JP6400360B2 - Substrate manufacturing method, mask blank substrate manufacturing method, mask blank manufacturing method, transfer mask manufacturing method, and substrate manufacturing apparatus - Google Patents

Description

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

  In recent years, in semiconductor devices, the density and accuracy of highly integrated circuits have been further increased. As a result, there is a demand for flattening, smoothing, and reducing defects at a finer size for mask blank substrates and transfer masks used for circuit pattern transfer.

  For example, as a mask blank used in the semiconductor design rule 1xnm generation and later (half pitch (hp) 14 nm, 10 nm, 7 nm, etc.), a reflective mask blank for EUV exposure, a binary mask blank for ArF excimer laser exposure, and a phase shift There are mask blanks, mask blanks for nanoimprints, etc., but in mask blanks used in these generations, defects of 30 nm class (SEVD (Sphere Equivalent Volume Diameter) of 20 nm or more and 34 nm or less) or smaller Size defects can be a problem. For this reason, it is preferable that the main surface of the substrate used for the mask blank (that is, the surface on the side where the transfer pattern is formed) has as few as possible 30 nm-class defects. Further, in a high-sensitivity defect inspection apparatus that performs defect inspection of 30 nm-class defects, the surface roughness affects background noise. That is, if the smoothness is insufficient, a large number of pseudo defects due to surface roughness are detected, and defect inspection cannot be performed. For this reason, the main surface of a substrate used for a mask blank used in the semiconductor design rule 1 × nm generation and later is required to have a smoothness of not more than 0.08 nm in terms of root mean square roughness (Rms).

  Further, in recent years, in the hard disk drive (HDD), the flying height of the recording / reading head with respect to the magnetic recording medium is further reduced as the recording capacity of the magnetic recording medium is increased. It has become. As such a head, a head mounted with a DFH (Dynamic Flying Height) mechanism is also widespread. The DFH mechanism operates so that the magnetic head thermally expands due to the heat generated by the heating element provided in the magnetic head, and the magnetic head projects slightly in the direction of the air bearing surface, thereby keeping the flying height constant. Can do. A head equipped with such a DFH mechanism has a flying height of about several nanometers, and thus a defect such as a head crash tends to occur when a magnetic recording medium is used. In order to reduce such defects, the surface of the magnetic recording medium substrate is required to have a low defect surface with high smoothness and substantially no protrusions.

  As a substrate for a magnetic recording medium, there is a metal substrate such as aluminum, but a glass substrate that is less likely to be plastically deformed than a metal substrate and that provides high surface smoothness when the main surface of the substrate is mirror-polished is preferably used. It has been.

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

  2. Description of the Related Art In recent years, a processing method using catalyst-based etching (hereinafter also referred to as “CARE”) has been proposed as a processing method for a substrate that requires a low defect and a highly smooth state substantially free of protrusions on the main plane. In catalyst-based etching (CARE) processing, a hydroxyl group is generated as an active species from a molecule in a processing fluid adsorbed on a processing reference surface formed from a catalyst substance, and the active species approaches or contacts the processing reference surface. It is considered that the fine convex portions on the surface undergo a hydrolysis reaction and the fine convex portions are selectively removed. Patent Document 1 describes a processing method by catalyst-based etching using a metal catalyst.

  In Patent Document 1, in the presence of water, the processing reference surface of the catalyst substance is brought into contact with or close to the surface of the workpiece made of a solid oxide such as glass, and the processing reference surface and the surface of the workpiece are moved relative to each other. In addition, a solid oxide processing method is described in which a hydrolysis product is removed from the surface of the workpiece, and the surface of the workpiece is processed (hereinafter, the solid oxide processing method is also referred to as a CARE processing method). Called). As the catalyst material, a material containing a metal element and having an electron d orbit near the Fermi level is used. Specific metal elements include, for example, platinum (Pt), gold (Au), silver ( Ag), copper (Cu), nickel (Ni), chromium (Cr), and molybdenum (Mo). It is described that the catalyst material does not need to be bulk, and may be a thin film in which a metal or a transition metal is formed by sputtering or the like on the surface of a base material that is inexpensive and has good shape stability. In addition, the base material on which the catalyst material is formed may be a hard elastic material, and for example, it is described that a fluorine-based rubber can be used.

International Publication No. 2013/084934

  Substrate processing by catalyst-based etching (CARE) is an excellent technique that can increase the smoothness of the main surface of the substrate. However, due to its processing mechanism, there is a problem that processing speed is generally slow, and as a result, There is a problem that manufacturing throughput is low.

  Patent Document 1 discloses a method in which the pH of a processing fluid used during processing, the potential applied to a catalyst material, and the like are changed during processing. This method is a method of performing a series of processing from rough processing to precision processing by changing the processing speed by continuously (seamlessly) changing electrochemical characteristics during CARE processing. However, this method has a problem in stability, particularly in mass production.

  The present invention has been made in view of the above-described problems, and it is possible to achieve both improvement in processing speed and reduction in surface roughness of the main surface of the substrate (improvement of smoothness), and stable production of the substrate. Manufacturing method of substrate, manufacturing method of mask blank substrate, manufacturing method of multilayer reflective substrate using this mask blank substrate, manufacturing method of mask blank using this mask blank substrate or multilayer reflective film-coated substrate, An object is to provide a method for manufacturing a transfer mask using a mask blank and a substrate manufacturing apparatus.

In order to solve the above-described problems, the present invention has the following configuration.
(Configuration 1)
A substrate preparation step of preparing a substrate having a main surface made of a material containing an oxide;
A substrate processing step of processing the main surface by catalytic reference etching in a state in which a processing reference surface of a catalytic substance is brought into contact with or close to the main surface and a processing fluid is interposed between the processing reference surface and the main surface When,
In a method of manufacturing a substrate having
In the substrate processing step, a plurality of stages of catalyst reference etching with different processing speeds are performed on the main surface due to differences in at least one of the material of the catalyst substance and mechanical characteristics of a processing reference surface. A method for manufacturing a substrate.
(Configuration 2)
In the substrate processing step,
The processing speed of the substrate is slower than the processing speed of the catalyst-based etching performed last, compared to the processing speed of the catalyst-based etching performed before,
A method for manufacturing a substrate according to Configuration 1, wherein:
(Configuration 3)
The substrate according to Configuration 1 or 2, wherein the plurality of stages of catalyst reference etching are performed by using a plurality of types of catalyst surface plates in which the catalyst material is formed on a base material having a predetermined hardness. Manufacturing method.
(Configuration 4)
In the substrate processing step,
The processing speed for the substrate is such that the processing speed of the catalyst-based etching performed last is slower than the processing speed of the catalyst-based etching performed before that. Selecting material,
A method of manufacturing a substrate according to Configuration 3, wherein:
(Configuration 5)
In the method for manufacturing a substrate according to any one of configurations 1 to 4,
A cleaning step with a cleaning liquid is performed after the last catalyst reference etching in the substrate processing step,
The catalytic material used for the last catalytic reference etching has solubility in the cleaning liquid of the cleaning step;
A method for manufacturing a substrate, characterized in that:
(Configuration 6)
6. The method of manufacturing a substrate according to Configuration 5, wherein the catalytic material used for the last catalytic reference etching includes a metal of Cr, Ni, Fe, or Cu, or an alloy containing the metal.
(Configuration 7)
6. The method for manufacturing a substrate according to Configuration 5, wherein the cleaning liquid is a solution that does not dissolve the main surface.
(Configuration 8)
8. The method of manufacturing a substrate according to any one of configurations 1 to 7, wherein the substrate is made of a glass material.
(Configuration 9)
9. The method of manufacturing a substrate according to any one of configurations 1 to 8, wherein the substrate is a mask blank substrate.
(Configuration 10)
A method for producing a substrate with a multilayer reflective film, comprising: forming a multilayer reflective film on a main surface of the substrate produced by the method for producing a substrate according to Configuration 9.
(Configuration 11)
Transfer onto the main surface of the substrate obtained by the method for producing a substrate according to Configuration 9, or onto the multilayer reflective film of the substrate with a multilayer reflective film obtained by the method for producing a substrate with a multilayer reflective film according to Configuration 10. A method for manufacturing a mask blank, comprising forming a pattern thin film.
(Configuration 12)
A method for producing a transfer mask, comprising: patterning a thin film for a transfer pattern of a mask blank obtained by the method for producing a mask blank according to Configuration 11 to form a transfer pattern.
(Configuration 13)
A substrate manufacturing apparatus for manufacturing a substrate by processing the main surface of the substrate by catalyst-based etching,
Substrate support means for supporting the substrate;
A substrate surface creation means having a processing reference surface of a catalytic substance disposed opposite to the main surface of the substrate supported by the substrate support means;
Processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface;
Drive means for bringing the processing reference surface into contact with or approaching the main surface in a state where a processing fluid is interposed between the processing reference surface and the main surface;
The substrate surface creation means includes a plurality of types of catalyst surface plates in which the catalyst material is formed on a base material having a predetermined hardness, and can be selected.
A substrate manufacturing apparatus.
(Configuration 14)
14. The substrate manufacturing apparatus according to the structure 13, further comprising a relative motion unit that relatively moves the processing reference surface and the main surface.

  According to the present invention, a plurality of stages of catalytic reference etching with different processing speeds are performed on the main surface of the substrate due to differences in at least one of the material of the catalyst substance or the mechanical characteristics of the processing reference surface. By performing multiple stages of catalyst-based etching with different processing speeds on the main surface of the substrate, both processing speed and surface roughness (smoothness) can be achieved, and there are low defects and low surface roughness. A substrate with high smoothness can be stably produced in large quantities. In particular, the surface roughness of the main surface of the substrate after processing can be sufficiently suppressed by performing the processing step with a high processing speed first and the processing step with a low processing speed at the last stage. It is possible to achieve both improvement in speed and smoothness.

  In addition, according to the method for manufacturing a substrate with a multilayer reflective film according to the present invention, since the substrate with the multilayer reflective film is manufactured using the substrate obtained by the above-described substrate manufacturing method, the multilayer reflective with desired characteristics is produced. A substrate with a film can be manufactured.

  Further, according to the mask blank manufacturing method of the present invention, the mask is obtained using the substrate obtained by the above-described substrate manufacturing method or the substrate with the multilayer reflective film obtained by the above-described method of manufacturing the substrate with the multilayer reflective film. Since a blank is manufactured, a mask blank having desired characteristics can be manufactured.

  Further, according to the transfer mask manufacturing method of the present invention, a transfer mask is manufactured using the mask blank obtained by the above-described mask blank manufacturing method. Can be manufactured.

It is a fragmentary sectional view showing composition of the 1st catalyst standard etching processing device which performs processing by catalyst standard etching to a mask blank substrate. It is a top view which shows the structure of the 1st catalyst reference | standard etching processing apparatus which processes to a mask blank board | substrate by a catalyst reference | standard etching. It is a fragmentary sectional view showing the composition of the 2nd catalyst standard etching processing device which performs processing by catalyst standard etching to a mask blank substrate. It is a top view which shows the structure of the 2nd catalyst reference | standard etching processing apparatus which processes to a mask blank board | substrate by a catalyst reference | standard etching. It is a top view which shows the structure of the 2nd catalyst reference | standard etching processing apparatus which processes to a mask blank board | substrate by a catalyst reference | standard etching. It is a top view which shows the structure of the 2nd catalyst reference | standard etching processing apparatus which processes to a mask blank board | substrate by a catalyst reference | standard etching. It is a fragmentary sectional view showing the composition of the 2nd catalyst standard etching processing device which performs processing by catalyst standard etching to a mask blank substrate. It is a top view which shows the structure of the 2nd catalyst reference | standard etching processing apparatus which processes to a mask blank board | substrate by a catalyst reference | standard etching.

Hereinafter, a method for manufacturing a substrate according to an embodiment of the present invention, a method for manufacturing a substrate with a multilayer reflective film using the substrate, a method for manufacturing a mask blank using the substrate or the substrate with a multilayer reflective film, and the mask blank A method of manufacturing a transfer mask using the above will be described in detail with reference to timely drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and the description thereof may be simplified or omitted.
Embodiment 1 FIG.
In the first embodiment, a method for manufacturing a first substrate and a substrate processing apparatus will be described.

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

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

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

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

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

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

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

2. Substrate processing process (Outline of substrate processing process)
Next, the main surface is processed by catalyst-based etching (CARE) with the processing reference surface of the catalytic material in contact with or close to the main surface of the substrate and the processing fluid interposed between the processing reference surface and the main surface. To do. In the first embodiment, the catalyst reference etching is performed in a plurality of stages using a plurality of catalyst reference etching apparatuses in which the conditions of the catalyst reference etching unit are changed. In the first embodiment, the catalyst reference etching step is performed twice, the first catalyst reference etching step is rough processing, and the last catalyst reference etching step is finishing. As will be described in detail later, in the finishing process that is performed at the end, in order to prioritize high smoothness, that is, reduction in surface roughness, the processing speed is set slower than the catalyst etching process that is performed before that. However, the number of times of the catalyst reference etching is not limited to two times, and it is needless to say that a plurality of times may be performed. Even in this case, the last process is the finishing process, which is the main factor for determining the smoothness (surface roughness). Therefore, the final processing speed of the finishing process is set slower than before.

(Configuration and function of substrate processing equipment)
An apparatus for performing catalyst-based etching will be described with reference to FIGS. 1 and 2 are examples of a substrate processing apparatus that performs processing by catalytic reference etching on the main surface of the substrate. FIG. 1 is a partial sectional view of the substrate processing apparatus, and FIG. 2 is a plan view of the substrate processing apparatus. FIG. In the following, the case where the upper surface M1 used as the main surface of the substrate M is CARE processed using the substrate processing apparatus shown in FIGS. 1 and 2 will be described. However, when the lower surface M2 of the substrate M is also used as the main surface. The upper surface M1 and the lower surface M2 are interchanged, and the lower surface M2 is also CARE processed. Even if the lower surface M2 is not used as the main surface, the lower surface M2 is also CARE processed as necessary. In that case, CARE processing of the upper surface M1 is performed after CARE processing of the lower surface M2.

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

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

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

The substrate surface creation means 3 includes a catalyst surface plate 31. The catalyst surface plate 31 is attached to a catalyst surface plate mounting portion 72 of the relative motion means 7 described later. The catalyst surface plate 31 includes a surface plate body 32, a base material formed on the entire surface of the surface plate body so as to cover the surface plate body, and a processing reference surface 33 on which the catalyst is deposited. . Therefore, the catalyst material on the processing reference surface 33 faces the substrate M.

  The overall shape of the catalyst surface plate 31 is not particularly limited. For example, the outer shape of a disk, a sphere, a cylinder, a cone, or a pyramid can be used. The surface shape of the portion of the catalyst surface plate 31 on which the processing reference surface 33 is formed is not particularly limited. For example, a flat, hemispherical, or rounded shape can be used.

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

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

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

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

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

(Roughing)
First, the first roughing is performed as follows. Here, when both the upper surface and the lower surface of the substrate M are used as the main surface, the lower surface CARE processing may be performed after the upper surface CARE processing, or the upper surface CARE processing may be performed after the lower surface CARE processing. However, CARE processing on both the upper surface and the lower surface may be performed simultaneously. Even if the lower surface is not used as the main surface, the lower surface is also processed by catalyst-based etching as necessary. When CARE processing is also performed on the lower surface that is not used as the main surface, the upper surface used as the main surface is required to have high quality in terms of defect quality. It is preferable to perform processing.

  In this case, first, the processing reference surface 33 made of a catalyst material is disposed so as to face the main surface of the substrate M. Then, the processing fluid is supplied between the processing reference surface 33 and the main surface, and the processing reference surface 33 is brought into contact with the main surface or the processing fluid is interposed between the processing reference surface 33 and the main surface. The processing reference surface 33 and the main surface are moved relative to each other while applying a predetermined load (processing pressure) to the substrate M. When the processing reference surface 33 and the main surface are moved relative to each other while the processing fluid is interposed between the processing reference surface 33 and the main surface, the molecules in the processing fluid adsorbed on the processing reference surface 33 are removed. The generated active species react with the main surface to process the main surface. The active species are generated only on the processing reference surface 33 and deactivated when they are separated from the vicinity of the processing reference surface 33. Therefore, there is almost no reaction with the active species other than the main surface with which the processing reference surface 33 contacts or approaches. In this way, the main surface is processed by catalyst-based etching. In the processing based on the catalyst-based etching, since no abrasive is used, damage to the mask blank substrate M is extremely small, and generation of new defects can be prevented.

The relative motion between the processing reference surface 33 and the main surface is not particularly limited as long as the processing reference surface 33 and the main surface move relative to each other. When the substrate M is fixed and the processing reference surface 33 is moved, the processing reference surface 33 is fixed and the substrate M is moved, or both the processing reference surface 33 and the substrate M are moved. When the processing reference plane 33 moves, the movement includes rotating around an axis perpendicular to the main surface of the substrate M, or reciprocating in a direction parallel to the main surface of the substrate M. Similarly, when the substrate M moves, the movement is when the substrate M rotates about an axis perpendicular to the main surface of the substrate M or when the substrate M reciprocates in a direction parallel to the main surface of the substrate M. .
The load (processing pressure) applied to the substrate M is preferably, for example, 5 to 350 hPa. Within this range, the processing speed can be increased by applying a moderate load while suppressing the generation of scratches and surface roughness due to the load on the surface of the substrate M.
The machining allowance in the process by the catalyst reference etching is, for example, 5 nm to 100 nm. When there is a protrusion protruding from the main surface on the main surface of the substrate M, the machining allowance is preferably set to a value larger than the height of the protrusion. By setting the machining allowance to a value larger than the height of the protrusion, the protrusion can be removed by CARE processing.

  The catalyst substance that forms the processing reference surface 33 at this stage may be any material that generates active species that hydrolyze the main surface of the substrate M with respect to the processing fluid, and is a group 3 to 12 of the periodic table. It is selected from at least one metal of a group metal element, an alloy containing them, or a metal compound or alloy compound containing at least one of oxygen, nitrogen, carbon, and fluorine. Preferably, at least one metal of transition metal elements, an alloy containing them, or a metal compound or alloy compound containing at least one of oxygen, nitrogen, carbon, and fluorine in these metals and alloys is preferable. Further, in consideration of the processing speed, at least one metal of Group 4 to Group 6 metal elements, Group 8 to Group 10 metal elements of the periodic table, alloys containing them, these metals, The alloy is preferably a metal compound or alloy compound containing at least one of oxygen, nitrogen, carbon, and fluorine. For example, at least one metal of chromium (Cr), nickel (Ni), molybdenum (Mo), iron (Fe), copper (Cu), platinum (Pt), gold (Au) or an alloy containing them, stainless steel In order to improve throughput, it is desirable to select a catalyst having a high processing speed at this stage. In particular, chromium (Cr) or a chromium alloy containing chromium (Cr) as a main component is preferable because the processing speed can be increased. The chromium alloy containing chromium (Cr) as a main component refers to a chromium alloy having a chromium content of 50 atomic% or more in the chromium alloy.

  This catalytic substance is formed on an elastic member such as a fluorine-based rubber or a urethane pad, for example. As the material of the elastic member, a material that is insoluble in the processing fluid, has an appropriate hardness, and has a property as an elastic body that is not easily chipped by a mechanical impact is desirable. Factors that affect the processing speed include the material of the elastic member and its hardness and catalyst material. In this rough processing, it is preferable to select the material of the elastic member, its hardness and the catalyst material so that the processing speed is increased in order to improve the manufacturing throughput. For example, as the elastic member, it is preferable to select a material having a hardness (Shore A) of 50 or more. Preferably, it is desirable to select a material having a hardness (Shore A) of 75 or more, more preferably 85 or more. For example, when a catalyst made of Cr is selected on an elastic member using a fluorine-based rubber having a hardness (Shore A) of 90, the processing speed is 105 nm / min when the processing pressure on the substrate is 120 hPa. Further, when a catalyst made of Ni is selected on this elastic member, the processing speed is 20 nm / min. When a catalyst made of Pt is selected, a catalyst made of Cu is selected. In this case, it is 4 nm / min. Thus, the combination of an elastic member made of a fluorine-based rubber having a high hardness (Shore A) and a Cr catalyst is excellent in terms of processing speed. With respect to the elastic member, when an elastic member having high hardness is used, a high processing speed can be obtained.

Area of the working reference face 33 is smaller than the area of the main surface of the substrate M, for ^example, a 100mm ² ~10000mm 2. By downsizing the processing reference surface 33, the substrate processing apparatus can be downsized and high-precision processing can be performed reliably.

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

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

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

Next, finish processing by catalyst-based etching will be described. This process basically conforms to rough machining, but the difference is the configuration of the processing reference surface 33 of the selected substrate processing apparatus and the cleaning liquid. In the rough machining, in order to improve the throughput, the elastic member and the catalyst material are selected with emphasis on the machining speed. On the other hand, in this finishing process, emphasis is placed on improving the smoothness of the main surface of the substrate (reducing the surface roughness), and the processing reference surface 33 and the cleaning liquid of the substrate processing apparatus are used so that the processing speed is slower than that during rough processing. Selected. Examples of the catalytic substance include at least one metal from Group 3 to Group 12 of the periodic table, alloys containing them, and at least one of oxygen, nitrogen, carbon, and fluorine. It is selected from metal compounds and alloy compounds including one. The catalyst that can remain on the substrate M is selected from materials that are dissolved and removed by a cleaning solution that does not etch the main surface of the substrate M. As such a catalyst, for example, any metal of chromium (Cr), nickel (Ni), iron (Fe), copper (Cu), an alloy containing the metal such as stainless steel (SUS), and the like can be given. . These metals are frequently used as a substrate cleaning solution that does not dissolve the substrate M composed of oxides such as synthetic quartz glass, such as sulfuric acid, hydrochloric acid, nitric acid, Cr etching solution containing ceric ammonium nitrate and perchloric acid. Can be used. The combination of the elastic member and the catalyst in the finishing process can be selected in consideration of the combination of the elastic member and the catalyst in the roughing performed before that. As the elastic member used in the finishing process, it is desirable to select a material having a hardness (Shore A) of 45 or less, more preferably 30 or less, and further preferably 10 or less.
As a combination of the elastic member and the catalyst in the roughing and finishing, for example, (a) roughing is a combination of a fluorine rubber pad and a Cr catalyst (processing speed 105 nm / min), and finishing is a fluorine rubber pad and Cu. Combination of catalyst (processing speed 4 nm / min), (b) Roughing is a combination of fluorine rubber pad and Cr catalyst (processing speed 105 nm / min), Finishing is a combination of urethane pad and Cr catalyst (processing speed 3.2 nm) / C), (c) rough machining is a combination of a fluoro rubber pad and a Cr catalyst (processing speed 105 nm / min), and finishing is a combination of a urethane pad and a Ni catalyst (processing speed 0.6 nm / min). . The processing speed is a value when the processing pressure on the substrate is 120 hPa. Generally, a urethane pad with low hardness is suitable for this finishing process, but a fluorine-based rubber pad can also be used for the finishing process as shown in (a). In addition, the hardness (Shore A) of the urethane pad used here is 3. In addition, by using the same material for the catalyst and elastic member for both roughing and finishing, the hardness of the elastic member is hard for roughing and soft for finishing. It can be adjusted later and used. As described above, in the final stage finishing process, a point to be considered is that the final stage process is performed rather than the rough process due to a difference in at least one of the material of the catalytic substance or the mechanical properties (material and hardness) of the processing reference surface 33. The processing speed of the finishing process is reduced, and the catalyst material used in the finishing process is a material that is dissolved and washed with a cleaning liquid that does not dissolve the substrate M.

  Using the substrate processing apparatus having the functions shown in FIG. 1 and FIG. Here, in this substrate processing apparatus, as described above, the catalyst and the pad portion are changed from those at the time of rough processing so that the processing speed of the catalyst reference etching is slower than at the time of rough processing. Since the machining process itself is the same as that during rough machining, the description thereof is omitted. When the catalyst reference etching is completed, the catalyst used in the finishing process is dissolved and the substrate M is cleaned using a cleaning solution that does not dissolve the substrate, and the substrate processing is ended. Here, as the cleaning solution, for example, when Cr is used as the catalyst, so-called Cr etching solution containing ceric ammonium nitrate and perchloric acid, when Ni is used as the catalyst, hydrochloric acid and Pt as the catalyst are used. In the case, aqua regia is used, and in the case where Cu is used as the catalyst, hot concentrated sulfuric acid is used.

The substrate M is manufactured through the substrate preparation process and the substrate processing process.
According to the manufacturing method of the substrate M of the first embodiment, the manufacturing throughput can be increased by rough processing with a high processing speed, and high surface smoothness (low surface roughness) can be achieved in finishing processing. Coexistence is possible. Further, since the rough processing and the finishing processing are completely separated and processed, it is possible to supply the substrate M having the manufacturing stability, that is, the stable high smoothness with a stable manufacturing throughput. Further, since the catalyst foreign matter remaining on the substrate M is removed without damaging the substrate M with the cleaning liquid, there are few defects.

In this embodiment, the present invention is applied to a substrate processing apparatus of a type in which the processing reference surface 33 of the substrate surface creation means 3 is pressed against the main surface of the substrate M. However, the processing reference surface of the substrate surface creation means is used. The present invention can also be applied to a substrate processing apparatus of a type in which the main surface of the substrate M is pressed onto the substrate 33.
In this embodiment, the present invention is applied to a substrate processing apparatus that processes one side of the substrate M. However, the present invention can also be applied to a substrate processing apparatus that processes both surfaces of the substrate M at the same time. In this case, a carrier that is a member that holds the side surface of the substrate M is used as the substrate support means.
In the case of the above two types of substrate processing apparatuses, the area of the processing reference plane may be larger than the area of the main surface of the substrate. Since the entire surface of the substrate can be processed, the processing time can be shortened, and the occurrence of defects such as scratches due to the edge of the processing reference surface can be suppressed.
Further, in this embodiment, the present invention is applied to a substrate processing apparatus of a type that supplies a processing fluid from the outside of the chamber toward the main surface of the substrate M. However, a processing fluid supply means is provided in the substrate surface creation means, The present invention can also be applied to the case where the processing fluid is supplied from the processing fluid supply means, or the case where the processing fluid supply means is provided in the substrate support means and the processing fluid is supplied from the substrate support means. The present invention can also be applied to the case where the processing fluid is stored in the chamber, and the processing based on the catalyst reference etching is performed in a state where the substrate surface creation means and the substrate support means are placed in the processing fluid.
In this embodiment, the present invention is applied to a substrate processing apparatus of a type that relatively moves the processing reference surface 33 and the main surface by rotating both the processing reference surface 33 and the main surface. The present invention can also be applied to a substrate processing apparatus of a type in which the processing reference surface 33 and the main surface are moved relative to each other by a method.
Further, in this embodiment, the present invention is applied to the substrate processing apparatus of the single sheet type that processes the substrates M one by one. However, the present invention is also applied to a batch type substrate processing apparatus that processes a plurality of substrates M at the same time. Can be applied. Moreover, although the case where it processed over the main surface whole surface of the board | substrate M was shown here, you may perform only the local process which processes only the predetermined local part in the main surface of the board | substrate M as needed. These processes may be used in combination.

Embodiment 2. FIG.
In Embodiment 2, a second substrate manufacturing method and a substrate processing apparatus will be described.
The feature of the second embodiment is to enable roughing, finishing and cleaning with a single substrate processing apparatus, which will be described with reference to FIGS. The difference between the first embodiment and the processing apparatus is that two or more types of catalyst surface plates are mounted and a cleaning liquid supply means is provided.

  In the substrate processing, rough processing and finishing processing (precision processing) are performed separately, and at the catalyst surface plate, at least one of the material of the catalyst substance or the mechanical property (material and hardness) of the processing reference surface 33 is different. Therefore, the configuration of the second embodiment in which the processing speed of the final finishing process is made lower than the roughing process and the catalyst material used in the finishing process is dissolved and cleaned with a cleaning solution that does not dissolve the substrate M is as follows. There is no difference from Form 1. The combination of the catalyst and the elastic member, the catalyst material, the processing fluid, and the cleaning liquid constituting the first and second catalyst plates are the same as in the first embodiment. The difference is that the first embodiment uses a plurality of substrate processing apparatuses, whereas the second embodiment performs all the processing with one substrate processing apparatus, and the apparatus configuration for that purpose is as follows. Functions and processing procedures will be described. Description of portions common to the first embodiment is omitted. Here, an example in which two types of catalyst surface plates are mounted will be described, but the present invention is not limited to two types, and a plurality of three or more types may be mounted. Further, since the substrate preparation process is the same as that of the first embodiment, it is omitted here.

  3 and 4 show an example of a substrate processing apparatus for processing the main surface of the substrate M by catalyst-based etching. FIG. 3 is a partial cross-sectional view of the substrate processing apparatus, and FIG. 4 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. 3 and 4 will be described. However, when the lower surface M2 of the substrate M is also used as the main surface. The upper surface M1 and the lower surface M2 are interchanged, and the lower surface M2 is also CARE processed. Even if the lower surface M2 is not used as the main surface, the lower surface M2 is also CARE processed as necessary. In that case, CARE processing of the upper surface M1 is performed after CARE processing of the lower surface M2.

  The substrate processing apparatus 101 includes a substrate supporting means 2 that supports a substrate M having a main surface made of an oxide-containing material, a substrate surface creation means 3 having a processing reference surface 33 of a first catalytic substance, Substrate surface creation means 103 having a processing reference surface 33, a processing reference surface 133 for the second catalytic material, a processing fluid supply means 4 for supplying a processing fluid between the main surface, and processing reference surfaces 33 and 133 Drive means 5 is provided for bringing the processing reference surfaces 33 and 133 into contact with or approaching the main surface in a state where the processing fluid is interposed between the main surface and the processing surface.

  The substrate support means 2 is disposed in a cylindrical chamber 6. The chamber 6 has an opening 61 formed in the center of the bottom 63 of the chamber 6 and the processing fluid supplied from the processing fluid supply means 4 in order to arrange a shaft portion 71 of the relative motion means 7 described later in the chamber 6. In order to discharge the fluid, the bottom 63 of the chamber 6 is provided with a discharge port 62 formed closer to the outer periphery than the opening 61. In FIG. 3, a state in which the processing fluid is discharged from the discharge port 62 is indicated by an arrow.

  The substrate support means 2 includes a support portion 21 that supports the substrate M and a flat portion 22 that fixes the support portion 21. The support portion 21 has a rectangular shape when the substrate processing apparatus 101 is viewed from above, and includes a receiving portion 21a that supports four sides of the periphery of the lower surface M2 of the substrate M. The planar portion 22 has a circular shape when the substrate processing apparatus 1 is viewed from above.

The substrate surface creation means 3 and 103 include catalyst surface plates 31 and 131, respectively. The catalyst surface plates 31 and 131 are attached to catalyst surface plate mounting portions 72 and 172 of the relative motion means 7 described later. The catalyst surface plates 31 and 131 are the surface plate bodies 32 and 132, the base material formed on the entire surface of the surface plate body so as to cover the surface plate body, and the processing reference surface on which the catalyst is deposited. 33 and 133. Therefore, the catalyst material on the processing reference surfaces 33 and 133 is arranged in a direction facing the substrate M.

  The overall shape of the catalyst surface plates 31 and 131 is not particularly limited. For example, the outer shape of a disk, a sphere, a cylinder, a cone, or a pyramid can be used. The surface shape of the portions of the catalyst surface plates 31 and 131 on which the processing reference surfaces 33 and 133 are formed is not particularly limited. For example, a flat, hemispherical, or rounded shape can be used.

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

  The cleaning liquid supply means 104 is provided at the distal end of the supply pipe 141 extending from the outside of the chamber 6 toward the main surface of the substrate M placed on the support section 21 and the lower end of the supply pipe 141. And an ejection nozzle 142 that ejects a processing fluid toward the main surface of the substrate M placed on the unit 21. The supply pipe 141 is connected to, for example, a cleaning liquid storage tank (not shown) and a pressure pump (not shown) provided outside the chamber 6. The cleaning liquid is supplied to the injection nozzle 142 through the supply pipe 141 and is supplied from the injection nozzle 142 onto the main surface of the substrate M placed on the support portion 21.

  The drive means 5 is connected to the upper end of a catalyst surface plate mounting portion 72 of the relative motion means 7 described later, and extends to the periphery of the chamber 6 in a direction parallel to the main surface of the substrate M placed on the support portion 21. The first arm portion 51 and the second arm portion 151 and the end portions of the arm portions 51 and 151 that extend to the periphery of the chamber 6 are supported, and in a direction perpendicular to the main surface of the substrate M placed on the support portion 21. A first shaft portion 52 and a second shaft portion 152 that extend, a base portion 53 that supports the lower ends of the shaft portions 52 and 152, a guide 54 that is disposed around the chamber 6 and defines a movement path of the base portion 53, It has. The arm portions 51 and 151 can move in the longitudinal direction (see double arrows C and C2 in FIGS. 3 and 4). The shaft portions 52 and 152 can move the arm portions 51 and 151 up and down independently by moving in the longitudinal direction (see double arrows D and D2 in FIG. 3). The base portion 53 can rotate the arm portions 51 and 151 independently by rotating a predetermined angle about an axis perpendicular to the main surface of the substrate M placed on the support portion 21 as a rotation center. (See double arrows E and E2 in FIG. 3). The guide 54 is disposed in a direction (first direction and second direction) parallel to two adjacent sides of the substrate M placed on the support portion 21, and forms an L-shaped movement path of the base portion 53. . The base portion 53 moves along the guide 54 in the first direction, thereby moving the arm portions 51 and 151 in the first direction (see the double arrow F in FIG. 4), and in the second direction. By moving along the guide 54, the arm portions 51 and 151 can be moved in the second direction (see the double arrow G in FIG. 4). By such movement of the arm portions 51 and 151, the first catalyst surface plate 31 and the second catalyst surface plate 131 can be disposed at predetermined positions on the main surface of the substrate M placed on the support portion 21. it can.

  The substrate processing apparatus 101 includes relative motion means 7 that relatively moves the processing reference surfaces 33 and 133 and the main surface. The relative motion means 7 includes a shaft portion 71 that supports the flat surface portion 22 and extends to the outside of the chamber 6 through the opening portion 61, and a rotation drive means (not shown) that rotates the shaft portion 71. . The shaft portion 71 extends in a direction perpendicular to the main surface of the substrate M placed on the support portion 21, and the main surface of the substrate M placed on the support portion 21 by rotation driving means (not shown). Can be rotated about an axis perpendicular to the axis of rotation (see arrow A in FIG. 3). The center of the flat surface portion 22 and the center of the substrate M placed on the support portion 21 are positioned in the extending direction of the rotation center of the shaft portion 71. By rotating the shaft portion 71, the flat surface portion 22 supported by the shaft portion 71 rotates around the center thereof, and the substrate M placed on the support portion 21 fixed to the flat surface portion 22. Rotates around the center of rotation. The relative motion means 7 includes catalyst surface plate mounting portions 72 and 172 to which the catalyst surface plates 31 and 131 are mounted, and rotation drive means (not shown) provided on the arm portions 51 and 151 of the drive means 5. I have. The catalyst surface plate mounting portions 72 and 172 can be rotated about the axis in the direction perpendicular to the main surface of the substrate M placed on the support portion 21 by a rotation driving means (not shown) (see FIG. 4 (see arrows B and B2).

The substrate processing apparatus 101 includes a first load control unit 8 and a second load control unit 108 that control a load (processing pressure) applied to the substrate M. Load control means 8 and 108, respectively, provided on the catalyst platen attachment portion 72 and 172, the air cylinder 81 and 181 to apply a load to the first catalyst platen 3 1 and the second catalyst platen 1 31 Then, the load applied to the catalyst surface plates 31 and 131 by the air cylinders 81 and 181 is measured, the air valve is turned on / off so as not to exceed a predetermined load, Load cells 82 and 182 for controlling the applied load are provided, respectively. When processing by catalyst reference etching is performed, the load (processing pressure) applied to the substrate M is controlled by the load control means 8 and 108.

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

When performing processing by catalyst-based etching using the substrate processing apparatus shown in FIGS. 3 and 4, first, the substrate M is placed and fixed on the support portion 21 with the upper surface M1 used as the main surface facing upward. .
Thereafter, rough processing is performed using the first substrate surface creation means 3. Therefore, the arm part 51 moves in the longitudinal direction (double arrow C), the arm part 51 turns (double arrow E), the arm part 51 moves in the first direction (double arrow F), and the arm part 51 moves in the second direction. The processing reference surface 33 of the substrate surface creation means 3 is arranged so as to face the upper surface M1 of the substrate M by (double arrow G). The second substrate surface creation means 103 is retracted out of the chamber 6. Thereafter, by rotating the shaft portion 71 and the catalyst surface plate mounting portion 72 at a predetermined rotation speed, the processing fluid is transferred from the injection nozzle 42 onto the upper surface M1 while rotating the processing reference surface 33 and the upper surface M1 at a predetermined rotation speed. And a processing fluid is interposed between the upper surface M1 and the processing reference surface 33. In this state, the processing reference surface 33 is brought into contact with or brought close to the upper surface M1 of the substrate M by the vertical movement of the arm portion 51 (double arrow D). At that time, the load applied to the substrate M is controlled to a predetermined value by the load control means 8.
Thereafter, when the predetermined machining allowance for rough machining is reached, the rotation of the shaft portion 71 and the catalyst surface plate mounting portion 72 and the supply of the processing fluid are stopped. Then, the machining reference surface 33 is separated from the upper surface M1 by a predetermined distance by the vertical movement of the arm portion 51 (double arrow D).

Thereafter, as shown in FIG. 5, which is a top view, the arm portion 51 is rotated to retract the first substrate surface creation means 3 out of the chamber 6.

  Next, the cleaning liquid is supplied from the injection nozzle 142 onto the upper surface M1, and the catalyst attached to the substrate surface by the first catalyst reference etching is removed. At this time, the substrate M is rotated by rotating the shaft portion 71 at a predetermined rotation speed so that the cleaning liquid is uniformly supplied over the upper surface M1 of the substrate. Since the substrate surface creation means 3 and 103 are retracted out of the chamber 6, the respective catalysts formed on the first and second processing reference surfaces 33 and 133 are protected from the cleaning liquid without being covered with the cleaning liquid. .

  Next, while rotating the shaft portion 71 at a predetermined rotation speed and rotating the substrate M, the processing fluid is supplied from the spray nozzle 42 onto the upper surface M1, rinsing is performed, and then the supply of the processing fluid is stopped. Then, the substrate M is rotated and dried.

Thereafter, finishing is performed using the second substrate surface creation means 103. Therefore, as shown in FIG. 6 which is a top view and FIG. 7 which is a cross-sectional view, the arm portion 151 is moved in the longitudinal direction (double arrow C2), the arm portion 151 is swung (double arrow E2), and the arm portion 151 is moved. The processing reference surface 133 of the substrate surface creation means 103 is disposed so as to face the upper surface M1 of the substrate M by the first direction movement (double arrow F) and the second direction movement of the arm 151 (double arrow G). At this time, the first substrate surface creation means 3 is kept retracted from the chamber 6. Thereafter, by rotating the shaft portion 71 and the catalyst surface plate mounting portion 72 at a predetermined rotation speed, the injection nozzle 42 while rotating the processing reference surface 133 and the upper surface M1 of the second processing surface plate at a predetermined rotation speed. The processing fluid is supplied onto the upper surface M1 from the upper surface, and the processing fluid is interposed between the upper surface M1 and the processing reference surface 133. In this state, the processing reference surface 133 is brought into contact with or close to the upper surface M1 of the substrate M by the vertical movement of the arm portion 151 (double arrow D2). At that time, the load applied to the substrate M is controlled to a predetermined value by the load control means 108.
Thereafter, when the predetermined machining allowance for finishing is reached, the rotation of the shaft portion 71 and the catalyst surface plate mounting portion 72 and the supply of the processing fluid are stopped. Then, the machining reference surface 133 is separated from the upper surface M1 by a predetermined distance by the vertical movement of the arm portion 51 (double arrow D).

Thereafter, as shown in FIG. 8 which is a top view, the arm portion 151 is rotated to retract the second substrate surface creation means 103 out of the chamber 6.

  Next, the cleaning liquid is supplied from the injection nozzle 142 onto the upper surface M1, and the catalyst attached to the substrate surface by the first catalyst reference etching is removed. At this time, the substrate is rotated by rotating the shaft portion 71 at a predetermined rotational speed so that the cleaning liquid is supplied over the upper surface M1 of the substrate M. Since the substrate surface creation means 3 and 103 are retracted out of the chamber 6, each catalyst formed on the first and second processing reference surfaces 33 and 133 is protected from the cleaning liquid without being covered with the cleaning liquid. . If the cleaning liquid is different from the catalyst used in the first catalyst reference etching and the catalyst used in the second catalyst reference etching, and thus the cleaning liquid is also different, add the cleaning liquid supply pipe and the injection nozzle as appropriate. Correspond. Alternatively, the substrate M is taken out from the processing apparatus 101, and the catalyst removal cleaning is performed by another cleaning apparatus.

Next, while rotating the shaft portion 71 at a predetermined rotational speed to rotate the substrate M, the processing fluid is supplied from the spray nozzle 42 onto the upper surface M1, rinsing is performed, and then the processing fluid supply is stopped. Then, the substrate M is rotated and dried. After completion of the rotary drying, the substrate M is taken out from the processing apparatus 101.
The substrate M is manufactured by such a substrate preparation step and a substrate processing step by two-stage catalyst-based etching including roughing and finishing.

According to the substrate manufacturing method of the second embodiment, it is possible to achieve high surface smoothness (low surface roughness) by finishing processing by increasing manufacturing throughput by rough processing with a high processing speed, and thus achieving both throughput and high smoothness. Is possible. Further, since the rough machining and the finishing process are completely separated and processed, it is possible to supply the substrate M having the stability of production, that is, the stable high smoothness with a stable production throughput. Furthermore, since a series of processing can be performed by one apparatus, it is possible to eliminate trouble and overhead time loss that occur when moving between apparatuses.
In addition, although the case where it processed over the main surface whole surface of the board | substrate M was shown here, only the local process which processes only a predetermined local part may be performed as needed, and these processes are used together. Also good.

Embodiment 3 FIG.
In the third embodiment, a method for manufacturing a substrate with a multilayer reflective film will be described.

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

  According to the method for manufacturing a substrate with a multilayer reflective film according to the third embodiment, the substrate with the multilayer reflective film is manufactured using the substrate M obtained by the method for manufacturing the substrate according to the first or second embodiment. It is possible to prevent the deterioration of characteristics due to the above, and it is possible to manufacture a substrate with a multilayer reflective film having desired characteristics.

  In the case of a substrate with a multilayer film for EUV lithography, it is necessary to pay attention to unevenness due to pits and bumps on the substrate surface and phase defects due to defects in the multilayer film. The inspection sensitivity of the phase defect is higher when the inspection is performed at the stage after the multilayer film is formed than at the substrate stage. At this time, if the surface of the substrate is rough and the surface smoothness is low, even if the inspection is performed after the multilayer film is formed, it becomes a background noise at the time of phase defect inspection and the inspection sensitivity is lowered. According to the embodiment of the present invention, since the surface smoothness including the multilayer film surface is high in addition to the substrate surface, the phase defect inspection sensitivity can be improved, and the substrate with the multilayer reflection film having high phase defect management quality. Can be manufactured.

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

  In the fourth embodiment, a binary mask blank is manufactured by forming a light-shielding film as a transfer pattern thin film on the main surface of the substrate M manufactured by the method described in the substrate manufacturing method of the first or second embodiment. Alternatively, a halftone phase shift mask blank is manufactured by forming a light translucent film as a transfer pattern thin film, or a halftone phase shift mask blank is sequentially formed as a transfer pattern thin film. A shift mask blank is manufactured.

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

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

Embodiment 5. FIG.
In Embodiment 5, a method for manufacturing a transfer mask will be described.

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

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

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

Example 1.
A. Production of glass substrate Substrate Preparation Step A low thermal expansion glass substrate, which is a 6025 size (152.4 mm × 152.4 mm × 6.35 mm) TiO ₂ —SiO ₂ glass substrate with the main surface and back surface 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 process Step 10 glass substrates that have undergone end chamfering and grinding were set in a double-side polishing apparatus, and rough polishing was performed under the following polishing conditions. A set of 10 sheets was performed twice, and a total of 20 glass substrates were roughly polished. The processing load and polishing time were adjusted as appropriate.
Polishing slurry: Aqueous solution containing cerium oxide (average particle size 2 to 3 μm) Polishing pad: Hard polisher (urethane pad)
After the rough polishing, in order to remove the abrasive grains adhering to the glass substrate, the glass substrate was immersed in a cleaning tank and cleaned by applying ultrasonic waves.

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

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

(4) Local processing step The flatness of the main surface and the back surface of the glass substrate after the rough polishing processing step, the precision polishing processing step, and the ultraprecision polishing processing step was measured using a flatness measuring device (UltraFlat200 manufactured by Tropel). . The flatness measurement was performed at a point of 1024 × 1024 with respect to an area of 148 mm × 148 mm excluding the peripheral area of the glass substrate. The measurement results of the flatness of the main surface and the back surface of the glass substrate were stored in a computer as height information (uneven shape information) with respect to the virtual absolute plane for each measurement point. The virtual absolute plane is a plane having a minimum value when the distance from the virtual absolute plane to the substrate surface is squared with respect to the entire flatness measurement region.
After that, the obtained uneven shape information was compared with the standard values of the flatness of the main surface and the back surface required for the glass substrate, and the difference was calculated by a computer for each predetermined region of the main surface and the back surface of the glass substrate. . This difference becomes a necessary removal amount (processing allowance) of each predetermined region in local surface processing.

Then, the processing conditions of the local surface processing according to the required removal amount were set for every predetermined area | region of the main surface and back surface of a glass substrate. The setting method is as follows. Using a dummy substrate in advance, the dummy substrate is processed at a certain point (spot) without moving the substrate for a certain period of time in the same manner as in actual processing, and the shape thereof is measured with a flatness measuring device (UltraFlat 200 manufactured by Tropel). Measurement was performed, and the processing volume at the spot per unit time was calculated. Then, the scanning speed for raster scanning of the glass substrate was determined according to the processing volume at the spot per unit time and the necessary removal amount of each predetermined area calculated as described above.
Then, the main surface and the back surface of the glass substrate were locally surface-treated by a magnet viscoelastic fluid polishing (MRF) using a substrate finishing device according to the processing conditions set for each predetermined region. At this time, a magnetic polishing slurry containing cerium oxide polishing particles was used.

  Thereafter, the glass substrate was immersed in a cleaning tank containing an aqueous hydrochloric acid solution having a concentration of about 10% (temperature: about 25 ° C.) for about 10 minutes, followed by rinsing with pure water and drying with isopropyl alcohol (IPA).

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

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

In this embodiment, for rough machining, a disk-shaped surface plate main body 32 made of stainless steel (SUS), a fluorine rubber pad formed on the entire surface of the surface plate main body 32 so as to cover the surface plate main body 32, and glass A catalyst surface plate 31 having a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the fluorine rubber pad on the side facing the substrate was used. Here, the diameter of the catalyst platen is 100 mm. The fluorine-based rubber pad used here has a hardness (Shore A) of 90. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
Using a glass substrate different from the above glass substrate, roughing to the same conditions, measuring the machining allowance using a non-contact type shape measuring device, and calculating the processing speed of the substrate by processing time and machining allowance did. As a result, the substrate processing speed under the above conditions was 10 nm / min.

First, the glass substrate was fixed by placing the support 2 1 toward the main surface on the upper side.
Thereafter, the longitudinal movement of the arm 51 (double arrow C), the swing movement of the arm 51 (double arrow E), the first movement of the arm 51 (double arrow F), and the second movement of the arm 51 ( By the double arrow G), the catalyst surface plate 31 was disposed in a state where the processing reference surface 33 of the catalyst surface plate 31 was disposed to face the main surface of the glass substrate. The arrangement position of the catalyst surface plate 31 is a position where the processing reference surface 33 of the catalyst surface plate 31 can contact or approach the entire main surface of the glass substrate when the glass substrate and the catalyst surface plate 31 are rotated. It is.
Thereafter, the glass substrate is rotated at a rotation speed of 10.3 rotations / minute and the catalyst surface plate 31 is rotated at a rotation speed of 10 rotations / minute. Here, the glass substrate and the catalyst platen 31 are rotated so that the rotation direction of the glass substrate and the rotation direction of the catalyst platen 31 are opposite to each other. Thereby, a peripheral speed difference can be taken between them, and the processing efficiency by catalyst reference | standard etching can be improved. Moreover, both rotation speeds are set to be slightly different. Thereby, the processing reference surface 33 of the catalyst surface plate 31 can be moved relative to the main surface of the glass substrate so as to draw different trajectories, and the processing efficiency by the catalyst reference etching can be increased.
While rotating the glass substrate and the catalyst surface plate 31, pure water was supplied from the injection nozzle 42 onto the main surface of the glass substrate, and the pure water was interposed between the main 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 approached to the back 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 10 hPa.
When processing allowance was taken, the rotation of the glass substrate and the catalyst surface plate 31 and the supply of pure water were stopped. Then, the catalyst surface plate 31 was separated from the main surface of the glass substrate by a predetermined distance by the vertical movement of the arm portion 51 (double arrow D).
Thereafter, the glass substrate was removed from the support portion 21.

  Thereafter, the glass substrate removed from the support portion 21 was washed as follows. First, after cleaning with a Cr etching solution containing ceric ammonium nitrate and perchloric acid, rinsing with pure water and drying were performed.

Next, the finishing process was performed as follows using another substrate processing apparatus 1 having the same structure that differs from the roughing process only in the catalyst surface plate 31. A disk-shaped surface plate body 32 made of stainless steel (SUS), a fluorine-based rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and a fluorine-based rubber pad on the side facing the glass substrate The catalyst surface plate 31 provided with the processing reference surface 33 made of Pt (platinum) formed on the entire surface of was used. Here, the diameter of the catalyst platen is 100 mm. The fluorine-based rubber pad used here has a hardness (Shore A) of 90. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Pt target on this pad. The film thickness of the deposited Pt is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 10nm
When the processing speed of the substrate was calculated by the same method as the above rough processing, the processing speed was 1 nm / min, the finishing processing speed was 1/10 of the rough processing, and the finishing processing speed was It was late.
In addition, the processing method with an apparatus is the same as the above-mentioned roughing process.

Thereafter, the glass substrate removed from the support portion 21 was washed with aqua regia, and subsequently rinsed with pure water and dried. The machining allowance for CARE processing was 30 nm for both roughing and finishing, and the CARE processing time was 12 minutes for both roughing and finishing.
In this way, a glass substrate was produced.

3. Evaluation The surface roughness of the main surface of the glass substrate before the catalyst-based etching, after the rough-processed catalyst-based etching, and after the finish-processed catalyst-based etching is measured with respect to a 1 μm × 1 μm region at the center of the substrate using an atomic force microscope ( AFM).
The surface roughness of the main surface before catalyst-based etching was 0.13 nm in terms of root mean square roughness (Rms).
The surface roughness of the main surface after rough processing catalyst reference etching is 0.08 nm in terms of root mean square roughness (Rms), and the surface roughness of the main surface after finishing processing catalyst reference etching is root mean square roughness. (Rms) was 0.05 nm. The surface roughness of the main surface was improved from 0.13 nm to 0.05 nm in terms of root mean square roughness (Rms) by the catalyst-based etching of the present invention.
In addition, the inspection of the main surface of the glass substrate before catalyst-based etching (after touch polishing and cleaning) and the main surface of the glass substrate after processing (and after cleaning) by catalyst-based etching (roughing and finishing) Then, a defect inspection apparatus (mask / blank defect inspection apparatus Teron 610 manufactured by KLA-Tencor) was used for a 132 mm × 132 mm area excluding the peripheral area of the substrate. The defect inspection was performed with a sensitivity capable of detecting a 23 nm size defect in terms of SEVD (Sphere Equivalent Volume Diameter). SEVD is the length of the diameter when the defect is assumed to be hemispherical.
After touch polishing before catalyst reference etching, the number of defects is 53, the number of defects after rough processing catalyst reference etching and cleaning is 70, the number of defects after finishing processing catalyst reference etching and cleaning is 32, and after processing Finally, the number of defects on the main surface was as small as 32.
Moreover, when 20 glass substrates were produced by the method of Example 1, the total number and the surface roughness were good, with the root mean square roughness (Rms) being 0.055 nm or less, and the number of defects was 35 or less. Stable and less.
By the method of Example 1, a glass substrate having high smoothness and low defects was stably obtained.

B. Next, a high refractive index layer (film thickness: 4.2 nm) made of a silicon film (Si) is formed on the main surface of the glass substrate thus produced by ion beam sputtering. A multilayer reflective film (thickness: 280 nm) is formed by alternately stacking 40 pairs of low refractive index layers (2.8 nm) made of a molybdenum film (Mo) alternately with one pair of high refractive index layer and low refractive index layer. Formed.
Thereafter, a protective film (thickness 2.5 nm) made of ruthenium (Ru) was formed on the multilayer reflective film by ion beam sputtering.
In this way, a substrate with a multilayer reflective film was produced.

About the obtained board | substrate with a multilayer reflective film, the reflectance of EUV light (wavelength 13.5nm) was measured with the EUV reflectance measuring apparatus.
Due to the high smoothness of the main surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
The defect inspection of the protective film surface of the obtained multilayer reflective film-coated substrate was performed in the same manner as the defect inspection of the glass substrate.
The number of defects on the surface of the protective film was as small as 27. The phase defect inspection was also performed. However, because of the high smoothness, the background noise at the time of inspection was small, and the phase defect inspection with high sensitivity could be performed.
By the method of Example 1, a substrate with a multilayer reflection film having high smoothness and low defects was obtained.

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

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

Example 2
In this example, only the CARE process in Example 1 was changed as described below, and the glass substrate, A substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced.

Roughing is the same as in Example 1, a disk-shaped surface plate body 32 made of stainless steel (SUS), a fluorine-based rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the fluorine rubber pad on the side facing the glass substrate was used. The film thickness of the deposited Cr was 100 nm and was formed by sputtering.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
When the processing speed of the substrate was calculated by the same method as in Example 1, the processing speed was 10 nm / min.

For finishing, a disk-shaped surface plate main body 32 made of stainless steel (SUS), a fluorine rubber pad formed on the entire surface of the surface plate main body 32 so as to cover the surface plate main body 32, and the glass substrate are opposed to each other. A catalyst surface plate 31 provided with a processing reference surface 33 made of Cu (copper) formed on the entire surface of the fluorine rubber pad on the side was used. The film thickness of the deposited Cu was 100 nm and was formed by sputtering.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 10nm
When measured using a non-contact type shape measuring apparatus, the processing speed of the substrate is 0.4 nm / min, the processing speed of the finishing process is 1/25 compared to the roughing process, and the processing speed of the finishing process is It was late.
Since the processing method is the same as in the first embodiment, a description thereof will be omitted.
For the cleaning after the roughing, the Cr catalyst was removed using a Cr etching solution containing ceric ammonium nitrate and perchloric acid, followed by rinsing with pure water and drying. Washing after finishing was performed after rinsing with concentrated sulfuric acid at 80 ° C., followed by rinsing with pure water and drying. The dissolution rate of the substrate by concentrated sulfuric acid cleaning is negligible at 0.001 nm / sec or less.
On the other hand, the dissolution rate of Cu with concentrated sulfuric acid at 80 ° C. was 50 nm / sec, which was a sufficient dissolution rate as a dissolution removal solution.
The machining allowance for CARE processing was 30 nm for both roughing and finishing, and the CARE processing time was 27 minutes for both roughing and finishing.
Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.14 nm in terms of root mean square roughness (Rms).
The surface roughness of the upper surface after roughing is 0.093 nm in terms of root mean square roughness (Rms), and the surface roughness of the top surface after finishing is 0.05 nm in terms of root mean square roughness (Rms). It was good. The surface roughness of the upper surface was improved from 0.14 nm to 0.05 nm in terms of root mean square roughness (Rms) by catalyst-based etching.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface before processing was 45, the number of defects on the upper surface after rough processing was 59, and the number of defects on the upper surface after finishing was as small as 30.
Moreover, when 20 glass substrates were produced by the method of Example 2, the total number and the surface roughness were as good as 0.052 nm or less in root mean square roughness (Rms), and the number of defects was 30 or less. There were few.
By the method of Example 2, a glass substrate having high smoothness and low defects was stably obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the high smoothness of the upper surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film was as small as 24.
By the method of Example 2, a substrate with a multilayer reflective film having a surface state with high smoothness and low defects was obtained.
In addition, according to the method of Example 2, a reflective mask blank and a reflective mask for EUV exposure having high smoothness and maintaining a low defect surface state were obtained.

Example 3
In this example, only the CARE process in Example 1 was changed as described below, and the glass substrate, A substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced.

Roughing is the same as in Example 1, a disk-shaped surface plate body 32 made of stainless steel (SUS), a fluorine-based rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the fluorine rubber pad on the side facing the glass substrate was used. The fluorine-based rubber pad used here has a hardness (Shore A) of 90. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
When the processing speed of the substrate was calculated by the same method as in Example 1, the processing speed was 10 nm / min.

For finishing, a disk-shaped surface plate body 32 made of stainless steel (SUS), a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and the side facing the glass substrate A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the urethane pad was used. The hardness (Shore A) of the urethane pad used here is 3. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 10nm
When the substrate processing speed was calculated by the same method as in Example 1, the processing speed was 0.3 nm / min, and the finishing processing speed was about 1/33 compared to the roughing processing. The processing speed of was slow.
The machining allowance for CARE processing was 30 nm for both roughing and finishing, and the CARE processing time was 35 minutes for both roughing and finishing.
Since the processing method is the same as in the first embodiment, a description thereof will be omitted.
In addition, after the roughing process and after the finishing process, the Cr catalyst is removed using a Cr etching solution containing cerium diammonium nitrate and perchloric acid, followed by rinsing and drying with pure water. went. The Cr etching solution is a chemical solution widely used for mask processing as a Cr stripping solution and does not attack the glass.
Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (Rms).
The surface roughness of the upper surface after rough processing is 0.093 nm in terms of root mean square roughness (Rms), and the surface roughness of the upper surface after finishing is 0.06 nm in terms of root mean square roughness (Rms). It was good. The surface roughness of the upper surface was improved from 0.13 nm to 0.06 nm in terms of root mean square roughness (Rms) by catalyst-based etching (roughing and finishing).
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface before processing was 48, the number of defects on the upper surface after rough processing was 84, and the number of defects on the upper surface after finishing was as small as 23.
Further, when 20 glass substrates were produced by the method of Example 3, the total number and the surface roughness were as good as 0.064 nm or less in root mean square roughness (Rms), and the number of defects was 26 or less. There were few.
By the method of Example 3, a glass substrate having a highly smooth and low defect surface state was stably obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the high smoothness of the upper surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film was as small as 20.
By the method of Example 3, a substrate with a multilayer reflective film having a high smoothness and a low defect surface state was obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which maintained the surface state with high smoothness and a low defect by the method of Example 3 were obtained.

Example 4
In this example, only the CARE process in Example 1 was changed as described below, and the glass substrate, A substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced.

Roughing is the same as in Example 1, a disk-shaped surface plate body 32 made of stainless steel (SUS), a fluorine-based rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the fluorine rubber pad on the side facing the glass substrate was used. The hardness of the fluorine-based rubber pad used here is 90 in Shore A evaluation. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
When the processing speed of the substrate was calculated by the same method as in Example 1, the processing speed was 10 nm / min.

For finishing, a disk-shaped surface plate body 32 made of stainless steel (SUS), a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and the side facing the glass substrate The catalyst surface plate 31 provided with the processing reference surface 33 made of Ni (nickel) formed on the entire surface of the urethane pad was used. The hardness of the urethane pad used here is 3 by Shore A evaluation. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Ni target on the pad. The film thickness of the deposited Ni is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / minute Rotation speed of catalyst surface plate mounting section 72 (rotation speed of catalyst surface plate 31): 10 rotation / minute Processing pressure : 50 hPa
Processing allowance: 10nm
When the substrate processing speed was calculated in the same manner as in Example 1, the processing speed was 0.3 nm / min, and the finishing processing speed was about 1/33 compared to the rough processing. The processing speed of processing was slow.
Since the processing method is the same as in the first embodiment, a description thereof will be omitted.
For the cleaning after the roughing, the Cr catalyst was removed using a Cr etching solution containing ceric ammonium nitrate and perchloric acid, followed by rinsing with pure water and drying. After finishing, the substrate was washed with hydrochloric acid, rinsed with pure water, and dried. The dissolution rate of the substrate by hydrochloric acid cleaning is negligible at 0.001 nm / sec or less.
On the other hand, the dissolution rate of Ni by hydrochloric acid was 56 nm / sec, which was a sufficient dissolution rate as a dissolution removal solution.
The machining allowance for CARE processing was 30 nm for both roughing and finishing, and the CARE processing time was 35 minutes for both roughing and finishing.
Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (Rms).
The surface roughness of the upper surface after rough processing is 0.10 nm in terms of root mean square roughness (Rms), and the surface roughness of the top surface after finishing is 0.05 nm in terms of root mean square roughness (Rms). It was good. The surface roughness of the upper surface was improved from 0.13 nm to 0.05 nm in terms of root mean square roughness (Rms) by catalyst-based etching.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface before processing was 51, the number of defects on the upper surface after rough processing was 80, and the number of defects on the upper surface after finishing was as small as 20.
Further, when 20 glass substrates were produced by the method of Example 4, the total number and the surface roughness were good, with the root mean square roughness (Rms) being 0.052 nm or less, and the number of defects was 25 or less. There were few.
By the method of Example 4, a glass substrate having a surface state with high smoothness and low defects was stably obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the high smoothness of the upper surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film was as small as 23.
By the method of Example 4, a substrate with a multilayer reflection film having high smoothness and low defects was obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which maintained the surface state with high smoothness and a low defect by the method of Example 4 were obtained.

Example 5 FIG.
A. Production of Glass Substrate In this example, a synthetic quartz glass substrate of 6025 size (152.4 mm × 152.4 mm × 6.35 mm) whose upper and lower surfaces were polished was prepared. This synthetic quartz glass substrate is obtained through the above-described rough polishing process, precision polishing process, and substrate preparation process by ultra-precision polishing.
CARE processing was performed on the synthetic quartz glass substrate in the same manner as in Example 1 to produce a glass substrate. Therefore, surface processing was performed on this synthetic quartz glass by using two processing apparatuses shown in FIGS. 1 and 2 each having one catalyst surface plate, each having a different catalyst surface plate portion.

In this embodiment, for rough machining, a disk-shaped surface plate main body 32 made of stainless steel (SUS), a fluorine rubber pad formed on the entire surface of the surface plate main body 32 so as to cover the surface plate main body 32, and glass A catalyst surface plate 31 having a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the fluorine rubber pad on the side facing the substrate was used. The film thickness of the formed Cr is 100 nm. The hardness (Shore A) of the fluorine rubber pad is 90.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
When the processing speed of the substrate was calculated by the same method as in Example 1, the processing speed was 10 nm / min.

For finishing, a disk-shaped surface plate body 32 made of stainless steel (SUS), a fluorine rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, a glass substrate, A catalyst surface plate 31 having a processing reference surface 33 made of Pt (platinum) formed on the entire surface of the fluorine rubber pad on the opposite side was used. The film thickness of the deposited Pt is 100 nm. The hardness (Shore A) of the fluorine rubber pad is 90.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 10nm
When the substrate processing speed was calculated in the same manner as in Example 1, the processing speed was 1 nm / min, the finishing processing speed was 1/10 compared to the rough processing, and the finishing processing speed. Was slow.
Since the processing method is the same as that of the first embodiment, a description thereof will be omitted.
For the cleaning after the roughing, the Cr catalyst was removed using a Cr etching solution containing ceric ammonium nitrate and perchloric acid, followed by rinsing with pure water and drying. Washing after finishing was performed after rinsing with aqua regia, followed by rinsing with pure water and drying. Aqua regia did not dissolve the synthetic quartz glass, and no damage to the substrate was observed.

The surface roughness of the main surface of the glass substrate before the catalyst-based etching, after the rough-processed catalyst-based etching, and after the finish-processed catalyst-based etching was measured with respect to a 1 μm × 1 μm region at the center of the substrate using an atomic force microscope (AFM). ).
The surface roughness of the main surface before catalyst-based etching was 0.13 nm in terms of root mean square roughness (Rms).
The surface roughness of the main surface after rough processing catalyst reference etching is 0.07 nm in terms of root mean square roughness (Rms), and the surface roughness of the main surface after finishing processing catalyst reference etching is root mean square roughness. (Rms) was 0.05 nm. The surface roughness of the main surface was improved from 0.13 nm to 0.05 nm in terms of root mean square roughness (Rms) by the catalyst-based etching of the present invention.
In addition, the main surface of the glass substrate before the catalyst-based etching (and after the cleaning thereof) and the defect inspection of the main surface of the glass substrate after the processing (and after the cleaning) by the catalyst-based etching (rough processing and finishing processing) are performed. A defect inspection apparatus (a mask / blank defect inspection apparatus Teron 610 manufactured by KLA-Tencor) was performed on a 132 mm × 132 mm area excluding the peripheral area. The defect inspection was performed with a sensitivity capable of detecting a 23 nm size defect in terms of SEVD (Sphere Equivalent Volume Diameter). SEVD is the length of the diameter when the defect is assumed to be hemispherical.
After ultra-precision polishing before catalyst reference etching, the number of defects is 48, the number of defects after rough processing catalyst reference etching and cleaning is 55, the number of defects after finishing processing catalyst reference etching and cleaning is 29, The number of defects on the main surface after processing was finally as small as 29.
In addition, when 20 glass substrates were produced by the method of Example 5, the total number and the surface roughness were good, with a root mean square roughness (Rms) of 0.055 nm or less, and the number of defects was 30 or less. Stable and less.
The machining allowance for CARE processing was 30 nm for both roughing and finishing, and the CARE processing time was 12 minutes for both roughing and finishing.
By the method of Example 5, a glass substrate having a surface state with high smoothness and low defects was stably obtained.

B. Production of Halftone Phase Shift Mask Blank Next, a molybdenum silicide (MoSi) target is used on the upper surface of the glass substrate thus produced, and argon (Ar), nitrogen (N ₂ ), and oxygen (O ₂ ) reactive sputtering was performed in a mixed gas atmosphere to form a light semi-transmissive film (film thickness: 88 nm) made of molybdenum silicide oxynitride (MoSiON). The film composition of the light translucent film analyzed by Rutherford backscattering analysis was Mo: 5 atomic%, Si: 30 atomic%, O: 39 atomic%, and N: 26 atomic%. The transmittance of the light semi-transmissive film with respect to the exposure light was 6%, and the phase difference caused by the exposure light passing through the light semi-transmissive film was 180 degrees.
Then, using a chromium (Cr) target on the light semi-transmissive film, reactive sputtering is performed in a mixed gas atmosphere of argon (Ar), carbon dioxide (CO ₂ ), nitrogen (N ₂ ), and helium (He). To form a chromium oxycarbonitride (CrOCN) layer (thickness 30 nm), and further, using a chromium (Cr) target, a mixed gas of argon (Ar) and nitrogen (N ₂ ) Reactive sputtering is performed in an atmosphere to form a chromium nitride (CrN) layer (film thickness: 4 nm), and a light-shielding layer comprising a laminate of a chromium oxycarbonitride (CrOCN) film and a chromium nitride (CrN) film Formed. Further, a chromium (Cr) target is used on the light shielding layer, and reactive sputtering is performed in a mixed gas atmosphere of argon (Ar), carbon dioxide (CO ₂ ), nitrogen (N ₂ ), and helium (He). Then, a surface antireflection layer (film thickness: 14 nm) made of chromium oxycarbonitride (CrOCN) was formed. In this way, a light shielding film composed of the light shielding layer and the surface antireflection 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 phase shift mask Next, a chemical amplification resist for electron beam drawing (exposure) is applied onto the light-shielding film of the halftone phase shift mask blank produced in this way by a spin coating method. Through a heating and cooling process, a resist film having a thickness of 150 nm was formed.
Thereafter, a desired pattern was drawn on the formed resist film using an electron beam drawing apparatus, and then developed with a predetermined developer to form a resist pattern.
Thereafter, using this resist pattern as a mask, the light shielding film was dry etched to form a light shielding film pattern on the light semi-transmissive film. As a dry etching gas, a mixed gas of chlorine (Cl ₂ ) and oxygen (O ₂ ) was used.
Thereafter, using the resist pattern and the light shielding film pattern as a mask, the light semi-transmissive film was dry-etched to form a light semi-transmissive film pattern. As the dry etching gas, a mixed gas of sulfur hexafluoride (SF ₆ ) and helium (He) was used.
Thereafter, the remaining resist pattern is peeled off, a resist film is applied again, pattern exposure is performed to remove an unnecessary light-shielding film pattern in the transfer region, and then the resist film is developed to form a resist pattern. .
Thereafter, wet etching was performed to remove an unnecessary light shielding film pattern.
Thereafter, the remaining resist pattern was peeled off and washed.
In this way, a halftone phase shift mask for ArF excimer laser exposure, which maintains a high smoothness and low defect surface state, was prepared.

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

Example 6
In this example, only the CARE process in Example 5 is changed as follows, and other than that, in the same manner as in Example 5 from the substrate material and its pretreatment to the manufacture of the halftone phase shift mask, A glass substrate, a halftone phase shift mask blank, and a halftone phase shift mask were produced.

Roughing is the same as in Example 1, a disk-shaped surface plate body 32 made of stainless steel (SUS), a fluorine-based rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the fluorine rubber pad on the side facing the glass substrate was used. The fluorine-based rubber pad used here has a hardness (Shore A) of 90. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
When the processing speed of the substrate was calculated by the same method as in Example 1, the processing speed was 10 nm / min.

For finishing, a disk-shaped surface plate body 32 made of stainless steel (SUS), a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and the side facing the glass substrate A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the urethane pad was used. The hardness of the urethane pad used here is 3 by Shore A evaluation. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Machining allowance: 10 nm When the substrate processing speed was calculated in the same manner as in Example 1, the processing speed was 0.3 nm / min, and the finishing processing speed was about 1/33 compared to rough processing. In terms of speed, the finishing speed was slow.
The machining allowance for CARE processing was 30 nm for both roughing and finishing, and the CARE processing time was 35 minutes for both roughing and finishing.
Since the processing method is the same as that in the fifth embodiment, a description thereof will be omitted.
In addition, after the roughing process and after the finishing process, the Cr catalyst is removed using a Cr etching solution containing cerium diammonium nitrate and perchloric acid, followed by rinsing and drying with pure water. went. The Cr etching solution is a chemical solution widely used for mask processing as a Cr stripping solution and does not attack the glass.
In the same manner as in Example 5, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (Rms).
The surface roughness of the upper surface after roughing is 0.083 nm in terms of root mean square roughness (Rms), and the surface roughness of the top surface after finishing is 0.05 nm in terms of root mean square roughness (Rms). It was good. The surface roughness of the upper surface was improved from 0.13 nm to 0.05 nm in terms of root mean square roughness (Rms) by catalyst-based etching.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by catalyst reference | standard etching (rough process and finishing process) was performed similarly to Example 5. FIG.
The number of defects on the upper surface before processing was 44, the number of defects on the upper surface after rough processing was 58, and the number of defects on the upper surface after finishing was 27, which was small.
Further, when 20 glass substrates were produced by the method of Example 6, the total number and the surface roughness were good, with a root mean square roughness (Rms) of 0.055 nm or less, and the number of defects was 30 or less. There were few.
By the method of Example 6, a glass substrate having a high smoothness and a low defect surface state was stably obtained.

By the method of Example 6, a halftone phase shift mask blank having a high smoothness and a low defect surface state was obtained.
In addition, a halftone phase shift mask having a high smoothness and a low defect surface state was obtained by the method of Example 6.

Example 7
In this example, only the CARE process in Example 5 is changed as follows, and other than that, in the same manner as in Example 5 from the substrate material and its pretreatment to the manufacture of the halftone phase shift mask, A glass substrate, a halftone phase shift mask blank, and a halftone phase shift mask were produced.

Roughing is the same as in Example 1, a disk-shaped surface plate body 32 made of stainless steel (SUS), a fluorine-based rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the fluorine rubber pad on the side facing the glass substrate was used. The hardness of the fluorine-based rubber pad used here is 90 in Shore A evaluation. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
When the processing speed of the substrate was calculated by the same method as in Example 1, the processing speed was 10 nm / min.

For finishing, a disk-shaped surface plate body 32 made of stainless steel (SUS), a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and the side facing the glass substrate The catalyst surface plate 31 provided with the processing reference surface 33 made of Ni (nickel) formed on the entire surface of the urethane pad was used. The hardness of the urethane pad used here is 3 by Shore A evaluation. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Ni target on the pad. The film thickness of the deposited Ni is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / minute Rotation speed of catalyst surface plate mounting section 72 (rotation speed of catalyst surface plate 31): 10 rotation / minute Processing pressure : 50 hPa
Processing allowance: 10nm
When the substrate processing speed was calculated by the same method as in Example 1, the processing speed was 0.3 nm / min, and the finishing processing speed was about 1/33 compared to the roughing processing. The processing speed of was slow.
Since the processing method is the same as that in the fifth embodiment, a description thereof will be omitted.
For the cleaning after the roughing, the Cr catalyst was removed using a Cr etching solution containing ceric ammonium nitrate and perchloric acid, followed by rinsing with pure water and drying. After finishing, the substrate was washed with hydrochloric acid, rinsed with pure water, and dried. The dissolution rate of the substrate by hydrochloric acid cleaning is negligible at 0.001 nm / sec or less.
On the other hand, the dissolution rate of Ni by hydrochloric acid was 56 nm / sec, which was a sufficient dissolution rate as a dissolution removal solution.
The machining allowance for CARE processing was 30 nm for both roughing and finishing, and the CARE processing time was 35 minutes for both roughing and finishing.
In the same manner as in Example 5, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (Rms).
The surface roughness of the upper surface after roughing is 0.09 nm in terms of root mean square roughness (Rms), and the surface roughness of the top surface after finishing is 0.06 nm in terms of root mean square roughness (Rms). It was good. The surface roughness of the upper surface was improved from 0.13 nm to 0.06 nm in terms of root mean square roughness (Rms) by catalyst-based etching (roughing and finishing).
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 5. FIG.
The number of defects on the upper surface before processing was 44, the number of defects on the upper surface after rough processing was 64, and the number of defects on the upper surface after finishing was as small as 28.
Further, when 20 glass substrates were produced by the method of Example 7, the total number and the surface roughness were as good as 0.062 nm or less in root mean square roughness (Rms), and the number of defects was also 35 or less. There were few.
By the method of Example 7, a glass substrate having a highly smooth and low defect surface state was stably obtained.

By the method of Example 7, a halftone phase shift mask blank having a surface state with high smoothness and low defects was obtained.
Moreover, the halftone phase shift mask which maintained the high smoothness and the surface state of low defect by the method of Example 7 was obtained.

Example 8 FIG.
In this example, only the CARE process in Example 1 was changed as described below, and the glass substrate, A substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced.

Roughing is performed by a stainless steel (SUS) disk-shaped surface plate body 32, a fluorine rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and the side facing the glass substrate. A catalyst surface plate 31 provided with a processing reference surface 33 made of Pt (platinum) formed on the entire surface of the fluorine rubber pad was used. The fluorine-based rubber pad used here has a hardness (Shore A) of 90. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Pt target on this pad. The film thickness of the deposited Pt is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
When the substrate processing speed was calculated in the same manner as in Example 1, the processing speed was 1 nm / min.

For finishing, a disk-shaped surface plate body 32 made of stainless steel (SUS), a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and the side facing the glass substrate A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the urethane pad was used. The hardness (Shore A) of the urethane pad used here is 3. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 10nm
When the substrate processing speed was calculated in the same manner as in Example 1, the processing speed was 0.3 nm / min, and the finishing processing speed was about 1/3 of the rough processing, and the finishing processing was performed. The processing speed of was slow.
The CARE processing time was 53 minutes including the roughing and finishing.
Since the processing method is the same as in the first embodiment, a description thereof will be omitted.
In addition, after the roughing process was completed, after washing with aqua regia, rinsing with pure water and drying were performed. Cleaning after finishing was performed by removing Cr catalyst using a Cr etching solution containing ceric ammonium nitrate and perchloric acid, followed by rinsing with pure water and drying. The Cr etching solution is a chemical solution widely used for mask processing as a Cr stripping solution and does not attack the glass.
Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (Rms).
The surface roughness of the upper surface after roughing is 0.093 nm in terms of root mean square roughness (Rms), and the surface roughness of the top surface after finishing is 0.05 nm in terms of root mean square roughness (Rms). It was good. The surface roughness of the upper surface was improved from 0.13 nm to 0.05 nm in terms of root mean square roughness (Rms) by catalyst-based etching.
Moreover, the defect inspection of the upper surface of the glass substrate after the process by catalyst reference | standard etching (rough process and finishing process) was performed similarly to Example 1. FIG.
The number of defects on the upper surface before processing was 51, the number of defects on the upper surface after rough processing was 80, and the number of defects on the upper surface after finishing was as small as 20.
In addition, when 20 glass substrates were produced by the method of Example 8, the total number and the surface roughness were good at 0.054 nm or less in root mean square roughness (Rms), and the number of defects was 30 or less. There were few.
By the method of Example 8, a glass substrate having a high smoothness and a low defect surface state was stably obtained.

In the same manner as in Example 1, the reflectance of EUV light (wavelength: 13.5 nm) was measured for the obtained substrate with a multilayer reflective film.
Due to the high smoothness of the upper surface of the glass substrate, the surface of the protective film also maintained high smoothness, and the reflectance was as high as 64%.
Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG.
The number of defects on the surface of the protective film after processing was as small as 20.
By the method of Example 8, a substrate with a multilayer reflective film having a high smoothness and a low defect surface state was obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure which maintained the surface state with high smoothness and a low defect by the method of Example 8 were obtained.

Example 9
In this example, only the CARE process in Example 5 is changed as follows, and other than that, in the same manner as in Example 5 from the substrate material and its pretreatment to the manufacture of the halftone phase shift mask, A glass substrate, a halftone phase shift mask blank, and a halftone phase shift mask were produced.

Roughing is performed by a stainless steel (SUS) disk-shaped surface plate body 32, a fluorine rubber pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and the side facing the glass substrate. A catalyst surface plate 31 provided with a processing reference surface 33 made of Pt (platinum) formed on the entire surface of the fluorine rubber pad was used. The hardness of the fluorine-based rubber pad used here is 90 in Shore A evaluation. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Pt target on this pad. The film thickness of the deposited Pt is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm
When the substrate processing speed was calculated in the same manner as in Example 1, the processing speed was 1 nm / min.

For finishing, a disk-shaped surface plate body 32 made of stainless steel (SUS), a urethane pad formed on the entire surface of the surface plate body 32 so as to cover the surface plate body 32, and the side facing the glass substrate A catalyst surface plate 31 provided with a processing reference surface 33 made of Cr (chromium) formed on the entire surface of the urethane pad was used. The hardness of the urethane pad used here is 3 by Shore A evaluation. A catalyst reference surface was formed by performing sputtering film formation in an Ar (argon) gas atmosphere using a Cr target on the pad. The film thickness of the formed Cr is 100 nm.
The processing conditions are as follows.
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 10nm
When the substrate processing speed was calculated in the same manner as in Example 1, the processing speed was 0.3 nm / min, and the finishing processing speed was about 1/3 of the rough processing, and the finishing processing was performed. The processing speed of was slow.
The machining allowance for CARE processing was 30 nm for both roughing and finishing, and the CARE processing time was 53 minutes for both roughing and finishing.
Since the processing method is the same as that in the fifth embodiment, a description thereof will be omitted.
In addition, after the roughing process was completed, after washing with aqua regia, rinsing with pure water and drying were performed. Cleaning after finishing was performed by removing Cr catalyst using a Cr etching solution containing ceric ammonium nitrate and perchloric acid, followed by rinsing with pure water and drying. The Cr etching solution is a chemical solution widely used for mask processing as a Cr stripping solution and does not attack the glass.
In the same manner as in Example 5, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (Rms).
The surface roughness of the upper surface after roughing is 0.08 nm in terms of root mean square roughness (Rms), and the surface roughness of the top surface after finishing is 0.05 nm in terms of root mean square roughness (Rms). It was good. The surface roughness of the upper surface was improved from 0.13 nm to 0.05 nm in terms of root mean square roughness (Rms) by catalyst-based etching (roughing and finishing).
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface before processing was 44, the number of defects on the upper surface after rough processing was 61, and the number of defects on the upper surface after finishing was as small as 23.
Further, when 20 glass substrates were produced by the method of Example 9, the total number and the surface roughness were good at 0.053 nm or less in root mean square roughness (Rms), and the number of defects was 30 or less. There were few.
By the method of Example 9, a glass substrate having a high smoothness and a low defect surface state was stably obtained.

By the method of Example 9, a halftone phase shift mask blank having a high smoothness and a low defect surface state was obtained.
In addition, a halftone phase shift mask having a high smoothness and a low defect surface state was obtained by the method of Example 9.

Comparative Example 1
In this comparative example, instead of the substrate processing by the two-step catalytic reference etching of the rough processing and the finishing processing in Example 1, a one-step using only a catalyst surface plate in which Pt (platinum) is formed on a fluorine-based rubber pad. Except for the catalyst-based etching, a glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced in the same manner as in Example 1 except for that.

Therefore, the substrate material and the substrate preparation process were the same as those in Example 1, and the catalyst-based etching was performed as follows.
Substrate processing was performed using only one stage of the catalyst surface plate in which Pt (platinum) was formed on the fluororesin pad base material. That is, as shown in FIG. 1 and FIG. 2, a disk-shaped surface plate body 32 made of stainless steel (SUS) having a diameter of 100 mm and the entire surface of the surface plate body 32 so as to cover the surface plate body 32 are formed. A catalyst surface plate 31 having a processing reference surface 33 (film thickness 100 nm) made of Pt formed on the entire surface of the fluorine rubber on the side facing the glass substrate with the fluorine rubber was used. The processing reference surface 33 was formed on a fluorine-based rubber by sputtering in an argon (Ar) gas atmosphere using a platinum (Pt) target. This is the same as performing only the second precision processing step of the first embodiment. As a cleaning liquid, aqua regia was used in the same manner as in Example 1, and then pure cleaning was performed, followed by drying to produce a glass substrate.
Thereafter, a substrate with a multilayer reflective film, a mask blank, and a reflective mask were produced in the same manner as in Example 1.

Similar to Example 1, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by the catalyst-based etching was measured.
The surface roughness of the upper surface after processing was 0.09 nm in terms of root mean square roughness (Rms).
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 1. FIG.
The number of defects on the upper surface after processing was as large as 45.
Moreover, when 20 glass substrates were produced by the method of Comparative Example 1, the total number and the surface roughness were 0.09 nm or more in terms of root mean square roughness (Rms), but the number of defects was 45 or more. There were many. Although the CARE processing time was as short as 30 minutes, the method of Comparative Example 1 did not provide a glass substrate having both high smoothness and low defects.

Moreover, the defect inspection of the protective film surface of the obtained board | substrate with a multilayer reflective film was performed similarly to Example 1. FIG. The number of defects on the surface of the protective film was as large as 76.
By the method of Comparative Example 1, a substrate with a multilayer reflective film having a high smoothness and a low defect surface state could not be obtained.
Moreover, the reflective mask blank and reflective mask for EUV exposure of the surface state of high smoothness and a low defect were not obtained by the method of the comparative example 1.

Comparative Example 2
In this comparative example, instead of the substrate processing by the two-step catalyst-based etching of roughing and finishing in Example 3, a one-step catalyst using only a catalyst surface plate in which Cr (chromium) is formed on a urethane pad. Reference etching was performed, and otherwise, a glass substrate, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced in the same manner as in Example 3.

Therefore, the substrate material and the substrate preparation process were the same as those in Example 3, and the catalyst-based etching (CARE) was performed as follows.
Substrate processing was performed using only one stage of the catalyst surface plate in which Cr (chromium) was formed on the urethane pad base material. That is, as shown in FIG. 1 and FIG. 2, a disk-shaped surface plate body 32 made of stainless steel (SUS) having a diameter of 100 mm and the entire surface of the surface plate body 32 so as to cover the surface plate body 32 are formed. A catalyst surface plate 31 provided with a processing reference surface 33 (film thickness 100 nm) made of Cr formed on the entire surface of the urethane pad on the side facing the glass substrate with the urethane pad was used. The processing reference surface 33 was formed on a urethane pad by sputtering in a argon (Ar) gas atmosphere using a Cr (chromium) target. Here, CARE processing was performed with a machining allowance of 30 nm. The processing time was 100 minutes, which was 2.86 times longer than the 35 minutes of Example 3. A Cr etching solution containing cerium diammonium nitrate and perchloric acid was used as the cleaning solution. After that, pure cleaning was performed, followed by drying to manufacture a glass substrate.
Thereafter, a substrate with a multilayer reflective film, a reflective mask blank, and a reflective mask were produced in the same manner as in Example 3.

In the same manner as in Example 3, the surface roughness of the upper surface used as the main surface of the glass substrate before and after processing by catalyst-based etching was measured.
The surface roughness of the upper surface before processing was 0.13 nm in terms of root mean square roughness (Rms), and the surface roughness of the upper surface after processing was 0.06 nm in terms of root mean square roughness (Rms).
Moreover, the defect inspection of the upper surface of the glass substrate after the process by a catalyst reference | standard etching was performed similarly to Example 3. FIG.
The number of defects on the upper surface after processing was 24. In addition, the number of defects on the surface of the protective film of the substrate with a multilayer reflective film was 35.
Further, when 20 glass substrates were produced by the method of Comparative Example 2, when the number of processed sheets exceeded 15, the surface roughness (Rms) of the upper surface before processing exceeded 0.13 nm and the number of defects was 50. That's it. In the method of Comparative Example 2, as described above, since the processing time is as long as 100 minutes, the processing reference surface 33 changes (surface damage) as compared with the initial state as the number of processed sheets increases. The cause is considered to be damage to the upper surface of the main surface of the glass substrate and processing variations.

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

Example 10
A. Production of glass substrate Substrate preparation step A 2.5-inch (φ65 mm) aluminosilicate glass substrate having an upper surface and a lower surface polished was prepared. The aluminosilicate glass substrate has the following press molding process, coring process, chamfering process, end face polishing process, grinding process, first polishing (main surface polishing) process, chemical strengthening process, and second polishing (final polishing). It was obtained through the process.

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

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

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

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

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

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

(7) Chemical strengthening process Next, the annular | circular shaped glass base plate after 1st grinding | polishing is chemically strengthened. As the chemical strengthening solution, for example, a mixed solution of potassium nitrate (60% by weight) and sodium nitrate (40% by weight) can be used. In the chemical strengthening, the chemical strengthening liquid is heated to, for example, 300 ° C. to 500 ° C., and the cleaned glass base plate is preheated to, for example, 200 ° C. to 300 ° C. For example, it is immersed for 1 to 4 hours. At the time of this immersion, using a cage (holder) that holds and stores the ends of a plurality of annular glass base plates so that the entire main surfaces of both annular glass base plates are chemically strengthened. Preferably it is done.

  Thus, by immersing the glass base plate in the chemical strengthening solution, Li ions and Na ions in the surface layer of the glass base plate are converted into Na ions and K ions having a relatively large ion radius in the chemical strengthening solution, respectively. It is replaced and strengthened by forming a compression layer on the surface of the glass base plate. Note that the chemically strengthened annular glass base plate is washed. For example, after washing with sulfuric acid, it is washed with pure water or the like.

(8) Second Polishing (Final Polishing) Step Next, second polishing is applied to the glass base plate that has been chemically strengthened and sufficiently cleaned. The second polishing is intended for mirror polishing of the main surface. In the second polishing, for example, a polishing apparatus having the same configuration as the first polishing is used. At this time, the difference from the first polishing is that the type and particle size of the loose abrasive grains are different and the hardness of the pad is different. As the pad, a urethane polishing pad such as foamed urethane, a suede pad, or the like is used.

  As the free abrasive grains used for the second polishing, for example, fine particles (particle size: diameter of about 10 to 50 nm) such as colloidal silica made of silica suspended in a polishing liquid are used. These fine particles are finer than the free abrasive grains used in the first polishing. The polishing liquid (slurry) in which fine particles such as colloidal silica are turbid contains, for example, 0.1 to 40% by mass, preferably 3 to 30% by mass of silica to ensure polishing processing efficiency and It is preferable at the point which raises roughness.

  The polished glass base plate is cleaned. In the cleaning, it is preferable to use a neutral cleaning solution or an alkaline cleaning solution from the viewpoint of not forming defects such as scratches on the glass surface by the cleaning and further reducing the surface roughness. Thereby, the arithmetic average roughness Ra of the main surface can be set to 0.15 nm or less, for example, 0.13 to 0.15 nm. In addition to the neutral cleaning solution, a plurality of cleaning treatments using pure water, acid (acid cleaning solution), IPA, or the like can be performed. Thus, a glass substrate is prepared by washing the glass base plate.

2. Substrate processing step Next, using the substrate processing apparatus shown in FIGS. 1 and 2, the upper and lower surfaces (both sides) used as the main surface of the glass substrate after the second polishing step were processed by catalyst-based etching. .
In this example, a catalyst surface plate 31 (coarse processing) having a processing reference surface 33 made of Cr on the fluorine-based rubber pad (Shore A: 90) used in Example 3, and a urethane pad (Shore A: 3). A catalyst surface plate 31 (finishing process) provided with a processing reference surface 33 made of Cr was used. In addition, the washing | cleaning after completion | finish of rough processing and completion | finish of finishing was performed similarly to Example 3. FIG.

The processing conditions are as follows.
<Roughing>
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 20nm

<Finishing>
Processing fluid: pure water Rotation speed of shaft 71 (rotation speed of glass substrate): 10.3 rotation / min. : 10 hPa
Processing allowance: 10nm
Similar to 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 0.13 nm in terms of root mean square roughness (RMS).
The surface roughness after processing was as good as 0.06 nm in terms of root mean square roughness (RMS). The surface roughness was improved from 0.13 nm to 0.06 nm in root mean square roughness (RMS) by catalyst-based etching.

B. Manufacture of magnetic recording medium (magnetic disk) Next, an adhesion layer, a soft magnetic layer, an underlayer, a magnetic recording layer, and a barrier layer are formed on both surfaces of the glass substrate thus manufactured in an Ar gas atmosphere by a DC magnetron sputtering method. An auxiliary recording layer was formed.
The adhesion layer was made of 20 nm thick CrTi. The soft magnetic layer has a laminate structure of a first soft magnetic layer, a spacer layer, and a second soft magnetic layer. The first soft magnetic layer and the second soft magnetic layer were CoFeTaZr with a film thickness of 25 nm, and the spacer layer was Ru with a film thickness of 1 nm. The underlayer was NiW with a thickness of 5 nm. The magnetic recording layer has a laminated structure of a first magnetic recording layer and a second magnetic recording layer, the first magnetic recording layer is 10 nm thick CoCrPt—Cr ₂ O ₃ , and the second magnetic recording layer is 10 nm thick. CoCrPt—SiO ₂ —TiO ₂ was used. The barrier layer was Ru-WO ₃ having a thickness of 0.3 nm. The auxiliary recording layer was made of CoCrPtB having a thickness of 10 nm.

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

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

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

  DESCRIPTION OF SYMBOLS 1 ... Substrate processing apparatus, 2 ... Substrate support means, 3 ... Substrate surface creation means, 4 ... Processing fluid supply means, 5 ... Drive means, 6 ... Chamber, 7 ... Relative motion means, 8 ... Load control means, 21 ... Support Part, 22 ... plane part, 22a ... accommodating part, 31 ... catalyst surface plate, 32 ... surface plate body, 33 ... processing reference surface, 41 ... supply pipe, 42 ... injection nozzle, 51 ... arm part, 52 ... shaft part, 53 ... Base part, 54 ... Guide, 61 ... Opening part, 62 ... Discharge port, 63 ... Bottom part, 71 ... Shaft part, 72 ... Catalyst platen mounting part, 81 ... Air cylinder, 82 ... Load cell, 103 ... Substrate surface creation Means: 104: Cleaning liquid supply means, 108: Load control means, 131: Catalyst surface plate, 132: Surface plate body, 133: Processing reference surface, 141: Supply pipe, 142: Injection nozzle, 151: Arm portion, 152: Shaft Part, 172... Catalyst surface plate mounting part, 181 Air cylinder, 182 ... load cell, M ... substrate, M1 ... top, M2 ... lower surface.

Claims (14)

A substrate preparation step of preparing a substrate having a main surface made of a material containing an oxide;
A substrate processing step of processing the main surface by catalytic reference etching in a state in which a processing reference surface of a catalytic substance is brought into contact with or close to the main surface and a processing fluid is interposed between the processing reference surface and the main surface When,
In a method of manufacturing a substrate having
In the substrate processing step, a plurality of stages of catalyst reference etching with different processing speeds are performed on the main surface due to differences in at least one of the material of the catalyst substance or the mechanical characteristics of the processing reference surface ,
The catalyst material is formed on a base material composed of an elastic member,
The multi-stage catalyst-based etching includes a finishing process performed last and a roughing process performed before the finishing process;
A method for manufacturing a substrate , wherein the hardness of the elastic member used in the finishing process is lower than the hardness of the elastic member used in the roughing process . In the substrate processing step,
The processing speed for the substrate is such that the processing speed of the finishing process is slower than the processing speed of the roughing process ,
The method of manufacturing a substrate according to claim 1. The catalyst reference etch multiple stages, according to claim 1 or 2, characterized in that is carried out by using a catalyst platen plurality of types of the catalytic material is formed on said substrate having a predetermined hardness Substrate manufacturing method. In the substrate processing step,
Processing speed for the substrate, as the processing speed of the finishing is delayed as compared with the processing speed of the roughing, selecting the catalytic material and the base material of the catalyst platen,
The method of manufacturing a substrate according to claim 3. In the manufacturing method of the board | substrate as described in any one of Claim 1 to 4,
A cleaning process using a cleaning liquid is performed after the finishing process in the substrate processing process,
The catalyst material used for the finishing, it has a solubility in the cleaning solution of the cleaning process,
A method for manufacturing a substrate, characterized in that: 6. The method for manufacturing a substrate according to claim 5, wherein the catalytic material used for the finishing process includes any one of Cr, Ni, Fe, and Cu, or an alloy containing the metal.   6. The substrate manufacturing method according to claim 5, wherein the cleaning liquid is a solution that does not dissolve the main surface.   The substrate manufacturing method according to claim 1, wherein the substrate is made of a glass material.   The substrate manufacturing method according to claim 1, wherein the substrate is a mask blank substrate.   A method for producing a substrate with a multilayer reflective film, comprising: forming a multilayer reflective film on a main surface of the substrate produced by the method for producing a substrate according to claim 9.   On the main surface of the substrate obtained by the method for producing a substrate according to claim 9, or on the multilayer reflective film of the substrate with a multilayer reflective film obtained by the method for producing a substrate with a multilayer reflective film according to claim 10. A method for producing a mask blank, comprising forming a transfer pattern thin film.   A method for producing a transfer mask, comprising: patterning a thin film for transfer pattern of a mask blank obtained by the method for producing a mask blank according to claim 11 to form a transfer pattern. A substrate manufacturing apparatus for manufacturing a substrate by processing the main surface of the substrate by catalyst-based etching,
Substrate support means for supporting the substrate;
A substrate surface creation means having a processing reference surface of a catalytic substance disposed opposite to the main surface of the substrate supported by the substrate support means;
Processing fluid supply means for supplying a processing fluid between the processing reference surface and the main surface;
Drive means for bringing the processing reference surface into contact with or approaching the main surface in a state where a processing fluid is interposed between the processing reference surface and the main surface;
The substrate surface creation means, Ri Na includes a plurality of types of catalyst platen which the catalytic material is formed on the substrates comprised of an elastic member can be selected to have a predetermined hardness,
Among the plurality of types of catalyst surface plates, the hardness of the elastic member used in the finishing process that is the catalyst reference etching performed last is used in the roughing process that is the catalyst reference etching performed before the finishing process. A substrate manufacturing apparatus having a lower hardness than the elastic member .   The substrate manufacturing apparatus according to claim 13, further comprising a relative motion unit configured to relatively move the processing reference surface and the main surface.

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