JP5281362B2 - Photomask blank, photomask and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A photo-mask blank, a photo-mask and a method for manufacturing the same are provided to suppress the surface reflectance of the photo-mask using a light shielding layer based on a transition metal silicide. CONSTITUTION: A light-shielding film(10) is formed on a light-transmissive substrate(1). The light-shielding film is composed of a light-shielding layer and an anti-surface reflection layer. The light-shielding layer is based on transition metal silicide. More than 20 atomic% and less than 40 atomic % of transition metal is contained in the transition metal silicide. The thickness of the light-shielding layer is less than 40nm. The anti-surface reflection layer is based on a silicide compound which includes oxygen or nitrogen. The thickness of the anti-surface reflection layer is less than 20nm.

Description

  The present invention relates to a photomask blank, a photomask, a manufacturing method thereof, and the like used in manufacturing a semiconductor device and the like.

Miniaturization of semiconductor devices and the like has an advantage of improving performance and functions (high-speed operation, low power consumption, etc.) and cost reduction, and miniaturization is increasingly accelerated. Lithography technology supports this miniaturization, and a transfer mask is a key technology along with an exposure apparatus and a resist material.
In recent years, development of half-pitch (hp) 45 nm to 32 nm generation, which is a design specification of semiconductor devices, has been advanced. This corresponds to ¼ to ６ of the wavelength 193 nm of ArF excimer laser exposure light. Especially in the generations after hp45nm, only application of conventional phase shift method, oblique incidence illumination method and pupil filter method such as super-resolution technology (Resolution Enhancement Technology: RET) and optical proximity effect correction (Optical Proximity Correction: OPC) technology. It has become insufficient, and ultra-high NA technology (immersion lithography) and double exposure method (double patterning) are becoming necessary.

  In general, when a photomask having a light shielding film pattern is formed on a transparent substrate, the mask pattern is transferred by dry etching the light shielding film using a resist film on which the mask pattern is formed as a mask. At this time, the resist film is also etched and consumed. In order to improve the resolution when the mask pattern is transferred to the light-shielding film, the resist film after dry etching needs to remain more than a predetermined thickness. However, if the thickness of the resist film is increased, a problem of resist pattern collapse occurs, so it is not desirable to increase the thickness. In order to improve the resolution when transferred to the light shielding film, it is effective to reduce the thickness of the light shielding film. However, when the light-shielding film is thinned, the OD value (optical density) decreases. In Patent Document 1, in order to reduce the thickness of the light shielding film, a transition metal silicide material having an absorption coefficient larger than that of a chromium-based material is applied, and molybdenum silicide is particularly preferable from the viewpoint of dry etching processability. Thereby, the film thickness of the light shielding film can be made thinner than before.

By the way, in order to form a fine pattern having a DRAM half pitch (hp) of 45 nm or more in the semiconductor design rule, it is necessary to use an ultra-high NA exposure method having a numerical aperture of NA> 1, for example, immersion exposure.
In immersion exposure, by filling the space between the wafer and the lowermost lens of the exposure device with liquid, the NA can be increased to double the refractive index of the liquid compared to air with a refractive index of 1, so the resolution is improved. This exposure method can be used. A numerical aperture (NA) is expressed by NA = n × sin θ. θ is an angle formed by the light beam entering the outermost side of the lowermost lens of the exposure apparatus and the optical axis, and n is a refractive index of the medium between the wafer and the lowermost lens of the exposure apparatus.
However, when an immersion exposure method with a numerical aperture of NA> 1 is applied to form a fine pattern with a DRAM half pitch (hp) of 45 nm or more in the semiconductor design rule, the expected resolution and CD accuracy (including linearity) ) Cannot be obtained.
The cause is that when the pattern width of the mask pattern is made smaller than the exposure wavelength, the incident angle to the photomask (the angle between the normal of the substrate and the incident light) is small (close to normal incidence). The emission angle of the ± 1st order diffracted light exiting from the lens increases, and the ± 1st order diffracted light does not enter the lens with a finite diameter and is not resolved. In order to avoid this, when the incident angle to the photomask is increased (oblique incidence), the emission angle of the ± 1st order diffracted light emitted from the photomask is reduced, and the ± 1st order diffracted light is applied to a lens having a finite diameter. Incident light is resolved.
However, if the incident angle to the photomask is increased in this way, a problem of shielding effect (shadowing) occurs, which adversely affects the resolution. Specifically, as shown in FIG. 13, when the exposure light is obliquely incident on the side wall of the light shielding pattern, a shadow is formed from the three-dimensional structure (particularly the height) of the light shielding pattern. Due to this shadow, the size on the photomask is not accurately transferred, and the amount of light is reduced (darkened).
As described above, even when transferring to a transfer object such as a wafer using a photomask manufactured from a blank, the thinning of the pattern results in a problem of resolution reduction due to the height of the side wall of the pattern. As a solution, there is a need to reduce the thickness of the transfer pattern. For this reason, it is necessary to further reduce the thickness of the light shielding film.
Japanese Patent Application No. 2007-78807

The inventors of the present invention have made extensive research and development for the following purposes.
(1) An object is to develop a material for a generation aiming at a resist film thickness of 200 nm or less (generally hp45 nm or more) and further a resist film thickness of 150 nm or less (generally hp32 nm or more).
(2) Thinning of the light-shielding film (and hence transfer pattern) that can handle the ultra-high NA technology and double patterning required for DRAM half-pitch (hp) 45 nm and later generations in semiconductor design rules, especially the hp32-22 nm generation Objective.
(3) An object is to provide a photomask blank capable of achieving a pattern resolution of 50 nm or less on the mask.

As a result, the inventors of the present invention have a composition outside this range (the transition metal content is 20%), which is mainly composed of a metal silicide whose transition metal content is 20 atomic% or more and 40 atomic% or less. Less than 40% by atom), a light-shielding layer having a relatively large light-shielding property in ArF excimer laser exposure light is obtained, and the thickness of the light-shielding layer is less than 40 nm. It has been found that a predetermined light-shielding property (optical density) can be obtained. In particular, a light-shielding layer made of molybdenum silicide metal having a molybdenum content of 20 atomic% or more and 40 atomic% or less has a composition outside this range (the molybdenum content is less than 20 atomic%, 40%, as shown in FIG. It has been found that a light-shielding layer having a relatively large light-shielding property in ArF excimer laser exposure light is obtained, and that the effect of reducing the thickness of the light-shielding layer is remarkable.
When the light shielding layer having the predetermined composition is used, the following effects can be obtained.
(1) The following effects can be obtained by reducing the thickness of the light shielding film (thinning the transfer pattern).
1) Prevents mask pattern collapse during mask cleaning.
2) Since the side wall height of the mask pattern is reduced by reducing the thickness of the light shielding film, the pattern accuracy particularly in the side wall height direction can be improved, and the CD accuracy (particularly linearity) can be increased.
3) Especially for photomasks used in the high NA (immersion) generation, it is necessary to make the mask pattern thin (to reduce the side wall height of the mask pattern) as a countermeasure against shadowing, but this requirement can be met. .

By the way, as described above, when a material (in particular, molybdenum silicide metal) containing the transition metal silicide having the predetermined composition as a main component is applied to the light shielding layer material in order to improve the light shielding performance, the transition metal silicide having the predetermined composition is used. Was found to have a particularly high surface reflectivity for ArF excimer laser exposure light (wavelength 193 nm).
Therefore, the present inventors can significantly reduce the surface reflectance (for example, 20%) even in a photomask using a light-shielding layer of a material (particularly molybdenum silicide metal) mainly composed of a transition metal silicide having the above predetermined composition. The surface antireflection layer (which can be made as follows) was studied earnestly.
As a result, a film thickness of 20 nm or less suitable as a surface antireflection layer (if the surface antireflection layer is simply made thicker than before to reduce the surface reflectance, there is no point in thinning the light shielding layer. It was found that a combination of the refractive index n and the extinction coefficient k of the surface antireflection layer such that the surface reflectance is 20% or less cannot be easily found.
In particular, for example, when MoSiON having Mo of 10 atomic% or less is used as the surface antireflection layer, the surface reflectance is 20% or less when the film thickness of 20 nm or less suitable as the surface antireflection layer is considered. It has been found that such a combination of the refractive index n and the extinction coefficient k of the surface antireflection layer cannot be easily found.
Furthermore, it is optimal among a plurality of candidates of “a combination of the thickness of the surface antireflection layer and n and k” such that the surface reflectance is 20% or less, which is appropriate for the surface antireflection layer. It is convenient if there is a method for selecting one.

  The present invention provides a photomask blank and a photomask that can have a surface reflectance of 20% or less even in a photomask blank and a photomask using a light-shielding layer made of a material mainly composed of a transition metal silicide having a predetermined composition. With the goal.

  The inventors of the present invention have selected the surface reflectance of the light shielding layer in the photomask blank and the photomask using the light shielding layer made of the material mainly composed of the transition metal silicide having the predetermined composition. The surface antireflection layer was examined so that the surface reflectance of the light-shielding film could be ensured to be at least 20% or less even when the value was higher than before. At the same time, in order to realize a reduction in the thickness of the entire light shielding film, it was examined that the thickness of the surface antireflection layer is at least 20 nm or less. As a result, the reflected light reflected on the surface of the surface antireflection layer and the exposure light are transmitted from the outside into the surface antireflection layer, reflected on the surface of the light shielding layer, and then transmitted through the surface antireflection layer and again outside. Obtaining a combination of the refractive index n, the extinction coefficient k, and the film thickness of the surface antireflection layer having such a characteristic that a high interference effect can be obtained with the outgoing reflected light, and from among the combinations A surface antireflection layer is formed by selecting one and forming a surface antireflection layer on the upper surface of the light shielding layer with a selected film thickness and a material having the selected refractive index n and extinction coefficient k. It was found that the film thickness was 20 nm or less, and the surface reflectance as a light-shielding film could be suppressed to 20% or less, leading to the present invention.

The present invention has the following configuration.
(Configuration 1)
A photomask blank comprising a light-shielding film on a translucent substrate used for producing a photomask to which exposure light having a wavelength of 200 nm or less is applied,
The light shielding film is
A light shielding layer having a transition metal content of 20 atom% or more and 40 atom% or less and a transition metal silicide as a main component, and a layer thickness of less than 40 nm;
A surface antireflection layer formed on and in contact with the light shielding layer;
The photomask blank, wherein the surface antireflection layer is made of a material having a refractive index n and an extinction coefficient k such that the film thickness is 20 nm or less and the surface reflectance is 20% or less.
(Configuration 2)
The photomask blank according to Configuration 1, wherein the surface antireflection layer has a refractive index n of 1.4 or more and 3.0 or less, and an extinction coefficient k of greater than 0 and 1.3 or less.
(Configuration 3)
3. The photomask blank according to claim 1, wherein the surface antireflection layer is made of a silicide compound containing at least one of oxygen and nitrogen.
(Configuration 4)
The photomask blank according to Configuration 3, wherein the surface antireflection layer further contains molybdenum.
(Configuration 5)
The photomask blank according to Configuration 4, wherein the surface antireflection layer contains more than 0 atomic% and not more than 10 atomic% of molybdenum.
(Configuration 6)
6. The photomask blank according to any one of configurations 1 to 5, wherein the transition metal of the transition metal silicide is molybdenum.
(Configuration 7)
The photomask blank according to any one of Structures 1 to 6, wherein the light shielding film includes a back surface antireflection layer formed in contact with the light shielding layer.
(Configuration 8)
The back surface antireflection layer is
8. The photomask blank according to Configuration 7, comprising a molybdenum silicide compound containing at least one of oxygen and nitrogen.
(Configuration 9)
The photomask blank according to any one of Configurations 1 and 8, wherein the photomask blank is a film formed on and in contact with the light-shielding film, and includes an etching mask film made of a material containing chromium as a main component.
(Configuration 10)
The etching mask film is
10. The photomask blank according to Configuration 9, wherein the photomask blank is made of a material mainly containing any one of chromium nitride, chromium oxide, chromium nitride oxide, and chromium oxycarbonitride.
(Configuration 11)
A method for manufacturing a photomask blank according to any one of Configurations 1 to 10,
The combination of the refractive index n and extinction coefficient k of the surface antireflection layer satisfying the condition that the surface reflectance of the light shielding film is 20% or less and the film thickness of the surface antireflection layer is 20 nm or less is obtained. Then, one of the obtained combinations is selected, and a surface antireflection layer is formed on the upper surface of the light shielding layer with a material having the selected combination of refractive index n and extinction coefficient k, and with the selected combination of film thicknesses. The manufacturing method of the photomask blank characterized by including the process to do.
(Configuration 12)
A photomask manufactured using the photomask blank according to any one of Configurations 1 to 10.
(Configuration 13)
A photomask manufacturing method using the photomask blank according to any one of Configurations 1 to 10.

  According to the present invention, there are provided a photomask blank and a photomask having a light-shielding film whose light-shielding property is improved by using a light-shielding layer composed of a transition metal silicide having a predetermined composition as a main component. The refractive index n, the extinction coefficient k, and the film of the antireflection layer have the characteristics that a high interference effect can be obtained when the surface reflectance with respect to the exposure light is higher than that of the prior art By obtaining a combination of thicknesses, selecting one of the combinations, and forming a surface antireflection layer with a selected film thickness using a material having the selected refractive index n and extinction coefficient k Even with a thin light-shielding film, a predetermined OD can be ensured, and the surface reflectance can be reduced to a desired value, for example, 20% or less.

Hereinafter, the present invention will be described in detail.
The photomask blank of the present invention is
A photomask blank comprising a light-shielding film on a translucent substrate used for producing a photomask to which exposure light having a wavelength of 200 nm or less is applied,
The light shielding film is
A light shielding layer having a transition metal content of 20 atom% or more and 40 atom% or less and a transition metal silicide as a main component, and a layer thickness of less than 40 nm;
A surface antireflection layer formed on and in contact with the light shielding layer;
The surface antireflection layer is made of a material having a refractive index n and an extinction coefficient k such that the film thickness is 20 nm or less and the surface reflectance is 20% or less (Configuration 1).
According to the above configuration, the surface antireflection layer is made of a material having a refractive index n and an extinction coefficient k such that the film thickness is 20 nm or less and the surface reflectance is 20% or less. Thus, even in a photomask blank and a photomask using a light shielding layer made of a material containing transition metal silicide having a predetermined composition as a main component, a photomask blank and a photomask that can have a surface reflectance of 20% or less can be provided.

In the present invention, for example, in relation to the complex refractive index (n, k) of the material of the light shielding layer made of the material mainly composed of the transition metal silicide on the lower surface, the surface reflectance can be made a desired value or less (for example, 20 The complex refractive index (n, k) and film thickness of the material of the surface antireflection layer can be selected.
For example, the present invention relates to the complex refractive index (n, k) and the complex refractive index (n, k) as described above in relation to the complex refractive index (n, k) of the material of the light shielding layer made of the material mainly composed of the transition metal silicide on the lower surface. The surface reflection rate can be significantly reduced (for example, about 5% to 20% can be reduced) compared to the surface reflectance (for example, about 25% to 40%) when the film thickness is not selected. The refractive index (n, k) and film thickness are selected.
In the present invention, for example, the target surface reflectance is set to 20%, 15%, and 10%, and the complex refractive index and film thickness of the material of the surface antireflection layer are selected.
In addition, the present invention obtains a combination of the thickness and n and k of the surface antireflection layer such that the surface reflectance is within a predetermined range (for example, the surface reflectance is in the range of 10% to 20%) (selection). To do).
In addition, the present invention provides, for example, a “thickness of surface antireflection layer and a combination of n and k” that has a film thickness of 20 nm or less suitable as a surface antireflection layer and a surface reflectance of 20% or less. It is possible to provide a method for selecting an optimum one from a plurality of candidates. For example, in order to make the thickness of the surface antireflection layer thinner, the one having a larger extinction coefficient k was selected as long as the target surface reflectance was obtained (surface antireflection layer). Is more advantageous. This is because the film thickness of the light shielding layer can be made as small as possible if a certain degree of OD can be obtained with the surface antireflection layer.

In the present invention, the refraction of the surface antireflection layer that can be less than a predetermined film thickness (for example, 20 nm or less) and less than a desired surface reflectance (for example, 20% or less) with respect to a predetermined light shielding layer. A combination of the rate n, the extinction coefficient k, and the film thickness is obtained, the range is defined by a graph or the like, and one of the combinations within the range is selected and used.
For example, a combination of the refractive index n, the extinction coefficient k, and the film thickness of the surface antireflection layer satisfying the condition that the surface reflectance of the light shielding film is 20% or less and the film thickness of the surface antireflection layer is 20 nm or less. Select and use one of the obtained combinations. (Configuration 11)
More specifically, for example, the material of the light shielding layer is fixed (in this case, n and k of the light shielding layer are determined), and then the thickness of the surface antireflection layer (for example, 20 nm in FIG. 3) is fixed. , N and k of the surface antireflection layer are changed stepwise (for example, n = 1.4, 1.7, 2.0, 2.32, 2.6, 2, 9), k = 0 , 0.1, 0.31, 0.6, 0.9, 1.2, 1.5)), the surface reflectance is obtained by optical simulation. Based on the obtained simulation data, on the plot area with the refractive index n and the extinction coefficient k as the vertical axis and the horizontal axis, respectively, the film thickness (20 nm) is below a predetermined surface reflectance (for example, FIG. 3). In FIG. 4, the combination of the refractive index n and the extinction coefficient k, which is 20% or less) is plotted, and the range of the combination of the refractive index n and the extinction coefficient k is determined. Similarly, for other film thicknesses (for example, 19 nm, 18 nm, 17 nm, 16 nm, and 15 nm in FIG. 3, 14 nm, 13 nm, 12 nm, 11 nm, 10 nm, 9 nm, 8 nm, and 7 nm in FIG. 4), predetermined surface reflections are performed. The range of the combination of the refractive index n and the extinction coefficient k that satisfies the condition of the refractive index (20% or less) is determined.
Further, according to the upper limit (for example, 15%, 10%, etc.) of the required surface reflectance as a photomask blank, the refractive index n and the extinction coefficient k for each film thickness of the surface antireflection layer are obtained in the same manner. Determine the range of combinations.

In the present invention, as described above, 14 types (14 levels) for the film thickness, 6 types (6 levels) for the refractive index n, and 7 types (7 levels) for the extinction coefficient k satisfy the predetermined conditions. In addition, an optical material that satisfies the above-mentioned specified conditions from the actual material group is further specified by satisfying the necessary conditions for the light-shielding film, such as ensuring an OD of a predetermined value or more for the entire light-shielding film. A preferred one having properties (n, k, etc.) is selected and used. In this way, a surface antireflection layer suitable for many conditions is used without using the technical idea of the present invention, such as thinning of the entire light shielding film, ensuring an OD of a predetermined value or more, and realizing a low surface reflectance for exposure light. It is not easy to select.
In the present invention, the optical simulation is performed by changing the film thickness to 14 levels, the refractive index n to 6 levels, and the extinction coefficient k to 7 levels, but by increasing the number of stages, The material selection accuracy is further improved.

In the present invention, the surface antireflection layer preferably has a refractive index n of 1.4 or more and 3.0 or less and an extinction coefficient k of more than 0 and 1.4 or less. (Configuration 2)
It is desirable that the surface reflectance for exposure light (ArF excimer laser exposure light, etc.) having a wavelength of 200 nm or less is 20% or less. Further, from the viewpoint of reducing the thickness of the light shielding film, the thickness of the surface antireflection layer is desirably 20 nm or less. Therefore, the surface antireflection layer is a material of the surface antireflection layer having a characteristic that the surface reflectance can be controlled to be 20% or less when the film thickness is 20 nm or less (n and k of the surface antireflection layer). It is preferable to select a combination. Examining the material of the surface antireflection layer that satisfies the above conditions based on the graphs of FIGS. 3 to 11, the conditions are as follows in the material group in which the refractive index n is in the range of 1.4 to 3.0. You can see that there is something to satisfy. On the other hand, the material group having an extinction coefficient k that is greater than 0 and less than or equal to 1.4 satisfies the condition. In the optical simulation, even if the extinction coefficient k is 0, it is satisfied. However, there is no material having an extinction coefficient k of 0 for exposure light having a wavelength of 200 nm or less with an actual material. As a result of the above studies, preferable ranges of the refractive index n and the extinction coefficient k are selected as the material applied to the surface antireflection layer.

In the present invention, the surface reflectance with respect to exposure light (ArF excimer laser exposure light, etc.) having a wavelength of 200 nm or less, which is a more desirable condition for a photomask blank and a photomask produced from the photomask blank, is 15% or less. When the surface antireflection layer satisfying the condition that the film thickness is 20 nm or less is considered, from the graphs of FIGS. 3 to 11, as a combination of the refractive index n and the extinction coefficient k of the material satisfying such condition. The refractive index n is in the range of 1.7 to 3.0 and the extinction coefficient k is preferably in the range of greater than 0 and 1.2 or less.
Furthermore, when considering the surface antireflection layer that satisfies the stricter condition that the surface reflectance is 10% or less and the film thickness is 20 nm or less, such conditions are satisfied from each graph of FIGS. As a combination of the refractive index n and the extinction coefficient k of the material, the refractive index n is in the range of 1.7 or more and 3.0 or less, and the extinction coefficient k is preferably in the range of 0 to 1.0. I understand that.

In the present invention, the film thickness of the surface antireflection layer is 20 nm or less, but preferably 15 nm as long as a predetermined surface reflectance (20% or less) is satisfied and an OD of a predetermined value or more can be secured over the entire light shielding film. It may be the following. This is because the light-shielding film can be made thinner, and higher transfer accuracy can be realized when a photomask is produced from a photomask blank having a light-shielding film that satisfies this condition. From the graphs of FIGS. 3 to 11, the combination of the refractive index n and the extinction coefficient k of the material satisfying such a condition is such that the refractive index n is in the range of 1.7 to 3.0, and the extinction It can be seen that the coefficient k is preferably in the range of greater than 0 and less than or equal to 1.4.
Further, if the predetermined surface reflectance (20% or less) is satisfied and a higher OD can be secured in the light shielding layer, it is more desirable that the thickness of the surface antireflection layer is 10 nm or less. From the graphs of FIGS. 3 to 11, the combination of the refractive index n and the extinction coefficient k of the material satisfying such a condition is such that the refractive index n is in the range of 1.8 to 3.0, and the extinction It can be seen that the coefficient k is preferably in the range of greater than 0 and less than or equal to 1.4.

From the optical simulation, it has been found that it is difficult for the surface antireflection layer to satisfy the condition that the surface reflectance is 20% or less when the film thickness is 6 nm or less. The thickness of the surface antireflection layer is desirably larger than 6 nm.
A material containing a transition metal silicide is used for the light shielding layer, but applicable transition metals include molybdenum, tantalum, tungsten, titanium, chromium, hafnium, nickel, vanadium, zirconium, ruthenium, rhodium, etc. One or more of these may be added to these.

In the present invention, the light shielding layer made of molybdenum silicide metal refers to a light shielding layer (a metallic film substantially free of oxygen, nitrogen, etc.) substantially composed of molybdenum and silicon. The term “substantially free of oxygen and nitrogen” includes a mode in which these elements are contained within a range in which the effect of the present invention can be obtained (both oxygen and nitrogen are less than 5 at% of each component in the light shielding layer). From the viewpoint of light shielding performance, it is preferably not originally contained in the light shielding layer. However, since it is often mixed as an impurity in the stage of the film formation process, the photomask manufacturing process, etc., it is allowed within a range that does not substantially affect the light shielding performance.
In the present invention, the light shielding layer made of molybdenum silicide metal may contain other elements (carbon, boron, helium, hydrogen, argon, xenon, etc.) as long as the above characteristics and effects are not impaired.
In the present invention, the light-shielding layer preferably has a thickness of 30 nm to less than 40 nm, and more preferably 30 nm to 35 nm.

In the present invention, the thickness of the surface antireflection layer is 20 nm or less (Configuration 1).
This is because, from the viewpoint of reducing the thickness of the light shielding film, the thickness of the surface antireflection layer constituting a part of the light shielding film needs to be 20 nm or less.

In the present invention, the light shielding layer containing molybdenum silicide is made of molybdenum silicide metal having a molybdenum content of 20 atomic% to 40 atomic% (Configuration 1).
From the viewpoint of reducing the thickness of the light-shielding film (the layer thickness is less than 40 nm), the light-shielding layer needs to have an OD of a predetermined value or more. Therefore, the MoSi metal film is used, and the Mo content ratio is 20 at% or more and 40 at%. This is because it is necessary to:
Specifically, as shown in FIG. 14, when the molybdenum content is 20 atomic% or more, ΔOD = 0.082 nm ⁻¹ @ 193.4 nm or more is preferable.

  In the photomask blank of the present invention, the material of the antireflection layer is, for example, one or two selected from molybdenum, chromium, tantalum, tungsten, titanium, hafnium, nickel, vanadium, zirconium, ruthenium, rhodium, and the like. Oxides, nitrides, oxynitrides, carbides, transition metal silicide materials containing these transition metals and silicon (Si), and oxides of these transition metal silicide materials , Nitrides, oxynitrides, carbides, transition metals and the like.

The photomask blank of the present invention is suitably applied when the antireflection layer is made of a silicide compound containing at least one of oxygen and nitrogen (Configuration 3). Furthermore, it is preferable to contain molybdenum (Configuration 4).
By using a surface antireflection layer containing the same silicon as the light shielding layer of the transition metal silicide, it is possible to obtain a light shielding film having excellent characteristics during mask pattern processing. By doing so, it is possible to obtain further excellent processing characteristics.

The photomask blank of the present invention is
It is suitably applied when the surface antireflection layer contains molybdenum in an amount of more than 0 atomic% and not more than 10 atomic% (Configuration 5).
As described above, in such a case, a combination of the refractive index n and the extinction coefficient k of the surface antireflection layer such that the film thickness is 20 nm or less and the surface reflectance is 20% or less can be easily found. Because you can't.

In addition, the inventor combined a light shielding layer having a relatively high Mo content with an antireflection layer having a relatively low Mo content, thereby satisfying the requirements for both optical properties and chemical resistance. I found out that the layer structure can be made.
According to the invention according to Configuration 3, the following operational effects are obtained.
(1) When the Mo content of the antireflection layer is within the predetermined range, the following effects can be obtained.
1) The chemical resistance (cleaning resistance) of the antireflection layer is relatively excellent with respect to the composition outside the predetermined range.
2) The antireflection layer is relatively excellent in heat treatment resistance with respect to a composition outside the predetermined range. Specifically, the antireflection layer having a Mo content in the predetermined range does not cause white turbidity due to heat treatment, and does not cause deterioration of the surface reflectance distribution.

The photomask blank of the present invention is
The light-shielding film includes an aspect including a back-surface antireflection layer formed under and in contact with the light-shielding layer (Configuration 7).
With such a configuration, it is possible to prevent reflection on the back side (translucent substrate side) of the light-shielding film.

The photomask blank of the present invention is
The back surface antireflection layer is
An embodiment comprising a molybdenum silicide compound containing at least one of oxygen and nitrogen is included (Configuration 8).
With such a configuration, sufficient antireflection is achieved on the back side (translucent substrate side) of the light-shielding film. In addition, by using a back surface antireflection film containing molybdenum silicide having a high light shielding property, it is possible to contribute to securing the OD of the entire light shielding film.

  In the present invention, examples of the front-surface antireflection layer or back-surface antireflection layer made of a molybdenum silicide compound containing at least one of oxygen and nitrogen include MoSiON, MoSiO, MoSiN, MoSiOC, and MoSiOCN. Among these, MoSiO and MoSiON are preferable from the viewpoint of chemical resistance and heat resistance, and MoSiON is preferable from the viewpoint of blanks defect quality.

In the present invention, in the case of MoSiON, MoSiO, MoSiN, MoSiOC, MoSiOCN, etc., which are surface antireflection layers, if the amount of Mo is increased, the cleaning resistance, particularly resistance to alkali (ammonia water or the like) or hot water is reduced. From this point of view, MoSiON, MoSiO, MoSiN, MoSiOC, MoSiOCN, and the like, which are surface antireflection layers, are preferably reduced as much as possible.
Further, it was found that when heat treatment (annealing) was performed at a high temperature for the purpose of stress control, a high Mo content causes a phenomenon that the surface of the film becomes clouded white (clouded). This is considered to be because MoO precipitates on the surface. From the viewpoint of avoiding such a phenomenon, in the MoSiON, MoSiO, MoSiN, MoSiOC, MoSiOCN, etc. which are the surface antireflection layers, the Mo content in the antireflection layer is preferably less than 10 at%. However, when the Mo content is too low, abnormal discharge during DC sputtering becomes significant, and the frequency of occurrence of defects increases. Therefore, it is desirable that Mo is contained within a range where it can be sputtered normally. Depending on other film formation techniques, film formation may be possible without containing Mo.
In the present invention, the antireflection layer preferably has a thickness of 5 nm to 15 nm.

In the present invention, the MoSi light-shielding layer can freely control tensile stress and compressive stress by Ar gas pressure, He gas pressure, and heat treatment. For example, by controlling the film stress of the MoSi light shielding layer to be a tensile stress, it is possible to match the compressive stress of the antireflection layer (for example, MoSiON). That is, the stress of each layer constituting the light shielding film can be offset, and the film stress of the light shielding film can be reduced as much as possible (can be substantially zero).
On the other hand, when the light shielding layer is MoSiN, the film stress of MoSiN is on the compression side, and it is difficult to adjust the stress of the light shielding layer. For this reason, it is difficult to match the compressive stress of the antireflection layer (for example, MoSiON).

In the present invention, it is preferable to include an etching mask layer that is formed on and in contact with the light-shielding film and is made of a material mainly composed of chromium (Configuration 9).
This is for reducing the thickness of the resist.

In the present invention, it is preferable that the etching mask film is formed of a material mainly containing any one of chromium nitride, chromium oxide, chromium nitride oxide, and chromium oxycarbonitride (Configuration 10).
This is because the etching selectivity to the antireflection layer and the light shielding layer made of molybdenum silicide compound formed under the etching mask film is high and the unnecessary etching mask film can be removed without damaging other layers. is there.
In the present invention, for the etching mask film, for example, a material such as chromium alone or a material containing at least one element composed of oxygen, nitrogen, carbon, and hydrogen in chromium (a material containing Cr) can be used. . The film structure of the etching mask film is often a single layer made of the above film material, but may be a multi-layer structure. In addition, the multi-layer structure can be a multi-layer structure formed in stages with different compositions or a film structure in which the composition is continuously changed.
Of the above, chromium oxycarbonitride (CrOCN) is preferable as the material for the etching mask layer from the viewpoint of stress controllability (a low stress film can be formed).
In the present invention, the etching mask film preferably has a thickness of 5 nm to 30 nm.

The photomask of the present invention is produced using the photomask blank according to the present invention (Configuration 12).
Thereby, the effect similar to having described to the said structures 1-10 is acquired.

The method for producing a photomask of the present invention uses the photomask blank according to the present invention (Configuration 13).
Thereby, the effect similar to having described to the said structures 1-10 is acquired.

In the present invention, for dry etching of a molybdenum-based thin film, a metal silicide-based thin film (surface antireflection film), or a molybdenum silicide-based thin film (light-shielding film), for example, SF ₆ , CF ₄ , C ₂ F ₆ , CHF _3, etc. Fluorine-based gases, mixed gases such as He, H ₂ , N ₂ , Ar, C ₂ H ₄ , O ₂ , chlorine-based gases such as Cl ₂ , CH ₂ Cl ₂ , and these, and He, H _{2, N} 2, _Ar, a mixed gas such as C 2 _{H 4} can be used.

In the present invention, it is preferable to use a dry etching gas composed of a chlorine-based gas or a mixed gas containing a chlorine-based gas and an oxygen gas for the dry etching of a chromium-based thin film (such as an etching mask film). The reason for this is that for a chromium-based thin film made of a material containing chromium and an element such as oxygen and nitrogen, the dry etching rate can be increased by performing dry etching using the above dry etching gas, This is because the dry etching time can be shortened and a light-shielding film pattern having a good cross-sectional shape can be formed. The chlorine-based gas used for dry etching gas, for _{example, Cl 2, SiCl 4, HCl} , CCl 4, CHCl 3 , and the like.

In the present invention, examples of the substrate include a synthetic quartz substrate, a CaF ₂ substrate, a soda lime glass substrate, a non-alkali glass substrate, a low thermal expansion glass substrate, and an aluminosilicate glass substrate.

In the present invention, the photomask blank includes a binary photomask blank that does not use the phase shift effect and a mask blank with a resist film.
In the present invention, the photomask includes a binary photomask that does not use the phase shift effect, and a Levenson type phase shift mask and an enhancer mask among the phase shift masks that use the phase shift effect. The photomask includes a reticle.
In the present invention, the photomask to which exposure light having a wavelength of 200 nm or less is applied includes a photomask for ArF excimer laser exposure.

  Hereinafter, experimental examples, examples, and comparative examples of the present invention will be described. In addition, each film | membrane, such as a light shielding film and an etching film in each experiment example, an Example, and a comparative example, was performed by sputtering method as a film-forming method, and was formed into a film using DC magnetron sputtering apparatus as a sputtering device. However, in carrying out the present invention, the film forming method and the film forming apparatus are not particularly limited, and other types of sputtering apparatuses such as an RF magnetron sputtering apparatus may be used.

Example 1
(Optical simulation and selection of surface antireflection layer)
A synthetic quartz substrate having a size of 6 inches square and a thickness of 0.25 inches is used as the light-transmitting substrate 1, and a MoSi film (light-blocking layer) under the same conditions as those applied as the light-blocking layer of the light-blocking film on the light-transmitting substrate 1 is used. ) Was formed.
Specifically, using a target of Mo: Si = 21: 79 (atomic% ratio), Ar is set to a sputtering gas pressure of 0.1 Pa, the power of the DC power source is 2.0 kW, and a light shielding layer made of molybdenum and silicon (Mo: 21.0 atomic%, Si: 79 atomic%) was formed with a film thickness of 35 nm.
Subsequently, the refractive index n and extinction coefficient k of the formed light shielding layer were measured with an optical thin film property measuring apparatus n & k1280 (manufactured by n & k Technology). This light-shielding layer had a refractive index n of 1.40 and an extinction coefficient k of 3.12, and was confirmed to have high light-shielding performance.

Next, based on the measured refractive index n and extinction coefficient k of the light shielding layer, an optical simulation for selecting a surface antireflection layer formed on the upper surface of the light shielding layer was performed. In the optical simulation, the film thickness of the surface antireflection layer is changed in 14 steps from 1 nm to 20 nm to 7 nm, and the refractive index n (n = 1.4, 1.7, 2.0, 2.32, 2.6, 2.9), extinction coefficient k (k = 0, 0.1, 0.31, 0.6, 0.9, 1.2, 1.5, 7) The surface reflectance was calculated for each parameter.
Based on the result of the optical simulation, the refractive index n and the extinction coefficient k are respectively plotted on the vertical axis and the horizontal axis for the combination of the refractive index n and the extinction coefficient k that satisfy the condition that the surface reflectance is 20% or less. The range of the combination of the refractive index n and the extinction coefficient k satisfying various conditions for each film thickness was determined (FIGS. 3 and 4).
Similarly, for the combination of the refractive index n and the extinction coefficient k satisfying the condition that the surface reflectivity is 15% or less, plot the refractive index n and the extinction coefficient k on the plot area with the vertical axis and the horizontal axis, respectively. The range of combinations of refractive index n and extinction coefficient k that satisfy various conditions for each film thickness was determined (FIGS. 5 and 6).
Similarly, for the combination of the refractive index n and the extinction coefficient k satisfying the condition that the surface reflectance is 10% or less, plot the refractive index n and the extinction coefficient k on the plot area with the vertical axis and the horizontal axis, respectively. The range of combinations of refractive index n and extinction coefficient k that satisfy various conditions for each film thickness was determined (FIGS. 7 and 8).
From FIG. 3 to FIG. 8, the refractive index n and extinction coefficient of the surface antireflection layer such that the surface reflectance is 20% or less when considering a film thickness of 20 nm or less suitable as a surface antireflection layer. It can be seen that the combination of k cannot be easily found.
For easy understanding in each of FIGS. 3 to 8, the extinction coefficient k that can be combined with the same film thickness and the same refractive index n is plotted with respect to the upper limit and the lower limit, and the upper limit side and the lower limit side of the extinction coefficient k are plotted. An approximate curve is drawn. From these tendencies, it can be seen that the refractive index n and extinction coefficient k that can be combined at each film thickness are within a certain annular area. In other words, if conditions for the desired surface reflectance and film thickness of the surface antireflection film are determined, a material having a combination of the refractive index n and the extinction coefficient k in the annular area that satisfies the conditions may be selected. become.

In the present invention, the surface antireflection layer is made of a material having a refractive index n and an extinction coefficient k such that the film thickness is 20 nm or less and the surface reflectance is 20% or less.
More specifically, in Example 1, in order to reduce the thickness of the light shielding film, the thickness of the surface antireflection layer is set to 10 nm, and the target surface reflectance is set to 15% or less, which is a high condition. A combination of a refractive index n and an extinction coefficient k (n = 2.32, k = 0.31 from the 10 nm-thick annular area shown in FIG. 6) is selected.

(Production of photomask blank)
(Formation of light-shielding film)
As a result of the above examination, a photomask blank was actually created with the selected light-shielding film configuration. A synthetic quartz substrate having a size of 6 inches square and a thickness of 0.25 inches is used as the light-transmitting substrate 1, and a MoSiON film 11 (back surface antireflection layer), MoSi (as a light-shielding film 10) is formed on the light-transmitting substrate 1. A light shielding layer 12 and a MoSiON film (surface antireflection layer) 13 were formed (FIG. 1).
Specifically, using a target of Mo: Si = 21: 79 (atomic% ratio), Ar, O ₂ , N _2, and He were mixed with a sputtering gas pressure of 0.2 Pa (gas flow ratio Ar: O ₂ : N ₂ : He = 5: 4: 49: 42), the power of the DC power source is 3.0 kW, and a film made of molybdenum, silicon, oxygen, and nitrogen (Mo: 0.3 atomic%, Si: 24.6 atomic%, O: 22) 0.5 atomic%, N: 52.6 atomic%) (n: 2.39, k: 0.78) with a film thickness of 7 nm,
Next, using a target of Mo: Si = 21: 79 (atomic% ratio), Ar is set to a sputtering gas pressure of 0.1 Pa, DC power is 2.0 kW, and a film made of molybdenum and silicon (Mo: 21. 0 atomic%, Si: 79 atomic%) (n: 1.40, k: 3.19) with a film thickness of 35 nm,
Next, using a target of Mo: Si = 4: 96 (atomic% ratio), Ar, O ₂ , N _2, and He were sputtered at a gas pressure of 0.2 Pa (gas flow ratio Ar: O ₂ : N ₂ : He = 5). : 4: 49: 42), the power of the DC power source was 3.0 kW, and a film made of molybdenum, silicon, oxygen, and nitrogen (n: 2.32, k: 0.31) was formed to a thickness of 10 nm. .
The total film thickness of the light-shielding film 10 was 52 nm. The optical density (OD) of the light-shielding film 10 was 3 at a wavelength of 193 nm of ArF excimer laser exposure light.
Next, the substrate was heat treated (annealed) at 450 ° C. for 30 minutes to reduce the film stress.

The light shielding film obtained in Example 1 has a refractive index such that the film thickness is 20 nm or less (specifically 10 nm) and the surface reflectance is 20% or less (specifically 12.6%). It can be made of a material having n and an extinction coefficient k.
More specifically, when a combination of n, k, and film thickness (for example, 10 nm, n = 2.32, k = 0.31) is selected as shown in the graph shown in FIG. Is obtained, a light-shielding film having a surface reflectance of 20% or less can be obtained.

(Formation of etching mask film)
Next, an etching mask film 20 was formed on the light shielding film 10 (FIG. 1). Specifically, a chromium target is used, and Ar, CO ₂ , N _2, and He are set to a sputtering gas pressure of 0.2 Pa (gas flow ratio Ar: CO ₂ : N ₂ : He = 21: 37: 11: 31). A CrOCN film (Cr content in the film: 33 atomic%) was formed with a film thickness of 15 nm at a power of 1.8 kW and a voltage of 334 V. At this time, by annealing the CrOCN film at a temperature lower than the annealing temperature of the MoSi light-shielding film, the stress of the CrOCN film is as low as possible without affecting the film stress of the MoSi light-shielding film (preferably substantially zero film stress). It adjusted so that it might become.
As described above, a photomask blank having a light shielding film for ArF excimer laser exposure was obtained.
For elemental analysis of the thin film, Rutherford backscattering analysis was used.

(Production of photomask)
On the etching mask film 20 of the photomask blank, a chemically amplified positive resist 50 (PRL009: manufactured by Fuji Film Electronics Materials Co., Ltd.) for electron beam drawing (exposure) is applied by spin coating so that the film thickness becomes 100 nm. (FIG. 1, FIG. 2 (1)).
Next, after drawing a desired pattern (40 nm, 45 nm, 50 nm, 55 nm, and 60 nm line and space) on the resist film 50 using an electron beam drawing apparatus, the resist film 50 is developed with a predetermined developer and then resist is applied. A pattern 50a was formed (FIG. 2 (2)).
Next, dry etching of the etching mask film 20 was performed using the resist pattern 50a as a mask (FIG. 2 (3)). As a dry etching gas, a mixed gas of Cl ₂ and O ₂ (Cl ₂ : O ₂ = 4: 1) was used.
Next, the remaining resist pattern 50a was peeled off with a chemical solution.
Next, using the etching mask film pattern 20a as a mask, the light shielding film 10 was dry-etched using a mixed gas of SF ₆ and He to form the light shielding film pattern 10a (FIG. 2 (4)).
Next, the etching mask film pattern 20a was peeled off by dry etching with a mixed gas of Cl ₂ and O ₂ (FIG. 2 (5)), and predetermined cleaning was performed to obtain a photomask 100.

(Evaluation)
A spectrophotometer U-4100 is used for the surface reflectance (% R), back surface reflectance (% Rb), and OD (% T) when the photomask obtained above is irradiated with light having a wavelength of 193 nm to 800 nm. When measured by (manufactured by Hitachi High-Technologies Corporation), results as shown in FIG. 12 were obtained. The characteristics (surface reflectance% R: 12.8%, backside reflectance% Rb: 28.1%) with respect to ArF exposure light (wavelength 193 nm) used in the photomask, and the film thickness of the surface antireflection layer is 10 nm. Although it was very thin, it was found that the surface reflectance could be greatly reduced.

(Example 2)
(Optical simulation and selection of surface antireflection layer)
A synthetic quartz substrate having a size of 6 inches square and a thickness of 0.25 inches is used as the light-transmitting substrate 1, and a MoSi film (light-blocking layer) under the same conditions as those applied as the light-blocking layer of the light-blocking film on the light-transmitting substrate 1 is used. ) Was formed.
Specifically, using a target of Mo: Si = 21: 79 (atomic% ratio), Ar and He are set to a sputtering gas pressure of 0.3 Pa (gas flow ratio Ar: He = 20: 120), and the power of the DC power source is 2 A light shielding layer (Mo: 21.0 atomic%, Si: 79 atomic%) made of molybdenum and silicon was formed at a thickness of 36 nm at 0.0 kW.
Subsequently, the refractive index n and extinction coefficient k of the formed light shielding layer were measured with an optical thin film property measuring apparatus n & k1280 (manufactured by n & k Technology). This light-shielding layer had a refractive index n: 2.42 and an extinction coefficient k: 2.89, and was confirmed to have high light-shielding performance.

Next, based on the measured refractive index n and extinction coefficient k of the light shielding layer, an optical simulation for selecting a surface antireflection layer formed on the upper surface of the light shielding layer was performed. In the optical simulation, the film thickness of the surface antireflection layer is changed in 7 steps from 20 nm to 10 nm, and the refractive index n (n = 1.5, 1.6, 1.7, 1.8) for each film thickness. , 2.1, 2.36, 2.7, 3.0), extinction coefficient k (k = 0, 0.3, 0.6, 0.9, 1.2, 1.5, (7 steps of 1.8) were varied, and the surface reflectance at each parameter was calculated.
Based on the result of the optical simulation, the refractive index n and the extinction coefficient k are respectively plotted on the vertical axis and the horizontal axis for the combination of the refractive index n and the extinction coefficient k that satisfy the condition that the surface reflectance is 20% or less. In the plot area, the range of the combination of the refractive index n and the extinction coefficient k satisfying various conditions for each film thickness was determined (FIG. 9).
Similarly, for the combination of the refractive index n and the extinction coefficient k satisfying the condition that the surface reflectivity is 15% or less, plot the refractive index n and the extinction coefficient k on the plot area with the vertical axis and the horizontal axis, respectively. The combination range of the refractive index n and the extinction coefficient k satisfying various conditions for each film thickness was determined (FIG. 10).
Similarly, for the combination of the refractive index n and the extinction coefficient k satisfying the condition that the surface reflectance is 10% or less, plot the refractive index n and the extinction coefficient k on the plot area with the vertical axis and the horizontal axis, respectively. The range of combinations of refractive index n and extinction coefficient k that satisfy various conditions for each film thickness was determined (FIG. 11).
From FIG. 9 to FIG. 11, the refractive index n and extinction coefficient of the surface antireflection layer such that the surface reflectance is 20% or less when considering a film thickness of 20 nm or less suitable as a surface antireflection layer. It can be seen that the combination of k cannot be easily found.
As a result of optical simulation on the light shielding layer of Example 2, it was found that unlike the light shielding layer of Example 1, there was no lower limit value of the extinction coefficient k. For this reason, the lower limit plots and approximate curves of the extinction coefficient k are not shown in FIGS. That is, it is sufficient if it is not more than the upper limit value of the extinction coefficient k. However, as can be seen from each of FIGS. 9 to 11, the upper limit of the extinction coefficient k that can be applied is lower than in the case of Example 1, and even with the same surface antireflection layer thickness, depending on the refractive index n, It can be seen that there is a considerable difference in the range in which the extinction coefficient k can be combined.

In the present invention, the surface antireflection layer is made of a material having a refractive index n and an extinction coefficient k such that the film thickness is 20 nm or less and the surface reflectance is 20% or less.
More specifically, in Example 2, in order to reduce the thickness of the light-shielding film, the refractive index is such that the thickness of the surface antireflection layer is 10 nm and the target surface reflectance is 15% or less. A combination of n and extinction coefficient k (n = 2.32, k = 0.31 from the area of the 10 nm-thick annular area in FIG. 9) is selected.

(Production of photomask blank)
(Formation of light-shielding film)
As a result of the above examination, a photomask blank was actually created with the selected light-shielding film configuration. A synthetic quartz substrate having a size of 6 inches square and a thickness of 0.25 inches is used as the light-transmitting substrate 1, and a MoSiON film 11 (back surface antireflection layer), MoSi (as a light-shielding film 10) is formed on the light-transmitting substrate 1. A light shielding layer 12 and a MoSiON film (surface antireflection layer) 13 were formed (FIG. 1).
Specifically, using a target of Mo: Si = 21: 79 (atomic% ratio), Ar, O ₂ , N _2, and He were mixed with a sputtering gas pressure of 0.2 Pa (gas flow ratio Ar: O ₂ : N ₂ : He = 5: 4: 49: 42), the power of the DC power source is 3.0 kW, and a film made of molybdenum, silicon, oxygen, and nitrogen (Mo: 0.3 atomic%, Si: 24.6 atomic%, O: 22) 0.5 atomic%, N: 52.6 atomic%) (n: 2.39, k: 0.78) with a film thickness of 7 nm,
Next, using a target of Mo: Si = 21: 79 (atomic% ratio), Ar and He are set to a sputtering gas pressure of 0.3 Pa (gas flow ratio Ar: He = 20: 120), and the power of the DC power source is 2. A light shielding layer (Mo: 21.0 atomic%, Si: 79 atomic%) (n: 2.42, k: 2.89) made of molybdenum and silicon was formed at a thickness of 36 nm at 0 kW.
Next, using a target of Mo: Si = 4: 96 (atomic% ratio), Ar, O ₂ , N _2, and He were sputtered at a gas pressure of 0.2 Pa (gas flow ratio Ar: O ₂ : N ₂ : He = 5). : 4: 49: 42), the power of the DC power source was 3.0 kW, and a film made of molybdenum, silicon, oxygen, and nitrogen (n: 2.32, k: 0.31) was formed to a thickness of 10 nm. .
The total film thickness of the light-shielding film 10 was 53 nm. The optical density (OD) of the light-shielding film 10 was 3 at a wavelength of 193 nm of ArF excimer laser exposure light.
Next, the substrate was heat treated (annealed) at 450 ° C. for 30 minutes to reduce the film stress.

The light shielding film obtained in Example 1 has a refractive index such that the film thickness is 20 nm or less (specifically 10 nm) and the surface reflectance is 15% or less (specifically 13.4%). It can be made of a material having n and an extinction coefficient k.
More specifically, when a combination of n, k, and film thickness (for example, 10 nm, n = 2.32, k = 0.31) is selected as shown in the graph shown in FIG. Is obtained, a light-shielding film having a surface reflectance of 15% or less can be obtained.

(Formation of etching mask film)
Next, an etching mask film 20 was formed on the light shielding film 10 under the same conditions as in Example 1.
As described above, a photomask blank having a light shielding film for ArF excimer laser exposure was obtained.
For elemental analysis of the thin film, Rutherford backscattering analysis was used.

(Production of photomask)
Using the photomask blank of Example 2, a photomask was produced in the same procedure as in Example 1.

(Evaluation)
A spectrophotometer U-4100 is used for the surface reflectance (% R), back surface reflectance (% Rb), and OD (% T) when the photomask obtained above is irradiated with light having a wavelength of 193 nm to 800 nm. When measured with (manufactured by Hitachi High-Technologies Corporation), results as shown in FIG. 13 were obtained. Characteristics (surface reflectance% R: 13.6%, back surface reflectance% Rb: 27.7%) with respect to ArF exposure light (wavelength 193 nm) used in the photomask, and the film thickness of the surface antireflection layer is 10 nm. Although it was very thin, it was found that the surface reflectance could be sufficiently reduced.

  As mentioned above, although this invention was demonstrated using the Example, the technical scope of this invention is not limited to the range as described in the said Example. It will be apparent to those skilled in the art that various modifications or improvements can be made to the above-described embodiments. It is apparent from the description of the scope of claims that embodiments with such changes or improvements can be included in the technical scope of the present invention.

It is a typical section showing an example of the photomask blank concerning Example 1 of the present invention. It is a typical section for explaining the manufacturing process of the photomask concerning Example 1 of the present invention. It is the figure calculated | required in Example 1 of this invention, Comprising: The refractive index n and extinction coefficient which can be applied as a surface reflection prevention layer for every film thickness (20 nm-15 nm) when surface reflectance is 20% or less It is a figure which shows the area | region of the combination of k. It is the figure calculated | required in Example 1 of this invention, Comprising: The refractive index n and extinction coefficient which can be applied as a surface reflection prevention layer for every film thickness (14 nm-7 nm) when surface reflectance is 20% or less It is a figure which shows the area | region of the combination of k. It is the figure calculated | required in Example 1 of this invention, Comprising: The refractive index n and extinction coefficient which can be applied as a surface reflection prevention layer for every film thickness (20 nm-15 nm) when surface reflectance is 15% or less It is a figure which shows the area | region of the combination of k. It is the figure calculated | required in Example 1 of this invention, Comprising: The refractive index n and extinction coefficient which can be applied as a surface reflection prevention layer for every film thickness (14 nm-7 nm) when surface reflectance is 15% or less It is a figure which shows the area | region of the combination of k. It is the figure calculated | required in Example 1 of this invention, Comprising: The refractive index n and extinction coefficient which can be applied as a surface reflection prevention layer for every film thickness (20 nm-15 nm) when surface reflectance is 10% or less It is a figure which shows the area | region of the combination of k. It is the figure calculated | required in Example 1 of this invention, Comprising: The refractive index n and extinction coefficient which can be applied as a surface reflection prevention layer for every film thickness (14 nm-7 nm) when surface reflectance is 10% or less It is a figure which shows the area | region of the combination of k. It is the figure calculated | required in Example 2 of this invention, Comprising: The area | region of the combination of the refractive index n and extinction coefficient k which can be applied as a surface reflection prevention layer for every film thickness when surface reflectance is 20% or less FIG. It is the figure calculated | required in Example 2 of this invention, Comprising: The area | region of the combination of the refractive index n and extinction coefficient k which can be applied as a surface antireflection layer for every film thickness when a surface reflectance is 15% or less FIG. It is the figure calculated | required in Example 2 of this invention, Comprising: The area | region of the combination of the refractive index n and extinction coefficient k which can be applied as a surface reflection prevention layer for every film thickness when surface reflectance is 10% or less FIG. It is a figure which shows the reflection and transmission spectrum of the light shielding film obtained in Example 1 of this invention. It is a figure which shows the reflection and transmission spectrum of the light shielding film obtained in Example 2 of this invention. It is a figure which shows the relationship between the molybdenum content ratio in the thin film which consists of molybdenum silicide metals, and the optical density per unit film thickness.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Translucent substrate 10 Light shielding film 11 Back surface antireflection layer 12 Light shielding layer 13 Surface antireflection layer 20 Etching mask film 50 Resist film 100 Photomask

Claims (14)

A photomask blank comprising a light-shielding film on a translucent substrate used for producing a photomask to which exposure light having a wavelength of 200 nm or less is applied,
The light shielding film is
It is made of a material mainly composed of a transition metal silicide having a transition metal content of 21 atomic% or more and 40 atomic% or less, the layer thickness is less than 40 nm , and the optical density per unit film thickness is 0.082 nm. A light shielding layer that is ⁻¹ or more ;
A surface antireflection layer formed on and in contact with the light shielding layer;
The surface antireflection layer includes a transition metal and silicon, has a film thickness of 15 nm or less, and a material having a refractive index n and an extinction coefficient k such that the surface reflectance with respect to the exposure light is 20% or less. Do Ri, photomask blank, wherein the refractive index n of 1.4 to 3.0, the extinction coefficient k is 1.4 or less greater than 0. The photomask blank according to claim 1 , wherein the light shielding film is a combination of the light shielding layer having a relatively high Mo content and the surface antireflection layer having a relatively low Mo content .   The photomask blank according to claim 1, wherein the surface antireflection layer is made of a silicide compound containing at least one of oxygen and nitrogen.   4. The photomask blank according to claim 3, wherein the surface antireflection layer further contains molybdenum.   5. The photomask blank according to claim 4, wherein the surface antireflection layer contains molybdenum in an amount of more than 0 atomic% and not more than 10 atomic%.   The photomask blank according to any one of claims 1 to 5, wherein the transition metal of the transition metal silicide is molybdenum.   The photomask blank according to any one of claims 1 to 6, wherein the light shielding film includes a back surface antireflection layer formed under and in contact with the light shielding layer.   8. The photomask blank according to claim 7, wherein the back antireflection layer is made of a molybdenum silicide compound containing at least one of oxygen and nitrogen. The photomask blank according to any one of claims 1 to 8, further comprising an etching mask film formed on and in contact with the light-shielding film and made of a material containing chromium as a main component.   10. The photomask blank according to claim 9, wherein the etching mask film is made of a material mainly containing any one of chromium nitride, chromium oxide, chromium nitride oxide, and chromium oxycarbonitride. The photomask blank according to any one of claims 1 to 10, wherein the light shielding layer is formed by sputtering using a sputtering gas containing He gas. It is a manufacturing method of the photomask blank in any one of Claim 1 to 11 ,
Obtaining a combination of the refractive index n, the extinction coefficient k, and the film thickness of the surface antireflection layer satisfying the condition that the surface reflectance of the light shielding film is 20% or less and the film thickness of the surface antireflection layer is 20 nm or less,
One of the obtained combinations is selected, and a surface antireflection layer is formed on the upper surface of the light shielding layer with a material having the selected combination of refractive index n and extinction coefficient k, and with the selected combination of film thicknesses. The manufacturing method of the photomask blank characterized by including the process to do. Photomask fabricated using the photomask blank according to any one of claims 1 to 11. A photomask manufacturing method using the photomask blank according to any one of claims 1 to 11 .

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