1. A photomask blank having a phase shift film on a transparent substrate,

the photomask blank is a master for forming a photomask having a phase shift film pattern on the transparent substrate, the phase shift film pattern being obtained by wet etching the phase shift film,

the phase shift film is composed of a single layer or a plurality of layers, and includes a MoZrSi-based material layer formed of a material containing molybdenum (Mo), zirconium (Zr), silicon (Si), and nitrogen in an amount of 50% to 100% of the entire thickness of the phase shift film,

the atomic ratio of molybdenum to zirconium in the MoZrSi material layer is Mo: zr is 1.5:1 to 1:4, and the content ratio of silicon to the total of molybdenum, zirconium and silicon is 70 to 88 atomic%.

2. The photomask blank of claim 1, wherein,

the phase shift film has the following optical properties: the transmittance of the exposure light with respect to the representative wavelength is 20% or more and 80% or less, and the phase difference is 160 ° or more and 200 ° or less.

3. The photomask blank of claim 1 or 2, wherein,

the phase shift film is a laminated film including a lower layer on the transparent substrate side and an upper layer laminated on the lower layer, and the lower layer is the MoZrSi-based material layer.

4. The photomask blank of claim 3, wherein,

the upper layer is formed of a material having a refractive index lower than that of the lower layer and a higher extinction coefficient than that of the lower layer at a representative wavelength of exposure light.

5. The photomask blank of claim 4, wherein,

the refractive index, extinction coefficient, and film thickness of each of the upper layer and the lower layer are set so that the back surface reflectance of the phase shift film with respect to a representative wavelength of exposure light is 15% or less.

6. The photomask blank of claim 1 or 2, wherein,

the phase shift film is provided with an etching mask film having a different etching selectivity to the phase shift film.

7. A method of manufacturing a photomask, the method comprising:

a step of preparing a photomask blank according to any one of claims 1 to 5; and

and a step of forming a resist film on the phase shift film, and wet-etching the phase shift film using a resist film pattern formed of the resist film as a mask to form a phase shift film pattern on the transparent substrate.

8. A method of manufacturing a photomask, the method comprising:

preparing the photomask blank according to claim 6;

forming a resist film on the etching mask film, and performing wet etching on the etching mask film using a resist film pattern formed of the resist film as a mask to form an etching mask film pattern on the phase shift film; and

and a step of forming a phase shift film pattern on the transparent substrate by wet etching the phase shift film using the etching mask film pattern as a mask.

9. A method of manufacturing a display device, the method comprising:

an exposure step of placing the photomask obtained by the method for manufacturing a photomask according to claim 7 or 8 on a mask stage of an exposure apparatus, and exposing and transferring a transfer pattern including the phase shift film pattern formed on the photomask to a resist formed on a substrate of a display device.

Background

In recent years, not only large screens and wide viewing angles but also high definition and high speed Display have been rapidly performed on Display devices such as FPDs (Flat Panel displays) represented by LCDs (Liquid Crystal displays). In order to achieve high definition and high speed display, it is one of the necessary elements to fabricate electronic circuit patterns such as fine and highly dimensionally accurate elements and wirings. Photolithography is often used for patterning electronic circuits for display devices. Therefore, a photomask such as a phase shift mask or a binary mask for manufacturing a display device having a fine and highly precise pattern formed thereon is required.

For example, patent document 1 discloses a phase reversal mask blank having a phase reversal film on a transparent substrate. In the mask blank, the phase reversal film is composed of a multilayer film with more than 2 layers formed by a metal silicide compound containing at least 1 light element substance of oxygen (O), nitrogen (N) and carbon (C), the phase reversal film has a reflectivity of less than 35% and a transmissivity of 1% -40% to exposure light with composite wavelength of i line (365nm), h line (405nm) and g line (436nm), and a gradient of a pattern section is formed rapidly when forming a pattern, and the metal silicide compound is formed by injecting a reactive gas containing the light element substance and an inactive gas with a ratio of 0.5: 9.5-4: 6.

As the metal silicide compound, a material is described which is formed by containing silicon (Si) In at least one or more metal substances of aluminum (Al), cobalt (Co), tungsten (W), molybdenum (Mo), vanadium (V), palladium (Pd), titanium (Ti), platinum (Pt), manganese (Mn), iron (Fe), nickel (Ni), cadmium (Cd), zirconium (Zr), magnesium (Mg), lithium (Li), selenium (Se), copper (Cu), yttrium (Y), sulfur (S), indium (In), tin (Sn), boron (B), beryllium (Be), sodium (Na), tantalum (Ta), hafnium (Hf), and niobium (Nb), or which is formed by further containing one or more light element substances of nitrogen (N), oxygen (O), carbon (C), boron (B), and hydrogen (H) In the metal silicide.

Documents of the prior art

Patent document

Patent document 1: korean granted patent No. 1801101 publication

Patent document 2: japanese patent No. 3988041

Disclosure of Invention

Problems to be solved by the invention

As a phase shift mask used for manufacturing a high-definition (1000ppi or more) panel in recent years, a phase shift mask having a fine phase shift film pattern with an aperture diameter of 6 μm or less and a line width of 4 μm or less is required in order to transfer a high-resolution pattern. Specifically, a phase shift mask having a fine phase shift film pattern with an aperture of 1.5 μm is required.

In order to realize pattern transfer with higher resolution, a phase shift mask blank having a phase shift film with a transmittance of 15% or more with respect to exposure light and a phase shift mask having a phase shift film pattern with a transmittance of 15% or more with respect to exposure light are required.

In order to satisfy the requirement for the transmittance of the exposure light, it is effective to increase the ratio of silicon in the atomic ratio of metal to silicon in the metal silicide compound (metal silicide-based material) constituting the phase shift film, but there are problems such as a large retardation in the wet etching rate (long wet etching time), damage to the substrate by the wet etching solution, and a decrease in the transmittance of the transparent substrate.

Patent document 2 discloses a halftone phase shift mask blank having a phase shift film formed of a metal silicide compound containing molybdenum as a 1 st metal component, 1 or more metals selected from tantalum, zirconium, chromium, and tungsten as a 2 nd metal component, and 1 or more elements selected from oxygen, nitrogen, and carbon on a transparent substrate. And discloses: from the viewpoint of chemical resistance of the phase shift film and processability in etching, the ratio of the 1 st metal component to the 2 nd metal component in the metal silicide compound is preferably the 1 st metal component: the 2 nd metal component is 100:1 to 2:1 (atomic ratio).

In the phase shift film disclosed in patent document 2, it is assumed that the phase shift film is patterned by dry etching when the phase shift mask is manufactured, and when the phase shift film is patterned by wet etching, there are problems such as a slow wet etching rate of the phase shift film, damage of the substrate by the wet etching solution, and a decrease in transmittance of the transparent substrate, as described above.

Accordingly, the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a photomask blank capable of forming a transfer pattern having a good cross-sectional shape and Line Edge Roughness (LER: Line Edge Roughness) and also having good chemical resistance by shortening a wet etching time of a phase shift film containing metal and silicon at the time of forming the transfer pattern included in a photomask and suppressing damage to a substrate, even when the transmittance of the phase shift film with respect to a representative wavelength of exposure light is high, a method for manufacturing a photomask, and a method for manufacturing a display device.

Means for solving the problems

The present inventors have conducted intensive studies on countermeasures for solving these problems. First, in order to form a phase shift film having a high transmittance at a typical wavelength of exposure light (for example, 313nm to 436nm), zirconium having a characteristic that an extinction coefficient at the typical wavelength is smaller than that of molybdenum is focused, and as a material constituting the phase shift film, a MoZrSi-based material containing molybdenum, zirconium, silicon, and nitrogen is selected.

It is known to use a MoZrSi-based material as a phase shift film in a mask blank for LSI used for manufacturing a semiconductor device or the like. However, it is known that if a MoZrSi-based material used for a mask blank for LSI is applied as it is to a phase shift mask blank for manufacturing a display device, it takes an excessive amount of time to wet-etch a phase shift film, and damage to a substrate and a decrease in transmittance of a transparent substrate cannot be sufficiently suppressed. Thus, even if the MoZrSi-based material used for the mask blank for LSI is simply applied to the phase shift mask blank for manufacturing the display device, the desired phase shift mask blank for manufacturing the display device cannot be obtained.

It is also known that the chemical resistance of the phase shift film is poor depending on the composition ratio of the MoZrSi-based material, and desired cleaning resistance cannot be obtained, and the reflectance is too high, and the transfer characteristics are degraded.

Therefore, the present inventors have further conducted extensive studies and found that it is effective to define the atomic ratio of molybdenum and zirconium and the content ratio of silicon to the total of molybdenum, zirconium and silicon as indexes in a MoZrSi-based material. That is, the present inventors have conducted intensive studies and as a result have found that: when the phase shift film is patterned by wet etching, the wet etching rate of the phase shift film is high, and when the phase shift film is patterned, the above-mentioned problems can be solved by adjusting the atomic ratio of molybdenum and zirconium and the content ratio of silicon to the total of molybdenum, zirconium and silicon in the MoZrSi-based material in order to suppress the occurrence of damage to the transparent substrate by the wet etching solution. As a result of the above intensive studies, the present invention has the following configurations.

(scheme 1) A photomask blank having a phase shift film on a transparent substrate,

the photomask blank is a master for forming a photomask having a phase shift film pattern obtained by wet etching the phase shift film on the transparent substrate,

the phase shift film is composed of a single layer or a plurality of layers, and includes a MoZrSi-based material layer made of a material containing molybdenum (Mo), zirconium (Zr), silicon (Si), and nitrogen in an amount of 50% to 100% of the entire thickness of the phase shift film,

the atomic ratio of molybdenum to zirconium in the MoZrSi-based material layer is Mo: zr is 1.5:1 to 1:4(1:0.67 to 1:4), and the content ratio of silicon to the total of molybdenum, zirconium, and silicon is 70 to 88 atomic%.

(scheme 2) the photomask blank according to scheme 1, wherein,

the phase shift film has the following optical characteristics: the transmittance of the exposure light with respect to the representative wavelength is 20% or more and 80% or less, and the phase difference is 160 ° or more and 200 ° or less.

(scheme 3) the photomask blank according to scheme 1 or 2, wherein,

the phase shift film is a laminated film including a lower layer on the transparent substrate side and an upper layer laminated on the lower layer, and the lower layer is the MoZrSi-based material layer.

(scheme 4) the photomask blank according to scheme 3, wherein,

the upper layer is formed of a material having a refractive index lower than that of the lower layer at a representative wavelength of exposure light and having an extinction coefficient higher than that of the lower layer.

(scheme 5) the photomask blank according to scheme 4, wherein,

the refractive index, extinction coefficient, and film thickness of the upper layer and the lower layer are set so that the back surface reflectance of the phase shift film with respect to a representative wavelength of exposure light is 15% or less.

(embodiment 6) the photomask blank according to any one of embodiments 1 to 5, wherein,

the phase shift film is provided with an etching mask film having a different etching selectivity to the phase shift film.

(scheme 7) a method of manufacturing a photomask, the method comprising:

preparing a photomask blank according to any one of claims 1 to 5; and

and a step of forming a resist film on the phase shift film, and wet-etching the phase shift film using a resist film pattern formed of the resist film as a mask to form a phase shift film pattern on the transparent substrate.

(scheme 8) a method of manufacturing a photomask, the method comprising:

preparing the photomask blank described in scheme 6;

forming a resist film on the etching mask film, and performing wet etching on the etching mask film using a resist film pattern formed of the resist film as a mask to form an etching mask film pattern on the phase shift film; and

and a step of forming a phase shift film pattern on the transparent substrate by wet etching the phase shift film using the etching mask film pattern as a mask.

(scheme 9) A method of manufacturing a display device, the method comprising

And an exposure step of placing the photomask obtained by the method for manufacturing a photomask according to claim 7 or 8 on a mask stage of an exposure apparatus, and exposing and transferring a transfer pattern including the phase shift film pattern formed on the photomask to a resist formed on a substrate of a display device.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the photomask blank of the present invention, even when the transmittance of the phase shift film with respect to the representative wavelength of the exposure light is high, the time required for wet etching of the phase shift film containing a metal and silicon can be shortened in forming the transfer pattern of the photomask, and a photomask blank having a transfer pattern with excellent cross-sectional shape, line edge roughness, and chemical resistance can be obtained.

In addition, according to the method for manufacturing a photomask of the present invention, a photomask is manufactured using the photomask blank described above. Therefore, even when the transmittance of the phase shift film with respect to the representative wavelength of the exposure light is high, the wet etching rate of the phase shift film is high, and the photomask having a transfer pattern (phase shift film pattern) excellent in transfer accuracy, line edge roughness, and chemical resistance can be manufactured without causing a decrease in the transmittance of the transparent substrate due to damage to the transparent substrate by the wet etching solution. The photomask can cope with the miniaturization of line, gap pattern and contact hole.

In addition, according to the method for manufacturing a display device of the present invention, a display device is manufactured using the photomask obtained by the method for manufacturing a photomask described above. Therefore, a display device having fine line and space patterns and contact holes can be manufactured.

In addition, according to the method for manufacturing a display device of the present invention, a display device is manufactured using the photomask obtained by the method for manufacturing a photomask. Therefore, a display device having fine line and space patterns and contact holes can be manufactured.

Drawings

Fig. 1 is an explanatory view showing a film structure (transparent substrate/phase shift film) of a phase shift mask blank according to embodiment 1.

Fig. 2 is an explanatory diagram illustrating a film structure (transparent substrate/phase shift film/etching mask film) of the phase shift mask blank according to embodiment 2.

Fig. 3 is an explanatory diagram illustrating a manufacturing process of the phase shift mask according to embodiment 3.

Fig. 4 is an explanatory diagram illustrating a manufacturing process of the phase shift mask according to embodiment 4.

Description of the symbols

10 … phase shift mask blank

20 … transparent substrate

30 … phase shift film

30a … phase shift film pattern

40 … etching mask film

40a … 1 st etch mask film pattern

40b … 2 nd etch mask film pattern

50 … No. 1 resist film Pattern

60 … No. 2 resist film Pattern

100 … phase shift mask

Detailed Description

Embodiments 1 and 2

In embodiments 1 and 2, a phase shift mask blank (photomask blank) will be described. The phase shift mask blank according to embodiment 1 is a master for forming a phase shift mask (photomask) having a transfer pattern including a phase shift film pattern on a transparent substrate, which is obtained by wet etching a phase shift film using an etching mask film pattern having a desired pattern formed on an etching mask film as a mask. The phase shift mask blank according to embodiment 2 is a master for forming a phase shift mask having a transfer pattern including a phase shift film pattern on a transparent substrate, which is obtained by wet etching a phase shift film using a resist film pattern having a desired pattern formed on a resist film as a mask. The transfer pattern in the present specification is obtained by patterning at least 1 optical film formed on a transparent substrate. The optical film may be used as a phase shift film or an etching mask film, and may further include other films (a light-shielding film, a film for suppressing reflection, a conductive film, and the like). That is, the transfer pattern may include a patterned phase shift film, an etching mask film, or may further include another patterned film.

Fig. 1 is an explanatory diagram illustrating a film structure of a phase shift mask blank 10 according to embodiment 1.

The phase shift mask blank 10 shown in fig. 1 includes: a transparent substrate 20, a phase shift film 30 formed on the transparent substrate 20, and an etching mask film 40 formed on the phase shift film 30.

Fig. 2 is an explanatory diagram illustrating a film structure of the phase shift mask blank 10 of embodiment 2.

The phase shift mask blank 10 shown in fig. 2 includes: a transparent substrate 20, and a phase shift film 30 formed on the transparent substrate 20.

The transparent substrate 20, the phase shift film 30, and the etching mask film 40 constituting the phase shift mask blank 10 according to embodiments 1 and 2 will be described below.

The transparent substrate 20 is transparent to the exposure light. When there is no surface reflection loss, the transparent substrate 20 has a transmittance of 85% or more, preferably 90% or more, with respect to the exposure light. The transparent substrate 20 is made of a material containing silicon and oxygen, and may be made of synthetic quartz glass, aluminosilicate glass, soda-lime glass, low thermal expansion glass (SiO)₂-TiO₂Glass, etc.). In the case where the transparent substrate 20 is composed of the low thermal expansion glass, the positional change of the phase shift film pattern caused by the thermal deformation of the transparent substrate 20 can be suppressed. The transparent substrate 20 used for the display device is usually a rectangular substrate, and a substrate having a short side of 300mm or more may be used. The phase shift mask blank 10 of the present invention can provide a phase shift mask 100, which enables stable transfer of a fine (e.g., having a width and diameter of less than 2.0 μm) phase shift film pattern formed on a transparent substrate 20, even when the phase shift mask 100 has a large size in which the length of the short side of the transparent substrate 20 is 300mm or more.

The phase shift film 30 is formed of a single layer or a plurality of layers, and a portion of 50% to 100% of the entire film thickness of the phase shift film 30 is formed of a MoZrSi-based material made of a material containing molybdenum (Mo), zirconium (Zr), silicon (Si), and nitrogen. The MoZrSi-based material may further contain transition metals tantalum (Ta), tungsten (W), and titanium (Ti).

Further, as long as the transmittance and the phase difference of the phase shift film 30 with respect to the representative wavelength of the exposure light have predetermined values, a portion of 50% or less with respect to the entire film thickness of the phase shift film 30 may be formed of a material other than the MoZrSi-based material. In this case, a metal silicide-based material containing a metal and silicon which can be etched by a wet etching solution in the same manner as the MoZrSi-based material is preferable. For example, as the metal silicide-based material other than the MoZrSi-based material, a molybdenum silicide-based material (MoSi-based material), a zirconium silicide-based material (ZrSi-based material), a tantalum silicide-based material (TaSi-based material), a tungsten silicide-based material (WSi-based material), and a titanium silicide-based material (TiSi-based material) can be cited. The MoSi material, ZrSi material, TaSi material, WSi material, TiSi material may contain elements such as nitrogen, oxygen, and carbon.

In the MoZrSi-based material layer, the atomic ratio of molybdenum to zirconium is Mo: zr is 1.5:1 to 1:4, that is, Mo: zr is 1:0.67 to 1: 4. In the case where the ratio of Zr is smaller than that of Mo: in the case of a MoZrSi-based material layer having an atomic ratio of Zr in the range, the wet etching rate with respect to the wet etching solution is low, and thus damage to the transparent substrate is likely to occur. In addition, it becomes difficult to obtain a phase shift film having a high transmittance for the representative wavelength of the exposure light. In addition, when the ratio of Zr is larger than the above Mo: in the case of a MoZrSi-based material layer having an atomic ratio of Zr in the range, the phase shift film 30 having a high transmittance (for example, 20% or more and 80% or less) with respect to the representative wavelength of the exposure light is easily obtained, but the chemical resistance (cleaning resistance) is not sufficient, and is not preferable from the viewpoint of the quality of defects generated at the time of film formation. The atomic ratio of molybdenum to zirconium is preferably Mo: zr is 1:0.8 to 1:3, and more preferably Mo: zr is 1:1 to 1: 2.

In addition, the content ratio of silicon to the total of molybdenum, zirconium, and silicon (Si/[ Mo + Zr + Si ]) in the MoZrSi-based material layer is desirably set to 70 to 88 atomic% of Si/[ Mo + Zr + Si ]. When Si/[ Mo + Zr + Si ] is less than 70 atomic%, it is difficult to realize the phase shift film 30 having high transmittance (for example, 20% or more and 80% or less) with respect to the representative wavelength of the exposure light and chemical resistance. In addition, when Si/[ Mo + Zr + Si ] exceeds 88 atomic%, the wet etching rate of the wet etching solution is low, and therefore damage to the transparent substrate 20 is likely to occur, and a decrease in transmittance due to roughness of the transparent substrate 20 is likely to occur. The content ratio of silicon to the total of molybdenum, zirconium and silicon is preferably 72 to 86 atomic% of Si/[ Mo + Zr + Si ], and more preferably 75 to 85 atomic% of Si/[ Mo + Zr + Si ].

The phase shift film 30 may be formed by a sputtering method.

In the MoZrSi-based material layer of the phase shift film 30 of the present embodiment, since the atomic ratio of molybdenum to zirconium and the content ratio of silicon to the total of molybdenum, zirconium, and silicon satisfy the above ranges, film formation can be performed in a favorable degree of vacuum within 0.5Pa, the overetching time can be shortened, damage to the transparent substrate 20 can be suppressed, and a phase shift film pattern 30a having a favorable cross-sectional shape and LER and also having favorable chemical resistance can be formed.

Note that the phase shift film 30 may have a columnar structure. The columnar structure can be confirmed by cross-sectional SEM observation of the phase shift film 30. That is, the columnar structure in the present invention means a state in which the particles of the transition metal silicide compound containing molybdenum, zirconium, and silicon constituting the phase shift film 30 have a columnar particle structure extending in the film thickness direction of the phase shift film 30 (the direction in which the particles are deposited). The phase shift film 30 having such a columnar structure is preferable in that high transmittance can be easily obtained.

The phase shift film 30 may contain oxygen in addition to the above-described nitrogen for the purpose of adjusting transmittance, and may further contain other elements such as helium and carbon for the purpose of controlling the film stress reduction and the wet etching rate.

The transmittance of the phase shift film 30 with respect to the exposure light satisfies a value necessary as the phase shift film 30. The transmittance of the phase shift film 30 with respect to light of a given wavelength (representative wavelength) included in the exposure light is preferably 20% or more and 80% or less, more preferably 25% or more and 75% or less, and further preferably 30% or more and 70% or less. That is, when the exposure light is composite light including light having a wavelength range of 313nm to 436nm, the phase shift film 30 has the transmittance described above with respect to light having a representative wavelength included in the wavelength range. For example, when the exposure light is composite light including i-line, h-line, and g-line, the phase shift film 30 has the transmittance described above with respect to any one of the i-line, h-line, and g-line.

The transmittance can be measured using a phase shift amount measuring device or the like.

The phase difference of the phase shift film 30 with respect to the exposure light satisfies a value necessary as the phase shift film 30. The phase difference of the phase shift film 30 is preferably 160 ° or more and 200 ° or less, more preferably 170 ° or more and 190 ° or less, with respect to light of a representative wavelength included in the exposure light. By utilizing this property, the phase of light of a representative wavelength included in the exposure light can be changed (shifted) to 160 ° or more and 200 ° or less. Therefore, a phase difference of 160 ° or more and 200 ° or less is generated between the light having the representative wavelength transmitted through the phase shift film 30 and the light having the representative wavelength transmitted only through the transparent substrate 20. That is, when the exposure light is the composite light including the light having the wavelength range of 313nm to 436nm, the phase shift film 30 has the above-described phase difference with respect to the light having the representative wavelength included in the wavelength range. For example, when the exposure light is composite light including i-line, h-line, and g-line, the phase shift film 30 has the above-described phase difference with respect to any one of the i-line, the h-line, and the g-line.

The phase difference can be measured using a phase shift amount measuring device or the like.

The phase shift film 30 may be a laminated film including a lower layer on the transparent substrate side and an upper layer laminated on the lower layer. In the case where the phase shift film 30 is a laminated film including a lower layer and an upper layer, the lower layer is preferably the MoZrSi-based material layer in terms of suppressing the defect quality of the phase shift film 30, preventing the transparent substrate 20 from being damaged by the wet etching solution, and improving the cross-sectional shape of the pattern when the phase shift film 30 is patterned by the wet etching. The upper layer in the phase shift film 30 may be a MoZrSi-based material layer similar to the lower layer, or may be different. When the material of the upper layer is different from that of the lower layer, a metal silicide-based material that can be etched with the same wet etching solution as the MoZrSi-based material, such as a MoSi-based material, a ZrSi-based material, a TaSi-based material, a WSi-based material, and a TiSi-based material, may be used.

The material of the phase shift film 30 is selected so that the upper layer is formed of a material having a refractive index n smaller than the refractive index n of the lower layer at the representative wavelength of the exposure light (for example, 313nm to 436nm) and having an extinction coefficient k higher than the extinction coefficient k of the lower layer, thereby reducing the back surface reflectance of the phase shift film 30 on the side on which the exposure light is incident.

Specifically, the refractive index, the extinction coefficient, and the film thickness of the upper layer and the lower layer may be set so that the back surface reflectance with respect to the representative wavelength of the exposure light is 15% or less. The back surface reflectance of the phase shift film 30 with respect to the representative wavelength of the exposure light is preferably 10% or less.

The etching mask film 40 is disposed on the upper side of the phase shift film 30, and is formed of a material having etching resistance (different from the etching selectivity of the phase shift film 30) to an etching solution for etching the phase shift film 30. The etching mask film 40 may have a function of blocking the transmission of the exposure light, and may have a function of reducing the film-surface reflectance so that the film-surface reflectance of the phase shift film 30 is 15% or less in a wavelength range of 313nm to 436nm with respect to the light incident from the phase shift film 30 side. The etching mask film 40 is made of a chromium-based material containing chromium (Cr). More specifically, the chromium-based material includes: chromium (Cr), or a material containing chromium (Cr) and at least one of oxygen (O), nitrogen (N), and carbon (C). Or, there may be mentioned: a material containing chromium (Cr) and at least one of oxygen (O), nitrogen (N) and carbon (C), and further containing fluorine (F). For example, as materials constituting the etching mask film 40, there can be mentioned: cr, CrO, CrN, CrF, CrCO, CrCN, CrON, CrCON, CrCONF.

The etching mask film 40 may be formed by a sputtering method.

When the etching mask film 40 has a function of blocking the transmission of the exposure light, the optical density with respect to the exposure light is preferably 3 or more, more preferably 3.5 or more, and further preferably 4 or more in a portion where the phase shift film 30 and the etching mask film 40 are laminated.

The optical density can be measured using a spectrophotometer, an OD meter, or the like.

Depending on the function, the etching mask film 40 may be formed of a single film having a uniform composition, may be formed of a plurality of films having different compositions, or may be formed of a single film having a composition continuously changing in the thickness direction.

The phase shift mask blank 10 shown in fig. 1 includes the etching mask film 40 on the phase shift film 30, and the present invention is also applicable to a phase shift mask blank that includes the etching mask film 40 on the phase shift film 30 and a resist film on the etching mask film 40.

Next, a method for manufacturing the phase shift mask blank 10 according to embodiments 1 and 2 will be described. The phase shift mask blank 10 shown in fig. 1 can be manufactured by performing the following phase shift film forming step and etching mask film forming step. The phase shift mask blank 10 shown in fig. 2 can be manufactured by a phase shift film forming process.

Hereinafter, each step will be described in detail.

1. Phase shift film formation step

First, the transparent substrate 20 is prepared. The transparent substrate 20 may be made of synthetic quartz glass, aluminosilicate glass, soda-lime glass, or low thermal expansion glass (SiO) as long as it is transparent to exposure light₂-TiO₂Glass, etc.) and the like.

Next, the phase shift film 30 is formed on the transparent substrate 20 by a sputtering method.

The sputtering target is a MoZrSi-based target containing molybdenum (Mo), zirconium (Zr), and silicon (Si), or a MoZrSiO-based target, a MoZrSiN-based target, and a MoZrSiON-based target containing molybdenum (Mo), zirconium (Zr), silicon (Si), and oxygen (O) and/or nitrogen (N), which are main components of the material constituting the phase shift film 30, and the film formation of the phase shift film 30 is performed in a sputtering gas atmosphere, for example, a sputtering gas atmosphere containing at least one inert gas selected from the group consisting of neon, argon, krypton, and xenon, or a helium sputtering gas atmosphere containing a mixture gas of the inert gas and an active gas selected from the group consisting of oxygen, nitrogen, carbon dioxide, nitrogen monoxide, and nitrogen dioxide, and containing at least nitrogen. The phase shift film 30 may be formed using a Mo target, a Zr target, or a Si target so as to satisfy the atomic ratios and the content ratios of Mo, Zr, and Si described above, or the phase shift film 30 may be formed using a MoSi target and a ZrSi target.

The composition and thickness of the phase shift film 30 may be adjusted so that the phase shift film 30 has the above-described phase difference and transmittance. The composition of the phase shift film 30 can be controlled by the content ratio of elements constituting the sputtering target (for example, the content ratio of Mo, Zr, and Si), the composition and flow rate of the sputtering gas, and the like. The thickness of the phase shift film 30 can be controlled by sputtering power, sputtering time, and the like. The phase shift film 30 is preferably formed by using an in-line sputtering apparatus. In the case where the sputtering apparatus is an in-line type sputtering apparatus, the thickness of the phase shift film 30 can be controlled by the transport speed of the transparent substrate 20.

When the phase shift film 30 is formed of a single film, the above-described film formation process is performed only 1 time while changing the composition and flow rate of the sputtering gas together with the elapsed time of the film formation process. When the phase shift film 30 is formed of a plurality of films having different compositions, the above-described film forming process is performed a plurality of times by changing the composition and flow rate of the sputtering gas in accordance with the film forming process. The phase shift film 30 can be formed using targets having different content ratios of elements constituting the sputtering target. In the case where the film formation process is performed a plurality of times, the sputtering power applied to the sputtering target can be reduced.

Thereby, the phase shift mask blank 10 of embodiment 2 can be obtained. The following etching mask film forming step may be performed in the production of the phase shift mask blank 10 according to embodiment 1.

3. Etching mask film formation process

After the surface treatment for adjusting the surface oxidation state of the surface of the phase shift film 30, an etching mask film 40 is formed on the phase shift film 30 by a sputtering method. The etching mask film 40 is preferably formed using an in-line type sputtering apparatus. In the case where the sputtering apparatus is an in-line type sputtering apparatus, the thickness of the etching mask film 40 can be controlled by the transport speed of the transparent substrate 20.

The etching mask film 40 is formed using a sputtering target containing chromium or a chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium oxycarbonitride, etc.) in a sputtering gas atmosphere containing at least one inert gas selected from helium, neon, argon, krypton, and xenon, or a mixed gas of an inert gas containing at least one selected from helium, neon, argon, krypton, and xenon and an active gas containing at least one selected from oxygen, nitrogen, nitric oxide, nitrogen dioxide, carbon dioxide, a hydrocarbon gas, and a fluorine-based gas. As the hydrocarbon gas, for example: methane gas, butane gas, propane gas, styrene gas, etc.

In the case where the etching mask film 40 is formed of a single film having a uniform composition, the above-described film formation process is performed only 1 time without changing the composition and flow rate of the sputtering gas. In the case where the etching mask film 40 is formed of a plurality of films having different compositions, the above-described film formation process is performed a plurality of times while changing the composition and flow rate of the sputtering gas in accordance with the film formation process. In the case where the etching mask film 40 is formed of a single film whose composition continuously changes in the thickness direction, the composition and flow rate of the sputtering gas are changed together with the elapsed time of the film formation process, and the above-described film formation process is performed only 1 time.

Thereby, the phase shift mask blank 10 of embodiment 1 can be obtained.

Since the phase shift mask blank 10 shown in fig. 1 includes the etching mask film 40 on the phase shift film 30, the etching mask film forming step is performed when manufacturing the phase shift mask blank 10. In the case of manufacturing a phase shift mask blank having the etching mask film 40 on the phase shift film 30 and the resist film on the etching mask film 40, the resist film is formed on the etching mask film 40 after the etching mask film forming step. In the phase shift mask blank 10 shown in fig. 2, when a phase shift mask blank having a resist film on the phase shift film 30 is manufactured, the resist film is formed after the phase shift film forming step.

The phase shift mask blank 10 according to embodiments 1 and 2 has a good cross-sectional shape by wet etching, and can form a phase shift film pattern 30a having high transmittance in a short etching time. Accordingly, the phase shift mask blank 10 capable of manufacturing the phase shift mask 100 in which the high-definition phase shift film pattern 30a can be accurately transferred without the transmittance of the transparent substrate 20 being lowered due to the damage of the wet etching solution to the transparent substrate 20 can be obtained.

Embodiments 3 and 4

In embodiments 3 and 4, a method for manufacturing the phase shift mask 100 will be described.

Fig. 3 is an explanatory diagram illustrating a method of manufacturing the phase shift mask 100 of embodiment 3. Fig. 4 is an explanatory diagram illustrating a method of manufacturing the phase shift mask 100 of embodiment 4.

The method of manufacturing the phase shift mask 100 shown in fig. 3 is a method of manufacturing the phase shift mask 100 using the phase shift mask blank 10 shown in fig. 1, the method including: a step of forming a resist film on the etching mask film 40 of the phase shift mask blank 10; a step (1 st resist pattern forming step) of forming a resist pattern 50 by drawing and developing a desired pattern into a resist film (1 st resist pattern forming step), and wet-etching the etching mask film 40 using the resist pattern 50 as a mask to form an etching mask film pattern 40a on the phase shift film 30; and a step (phase shift film pattern forming step) of wet-etching the phase shift film 30 using the etching mask film pattern 40a as a mask to form a phase shift film pattern 30a on the transparent substrate 20. Further, the method includes a 2 nd resist film pattern forming step and a 2 nd etching mask film pattern forming step.

The method of manufacturing the phase shift mask 100 shown in fig. 4 is a method of manufacturing the phase shift mask 100 using the phase shift mask blank 10 shown in fig. 2, the method including: a step of forming a resist film on the phase shift mask blank 10; a step (phase shift film pattern forming step) of forming a resist pattern 50 by drawing and developing a desired pattern on a resist (step 1 resist pattern forming step), and wet etching the phase shift film 30 using the resist pattern 50 as a mask to form a phase shift film pattern 30a on the transparent substrate 20.

Hereinafter, each step of the manufacturing process of the phase shift mask 100 according to embodiments 3 and 4 will be described in detail.

Process for manufacturing phase shift mask 100 according to embodiment 3

1. 1 st resist film Pattern Forming Process

In the 1 st resist pattern forming step, first, a resist film is formed on the etching mask film 40 of the phase shift mask blank 10 of embodiment 1. The resist film material used is not particularly limited. For example, the material may be any material that can be exposed to laser light having any wavelength selected from the wavelength range of 350nm to 436nm, which will be described later. The resist film may be either a positive type or a negative type.

Then, a desired pattern is drawn on the resist film using a laser having an arbitrary wavelength selected from a wavelength range of 350nm to 436 nm. The pattern drawn on the resist film is the pattern formed on the phase shift film 30. Examples of the pattern drawn on the resist film include: line and space patterns, hole patterns.

Then, the resist film is developed with a given developing solution, and a 1 st resist film pattern 50 is formed on the etching mask film 40 as shown in fig. 3 (a).

2. 1 st etching mask film pattern forming process

In the 1 st etching mask film pattern forming step, first, the etching mask film 40 is etched using the 1 st resist film pattern 50 as a mask to form a 1 st etching mask film pattern 40 a. The etching mask film 40 is formed of a chromium-based material containing chromium (Cr). The etching solution for etching the etching mask film 40 is not particularly limited as long as it can selectively etch the etching mask film 40. Specifically, an etching solution containing cerium ammonium nitrate and perchloric acid may be mentioned.

Then, the 1 st resist pattern 50 is stripped as shown in fig. 3(b) by using a resist stripping solution or by ashing. In some cases, the following phase shift film pattern forming step may be performed without peeling the 1 st resist pattern 50.

3. Phase shift film pattern formation process

In the phase shift film pattern forming step 1, the phase shift film 30 is wet-etched using the 1 st etching mask film pattern 40a as a mask, thereby forming a phase shift film pattern 30a as shown in fig. 3 (c). As the phase shift film pattern 30a, there can be mentioned: line and space patterns, hole patterns. The etching solution for etching the phase shift film 30 is not particularly limited as long as it can selectively etch the phase shift film 30. For example, there may be mentioned: the etching solution comprises ammonium fluoride, phosphoric acid and hydrogen peroxide, and the etching solution comprises ammonium bifluoride and hydrogen peroxide.

In order to improve the cross-sectional shape of the phase shift film pattern 30a, it is preferable to perform wet etching for a time (over-etching time) longer than the time (appropriate etching time) until the transparent substrate 20 is exposed in the phase shift film pattern 30 a. The over-etching time is preferably a time obtained by adding 10 to 20% of the proper etching time to the proper etching time in consideration of the influence on the transparent substrate 20 and the like.

4. 2 nd resist film Pattern Forming Process

In the 2 nd resist pattern forming step, first, a resist film is formed to cover the 1 st etching mask film pattern 40 a. The resist film material used is not particularly limited. For example, the material may be any material that can be exposed to laser light having any wavelength selected from the wavelength range of 350nm to 436nm, which will be described later. The resist film may be either a positive type or a negative type.

Then, a desired pattern is drawn on the resist film using a laser having an arbitrary wavelength selected from a wavelength range of 350nm to 436 nm. The pattern drawn on the resist film is a light-shielding band pattern for shielding the outer peripheral region of the region where the pattern 30a is formed on the phase shift film, a light-shielding band pattern for shielding the central portion of the phase shift film pattern 30a, or the like. The pattern drawn on the resist film also includes a pattern of a light shielding band pattern that does not shield the central portion of the phase shift film pattern 30a from light, depending on the transmittance of the phase shift film 30 to the exposure light.

Then, the resist film is developed with a given developing solution, and as shown in fig. 3(d), a 2 nd resist film pattern 60 is formed on the 1 st etching mask film pattern 40 a.

5. 2 nd etching mask film patterning process

In the 2 nd etching mask film pattern forming step, the 1 st etching mask film pattern 40a is etched using the 2 nd resist film pattern 60 as a mask, and a 2 nd etching mask film pattern 40b is formed as shown in fig. 3 (e). The 1 st etching mask film pattern 40a is formed of a chromium-based material containing chromium (Cr). The etching solution for etching the 1 st etching mask film pattern 40a is not particularly limited as long as it can selectively etch the 1 st etching mask film pattern 40 a. For example, an etching solution containing cerium ammonium nitrate and perchloric acid may be mentioned.

Then, the 2 nd resist film pattern 60 is peeled off using a resist peeling liquid or by ashing.

Thereby, the phase shift mask 100 can be obtained. That is, the transfer pattern of the phase shift mask 100 of embodiment 3 may include the phase shift film pattern 30a and the 2 nd etching mask film pattern 40 b.

In the above description, although the case where the etching mask film 40 has the function of blocking the transmission of the exposure light has been described, in the case where the etching mask film 40 has only the function of a hard mask in etching the phase shift film 30, the phase shift mask 100 is produced by removing the 1 st etching mask film pattern after the phase shift film pattern forming step without performing the 2 nd resist pattern forming step and the 2 nd etching mask film pattern forming step in the above description. That is, the transfer pattern of the phase shift mask 100 of embodiment 3 may be formed of only the phase shift film pattern 30 a. The transfer pattern may further include other film patterns. Examples of the other film include: a film for suppressing reflection, a conductive film, and the like.

According to the method of manufacturing the phase shift mask 100 of embodiment 3, since the phase shift mask blank 10 of embodiment 1 is used, the etching time can be shortened, and the phase shift film pattern 30a having a good cross-sectional shape, line edge roughness, and chemical resistance can be formed without causing a decrease in transmittance of the transparent substrate 20 due to damage to the transparent substrate 20 by the wet etching solution. Therefore, the phase shift mask 100 capable of transferring the high-definition phase shift film pattern 30a with good accuracy can be manufactured. The phase shift mask 100 thus manufactured can cope with the miniaturization of the line, space pattern, and contact hole.

Process for manufacturing phase shift mask 100 according to embodiment 4

1. Resist film pattern formation step

In the resist pattern forming step, first, a resist film is formed on the phase shift film 30 of the phase shift mask blank 10 of embodiment 2. The resist film material used is the same as that described in embodiment 3. In order to improve the adhesion to the phase shift film 30, the phase shift film 30 may be subjected to a surface modification treatment before the resist film is formed, if necessary. After the resist film is formed in the same manner as described above, a desired pattern is drawn on the resist film using a laser beam having an arbitrary wavelength selected from the wavelength range of 350nm to 436 nm. Then, the resist film is developed with a given developing solution, and a resist film pattern 50 is formed on the phase shift film 30 as shown in fig. 4 (a).

2. Phase shift film pattern formation process

In the phase shift film pattern forming step, the phase shift film 30 is etched using the resist pattern as a mask, thereby forming a phase shift film pattern 30a as shown in fig. 4 (b). Thereby forming a transfer pattern. The etching solution and the over-etching time for etching the phase shift film pattern 30a and the phase shift film 30 are the same as those described in embodiment 3.

Then, the resist film pattern 50 is peeled off by using a resist stripping liquid or by ashing (fig. 4 (c)).

Thereby, the phase shift mask 100 can be obtained. The transfer pattern of the phase shift mask of the present embodiment may be formed of only the phase shift film pattern 30a, or may further include another film pattern. Examples of the other film include: a film for suppressing reflection, a conductive film, and the like.

According to the method of manufacturing the phase shift mask 100 of embodiment 4, since the phase shift mask blank 10 of embodiment 2 is used, the etching time can be shortened, and the phase shift film pattern 30a having a good cross-sectional shape, line edge roughness, and chemical resistance can be formed without causing a decrease in transmittance of the transparent substrate 20 due to damage to the transparent substrate 20 by the wet etching solution. Therefore, the phase shift mask 100 capable of transferring the high-definition phase shift film pattern 30a with good accuracy can be manufactured. The phase shift mask 100 thus manufactured can cope with the miniaturization of the line, space pattern, and contact hole.

Embodiment 5.

In embodiment 5, a method for manufacturing a display device will be described. The display device can be manufactured by a process (mask placing process) using the phase shift mask 100 and a process (exposure process) of exposing and transferring a transfer pattern including the phase shift film pattern 30a to a resist film on a substrate for a display device, the phase shift mask 100 being manufactured using the above-described phase shift mask blank 10 or the above-described method of manufacturing the phase shift mask 100.

Hereinafter, each step will be described in detail.

1. Placing procedure

In the placing step, the phase shift mask 100 manufactured in embodiment mode 3 or 4 is placed on a mask stage of an exposure apparatus. Here, the phase shift mask 100 is disposed so as to face a resist film formed on a substrate of a display device with a projection optical system of an exposure device interposed therebetween.

2. Pattern transfer process

In the pattern transfer step, the phase shift mask 100 is irradiated with exposure light, and a transfer pattern including the phase shift film pattern 30a is transferred to a resist film formed on a substrate for a display device. The exposure light may be a composite light including light having a plurality of wavelengths selected from a wavelength range of 365nm to 436nm, or a monochromatic light selected by removing a certain wavelength range from the wavelength range of 365nm to 436nm by an optical filter. For example, the exposure light is a composite light including at least 1 of i-line, h-line, and g-line, or an i-line monochromatic light. When the composite light is used as the exposure light, the exposure light intensity can be increased to increase the light flux, so that the manufacturing cost of the display device can be reduced.

According to the method for manufacturing a display device of embodiment 5, a high-resolution, high-definition display device having fine line and space patterns and contact holes can be manufactured.

Examples

Example 1

A. Phase shift mask blank

To manufacture the phase shift mask blank 10 of example 1, first, a synthetic quartz glass substrate of 1214 size (1220mm × 1400mm) was prepared as the transparent substrate 20.

Then, the synthetic quartz glass substrate was placed on a tray (not shown) with one main surface facing downward, and was transported into a chamber of the in-line sputtering apparatus.

In order to form the phase shift film 30 on the other main surface of the transparent substrate 20, first, argon (Ar) and nitrogen (N) were introduced into the 1 st chamber in which the sputtering gas pressure was set to 0.5Pa₂) Forming a mixed gas. Then, a composition prepared by mixing Mo, Zr and Si in an atomic ratio of Mo: zr: a MoZrSiN-based phase shift film 30 containing molybdenum, zirconium, silicon, and nitrogen and having a thickness of 143nm was formed on the main surface of the transparent substrate 20 by reactive sputtering. The atomic ratio in the above target for sputtering is an example, and can be appropriately selected according to the desired composition of the phase shift film 30.

Subsequently, the transparent substrate 20 with the phase shift film 30 is transferred into the 2 nd chamber, and argon (Ar) and nitrogen (N) are introduced into the 2 nd chamber₂) The mixed gas of (2) forms chromium nitride (CrN) (film thickness 15nm) containing chromium and nitrogen on the phase shift film 30 by reactive sputtering. Subsequently, a mixed gas of argon (Ar) and methane gas was introduced in a state where the 3 rd chamber was brought into a predetermined degree of vacuum, and chromium carbide (CrC) containing chromium and carbon was formed on CrN by reactive sputtering (film thickness 60 nm). Finally, a mixed gas of argon (Ar) and methane gas, and nitrogen (N) gas were introduced into the 4 th chamber in a state of a predetermined degree of vacuum₂) With oxygen (O)₂) The mixed gas of the gases formed chromium oxycarbonitride (CrCON) (film thickness 30nm) containing chromium, carbon, oxygen and nitrogen on CrC by reactive sputtering. As described above, the etching mask film 40 having a laminated structure of the CrN layer, the CrC layer, and the CrCON layer is formed on the phase shift film 30.

Thus, a phase shift mask blank 10 in which the phase shift film 30 and the etching mask film 40 are formed on the transparent substrate 20 is obtained.

The refractive index and extinction coefficient of the phase shift film 30 of the phase shift mask blank 10 thus obtained were measured using a phase shift film-attached substrate (dummy substrate) prepared by mounting on the same tray and having the phase shift film 30 formed on the main surface of a synthetic quartz glass substrate.

As a result, the refractive index n of the MoZrSiN based phase shift film was 2.45 (wavelength 405nm) and the extinction coefficient k was 0.11 (wavelength 405 nm).

The transmittance and the phase difference were measured on the surface of the phase shift film 30 of the obtained phase shift mask blank 10 using MPM-100 manufactured by Lasertec corporation. The transmittance and the phase difference of the phase shift film 30 were measured by using a substrate with a phase shift film (dummy substrate) prepared by mounting on the same tray and having the phase shift film 30 formed on the main surface of the synthetic quartz glass substrate, as described above. Before the etching mask film 40 was formed, the substrate with the phase shift film (dummy substrate) was taken out from the chamber, and the transmittance and the phase difference of the phase shift film 30 were measured. As a result, the transmittance was 50% (wavelength: 405nm), the retardation was 180 ° (wavelength: 405nm), the back surface reflectance was 15.4% (wavelength: 405nm), and the surface reflectance was 21.3% (wavelength 405 nm).

Further, the composition of the phase shift film 30 of the obtained phase shift mask blank 10 in the depth direction was analyzed by X-ray photoelectron spectroscopy (XPS).

As a result of analyzing the composition of the phase shift mask blank 10 in the depth direction by XPS, the content of each constituent element in the phase shift film 30 in the depth direction was substantially constant, with 3 atomic% of Mo, 5 atomic% of Zr, 42 atomic% of Si, 47 atomic% of N, and 3 atomic% of O, except for the composition gradient region of the interface between the transparent substrate 20 and the phase shift film 30 and the composition gradient region of the interface between the phase shift film 30 and the etching mask film 40. In addition, the atomic ratio of molybdenum to zirconium is 1:1, where Mo: zr is in the range of 1:0.67 to 1: 4. The content ratio of silicon to the total of molybdenum, zirconium and silicon is 84 atomic%, and is within the range of [ Si/(Mo + Zr + Si) ] 70 to 88 atomic%. It is considered that the reason why the oxygen is contained in the phase shift film 30 is that a very small amount of oxygen is present in the chamber during film formation.

B. Phase shift mask and method of manufacturing the same

To manufacture the phase shift mask 100 using the phase shift mask blank 10 manufactured as described above, first, a photoresist film is coated on the etching mask film 40 of the phase shift mask blank 10 using a resist coating apparatus.

Then, a photoresist film having a film thickness of 520nm was formed through the heating/cooling process.

Then, a photoresist film was drawn using a laser drawing device, and a resist film pattern having a hole pattern with a hole diameter of 1.5 μm was formed on the etching mask film through a developing/rinsing process.

Then, the etching mask film was wet-etched using a chromium etching solution containing ammonium cerium nitrate and perchloric acid with the resist film pattern as a mask, to form a 1 st etching mask film pattern 40 a.

Then, the phase shift film 30 is wet-etched using a molybdenum silicide etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water using the 1 st etching mask film pattern 40a as a mask, thereby forming a phase shift film pattern 30 a. The wet etching was performed with an over-etching time of 10% in order to make the cross-sectional shape vertical and to form a desired fine pattern.

Then, the resist pattern is peeled off.

Then, a photoresist film is coated using a resist coating apparatus in such a manner as to cover the 1 st etching mask film pattern 40 a.

Then, a photoresist film having a film thickness of 520nm was formed through the heating/cooling process.

Then, a photoresist film is drawn using a laser drawing device, and a 2 nd resist film pattern 60 for forming a light shielding tape is formed on the 1 st etching mask film pattern 40a through a developing/rinsing process.

Then, the 1 st etching mask film pattern 40a formed in the transfer pattern forming region was wet-etched using a chromium etching solution containing cerium ammonium nitrate and perchloric acid with the 2 nd resist film pattern 60 as a mask.

Then, the 2 nd resist film pattern 60 is peeled off.

Thus, a phase shift mask 100 was obtained in which the transfer pattern formation region on the transparent substrate 20 had a phase shift film pattern 30a with an aperture diameter of 1.5 μm, and a light-shielding tape having a laminated structure of the phase shift film pattern 30a and the etching mask film pattern 40b was formed on the transparent substrate 20.

The cross section of the obtained phase shift mask was observed with a scanning electron microscope. In the cross-sectional view, the angle of the edge of the phase shift film pattern 30a of the phase shift mask with the main surface of the transparent substrate 20 was 76 °, and the phase shift film pattern 30a had a nearly vertical cross-sectional shape. As a result of observing the LER of the phase shift film pattern 30a by observing the phase shift film pattern 30a from above, the edge of the phase shift film pattern (hole pattern) 30a is smooth, substantially linear, and good. That is, no distinct uneven shape was observed at the edge of the phase shift film pattern 30a in a plan view. The phase shift film pattern 30a formed in the phase shift mask of example 1 has a cross-sectional shape capable of sufficiently exerting a phase shift effect. The surface of the transparent substrate 20 exposed after the phase shift film 30 is removed is smooth, and the decrease in transmittance due to the surface roughness of the transparent substrate 20 can be ignored. Further, as a result of observing the obtained phase shift mask 100 by electron beam diffraction, it was confirmed that the structure was amorphous. In addition, no permeation of an etching solution or the like is observed at any of the interface between the phase shift film pattern 30a and the etching mask film pattern 40b and the interface between the phase shift film pattern 30a and the transparent substrate 20, and the chemical resistance is also good. Therefore, a phase shift mask having an excellent phase shift effect is obtained for exposure light including light in a wavelength range of 313nm to 500nm, more specifically, for exposure light including at least 1 of i-line, h-line, and g-line.

Therefore, when the phase shift mask 100 of example 1 is set on the mask stage of the exposure apparatus and is exposed and transferred to the resist film on the substrate for display device, a fine pattern smaller than 2.0 μm can be transferred with high precision. Further, by forming the phase shift film 30 (phase shift film pattern 30a) in a state in which the degree of vacuum is as low as 0.5Pa or less to form a dense film, it can be expected that the light resistance under exposure light is also good.

Examples 2 to 4.

A. Phase shift mask blank

In examples 2 to 4, except for the phase shift film 30, the phase shift mask blank 10 and the phase shift mask 100 were manufactured by the same structure and method as in example 1. In examples 2 to 4, the atomic ratios of Mo, Zr, and Si of the sputtering target in the deposition of the phase-shift film 30 in example 1 were appropriately adjusted. The film thickness of the phase shift film 30 is appropriately adjusted so that the transmittance at a wavelength of 405nm is 20% or more and 80% or less and the retardation is in the range of 160 ° to 200 °.

As a result of composition analysis of the MoZrSiN-based phase shift film 30 obtained in the same manner as in example 1, the atomic ratio of Mo to Zr is as follows.

Example 2 Mo: 1.5:1(1:0.67) Zr,

Example 3 Mo: zr 1:2,

Example 4 Mo: zr 1:4,

Thus, in all of examples 2 to 4, Mo: zr is in the range of 1:0.67 to 1: 4. The content ratio of silicon to the total of molybdenum, zirconium and silicon is in the range of 70 to 88 atomic% in each of examples 2 to 4 [ Si/(Mo + Zr + Si) ].

B. Phase shift mask and method of manufacturing the same

A phase shift mask 100 was fabricated in the same manner as in example 1, and the cross-sectional shape of the phase shift film pattern 30a was confirmed, and the surface state of the transparent substrate 20 exposed after the phase shift film 30 was removed was also confirmed. As a result, in examples 2 to 4, the angles formed by the edges of the phase shift film patterns 30a of the phase shift mask 100 and the main surface of the transparent substrate 20 in the cross-sectional view were all over 70 °, and any of the phase shift film patterns 30a had a cross-sectional shape close to perpendicular. As a result of observing LER of these phase shift film patterns 30a in the same manner as in example 1, in examples 2 to 4, the edges of the phase shift film patterns (hole patterns) 30a were all smooth, substantially linear, and good. That is, no distinct uneven shape was observed at the edge of the phase shift film pattern 30a in a plan view. The phase shift film patterns 30a formed in the phase shift masks of examples 2 to 4 have cross-sectional shapes that can sufficiently exhibit the phase shift effect. In examples 2 to 4, the surface of the transparent substrate 20 exposed after the phase shift film 30 was removed was smooth, and the decrease in transmittance due to the surface roughness of the transparent substrate 20 was negligible. Further, as a result of observing the phase shift mask 100 obtained by the electron beam diffraction, it was confirmed that the phase shift mask had an amorphous structure in any of examples 2 to 4. In examples 2 to 4, no permeation of an etching solution or the like was observed at any of the interface between the phase shift film pattern 30a and the etching mask film pattern 40b and the interface between the phase shift film pattern 30a and the transparent substrate 20, and the chemical resistance was also good. Therefore, in examples 2 to 4, the phase shift mask 100 having an excellent phase shift effect was obtained for the exposure light including the light in the wavelength range of 313nm to 500nm, more specifically, for the exposure light including the composite light of at least one of the i-line, the h-line, and the g-line.

Therefore, when the phase shift mask 100 of examples 2 to 4 was set on the mask stage of the exposure apparatus and exposed and transferred to the resist film on the substrate for display device, a fine pattern smaller than 2.0 μm could be transferred with high precision. Further, by forming the phase shift film 30 (phase shift film pattern 30a) in a state in which the degree of vacuum is as low as 0.5Pa or less to form a dense film, it can be expected that the light resistance under exposure light is also good.

Example 5.

A. Phase shift mask blank

The phase shift mask blank 10 of example 5 is a phase shift mask blank 10 in which the back surface reflectance of the phase shift film 30 under exposure light is reduced. In the deposition of the phase shift film 30 of example 1, first, argon (Ar) and nitrogen (N) were introduced into the 1 st chamber with the sputtering gas pressure set to 0.5Pa₂) Forming a mixed gas. Then, a composition prepared by mixing Mo, Zr and Si in an atomic ratio of Mo: zr: a MoZrSiN-based underlayer film containing molybdenum, zirconium, silicon, and nitrogen and having a thickness of 105nm was formed on the main surface of the transparent substrate 20 by reactive sputtering of a MoZrSi target made of a material having Si of 10:10: 80. The atomic ratio in the target for sputtering is an example, and can be appropriately selected according to the desired composition of the phase shift film 30.

Then, argon (Ar) and nitrogen (N) were introduced into the 2 nd chamber with the sputtering gas pressure set to 1.6Pa₂) And Nitric Oxide (NO) gas. Then, use the mixture ofThe atomic ratio of Mo to Si is Mo: an MoSi target made of a material having Si of 8:92 was formed by reactive sputtering to form a 44nm MoSiON-based upper film containing molybdenum, silicon, oxygen, and nitrogen on the MoZrSiN-based lower film, and a phase shift film 30 was formed from a laminated film including the MoZrSiN-based lower film and the MoSiON-based upper film.

Next, an etching mask film 40 having a laminated structure of a CrN layer, a CrC layer, and a CrCON layer was formed on the phase shift film 30 in the same manner as in example 1, and a phase shift mask blank 10 in which the phase shift film 30 and the etching mask film 40 were formed on the transparent substrate 20 was obtained.

The refractive index and extinction coefficient of the lower layer film and the upper layer film constituting the phase shift film 30 of the obtained phase shift mask blank 10 were measured using a model substrate mounted on the same tray.

As a result, the refractive index n of the lower film of MoZrSiN was 2.45 (wavelength: 405nm) and the extinction coefficient k was 0.11 (wavelength: 405 nm). The refractive index n of the MoSiN-based upper layer film was 2.24 (wavelength: 405nm), and the extinction coefficient k was 0.14 (wavelength: 405 nm).

Further, the transmittance and the phase difference were measured for the phase shift film 30 of the obtained phase shift mask blank 10 in the same manner as in example 1. As a result, the transmittance was 51% (wavelength: 405nm), the retardation was 180 ° (wavelength: 405nm), the back surface reflectance was 9.8% (wavelength: 405nm), and the surface reflectance was 14.9% (wavelength: 405 nm).

Further, the composition of the phase shift film 30 of the obtained phase shift mask blank 10 in the depth direction was analyzed by X-ray photoelectron spectroscopy (XPS) in the same manner as in example 1. As a result of analyzing the composition of the phase shift mask blank 10 in the depth direction by XPS, the content of each constituent element in the phase shift film 30 in the depth direction was substantially constant, and the content of Mo, Zr, Si, N, and O in the lower layer film were 3 atomic%, 5 atomic%, 42 atomic%, 47 atomic%, and 3 atomic%, except for the composition gradient region at the interface between the transparent substrate 20 and the phase shift film 30 and the composition gradient region at the interface between the phase shift film 30 and the etching mask film 40. In addition, the atomic ratio of molybdenum to zirconium is Mo: zr 1:1, in Mo: zr is in the range of 1:0.67 to 1: 4. The content ratio of silicon to the total of molybdenum, zirconium and silicon is 84 atomic%, and is within the range of [ Si/(Mo + Zr + Si) ] 70 to 88 atomic%. In addition, Mo, Si, N, and O in the upper layer film were 6 atom%, 41 atom%, 47 atom%, and 6 atom%, respectively. It is considered that the oxygen contained in the underlayer film is due to the presence of a trace amount of oxygen in the chamber during film formation.

B. Phase shift mask and method of manufacturing the same

The phase shift mask 100 was fabricated in the same manner as in the above-described embodiment, and the cross-sectional shape of the phase shift film pattern 30a and the surface state of the transparent substrate 20 exposed after the phase shift film 30 was removed were confirmed. In the cross-sectional view, the angle of the edge of the phase shift film pattern 30a of the phase shift mask 100 with the main surface of the transparent substrate 20 is 72 ° over 70 °, and the phase shift film pattern 30a has a nearly vertical cross-sectional shape. As a result of observing the LER of the phase shift film pattern 30a in the same manner as in example 1, the edge of the phase shift film pattern (hole pattern) 30a was smooth, substantially linear, and good. That is, no distinct uneven shape was observed at the edge of the phase shift film pattern 30a in a plan view. The phase shift film pattern 30a formed in the phase shift mask 100 of example 5 has a cross-sectional shape capable of sufficiently exerting a phase shift effect. The surface of the transparent substrate 20 exposed after the phase shift film 30 is removed is smooth, and the decrease in transmittance due to the surface roughness of the transparent substrate 20 can be ignored. As a result of observation of the obtained phase shift mask 100 by electron beam diffraction, it was confirmed that the structure was amorphous. In addition, no permeation of an etching solution or the like is observed at any of the interface between the phase shift film pattern 30a and the etching mask film pattern 40b and the interface between the phase shift film pattern 30a and the transparent substrate 20, and the chemical resistance is also good. Therefore, the phase shift mask 100 having an excellent phase shift effect is obtained for exposure light including light in a wavelength range of 313nm to 500nm, more specifically, for exposure light including at least one of i-line, h-line, and g-line multiplexed light.

Therefore, when the phase shift mask 100 of example 5 is set on the mask stage of the exposure apparatus and is exposed to the resist film transferred onto the substrate for display device, a fine pattern smaller than 2.0 μm can be transferred with high accuracy. Further, by forming the phase shift film 30 (phase shift film pattern 30a) in a state in which the degree of vacuum is as low as 0.5Pa or less to form a dense film, it can be expected that the light resistance under exposure light is also good.

Comparative example 1.

A. Phase shift mask blank

In comparative example 1, a phase shift mask blank 10 and a phase shift mask 100 were produced by the same structure and method as in example 1 except for the phase shift film 30. In comparative example 1, the atomic ratios of Mo, Zr, and Si of the sputtering target in the deposition of the phase-shift film 30 in example 1 were appropriately adjusted. The film thickness is appropriately adjusted so that the transmittance at a wavelength of 405nm of the phase shift film is 20% or more and 80% or less and the phase difference is in the range of 160 ° to 200 °.

As a result of composition analysis of the MoZrSiN-based phase shift film 30 obtained in the same manner as in example 1, the atomic ratio of Mo to Zr is as follows.

Comparative example 1

Mo: zr 1:1, [ Si/(Mo + Zr + Si) ] 90 atom%

Thus, in comparative example 1, Mo: zr is in the range of 1:0.67 to 1:4, but outside [ Si/(Mo + Zr + Si) ] 70 to 88 atomic%.

B. Phase shift mask and method of manufacturing the same

A phase shift mask 100 was fabricated in the same manner as in example 1, and the cross-sectional shape of the phase shift film pattern 30a and the surface state of the transparent substrate 20 exposed after the phase shift film 30 was removed were confirmed.

As a result, in comparative example 1, the cross-sectional shape of the phase shift film pattern 30a was not greatly different from that of the other examples, and was good, but the surface of the transparent substrate 20 exposed after the phase shift film 30 was removed was rough, and was in a state of white turbidity when observed with naked eyes. Therefore, the transmittance is remarkably reduced due to the surface roughness of the transparent substrate 20.

Therefore, it is predicted that when the phase shift mask 100 of comparative example 1 is set on the mask stage of the exposure apparatus and is exposed and transferred to the resist film on the substrate for display device, a fine pattern smaller than 2.0 μm cannot be transferred.

Comparative example 2.

A. Phase shift mask blank

In comparative example 2, a phase shift mask blank 10 and a phase shift mask 100 were produced by the same structure and method as in example 1 except for the phase shift film 30. In comparative example 2, the atomic ratios of Mo, Zr, and Si of the sputtering target in the deposition of the phase-shift film 30 in example 1 were appropriately adjusted. The film thickness of the phase shift film 30 is appropriately adjusted so that the transmittance at a wavelength of 405nm is 20% or more and 80% or less and the retardation is in the range of 160 ° to 200 °.

As a result of composition analysis of the MoZrSiN-based phase shift film 30 obtained in the same manner as in example 1, the atomic ratio of Mo to Zr is as follows.

Comparative example 2

Mo: zr 1:1, [ Si/(Mo + Zr + Si) ] 65 atom%

Thus, Mo in comparative example 2: zr is in the range of 1:0.67 to 1:4, but outside [ Si/(Mo + Zr + Si) ] 70 to 88 atomic%.

B. Phase shift mask and method of manufacturing the same

A phase shift mask 100 was fabricated in the same manner as in example 1, and the cross-sectional shape of the phase shift film pattern 30a and the surface state of the transparent substrate 20 exposed after the phase shift film 30 was removed were confirmed.

As a result, in comparative example 2, the surface of the transparent substrate 20 exposed after the phase shift film 30 was removed was smooth, and the decrease in transmittance due to the surface roughness of the transparent substrate 20 was negligible, but the cross-sectional shape of the phase shift film pattern 30a was poor, and the cross-sectional shape that could sufficiently exhibit the phase shift effect was not obtained.

Therefore, it is predicted that when the phase shift mask 100 of comparative example 2 is set on the mask stage of the exposure apparatus and is exposed and transferred to the resist film on the substrate for display device, a fine pattern smaller than 2.0 μm cannot be transferred.

Comparative example 3.

A. Phase shift mask blank

In comparative example 3, a phase shift mask blank 10 and a phase shift mask 100 were produced by the same structure and method as in example 1 except for the phase shift film 30. In comparative example 3, the atomic ratios of Mo, Zr, and Si of the sputtering target in the deposition of the phase-shift film 30 in example 1 were appropriately adjusted.

As a result of composition analysis of the MoZrSiN-based phase shift film 30 obtained in the same manner as in example 1, in comparative example 3, the atomic ratio was Mo: zr is out of the range of 2:1, 1:0.67 to 1: 4. On the other hand, the content ratio of silicon to the total of molybdenum, zirconium and silicon is in the range of 70 to 88 atomic%.

B. Phase shift mask and method of manufacturing the same

A phase shift mask 100 was fabricated in the same manner as in example 1, and the cross-sectional shape of the phase shift film pattern 30a and the surface state of the transparent substrate 20 exposed after the phase shift film 30 was removed were confirmed.

As a result, in comparative example 3, the surface of the transparent substrate 20 exposed after the phase shift film 30 was removed was smooth, and the decrease in transmittance due to the surface roughness of the transparent substrate 20 was negligible. In addition, the sectional shape of the phase shift film pattern 30a is good without a large difference from those of the other embodiments. On the other hand, the transmittance at a wavelength of 405nm is less than 15%, and a sufficient transmittance cannot be obtained. The film thickness was adjusted in the same manner as in the other examples and comparative examples, but sufficient transmittance was still not obtained.

Therefore, it is predicted that when the phase shift mask 100 of comparative example 3 is set on the mask stage of the exposure apparatus and is exposed and transferred to the resist film on the substrate for display device, a fine pattern smaller than 2.0 μm cannot be transferred.

Comparative example 4.

A. Phase shift mask blank

In comparative example 4, a phase shift mask blank 10 and a phase shift mask 100 were produced by the same structure and method as in example 1 except for the phase shift film 30. In comparative example 4, the atomic ratios of Mo, Zr, and Si of the sputtering target in the phase shift film formation in example 1 were appropriately adjusted. The film thickness of the phase shift film 30 is appropriately adjusted so that the transmittance at a wavelength of 405nm is 20% or more and 80% or less and the retardation is in the range of 160 ° to 200 °.

As a result of composition analysis of the MoZrSiN-based phase shift film 30 obtained in the same manner as in example 1, in comparative example 4, the atomic ratio of molybdenum to zirconium was Mo: zr is not more than 1:5, 1: 0.67-1: 4. On the other hand, the content ratio of silicon to the total of molybdenum, zirconium and silicon is in the range of 70 to 88 atomic%.

B. Phase shift mask and method of manufacturing the same

The phase shift mask 100 was fabricated in the same manner as in example 1, and the cross-sectional shape of the phase shift film pattern and the surface state of the transparent substrate 20 exposed after the phase shift film 30 was removed were confirmed.

As a result, in comparative example 4, the surface of the transparent substrate 20 exposed after the phase shift film 30 was removed was smooth, and the decrease in transmittance due to the surface roughness of the transparent substrate 20 was negligible, but sufficient chemical resistance could not be obtained, and the cross-sectional shape of the phase shift film pattern 30a was inferior to that of the other examples. In addition, the surface reflectance and the back surface reflectance at a wavelength of 405nm are both high, and sufficient transfer accuracy cannot be obtained.

Therefore, it is predicted that when the phase shift mask 100 of comparative example 4 is set on the mask stage of the exposure apparatus and is exposed and transferred to the resist film on the substrate for display device, a fine pattern smaller than 2.0 μm cannot be transferred.