JP6407582B2 - Manufacturing method of substrate, manufacturing method of substrate with multilayer reflective film, manufacturing method of mask blank, manufacturing method of transfer mask, and substrate processing apparatus - Google Patents

Description

  The present invention relates to a method for producing a substrate, a method for producing a substrate with a multilayer reflective film using the substrate, a method for producing a mask blank using the substrate or the substrate with a multilayer reflective film, and a transfer mask using the mask blank. The present invention relates to a manufacturing method and a substrate processing apparatus.

  As a mask blank used in the semiconductor design rule 1x generation (half pitch (hp) 14 nm, 10 nm, 7 nm, etc.), a reflective mask blank for EUV exposure, a binary mask blank for ArF excimer laser exposure, and a phase shift mask blank, There is also a nanoimprint mask blank.

  In the mask blank used in the semiconductor design rule 1x generation, a defect of 30 nm class (defect of SEVD of 21.5 nm or more and 34 nm or less) or a defect having a smaller size may be a problem. For this reason, it is preferable that the main surface of the substrate used for the mask blank (that is, the surface on the side where the transfer pattern is formed) has as few as possible 30 nm-class defects. Further, in a high-sensitivity defect inspection apparatus that performs defect inspection of 30 nm-class defects, the surface roughness affects background noise. That is, if the smoothness is insufficient, a large number of pseudo defects due to surface roughness are detected, and defect inspection cannot be performed. For this reason, the main surface of the substrate used for the mask blank used in the semiconductor design rule 1x generation is required to have a smoothness of Root Mean Square Roughness (Rms) of 0.10 nm or less, more preferably 0.08 nm or less. It has been.

  In recent years, with the increase in capacity and density of magnetic recording media used in hard disk drives (HDDs), the flying height of the recording / reading magnetic head with respect to the magnetic recording media has become even lower. Yes. In order to realize a low flying height, a magnetic head equipped with a DFH (Dynamic Flying Height) mechanism is widely used. In a magnetic head equipped with a DFH mechanism, a flying height is controlled to be constant by disposing a thermal expansion body on the magnetic head and heating and expanding the thermal expansion body.

  In a magnetic head equipped with a DFH mechanism, the flying height is controlled to about several nanometers, so that defects such as head crashes are likely to occur. In order to reduce such defects, the main surface of the substrate used for the magnetic recording medium (the surface on the side on which the magnetic layer containing the magnetic material is formed) is highly smooth and has no protrusions protruding from the main surface. The state is preferred. When the magnetic layer is formed on both the upper surface and the lower surface of the magnetic recording medium, both surfaces become the main surface.

  Various processing methods have been proposed so far in order to make the main surface of a mask blank substrate or a magnetic recording medium substrate have a high smoothness, a low defect, and no protrusions. It was difficult to realize a substrate having a main surface satisfying the above.

  In recent years, a processing method using catalyst-based etching (CARE) has been proposed as a substrate processing method that requires high smoothness, low defects, and no protrusions on the main surface. In catalyst-based etching (CARE) processing, a hydroxyl group is generated as an active species from a molecule in a processing fluid adsorbed on a processing reference surface formed from a catalyst substance, and the active species approaches or contacts the processing reference surface. It is considered that the fine convex portions on the surface undergo a hydrolysis reaction and the fine convex portions are selectively removed. Patent Document 1 describes a processing method by catalyst-based etching using a metal catalyst.

  In Patent Document 1, in the presence of water, the processing reference surface of the catalyst substance is brought into contact with or close to the surface of the workpiece made of a solid oxide such as glass, and the processing reference surface and the surface of the workpiece are moved relative to each other. In addition, a solid oxide processing method is described in which a hydrolysis product is removed from the surface of the workpiece, and the surface of the workpiece is processed (hereinafter, the solid oxide processing method is also referred to as a CARE processing method). Called). As the catalyst material, a material containing a metal element and having an electron d orbit near the Fermi level is used. Specifically, as the metal element, for example, platinum (Pt), gold (Au), silver ( Ag), copper (Cu), nickel (Ni), chromium (Cr), and molybdenum (Mo).

  In CARE processing, a catalyst surface plate is used in which a processing reference surface made of a catalyst material is provided on the surface facing the processing surface. Generally, the processing reference surface has a film-like configuration provided on the surface of the base material or a bulk-like configuration formed by processing a bulk material. In particular, in CARE processing of a glass substrate, a processing reference surface is usually formed by vapor deposition, sputtering, electroplating, or the like of a catalyst material on the surface of a pad that is inexpensive and has good shape stability.

If the processing reference surface is brittle or soft, the processing reference surface may be peeled off during CARE processing, and the substrate surface may be damaged. Further, when the processing reference surface is peeled off, the peeled portion loses the function as a catalyst, and there is a possibility that uniform and stable processing of the substrate surface cannot be performed. For this reason, in order to stably manufacture a substrate having a highly smooth and low-defect surface by CARE processing, it is preferable to use a processing reference surface having good mechanical durability (not brittle or hard).
Further, if the processing reference surface is rusted by the processing fluid during the CARE processing, the rusted portion may lose its function as a catalyst, and the substrate surface may not be uniformly and stably processed. Further, when the processing reference surface is rusted, the processing reference surface becomes brittle, and as described above, the substrate surface may be damaged. For this reason, in order to stably manufacture a substrate having a highly smooth and low-defect surface by CARE processing, it is preferable to use a processing reference surface having good chemical stability (not easily rusted by the processing fluid). .
Further, if the surface state of the processing reference surface is rough, a minute region of the processing reference surface may be peeled off during the CARE processing, and the substrate surface may be damaged or the substrate surface may not be uniformly processed. Further, the roughness of the surface state of the processing reference surface is transferred to the substrate surface, and the smoothness of the substrate surface may be impaired. For this reason, in order to stably manufacture a substrate having a highly smooth and low defect surface by CARE processing, it is preferable to use a flat processing reference surface.
In addition, if the oxidation of the processing reference surface progresses during CARE processing, the catalytic function of the processing reference surface changes, so the processing rate during CARE processing changes, the processing time does not become constant, and the throughput, manufacturing cost, etc. There is a possibility that stable processing cannot be performed on the surface. For this reason, in order to stably manufacture a substrate having a highly smooth and low-defect surface by CARE processing, it is preferable to use a processing reference surface on which oxidation does not proceed easily.
Further, when the processing reference surface has a film-like configuration, it is preferable to form the processing reference surface with a catalyst material that is easy to form a film, and when the processing reference surface has a bulk-like configuration, a catalyst that is easy to process. It is preferable to form the processing reference surface with a substance.
Further, there is a possibility that the catalyst material that forms the processing reference surface remains on the substrate surface after the CARE processing. If the catalyst material remains on the substrate surface, defects due to the remaining catalyst material may occur. Therefore, in order to remove the catalyst substance remaining on the substrate surface, it is necessary to clean the substrate surface after CARE processing. At this time, if a cleaning liquid that damages the substrate surface (impairs the smoothness) is used, the smoothness of the substrate surface is impaired. For this reason, in order to manufacture a substrate having a highly smooth and low-defect surface by CARE processing, the processing reference surface is made of a catalytic substance that does not damage the substrate surface (does not impair smoothness) and is easily dissolved in a cleaning solution. It is preferable to form.
It is preferable that the processing reference surface has the above characteristics.

International Publication No. 2013/084934

However, when the processing reference surface is formed of a single metal, only the characteristics of the metal can be obtained on the processing reference surface, and mechanical durability and chemical stability may be insufficient. If the mechanical durability is insufficient, as described above, the processing reference surface may be peeled off during CARE processing, and the substrate surface may be damaged. Further, if the processing reference surface is peeled off, there is a possibility that uniform and stable processing of the substrate surface cannot be performed. Further, if the chemical stability is insufficient, as described above, the processing reference surface may rust during CARE processing, and the substrate surface may not be uniformly and stably processed. Moreover, if the processing reference surface is rusted, it becomes brittle and may damage the substrate surface.
Further, when the processing reference surface is crystalline, surface roughness (uneven shape) caused by the crystal grain boundary is generated on the processing reference surface, and the flatness of the processing reference surface is lost. For this reason, as described above, there is a problem that uniform and stable processing of the substrate surface may not be possible. Further, there is a problem that the roughness (uneven shape) of the surface state of the processing reference surface is transferred to the substrate surface and the smoothness of the substrate surface may be impaired.

  For this reason, the present invention has been made in view of the above-described problems, and a substrate manufacturing method capable of stably manufacturing a substrate having a main surface with high smoothness and low defects, and this substrate. To provide a method for manufacturing a substrate with a multilayer reflective film, a method for manufacturing a mask blank using the substrate or a substrate with a multilayer reflective film, a method for manufacturing a transfer mask using the mask blank, and a substrate processing apparatus. Objective.

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

(Configuration 1) a substrate preparation step of preparing a substrate having a main surface made of a material containing an oxide;
A substrate processing step of processing the main surface by catalytic reference etching in a state in which a processing reference surface of a catalytic substance is brought into contact with or close to the main surface and a processing fluid is interposed between the processing reference surface and the main surface Including
The catalyst material includes an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and oxygen, nitrogen, and A method for producing a substrate, comprising a material selected from the group consisting of alloy compounds containing at least one component of carbon.

(Structure 2) The method of manufacturing a substrate according to Structure 1, wherein the alloy compound is an oxide, nitride, carbide, oxynitride, oxycarbide, nitride carbide, or oxynitride carbide of the alloy. .

(Configuration 3) a substrate preparation step of preparing a substrate having a main surface made of a material containing an oxide;
A substrate processing step of processing the main surface by catalytic reference etching in a state in which a processing reference surface of a catalytic substance is brought into contact with or close to the main surface and a processing fluid is interposed between the processing reference surface and the main surface Including
The catalyst material includes an alloy containing at least one of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and an alloy compound containing nitrogen in the alloy. And the manufacturing method of the board | substrate characterized by including the material of the amorphous structure selected from the group which consists of the metal compound in which nitrogen was contained in the said metal.

(Structure 4) The method for manufacturing a substrate according to Structure 3, wherein the alloy compound is a nitride of the alloy.

(Structure 5) The method for manufacturing a substrate according to Structure 3, wherein the metal compound is a nitride of the metal.

(Configuration 6) a substrate preparation step of preparing a substrate having a main surface made of a material containing an oxide;
A substrate processing step of processing the main surface by catalytic reference etching in a state in which a processing reference surface of a catalytic substance is brought into contact with or close to the main surface and a processing fluid is interposed between the processing reference surface and the main surface Including
The catalyst material includes an alloy compound in which carbon is contained in an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and A method for producing a substrate, comprising a material selected from the group consisting of metal compounds containing carbon in the metal.

(Structure 7) The substrate manufacturing method according to structure 6, wherein the alloy compound is a carbide, oxide carbide, nitride carbide, or oxynitride carbide of the alloy.

(Structure 8) The method for manufacturing a substrate according to Structure 6, wherein the metal compound is a carbide, oxide carbide, nitride carbide, or oxynitride carbide of the metal.

(Structure 9) The substrate processing step is characterized in that the main surface is processed by catalyst reference etching by relatively moving the catalyst surface and the main surface. Substrate manufacturing method.

(Structure 10) Manufacture of a substrate according to any one of Structures 1 to 9, wherein a main surface of the substrate prepared in the substrate preparation step has a root mean square roughness of 0.3 nm or less. Method.

(Structure 11) The substrate manufacturing method according to any one of structures 1 to 10, wherein the substrate is made of a glass material.

(Structure 12) The substrate manufacturing method according to any one of Structures 1 to 11, wherein the processing fluid comprises a solvent that is not normally soluble in the substrate.

(Structure 13) The substrate manufacturing method according to structure 12, wherein the processing fluid is made of pure water.

(Structure 14) The method for manufacturing a substrate according to any one of structures 1 to 13, wherein the substrate is a mask blank substrate.

(Structure 15) A method for producing a substrate with a multilayer reflective film, comprising forming a multilayer reflective film on a main surface of the substrate obtained by the method for producing a substrate according to Structure 14.

(Configuration 16) Multilayer reflection film of substrate with multilayer reflection film obtained by manufacturing method of substrate with multilayer reflection film according to configuration 15 on main surface of substrate obtained by method of manufacturing substrate according to configuration 14 A method of manufacturing a mask blank, comprising forming a transfer pattern thin film on the top.

(Structure 17) A transfer mask manufacturing method, wherein a transfer pattern is formed by patterning a transfer pattern thin film of a mask blank obtained by the mask blank manufacturing method described in Structure 16.

(Configuration 18) A substrate processing apparatus for processing a main surface of a substrate by catalyst-based etching,
Substrate support means for supporting a substrate having a main surface made of a material containing an oxide;
A substrate surface creation means having a processing reference surface of the catalyst material;
Processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface;
Drive means for bringing the processing reference surface into contact with or approaching the main surface in a state where a processing fluid is interposed between the processing reference surface and the main surface;
The catalyst material includes an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and oxygen, nitrogen, and A substrate processing apparatus comprising a material selected from the group consisting of an alloy compound containing at least one component of carbon.

(Configuration 19) A substrate processing apparatus for processing a main surface of a substrate by catalyst-based etching,
Substrate support means for supporting a substrate having a main surface made of a material containing an oxide;
A substrate surface creation means having a processing reference surface of the catalyst material;
Processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface;
Drive means for bringing the processing reference surface into contact with or approaching the main surface in a state where a processing fluid is interposed between the processing reference surface and the main surface;
The catalyst material includes an alloy containing at least one of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and an alloy compound containing nitrogen in the alloy. And the substrate processing apparatus characterized by including the material of the amorphous structure selected from the group which consists of the metal compound in which nitrogen was contained in the said metal.

(Configuration 20) A substrate processing apparatus for processing a main surface of a substrate by catalyst-based etching,
Substrate support means for supporting a substrate having a main surface made of a material containing an oxide;
A substrate surface creation means having a processing reference surface of the catalyst material;
A processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface of the substrate;
Drive means for bringing the processing reference surface into contact with or approaching the main surface in a state where a processing fluid is interposed between the processing reference surface and the main surface;
The catalyst material includes an alloy compound in which carbon is contained in an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and A substrate processing apparatus comprising a material selected from the group consisting of metal compounds containing carbon in the metal.

(Structure 21) The substrate processing apparatus according to any one of Structures 18 to 20, further comprising a relative motion unit configured to relatively move the processing reference surface and the main surface.

  As described above, according to the substrate manufacturing method of the present invention, the processing reference surface of the catalytic substance is brought into contact with or close to the main surface of the substrate, and the processing fluid is interposed between the processing reference surface and the main surface. In this state, the main surface is processed by catalyst-based etching. At that time, as a catalyst substance, an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and oxygen, nitrogen And an alloy compound containing at least one component of carbon. When such an alloy or alloy compound is used, the mechanical durability and chemical stability of the processing reference surface can be improved. When the mechanical durability of the processing reference surface is improved, the processing reference surface is peeled off during CARE processing, and the possibility that the main surface of the substrate is damaged or the peeled portion loses its function as a catalyst is reduced. In addition, when the chemical stability of the processing reference surface is improved, the processing reference surface is rusted by the processing fluid during CARE processing, the rusted part loses its function as a catalyst, or the rusted part is peeled off, and the main surface of the substrate is removed. The risk of damaging is reduced. For this reason, a substrate having a main surface with high smoothness and low defects can be stably manufactured by CARE processing.

  Further, according to another substrate manufacturing method of the present invention, the catalyst substance is at least one of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium. An amorphous alloy containing metal, an amorphous alloy compound containing nitrogen in this alloy, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium A metal compound having an amorphous structure in which nitrogen is contained in a simple metal is used. When such an amorphous structure alloy, alloy compound, or metal compound is used, the smoothness of the processing reference surface can be improved. When the smoothness of the processing reference surface is improved, many portions of the processing reference surface can be brought close to or in contact with the main surface of the substrate during the CARE processing. In addition, the surface shape of the processing reference surface is transferred to the main surface of the substrate. For this reason, a substrate having a main surface with high smoothness and low defects can be stably manufactured by CARE processing.

  According to still another substrate manufacturing method of the present invention, the catalyst substance is at least one of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium. Alloys containing carbon in an alloy containing two metals and metals containing carbon in metals such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium Use compounds. When such a processing reference surface containing an alloy compound or metal compound containing carbon is used, the toughness of the processing reference surface can be improved. When the toughness of the processing reference surface is improved, the durability of the processing reference surface is improved. For this reason, a substrate having a main surface with high smoothness and low defects can be stably manufactured by CARE processing.

  Further, according to the method for manufacturing a substrate with a multilayer reflective film according to the present invention, it is possible to prevent deterioration of characteristics due to substrate factors, and it is possible to manufacture a substrate with a multilayer reflective film having desired characteristics.

  Moreover, according to the mask blank manufacturing method of the present invention, it is possible to prevent deterioration of characteristics due to substrate factors, and it is possible to manufacture a mask blank having desired characteristics.

  In addition, according to the method for manufacturing a transfer mask according to the present invention, it is possible to prevent deterioration of characteristics due to substrate factors, and it is possible to manufacture a transfer mask having desired characteristics.

  Further, according to the substrate processing apparatus of the present invention, the substrate support means for supporting the substrate having the main surface made of the oxide-containing material, the substrate surface creation means having the processing reference surface of the catalytic substance, and the processing reference surface A processing fluid supply means for supplying a processing fluid between the main surface and the processing fluid supply means, and a driving means for bringing the processing reference surface into contact with or approaching the main surface in a state where the processing fluid is interposed between the processing reference surface and the main surface. It has. At that time, as a catalyst substance, an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and oxygen, nitrogen And an alloy compound containing at least one component of carbon. For this reason, as described above, the main surface of the substrate can be stably processed in a highly smooth and low defect state by CARE processing.

  Further, according to another substrate processing apparatus according to the present invention, as a catalyst substance, at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium is used. Amorphous alloy containing nitrogen, amorphous alloy compound with nitrogen contained in this alloy, such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium An amorphous metal compound containing nitrogen in the metal is used. For this reason, as described above, the main surface of the substrate can be stably processed in a highly smooth and low defect state by CARE processing.

  According to yet another substrate processing apparatus of the present invention, the catalyst material is at least one of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium. Alloy compounds containing carbon in alloys containing metals and metal compounds containing carbon in metals such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium Is used. For this reason, as described above, the main surface of the substrate can be stably processed in a highly smooth and low defect state by CARE processing.

It is a fragmentary sectional view which shows the structure of the board | substrate processing apparatus which performs the process by a catalyst reference | standard etching with respect to the main surface of a board | substrate. It is a top view which shows the structure of the board | substrate processing apparatus which performs the process by a catalyst reference | standard etching with respect to the main surface of a board | substrate.

  Hereinafter, a method for manufacturing a substrate according to an embodiment of the present invention, a method for manufacturing a substrate with a multilayer reflective film using the substrate, a method for manufacturing a mask blank using the substrate or a substrate with a multilayer reflective film, The manufacturing method of the used transfer mask and the substrate processing apparatus will be described in detail.

Embodiment 1 FIG.
In Embodiment 1, a substrate manufacturing method and a substrate processing apparatus will be described.

In the first embodiment, a substrate preparation step for preparing a substrate having a main surface made of an oxide-containing material, and a processing reference surface of the catalytic substance is brought into contact with or close to the main surface of the substrate, so that the processing reference surface and the main surface are obtained. A substrate is manufactured by a substrate processing step in which the main surface of the substrate is processed by catalyst-based etching with a processing fluid interposed therebetween.
Hereinafter, each process will be described in detail.

1. Substrate Preparation Step In the substrate manufacturing method, first, a substrate having a main surface made of a material containing an oxide is prepared.

The substrate to be prepared is, for example, a substrate made of a material containing an oxide as a whole, a substrate in which a thin film made of a material containing an oxide is formed on an upper surface used as a main surface, or both an upper surface and a lower surface used as a main surface A substrate on which a thin film made of a material containing an oxide is formed.
The substrate on which the thin film is formed may be a substrate in which a thin film made of a material containing oxide is formed on an upper surface or a lower surface used as a main surface of a substrate body made of a material containing oxide. The board | substrate with which the thin film which consists of a material containing an oxide was formed in the upper surface used as a main surface of the board | substrate main body which consists of materials other than the lower surface, and a lower surface may be sufficient.
Examples of the material of the substrate and the substrate body made of a material containing an oxide include glass such as synthetic quartz glass, soda lime glass, borosilicate glass, aluminosilicate glass, SiO ₂ —TiO ₂ glass, and glass ceramics. . Moreover, silicon, carbon, and a metal are mentioned as a material of the board | substrate body which consists of other than the material containing an oxide.
Examples of the oxide that forms the thin film include silicon oxide, metal oxide, and alloy oxide. Specifically, as the silicon oxide, silicon oxide (SiO _x , x> 0) or metal silicide oxide containing metal and silicon (Me _x Si _y O _z , Me: metal, x> 0, y > 0, and z> 0). Examples of the metal oxide include tantalum oxide (TaO _x , x> 0), chromium oxide (CrO _x , x> 0), ruthenium oxide (RuO _x , x> 0), titanium oxide (TiO _x , X> 0). As the alloy oxide, tantalum boron oxide _{(Ta x B y O z,} x, y, z> 0), tantalum hafnium oxide _{(Ta x Hf y O z,} x, y, z> 0), tantalum chromium oxide _{(Ta x Cr y O z,} x, y, z> 0) and the like. A thin film made of a material containing such an oxide can be formed by, for example, vapor deposition, sputtering, or electroplating.
In addition, the above-described oxide may contain elements such as nitrogen, carbon, hydrogen, fluorine and the like without departing from the effects of the present invention.
The substrate to be prepared is preferably a glass substrate that is difficult to be plastically deformed and easily obtains a highly smooth main surface, or an upper surface or a lower surface that is the main surface of the glass substrate body, and silicon oxide (SiO _x , x> 0). Is a substrate on which a thin film is formed.

The substrate to be prepared may be a mask blank substrate or a magnetic recording medium substrate. The mask blank substrate may be used for manufacturing any of a reflective mask blank, a binary mask blank, a phase shift mask blank, and a nanoimprint mask blank. In the binary mask blank, the material of the light shielding film may be any of MoSi, Ta, and Cr. The phase shift mask blank may be any of a halftone type phase shift mask blank, a Levenson type phase shift mask blank, and a chromeless type phase shift mask blank. The substrate material used for the reflective mask blank needs to be a material having low thermal expansion. For this reason, the substrate material used for the reflective mask blank for EUV exposure is preferably, for example, SiO ₂ —TiO ₂ glass. Further, the substrate material used for the transmissive mask blank needs to be a material having translucency with respect to the exposure wavelength to be used. For this reason, as a substrate material used for the binary mask blank and the phase shift mask blank for ArF excimer laser exposure, for example, synthetic quartz glass is preferable. In addition, the substrate material used for the magnetic recording medium substrate needs to be chemically strengthened after the polishing step in order to improve impact resistance, strength and rigidity. For this reason, the substrate material used for the magnetic disk substrate is preferably, for example, a multicomponent glass such as borosilicate glass or aluminosilicate glass.

  The substrate to be prepared is preferably a substrate whose main surface has been polished using fixed abrasive grains, loose abrasive grains, or the like. For example, the upper and lower surfaces used as the main surface are polished using the following processing method so as to have predetermined smoothness and flatness. Even when the lower surface is not used as the main surface, the lower surface is also polished using the following processing method as necessary so as to have predetermined smoothness and flatness. However, it is not necessary to perform all the following processing methods, and it is performed by selecting appropriately so as to have predetermined smoothness and flatness.

As a processing method for reducing the surface roughness, for example, there are polishing and lapping using abrasive grains such as cerium oxide and colloidal silica.
As processing methods for improving the flatness, for example, magneto-rheological fluid polishing (Magneto Rheological Finishing: MRF), local chemical mechanical polishing (LCMP), gas cluster ion beam etching (Gas Cluster Ion Beam etching). : GCIB), and dry chemical planarization (DCP) using local plasma etching.
MRF is a local processing method in which a magnetic polishing slurry obtained by mixing a polishing slurry in a magnetic fluid is brought into contact with a workpiece at high speed and polishing is performed locally by controlling the residence time of the contact portion.
In LCMP, a polishing slurry containing abrasive grains such as a small-diameter polishing pad and colloidal silica is used. By controlling the residence time of the contact portion between the small-diameter polishing pad and the workpiece, the surface of the workpiece is mainly projected. This is a local processing method for polishing a portion.
GCIB generates gas cluster ions by ejecting a gaseous reactive substance (source gas) at room temperature and normal pressure while adiabatic expansion in a vacuum device, and ionizing it by electron irradiation. This is a local processing method in which ions are accelerated by a high electric field to form a gas cluster ion beam, which is irradiated to a workpiece to be etched.
DCP is a local processing method in which dry etching is locally performed by locally performing plasma etching and controlling the amount of plasma etching according to the degree of convexity.
In order to improve the surface roughness damaged by the above-described processing method for improving the flatness, as a processing method for improving the surface roughness while maintaining the flatness as much as possible, for example, float polishing, EEM (Elastic Emission Machining), hydroplane polishing.

  In order to shorten the processing time by the catalyst reference etching, it is preferable that the main surface of the substrate to be prepared has a root mean square roughness (Rms) of 0.3 nm or less, more preferably 0.15 nm or less.

2. Substrate processing step Next, the processing surface of the catalyst material is brought into contact with or close to the main surface of the substrate, and the main surface is processed by catalyst-based etching with a processing fluid interposed between the processing reference surface and the main surface. To do.
When both the upper surface and the lower surface of the substrate are used as the main surface, the lower surface CARE processing may be performed after the upper surface CARE processing, or the upper surface CARE processing may be performed after the lower surface CARE processing. CARE processing on both sides of the lower surface may be performed simultaneously. Even if the lower surface is not used as the main surface, the lower surface is also processed by catalyst-based etching as necessary. When CARE processing is also performed on the lower surface that is not used as the main surface, the upper surface used as the main surface is required to have high quality in terms of defect quality. It is preferable to perform processing.

  In this case, first, a processing reference surface made of a catalyst material is disposed so as to face the main surface of the substrate. Then, a processing fluid is supplied between the processing reference surface and the main surface, and in a state where the processing fluid is interposed between the processing reference surface and the main surface, the processing reference surface is brought into contact with or close to the main surface, While applying a predetermined load (processing pressure) to the substrate, the processing reference surface and the main surface are moved relative to each other. When the processing reference surface and the main surface are moved relative to each other with the processing fluid interposed between the processing reference surface and the main surface, the activity generated from the molecules in the processing fluid adsorbed on the processing reference surface The seed and the main surface react and the main surface is processed. The active species are generated only on the processing reference surface and deactivated when they are separated from the vicinity of the processing reference surface. Therefore, there is almost no reaction with the active species other than the main surface with which the processing reference surface contacts or approaches. In this way, the main surface is processed by catalyst-based etching. In the processing based on the catalyst-based etching, since no abrasive is used, damage to the substrate is extremely small, and generation of new defects can be prevented.

The relative motion between the processing reference surface and the main surface is not particularly limited as long as the processing reference surface and the main surface move relative to each other. When the substrate is fixed and the processing reference surface is moved, the processing reference surface is fixed and the substrate is moved, or both the processing reference surface and the substrate are moved. When the processing reference plane moves, the movement may be a case where the machining reference plane rotates around an axis in a direction perpendicular to the main surface of the substrate or a case where the processing reference plane reciprocates in a direction parallel to the main surface of the substrate. Similarly, when the substrate moves, the movement may be when the substrate rotates about an axis perpendicular to the main surface of the substrate or when the substrate reciprocates in a direction parallel to the main surface of the substrate.
The load (processing pressure) applied to the substrate is, for example, 5 to 350 hPa.
The machining allowance in the process by the catalyst reference etching is, for example, 5 nm to 100 nm. When there is a protrusion protruding from the main surface on the main surface of the substrate, the machining allowance is preferably set to a value larger than the height of the protrusion. By setting the machining allowance to a value larger than the height of the protrusion, the protrusion can be removed by CARE processing.

  For example, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo) can be used as the catalyst material for forming the processing reference surface. ), Tungsten (W), iron (Fe), ruthenium (Ru), and osmium (Os), an alloy containing at least one metal, oxygen (O), nitrogen (N), and carbon ( An alloy compound containing at least one component of C) is mentioned. Examples of the alloy compound described above include oxides, nitrides, carbides, oxynitrides, oxycarbides, nitride carbides, and oxynitride carbides of the above-described alloys. When such an alloy or alloy compound is used, the mechanical durability and chemical stability of the processing reference surface can be improved.

Specifically, as an alloy containing chromium (Cr), chromium titanium (CrTi), chromium zirconium (CrZr), chromium hafnium (CrHf), chromium vanadium (CrV), chromium niobium (CrNb), chromium tantalum (CrTa), chromium Examples include molybdenum (CrMo), chromium tungsten (CrW), chromium manganese (CrMn), chromium rhenium (CrRe), chromium iron (CrFe), chromium ruthenium (CrRu), and chromium osmium (CrOs). The composition ratio of the alloy containing chromium (Cr) is arbitrary.
Alloys containing molybdenum (Mo) include molybdenum titanium (MoTi), molybdenum zirconium (MoZr), molybdenum hafnium (MoHf), molybdenum vanadium (MoV), molybdenum niobium (MoNb), molybdenum tantalum (MoTa), and molybdenum chromium (MoCr). , Molybdenum tungsten (MoW), molybdenum iron (MoFe), molybdenum ruthenium (MoRu), and molybdenum osmium (MoOs). The composition ratio of these alloys containing molybdenum (Mo) is arbitrary.
As an alloy containing tungsten (W), tungsten titanium (WTi), tungsten zirconium (WZr), tungsten hafnium (WHf), tungsten vanadium (WV), tungsten niobium (WNb), tungsten tantalum (WTa), tungsten chromium (WCr) , Tungsten molybdenum (WMo), tungsten iron (WFe), tungsten ruthenium (WRu), and tungsten osmium (WOs). The composition ratio of these alloys containing tungsten (W) is arbitrary.
Examples of the alloy containing iron (Fe) include iron nickel (FeNi), iron nickel chromium (FeNiCr), iron chromium (FeCr), iron molybdenum (FeMo), iron chromium molybdenum (FeCrMo), and stainless steel (SUS). When the substrate for CARE processing is a glass substrate, ferritic stainless steel or martensitic stainless steel is preferable as stainless steel (SUS). Ferritic stainless steel and martensitic stainless steel remaining on the surface of the glass substrate after CARE processing dissolve in a cleaning solution that does not damage the glass substrate, and can reduce defects due to the catalytic substance. Examples of the ferritic stainless steel include SUS430, SUS434, and SUS436. Examples of martensitic stainless steel include SUS410, SUS410S, SUS420J1, and SUS420J2. The composition ratio of these alloys containing iron (Fe) is arbitrary.
As an alloy containing ruthenium (Ru), ruthenium titanium (RuTi), ruthenium zirconium (RuZr), ruthenium hafnium (RuHf), ruthenium vanadium (RuV), ruthenium niobium (RuNb), ruthenium tantalum (RuTa), ruthenium chromium (RuCr) , Ruthenium molybdenum (RuMo), and ruthenium tungsten (RuW). The composition ratio of these alloys containing ruthenium (Ru) is arbitrary.
As alloys containing tantalum (Ta), tantalum titanium (TaTi), tantalum zirconium (TaZr), tantalum hafnium (TaHf), tantalum vanadium (TaV), tantalum niobium (TaNb), tantalum chromium (TaCr), tantalum molybdenum (TaMo) Tantalum tungsten (TaW), tantalum iron (TaFe), tantalum ruthenium (TaRu), and tantalum osmium (TaOs). The composition ratio of these alloys containing tantalum (Ta) is arbitrary.
As an alloy containing zirconium (Zr), zirconium titanium (ZrTi), zirconium hafnium (ZrHf), zirconium vanadium (ZrV), zirconium niobium (ZrNb), zirconium tantalum (ZrTa), zirconium chromium (ZrCr), zirconium molybdenum (ZrMo) Zirconium Tungsten (ZrW), Zirconium Iron (ZrFe), Zirconium Ruthenium (ZrRu), Zirconium Osmium (ZrOs). The composition ratio of these alloys containing zirconium (Zr) is arbitrary.
In addition, the above-mentioned titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), an alloy containing at least one metal of osmium (Os), and at least one of oxygen (O), nitrogen (N), and carbon (C) in the alloy. In the alloy compound containing one component, elements other than those listed above (for example, Group 3, Group 7, Group 10, Group 11, Group, Group 12 element) may be included.

  Other catalytic materials for forming the processing reference surface include, for example, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), and chromium (Cr). , Molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), an alloy having an amorphous structure containing at least one metal of osmium (Os), and this alloy contains nitrogen (N) Alloy compounds of amorphous structure, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), and amorphous structure in which nitrogen (N) is contained in a metal such as osmium (Os) Metal compounds. Examples of the alloy compound described above include nitrides of the above-described alloys. Examples of the metal compound described above include the metal nitride described above. If such an amorphous structure alloy, alloy compound, or metal compound is used, the flatness of the processing reference surface can be improved. An amorphous alloy, alloy compound, or metal compound is obtained at a predetermined composition ratio.

Specifically, such as chromium titanium (CrTi), chromium molybdenum (CrMo), chromium tungsten (CrW), ruthenium zirconium (RuZr), ruthenium titanium (RuTi), ruthenium niobium (RuNb), and ruthenium molybdenum (RuMo). Alloys, nitrides of these alloys, and metal nitrides such as chromium nitride (CrN) and tantalum nitride (TaN) can be mentioned.
In addition, the above-mentioned titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), and an alloy having an amorphous structure containing at least one metal of osmium (Os), an alloy compound having an amorphous structure in which nitrogen (N) is contained in the alloy, and titanium (Ti ), Zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru) ), And a metal compound having an amorphous structure in which nitrogen (N) is contained in a metal such as osmium (Os), deviates from the effect of the present invention. As long as the amorphous structure is maintained, elements other than those listed above (for example, elements of Group 3, Group 7, Group 9, Group 10, Group 11 and Group 12 of the periodic table) are included. Also good.

  Further, as other catalytic materials for forming other processing reference surfaces, for example, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr ), Molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), an alloy compound containing carbon (C) in an alloy containing at least one metal of osmium (Os), Titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), Examples thereof include a metal compound in which carbon (C) is contained in a metal such as ruthenium (Ru) and osmium (Os). Examples of the alloy compound described above include carbide, oxide carbide, nitride carbide, or oxynitride carbide of the above-described alloy. Examples of the metal compound described above include the metal carbide, oxide carbide, nitride carbide, and oxynitride carbide described above. When the processing reference surface containing such an alloy compound or metal compound containing carbon (C) is used, the toughness of the processing reference surface can be improved.

Specifically, the carbide of the alloy listed as the alloy containing chromium (Cr) mentioned above, the carbide of the alloy listed as the alloy containing molybdenum (Mo) mentioned above, and the alloy containing the tungsten (W) mentioned above. Carbides of the alloys listed above, carbides of the alloys listed as alloys containing iron (Fe) as described above, carbides of alloys listed as alloys containing ruthenium (Ru) as described above, and alloys containing tantalum (Ta) as described above Carbides of alloys such as carbides of listed alloys, carbides of alloys listed as alloys containing zirconium as described above, and metals such as tungsten carbide (WC), chromium carbide (CrC), and molybdenum carbide (MoC) Of carbides.
In addition, the above-mentioned titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), and an alloy compound containing carbon (C) in an alloy containing at least one of osmium (Os), titanium (Ti), zirconium (Zr), hafnium ( Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), and osmium (Os) The metal compound containing carbon (C) in a simple metal includes elements other than those listed above (for example, group 3 of the periodic table, 7 , Group 9, Group 10, Group 11, Group 12 elements) may be included.

Area of the working reference plane is smaller than the area of the main surface of the substrate, for ^example, a 100mm ² ~10000mm 2. By downsizing the processing reference surface, the substrate processing apparatus can be downsized and high-precision processing can be performed reliably.
Further, the area of the processing reference plane may be larger than the area of the main surface of the substrate. Since the entire surface of the substrate can be processed, the processing time can be shortened, and the occurrence of defects such as scratches due to the edge of the processing reference surface can be suppressed.

  The processing fluid is not particularly limited as long as it does not exhibit solubility in a normal state with respect to the substrate. By using such a processing fluid, the substrate is not dissolved by the processing fluid, and unnecessary deformation of the substrate can be prevented. For example, pure water, ozone water, carbonated water, hydrogen water, a low concentration alkaline aqueous solution, or a low concentration acidic aqueous solution can be used. In the case where the substrate does not normally dissolve in a solution containing halogen-containing molecules, a solution containing halogen-containing molecules can be used.

  When the substrate is made of a glass material, the above-described catalyst substance is used, and pure water is used as a processing fluid, so that processing by catalyst-based etching can be performed. It is considered that the hydrolysis reaction proceeds by using the above-described catalyst substance and using pure water as a processing fluid. For this reason, when a board | substrate consists of glass materials, it is preferable to use the catalyst substance mentioned above from a viewpoint of cost or a process characteristic, and to use a pure water as a process fluid.

  1 and 2 show an example of a substrate processing apparatus that performs processing by catalyst-based etching on the main surface of the substrate. FIG. 1 is a partial cross-sectional view of the substrate processing apparatus, and FIG. 2 is a plan view of the substrate processing apparatus. In the following, the case where the upper surface M1 used as the main surface of the substrate M is CARE processed using the substrate processing apparatus shown in FIGS. 1 and 2 will be described. However, when the lower surface M2 of the substrate M is also used as the main surface. The upper surface M1 and the lower surface M2 are interchanged, and the lower surface M2 is also CARE processed. Even if the lower surface M2 is not used as the main surface, the lower surface M2 is also CARE processed as necessary. In that case, CARE processing of the upper surface M1 is performed after CARE processing of the lower surface M2.

  The substrate processing apparatus 1 includes a substrate support means 2 for supporting a substrate M having a main surface made of an oxide-containing material, a substrate surface creation means 3 having a processing reference surface 33 for a catalytic substance, a processing reference surface 33 and a main processing surface. Processing fluid supply means 4 for supplying a processing fluid to the surface, and driving means for bringing the processing reference surface 33 into contact with or approaching the main surface in a state where the processing fluid is interposed between the processing reference surface 33 and the main surface And 5.

  The substrate support means 2 is disposed in a cylindrical chamber 6. The chamber 6 has an opening 61 formed in the center of the bottom 63 of the chamber 6 and the processing fluid supplied from the processing fluid supply means 4 in order to arrange a shaft portion 71 of the relative motion means 7 described later in the chamber 6. In order to discharge the fluid, the bottom 63 of the chamber 6 is provided with a discharge port 62 formed closer to the outer periphery than the opening 61. In FIG. 1, the state in which the processing fluid is discharged from the discharge port 62 is indicated by an arrow.

  The substrate support means 2 includes a support portion 21 that supports the substrate M and a flat portion 22 that fixes the support portion 21. The support portion 21 has a rectangular shape when the substrate processing apparatus 1 is viewed from above, and includes a receiving portion 21a that supports four sides of the periphery of the lower surface M2 of the substrate M. The planar portion 22 has a circular shape when the substrate processing apparatus 1 is viewed from above.

  The substrate surface creation means 3 includes a catalyst surface plate 31. The catalyst surface plate 31 is attached to a catalyst surface plate mounting portion 72 of the relative motion means 7 described later. The catalyst surface plate 31 includes a surface plate body 32, a base material (not shown) formed on the entire surface of the surface plate body so as to cover the surface plate body, and the entire surface of the base material on the side facing the substrate M. And a processing reference surface 33 formed by coating a catalyst material on the substrate. Examples of the coating method include vapor deposition, sputtering, and electroplating. The material of the base material on which the processing reference surface is formed is not particularly limited. For example, rubber, light transmissive resin, foamable resin, and non-woven fabric can be used. The overall shape of the catalyst platen is not particularly limited. For example, the outer shape of a disk, a sphere, a cylinder, a cone, or a pyramid can be used. The surface shape of the portion of the catalyst surface plate on which the processing reference surface is formed is not particularly limited. For example, a flat, hemispherical, or rounded shape can be used.

  The processing fluid supply means 4 is provided at the tip of the lower end of the supply pipe 41 and the supply pipe 41 extending from the outside of the chamber 6 toward the main surface of the substrate M placed on the support 21. And an injection nozzle 42 for injecting a processing fluid toward the main surface of the substrate M placed on the substrate 21. The supply pipe 41 is connected to, for example, a processing fluid storage tank (not shown) and a pressurizing pump (not shown) provided outside the chamber 6. The processing fluid is supplied to the injection nozzle 42 through the supply pipe 41 and is supplied from the injection nozzle 42 onto the main surface of the substrate M placed on the support portion 21. The method for supplying the processing fluid is not limited to this, and the processing fluid may be supplied from the catalyst surface plate 31.

  The drive means 5 is connected to the upper end of a catalyst platen mounting portion 72 of the relative motion means 7 described later, and extends to the periphery of the chamber 6 in a direction parallel to the main surface of the substrate M placed on the support portion 21. A shaft portion 52 extending in a direction perpendicular to the main surface of the substrate M placed on the support portion 21, and a lower end of the shaft portion 52. The base part 53 to support is provided, and the guide 54 which is arrange | positioned around the chamber 6 and defines the movement path | route of the base part 53 is provided. The arm portion 51 can move in the longitudinal direction (see a double arrow C in FIGS. 1 and 2). The shaft part 52 can move the arm part 51 up and down by moving in the longitudinal direction (see a double-headed arrow D in FIG. 1). The base portion 53 can turn the arm portion 51 by rotating a predetermined angle about an axis in a direction perpendicular to the main surface of the substrate M placed on the support portion 21 (FIG. 1, FIG. 1). (See double arrow E in 2). The guide 54 is disposed in a direction (first direction and second direction) parallel to two adjacent sides of the substrate M placed on the support portion 21, and forms an L-shaped movement path of the base portion 53. . The base portion 53 moves along the guide 54 in the first direction, thereby moving the arm portion 51 in the first direction (see the double arrow F in FIG. 2), and the guide 54 in the second direction. The arm portion 51 can be moved in the second direction by moving along (see the double arrow G in FIG. 2). By such movement of the arm portion 51, the catalyst surface plate 31 can be disposed at a predetermined position on the main surface of the substrate M placed on the support portion 21.

  The substrate processing apparatus 1 includes relative motion means 7 that relatively moves the processing reference surface 33 and the main surface. The relative motion means 7 includes a shaft portion 71 that supports the flat surface portion 22 and extends to the outside of the chamber 6 through the opening portion 61, and a rotation drive means (not shown) that rotates the shaft portion 71. . The shaft portion 71 extends in a direction perpendicular to the main surface of the substrate M placed on the support portion 21, and the main surface of the substrate M placed on the support portion 21 by rotation driving means (not shown). And an axis perpendicular to the axis of rotation (see arrow A in FIG. 1). The center of the flat surface portion 22 and the center of the substrate M placed on the support portion 21 are positioned in the extending direction of the rotation center of the shaft portion 71. By rotating the shaft portion 71, the flat surface portion 22 supported by the shaft portion 71 rotates around the center thereof, and the substrate M placed on the support portion 21 fixed to the flat surface portion 22. Rotates around the center of rotation. The relative motion means 7 includes a catalyst surface plate mounting portion 72 to which the catalyst surface plate 31 is mounted, and a rotation drive means (not shown) provided on the arm portion 51 of the drive means 5. The catalyst surface plate mounting portion 72 can be rotated by a rotation driving means (not shown) around an axis in a direction perpendicular to the main surface of the substrate M placed on the support portion 21 (FIG. 1, FIG. 1). (See arrow B in 2).

  The substrate processing apparatus 1 includes load control means 8 that controls a load (processing pressure) applied to the substrate M. The load control means 8 is provided in the catalyst surface plate mounting portion 72, measures an air cylinder 81 for applying a load to the catalyst surface plate 3, and a load applied to the catalyst surface plate 31 by the air cylinder 81, and applies a predetermined load. A load cell 82 is provided for controlling the load applied to the catalyst platen 31 by the air cylinder 81 by turning on and off the air valve so as not to exceed. When processing by catalyst reference etching is performed, the load (processing pressure) applied to the substrate M is controlled by the load control means 8.

  As a control method for securing the machining allowance as set, for example, various local processing conditions (processing pressure, rotational speed (catalyst platen, substrate), processing fluid, Flow rate), machining time and machining allowance are determined, the machining condition and machining time to be the desired machining allowance are determined, and the machining allowance is controlled by controlling the machining time. it can. The method is not limited to this, and various methods may be selected as long as the machining allowance can be ensured as set.

When performing processing by catalyst-based etching using the substrate processing apparatus shown in FIGS. 1 and 2, first, the substrate M is placed and fixed on the support portion 21 with the upper surface M1 used as the main surface facing upward. .
Thereafter, the arm part 51 moves in the longitudinal direction (double arrow C), the arm part 51 pivots (double arrow E), the arm part 51 moves in the first direction (double arrow F), and the arm part 51 moves in the second direction ( By the double arrow G), the processing reference surface 33 of the substrate surface creation means 3 is disposed so as to face the upper surface M1 of the substrate M.
Thereafter, by rotating the shaft portion 71 and the catalyst surface plate mounting portion 72 at a predetermined rotation speed, the processing fluid is transferred from the injection nozzle 42 onto the upper surface M1 while rotating the processing reference surface 33 and the upper surface M1 at a predetermined rotation speed. And a processing fluid is interposed between the upper surface M1 and the processing reference surface 33. In this state, the processing reference surface 33 is brought into contact with or brought close to the upper surface M1 of the substrate M by the vertical movement of the arm portion 51 (double arrow D). At that time, the load applied to the substrate M is controlled to a predetermined value by the load control means 8.
Thereafter, when the predetermined machining allowance is reached, the rotation of the shaft portion 71 and the catalyst surface plate mounting portion 72 and the supply of the processing fluid are stopped. Then, the machining reference surface 33 is separated from the upper surface M1 by a predetermined distance by the vertical movement of the arm portion 51 (double arrow D).

  The substrate M is manufactured through the substrate preparation process and the substrate processing process.

  According to the substrate manufacturing method of the first embodiment, the catalyst material for forming the processing reference plane is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium. When using an alloy containing at least one of these metals or an alloy compound containing at least one of oxygen, nitrogen, and carbon in this alloy, the mechanical durability and chemical stability of the processing reference surface are improved. Can be improved. When the mechanical durability of the processing reference surface is improved, the processing reference surface is peeled off during CARE processing, and the possibility that the main surface of the substrate is damaged or the peeled portion loses its function as a catalyst is reduced. In addition, when the chemical stability of the processing reference surface is improved, the processing reference surface is rusted by the processing fluid during CARE processing, the rusted part loses its function as a catalyst, or the rusted part is peeled off, and the main surface of the substrate is removed. The risk of damaging is reduced. For this reason, a substrate having a main surface with high smoothness and low defects can be stably manufactured by CARE processing.

  Further, as a catalytic material for forming the processing reference surface, an amorphous structure alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, This alloy contains nitrogen-containing alloy compounds with amorphous structure and metals such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium. In the case of using a metal compound having an amorphous structure, the smoothness of the processing reference surface can be improved. When the smoothness of the processing reference surface is improved, many portions of the processing reference surface can be brought close to or in contact with the main surface of the substrate during the CARE processing. In addition, the surface shape of the processing reference surface is transferred to the main surface of the substrate. For this reason, a substrate having a main surface with high smoothness and low defects can be stably manufactured by CARE processing.

  In addition, as a catalyst material that forms the processing reference surface, carbon is contained in an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium. When using metal compounds containing carbon in metals such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, Toughness can be improved. When the toughness of the processing reference surface is improved, the durability of the processing reference surface is improved. For this reason, a substrate having a main surface with high smoothness and low defects can be stably manufactured by CARE processing.

In this embodiment, the present invention is applied to a substrate processing apparatus of a type in which the processing reference surface 33 of the substrate surface creation means 3 is pressed against the main surface of the substrate M. However, the processing reference surface of the substrate surface creation means is used. Furthermore, the present invention can also be applied to a substrate processing apparatus that presses the main surface of the substrate.
In this embodiment, the present invention is applied to a substrate processing apparatus that processes one side of a substrate. However, the present invention can also be applied to a substrate processing apparatus that processes both surfaces of a substrate simultaneously. In this case, a carrier that is a member that holds the side surface of the substrate is used as the substrate support means.
Further, in this embodiment, the present invention is applied to a substrate processing apparatus of a type that supplies a processing fluid from the outside of the chamber toward the main surface of the substrate M. However, a processing fluid supply means is provided in the substrate surface creation means, The present invention can also be applied to the case where the processing fluid is supplied from the processing fluid supply means, or the case where the processing fluid supply means is provided in the substrate support means and the processing fluid is supplied from the substrate support means. The present invention can also be applied to the case where the processing fluid is stored in the chamber, and the processing based on the catalyst reference etching is performed in a state where the substrate surface creation means and the substrate support means are placed in the processing fluid.
In this embodiment, the present invention is applied to a substrate processing apparatus of a type that relatively moves the processing reference surface 33 and the main surface by rotating both the processing reference surface 33 and the main surface. The present invention can also be applied to a substrate processing apparatus of a type in which the processing reference surface 33 and the main surface are moved relative to each other by a method.
Further, in this embodiment, the present invention is applied to a substrate type processing apparatus that processes substrates one by one. However, the present invention is also applied to a batch type substrate processing apparatus that processes a plurality of substrates simultaneously. it can.

Embodiment 2. FIG.
In Embodiment 2, a method for manufacturing a substrate with a multilayer reflective film will be described.

  In the second embodiment, a multilayer reflective film in which high refractive index layers and low refractive index layers are alternately laminated on the main surface of the substrate M manufactured by the method described in the substrate manufacturing method of the first embodiment. Then, a substrate with a multilayer reflective film is produced, or a protective film is formed on the multilayer reflective film to produce a substrate with a multilayer reflective film.

  According to the method for manufacturing a substrate with a multilayer reflective film according to the second embodiment, a substrate with a multilayer reflective film is manufactured using the substrate M obtained by the method for manufacturing a substrate according to the first embodiment. Can be prevented, and a substrate with a multilayer reflective film having desired characteristics can be manufactured.

Embodiment 3 FIG.
In Embodiment 3, a mask blank manufacturing method will be described.

  In this third embodiment, a binary mask blank is manufactured by forming a light shielding film as a transfer pattern thin film on the main surface of the substrate M manufactured by the method described in the substrate manufacturing method of the first embodiment. Alternatively, a half-tone phase shift mask blank is manufactured by forming a light semi-transmissive film as a transfer pattern thin film, or a half-tone phase shift mask by sequentially forming a light semi-transmissive film and a light-shielding film as a transfer pattern thin film. A blank is manufactured.

  In the third embodiment, an absorber film as a transfer pattern thin film is formed on the protective film of the multilayer reflective film-coated substrate manufactured by the method described for the multilayer reflective film-coated substrate of the second embodiment. Alternatively, a protective film and an absorber film as a transfer pattern thin film are formed on the multilayer reflective film of the substrate with the multilayer reflective film, and a back conductive film is formed on the back surface on which the multilayer reflective film is not formed. A mold mask blank is manufactured.

  According to the third embodiment, the substrate M obtained by the substrate manufacturing method of the first embodiment or the substrate with the multilayer reflective film obtained by the method of manufacturing the substrate with the multilayer reflective film of the second embodiment is used. Since the mask blank is manufactured, it is possible to prevent deterioration of characteristics due to substrate factors, and it is possible to manufacture a mask blank having desired characteristics.

Embodiment 4 FIG.
In the fourth embodiment, a method for manufacturing a transfer mask will be described.

  In the fourth embodiment, an exposure / development process is performed on the transfer pattern thin film of the binary mask blank, phase shift mask blank, or reflective mask blank manufactured by the method described in the mask blank manufacturing method of the third embodiment. To form a resist pattern. Using this resist pattern as a mask, the transfer pattern thin film is etched to form a transfer pattern to manufacture a transfer mask.

  According to the fourth embodiment, since the transfer mask is manufactured using the mask blank obtained by the mask blank manufacturing method of the third embodiment, it is possible to prevent the deterioration of the characteristics due to the substrate factor. A transfer mask having the above characteristics can be manufactured.

Hereinafter, based on an Example, this invention is demonstrated more concretely.

Example 1.
A. Production of glass substrate Substrate Preparation Step A TiO ₂ —SiO ₂ glass substrate of 6025 size (152 mm × 152 mm × 6.35 mm) whose upper and lower surfaces were polished was prepared. Note that the TiO ₂ —SiO ₂ glass substrate is obtained through the following rough polishing process, precision polishing process, ultra-precision polishing process, local processing process, and touch polishing process.

(1) Rough polishing process Step 10 glass substrates that have undergone end chamfering and grinding were set in a double-side polishing apparatus, and rough polishing was performed under the following polishing conditions. A set of 10 sheets was performed twice, and a total of 20 glass substrates were roughly polished. The processing load and polishing time were adjusted as appropriate.
Polishing slurry: Aqueous solution containing cerium oxide (average particle size 2 to 3 μm) Polishing pad: Hard polisher (urethane pad)
After the rough polishing, in order to remove the abrasive grains adhering to the glass substrate, the glass substrate was immersed in a cleaning tank and cleaned by applying ultrasonic waves.

(2) Precision polishing process step Ten glass substrates after rough polishing were set in a double-side polishing apparatus, and precision polishing was performed under the following polishing conditions. A 10-sheet set was performed twice, and a total of 20 glass substrates were precisely polished. The processing load and polishing time were adjusted as appropriate.
Polishing slurry: Aqueous solution containing cerium oxide (average particle size 1 μm) Polishing pad: Soft polisher (suede type)
After the precision polishing, in order to remove abrasive grains adhering to the glass substrate, the glass substrate was immersed in a cleaning tank and cleaned by applying ultrasonic waves.

(3) Ultra-precision polishing process Step 10 glass substrates that had been subjected to precision polishing were again set in a double-side polishing apparatus, and ultra-precision polishing was performed under the following polishing conditions. A set of 10 sheets was performed twice and a total of 20 glass substrates were subjected to ultra-precision polishing. The processing load and polishing time were adjusted as appropriate.
Polishing slurry: alkaline aqueous solution (pH 10.2) containing colloidal silica
(Colloidal silica content 50wt%)
Polishing pad: Super soft polisher (suede type)
After ultra-precision polishing, the glass substrate was immersed in a cleaning tank containing an alkali cleaning solution of sodium hydroxide and cleaned by applying ultrasonic waves.

(4) Local processing step The flatness of the upper surface and the lower surface of the glass substrate after the rough polishing processing step, the precision polishing processing step, and the ultraprecision polishing processing step was measured using a flatness measuring device (UltraFlat 200 manufactured by Tropel). The flatness measurement was performed at a point of 1024 × 1024 with respect to an area of 148 mm × 148 mm excluding the peripheral area of the glass substrate. The measurement results of the flatness of the upper and lower surfaces of the glass substrate were stored in a computer as height information (uneven shape information) with respect to the virtual absolute plane for each measurement point. The virtual absolute plane is a plane having a minimum value when the distance from the virtual absolute plane to the substrate surface is squared with respect to the entire flatness measurement region.
Then, the acquired uneven | corrugated shape information and the reference value of the flatness of the upper surface and lower surface which are requested | required of a glass substrate were compared, and the difference was computed with the computer for every predetermined area | region of the upper surface and lower surface of a glass substrate. This difference becomes a necessary removal amount (processing allowance) of each predetermined region in local surface processing described later.
Then, the processing conditions of the local surface processing according to required removal amount were set for every predetermined area | region of the upper surface and lower surface of a glass substrate. The setting method is as follows. Using a dummy substrate in advance, the dummy substrate is processed at a certain point (spot) without moving the substrate for a certain time in the same way as in actual processing, and the shape is measured with a flatness measuring device (UltraFlat 200 manufactured by Tropel). Then, the processing volume at the spot per unit time was calculated. Then, the scanning speed for raster scanning of the glass substrate was determined according to the processing volume at the spot per unit time and the necessary removal amount of each predetermined area calculated as described above.
Thereafter, the upper surface and the lower surface of the glass substrate were locally surface-treated according to the processing conditions set for each predetermined region by magnetic viscoelastic fluid polishing (MRF) using a substrate finishing apparatus. At this time, a magnetic polishing slurry containing cerium oxide polishing particles was used.
Thereafter, the glass substrate was immersed in a cleaning tank containing an aqueous hydrochloric acid solution having a concentration of about 10% (temperature: about 25 ° C.) for about 10 minutes.
Thereafter, rinsing with pure water and drying with isopropyl alcohol (IPA) were performed.

(5) Touch polishing process In order to improve the smoothness of the upper and lower surfaces of the glass substrate roughened by the local processing process, the upper and lower surfaces of the glass substrate are polished by a minute amount by low-load mechanical polishing using polishing slurry. did. This polishing is performed by setting a glass substrate held by a carrier between upper and lower polishing surface plates to which a polishing pad larger than the size of the substrate is attached, and containing a colloidal silica abrasive grain (average particle diameter of 50 nm). The glass substrate was revolved while rotating in the upper and lower polishing surface plates while feeding.
Thereafter, the glass substrate was immersed in an alkali cleaning solution of sodium hydroxide and cleaned by applying ultrasonic waves.

2. Substrate processing step Next, using the substrate processing apparatus shown in FIGS. 1 and 2, the upper surface used as the main surface of the glass substrate after the touch polishing step was processed by catalyst-based etching.

In this embodiment, a disk-shaped surface plate body 32 made of stainless steel (SUS) having a diameter of 50 mm, a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, a glass substrate, A catalyst surface plate 31 provided with a processing reference surface 33 (film thickness 100 nm) made of a chromium titanium (CrTi) alloy formed on the entire surface of the urethane pad on the opposite side was used. The processing reference surface 33 was formed by performing sputtering in an argon (Ar) gas atmosphere using a chromium titanium (CrTi) target. When the crystal structure of the processing reference surface 33 made of a chromium titanium (CrTi) alloy was measured by an X-ray diffractometer (XRD), it was an amorphous structure. The composition of the processing reference surface 33 analyzed by X-ray photoelectron spectroscopy (XPS) was Cr: 60 atomic% and Ti: 40 atomic%.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / minute Rotation speed of catalyst surface plate mounting section 72 (rotation speed of catalyst surface plate 31): 10 rotation / minute Processing pressure : 50 hPa
Processing allowance: 30nm

First, the glass substrate was placed and fixed on the support portion 21 with the upper surface used as the main surface facing upward.
Thereafter, the longitudinal movement of the arm 51 (double arrow C), the swing movement of the arm 51 (double arrow E), the first movement of the arm 51 (double arrow F), and the second movement of the arm 51 ( With the double arrow G), the catalyst surface plate 31 was disposed in a state where the processing reference surface 33 of the catalyst surface plate 31 was disposed opposite to the upper surface of the glass substrate. The arrangement position of the catalyst surface plate 31 is a position where the processing reference surface 33 of the catalyst surface plate 31 can contact or approach the entire upper surface of the glass substrate when the glass substrate and the catalyst surface plate 31 are rotated. is there.
Thereafter, the glass substrate is rotated at a rotation speed of 10.3 rotations / minute and the catalyst surface plate 31 is rotated at a rotation speed of 10 rotations / minute. Here, the glass substrate and the catalyst platen 31 are rotated so that the rotation direction of the glass substrate and the rotation direction of the catalyst platen 31 are opposite to each other. Thereby, a peripheral speed difference can be taken between them, and the processing efficiency by catalyst reference | standard etching can be improved. Moreover, both rotation speeds are set to be slightly different. Accordingly, the processing reference surface 33 of the catalyst surface plate 31 can be moved relative to the upper surface of the glass substrate so as to draw different trajectories, and the processing efficiency by the catalyst reference etching can be increased.
While rotating the glass substrate and the catalyst surface plate 31, pure water was supplied from the spray nozzle 42 onto the upper surface of the glass substrate, and the pure water was interposed between the upper surface of the glass substrate and the processing reference surface 33. In that state, the processing reference surface 33 of the catalyst surface plate 41 was brought into contact with or brought close to the upper surface of the glass substrate by the vertical movement of the arm portion 51 (double arrow D). At that time, the load (processing pressure) applied to the glass substrate was controlled to 50 hPa.
Thereafter, when the machining allowance reached 30 nm, the rotation of the glass substrate and the catalyst surface plate 31 and the supply of pure water were stopped. Then, the catalyst surface plate 31 was separated from the upper surface of the glass substrate by a predetermined distance by the vertical movement of the arm portion 51 (double arrow D).
Thereafter, the glass substrate was removed from the support portion 21.

Thereafter, the glass substrate removed from the support portion 21 was washed as follows. First, neutral detergent and water were supplied to the upper surface of the glass substrate, and brush cleaning was performed by rubbing the upper surface of the glass substrate with a brush made of polyvinyl alcohol (PVA) to scrape off foreign substances adhering to the upper surface. Thereafter, hydrogen water (H ₂ concentration: 1.2 ppm) is supplied to the upper surface of the glass substrate after the brush cleaning, and ultrasonic vibration (frequency: 3 MHz) is applied to the upper surface to float and remove the foreign matter adhering to the upper surface. Sonic cleaning was performed. Thereafter, two-fluid cleaning with nitrogen (N ₂ ) gas and carbonated water (electrical resistivity: 0.2 MΩ · cm) was performed. Thereafter, rinsing with pure water and drying were performed.
In this way, a glass substrate was produced.

3. Evaluation The surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst-based etching was measured using an atomic force microscope (AFM) for a 1 μm × 1 μm region at the center of the substrate.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.061 nm in terms of root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.061 nm in terms of root mean square roughness (RMS) by catalyst-based etching. Moreover, the surface roughness of the upper surface after processing was as good as 0.519 nm at the maximum height (Rmax). The ratio of the root mean square roughness to the maximum height (Rmax / RMS) was as good as 8.5.
A defect inspection apparatus (mask / blank defect inspection apparatus Teron 610 manufactured by KLA-Tencor) is used for a defect inspection of the upper surface of the glass substrate after processing by catalyst-based etching for a 132 nm × 132 nm area excluding the peripheral area of the substrate. Used. The defect inspection was performed at a sensitivity with which a 21.5 nm size defect could be detected in terms of SEVD (Sphere Equivalent Volume Diameter). SEVD is the length of the diameter when the defect is assumed to be hemispherical.
The number of defects on the upper surface after processing was as small as 42.
Moreover, when 20 glass substrates were produced by the method of Example 1, the total number and the surface roughness were as good as 0.08 nm or less in root mean square roughness (RMS), and the number of defects was 50 or less. There were few.
By the method of Example 1, a glass substrate having a high smoothness and a low-defect main surface was stably obtained.

B. Production of Multilayer Reflective Substrate Next, a high refractive index layer (thickness: 4.) made of a silicon film (Si) is formed on the upper surface used as the main surface of the glass substrate thus produced by ion beam sputtering. 2 nm) and a low refractive index layer (2.8 nm) made of a molybdenum film (Mo) alternately, one pair of a high refractive index layer and a low refractive index layer, and 40 pairs are laminated to form a multilayer reflective film (film) A thickness of 280 nm) was formed.
Thereafter, a protective film (thickness 2.5 nm) made of ruthenium (Ru) was formed on the multilayer reflective film by ion beam sputtering.
In this way, a substrate with a multilayer reflective film was produced.

About the obtained board | substrate with a multilayer reflective film, the reflectance of EUV light (wavelength 13.5nm) was measured with the EUV reflectance measuring apparatus.
Due to the high smoothness of the upper surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
The defect inspection of the protective film surface of the obtained multilayer reflective film-coated substrate was performed in the same manner as the defect inspection of the glass substrate.
The number of defects on the surface of the protective film after processing was as small as 38.
By the method of Example 1, a multilayer reflective film-coated substrate having a highly smooth and low-defect protective film surface was obtained.

C. Production of Reflective Mask Blank Next, a tantalum boride (TaB) target is used on the protective film of the multilayer reflective film substrate thus produced, and argon (Ar) gas and nitrogen (N ₂ ) gas are used. Reactive sputtering is performed in a mixed gas atmosphere to form a lower absorber layer (film thickness 50 nm) made of tantalum boron nitride (TaBN), and tantalum boride (TaB) is further formed on the lower absorber film. Using a target, reactive sputtering is performed in a mixed gas atmosphere of argon (Ar) gas and oxygen (O ₂ ) gas to form an upper absorber layer (thickness 20 nm) made of tantalum boron oxide (TaBO). As a result, an absorber film (thickness 70 nm) composed of the lower absorber layer and the upper absorber layer was formed.
Thereafter, a reaction in a mixed gas atmosphere of argon (Ar) gas and nitrogen (N ₂ ) gas using a chromium (Cr) target on the back surface of the substrate with the multilayer reflective film on which the multilayer reflective film is not formed. A back conductive film (thickness 20 nm) made of chromium nitride (CrN) was formed by reactive sputtering.
In this way, a reflective mask blank for EUV exposure that maintains a highly smooth and low-defect surface state was produced.

D. Production of Reflective Mask Next, a chemically amplified resist for electron beam drawing (exposure) is applied onto the absorber film of the thus produced reflective mask blank by a spin coating method, and heating and cooling steps are performed. Then, a resist film having a thickness of 150 nm was formed.
Thereafter, a desired pattern was drawn on the formed resist film using an electron beam drawing apparatus, and then developed with a predetermined developer to form a resist pattern.
Thereafter, using this resist pattern as a mask, the absorber film was dry-etched to form an absorber film pattern on the protective film. As a dry etching gas, chlorine (Cl ₂ ) gas was used.
Thereafter, the remaining resist pattern was peeled off and washed.
In this way, a reflective mask for EUV exposure that maintains a highly smooth and low-defect surface state was produced.

Example 2
In this embodiment, a disk-shaped surface plate body 32 made of stainless steel (SUS) having a diameter of 50 mm, a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, a glass substrate, A catalyst surface plate 31 having a processing reference surface 33 (film thickness 100 nm) made of a ruthenium niobium (RuNb) alloy formed on the entire surface of the urethane pad on the opposite side was used. The processing reference surface 33 was formed by using a ruthenium niobium (RuNb) target and performing sputtering in an argon (Ar) gas atmosphere. When the crystal structure of the processing reference plane 33 made of a ruthenium niobium (RuNb) alloy was measured with an X-ray diffractometer (XRD), it was an amorphous structure. The composition of the processing reference surface 33 analyzed by X-ray photoelectron spectroscopy was Ru: 80 atomic% and Nb: 20 atomic%.
Otherwise, a glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced in the same manner as in Example 1.

Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.043 nm in terms of root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.043 nm in terms of root mean square roughness (RMS) by catalyst-based etching. Moreover, the surface roughness of the upper surface after processing was as good as 0.335 nm at the maximum height (Rmax). The ratio of the root mean square roughness to the maximum height (Rmax / RMS) was as good as 7.8.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface after processing was as small as 16.
Moreover, when 20 glass substrates were produced by the method of Example 2, the total number and the surface roughness were as good as 0.08 nm or less in terms of root mean square roughness (RMS), and the number of defects was also 50 or less. There were few.
By the method of Example 2, a glass substrate having a highly smooth and low-defect main surface was stably obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the high smoothness of the upper surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film after processing was as small as 14.
By the method of Example 2, a substrate with a multilayer reflective film having a highly smooth and low-defect protective film surface was obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which maintained the surface state of high smoothness and a low defect by the method of Example 2 were obtained.

Example 3
In this embodiment, a disk-shaped surface plate body 32 made of stainless steel (SUS) having a diameter of 50 mm, a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, a glass substrate, A catalyst surface plate 31 having a processing reference surface 33 (film thickness 100 nm) made of a tantalum hafnium (TaHf) alloy formed on the entire surface of the urethane pad on the opposite side was used. The processing reference surface 33 was formed by using a tantalum hafnium (TaHf) target and performing sputtering in an argon (Ar) gas atmosphere. When the crystal structure of the processing reference plane 33 made of a tantalum hafnium (TaHf) alloy was measured by an X-ray diffractometer (XRD), it was not an amorphous structure. The composition of the processing reference surface 33 analyzed by X-ray photoelectron spectroscopy was Ta: 80 atomic% and Hf: 20 atomic%.
Otherwise, a glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced in the same manner as in Example 1.

Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.047 nm in root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.047 nm in terms of root mean square roughness (RMS) by catalyst-based etching. Further, the surface roughness of the upper surface after processing was as good as 0.442 nm at the maximum height (Rmax). The ratio of the root mean square roughness to the maximum height (Rmax / RMS) was as good as 9.4.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface after processing was as small as 22.
Moreover, when 20 glass substrates were produced by the method of Example 3, the total number and the surface roughness were as good as 0.08 nm or less in root mean square roughness (RMS), and the number of defects was 50 or less. There were few.
By the method of Example 3, a glass substrate having a highly smooth and low-defect main surface was stably obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the high smoothness of the upper surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film after processing was as small as 19 pieces.
By the method of Example 3, a substrate with a multilayer reflective film having a highly smooth and low defect protective film surface was obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which maintained the surface state of high smoothness and a low defect by the method of Example 3 were obtained.

Example 4
In this embodiment, a disk-shaped surface plate body 32 made of stainless steel (SUS) having a diameter of 50 mm, a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, a glass substrate, A catalyst surface plate 31 having a processing reference surface 33 (film thickness 100 nm) made of an iron nickel chromium (FeNiCr) alloy formed on the entire surface of the urethane pad on the opposite side was used. The processing reference surface 33 was formed by sputtering in an argon (Ar) gas atmosphere using an iron nickel chromium (FeNiCr) target. When the crystal structure of the processing reference surface 33 made of an iron nickel chromium (FeNiCr) alloy was measured by an X-ray diffractometer (XRD), it was not an amorphous structure. The composition of the processing reference surface 33 analyzed by X-ray photoelectron spectroscopy was Ni: 0.5 atomic%, Cr: 14 atomic%, and Fe: balance.
Otherwise, a glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced in the same manner as in Example 1.

Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.060 nm in terms of root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.060 nm in root mean square roughness (RMS) by catalyst-based etching. Further, the surface roughness of the upper surface after processing was as good as 0.582 nm at the maximum height (Rmax). The ratio of the root mean square roughness to the maximum height (Rmax / RMS) was as good as 9.8.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface after processing was as small as 40.
Moreover, when 20 glass substrates were produced by the method of Example 4, the total number and the surface roughness were as good as 0.08 nm or less in root mean square roughness (RMS), and the number of defects was 50 or less. There were few.
By the method of Example 4, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the high smoothness of the upper surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film after processing was as small as 58.
By the method of Example 4, a substrate with a multilayer reflective film having a highly smooth and low defect protective film surface was obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which maintained the surface state of high smoothness and a low defect by the method of Example 4 were obtained.

Example 5 FIG.
In this embodiment, a disk-shaped surface plate body 32 made of stainless steel (SUS) having a diameter of 50 mm, a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, a glass substrate, A catalyst surface plate 31 having a processing reference surface 33 (film thickness 100 nm) made of chromium carbide (CrC) formed on the entire surface of the urethane pad on the opposite side was used. The processing reference surface 33 was formed by performing reactive sputtering in a mixed gas atmosphere of argon (Ar) gas and methane (CH ₄ ) gas using a chromium (Cr) target. The composition of the processing reference surface 33 analyzed by X-ray photoelectron spectroscopy was Cr: 96 atomic% and C: 4 atomic%.
Moreover, in this Example, the glass substrate removed from the support part 21 was washed as follows. First, the glass substrate was immersed in a cleaning tank containing a chromium etching solution containing ceric ammonium nitrate and perchloric acid for about 10 minutes. After that, neutral detergent and water were supplied to the upper surface used as the main surface of the glass substrate, and brush cleaning was performed to scrape off foreign matter adhering to the upper surface by rubbing the upper surface of the glass substrate with a polyvinyl alcohol (PVA) brush. . Thereafter, hydrogen water (H ₂ concentration: 1.2 ppm) is supplied to the upper surface of the glass substrate after the brush cleaning, and ultrasonic vibration (frequency: 3 MHz) is applied to the upper surface to float and remove the foreign matter adhering to the upper surface. Sonic cleaning was performed. Thereafter, two-fluid cleaning with nitrogen (N ₂ ) gas and carbonated water (electrical resistivity: 0.2 MΩ · cm) was performed. Thereafter, rinsing with pure water and drying were performed.
Otherwise, a glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced in the same manner as in Example 1.

Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.063 nm in terms of root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.063 nm in terms of root mean square roughness (RMS) by catalyst-based etching. Further, the surface roughness of the upper surface after processing was as good as 0.523 nm at the maximum height (Rmax). The ratio of the root mean square roughness to the maximum height (Rmax / RMS) was as good as 8.3.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface after processing was as small as 14.
Moreover, when 20 glass substrates were produced by the method of Example 5, the total number and the surface roughness were as good as 0.08 nm or less in terms of root mean square roughness (RMS), and the number of defects was also 50 or less. There were few.
By the method of Example 5, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the high smoothness of the main surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film after processing was as small as 12.
By the method of Example 5, a substrate with a multilayer reflective film having a highly smooth and low defect protective film surface was obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which maintained the surface state of high smoothness and a low defect by the method of Example 5 were obtained.

Example 6
A. Production of Glass Substrate In this example, a synthetic quartz glass substrate of 6025 size (152 mm × 152 mm × 6.35 mm) whose upper and lower surfaces were polished was prepared. The synthetic quartz glass substrate is obtained through the above-described rough polishing process, precision polishing process, and ultraprecision polishing process.
Otherwise, a glass substrate was produced in the same manner as in Example 1.

Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.17 nm in terms of root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.059 nm in terms of root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.17 nm to 0.059 nm in terms of root mean square roughness (RMS) by catalyst-based etching. Further, the surface roughness of the upper surface after processing was as good as 0.472 nm at the maximum height (Rmax). The ratio of the root mean square roughness to the maximum height (Rmax / RMS) was as good as 8.0.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface after processing was as small as 37.
Moreover, when 20 glass substrates were produced by the method of Example 6, the total number and the surface roughness were as good as 0.08 nm or less in root mean square roughness (RMS), and the number of defects was 50 or less. There were few.
By the method of Example 6, a glass substrate having a highly smooth and low-defect main surface was stably obtained.

B. Production of Halftone Phase Shift Mask Blank Next, a molybdenum silicide (MoSi) target is used on the upper surface of the glass substrate thus produced, and argon (Ar) gas, nitrogen (N ₂ ) gas, and oxygen are used. Reactive sputtering was performed in a mixed gas atmosphere with (O ₂ ) gas to form a light semi-transmissive film (film thickness: 88 nm) made of molybdenum silicide oxynitride (MoSiON). The film composition of the light translucent film analyzed by Rutherford backscattering analysis was Mo: 5 atomic%, Si: 30 atomic%, O: 39 atomic%, and N: 26 atomic%. The transmittance of the light semi-transmissive film with respect to the exposure light was 6%, and the phase difference caused by the exposure light passing through the light semi-transmissive film was 180 degrees.
Thereafter, a chromium (Cr) target is used on the light semi-transmissive film, and in a mixed gas atmosphere of argon (Ar) gas, carbon dioxide (CO ₂ ), nitrogen (N ₂ ) gas, and helium (He) gas. Reactive sputtering (DC sputtering) is performed to form a chromium oxycarbonitride (CrOCN) layer (thickness 30 nm), and further, a chromium (Cr) target is used thereon, and argon (Ar) gas and nitrogen are formed. Reactive sputtering is performed in a mixed gas atmosphere with (N ₂ ) gas to form a chromium nitride (CrN) layer (film thickness: 4 nm), and a chromium oxycarbonitride (CrOCN) layer and chromium nitride (CrN) A light-shielding layer comprising a laminate with the layer was formed. Further, a chromium (Cr) target is used on the light shielding layer, and a mixed gas atmosphere of argon (Ar) gas, carbon dioxide (CO ₂ ) gas, nitrogen (N ₂ ) gas, and helium (He) gas is used. Reactive sputtering was performed to form a surface antireflection layer (film thickness: 14 nm) made of chromium oxycarbonitride (CrOCN). In this way, a light shielding film composed of the light shielding layer and the surface antireflection layer was formed.
Thus, to produce a half-preparative chromatography emission type phase shift mask blank for ArF excimer laser exposure was maintained surface condition of and low defect at high smoothness.

C. Production of halftone phase shift mask Next, a chemical amplification resist for electron beam drawing (exposure) is applied onto the light-shielding film of the halftone phase shift mask blank produced in this way by a spin coating method. Through a heating and cooling process, a resist film having a thickness of 150 nm was formed.
Thereafter, a desired pattern was drawn on the formed resist film using an electron beam drawing apparatus, and then developed with a predetermined developer to form a resist pattern.
Thereafter, using this resist pattern as a mask, the light shielding film was dry etched to form a light shielding film pattern on the light semi-transmissive film. As the dry etching gas, a mixed gas of chlorine (Cl ₂ ) gas and oxygen (O ₂ ) gas was used.
Thereafter, using the resist pattern and the light shielding film pattern as a mask, the light semi-transmissive film was dry-etched to form a light semi-transmissive film pattern. As the dry etching gas, a mixed gas of sulfur hexafluoride (SF ₆ ) gas and helium (He) gas was used.
Thereafter, the remaining resist pattern is peeled off, a resist film is applied again, pattern exposure is performed to remove an unnecessary light-shielding film pattern in the transfer region, and then the resist film is developed to form a resist pattern. .
Thereafter, wet etching was performed to remove an unnecessary light shielding film pattern.
Thereafter, the remaining resist pattern was peeled off and washed.
In this manner, a halftone phase shift mask for ArF excimer laser exposure, which maintains a high smoothness and a low defect surface state, was prepared.

In this embodiment, the present invention is applied to a halftone phase shift mask or a phase shift mask blank having a light semi-transmissive film made of molybdenum silicide oxynitride (MoSiON), but from molybdenum silicide nitride (MoSiN). The present invention can also be applied to a halftone phase shift mask or a phase shift mask blank having a light semi-transmissive film. The present invention is not limited to halftone phase shift masks and phase shift mask blanks having a single-layer light semi-transmissive film, but also to halftone phase shift masks and phase shift mask blanks having a multi-layered light semi-transmissive film. The invention can be applied. Further, the present invention can be applied not only to a halftone phase shift mask and a phase shift mask blank having a multi-layered light shielding film, but also to a halftone phase shift mask and a phase shift mask blank having a single-layer light shielding film. . Further, the present invention can be applied not only to the halftone phase shift mask blank and the phase shift mask blank but also to a Levenson type phase shift mask blank, a phase shift mask blank, a chromeless type phase shift mask blank, and a phase shift mask blank.
In this example, the present invention was applied to the case where the main surface of the glass substrate obtained through the rough polishing process, the precision polishing process, and the ultraprecision polishing process was subjected to processing by catalyst-based etching. However, the present invention can also be applied to the case where the main surface of the glass substrate obtained through the local processing step and the touch polishing step performed in Example 1 is processed by catalyst-based etching.

Comparative Example 1
In this embodiment, a disk-shaped surface plate body 32 made of stainless steel (SUS) having a diameter of 50 mm, a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, a glass substrate, A catalyst surface plate 31 provided with a processing reference surface 33 (film thickness 100 nm) made of iron (Fe) formed on the entire surface of the urethane pad on the opposite side was used. The processing reference surface 33 was formed on a urethane pad by using an iron (Fe) target and performing sputtering in an argon (Ar) gas atmosphere.
Otherwise, a glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced in the same manner as in Example 1.

Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (RMS).
The surface roughness of the upper surface after processing was insufficient at 0.140 nm in terms of root mean square roughness (RMS). The surface roughness of the upper surface deteriorated from 0.13 nm to 0.140 nm in terms of root mean square roughness (RMS) by catalyst-based etching. Further, the surface roughness of the upper surface after processing was insufficient at 2.954 nm in terms of the maximum height (Rmax). The ratio of the root mean square roughness to the maximum height (Rmax / RMS) was 21.1, which was insufficient.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface after processing was as large as 2118.
Moreover, when 20 glass substrates were produced by the method of Comparative Example 1, the total number and the surface roughness were insufficient, such as the root mean square roughness (RMS) of 0.08 nm or more, and the number of defects was 2000 or more. There were many.
By the method of Comparative Example 1, a glass substrate having a main surface with high smoothness and low defects could not be obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the insufficient smoothness of the main surface of the glass substrate, the smoothness of the surface of the protective film was also insufficient, and the reflectance decreased by 2% compared with Example 1 to 62%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film after processing was as large as 3089.
By the method of Comparative Example 1, a substrate with a multilayer reflective film having a highly smooth and low defect protective film surface could not be obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which have the surface of high smoothness and a low defect by the method of the comparative example 1 were not obtained.

In the above-described embodiment, the present invention is applied to the case where the main surface of the reflective mask blank substrate or the phase shift mask blank substrate is processed by catalyst-based etching. However, the present invention is applied to binary mask blanks and nanoimprints. The present invention can also be applied to a case where the main surface of the mask blank is processed by catalyst-based etching.
In the above-described embodiment, the present invention is applied to the case where the main surface of the mask blank substrate is processed by the catalyst reference etching. However, the catalyst reference etching is performed on the main surface of the magnetic recording medium substrate. The present invention can also be applied when processing according to the above.

Example 7
A. Production of glass substrate Substrate preparation step A 2.5-inch (φ65 mm) aluminosilicate glass substrate having an upper surface and a lower surface polished was prepared. The aluminosilicate glass substrate has the following press molding process, coring process, chamfering process, end face polishing process, grinding process, first polishing (main surface polishing) process, chemical strengthening process, and second polishing (final polishing). It was obtained through the process.

(1) Press molding process (production of plate-shaped glass blank)
In production of a plate-shaped glass blank, a glass blank is produced by press-molding molten glass using a press mold.
In the press molding process, for example, a glass gob (glass lump) made of molten glass is supplied onto a lower mold that is a receiving gob forming mold, and a glass gob is used by using an upper mold that is a gob forming mold facing the lower mold. Is press-molded. Thereby, the disk-shaped glass blank used as the origin of the glass substrate for magnetic discs is shape | molded. Even if the surface processing amount (lapping amount + grinding amount + polishing amount), which is a machining allowance in lapping, grinding, first polishing, and second polishing, which will be described later, is reduced, the target plate thickness, for example, 0.8 mm is achieved. The target surface roughness, for example, the arithmetic average roughness Ra can be 0.15 nm or less, and the thickness of the glass blank produced by press molding is reduced from the viewpoint of suppressing an increase in cost. It is preferable to press-mold so that it may become 0.9 mm or less.
In addition, the plate-shaped glass immediately after shaping | molding is called a glass blank, and when subsequent processing is performed using this glass blank, this plate-shaped glass is called a glass base plate.

(2) Coring process Next, coring is performed using the produced disk-shaped glass blank as a glass base plate of the glass substrate for magnetic disks. In the coring step, specifically, an annular glass base plate is formed by forming an inner hole at the center of a disc-shaped glass base plate using a cylindrical diamond drill. At this time, an inner hole is formed by placing and fixing the glass base plate on a support base. The glass substrate is supported and fixed by the support base by sucking the glass base plate through a suction port provided on the surface of the support base. That is, a hole penetrating the glass base plate is formed by supporting and fixing one of the main surfaces of the glass base plate having a surface irregularity state on the main surface during press molding. In addition, the support base is provided with an elastic member in a portion in contact with the main surface of the glass base plate, and supporting and fixing the glass base plate using the elastic member does not damage the main surface of the glass base plate. This is preferable.

(3) Chamfering step After the coring step, a chamfering (chamfering) step of forming a chamfered surface at the ends (outer peripheral end surface and inner peripheral end surface) of the disk-shaped glass base plate is performed. In the chamfering step, the outer peripheral surface and the inner peripheral surface of the glass base plate processed into an annular shape by the coring step are chamfered by, for example, a general-purpose grindstone using diamond abrasive grains. The total type grindstone is a grinding tool in which a plurality of grindstone types having different abrasive grain sizes and different inclination angles of a grindstone surface that abuts the glass base plate for chamfering are prepared. Examples of the general grinding wheel include a tool described in Japanese Patent No. 3061605. With this general-purpose grindstone, the diameter of the glass base plate is adjusted to a predetermined size, for example, 65 mm, while chamfering. The end portion of the glass base plate has a side wall surface that is not chamfered perpendicular to the main surface and a chamfered chamfer surface. Hereinafter, the side wall surface and the chamfer surface are collectively referred to as an end surface.

(4) End face polishing step Next, end face polishing (edge polishing) of an annular glass base plate is performed.
In the end surface polishing, the inner peripheral end surface and the outer peripheral end surface of the annular glass base plate are mirror-finished by brush polishing. At this time, a plurality of glass base plates laminated by sandwiching end face polishing jigs such as spacers between the glass base plates are polished using a polishing brush. Further, the polishing liquid used for polishing contains fine particles such as cerium oxide as free abrasive grains. By polishing the end face, removing contamination such as dirt, damage or scratches attached to the end face of the glass base plate, preventing the occurrence of thermal asperity and causing corrosion such as Na and K It is possible to prevent the occurrence of ion precipitation.

(5) Grinding process Grinding is performed on the main surfaces on both sides of the annular and plate-shaped glass base plate using a double-side grinding apparatus. In the double-side grinding apparatus, a diamond sheet in which diamond abrasive grains are dispersed is used instead of the pad in the double-side polishing apparatus. In addition to the grinding process using fixed abrasive grains, a grinding process using loose abrasive grains may be performed. This grinding step improves the flatness, aligns the plate thickness, or further reduces the waviness before polishing (first polishing and second polishing) for reducing the main surface roughness of the glass base plate, which will be described later. To do.

(6) 1st grinding | polishing (main surface grinding | polishing) process Next, 1st grinding | polishing is given to the main surface of an annular | circular shaped glass base plate. The first polishing is performed with loose abrasive grains using a double-side polishing apparatus that performs planetary motion. Fine particles such as cerium oxide, zirconium oxide, and titanium oxide having a particle size (diameter) of about 0.5 to 2.0 μm are used for the free abrasive grains that are abrasives. This particle size is smaller than the particle size of diamond abrasive grains used for grinding. The purpose of the first polishing is to remove scratches and distortions remaining on the main surface by the grinding of (5), to adjust the waviness, and the fine waviness.

(7) Chemical strengthening process Next, the annular | circular shaped glass base plate after 1st grinding | polishing is chemically strengthened. As the chemical strengthening solution, for example, a mixed solution of potassium nitrate (60% by weight) and sodium nitrate (40% by weight) can be used. In the chemical strengthening, the chemical strengthening liquid is heated to, for example, 300 ° C. to 500 ° C., and the cleaned glass base plate is preheated to, for example, 200 ° C. to 300 ° C. For example, it is immersed for 1 to 4 hours. At the time of this immersion, using a cage (holder) that holds and stores the ends of a plurality of annular glass base plates so that the entire main surfaces of both annular glass base plates are chemically strengthened. Preferably it is done.
Thus, by immersing the glass base plate in the chemical strengthening solution, Li ions and Na ions in the surface layer of the glass base plate are converted into Na ions and K ions having a relatively large ion radius in the chemical strengthening solution, respectively. It is replaced and strengthened by forming a compression layer on the surface of the glass base plate. In addition, the annular | circular shaped glass base plate by which the chemical strengthening process was carried out is wash | cleaned. For example, after washing with sulfuric acid, it is washed with pure water or the like.

(8) Second Polishing (Final Polishing) Step Next, second polishing is applied to the glass base plate that has been chemically strengthened and sufficiently cleaned. The second polishing is intended for mirror polishing of the main surface. In the second polishing, for example, a polishing apparatus having the same configuration as the first polishing is used. At this time, the difference from the first polishing is that the type and particle size of the loose abrasive grains are different and the hardness of the pad is different. As the pad, a urethane polishing pad such as foamed urethane, a suede pad, or the like is used.
As the free abrasive grains used for the second polishing, for example, fine particles (particle size: diameter of about 10 to 50 nm) such as colloidal silica made of silica suspended in a polishing liquid are used. These fine particles are finer than the free abrasive grains used in the first polishing. The polishing liquid (slurry) in which fine particles such as colloidal silica are turbid contains, for example, 0.1 to 40% by mass, preferably 3 to 30% by mass of silica to ensure polishing processing efficiency and It is preferable at the point which raises roughness.
The polished glass base plate is cleaned. In the cleaning, it is preferable to use a neutral cleaning solution or an alkaline cleaning solution from the viewpoint of not forming defects such as scratches on the glass surface by the cleaning and further reducing the surface roughness. Thereby, the arithmetic average roughness Ra of the main surface can be set to 0.15 nm or less, for example, 0.13 to 0.15 nm. In addition to the neutral cleaning solution, a plurality of cleaning treatments using pure water, acid (acid cleaning solution), IPA, or the like can be performed. Thus, a glass substrate is prepared by washing the glass base plate.

2. Substrate processing step Next, using the substrate processing apparatus shown in FIGS. 1 and 2, the upper and lower surfaces (both sides) used as the main surface of the glass substrate after the second polishing step were processed by catalyst-based etching. .
In this example, a catalyst surface plate 31 provided with a processing reference surface 33 made of a ruthenium niobium (RuNb) alloy used in Example 2 was used.
The processing conditions are as follows.
Processing fluid: Pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 35 hPa
Processing allowance: 25nm

3. Evaluation In the same manner as in Example 1, the surface roughness of the main surface of the glass substrate before and after processing by catalyst-based etching was measured.
The surface roughness before processing was 0.12 nm in terms of root mean square roughness (RMS).
The surface roughness after processing was as good as 0.049 nm in terms of root mean square roughness (RMS).
The surface roughness was improved from 0.12 nm to 0.049 nm in terms of root mean square roughness (RMS) by catalyst-based etching. Further, the surface roughness after processing was as good as 0.38 nm in terms of the maximum height (Rmax). The ratio of the root mean square roughness to the maximum height (Rmax / RMS) was as good as 7.8.

B. Manufacture of magnetic recording medium (magnetic disk) Next, an adhesion layer, a soft magnetic layer, an underlayer, a magnetic recording layer, and a barrier layer are formed on both surfaces of the glass substrate thus prepared in an Ar gas atmosphere by a DC magnetron sputtering method. The auxiliary recording layers were sequentially formed.
The adhesion layer was made of 20 nm thick CrTi. The soft magnetic layer has a laminate structure of a first soft magnetic layer, a spacer layer, and a second soft magnetic layer. The first soft magnetic layer and the second soft magnetic layer were CoFeTaZr with a film thickness of 25 nm, and the spacer layer was Ru with a film thickness of 1 nm. The underlayer was NiW with a thickness of 5 nm. The magnetic recording layer has a laminated structure of a first magnetic recording layer and a second magnetic recording layer, the first magnetic recording layer is 10 nm thick CoCrPt—Cr ₂ O ₃ , and the second magnetic recording layer is 10 nm thick. CoCrPt—SiO ₂ —TiO ₂ was used. The barrier layer was Ru-WO ₃ having a thickness of 0.3 nm. The auxiliary recording layer was made of CoCrPtB having a thickness of 10 nm.
Next, a protective layer having a laminated structure of a hydrogenated carbon layer (C ₂ H ₄ ) and a carbon nitride layer (CN) with a thickness of 4 nm is formed on the auxiliary recording layer by a CVD method, and finally a par layer is formed by a dip coating method. A lubricating layer made of fluoropolyether (PFPE) having a film thickness of 1.3 nm was formed to produce a magnetic recording medium compatible with the DFH head.
In this way, the adhesion layer, the soft magnetic layer (the first soft magnetic layer, the spacer layer, the second soft magnetic layer), the underlayer, and the magnetic recording layer (the first magnetic recording layer and the first magnetic recording layer) are formed on both surfaces of the glass substrate, respectively. 2 magnetic recording layer), a barrier layer, an auxiliary recording layer, a protective layer, and a lubrication layer were sequentially formed to produce a magnetic recording medium (magnetic disk).
In addition, although the said adhesion layer was CrTi, it is not limited to this, For example, you may select from CoW type | system | group, CrW type | system | group, CrTa type | system | group, and CrNb type | system | group material. The first soft magnetic layer and the second soft magnetic layer of the soft magnetic layer are CoFeTaZr. However, the present invention is not limited to this. For example, other Co—Fe based alloys such as CoCrFeB, and cobalt based alloys such as CoTaZr. , [Ni-Fe / Sn] _n Ni-Fe alloy such as _n multilayer structure may be selected. The first magnetic recording layer of the magnetic recording layer is made of CoCrPt—Cr ₂ O ₃ and the second magnetic recording layer is made of CoCrPt—SiO ₂ —TiO _2. The second magnetic recording layer may have the same composition and type. Examples of nonmagnetic substances for forming nonmagnetic regions in these magnetic recording layers include chromium oxide (CrxOy) and titanium oxide as described above, for example, silicon oxide (SiOx), zircon oxide (ZrO ₂ ), Select from oxides such as tantalum oxide (Ta ₂ O ₅ ), iron oxide (Fe ₂ O ₃ ), boron oxide (B ₂ O ₃ ), nitrides such as BN, carbides such as B ₄ C ₃ , Cr, etc. May be. The barrier layer is Ru—WO ₃ , but is not limited thereto, and may be selected from Ru and other Ru alloys. The auxiliary recording layer is made of CoCrPtB, but is not limited to this. For example, the auxiliary recording layer may be selected from CoCrPt and may contain a small amount of oxide.
In addition, a pre-underlayer may be formed between the soft magnetic layer and the underlayer, or a nonmagnetic granular layer may be formed between the underlayer and the magnetic recording layer. The material of the front ground layer is selected from, for example, Ni, Cu, Pt, Pd, Zr, Hf, Nb, and Ta. The composition of the nonmagnetic granular layer can be a granular structure by forming a grain boundary by segregating a nonmagnetic substance between nonmagnetic crystal grains made of a Co-based alloy.

C. Load unload (LUL) durability test and DFH touchdown test The obtained magnetic recording medium (magnetic disk) was subjected to a LUL test in which the rotation speed was 7200 rpm and the flying height of the DFH head was 9 to 10 nm. As a result of the LUL test, no failure occurred even after repeated 1 million times. Normally, in the LUL durability test, it is necessary that the number of LULs continuously exceed 400,000 times without failure. The LUL number of 400,000 times is equivalent to the use for about 10 years in the normal HDD usage environment. In this way, an extremely reliable magnetic recording medium compatible with the DFH head was produced.
Further, a DFH touchdown test was performed on the obtained magnetic recording medium (magnetic disk). In the DFH touchdown test, the DFH head element unit is gradually projected from the obtained magnetic recording medium (magnetic disk) by the DFH mechanism, and contact with the surface of the magnetic disk is detected. This is a test for evaluating the distance contacted by the magnetic recording medium. As the head, a DFH head for a 320 GB / P magnetic disk (2.5 inch size) was used. The flying height when the DFH head element portion did not protrude was 10 nm, the evaluation radius was 22 mm, and the rotational speed of the magnetic disk was 5400 rpm. Moreover, the temperature at the time of a test was 25 degreeC, and the humidity was 60%. As a result, the distance that the DFH head element portion and the magnetic recording medium contacted each other was as good as 1.0 nm or less.

The main surface of the glass substrate for a magnetic recording medium obtained by the method for producing a substrate according to any one of the above-described configurations 1 to 13 has a root mean square roughness (RMS) of 0.05 nm or less and a maximum height. A glass substrate for a magnetic recording medium having a high smoothness of 0.5 nm or less (Rmax) and a ratio of root mean square roughness to maximum height (Rmax / RMS) of 8 or less is obtained.
A method for manufacturing a magnetic recording medium in which a magnetic recording layer is formed on the main surface of the substrate obtained by the method for manufacturing a substrate according to any one of the above-described configurations 1 to 13 can be used for a highly reliable DFH head. A magnetic recording medium can be obtained.

DESCRIPTION OF SYMBOLS 1 Substrate processing apparatus, 2 Substrate support means, 3 Substrate surface creation means, 4 Processing fluid supply means, 5 Drive means, 6 Chamber, 7 Relative motion means, 8 Load control means, 21 Support part, 22 Plane part, 22a Storage part 31 catalyst surface plate, 32 surface plate body, 33 processing reference surface, 41 supply pipe, 42 injection nozzle, 51 arm portion, 52 shaft portion, 53 base portion, 54 guide, 61 opening portion, 62 discharge port, 63 bottom portion, 71 Shaft part , 72 Catalyst surface plate mounting part, 81 Air cylinder, 82 Load cell, M substrate, M1 upper surface, M2 lower surface.

Claims (21)

A substrate preparation step of preparing a substrate having a main surface made of a material containing an oxide;
A processing reference surface formed by a catalyst material is brought into contact with or close to the main surface, and the main surface is processed by catalyst reference etching with a processing fluid interposed between the processing reference surface and the main surface. Substrate processing step,
The catalytic material, an alloy containing titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, data tungsten, iron, ruthenium, and at least two or more metals of osmium, as well as oxygen in the alloy, nitrogen, and A method for producing a substrate, comprising a material selected from the group consisting of alloy compounds containing at least one component of carbon.   2. The method for manufacturing a substrate according to claim 1, wherein the alloy compound is an oxide, nitride, carbide, oxynitride, oxycarbide, nitride carbide, or oxynitride carbide of the alloy. A substrate preparation step of preparing a substrate having a main surface made of a material containing an oxide;
A processing reference surface formed by a catalyst material is brought into contact with or close to the main surface, and the main surface is processed by catalyst reference etching with a processing fluid interposed between the processing reference surface and the main surface. Substrate processing step,
The catalytic material, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and alloys compounds which nitrogen is contained in the alloy containing at least one metal of osmium, and A method for producing a substrate, comprising a material having an amorphous structure selected from the group consisting of metal compounds containing nitrogen in the metal.   4. The method for manufacturing a substrate according to claim 3, wherein the alloy compound is a nitride of the alloy.   The method for manufacturing a substrate according to claim 3, wherein the metal compound is a nitride of the metal. A substrate preparation step of preparing a substrate having a main surface made of a material containing an oxide;
A processing reference surface formed by a catalyst material is brought into contact with or close to the main surface, and the main surface is processed by catalyst reference etching with a processing fluid interposed between the processing reference surface and the main surface. Substrate processing step,
The catalyst material includes an alloy compound in which carbon is contained in an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and A method for producing a substrate, comprising a material selected from the group consisting of metal compounds containing carbon in the metal.   The method of manufacturing a substrate according to claim 6, wherein the alloy compound is a carbide, oxide carbide, nitride carbide, or oxynitride carbide of the alloy.   The method for manufacturing a substrate according to claim 6, wherein the metal compound is a carbide, oxide carbide, nitride carbide, or oxynitride carbide of the metal.   9. The substrate according to claim 1, wherein in the substrate processing step, the main surface is processed by catalyst-based etching by relatively moving the catalyst surface and the main surface. Production method.   The substrate manufacturing method according to claim 1, wherein the main surface of the substrate prepared in the substrate preparation step has a root mean square roughness of 0.3 nm or less.   The method for manufacturing a substrate according to claim 1, wherein the substrate is made of a glass material.   The method for manufacturing a substrate according to claim 1, wherein the processing fluid is made of a solvent that is not normally soluble in the substrate.   The method for manufacturing a substrate according to claim 12, wherein the processing fluid is made of pure water.   The substrate manufacturing method according to claim 1, wherein the substrate is a mask blank substrate.   A method for producing a substrate with a multilayer reflective film, comprising: forming a multilayer reflective film on a main surface of the substrate obtained by the method for producing a substrate according to claim 14.   On the main surface of the substrate obtained by the method for producing a substrate according to claim 14, or on the multilayer reflective film of the substrate with a multilayer reflective film obtained by the method for producing a substrate with a multilayer reflective film according to claim 15. A method for producing a mask blank, comprising forming a transfer pattern thin film.   A method for manufacturing a transfer mask, comprising: patterning a thin film for transfer pattern of a mask blank obtained by the method for manufacturing a mask blank according to claim 16 to form a transfer pattern. A substrate processing apparatus for processing the main surface of a substrate by catalyst-based etching,
Substrate support means for supporting a substrate having a main surface made of a material containing an oxide;
A substrate surface creation means having a processing reference surface formed by a catalyst material;
Processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface;
Drive means for bringing the processing reference surface into contact with or approaching the main surface in a state where a processing fluid is interposed between the processing reference surface and the main surface;
The catalytic material, an alloy containing titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, data tungsten, iron, ruthenium, and at least two or more metals of osmium, as well as oxygen in the alloy, nitrogen, and A substrate processing apparatus comprising a material selected from the group consisting of an alloy compound containing at least one component of carbon. A substrate processing apparatus for processing the main surface of a substrate by catalyst-based etching,
Substrate support means for supporting a substrate having a main surface made of a material containing an oxide;
A substrate surface creation means having a processing reference surface formed by a catalyst material;
Processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface;
Drive means for bringing the processing reference surface into contact with or approaching the main surface in a state where a processing fluid is interposed between the processing reference surface and the main surface;
The catalytic material, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and alloys compounds which nitrogen is contained in the alloy containing at least one metal of osmium, and A substrate processing apparatus comprising an amorphous material selected from the group consisting of metal compounds containing nitrogen in the metal. A substrate processing apparatus for processing the main surface of a substrate by catalyst-based etching,
Substrate support means for supporting a substrate having a main surface made of a material containing an oxide;
A substrate surface creation means having a processing reference surface formed by a catalyst material;
A processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface of the substrate;
Drive means for bringing the processing reference surface into contact with or approaching the main surface in a state where a processing fluid is interposed between the processing reference surface and the main surface;
The catalyst material includes an alloy compound in which carbon is contained in an alloy containing at least one metal of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, ruthenium, and osmium, and A substrate processing apparatus comprising a material selected from the group consisting of metal compounds containing carbon in the metal.   21. The substrate processing apparatus according to claim 18, further comprising a relative motion unit that relatively moves the processing reference surface and the main surface.

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