JP6534506B2 - Method of manufacturing substrate, method of manufacturing substrate with multilayer reflective film, method of manufacturing mask blank, method of manufacturing transfer mask, and substrate processing apparatus - Google Patents

Description

  The present invention relates to a method of manufacturing a substrate, a method of manufacturing a multilayer reflective film coated substrate using this substrate, a method of manufacturing a mask blank using this substrate or a multilayer reflective film coated substrate, a transfer mask using this mask blank The present invention relates to a manufacturing method and a substrate processing apparatus.

  Reflective mask blanks for EUV exposure, binary mask blanks and phase shift mask blanks for ArF excimer laser exposure, and nanoimprints as mask blanks used in semiconductor design rule 1x generation (half pitch (hp) 14 nm, 10 nm, etc.) There is a mask blank for

  In mask blanks used in the semiconductor design rule 1x generation, defects of 30 nm grade (defects with SEVD of 21.5 nm or more and 34 nm or less) or defects of smaller size may become a problem. For this reason, it is preferable that the main surface (that is, the surface on which the transfer pattern is formed) of the substrate used for the mask blank have as few defects as 30 nm grade as possible. Also, in a high sensitivity defect inspection apparatus for inspecting defects of 30 nm class defects, surface roughness affects background noise. That is, when the smoothness is insufficient, many pseudo defects caused by surface roughness are detected, and defect inspection can not be performed. Therefore, 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 0.10 nm or less, more preferably 0.08 nm or less in root mean square roughness (Rms) It is done.

  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 magnetic head for recording and reading on the magnetic recording media has become increasingly lower. There is. In order to realize low flying height, magnetic heads equipped with a dynamic flying height (DFH) mechanism are in widespread use. In the magnetic head having the DFH mechanism mounted thereon, the thermal expansion body is disposed on the magnetic head, and the thermal expansion body is heated and expanded to control the flying height uniformly.

  In the magnetic head equipped with the DFH mechanism, since the flying height is controlled to about several nm, defects such as head crash are likely to occur. In order to reduce such defects, the main surface (the surface on which the magnetic layer containing the magnetic material is formed) of the substrate used for the magnetic recording medium has high smoothness and there are no protrusions projecting from the main surface. The state is preferred. In the case where the magnetic layer is formed on both the upper surface and the lower surface of the magnetic recording medium, both surfaces are the main surfaces.

  Heretofore, various processing methods have been proposed in order to make the main surfaces of the mask blank substrate and the magnetic recording medium substrate high-smoothness, low-defect, and free from protrusions, but desired characteristics are desired. It is difficult to realize a substrate having a main surface that satisfies

  In recent years, a processing method using catalyst-based etching (CARE) has been proposed as a processing method of a substrate for which a main surface is required to have high smoothness, low defects, and no projections. In catalytic reference etching (CARE) processing, a hydroxyl group is generated as an active species from molecules in a processing fluid adsorbed on a processing reference surface formed of a catalyst substance, and the substrate brings the processing reference surface into or out of contact with this substrate. It is thought 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 approached the surface of a workpiece made of solid oxide such as glass, and the processing reference surface and the surface of the workpiece are moved relative to each other. Describes a method of processing a solid oxide which removes the decomposition product by hydrolysis from the surface of the workpiece and processes the surface of the workpiece (hereinafter, the method of processing the solid oxide is also referred to as CARE processing) ). As the catalyst substance, one containing a metal element and having the d orbital of the electron of the metal element near the Fermi level is used. Specifically, as the metal element, for example, platinum (Pt), gold (Au), silver (Ag) And copper (Cu), nickel (Ni), chromium (Cr) and molybdenum (Mo).

  In CARE processing, a catalyst platen is used in which a processing reference surface made of a catalyst material is provided on the surface opposite to 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 which is inexpensive and has good shape stability.

If the processing reference surface is fragile or soft, the processing reference surface may be peeled off during CARE processing, which may damage the substrate surface. In addition, if the processing reference surface is peeled off, the peeled portion may lose its function as a catalyst, and uniform and stable processing of the substrate surface may not be possible. For this reason, in order to stably manufacture a substrate having a surface with high smoothness and low defects by CARE processing, it is preferable to use a processing reference surface with good (not brittle, hard) mechanical durability.
Also, if the processing reference surface is rusted by the processing fluid during CARE processing, the rusted portion may lose its function as a catalyst, and uniform and stable processing of the substrate surface may not be possible. In addition, if the processing reference surface is rusted, it may become brittle and damage the substrate surface as described above. For this reason, in order to stably produce a substrate having a surface with high smoothness and low defects by CARE processing, it is preferable to use a processing reference surface that has good chemical stability (it is difficult to rust due to the processing fluid) .
In addition, when the processing reference surface is uneven, since the recess is separated from the substrate surface during CARE processing, it does not function as a catalyst, and uniform and stable processing of the substrate surface may not be possible. In addition, the uneven shape of the processing reference surface may be transferred to the substrate surface, and the smoothness of the substrate surface may be impaired. For this reason, it is preferable to use a flat processing reference surface in order to stably manufacture a substrate having a surface with high smoothness and low defects by CARE processing.
In addition, if oxidation of the processing reference surface progresses during CARE processing, the catalytic function of the processing reference surface changes, so that the processing rate during CARE processing changes, processing time is not constant, and throughput and manufacturing cost etc. There is a possibility that stable processing can not be performed on the surface. For this reason, in order to stably manufacture a substrate having a surface with high smoothness and low defects by CARE processing, it is preferable to use a processing reference surface in which oxidation does not easily progress.
Further, when the processing reference surface has a film-like configuration, it is preferable to form the processing reference surface with a catalyst substance that is easy to form a film, and when the processing reference surface has a bulk configuration, the catalyst that can be easily processed. Preferably, the material forms a processing reference surface.
In addition, there is a possibility that the catalyst material forming the processing reference surface may remain on the substrate surface after the CARE processing. Remaining catalytic material on the substrate surface may cause defects due to the remaining catalytic material. Therefore, in order to remove the catalyst material remaining on the substrate surface, it is necessary to clean the substrate surface after CARE processing. At this time, if the cleaning liquid which 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 surface with high smoothness and low defects by CARE processing, the processing reference surface is made of a catalyst material that is easily soluble in the cleaning liquid that does not damage the substrate surface (does not impair the smoothness). It is preferable to form.
The processing reference surface preferably has the above-mentioned characteristics.

International Publication No. 2013/084934

  However, when the processing reference surface is formed of the conventional metal alone, only the characteristics of the metal alone can be obtained on the processing reference surface, and the mechanical durability and chemical stability are insufficient, or CARE processing Oxidation may progress during the process. If the mechanical durability is insufficient, as described above, the processing reference surface may peel during CARE processing, which may damage the substrate surface. In addition, if the processing reference surface is peeled off, there is a possibility that uniform and stable processing of the substrate surface can not be performed. In addition, if the chemical stability is insufficient, as described above, the processing reference surface may rust during CARE processing, and uniform and stable processing of the substrate surface may not be possible. Also, if the processing reference surface is rusted, it may become brittle and damage the substrate 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 may change.

  Therefore, the present invention has been made in view of the above-mentioned problems, and a method of manufacturing a substrate capable of stably manufacturing a substrate having a main surface with high smoothness and low defects, and the substrate A method of manufacturing a multilayer reflective film coated substrate, a method of manufacturing a mask blank using the substrate or a multilayer reflective film coated substrate, a method of manufacturing a transfer mask using the mask blank, and a substrate processing apparatus To aim.

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

(Structure 1) A substrate preparing 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 catalyst reference etching in a state in which a processing reference surface of a catalyst material 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 and
The catalyst material includes a material selected from the group consisting of a metal belonging to Groups 3 to 12 of the periodic table of elements and an alloy containing at least one of the metals,
The processing reference surface has, in its surface layer, an oxidation progress inhibiting layer formed by including at least one of nitrogen and oxygen in the metal or the alloy, or a nitride of the metal or the alloy in the surface layer. And a method of manufacturing a substrate comprising a film having an oxidation progress suppressing film made of an oxide or an oxynitride.

(Configuration 2) A removal step of removing all or part of the oxidation progress suppression layer or all or part of the oxidation progress suppression film,
The processing reference surface includes the metal or the alloy exposed in the removal step, or the oxidation progress suppression layer or the oxidation progress suppression film exposed in the removal step on the surface layer of the processing reference surface. 7. A method of manufacturing a substrate according to configuration 1 comprising the one having:

(Structure 3) The method for manufacturing a substrate according to Structure 2, wherein the removing step utilizes at least one of physical action and chemical action.

(Structure 4) In the substrate processing step, the main surface is processed by catalyst reference etching by causing the processing reference surface and the main surface to move relative to each other. The manufacturing method of the described board | substrate.

(Structure 5) The main surface of the substrate prepared in the substrate preparation step has a root mean square roughness of 0.3 nm or less, and the manufacture of the substrate according to any one of the structures 1 to 4 Method.

(Structure 6) The method for manufacturing a substrate according to any one of the structures 1 to 5, wherein the substrate is made of a glass material.

(Structure 7) The method for manufacturing a substrate according to any one of the structures 1 to 6, wherein the processing fluid is a solvent that does not exhibit solubility in the normal state with respect to the substrate.

(Structure 8) The method for manufacturing a substrate according to structure 7, wherein the processing fluid is pure water.

(Structure 9) The method according to any one of structures 1 to 8, wherein the substrate is a mask blank substrate.

(Structure 10) A method for manufacturing a multilayer reflective film coated substrate, comprising forming a multilayer reflective film on the main surface of the substrate obtained by the method for manufacturing a substrate according to the configuration 9.

(Structure 11) On the main surface of the substrate obtained by the method for manufacturing a substrate according to Structure 9 or on the multilayer reflective film obtained with the method for manufacturing a substrate with a multilayer reflection film according to Structure 10 A method of manufacturing a mask blank, comprising: forming a thin film for transfer pattern.

(Structure 12) A transfer mask is formed by patterning the thin film for transfer pattern formation of the mask blank obtained by the method for manufacturing a mask blank according to Structure 11 to form a transfer pattern on the main surface. Production method.

(Structure 13) A substrate processing apparatus for processing a main surface of a substrate by catalyst-based etching,
Substrate supporting means for supporting a substrate having a main surface made of an oxide-containing material;
A substrate surface creation means having a processing reference surface of a catalytic substance;
Processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface;
And driving means for bringing the processing reference surface into contact with or close to the main surface, with a processing fluid being interposed between the processing reference surface and the main surface.
The catalyst material includes a material selected from the group consisting of a metal belonging to Groups 3 to 12 of the periodic table of elements and an alloy containing at least one of the metals,
The processing reference surface has, in its surface layer, an oxidation progress inhibiting layer formed by including at least one of nitrogen and oxygen in the metal or the alloy, or a nitride of the metal or the alloy in the surface layer. What is claimed is: 1. A substrate processing apparatus comprising: an oxidation progress suppression film made of an oxide or an oxynitride.

(Structure 14) A substrate processing apparatus according to structure 13, characterized in that it has a removing means for removing all or part of the oxidation progress suppression layer or all or part of the oxidation progress suppression film.

(Structure 15) A substrate processing apparatus according to structure 13 or 14, further comprising relative movement means for moving the processing reference surface and the main surface relative to each other.

  As described above, according to the method of manufacturing a substrate according to the present invention, the processing reference surface of the catalyst material is brought into contact with or in close proximity to the main surface of the substrate, and the processing fluid is interposed between the processing reference surface and the main surface. In the state, the main surface is processed by catalyst reference etching. At that time, a material selected from the group consisting of a metal belonging to Groups 3 to 12 of the periodic table of the elements and an alloy containing at least one of the metals is used as a catalyst substance, and it is used as a processing reference surface A surface layer comprising an oxidation progress inhibiting layer comprising the metal or the alloy containing at least one of nitrogen and oxygen in the surface layer, or a nitride, oxide or oxynitride of the metal or the alloy in the surface layer What has an oxidation progress suppression film which consists of these is used. When such a processing reference surface is used, the mechanical resistance and chemical stability of the processing reference surface are improved by the oxidation progress suppression layer and the oxidation progress suppression film, and the progress of oxidation of the processing reference surface during CARE processing Can be suppressed. If the mechanical durability of the processing reference surface is improved, the processing reference surface may be peeled off during CARE processing, and there is less concern that the main surface of the substrate may be damaged or the peeled portion may lose its function as a catalyst. In addition, when the chemical stability of the processing reference surface is improved, the processing reference surface is rusted by the processing fluid during the CARE processing, the rusted portion loses the function as a catalyst, or the rusted portion is peeled off, on the main surface of the substrate. There is less risk of damage. In addition, when the progress of oxidation of the processing reference surface during CARE processing is suppressed, the catalytic function of the processing reference surface can be maintained, so that the processing rate can be maintained constant. Therefore, a substrate having a main surface with high smoothness and low defects can be stably manufactured by CARE processing performed while preventing deterioration of characteristics due to processing reference surface factors.

  Further, according to the method of manufacturing a multilayer reflective film coated substrate according to the present invention, deterioration of the characteristics due to the substrate factor can be prevented, and a multilayer reflective film coated substrate having desired characteristics can be manufactured.

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

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

  Further, according to the substrate processing apparatus according to the present invention, a substrate support means for supporting a substrate having a main surface made of an oxide-containing material, a substrate surface creation means having a processing reference surface of a catalyst substance, and a processing reference surface A processing fluid supply means for supplying a processing fluid between the surface and the main surface; driving means for bringing the processing reference surface into contact with or approach the main surface with the processing fluid being interposed between the processing reference surface and the main surface Is equipped. At that time, a material selected from the group consisting of a metal belonging to Groups 3 to 12 of the periodic table of the elements and an alloy containing at least one of the metals is used as a catalyst substance, and it is used as a processing reference surface A surface layer comprising an oxidation progress inhibiting layer comprising the metal or the alloy containing at least one of nitrogen and oxygen in the surface layer, or a nitride, oxide or oxynitride of the metal or the alloy in the surface layer What has an oxidation progress suppression film which consists of these is used. Therefore, as described above, it is possible to stably process the main surface of the substrate into a highly smooth and low defect state by CARE processing performed while preventing deterioration of the characteristics due to processing reference surface factors.

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

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

Embodiment 1
In the first embodiment, a method of manufacturing a substrate and a substrate processing apparatus will be described.

In the first embodiment, a substrate preparing step of preparing a substrate having a main surface made of an oxide-containing material, and bringing a processing reference surface of a catalytic substance into contact with or close to the main surface of the substrate, the processing reference surface and the main surface And a substrate processing step of processing the main surface of the substrate by catalyst-based etching while the processing fluid is interposed therebetween.
Each step will be described in detail below.

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

The substrate to be prepared may be, for example, a substrate made of a material containing the oxide as a whole, a substrate having a thin film made of a material containing the oxide on the top surface used as the main surface, and both the top and the bottom And a thin film made of a material containing an oxide.
The substrate on which the thin film is formed may be a substrate on which a thin film made of an oxide-containing material is formed on the upper and lower surfaces used as the main surface of the substrate main body made of an oxide-containing material. It may be a substrate in which a thin film made of an oxide-containing material is formed on the upper and lower surfaces used as the main surface of a substrate main body made of a material other than the contained material.
Examples of the material of the substrate and the substrate body made of an oxide-containing material include glasses such as synthetic quartz glass, soda lime glass, borosilicate glass, aluminosilicate glass, SiO ₂ -TiO ₂ glass, and glass ceramics. . Moreover, a silicon | silicone, carbon, and a metal are mentioned as a material of the board | substrate body which consists of materials other than the material containing an oxide.
As an oxide which forms a thin film, a silicon oxide, a metal oxide, and an alloy oxide are mentioned, for example. Specifically, as the silicon oxide, silicon oxide _(SiO x, x> 0) and a metal silicide oxide containing a metal and silicon _{(Me x Si y O z,} Me: metal, x> 0, y > 0, and z> 0). Further, as the metal oxide, tantalum oxide _{(TaO x, x> 0)} , ruthenium oxide (RuO _{x, x>} 0) and the like. As the alloy oxide, tantalum boron oxide _{(Ta x B y O z,} x> 0, y> 0, and z> 0), tantalum hafnium oxide _{(Ta x Hf y O z,} x> 0, y> 0, and z> 0), tantalum chromium oxide _{(Ta x Cr y O z,} x> 0, y> 0, and z> 0) and the like. A thin film made of such an oxide-containing material can be formed, for example, by vapor deposition, sputtering, or electroplating.
The substrate to be prepared is preferably a glass substrate which is resistant to plastic deformation and from which a high smoothness main surface can be easily obtained, or a thin film made of silicon oxide (SiO ₂ ) on the upper and lower surfaces which is the main surface of the glass substrate body. Is the formed substrate.

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 nanoimprinting mask blank. In the binary mask blank, the material of the light shielding film may be any of MoSi-based, Ta-based and Cr-based. The phase shift mask blank may be any of a halftone phase shift mask blank, a Levenson type phase shift mask blank, and a chromeless phase shift mask blank. The substrate material used for the reflective mask blank needs to be a material having low thermal expansion. Therefore, as a substrate material used for a reflective mask blank for EUV exposure, for example, a SiO ₂ -TiO ₂ based glass is preferable. In addition, the substrate material used for the transmission mask blank needs to be a material having transparency to the exposure wavelength to be used. Therefore, 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 process in order to enhance impact resistance, strength and rigidity. For this reason, as a substrate material used for the magnetic disk substrate, for example, multicomponent glasses such as borosilicate glass and aluminosilicate glass are preferable.

  The substrate to be prepared is preferably a substrate whose main surface has been polished using fixed abrasives or loose abrasives. For example, in order to have predetermined smoothness and flatness, the upper surface and the lower surface used as the main surface are polished using the following processing method. Even if the lower surface is not used as the main surface, the lower surface is also polished using the following processing method so as to have predetermined smoothness and flatness, as necessary. However, it is not necessary to carry out all the following processing methods, and it is appropriately selected and carried out so as to have predetermined smoothness and flatness.

Examples of processing methods for reducing surface roughness include polishing and lapping using abrasive grains such as cerium oxide and colloidal silica.
As a processing method for improving flatness, for example, magneto-viscoelastic fluid polishing (MRF), local chemical mechanical polishing (LCMP), gas cluster ion beam etching (Gas Cluster Ion Beam etching) GCIB), and Dry Chemical Planarization (DCP) using localized plasma etching.
MRF is a local processing method in which polishing is performed locally by bringing a magnetic polishing slurry prepared by mixing a polishing slurry into a magnetic fluid and contacting the workpiece at a high speed, and controlling the residence time of the contact portion.
LCMP uses a polishing slurry containing polishing abrasives such as a small-diameter polishing pad and colloidal silica, and mainly controls the convexity of the surface of the workpiece by controlling the residence time of the contact portion between the small-diameter polishing pad and the workpiece. This is a local processing method of polishing the part.
GCIB generates a gas cluster ion by injecting a reactive substance (source gas) gaseous at a normal temperature and normal pressure while adiabatically expanding into a vacuum device, thereby generating a gas cluster ionized by electron irradiation. This is a local processing method in which ions are accelerated in 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 of locally performing dry etching by locally performing plasma etching and controlling the plasma etching amount in accordance with the degree of convexity.
As a processing method for improving the surface roughness while maintaining the flatness as much as possible in order to improve the surface roughness damaged by the processing method for improving the flatness described above, for example, float polishing, EEM (Elastic (Elastic) There is Emission Machining) and hydroplane polishing.

  In order to shorten the processing time by the catalyst reference etching, the main surface of the prepared substrate preferably 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 main surface is processed by catalyst reference etching in a state where the processing reference surface of the catalyst material is brought into contact with or in close proximity to the main surface of the substrate and the processing fluid is interposed between the processing reference surface and the main surface. Do.
When both surfaces of the upper surface and lower surface of the substrate are used as the main surface, CARE processing of the lower surface may be performed after CARE processing of the upper surface, or CARE processing of the upper surface may be performed after CARE processing of the lower surface, or the upper surface CARE processing of both surfaces 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, if necessary. When CARE processing is also performed on the lower surface not used as the main surface, high quality is required for the upper surface used as the main surface in terms of defect quality, so after processing the lower surface, the upper surface used as the main surface It is preferable to carry out processing.

  In this case, first, a processing reference surface made of a catalyst material is disposed to face the main surface of the substrate. Then, a processing fluid is supplied between the processing reference surface and the main surface, and the processing reference surface is brought into contact with or close to the main surface, with the processing fluid being interposed between the processing reference surface and the main surface, The processing reference surface and the main surface are moved relative to each other while applying a predetermined load (processing pressure) to the substrate. 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 to process the main surface. The active species are generated only on the processing reference surface and deactivated when separated from the vicinity of the processing reference surface, so that almost no reaction with the active species occurs except on the main surface to which the processing reference surface contacts or approaches. Thus, the main surface is processed by catalyst-based etching. In the processing by the catalyst reference etching, since the polishing agent is not used, damage to the substrate is extremely small, and the 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, when the processing reference surface is fixed and the substrate is moved, either of the processing reference surface and the substrate may be moved. When the processing reference surface moves, the movement may be, for example, when it rotates around an axis in a direction perpendicular to the main surface of the substrate, or when it reciprocates in a direction parallel to the main surface of the substrate. Similarly, when the substrate is moved, the movement may be, for example, when it rotates around an axis in a direction perpendicular to the main surface of the substrate, or when it 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 processing allowance in the processing by the catalyst reference etching is, for example, 5 nm to 100 nm. When a protrusion protruding from the main surface is present 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 protrusions, the protrusions can be removed by CARE processing.

  A material selected from the group consisting of metals belonging to Groups 3 to 12 of the periodic table of the elements and an alloy containing at least one of the metals is used as a catalyst material for forming the processing reference surface. As a processing reference surface, the surface layer thereof has an oxidation progress inhibiting layer formed by adding at least one of the metal or the alloy to nitrogen and oxygen, or the surface layer includes a nitride of the metal or the alloy, A film having an oxidation progress suppressing film made of oxide or oxynitride is used. That is, the processing reference surface is configured to have the above-described oxidation progress suppression layer and oxidation progress suppression film on the base made of the above-described metal or alloy. When such a processing reference surface is used, the mechanical resistance and chemical stability of the processing reference surface are improved by the oxidation progress suppression layer and the oxidation progress suppression film, and the progress of oxidation of the processing reference surface during CARE processing Can be suppressed.

  Specifically, scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V) as metals belonging to Groups 3 to 12 of the periodic table of the elements , Niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru) Osmium (Os), Borium (Bh), Cobalt (Co), Rhodium (Rh), Iridium (Ir), Hassium (Hs), Nickel (Ni), Palladium (Pd), Platinum (Pt), Copper (Cu) And silver (Ag), gold (Au), zinc (Zn), and cadmium (Cd).

Examples of the alloy containing at least one of the above metals include yttrium nickel (YNi), yttrium niobium (YNb), and yttrium magnesium (YMg) as an alloy containing yttrium belonging to the third group. The composition ratio of the alloy containing these yttrium (Y) is arbitrary.
Examples of alloys containing zirconium belonging to Group 4 include 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), and zirconium osmium (ZrOs). The composition ratio of these alloys containing zirconium (Zr) is arbitrary.
As an alloy containing tantalum (Ta) belonging to Group 5, tantalum titanium (TaTi), tantalum zirconium (TaZr), tantalum hafnium (TaHf), tantalum vanadium (TaV), tantalum niobium (TaNb), tantalum chromium (TaCr), Examples thereof include tantalum molybdenum (TaMo), tantalum tungsten (TaW), tantalum iron (TaFe), tantalum ruthenium (TaRu), and tantalum osmium (TaOs). The composition ratio of these tantalum (Ta) -containing alloys is arbitrary.
As an alloy containing chromium (Cr) belonging to group 6, chromium titanium (CrTi), chromium zirconium (CrZr), chromium hafnium (CrHf), chromium vanadium (CrV), chromium niobium (CrNb), chromium tantalum (CrTa), chromium Molybdenum (CrMo), chromium tungsten (CrW), chromium manganese (CrMn), chromium rhenium (CrRe), chromium iron (CrFe), chromium ruthenium (CrRu), chromium osmium (CrOs) may be mentioned. The composition ratio of the alloy containing these chromium (Cr) is arbitrary.
Molybdenum titanium (MoTi), molybdenum zirconium (MoZr), molybdenum hafnium (MoHf), molybdenum vanadium (MoV), molybdenum niobium (MoNb), molybdenum tantalum (MoTa), and alloys containing molybdenum (Mo) belonging to Group 6 Molybdenum chromium (MoCr), molybdenum tungsten (MoW), molybdenum iron (MoFe), molybdenum ruthenium (MoRu), molybdenum osmium (MoOs) may be mentioned. The composition ratio of the alloy containing these molybdenum (Mo) is arbitrary.
As alloys containing tungsten (W) belonging to Group 6, 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), tungsten osmium (WOs) may be mentioned. The composition ratio of these alloys containing tungsten (W) is arbitrary.
Examples of the alloy containing manganese (Mn) belonging to Group 7 include manganese iron (MnFe), manganese aluminum (MnAl), manganese nickel (MnNi), and manganese copper (MnCu). The composition ratio of the alloy containing these manganese (Mn) is arbitrary.
Alloys containing iron (Fe) belonging to Group 8 include iron nickel (FeNi), iron nickel chromium (FeNiCr), iron chromium (FeCr), iron molybdenum (FeMo), iron chromium molybdenum (FeCrMo), stainless steel (SUS) Can be mentioned. The composition of the alloy containing these iron (Fe) is arbitrary. When the substrate on which the CARE processing is performed 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 can be dissolved in a cleaning solution that does not damage the glass substrate, and defects due to the catalyst material can be reduced. Examples of ferrite stainless steel include SUS430, SUS434, and SUS436. Examples of martensitic stainless steels include SUS410, SUS410S, SUS420J1, and SUS420J2.
Examples of alloys containing ruthenium (Ru) belonging to Group 8 include ruthenium titanium (RuTi), ruthenium zirconium (RuZr), ruthenium hafnium (RuHf), ruthenium vanadium (RuV), ruthenium niobium (RuNb), ruthenium tantalum (RuTa), Ruthenium chromium (RuCr), ruthenium molybdenum (RuMo), ruthenium tungsten (RuW) are mentioned. The composition ratio of these ruthenium (Ru) -containing alloys is arbitrary.
Examples of alloys containing cobalt (Co) belonging to Group 9 include iron-nickel-cobalt (FeNiCo), cobalt-chromium-nickel (CoCrNi), and cobalt-chromium-molybdenum (CoCrMo). The composition ratio of alloys containing these cobalt (Co) is arbitrary.
As an alloy containing nickel (Ni) belonging to Group 10, nickel copper (white copper) in addition to iron nickel (FeNi), iron nickel chromium (FeNiCr), iron nickel cobalt (FeNiCo), cobalt chromium nickel (CoCrNi) described above , NiCu). The composition ratio of these alloys containing nickel (Ni) is arbitrary.
Examples of the alloy containing copper (Cu) belonging to Group 11 include brass (ZnCu) and bronze (SnCu) in addition to the above-mentioned nickel copper (white copper, NiCu). The composition ratio of the alloy containing these copper (Cu) is arbitrary.
Examples of an alloy containing zinc (Zn) belonging to Group 12 include zinc copper (ZnCu), zinc iron (ZnFe), zinc aluminum (ZnAl), and zinc tin (ZnSn). The composition ratio of the alloy containing these zinc (Zn) is arbitrary.
The metals belonging to Groups 3 to 12 of the periodic table of elements forming the processing reference plane and the alloys containing at least one of the metals are not limited to the above without departing from the effects of the present invention. The element of may be contained.

As described above, the processing reference surface formed of such a catalytic substance is constituted of one having an oxidation progress suppression layer on the surface layer of the processing reference surface, or one having an oxidation progress suppression film on the surface layer. .
The oxidation progress suppression layer and the oxidation progress suppression film each have a function as a catalyst by themselves, and at least at least one of the above-described metal surfaces as a catalyst substance forming the processing reference surface and among these metals It blocks the ingress of oxygen atoms to the alloy surface including one and suppresses the progress of oxidation.
The oxidation progress suppressing layer is formed by including nitrogen, oxygen, or both nitrogen and oxygen in the surface layer of the processing reference surface formed of the metal, or includes at least one of the metals. It is formed by adding nitrogen, oxygen, or both nitrogen and oxygen to the surface layer of the processing reference surface formed from the alloy, and processing the reference surface including metal and alloy surface nitriding, surface oxidation, or It is preferable that the surface be oxidized and formed.
The oxidation progress suppressing film is made of a nitride, an oxide or an oxynitride of the metal, or a nitride, an oxide or an oxynitride of an alloy containing at least one of the metals. This oxidation progress suppression film may be formed on the above-mentioned oxidation progress suppression layer, and in this case, the processing reference plane has both the oxidation progress suppression layer and the oxidation progress suppression film on its surface. .

For example, titanium nitride (TiN) as a nitride of a metal belonging to group 4 and tantalum nitride (a nitride of a metal belonging to group 5) as a metal nitride for forming an oxidation progress suppression layer or an oxidation progress suppression film Examples of nitrides of metals belonging to TaN) and Group 6 include chromium nitride (CrN), but are not limited thereto.
Moreover, as an oxide of a metal which forms an oxidation progress suppression layer or an oxidation progress suppression film, for example, a titanium oxide (TiO ₂ ) as an oxide of a metal belonging to the fourth group, an oxide of a metal belonging to the sixth group Examples include, but are not limited to, chromium oxide (Cr ₂ O ₃ ).
Moreover, as a metal oxynitride forming the oxidation progress suppression layer or the oxidation progress suppression film, for example, titanium oxynitride can be mentioned as the oxynitride of a metal belonging to the fourth group, but it is not limited thereto Absent.

Examples of the nitride of the alloy forming the oxidation progress suppression layer and the oxidation progress suppression film include iron nickel chromium nitride (FeNiCrN) as a nitride of an alloy containing a metal belonging to group 4, and a metal belonging to group 10 Although nickel copper nitride (NiCuN) is mentioned as a nitride of the alloy containing, It is not limited to these.
Moreover, as an oxide of an alloy forming an oxidation progress suppression layer or an oxidation progress suppression film, for example, titanium copper alloy oxide can be mentioned as an oxide of an alloy containing a metal belonging to group 4, but it is limited thereto It is not a thing.
In addition, as the oxynitride of the alloy forming the oxidation progress suppression layer or the oxidation progress suppression film, for example, an alloy oxynitride including titanium and silicon is cited as an oxynitride of an alloy containing a metal belonging to the fourth group. Although it is not limited to this.

When forming the processing reference plane having the oxidation progress suppressing layer on the base composed of the above-described metal or alloy, first, the above-described metal film or alloy film is formed by, for example, vapor deposition, sputtering, or metal plating. Thereafter, nitrogen or oxygen is injected into the surface layer of the metal film or alloy film without impairing the flatness or smoothness of the metal film or alloy film, and surface nitriding, surface oxidation or surface oxynitridation of the metal film or alloy film is known. As a result, it is possible to form an oxidation progress suppression layer on the surface layer of the above-described metal film or alloy film and to form a processing reference surface.
For example, in the case of forming an oxidation progress suppression layer by surface nitriding, first, sputtering is performed in an argon (Ar) gas atmosphere using the above metal or alloy as a target to form the above metal film or alloy film on a substrate Do. Thereafter, the metal film or alloy film is exposed in a nitrogen (N ₂ ) gas atmosphere to form an oxidation progress suppression layer by surface nitriding on the surface layer.
In the case of forming an oxidation progress suppression layer by surface oxidation, first, a metal film or an alloy film is formed as described above. Thereafter, the metal film or the alloy film is exposed in an oxygen (O ₂ ) gas atmosphere to form an oxidation progress suppressing layer by surface oxidation on the surface layer.
In the case of forming an oxidation progress suppression layer by surface oxynitridation, first, a metal film or an alloy film is formed as described above. After that, the metal film or alloy film is mixed in a mixed gas atmosphere of nitrogen (N ₂ ) gas and oxygen (O ₂ ) gas, in a nitrogen monoxide (NO) gas atmosphere, in a nitrous oxide (N ₂ O) gas atmosphere, It is made to expose by the etc., and the oxidation progress control layer by surface oxynitridation is formed in the surface.
In these cases, the exposure time is preferably determined appropriately in consideration of the amount of nitrogen or oxygen injected or the depth of injection.
Although the example in which the formation of the metal film and the alloy film and the formation of the oxidation progress suppression layer are discontinuously described here, the formation of the metal film and the alloy film and the formation of the oxidation progress suppression layer is continuously performed. It is also good.

When forming the processing reference plane having the oxidation progress suppressing film on the base composed of the above-described metal or alloy, first, the above-described metal film or alloy film is formed by, for example, vapor deposition, sputtering, or metal plating. Thereafter, nitrides, oxides or oxynitrides of the above-mentioned metals or alloys are formed on the metal film or alloy film by a known method without impairing the flatness or smoothness of the metal film or alloy film. As a result, it is possible to form an oxidation progress suppression film on the above-mentioned metal film or alloy film and to form a processing reference surface.
For example, in the case of forming the above-described oxidation progress suppressing film made of nitride, first, sputtering is performed in the atmosphere of argon (Ar) gas using the above metal or alloy as a target, and the above metal film or alloy is formed on the substrate. Form a film. Thereafter, sputtering is performed in a mixed gas atmosphere containing argon (Ar) gas and nitrogen (N ₂ ) gas, using the above-described metal or alloy or nitride thereof as a target, to form a film on the above-described metal film or alloy film To form.
In the case of forming the oxidation progress suppressing film made of the above-described oxide, first, a metal film or an alloy film is formed in the same manner as described above. Thereafter, sputtering is performed in a mixed gas atmosphere containing argon (Ar) gas and oxygen (O ₂ ) gas, using the above-described metal or alloy or these oxides as a target, to form a film on the above-described metal film or alloy film To form.
Further, in the case of forming the above-described oxidation progress suppressing film made of oxynitride, first, a metal film or an alloy film is formed in the same manner as described above. Thereafter, argon is used in a mixed gas atmosphere containing argon (Ar) gas, nitrogen (N ₂ ) gas, and oxygen (O ₂ ) gas, using the above-mentioned metals, alloys, or oxides thereof, nitrides or oxynitrides thereof as targets. Sputtering is performed in a mixed gas atmosphere containing argon (Ar) gas and nitrous oxide (N ₂ O) gas in a mixed gas atmosphere containing (Ar) gas and nitrogen monoxide (NO) gas, and the above-mentioned metal film Or formed on the alloy film.
Here, although the example in which the formation of the metal film or the alloy film and the formation of the oxidation progress suppression film are discontinuously described, the formation of the metal film or the alloy film and the formation of the oxidation progress suppression film is continuously performed. It is also good.

In addition, the above-mentioned oxidation progress suppression layer and oxidation progress suppression film may be formed preferably immediately after removing foreign substances attached to the above-mentioned metal film and alloy film. In this case, since the oxidation progress suppression layer and the oxidation progress suppression film can be formed on the above-mentioned metal film or alloy film in the state where foreign matter has been removed, the flatness and smoothness of the processing reference plane can be Can be reduced.
In addition, the above-described oxidation progress suppression layer or oxidation progress suppression film may be formed on the processing reference surface immediately after CARE processing. In this case, the progress of oxidation of the processing reference surface can be suppressed by the new oxidation progress suppression layer or the oxidation progress suppression film formed on the processing reference surface in a state in which oxidation has hardly progressed.

A removal step may be included to remove all or part of such an oxidation progress suppression layer, or all or part of the oxidation progress suppression film. In this removal step, the oxidation progress suppression layer or the oxidation progress suppression film is formed in the surface direction without losing the flatness or smoothness of the above-described metal or alloy exposed by the removal, or the oxidation progress suppression layer or the oxidation progress suppression film. It is preferable that it is a process of removing uniformly and at a desired machining allowance.
The processing reference surface that has undergone this removal step is made of the metal or alloy exposed in the removal step, or on the surface layer of the processing reference surface, the oxidation progress suppression layer or oxidation progress suppression exposed in the removal step It is composed of one having a membrane.
Specifically, in the case where the processing reference surface has the oxidation progress suppression layer in the surface layer, when the entire oxidation progress suppression layer is removed, the processing reference surface is made of the metal or alloy exposed in the removal step. In addition, when a part of the oxidation progression suppression layer is removed, the processing reference surface has the oxidation progression suppression layer exposed in the removal step on the surface thereof.
In addition, when the processing reference surface has the oxidation progress suppression film on the surface layer, when the entire oxidation progress suppression film is removed, the processing reference surface is made of the metal or alloy exposed in the removal step. In addition, when a part of the oxidation progress suppression film is removed, the processing reference surface has the oxidation progress suppression film exposed in the removal step on the surface thereof.
In addition, when the processing reference surface has both the oxidation progress suppression layer and the oxidation progress suppression film in the surface layer, the processing reference surface is removed when all of the oxidation progress suppression layer and the oxidation progress suppression film are removed. The processing reference surface is made of the metal or alloy exposed in the process, and when the oxidation progress suppression film is partially removed, the processing reference surface has the oxidation progress suppression film exposed in the removal process on the surface thereof, In addition, when only the oxidation progress suppression film is completely removed without removing the oxidation progress suppression layer, or when all of the oxidation progress suppression film and a part of the oxidation progress suppression layer are removed, the processing reference surface is the surface layer, It will have an oxidation progress suppression layer exposed by the removal step.

  Such removal process utilizes at least one of physical action and chemical action. That is, as this removal step, a chemical removal step utilizing chemical action, a physical removal step utilizing physical action, or physical advantage utilizing both physical action and chemical action A chemical removal step can be mentioned.

Examples of the chemical removal step include those using a removal fluid such as a liquid or gas having a chemical action such as dissolving an oxidation progress inhibition layer or an oxidation progress inhibition film. As this removal fluid, for example, a liquid such as an etching solution suitable for dissolving the oxidation progress suppression layer or the oxidation progress suppression film and removing the melt from the processing reference surface is preferable.
In this chemical removal process, for example, while etching liquid is applied to a dummy substrate (a substrate formed of the same material as the substrate material to be processed), the processing reference surface is brought into contact with or approached to the dummy substrate. Accordingly, it is preferable to rotate at least one of them and to interpose an etching solution between the two. When such a dummy substrate is used, the etching solution interposed between the two is uniformly supplied to the entire oxidation progress suppression layer and the oxidation progress suppression film, so that the above-mentioned metal or alloy exposed by removal, or The oxidation progress suppression layer and the oxidation progress suppression film can be removed without impairing the flatness and smoothness of the oxidation progress suppression layer and the oxidation progress suppression film.
Further, it is preferable that the type of the removal fluid having the above-described chemical action be appropriately determined in consideration of the constituent material of the oxidation progress suppression layer and the oxidation progress suppression film to be removed and the machining allowance.

As a physical removal process, what gives physical effects, such as scraping off an oxidation progress suppression layer or an oxidation progress suppression film | membrane, to a process reference surface, is mentioned, for example. As a member which gives a physical effect | action to a process reference | standard surface, the brush made from PVA (polyvinyl alcohol) which scrapes off an oxidation progress suppression layer or an oxidation progress suppression film, for example is mentioned.
Note that this physical removal step is preferably performed, for example, by interposing a liquid such as water between the brush and the processing reference surface. When a liquid such as water intervenes, the frictional force generated between the brush being removed and the processing reference surface can be reduced, and the removal residue of the oxidation progress inhibiting layer or the oxidation progress inhibiting film can be removed.

As a physical and chemical removal process, what combines the physical removal process mentioned above and the chemical removal process and uses physical removal and chemical removal together is mentioned.
When this physical and chemical removal step is used, for example, with the processing reference surface and the dummy substrate in contact or in proximity, at least one of them is rotated as necessary, and an etching solution is interposed between them. While the oxidation progress suppression layer and the oxidation progress suppression film are dissolved by the etching solution, the oxidation progress suppression layer and the oxidation progress suppression film can be scraped off with a brush, and the removal residue and the melt can be removed by the etching solution. This can reduce the removal time.
When the removal time is shortened, it is possible to minimize the dissolution action by the etching solution on the processing reference surface and the friction action by the brush to the minimum necessary, so the above-mentioned metal or alloy exposed by removal or the oxidation progress suppression layer It is possible to reduce the possibility that the flatness and the smoothness of the oxidation progress suppressing film are impaired.

  It is preferable to perform such a removal process just before CARE processing. If the removal step is performed immediately before the CARE processing, the CARE processing can be performed using the processing reference surface in a state in which the surface layer newly exposed by the removal step is present and oxidation hardly progresses.

  Also, immediately after CARE processing, when a new oxidation progress suppression layer or oxidation progress suppression film is formed on the processing reference surface, the processing reference surface is used for the next CARE processing, so that the CARE processing Immediately before, the oxidation progress suppression layer and the oxidation progress suppression film may be removed by the above-described removal step. Thus, immediately after CARE processing, a new oxidation progress suppression layer or oxidation progress suppression film is formed on the processing reference surface, and immediately before the next CARE processing, the oxidation progress suppression layer or oxidation progress suppression film is removed. As a result, since the processing reference surface can be used for CARE processing a plurality of times, the manufacturing cost of the processing reference surface can be reduced.

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 miniaturizing the processing reference surface, it is possible to suppress bending or settling that may occur in a large processing reference surface, and therefore, processing by catalyst-based etching can be reliably performed on the entire main surface of the substrate.

  The processing fluid is not particularly limited as long as it does not exhibit normal solubility in the substrate. By using such 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 addition, when the substrate is not dissolved by a solution in which a molecule containing halogen is dissolved, a solution in which a molecule containing halogen is dissolved can also be used.

  When the substrate is made of a glass material, processing using catalyst-based etching can be performed by using the above-described processing reference surface and using pure water as the processing fluid. It is considered that the hydrolysis reaction proceeds by using the above-described processing reference surface and using pure water as the processing fluid. Therefore, when the substrate is made of a glass material, it is preferable to use the above-mentioned processing reference surface and use pure water as the processing fluid from the viewpoint of cost and processing characteristics.

  FIG. 1 and FIG. 2 show an example of a substrate processing apparatus for processing the main surface of a substrate by catalyst reference etching. FIG. 1 is a partial cross-sectional view of a 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, but 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 comprises a substrate support means 2 for supporting a substrate M having a main surface made of a material containing an oxide, a substrate surface creation means 3 having a processing reference surface 33 of a catalytic substance, a processing reference surface 33 and the main Drive means for bringing the processing reference surface 33 into contact or approach to the main surface with the processing fluid supply means 4 for supplying the processing fluid to the surface and the processing fluid being interposed between the processing reference surface 33 and the main surface It is equipped with five.

  The substrate support means 2 is disposed in a cylindrical chamber 6. The chamber 6 is provided with an opening 61 formed at the center of the bottom 63 of the chamber 6 and a process supplied from the processing fluid supply means 4 in order to arrange the shaft 71 of the relative movement 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 on the outer periphery of 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 for supporting the substrate M and a flat portion 22 for fixing the support portion 21. The support portion 21 has a rectangular shape when the substrate processing apparatus 1 is viewed from the top, and includes a housing portion 21 a that supports four sides of the periphery of the lower surface M2 of the substrate M. The flat portion 22 is circular when the substrate processing apparatus 1 is viewed from above.

  The substrate surface creating means 3 is provided with a catalyst surface plate 31. The catalyst surface plate 31 is attached to a catalyst surface plate mounting portion 72 of the relative movement means 7 described later. The catalyst surface plate 31 includes a surface plate main body 32, a substrate (not shown) formed on the entire surface of the surface plate main body so as to cover the surface plate main body, and the entire surface of the substrate facing the substrate M. And a processing reference surface 33 formed on the The material of the substrate on which the processing reference surface is formed is not particularly limited. For example, rubber, light transmitting resin, foamable resin, non-woven fabric can be used. The overall shape of the catalyst plate is not particularly limited. For example, disks, spheres, cylinders, cones, pyramidal outer shapes can be used. The surface shape of the portion of the catalyst platen on which the processing reference surface is formed is also not particularly limited. For example, flat, hemispherical, or rounded shapes can be used.

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

  The driving means 5 is connected to the upper end of the catalyst base plate mounting portion 72 of the relative movement 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 mounted on the support 21. A shaft 51 supporting the end of the arm 51 extending to the periphery of the chamber 6 and extending in a direction perpendicular to the main surface of the substrate M placed on the support 21; and the lower end of the shaft 52 A support 53 is provided, and a guide 54 disposed around the chamber 6 and defining a movement path of the support 53 is provided. The arm 51 can move in its longitudinal direction (see the double arrow C in FIGS. 1 and 2). The axial part 52 can move the arm part 51 up and down by moving in the longitudinal direction (see the double arrow D in FIG. 1). The base portion 53 can turn the arm portion 51 by rotating the axis in the direction perpendicular to the main surface of the substrate M placed on the support portion 21 by a predetermined angle (FIG. 1, 1, See double arrow E in 2). The guide 54 is disposed in a direction (first and second directions) parallel to two adjacent sides of the substrate M placed on the support portion 21 and forms an L-shaped moving path of the base portion 53. . The base portion 53 moves the arm portion 51 in the first direction by moving along the guide 54 in the first direction (see the double arrow F in FIG. 2), and the guide 54 in the second direction. The arm unit 51 can be moved in the second direction by moving along (refer to the double arrow G in FIG. 2). By such movement of the arm unit 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 unit 21.

  The substrate processing apparatus 1 includes relative movement means 7 for moving the processing reference surface 33 and the main surface relative to each other. The relative movement means 7 includes a shaft 71 supporting the flat surface 22 and extending to the outside of the chamber 6 through the opening 61, and a rotation driving means (not shown) for rotating the shaft 71. . The shaft portion 71 extends in a direction perpendicular to the main surface of the substrate M mounted on the support portion 21, and the main surface of the substrate M mounted on the support portion 21 by a rotation driving means (not shown). , And can be rotated about an axis in a direction perpendicular to (see arrow A in FIG. 1). The center of the flat portion 22 and the center of the substrate M placed on the support portion 21 are located in the direction of extension of the rotation center of the shaft portion 71. The rotation of the shaft portion 71 causes the plane portion 22 supported by the shaft portion 71 to rotate about its center, and the substrate M placed on the support portion 21 fixed to the plane portion 22. Rotates about its center of rotation. Further, the relative movement means 7 is provided with a catalyst base plate attaching portion 72 to which the catalyst base plate 31 is attached, and a rotational drive means (not shown) provided on the arm portion 51 of the drive means 5. The catalyst fixed plate mounting portion 72 can be rotated about an axis perpendicular to the main surface of the substrate M mounted on the support portion 21 by a rotation driving means (not shown) (FIG. 1, 1 See arrow B in 2).

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

The substrate processing apparatus 1 includes a removing means 9 for removing all or part of the oxidation progress suppressing layer, or all or part of the oxidation progress suppressing film.
The removal means 9 uses the chemical action to suppress the oxidation progress without impairing the flatness or smoothness of the above-described metal or alloy exposed by the removal, or the oxidation progress suppression layer or the oxidation progress suppression film. It is preferable that the layer and the oxidation progress suppressing film can be removed uniformly along the surface direction and with a desired allowance.
For example, as shown in FIGS. 1 and 2, the removing means 9 includes a supply pipe 91 extending from the outside of the chamber 6 toward the surface of a dummy substrate (not shown) placed on the support portion 21. The injection nozzle 92 is provided at the lower end of the supply pipe 91 and ejects the removal fluid toward the surface of a dummy substrate (not shown) placed on the support portion 21. The supply pipe 91 is connected to, for example, a removal fluid storage tank (not shown) provided outside the chamber 6 and a pressure pump (not shown). The removal fluid is supplied to the injection nozzle 92 through the supply pipe 91 and is supplied from the injection nozzle 92 onto the surface of the dummy substrate (not shown).

According to the removal means 9, removal of the oxidation progress suppression layer and the oxidation progress suppression film can be performed as follows.
First, a dummy substrate (not shown) placed on the support portion 21 is prepared. Next, a catalyst base 31 provided with a processing reference surface 33 having an oxidation progress suppression layer and an oxidation progress suppression film on the surface is prepared, and the surface of the processing reference surface 33 faces the dummy substrate (not shown). Then, the catalyst base 31 is attached to the catalyst base mounting portion 72. Next, while rotating the processing reference surface 33 by the relative movement means 7, the removal fluid is supplied from the injection nozzle 92 onto the surface of the dummy substrate (not shown), and in this state, the processing reference surface 33 is processed by the drive means 5. Are in contact with the dummy substrate (not shown). At this time, the removal fluid dissolves all or a part of the oxidation progress suppression layer or the oxidation progress suppression film of the processing reference surface by its chemical action, removes the melt, and removes the aforementioned metal or alloy, or , And an oxidation progress suppression layer and an oxidation progress suppression film are exposed.

Although the removing fluid is supplied from the jet nozzle 92 onto the surface of the dummy substrate (not shown) in the removing means 9 described above, it may be supplied to the processing reference surface 33. When the removal fluid is supplied, the chemical action can be directly applied to the oxidation progress suppression layer and the oxidation progress suppression film, and the time required for the dissolution and removal can be shortened.
Further, the removing means 9 may be provided with a moving means (not shown) for moving the supply pipe 91 along a dummy substrate (not shown) or the surface direction of the processing reference surface 33. The removal fluid is uniformly supplied to the surface of the dummy substrate (not shown) by moving the supply pipe 91 along the surface of the dummy substrate (not shown) by this moving means (not shown). Can.
Further, the removing means 9 is not limited to chemical removing means, but may be physical removing means utilizing physical action, or physical advantage utilizing both physical action and chemical action. It may be a chemical removal means.

As the above-mentioned physical removal means, for example, a means capable of giving a physical action such as scraping off the oxidation progress suppression layer or the oxidation progress suppression film can be mentioned. Specifically, as a physical removal means, a brush (not shown) which scrapes off the oxidation progress inhibition layer or the oxidation progress inhibition film, and this brush is brought into contact with the standby position and the oxidation progress inhibition layer or oxidation progress inhibition film It has a movement device (not shown) that moves horizontally between positions and a drive device (not shown) that rotates the brush when the brush is in contact with the oxidation progress suppression layer or the oxidation progress suppression film. Are preferred. According to this physical removal means, all of the oxidation progress suppression layer and the oxidation progress suppression film are rotated by the brush rotating while being in contact with the oxidation progress suppression layer and the oxidation progress suppression film of the processing reference surface placed on the horizontal surface. Or part of it can be removed.
As the above-mentioned brush, for example, a brush made of PVA (polyvinyl alcohol) is preferably used, but it is not limited thereto.
In addition, in the removal by the above-mentioned physical removal means, it is preferable to carry out by interposing liquids, such as water, between the above-mentioned brush and a process reference surface. When a liquid such as water intervenes, the frictional force generated between the brush and the processing reference surface can be reduced, and the removal residue of the oxidation progress suppression layer and the oxidation progress suppression film can be removed. The processing fluid supply means 4 may be used as a means for supplying a liquid such as water. The processing fluid supply means 4 in this case constitutes a part of the above-mentioned physical removal means.

  As the above-mentioned physical and chemical removal means, for example, means combining the removal means 9 as the above-mentioned chemical removal means and the above-mentioned physical removal means, and utilizing both physical action and chemical action Although it is mentioned, it is not limited to this.

  As a control method for securing the machining allowance as set, for example, various local processing conditions (processing pressure, rotation number (catalyst surface plate, substrate), processing fluid, etc.) for the substrate M separately prepared in advance separately It is possible to control the machining allowance by determining the processing conditions and machining time to be the desired machining allowance, and managing the machining time, by obtaining the relationship between the flow rate) and the machining time and the machining allowance. it can. The present invention is not limited to this, and various methods may be selected as long as the machining allowance can be secured as set.

When processing by catalyst reference etching is performed using the substrate processing apparatus 1 shown in FIG. 1 and FIG. 2, first, the catalyst platen 31 is attached to the catalyst platen mounting portion 72.
When removing the oxidation progress suppression layer and the oxidation progress suppression film on the processing reference surface 33 used for the processing prior to the processing by the catalyst reference etching, a dummy substrate (not shown) is then placed on the support portion 21 Fix it. Thereafter, while rotating the processing reference surface 33 by rotating the catalyst surface plate mounting portion 72, the removal fluid is supplied from the injection nozzle 92 onto the surface of the dummy substrate (not shown), and in this state, the arm portion 51 The processing reference surface 33 is brought into contact with the dummy substrate (not shown) by the up and down movement (double arrow D). After removing the oxidation progress suppression layer and the oxidation progress suppression film in this manner, the dummy substrate is removed from the support portion 21. Thereafter, the substrate M is placed and fixed on the support portion 21 with the upper surface M1 used as the main surface facing upward. In this case, the processing reference surface 33 used for processing by the following catalyst reference etching is the above-mentioned metal or alloy exposed by the removal means 9 in the surface layer, or the removal means 9 in the surface layer of the processing reference surface 33. And an oxidation progress suppression layer or an oxidation progress suppression film exposed.
In the case where it is not necessary to remove the oxidation progress suppression layer and the oxidation progress suppression film on the processing reference surface 33 used for the processing prior to the processing by the catalyst reference etching, thereafter, the upper surface M1 using the substrate M as the main surface It mounts and fixes to the support part 21 toward upper side. In this case, the processing reference surface 33 used for processing by the catalyst reference etching described below is configured to have an oxidation progress suppression layer and an oxidation progress suppression film on the surface layer.
Thereafter, longitudinal movement of the arm 51 (double arrow C), pivotal movement of the arm 51 (double arrow E), movement of the arm 51 in the first direction (double arrow F), movement of the arm 51 in the second direction With the double arrow G), the processing reference surface 33 of the substrate surface creation means 3 is arranged to face the upper surface M1 of the substrate M.
Thereafter, by rotating the shaft portion 71 and the catalyst fixed plate mounting portion 72 at a predetermined rotational speed, the processing reference surface 33 and the upper surface M1 are rotated at a predetermined rotational speed, and the processing fluid is transferred To interpose the processing fluid between the upper surface M1 and the processing reference surface 33. In that state, the processing reference surface 33 is brought into contact with or close to the upper surface M1 of the substrate M by the vertical movement (double arrow D) of the arm portion 51. At that time, the load control means 8 controls the load applied to the substrate M to a predetermined value.
After that, when the predetermined machining allowance is reached, the rotation of the shaft portion 71 and the catalyst base plate attachment portion 72 and the supply of the processing fluid are stopped. Then, the processing reference surface 33 is separated from the upper surface M1 by a predetermined distance by the vertical movement (double arrow D) of the arm portion 51.

  The substrate M is manufactured by such a substrate preparation process and a substrate processing process.

  According to the method of manufacturing a substrate of the first embodiment, the metal belonging to the third to twelfth groups of the periodic table of elements and the alloy containing at least one of the metals are used as the catalyst material forming the processing reference surface. A material having at least one of nitrogen and oxygen in the metal or the alloy is contained in the surface layer as a processing reference surface using a material selected from the group consisting of An oxide film is used which has an oxidation progress suppression film made of the metal, or the nitride, oxide or oxynitride of the alloy. When such a processing reference surface is used, the mechanical resistance and chemical stability of the processing reference surface are improved by the oxidation progress suppression layer and the oxidation progress suppression film, and the oxidation progress of the processing reference surface during CARE processing Can be suppressed. If the mechanical durability of the processing reference surface is improved, the processing reference surface may be peeled off during CARE processing, and there is less concern that the main surface of the substrate may be damaged or the peeled portion may lose its function as a catalyst. In addition, when the chemical stability of the processing reference surface is improved, the processing reference surface is rusted by the processing fluid during the CARE processing, the rusted portion loses the function as a catalyst, or the rusted portion is peeled off, on the main surface of the substrate. There is less risk of damage. In addition, when the progress of oxidation of the processing reference surface during CARE processing is suppressed, the catalytic function of the processing reference surface can be maintained, so that the processing rate can be maintained constant. Therefore, a substrate having a main surface with high smoothness and low defects can be stably manufactured by CARE processing performed while preventing deterioration of characteristics due to processing reference surface factors.

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 creating means 3 is pressed onto the main surface of the substrate M, but the processing reference surface of the substrate surface creating means is Furthermore, the present invention can be applied to a substrate processing apparatus of a type in which the main surface of the substrate is pressed.
Further, in this embodiment, the present invention is applied to a substrate processing apparatus of a type for processing one side of a substrate, but the present invention can be applied to a substrate processing apparatus of a type for simultaneously processing both sides of a substrate. In this case, a carrier, which is a member for holding 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 in which the processing fluid is supplied from the outside of the chamber toward the main surface of the substrate M. The present invention can also be applied to the case where the process fluid is supplied from the process fluid supply means, or the case where the process fluid supply means is provided on the substrate support means and the process fluid is supplied from the substrate support means. The present invention is also applicable to the case where processing fluid is stored in a chamber, and processing is performed by catalyst-based etching in a state where substrate surface creation means and substrate support means are placed in the processing fluid.
Further, in this embodiment, the present invention is 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 rotating both the processing reference surface 33 and the main surface. The present invention can also be applied to a type of substrate processing apparatus in which the processing reference surface 33 and the main surface are moved relative to each other according to a method.
Further, in the present embodiment, the present invention is applied to a sheet-type substrate processing apparatus for processing a substrate one by one, but the present invention is also applied to a batch-type substrate processing apparatus for processing a plurality of substrates simultaneously. it can.

Second Embodiment
In the second embodiment, a method of manufacturing a multilayer reflective film coated substrate will be described.

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

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

Third Embodiment
In the third embodiment, a method of manufacturing a mask blank will be described.

  In the third embodiment, a light shielding film as a thin film for transfer pattern is formed on the main surface of the substrate M manufactured by the method described in the method for manufacturing a substrate of the first embodiment to manufacture a binary mask blank, Alternatively, a light transflective film is formed as a thin film for transfer pattern to manufacture a halftone phase shift mask blank, or a light transflective film and a light shielding film are sequentially formed as a thin film for transfer pattern to form a halftone phase shift mask Make a blank.

  In the third embodiment, an absorber film as a thin film for transfer pattern is formed on the protective film of the multilayer reflective film coated substrate manufactured by the method described in the method of manufacturing the multilayer reflective film coated substrate of the second embodiment. Or an absorber film as a thin film for a transfer film and a protective film is formed on the multilayer reflective film of the multilayer reflective film coated substrate, and a back surface conductive film is formed on the rear surface where the multilayer reflective film is not formed. Manufacture a mold mask blank.

  According to the third embodiment, using the substrate M obtained by the manufacturing method of the substrate of the first embodiment or the multilayer reflection film-provided substrate obtained by the manufacturing method of the multilayer reflective film-coated substrate of the second embodiment Since the mask blank is manufactured, the deterioration of the characteristics due to the substrate factor can be prevented, and the mask blank having the desired characteristics can be manufactured.

Fourth Embodiment
In the fourth embodiment, a method of manufacturing a transfer mask will be described.

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

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

Hereinafter, the present invention will be more specifically described based on examples.

Example 1
A. Production of Glass Substrate Substrate Preparation Step A 6025 size (152 mm × 152 mm × 6.35 mm) TiO ₂ —SiO ₂ glass substrate with its upper and lower surfaces polished was prepared. 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 Step 10 glass substrates having been subjected to end face chamfering and grinding were set in a double-sided polishing apparatus, and rough polishing was performed under the following polishing conditions. A set of 10 sheets was performed twice to perform rough polishing of a total of 20 glass substrates. The processing load and polishing time were adjusted appropriately.
Polishing slurry: aqueous solution containing cerium oxide (average particle diameter 2 to 3 μm) Polishing pad: hard polisher (urethane pad)
After rough polishing, in order to remove abrasive grains attached to the glass substrate, the glass substrate was immersed in a cleaning tank, and ultrasonic waves were applied to perform cleaning.

(2) Precision Polishing Step 10 glass substrates having undergone rough polishing were set in a double-sided polishing apparatus, and precision polishing was performed under the following polishing conditions. A 10-sheet set was performed twice and precision polishing of a total of 20 glass substrates was performed. The processing load and polishing time were adjusted appropriately.
Polishing slurry: aqueous solution containing cerium oxide (average particle size 1 μm) Polishing pad: soft polisher (swede type)
After precision polishing, in order to remove the abrasive grains attached to the glass substrate, the glass substrate was immersed in a cleaning tank, and ultrasonic waves were applied to perform cleaning.

(3) Ultra-Precision Polishing Process The glass substrates having undergone precision polishing were again set in a double-sided polishing apparatus, and 10 ultra-precision polishing was performed under the following polishing conditions. A 10-sheet set was performed twice to perform ultra-precision polishing of a total of 20 glass substrates. The processing load and polishing time were adjusted appropriately.
Polishing slurry: alkaline aqueous solution containing colloidal silica (pH 10.2)
(Colloidal silica content 50 wt%)
Polishing pad: Super soft polisher (Swede type)
After ultra precision polishing, the glass substrate was immersed in a cleaning tank containing an alkaline cleaning solution of sodium hydroxide, and ultrasonic waves were applied to perform cleaning.

(4) Local Processing Step The flatness of the upper and lower surfaces of the glass substrate after the rough polishing step, the precision polishing step, and the ultra-precision polishing step was measured using a flatness measuring device (UltraFlat 200 manufactured by Tropel). The flatness measurement was performed at 1024 × 1024 points on an area of 148 mm × 148 mm excluding the peripheral area of the glass substrate. The measurement results of the flatness of the upper surface and the lower surface of the glass substrate were stored in a computer as information of height relative to a virtual absolute plane (concave shape information) for each measurement point. The virtual absolute plane is a plane that has a minimum value when the distance from the virtual absolute plane to the substrate surface is squared with respect to the entire flatness measurement area.
Then, the acquired uneven | corrugated shape information and the reference value of the flatness of the upper surface and lower surface requested | required of a glass substrate were compared, and the difference was computed by computer for every predetermined area | region of the upper surface and lower surface of a glass substrate. This difference is the necessary removal amount (processing allowance) of each predetermined area in the local surface processing described later.
Thereafter, processing conditions for local surface processing according to the required removal amount were set for each of the predetermined regions of the upper surface and the lower surface of the 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 period of time as in actual processing, and the shape is processed by a flatness measuring device (UltraFlat 200 made by Tropel) It measured and calculated the processing volume in the spot per unit time. Then, according to the processing volume at the spot per unit time and the required removal amount of each predetermined area calculated as described above, the scanning speed at the time of raster scanning the glass substrate was determined.
Thereafter, the upper surface and the lower surface of the glass substrate were locally surface-processed by Magneto-Visco-elastic fluid polishing (Magneto Rheological Finishing: MRF) using a substrate finishing apparatus in accordance with processing conditions set for each predetermined region. At this time, a magnetic polishing slurry containing abrasive particles of cerium oxide was used.
Thereafter, the glass substrate was immersed for about 10 minutes in a washing tank containing an aqueous solution of hydrochloric acid having a concentration of about 10% (temperature: about 25 ° C.).
Thereafter, rinsing with pure water and drying with isopropyl alcohol (IPA) were performed.

(5) Touch polishing process In order to enhance the smoothness of the upper surface and the lower surface of the glass substrate roughened by the local processing process, the upper surface and the lower surface of the glass substrate are polished by a minute amount by low load mechanical polishing using polishing slurry. did. In this polishing, a glass substrate held by a carrier is set between upper and lower polishing plates to which a polishing pad larger than the size of the substrate is attached, and a polishing slurry containing colloidal silica abrasive grains (average particle diameter 50 nm) By rotating the glass substrate in the upper and lower polishing plates while supplying
Thereafter, the glass substrate was immersed in an alkaline cleaning solution of sodium hydroxide, and ultrasonic waves were applied to perform cleaning.

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

In this embodiment, first, a disc-shaped surface plate main body 32 made of stainless steel (SUS) and having a diameter of 50 mm, and a urethane pad formed on the entire surface of the surface plate main body 32 so as to cover the surface plate main body 32 And a reference surface 33 (film having a chromium nitride layer (CrN) on a base composed of a chromium film (Cr) formed on the entire surface of the urethane pad on the side facing the glass substrate A catalyst plate 31 provided with a thickness of 100 nm) was prepared. The catalyst plate 31 was formed as follows. First, place the platen main body 32 covered with a urethane pad in a sputtering apparatus (not shown), use a chromium (Cr) target, and perform sputtering in an argon (Ar) gas atmosphere to form a urethane pad (see FIG. A chromium film (Cr, film thickness 100 nm) was formed on the surface of the substrate (not shown). Then, it was exposed to a nitrogen (N ₂ ) atmosphere for 30 minutes to nitride the surface of the chromium film (Cr) to form a chromium nitrided layer (CrN, about 1 nm thick).
Thereafter, the prepared catalyst plate 31 was attached to the catalyst plate mounting portion 72.
Thereafter, a dummy substrate (a substrate formed of the same material as the substrate material to be processed, not shown) was placed on the support portion 21 and solidified. Thereafter, while rotating the processing reference surface 33 by rotating the catalyst surface plate mounting portion 72, a chromium etching solution containing ceric ammonium nitrate and perchloric acid is sprayed from the injection nozzle 92 onto the surface of the dummy substrate, In this state, the processing reference surface 33 is brought into contact with the dummy substrate by the vertical movement (double arrow D) of the arm portion 51, and the chromium nitride solution (CrN) is dissolved and removed by the chromium etching solution.
Thereafter, the dummy substrate was removed from the support portion 21. Then, the glass substrate was placed on and fixed to the support 21 with the upper surface used as the main surface facing upward.
Thereafter, using the processing reference surface 33 with the chromium film (Cr) exposed, processing by catalyst reference etching was performed on the upper surface of the glass substrate placed on the support portion 21 as follows.
The processing conditions are as follows.
Processing fluid: rotation speed of pure water shaft portion 71 (rotational speed of glass substrate): 10.3 rotations / minute Rotational speed of catalyst surface plate mounting portion 72 (rotational speed of catalyst surface plate 31): 10 rotations / minute Processing pressure : 50 hPa
Machining allowance: 30 nm

First, longitudinal movement of the arm 51 (double arrow C), swing movement of the arm 51 (double arrow E), movement of the arm 51 in the first direction (double arrow F), movement of the arm 51 in the second direction ( According to the double arrow G), the catalyst surface plate 31 is disposed in a state where the processing reference surface 33 of the catalyst surface plate 31 is disposed to face the upper surface of the glass substrate. The arrangement position of the catalyst base 31 is such that when the glass substrate and the catalyst base 31 are rotated, the processing reference surface 33 of the catalyst base 31 can contact or approach the entire upper surface of the glass substrate. is there.
Thereafter, the glass substrate is rotated at a rotation speed of 10.3 rotations / minute and the catalyst surface plate 31 at a rotation speed of 10 rotations / minute. Here, the glass substrate and the catalyst surface plate 31 are rotated so that the rotation direction of the glass substrate and the rotation direction of the catalyst surface plate 31 become opposite to each other. As a result, the peripheral velocity difference can be taken between the two, and the processing efficiency by the catalyst reference etching can be enhanced. Also, the rotational speeds of both are set to be slightly different. Thus, 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 enhanced.
Pure water was supplied onto the upper surface of the glass substrate from the injection nozzle 42 while rotating the glass substrate and the catalyst surface plate 31, 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 31 was brought into contact with or 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 100 to 350 hPa.
After that, when the machining allowance became 100 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 is separated from the upper surface of the glass substrate by a predetermined distance by the vertical movement (double arrow D) of the arm portion 51.
Thereafter, the glass substrate was removed from the support portion 21.

Then, the glass substrate removed from the support part 21 was wash | cleaned as follows. First, the glass substrate was immersed for about 10 minutes in a cleaning tank containing a chromium etching solution containing ceric ammonium nitrate and perchloric acid. After that, neutral detergent and water were supplied to the upper surface of the glass substrate, and brush cleaning was performed to rub the upper surface of the glass substrate with a polyvinyl alcohol (PVA) brush to scrape 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 brush cleaning, ultrasonic vibration (frequency: 3 MHz) is applied to the upper surface, and foreign matter adhering to the upper surface is floated and removed Sonic cleaning was performed. Thereafter, a 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.
Thus, 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 reference etching was measured using an atomic force microscope (AFM) in 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 root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.056 nm in root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.056 nm in root mean square roughness (RMS) by catalyst reference etching. Further, the surface roughness of the upper surface after processing was as good as 0.468 nm in maximum height (Rmax). In addition, the ratio of root mean square roughness to maximum height (Rmax / RMS) was as good as 8.4.
The defect inspection of the upper surface of the glass substrate after processing by catalyst reference etching was performed using a defect inspection system (Mask / blank defect inspection system Teron 610 made by KLA-Tencor) for the 132 nm × 132 nm region excluding the peripheral region of the substrate. It did. The defect inspection was performed with a sensitivity that can detect a defect of 21.5 nm in size in terms of sphere equivalent volume diameter (SEVD). SEVD is the length of the diameter assuming that the defect is hemispherical.
The number of defects on the upper surface after processing was as small as 39.
In addition, according to the method of Example 1, the processing standard of surface nitriding of the chromium film (Cr) as the catalyst substance and removal of the chromium nitride layer (Cr) formed by the surface nitriding between the processing of each glass substrate When 20 sheets of glass substrates were produced using a surface, the total number and surface roughness were within the range of 0.051 to 0.063 nm in root mean square roughness (RMS), and the processing stability was good. there were.
By the method of Example 1, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

B. Production of Multilayer Reflective Film Coated Substrate Next, a high refractive index layer (film thickness 4.) made of a silicon film (Si) is formed on the upper surface of the glass substrate thus produced by the ion beam sputtering method. (2 nm) and a low refractive index layer (2.8 nm) consisting of a molybdenum film (Mo) are alternately laminated into 40 pairs of a high refractive index layer and a low refractive index layer to form a multilayer reflective film (film 280 nm thick).
Thereafter, a protective film (film thickness 2.5 nm) made of ruthenium (Ru) was formed on the multilayer reflective film by ion beam sputtering.
Thus, a multilayer reflective film coated substrate was produced.

The reflectivity of EUV light (wavelength 13.5 nm) of the obtained multilayer reflective film coated substrate was measured by an EUV reflectivity 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 conducted 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 20.
According to 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 coated substrate thus produced, and argon (Ar) gas and nitrogen (N ₂ ) gas are used. Reactive sputtering in a mixed gas atmosphere with the above to form a lower absorber layer (film thickness 50 nm) made of tantalum boron nitride (TaBN), and further, tantalum boride (TaB) on the lower absorber film Reactive sputtering is performed in a mixed gas atmosphere of argon (Ar) gas and oxygen (O ₂ ) gas using a target to form an upper absorber layer (film thickness 20 nm) made of tantalum boron oxide (TaBO) By doing this, an absorber film (film thickness 70 nm) consisting of the lower layer absorber layer and the upper layer absorber layer was formed.
After that, a chromium (Cr) target is used on the back surface of the multilayer reflective film coated substrate where the multilayer reflective film is not formed, and a reaction in a mixed gas atmosphere of argon (Ar) gas and nitrogen (N ₂ ) gas The back surface conductive film (film thickness 20 nm) which consists of chromium nitrides (CrN) was formed by reactive sputtering.
In this way, a reflective mask blank for EUV exposure was produced which maintained a highly smooth and low defect surface state.

D. Next, a chemically amplified resist for electron beam drawing (exposure) is applied by spin coating on the absorber film of the thus produced reflective mask blank, and heating and cooling steps are carried out. 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 the resist film was developed with a predetermined developer to form a resist pattern.
Thereafter, using this resist pattern as a mask, dry etching of the absorber film was performed to form an absorber film pattern on the protective film. Chlorine (Cl ₂ ) gas was used as a dry etching gas.
Thereafter, the remaining resist pattern was peeled off and washed.
In this way, a reflective mask for EUV exposure was produced which maintained a highly smooth and low defect surface state.

Example 2
In this embodiment, a disc-shaped surface plate main body 32 made of stainless steel (SUS) and having a diameter of 50 mm, and a urethane pad (not shown) formed on the entire surface of the surface plate main body 32 to cover the surface plate main body 32. And a processing reference surface 33 (film thickness 120 nm) having a chromium nitride film (CrN) on a base composed of a chromium film (Cr) formed on the entire surface of the urethane pad on the side facing the glass substrate The catalyst plate 31 was prepared. The catalyst surface plate 31 was formed as follows. First, place the platen main body 32 covered with a urethane pad in a sputtering apparatus (not shown), use a chromium (Cr) target, and perform sputtering in an argon (Ar) gas atmosphere to form a urethane pad (see FIG. A chromium film (Cr, film thickness 100 nm) is formed on the surface of the substrate (not shown), and reactive sputtering is then performed in a mixed gas atmosphere of argon (Ar) gas and nitrogen (N ₂ ) gas to A chromium nitride film (CrN, film thickness 20 nm) was formed on Cr.
Using the prepared catalyst surface plate 31, processing by catalyst-based etching was performed on the upper surface of the glass substrate placed on the support portion 21.
A glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were manufactured in the same manner as in Example 1 except for the above.

As in Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst reference etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.055 nm in root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.055 nm in root mean square roughness (RMS) by catalyst reference etching. Moreover, the surface roughness of the upper surface after processing was as good as 0.446 nm in maximum height (Rmax). In addition, the ratio of root mean square roughness to maximum height (Rmax / RMS) was as good as 8.1.
Further, in the same manner as in Example 1, a defect inspection of the upper surface of the glass substrate after processing by catalyst reference etching was performed.
The number of defects on the upper surface after processing was as small as 34.
In addition, when 20 sheets of glass substrates were produced by the method of Example 2, the total number and surface roughness were within the range of 0.050 to 0.062 nm in root mean square roughness (RMS), and processing stability was achieved. The sex was good.
According to the method of Example 2, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

Similar to Example 1, the reflectance of EUV light (wavelength 13.5 nm) was measured for the obtained multilayer reflective film coated substrate.
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%.
Further, in the same manner as in Example 1, a defect inspection was performed on the surface of the protective film of the obtained multilayer reflective film coated substrate.
The number of defects on the surface of the protective film after processing was as small as 23 pieces.
By the method of Example 2, a multilayer reflective film coated substrate having a highly smooth and low defect protective layer surface was obtained.
In addition, the method of Example 2 provided a reflective mask blank and a reflective mask for EUV exposure maintaining high smoothness and a low defect surface state.

Example 3
In this embodiment, a disc-shaped surface plate main body 32 made of stainless steel (SUS) and having a diameter of 50 mm, and a urethane pad (not shown) formed on the entire surface of the surface plate main body 32 so as to cover the surface plate main body 32. And a processing reference surface 33 (film thickness 120 nm) having a tantalum nitride film (TaN) on a base composed of a tantalum film (Ta) formed on the entire surface of the urethane pad on the side facing the glass substrate The catalyst plate 31 was prepared. The catalyst surface plate 31 was formed as follows. First, place the platen main body 32 covered with a urethane pad in a sputtering apparatus (not shown), use a tantalum (Ta) target, and perform sputtering in an argon (Ar) gas atmosphere to form a urethane pad (see FIG. A tantalum film (Ta, film thickness 100 nm) is formed on the surface of the film (not shown), and reactive sputtering is performed in a mixed gas atmosphere of argon (Ar) gas and nitrogen (N ₂ ) gas to form a tantalum film A tantalum nitride film (TaN, film thickness 20 nm) was formed on Ta).
Using the prepared catalyst surface plate 31, processing by catalyst-based etching was performed on the upper surface of the glass substrate placed on the support portion 21.
Further, cleaning after processing of the glass substrate was performed in the same manner as in Example 1 except that cleaning with a chromium etching solution was not performed.
A glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were manufactured in the same manner as in Example 1 except for the above.

As in Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst reference etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.042 nm in root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.042 nm in root mean square roughness (RMS) by catalyst reference etching. Further, the surface roughness of the upper surface after processing was as good as 0.333 nm in maximum height (Rmax). Further, the ratio of root mean square roughness to maximum height (Rmax / RMS) was as good as 7.9.
Further, in the same manner as in Example 1, a defect inspection of the upper surface of the glass substrate after processing by catalyst reference etching was performed.
The number of defects on the upper surface after processing was as small as 19 pieces.
In addition, when 20 glass substrates were produced by the method of Example 3, the total number and surface roughness were within the range of 0.040 to 0.053 nm in root mean square roughness (RMS), and processing stability was achieved. The sex was good.
According to the method of Example 3, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

Similar to Example 1, the reflectance of EUV light (wavelength 13.5 nm) was measured for the obtained multilayer reflective film coated substrate.
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%.
Further, in the same manner as in Example 1, a defect inspection was performed on the surface of the protective film of the obtained multilayer reflective film coated substrate.
The number of defects on the surface of the protective film after processing was as small as 17.
According to the method of Example 3, a multilayer reflective film coated substrate having a highly smooth and low defect protective layer surface was obtained.
In addition, the method of Example 3 provided a reflective mask blank and a reflective mask for EUV exposure maintaining high surface smoothness and low defect surface state.

Example 4
In this embodiment, a disc-shaped surface plate main body 32 made of stainless steel (SUS) and having a diameter of 50 mm, and a urethane pad (not shown) formed on the entire surface of the surface plate main body 32 so as to cover the surface plate main body 32. And a processing reference surface 33 (film thickness 120 nm) having a titanium nitride film (TiN) on a base composed of a titanium film (Ti) formed on the entire surface of the urethane pad on the side facing the glass substrate The catalyst plate 31 was prepared. The catalyst surface plate 31 was formed as follows. First, place the platen main body 32 covered with a urethane pad in a sputtering apparatus (not shown), use a titanium (Ti) target, and perform sputtering in an argon (Ar) gas atmosphere to form a urethane pad (see FIG. A titanium film (Ti, 100 nm in film thickness) is formed on the surface of the film (not shown), and then reactive sputtering is performed in a mixed gas atmosphere of argon (Ar) gas and nitrogen (N ₂ ) gas to A titanium nitride film (TiN, film thickness 20 nm) was formed on Ti.
Using the prepared catalyst surface plate 31, processing by catalyst-based etching was performed on the upper surface of the glass substrate placed on the support portion 21.
Further, cleaning after processing of the glass substrate was performed in the same manner as in Example 1 except that cleaning with a chromium etching solution was not performed.
A glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were manufactured in the same manner as in Example 1 except for the above.

As in Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst reference etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.045 nm in root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.045 nm in root mean square roughness (RMS) by catalyst reference etching. Moreover, the surface roughness of the upper surface after processing was as good as 0.401 nm in maximum height (Rmax). In addition, the ratio of root mean square roughness to maximum height (Rmax / RMS) was as good as 8.9.
Further, in the same manner as in Example 1, a defect inspection of the upper surface of the glass substrate after processing by catalyst reference etching was performed.
The number of defects on the upper surface after processing was as small as 25.
In addition, when 20 glass substrates were produced by the method of Example 4, the total number and surface roughness were within the range of 0.043 to 0.057 nm in root mean square roughness (RMS), and processing stability was achieved. The sex was good.
According to the method of Example 4, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

Similar to Example 1, the reflectance of EUV light (wavelength 13.5 nm) was measured for the obtained multilayer reflective film coated substrate.
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%.
Further, in the same manner as in Example 1, a defect inspection was performed on the surface of the protective film of the obtained multilayer reflective film coated substrate.
The number of defects on the surface of the protective film after processing was as small as 50.
According to the method of Example 4, a multilayer reflective film coated substrate having a highly smooth and low defect protective layer surface was obtained.
In addition, the method of Example 4 provided a reflective mask blank and a reflective mask for EUV exposure maintaining high smoothness and a low defect surface state.

Example 5
In this embodiment, a disc-shaped surface plate main body 32 made of stainless steel (SUS) and having a diameter of 50 mm, and a urethane pad (not shown) formed on the entire surface of the surface plate main body 32 so as to cover the surface plate main body 32. And a processing reference surface 33 having an iron-nickel-chromium nitride film (FeNiCrN) on a base composed of an iron-nickel-chromium alloy film (FeNiCr) formed on the entire surface of the urethane pad on the side facing the glass substrate. A catalyst plate 31 provided with a (film thickness of 120 nm) was prepared. The catalyst surface plate 31 was formed as follows. First, place the platen main body 32 covered with a urethane pad in a sputtering apparatus (not shown), use an iron-nickel chromium alloy (FeNiCr) target, and perform sputtering in an argon (Ar) gas atmosphere to An iron-nickel-chromium alloy film (FeNiCr, 100 nm film thickness) is formed on the surface of the pad (not shown), and then reactive sputtering is performed in a mixed gas atmosphere of argon (Ar) gas and nitrogen (N ₂ ) gas. Then, an iron-nickel-chromium nitride film (FeNiCrN, film thickness 20 nm) was formed on the iron-nickel-chromium alloy film (FeNiCr).
Using the prepared catalyst surface plate 31, processing by catalyst-based etching was performed on the upper surface of the glass substrate placed on the support portion 21.
Moreover, in this example, the glass substrate removed from the support portion 21 was cleaned as follows. First, the glass substrate was immersed in a cleaning tank containing concentrated sulfuric 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 rub the upper surface of the glass substrate with a polyvinyl alcohol (PVA) brush and scrape 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 brush cleaning, ultrasonic vibration (frequency: 3 MHz) is applied to the upper surface, and foreign matter adhering to the upper surface is floated and removed Sonic cleaning was performed. Thereafter, a 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.
A glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were manufactured in the same manner as in Example 1 except for the above.

As in Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst reference etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.051 nm in root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.051 nm in root mean square roughness (RMS) by catalyst reference etching. Further, the surface roughness of the upper surface after processing was as good as 0.485 nm in maximum height (Rmax). In addition, the ratio of root mean square roughness to maximum height (Rmax / RMS) was as good as 9.5.
Further, in the same manner as in Example 1, a defect inspection of the upper surface of the glass substrate after processing by catalyst reference etching was performed.
The number of defects on the upper surface after processing was as small as 25.
In addition, when 20 glass substrates were produced by the method of Example 5, the total number and surface roughness were within the range of 0.048 to 0.066 nm in root mean square roughness (RMS), and processing stability was achieved. The sex was good.
According to the method of Example 5, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

Similar to Example 1, the reflectance of EUV light (wavelength 13.5 nm) was measured for the obtained multilayer reflective film coated substrate.
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%.
Further, in the same manner as in Example 1, a defect inspection was performed on the surface of the protective film of the obtained multilayer reflective film coated substrate.
The number of defects on the surface of the protective film after processing was as small as 30.
By the method of Example 5, a multilayer reflective film coated substrate having a highly smooth and low defect protective layer surface was obtained.
In addition, the method of Example 5 provided a reflective mask blank and a reflective mask for EUV exposure maintaining high smoothness and a low defect surface state.

Example 6
In this embodiment, a disc-shaped surface plate main body 32 made of stainless steel (SUS) and having a diameter of 50 mm, and a urethane pad (not shown) formed on the entire surface of the surface plate main body 32 so as to cover the surface plate main body 32. And a processing reference surface 33 (a film having a nickel copper nitride film (NiCuN) on a base made of a nickel copper alloy film (NiCu) formed on the entire surface of the urethane pad on the side facing the glass substrate. A catalyst plate 31 provided with a thickness of 120 nm) was prepared. The catalyst surface plate 31 was formed as follows. First, place the platen main body 32 covered with a urethane pad in a sputtering apparatus (not shown), use a nickel copper alloy (NiCu) target, and perform sputtering in an argon (Ar) gas atmosphere to form a urethane pad A nickel copper alloy film (NiCu, 100 nm thick) is formed on the surface (not shown), and then reactive sputtering is performed in a mixed gas atmosphere of argon (Ar) gas and nitrogen (N ₂ ) gas. Then, a nickel copper nitride film (NiCuN, film thickness 20 nm) was formed on the nickel copper alloy film (NiCu).
Using the prepared catalyst surface plate 31, processing by catalyst-based etching was performed on the upper surface of the glass substrate placed on the support portion 21.
Moreover, in this example, the glass substrate removed from the support portion 21 was cleaned as follows. First, the glass substrate was immersed in a cleaning tank containing concentrated sulfuric 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 rub the upper surface of the glass substrate with a polyvinyl alcohol (PVA) brush and scrape 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 brush cleaning, ultrasonic vibration (frequency: 3 MHz) is applied to the upper surface, and foreign matter adhering to the upper surface is floated and removed Sonic cleaning was performed. Thereafter, a 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.
A glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were manufactured in the same manner as in Example 1 except for the above.

As in Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst reference etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.050 nm in root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.13 nm to 0.050 nm in root mean square roughness (RMS) by catalyst reference etching. Further, the surface roughness of the upper surface after processing was as good as 0.486 nm in maximum height (Rmax). Further, the ratio of root mean square roughness to maximum height (Rmax / RMS) was as good as 9.7.
Further, in the same manner as in Example 1, a defect inspection of the upper surface of the glass substrate after processing by catalyst reference etching was performed.
The number of defects on the upper surface after processing was as small as 31.
In addition, when 20 glass substrates were produced by the method of Example 6, the total number and surface roughness were within the range of 0.048 to 0.066 nm in root mean square roughness (RMS), and processing stability was achieved. The sex was good.
According to the method of Example 6, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

Similar to Example 1, the reflectance of EUV light (wavelength 13.5 nm) was measured for the obtained multilayer reflective film coated substrate.
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%.
Further, in the same manner as in Example 1, a defect inspection was performed on the surface of the protective film of the obtained multilayer reflective film coated substrate.
The number of defects on the surface of the protective film after processing was as small as 37.
According to the method of Example 6, a multilayer reflective film coated substrate having a highly smooth and low defect protective layer surface was obtained.
In addition, the method of Example 6 provided a reflective mask blank and a reflective mask for EUV exposure maintaining high smoothness and low defect surface state.

Example 7
A. Production of Glass Substrate In this example, a 6025 size (152 mm × 152 mm × 6.35 mm) synthetic quartz glass substrate whose upper and lower surfaces were polished was prepared. The synthetic quartz glass substrate is obtained through the above-mentioned rough polishing process, precision polishing process, and ultra-precision polishing process.
A glass substrate was produced in the same manner as in Example 2 except for the above.

As in Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst reference etching was measured.
The surface roughness of the upper surface before processing was 0.17 nm in root mean square roughness (RMS).
The surface roughness of the upper surface after processing was as good as 0.049 nm in root mean square roughness (RMS). The surface roughness of the upper surface was improved from 0.17 nm to 0.049 nm in root mean square roughness (RMS) by catalyst reference etching. Moreover, the surface roughness of the upper surface after processing was as favorable as 0.392 nm in maximum height (Rmax). Further, the ratio of root mean square roughness to maximum height (Rmax / RMS) was as good as 8.0.
Further, in the same manner as in Example 1, a defect inspection of the upper surface of the glass substrate after processing by catalyst reference etching was performed.
The number of defects on the upper surface after processing was as small as 18 pieces.
In addition, when 20 glass substrates were produced by the method of Example 7, the total number and surface roughness were within the range of 0.046 to 0.057 nm in root mean square roughness (RMS), and processing stability was achieved. The sex was good.
By the method of Example 7, a glass substrate having a main surface with high smoothness and low defects was stably obtained.

B. Next, a molybdenum silicide (MoSi) target is used on the upper surface of the glass substrate thus manufactured, 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 semipermeable film analyzed by Rutherford backscattering analysis was 5 atomic% Mo, 30 atomic% Si, 39 atomic% O, and 26 atomic% N. The transmittance of the light semitransparent film to exposure light was 6%, and the phase difference caused by the exposure light passing through the light semitransparent film was 180 degrees.
After that, a chromium (Cr) target is used on the light semipermeable membrane, and a mixed gas atmosphere of argon (Ar) gas, carbon dioxide (CO ₂ ) gas, nitrogen (N ₂ ) and helium (He) gas is used. Reactive sputtering is performed to form a chromium oxycarbonitride (CrOCN) layer (film thickness 30 nm), and a chromium (Cr) target is further used thereon, and argon (Ar) gas and nitrogen (N ₂ ) are used. Reactive sputtering is performed in a mixed gas atmosphere with a gas to form a chromium nitride (CrN) layer (film thickness 4 nm), and lamination of a chromium oxycarbonitride (CrOCN) layer and a chromium nitride (CrN) layer To form a light shielding layer. Furthermore, 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 antireflective layer (film thickness 14 nm) made of chromium oxycarbonitride (CrOCN). Thus, the light shielding film which consists of a light shielding layer and a surface anti-reflection layer was formed.
In this way, a halftone phase shift mask blank for ArF excimer laser exposure was produced which maintained a highly smooth and low defect surface state.

C. Production of Halftone Type Phase Shift Mask Next, a chemically amplified resist for electron beam drawing (exposure) is applied by spin coating on the light shielding film of the thus produced halftone type phase shift mask blank, After the heating and cooling steps, 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 the resist film was 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 semitransparent film. A mixed gas of chlorine (Cl ₂ ) gas and oxygen (O ₂ ) gas was used as the dry etching gas.
Thereafter, using the resist pattern and the light shielding film pattern as a mask, the light semitransparent film was subjected to dry etching to form a light semitransparent film pattern. As a dry etching gas, a mixed gas of sulfur hexafluoride (SF ₆ ) and helium (He) was used.
Thereafter, the remaining resist pattern was peeled off, a resist film was applied again, pattern exposure for removing an unnecessary light shielding film pattern in the transfer region was performed, and then this resist film was developed to form a resist pattern. .
Thereafter, wet etching was performed to remove unnecessary light shielding film patterns.
Thereafter, the remaining resist pattern was peeled off and washed.
In this manner, a halftone phase shift mask for ArF excimer laser exposure was produced, which has a high smoothness and a low defect surface state.

In this embodiment, the present invention is applied to a halftone phase shift mask or phase shift mask blank having a light semitransmissive 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 transflective film. Further, the present invention is not limited to a halftone phase shift mask or phase shift mask blank having a single-layer light semitransmissive film, and a halftone phase shift mask or phase shift mask blank having a multi-layered light semitransmissive film. The invention can be applied. Further, the present invention can be applied not only to a halftone phase shift mask or a phase shift mask blank having a light shielding film of a multilayer structure, but also to a halftone phase shift mask or a phase shift mask blank having a single layer light shielding film. . The present invention can be applied not only to halftone phase shift mask blanks and phase shift mask blanks, but also to Levenson phase shift mask blanks, phase shift mask blanks, chromiumless phase shift mask blanks and phase shift mask blanks.
Moreover, in this embodiment, the present invention is applied to the case where the main surface of the glass substrate obtained through the rough polishing process, the precision polishing process, and the super precision polishing process is processed 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 disc-shaped surface plate main body 32 made of stainless steel (SUS) and having a diameter of 50 mm, a urethane pad formed on the entire surface of the surface plate main body 32 to cover the surface plate main body 32, a glass substrate The catalyst surface plate 31 provided with the processing reference surface 33 (film thickness of 100 nm) which consists of an iron film (Fe) formed on the whole surface of the urethane pad of the side which opposes was used. The processing reference surface 33 was formed by sputtering on a urethane pad using an iron (Fe) target in an argon (Ar) gas atmosphere.
Further, cleaning after processing of the glass substrate was performed in the same manner as in Example 1 except that cleaning with a chromium etching solution was not performed.
A glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were manufactured in the same manner as in Example 1 except for the above.

Moreover, the surface roughness of the upper surface used as a main surface of the glass substrate before and behind the process by catalyst reference | standard etching was measured like Example 1. FIG.
The surface roughness of the upper surface before processing was 0.13 nm in root mean square roughness (RMS).
The surface roughness of the upper surface after processing was insufficient at 0.140 nm in root mean square roughness (RMS). The surface roughness of the top surface was degraded by catalyst based etching from 0.13 nm to 0.140 nm in root mean square roughness (RMS). Moreover, the surface roughness of the upper surface after processing was inadequate with 2.954 nm in maximum height (Rmax). Further, the ratio of root mean square roughness to maximum height (Rmax / RMS) was insufficient at 21.1.
Further, in the same manner as in Example 1, a defect inspection of the upper surface of the glass substrate after processing by catalyst reference etching was performed.
The number of defects on the upper surface after processing was as large as 2118.
In addition, when 20 glass substrates were produced by the method of Comparative Example 1, the result is that the surface roughness largely varies from 0.085 to 0.224 nm in root mean square roughness (RMS), and the processing stability is obtained. Was bad.
By the method of Comparative Example 1, a glass substrate having a main surface with high smoothness and low defects was not obtained.

Similar to Example 1, the reflectance of EUV light (wavelength 13.5 nm) was measured for the obtained multilayer reflective film coated substrate.
Due to the insufficient smoothness of the glass substrate main surface, the smoothness of the protective film surface is also insufficient, and the reflectance is 62%, which is 2% lower than Example 1.
Further, in the same manner as in Example 1, a defect inspection was performed on the surface of the protective film of the obtained multilayer reflective film coated substrate.
The number of defects on the surface of the protective film after processing was as large as 3089.
According to the method of Comparative Example 1, a multilayer reflective film coated substrate having a highly smooth and low defect protective film surface was not obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which maintained the surface state of high smoothness and low defects by the method of Comparative Example 1 were not obtained.

In the above-described embodiment, the metal nitride layer is formed on the metal film made of the catalyst material, the metal nitride layer is removed immediately before the CARE processing, and the CARE processing is performed using the metal film exposed by the removal. Examples (Example 1) in which a metal nitride film was formed on a metal film composed of a catalyst substance and examples in which CARE processing was performed using the metal nitride film (Examples 2 to 4 and 7), catalyst Although an alloy nitride film was formed on an alloy film of a substance, and CARE processing was performed using the alloy nitride film, the examples (Examples 5 and 6) were mentioned and described, but the present invention is limited thereto is not.
For example, a metal oxide layer or a metal oxynitride layer is formed on a metal film composed of a catalyst substance, and the metal oxide layer or the metal oxynitride layer is removed immediately before CARE processing, and the metal film exposed by the removal is removed. You may use and carry out CARE processing. Further, an alloy oxide layer or an alloy oxynitride layer is formed on an alloy film made of a catalyst substance, and the alloy oxide layer or the alloy oxynitride layer is removed immediately before CARE processing, and the alloy film exposed by the removal is removed. You may use and carry out CARE processing.
Alternatively, CARE processing may be performed using a metal nitride film or an alloy nitride film which is simply made of a catalyst material. In addition, CARE processing may be performed using an oxide film, an oxide layer, an oxynitride film, or an oxynitride layer of a metal or alloy formed of a catalyst substance.
Further, in the above-described embodiment, the present invention is applied to the case where processing by catalyst reference etching is performed on the main surfaces of the reflective mask blank substrate and the phase shift mask blank substrate, but for binary mask blanks and nanoimprints The present invention can also be applied to the case where processing by catalyst reference etching is performed on the main surface of the mask blank.
In the above-described embodiment, the present invention is applied to the case where processing by catalyst reference etching is performed on the main surface of the mask blank substrate. However, catalyst reference etching is performed on the main surface of the magnetic recording medium substrate. The present invention can also be applied to the case of processing by

Example 8
A. Production of Glass Substrate Substrate Preparation Step A 2.5-inch size (φ 65 mm) aluminosilicate glass substrate with its upper and lower surfaces polished was prepared. In the aluminosilicate glass substrate, the following press forming process, coring process, chamfering process, end face polishing process, grinding process, first polishing (main surface polishing) process, chemical strengthening process, second polishing (final polishing) It is obtained through the process.

(1) Press forming process (preparation of plate-like glass blank)
In preparation of a plate-like glass blank, a glass blank is produced by press-forming molten glass using a press die.
In the step of press forming, for example, a glass gob (glass lump) made of molten glass is supplied onto a lower mold which is a receiving gob forming type, and a glass gob is used using an upper mold which is a gob forming type facing the lower mold. Is sandwiched and press-formed. As a result, a disk-shaped glass blank to be a source of the glass substrate for a magnetic disk is formed. Even if the surface processing amount (lapping amount + grinding amount + polishing amount), which is the machining allowance in lapping, grinding, first polishing and second polishing described later, is reduced, the target plate thickness, for example, 0.8 mm The plate thickness of the glass blank produced by press molding can be secured and the target surface roughness, for example, the arithmetic average roughness Ra can be 0.15 nm or less, and the increase in cost can be suppressed. It is preferable to press-mold so that it may be 0.9 mm or less.
In addition, the plate-like glass immediately after shaping | molding is called glass blank, and when a subsequent processing is performed using this glass blank, this plate-like glass is called glass base plate.

(2) Coring process Next, coring is given using the produced disk shaped glass blank as a glass base plate of the glass substrate for magnetic discs. Specifically, in the coring step, a cylindrical diamond drill is used to form an inner hole at the center of the disk-shaped glass base plate, thereby forming an annular glass base plate. At this time, the glass base plate is placed on a support and fixed to form an inner hole. The support and fixation of the glass base plate by the support table is performed by suctioning the glass base plate through a suction port provided on the surface of the support table. That is, one of the main surfaces of the glass base plate having a state of surface irregularities on the main surface at the time of press molding is supported and fixed, and a hole penetrating the glass base plate is made. In addition, an elastic member is provided on a portion of the support table in contact with the main surface of the glass base plate, and supporting and fixing the glass base plate using this elastic member does not damage the main surface of the glass base plate It is preferable in point.

(3) Chamfering process After the coring process, the chamfering process which forms a chamfering surface in the edge part (an outer peripheral end surface and an inner peripheral end surface) of a disk-shaped glass base plate is performed. In the chamfering process, the outer peripheral surface and the inner peripheral surface of the glass base plate processed into an annular shape in the coring process are chamfered by, for example, a full shape grinding wheel using diamond abrasive grains. The full-shaped grindstone is a grinding tool in which a plurality of grindstone types having different abrasive grain sizes and different inclination angles of the grindstone surface with which the glass base plate is brought into contact for chamfering are prepared. For example, a tool described in Japanese Patent No. 3061605 is exemplified as the all-shaped grindstone. With this general-purpose grindstone, while chamfering, the diameter of the glass base plate is also made equal to a predetermined size, for example, 65 mm. The end of the glass base plate has a side wall surface which is not chamfered perpendicular to the main surface and a chamfered chamfered surface. Hereinafter, the side wall surface and the chamfered surface are collectively referred to as an end surface.

(4) End Surface Polishing Step Next, end surface polishing (edge polishing) of an annular glass base plate is performed.
In the end face polishing, the inner peripheral end face and the outer peripheral end face of the annular glass base plate are mirror-finished by brush polishing. At this time, polishing is performed using a polishing brush on a plurality of glass base plates stacked by sandwiching a jig for polishing an end face such as a spacer between the glass base plates. Furthermore, the polishing liquid used for polishing contains fine particles of cerium oxide or the like as free abrasives. By performing end face polishing, contamination such as dust or the like on the end face of the glass base plate is removed, damage such as contamination or damage is removed, thereby preventing the occurrence of thermal asperity or causing corrosion of Na, K, etc. It is possible to prevent the occurrence of ion deposition that

(5) Grinding process The main surface on both sides of a ring-shaped plate-like glass base plate is ground using a double-sided grinding apparatus. In the double-side grinding apparatus, a diamond sheet or the like in which diamond abrasives are dispersed is used instead of the pad in the double-side grinding apparatus. Besides the grinding process using fixed abrasives, a grinding process using free abrasives may be performed. In this grinding process, the flatness is improved, the plate thickness is equalized, or the waviness is further reduced before polishing (first polishing and second polishing) to reduce the main surface roughness of the glass base plate described later. To do.

(6) First Polishing (Main Surface Polishing) Step Next, the first polishing is applied to the main surface of the annular glass base plate. The first polishing is performed with free abrasive using a double-side polishing apparatus that performs planetary motion. Fine particles of cerium oxide, zirconium oxide, titanium oxide or the like having a particle size (diameter) of about 0.5 to 2.0 μm are used for the free abrasive particles which are abrasives. This particle size is smaller than the particle size of the diamond abrasive used in grinding. The first polishing aims at the adjustment of scratches, distortions, waviness, and micro waviness remaining on the main surface by the grinding of (5).

(7) Chemical strengthening step Next, the annular glass base plate after the first 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 chemical strengthening, the chemical strengthening solution 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., and then the annular glass base plate is in the chemical strengthening solution. For example, 1 hour to 4 hours. In the case of this immersion, using a cage (holder) which holds and stores the end portions of a plurality of annular glass base plates so that both main surfaces of the annular glass base plate are chemically strengthened. It is preferred to do.
Thus, by immersing the glass base plate in the chemical strengthening solution, the Li ions and the Na ions in the surface layer of the glass base plate become respectively Na ions and K ions having a relatively large ion radius in the chemical strengthening solution. It is substituted and reinforced by forming a compression layer on the surface of a glass base plate. The chemically strengthened annular glass base plate is cleaned. For example, after being washed with sulfuric acid, it is washed with pure water or the like.

(8) Second Polishing (Final Polishing) Step Next, the second polishing is applied to the chemically strengthened and sufficiently cleaned glass base plate. The second polishing aims at mirror polishing of the main surface. In the second polishing, for example, a polishing apparatus having a configuration similar to that of the first polishing is used. At this time, the difference from the first polishing is that the type and particle size of the free abrasive grains are different, and the hardness of the pad is different. As the pad, a urethane-made polishing pad such as urethane foam, a suede pad or the like is used.
As the free abrasive used for the second polishing, for example, fine particles (particle size: about 10 to 50 nm in diameter) of colloidal silica or the like made of silica turbid in a polishing liquid are used. The fine particles are finer than the free abrasive used in the first polishing. In the polishing liquid (slurry) in which fine particles such as colloidal silica are turbid, containing 0.1 to 40% by mass, preferably 3 to 30% by mass of silica, for example, ensures processing efficiency of polishing, and the surface It is preferable in terms of increasing the roughness.
The ground glass plate is cleaned. In the washing, washing with a neutral washing solution or alkaline washing solution is preferable in that defects such as scratches are not formed on the glass surface by washing and the surface roughness is not roughened. Thereby, arithmetic mean roughness Ra of the main surface can be 0.15 nm or less, for example, 0.13 to 0.15 nm. In addition to the neutral washing solution, a plurality of washing processes using pure water, an acid (acid washing solution), IPA or the like can also be performed. Thus, the glass substrate is prepared by cleaning the glass base plate.

2. Substrate Processing Process Next, using the substrate processing apparatus shown in FIG. 1 and FIG. .
In this embodiment, a catalyst surface plate 31 was used which had a processing reference surface 33 having a tantalum nitride film (TaN) on a base composed of a tantalum film (Ta) used in the third embodiment.
The processing conditions are as follows.
Processing fluid: rotation speed of pure water shaft portion 71 (rotational speed of glass substrate): 10.3 rotations / minute Rotational speed of catalyst platen mounting portion 72 (rotational speed of catalyst platen 31): 10 rotations / minute : 35 hPa
Processing allowance: 25 nm

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 root mean square roughness (RMS).
The surface roughness after processing was as good as 0.047 nm in root mean square roughness (RMS).
The surface roughness improved from 0.12 nm to 0.047 nm in root mean square roughness (RMS) by catalyst based etching. In addition, the surface roughness after processing was as good as 0.38 nm in maximum height (Rmax). Further, the ratio of root mean square roughness to maximum height (Rmax / RMS) was as good as 8.0.
Moreover, when the glass substrate was produced 20 sheets by the method of Example 8, as a total, surface roughness was settled in the range of 0.046 nm-0.056 nm, and processing stability was favorable.
According to the method of Example 8, a glass substrate having a high smoothness main surface was stably obtained.

B. Production of Magnetic Recording Medium (Magnetic Disk) Next, the adhesion layer, soft magnetic layer, underlayer, magnetic recording layer, and barrier layer are formed on both sides of the glass substrate thus manufactured in an Ar gas atmosphere by DC magnetron sputtering. , And the auxiliary recording layer was formed sequentially.
The adhesion layer was CrTi with a thickness of 20 nm. 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 each 25 nm thick CoFeTaZr, and the spacer layer was 1 nm thick Ru. The underlayer was NiW with a film thickness of 5 nm. The magnetic recording layer has a stacked 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. It was a _CoCrPt-SiO 2 -TiO _2. Barrier layer was Ru-WO ₃ having a thickness of 0.3 nm. The auxiliary recording layer was CoCrPtB with a thickness of 10 nm.
Next, on the auxiliary recording layer, a protective layer consisting of a laminated structure of a hydrogenated carbon layer (C ₂ H ₄ ) and a carbon nitride layer (CN) having a film thickness of 4 nm is formed by the CVD method. A lubricating layer of 1.3 nm thick made of fluoropolyether (PFPE) was formed to produce a magnetic recording medium compatible with DFH heads.
Thus, the adhesion layer, the soft magnetic layer (the first soft magnetic layer, the spacer layer, the second soft magnetic layer), the underlayer, the magnetic recording layer (the first magnetic recording layer and the first magnetic recording layer) are formed on both sides of the glass substrate, respectively. 2. Magnetic recording medium (magnetic disk) was manufactured by sequentially forming a magnetic recording layer), a barrier layer, an auxiliary recording layer, a protective layer, and a lubricating layer.
Although the adhesion layer is made of CrTi, the present invention is not limited to this. For example, the adhesion layer may be selected from CoW, CrW, CrTa, and CrNb materials. Although the first soft magnetic layer and the second soft magnetic layer of the soft magnetic layer are made of CoFeTaZr, the present invention is not limited to this. For example, other Co-Fe based alloys such as CoCrFeB, cobalt based alloys such as CoTaZr And [Ni-Fe / Sn] _n multilayer structure may be selected from Ni-Fe based alloys. Although the first magnetic recording layer of the magnetic recording layer is CoCrPt-Cr ₂ O ₃ and the second magnetic recording layer is CoCrPt-SiO ₂ -TiO ₂ , the present invention is not limited to these, and the first magnetic recording layer The second magnetic recording layer may have the same composition and type. As nonmagnetic materials for forming nonmagnetic regions in these magnetic recording layers, in addition to chromium oxide (CrxOy) and titanium oxide as described above, for example, silicon oxide (SiOx), zircon oxide (ZrO ₂ ), etc. 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 , and Cr. May be The barrier layer has been a Ru-WO _3, is not limited thereto and may be selected from Ru alloy other than Ru or above. Although the above auxiliary recording layer is made of CoCrPtB, the present invention is not limited to this. For example, it may be selected from CoCrPt, and may contain a very small amount of oxide.
Also, 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 pre-underlayer is, for example, selected from Ni, Cu, Pt, Pd, Zr, Hf, Nb, and Ta. The composition of the nonmagnetic granular layer can be made a granular structure by segregating nonmagnetic substances between nonmagnetic crystal grains made of a Co-based alloy to form grain boundaries.

C. Load Unload (LUL) Durability Test, DFH Touchdown Test The obtained magnetic recording medium (magnetic disk) was subjected to a LUL test with the number of revolutions of 7200 rpm and the flying height of the DFH head of 9 to 10 nm. As a result of the LUL test, no failure occurred even after repeating 1,000,000 times. In general, in the LUL durability test, it is required that the number of LULs continuously exceeds 400,000 without failure. The LUL number of 400,000 times is equivalent to about ten years of use in a normal HDD use environment. Thus, a highly reliable DFH head compatible magnetic recording medium was manufactured.
In addition, the DFH touchdown test was performed on the obtained magnetic recording medium (magnetic disk). In the DFH touch down test, the DFH mechanism gradually protrudes the DFH head element portion to the obtained magnetic recording medium (magnetic disk) by detecting the contact with the magnetic disk surface. It is a test to evaluate the distance which the magnetic recording medium contacted. The head used was a DFH head for a 320 GB / P magnetic disk (2.5 inches in size). The flying height when there was no protrusion of the DFH head element portion 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 the test was 25 ° C., and the humidity was 60%. As a result, the distance between the DFH head element portion and the magnetic recording medium 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 of manufacturing a substrate according to any one of the above-mentioned constitutions 1 to 8 has a root mean square roughness (RMS) of at most 0.075 nm, and a maximum height A glass substrate for a magnetic recording medium is obtained which has a high smoothness of 0.75 nm or less at (Rmax) and 8.5 or less at the ratio of root mean square roughness to the maximum height (Rmax / RMS).
A highly reliable DFH head compatible by a method of manufacturing a magnetic recording medium on a main surface of a substrate obtained by the method of manufacturing a substrate according to any one of the configurations 1 to 8 above. A magnetic recording medium can be obtained.

1 substrate processing apparatus 2 substrate support means 3 substrate surface creation means 4 processing fluid supply means 5 drive means 6 chambers 7 relative motion means 8 load control means 9 removal means 21 support portion 22 flat portion , 22a housing portion, 31 catalyst surface plate, 32 surface plate main 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 part, 71 shaft part , 72 catalyst surface plate mounting part, 81 air cylinder, 82 load cell, 91 supply pipe, 92 injection nozzle, M substrate, M1 upper surface, M2 lower surface.

Claims (13)

A substrate preparing 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 catalyst reference etching in a state in which a processing reference surface of a catalyst material 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 and
The catalyst material includes a material selected from the group consisting of a metal belonging to Groups 3 to 12 of the periodic table of elements and an alloy containing at least one of the metals,
Before the substrate processing step, all or a part of the oxidation progress suppression layer on the processing reference surface having the oxidation progress suppression layer formed by including nitrogen in the metal or the alloy in the surface layer, or the metal or the metal Including a removing step of removing all or part of the oxidation progress suppressing film on the processing reference surface having the oxidation progress suppressing film formed of an alloy nitride on the surface layer,
The processing reference surface that has passed the removal step is the metal or the alloy that is exposed in the removal step, or the oxidation progress suppression layer or the exposure layer that is exposed in the removal step on the surface layer of the processing reference surface. A method of manufacturing a substrate comprising the one having the oxidation progress suppression film . The method according to claim 1 , wherein the removing step uses at least one of physical action and chemical action. The substrate processing step, by relative movement between the machining reference surface and the main surface, a manufacturing method of a substrate according to claim 1 or 2, characterized in that processing the main surface by the catalyst based etching. The method according to any one of claims 1 to 3 , 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 any one of claims 1 to 4 , wherein the substrate is made of a glass material. The method for manufacturing a substrate according to any one of claims 1 to 5 , wherein the processing fluid comprises a solvent which does not normally exhibit solubility in the substrate. The method according to claim 6 , wherein the processing fluid is pure water. The method for manufacturing a substrate according to any one of claims 1 to 7 , wherein the substrate is a mask blank substrate. A method for producing a multilayer reflective film coated substrate, comprising forming a multilayer reflective film on the main surface of the substrate obtained by the method for producing a substrate according to claim 8 . A main surface of a substrate obtained by the method of manufacturing a substrate according to claim 8 , or a multilayer reflective film of a substrate with a multilayer reflection film obtained by the method of manufacturing a substrate with a multilayer reflection film according to claim 9 . A method of producing a mask blank, comprising forming a thin film for transfer pattern. A method for producing a transfer mask, comprising patterning the thin film for transfer pattern of the mask blank obtained by the method for producing a mask blank according to claim 10 to form a transfer pattern on the main surface. A substrate processing apparatus for processing a main surface of a substrate by catalyst reference etching, comprising:
Substrate supporting means for supporting a substrate having a main surface made of an oxide-containing material;
A substrate surface creation means having a processing reference surface of a catalytic substance, wherein the catalytic substance is selected from the group consisting of metals belonging to Groups 3 to 12 of the periodic table of the elements and alloys containing at least one of the metals Containing the above-described material, and the processing reference surface having, in the surface layer thereof, an oxidation progress inhibiting layer comprising the metal or the alloy containing nitrogen, or the surface layer comprising the nitride of the metal or the alloy Substrate surface creation means comprising a film having an oxidation progress suppression film comprising
Processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface;
Wherein in a state where the process fluid is interposed, and a drive means for contacting or approaching the working reference plane in the main surface between said working reference plane and said main surface,
The whole or part of inhibiting the progress of oxidation layer, or a substrate processing apparatus characterized by obtaining Bei and removing means for removing all or part of the oxide suppressing progression film. The substrate processing apparatus according to claim 12 , further comprising relative movement means for moving the processing reference surface and the main surface relative to each other.

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