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CN113406856B - Mask blank, phase shift mask, method for manufacturing mask blank, and method for manufacturing phase shift mask - Google Patents

Mask blank, phase shift mask, method for manufacturing mask blank, and method for manufacturing phase shift mask Download PDF

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Publication number
CN113406856B
CN113406856B CN202110268167.6A CN202110268167A CN113406856B CN 113406856 B CN113406856 B CN 113406856B CN 202110268167 A CN202110268167 A CN 202110268167A CN 113406856 B CN113406856 B CN 113406856B
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layer
etching
phase shift
mask blank
light shielding
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CN113406856A (en
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诸沢成浩
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Ulvac Coating Corp
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Ulvac Coating Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/80—Etching

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention relates to a mask blank, a phase shift mask, a method for manufacturing a mask blank, and a method for manufacturing a phase shift mask. The mask blank of the present invention is a mask blank having a layer to be a phase shift mask. The mask blank has: a phase shift layer laminated on the transparent substrate; an etch stop layer disposed at a position farther from the transparent substrate than the phase shift layer; and a light shielding layer provided at a position farther from the transparent substrate than the etching stopper layer. The phase shift layer contains chromium. The light-shielding layer contains chromium and oxygen. The etching stop layer contains molybdenum silicide and nitrogen, and has a peak region where the nitrogen concentration reaches a peak at a position close to the light shielding layer in the film thickness direction.

Description

Mask blank, phase shift mask, method for manufacturing mask blank, and method for manufacturing phase shift mask
Technical Field
The present invention relates to a technique suitable for use in a mask blank, a phase shift mask, a method for manufacturing a mask blank, and a method for manufacturing a phase shift mask.
Background
In recent years, in flat panel displays (FLAT PANEL DISPLAY, FPD) such as liquid crystal displays and organic EL displays, the panel has been greatly refined. With the high definition of the panel, the miniaturization of the photomask is also advancing. Therefore, not only the necessity of a mask using a light shielding film, which has been conventionally employed, but also the necessity of an edge-enhanced phase shift mask is increased.
In FPDs and the like, miniaturization is required for patterns of Line & Space and contact holes. A phase shift mask is required to form a fine pattern.
For example, a contact hole pattern may require a large contrast in exposure, and a collar phase shift mask may be used. The flange-type phase shift mask is constructed by forming a phase shift layer using a chromium compound on a quartz substrate, forming an etch stop layer using a molybdenum silicide compound on an upper portion of the phase shift layer, and forming a light shielding layer using a metal film such as a chromium film on an upper portion of the etch stop layer.
For large masks used for FPDs and the like, WET etching is generally used for patterning. As an etching stopper film used for such WET etching, an etching stopper film formed of a silicide film such as a molybdenum silicide film is known (patent document 1).
Patent document 1: international publication No. 2013/190786
When an etching stopper film is formed of a silicide film such as a molybdenum silicide film, a fluorine acid is contained in an etching liquid for the molybdenum silicide film. Therefore, there is a problem that the quartz substrate is etched and the optical characteristics of the phase shift mask are changed during WET etching of the molybdenum silicide film.
Further, if an appropriate etching stopper film is not used, etching is excessively performed at the interface between the etching stopper film and the light shielding film at the time of patterning. Therefore, it is also clear that there is a problem that the etching stopper film disappears after etching and the cross-sectional shape becomes abnormal.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and it is an object of the present invention to achieve the following.
1. The etching layer has good etching stopping property in etching the layer above the etching stopping layer.
2. In etching of the etching stop layer, influence on other portions is suppressed.
3. Static electricity damage is suppressed.
4. The accuracy of the shape in patterning is improved.
5. High definition in mask manufacturing can be achieved.
The mask blank of the present invention is a mask blank having a layer to be a phase shift mask, comprising: a phase shift layer laminated on the transparent substrate; an etch stop layer disposed at a position farther from the transparent substrate than the phase shift layer; and a light shielding layer provided at a position farther from the transparent substrate than the etching stop layer, the phase shift layer containing chromium, the light shielding layer containing chromium and oxygen, the etching stop layer containing molybdenum silicide and nitrogen, and having a peak region where a nitrogen concentration reaches a peak at a position closer to the light shielding layer in a film thickness direction. Thereby, the above-mentioned problems are solved.
In the mask blank of the present invention, the etching stopper layer may have the peak region on an upper surface close to the light shielding layer in a film thickness direction.
In the mask blank of the present invention, the resistivity in the peak region of the etching stopper layer may be set to 1.0×10 -3 Ω cm or more.
In the present invention, the nitrogen concentration in the peak region of the etching stopper layer is preferably set to 30 atomic% or more.
In the mask blank of the present invention, a method may be employed in which the silicon concentration in the peak region of the etching stopper layer is set to 35 atomic% or less.
In the mask blank of the present invention, the molybdenum concentration in the peak region of the etching stop layer may be set to 30 at% or less.
In the mask blank of the present invention, the film thickness of the peak region may be set in a range of 1/3 or less of the film thickness of the etching stopper layer.
In the mask blank of the present invention, the resistivity of the etching stopper layer other than the peak region may be set to 1.0×10 -3 Ω cm or less.
In the mask blank of the present invention, the nitrogen concentration of the etching stop layer other than the peak region may be set to 25 atomic% or less.
In the mask blank of the present invention, the composition ratio of molybdenum to silicon of the etching stop layer other than the peak region may be set to 1.ltoreq.Si/Mo.
In the mask blank of the present invention, the thickness of the etching stopper layer may be set in a range of 10nm to 100 nm.
The method for manufacturing a mask blank according to the present invention is the method for manufacturing a mask blank according to any one of the above, and may further include: a phase shift layer forming step of laminating the phase shift layer containing chromium on the transparent substrate; an etching stop layer forming step of stacking the etching stop layer containing molybdenum silicide and nitrogen at a position farther from the transparent substrate than the phase shift layer; and a light shielding layer forming step of forming the etching stop layer by stacking the light shielding layer containing chromium and oxygen at a position farther from the transparent substrate than the etching stop layer, and controlling the nitrogen concentration in the peak region in the film thickness direction by setting the partial pressure of a nitrogen-containing gas as a supply gas during sputtering.
In the method for manufacturing a mask blank according to the present invention, in the etching stop layer forming step, the sheet resistance in the etching stop layer may be increased with an increase in the nitrogen content by setting the partial pressure of the nitrogen-containing gas.
In the method for manufacturing a mask blank according to the present invention, the peak region may be formed by setting the partial pressure ratio of the nitrogen-containing gas to a range of 30% or more in the etching stop layer forming step.
In the method for manufacturing a mask blank according to the present invention, in the etching stop layer forming step, the nitrogen-containing gas may be N 2.
In the method for producing a mask blank according to the present invention, a target in which the composition ratio of molybdenum to silicon is set to 2.3 Si/Mo 3.0 or less may be used in the etching stopper layer forming step.
The phase shift mask of the present invention may be manufactured from a mask blank according to any of the above.
The method for manufacturing a phase shift mask blank according to the present invention is a method for manufacturing the phase shift mask, comprising: a phase shift pattern forming step of forming a pattern on the phase shift layer; an etching stop pattern forming step of forming a pattern on the etching stop layer; and a light shielding pattern forming step of forming a pattern on the light shielding layer, wherein an etching solution in the phase shift pattern forming step and the light shielding pattern forming step is different from an etching solution in the etching stop pattern forming step.
The mask blank of the present invention is a mask blank having a layer to be a phase shift mask, comprising: a phase shift layer laminated on the transparent substrate, and an etching stop layer provided at a position farther from the transparent substrate than the phase shift layer; and a light shielding layer provided at a position farther from the transparent substrate than the etching stopper layer. The phase shift layer contains chromium, the light shielding layer contains chromium and oxygen, the etching stop layer contains molybdenum silicide and nitrogen, and has a peak region where the nitrogen concentration reaches a peak in a position close to the light shielding layer in a film thickness direction.
Thus, in etching of the light shielding layer, chemical resistance on the surface of the etching stopper layer can be improved. Therefore, the adhesion between the light shielding layer and the etching stopper layer can be improved, and the accuracy of the cross-sectional shape during etching of the light shielding layer can be improved, thereby improving the shape accuracy of the mask pattern.
In addition, in etching of the etching stopper layer, the etching rate (e.r.) in the etching stopper layer can be increased. Therefore, the etching time in the etching stop layer can be shortened, and the influence of etching on the transparent substrate serving as the glass substrate can be reduced. This is because, when the etching stop layer is etched, the glass substrate may be exposed, and the etchant of the etching stop layer containing molybdenum silicon may act on the exposed portion. Meanwhile, the etching stop layer can be surely removed by etching.
In the mask blank of the present invention, the etching stopper layer has the peak region on an upper surface close to the light shielding layer in a film thickness direction.
Thus, in etching of the light shielding layer, chemical resistance on the surface of the etching stopper layer can be improved. Therefore, the adhesion between the light shielding layer and the etching stopper layer can be improved, and the accuracy of the cross-sectional shape during etching of the light shielding layer can be improved, thereby improving the shape accuracy of the mask pattern.
In addition, in etching of the etching stopper layer, after the peak region is removed, the etching rate (e.r.) in the etching stopper layer can be increased. Therefore, the etching time in the etching stop layer can be shortened, and the influence of etching on the transparent substrate serving as the glass substrate can be reduced.
In the mask blank of the present invention, the resistivity in the peak region of the etching stopper layer is set to 1.0X10 -3. OMEGA.cm or more.
Thus, in etching of the light shielding layer, chemical resistance on the surface of the etching stopper layer can be improved. Therefore, a mask having a favorable cross-sectional shape can be formed.
Further, particles adhering to the surface of the etching stopper layer can be reduced. This can suppress the occurrence of pinholes.
In the present invention, the nitrogen concentration in the peak region of the etching stopper layer is set to 30 atomic% or more.
By setting the sheet resistance in the peak region in the above range, the chemical resistance on the surface of the etching stopper layer can be improved during etching of the light shielding layer. Therefore, a mask having a favorable cross-sectional shape can be formed.
Further, particles adhering to the surface of the etching stopper layer can be reduced. This can suppress the occurrence of pinholes.
In the mask blank of the present invention, the silicon concentration in the peak region of the etching stopper layer is set to 35 atomic% or less.
Thus, a mask blank capable of forming a phase shift mask having a good cross-sectional shape can be provided.
In the mask blank of the present invention, a molybdenum concentration in the peak region of the etching stopper layer is set to 30 at% or less.
Thus, a mask blank capable of forming a phase shift mask having a good cross-sectional shape can be provided.
In the mask blank of the present invention, the film thickness in the peak region is set to a range of 1/3 or less of the film thickness of the etching stopper layer.
Thus, sufficient etching stopping performance in the etching stop layer and a large etching rate (e.r.) in the etching stop layer can be simultaneously achieved. Therefore, in etching of the light shielding layer, chemical resistance on the surface of the etching stopper layer can be improved, and in etching of the etching stopper layer, after the peak region is removed, the etching rate (e.r.) in the etching stopper layer can be improved.
In the mask blank of the present invention, the resistivity of the etching stopper layer other than the peak region is set to 1.0X10 -3. OMEGA.cm or less.
Thus, in etching of the etching stopper layer, after the peak region is removed, the etching rate (e.r.) in the etching stopper layer can be increased. Therefore, the etching time in the etching stop layer can be shortened, and the influence of etching on the transparent substrate serving as the glass substrate can be reduced.
Further, by using a molybdenum silicide film having low resistivity as an etching stop layer, electrostatic breakdown can be suppressed.
In the mask blank of the present invention, the nitrogen concentration of the etching stop layer other than the peak region is set to 25 atomic% or less.
Thus, in the etching stop layer located closer to the phase shift layer than the peak region, the etching rate (e.r.) can be increased. Therefore, the etching time in the etching stop layer can be shortened, and the influence of etching on the transparent substrate serving as the glass substrate can be reduced.
Further, by using a molybdenum silicide film having low resistivity as an etching stop layer, electrostatic breakdown can be suppressed.
In the mask blank of the present invention, the composition ratio of molybdenum to silicon of the etching stop layer other than the peak region is set to 1.ltoreq.Si/Mo.
Thus, a mask blank capable of forming a phase shift mask having a good cross-sectional shape can be provided.
In the mask blank of the present invention, the thickness of the etching stopper layer is set to a range of 10nm to 100 nm.
Thus, a mask blank capable of forming a phase shift mask having a good cross-sectional shape can be provided.
The method for producing a mask blank according to the present invention is the method for producing a mask blank according to any one of the above, comprising: a phase shift layer forming step of laminating the phase shift layer containing chromium on the transparent substrate; an etching stop layer forming step of stacking the etching stop layer containing molybdenum silicide and nitrogen at a position farther from the transparent substrate than the phase shift layer; and a light shielding layer forming step of stacking the light shielding layer containing chromium and oxygen at a position farther from the transparent substrate than the etching stopper layer. In the etching stop layer forming step, the etching stop layer is formed by controlling the nitrogen concentration in the peak region in the film thickness direction by setting the partial pressure of the nitrogen-containing gas as the supply gas during sputtering.
In the method for manufacturing a mask blank according to the present invention, in the etching stop layer forming step, the sheet resistance in the etching stop layer is increased with an increase in the nitrogen content by setting the partial pressure of the nitrogen-containing gas.
Thus, a mask blank having an etching stop layer with a larger nitrogen concentration at a position closer to the light shielding layer than at a position closer to the phase shift layer in the film thickness direction can be manufactured.
Further, a peak region where the nitrogen concentration reaches a peak can be formed on the etching stopper layer in the vicinity of the interface with the light shielding layer. In addition, in the etching stopper layer, the nitrogen concentration at a position close to the phase shift layer can be reduced as compared with the nitrogen concentration at the peak region. Further, during formation of the etching stop layer by sputtering, the etching stop layer having such a structure can be realized by controlling the partial pressure of the nitrogen-containing gas in the atmosphere gas.
Therefore, a mask blank having a sufficient etching stop capability and capable of forming a phase shift mask having a good cross-sectional shape can be manufactured.
In the method for manufacturing a mask blank according to the present invention, in the etching stopper layer forming step, the peak region is formed by setting the partial pressure ratio of the nitrogen-containing gas to a range of 30% or more.
Thus, the peak region in the etching stopper layer can be set to a predetermined nitrogen concentration, and the sheet resistance can be formed.
In the method for manufacturing a mask blank according to the present invention, in the etching stopper layer forming step, the nitrogen-containing gas is N 2.
Thus, the peak region in the etching stopper layer can be set to a predetermined nitrogen concentration, and the resistivity can be set as described above.
In the method for producing a mask blank of the present invention, a target in which the composition ratio of molybdenum to silicon is set to 2.3 to 3.0 inclusive is used in the etching stopper layer forming step.
Thus, a mask blank having a predetermined nitrogen concentration in the peak region of the etching stopper layer and the sheet resistance can be manufactured, and a phase shift mask having a good cross-sectional shape can be formed with a sufficient etching stopper capability.
The phase shift mask of the present invention is manufactured from the mask blank according to any one of the above. Thus, a phase shift mask having a good cross-sectional shape and sufficient etching stopping ability can be provided.
The method for manufacturing a phase shift mask blank according to the present invention is a method for manufacturing the phase shift mask, comprising: a phase shift pattern forming step of forming a pattern on the phase shift layer; an etching stop pattern forming step of forming a pattern on the etching stop layer; and a light shielding pattern forming step of forming a pattern on the light shielding layer. The phase shift pattern forming step and the light shielding pattern forming step are performed with different etching solutions from each other. Thus, a phase shift mask having a good cross-sectional shape can be formed while having a sufficient etching stop capability.
According to the present invention, the following effects can be achieved: that is, it is possible to provide a mask blank capable of forming a phase shift mask having a good cross-sectional shape while reducing the influence on the surface of a glass substrate.
Drawings
Fig. 1 is a cross-sectional view showing a mask blank according to a first embodiment of the present invention.
Fig. 2 is a cross-sectional view showing a method for manufacturing a mask blank according to a first embodiment of the present invention.
Fig. 3 is a cross-sectional view showing a process of a method for manufacturing a phase shift mask according to a first embodiment of the present invention.
Fig. 4 is a cross-sectional view showing a process of a method for manufacturing a phase shift mask according to a first embodiment of the present invention.
Fig. 5 is a cross-sectional view showing a process of a method for manufacturing a phase shift mask according to a first embodiment of the present invention.
Fig. 6 is a cross-sectional view showing a process of a method for manufacturing a phase shift mask according to the first embodiment of the present invention.
Fig. 7 is a cross-sectional view showing a process of a method for manufacturing a phase shift mask according to the first embodiment of the present invention.
Fig. 8 is a cross-sectional view showing a process of a method for manufacturing a phase shift mask according to the first embodiment of the present invention.
Fig. 9 is a cross-sectional view showing a process of a method for manufacturing a phase shift mask according to a first embodiment of the present invention.
Fig. 10 is a cross-sectional view showing a phase shift mask according to a first embodiment of the present invention.
Fig. 11 is a schematic view showing a film forming apparatus in the method for manufacturing a mask blank according to the first embodiment of the present invention.
Fig. 12 is a graph showing a relationship between an etching rate (e.r.) and a nitrogen concentration of an etching stop layer in a method for manufacturing a mask blank and a phase shift mask according to the first embodiment of the present invention.
Fig. 13 is a graph showing a composition ratio in a film thickness direction of an etching stop layer in a mask blank and a phase shift mask according to the first embodiment of the present invention.
Detailed Description
Next, a mask blank, a phase shift mask, and a method of manufacturing the same according to a first embodiment of the present invention will be described with reference to the drawings.
Fig. 1 is a cross-sectional view showing a mask blank according to the present embodiment, fig. 2 is a cross-sectional view showing a mask blank according to the present embodiment, and reference numeral 10B is a mask blank in fig. 1 and 2.
The mask blank 10B according to the present embodiment is provided to a phase shift mask (photomask) used in a range of 365nm to 436nm as an exposure light. As shown in fig. 1, a mask blank 10B according to the present embodiment includes: a glass substrate (transparent substrate) 11; a phase shift layer 12 formed on the glass substrate 11; an etch stop layer 13 formed on the phase shift layer 12; and a light shielding layer 14 formed on the etching stop layer 13.
That is, the etching stopper layer 13 is provided at a position farther from the glass substrate 11 than the phase shift layer 12. In addition, the light shielding layer 14 is provided at a position farther from the glass substrate 11 than the etching stop layer 13.
These phase shift layer 12, etch stop layer 13, and light shielding layer 14 constitute a mask layer, which is a laminated film having optical characteristics required for a photomask.
As shown in fig. 2, the mask blank 10B according to the present embodiment may be configured such that a photoresist layer 15 is formed in advance on a mask layer in which the phase shift layer 12, the etching stop layer 13, and the light shielding layer 14 are laminated as shown in fig. 1.
The mask blank 10B according to the present embodiment may have a structure in which an antireflection layer, a chemical resistant layer, a protective layer, an adhesion layer, and the like are laminated in addition to the phase shift layer 12, the etching stop layer 13, and the light shielding layer 14. As shown in fig. 2, a photoresist layer 15 may be formed on these laminated films.
As the glass substrate 11, a material excellent in transparency and optical isotropy can be used, and for example, a quartz glass substrate can be used. The size of the glass substrate 11 is not particularly limited, and may be appropriately selected according to a substrate (for example, a substrate for an FPD such as an LCD (liquid crystal display), a plasma display, or an organic EL (electro luminescence) display) to be exposed using the mask.
In the present embodiment, as the glass substrate 11, a rectangular substrate having a side of about 100mm to a side of 2000mm or more can be used, and a substrate having a thickness of 1mm or less, a substrate having a thickness of several millimeters, or a substrate having a thickness of 10mm or more can be used.
Further, the flatness of the glass substrate 11 may be reduced by polishing the surface of the glass substrate 11. The flatness of the transparent substrate 11 may be, for example, 20 μm or less. This makes the depth of focus of the mask deeper, and can contribute significantly to fine and highly accurate patterning. Further, the flatness is preferably a small value of 10 μm or less.
The phase shift layer 12 is a layer containing Cr (chromium) as a main component, and contains C (carbon), O (oxygen), and N (nitrogen).
Furthermore, the phase shift layer 12 may have a different composition in the thickness direction. In this case, the phase shift layer 12 may be formed by stacking one or two or more selected from Cr alone and Cr oxide, nitride, carbide, oxynitride, carbonitride, and oxycarbonitride.
As will be described later, the thickness of the phase shift layer 12, the composition ratio (at%) of Cr, N, C, O, and the like are set so as to obtain predetermined optical characteristics and resistivity.
The film thickness of the phase shift layer 12 is set according to the optical characteristics required for the phase shift layer 12, and varies according to the composition ratio of Cr, N, C, O or the like. The film thickness of the phase shift layer 12 may be 50nm to 150nm.
For example, the composition ratio in the phase shift layer 12 may be set to have a carbon content (carbon concentration) of 2.3 to 10.3 atomic%, an oxygen content (oxygen concentration) of 8.4 to 72.8 atomic%, a nitrogen content (nitrogen concentration) of 1.8 to 42.3 atomic%, and a chromium content (chromium concentration) of 20.3 to 42.4 atomic%.
Thus, the phase shift layer 12 can be set to have a film thickness of about 90nm when the refractive index is about 2.4 to 3.1 and the extinction coefficient is about 0.3 to 2.1 in the wavelength range of about 365nm to 436 nm.
The composition ratio and film thickness of the phase shift layer 12 are set according to the optical characteristics required for the manufactured phase shift mask 10, and are not limited to the above values.
The etching stopper layer 13 is a material different from the phase shift layer 12, and may be a metal silicide film, for example, a film containing a metal such as Ta (tantalum), ti (titanium), W (tungsten), mo (molybdenum), zr (zirconium), or an alloy of these metals and silicon. Particularly, among metal silicide films, molybdenum silicide films are also preferably used, and MoSi X (X.gtoreq.2) films (for example, moSi 2 film, moSi 3 film, moSi 4 film, or the like) are exemplified.
The etching stopper layer 13 is preferably a molybdenum silicide film containing O (oxygen), N (nitrogen), and C (carbon).
The etching stopper layer 13 may contain C (carbon).
In the etching stopper layer 13, the oxygen content (oxygen concentration) may be set to a range of 2.6 atomic% to 10.9 atomic%, the nitrogen content (nitrogen concentration) may be set to a range of 1.5 atomic% to 40.9 atomic%, and the carbon content (carbon concentration) may be set to a range of 2.4 atomic% to 4.3 atomic%.
The film thickness of the etching stopper layer 13 may be set in the range of 10nm to 100 nm.
The etching stopper layer 13 has a peak region 13A where the nitrogen concentration reaches a peak at a position close to the light shielding layer 14 in the film thickness direction.
The etching stopper layer 13 has a nitrogen concentration lower than that of the peak region 13A at a position close to the phase shift layer 12 in the film thickness direction.
The peak region 13A may be formed in the etching stopper layer 13 so as to be exposed on the upper surface close to the light shielding layer 14 in the film thickness direction. That is, the peak region 13A is formed at the interface between the etching stop layer 13 and the light shielding layer 14.
The resistivity in the peak region 13A of the etching stopper layer 13 is set to 1.0×10 -3 Ω cm or more.
The nitrogen concentration in the peak region 13A of the etching stopper layer 13 is set to 30 atomic% or more.
The silicon concentration in the peak region 13A of the etching stopper layer 13 is set to be in the range of 20 atomic% to 70 atomic%.
The molybdenum concentration in the peak region 13A of the etching stopper layer 13 is set to be in the range of 20 atomic% to 40 atomic%.
The film thickness of the peak region 13A is set to a range of 1/3 or less of the film thickness of the etching stopper layer 13.
The resistivity of the etching stopper layer 13 at a position other than the peak region 13A, that is, at a position closer to the phase shift layer 12 than the peak region 13A is set to 1.0×10 -3 Ω cm or less.
The nitrogen concentration of the etching stopper layer 13 at a position other than the peak region 13A, that is, at a position closer to the phase shift layer 12 than the peak region 13A is set to 25 atomic% or less.
The composition ratio of molybdenum to silicon of the etching stopper layer 13 except the peak region 13A, i.e., at a position closer to the phase shift layer 12 than the peak region 13A, is set to 1.ltoreq.si/Mo.
The nitrogen concentration of the etching stopper layer 13 other than the peak region 13A, that is, at a position closer to the phase shift layer 12 than the peak region 13A may be a uniform constant value, may have a gradient, or may have a predetermined change in the film thickness direction, as long as the nitrogen concentration is lower than that of the peak region 13A.
In addition, as for the etching stopper layer 13, as long as the peak region 13A has a portion with a high nitrogen concentration, in other portions, it is preferable that the nitrogen concentration is as low as possible and the etching rate (e.r.) is large. In addition, as for the etching stopper layer 13, as long as the peak region 13A has a portion with a high nitrogen concentration, in other portions, it is preferable that the nitrogen concentration is as low as possible and the resistivity is low.
The light shielding layer 14 is a layer containing Cr (chromium) and O (oxygen) as main components, and contains C (carbon) and N (nitrogen).
In this case, the light shielding layer 14 may be formed by stacking one or two or more kinds selected from the group consisting of an oxide, a nitride, a carbide, an oxynitride, a carbonitride, and an oxycarbonitride of Cr. In addition, the light shielding layer 14 may have a different composition in the thickness direction.
As will be described later, the thickness of the light shielding layer 14, the composition ratio (at%) of Cr, N, C, O, si, and the like are set so as to obtain predetermined adhesion (hydrophobicity) and predetermined optical characteristics for the light shielding layer 14.
The film thickness of the light shielding layer 14 is set according to film characteristics such as adhesion (hydrophobicity) and optical characteristics between the photoresist layer 15 and the light shielding layer 14, which are conditions required for the light shielding layer 14, which will be described later. The film characteristics in these light shielding layers 14 vary according to the composition ratio Cr, N, C, O and the like. In particular, the film thickness of the light shielding layer 14 may be set according to the optical characteristics required for the phase shift mask 10.
By setting the film thickness and composition of the light shielding layer 14 in the above manner, adhesion between the light shielding layer 14 and the photoresist layer 15 used for the chromium system is improved during pattern formation in the photolithography. Thus, the etching liquid does not enter at the interface between the photoresist layer 15 and the light shielding layer 14. Thus, a good pattern shape can be obtained, and a desired pattern can be formed.
In addition, when the light shielding layer 14 is not set under the above conditions, adhesion between the photoresist layer 15 and the light shielding layer 14 cannot be in a predetermined state, and etching solution enters the interface due to peeling of the photoresist layer 15, so that patterning cannot be performed, which is not preferable. In addition, when the film thickness of the light shielding layer 14 is not set as in the above-described conditions, it is difficult to set the optical characteristics of the photomask to desired conditions, or the cross-sectional shape of the mask pattern may not be in a desired state, which is not preferable.
The light shielding layer 14 can be reduced in hydrophilicity by increasing the oxygen concentration and the nitrogen concentration in the chromium compound, and can be increased in hydrophobicity and adhesion.
Meanwhile, for the light shielding layer 14, the values of the refractive index and the extinction coefficient can be reduced by increasing the oxygen concentration and the nitrogen concentration in the chromium compound, or the values of the refractive index and the extinction coefficient can be increased by decreasing the oxygen concentration and the nitrogen concentration in the chromium compound.
The method of manufacturing the mask blank according to the present embodiment is to form the phase shift layer 12 on the glass substrate 11, then form the etching stopper layer 13, and then form the light shielding layer 14.
In the case of laminating a protective layer, a light shielding layer, a chemical resistant layer, an antireflection layer, and the like in addition to the phase shift layer 12, the etching stop layer 13, and the light shielding layer 14, the mask blank manufacturing method may have a lamination process of these layers.
As an example, an adhesion layer containing chromium is given.
Fig. 3 is a cross-sectional view showing a process for manufacturing the phase shift mask according to the present embodiment. Fig. 4 is a cross-sectional view showing a process for manufacturing the phase shift mask according to the present embodiment. Fig. 5 is a cross-sectional view showing a process for manufacturing the phase shift mask according to the present embodiment. Fig. 6 is a cross-sectional view showing a process for manufacturing the phase shift mask according to the present embodiment. Fig. 7 is a cross-sectional view showing a process for manufacturing the phase shift mask according to the present embodiment. Fig. 8 is a cross-sectional view showing a process for manufacturing the phase shift mask according to the present embodiment. Fig. 9 is a cross-sectional view showing a process for manufacturing the phase shift mask according to the present embodiment. Fig. 10 is a cross-sectional view showing a phase shift mask in the present embodiment.
As shown in fig. 10, a phase shift mask (photomask) 10 in this embodiment is obtained by forming a pattern on a phase shift layer 12, an etching stop layer 13, and a light shielding layer 14, which are stacked as a mask blank 10B.
Next, a method for manufacturing the phase shift mask 10 from the mask blank 10B according to the present embodiment will be described.
As a resist pattern forming process, as shown in fig. 2, a photoresist layer 15 is formed on the outermost surface of the mask blank 10B. Alternatively, the mask blank 10B having the photoresist layer 15 formed on the outermost surface may be prepared in advance. The photoresist layer 15 may be either positive or negative. As a material of the photoresist layer 15, a material that can cope with etching of a chromium-based material and etching of a molybdenum silicide-based material can be used. As the photoresist layer 15, a liquid resist may be used.
Then, the photoresist layer 15 is exposed and developed, whereby a resist pattern 15P1 is formed on the outer side of the light shielding layer 14. The resist pattern 15P1 functions as an etching mask used for etching the phase shift layer 12, the etching stop layer 13, and the light shielding layer 14.
The shape of the resist pattern 15P1 is appropriately determined according to the etching patterns of the phase shift layer 12, the etching stop layer 13, and the light shielding layer 14. As an example, the transparent region 10L (see fig. 6 to 10) is set to have a shape having an opening width corresponding to the opening width dimension of the formed transparent region.
Next, as a light shielding pattern forming step, the light shielding layer 14 is wet etched with an etching solution through the resist pattern 15P1, and as shown in fig. 3, a light shielding pattern 14P1 is formed.
As the etching liquid in the light shielding pattern forming step, an etching liquid containing ceric ammonium nitrate can be used as the etching liquid for the chromium-based material. For example, ceric ammonium nitrate containing an acid such as nitric acid or perchloric acid is preferably used.
In the light shielding pattern forming step, the etching stopper layer 13 made of molybdenum silicide is hardly etched by the chromium-based etching liquid.
At this time, since the peak region 13A is provided in the etching stopper layer 13, the etching resistance to the chromium-based etching solution can be improved. Meanwhile, since the peak region 13A is provided on the etching stopper layer 13, adhesion between the light shielding layer 14 and the etching stopper layer 13 can be improved, and collapse of the etched shape can be prevented.
Next, as an etching stop pattern forming step, the etching stop layer 13 is wet etched with an etching solution through the light shielding pattern 14P1, and as shown in fig. 4, an etching stop pattern 13P1 is formed.
As the etching liquid in the etching stop pattern forming step, an etching liquid capable of etching the etching stop layer 13 made of molybdenum silicide can be used. As such an etching liquid, an etching liquid containing at least one fluorine compound selected from the group consisting of hydrogen fluoride acid, hydrogen silicon fluoride acid, and ammonium bifluoride and at least one oxidizing agent selected from the group consisting of hydrogen peroxide, nitric acid, and sulfuric acid is preferably used.
At this time, since the peak region 13A is provided in the etching stop layer 13, the etching rate (e.r.) of the molybdenum silicide-based etching liquid is reduced, but since the film thickness of the peak region 13A is set to be small, the etching time can be prevented from becoming long. Further, since the nitrogen concentration of the etching stopper layer 13 is set to be low on the lower side of the peak region 13A, that is, on the position closer to the phase shift layer 12, the etching rate (e.r.) of the molybdenum silicide-based etching liquid is increased, and the etching time can be shortened.
This can shorten the etching time and suppress the influence on the glass substrate 11 affected by the etching liquid.
Next, as a phase shift pattern forming step, the phase shift layer 12 is wet etched through the patterned etching stop pattern 13P1, the light shielding pattern 14P1, and the resist pattern 15P 1. Thereby, as shown in fig. 5, the phase shift pattern 12P1 is formed.
Thus, the light-transmitting region 10L exposed on the surface of the glass substrate 11 can be formed.
As the etching liquid in the phase shift pattern forming step, an etching liquid containing ceric ammonium nitrate can be used as in the light shielding pattern forming step. For example, ceric ammonium nitrate containing an acid such as nitric acid or perchloric acid is preferably used.
For example, the molybdenum silicide compound constituting the etching stopper layer 13 can be etched by using a mixed solution of ammonium bifluoride and hydrogen peroxide. In contrast, for example, the chromium compound forming the light shielding layer 14 and the phase shift layer 12 can be etched using a mixed solution of ceric ammonium nitrate and perchloric acid.
Therefore, the selectivity at the time of etching of each wafer becomes very large. Therefore, after the light shielding pattern 14P1, the etching stop pattern 13P1, and the phase shift pattern 12P1 are formed by etching, a favorable cross-sectional shape close to vertical can be obtained as the cross-sectional shape of the phase shift mask 10.
In the phase shift pattern forming step, the oxygen concentration of the light shielding layer 14 is set to be higher than the oxygen concentration of the phase shift layer 12, thereby reducing the etching rate. Therefore, the progress of etching of the light shielding pattern 14P1 is delayed compared to that of the phase shift layer 12.
In these cases, the angle (taper angle) θ formed by the etching of the light shielding pattern 14P1, the etching stop pattern 13P1, and the phase shift pattern 12P1 and the surface of the glass substrate 11 is close to a right angle, and may be, for example, about 90 °.
Further, by forming the peak region 13A on the etching stop pattern 13P1 so as to contact the light shielding pattern 14P1, adhesion between the light shielding pattern 14P1 and the etching stop pattern 13P1 is improved. Thus, in the phase shift pattern forming step, the etching liquid does not enter the interface between the light shielding pattern 14P1 and the etching stop pattern 13P 1. Therefore, a reliable pattern formation can be performed.
In the present embodiment, as shown in fig. 6, the resist pattern 15P2 is formed outside the light shielding pattern 14P1 by exposing and developing the photoresist layer 15 as a resist pattern forming step. The resist pattern 15P2 functions as an etching mask for the etching stop pattern 13P1 and the light shielding pattern 14P 1.
The shape of the resist pattern 15P2 is appropriately determined according to the etching patterns of the etching stop pattern 13P1 and the light shielding pattern 14P 1. As an example, the phase shift region 10P2 and the exposure region 10P1 (see fig. 8 to 10) are formed to have an opening width corresponding to the opening width.
Next, as a pattern forming step for a light shielding pattern, the light shielding pattern 14P1 is wet etched with an etching solution through the resist pattern 15P2, and as shown in fig. 7, the light shielding pattern 14P2 is formed.
As the etching liquid in the pattern forming step for the light shielding pattern, an etching liquid containing ceric ammonium nitrate can be similarly used as the etching liquid for the chromium-based material. For example, ceric ammonium nitrate containing an acid such as nitric acid or perchloric acid is preferably used.
In the light shielding pattern forming step, the etching stop pattern 13P1 made of molybdenum silicide is hardly etched by the chromium-based etching liquid.
At this time, since the peak region 13A is provided in the etching stop pattern 13P1, the etching resistance to the chromium-based etching solution can be improved. Meanwhile, since the peak region 13A is provided in the etching stop pattern 13P1, the adhesion between the light shielding pattern 14P2 and the etching stop pattern 13P1 can be improved, and collapse of the etched shape can be prevented.
Next, as an etching stop pattern forming step, the etching stop pattern 13P1 is wet etched with an etching solution through the light shielding pattern 14P 2. Then, as shown in fig. 8, an etching stop pattern 13P2 is formed.
Thereby, the etching stop pattern 13P2 exposed on the surface of the phase shift pattern 12P1 can be formed corresponding to the exposure region 10P 1.
As the etching liquid in the etching stop pattern forming step, the etching liquid capable of etching the etching stop pattern 13P1 made of molybdenum silicide can be similarly used. As such an etching liquid, an etching liquid containing at least one fluorine compound selected from the group consisting of hydrogen fluoride acid, hydrogen silicon fluoride acid, and ammonium bifluoride and at least one oxidizing agent selected from the group consisting of hydrogen peroxide, nitric acid, and sulfuric acid is preferably used.
At this time, since the peak region 13A is provided in the etching stop pattern 13P1, the etching rate (e.r.) of the molybdenum silicide-based etching liquid is reduced. On the other hand, since the film thickness of the peak region 13A is set to be small, the etching time for forming the etching stop pattern 13P2 can be prevented from becoming long. Further, the nitrogen concentration of the etching stop pattern 13P1 is set to be low at a position lower than the peak region 13A, that is, at a position closer to the phase shift pattern 12P 1. Therefore, the etching rate (e.r.) of the molybdenum silicide-based etching liquid is increased, and the etching time for forming the etching stop pattern 13P2 can be shortened.
This can shorten the etching time and suppress the influence of the etching liquid on the glass substrate 11 exposed in the light-transmitting region 10L and other regions.
Next, as a phase shift pattern forming step, the phase shift pattern 12P1 is wet etched with an etching solution through the resist pattern 15P2, the light shielding pattern 14P2, and the etching stop pattern 13P 2. Thereby, as shown in fig. 9, the phase shift pattern 12P2 is formed.
As the etching liquid in the phase shift pattern forming step, an etching liquid containing ceric ammonium nitrate can be used as in the pattern forming step for the light shielding pattern. For example, ceric ammonium nitrate containing an acid such as nitric acid or perchloric acid is preferably used.
At this time, the exposed surface of the light shielding pattern 14P2 is wet etched simultaneously with the wet etching of the phase shift pattern 12P 1. Wet etching of the exposed surface of the light shielding pattern 14P2 is performed in the lateral direction in the drawing, and as shown in fig. 9, a light shielding pattern 14P3 having a larger opening width than the phase shift pattern 12P2 is formed.
The selection ratio at the time of wet etching becomes extremely large in the molybdenum silicide compound constituting the etching stopper layer 13 and the chromium compound forming the light shielding layer 14 and the phase shift layer 12, respectively. Therefore, etching of the phase shift pattern 12P1 covered with the etching stopper layer 13 is not performed. In contrast, the light shielding pattern 14P2 with the exposed pattern cross section and the phase shift pattern 12P1 in the region where the etching stopper layer 13 is removed are etched.
Here, the light shielding pattern 14P2 is etched in a direction along the surface of the glass substrate 11, and the phase shift pattern 12P1 in a region where the etching stopper layer 13 is removed is etched in the thickness direction.
Thus, the phase shift pattern 12P2 protruding toward the exposure region 10P1 than the light shielding pattern 14P3 and having the phase shift region 10P2, which is required for the cross-sectional shape of the phase shift mask 10, can be formed.
In this case, a favorable cross-sectional shape close to vertical can be obtained as the cross-sectional shape of the phase shift mask 10.
In the phase shift pattern forming step, the oxygen concentration of the light shielding layer 14 is set to be higher than the oxygen concentration of the phase shift layer 12, thereby reducing the etching rate. Therefore, for the etching of the phase shift pattern 12P1, the etching progress of the light shielding pattern 14P2 is set to a prescribed state, and the width dimension of the phase shift region 10P2 is set.
In these cases, in the light shielding pattern 14P3, the etching stop layer 13P2, and the phase shift pattern 12P2, the angle θ formed by the wall surface formed by the etching and the surface of the glass substrate 11 (taper angle) is close to a right angle, and may be, for example, about 90 °.
Further, by forming the peak region 13A on the etching stop pattern 13P1 so as to contact the light shielding pattern 14P2, adhesion between the light shielding pattern 14P2 and the etching stop pattern 13P2 is improved. Thus, in the phase shift pattern forming step, the etching liquid does not enter the interface between the light shielding pattern 14P2 and the etching stop pattern 13P 1. Therefore, a reliable pattern formation can be performed.
Next, as a resist removing step, the resist pattern 15P2 is removed, and as shown in fig. 10, the phase shift mask 10 is manufactured.
Next, a method for manufacturing a mask blank according to the present embodiment will be described with reference to the drawings.
Fig. 11 is a schematic diagram showing a mask blank manufacturing apparatus according to the present embodiment.
The mask blank 10B in the present embodiment is manufactured by the manufacturing apparatus shown in fig. 11.
The manufacturing apparatus S10 shown in fig. 11 is a reciprocating type device for sputtering. The manufacturing apparatus S10 includes a loading chamber S11, an unloading chamber S16, and a film forming chamber (vacuum processing chamber) S12. The film forming chamber S12 is located between the loading chamber S11 and the unloading chamber S16. The film forming chamber S12 is connected to the loading chamber S11 through a sealing mechanism S17, and is connected to the unloading chamber S16 through a sealing mechanism S18.
The loading chamber S11 is provided with a conveying mechanism S11a for conveying the glass substrate 11, which is conveyed from the outside of the manufacturing apparatus S10 to the inside thereof, to the film forming chamber S12, and an exhaust mechanism S11f such as a rotary pump for performing rough vacuum on the inside of the loading chamber S11.
The unloading chamber S16 is provided with a conveying mechanism S16a for conveying the film-formed glass substrate 11 from the film forming chamber S12 to the outside of the manufacturing apparatus S10, and an exhaust mechanism S16f such as a rotary pump for performing rough vacuum in the unloading chamber S16.
The film forming chamber S12 is provided with a substrate holding mechanism S12a and three-stage film forming mechanisms S13, S14, S15 as mechanisms for coping with three film forming processes.
The substrate holding mechanism S12a holds the glass substrate 11 so that the glass substrate 11 conveyed by the conveying mechanism S11a faces the targets S13b, S14b, S15b during film formation. The substrate holding mechanism S12a can carry in the glass substrate 11 from the loading chamber S11 and can carry out the glass substrate 11 to the unloading chamber S16.
The film forming mechanism S13 for supplying the film forming material of the first stage is provided at a position closest to the loading chamber S11 among the three stages of film forming mechanisms S13, S14, S15 of the film forming chamber S12.
The film forming mechanism S13 includes: a cathode electrode (backing plate) S13c having a target S13 b; and a power supply S13d for applying a negative potential sputtering voltage to the backing plate S13 c.
The film forming mechanism S13 includes: a gas introduction mechanism S13e for introducing a gas to the vicinity of the cathode electrode (back plate) S13c in the film formation chamber S12; and a high vacuum evacuation mechanism S13f such as a turbo molecular pump for applying high vacuum to the vicinity of the cathode electrode (back plate) S13c in the film formation chamber S12.
Further, a film forming mechanism S14 is provided at an intermediate position between the loading chamber S11 and the unloading chamber S16 in the film forming chamber S12, and the film forming mechanism S14 is configured to supply the film forming material of the second stage of the three stages of film forming mechanisms S13, S14, S15.
The film forming mechanism S14 includes: a cathode electrode (backing plate) S14c having a target S14 b; and a power supply S14d for applying a negative potential sputtering voltage to the backing plate S14 c.
The film forming mechanism S14 includes: a gas introduction mechanism S14e for introducing a gas to the vicinity of the cathode electrode (back plate) S14c in the film formation chamber S12; and a high vacuum evacuation mechanism S14f such as a turbo molecular pump for applying high vacuum to the vicinity of the cathode electrode (back plate) S14c in the film formation chamber S12.
Further, among the three-stage film forming mechanisms S13, S14, S15 of the film forming chamber S12, the film forming mechanism S15 is provided at a position closest to the unloading chamber S16, and the film forming mechanism S15 is configured to supply the film forming material of the third-stage film forming mechanism.
The film forming mechanism S15 includes: a cathode electrode (backing plate) S15c having a target S15 b; and a power supply S15d for applying a negative potential sputtering voltage to the backing plate S15 c.
The film forming mechanism S15 includes: a gas introduction mechanism S15e for introducing a gas to the vicinity of the cathode electrode (back plate) S15c in the film formation chamber S12; and a high vacuum evacuation mechanism S15f such as a turbo molecular pump for applying high vacuum to the vicinity of the cathode electrode (back plate) S15c in the film formation chamber S12.
In the film forming chamber S12, a gas barrier S12g for suppressing the flow of gas is provided near the cathode electrodes (back plates) S13c, S14c, S15c, respectively, so that the gases supplied from the gas introduction mechanisms S13e, S14e, S15e, respectively, do not mix into the adjacent film forming mechanisms S13, S14, S15. These gas barriers S12g are configured such that the substrate holding mechanism S12a can move between the film forming mechanisms S13, S14, S15 adjacent to each other, respectively.
In the film forming chamber S12, each of the three-stage film forming mechanisms S13, S14, S15 has a composition required for sequentially forming films on the glass substrate 11, and can form films under conditions required for film formation.
In the present embodiment, the film formation mechanism S13 is used for forming the phase shift layer 12. The film formation mechanism S14 is used for forming the etching stopper layer 13. The film forming mechanism S15 is used for forming the light shielding layer 14.
Specifically, in the film forming mechanism S13, the target S13b is formed of a material having chromium, which is a composition necessary for forming the phase shift layer 12 on the glass substrate 11.
Meanwhile, in the film forming means S13, the process gas, which is the gas supplied from the gas introducing means S13e, contains carbon, nitrogen, oxygen, etc. in correspondence with the film formation of the phase shift layer 12, and is set to a predetermined partial pressure of the gas together with the sputtering gas such as argon, nitrogen, etc.
In addition, the high vacuum evacuation mechanism S13f is evacuated according to the film formation conditions.
In the film forming mechanism S13, a sputtering voltage applied from the power source S13d to the backing plate S13c is set in correspondence with the film formation of the phase shift layer 12.
In the film formation mechanism S14, the target S14b is formed of a material having molybdenum silicide, which is a composition necessary for forming the etching stopper layer 13 on the phase shift layer 12.
Meanwhile, in the film forming means S14, the process gas, which is the gas supplied from the gas introducing means S14e, contains carbon, nitrogen, oxygen, etc. in correspondence with the film formation of the etching stopper layer 13, and is set to a predetermined partial pressure of the gas together with the sputtering gas, such as argon, inert gas, etc.
The gas supplied from the gas introduction means S14e is configured to be able to adjust the partial pressure of the nitrogen-containing gas or the like so that the partial pressure becomes a predetermined amount of change depending on the film thickness of the etching stop layer 13 to be formed.
In addition, the high vacuum evacuation mechanism S14f is evacuated according to the film formation conditions.
In the film forming mechanism S14, a sputtering voltage applied from the power source S14d to the backing plate S14c is set in correspondence with the film formation of the etching stopper layer 13.
In the film forming mechanism S15, the target S15b is formed of a material having chromium, which is a composition necessary for forming the light shielding layer 14 on the etching stopper layer 13.
Meanwhile, in the film forming means S15, the process gas which is the gas supplied from the gas introducing means S15e contains carbon, nitrogen, oxygen, etc. in correspondence with the film formation of the light shielding layer 14, and is set to a predetermined partial pressure of the gas together with the sputtering gas such as argon, nitrogen, etc. which is the inert gas.
In addition, the high vacuum evacuation mechanism S15f is evacuated according to the film formation conditions.
In the film forming mechanism S15, a sputtering voltage applied from the power source S15d to the backing plate S15c is set in correspondence with the film formation of the light shielding layer 14.
In the manufacturing apparatus S10 shown in fig. 11, three-stage sputtering film formation is performed while the glass substrate 11 carried in from the loading chamber S11 through the carrying mechanism S11a is carried in the film forming chamber S12 through the substrate holding mechanism S12 a. Then, the glass substrate 11 having been film-formed is transported out of the unloading chamber S16 to the outside of the manufacturing apparatus S10 by the transport mechanism S16 a.
In the phase shift layer forming step, a sputtering gas and a reaction gas are supplied from the gas introduction mechanism S13e to the vicinity of the backing plate S13c of the film forming chamber S12 in the film forming mechanism S13. In this state, a sputtering voltage is applied from an external power source to the backing plate (cathode electrode) S13 c. In addition, a predetermined magnetic field may be formed on the target S13b by a magnetron magnetic circuit.
Ions of the sputtering gas are excited by the plasma in the vicinity of the backing plate S13c in the film forming chamber S12, and collide with the target S13b of the cathode electrode S13c to fly out particles of the film forming material. Then, since the flying particles are bonded to the reaction gas and then attached to the glass substrate 11, the phase shift layer 12 is formed on the surface of the glass substrate 11 with a predetermined composition.
Similarly, in the etching stopper layer forming step, the film forming means S14 supplies the sputtering gas and the reaction gas as the supply gases from the gas introducing means S14e to the vicinity of the backing plate S14c of the film forming chamber S12. In this state, a sputtering voltage is applied from an external power source to the backing plate (cathode electrode) S14 c. In addition, a predetermined magnetic field may be formed on the target S14b by a magnetron magnetic circuit.
Ions of the sputtering gas are excited by the plasma in the vicinity of the backing plate S14c in the film forming chamber S12, and collide with the target S14b of the cathode electrode S14c to fly out particles of the film forming material. The flying particles are bonded to the reaction gas and then attached to the glass substrate 11, and the etching stopper layer 13 is formed by laminating the particles on the surface of the glass substrate 11 with a predetermined composition on the phase shift layer 12.
Similarly, in the light shielding layer forming step, in the film forming mechanism S15, a sputtering gas and a reaction gas as supply gases are supplied from the gas introducing mechanism S15e to the vicinity of the backing plate S15c of the film forming chamber S12. In this state, a sputtering voltage is applied from an external power source to the backing plate (cathode electrode) S15 c. In addition, a predetermined magnetic field may be formed on the target S15b by a magnetron magnetic circuit.
Ions of the sputtering gas are excited by the plasma in the vicinity of the backing plate S15c in the film forming chamber S12, and collide with the target S15b of the cathode electrode S15c to fly out particles of the film forming material. The particles that have flown out are bonded to the reaction gas and then attached to the glass substrate 11, and the particles are laminated on the etching stopper layer 13 with a predetermined composition on the surface of the glass substrate 11 to form the light shielding layer 14.
At this time, during the formation of the phase shift layer 12, a sputtering gas, an oxygen-containing gas, or the like having a predetermined partial pressure is supplied from the gas introduction mechanism S13e, and the partial pressure is controlled to be switched, so that the composition of the phase shift layer 12 is set within a set range. Meanwhile, when the composition is changed in the film thickness direction to form the phase shift layer 12, the respective gas partial pressures in the atmosphere gas may also be changed according to the film thickness of the film formation.
In addition, during the formation of the etching stopper layer 13, a sputtering gas, a nitrogen-containing gas, or the like having a predetermined partial pressure is supplied from the gas introduction mechanism S14e, and the partial pressure of the nitrogen-containing gas is switched so as to be controlled. Thus, the composition of the etching stopper layer 13 is set to a concentration ratio or a concentration that varies in advance.
In particular, as described above, the partial pressure ratio of the nitrogen-containing gas is controlled so that the peak region 13A having a high nitrogen concentration and another region having a nitrogen concentration lower than that of the peak region 13A are formed in the film thickness direction.
Specifically, at the time of forming the molybdenum silicide film, the peak region 13A can be formed by increasing the partial pressure of nitrogen gas from the time of forming the film to a predetermined film thickness such as 2/3 of the film thickness of the etching stopper layer 13 as the film thickness increases.
Meanwhile, in order to set the etching stopping ability in the etching stop layer 13 to a predetermined state, the composition ratio of molybdenum to silicon and the composition ratio of molybdenum to a content other than silicon in the target S14b may be set to a predetermined state. In addition, targets S14b having different composition ratios are preferably selected appropriately.
In addition, during the formation of the light shielding layer 14, nitrogen gas, oxygen-containing gas, or the like having a predetermined partial pressure is supplied from the gas introduction mechanism S15e, and the partial pressure is controlled to be switched, so that the composition of the light shielding layer 14 is set within a set range.
Examples of the oxygen-containing gas include CO 2 (carbon dioxide), O 2 (oxygen), N 2 O (nitrous oxide), NO (nitric oxide), and CO (carbon monoxide).
Examples of the carbon-containing gas include CO 2 (carbon dioxide), CH 4 (methane), C 2H6 (ethane), and CO (carbon monoxide).
Examples of the nitrogen-containing gas include N 2 (nitrogen gas), N 2 O (nitrous oxide), NO (nitric oxide), and NH 3 (ammonia).
In addition, in the film formation of the phase shift layer 12, the etching stop layer 13, and the light shielding layer 14, the targets S13b, S14b, and S15b may be replaced if necessary.
In addition to the formation of the phase shift layer 12, the etching stopper layer 13, and the light shielding layer 14, another film may be stacked over the glass substrate 11. In this case, the following method can be exemplified: this method uses a target corresponding to the material of the film laminated on the glass substrate 11, and sets sputtering conditions such as gas, and forms a film by sputtering. Alternatively, a film may be laminated by a film forming method other than sputtering, to obtain the mask blank 10B of the present embodiment.
Next, film characteristics of the phase shift layer 12, the etching stop layer 13, and the light shielding layer 14, particularly film characteristics of the etching stop layer in the present embodiment will be described.
On the glass substrate 11 for forming a mask, a phase shift layer 12 constituting a chromium compound film is formed using a sputtering method or the like. The chromium compound film formed here is preferably a film containing chromium, oxygen, nitrogen, carbon, or the like. By controlling the composition and film thickness of chromium, oxygen, nitrogen, and carbon contained in the film at this time, the phase shift layer 12 having a desired transmittance and phase can be formed.
Next, a molybdenum silicide compound film serving as the etching stopper layer 13 is formed by a sputtering method or the like. The molybdenum silicide compound film formed here is preferably a film containing molybdenum, silicon, oxygen, nitrogen, carbon, or the like.
Then, a chromium compound film serving as the light shielding layer 14 is formed by a sputtering method or the like. The chromium compound film formed here is preferably a film containing chromium, oxygen, nitrogen, carbon, or the like.
By forming the mask blank 10B of such a film structure, the phase shift mask 10 in which the phase shift layer 12 and the light shielding layer 14 are formed of a chromium compound can be formed.
When the etching stopper layer 13 is formed using a molybdenum silicide film, etching needs to be performed using an etching solution containing fluoric acid. Therefore, it is necessary to reduce the influence of etching on the glass substrate 11. Therefore, it is preferable to accelerate the etching rate (e.r.) in the molybdenum silicide film as much as possible and use it.
Fig. 12 shows the relationship between the nitrogen concentration and the etching rate in the film when molybdenum silicide film is formed using molybdenum silicide targets having different target compositions. As is clear from fig. 12, by using a molybdenum silicide target having a small silicon composition among target compositions, a molybdenum silicide film having a high etching rate can be formed.
Further, as for the molybdenum silicide target, a target of a desired composition ratio can be formed by mixing MoSi 2, which is a crystal of molybdenum silicide, with a material of Si.
Here, if silicon above a constant is not present in excess of MoSi 2, it is difficult to form a target with stable composition.
In contrast, the present inventors found that if the silicon composition is increased until the composition ratio of molybdenum to silicon is 1:2.3, a target having a relatively high density can be stably formed. Therefore, by using a target having a composition ratio of molybdenum silicide of 1:2.3, a high-density target can be used while suppressing etching of the glass substrate 11.
Thus, the mask blank 10B suitable for producing the phase shift mask 10 with reduced influence of defects can be manufactured as a product.
These manufacturing conditions and film characteristics in the etching stopper layer 13 were verified.
First, a molybdenum silicide film was formed as the etching stopper layer 13 using a target having a composition ratio of molybdenum to silicon of 1:2.3, and the molybdenum silicide film was formed by changing the flow rates of argon and nitrogen at the time of film formation.
In the manufacturing process of the phase shift mask 10, a chemical liquid such as an acid or an alkali is generally used, but it is necessary to suppress the transmittance change in the process.
The present inventors have found that by increasing the nitrogen concentration of the molybdenum silicide film, the resistance to chemical liquids to acids and bases is improved.
Thus, as the mask blank 10B, a peak region 13A made of a molybdenum silicide film having a high nitrogen concentration is formed at the interface between the light shielding layer 14 and the etching stopper layer 13. As the mask blank 10B, a molybdenum silicide film having a low nitrogen concentration is used in a portion of the etching stopper layer 13 below the peak region 13A (a portion close to the glass substrate 11).
Thus, the etching time of the etching stopper film can be shortened, and the influence of the contact between the glass substrate 11 and the etching liquid can be reduced, thereby forming the etching stopper film having high chemical liquid resistance.
Further, the present inventors have found that the etching stopper layer 13, which forms a molybdenum silicide film having a high nitrogen concentration on the surface, has a high etching stopper function with less penetration of an etching liquid or the like when the light shielding layer 14 as a chromium film is etched.
Therefore, it is preferable to use a molybdenum silicide film having a high nitrogen concentration as much as possible for the etching stopper layer 13.
Therefore, by forming the peak region 13A as a molybdenum silicide film having a high nitrogen concentration on the upper layer of the etching stopper layer 13, the following effects are also obtained: that is, when etching the light shielding layer 14, penetration of the etching liquid is suppressed in the vicinity of the interface between the light shielding layer 14 and the etching stopper layer 13.
Further, the inventors examined the relationship between the etching rate and sheet resistance of the molybdenum silicide film, and as a result, found that if the sheet resistance becomes low, the etching rate of the molybdenum silicide film is accelerated.
It is found that an etching stopper layer having a high etching rate can be formed by using a molybdenum silicide film having a resistivity of 1.0X10 -3. OMEGA cm or less as the etching stopper layer. It has also been found that electrostatic breakdown can be suppressed by using a molybdenum silicide film having low resistivity.
In the case of using a molybdenum silicide film as the etching stopper layer 13, a target in which the ratio of molybdenum to silicon is 1:3 or less is used. A nitrogen-containing gas is used as an atmosphere gas in sputtering. By controlling the partial pressure of the nitrogen-containing gas, a peak region 13A having a nitrogen concentration of 30% or more is formed at the interface between the light shielding layer 14 and the etching stopper layer 13. The nitrogen concentration in the lower portion of the peak region 13A on the glass substrate 11 side is 25% or less.
The film thickness of the etching stopper layer 13 as a molybdenum silicide film is 10nm to 100nm, and the specific resistance of the lower portion of the peak region 13A on the glass substrate 11 side is 1.0×10 -3 Ω cm. By using such a molybdenum silicide film as the etching stopper layer 13, the phase shift mask 10 having a good cross-sectional shape and less influence on etching of the glass substrate 11 can be formed.
Examples (example)
Next, examples according to the present invention will be described.
In addition, a verification test will be described as a specific example of the etching stopper layer 13 in the present invention.
< Example >
As example 1, a molybdenum silicide compound film was formed as an etching stop layer on a glass substrate using a sputtering method or the like. The molybdenum silicide compound film formed here is a film containing molybdenum, silicon, oxygen, nitrogen, carbon, or the like. The film was subjected to composition evaluation by auger electron spectroscopy.
The results are shown in fig. 13.
As shown in fig. 13, it was confirmed that a peak region with a high nitrogen concentration was formed on the left side of the figure.
Next, in sputtering for forming a molybdenum silicide compound film, a target having a ratio of molybdenum to silicon of 1:2.3 is used, and a nitrogen partial pressure is changed within 0 to 100% to perform film formation.
The atmosphere gas during sputtering was carbon dioxide or argon in addition to nitrogen.
As examples 1 to 4, the composition ratio, the etching rate of molybdenum silicon, and the ratio of the etching rate to the etching rate of glass were measured.
The results are shown in Table 1.
Also, in sputtering for forming a molybdenum silicide compound film, a target having a molybdenum to silicon ratio of 1:3.7 is used, and the partial pressure of nitrogen is varied within 0 to 100% to perform film formation.
The atmosphere gas during sputtering was carbon dioxide or argon in addition to nitrogen.
As examples 5 to 8, the composition ratio, the etching rate of molybdenum silicon, and the ratio of the etching rate to the etching rate of glass were measured.
The results are shown in Table 1.
In examples 1 to 8, the relationship between the etching rate and the sheet resistance of the molybdenum silicide film was examined.
From these results, it was found that the nitrogen concentration in the molybdenum silicide film can be controlled by the partial pressure of nitrogen gas at the time of film formation. Further, by sputtering using a mosi2.3 target having a composition ratio of Si/mo=2.3, a molybdenum silicide film having low resistivity can be formed. Thus, it was found that the influence of electrostatic breakdown can be reduced.
Further, it was revealed that by using a stacked structure of a molybdenum silicide film having a high nitrogen concentration and a molybdenum silicide film having a low nitrogen concentration, a molybdenum silicide film suitable for use in a phase shift mask can be formed, and the molybdenum silicide film has a favorable cross-sectional shape and can shorten the etching time.
Further, it is known that the chemical resistance to acids and bases is improved by increasing the nitrogen concentration of the molybdenum silicide film. It is known that an etching stopper film using a molybdenum silicide film having a high nitrogen concentration has a high etching stopper function with less penetration of an etching solution or the like during etching of a chromium film. As a result of examining the relationship between the etching rate of the molybdenum silicide film and the sheet resistance, it was found that if the sheet resistance was low, the etching rate of the molybdenum silicide film was increased. It has also been found that the use of a molybdenum silicide film having a low resistivity can suppress electrostatic breakdown.
The present inventors have completed the present invention based on these circumstances. Thus, a mask having a good cross-sectional shape and less influence on etching of the glass substrate can be formed
Description of the reference numerals
10 … Phase shift mask
10B … mask blank
10L … light-transmitting region
10P1 … Exposure region
10P2 … phase shift region
11 … Glass substrate (transparent substrate)
12 … Phase shift layer
12P1 … phase shift pattern
13 … Etch stop layer
13P1, 13P2 … etch stop pattern
14 … Light shielding layer
14P1, 14P2 … light shielding pattern
15 … Photoresist layer
15P1, 15P2 … resist pattern

Claims (18)

1. A mask blank having a layer that becomes a phase shift mask, the mask blank having:
A phase shift layer laminated on the transparent substrate;
an etch stop layer disposed at a position farther from the transparent substrate than the phase shift layer; and
A light shielding layer provided at a position farther from the transparent substrate than the etching stopper layer,
The phase-shift layer contains chromium and,
The light-shielding layer contains chromium and oxygen,
The etching stop layer contains molybdenum silicide and nitrogen, and has a peak region where the nitrogen concentration reaches a peak at a position close to the light shielding layer in the film thickness direction,
The nitrogen concentration in the peak region of the etching stopper layer is set to 30 atomic% or more.
2. The mask blank according to claim 1, wherein,
The etching stop layer has the peak region on an upper surface close to the light shielding layer in a film thickness direction.
3. The mask blank according to claim 1, wherein,
The resistivity in the peak region of the etching stopper layer is set to 1.0×10 -3 Ω cm or more.
4. The mask blank according to claim 2, wherein,
The resistivity in the peak region of the etching stopper layer is set to 1.0×10 -3 Ω cm or more.
5. The mask blank according to any one of claims 1 to 4, wherein,
The silicon concentration in the peak region of the etch stop layer is set to 35 atomic% or less.
6. The mask blank according to any one of claims 1 to 4, wherein,
The molybdenum concentration in the peak region of the etching stopper layer is set to 30 at% or less.
7. The mask blank according to any one of claims 1 to 4, wherein,
The film thickness of the peak region is set to a range of 1/3 or less of the film thickness of the etching stop layer.
8. The mask blank according to any one of claims 1 to 4, wherein,
The resistivity of the etching stopper layer other than the peak region is set to 1.0X10 -3. OMEGA cm or less.
9. The mask blank according to any one of claims 1 to 4, wherein,
The nitrogen concentration of the etching stop layer other than the peak region is set to 25 atomic% or less.
10. The mask blank according to any one of claims 1 to 4, wherein,
The composition ratio of molybdenum to silicon of the etching stop layer other than the peak region is set to 1.ltoreq.Si/Mo.
11. The mask blank according to any one of claims 1 to 4, wherein,
The film thickness of the etching stop layer is set to be in the range of 10nm to 100 nm.
12. A method of manufacturing the mask blank according to any one of claims 1 to 11, comprising:
A phase shift layer forming step of laminating the phase shift layer containing chromium on the transparent substrate;
An etching stop layer forming step of stacking the etching stop layer containing molybdenum silicide and nitrogen at a position farther from the transparent substrate than the phase shift layer; and
A light shielding layer forming step of laminating the light shielding layer containing chromium and oxygen at a position farther from the transparent substrate than the etching stopper layer,
In the etching stop layer forming step, the etching stop layer is formed by controlling the nitrogen concentration in the peak region in the film thickness direction by setting the partial pressure of the nitrogen-containing gas as the supply gas during sputtering.
13. The method for manufacturing a mask blank according to claim 12, wherein,
In the etching stop layer forming step, the sheet resistance in the etching stop layer is increased with an increase in nitrogen content by setting the partial pressure of the nitrogen-containing gas.
14. The method for manufacturing a mask blank according to claim 13, wherein,
In the etching stop layer forming step, the peak region is formed by setting the partial pressure ratio of the nitrogen-containing gas to a range of 30% or more.
15. The method for manufacturing a mask blank according to claim 14, wherein,
In the etching stop layer forming step, the nitrogen-containing gas is N 2.
16. The method for manufacturing a mask blank according to any one of claims 12 to 15, wherein,
In the etching stopper layer forming step, a target in which the composition ratio of molybdenum to silicon is set to 2.3.ltoreq.Si/Mo.ltoreq.3.0 is used.
17. A phase shift mask fabricated from the mask blank of any one of claims 1 to 11.
18. A method for manufacturing a phase shift mask according to claim 17, comprising:
a phase shift pattern forming step of forming a pattern on the phase shift layer;
An etching stop pattern forming step of forming a pattern on the etching stop layer; and
A light shielding pattern forming step of forming a pattern on the light shielding layer,
The phase shift pattern forming step and the light shielding pattern forming step are performed with different etching solutions from each other.
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