US20040137828A1 - Glass substrate for a mask blank, method of producing a glass substrate for a mask blank, mask blank, method of producing the mask blank, transfer mask, and method of producing a transfer mask - Google Patents

Glass substrate for a mask blank, method of producing a glass substrate for a mask blank, mask blank, method of producing the mask blank, transfer mask, and method of producing a transfer mask Download PDF

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Publication number
US20040137828A1
US20040137828A1 US10/619,181 US61918103A US2004137828A1 US 20040137828 A1 US20040137828 A1 US 20040137828A1 US 61918103 A US61918103 A US 61918103A US 2004137828 A1 US2004137828 A1 US 2004137828A1
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Prior art keywords
glass substrate
mask blank
producing
main surface
precision polishing
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US10/619,181
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English (en)
Inventor
Kouji Takahashi
Hiroo Itoh
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Hoya Corp
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Hoya Corp
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Publication of US20040137828A1 publication Critical patent/US20040137828A1/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C03C15/02—Surface treatment of glass, not in the form of fibres or filaments, by etching for making a smooth surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/60—Substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31—Surface property or characteristic of web, sheet or block
    • Y10T428/315—Surface modified glass [e.g., tempered, strengthened, etc.]

Definitions

  • the present invention relates to a glass substrate for a mask blank used for a transfer mask (and a mask blank which is an original plate of the transfer mask) employed to produce semiconductor integrated circuits, liquid crystal display panels or the like, to a method of producing the glass substrate, and to a method of producing a mask blank and a transfer mask using the substrate.
  • a photomask blank using a glass substrate for an electronic device or an information recording medium is produced by forming a single or a plurality of layers of a functional thin film, such as a light shielding film (opaque film) that imparts optical changes in response to transfer exposure light or a phase shift film or the like, or a recording film or the like for recording information, on a glass substrate for electronic devices.
  • a functional thin film such as a light shielding film (opaque film) that imparts optical changes in response to transfer exposure light or a phase shift film or the like, or a recording film or the like for recording information
  • the information recording medium, or other electronic devices a defect inspection for checking for cracks existing in glass substrates is usually performed, or a defect inspection is usually performed after producing electronic devices. Defects on the glass substrates for electronic devices include scratches, stains, bubbles, striae, etc. These defects are detected by visual inspections or by using a defect inspection apparatus adapted to apply inspection light to a surface of a glass substrate to make use
  • the defect inspection after an electronic device is fabricated is for checking for foreign matters or pinholes in or on a functional thin film, or checking optical characteristics, recording characteristics, etc. for any problems.
  • defects of cracked states referred to as “cracks” among the defects existing in glass substrates for electronic devices are formed during a grinding process or a polishing step preceding a finish polishing step that uses abrasive particles having a relatively large diameter (e.g., a polishing step using a cerium oxide as the primary ingredient).
  • the cracks cannot be detected at all in a certain direction or are difficult to detect, because they hardly have width on the surface of a glass substrate in a certain direction.
  • the visual inspections are carried out because they advantageously permit instant inspection of a glass substrate from any directions, achieving higher efficiency and reliability, and also permit discrimination of the types of defects.
  • defects of sizes that cannot be detected by human eyes, and cracks on the surface of a glass substrate are extremely small, so that they are frequently overlooked.
  • a glass substrate that has passed a defect inspection despite of a small crack on the surface of a glass substrate is subjected to the step of forming functional thin films on the glass substrate to produce an electronic device, and the defect is detected by a defect inspection machine for the first time in the defect inspection process carried out after the electronic device is fabricated.
  • the crack underlies the films, making it impossible to correct it after the electronic device is fabricated.
  • the electronic device has to be discarded or reworked by precision-polishing the surface of the glass substrate again after removing the functional thin films. This has been posing a problem of a poor production yield and high production cost.
  • the photomask used as an exposure original plate has a patterned light shielding film formed on a transparent substrate.
  • the light shielding film pattern is transferred onto a transfer material, such as a silicon wafer or a glass substrate, through an exposure apparatus to make a semiconductor integrated circuit or a liquid crystal display panel.
  • the characteristics of the pattern to be transferred onto the silicon wafer or the glass substrate are directly related to the light shielding film pattern formed on the photomask. It is important that the light shielding film pattern is free of any pattern defects.
  • the pattern defects are considered to be caused by defects underlying a film due to the defects (scratches, the adhesion of foreign matters, etc.) on the surface of the glass substrate for an electronic device, or in-film or on-film defects caused by a defect of a photomask blank (the adhesion of foreign matters or half pinholes (the pinholes formed when foreign matters on a film fall off) or the like).
  • a defect of a photomask blank the adhesion of foreign matters or half pinholes (the pinholes formed when foreign matters on a film fall off) or the like.
  • the glass substrates for electronic devices are produced according to a polishing method in which they are polished with an abrasive material primarily composed of cerium oxide, then subjected to finish-polishing (precision polishing) with colloidal silica.
  • FIG. 6 is a diagram showing a conventional method of producing the glass substrates for electronic devices.
  • a rough polishing step (S 601 ) in which the main surface of a glass substrate is polished with relatively large abrasive particles having an average particle size of about 1 ⁇ m to about 3 ⁇ m is carried out, then a precision polishing step (S 602 ) for polishing it with relatively small abrasive particles having an average particle size of about 1 ⁇ m or less is carried out, and thereafter, a defect inspection step (S 603 ) by visual check or the like is carried out, thus producing glass substrates.
  • a method for screening glass substrates has been proposed in Japanese Unexamined Patent Application Publication No. 2002-201042. This method is characterized in that silica glass substrates obtained by polishing, cleaning, drying and etching sliced silica glass substrate materials are inspected to select silica glass substrates whose surfaces have no defects of 0.3 ⁇ m or more in a direction parallel to the surfaces of the substrates.
  • the problematic cracks (latent flaws) responsible for concave defects of glass substrates take place mostly in a grinding step (lapping step).
  • the polishing step (rough polishing and precision polishing) following the grinding step is aimed at removing the cracks or other defects, such as scratches.
  • the surfaces of glass substrates are etched after lapping, rough polishing and final precision polishing, thus giving no considerations to the roughening of the glass substrate surfaces caused by etching. Furthermore, when this method is used, because of the properties of silica glass, the cracks developed in a lapping step tend to extend in the depth direction due to local pressure applied to the cracks by an abrasive composed of cerium oxide or the like during rough polishing. Thus, the cracks cannot be removed unless excessive final precision polishing (obtaining more polishing-off amount means longer polishing time) is carried out. This presents a problem of lower productivity and larger turned-down edges on the edge surfaces of glass substrates.
  • the amount of removal by chemical etching after the final precision polishing is 0.2 to 0.5 ⁇ m, so that the surfaces of silica glass substrates are roughened even if there are no concave defects.
  • the glass substrates used for lithography of mask blank glass substrates are required to exhibit higher flatness and smoothness as exposure wavelengths become shorter (with increased miniaturization of patterns).
  • the smoothness is required to be 0.2 nm or less in terms of the root mean square roughness (RMS), or 0.15 nm or less in terms of the root mean square roughness (RMS) at EUV (wavelengths of 13 to 14 nm).
  • the surfaces of the glass substrates are roughened, failing to meet the requirements.
  • a first object thereof is to provide a glass substrate for a mask blank with high smoothness that can be used for short wavelength ranges of the ArF excimer laser, the F2 excimer laser, the EUV, etc., and a method of producing the same.
  • a second object of the invention is to provide a glass substrate for a mask blank that has no surface defects on a main surface of the glass substrate, and a glass substrate for a mask blank that is free of influences of a turned-down edge on an edge surface of the glass substrate, and a method of producing the same.
  • a third object of the invention is to provide a mask blank that is free of under-film defects and can be securely loaded on a stepper of an exposure machine, and a method of producing the same.
  • a fourth object of the invention is to provide a transfer mask that is free of pattern defects (pattern disconnection or the like) and can be securely loaded on a stepper of an exposure machine, and a method of producing the same.
  • the present invention provides the following constructions.
  • a glass substrate for a mask blank obtained by etching followed by post-processing steps, including a precision polishing step, wherein the surface roughness of a main surface of the glass substrate is 0.2 nm or less in terms of root mean square roughness (RMS).
  • RMS root mean square roughness
  • a mask blank having a thin film that causes an optical change in response to transfer exposure light the thin film being formed on the main surface of the glass substrate for a mask blank described in any one of Constructions 1 to 4.
  • a transfer mask having a thin film pattern that causes an optical change in response to transfer exposure light, the thin film pattern being formed on the main surface of the glass substrate for a mask blank described in any one of Constructions 1 to 4.
  • a method of producing a glass substrate for a mask blank having a step for eliciting a defect remaining on the main surface of the glass substrate, wherein a post-processing step that includes precision polishing is carried out after the step for eliciting a defect.
  • a method of producing a glass substrate for a mask blank whereby to produce a glass substrate by carrying out a rough polishing step for polishing a surface of the glass substrate by using abrasive particles having a predetermined average particle size, then a precision polishing step for polishing the surface of the glass substrate by using abrasive particles having an average particle size that is smaller than the aforesaid predetermined average particle size,
  • the surface of the glass substrate is etched to elicit a crack, which extends from the surface of the glass substrate in the direction of the depth and remains after the precision polishing step, in a defect inspection step carried out after the precision polishing step.
  • a method of producing a transfer mask wherein the thin film in the mask blank described in Construction 18 is patterned to form a thin film pattern.
  • FIG. 1 is a flowchart illustrating a method of producing a glass substrate for an electronic device in accordance with the present invention
  • FIG. 2 is a diagram showing the method of producing a glass substrate for an electronic device in accordance with the present invention
  • FIG. 3 is a diagram showing the method of producing a glass substrate for an electronic device in accordance with the present invention.
  • FIG. 4 is a sectional view of the vicinity of a surface of a glass substrate before the step for eliciting latent defects
  • FIG. 5 is a sectional view of the vicinity of the surface of the glass substrate after the step for eliciting latent defects.
  • FIG. 6 is a flowchart illustrating a conventional method of producing a glass substrate for an electronic device.
  • the glass substrate for a mask blank in Construction 1 is the glass substrate for a mask blank obtained by being subjected to post-processing steps, including a precision polishing step, after etching, and is characterized in that the surface roughness of the major surface of the glass substrate is 0.2 nm or less in terms of the root mean square roughness (RMS). Preferably, the surface roughness is 0.15 nm or less in terms of the root mean square roughness (RMS).
  • the surface roughness of the main surface of the glass substrate for a mask blank has high smoothness, specifically 0.2 nm or less in terms of the root mean square (RMS), making it possible to provide glass substrates for mask blanks that can be used for short wavelength ranges of an ArF excimer laser, an F2 excimer laser, an EUV, etc.
  • RMS root mean square
  • the etching in Construction 1 is characterized by its operation for eliciting defects remaining on the major surface of the glass substrate.
  • the etching that has the operation for eliciting defects remaining on the main surface of the glass substrate is carried out before a precision polishing step, thus making it possible to obtain a glass substrate for a mask blank that has high smoothness.
  • the defects remaining on the main surface of the glass substrate in this embodiment refer to concave surface defects, such as cracks.
  • the glass substrate for a mask blank in Construction 3 is characterized in that the surface defects of the main surface of the glass substrate in Construction 1 or 2 cannot be detected by visual inspection.
  • the glass substrate for a mask blank in Construction 4 is characterized in that the turned-down edge amount of the peripheral portion of the main surface of the glass substrate in any one of Constructions 1 to 3 is ⁇ 2 ⁇ m to 0 ⁇ m. Restricting the turned-down edge amount of the peripheral portion to ⁇ 2 ⁇ m to 0 ⁇ m permits improved positioning accuracy for loading the substrate on a stepper of an exposure machine.
  • the turned-down edge amount of the peripheral portion (end surface) of the main surface of the glass substrate is preferably ⁇ 1 ⁇ m to 0 ⁇ m, and more preferably ⁇ 0.5 ⁇ m to 0 ⁇ m.
  • the turned-down edge amount is defined by the maximum height in the distance range of 3 mm from the boundary between the main surface and the chamfered surface when a virtual reference surface that extends 3 to 16 mm toward the center from the boundary between the main surface and the chamfered surface of the glass substrate is provided, and the height of the virtual reference surface is defined as 0, as shown in FIG. 2.
  • a negative ( ⁇ ) maximum height means that the peripheral portion of the main surface of the substrate has a turned-down configuration (a turned-down edge configuration), while a positive (+) maximum height means that the peripheral portion of the main surface of the substrate has a protuberant configuration.
  • the mask blank in Construction 5 is characterized in that a thin film that causes an optical change in response to transfer exposure light is formed on the main surface of the glass substrate for a mask blank in any one of Constructions 1 to 4.
  • the mask blank uses the glass substrate for a mask blank in any one of Constructions 1 to 4, allowing the mask blank to be used for the short wavelength ranges of an ArF excimer laser, an F2 excimer laser, an EUV, etc.
  • a mask blank can be obtained, which is free of under-film defects and can be securely loaded on a stepper of an exposure machine when the mask blank is processed into a transfer mask.
  • the transfer mask in Construction 6 is characterized in that a thin film pattern that causes an optical change in response to transfer exposure light is formed on the main surface of the glass substrate for a mask blank in any one of Constructions 1 to 4.
  • the transfer mask uses the glass substrate for a mask blank in any one of Constructions 1 to 4, allowing the transfer mask to be used for the short wavelength ranges of an ArF excimer laser, an F2 excimer laser, an EUV, etc.
  • a transfer mask can be obtained, which is free of pattern defects (pattern disconnection or the like) and has a controlled turned-down edge on the glass substrate edge surface (the peripheral portion of the glass substrate main surface), so that the transfer mask can be securely loaded on a stepper of an exposure machine.
  • the method of producing a glass substrate for a mask blank in Construction 7 is a method of producing a glass substrate for a mask blank that has a step for eliciting a defect remaining on the main surface of the glass substrate, and is characterized in that a post-processing step that includes precision polishing is carried out after the step for eliciting a defect.
  • the step for eliciting a defect remaining on the main surface of a glass substrate is carried out before the post-processing step that includes precision polishing, a glass substrate for a mask blank that exhibits high smoothness can be obtained.
  • the defects remaining on the main surface of the glass substrate in this embodiment refer to concave surface defects, such as cracks.
  • the method of producing a glass substrate for a mask blank in Construction 8 is characterized in that the post-processing step in Construction 7 includes a precision polishing step for providing the main surface with precision polishing and a cleaning step for cleaning the main surface after the precision polishing step.
  • the cleaning step for cleaning the main surface is carried out after the precision polishing step, the abrasive particles used in the precision polishing step or the foreign matters on the substrate surface can be removed. This makes it possible to obtain a glass substrate for a mask blank that is free of surface defects attributable primarily to substances stuck on the main surface of the glass substrate.
  • the cleaning solution used in the cleaning step may be an acid solution, such as a hydrofluoric acid, hydrofluorosilic acid or sulfuric acid solution, or an alkaline aqueous solution, such as a sodium hydroxide or potassium hydroxide, or pure water.
  • an acid solution such as a hydrofluoric acid, hydrofluorosilic acid or sulfuric acid solution
  • an alkaline aqueous solution such as a sodium hydroxide or potassium hydroxide, or pure water.
  • a solution having the etching function an acidic solution or an alkaline aqueous solution
  • the cleaning conditions including the type and concentration of a chemical solution and time and temperature, are to be appropriately adjusted to set a predetermined amount of removal from the glass substrate by etching.
  • the cleaning conditions are to be set such that the removal amount is more than 0 ⁇ m and below 0.01 ⁇ m in order to restrain the surface from being roughened by cleaning.
  • the use of hydrofluoric acid or hydrofluorosilic acid is desirable, and the concentration of the hydrofluoric acid or hydrofluorosilic acid is preferably low, 0.5% or less.
  • the method of producing a glass substrate for a mask blank in Construction 9 is characterized in that the main surface of the glass substrate after the cleaning step in Construction 8 has roughness of 0.2 nm or less in terms of the root mean square roughness (RMS).
  • RMS root mean square roughness
  • the main surface of the glass substrate has high smoothness, the surface roughness being 0.2 nm or less in terms of root mean square roughness (RMS), thus making it possible to provide a glass substrate for a mask blank for the short wavelength ranges of an ArF excimer laser, an F2 excimer laser, an EUV, etc.
  • the surface roughness is 0.15 nm or less in terms of the root mean square roughness (RMS).
  • the method of producing a glass substrate for a mask blank in Construction 10 is characterized in that the step for eliciting a defect in Construction 9 is carried out by etching the main surface of the glass substrate.
  • the production method allows a defect remaining on the main surface to be effectively elicited and provides cleaning effect, thus making the production method desirable.
  • the method of producing a glass substrate for a mask blank in Construction 11 is characterized by further including a defect inspection step that follows the cleaning step in Construction 8 or 9. After the cleaning step, the defect inspection step is carried out so as to select glass substrates free of surface defects, thus making it possible to provide glass substrates with extremely high reliability, having no surface defects that lead to pattern defects.
  • the method of producing a glass substrate for a mask blank in Construction 12 is a method of producing a glass substrate for a mask blank whereby to make a glass substrate by carrying out a rough polishing step for polishing a surface of the glass substrate by using abrasive particles having a predetermined average particle size, then a precision polishing step for polishing the surface of the glass substrate by using abrasive particles having an average particle size that is smaller than the aforesaid predetermined average particle size.
  • the production method is characterized in that, prior to the precision polishing step, the surface of the glass substrate is etched to elicit a crack, which extends from the surface of the glass substrate in the direction of the depth and remains after the precision polishing step, in a defect inspection step carried out after the precision polishing step.
  • a glass substrate for a mask blank can be obtained that has no surface defects on the main surface of the glass substrate and a less turned-down edge on a glass substrate edge surface (the peripheral portion of the main surface of the glass substrate).
  • the rough polishing step in the present invention is carried out to remove scratches from the main surface of a glass substrate formed by a grinding step or the like so as to maintain the flatness obtained by the grinding step.
  • relatively large abrasive particles having the average particle size of about 1 ⁇ m to about 3 ⁇ m are used.
  • the material of the abrasive particles is appropriately selected mainly according to the material of the glass substrates.
  • a cerium oxide, a zirconium oxide or the like is used.
  • the rough polishing step may include a single cycle or a plurality of cycles.
  • the polishing pad used in the rough polishing step may be either a hard polisher or a soft polisher.
  • the precision polishing step in the present invention is carried out to remove, by the rough polishing step or the like described above, the texture formed on the main surface of the substrate so as to provide the substrate with a mirror finished surface.
  • the step uses relatively small abrasive particles having an average particle size of about 1 ⁇ m or less (e.g., 30 nm to 1 ⁇ m).
  • the material of the abrasive particles is appropriately selected according mainly to the material of the glass substrate, as in the case set forth above.
  • colloidal silica is used, because it has a small average particle size and permits a smooth substrate surface to be obtained.
  • the colloidal silica for the abrasive particles makes it possible to provide the main surface of the glass substrate with a mirror finish by precision polishing, so that the cracks remaining after the precision polishing step exist in the smooth surface state, allowing the cracks to be easily detected.
  • the average particle size is preferably small.
  • the polishing pad used in the precision polishing step is preferably a soft or supersoft polisher to achieve the mirror finish.
  • the surface roughness of the mask blank glass substrate that is lastly obtained after the precision polishing step is preferably 0.2 nm or less in terms of an average surface roughness, namely, a center-line mean roughness Ra and further 0.2 nm or less in terms of the root mean square roughness (RMS).
  • To elicit cracks in the defect inspection step carried out after the precision polishing step in the present invention means to enlarge, by etching, the latent cracks that cannot be or are difficult to be visually checked before etching and to make it possible to check them more clearly by precision polishing.
  • etching enlarges such latent cracks to such sizes that make the cracks in a glass substrate recognizable in the defect inspection step carried out after the precision polishing step.
  • the cracks are enlarged to a width that allows the defects to be recognized in the visual inspection in Construction 15.
  • the cracks are preferably enlarged to a width of 0.2 ⁇ m or more on the glass substrate surface.
  • the etching described in Constructions 1, 2, 10 and 12 set forth above is performed before the precision polishing step aimed at providing the glass substrate surface with a mirror finish.
  • the etching may be performed before the rough polishing step, or after the rough polishing step and before the precision polishing step, or both before the rough polishing step and before the precision polishing step following the rough polishing step.
  • the etching is preferably carried out at least after the rough polishing step and prior to the precision polishing step.
  • etching either the dry etching method or the wet etching method may be used.
  • the cracks are magnified by the etching. For instance, if the wet etching is performed, a crack extending from the glass substrate surface toward the center is isotropically etched. Hence, the depth of the crack toward the center does not change much due to the amount of etching on the glass substrate surface, whereas the size (width) of the crack in the direction of the surface increases.
  • the etching step is carried out before the precision polishing step, then the precision polishing for mirror finishing is implemented.
  • the glass substrate surface which has been turned into an extremely smooth surface by the precision polishing step, makes it easy to detect the crack having the certain size (width) by the etching, the crack being present in the smooth surface.
  • the etching is performed before the precision polishing (especially when the etching is performed after the rough polishing step but before the precision polishing step), the glass substrate surface becomes relatively even. This makes it possible to restrain the load in the precision polishing step for turning the glass substrate surface to a mirror surface, and to improve the configuration of an edge surface of the glass substrate (to reduce the amount of the turned-down edge of the peripheral portion of the main surface of the glass substrate).
  • glass substrates are generally polished using polishing pads of soft polishers or supersoft polishers, so that the edge surfaces of glass substrates tend to develop turned-down edges as the polishing time passes.
  • the load in the precision polishing step can be restrained, thus permitting the amount of the turned-down edge of a glass substrate edge surface to be controlled.
  • the amount of the turned-down edges of the glass substrate edge surfaces can be controlled to ⁇ 2 ⁇ m to 0 ⁇ m, and may be preferably controlled to ⁇ 1 ⁇ m to 0 ⁇ m, and further preferably to ⁇ 0.5 ⁇ m to 0 ⁇ m.
  • the cracks refer to fissures that extend in the direction of depth from the surfaces of glass substrate.
  • the cracks are produced in a grinding step or a polishing step before a finish polishing step that uses abrasive particles having a relatively large particle size (e.g., a polishing step using cerium oxide as a primary abrasive), and hardly have widths on the surfaces of glass substrate, making it almost impossible to detect them.
  • the problematic cracks in the present invention refer to the cracks remaining after the precision polishing step, that is, the cracks having such depths that cannot be removed by the precision polishing step. In other words, if the cracks are shallow enough to be removed by the precision polishing step, then they will disappear after the precision polishing step.
  • the etching is preferably performed using an alkaline aqueous solution.
  • the alkaline aqueous solution is preferably an aqueous solution of sodium hydroxide (NaOH) or potassium hydroxide (KOH) or the like or a mixed solution of these.
  • the method of producing a glass substrate for a mask blank in Construction 13 is characterized in that a cleaning step for cleaning the main surface of a glass substrate is carried out after the precision polishing step in Construction 12.
  • the cleaning step for cleaning the main surface is carried out after the precision polishing step, so that the abrasive particles used in the precision polishing step or the foreign matters or the like stuck to the substrate surface can be removed, thus making it possible to obtain a glass substrate for a mask blank free of surface defects attributable mainly to the substances stuck to the main surface of the glass substrate.
  • the method of producing a glass substrate for a mask blank in Construction 14 is characterized in that the main surface of a glass substrate after the cleaning step in Construction 13 has roughness of 0.2 nm or less in terms of the root mean square roughness (RMS).
  • RMS root mean square roughness
  • the surface roughness of the main surface of the glass substrate has high smoothness, specifically 0.2 nm or less in terms of the root mean square roughness (RMS), making it possible to provide glass substrates for mask blanks that can be used for short wavelength ranges of an ArF excimer laser, an F2 excimer laser, an EUV, etc.
  • the surface roughness is 0.15 nm or less in terms of the root mean square roughness (RMS).
  • the method of producing a glass substrate for a mask blank in Construction 15 is characterized in that the cleaning step uses a solution having an etching function as a cleaning solution, and the cleaning step is carried out under a condition that causes the glass substrate to be removed by more than 0 ⁇ m and below 0.01 ⁇ m by etching in Construction 13 or 14.
  • the cleaning carried out mainly to remove abrasive particles or foreign matters stuck to a substrate surface uses a detergent, acid, alkali or the like.
  • a cleaning solution acid, alkali
  • the cleaning step is carried out under a condition such that the surface of the glass substrate is removed by more than 0 ⁇ m and below 0.01 ⁇ m. This is because, if the amount of removal by etching in the cleaning step is 0.01 ⁇ m or more, then etching residues causes unevenness.
  • the method of producing a glass substrate for a mask blank in Construction 16 is characterized in that a defect inspection step is implemented by a visual inspection in Construction 11 or 12.
  • the defect inspection may be performed by visual inspection or by using a defect inspection apparatus that carries out the defect inspection by applying inspection light to glass substrates and detect scattered light or the light leaked out of the glass substrates.
  • visual inspection is preferred because it is advantageous in efficiency and certainty of inspection and in determining the types of defects.
  • the method of producing a glass substrate for a mask blank described in Construction 17 is characterized in that the etching removes the surface of the glass substrate that is subjected to precision polishing by 0.01 to 0.2 ⁇ m in Construction 10 or 12.
  • the etching rate in the etching process is preferably 0.2 nm/min. to 2.0 nm/min.
  • An etching rate below 0.2 nm/min. is not desirable, because it would not sufficiently elicit latent defects.
  • an etching rate over 2 nm/min. is not desirable, either, because it would badly affect the surface roughness and the surface configuration (flatness) due to quick corrosion of the glass substrate.
  • a preferable range is 0.3 nm/min. to 0.7 nm/min.
  • the method of producing a glass substrate for a mask blank in Configuration 18 is characterized in that a thin film that causes an optical change in response to transfer exposure light is formed on the main surface of the glass substrate obtained by the method of producing a glass substrate for a mask blank described in any one of Constructions 7 to 17.
  • the glass substrates free of surface defects that have been obtained by removing the glass substrates with cracks remaining therein that have been obtained in Constructions in 7 to 17, so that mask blanks free of under-film defects can be obtained.
  • the method of producing a transfer mask in Construction 19 is characterized in that the thin film of the mask blank in Construction 18 is patterned to form a thin film pattern.
  • the transfer mask is fabricated by using a mask blank free of under-film defects that has been obtained in Construction 17, making it possible to obtain a transfer mask that is free of pattern defects (pattern disconnections) and can be securely loaded on a stepper of an exposure machine.
  • the mask blank in the present invention is used as a generic term, and includes a photomask blank in which only a light shielding film that has a function for blocking transfer exposure light is formed on the main surface of a glass substrate, a phase shift mask blank having a phase shift film that has a phase shift function for causing a phase difference change in response to transfer exposure light, and a reflective mask blank having a reflective film that reflects transfer exposure light or an absorbent film that absorbs transfer exposure light.
  • the mask blanks further include other types of mask blanks, including the ones with resist films deposited on the foregoing light shielding film, phase shift film, reflective film, or the like.
  • the material of the glass substrate in the present invention there are no particular restrictions on the material of the glass substrate in the present invention.
  • Materials used for the glass substrate in the present invention include silica glass, non-alkali glass, soda lime glass, and alumino borocilicic acid glass.
  • Silica glass in particular, is a hard, brittle material, as compared with other glass materials, so that the surface of a glass substrate easily develops cracks in a grinding step or a rough polishing step. For this reason, the glass substrate for a mask blank and the method of producing the same described above are especially effective when the material of the glass substrate is silica glass.
  • the glass substrate for a mask blank is referred to as the glass substrate for an electronic device.
  • the method of producing a glass substrate for an electronic device shown in FIG. 1 includes:
  • a rough polishing step for polishing, with relatively large abrasive particles, both main surfaces of a glass substrate for an electronic device that has been subjected to the shaping of the glass substrate and the grinding of the both main surfaces of the substrate by a lapping machine or the like (S 101 );
  • an etching step for eliciting a latent crack that extends in the direction of the depth from a surface of a glass substrate by etching (S 102 );
  • a defect inspection step (S 104 ) for inspecting defects in the glass substrate [0119] a defect inspection step (S 104 ) for inspecting defects in the glass substrate.
  • the defect inspection step (S 104 ) in FIG. 1 is carried out in order to exclude, as defectives, the glass substrates with still remaining defects after the precision polishing step is carried out to provide the main surfaces of the glass substrates with mirror finish.
  • condition are to be set such that cracks extending in the depth direction from the surfaces of glass substrates are magnified to sizes that permit the cracks to be securely detected and checked and to be elicited.
  • the cracks remaining after the precision polishing step are magnified by etching performed before the precision polishing step.
  • the etching conditions are set so as to allow such cracks to be detected and checked accurately and securely in the defect inspection step following the precision polishing step. More specifically, the etching conditions are set such that the amount of removal by etching is 0.01 to 0.2 ⁇ m. This makes it possible to enlarge cracks to widths of 0.2 ⁇ m or more on the surfaces of glass substrates, so that the defects existing on the surface of the glass substrates can be securely detected and checked.
  • the step (S 102 ) is carried out such that the flatness of glass substrates and the turned-down edge amount of the edge surfaces of the glass substrates will be within a predetermined range (specifically, the flatness and the turned-edge amount that allow a predetermined pattern position accuracy to be obtained when transfer masks (e.g., photomasks) are made using glass substrates and the photomasks are loaded on the steppers of an exposure machine) after the precision polishing step aimed at providing glass substrates with mirror finish.
  • transfer masks e.g., photomasks
  • the precision polishing step aimed at providing glass substrates with mirror finish.
  • the conditions are set so as to permit reduced variation in the substrate edge surfaces in the precision polishing step.
  • the etching speed in the etching process is relatively slow.
  • the etching speed is set to 0.2 nm/min. to 2 nm/min. It is desirable to use an alkaline aqueous solution having a mild etching action on glass substrates.
  • the polishing method in the rough polishing step and the precision polishing step may be a single-sided polishing method or a both-sided polishing method. Further, a sheet system or a batch system may be used.
  • a cleaning step is provided, as necessary, to remove abrasive particles so as to prevent the abrasive particles used in the rough polishing step or the precision polishing step from being carried over to the next step, and also to remove foreign matters stuck to the surfaces of glass substrates.
  • the cleaning methods one or multiple cleaning methods are selected according to the objects to be removed, the cleaning methods including the cleaning methods using chemical solutions (acid or alkali), detergents, pure water or ultrapure water, a wet cleaning method using a functional water, such as hydrogen water, and dry cleaning methods involving the application of UV (ultra-violet rays) or ozone treatment.
  • the etching removal amount is preferably set to be over 0 ⁇ m and below 0.01 ⁇ m, and preferably over 0 ⁇ m and below 0.005 ⁇ m so as not to cause irregularities to be formed due to etching residues.
  • FIG. 3 through FIG. 5 are sectional views of the vicinity of a surface of a glass substrate before and after cracks are elicited by etching performed with an alkaline aqueous solution.
  • the amount to be polished off in the precision polishing step is set to 1 ⁇ m in the explanation.
  • FIG. 3 is a sectional view of the vicinity of the surface of the glass substrate before etching, the glass substrate having undergone the rough polishing step.
  • the surface of a glass substrate 1 after the rough polishing step has not been fully turned into a mirror surface, and the entire surface of the substrate has irregularities like textures.
  • a fissure-like crack 2 formed from the surface of the glass substrate 1 toward the center exists at places where the texture-like irregularities are formed.
  • the cracks are formed in a grinding step or a rough polishing step using abrasive particles of relatively large particle sizes.
  • Various cracks exist, including cracks 21 and 22 having depths that exceed 1 ⁇ m, and a crack 23 having a depth below 1 ⁇ m.
  • the shallow crack 23 is removed by the subsequent precision polishing step, whereas the cracks 21 and 22 having depths of 1 ⁇ m or more that is greater than the polishing-off amount in the precision polishing step cannot be removed by the subsequent precision polishing step.
  • FIG. 4 is a sectional view showing the vicinity of the surface of the glass substrate after etching.
  • the dotted lines indicate the surface of the glass substrate before etching, while the solid line indicates the substrate surface after etching.
  • the surface of the glass substrate is isotropically etched in the direction of the inside the surface and the depth by etching, so that the crack 2 is magnified. In this state, however, the glass substrate surface hardly shows a difference from the state illustrated in FIG. 3. Hence, even if the crack has been enlarged, the crack is hidden behind the texture irregularities, making it difficult to be visually checked, and overlooked in some cases.
  • FIG. 5 is a sectional view of the vicinity of a surface of a glass substrate that has undergone the precision polishing step.
  • the surface of the glass substrate 1 after the precision polishing step has a mirror finish with average surface roughness Ra of 0.2 nm or less.
  • the cracks present at the positions deeper than a polishing-off amount in the precision polishing step, the depths thereof from the surface of the glass substrate being over 1 ⁇ m are enlarged by etching, as illustrated. Since the enlarged cracks 31 and 32 are present in the mirror surface state of the surface of the glass substrate 1 , they can be detected securely and easily in the defect inspection step (visual inspection) after the precision polishing step.
  • Polishing solution Cerium oxide (average particle size: 1 to 2 ⁇ m)+water
  • Polishing pad Hard polisher (urethane pad)
  • the glass substrates were cleaned by immersing them in an aqueous solution containing hydrofluorosilic acid to remove the polishing abrasive particles from the glass substrates.
  • the obtained glass substrates were immersed in a chemical solution (alkali: sodium hydroxide) to remove the surfaces of the glass substrates by about 0.05 nm by etching so as to magnify the cracks existing in the vicinities of the surfaces of the glass substrates.
  • concentration of the chemical solution used for this purpose was set so that the etching rate with respect to the glass substrates was 0.8 nm/min.
  • the twelve obtained glass substrates were loaded on the aforesaid double-side polishing apparatus, and subjected to precision polishing under the following polishing conditions.
  • the machining load and the polishing conditions were adjusted, as necessary.
  • the polishing time was set so as to minimize a configuration change of substrate end surfaces caused by the precision polishing and to be long enough to turn the surfaces of the glass substrates into mirror surfaces (a polishing time was set so as to polish off about 1 ⁇ m)).
  • Polishing solution Colloidal silica (average particle size: 50 to 80 nm)+water
  • Polishing pad Soft polisher (suede type)
  • the glass substrates were cleaned by immersing them in a cleaning tank of an alkaline aqueous solution to remove the polishing abrasive particles from the glass substrates.
  • the conditions of cleaning by using the alkaline aqueous solution were set such that the amount of removal by etching the glass substrates was about 0.005 ⁇ m.
  • the obtained glass substrates can be used as the glass substrates for the mask blanks for ArF excimer lasers and the glass substrates for the mask blanks for F2 excimer lasers.
  • Glass substrates were fabricated in the same manner as that in the first embodiment except for some changes in the cleaning step after the completion of the precision polishing step in the first embodiment. Specifically, the immersion time of the cleaning conditions, in which the glass substrates are cleaned by immersing them in a cleaning tank of a low-concentration of hydrofluorosilic acid (concentration: 0.15%) to remove the polishing abrasive particles from the glass substrates, was set such that the amount of removal by etching on the glass substrates would be about 0.003 ⁇ m.
  • the obtained glass substrates can be used as the glass substrates for the mask blanks for EUV.
  • Glass substrates for electronic devices were fabricated under the same conditions according to the method of producing the glass substrate for an electronic device in the first embodiment except that the etching process in (2) was not carried out (first comparative example).
  • Glass substrates for electronic devices were fabricated under the same conditions according to the method of producing the glass substrate for an electronic device in the first embodiment except that the etching process in (2) was not carried out, and the polishing conditions in the precision polishing step of (3) were changed. Specifically, the polishing time required to obtain the polishing-off amount to completely remove scratches in the rough polishing step in (1) (the polishing time for obtaining a polishing-off amount of 5 ⁇ m) was set (second comparative example).
  • the glass substrates for electronic devices in the first comparative example were visually inspected for defects, but no surface defects were recognized.
  • Photomask blanks were fabricated by depositing a chromium nitride film, a chromium carbide film and a chromium oxynitride film (total film thickness: 900 angstroms) by sputtering on one main surface of each of the glass substrates obtained in the first embodiment and the first and second comparative examples described above.
  • a phase shift mask blank was fabricated by forming a nitrified molybdenum silicide film (film thickness: 800 angstroms) by sputtering on one main surface of each of the glass substrates obtained in the first embodiment and the first and second comparative examples described above. After depositing the film, scrub cleaning was performed to fabricate photomask blanks and phase shift mask blanks.
  • the obtained photomask blanks and the phase shift mask blanks were inspected using a surface defect inspection apparatus.
  • No under-film defects were found in the first embodiment (the glass substrates for electronic devices free of concave surface defects) and the photomask blanks fabricated using the glass substrates for electronic devices in the second comparative example.
  • under-film defects were found in three out of twelve photomask blanks fabricated using the glass substrates for electronic devices in the first comparative example (when the films formed on the glass substrates were peeled off and the surfaces of the glass substrates were process by the etching in (2), the configurations of the defects were found to be similar to that of the concave surface defect found in one of the twelve glass substrates in the defect inspection step in the first embodiment.
  • the defects are considered to be the cracks magnified by etching.
  • the cracks on the glass substrates are magnified by performing the alkali treatment before the precision polishing step to allow surface defects to be found in the defect inspection step after the precision polishing step, thus making it possible to produce photomask blanks by using glass substrates free of surface defects.
  • This enables photomask blanks free of under-film defects to be obtained.
  • the glass substrates are fabricated without magnifying cracks existing in the glass substrates and subjected to the defect inspection.
  • the glass substrates having surface defects, which should be have been checked are determined to be non-defective, and sent to the production process of the photomask blanks.
  • photomask blanks with under-film defects were obtained, causing the production yield of the photomask blanks to be significantly reduced.
  • resist films were deposited on the aforesaid films by spin coating to make photomasks and phase shift masks having desired patterns.
  • pattern defects such as pattern disconnection, were found when photomasks were made by using the photomask blanks, in which under-film defects had been found, among the photomask blanks made by using the glass substrates for electronic devices in the first comparative example.
  • a board holding testing machine adapted to vacuum-chuck two sides of a substrate was prepared to simulate the loading onto the steppers of an exposure machine.
  • the flatness changes observed when loading the obtained photomasks discussed above were measured by an optical interferometer (Zygo Mark GPI).
  • the flatness changes of the photomasks fabricated by using the glass substrates for electronic devices in the first embodiment and the first comparative example were 0.1 ⁇ m, showing very little changes.
  • the flatness changes of the photomasks fabricated by using the glass substrates for electronic devices in the second comparative example exceeded 0.5 ⁇ m, and loading failure attributable to turned-down edges was found.
  • the present invention makes it possible to obtain the glass substrates for electronic devices having high smoothness that can be used for the short wavelength ranges of ArF excimer lasers, F2 excimer lasers, EUVs, etc. Furthermore, the description has been given of the glass substrates for mask blanks as most useful examples in the embodiment set forth above; however, the production method in accordance with the present invention can be also applied to the glass substrates for liquid crystal displays, the glass substrates for information recording media (magnetic disks, magneto-optical disks and optical disks), and semiconductor wafers or the like.
  • the configurations of the substrates are mainly square (e.g., rectangular (quadrate or rectangular)), discoid or substantially round.
  • Rectangular substrates include the glass substrates for mask blanks, such as photomask blanks, phase shift blanks and reflective mask blanks, and the glass substrates for liquid crystal displays.
  • Discoid substrates include the glass substrates for information recording media, and circular substrates include semiconductor wafers, etc.

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US10/619,181 2002-07-17 2003-07-15 Glass substrate for a mask blank, method of producing a glass substrate for a mask blank, mask blank, method of producing the mask blank, transfer mask, and method of producing a transfer mask Abandoned US20040137828A1 (en)

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