected by the composition of the light-transmitting substrate 20, so it is difficult to analyze the composition and bonding. The number of existences of specifies a numeric value. However, the same configuration as the above-mentioned inner region can be assumed.

P _N / _PS is more preferably 1.19 or more, and still more preferably 1.20 or more.

In addition, P _N / _PS is preferably 3.00 or less, more preferably 2.50 or less, and still more preferably 2.00 or less.

_In addition, the Ti2p narrow spectrum analyzed by X-ray photoelectron spectroscopy with respect to the inner region preferably satisfies the relationship that the P _NU / _PS ratio is greater than 1.05, and more preferably 1.10 or more, and more preferably 1.15 or more.

Here, the binding energy of 461 eV corresponds to the binding energy of the TiN bond at the peak of Ti2p 1/2 (see FIG. 5 and FIG. 7 ).

As described above, even in the peak of Ti2p 1/2, the binding energy of Ti existing in the bonded state of TiN is higher than that of Ti existing alone. Therefore, when the content of nitrogen is 30 atomic % or more and the relationship of P _NU / _PS ratio of 1.10 is satisfied, it can be considered that Ti exists in TiN at a certain ratio or more in a state where Si and nitrogen are bonded to a certain extent. In the bonded state, therefore, it is presumed to have high light resistance to exposure light including ultraviolet rays. However, this speculation is based on current knowledge and is not intended to limit the scope of rights of the present invention.

In addition, P _NU / _PS is preferably 2.50 or less, more preferably 2.00 or less.

In addition, the Ti2p narrow spectrum and the Si2p narrow spectrum analyzed by X-ray photoelectron spectroscopy in the inner region preferably satisfy the relationship that the (P _N +P _NU )/ _PS ratio is greater than 2.22.

As described above, in any of the peaks of Ti2p 3/2 and Ti2p 1/2, the binding energy of Ti existing in the bonding state of TiN and Ti existing in the bonding state of TiO is higher than that of Ti existing in the monomeric state. The binding energy of Ti is high. Therefore, when the content of nitrogen is 30 atomic % or more and satisfies the relationship that the P _NU / _PS ratio is greater than 1.10, in the state where Si and nitrogen are bonded to a certain extent, it can be considered that Ti exists in a certain proportion or more. In the bonded state of TiN, therefore, it is presumed to have high light resistance to exposure light including ultraviolet rays. However, this speculation is based on current knowledge and is not intended to limit the scope of rights of the present invention.

(P _N +P _NU )/ _PS is more preferably 2.25 or more, and still more preferably 2.30 or more.

In addition, (P _N +P _NU )/ _PS is preferably 5.00 or less, more preferably 4.50 or less.

In addition, the Ti2p narrow spectrum and the Si2p narrow spectrum analyzed by X-ray photoelectron spectroscopy in the inner region preferably satisfy the P _N /P _TS ratio of 2.13 when the photoelectron intensity at a binding energy of 453 eV is P _TS relation.

Here, the binding energy of 453 eV corresponds to the binding energy of the TiSi ₂ bond of the Ti2p 3/2 peak (see FIG. 5 and FIG. 7 ).

P _N /P _TS is more preferably 2.20 or more, and still more preferably 2.50 or more.

P _N /P _TS is preferably 4.00 or less, more preferably 3.50 or less.

In addition, the Ti2p narrow spectrum and the Si2p narrow spectrum analyzed by X-ray photoelectron spectroscopy in the inner region preferably satisfy (P _N + _PT )/P when the photoelectron intensity with a binding energy of 454eV is _{P TS} is greater than 3.53.

Here, the binding energy of 454 eV corresponds to the binding energy of a Ti monomer at the peak of Ti2p 3/2 (see FIG. 5 and FIG. 7 ).

(P _N + _PT )/P _TS is more preferably 3.60 or more, and still more preferably 3.90 or more.

(P _N + _PT )/P _TS is preferably 5.50 or less, more preferably 5.00 or less.

The ratio of the titanium content in the inner region to the total content of titanium and silicon (hereinafter sometimes referred to as Ti/[Ti+Si] ratio) is preferably 0.05 or more, more preferably 0.10 or more. When the ratio of Ti/[Ti+Si] in the inner region is too small, it is difficult to obtain advantages in optical characteristics and chemical resistance by using a titanium silicide-based material for the pattern forming thin film 30 . On the other hand, the Ti/[Ti+Si] ratio in the inner region is preferably 0.50 or less, more preferably 0.45 or less.

The total content of titanium, silicon, and nitrogen in the inner region is preferably 90 atomic % or more, more preferably 95 atomic % or more. In the inner region, when the content of elements other than titanium, silicon, and nitrogen increases, various properties such as optical characteristics, chemical resistance, and light resistance to ultraviolet light may decrease.

The thin film 30 for pattern formation may contain oxygen in the range which does not deteriorate the performance of the thin film 30 for pattern formation. Oxygen, which is a light element component, has an effect of lowering the extinction coefficient compared with nitrogen, which is also a light element component. However, when the oxygen content of the pattern-forming thin film 30 is high, it may adversely affect the acquisition of a cross-section of a fine pattern close to vertical and high resistance to mask cleaning. Therefore, the oxygen content of the thin film 30 for pattern formation is preferably 7 atomic % or less, more preferably 5 atomic % or less. The thin film 30 for pattern formation may not contain oxygen.

It should be noted that, as shown in Figure 5 and Figure 7, the photoelectron intensity with a binding energy of 453eV corresponds to the binding energy of the TiSi ₂ bond in the peak of Ti2p 3/2, and the photoelectron intensity with a binding energy of 454eV corresponds to the Ti2p 3/2 The binding energy of Ti monomer in the peak of 2, the binding energy of 455eV corresponds to the binding energy of TiN bond in the peak of Ti2p 3/2, and the binding energy of 456.9eV corresponds to the binding of TiO bond in the peak of Ti2p 3/2 The binding energy of 458.5eV corresponds to the binding energy of TiO ₂ bond in the peak of Ti2p 3/2, the binding energy of 460eV corresponds to the binding energy of Ti monomer in the peak of Ti2p 1/2, and the binding energy of 461eV corresponds to The binding energy of the TiN bond in the peak of Ti2p 1/2.

In addition, the thin film 30 for pattern formation may contain other light element components such as carbon and helium for the purpose of reducing the film stress and/or controlling the wet etching rate in addition to the above-mentioned oxygen and nitrogen.

The atomic ratio of titanium and silicon contained in the thin film 30 for pattern formation is preferably in the range of titanium:silicon=1:1 to 1:19. When it exists in this range, the effect which suppresses the fall of the wet etching rate at the time of pattern formation of the thin film 30 for pattern formations can be increased. In addition, the cleaning resistance of the pattern forming film 30 can be improved, and the transmittance can also be easily improved. From the viewpoint of improving the cleaning resistance of the pattern-forming film 30, the atomic ratio of titanium to silicon (titanium:silicon) contained in the pattern-forming film 30 is preferably in the range of 1:1 to 1:19, more preferably in the range of 1:1 to 1:19. 1:1 to 1:11, and more preferably 1:1 to 1:9.

The pattern forming film 30 may be composed of a plurality of layers, or may be composed of a single layer. The pattern-forming film 30 composed of a single layer is preferable since it is difficult to form an interface in the pattern-forming film 30 and it is easy to control the cross-sectional shape. On the other hand, the film 30 for pattern formation which consists of several layers is easy to form a film etc., and is preferable.

In order to ensure optical performance, the film thickness of the thin film 30 for pattern formation is preferably 200 nm or less, more preferably 180 nm or less, and still more preferably 150 nm or less. In addition, in order to ensure the function of generating a desired retardation, the film thickness of the thin film 30 for pattern formation is preferably 80 nm or more, more preferably 90 nm or more.

"Transmittance and Retardation of Pattern Forming Film 30"

The mask blank 10 for manufacturing a display device according to this embodiment preferably has a transmittance of not less than 1% and not more than 80% with respect to a representative wavelength of exposure light (light having a wavelength of 365 nm), and a phase difference. It is a phase shift film with an optical characteristic of 150 degrees or more and 210 degrees or less. Unless otherwise specified, the transmittance in this specification is converted based on the transmittance of the light-transmitting substrate (100%).

When the pattern forming film 30 is a phase shift film, the pattern forming film 30 has the function of adjusting the reflectance (hereinafter sometimes referred to as the back reflectance) with respect to the light incident from the light-transmitting substrate 20 side, and the function of adjusting the reflectance relative to the light incident from the light-transmitting substrate 20 side. A function of the transmittance and phase difference of the exposure light.

The transmittance of the pattern forming film 30 with respect to exposure light satisfies a value required as the pattern forming film 30 . The transmittance of the pattern forming film 30 is preferably not less than 1% and not more than 80%, more preferably not less than 3% and not more than 65%, with respect to light of a predetermined wavelength (hereinafter referred to as a representative wavelength) included in the exposure light, and further preferably Preferably it is 5% or more and 60% or less. That is, when the exposure light is composite light including light in the wavelength range of 313 nm to 436 nm, the pattern forming film 30 has the above-mentioned transmittance with respect to light of representative wavelengths included in the wavelength range. For example, when the exposure light is composite light including i-line, h-line, and g-line, the pattern-forming film 30 may have the above-mentioned transmittance with respect to any of the i-line, h-line, and g-line. The representative wavelength may be, for example, the i-line with a wavelength of 365 nm. By having the above characteristics with respect to the i-line, when composite light including the i-line, h-line, and g-line is used as exposure light, the transmittance at the wavelength of the h-line and g-line can also be expected similar effect.

In addition, when the exposure light is monochromatic light selected from a wavelength range of 313 nm to 436 nm by using a filter or the like, and monochromatic light selected from a wavelength range of 313 nm to 436 nm In this case, the film 30 for pattern formation has the above-mentioned transmittance with respect to the monochromatic light of the single wavelength.

The transmittance can be measured using a phase shift measuring device or the like.

The phase difference of the pattern forming film 30 with respect to exposure light satisfies the value required as the pattern forming film 30 . The phase difference of the pattern forming film 30 is preferably 150 degrees or more and 210 degrees or less, more preferably 160 degrees or more and 200 degrees or less, and still more preferably 170 degrees or more and 190 degrees or less with respect to the light of the representative wavelength included in the exposure light. below the degree. Utilizing this property, it is possible to change the phase of the light of the representative wavelength included in the exposure light to 150 degrees or more and 210 degrees or less. Therefore, a phase difference of not less than 150 degrees and not more than 210 degrees occurs between the light of the representative wavelength transmitted through the pattern-forming film 30 and the light of the representative wavelength transmitted only through the light-transmitting substrate 20 . That is, when the exposure light is composite light including light in the wavelength range of 313 nm to 436 nm, the pattern forming film 30 has the above-mentioned phase difference with respect to light of representative wavelengths included in the wavelength range. For example, when the exposure light is composite light including i-line, h-line, and g-line, the pattern-forming film 30 may have the above-mentioned phase difference with respect to any of i-line, h-line, and g-line. The representative wavelength may be, for example, the h-line with a wavelength of 405 nm. By having the above characteristics with respect to the h-line, when composite light including the i-line, h-line, and g-line is used as exposure light, it can be expected that the phase difference at the wavelength of the i-line and g-line is similar Effect.

The phase difference can be measured using a phase shift amount measuring device or the like.

The back surface reflectance of the pattern forming film 30 is 15% or less, preferably 10% or less in the wavelength region of 365 nm to 436 nm. In addition, the back surface reflectance of the pattern forming film 30 is preferably 20% or less, more preferably 17% or less, relative to light in the wavelength region of 313 nm to 436 nm when the exposure light includes j-line (wavelength: 313 nm). Furthermore, it is preferably 15% or less. In addition, the back surface reflectance of the pattern forming film 30 is 0.2% or more in the wavelength region of 365nm to 436nm, and preferably 0.2% or more with respect to light in the wavelength region of 313nm to 436nm.

The back reflectance can be measured using a spectrophotometer or the like.

The thin film 30 for pattern formation can be formed by a known film-forming method such as a sputtering method.

<Etching mask film 40>

The mask blank 10 for manufacturing a display device according to the present embodiment preferably has an etching mask film 40 having an etching selectivity different from that of the thin film 30 for pattern formation on the thin film 30 for pattern formation.

The etching mask film 40 is arranged on the upper side of the pattern forming film 30 and is formed of a material having etching resistance (different etching selectivity from the pattern forming film 30 ) to an etchant for etching the pattern forming film 30 . In addition, the etching mask film 40 may have a function of blocking transmission of exposure light. In addition, the etching mask film 40 may also have the function of reducing the film surface reflectance, so that the film surface reflectance of the pattern forming film 30 relative to the light incident from the pattern forming film 30 side is 15% or less.

The etching mask film 40 is preferably made of a chromium-based material containing chromium (Cr). The etching mask film 40 is more preferably made of a material that contains chromium and substantially does not contain silicon. Actually not containing silicon means that the content of silicon is less than 2% (however, excluding the region where the composition of the interface between the pattern forming thin film 30 and the etching mask film 40 is inclined). More specifically, the chromium-based material may, for example, be chromium (Cr), or a material containing chromium (Cr) and at least any one of oxygen (O), nitrogen (N), and carbon (C). In addition, as the chromium-based material, a material containing chromium (Cr) and at least any one element of oxygen (O), nitrogen (N), and carbon (C) and further containing fluorine (F) can be exemplified. For example, as a material constituting the etching mask film 40 , Cr, CrO, CrN, CrF, CrCO, CrCN, CrON, CrCON, and CrCONF may, for example, be mentioned.

The etching mask film 40 can be formed by a known film forming method such as a sputtering method.

In the case where the etching mask film 40 has a function of blocking exposure light from passing through, the optical density of the portion where the pattern forming film 30 and the etching mask film 40 are laminated with respect to the exposure light is preferably 3 or more, more preferably 3 or more. 3.5 or more, and more preferably 4 or more. The optical density can be measured with a spectrophotometer, an OD meter, or the like.

The etching mask film 40 may be a single film having a uniform composition depending on the function. In addition, the etching mask film 40 may be a plurality of films having different compositions. In addition, the etching mask film 40 may be a single film whose composition continuously changes in the thickness direction.

In addition, the mask blank 10 of this embodiment shown in FIG. 1 has the etching mask film 40 on the thin film 30 for pattern formation. The mask blank 10 of the present embodiment includes the mask blank 10 having an etching mask film 40 on the pattern forming film 30 and a resist film on the etching mask film 40 .

<Manufacturing method of mask blank 10>

Next, a method for manufacturing the mask blank 10 of the embodiment shown in FIG. 1 will be described. The mask blank 10 shown in FIG. 1 is manufactured by performing the following thin film formation process for pattern formation and the etching mask film formation process. The mask blank 10 shown in FIG. 2 is manufactured through a pattern forming thin film forming process.

Next, each step will be described in detail.

"Thin Film Formation Process for Pattern Formation"

First, the light-transmitting substrate 20 is prepared. When the light-transmitting substrate 20 is transparent with respect to the exposure light, it can be made of a glass material selected from synthetic quartz glass, quartz glass, aluminosilicate glass, soda lime glass, and low thermal expansion glass ( _SiO2 - _TiO2 glass, etc.) constitute.

Next, the thin film 30 for pattern formation is formed on the light-transmitting substrate 20 by a sputtering method.

Formation of the thin film 30 for pattern formation can be performed in a predetermined sputtering gas atmosphere using a predetermined sputtering target. The predetermined sputtering target is, for example, a titanium silicide target containing titanium and silicon as main components of the material constituting the pattern forming thin film 30 , or a titanium silicide target containing titanium, silicon, and nitrogen. The specified sputtering gas environment means, for example, that the sputtering gas environment is formed by at least one inert gas selected from the group consisting of helium, neon, argon, krypton, and xenon, or the sputtering gas environment is formed by the above-mentioned inert gas, The sputtering gas atmosphere is formed of a nitrogen gas, and a mixed gas of a gas selected from the group consisting of oxygen, carbon dioxide gas, nitrogen monoxide gas, and nitrogen dioxide gas as the case may be. Formation of the thin film 30 for pattern formation can be performed in the state where the gas pressure in the film formation chamber is 0.3 Pa to 2.0 Pa, preferably 0.43 Pa to 0.9 Pa during sputtering. Side etching at the time of pattern formation can be suppressed, and a high etching rate can be achieved. The atomic ratio of titanium to silicon in the titanium silicide target is preferably in the range of titanium:silicon = 1:1 to 1:19 from the viewpoint of improving light resistance and chemical resistance and adjusting transmittance.

The composition and thickness of the pattern forming film 30 are adjusted so that the pattern forming film 30 has the above retardation and transmittance. The composition of the thin film 30 for pattern formation can be controlled by the content ratio of elements constituting the sputtering target (for example, the ratio of titanium content to silicon content), the composition and flow rate of sputtering gas, and the like. The thickness of the thin film 30 for pattern formation can be controlled by sputtering power, sputtering time, and the like. In addition, the thin film 30 for pattern formation is preferably formed using a continuous type (inline type) sputtering device. When the sputtering device is a continuous type sputtering device, the thickness of the thin film 30 for pattern formation can also be controlled by the transport speed of the substrate. In this way, it is controlled so that the thin film 30 for pattern formation contains titanium, silicon, and nitrogen, the content of nitrogen in the inner region of the thin film 30 is 30 atomic % or more, and the Ti2p narrow spectrum and the Si2p narrow spectrum satisfy the desired relationship (P _N / _PT greater than 1.52, etc.).

When the pattern-forming thin film 30 is formed of a single film, the composition and flow rate of the sputtering gas are appropriately adjusted, and the above-mentioned film-forming process is performed only once. When the pattern-forming thin film 30 is formed of a plurality of films with different compositions, the above-described film-forming process is performed a plurality of times by appropriately adjusting the composition and flow rate of the sputtering gas. The thin film for pattern formation 30 may be formed into a film using the target which differs in content ratio of the element which comprises a sputtering target. When performing a plurality of film forming processes, the sputtering power applied to the sputtering target may be changed for each film forming process.

"Surface Treatment Process"

The pattern forming thin film 30 can be formed of a titanium silicide material (titanium silicide oxynitride) containing oxygen in addition to titanium, silicon, and nitrogen. However, the content of oxygen is more than 0 atomic % and not more than 7 atomic %. In this way, when the pattern-forming film 30 contains oxygen, the surface oxidation state of the pattern-forming film 30 can also be adjusted in order to suppress the intrusion of the etching solution due to the presence of titanium oxide on the surface of the pattern-forming film 30. surface treatment process. It should be noted that, when the thin film 30 for pattern formation is formed of titanium silicide nitride containing titanium, silicon, and nitrogen, the content of titanium oxide is smaller than that of the above-mentioned titanium silicide material containing oxygen. Therefore, when the material of the thin film 30 for pattern formation is titanium silicide nitride, the above-mentioned surface treatment step may be performed or may not be performed.

As the surface treatment process for adjusting the oxidation state of the surface of the pattern-forming film 30, a method of surface treatment with an acidic aqueous solution, a method of surface treatment with an alkaline aqueous solution, and a method of surface treatment with drying such as ashing are mentioned. method etc.

In this way, the mask blank 10 of this embodiment can be obtained.

"Etching mask film formation process"

The mask blank 10 of the present embodiment may further have an etching mask film 40 . In addition, the following etching mask film forming process was performed. It should be noted that the etching mask film 40 is preferably made of a material that contains chromium and substantially does not contain silicon.

After the pattern forming thin film forming step, if necessary, surface treatment is performed to adjust the oxidation state of the surface of the pattern forming thin film 30 , and then an etching mask film 40 is formed on the pattern forming thin film 30 by sputtering. The etching mask film 40 is preferably formed using a continuous sputtering device. When the sputtering device is a continuous type sputtering device, the thickness of the etching mask film 40 can also be controlled by utilizing the transport speed of the light-transmitting substrate 20 .

The film formation of etching mask film 40 can use the sputtering target that comprises chromium or chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium carbonitride, and chromium oxycarbonitride etc.), by inert The sputtering gas environment formed by gas, or the sputtering gas environment formed by the mixed gas of an inert gas and an active gas is carried out. The inert gas may include, for example, at least one selected from the group consisting of helium, neon, argon, krypton, and xenon. The reactive gas may include at least one selected from the group consisting of oxygen, nitrogen, nitrogen monoxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon-based gas, and fluorine-based gas. As hydrocarbon-based gas, methane gas, ethane gas, propane gas, styrene gas, etc. are mentioned, for example. By adjusting the gas pressure in the film-forming chamber during sputtering, the etching mask film 40 can have a columnar structure similar to the pattern-forming thin film 30 . Thereby, side etching during pattern formation described later can be suppressed, and a high etching rate can be realized.

When the etching mask film 40 is formed of a single film having a uniform composition, the above-mentioned film forming process is performed only once without changing the composition and flow rate of the sputtering gas. When the etching mask film 40 is formed of a plurality of films with different compositions, the above-mentioned film forming process is performed a plurality of times while changing the composition and flow rate of the sputtering gas for each film forming process. When the etching mask film 40 is formed of a single film whose composition continuously changes in the thickness direction, the composition and flow rate of the sputtering gas are changed with the elapsed time of the film forming process, and the above film forming process is performed only once.

Thus, the mask blank 10 of this embodiment which has the etching mask film 40 can be obtained.

In addition, since the mask blank 10 shown in FIG. 1 has the etching mask film 40 on the thin film 30 for pattern formation, when manufacturing the mask blank 10, the process of forming an etching mask film is performed. In addition, when manufacturing the mask blank 10 having the etching mask film 40 on the pattern forming film 30 and the resist film on the etching mask film 40, after the etching mask film forming process, the etching mask A resist film is formed on the film 40 . In addition, in the mask blank 10 shown in FIG. 2, when manufacturing the mask blank 10 having a resist film on the pattern forming film 30, the resist is formed after the pattern forming film forming process. membrane.

In the mask blank 10 of the embodiment shown in FIG. 1 , an etching mask film 40 is formed on the pattern forming thin film 30 . Moreover, the mask blank 10 of embodiment shown in FIG. 2 is formed with the thin film 30 for pattern formation. In any case, the thin film 30 for pattern formation contains titanium, silicon, and nitrogen, the content of nitrogen in the inner region of the thin film 30 is 30 atomic % or more, and the Ti2p narrow spectrum and the Si2p narrow spectrum satisfy the desired relationship (P _N /P _S is greater than 1.18, etc.).

The mask blank 10 of the embodiment shown in FIGS. 1 and 2 has high light resistance to exposure light of a wavelength including an ultraviolet region, and also has high chemical resistance. In addition, when the pattern forming thin film 30 is patterned by wet etching, etching in the film thickness direction can be promoted, while side etching can be suppressed. Therefore, the thin-film pattern 30a for pattern formation obtained by patterning has a favorable cross-sectional shape, and has desired transmittance (for example, high transmittance). By using the mask blank 10 of the embodiment, the thin film pattern 30a for pattern formation can be formed in a short etching time. In addition, even after cumulative irradiation of exposure light having wavelengths in the ultraviolet range, the pattern-forming thin film pattern 30a capable of maintaining the exposure transfer characteristics within a desired range can be formed.

Therefore, by using the mask blank 10 of the present embodiment, it is possible to manufacture a mask for forming a high-definition pattern that has high light resistance to exposure light having a wavelength in the ultraviolet range, has high chemical resistance, and can be accurately transferred for high-definition pattern formation. The mask 100 for transfer of the thin film pattern 30a.

<Manufacturing method of transfer mask 100>

Next, the manufacturing method of the transfer mask 100 of this embodiment is demonstrated. This transfer mask 100 has the same technical features as the mask blank 10 . Matters related to the light-transmitting substrate 20 of the transfer mask 100 , the thin film 30 for pattern formation, and the etching mask film 40 are the same as those of the mask blank 10 .

FIG. 3 is a schematic diagram illustrating a method of manufacturing the transfer mask 100 according to the present embodiment. FIG. 4 is a schematic diagram showing another method of manufacturing the transfer mask 100 according to this embodiment.

<<Manufacturing method of transfer mask 100 shown in FIG. 3>>

The method of manufacturing the transfer mask 100 shown in FIG. 3 is a method of manufacturing the transfer mask 100 using the mask blank 10 shown in FIG. 1 . The manufacturing method of the transfer mask 100 shown in FIG. 3 includes the steps of preparing the mask blank shown in FIG. 1 , forming a resist film on the etching mask film 40, and forming The resist film pattern is used as a mask to wet-etch the etching mask film 40 to form an etching mask film pattern (first etching mask film pattern 40a) on the pattern forming film 30; the etching mask The mold film pattern (the first etching mask film pattern 40 a ) is used as a mask, and the pattern forming thin film 30 is wet-etched to form a transfer pattern on the light-transmitting substrate 20 . It should be noted that the pattern for transfer in this specification is obtained by patterning at least one optical film formed on the light-transmitting substrate 20 . The above-mentioned optical film may be the thin film for pattern formation 30 and/or the etching mask film 40 , and may also include other films (light-shielding film, film for suppressing reflection, conductive film, etc.). That is, the transfer pattern may include a patterned thin film for pattern formation and/or an etching mask film, and may also include another patterned film.

The method of manufacturing the transfer mask 100 shown in FIG. 3 specifically forms a resist film on the etching mask film 40 of the mask blank 10 shown in FIG. 1 . Next, a resist film pattern 50 is formed by drawing and developing a desired pattern on the resist film (see FIG. 3( a ), a step of forming the first resist film pattern 50 ). Next, using the resist film pattern 50 as a mask, the etching mask film 40 is wet-etched to form an etching mask film pattern 40a on the pattern forming film 30 (refer to FIG. Formation process of the mask film pattern 40a). Next, using the above-mentioned etching mask film pattern 40a as a mask, the pattern forming film 30 is wet-etched to form a pattern forming film pattern 30a on the light-transmitting substrate 20 (referring to FIG. pattern 30a formation process). Thereafter, a step of forming the second resist film pattern 60 and a step of forming the second etching mask pattern 40b may be included (see FIG. 3( d ) and FIG. 3( e )).

More specifically, in the step of forming the first resist film pattern 50 , first, a resist film is formed on the etching mask film 40 of the mask blank 10 of the present embodiment shown in FIG. 1 . The resist film material used is not particularly limited. The resist film can be sensitive to, for example, a laser beam having any wavelength selected from the wavelength region of 350 nm to 436 nm described later. In addition, the resist film may be either a positive type or a negative type.

Thereafter, a desired pattern is drawn on the resist film using a laser beam having an arbitrary wavelength selected from the wavelength region of 350 nm to 436 nm. The pattern drawn on the resist film is a pattern formed on the pattern forming thin film 30 . As the pattern drawn on the resist film, a line and space pattern and a hole pattern can be exemplified.

Thereafter, as shown in FIG. 3( a ), the resist film is developed with a predetermined developer to form a first resist film pattern 50 on the etching mask film 40 .

<<<Formation process of the first etching mask film pattern 40a>>>

In the step of forming the first etching mask film pattern 40a, first, the etching mask film 40 is etched using the first resist film pattern 50 as a mask to form the first etching mask film pattern 40a. The etching mask film 40 may be formed of a chromium-based material containing chromium (Cr). When the etching mask film 40 has a columnar structure, the etching rate is fast and side etching can be suppressed, which is preferable. The etchant for etching the etching mask film 40 is not particularly limited as long as it can selectively etch the etching mask film 40 . Specifically, an etching solution containing diceric ammonium nitrate and perchloric acid may be mentioned.

Thereafter, as shown in FIG. 3( b ), the first resist film pattern 50 is stripped using a resist stripping solution or by ashing. Depending on circumstances, the next step of forming the thin film pattern 30 a for pattern formation may be performed without peeling off the first resist film pattern 50 .

<<<Formation process of thin film pattern 30a for pattern formation>>>

As shown in FIG. 3( c), in the forming process of the first pattern-forming thin film pattern 30a, the first etching mask film pattern 40a is used as a mask to wet-etch the pattern-forming thin film 30 to form a pattern forming pattern. Use thin film pattern 30a. As the thin film pattern 30a for pattern formation, a line and space pattern and a hole pattern are mentioned. The etchant for etching the thin film 30 for pattern formation is not particularly limited as long as it can selectively etch the thin film 30 for pattern formation. For example, etching solution A (etching solution containing ammonium hydrogen fluoride and hydrogen peroxide, etc.), etching solution B (etching solution containing ammonium fluoride, phosphoric acid, and hydrogen peroxide, etc.) are mentioned.

In order to improve the cross-sectional shape of the thin film pattern 30a for pattern formation, wet etching is preferably performed for a time (overetching time) longer than the time for which the light-transmitting substrate 20 is exposed in the thin film pattern 30a for pattern formation (only etching time). As the overetching time, in consideration of the influence on the light-transmitting substrate 20, etc., it is preferably a time after adding 20% of the etching time only, and more preferably 10% of the etching time only. time after time.

<<<Formation Step of Second Resist Film Pattern 60>>>

In the formation process of the second resist film pattern 60, first, a resist film covering the first etching mask film pattern 40a is formed. The resist film material used is not particularly limited. For example, it only needs to be sensitive to a laser beam having an arbitrary wavelength selected from a wavelength region of 350 nm to 436 nm described later. In addition, the resist film may be either a positive type or a negative type.

Thereafter, a desired pattern is drawn on the resist film using a laser beam having an arbitrary wavelength selected from the wavelength region of 350 nm to 436 nm. The pattern drawn on the resist film is a light-shielding band pattern for shielding the outer peripheral region of the region where the pattern-forming thin film pattern 30a is formed, a light-shielding band pattern for shielding the central part of the pattern-forming thin-film pattern 30a, and the like. It should be noted that, depending on the transmittance of the pattern forming film 30 with respect to exposure light, the pattern drawn on the resist film may not have a light-shielding band pattern that shields the central portion of the pattern forming film pattern 30a. pattern.

Thereafter, as shown in FIG. 3( d ), the resist film is developed with a predetermined developer to form a second resist film pattern 60 on the first etching mask film pattern 40 a.

<<<Formation process of the second etching mask film pattern 40b>>>

As shown in FIG. 3( e), in the formation process of the second etching mask film pattern 40b, the second resist film pattern 60 is used as a mask to etch the first etching mask film pattern 40a to form the second etching mask film pattern 40a. Second, the mask film pattern 40b is etched. The first etch mask film pattern 40a may be formed of a chromium-based material containing chromium (Cr). The etchant for etching the first etching mask film pattern 40a is not particularly limited as long as it can selectively etch the first etching mask film pattern 40a. For example, an etching solution containing diceric ammonium nitrate and perchloric acid may be mentioned.

Thereafter, the second resist film pattern 60 is stripped using a resist stripping liquid, or by ashing.

In this way, the transfer mask 100 can be obtained. That is, the transfer pattern included in the transfer mask 100 of the present embodiment may include the thin film pattern 30a for pattern formation and the second etching mask film pattern 40b.

It should be noted that, in the above description, the case where the etching mask film 40 has a function of blocking the transmission of exposure light has been described. In the case where the etching mask film 40 simply has the function of a hard mask when etching the thin film 30 for pattern formation, in the above description, the formation process of the second resist film pattern 60 and the second etching mask are not performed. Forming process of the mold film pattern 40b. In this case, after the formation process of the thin film pattern 30a for pattern formation, the 1st etching mask film pattern 40a is peeled off, and the mask 100 for transfer is produced. That is, the pattern for transfer which the mask 100 for transfer has may consist only of the thin film pattern 30a for pattern formation.

According to the manufacturing method of the transfer mask 100 of this embodiment, since the mask blank 10 shown in FIG. 1 is used, etching time can be shortened, and the thin film pattern 30a for pattern formation with a good cross-sectional shape can be formed. Therefore, the mask 100 for transfer which can transfer the transfer pattern including the high-definition thin film pattern 30a for pattern formation with high precision can be manufactured. The transfer mask 100 manufactured in this way can correspond to the refinement of a line and space pattern and/or a contact hole.

<<Manufacturing method of transfer mask 100 shown in FIG. 4>>

The method of manufacturing the transfer mask 100 shown in FIG. 4 is a method of manufacturing the transfer mask 100 using the mask blank 10 shown in FIG. 2 . The manufacturing method of the transfer mask 100 shown in FIG. 4 has: the process of preparing the mask blank 10 shown in FIG. 2; forming a resist film on the pattern forming film 30; The resist film pattern is used as a mask, and the pattern forming thin film 30 is wet-etched to form a transfer pattern on the light-transmitting substrate 20 .

Specifically, in the manufacturing method of the transfer mask 100 shown in FIG. 4 , a resist film is formed on the mask blank 10 . Next, a resist film pattern 50 is formed by drawing and developing a desired pattern on the resist film ( FIG. 4( a ), step of forming the first resist film pattern 50 ). Next, using the resist film pattern 50 as a mask, the pattern forming thin film 30 is wet-etched to form a pattern forming thin film pattern 30a on the light-transmitting substrate 20 (Fig. 4(b) and (c), pattern Step of forming thin film pattern 30a for formation).

More specifically, in the resist film pattern forming step, first, a resist film is formed on the pattern forming thin film 30 of the mask blank 10 of the present embodiment shown in FIG. 2 . The resist film material used is the same as that described above. In addition, before forming a resist film as needed, surface modification treatment may be performed on the pattern forming thin film 30 in order to make the pattern forming thin film 30 and the resist film good contact property. In the same manner as above, after the resist film is formed, a desired pattern is drawn on the resist film using a laser beam having an arbitrary wavelength selected from the wavelength region of 350 nm to 436 nm. Thereafter, as shown in FIG. 4( a ), the resist film is developed with a predetermined developer to form a resist film pattern 50 on the pattern forming thin film 30 .

<<<Formation process of thin film pattern 30a for pattern formation>>>

As shown in FIG. 4( b ), in the step of forming the thin film pattern 30 a for pattern formation, the thin film 30 for pattern formation is etched using the resist film pattern as a mask to form the thin film pattern 30 a for pattern formation. The etchant and overetching time for etching the thin film pattern 30a for pattern formation and the thin film 30 for pattern formation are the same as those described in the above-mentioned embodiment shown in FIG. 3 .

Thereafter, the resist film pattern 50 is stripped using a resist stripping solution or by ashing ( FIG. 4( c )).

In this way, the transfer mask 100 can be obtained. In addition, although the transfer pattern which the transfer mask 100 of this embodiment has consists only of the thin film pattern 30a for pattern formation, it may also include other film patterns. As another film, the film which suppresses reflection, a conductive film, etc. are mentioned, for example.

According to the manufacturing method of the transfer mask 100 of this embodiment, since the mask blank 10 shown in FIG. 2 is used, the transparent substrate 20 will not be damaged by the wet etching solution The yield is reduced, the etching time can be shortened, and the thin film pattern 30a for pattern formation with a good cross-sectional shape can be formed. Therefore, the mask 100 for transfer which can transfer the transfer pattern including the high-definition thin film pattern 30a for pattern formation with high precision can be manufactured. The transfer mask 100 manufactured in this way can correspond to the refinement of a line and space pattern and/or a contact hole.

<Manufacturing method of display device>

A method of manufacturing the display device of this embodiment will be described. The method for manufacturing a display device according to this embodiment includes an exposure step of placing the above-mentioned transfer mask 100 of this embodiment on a mask stage of an exposure device, and placing the transfer mask 100 on a display device manufacturing The pattern for transfer formed on 100 is exposed and transferred to the resist formed on the substrate for a display device.

Specifically, the method for manufacturing a display device according to this embodiment includes the step of placing the transfer mask 100 manufactured using the above-mentioned mask blank 10 on a mask stage of an exposure device (mask placing step ), and a step of exposing and transferring a pattern for transfer on the resist film on the substrate for a display device (exposure step). Next, each step will be described in detail.

"Loading process"

In the mounting step, the transfer mask 100 of the present embodiment is mounted on a mask stage of an exposure device. Here, the transfer mask 100 is arranged to face the resist film formed on the substrate for a display device via the projection optical system of the exposure device.

"Pattern transfer process"

In the pattern transfer step, the transfer mask 100 is irradiated with exposure light, and the resist film formed on the display device substrate transfers the transfer pattern including the thin film pattern 30 a for pattern formation. Exposure light is composite light including light of multiple wavelengths selected from the wavelength range of 313nm to 436nm, or monochromatic light selected by cutting a certain wavelength range from the wavelength range of 313nm to 436nm by a filter or the like , or monochromatic light emitted from a light source having a wavelength range of 313nm to 436nm. For example, the exposure light is composite light including at least one of i-line, h-line, and g-line, or monochromatic light of i-line. By using composite light as exposure light, it is possible to increase the intensity of exposure light, thereby improving throughput. Therefore, the manufacturing cost of the display device can be reduced.

According to the method of manufacturing a display device of this embodiment, it is possible to manufacture a high-definition display device having high resolution, fine line and space patterns and/or contact holes.

In addition, in the said embodiment, the case where the mask blank 10 which has the film 30 for pattern formations, and the mask 100 for transfer which has the film pattern 30a for pattern formations was used was demonstrated. The thin film 30 for pattern formation may be, for example, a phase shift film having a phase shift effect, or a light shielding film. Therefore, the transfer mask 100 of the present embodiment includes a phase shift mask having a phase shift film pattern and a binary mask having a light shielding film pattern. In addition, the mask blank 10 of the present embodiment includes a phase shift mask blank and a binary mask blank which are raw materials of a phase shift mask and a binary mask.

[Example]

Hereinafter, the present invention will be specifically described through examples, but the present invention is not limited thereto.

(first embodiment)

In order to manufacture the mask blank 10 of the first embodiment, first, as the light-transmitting substrate 20 , a synthetic quartz glass substrate having a size of 1214 (1220 mm×1400 mm) 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 a chamber of a continuous sputtering apparatus.

In order to form the pattern-forming thin film 30 on the main surface of the light-transmitting substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced into the first chamber. Next, using a first sputtering target (titanium:silicon=5:7) containing titanium and silicon, a nitrogen-containing titanium silicide containing titanium, silicon, and nitrogen is laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering. compounds. In this way, the pattern-forming thin film 30 (Ti:Si:N:O=20.4:26.7:51.3:1.6 atomic % ratio) was formed using titanium silicide nitride as a material and having a film thickness of 115 nm. Here, the composition of the thin film 30 for pattern formation is the result obtained by the measurement by X-ray photoelectron spectroscopy (XPS). Next, for other films, the method of measuring the film composition is also the same (the same applies to the second to fourth examples and the first and second comparative examples). It should be noted that the thin film 30 for pattern formation is a phase shift film having a phase shift effect.

Next, the transparent substrate 20 with the thin film 30 for pattern formation is sent into the second chamber, and a mixed gas of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced into the second chamber. Then, chromium nitride (CrN) containing chromium and nitrogen is formed on the pattern forming thin film 30 by reactive sputtering using a second sputtering target made of chromium. Next, a mixed gas of argon (Ar) gas and methane (CH4) gas is introduced into the third chamber with a predetermined vacuum degree, and reactive sputtering is performed using a third sputtering target made of chromium. Chromium carbide (CrC) containing chromium and carbon is formed on the CrN. Finally, a mixed gas of argon (Ar) gas and methane (CH ₄ ) gas and a mixed gas of nitrogen (N ₂ ) gas and oxygen (O ₂ ) gas are introduced in the fourth chamber with a predetermined vacuum degree. , using a fourth sputtering target formed of chromium, chromium carbon oxynitride (CrCON) containing chromium, carbon, oxygen, and nitrogen was formed on CrC by reactive sputtering. As described above, the etching mask film 40 of the laminated structure of the CrN layer, the CrC layer, and the CrCON layer is formed on the pattern forming thin film 30 .

In this way, the mask blank 10 in which the thin film 30 for pattern formation and the etching mask film 40 were formed on the light-transmitting substrate 20 is obtained.

The thin film for pattern formation of the first example was formed on the main surface of another synthetic quartz substrate (about 152 mm×about 152 mm), and other thin films for pattern formation were formed under the same film-forming conditions as in the first example above. . Next, X-ray photoelectron spectroscopy was performed on the thin film for pattern formation on the other synthetic quartz substrate. In this X-ray photoelectron spectroscopy, X-rays (AlKα line: 1486eV) are irradiated to the inner region of the pattern-forming film, and the intensity of photoelectrons released from the pattern-forming film is measured, and by Ar gas sputtering, Excavate the inner region of the thin film for pattern formation at a voltage of 2.0kV and a sputtering rate of about 5nm/min ( _SiO2 conversion), and irradiate the inner region of the excavated region with X-rays, and the X-rays released from the region The intensity of the photoelectron is measured, and by repeating the above steps, the Ti2p narrow spectrum at each depth of the inner region of the pattern forming thin film is respectively obtained (the same applies to the second to fourth examples, the first and the second comparative examples hereafter) .

5 is a graph showing the results of X-ray photoelectron spectroscopy analysis (Ti2p narrow spectrum) of thin films for pattern formation on other synthetic quartz substrates in each example of the present invention. 6 is a graph showing the results of X-ray photoelectron spectroscopy analysis (Si2p narrow spectrum) of the phase shift film of the mask blank of each Example of the present invention. Each narrow spectrum shown in FIGS. 5 and 6 is obtained at a predetermined depth position (a depth position approximately at the center in the film thickness direction of the inner region) of the thin film for pattern formation on another synthetic quartz substrate in each example. As obtained from the values shown in FIGS. 5 and 6, in the Ti2p narrow spectrum and Si2p narrow spectrum of the first embodiment, P _N / _PS is 1.84, which satisfies a relationship greater than 1.18 (as described above, let The photoelectron intensity with a binding energy of 455eV is P _N , and the photoelectron intensity with a binding energy of 102eV is P _S . The same below).

In addition, in the Ti2p narrow spectrum and Si2p narrow spectrum of the first embodiment, P _NU / _PS is 1.60, which satisfies a relationship greater than 1.05 (as described above, let the photoelectron intensity at which the binding energy is 461eV be P _NU . same).

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the first example, (P _N +P _NU )/ _PS is 3.44, which satisfies a relationship greater than 2.22.

In addition, in the Ti2p narrow spectrum of the first example, P _N /P _TS is 3.06, which satisfies a relationship greater than 2.13 (as described above, the photoelectron intensity at which the binding energy is 453eV is P _TS . The same applies below).

In addition, in the narrow spectrum of Ti2p in the first example, (P _N + _PT )/P _TS is 4.62, which satisfies a relationship larger than 3.53.

It should be noted that, in the first embodiment, each Ti2p narrow spectrum and each Si2p narrow spectrum at other depth positions in the inner region also satisfy the above ratios.

<Measurement of transmittance and phase difference>

The transmittance (wavelength: 365nm) and phase difference (wavelength: 365nm) were measured on the surface of the pattern-forming film 30 of the mask blank 10 of the first embodiment using MPM-100 manufactured by LaserTech (USA). Measurement. The measurement of the transmittance and phase difference of the pattern forming film 30 used a substrate with a film formed by forming another pattern forming film on the main surface of the above-mentioned other synthetic quartz glass substrate (second and second hereinafter). Three, the fourth embodiment, the first, the second comparative example are also the same). As a result, the transmittance of the pattern forming film 30 of the first example was 6%, and the phase difference was 180 degrees.

<Transfer mask 100 and its manufacturing method>

Using the mask blank 10 of the first embodiment manufactured as described above, a transfer mask 100 was manufactured. First, a photoresist film is coated on the etching mask film 40 of the mask blank 10 using a resist coating device.

Thereafter, a photoresist film is formed through a heating/cooling process.

Thereafter, a photoresist film was drawn using a laser drawing device, and a resist film pattern of a hole pattern with a pore diameter of 1.5 μm was formed on the etching mask film 40 through developing and rinsing steps.

Thereafter, using the resist film pattern as a mask, the etching mask film 40 is wet-etched using a chromium etchant containing diceric ammonium nitrate and perchloric acid to form a first etching mask film pattern 40a.

Afterwards, using the first etching mask film pattern 40a as a mask, wet etching is performed on the thin film 30 for pattern formation using a titanium silicide etchant obtained by diluting a mixed solution of ammonium bifluoride and hydrogen peroxide with pure water, thereby The thin film pattern 30a for pattern formation is formed.

After that, the resist film pattern is peeled off.

After that, using a resist coating device, a photoresist film is coated so as to cover the first etching mask film pattern 40a.

Thereafter, a photoresist film is formed through a heating/cooling process.

Thereafter, a photoresist film is drawn using a laser drawing device, and a second resist film pattern 60 for forming a light-shielding band is formed on the first etching mask film pattern 40a through a developing/rinsing process.

Thereafter, using the second resist film pattern 60 as a mask, the first etching mask film pattern 40a formed in the transfer pattern forming region is wetted with a chromium etchant containing dicerium ammonium nitrate and perchloric acid. etched.

After that, the second resist film pattern 60 is peeled off.

In this way, on the light-transmitting substrate 20, a thin film pattern 30a for pattern formation with a hole diameter of 1.5 μm is formed in the pattern formation region for transfer, and a laminated structure consisting of the thin film pattern 30a for pattern formation and the etching mask film pattern 40b is obtained. The transfer mask 100 of the first embodiment of the formed light-shielding belt.

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed with a scanning electron microscope.

The thin film pattern 30 a for pattern formation of the transfer mask 100 of the first embodiment has a nearly vertical cross-sectional shape. Therefore, the pattern forming thin film pattern 30 a formed on the transfer mask 100 of the first embodiment has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

From the above description, it can be said that when the transfer mask 100 of the first embodiment is placed on the mask stage of the exposure device, and the resist film on the substrate for the display device is exposed and transferred, A pattern for transfer including a fine pattern of less than 2.0 μm is transferred with high precision.

〈Lightfastness/Chemical Resistance〉

A sample in which the pattern-forming thin film 30 used in the mask blank 10 of the first embodiment was formed on the light-transmitting substrate 20 was prepared. The pattern-forming thin film 30 of the sample of the first example was irradiated with light from a metal halide light source including ultraviolet light having a wavelength of 365 nm so that the total irradiation dose was 10 kJ/cm ² . The transmittance is measured before and after prescribed ultraviolet irradiation, and the change in transmittance is calculated [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)]. 30 for light fastness evaluation. Transmittance was measured using a spectrophotometer.

In the first example, the change in transmittance before and after ultraviolet irradiation was good at 0.09% (0.09 points). From the above description, it can be seen that the film for pattern formation of the first example is a film having sufficiently high light resistance in practical use.

A sample in which the pattern-forming thin film 30 used in the mask blank 10 of the first embodiment was formed on the light-transmitting substrate 20 was prepared. With respect to the pattern-forming thin film 30 of the sample of the first embodiment, SPM cleaning (cleaning time: 5 minutes) with a mixed solution of sulfuric acid and hydrogen peroxide, and a mixed solution of ammonia, hydrogen peroxide, and water were performed. The performed SC-1 cleaning (cleaning time: 5 minutes) was regarded as one cycle, and five cycles of cleaning tests were performed to evaluate the chemical resistance of the thin film 30 for pattern formation.

Measure the reflectance spectrum in the wavelength range of 200nm to 500nm before and after the cleaning test. According to the change in the wavelength (bottom peak wavelength) corresponding to the lowest reflectance where the reflectance protrudes downward, The chemical resistance of the pattern-forming thin film 30 was evaluated.

As a result of the chemical resistance evaluation, in the first example having the titanium silicide-based pattern-forming thin film, the amount of change in the bottom peak wavelength per cleaning cycle was less than 1.0 nm toward the short wavelength side, and the chemical resistance was good.

From this, it is clear that the pattern-forming thin film of the first example satisfies the desired optical properties (transmittance, phase difference), and also has high light resistance (chemical resistance), high etching rate, and good cross-sectional shape. An unprecedented good film.

(second embodiment)

The mask blank 10 of the second embodiment was manufactured in the same flow as the mask blank 10 of the first embodiment except for the pattern forming film 30 as described below.

The method of forming the pattern-forming thin film 30 of the second embodiment is as follows.

In order to form the pattern-forming thin film 30 on the main surface of the light-transmitting substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced into the first chamber. Then, a titanium silicide nitrogen oxide containing titanium, silicon, and nitrogen is laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering using a first sputtering target containing titanium and silicon (titanium:silicon=1:2). compounds. In this way, the pattern-forming thin film 30 (Ti:Si:N:O=15.4:31.6:50.9:2.1 atomic % ratio) was formed using titanium silicide nitride as a material and having a film thickness of 130 nm.

Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.

Then, another pattern-forming thin film was formed on the main surface of another synthetic quartz substrate under the same film-forming conditions as in the second embodiment described above. Next, X-ray photoelectron spectroscopy was performed on the thin film for pattern formation on this other synthetic quartz substrate in the same manner as in the first example.

As determined from the values shown in FIGS. 5 and 6 , in the Ti2p narrow spectrum and Si2p narrow spectrum of the second embodiment, P _N / _PS is 1.36, which satisfies a relationship greater than 1.18.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the second example, P _NU / _PS is 1.23, which satisfies a relationship greater than 1.05.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the second example, (P _N +P _NU )/ _PS is 2.59, which satisfies a relationship greater than 2.22.

In addition, in the narrow spectrum of Ti2p in the second example, P _N /P _TS is 2.53, which satisfies a relationship larger than 2.13.

In addition, in the narrow spectrum of Ti2p in the second example, (P _N + _PT )/P _TS is 3.96, which satisfies a relationship greater than 3.53.

It should be noted that, in the second embodiment, each Ti2p narrow spectrum and each Si2p narrow spectrum at other depth positions in the inner region also satisfy the above ratios.

<Measurement of transmittance and phase difference>

The transmittance (wavelength: 365nm) and retardation (wavelength: 365nm) of the surface of the pattern-forming film 30 of the mask blank 10 of the second embodiment were measured using MPM-100 manufactured by LaserTech (USA). Measurement. As a result, the transmittance of the pattern forming film 30 of the second example was 14%, and the phase difference was 180 degrees.

<Transfer mask 100 and its manufacturing method>

Using the mask blank 10 of the second embodiment manufactured as described above, the transfer mask 100 was manufactured in the same flow as that of the first embodiment, and a pattern formed in the transfer pattern formation region was obtained on the light-transmitting substrate 20. The transfer mask 100 of the second embodiment of the pattern forming thin film pattern 30a with a pore diameter of 1.5 μm, and the light-shielding tape formed by the laminated structure of the pattern forming thin film pattern 30a and the etching mask film pattern 40b.

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed with a scanning electron microscope.

The thin film pattern 30 a for pattern formation of the transfer mask 100 of the second embodiment has a cross-sectional shape close to vertical. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of the second embodiment has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

From the above description, it can be said that when the transfer mask 100 of the second embodiment is placed on the mask stage of the exposure device, and the resist film on the substrate for the display device is exposed and transferred, A pattern for transfer including a fine pattern of less than 2.0 μm is transferred with high precision.

〈Lightfastness/Chemical Resistance〉

A sample in which the pattern-forming thin film 30 used in the mask blank 10 of the second embodiment was formed on the light-transmitting substrate 20 was prepared. The pattern-forming thin film 30 of the sample of the second example was irradiated with light from a metal halide light source including ultraviolet light having a wavelength of 365 nm so that the total irradiation dose was 10 kJ/cm ² . The transmittance is measured before and after the specified ultraviolet irradiation, and the change in transmittance is calculated [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)], and the pattern forming film 30 for light fastness evaluation. Transmittance was measured using a spectrophotometer.

In Example 2, the change in transmittance before and after ultraviolet irradiation was good at 0.34% (0.34 points). From the above description, it can be seen that the film for pattern formation of the second example is a film having sufficiently high light resistance for practical use.

In addition, a sample in which the pattern-forming film 30 used in the mask blank 10 of the second example was formed on the light-transmitting substrate 20 was prepared, and the chemical resistance of the pattern-forming film 30 was the same as that of the first example. to evaluate.

As a result of the chemical resistance evaluation, in Example 2 having the titanium silicide-based pattern-forming thin film, the amount of change in the bottom peak wavelength per cleaning cycle was less than 1.0 nm toward the shorter wavelength side, indicating good chemical resistance.

From this, it can be clarified that the pattern-forming thin film of the second embodiment satisfies the desired optical characteristics (transmittance, phase difference), and also has high light resistance (chemical resistance), high etching rate, and good cross-sectional shape. , An unprecedented good film.

(third embodiment)

The mask blank 10 of the third embodiment was manufactured in the same flow as the mask blank 10 of the first embodiment except for the pattern forming film 30 as described below.

The method of forming the pattern-forming thin film 30 of the third embodiment is as follows.

In order to form the pattern-forming thin film 30 on the main surface of the light-transmitting substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced into the first chamber. Then, a titanium silicide nitrogen oxide containing titanium, silicon, and nitrogen is laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering using a first sputtering target containing titanium and silicon (titanium:silicon=1:3). compounds. In this manner, the pattern-forming thin film 30 (Ti:Si:N:O=11.4:35.4:52.4:0.8 atomic % ratio) was formed using titanium silicide nitride as a material and having a film thickness of 131 nm.

Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.

Then, other thin films for pattern formation were formed on the main surfaces of other synthetic quartz substrates under the same film-forming conditions as in the third embodiment described above. Next, X-ray photoelectron spectroscopy was performed on the thin film for pattern formation on this other synthetic quartz substrate in the same manner as in the first example.

As determined from the values shown in FIGS. 5 and 6 , in the Ti2p narrow spectrum and the Si2p narrow spectrum of the third embodiment, P _N / _PS is 1.25, which satisfies a relationship larger than 1.18.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the third example, P _NU / _PS is 1.18, which satisfies a relationship greater than 1.05.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the third embodiment, (P _N +P _NU )/ _PS is 2.43, which satisfies a relationship greater than 2.22.

It should be noted that, in the third embodiment, each Ti2p narrow spectrum and each Si2p narrow spectrum at other depth positions in the inner region also satisfy the above ratios.

<Measurement of transmittance and phase difference>

The transmittance (wavelength: 365nm) and retardation (wavelength: 365nm) of the surface of the pattern-forming film 30 of the mask blank 10 of the third embodiment were measured using MPM-100 manufactured by LaserTech (USA). Measurement. As a result, the transmittance of the pattern forming film 30 of the third example was 18%, and the phase difference was 180 degrees.

<Transfer mask 100 and its manufacturing method>

Using the mask blank 10 of the third embodiment manufactured as described above, the transfer mask 100 was manufactured in the same flow as that of the first embodiment, and the pattern formed in the transfer pattern formation region was obtained on the light-transmitting substrate 20. The transfer mask 100 of the third embodiment of the pattern-forming thin film pattern 30a with a pore diameter of 1.5 μm, and the light-shielding tape formed by the lamination structure of the pattern-forming thin film pattern 30a and the etching mask film pattern 40b.

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed with a scanning electron microscope.

The thin film pattern 30 a for pattern formation of the transfer mask 100 of the third embodiment has a cross-sectional shape close to vertical. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of the third embodiment has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

According to the above description, it can be said that when the transfer mask 100 of the third embodiment is placed on the mask table of the exposure device, and the resist film on the substrate for the display device is exposed and transferred, A pattern for transfer including a fine pattern of less than 2.0 μm is transferred with high precision.

〈Lightfastness/Chemical Resistance〉

A sample in which the pattern-forming thin film 30 used in the mask blank 10 of the third embodiment was formed on the light-transmitting substrate 20 was prepared. The pattern-forming thin film 30 of the sample of the third example was irradiated with light from a metal halide light source including ultraviolet light having a wavelength of 365 nm so that the total irradiation dose was 10 kJ/cm ² . The transmittance is measured before and after the specified ultraviolet irradiation, and the change in transmittance is calculated [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)], thereby determining the pattern forming film. 30 for light fastness evaluation. Transmittance was measured using a spectrophotometer.

In the third example, the change in transmittance before and after ultraviolet irradiation was good at 0.45% (0.45 points). From the above description, it can be seen that the film for pattern formation of the third example is a film having sufficiently high light resistance for practical use.

In addition, a sample in which the pattern-forming film 30 used in the mask blank 10 of the third example was formed on the light-transmitting substrate 20 was prepared, and the chemical resistance of the pattern-forming film 30 was the same as that of the first example. to evaluate.

As a result of the chemical resistance evaluation, in Example 3 having the titanium silicide-based pattern-forming thin film, the amount of change in the bottom peak wavelength per cleaning cycle was less than 1.0 nm toward the short wavelength side, and the chemical resistance was good.

From this, it can be clarified that the pattern-forming thin film of the third embodiment has desired optical characteristics (transmittance, phase difference), and also has high light resistance (chemical resistance), high etching rate, and good cross-sectional shape. , An unprecedented good film.

(fourth embodiment)

The mask blank 10 of the fourth embodiment is manufactured in the same flow as the mask blank 10 of the first embodiment except for the pattern forming film 30 as described below.

The method of forming the pattern-forming thin film 30 of the fourth embodiment is as follows.

In order to form the pattern-forming thin film 30 on the main surface of the light-transmitting substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced into the first chamber. Then, a titanium silicide nitrogen oxide containing titanium, silicon, and nitrogen is laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering using a first sputtering target containing titanium and silicon (titanium:silicon=1:3). compounds. In this manner, a pattern-forming thin film 30 (Ti:Si:N:O=11.7:35.0:52.0:1.3 atomic % ratio) was formed using titanium silicide nitride as a material and having a film thickness of 134 nm.

Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.

Then, under the same film-forming conditions as in the above-mentioned fourth embodiment, other thin films for pattern formation and etching mask films were respectively formed on the main surfaces of other light-transmitting substrates. Next, X-ray photoelectron spectroscopy was performed on the thin film for pattern formation on this other light-transmitting substrate in the same manner as in the first example.

As determined from the values shown in FIGS. 5 and 6 , in the Ti2p narrow spectrum and Si2p narrow spectrum of the fourth embodiment, P _N / _PS is 1.19, which satisfies a relationship greater than 1.18.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the fourth embodiment, P _NU / _PS is 1.11, which satisfies a relationship greater than 1.05.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the fourth embodiment, (P _N +P _NU )/ _PS is 2.30, which satisfies a relationship larger than 2.22.

It should be noted that, in the fourth embodiment, each Ti2p narrow spectrum and each Si2p narrow spectrum at other depth positions in the inner region also satisfy the above ratios.

<Measurement of transmittance and phase difference>

The transmittance (wavelength: 365nm) and retardation (wavelength: 365nm) of the surface of the pattern-forming film 30 of the mask blank 10 of the fourth embodiment were measured using MPM-100 manufactured by LaserTech (USA). Measurement. As a result, the transmittance of the pattern forming film 30 of the fourth example was 22%, and the phase difference was 180 degrees.

<Transfer mask 100 and its manufacturing method>

Using the mask blank 10 of the fourth embodiment manufactured as described above, the transfer mask 100 was manufactured in the same flow as that of the first embodiment, and a pattern formed in the transfer pattern formation region was obtained on the light-transmitting substrate 20. The transfer mask 100 of the fourth embodiment of the pattern-forming thin film pattern 30a with a pore diameter of 1.5 μm, and the light-shielding tape formed by the lamination structure of the pattern-forming thin film pattern 30a and the etching mask film pattern 40b.

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed with a scanning electron microscope.

The thin film pattern 30 a for pattern formation of the transfer mask 100 of the fourth embodiment has a cross-sectional shape close to vertical. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of the fourth embodiment has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

According to the above description, it can be said that when the transfer mask 100 of the fourth embodiment is placed on the mask table of the exposure device, and the resist film on the substrate for the display device is exposed and transferred, A pattern for transfer including a fine pattern of less than 2.0 μm is transferred with high precision.

〈Lightfastness/Chemical Resistance〉

A sample in which the pattern-forming thin film 30 used in the mask blank 10 of the fourth embodiment was formed on the light-transmitting substrate 20 was prepared. The pattern-forming thin film 30 of the sample of the fourth example was irradiated with light from a metal halide light source including ultraviolet light having a wavelength of 365 nm so that the total irradiation dose was 10 kJ/cm ² . The transmittance is measured before and after predetermined ultraviolet irradiation, and the change in transmittance [(transmittance after ultraviolet irradiation)−(transmittance before ultraviolet irradiation)] is calculated, and the pattern forming film 30 The light fastness was evaluated. Transmittance was measured using a spectrophotometer.

In the fourth example, the change in transmittance before and after ultraviolet irradiation was good at 1.48% (0.34 points). From the above description, it can be seen that the film for pattern formation of the fourth example is a film having sufficiently high light resistance for practical use.

In addition, a sample in which the pattern-forming thin film 30 used in the mask blank 10 of the fourth embodiment was formed on the light-transmitting substrate 20 was prepared, and the chemical resistance of the pattern-forming thin film 30 was the same as that of the first embodiment. to evaluate.

As a result of the chemical resistance evaluation, in Example 4 having the titanium silicide-based pattern-forming thin film, the amount of change in the bottom peak wavelength per cleaning cycle was less than 1.0 nm toward the short wavelength side, and the chemical resistance was good.

From this, it is clear that the pattern-forming thin film of the fourth embodiment satisfies the desired optical characteristics (transmittance, phase difference), and also has high light resistance (chemical resistance), high etching rate, and good cross-sectional shape. An unprecedented good film.

(first comparative example)

The mask blank 10 of the first comparative example was manufactured in the same flow as the mask blank 10 of the first example except that the pattern-forming film 30 was described below.

The method of forming the pattern-forming thin film 30 of the first comparative example is as follows.

In order to form the pattern-forming thin film 30 on the main surface of the light-transmitting substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced into the first chamber. Then, a titanium silicide nitrogen oxide containing titanium, silicon, and nitrogen is laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering using a first sputtering target containing titanium and silicon (titanium:silicon=1:3). compounds. In this manner, a pattern-forming thin film 30 (Ti:Si:N:O=11.7:35.5:51.0:1.8 atomic % ratio) was formed using titanium silicide nitride as a material and having a film thickness of 130 nm.

Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.

Then, other pattern-forming thin films were formed on the main surfaces of other synthetic quartz substrates under the same film-forming conditions as those of the above-mentioned first comparative example. Next, X-ray photoelectron spectroscopy was performed on the thin film for pattern formation on this other synthetic quartz substrate in the same manner as in the first example.

7 is a graph showing the results of X-ray photoelectron spectroscopy analysis (Ti2p narrow spectrum) on the phase shift film of the mask blank of each comparative example of the present invention. 8 is a graph showing the results of X-ray photoelectron spectroscopy analysis (Si2p narrow spectrum) on the phase shift film of the mask blank of each comparative example of the present invention. The respective narrow spectra shown in FIGS. 7 and 8 are obtained at predetermined depth positions (depth positions located approximately in the center in the film thickness direction of the inner region) of the thin film for pattern formation on other synthetic quartz substrates of each comparative example. As determined from the values shown in FIGS. 7 and 8 , in the Ti2p narrow spectrum and Si2p narrow spectrum of the first comparative example, P _N / _PS was 1.18, and the relationship greater than 1.18 was not satisfied.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the first comparative example, P _NU / _PS was 1.05, and the relationship greater than 1.05 was not satisfied.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the first comparative example, (P _N +P _NU )/ _PS is 2.22, which does not satisfy the relationship greater than 2.22.

In addition, in the narrow spectrum of Ti2p in the first comparative example, P _N /P _TS was 2.13, and the relationship larger than 2.13 was not satisfied.

In addition, in the narrow spectrum of Ti2p in the first comparative example, (P _N + _PT )/P _TS is 3.53, and the relationship larger than 3.53 is not satisfied.

<Measurement of transmittance and phase difference>

The transmittance (wavelength: 365nm) and phase difference (wavelength: 365nm) were measured on the surface of the pattern-forming film 30 of the mask blank 10 of the first comparative example using MPM-100 manufactured by LaserTech (U.S.A.). Measurement. As a result, the transmittance of the pattern-forming film 30 of the first comparative example was 23%, and the phase difference was 180 degrees.

<Transfer mask 100 and its manufacturing method>

Using the mask blank 10 of the first comparative example manufactured as described above, the transfer mask 100 was manufactured in the same flow as that of the first embodiment, and a pattern formed in the transfer pattern formation region was obtained on the light-transmitting substrate 20. The transfer mask 100 of the first comparative example of the thin film pattern for pattern formation 30a with a hole diameter of 1.5 μm, and the light-shielding band formed by the lamination structure of the thin film pattern for pattern formation 30a and the etching mask film pattern 40b.

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed with a scanning electron microscope.

The thin film pattern 30 a for pattern formation of the transfer mask 100 of the first comparative example has a nearly vertical cross-sectional shape. Therefore, the thin film pattern 30a for pattern formation formed in the transfer mask 100 of the 1st comparative example has the cross-sectional shape which can fully exhibit a phase shift effect.

From the above description, it can be said that when the transfer mask 100 of the first comparative example is placed on the mask table of the exposure device, and the resist film on the substrate for the display device is exposed and transferred, A pattern for transfer including a fine pattern of less than 2.0 μm is transferred well with high precision.

〈Lightfastness/Chemical Resistance〉

The pattern forming thin film 30 used in the mask blank 10 of the first comparative example was prepared and formed on the light-transmitting substrate 20 . The pattern-forming film 30 of the sample of the first comparative example was irradiated with light from a metal halide light source including ultraviolet light having a wavelength of 365 nm so that the total irradiation dose was 10 kJ/cm ² . The transmittance is measured before and after predetermined ultraviolet irradiation, and the change in transmittance [(transmittance after ultraviolet irradiation)−(transmittance before ultraviolet irradiation)] is calculated, and the pattern forming film 30 The light fastness was evaluated. Transmittance was measured using a spectrophotometer.

In the first comparative example, the change in transmittance before and after ultraviolet irradiation was 2.00% (2.00 points), which was out of the allowable range. From the above description, it is clear that the film for pattern formation of the 1st comparative example does not have sufficient light resistance practically.

In addition, a sample in which the pattern-forming film 30 used in the mask blank 10 of the first comparative example was formed on the light-transmitting substrate 20 was prepared, and the chemical resistance of the pattern-forming film 30 was the same as that of the first example. to evaluate.

As a result of the chemical resistance evaluation, in the first comparative example having the titanium silicide-based pattern-forming thin film, the amount of change in the bottom peak wavelength per cleaning cycle was 1.0 nm or less smaller toward the shorter wavelength side, and the chemical resistance was sufficient.

Thus, the pattern-forming film of the first comparative example did not have sufficient performance in light resistance.

(second comparative example)

The mask blank 10 of the second comparative example was manufactured in the same flow as the mask blank 10 of the first example except for the pattern forming film 30 as described below.

The method of forming the pattern-forming thin film 30 of the second comparative example is as follows.

In order to form the pattern-forming thin film 30 on the main surface of the light-transmitting substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N ₂ ) gas is introduced into the first chamber. Next, using a first sputtering target (titanium:silicon=1:4) containing titanium and silicon, a titanium silicide nitrogen sputtering layer containing titanium, silicon, and nitrogen is laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering. compounds. In this manner, the pattern-forming thin film 30 (Ti:Si:N:O=7.6:33.6:40.6:18.2 atomic % ratio) was formed using titanium silicide nitride as a material and having a film thickness of 186 nm. The high oxygen content of the thin film 30 is not due to intentionally introduced oxygen components, but is due to residual moisture in the film forming apparatus or absorbed moisture.

Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.

Then, another pattern-forming thin film was formed on the main surface of another synthetic quartz substrate under the same film-forming conditions as in the above-mentioned second comparative example. Next, X-ray photoelectron spectroscopy was performed on the thin film for pattern formation on this other synthetic quartz substrate in the same manner as in the first example.

As determined from the values shown in FIGS. 7 and 8 , in the Ti2p narrow spectrum and Si2p narrow spectrum of the second comparative example, P _N / _PS was 0.31, which did not satisfy the relationship greater than 1.18.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the second comparative example, P _NU / _PS was 0.33, which did not satisfy the relationship larger than 1.05.

In addition, in the Ti2p narrow spectrum and the Si2p narrow spectrum of the second comparative example, (P _N +P _NU )/ _PS was 0.64, which did not satisfy the relationship greater than 2.22.

In addition, in the narrow spectrum of Ti2p in the second comparative example, P _N /P _TS was 1.53, which did not satisfy the relationship larger than 2.13.

In addition, in the narrow spectrum of Ti2p in the second comparative example, (P _N + _PT )/P _TS is 2.64, which does not satisfy the relationship larger than 3.53.

<Measurement of transmittance and phase difference>

The transmittance (wavelength: 365nm) and phase difference (wavelength: 365nm) were measured on the surface of the pattern-forming film 30 of the mask blank 10 of the second comparative example using MPM-100 manufactured by LaserTech (U.S.A.). Measurement. As a result, the transmittance of the pattern forming film 30 of the second comparative example was 57%, and the phase difference was 180 degrees.

<Transfer mask 100 and its manufacturing method>

Using the mask blank 10 of the second comparative example manufactured as described above, the transfer mask 100 was manufactured in the same flow as that of the first embodiment, and a pattern formed in the transfer pattern formation region was obtained on the light-transmitting substrate 20. The transfer mask 100 of the second comparative example of the thin film pattern 30a for pattern formation with a hole diameter of 1.5 μm, and the light-shielding tape formed by the lamination structure of the thin film pattern 30a for pattern formation and the etching mask film pattern 40b.

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed with a scanning electron microscope.

The thin film pattern 30 a for pattern formation of the transfer mask 100 of the second comparative example has a cross-sectional shape in which the boundary portion with the light-transmitting substrate 20 is over-etched. Therefore, the thin film pattern 30a for pattern formation formed in the transfer mask 100 of the 2nd comparative example does not have a cross-sectional shape which can fully exhibit a phase shift effect.

According to the above description, when the transfer mask 100 of the second comparative example is placed on the mask table of the exposure device, and the resist film on the substrate for the display device is exposed and transferred, it is difficult to achieve high accuracy. A pattern for transfer including a fine pattern of less than 2.0 μm is perfectly transferred.

〈Lightfastness/Chemical Resistance〉

A sample in which the pattern-forming thin film 30 used in the mask blank 10 of the second comparative example was formed on the light-transmitting substrate 20 was prepared. The pattern-forming film 30 of the sample of the second comparative example was irradiated with light from a metal halide light source including ultraviolet light having a wavelength of 365 nm so that the total irradiation dose was 10 kJ/cm ² . The transmittance is measured before and after the specified ultraviolet irradiation, and the change in transmittance is calculated [(transmittance after ultraviolet irradiation) - (transmittance before ultraviolet irradiation)], and the pattern forming film 30 for light fastness evaluation. Transmittance was measured using a spectrophotometer.

In the second comparative example, the change in transmittance before and after ultraviolet irradiation was 2.55% (2.55 points), which was out of the allowable range. From the above description, it can be seen that the film for pattern formation of the second comparative example does not have sufficient light resistance practically.

In addition, a sample in which the pattern-forming film 30 used in the mask blank 10 of the second comparative example was formed on the light-transmitting substrate 20 was prepared, and the chemical resistance of the pattern-forming film 30 was the same as that of the first example. to evaluate.

As a result of the chemical resistance evaluation, in the second comparative example having a titanium silicide-based pattern-forming thin film containing 8 atomic % or more of oxygen, the amount of change in the bottom peak wavelength per cleaning cycle was larger by 1.0 nm toward the shorter wavelength side. As mentioned above, the drug resistance is not enough.

Thus, the pattern-forming film of the second comparative example did not have sufficient performance in light resistance and chemical resistance.

In the above-mentioned embodiment, the example of the transfer mask 100 for display device manufacture and the mask blank 10 for manufacturing the transfer mask 100 for display device manufacture was demonstrated, but it is not limited to this. The mask blank 10 and/or the transfer mask 100 of the present invention can also be applied to semiconductor device manufacturing, MEMS manufacturing, printing substrate manufacturing, and the like. In addition, the present invention can also be applied to a binary mask stock having a light-shielding film as the pattern-forming film 30 and a binary mask having a light-shielding film pattern.

In addition, in the above-mentioned embodiments, an example in which the size of the light-transmitting substrate 20 is 1214 (1220 mm×1400 mm×13 mm) has been described, but the present invention is not limited thereto. In the case of the mask blank 10 for display device manufacture, a large-size (LargeSize) light-transmitting substrate 20 having a size of one side of the main surface of 300 mm or more is used. The size of the light-transmitting substrate 20 used in the mask blank 10 for display device manufacture is, for example, 330 mm×450 mm or more and 2280 mm×3130 mm or less.

In addition, in the case of the mask stock 10 for semiconductor device manufacturing, MEMS manufacturing, and printing substrate manufacturing, a small-sized (Small Size) light-transmitting substrate 20 is used. Among the dimensions of the light-transmitting substrate 20, the length of one side is 9 inches or less. The size of the light-transmitting substrate 20 used in the mask blank 10 for the above application is, for example, 63.1 mm×63.1 mm or more and 228.6 mm×228.6 mm or less. Usually, a 6025 size (152 mm×152 mm) or a 5009 size (126.6 mm×126.6 mm) is used as the light-transmitting substrate 20 used for the transfer mask 100 for semiconductor device manufacturing and MEMS manufacturing. In addition, generally, a 7012 size (177.4 mm×177.4 mm) or a 9012 size (228.6 mm×228.6 mm) is used as the light-transmitting substrate 20 used for the transfer mask 100 for printing substrate production.

Claims (21)

1. A mask blank having a light-transmitting substrate and a pattern-forming film provided on a main surface of the light-transmitting substrate, characterized in that,

the film contains titanium, silicon and nitrogen,

an photoelectron intensity P of 455eV as a binding energy in a narrow spectrum of Ti2P obtained by analyzing an inner region of the film by X-ray photoelectron spectroscopy _N In Si2p narrow spectrumThe photoelectron intensity of 102eV is P _S When meeting P _N /P _S A relationship greater than 1.18,

the inner region is a region of the film other than a vicinity region on the light-transmitting substrate side and a surface layer region on the opposite side of the light-transmitting substrate,

the nitrogen content in the internal region is 30 atomic% or more.

2. The mask blank of claim 1,

an photoelectron intensity P of 461eV which makes the binding energy in the Ti2P narrow spectrum _NU When meeting P _NU /P _S Greater than 1.05.

3. A mask blank as claimed in claim 1 or 2, wherein,

the ratio of the titanium content in the inner region to the total content of titanium and silicon is 0.05 or more.

4. A mask blank as claimed in claim 1 or 2, wherein,

The total content of titanium, silicon and nitrogen in the internal region is 90 at% or more.

5. A mask blank as claimed in claim 1 or 2, wherein,

the oxygen content of the inner region is 7 at% or less.

6. A mask blank as claimed in claim 1 or 2, wherein,

the surface layer region on the side opposite to the light-transmitting substrate side is a region extending from the surface on the side opposite to the light-transmitting substrate side to a depth of 10 nm.

7. A mask blank as claimed in claim 1 or 2, wherein,

the vicinity area on the light-transmitting substrate side is an area extending from the surface on the light-transmitting substrate side to a depth of 10nm on the opposite side to the light-transmitting substrate.

8. A mask blank as claimed in claim 1 or 2, wherein,

the thin film is a phase-shifting film,

the phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365nm, and a phase difference of 150 DEG to 210 DEG with respect to light having a wavelength of 365 nm.

9. A mask blank as claimed in claim 1 or 2, wherein,

an etching mask film having a different etching selectivity with respect to the thin film is provided on the thin film.

10. The mask blank of claim 9, wherein,

the etching mask film contains chromium.

11. A transfer mask having a light-transmitting substrate and a film provided on a main surface of the light-transmitting substrate and having a transfer pattern, characterized in that,

the film contains titanium, silicon and nitrogen,

an photoelectron intensity P of 455eV as a binding energy in a narrow spectrum of Ti2P obtained by analyzing an inner region of the film by X-ray photoelectron spectroscopy _N The photoelectron intensity of the Si2P narrow spectrum with the binding energy of 102eV is P _S When meeting P _N /P _S A relationship greater than 1.18,

the inner region is a region of the film other than a vicinity region on the light-transmitting substrate side and a surface layer region on the opposite side of the light-transmitting substrate,

the nitrogen content in the internal region is 30 atomic% or more.

12. The transfer mask according to claim 11, wherein,

an photoelectron intensity P of 461eV which makes the binding energy in the Ti2P narrow spectrum _NU When meeting P _NU /P _S Greater than 1.05.

13. A transfer mask according to claim 11 or 12,

the ratio of the titanium content in the inner region to the total content of titanium and silicon is 0.05 or more.

14. A transfer mask according to claim 11 or 12,

the total content of titanium, silicon and nitrogen in the internal region is 90 at% or more.

15. A transfer mask according to claim 11 or 12,

the oxygen content of the inner region is 7 at% or less.

16. A transfer mask according to claim 11 or 12,

the surface layer region on the side opposite to the light-transmitting substrate side is a region extending from the surface on the side opposite to the light-transmitting substrate side to a depth of 10 nm.

17. A transfer mask according to claim 11 or 12,

the vicinity area on the light-transmitting substrate side is an area extending from the surface on the light-transmitting substrate side to a depth of 10nm on the opposite side to the light-transmitting substrate.

18. A transfer mask according to claim 11 or 12,

the thin film is a phase-shifting film,

the phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365nm, and a phase difference of 150 DEG to 210 DEG with respect to light having a wavelength of 365 nm.

19. A method for manufacturing a transfer mask is characterized by comprising:

A step of preparing the mask blank according to any one of claims 1 to 8;

forming a resist film having a transfer pattern on the thin film;

and performing wet etching using the resist film as a mask, thereby forming a transfer pattern on the thin film.

20. A method for manufacturing a transfer mask is characterized by comprising:

preparing the mask blank according to claim 9 or 10;

forming a resist film having a transfer pattern on the etching mask film;

performing wet etching using the resist film as a mask, and forming a transfer pattern on the etching mask film;

and performing wet etching using the etching mask film having the transfer pattern formed thereon as a mask, thereby forming a transfer pattern on the thin film.

21. A method for manufacturing a display device, comprising:

a step of placing the transfer mask according to any one of claims 11 to 18 on a mask stage of an exposure apparatus;

and a step of irradiating the transfer mask with exposure light and transferring the transfer pattern to a resist film provided on the display device substrate.