# Patent

## Title
Photomask blank and method for manufacturing photomask blank

## Abstract

A method for manufacturing a photomask blank having at least a silicon-containing inorganic film over a transparent substrate includes forming the silicon-containing inorganic film such that a surface has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent, the silicon-containing inorganic film being an SiO film or an SiON film and serving as a hard mask film.

## Background
This application is a continuation application of U.S. patent application Ser. No. 14/489,019 filed Sep. 17, 2014, the entire disclosure of which is incorporated herein by reference.


BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a photomask blank for a photomask for use in fabrication of a semiconductor integrated circuit and the like and a method for manufacturing a photomask blank.
Description of the Related Art
In recent semiconductor processes, particularly the increasing scale of integration of large-scale integrated circuits increasingly requires the shrinking of circuit patterns. There is a growing demand for shrinking techniques of wiring patterns formed in circuits or contact hole patterns for wiring between layers formed in cells. In production of photomasks, in which circuit patterns are formed, for use in optical photolithography for forming these wiring patterns or contact hole patterns, there is accordingly a need for a technique to precisely form finer circuit patterns due to the above shrinking of the patterns.
Forming a resist pattern with high precision on a photomask blank is first needed to form a photomask pattern with higher precision on a photomask substrate. When an actual semiconductor substrate is processed, since optical photolithography employs reduced-size projection, the photomask pattern needs a size that is about four times greater than an actually needed pattern size. This however does not mean that the required precision is accordingly lowered, but a higher precision than that of the pattern after exposure is rather needed for a photomask serving as an original.
In addition, photolithography currently employed draws a circuit pattern with a significantly lower size compared with a wavelength of light to be used. Accordingly, if a photomask pattern having a size four times greater than that of a circuit form is used, then the photomask pattern form is not accurately transferred to a resist film due to influence of light interference occurring when the optical photolithography is performed, etc. For the purpose of reducing the influence, the photomask pattern sometimes needs to be formed into a more complex form (a form to which optical proximity correction (the so-called OPC) is applied) than an actual circuit pattern. There is accordingly a need for a higher-precision processing method in the photolithography technique to obtain photomask patterns. The performance of lithography may be represented by a resolution limit. The lithography technique in photomask forming processes requires a resolution limit substantially identical to or more than the resolution limit needed in optical photolithography employed in semiconductor processes using photomasks.
The procedure for forming a photomask pattern typically involves forming a photoresist film on a photomask blank having a light-shielding film on a transparent substrate, drawing a pattern by an electron beam, obtaining a resist pattern through development, and then etching the light-shielding film to form a light-shielding pattern while using the obtained resist pattern as an etching mask. If it attempts to achieve the shrinking of the light-shielding pattern while the same thickness of the resist film as that before the shrinking is maintained, then a ratio of a film thickness to the pattern, i.e., the an aspect ratio, becomes larger and pattern transfer thereby fails due to deterioration of the pattern form of the resist, or the resist pattern is broken or separated in some cases. The shrinking accordingly necessitates thinning a resist film thickness.
Use of hard masks has been tried before to reduce a burden on resists during dry etching. For example, Patent Document 1 reports that an SiO2 film formed on MoSi2 is used as an etching mask when MoSi2 is dry etched with a gas containing chlorine, and the SiO2 film can also function as an antireflection coating. In addition, there is disclosed that chromium is used for a light-shielding film on a phase shift film and an SiO2 film on the light-shielding film is used as a hard mask in, for example, Patent Document 2.
PRIOR ART REFERENCES
Patent Literature


    Patent Document 1: Japanese Unexamined Patent publication (Kokai) No. S63-85553
    Patent Document 2: Japanese Unexamined Patent publication (Kokai) No. H7-49558


SUMMARY OF THE INVENTION
Technical Problem
The above-described shrinking of patterns makes adhesion of resists important. If a fine pattern with a size of, e.g., 50 nm or less is formed in a film containing Si on its surface above a photomask, then the resist pattern is separated due to poor adhesion to the film containing Si during development. It has been known that performing a silylation process using, e.g., hexamethyldisilazane is effective in avoiding the separation.
There however arises a problem in that the silylation process gives hydrophobicity to a surface and thereby makes cleaning of the surface difficult; thereby many resist residues remain in a cleaning process after development, resulting in defects. It is only necessary for improvement in cleaning ability to improve wettability by using isopropyl alcohol or the like. These solvents however adversely affect resist patterns.
The present invention was accomplished in view of the above-described problems and relates to a photomask blank in which a resist film is formed after a silicon-containing inorganic film is subjected to a silylation process. It is an object of the present invention to provide a photomask blank and a method for manufacturing a photomask blank that can inhibit generation of defects due to resist residues or the like after development.
Solution To Problem
To achieve this object, the present invention provides a method for manufacturing a photomask blank having at least a silicon-containing inorganic film over a transparent substrate and a resist film on the silicon-containing inorganic film, comprising: forming the silicon-containing inorganic film such that a surface that will contact the resist film has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent; performing a silylation process after forming the silicon-containing inorganic film; and then forming the resist film by application.
Te present invention also provides a method for manufacturing a photomask blank having at least a silicon-containing inorganic film over a transparent substrate and a resist film on the silicon-containing inorganic film, comprising: forming the silicon-containing inorganic film such that when a surface that will contact the resist film is subjected to X-ray photoelectron spectroscopy, a detected intensity with respect to an Si—O bond energy is larger than a detected intensity with respect to an Si—Si bond energy; performing a silylation process after forming the silicon-containing inorganic film; and then forming the resist film by application.
According to the above methods, the adhesion between the silicon-containing inorganic film and the resist film can be improved by the silylation process, and even when a fine pattern is formed in the resist film, falling and separation of the resist pattern can be inhibited.
In addition, since the resist film is formed after the silicon-containing inorganic film having a surface fulfilling the above conditions is formed, generation of resist residues after development, which are conventionally generated in the case of performing a silylation process, can be inhibited, and the number of defects can thereby be reduced.
Moreover, the silicon-containing inorganic film (when a surface that will contact the resist film is subjected to X-ray photoelectron spectroscopy, a detected intensity with respect to an Si—O bond energy is larger than a detected intensity with respect to an Si—Si bond energy) may be formed such that the surface that will contact the resist film has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent.
According to the above method, the number of defects can be more assuredly reduced.
In the method, hexamethyldisilazane may be used for the silylation process.
Use of Hexamethyldisilazane (also referred to as HMDS, hereinafter) is preferred because it is commonly used in processes of semiconductor fabrication, such as photomask blanks.
Moreover, the silicon-containing inorganic film may further contain at least one of oxygen and nitrogen.
Forming the silicon-containing inorganic film further containing at least one of oxygen and nitrogen as above is more preferable.
Moreover, the silicon-containing inorganic film may be an SiO film or an SiON film.
Thus, an SiO film or an SiON film is particularly preferable as the silicon-containing inorganic film.
In the method, the silicon-containing inorganic film may be formed in such a manner that an inorganic film containing silicon is deposited over the transparent substrate and then subjected to a heat treatment, an ozonation treatment, or a plasma treatment.
The silicon-containing inorganic film may be alternatively formed over the transparent substrate through deposition by sputtering.
In this manner, a silicon-containing inorganic film having a surface fulfilling the above conditions can readily be formed.
Furthermore, the present invention provides a photomask blank comprising at least a silicon-containing inorganic film over a transparent substrate, the silicon-containing inorganic film being subjected to a silylation process, and a resist film on the silicon-containing inorganic film, wherein the silicon-containing inorganic film is configured such that a surface that contacts the resist film has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent.
The present invention also provides a photomask blank comprising at least a silicon-containing inorganic film over a transparent substrate, the silicon-containing inorganic film being subjected to a silylation process, and a resist film on the silicon-containing inorganic film, wherein the silicon-containing inorganic film is configured such that when a surface that contacts the resist film is subjected to X-ray photoelectron spectroscopy, a detected intensity with respect to an Si—O bond energy is larger than a detected intensity with respect to an Si—Si bond energy.
Such photomask blanks can inhibit falling and separation of the resist pattern even when a fine pattern is formed in the resist film, and also inhibit generation of resist residues, thereby reducing the number of defects.
Moreover, the silicon-containing inorganic film (when a surface that contacts the resist film is subjected to X-ray photoelectron spectroscopy, a detected intensity with respect to an Si—O bond energy is larger than a detected intensity with respect to an Si—Si bond energy) may be configured such that the surface that contacts the resist film has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent.
Such photomask blank can more assuredly reduce the number of defects.
Moreover, Hexamethyldisilazane may be used for the silylation process.
HMDS is preferred because it is commonly used in processes of semiconductor fabrication, such as photomask blanks.
Moreover, the silicon-containing inorganic film may further contain at least one of oxygen and nitrogen.
Forming the silicon-containing inorganic film further containing at least one of oxygen and nitrogen as above is more preferable.
Moreover, the silicon-containing inorganic film may be an SiO film or an SiON film.
Thus, an SiO film or an SiON film is particularly preferable as the silicon-containing inorganic film.
Advantageous Effects of Invention
As described above, the inventive photomask blank and method for manufacturing a photomask blank can inhibit falling and separation of a resist pattern and generation of resist residues after exposure and development, so the number of defects can be reduced.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of an example of the inventive photomask blank;
FIG. 2 is a flowchart of an example of the inventive method for manufacturing a photomask blank;
FIG. 3 is a graph showing a detected intensity with respect to an Si—O bond energy and a detected intensity with respect to an Si—Si bond energy by an ESCA method (an XPS method) in Examples 1, 2 and Comparative Example.
FIG. 4 is an observation view showing defects distribution after development in Example 1; and
FIG. 5 is an observation view showing defects distribution after development in Comparative Example.



DESCRIPTION OF EMBODIMENTS
An embodiment of the present invention will now be specifically described with reference to figures, but the present invention is not limited to this embodiment.
The present inventors diligently studied photomask blanks. As described above, when a resist film is formed after a silicon-containing inorganic film is subjected to a silylation process, conventionally, many resist residues are generated after the resist film is exposed and developed. The present inventors, in contrast, found that adjusting the oxygen concentration or the like of a surface of a silicon-containing inorganic film enables defects such as resist residues to be dramatically reduced even when a resist pattern is formed through the following silylation process, application of a resist, and development, thereby brought the present invention to completion.
FIG. 1 shows an example of the inventive photomask blank. As shown in FIG. 1, in a photomask blank 1 of the present invention, for example, a phase shift film 3, a light-shielding film 4, a silicon-containing inorganic film 5, and a resist film 6 is formed in this order on a transparent substrate 2.
The transparent substrate 2 for use in the photomask blank 1 may be composed of, but not limited to, a material that is transparent to an exposure light wavelength and has small amounts of thermal deformation at temperatures in manufacturing processes; a quartz substrate is given as an example of this material.
Next, the structure of films over the transparent substrate 2 will be described.
The silicon-containing inorganic film 5 needs to fulfill predetermined conditions, such as an oxygen concentration, of its surface that contacts the resist film 6, as described below. The silicon-containing inorganic film 5 itself may be an inorganic film containing, for example, silicon; or silicon and at least one selected from a group including oxygen, nitrogen and carbon; or silicon and transition metal; or silicon, transition metal and at least one selected from a group including oxygen, nitrogen and carbon. Examples of such an inorganic film include an inorganic film composed of silicon; or oxygen and silicon; or nitrogen and silicon; or oxygen, nitrogen and silicon; or carbon and silicon; or carbon, oxygen and silicon; or carbon, nitrogen and silicon; or carbon, oxygen, nitrogen and silicon. Examples of an inorganic film containing transition metal include an inorganic film composed of transition metal and silicon; or transition metal, silicon and oxygen; or transition metal, nitrogen and silicon; or transition metal, oxygen, nitrogen and silicon; or transition metal, carbon and silicon; or transition metal, carbon, oxygen and silicon; or transition metal, carbon, nitrogen and silicon; or transition metal, carbon, oxygen, nitrogen and silicon. A silicon-containing inorganic film composed of silicon, oxygen and nitrogen (an SiON film); or silicon and oxygen (an SiO film) is particularly desirable.
Examples of the transition metal include molybdenum, tungsten, tantalum, titanium, zirconia, and hafnium. The silicon-containing inorganic film 5 is not limited to a kind of a contained transition metal and may contain two kinds or more of transition metals.
Hydrogen may also be contained.
The silicon-containing inorganic film 5 is subjected to the silylation process. The silicon-containing inorganic film 5, which is subjected to the silylation process, thereby has high adhesion to the resist film 6 formed thereon. The occurrence of falling and separation of a resist pattern can thereby be inhibited even when a fine pattern is formed in the resist film 6.
The silylation process performed on the silicon-containing inorganic film 5 may be for example, but not limited to, a process using HMDS, which is commonly used in semiconductor fabrication processes.
In addition, the silicon-containing inorganic film 5 is configured such that its surface that contacts the resist film 6, i.e., a contact surface 7, has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent (the first embodiment).
In conventional photomask blanks using a silylation process, many resist residues are generated and cause defects after development. In contrast, the inventive photomask blank 1 having the contact surface 7 satisfying the above condition can inhibit the generation of resist residues, which are generated in conventional photomask blanks, and reduce the number of defects.
The reason for the reduction in defects by the oxygen concentration of the contact surface 7 of the silicon-containing inorganic film 5 is unclear; for example, it can be understood that the reason is that the amount of OH in the contact surface 7 or a bonding status of atoms in the contact surface 7 changes.
Alternatively, the silicon-containing inorganic film 5 is configured such that when the contact surface 7 is subjected to X-ray photoelectron spectroscopy (the XPS method), a detected intensity with respect to an Si—O bond energy is larger than a detected intensity with respect to an Si—Si bond energy (the second embodiment).
Such a silicon-containing inorganic film, which has the above relationship between detected intensities with respect to the Si—O bond energy and the Si—Si bond energy, can inhibit resist residues and reduce its defects after development as in the first embodiment.
Alternatively, the silicon-containing inorganic film 5 may meet both of the above conditions. Such photomask blank can more assuredly reduce the number of defects.
It is only necessary for the structure of films to locate the silicon-containing inorganic film 5 directly under the resist film 6; the silicon-containing inorganic film 5 may function as, for example, an optical film such as a light-shielding film or a phase shift film, or a hard mask film for use in forming a pattern on the optical film, and also have an etching stopper.
The present invention is particularly effective when a fine pattern, e.g., with a size of 50 nm or less, is formed. This effect is increased when the silicon-containing inorganic film 5 is used as a hard mask film.
When the silicon-containing inorganic film 5 is used as a hard mask film, the film thickness of the hard mask film is preferably 1 to 30 nm, further preferably 1 to 20 nm, more preferably 1 to 10 nm.
In the configuration in this embodiment, a light-shielding film 4 and a phase shift film 3 below the light-shielding film 4 are formed between the silicon-containing inorganic film 5 serving as the hard mask film and the transparent substrate 2. The silicon-containing inorganic film 5 serving as the hard mask film and the light-shielding film 4 preferably have etching selectiveness.
If the hard mask (etching mask) film (i.e., the silicon-containing inorganic film 5) is composed of a material that can be dry etched with a fluorine-based etching gas containing fluorine such as CF4 or SF6, then the etching process becomes easier; if the light-shielding film 4 and the other inorganic films formed below the above hard mask film are composed of a material that has resistance against the fluorine-based dry etching and can be etched by chlorine-based dry etching with an etching gas containing chlorine or chlorine and oxygen, then the etching process becomes easier. The light-shielding film 4 and the other inorganic films formed below the above hard mask film are desirably inorganic films containing chromium: for example, a film containing chromium, or chromium and at least one selected from a group including oxygen, nitrogen and carbon. An antireflection layer may be formed on the hard mask film side of the light-shielding film 4, and a film containing a large amount of oxygen or nitrogen may be formed on its transparent substrate side to improve the adhesion and to be used as an antireflection film.
When the phase shift film 3 is formed between the light-shielding film 4 and the transparent substrate 2, the phase shift film 3 preferably has different etching properties from the light-shielding film 4. If the light-shielding film 4 has resistance against the fluorine-based dry etching and can be dry etched with an etching gas containing chlorine and oxygen as above, the phase shift film 3 need only be composed of a material that has resistance against dry etching with an etching gas containing chlorine and oxygen and can be etched by the fluorine-based etching; for example, a material containing silicon and at least one selected from a group including oxygen, nitrogen, and carbon may be used, or a transition metal may further be contained. Examples of the transition metal include molybdenum, tungsten, tantalum, titanium, zirconia, and hafnium. Hydrogen may further be contained.
If a light-shielding film is located below the resist film 6, then the material containing silicon may be the above-described material and the entire light-shielding film may serve as the silicon-containing inorganic film 5. If an antireflection layer is formed on the surface of a light-shielding film, then the antireflection layer (only) may serve as the silicon-containing inorganic film 5 and the light-shielding film may be formed of another material such as a chromium-containing film.
The material of the resist film 6 may be an electron beam resist for use in drawing with an electron beam or a photoresist for use in drawing with light. A chemically amplified resist is particularly effective. The chemically amplified resist may be either a positive type or a negative type, and composed of a resin based on hydroxystyrene or mainly an acid generating agent; a cross-linking agent may be added; at least one of quencher, surfactant and the like may be added; a (meth)acrylic acid resin may be used.
Next, the inventive method for manufacturing a photomask blank 1 as shown in FIG. 1 will be described. FIG. 2 is a flowchart of an example of the inventive manufacturing method.
A transparent substrate 2 is first prepared (FIG. 2 at (A)). The above transparent substrate, for example a quartz substrate, may be prepared as the transparent substrate 2.
Next, a phase shift film 3 (FIG. 2 at (B)) composed of the above material, and a light-shielding film 4 (FIG. 2 at (C)) are formed in this order. The method of forming these films may be for example, but not limited to, sputtering.
Next, a silicon-containing inorganic film 5 composed of the above-described material is formed (FIG. 2 at (D1) or FIG. 2 at (D2a)-(D2b)). The silicon-containing inorganic film 5 is formed such that a surface (i.e., a surface that will contact a resist film 6 formed in a later step) has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent, or when being subjected to X-ray photoelectron spectroscopy, the surface exhibits a detected intensity with respect to an Si—O bond energy larger than a detected intensity with respect to an Si—Si bond energy. Alternatively, the silicon-containing inorganic film 5 may be formed such that the silicon-containing inorganic film meets both of the above conditions.
After the oxygen concentration of the surface is adjusted as above, a silylation process, which is described later, is performed, and a resist film is then formed by application. This procedure enables generation of resist residues to be inhibited when a pattern is drawn in the resist film 6 and developed as compared with conventional products, thereby significantly reducing the number of defects.
For the purpose of forming the silicon-containing inorganic film 5 in which its surface fulfills conditions such as oxygen concentration, for example, conditions under which the silicon-containing inorganic film 5 is deposited by sputtering may be adjusted (FIG. 2 at (D1)).
Alternatively, an inorganic film containing silicon (a preliminary inorganic film 8) is first deposited (FIG. 2 at (D2a)) and then subjected to a heat treatment, an ozonation treatment, a plasma treatment, or the like to adjust the oxygen concentration or the like of the surface, whereby the silicon-containing inorganic film 5 can be formed (FIG. 2 at (D2b)).
These methods are preferable because the silicon-containing inorganic film 5 having such a surface can readily be formed.
The method of forming the silicon-containing inorganic film 5 and the preliminary inorganic film 8 may be chemical vapor deposition (CVD) with a gas containing silicon, such as, for example, monosilane, dichlorosilane, or trichlorosilane; forming the film by sputtering using at least one target containing silicon is preferable because this sputtering is easier and has good controllability.
The method of forming the film by sputtering may be, but not particularly limited to, DC sputtering, RF sputtering, or the like. In formation of the silicon-containing inorganic film 5, when the inorganic film to be formed contains, for example, silicon and oxygen, reactive sputtering may be performed with silicon as a target and a gas of argon and oxygen as a sputtering gas. When the inorganic film to be formed contains nitrogen instead of oxygen, a nitrogen gas may be used instead of the oxygen gas. When the inorganic film to be formed contains both nitrogen and oxygen, a nitrogen gas and an oxygen gas may be used at the same time, or a nitrogen oxide gas such as nitrogen monoxide or nitrogen dioxide may be used. When the inorganic film to be formed further contains carbon, a gas containing carbon such as a methane gas, a carbon monoxide gas, or a carbon dioxide gas may be used. When the inorganic film to be formed further contains transition metal, a target including transition metal and silicon may be used, or cosputtering with both a silicon target and a transition metal target may be performed.
In addition, the silicon-containing inorganic film formed by deposition as above preferably has the Si—Si bonds because the Si—O bonds of the surface of this film can be controlled by a heat treatment under an oxygen-containing gas.
If the oxygen concentration of the surface is adjusted by adjusting depositing conditions in sputtering, for example, then the oxygen concentration may be adjusted by adjusting a ratio of an oxidizing gas such as oxygen or carbon dioxide to an inert gas such as argon in an atmosphere gas under which deposition is performed.
If the oxygen concentration of the surface is adjusted by a heat treatment, on the other hand, the oxygen concentration in a heat treatment atmosphere may be for example, but not limited to, 1 to 100%. The heat treatment may be, but not limited to, infrared heating, resistance heating, or the like.
The temperature of the heat treatment in the atmosphere including oxygen is preferably 200° C. or more, further preferably 400° C. or more.
Conditions under which an ozonation treatment, a plasma treatment, or the like is performed are also not limited. The conditions of these treatment may be adjusted appropriately such that the oxygen concentration of the surface, etc., fulfills the above condition.
Cleaning may be then performed (FIG. 2 at (E)). This cleaning to remove particles present on the surface of a photomask blank may be performed by using ultrapure water, or functional water, such as ultrapure water containing ozone, hydrogen, or the like, and applying ultrasonic waves. Alternatively, cleaning with ultrapure water including surfactant may be followed by rinsing with ultrapure water, and the above functional water cleaning, ultraviolet light irradiation, or the combination thereof may be performed.
The silylation process is then performed to reduce surface energy of a photomask blank surface such that the photomask blank surface is alkylsilylated (FIG. 2 at (F)). Such a silylation process allows a fine resist pattern to be prevented from being separated and fallen.
The above HMDS is given as an example of a silylation agent, but does not limit the silylation agent.
Known silylation processes include a method of directly applying the silylation agent to the silicon-containing inorganic film of the substrate and a method of exposing the substrate to the silylation agent. Known exposing methods include a method of evaporating the silylation agent in a container holding the substrate and a method of vaporizing the silylation agent by bubbling of a nitrogen gas. The temperature at which the silylation agent is reacted may be, for example, in the range from 40° C. to 200° C. The process time, for example, is preferably adjusted such that the wettability of the substrate becomes a proper value by previously measuring a contact angle of water under the same conditions as the silylation processes.
The above-described resist film 6 is then formed on the silicon-containing inorganic film 5 by application after the silylation process, whereby the inventive photomask blank 1 can be obtained (FIG. 2 at (G)).
The applying method is not particularly limited and may be performed, for example, in the same manner as a conventional method. The thickness of the resist film may be appropriately determined to obtain a good pattern form.
EXAMPLE
The present invention will be specifically described below through examples and comparative example, but the present invention is not limited these examples.
Example 1
The inventive photomask blank was manufactured by the inventive manufacturing method.
A phase shift film of MoSiON with a thickness of 75 nm was formed on 152 mm squares of a quartz substrate having a thickness of about 6 mm by sputtering. A gas of oxygen, nitrogen, and argon was used as a sputtering gas; MoSi2 and Si were used as two types of targets. The substrate was rotated at 30 rpm to form the film.
The composition of the phase shift film was Mo:Si:O:N=1:4:1:4 (atomic ratio), which was investigated by an electron spectroscopy for chemical analysis (ESCA) method (also referred to as an XPS method) with K-Alpha (manufactured by Thermo Fisher Scientific K.K.).
On the phase shift film, a CrN layer (30 nm) and a CrON layer (20 nm) as light-shielding films were formed in order from a substrate side upward by sputtering. A gas of argon and nitrogen was used as a sputtering gas for the CrN layer; a gas of oxygen, nitrogen, and argon was used as a sputtering gas for the CrON layer; a chrome metal was used as a target. The substrate was rotated at 30 rpm to form the film.
The compositions of the light-shielding films were Cr:N=9:1 (atomic ratio) for the CrN layer and Cr:O:N=4:5:1 (atomic ratio) for the CrON layer, which were investigated by the ESCA.
On the top of the light-shielding films, an SiO film with a thickness of 5 nm as an etching mask film (a hard mask) containing silicon was formed by sputtering. A gas of oxygen and argon was used as a sputtering gas; Si was used as a target. The substrate was rotated at 30 rpm to form the film.
A heat treatment was then performed on the resultant at 500° C. under an oxygen-containing atmosphere.
The composition of the etching mask film was investigated by the ESCA; the oxygen concentration of the surface was 61.5 atomic percent.
The surface of the etching mask film was also investigated by the ESCA. FIG. 3 shows detected intensities with respect to the Si—O bond energy and with respect to the Si—Si bond energy.
From the result, it is seen that the detected intensity (the area intensity) with respect to the Si—O bond energy is larger than the detected intensity with respect to the Si—Si bond energy (See FIG. 3).
The resultant was subjected to the silylation process with HMDS. After that, a negative type of electron beam resist (manufactured by Shin-Etsu Chemical Co., Ltd.,) was applied and developed with tetramethylammonium hydroxide to obtain a resist pattern. The resultant was then rinsed with pure water.
The investigation of the resultant with a defect inspection apparatus MAGICS 2350 (manufactured by Lasertec Corporation) demonstrated a good result in which, as shown in FIG. 4, the number of defects was extremely small.
The number of detected defects having a size of 0.1 μm or more was 42.
Example 2
The inventive photomask blank in which the oxygen concentration of the surface of the etching mask film after the heat treatment was 55.6 atomic percent and the detected intensity of the Si—O bond energy was larger than the detected intensity of the Si—Si bond energy was obtained (See FIG. 3) as in Example 1 except that the temperature of the heat treatment was changed into 300° C.
The number of defects after development was consequently 1180.
Example 3
The inventive photomask blank in which the oxygen concentration of the surface of the etching mask film was 71.0 atomic percent and the detected intensity of the Si—O bond energy was larger than the detected intensity of the Si—Si bond energy was obtained as in Example 1 except that the amount of oxygen in a sputtering gas was adjusted when SiO was formed by sputtering and the heat treatment was not performed after the sputtering.
The number of defects after development was consequently 30.
Comparative Example
A photomask blank in which the oxygen concentration of the surface of the etching mask film was 52.6 atomic percent and the detected intensity of the Si—O bond energy was smaller than the detected intensity of the Si—Si bond energy was manufactured as in Example 1 except that the heat treatment was not performed.
The investigation of defects after development revealed that, as shown in FIG. 5, many resist residues remained. The number of detected defects having a size of 0.1 μm or more was 4704, which was very large.
Note that at this time, the detected intensity of the Si—O bond energy was smaller than the detected intensity of the Si—Si bond energy (See FIG. 3).
As seen particularly from comparison between Example 2 and Comparative Example, Example 2 in which the oxygen concentration of the etching mask film surface was 55 atomic percent or more (or the detected intensity of the Si—O bond energy>the detected intensity of the Si—Si bond energy) greatly reduced the number of defects to a quarter or less of the number of defects in Comparative Example in which the oxygen concentration was less than 55 atomic percent (or the detected intensity of the Si—O bond energy<the detected intensity of the Si—Si bond energy).
In addition, as seen from Example 1 (an oxygen concentration of 61.5 atomic percent, 42 defects) and Example 3 (an oxygen concentration of 71.0 atomic percent, 30 defects), it is understood that in order to inhibit the number of defects, it is sufficient to adjust the oxygen concentration up to about 75%.
It is to be noted that the present invention is not limited to the foregoing embodiment. The embodiment is just an exemplification, and any examples that have substantially the same feature and demonstrate the same functions and effects as those in the technical concept described in claims of the present invention are included in the technical scope of the present invention.

## Claims

1. A method for manufacturing a photomask blank having at least a silicon-containing inorganic film over a transparent substrate, comprising
forming the silicon-containing inorganic film such that a surface has an oxygen concentration not less than 61.5 atomic percent and not more than 75 atomic percent,
the silicon-containing inorganic film being an SiO film or an SiON film and serving as a hard mask film.

2. The method for manufacturing a photomask blank according to claim 1, wherein a silylation process is performed after forming the silicon-containing inorganic film and hexamethyldisilazane is used for the silylation process.

3. The method for manufacturing a photomask blank according to claim 1, wherein the silicon-containing inorganic film is formed in such a manner that an inorganic film containing silicon is deposited over the transparent substrate and then subjected to a heat treatment, an ozonation treatment, or a plasma treatment.

4. The method for manufacturing a photomask blank according to claim 1, wherein the silicon-containing inorganic film is formed over the transparent substrate through deposition by sputtering.

5. The method for manufacturing a photomask blank according to claim 1, wherein the surface will contact a resist film.

6. A method for manufacturing a photomask blank having at least a silicon-containing inorganic film over a transparent substrate, comprising
forming the silicon-containing inorganic film such that when a surface is subjected to X-ray photoelectron spectroscopy, a detected intensity with respect to an Si—O bond energy is larger than a detected intensity with respect to an Si—Si bond energy,
the silicon-containing inorganic film being an SiO film or an SiON film and serving as a hard mask film.

7. The method for manufacturing a photomask blank according to claim 6, wherein the silicon-containing inorganic film is formed such that the surface has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent.

8. The method for manufacturing a photomask blank according to claim 6, wherein a silylation process is performed after forming the silicon-containing inorganic film and hexamethyldisilazane is used for the silylation process.

9. The method for manufacturing a photomask blank according to claim 7, wherein a silylation process is performed after forming the silicon-containing inorganic film and hexamethyldisilazane is used for the silylation process.

10. The method for manufacturing a photomask blank according to claim 6, wherein the silicon-containing inorganic film is formed in such a manner that an inorganic film containing silicon is deposited over the transparent substrate and then subjected to a heat treatment, an ozonation treatment, or a plasma treatment.

11. The method for manufacturing a photomask blank according to claim 9, wherein the silicon-containing inorganic film is formed in such a manner that an inorganic film containing silicon is deposited over the transparent substrate and then subjected to a heat treatment, an ozonation treatment, or a plasma treatment.

12. The method for manufacturing a photomask blank according to claim 6, wherein the silicon-containing inorganic film is formed over the transparent substrate through deposition by sputtering.

13. The method for manufacturing a photomask blank according to claim 11, wherein the silicon-containing inorganic film is formed over the transparent substrate through deposition by sputtering.

14. The method for manufacturing a photomask blank according to claim 6, wherein the surface will contact a resist film.

15. The method for manufacturing a photomask blank according to claim 13, wherein the surface will contact a resist film.

16. A photomask blank comprising at least a silicon-containing inorganic film over a transparent substrate, wherein
the silicon-containing inorganic film is configured such that a surface has an oxygen concentration not less than 61.5 atomic percent and not more than 75 atomic percent,
the silicon-containing inorganic film being an SiO film or an SiON film and serving as a hard mask film.

17. The photomask blank according to claim 16, wherein a silylation process will be performed to the surface and hexamethyldisilazane is used for the silylation process.

18. The photomask blank according to claim 16, wherein the surface will contact a resist film.

19. A photomask blank comprising at least a silicon-containing inorganic film over a transparent substrate, wherein
the silicon-containing inorganic film is configured such that when a surface is subjected to X-ray photoelectron spectroscopy, a detected intensity with respect to an Si—O bond energy is larger than a detected intensity with respect to an Si—Si bond energy,
the silicon-containing inorganic film being an SiO film or an SiON film and serving as a hard mask film.

20. The photomask blank according to claim 19, wherein the silicon-containing inorganic film is configured such that the surface has an oxygen concentration not less than 55 atomic percent and not more than 75 atomic percent.

21. The photomask blank according to claim 19, wherein a silylation process will be performed to the surface and hexamethyldisilazane is used for the silylation process.

22. The photomask blank according to claim 20, wherein a silylation process will be performed to the surface and hexamethyldisilazane is used for the silylation process.

23. The photomask blank according to claim 19, wherein the surface will contact a resist film.

24. The photomask blank according to claim 22, wherein the surface will contact a resist film.