JP2002189284A - Phase shift mask blank, phase shift mask and method for producing these - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phase shift mask blank having a phase shifter formed with molybdenum silicide oxycarbide or molybdenum silicide oxycarbonitride as a phase shift mask blank obtained by forming at least one phase shifter on a transparent substrate and to provide a phase shift mask and a method for producing the phase shift mask blank and phase shift mask. SOLUTION: When an MoSi phase shift film is formed by reactive sputtering, a CO2-containing gas is used as a sputtering gas to obtain the objective phase shift mask blank and phase shift mask having high intrasurface uniformity, good controllability in production and high quality.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phase shift mask blank and a phase shift mask used for manufacturing a semiconductor integrated circuit and the like, and a method of manufacturing the phase shift mask blank and the phase shift mask. The present invention relates to a halftone type phase shift mask blank and a phase shift mask for attenuating light having a wavelength, and a method for manufacturing the phase shift mask blank and a phase shift mask.

[0002]

2. Description of the Related Art ICs,
Photomasks used for a wide range of applications, including the manufacture of semiconductor integrated circuits such as LSI and VLSI, are basically photomask blanks having a light-shielding film containing chromium as a main component on a light-transmitting substrate. A predetermined pattern is formed on the light-shielding film by applying a photolithography method and using an ultraviolet ray, an electron beam, or the like.
In recent years, pattern miniaturization has rapidly progressed with market demands for higher integration of semiconductor integrated circuits and the like, and this has been responded to by shortening the exposure wavelength.

[0003] However, while shortening the exposure wavelength improves the resolution, it causes a decrease in the depth of focus, lowers the stability of the process, and adversely affects the product yield.

A phase shift method is one of the effective pattern transfer methods for solving such a problem, and a phase shift mask is used as a mask for transferring a fine pattern.

The phase shift mask (halftone type phase shift mask) includes, for example, a phase shifter portion b forming a pattern portion on the mask as shown in FIGS. 9A and 9B. It consists of a part a where the substrate where the phase shifter does not exist is exposed, and the phase difference between the light passing through both parts is set to about 180 °. Is zero, and the contrast of the transferred image can be improved. In addition, by using the phase shift method, it is possible to increase the depth of focus for obtaining the required resolution, compared to a case where a normal mask having a general light shielding pattern made of a chrome film or the like is used. It is possible to improve the resolution and the margin of the exposure process.

The above-mentioned phase shift masks can be practically classified into a complete transmission type phase shift mask and a halftone type phase shift mask depending on the light transmission characteristics of the phase shifter. The complete transmission type phase shift mask is a mask in which the light transmittance of the phase shifter portion is equal to that of the substrate exposed portion, and is transparent to the exposure wavelength. The halftone type phase shift mask has a phase shifter portion having a light transmittance of several% to several tens% of the exposed portion of the substrate.

FIG. 1 shows a basic structure of a halftone type phase shift mask blank, and FIG. 2 shows a basic structure of a halftone type phase shift mask. The halftone phase shift mask blank of FIG. 1 has a halftone phase shift film 2 formed on almost the entire surface of a transparent substrate 1. FIG.
The halftone type phase shift mask is obtained by patterning the phase shift film 2 and includes a phase shifter portion 2a for forming a pattern portion on the substrate 1, and a substrate exposed portion 1a having no phase shifter. Here, the light transmitted through the phase shifter 2a is phase-shifted with respect to the light transmitted through the substrate exposed portion 1a, and the transmittance of the phase shifter 2a is set to a light intensity that is not sensitive to the resist on the substrate to be transferred. Is set. Therefore, it has a light shielding function of substantially blocking exposure light.

As the halftone type phase shift mask, there is a single layer type halftone type phase shift mask which has a simple structure and is easy to manufacture. The single-layer halftone phase shift mask is disclosed in Japanese Patent Application Laid-Open No. H7-140635.
A device having a phase shifter made of a MoSi-based material such as MoSiO and MoSiON described in Japanese Patent Application Laid-Open No. H11-15064 has been proposed.

What is important in such a phase shift mask and a phase shift mask blank is control of optical characteristics such as transmittance, reflectance and refractive index at the exposure wavelength to be used. Significantly influenced by composition.

In this case, the phase shift mask blank and the phase shift mask having a molybdenum silicide (MoSi) phase shifter used for the phase shift mask are usually produced by a reactive sputtering method. As a reactive gas used during the production, an oxygen gas or a nitrogen monoxide gas is usually used as an oxygen source. When such a gas is used to form MoSiO or MoSiON as a MoSi-based phase shift film, the transmittance becomes higher. There is a problem that optical characteristics such as reflectance, refractive index, and the like are likely to be non-uniform in the substrate surface. This phenomenon is due to the high reactivity of oxidizing gas such as oxygen gas and nitric oxide gas, so the reaction amount is large near the gas supply port, and the amount of gas flowing substantially decreases as the distance from the gas supply port increases Arises. In addition, since the reactivity is high, the optical characteristics are rather sensitive to fluctuations in the gas flow rate, which is not preferable for stable mass production.

The present invention has been made to solve the above problems, and has high uniformity of optical characteristics in a substrate surface.
It is another object of the present invention to provide a high-quality phase shift mask blank, a phase shift mask, and a method of manufacturing a phase shift mask blank and a phase shift mask that can be easily controlled and stably manufactured even when a phase shift film is formed. .

[0012]

The inventor of the present invention has made intensive studies to solve the above-mentioned problems, and as a result, has found that a phase shift mask blank having at least one phase shift film formed on a substrate transparent to an exposure wavelength. In, using a target of molybdenum silicide, by performing sputtering using a sputtering gas containing carbon dioxide as an oxygen source gas and optionally a nitrogen gas as a nitrogen source gas,
High uniformity of the optical characteristics in the substrate plane, easy to control even when forming the phase shift film, and stably mass-produced, having a phase shift film formed of molybdenum silicide oxycarbide or molybdenum silicide oxynitride carbide The inventors have found that a high quality phase shift mask blank and phase shift mask can be obtained, and have accomplished the present invention.

That is, the present invention provides the following phase shift mask blank, phase shift mask, and a method of manufacturing the phase shift mask blank and phase shift mask.
Claim 1: A phase shift mask blank comprising at least one phase shift film provided on a transparent substrate, wherein the phase shift film is formed of molybdenum silicide oxycarbide or molybdenum silicide oxynitride carbide. . Claim 2: A phase shift mask blank comprising at least one phase shift film provided on a transparent substrate, wherein the phase shift film is formed of molybdenum silicide oxycarbide or molybdenum silicide oxynitride carbide, and chromium is formed on the phase shift film. A phase shift mask blank comprising a light-shielding film or a chromium-based antireflection film, or a multilayer film in which at least one chromium-based light-shielding film and one or more chromium-based antireflection films are stacked. In a preferred embodiment, the chromium-based light-shielding film or the chromium-based antireflection film is made of chromium oxycarbide or chromium oxynitride carbide. In a preferred embodiment, the phase shift film converts the phase of the transmitted exposure light by 180 ± 5 degrees and has a transmittance of 3 to 40%. . [5] A phase shift mask, wherein the phase shift film of the phase shift mask blank according to any one of [1] to [4] is patterned. In a sixth aspect of the present invention, there is provided a method for manufacturing a phase shift mask blank comprising at least one phase shift film provided on a transparent substrate, wherein the phase shift film uses a molybdenum silicide target and uses a sputtering gas containing carbon dioxide as an oxygen source gas. A method for manufacturing a phase shift mask blank, which is formed by performing sputtering. Claim 7: In a method of manufacturing a phase shift mask blank comprising at least one layer of a phase shift film provided on a transparent substrate, using a target of molybdenum silicide for the phase shift film, carbon dioxide as an oxygen source gas and nitrogen gas as a nitrogen source gas. A method for manufacturing a phase shift mask blank, characterized in that the phase shift mask blank is formed by sputtering using a sputtering gas containing: Claim 8: After forming the phase shift film by the method of claim 6 or 7, chromium is formed by sputtering using chromium alone or a target obtained by adding one or more of oxygen, nitrogen and carbon to chromium. A method for manufacturing a phase shift mask blank, comprising forming a system light-shielding film, a chromium system antireflection film, or a multilayer film in which at least one of them is laminated. In a preferred embodiment, the phase shift film converts the phase of the transmitted exposure light by 180 ± 5 degrees and has a transmittance of 3 to 40%. . Claim 10: After forming a resist pattern by a photolithography method on the phase shift film of the phase shift mask blank obtained by the method of claim 6 or 7,
A method for manufacturing a phase shift mask, comprising removing an uncovered portion of the phase shift film by a resist film by an etching method, and then removing the resist film. Claim 11: The phase shift of the phase shift mask blank obtained by the method according to claim 8 by removing a portion necessary for exposure of the chrome-based light-shielding film or the chrome-based antireflection film or the multilayer film by etching. After exposing the film on the surface, forming a resist pattern on the phase shift film by photolithography, removing the resist film non-coated portion of the phase shift film by etching, and then removing the resist film. A method for manufacturing a phase shift mask.

In this case, according to the present invention, when a molybdenum silicide oxide film is formed by a reactive sputtering method,
By using carbon dioxide gas, which has lower reactivity than oxygen and nitric oxide gas, as the oxidizing gas, the gas can be uniformly circulated over a wide area because of low reactivity, and the MoSi-based film is formed. The optical characteristics of the phase shift film are uniform in the plane.

In addition, since the reactivity of carbon dioxide gas is low, the margin for unexpected fluctuations of various parameters of the film forming process is rather increased, and the MoSi-based phase shift film can be stably formed with good controllability. Can be done.

Further, the phase shift film is formed of molybdenum silicide oxycarbide or molybdenum silicide oxynitride carbide, and a chromium-based light-shielding film or a chromium-based antireflection film, or at least one layer of each of these is laminated on the phase shift film. By forming a multi-layered film, these can be combined to perform more precise patterning, and sufficiently cope with further miniaturization and high integration of a semiconductor integrated circuit.

Hereinafter, the present invention will be described in more detail. As shown in FIG. 1, a phase shift mask blank according to the present invention includes a substrate 1 made of quartz, CaF ₂ or the like, through which exposure light is transmitted.
On top, molybdenum silicide oxycarbide (MoSiO
C) or molybdenum silicide oxynitride carbide (MoS
It is formed by forming a phase shift film 2 made of iONC). The phase shift mask of the present invention is formed by patterning a phase shift film of a phase shift mask blank, and as shown in FIG. 2, a first light transmitting portion 1a (substrate) is formed between the patterned phase shifter portions. The exposed phase shifter 2 is the second light transmitting portion 2a.

The phase shift mask blank of the present invention is formed on a transparent substrate by a reactive sputtering method using a sputtering gas containing carbon dioxide as an oxygen source gas, and has a transmittance of several percent to several tens of exposure light. % (Especially preferably 3 to 40%), and the phase of the light transmitted through the phase shifter portion is 180 degrees ± with respect to the light transmitted only through the transparent substrate.
At least one phase shift film made of MoSi-based molybdenum silicide oxycarbide (MoSiOC) or molybdenum silicide oxynitride carbide (MoSiONC) having a phase difference of 5 degrees is provided.

As a method of forming the phase shift film of the present invention, a reactive sputtering method is preferable. In this case, molybdenum silicide is used as a sputtering target. In order to keep the composition of the film constant, molybdenum silicide added with any of oxygen, nitrogen, and carbon, or a combination thereof may be used.

In the present invention, the sputtering method comprises:
A device using a DC power source or a device using a high-frequency power source may be used, and a magnetron sputtering method or a conventional method may be used. Note that the film forming apparatus may be a passing type or a single wafer type.

The composition of the sputtering gas is argon,
It consists of an inert gas such as xenon and carbon dioxide gas,
In addition to these, nitrogen gas, oxygen gas, various nitric oxide gases,
The film is formed by appropriately adding a carbon oxide gas or the like so that the phase shift film to be formed has a desired composition.

In this case, when it is desired to increase the transmittance of the formed phase shift film, a method of increasing the amount of a gas containing oxygen or nitrogen to be added to the sputtering gas so that a large amount of oxygen and nitrogen is taken into the film. Alternatively, it can be prepared by a method using molybdenum silicide to which a large amount of oxygen or nitrogen is added in advance to a sputtering target.

More specifically, when forming MoSiOC, molybdenum silicide is used as a target.
It is preferable to perform reactive sputtering with a sputtering gas containing an argon gas and a carbon dioxide gas as the sputtering gas. When forming a MoSiONC film,
It is preferable to use molybdenum silicide as a target and perform reactive sputtering with a sputtering gas containing an argon gas, a carbon dioxide gas, and a nitrogen gas.

The composition of the MoSiOC film thus formed is Mo: 5 to 25 atomic%, Si: 10 to 35 atomic%, O: 30 to 60 atomic%, and C: 3 to 20 atomic%. Is preferred. The composition of the molybdenum silicide oxynitride carbide (MoSiONC) film is Mo: 5 to 25 atomic%, Si: 10 to 35 atomic%, O: 30 to 60 atomic%,
It is preferable that N: 5 to 30 atomic% and C: 3 to 20 atomic%.

The phase shift mask blank of the present invention uses a carbon dioxide gas as an oxygen source gas, and when the reflectance at a wavelength of, for example, 450 nm is measured, the standard deviation of the reflectance in the substrate surface is 0.5. % Or less, preferably 0.1% or less, and has uniform optical characteristics.

In the phase shift mask blank of the present invention, the phase shift film may be formed in two or more layers.

As shown in FIG. 3, a Cr-based light-shielding film 3 is provided on a phase shift film 2 made of a molybdenum silicide oxycarbide film or a molybdenum silicide oxynitride carbide film, or as shown in FIG. In addition, a Cr-based antireflection film 4 for reducing reflection from the Cr-based light-shielding film 3 may be formed on the Cr-based light-shielding film 3. Further, as shown in FIG. 5, a phase shift film 2, a first Cr-based antireflection film 4, a Cr-based light-shielding film 3, and a second Cr-based antireflection film 4 'are formed in this order from the substrate 1. Can also.

In this case, it is preferable to use chromium oxycarbide (CrOC), chromium oxynitride carbide (CrONC), or a laminate thereof as the Cr-based light-shielding film or Cr-based antireflection film.

Such a Cr-based light-shielding film or Cr-based antireflection film is formed by using a target obtained by adding any one of oxygen, nitrogen, and carbon to chromium alone or a combination thereof, such as argon or krypton. A film can be formed by reactive sputtering using a sputtering gas obtained by adding carbon dioxide gas as a carbon source to an inert gas.

Specifically, when a CrONC film is formed, a gas containing carbon such as CH ₄ , CO ₂ and CO and a gas containing nitrogen such as NO, NO ₂ and N ₂ are used as sputtering gases. , CO ₂ , NO, O _{2 and} other gases containing oxygen
It is also possible to introduce more than one species, or to use a gas in which an inert gas such as Ar, Ne, or Kr is mixed with these. In particular,
It is preferable to use a CO ₂ gas as a carbon source gas and an oxygen source gas from the viewpoint of uniformity within the substrate surface and controllability during production. As an introduction method, various sputtering gases may be separately introduced into the chamber, or some gases may be introduced together or all gases may be mixed and introduced.

In the CrOC film, Cr is 20 to 95 atomic%, particularly 30 to 85 atomic%, C is 1 to 30 atomic%, particularly 5 to 20 atomic%, O is 1 to 60 atomic%, particularly 5 to 60 atomic%. 50
Atomic%, and the CrONC film is
Cr is 20 to 95 at%, especially 30 to 80 at%, C is 1 to 20 at%, especially 2 to 15 at%, O is 1 to 60 at%, especially 5 to 50 at%, and N is 1 to 30 at%. Atomic%, particularly preferably 3 to 20 atomic%.

The phase shift mask of the present invention is obtained by patterning the phase shift film of the phase shift mask blank obtained as described above.

Specifically, in the case of manufacturing the phase shift mask as shown in FIG. 2, as shown in FIG. 6A, the molybdenum silicide oxycarbide layer ( Or a molybdenum silicide oxynitride carbonized layer) 12, a resist film 13 is formed, and FIG.
As shown in FIG. 6B, the resist film 13 is patterned by a lithography method, and further, as shown in FIG. 6C, the molybdenum silicide oxycarbide layer (or molybdenum silicide oxynitride carbon layer) 12 is etched. After that, as shown in FIG. 6D, a method of removing the resist film 13 can be adopted. In this case, application, patterning (exposure, development), etching, and removal of the resist film can be performed by a known method.

When a Cr-based light-shielding film and / or a Cr-based antireflection film (Cr-based film) are formed on the MoSi-based phase shift film, a light-shielding film and / or an antireflection film in a region required for exposure are provided. Is removed by etching to expose the phase shift film on the surface, and then the phase shift film is patterned in the same manner as described above, so that the Cr-based film 3 remains on the outer peripheral side of the substrate as shown in FIG. Can be obtained. In addition, a resist is applied on the Cr-based film, patterning is performed, the Cr-based film and the phase shift film are patterned by etching, and only the Cr-based film in a region necessary for exposure is removed by selective etching. The phase shift mask can be obtained by exposing the phase shift pattern to the surface.

[0035]

EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 A molybdenum silicide oxycarbide film (MoSiOC film) was formed on a quartz substrate using a DC sputtering apparatus shown in FIG. In FIG. 8, reference numeral 20 denotes a DC sputtering main body, reference numeral 21 denotes a quartz substrate, reference numeral 22 denotes a target. Molybdenum silicide is used as the target, and argon gas and carbon dioxide gas are used as sputtering gases at a flow ratio of about 7: 8. Using a mixed gas, this mixed gas was introduced from the side wall as shown in FIG. 8, and reactive sputtering was performed. The gas pressure during sputtering was set to 0.3 Pa.

As the optical characteristics of the sample thus manufactured, the reflectance at a wavelength of 450 nm was measured by NANOME.
The average value in the substrate surface was 9.4% and the standard deviation was 0.01% when measured by TRINOS NANOSPEC. X-ray photoelectron spectroscopy (XP)
As a result of analysis by S), molybdenum was contained at 11.4 at%, silicon was at 25.3 at%, oxygen was at 51.6 at%, and carbon was at 11.6 at%. The results are summarized in Table 1.

Example 2 The same sputtering apparatus as in Example 1 was used, except that a mixed gas of argon gas, carbon dioxide gas and nitrogen gas at a flow ratio of 5: 3: 3 was used as a sputtering gas. A molybdenum silicide oxynitride carbide film (MoSiONC) was formed on a quartz substrate under the same conditions as in Example 1.
Film) to a thickness of 140 nm.

The average value of the reflectance at a wavelength of 450 nm as an optical characteristic of the sample thus prepared was 7.
At 8%, the standard deviation was 0.02%. 248n
The phase difference at a wavelength of m was 182 degrees, and the transmittance was 8.3%. X-ray photoelectron spectroscopy (XP)
As a result of analysis by S), it was found that 14.0 atomic% of molybdenum, 23.0 atomic% of silicon, 46.0 atomic% of oxygen, 9.0 atomic% of nitrogen, and 8.0 atomic% of carbon were contained. . The results are summarized in Table 1.

[Embodiment 3] On the phase shift film obtained in Embodiment 2, Cr was deposited by using the same sputtering apparatus as in Embodiment 1.
Was used as a target, and a CrOCN film having a thickness of 100 nm was formed using argon gas, carbon dioxide gas, and nitrogen gas as a sputtering gas at a flow ratio of 7: 4: 3.

The reflectance of the obtained CrOCN film at 450 nm was 30%, and the in-plane variation D was 0.019%. The formula for calculating the variation is as follows. In the equation, max is the maximum value of the reflectivity in the plane, and min is the minimum value of the reflectivity in the plane. D = (max-min) / (max + min)

The composition of the CrOCN film was such that chromium was 51 at%, carbon was 6 at%, oxygen was 20 at%, and nitrogen was 23 at%.

Comparative Example 1 A MoSiO film was formed in the same manner as in Example 1 except that oxygen gas was used instead of carbon dioxide gas, and the reflectance at a wavelength of 450 nm was similarly evaluated. The average value in the substrate surface was 27.0%, and the standard deviation was 0.95%. The film composition of this sample was evaluated in the same manner. As a result, it was found that molybdenum was contained at 25.2 atomic%, silicon was at 38.0 atomic%, and oxygen was at 36.8 atomic%, and carbon was below the quantification limit. The results are summarized in Table 1.

[0044]

[Table 1]

From the results in Table 1, it is found that Examples 1 and 2 and Comparative Example 1
When carbon dioxide gas is used as the oxygen source gas, the standard deviation of the in-plane reflectivity of the molybdenum silicide oxycarbide film and the molybdenum silicide oxynitride carbon film is improved by almost two orders of magnitude. I understand. In addition, when carbon dioxide gas is used as the oxygen source gas, the reflectance is reduced. This is because the oxygen is efficiently taken into the film to increase the transmittance, and as a result, the reflectance is reduced. It is.

With respect to the film composition, since molybdenum, silicon, oxygen,
In addition to nitrogen, carbon contains more than 10 atomic%, and molybdenum silicide oxycarbide or molybdenum silicide oxynitride carbide is formed.

Further, with respect to the stability of the film formation, the use of carbon dioxide gas increases the margin for fluctuations of various parameters in the film formation process as compared with the case where oxygen gas is used, and achieves good reproducibility. It was confirmed that the film could be formed.

[0048]

As described above, according to the present invention,
When a MoSi-based phase shift film is formed by a reactive sputtering method, by using a gas containing carbon dioxide as a sputtering gas, a phase shift film made of molybdenum silicide oxycarbide or molybdenum silicide oxynitride carbide is provided. A high-quality phase shift mask blank and phase shift mask having high uniformity and good controllability during manufacturing can be obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view of a phase shift mask blank according to one embodiment of the present invention.

FIG. 2 is a sectional view of the phase shift mask.

FIG. 3 is a cross-sectional view of a phase shift mask blank provided with a Cr-based light shielding film according to one embodiment of the present invention.

FIG. 4 shows a Cr-based light-shielding film and Cr according to an embodiment of the present invention.
FIG. 3 is a cross-sectional view of a phase shift mask blank provided with a system anti-reflection film.

FIG. 5 is a sectional view of another phase shift mask blank.

6A and 6B are explanatory diagrams showing a method of manufacturing a phase shift mask, wherein FIG. 6A shows a state in which a resist film is formed, FIG. 6B shows a state in which the resist film is patterned, and FIG. (D) is a schematic sectional view in a state where the resist film is removed.

FIG. 7 is a sectional view showing another embodiment of the phase shift mask.

FIG. 8 is a schematic diagram of a DC sputtering apparatus used in an example.

9A and 9B are diagrams for explaining the principle of a halftone type phase shift mask, and FIG. 9B is a partially enlarged view of a portion X in FIG. 9A.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 11 21 Substrate 2 12 Molybdenum silicide oxycarbide film (or oxynitride carbon film) 3 Chromium-based light-shielding film 4 4 'Chrome-based antireflection film 1a Substrate exposed portion 2a Phase shifter portion 13 Resist film 22 Target

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tamotsu Maruyama 28-1 Nishifukushima, Nishifukushima, Nakakushijo-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd.Precision Functional Materials Research Laboratories (72) Inventor Satoshi Okazaki Nakatsuku-gun, Niigata 28-1 Nishifukushima, Nishifukushima, Fukushima-mura Shin-Etsu Chemical Co., Ltd. Precision Functional Materials Laboratory F-term (reference) 2H095 BB03 BB25 BC05 BC14

Claims (11)

[Claims] 1. A phase shift mask blank comprising at least one phase shift film provided on a transparent substrate, wherein the phase shift film is formed of molybdenum silicide oxycarbide or molybdenum silicide oxynitride carbide. blank. 2. A phase shift mask blank comprising at least one phase shift film provided on a transparent substrate, wherein said phase shift film is formed of molybdenum silicide oxycarbide or molybdenum silicide oxynitride carbide, and said phase shift film is formed on said phase shift film. A phase shift mask blank comprising a chromium-based light-shielding film or a chromium-based antireflection film, or a multilayer film in which at least one chromium-based light-shielding film and at least one chromium-based antireflection film are laminated. 3. The phase shift mask blank according to claim 2, wherein said chromium-based light-shielding film or chromium-based antireflection film is made of chromium oxycarbide or chromium oxynitride carbide. 4. The phase shift mask according to claim 1, wherein the phase shift film converts the phase of the transmitted exposure light by 180 ± 5 degrees and has a transmittance of 3 to 40%. blank. 5. A phase shift mask, wherein the phase shift film of the phase shift mask blank according to claim 1 is formed by patterning. 6. A method of manufacturing a phase shift mask blank comprising at least one phase shift film provided on a transparent substrate, wherein a molybdenum silicide target is used for the phase shift film, and a sputtering gas containing carbon dioxide is used as an oxygen source gas. A method for manufacturing a phase shift mask blank, characterized by being formed by sputtering. 7. A method for manufacturing a phase shift mask blank comprising at least one phase shift film provided on a transparent substrate, wherein the phase shift film uses a molybdenum silicide target, and uses carbon dioxide as an oxygen source gas and nitrogen as a nitrogen source gas. A method for producing a phase shift mask blank, characterized in that the phase shift mask blank is formed by sputtering using a sputtering gas containing a gas. 8. After forming a phase shift film by the method according to claim 6, the chromium alone or chromium is added with oxygen, nitrogen,
A chromium-based light-shielding film or a chromium-based antireflection film, or a multilayer film obtained by laminating at least one of these, is formed by a sputtering method using a target to which one or more kinds of carbon are added. A method for manufacturing a phase shift mask blank. 9. The production of a phase shift mask blank according to claim 6, wherein the phase shift film converts the phase of the transmitted exposure light by 180 ± 5 degrees and has a transmittance of 3 to 40%. Method. 10. A resist pattern is formed on a phase shift film of a phase shift mask blank obtained by the method according to claim 6 by a photolithography method, and then the resist film of the phase shift film is removed by an etching method. A method for manufacturing a phase shift mask, comprising removing a covering portion and then removing a resist film. 11. A phase shift mask blank obtained by the method according to claim 8, wherein a portion necessary for exposure of the chrome-based light-shielding film, the chrome-based antireflection film, or the multilayer film is removed by etching. After exposing the shift film on the surface, forming a resist pattern on the phase shift film by photolithography, removing the resist film non-coated portion of the phase shift film by etching, and then removing the resist film. A method for manufacturing a phase shift mask, characterized in that: