KR20240100256A - Mask blank, transfer mask, method for manufactuaring transfer mask, and method for manufacturing display device - Google Patents

Abstract

The object is to provide a mask blank that satisfies the requirement of high light resistance to exposure light containing a wavelength in the ultraviolet region. It is a mask blank provided with a thin film for pattern formation on a translucent substrate. The thin film contains a transition metal and silicon, and the surface layer X-ray absorption spectrum of the thin film obtained by the all-electron quantity method shows that the incident X-ray energy EL is 3180 eV. When the X-ray absorption coefficient at IL is IL and the incident X-ray energy EH is 3210 eV, (IH-IL)/(EH-EL) is ^-6.0 .

Description

Mask blank, transfer mask, method of manufacturing transfer mask, and method of manufacturing display device {MASK BLANK, TRANSFER MASK, METHOD FOR MANUFACTUARING TRANSFER MASK, AND METHOD FOR MANUFACTURING DISPLAY DEVICE}

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

In recent years, in display devices such as FPD (Flat Panel Display), represented by OLED (Organic Light Emitting Diode), high-precision and high-speed displays are rapidly progressing along with flexibility such as large screens, wide viewing angles, and folding. . One of the elements necessary for this high-precision, high-speed display is the production of electronic circuit patterns, such as elements and wiring, that are fine and have high dimensional accuracy. Photolithography is often used for patterning electronic circuits for these display devices. For this reason, a transfer mask (photomask) such as a phase shift mask and a binary mask for manufacturing display devices with fine, high-precision patterns is needed.

For example, Patent Document 1 describes a photomask for exposing a fine pattern. In Patent Document 1, a mask pattern formed on a transparent substrate of a photomask is divided into a light transmitting portion that transmits light with an intensity that substantially contributes to exposure, and a light semitransmissive portion that transmits light with an intensity that does not substantially contribute to exposure. What it consists of is described. Additionally, Patent Document 1 describes improving the contrast of the boundary portion by using a phase shift effect to cause light passing near the boundary portion of the light semitransmissive portion and the light transmissive portion to cancel each other out. In addition, in Patent Document 1, the photomask is composed of the light semi-transmissive portion as a thin film made of a material containing nitrogen, metal, and silicon as main components, and silicon, which is a component of the material constituting the thin film, is included. It is described that it contains 34 to 60 atomic%.

Patent Document 2 describes a halftone type phase shift mask blank used in lithography. Patent Document 2 describes that a mask blank includes a substrate, an etch stop layer deposited on the substrate, and a phase shift layer deposited on the etch stop layer. Additionally, Patent Document 2 describes that using this mask blank, it is possible to manufacture a photomask having a phase shift of approximately 180 degrees and a light transmittance of at least 0.001% at a selected wavelength of less than 500 nm.

Japanese Patent No. 2966369 Publication Japanese Patent Publication No. 2005-522740

The transfer mask used in recent high-precision (1000 ppi or more) panel production is a transfer mask to enable high-resolution pattern transfer, and also has a fine pattern of 6 μm or less in hole diameter and 4 μm or less in line width. There is a demand for a transfer mask on which a transfer pattern including a forming thin film pattern is formed. Specifically, there is a demand for a transfer mask with a transfer pattern formed including a fine pattern with a diameter or width of 1.5 μm.

On the other hand, since the transfer mask obtained by patterning the thin film for pattern formation of the mask blank is repeatedly used for pattern transfer to the transfer object, it is desired to have high light resistance to ultraviolet rays (ultraviolet light resistance) assuming actual pattern transfer. .

However, it has conventionally been difficult to manufacture a mask blank provided with a thin film for pattern formation that satisfies the requirements of ultraviolet light resistance (hereinafter simply light resistance) to exposure light containing a wavelength in the ultraviolet region.

The present invention was made to solve the above-mentioned problems. That is, the purpose of the present invention is to provide a mask blank that satisfies the requirement of high light resistance to exposure light including wavelengths in the ultraviolet region.

In addition, the present invention provides a transfer mask with a good transfer pattern that satisfies the requirement of high light resistance to exposure light containing a wavelength in the ultraviolet region, a method of manufacturing the transfer mask, and a method of manufacturing a display device. The purpose.

The present invention is a means of solving the above problems and has the following structure.

(Configuration 1)

It is a mask blank provided with a thin film for pattern formation on a translucent substrate,

The thin film contains a transition metal and silicon,

The surface layer X-ray absorption spectrum of the thin film obtained by the all-electron quantity method is IL as the X-ray absorption coefficient when the incident When using IH,

(IH-IL)/(EH-EL) is -6.0×10 ^-4 or more

A mask blank characterized in that.

(Configuration 2)

In the X-ray absorption spectrum of the thin film obtained by fluorescence quantification, the X-ray absorption coefficient at an incident X-ray energy EH of 3210 eV is larger than the X-ray absorption coefficient at an incident X-ray energy EL of 3180 eV. The mask blank described in configuration 1, characterized in that.

(Configuration 3)

The mask blank according to Configuration 1, wherein the thin film contains at least titanium as the transition metal.

(Configuration 4)

The mask blank according to configuration 1, wherein the thin film further contains nitrogen.

(Configuration 5)

The mask blank according to Configuration 1, wherein the content ratio of the transition metal to the total content of the transition metal and silicon in the thin film is 0.05 or more.

(Configuration 6)

The mask blank according to configuration 1, wherein an etching mask film having different etching selectivity with respect to the thin film is provided on the thin film.

(Configuration 7)

The mask blank according to configuration 6, wherein the etching mask film contains chromium.

(Configuration 8)

It is a transfer mask including a thin film with a transfer pattern on a translucent substrate,

The thin film contains a transition metal and silicon,

The surface layer X-ray absorption spectrum of the thin film obtained by the all-electron quantity method is IL as the X-ray absorption coefficient when the incident When using IH,

(IH-IL)/(EH-EL) is -6.0×10 ^-4 or more

A transfer mask characterized in that.

(Configuration 9)

In the X-ray absorption spectrum of the thin film obtained by fluorescence quantification, the X-ray absorption coefficient at an incident X-ray energy EH of 3210 eV is larger than the X-ray absorption coefficient at an incident X-ray energy EL of 3180 eV. The transfer mask according to configuration 8, characterized in that.

(Configuration 10)

The transfer mask according to configuration 8, wherein the thin film contains at least titanium as the transition metal.

(Configuration 11)

The transfer mask according to configuration 8, wherein the thin film further contains nitrogen.

(Configuration 12)

The transfer mask according to configuration 8, wherein the ratio of the content of the transition metal to the total content of the transition metal and silicon in the thin film is 0.05 or more.

(Composition 13)

A process of preparing the mask blank according to configuration 6 or 7;

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

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

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

A method of manufacturing a transfer mask characterized by having a.

(Configuration 14)

A step of loading the transfer mask according to any one of Configurations 8 to 12 on a mask stage of an exposure apparatus;

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

A method of manufacturing a display device comprising:

According to the present invention, it is possible to provide a mask blank that satisfies the requirement of high light resistance to exposure light including a wavelength in the ultraviolet region.

In addition, according to the present invention, a transfer mask with a good transfer pattern that satisfies the requirement of high light resistance to exposure light containing a wavelength in the ultraviolet region, a method of manufacturing the transfer mask, and a method of manufacturing a display device are provided. can do.

1 is a cross-sectional schematic diagram showing the film structure of a mask blank according to an embodiment of the present invention.
Figure 2 is a cross-sectional schematic diagram showing another film configuration of a mask blank according to an embodiment of the present invention.
Figure 3 is a cross-sectional schematic diagram showing the manufacturing process of the transfer mask according to the embodiment of the present invention.
Figure 4 is a cross-sectional schematic diagram showing another manufacturing process of the transfer mask according to the embodiment of the present invention.
Figure 5 shows the X-ray absorption spectrum derived from Ar (horizontal axis: X-ray energy, vertical axis: This is a diagram showing the X-ray absorption coefficient of the thin film relative to the X-ray energy.
Figure 6 shows the X-ray absorption spectrum derived from Ar acquired by the all-electron quantity method for the thin film surface layer for pattern formation of the mask blank according to Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention (horizontal axis: thin film This is a diagram showing the X-ray energy incident on the surface layer, the vertical axis: the surface layer X-ray absorption coefficient of the thin film relative to the X-ray of that energy.
Figure 7 shows the relationship between (IH-IL)/(EH-EL) and the amount of change in transmittance in the thin film for forming a pattern of a mask blank according to Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention. It is a drawing. Here, IL is the X-ray absorption coefficient when the incident X-ray energy EL is 3180 eV, and IH is the X-ray absorption coefficient when the incident X-ray energy EH is 3210 eV.

First, the process leading to completion of the present invention will be explained. The present inventor conducted intensive studies on the construction of a mask blank that satisfies the requirement of high light resistance to exposure light containing a wavelength in the ultraviolet region (hereinafter sometimes simply referred to as “exposure light”).

The present inventor was considering using a transition metal silicide-based material containing a transition metal and silicon as a thin film pattern material for a transfer mask used to manufacture display devices such as FPD (Flat Panel Display). It has been found that, in thin films formed using transition metal silicide-based materials, there may be significant differences in light resistance to exposure light even though the compositions are almost the same. For this reason, the present inventor conducted various verifications on the difference between a thin film of a transition metal silicide-based material with high light resistance to exposure light and a thin film of a transition metal silicide-based material with low light resistance to exposure light. First, the present inventor studied the relationship between the composition of the thin film and the light resistance to exposure light, but was unable to obtain a clear correlation between the composition of the thin film and the light resistance. In addition, although cross-sectional SEM images, planar STEM images, and electron diffraction images were observed, a clear relationship with light resistance could not be obtained in any of them.

Accordingly, the present inventor focused on the gas component used when forming a thin film. When forming a thin film of a transition metal silicide-based material on a light-transmissive substrate, sputtering is generally used. When forming a thin film of a transition metal silicide-based material by a sputtering method, it is common to introduce noble gas in addition to the reactive gas into the film formation chamber. This is because turning the ear gas into plasma and colliding it with the target can increase sputter efficiency. Additionally, argon is widely used as the noble gas. It is believed that the thin film formed in this way contains components of noble gas, albeit in extremely small amounts.

Based on this viewpoint, the X-ray absorption spectra derived from Ar were acquired and analyzed by a fluorescence quantitative method for thin films of transition metal silicide-based materials with greatly different light resistance to exposure light (see Figure 5). As a result, it was confirmed that argon derived from sputter gas was introduced into both thin films, but a clear correlation with light resistance could not be obtained.

As a result of further intensive research, the present inventors have found that the X-ray absorption spectra derived from Ar ( Analysis was performed by obtaining the horizontal axis: X-ray energy incident on the surface layer of the thin film, and the vertical axis: the X-ray absorption coefficient of the surface layer of the thin film relative to the X-rays of that energy (see FIGS. 6 and 7). The X-ray absorption spectrum of a thin film acquired by a fluorescence quantitative method has a sufficiently deep range in the film thickness direction, and a spectrum reflecting the overall state of the thin film in the film thickness direction (surface layer + other regions) is obtained. It is a spectrum in which information about the state of the surface layer of the thin film and other regions is mixed, and it is difficult to separate the states of the surface layer of the thin film and other regions. In contrast, the X-ray absorption spectrum of the thin film obtained by the all-electron quantity method has a very shallow range in the film thickness direction, and is a spectrum that largely reflects the surface layer state of the thin film. For thin films with greatly different light resistances, the X-ray absorption spectra obtained by the all-electron quantity method were analyzed, and it was found that there was a clear difference in the tendency of the X-ray absorption coefficient between the two.

The mask blank of the present invention was derived as a result of the above-mentioned research. That is, it is a mask blank provided with a thin film for pattern formation on a translucent substrate, the thin film contains a transition metal and silicon, and the surface layer X-ray absorption spectrum of the thin film obtained by the all-electron quantity method is the incident X-ray energy EL. When the X-ray absorption coefficient at 3180 eV is IL and the incident X-ray energy EH is 3210 eV, the X-ray absorption coefficient is IH,

It is characterized by (IH-IL)/(EH-EL) being -6.0×10 ^-4 or more.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, the following embodiment is a form for actualizing the present invention and does not limit the present invention to its scope.

Fig. 1 is a schematic diagram showing the film structure of the mask blank 10 of this embodiment. The mask blank 10 shown in FIG. 1 includes a translucent substrate 20, a thin film 30 for pattern formation (for example, a phase shift film) formed on the translucent substrate 20, and a thin film 30 for pattern formation. It is provided with an etching mask film (for example, a light-shielding film) 40 formed.

FIG. 2 is a schematic diagram showing the film structure of the mask blank 10 according to another embodiment. The mask blank 10 shown in FIG. 2 includes a translucent substrate 20 and a pattern forming thin film 30 (for example, a phase shift film) formed on the translucent substrate 20.

In this specification, the “thin film 30 for pattern formation” refers to a thin film on which a predetermined fine pattern is formed in the transfer mask 100, such as a light-shielding film and a phase shift film (hereinafter simply referred to as “thin film 30 )”). In addition, in the description of the present embodiment, a phase shift film is used as a specific example of the thin film 30 for pattern formation, and the thin film pattern 30a for pattern formation (hereinafter sometimes simply referred to as the “thin film pattern 30a”) As a specific example, there are cases where a phase shift film pattern is used as an example. The same applies to the thin film 30 for pattern formation and the thin film pattern 30a for pattern formation, such as a light-shielding film and a light-shielding film pattern, a transmittance adjustment film, and a transmittance adjustment film pattern, as well as the phase shift film and the phase shift film pattern.

Hereinafter, the translucent substrate 20, the thin film 30 for pattern formation (for example, a phase shift film), and the etching mask film 40, which constitute the mask blank 10 for manufacturing the display device of the present embodiment, will be described in detail. Explain.

<Light-transmitting substrate (20)>

The translucent substrate 20 is transparent to exposure light. The translucent substrate 20 has a transmittance of 85% or more, preferably 90% or more, to the exposure light, assuming no surface reflection loss. The light-transmitting substrate 20 is made of a material containing silicon and oxygen, and is 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.). It can be configured. When the translucent substrate 20 is made of low thermal expansion glass, a change in the position of the thin film pattern 30a due to thermal deformation of the translucent substrate 20 can be suppressed. Additionally, the light-transmitting substrate 20 used for display devices is generally a rectangular-shaped substrate. Specifically, a translucent substrate 20 whose short side length of the main surface (the surface on which the pattern forming thin film 30 is formed) is 300 mm or more can be used. In the mask blank 10 of this embodiment, a large-sized translucent substrate 20 whose main surface has a short side length of 300 mm or more can be used. Using the mask blank 10 of the present embodiment, a transfer pattern including a thin film pattern 30a for forming a fine pattern having, for example, a width dimension and/or a diameter dimension of less than 2.0 μm is provided on the translucent substrate 20. A transfer mask 100 can be manufactured. By using the transfer mask 100 of this embodiment, it is possible to stably transfer a transfer pattern including a predetermined fine pattern to a transfer object.

<Thin film for pattern formation (30)>

The thin film 30 for pattern formation 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”) contains a transition metal and silicon. , the surface layer X-ray absorption spectrum of the thin film 30 acquired by the all-electron quantity method is the X-ray absorption coefficient IL when the incident When the absorption coefficient is IH,

(IH-IL)/(EH-EL) is -6.0×10 ^-4 or more.

Here, the surface layer is, for example, a region extending from the surface on the opposite side to the translucent substrate 20 to a depth of 10 nm toward the translucent substrate 20.

In addition, (IH-IL ⁾ /(EH-EL), which is the slope of ^the

Generally, as the X-ray energy increases, the degree of attenuation of X-rays when propagating through a medium decreases (making it more difficult to be absorbed within the medium). In other words, the X-ray absorption spectrum is a numerical value in which, when an element that greatly absorbs X-rays of The spectrum becomes smaller (the slope is negative). And, as the content of the element that greatly absorbs X-rays increases, the negative value of the slope of the X-ray absorption spectrum decreases and soon reverses to a positive value. For this reason, it is not contradictory that the slope of the .

The present inventor estimates the relationship between the tendency of this X-ray absorption coefficient and light resistance as follows.

In the step of forming the pattern forming thin film 30 containing a transition metal and silicon on the translucent substrate 20 by sputtering with a sputter gas containing argon in the film formation chamber, the thin film 30 in the thickness direction of the thin film 30 is formed. It is thought that argon is introduced throughout. On the other hand, based on the shape of the It is believed that the thin film 30, which has a low light resistance to exposure light containing a wavelength, has relatively more argon desorbed in the surface layer on the side in contact with the atmosphere, and a gap is generated, compared to the thin film 30, which has a high light resistance. . It is presumed that moisture in the air is adsorbed into the gap, and oxidation of silicon and transition metals in the surface layer progresses due to exposure light irradiation, causing an increase in the transmittance of the thin film 30 and a shift toward the short wavelength side of the film surface reflectance spectrum. . However, this estimate is based on knowledge at the current stage and does not limit the scope of rights of the present invention at all.

The X-ray absorption spectrum of the thin film 30 for pattern formation (hereinafter sometimes simply referred to as “thin film 30”) obtained by fluorescence quantification is the X-ray absorption when the incident X-ray energy EL is 3180 eV. It is preferable that the X-ray absorption coefficient at an incident X-ray energy EH of 3210 eV is larger than the coefficient.

In the An absorption edge (K absorption edge) is emerging. The absorption edge in this region of incident X-ray energy originates from argon. That is, thin films with this tendency contain argon. On the other hand, in the X-ray absorption spectra obtained by the fluorescence quantification method in FIG. 5 among a plurality of thin films with clear differences in the X-ray absorption spectra obtained by the all-electron quantification method in FIG. There is no clear difference. From these viewpoints, in the X-ray absorption spectrum obtained by the fluorescence quantitative method, the X-ray absorption coefficient when the incident A large thin film can be said to contain argon in areas other than the surface layer of the thin film.

The thin film 30 for pattern formation may be made of a material containing a transition metal and silicon (Si). Suitable transition metals include molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), and zirconium (Zr), with titanium and molybdenum being more preferable. In addition, it is particularly preferable that the thin film 30 for pattern formation contains at least titanium as a transition metal.

This pattern forming thin film 30 may be a phase shift film having a phase shift function.

The content ratio of the transition metal to the total content of the transition metal and silicon in the pattern forming thin film 30 is preferably 0.05 or more, and more preferably 0.10 or more. By meeting these ratios, both optical properties and tolerability can be excellent. In addition, the ratio of the content of the transition metal to the total content of the transition metal and silicon in the pattern forming thin film 30 is preferably 0.50 or less, and more preferably 0.40 or less. By satisfying these ratios, excessive increase in the wet etching rate during pattern formation of the thin film 30 for pattern formation can be suppressed.

The thin film 30 for pattern formation preferably contains nitrogen. In the transition metal silicide, nitrogen, which is a light element component, has the effect of not lowering the refractive index compared to oxygen, which is also a light element component. Therefore, because the thin film 30 for pattern formation contains nitrogen, the film thickness for obtaining the desired phase difference (also referred to as the phase shift amount) can be reduced. Additionally, the nitrogen content contained in the thin film 30 for pattern formation is preferably 10 atomic% or more, and more preferably 20 atomic% or more. On the other hand, the nitrogen content is preferably 60 atomic% or less, and more preferably 55 atomic% or less. By having a large nitrogen content in the thin film 30, excessive increase in transmittance to exposure light can be suppressed.

The thin film 30 for pattern formation preferably contains argon in all regions in the film thickness direction. A thin film 30 with higher light resistance to exposure light containing a wavelength in the ultraviolet region is obtained. On the other hand, the thin film 30 for pattern formation may contain at least one element selected from argon, krypton, and xenon in all regions in the film thickness direction. In this case, the noble gas is contained in the sputter gas used when forming the thin film 30 for pattern formation by the sputtering method. In addition, in the case where the thin film 30 for pattern formation is formed in a sputter gas containing krypton, the X-ray absorption spectrum of the thin film 30 acquired by the fluorescence quantitative method is The X-ray absorption coefficient at an incident X-ray energy EH of 14330 eV is greater than the , it is preferable that the X-ray absorption coefficient at the incident X-ray energy EH of 1680 eV is larger (in the case of the L3 absorption edge). Additionally, in the case where the thin film 30 for pattern formation is formed in a sputter gas containing xenon, the X-ray absorption spectrum of the thin film 30 acquired by the fluorescence quantitative method is at an incident The X-ray absorption coefficient at an incident X-ray energy EH of 34570 eV is greater than the , it is preferable that the incident X-ray energy EH has a larger X-ray absorption coefficient at 4790 eV (in the case of the L3 absorption edge).

On the other hand, when the thin film 30 for pattern formation is formed in a sputter gas containing krypton, the surface layer X-ray absorption spectrum of the thin film 30 obtained by the all-electron quantity method shows that the incident X-ray energy EL is 14300 eV. The X-ray absorption coefficient at an incident X-ray energy EH of 14330 eV is greater than the It is preferable that the X-ray absorption coefficient at an incident X-ray energy EH of 1680 eV is larger than the coefficient (in the case of the L3 absorption edge). In addition, when the thin film 30 for pattern formation is formed in a sputter gas containing xenon, the surface layer X-ray absorption spectrum of the thin film 30 obtained by the all-electron quantity method shows that the incident X-ray energy EL is 34540 eV. The X-ray absorption coefficient at an incident X-ray energy EH of 34570 eV is greater than the It is preferable that the X-ray absorption coefficient at an incident X-ray energy EH of 4790 eV is larger than the absorption coefficient (in the case of the L3 absorption edge).

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

This thin film 30 for pattern formation may be composed of a plurality of layers, or may be composed of a single layer. The pattern forming thin film 30 composed of a single layer is preferable because it is difficult for an interface to be formed in the pattern forming thin film 30 and the cross-sectional shape is easy to control. On the other hand, the thin film 30 for pattern formation composed of a plurality of layers is preferable in terms of ease of film formation.

In order to ensure optical performance, the thickness of the thin film 30 for pattern formation is preferably 200 nm or less, more preferably 180 nm or less, and even more preferably 150 nm or less. In addition, the film thickness of the thin film 30 for pattern formation is preferably 50 nm or more, and more preferably 60 nm or more, in order to secure the desired transmittance.

<<Transmittance and phase difference of the thin film 30 for pattern formation>>

In the mask blank 10 for manufacturing a display device of the present embodiment, the thin film 30 for pattern formation has a transmittance of 1% to 80% and a phase difference with respect to the representative wavelength of exposure light (light with a wavelength of 405 nm: h line). It is preferable that it is a phase shift film with optical characteristics of 140 degrees or more and 210 degrees or less. Unless otherwise specified, the transmittance in this specification refers to the transmittance of the light-transmitting substrate converted to a standard (100%).

When the thin film 30 for pattern formation is a phase shift film, the thin film 30 for pattern formation adjusts the reflectance (hereinafter sometimes referred to as back surface reflectance) for light incident from the translucent substrate 20 side. It has the function of adjusting the transmittance and phase difference for the exposure light.

The transmittance of the thin film 30 for pattern formation with respect to exposure light satisfies the value required for the thin film 30 for pattern formation. The transmittance of the thin film 30 for pattern formation is preferably 1% or more and 80% or less, and more preferably 3%, with respect to light of a predetermined wavelength (hereinafter referred to as representative wavelength) included in the exposure light. It is 65% or less, and more preferably 5% or more and 60% or less. That is, when the exposure light is a composite light containing light in a wavelength range of 313 nm to 436 nm, the pattern forming thin film 30 has the above-described transmittance for light of a representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i-lines, h-lines, and g-lines, the pattern forming thin film 30 may have the above-described transmittance for any of the i-lines, h-lines, and g-lines. The representative wavelength can be, for example, the h-line with a wavelength of 405 nm. By having such characteristics for the h-line, when a composite light containing the i-line, h-line, and g-line is used as exposure light, a similar effect can be expected for the transmittance at the wavelength of the i-line and the g-line.

In addition, in the case where the exposure light is monochromatic light selected from a wavelength range of 313 nm to 436 nm and a certain wavelength range is cut with a filter, etc., and monochromatic light selected from a wavelength range of 313 nm to 436 nm, the thin film 30 for pattern formation is It has the above-described transmittance for monochromatic light of a single wavelength.

Transmittance can be measured using a phase shift measurement device or the like.

The phase difference of the thin film 30 for pattern formation with respect to the exposure light satisfies the value required for the thin film 30 for pattern formation. The phase difference of the thin film 30 for pattern formation is preferably 140 degrees or more and 210 degrees or less, more preferably 160 degrees or more and 200 degrees or less, with respect to light of a representative wavelength included in the exposure light, and still more preferably is greater than or equal to 170 degrees and less than or equal to 190 degrees. Due to this property, the optical phase of the representative wavelength included in the exposure light can be changed from 140 degrees to 210 degrees. For this reason, a phase difference of 140 degrees or more and 210 degrees or less occurs between light of a representative wavelength that has transmitted through the pattern forming thin film 30 and light of a representative wavelength that has passed through only the translucent substrate 20. That is, when the exposure light is a complex light containing light in a wavelength range of 313 nm to 436 nm, the pattern forming thin film 30 has the above-described phase difference with respect to light of a representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i-lines, h-lines, and g-lines, the pattern forming thin film 30 may have the above-described phase difference with respect to any of the i-lines, h-lines, and g-lines. The representative wavelength can be, for example, the h-line with a wavelength of 405 nm. By having these characteristics for the h-line, when composite light containing the i-line, h-line, and g-line is used as exposure light, a similar effect can be expected for the phase difference at the wavelengths of the i-line and the g-line.

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

The back surface reflectance of the thin film 30 for pattern formation is 15% or less in the wavelength range of 365 nm to 436 nm, and is preferably 10% or less. In addition, the back reflectance of the thin film 30 for pattern formation is preferably 20% or less for light in the wavelength range of 313 nm to 436 nm when the exposure light includes j-line (wavelength 313 nm), and is preferably 17%. It is more preferable if it is below. More preferably, it is 15% or less. In addition, the back surface reflectance of the thin film 30 for pattern formation is 0.2% or more in the wavelength range of 365 nm to 436 nm, and is preferably 0.2% or more for light in the wavelength range of 313 nm to 436 nm.

The back surface 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 sputtering.

<Etching mask film (40)>

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

The etching mask film 40 is disposed on the upper side of the thin film 30 for pattern formation, and has etching resistance to the etchant for etching the thin film 30 for pattern formation (but has no etching selectivity with respect to the thin film 30 for pattern formation). It is made of different) materials. Additionally, the etching mask layer 40 may have a function of blocking exposure light from being transmitted. In addition, the etching mask film 40 is formed so that the surface reflectance of the pattern forming thin film 30 with respect to the light incident from the pattern forming thin film 30 is 15% or less in the wavelength range of 350 nm to 436 nm. It may have a function to reduce reflectance.

The etching mask film 40 is preferably made of a chromium-based material containing chromium (Cr). It is more preferable that the etching mask film 40 is made of a material containing chromium and substantially no silicon. Substantially containing no silicon means that the silicon content is less than 2% (however, excluding the composition gradient region at the interface between the pattern forming thin film 30 and the etching mask film 40). More specifically, chromium-based materials include chromium (Cr) or materials containing at least one of chromium (Cr), oxygen (O), nitrogen (N), and carbon (C). Additionally, examples of the chromium-based material include materials containing chromium (Cr), at least one of oxygen (O), nitrogen (N), and carbon (C), and also containing fluorine (F). For example, materials constituting the etching mask film 40 include Cr, CrO, CrN, CrF, CrCO, CrCN, CrON, CrCON, and CrCONF.

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

When the etching mask film 40 has a function of preventing the transmission of exposure light, the optical density with respect to the exposure light in the portion where the pattern forming thin film 30 and the etching mask film 40 are stacked is preferably 3. or more, more preferably 3.5 or more, and still more preferably 4 or more. Optical density can be measured using a spectrophotometer or OD meter.

The etching mask film 40 can be a single film with a uniform composition depending on its function. Additionally, the etching mask film 40 can be made of a plurality of films with different compositions. Additionally, the etching mask film 40 can 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 is provided with an etching mask film 40 on the thin film 30 for pattern formation. The mask blank 10 of this embodiment includes an etching mask film 40 on a thin film 30 for pattern formation, and a resist film on the etching mask film 40.

<Method for manufacturing 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 forming process for pattern formation and the etching mask film forming process. The mask blank 10 shown in FIG. 2 is manufactured through a thin film forming process for pattern formation.

Hereinafter, each process will be described in detail.

<<Thin film formation process for pattern formation>>

First, prepare a translucent substrate 20. The translucent substrate 20 may be made of a glass material selected from synthetic quartz glass, quartz glass, aluminosilicate glass, soda lime glass, and low thermal expansion glass (SiO ₂ -TiO ₂ glass, etc.) as long as it is transparent to exposure light. there is.

Next, a thin film 30 for pattern formation is formed on the translucent substrate 20 by sputtering.

The thin film 30 for pattern formation can be formed using a predetermined sputter target and in a predetermined sputter gas atmosphere. A predetermined sputter target is, for example, a transition metal silicide target containing a transition metal and silicon, which are the main components of the material constituting the pattern forming thin film 30, or a transition metal silicon nitride containing a transition metal, silicon, and nitrogen. It's a target. The predetermined sputter gas atmosphere is, for example, a sputter gas atmosphere made of an inert gas containing argon gas, or a sputter gas atmosphere made of the inert gas, nitrogen gas, and, in some cases, oxygen gas, carbon dioxide gas, nitrogen monoxide gas, and nitrogen dioxide gas. It is a sputter gas atmosphere consisting of a mixed gas containing a gas selected from the group. The formation of the thin film 30 for pattern formation can be performed in a state where the gas pressure in the film formation chamber during sputtering is 0.3 Pa or more and 2.0 Pa or less, and preferably 0.43 Pa or more and 0.9 Pa or less. Side etching during pattern formation can be suppressed and a high etching rate can be achieved. The atomic ratio of the transition metal to silicon in the transition metal silicide target is preferably in the range of transition metal:silicon = 1:1 to 1:19 from the viewpoint of improving light resistance and adjusting transmittance.

The composition and thickness of the thin film 30 for pattern formation are adjusted so that the thin film 30 for pattern formation has the above-described phase difference and transmittance. The composition of the thin film 30 for pattern formation can be controlled by the content ratio of the elements constituting the sputter target (for example, the ratio of the transition metal content to the silicon content), the composition and flow rate of the sputter gas, etc. The thickness of the thin film 30 for pattern formation can be controlled by sputtering power, sputtering time, etc. In addition, the thin film 30 for pattern formation is preferably formed using an in-line sputtering device. When the sputtering device is an in-line sputtering device, the thickness of the thin film 30 for pattern formation can be controlled also by the transfer speed of the substrate. In this way, control is performed so that the X-ray absorption spectrum of the thin film 30 for pattern formation satisfies the desired relationship ((IH-IL)/(EH-EL) is -6.0×10 ^-4 or more, etc.).

When the thin film 30 for pattern formation is made of a single film, the above-described film forming process is performed only once by appropriately adjusting the composition and flow rate of the sputter gas. When the thin film 30 for pattern formation is made of a plurality of films with different compositions, the above-described film forming process is performed multiple times by appropriately adjusting the composition and flow rate of the sputter gas. The thin film 30 for pattern formation may be formed using targets having different content ratios of elements constituting the sputter target. When performing the film forming process multiple times, the sputter power applied to the sputter target may be changed for each film forming process.

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

<<Etching mask film formation process>>

The mask blank 10 of this embodiment may also have an etching mask film 40. The following etching mask film formation process is further performed. Additionally, the etching mask film 40 is preferably made of a material containing chromium.

After the thin film for pattern formation process, surface treatment to adjust the surface oxidation state of the surface of the thin film for pattern formation 30 is performed as necessary, and then, the thin film for pattern formation 30 is deposited on the thin film for pattern formation by the sputtering method. An etching mask film 40 is formed. The etching mask film 40 is preferably formed using an in-line sputtering device. When the sputtering device is an in-line sputtering device, the thickness of the etching mask film 40 can be controlled also by the transfer speed of the translucent substrate 20.

The etching mask film 40 is formed using a sputter target containing chromium or a chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium nitride carbide, chromium oxynitride carbide, etc.), and using an inert gas. It can be performed in a sputter gas atmosphere or a sputter gas atmosphere consisting of a mixed gas of an inert gas and an active gas. The inert gas may include, for example, at least one selected from the group consisting of helium gas, neon gas, argon gas, krypton gas, and xenon gas. The active gas may include at least one selected from the group consisting of oxygen gas, nitrogen gas, nitrogen monoxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon-based gas, and fluorine-based gas. Examples of hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas. By adjusting the gas pressure in the film formation chamber during sputtering, the etching mask film 40 can be formed into a pillar-like structure like the thin film 30 for pattern formation. As a result, side etching during pattern formation, which will be described later, can be suppressed, and a high etching rate can be achieved.

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

In this way, the mask blank 10 of this embodiment having the etching mask film 40 can be obtained.

In addition, since the mask blank 10 shown in FIG. 1 is provided with an etching mask film 40 on the thin film 30 for pattern formation, an etching mask film forming process is performed when manufacturing the mask blank 10. . In addition, when manufacturing the mask blank 10 including the etching mask film 40 on the thin film 30 for pattern formation and the resist film on the etching mask film 40, after the etching mask film forming process, the etching mask is used. 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 including a resist film on the thin film 30 for pattern formation, the resist film is formed after the thin film formation process for pattern formation.

In the mask blank 10 of the embodiment shown in FIG. 1, an etching mask film 40 is formed on a thin film 30 for pattern formation. In addition, the mask blank 10 of the embodiment shown in FIG. 2 has a thin film 30 for pattern formation formed thereon. In either case, the thin film 30 for pattern formation has an X-ray absorption spectrum that satisfies the desired relationship ((IH-IL)/(EH-EL) is ^-6.0 It is said to be.

The mask blank 10 of the embodiment shown in FIGS. 1 and 2 has high light resistance to exposure light including a wavelength in the ultraviolet region. Therefore, by using the mask blank 10 of the present embodiment, it has high light resistance to exposure light including a wavelength in the ultraviolet region and can transfer the thin film pattern 30a for high-precision pattern formation with high precision. A transfer mask 100 can be manufactured.

<Method of manufacturing transfer mask 100>

Next, the manufacturing method of the transfer mask 100 of this embodiment will be described. This transfer mask 100 has the same technical characteristics as the mask blank 10. Matters pertaining to the translucent substrate 20, thin film 30 for pattern formation, and etching mask film 40 in the transfer mask 100 are the same as those for the mask blank 10.

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

<<Method of manufacturing the 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 a process of preparing the mask blank shown in FIG. 1, a process of forming a resist film having a transfer pattern on the etching mask film 40, and this resist A process of performing wet etching using the film as a mask, forming a transfer pattern on the etching mask film 40, and wet etching using the etching mask film (first etching mask film pattern 40a) on which the transfer pattern was formed as a mask. and forming a transfer pattern on the thin film 30 for pattern formation. In addition, the transfer pattern in this specification is obtained by patterning at least one optical film formed on the translucent substrate 20. The optical film can be a pattern forming thin film 30 and/or an etching mask film 40, and may further include other films (a light-shielding film, a film for suppressing reflection, a conductive film, etc.). . That is, the transfer pattern may include a patterned thin film for forming a pattern and/or an etching mask film, and may further include other patterned films.

Specifically, the method of manufacturing the transfer mask 100 shown in FIG. 3 forms a resist film on the etching mask film 40 of the mask blank 10 shown in FIG. 1. Next, the resist film pattern 50 is formed by drawing and developing a desired pattern on the resist film (see Fig. 3(a), step of forming the first resist film pattern 50). Next, the etching mask film 40 is wet-etched using the resist film pattern 50 as a mask to form an etching mask film pattern 40a on the pattern forming thin film 30 (FIG. 3(b) Reference, formation process of the first etching mask layer pattern 40a). Next, using the etching mask film pattern 40a as a mask, the thin film 30 for pattern formation is wet-etched to form the thin film pattern 30a for pattern formation on the light-transmissive substrate 20 (Figure 3(c) ) Reference, formation process of thin film pattern 30a for pattern formation). After that, a process of forming a second resist layer pattern 60 and a process of forming a second etching mask layer pattern 40b may be further included (see Figures 3 (d) and (e)).

More specifically, in the formation process of the first resist film pattern 50, first, a resist film is formed on the etching mask film 40 of the mask blank 10 of this embodiment shown in FIG. 1. The resist film material used is not particularly limited. The resist film can be any one that is sensitive to laser light having a wavelength selected from, for example, a wavelength range of 350 nm to 436 nm, which will be described later. Additionally, the resist film may be either positive or negative.

Thereafter, a desired pattern is drawn on the resist film using laser light having a wavelength selected from the wavelength range of 350 nm to 436 nm. The pattern drawn on the resist film is the pattern formed on the thin film 30 for pattern formation. Patterns drawn on the resist film include line and space patterns and hole patterns.

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

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

In the formation process of 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 layer 40 may be formed of a chromium-based material containing chromium (Cr).

Thereafter, the first resist film pattern 50 is peeled off using a resist stripper or by ashing, as shown in FIG. 3(b). In some cases, the forming process of the thin film pattern 30a for forming the next pattern may be performed without peeling the first resist film pattern 50.

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

In the process of forming the thin film pattern 30a for forming the first pattern, the thin film 30 for pattern formation is wet-etched using the first etching mask film pattern 40a as a mask, as shown in (c) of FIG. 3. Likewise, a thin film pattern 30a for pattern formation is formed. Examples of the thin film pattern 30a for pattern formation include a line and space pattern and a hole pattern. The etching solution 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, an etching liquid containing ammonium hydrogen fluoride and hydrogen peroxide, an etching liquid containing ammonium fluoride, phosphoric acid, and hydrogen peroxide, etc.

In order to improve the cross-sectional shape of the thin film pattern 30a for pattern formation, wet etching is performed longer than the time until the light-transmitting substrate 20 is exposed in the thin film pattern 30a for pattern formation (just etching time). It is preferable to perform it on time (over-etching time). Considering the influence on the translucent substrate 20, etc., the over-etching time is preferably within the just-etching time plus 20% of the just-etching time, and is the time added by 10% of the just-etching time. It is more desirable to do it within.

<<<Formation process of second resist film pattern 60>>>

In the process of forming 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 may be sensitive to laser light having any wavelength selected from the wavelength range of 350 nm to 436 nm, which will be described later. Additionally, the resist film may be either positive or negative.

Thereafter, a desired pattern is drawn on the resist film using laser light having a wavelength selected from the wavelength range of 350 nm to 436 nm. The pattern drawn on the resist film includes a light-shielding band pattern that blocks light from the outer peripheral area of the area where the pattern forming thin film pattern 30a is formed, and a light-shielding band pattern that blocks light from the central portion of the pattern forming thin film pattern 30a. In addition, the pattern drawn on the resist film may be a pattern without a light-shielding band pattern that blocks light from the central portion of the pattern forming thin film 30a, depending on the transmittance of the pattern forming thin film 30 with respect to the exposure light. .

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

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

In the process of forming the second etching mask film pattern 40b, the first etching mask film pattern 40a is etched using the second resist film pattern 60 as a mask, as shown in FIG. 3(e). , to form a second etching mask pattern 40b. The first etching mask layer 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 ammonium cerium nitrate and perchloric acid can be mentioned.

Thereafter, the second resist film pattern 60 is peeled off using a resist stripper or by ashing.

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

In addition, 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 a hard mask function when etching the thin film 30 for pattern formation, in the above description, the forming process of the second resist film pattern 60 and the second The process of forming the etching mask film pattern 40b is not performed. In this case, after the forming process of the thin film pattern 30a for pattern formation, the first etching mask film pattern 40a is peeled off and the transfer mask 100 is manufactured. That is, the transfer pattern of the transfer mask 100 may be composed of only the thin film pattern 30a for pattern formation.

According to the manufacturing method of the transfer mask 100 of the present embodiment, in order to use the mask blank 10 shown in FIG. 1, it has high light resistance to exposure light including a wavelength in the ultraviolet region and has high precision. A transfer mask 100 capable of transferring the thin film pattern 30a for pattern formation with high precision can be manufactured. The transfer mask 100 manufactured in this way can respond to miniaturization of line and space patterns and/or contact holes.

<<Method of manufacturing the 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 includes steps of preparing the mask blank 10 shown in FIG. 2, forming a resist film on the thin film 30 for pattern formation, and forming a resist film from the resist film. There is a process of wet etching the pattern forming thin film 30 using the resist film pattern as a mask to form a transfer pattern on the translucent 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, the resist film pattern 50 is formed by drawing and developing a desired pattern on the resist film (FIG. 4(a), forming process of the first resist film pattern 50). Next, the thin film 30 for pattern formation is wet-etched using the resist film pattern 50 as a mask to form the thin film pattern 30a for pattern formation on the translucent substrate 20 ((b) in FIG. 4). and (c), process of forming the thin film pattern 30a for pattern formation).

More specifically, in the resist film pattern formation process, a resist film is first formed on the pattern forming thin film 30 of the mask blank 10 of this embodiment shown in FIG. 2. The resist film material used is the same as that described above. Additionally, before forming the resist film, if necessary, the pattern forming thin film 30 may be subjected to surface modification treatment in order to improve the adhesion between the pattern forming thin film 30 and the resist film. As described above, after forming a resist film, a desired pattern is drawn on the resist film using laser light having a wavelength selected from the wavelength range of 350 nm to 436 nm. Thereafter, the resist film is developed with a predetermined developer, and a resist film pattern 50 is formed on the thin film 30 for pattern formation, as shown in FIG. 4(a).

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

In the process of forming the thin film pattern 30a 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 30a for pattern formation, as shown in (b) of FIG. 4. ) is formed. The etching solution and over-etching time for etching the thin film pattern 30a and the thin film 30 for pattern formation are the same as those described in the embodiment shown in FIG. 3 described above.

Thereafter, the resist film pattern 50 is peeled off using a resist stripper or by ashing (FIG. 4(c)).

In this way, the transfer mask 100 can be obtained. In addition, the transfer pattern of the transfer mask 100 according to the present embodiment is composed only of the thin film pattern 30a for pattern formation, but may further include other film patterns. Other films include, for example, a film that suppresses reflection, a conductive film, etc.

According to the manufacturing method of the transfer mask 100 of this embodiment, in order to use the mask blank 10 shown in FIG. 2, it has high light resistance to exposure light including a wavelength in the ultraviolet region and has high precision. A transfer mask 100 capable of transferring the thin film pattern 30a for pattern formation with high precision can be manufactured. The transfer mask 100 manufactured in this way can respond to miniaturization of line and space patterns and/or contact holes.

<Method of manufacturing display device>

The manufacturing method of the display device of this embodiment will be described. In the display device manufacturing method of the present embodiment, the transfer mask 100 of the present embodiment described above is placed on a mask stage of an exposure apparatus, and the transfer pattern formed on the display device manufacturing transfer mask 100 is applied to the display device manufacturing method. It has an exposure process of exposure and transfer to a resist formed on a substrate.

Specifically, the manufacturing method of the display device of the present embodiment includes a step of loading the transfer mask 100 manufactured using the above-described mask blank 10 on the mask stage of an exposure apparatus (mask loading step), It includes a process (exposure process) of transferring a transfer pattern to a resist film on a display device substrate. Hereinafter, each process will be described in detail.

<<Loading process>>

In the loading process, the transfer mask 100 of this embodiment is loaded on the mask stage of the exposure apparatus. Here, the transfer mask 100 is disposed to face the resist film formed on the display device substrate via the projection optical system of the exposure device.

<<Pattern transfer process>>

In the pattern transfer process, exposure light is irradiated to the transfer mask 100 to transfer a transfer pattern including the thin film pattern 30a for pattern formation to a resist film formed on a display device substrate. The exposure light is composite light containing light of a plurality of wavelengths selected from the wavelength range of 313 nm to 436 nm, monochromatic light selected by cutting a certain wavelength range from the wavelength range of 313 nm to 436 nm with a filter, etc., or 313 nm to 313 nm. It is monochromatic light emitted from a light source with a wavelength range of 436 nm. For example, the exposure light is a composite light containing at least one of the i-line, h-line, and g-line, or the monochromatic light of the i-line. By using composite light as the exposure light, the intensity of the exposure light can be increased and throughput can be improved. Therefore, the manufacturing cost of the display device can be lowered.

According to the display device manufacturing method of this embodiment, a high-precision display device having high resolution and fine line and space patterns and/or contact holes can be manufactured.

In addition, in the above embodiment, the case of using the mask blank 10 having the thin film 30 for pattern formation and the transfer mask 100 having the thin film pattern 30a for pattern formation has been described. The thin film 30 for pattern formation may be, for example, a phase shift film or a light-shielding film having a phase shift effect. Accordingly, the transfer mask 100 of this embodiment includes a phase shift mask having a phase shift film pattern and a binary mask having a light-shielding film pattern. Additionally, the mask blank 10 of this embodiment includes a phase shift mask blank and a binary mask blank that are raw materials for the phase shift mask and the binary mask.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these.

(Example 1)

To manufacture the mask blank 10 of Example 1, first, a synthetic quartz glass substrate of size 1214 (1220 mm x 1400 mm) was prepared as the light-transmitting substrate 20.

Thereafter, the synthetic quartz glass substrate was placed on a tray (not shown) with its main surface facing downward and loaded into the chamber of the in-line sputtering apparatus.

In order to form the thin film 30 for pattern formation on the main surface of the translucent substrate 20, first, a mixed gas consisting of argon (Ar) gas and nitrogen (N ₂ ) gas was introduced into the first chamber. Then, using a first sputter target containing titanium and silicon, nitride of titanium silicide containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a film thickness of 113 nm (Ti:Si:N:O = 10.7:34.9:50.3:4.1 atomic% ratio) made of titanium silicide nitride was formed. Here, the composition of the thin film 30 for pattern formation is a result obtained by measurement by X-ray photoelectron spectroscopy (XPS) on a thin film formed under the same film forming conditions as in Example 1. Hereinafter, the method of measuring the membrane composition is the same for other membranes (the same applies to Examples 2 and 3 and Comparative Examples 1 and 2). The ratio of titanium content to the total content of titanium and silicon in this pattern forming thin film 30 was 0.235, which was 0.05 or more.

Additionally, this pattern forming thin film 30 is a phase shift film having a phase shift effect.

Next, the translucent substrate 20 having the thin film 30 for pattern formation was brought into the second chamber, and a mixed gas of argon (Ar) gas and nitrogen (N ₂ ) gas was introduced into the second chamber. Then, chromium nitride (CrN) containing chromium and nitrogen was formed on the pattern forming thin film 30 by reactive sputtering using a second sputter target made of chromium. Next, with the inside of the third chamber at a predetermined vacuum level, a mixed gas of argon (Ar) gas and methane (CH ₄ ) gas is introduced, and a third sputter target made of chromium is used to perform reactive sputtering. Chromium carbide (CrC) containing chromium and carbon was formed on CrN. Finally, with the fourth chamber at a predetermined vacuum level, 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. And, using the fourth sputter target made of chromium, chromium carboxynitride (CrCON) containing chromium, carbon, oxygen, and nitrogen was formed on CrC by reactive sputtering. As described above, an etching mask film 40 having a stacked structure of a CrN layer, a CrC layer, and a CrCON layer was formed on the pattern forming thin film 30.

In this way, a mask blank 10 in which the thin film 30 for pattern formation and the etching mask film 40 were formed on the translucent substrate 20 was obtained.

The pattern forming thin film of Example 1 was deposited on the main surface of another synthetic quartz substrate (about 152 mm x about 152 mm), and another pattern forming thin film was formed under the same film forming conditions as Example 1. Next, an X-ray absorption fine structure analysis was performed using Absorption spectra were acquired. Specifically, it was carried out with BL6N1 of the Aichi Synchrotron optical center (the same applies to subsequent Examples 2 and 3 and Comparative Examples 1 and 2).

Figure 5 shows the X-ray absorption spectrum derived from Ar (horizontal axis: incident on the thin film) obtained by fluorescence quantification for the thin films for forming patterns of mask blanks according to Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention. This is a diagram showing the X-ray energy generated, vertical axis: X-ray absorption coefficient of the thin film for that X-ray energy. As shown in Figure 5, in the X-ray absorption spectrum derived from Ar obtained by the fluorescence quantitative method in Example 1, the incident X-ray energy EL is higher than the X-ray absorption coefficient at 3180 eV. The X-ray absorption coefficient at 3210 eV was found to be larger, and it was confirmed that Ar exists in at least a certain region in the film thickness direction of the thin film 30.

Figure 6 shows the X-ray absorption spectrum derived from Ar obtained by the all-electron quantity method for the thin film surface layer for pattern formation of the mask blank according to Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention (horizontal axis: thin film This is a diagram showing the X-ray energy incident on the surface layer, the vertical axis: the X-ray absorption coefficient of the surface layer of the thin film relative to the X-ray of that energy.

As obtained from the values shown in FIG. 6, the surface layer X-ray absorption spectrum of the thin film 30 of Example 1 is (IH-IL)/(EH-EL) of ^7.933 It satisfied the relationship of 10 ^-4 or more. Here, IL is the X-ray absorption coefficient when the incident X-ray energy EL is 3180 eV, and IH is the X-ray absorption coefficient when the incident 1 and 2 are also the same).

In addition, as shown in FIG. 6, the surface layer X-ray absorption spectrum of the thin film 30 of Example 1 has an incident The X-ray absorption coefficient IH was larger.

<Measurement of transmittance and phase difference>

Transmittance (wavelength: 405 nm) and phase difference (wavelength: 405 nm) were measured on the surface of the pattern forming thin film 30 of the mask blank 10 of Example 1. To measure the transmittance and phase difference of the pattern forming thin film 30, a substrate having a thin film in which another pattern forming thin film was deposited on the main surface of the other synthetic quartz glass substrate described above was used (following Examples 2 and 3, The same applies to Comparative Examples 1 and 2). As a result, the transmittance of the other pattern forming thin film (pattern forming thin film 30) in Example 1 was 35.2%, and the phase difference was 140 degrees.

<Transfer mask 100 and manufacturing method thereof>

A transfer mask 100 was manufactured using the mask blank 10 of Example 1 manufactured as described above. First, a photoresist film was applied onto the etching mask film 40 of the mask blank 10 using a resist coating device.

Afterwards, a photoresist film was formed through a heating/cooling process.

After that, the photoresist film was drawn using a laser drawing device, and through a development/rinsing process, a resist film pattern with a hole pattern having a hole diameter of 1.5 μm was formed on the etching mask film 40.

Thereafter, using the resist film pattern as a mask, the etching mask film 40 was wet-etched with a chromium etching solution containing cerium ammonium nitrate and perchloric acid to form the first etching mask film pattern 40a.

Thereafter, using the first etching mask film pattern 40a as a mask, the thin film for pattern formation 30 is wet-etched using a titanium silicide etching solution obtained by diluting a mixture of ammonium hydrogen fluoride and hydrogen peroxide with pure water to form a thin film for pattern formation. A pattern 30a was formed.

After that, the resist film pattern was peeled off.

After that, a photoresist film was applied to cover the first etching mask film pattern 40a using a resist coating device.

Afterwards, a photoresist film was formed through a heating/cooling process.

After that, the photoresist film was drawn using a laser drawing device, and through a development/rinsing process, a second resist film pattern 60 for forming a light-shielding zone was formed on the first etching mask film pattern 40a.

Thereafter, using the second resist film pattern 60 as a mask, the first etching mask film pattern 40a formed in the transfer pattern formation area was wet-etched with a chromium etching solution containing cerium ammonium nitrate and perchloric acid. .

Afterwards, the second resist film pattern 60 was peeled off.

In this way, a stacked structure of the thin film pattern 30a for pattern formation with a hole diameter of 1.5 ㎛, the thin film pattern 30a for pattern formation, and the etching mask film pattern 40b in the transfer pattern formation area on the translucent substrate 20. The transfer mask 100 of Example 1, in which a light-shielding band consisting of was formed, was obtained.

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed using a scanning electron microscope. The thin film pattern 30a for pattern formation of the transfer mask 100 of Example 1 had a cross-sectional shape close to vertical. Accordingly, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of Example 1 had a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

In view of the above, when the transfer mask 100 of Example 1 is set on the mask stage of an exposure apparatus and exposed and transferred to a resist film on a display device substrate, a transfer pattern containing a fine pattern of less than 2.0 μm is formed. It can be said that transcription can be done with high precision.

<Lightfastness>

A sample was prepared in which the thin film 30 for pattern formation used in the mask blank 10 of Example 1 was formed on a translucent substrate 20. The thin film 30 for forming a sample pattern of Example 1 was irradiated with light from a metal halide light source containing ultraviolet rays with a wavelength of 405 nm at a total irradiation amount of 10 kJ/cm2. The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation of a predetermined ultraviolet ray and calculating the change in transmittance [(transmittance after irradiation with ultraviolet rays) - (transmittance before irradiation with ultraviolet rays)]. Transmittance was measured using a spectrophotometer.

Figure 7 shows the relationship between (IH-IL)/(EH-EL) and the amount of change in transmittance in the thin film for forming a pattern of a mask blank according to Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention. This is a drawing that represents. As shown in Figure 7, in Example 1, the change in transmittance before and after ultraviolet irradiation was good at 0.34%. From the above points, it was found that the thin film for pattern formation of Example 1 was a film with sufficiently high light resistance for practical use.

As a result of the above, the thin film for pattern formation of Example 1 is superior than before in that it satisfies the desired optical properties (transmittance, phase difference) and the requirement for high light resistance to exposure light containing a wavelength in the ultraviolet region. This has become clear.

(Example 2)

The mask blank 10 of Example 2 was manufactured in the same manner as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was formed as follows. The method of forming the thin film 30 for pattern formation in Example 2 is as follows. In order to form the thin film 30 for pattern formation on the main surface of the translucent substrate 20, first, a mixed gas consisting of argon (Ar) gas and nitrogen (N ₂ ) gas was introduced into the first chamber. Then, using a first sputter target containing titanium and silicon, nitride of titanium silicide containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a film thickness of 126 nm (Ti:Si:N:O = 10.2:36.2:52.7:0.9 atomic% ratio) made of titanium silicide nitride was formed. The ratio of titanium content to the total content of titanium and silicon in this pattern forming thin film 30 was 0.220, which was 0.05 or more.

After that, as in Example 1, an etching mask film 40 was formed.

Then, another pattern forming thin film was formed on the main surface of another synthetic quartz substrate under the same film formation conditions as in Example 2. Next, as in Example 1, the X-ray absorption fine structure was measured by Analysis was performed and an X-ray absorption spectrum was acquired.

As shown in Figure 5, in the X-ray absorption spectrum derived from Ar obtained by the fluorescence quantitative method in Example 2, the incident X-ray energy EL is higher than the X-ray absorption coefficient at 3180 eV. The X-ray absorption coefficient at 3210 eV was found to be larger, and it was confirmed that Ar exists in at least a certain region in the film thickness direction of the thin film 30.

In addition, as obtained from the values shown in FIG. 6, the surface ^layer It satisfied a relationship of 6.0×10 ^-4 or more.

Additionally, as shown in FIG. 6, the surface layer X-ray absorption spectrum of the thin film 30 of Example 2 has an incident X-ray energy EH of 3210 eV than the The X-ray absorption coefficient IH was larger.

<Measurement of transmittance and phase difference>

Transmittance (wavelength: 405 nm) and phase difference (wavelength: 405 nm) were measured on the surface of the pattern forming thin film 30 of the mask blank 10 of Example 2. As a result, the transmittance of the thin film 30 for pattern formation in Example 2 was 30.9%, and the phase difference was 151 degrees.

<Transfer mask 100 and manufacturing method thereof>

Using the mask blank 10 of Example 2 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as Example 1, and a hole was formed in the transfer pattern formation area on the translucent substrate 20. The transfer mask 100 of Example 2 was formed with a thin film pattern 30a for pattern formation having a diameter of 1.5 ㎛, and a light-shielding zone made of a stacked structure of the thin film pattern 30a for pattern formation and an etching mask film pattern 40b. got it

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed using a scanning electron microscope. The thin film pattern 30a for pattern formation of the transfer mask 100 of Example 2 had a cross-sectional shape close to vertical. Accordingly, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of Example 2 had a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

In view of the above, when the transfer mask 100 of Example 2 is set on the mask stage of an exposure apparatus and exposed and transferred to a resist film on a display device substrate, a transfer pattern containing a fine pattern of less than 2.0 μm is formed. It can be said that transcription can be done with high precision.

<Lightfastness>

A sample was prepared in which the pattern forming thin film 30 used in the mask blank 10 of Example 2 was formed on a translucent substrate 20. The sample pattern forming thin film 30 of Example 2 was irradiated with light from a metal halide light source containing ultraviolet rays with a wavelength of 405 nm at a total irradiation amount of 10 kJ/cm2. The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation of a predetermined ultraviolet ray and calculating the change in transmittance [(transmittance after irradiation with ultraviolet rays) - (transmittance before irradiation with ultraviolet rays)]. Transmittance was measured using a spectrophotometer.

As shown in Figure 7, in Example 2, the change in transmittance before and after ultraviolet irradiation was good at 0.37%. From the above points, it was found that the thin film for pattern formation of Example 2 was a film with sufficiently high light resistance for practical use.

As a result of the above, the thin film for pattern formation of Example 2 is superior than ever before in that it satisfies the desired optical properties (transmittance, phase difference) and the requirement for high light resistance to exposure light containing a wavelength in the ultraviolet region. This has become clear.

(Example 3)

The mask blank 10 of Example 3 was manufactured in the same manner as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was prepared as follows. The method of forming the thin film 30 for pattern formation in Example 3 is as follows. In order to form the thin film 30 for pattern formation on the main surface of the translucent substrate 20, first, a mixed gas consisting of argon (Ar) gas and nitrogen (N ₂ ) gas was introduced into the first chamber. Then, using a first sputter target containing titanium and silicon, nitride of titanium silicide containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a film thickness of 109 nm (Ti:Si:N:O = 11.4:35.4:52.4:0.8 atomic% ratio) made of titanium silicide nitride was formed. The ratio of titanium content to the total content of titanium and silicon in this pattern forming thin film 30 was 0.244, which was 0.05 or more.

After that, as in Example 1, an etching mask film 40 was formed.

Then, another pattern forming thin film was formed on the main surface of another synthetic quartz substrate under the same film formation conditions as in Example 3. Next, as in Example 1, the X-ray absorption fine structure was measured by Analysis was performed and an X-ray absorption spectrum was acquired.

As shown in Figure 5, in the X-ray absorption spectrum derived from Ar obtained by the fluorescence quantitative method in Example 3, the incident X-ray energy EL is higher than the X-ray absorption coefficient at 3180 eV. The X-ray absorption coefficient at 3210 eV was found to be larger, and it was confirmed that Ar exists in at least a certain region in the film thickness direction of the thin film 30.

Additionally, as obtained from the values shown in FIG. 6, the surface layer X-ray absorption spectrum of the thin film 30 of Example 3 is (IH-IL)/(EH-EL) of -1.467×10 ^-4 , It satisfied the relationship of -6.0×10 ^-4 or more.

<Measurement of transmittance and phase difference>

Transmittance (wavelength: 405 nm) and phase difference (wavelength: 405 nm) were measured on the surface of the pattern forming thin film 30 of the mask blank 10 of Example 3. As a result, the transmittance of the thin film 30 for pattern formation in Example 3 was 30.9%, and the phase difference was 143 degrees.

<Transfer mask 100 and manufacturing method thereof>

Using the mask blank 10 of Example 3 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as Example 1, and a hole was formed in the transfer pattern formation area on the translucent substrate 20. The transfer mask 100 of Example 3 is formed with a thin film pattern 30a for pattern formation having a diameter of 1.5 ㎛, and a light-shielding zone made of a stacked structure of the thin film pattern 30a for pattern formation and an etching mask film pattern 40b. got it

<Cross-sectional shape of transfer mask 100>

The cross section of the obtained transfer mask 100 was observed using a scanning electron microscope. The thin film pattern 30a for pattern formation of the transfer mask 100 of Example 3 had a cross-sectional shape close to vertical. Accordingly, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of Example 3 had a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

In view of the above, when the transfer mask 100 of Example 3 is set on the mask stage of an exposure apparatus and exposed and transferred to a resist film on a display device substrate, a transfer pattern containing a fine pattern of less than 2.0 μm is formed. It can be said that transcription can be done with high precision.

<Lightfastness>

A sample was prepared in which the thin film 30 for pattern formation used in the mask blank 10 of Example 3 was formed on a translucent substrate 20. The thin film 30 for forming a sample pattern of Example 3 was irradiated with light from a metal halide light source containing ultraviolet rays with a wavelength of 405 nm so that the total irradiation amount was 10 kJ/cm2. The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation of a predetermined ultraviolet ray and calculating the change in transmittance [(transmittance after irradiation with ultraviolet rays) - (transmittance before irradiation with ultraviolet rays)]. Transmittance was measured using a spectrophotometer.

As shown in Figure 7, in Example 3, the change in transmittance before and after ultraviolet irradiation was good at 0.74%. From the above points, it was found that the thin film for pattern formation of Example 3 was a film with sufficiently high light resistance for practical use.

As a result of the above, the thin film for pattern formation of Example 3 is an excellent product that has never been seen before, meeting the requirements for high light resistance to exposure light containing a wavelength in the ultraviolet region while satisfying the desired optical properties (transmittance, phase difference). This has become clear.

(Comparative Example 1)

The mask blank 10 of Comparative Example 1 was manufactured in the same manner as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was prepared as follows.

The method of forming the thin film 30 for pattern formation in Comparative Example 1 is as follows. In order to form the thin film 30 for pattern formation on the main surface of the translucent substrate 20, first, a mixed gas consisting of argon (Ar) gas and nitrogen (N ₂ ) gas was introduced into the first chamber. Then, using a first sputter target containing titanium and silicon, nitride of titanium silicide containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a film thickness of 118 nm (Ti:Si:N:O = 11.1:34.0:50.7:4.2 atomic% ratio) made of titanium silicide nitride was formed.

After that, as in Example 1, an etching mask film 40 was formed.

Then, another pattern forming thin film was formed on the main surface of another synthetic quartz substrate under the same film formation conditions as in Comparative Example 1 above. Next, as in Example 1, the X-ray absorption fine structure was measured by Analysis was performed and an X-ray absorption spectrum was acquired.

As shown in FIG. 5, in the X-ray absorption spectrum derived from Ar obtained by the fluorescence quantitative method of Comparative Example 1, the incident X-ray energy EL is higher than the The X-ray absorption coefficient at 3210 eV was found to be larger, and it was confirmed that Ar exists in at least a certain region in the film thickness direction of the thin film 30.

In addition, as obtained from the values shown in FIG. 6, ^the surface layer It did not satisfy a relationship of -6.0×10 ^-4 or more.

<Measurement of transmittance and phase difference>

Transmittance (wavelength: 405 nm) and phase difference (wavelength: 405 nm) were measured on the surface of the pattern forming thin film 30 of the mask blank 10 of Comparative Example 1. As a result, the transmittance of the thin film 30 for pattern formation in Comparative Example 1 was 31.7%, and the phase difference was 154 degrees.

<Transfer mask 100 and manufacturing method thereof>

Using the mask blank 10 of Comparative Example 1 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as Example 1, and a hole was formed in the transfer pattern formation area on the translucent substrate 20. The transfer mask 100 of Comparative Example 1 was formed with a thin film pattern 30a for pattern formation having a diameter of 1.5 ㎛, and a light-shielding zone made of a stacked structure of the thin film pattern 30a for pattern formation and an etching mask film pattern 40b. got it

<Cross-sectional shape of transfer mask 100>

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

The thin film pattern 30a for pattern formation of the transfer mask 100 of Comparative Example 1 had a cross-sectional shape close to vertical. Accordingly, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of Comparative Example 1 had a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

In view of the above, when the transfer mask 100 of Comparative Example 1 is set on the mask stage of an exposure apparatus and exposed and transferred to a resist film on a display device substrate, a transfer pattern containing a fine pattern of less than 2.0 μm is formed. It can be said that transcription can be done with high precision.

<Lightfastness>

A sample was prepared in which the thin film 30 for pattern formation used in the mask blank 10 of Comparative Example 1 was formed on a translucent substrate 20. The thin film 30 for forming a sample pattern of Comparative Example 1 was irradiated with light from a metal halide light source containing ultraviolet rays with a wavelength of 405 nm at a total irradiation amount of 10 kJ/cm2. The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation of a predetermined ultraviolet ray and calculating the change in transmittance [(transmittance after irradiation with ultraviolet rays) - (transmittance before irradiation with ultraviolet rays)]. Transmittance was measured using a spectrophotometer.

As shown in Figure 7, in Comparative Example 1, the change in transmittance before and after ultraviolet irradiation was 2.32%, which was outside the allowable range. From the above, it was found that the thin film for pattern formation of Comparative Example 1 did not have sufficient light resistance for practical use.

(Comparative Example 2)

The mask blank 10 of Comparative Example 2 was manufactured in the same manner as the mask blank 10 of Example 1, except that the thin film 30 for pattern formation was formed as follows.

The method of forming the thin film 30 for pattern formation in Comparative Example 2 is as follows. In order to form the thin film 30 for pattern formation on the main surface of the translucent substrate 20, first, a mixed gas consisting of argon (Ar) gas and nitrogen (N ₂ ) gas was introduced into the first chamber. Then, using a first sputter target containing titanium and silicon, nitride of titanium silicide containing titanium, silicon, and nitrogen was deposited on the main surface of the translucent substrate 20 by reactive sputtering. In this way, a thin film 30 for pattern formation with a film thickness of 117 nm (Ti:Si:N:O = 11.7:35.0:52.0:1.3 atomic% ratio) made of titanium silicide nitride was formed.

After that, as in Example 1, an etching mask film 40 was formed.

Then, another pattern forming thin film was formed on the main surface of another synthetic quartz substrate under the same film formation conditions as in Comparative Example 2. Next, as in Example 1, the X-ray absorption fine structure was measured by Analysis was performed and an X-ray absorption spectrum was acquired.

As shown in FIG. 5, in the X-ray absorption spectrum derived from Ar obtained by the fluorescence quantitative method of Comparative Example 2, the incident X-ray energy EL is higher than the The X-ray absorption coefficient at 3210 eV was found to be larger, and it was confirmed that Ar exists in at least a certain region in the film thickness direction of the thin film 30.

In addition, as obtained from the values shown in FIG. 6, ^the surface layer It did not satisfy a relationship of -6.0×10 ^-4 or more.

<Measurement of transmittance and phase difference>

Transmittance (wavelength: 405 nm) and phase difference (wavelength: 405 nm) were measured on the surface of the pattern forming thin film 30 of the mask blank 10 of Comparative Example 2. As a result, the transmittance of the thin film 30 for pattern formation in Comparative Example 2 was 33.5%, and the phase difference was 144 degrees.

<Transfer mask 100 and manufacturing method thereof>

Using the mask blank 10 of Comparative Example 2 manufactured as described above, a transfer mask 100 was manufactured in the same procedure as Example 1, and a hole was formed in the transfer pattern formation area on the translucent substrate 20. The transfer mask 100 of Comparative Example 2 was formed with a thin film pattern 30a for pattern formation having a diameter of 1.5 ㎛, and a light blocking zone made of a stacked structure of the thin film pattern 30a for pattern formation and an etching mask film pattern 40b. got it

<Cross-sectional shape of transfer mask 100>

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

The thin film pattern 30a for pattern formation of the transfer mask 100 of Comparative Example 2 had a cross-sectional shape close to vertical. Accordingly, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of Comparative Example 2 had a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.

In view of the above, when the transfer mask 100 of Comparative Example 2 is set on the mask stage of an exposure apparatus and exposed and transferred to a resist film on a display device substrate, a transfer pattern containing a fine pattern of less than 2.0 μm is formed. It can be said that transcription can be done with high precision.

<Lightfastness>

A sample was prepared in which the thin film 30 for pattern formation used in the mask blank 10 of Comparative Example 2 was formed on a translucent substrate 20. The thin film 30 for forming a sample pattern of Comparative Example 1 was irradiated with light from a metal halide light source containing ultraviolet rays with a wavelength of 405 nm at a total irradiation amount of 10 kJ/cm2. The light resistance of the thin film 30 for pattern formation was evaluated by measuring the transmittance before and after irradiation of a predetermined ultraviolet ray and calculating the change in transmittance [(transmittance after irradiation with ultraviolet rays) - (transmittance before irradiation with ultraviolet rays)]. Transmittance was measured using a spectrophotometer.

As shown in Figure 7, in Comparative Example 2, the change in transmittance before and after ultraviolet irradiation was 2.06%, which was outside the allowable range. From the above points, it was found that the thin film for pattern formation of Comparative Example 2 did not have sufficient light resistance for practical use.

In the above-described embodiment, examples of the transfer mask 100 for manufacturing a display device and the mask blank 10 for manufacturing the transfer mask 100 for manufacturing a display device have been described, but the present invention 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, and printed circuit board manufacturing. In addition, the present invention can be applied also to a binary mask blank having a light-shielding film as the pattern forming thin film 30 and a binary mask having a light-shielding film pattern.

In addition, in the above-described embodiment, the size of the light-transmitting substrate 20 has been described as an example of size 1214 (1220 mm x 1400 mm x 13 mm), but it is not limited to this. In the case of the mask blank 10 for display device manufacturing, a large-sized translucent substrate 20 is used, and the size of the translucent substrate 20 is such that the length of one side of the main surface is 300 mm or more. The size of the translucent substrate 20 used for the mask blank 10 for manufacturing a display device is, for example, 330 mm x 450 mm or more and 2280 mm x 3130 mm or less.

In addition, in the case of the mask blank 10 for semiconductor device manufacturing, MEMS manufacturing, and printed circuit board manufacturing, a small size translucent substrate 20 is used, and the size of the translucent substrate 20 is such that the length of one side is 9. less than an inch. The size of the translucent substrate 20 used for the mask blank 10 for the above purpose is, for example, 63.1 mm x 63.1 mm or more and 228.6 mm x 228.6 mm or less. Usually, as the translucent substrate 20 for the transfer mask 100 for semiconductor device manufacturing and MEMS manufacturing, size 6025 (152 mm × 152 mm) or size 5009 (126.6 mm × 126.6 mm) is used. Additionally, as the translucent substrate 20 for the transfer mask 100 for manufacturing printed circuit boards, size 7012 (177.4 mm x 177.4 mm) or size 9012 (228.6 mm x 228.6 mm) is usually used.

10: Mask blank
20: Translucent substrate
30: Thin film for pattern formation
30a: thin film pattern
40: Etching mask film
40a: First etching mask pattern
40b: Second etching mask pattern
50: first resist film pattern
60: Second resist film pattern
100: Transfer mask

Claims (14)

It is a mask blank provided with a thin film for pattern formation on a translucent substrate,
The thin film contains a transition metal and silicon,
The surface layer X-ray absorption spectrum of the thin film obtained by the all-electron quantity method is IL as the X-ray absorption coefficient when the incident When using IH,
(IH-IL)/(EH-EL) is -6.0×10 ^-4 or more
A mask blank characterized in that. According to paragraph 1,
In the X-ray absorption spectrum of the thin film obtained by fluorescence quantification, the X-ray absorption coefficient at an incident X-ray energy EH of 3210 eV is larger than the X-ray absorption coefficient at an incident X-ray energy EL of 3180 eV. A mask blank characterized in that. According to paragraph 1,
A mask blank characterized in that the thin film contains at least titanium as the transition metal. According to paragraph 1,
A mask blank, characterized in that the thin film further contains nitrogen. According to paragraph 1,
A mask blank, wherein the ratio of the transition metal content to the total content of the transition metal and silicon in the thin film is 0.05 or more. According to paragraph 1,
A mask blank, characterized in that an etching mask film having different etching selectivity with respect to the thin film is provided on the thin film. According to clause 6,
A mask blank characterized in that the etching mask film contains chromium. It is a transfer mask including a thin film with a transfer pattern on a translucent substrate,
The thin film contains a transition metal and silicon,
The surface X-ray absorption spectrum of the thin film obtained by the all-electron quantity method is,
When the incident X-ray energy EL is 3180 eV, the X-ray absorption coefficient is IL,
When the incident X-ray energy EH is 3210 eV and the X-ray absorption coefficient is IH,
(IH-IL)/(EH-EL) is -6.0×10 ^-4 or more
A transfer mask characterized in that. According to clause 8,
In the X-ray absorption spectrum of the thin film obtained by fluorescence quantification, the X-ray absorption coefficient at an incident X-ray energy EH of 3210 eV is larger than the X-ray absorption coefficient at an incident X-ray energy EL of 3180 eV. A transfer mask characterized in that. According to clause 8,
A transfer mask, characterized in that the thin film contains at least titanium as the transition metal. According to clause 8,
A transfer mask, characterized in that the thin film further contains nitrogen. According to clause 8,
A transfer mask, wherein the ratio of the transition metal content to the total content of the transition metal and silicon in the thin film is 0.05 or more. A process of preparing the mask blank according to claim 6 or 7,
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 process of performing wet etching using the etching mask film on which the transfer pattern is formed as a mask, and forming a transfer pattern on the thin film.
A method for manufacturing a transfer mask, characterized in that it has a. A step of loading the transfer mask according to any one of claims 8 to 12 on a mask stage of an exposure apparatus;
A process of irradiating exposure light to the transfer mask and transferring the transfer pattern to a resist film provided on a display device substrate.
A method of manufacturing a display device comprising:

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