KR20210116264A - Photomask blank, method for manufacturing photomask, and method for manufacturing display device - Google Patents

Abstract

Provided is a photomask blank in which an over-etching time is shortened to suppress damage to a substrate when a phase shift film is wet-etched, so that a transfer pattern having an excellent sectional shape or line edge roughness (LER) and an excellent chemical resistance is formed. The present invention provides the photomask blank, which is an original plate for forming a photomask, wherein the photomask is configured such that a phase shift film pattern obtained by wet-etching a phase shift film is formed on a transparent substrate; the phase shift film includes a single layer or a plurality of layers; 50% or more and 100% or less of a total film thickness of the phase shift film includes a MoZrSi-based material layer formed of a material including molybdenum, zirconium, silicon, and nitrogen; and the MoZrSi-based material layer is configured such that an atomic ratio of the molybdenum and the zirconium is Mo:Zr = 1.5:1 to 1:4, and a content ratio of the silicon with respect to a total of the molybdenum, the zirconium, and the silicon is 70 to 88 atom%.

Description

A photomask blank, a manufacturing method of a photomask, and a manufacturing method of a display device TECHNICAL FIELD

The present invention relates to a photomask blank, a method for manufacturing a photomask, and a method for manufacturing a display device.

DESCRIPTION OF RELATED ART In recent years, display apparatuses, such as a FPD (Flat Panel Display) which are representative of LCD (Liquid Crystal Display), high-definition and high-speed display are progressing rapidly along with the enlargement of a screen and a wide viewing angle. One of the elements necessary for this high-definition and high-speed display is the production of fine and high-dimensional precision elements and electronic circuit patterns such as wiring. Photolithography is often used for patterning this electronic circuit for a display device. For this reason, the photomask like a phase shift mask for display apparatus manufacture in which a fine, high-precision pattern was formed and a binary mask is needed.

For example, Patent Document 1 discloses a phase reversal mask blank provided with a phase reversal film on a transparent substrate. In this mask blank, the phase reversal film has a reflectance of 35% or less and a reflectance of 1% to 40 with respect to exposure light having a complex wavelength including i-line (365 nm), h-line (405 nm), and g-line (436 nm). %, including a metal silicide compound containing at least one light element of oxygen (O), nitrogen (N), and carbon (C) so that the inclination of the cross-section of the pattern is rapidly formed during pattern formation The metal silicide compound is formed by injecting a reactive gas containing the light element substance and an inert gas in a ratio of 0.5:9.5 to 4:6.

Examples of the metal silicide compound include aluminum (Al), cobalt (Co), tungsten (W), molybdenum (Mo), vanadium (V), palladium (Pd), titanium (Ti), platinum (Pt), and 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), niobium (Nb) in any one or more metal materials of silicon (Si) ) is included, or the metal silicide contains a compound further comprising at least one light element of nitrogen (N), oxygen (O), carbon (C), boron (B), and hydrogen (H). Characterized materials are described.

Korean Patent No. 1801101 Publication Japanese Patent No. 3988041 Publication

In recent years, as a phase shift mask used for high-precision (1000 ppi or more) panel production, it is a phase shift mask in order to enable high-resolution pattern transfer, and a fine phase shift of 6 μm or less in hole diameter and 4 μm or less in line width. The phase shift mask in which the film|membrane pattern was formed is calculated|required. The phase shift mask in which the fine phase shift film pattern of 1.5 micrometers was specifically, formed with a hole diameter is calculated|required.

Further, in order to realize higher-resolution pattern transfer, a phase shift mask blank having a phase shift film having a transmittance of 15% or more to exposure light, and a phase shift mask having a phase shift film pattern having a transmittance of 15% or more to exposure light are required. is becoming

In order to satisfy the request|requirement of the transmittance|permeability with respect to exposure light, although it is effective to raise the ratio of the silicon in the atomic ratio of the metal in the metal silicide compound (metal silicide type material) which comprises a phase shift film, and silicon, a wet etching rate is significantly slower (wet etching time becomes longer), and there are problems such as damage to the substrate by the wet etching solution and a decrease in transmittance of the transparent substrate.

Further, in Patent Document 2, on a transparent substrate, molybdenum as a first metal component and at least one metal selected from tantalum, zirconium, chromium and tungsten as a second metal component, and 1 selected from oxygen, nitrogen and carbon A halftone phase shift mask blank having a phase shifter film containing a metal silicide compound containing at least one element is disclosed. And from the viewpoint of chemical resistance of the phase shifter film and workability during etching, the ratio of the first metal component to the second metal component in the metal silicide compound is first metal component: second metal component = 100:1 to 2:1 (atomic ratio) ) is preferred.

As for the phase shifter film disclosed in this patent document 2, it is assumed that a phase shifter film is patterned by dry etching when producing a phase shift mask, When this phase shifter film is patterned by wet etching, a phase shifter is similar to what was mentioned above. The wet etching rate of the film was slow, damage to the substrate by the wet etching solution occurred, and there was a problem in that the transmittance of the transparent substrate was lowered.

Then, this invention was made|formed in order to solve the above-mentioned problem, and the objective of this invention is formation of the transfer pattern which a photomask has even when the transmittance|permeability with respect to the representative wavelength of exposure light of a phase shift film is high. WHEREIN: Metal and silicon The photo which can reduce the wet etching time of the said phase shift film containing, can suppress the damage to a board|substrate, has a favorable cross-sectional shape and line edge roughness (LER: Line Edge Roughness), and can form a transfer pattern with good chemical resistance also A mask blank, a photomask manufacturing method, and a display device manufacturing method are provided.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined the measure for solving these problems. First, in order to obtain a phase shift film having a high transmittance with respect to a representative wavelength of exposure light (for example, 313 nm to 436 nm), the extinction coefficient at the representative wavelength is smaller than that of molybdenum, focusing on zirconium, MoZrSi-based material containing molybdenum, zirconium, silicon, and nitrogen was selected as a material constituting the phase shift film.

It is known in the mask blank for LSI used for manufacture of a semiconductor device etc. to use a MoZrSi type|system|group material as a phase shift film. However, if the MoZrSi-based material used for the LSI mask blank is applied as it is to the phase shift mask blank for display device manufacturing, the wet etching of the phase shift film takes too much time, causing damage to the substrate and It became clear that the transmittance|permeability fall could not fully be suppressed. In this way, even if the MoZrSi-based material used for the mask blank for LSI was simply applied to the phase shift mask blank for display device manufacturing, the desired phase shift mask blank for display device manufacturing could not be obtained.

Moreover, depending on the composition ratio of MoZrSi-type material, the chemical resistance of a phase shift film was bad, and desired washing|cleaning tolerance was not acquired, and also it became clear that a reflectance was too high and a transcription|transfer characteristic fell.

Therefore, the present inventors further earnestly studied, and found that it is effective to prescribe the atomic ratio of molybdenum and zirconium and the content ratio of silicon with respect to the sum of molybdenum, zirconium and silicon as indexes in the MoZrSi-based material. That is, in order to suppress that the wet etching rate of a phase shift film is high when patterning the said phase shift film by wet etching, and the damage to the transparent substrate by a wet etching liquid occurs when patterning a phase shift film, MoZrSi type material. It became clear as a result of earnest examination by this inventor that the said problem could be solved by adjusting the atomic ratio of molybdenum, zirconium, and the content ratio of silicon with respect to the sum total of molybdenum, zirconium, and silicon. This invention was made as a result of the above-mentioned earnest examination, and the following structure is required.

(Structure 1) It is a photomask blank which has a phase shift film on a transparent substrate,

The said photomask blank is an original plate for forming a photomask, this photomask is a photomask which has a phase shift film pattern obtained by wet-etching the said phase shift film on the said transparent substrate,

The phase shift film is composed of a single layer or multiple layers, and 50% or more and 100% or less of the total film thickness of the phase shift film is a material containing molybdenum (Mo), zirconium (Zr), silicon (Si) and nitrogen. Including a MoZrSi-based material layer made of,

In the MoZrSi-based material layer, the atomic ratio of molybdenum and zirconium is Mo: Zr = 1.5:1 to 1:4 (1:0.67 to 1:4), and the content ratio of silicon to the sum of molybdenum, zirconium, and silicon The photomask blank, characterized in that it is 70 to 88 atomic%.

(Structure 2) The said phase shift film is equipped with the optical characteristic that transmittance|permeability is 20 % or more and 80 % or less with respect to the representative wavelength of exposure light, and phase difference is 160 degrees or more and 200 degrees or less, The photomask blank of structure 1 characterized by the above-mentioned. .

(Composition 3) The said phase shift film is a laminated|multilayer film containing the lower layer by the side of the said transparent substrate, and the upper layer laminated|stacked on the said lower layer, The said lower layer is the said MoZrSi system material layer, The structure 1 or 2 characterized by the above-mentioned Described photomask blank.

(Configuration 4) The photomask blank according to Configuration 3, wherein the upper layer is made of a material smaller than the refractive index of the lower layer and higher than the extinction coefficient at a representative wavelength of exposure light.

(Structure 5) In the said phase shift film, the refractive index, extinction coefficient, and film thickness of each of the said upper layer and the said lower layer are set so that the back surface reflectance with respect to the representative wavelength of exposure light may be 15 % or less, The structure 4 characterized by the above-mentioned. photomask blank.

(Structure 6) The etching mask film from which etching selectivity differs with respect to this phase shift film is provided on the said phase shift film, The photomask blank in any one of structures 1-5 characterized by the above-mentioned.

(Configuration 7) A step of preparing the photomask blank according to any one of Configurations 1 to 5;

A resist film is formed on the said phase shift film, the said phase shift film is wet-etched using the resist film pattern formed from the said resist film as a mask, It has the process of forming a phase shift film pattern on the said transparent substrate, It is characterized by the above-mentioned A method of manufacturing a photomask.

(Configuration 8) A step of preparing the photomask blank according to Configuration 6;

The process of forming a resist film on the said etching mask film, wet-etching the said etching mask film using the resist film pattern formed from the said resist film as a mask, and forming an etching mask film pattern on the said phase shift film;

The said etching mask film pattern is used as a mask, the said phase shift film is wet-etched, and it has the process of forming a phase shift film pattern on the said transparent substrate, The manufacturing method of the photomask characterized by the above-mentioned.

(Structure 9) The transfer pattern containing the said phase shift film pattern formed on the said photomask by loading the photomask obtained by the manufacturing method of the photomask of the structure 7 or 8 on the mask stage of an exposure apparatus, a display device A method of manufacturing a display device, comprising an exposure step of exposing and transferring a resist formed on a substrate.

According to the photomask blank which concerns on this invention, even when the transmittance|permeability with respect to the representative wavelength of exposure light of a phase shift film is high, in formation of the transfer pattern which a photomask has, the wet etching time of the said phase shift film containing metal and silicon is shortened. Thus, it is possible to obtain a photomask blank capable of forming a transfer pattern having a good cross-sectional shape, line edge roughness, and chemical resistance.

In addition, according to the method for manufacturing a photomask according to the present invention, a photomask is manufactured using the photomask blank. For this reason, even when the transmittance of the phase shift film with respect to the representative wavelength of exposure light is high, the wet etching rate of the phase shift film is fast, and there is no decrease in the transmittance of the transparent substrate due to the damage to the transparent substrate by the wet etching solution. A photomask having a transfer pattern (phase shift film pattern) having good line edge roughness and good tolerance can be manufactured. This photomask can respond to line-and-space patterns and miniaturization of contact holes.

In addition, according to the method for manufacturing a display device according to the present invention, the display device is manufactured using the photomask obtained by the method for manufacturing the photomask. For this reason, a display device having a fine line-and-space pattern or contact hole can be manufactured.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the film|membrane structure (transparent board|substrate/phase shift film) of the phase shift mask blank which concerns on Embodiment 1. FIG.
It is a schematic diagram which shows the film|membrane structure (transparent substrate/phase shift film/etching mask film) of the phase shift mask blank which concerns on Embodiment 2. FIG.
It is a schematic diagram which shows the manufacturing process of the phase shift mask which concerns on Embodiment 3. FIG.
It is a schematic diagram which shows the manufacturing process of the phase shift mask which concerns on Embodiment 4. FIG.

Embodiment 1. 2.

In Embodiments 1 and 2, a phase shift mask blank (photomask blank) is demonstrated. The phase shift mask blank of Embodiment 1 is an original plate for forming a phase shift mask (photomask), This phase shift mask makes the etching mask film pattern in which the desired pattern was formed in the etching mask film as a mask, and wets the phase shift film. It is a phase shift mask which has the transcription|transfer pattern containing the phase shift film pattern obtained by etching on a transparent substrate. Moreover, the phase shift mask blank of Embodiment 2 is an original plate for forming a phase shift mask, This phase shift mask uses the resist film pattern in which the desired pattern was formed in a resist film as a mask, The phase shift obtained by wet-etching a phase shift film It is a phase shift mask which has a transfer pattern containing a film|membrane pattern on a transparent substrate. The transfer pattern in the present specification is obtained by patterning at least one optical film formed on a transparent substrate. The said optical film can be used as a phase shift film or an etching mask film, and other films (a light-shielding film|membrane, the film|membrane for reflection suppression, an electroconductive film|membrane, etc.) may further be contained. That is, a transfer pattern can contain the phase shift film or etching mask film which were patterned, and the patterned other film|membrane may further be contained.

1 : is a schematic diagram which shows the film|membrane structure of the phase shift mask blank 10 which concerns on Embodiment 1. As shown in FIG.

Phase shift mask blank 10 shown in FIG. 1 is transparent substrate 20, phase shift film 30 formed on transparent substrate 20, and etching mask film ( 40) is provided.

FIG. 2 : is a schematic diagram which shows the film|membrane structure of the phase shift mask blank 10 which concerns on Embodiment 2. FIG.

The phase shift mask blank 10 shown in FIG. 2 is equipped with the transparent substrate 20 and the phase shift film 30 formed on the transparent substrate 20. As shown in FIG.

Hereinafter, the transparent substrate 20 which comprises the phase shift mask blank 10 of Embodiment 1 and 2, the phase shift film 30, and the etching mask film 40 are demonstrated.

The transparent substrate 20 is transparent to exposure light. Assuming that there is no surface reflection loss, the transparent substrate 20 has a transmittance of 85% or more with respect to the exposure light, and preferably has a transmittance of 90% or more. The transparent substrate 20 is made of a material containing silicon and oxygen, and a glass material such as synthetic quartz glass, quartz glass, aluminosilicate glass, soda-lime glass, low thermal expansion glass (SiO ₂ -TiO ₂ glass, etc.) can be configured as When the transparent substrate 20 is comprised with low thermal expansion glass, the position change of the phase shift film pattern resulting from the thermal deformation of the transparent substrate 20 can be suppressed. In addition, the transparent substrate 20 used for a display device use is a board|substrate of a generally rectangular shape, and a thing 300 mm or more in length of the short side of this transparent substrate is used. Even if the phase shift mask blank 10 of the present invention has a large size in which the short side length of the transparent substrate 20 is 300 mm or more, it is formed on the transparent substrate 20 with a fine (for example, a dimension of width or diameter of 2.0 µm). It is the phase shift mask blank 10 which can provide the phase shift mask 100 which can transcribe a phase shift film pattern stably.

The phase shift film 30 is comprised from a single layer or a multilayer, and 50% or more and 100% or less of the parts with respect to the total film thickness of the said phase shift film 30 are molybdenum (Mo), zirconium (Zr), and silicon (Si). ) and a MoZrSi-based material made of a material containing nitrogen. The MoZrSi-based material may also contain transition metals of tantalum (Ta), tungsten (W), and titanium (Ti).

In addition, as for the phase shift film 30, if the transmittance|permeability and phase difference with respect to the representative wavelength of exposure light become a predetermined value, 50% or less of the part with respect to the total film thickness of the said phase shift film 30 other than MoZrSi system material. It may consist of materials. In this case, a metal silicide-based material containing a metal and silicon that can be etched with the same wet etching solution as the MoZrSi-based material is preferable. For example, as a metal silicide-based material other than MoZrSi-based material, molybdenum silicide-based material (MoSi-based material), zirconium silicide-based material (ZrSi-based material), tantalum silicide-based material (TaSi-based material), tungsten silicide-based material (WSi-based material) ) and a titanium silicide-based material (TiSi-based material). The MoSi-based material, ZrSi-based material, TaSi-based material, WSi-based material, and TiSi-based material may contain elements such as nitrogen, oxygen, and carbon.

In the MoZrSi-based material layer, the atomic ratio of molybdenum and zirconium is Mo:Zr=1.5:1 to 1:4, that is, Mo:Zr=1:0.67 to 1:4. In the case of the MoZrSi-based material layer in which the ratio of Zr is smaller than the range of the Mo:Zr atomic ratio, the wet etching rate with respect to the wet etching solution becomes slow, so that damage to the transparent substrate is likely to occur. Moreover, it becomes difficult to obtain the phase shift film which has a high transmittance|permeability with respect to the representative wavelength of exposure light. Further, in the case of a MoZrSi-based material layer having a larger Zr ratio than the Mo:Zr atomic ratio range, a phase shift film 30 having a high transmittance (for example, 20% or more and 80% or less) with respect to a representative wavelength of exposure light. Although this becomes easy to obtain, chemical resistance (washing resistance) is not enough, and it is unpreferable also from a viewpoint of the defect quality which generate|occur|produces at the time of film-forming. The atomic ratio of molybdenum and zirconium is preferably Mo:Zr=1:0.8 to 1:3, more preferably Mo:Zr=1:1 to 1:2.

In addition, in the MoZrSi-based material layer, the content ratio of silicon to the total of molybdenum, zirconium, and silicon (Si/[Mo+Zr+Si]) is Si/[Mo+Zr+Si]=70 to 88 atomic%. It is preferable to do When Si/[Mo+Zr+Si] is less than 70 atomic%, realization of the phase shift film 30 with high transmittance (for example, 20% or more and 80% or less) with respect to the representative wavelength of exposure light and chemical resistance becomes difficult. . In addition, when Si/[Mo+Zr+Si] is more than 88 atomic %, the wet etching rate with respect to the wet etching solution becomes slow, so damage to the transparent substrate 20 tends to occur, and It becomes easy to produce the fall of the transmittance|permeability by s. The content ratio of silicon to the total of molybdenum, zirconium and silicon is preferably Si/[Mo+Zr+Si]=72 to 86 atomic%, more preferably Si/[Mo+Zr+Si]=75 to 85 atomic % is preferable.

This phase shift film 30 can be formed by the sputtering method.

Since the MoZrSi system material layer of the phase shift film 30 in this embodiment satisfies the range mentioned above, the atomic ratio of molybdenum and zirconium, and the content ratio of silicon with respect to the sum total of molybdenum, zirconium, and silicon, A phase shift film pattern 30a that can form a film with a good degree of vacuum within 0.5 Pa, can shorten the overetching time, can suppress damage to the transparent substrate 20, have a good cross-sectional shape and LER, and also have good chemical resistance. can be formed

Moreover, this phase shift film 30 may have a columnar structure. This columnar structure can be confirmed by cross-sectional SEM observation of the phase shift film 30. That is, as for the columnar structure in this invention, the particle|grains of the transition metal silicide compound containing molybdenum, zirconium, and silicon which comprise the phase shift film 30 are the film thickness direction of the phase shift film 30 (the said particle|grains are It refers to a state having a columnar grain structure extending toward the deposition direction). If it is the phase shift film 30 which has this columnar structure, it is preferable at the point from which a high transmittance|permeability becomes easy to be obtained.

Moreover, the phase shift film 30 may contain oxygen other than nitrogen mentioned above for the purpose of adjusting a transmittance|permeability, and may contain other elements, such as helium and carbon, for the purpose of reducing film stress and controlling a wet etching rate.

The transmittance|permeability of the phase shift film 30 with respect to exposure light satisfy|fills the value required as the phase shift film 30. Preferably the transmittance|permeability of the phase shift film 30 is 20 % or more with respect to the light (representative wavelength) of the predetermined wavelength contained in exposure light (representative wavelength), More preferably, they are 25 % or more and 75 % or less, further Preferably it is 30 % or more and 70 % or less. That is, when exposure light is composite light containing the light of the wavelength range of 313 nm or more and 436 nm or less, the phase shift film 30 has the transmittance|permeability mentioned above with respect to the light of the representative wavelength contained in the wavelength range. For example, when exposure light is composite light containing i line|wire, h line|wire, and g line|wire, the phase shift film 30 has the transmittance|permeability mentioned above about any of i line|wire, h line|wire, and g line|wire.

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 exposure light satisfy|fills the value required as the phase shift film 30. Preferably the phase difference of the phase shift film 30 is 160 degrees or more and 200 degrees or less with respect to the light of the representative wavelength contained in exposure light, More preferably, they are 170 degrees or more and 190 degrees or less. According to this property, the phase of the light of the representative wavelength contained in the exposure light can be changed (shifted) to 160 degrees or more and 200 degrees or less. For this reason, 160 degrees or more and 200 degrees or less phase difference arises between the light of the representative wavelength which permeate|transmitted the phase shift film 30, and the light of the representative wavelength which permeate|transmitted only the transparent substrate 20. That is, when exposure light is composite light containing the light of the wavelength range of 313 nm or more and 436 nm or less, the phase shift film 30 has the phase difference mentioned above with respect to the light of the representative wavelength contained in the wavelength range. For example, when exposure light is composite light containing i line|wire, h line|wire, and g line|wire, the phase shift film 30 has the phase difference mentioned above with respect to any one of i line|wire, h line|wire, and g line|wire.

A phase difference can be measured using a phase shift amount measuring apparatus etc.

Moreover, the laminated|multilayer film containing the lower layer by the side of the said transparent substrate, and the upper layer laminated|stacked on the lower layer may be sufficient as the phase shift film 30. When the phase shift film 30 is a laminated film containing a lower layer and an upper layer, the defect quality of the phase shift film 30, suppression of the damage to the transparent substrate 20 by wet etching liquid, the phase shift film 30 From the viewpoint of making a pattern cross-sectional shape favorable when patterned by wet etching, it is preferable that the lower layer is the MoZrSi-based material layer. The MoZrSi system material layer same as the said lower layer may be sufficient as the said upper layer in the phase shift film 30, and even if it differs, it is not cared about. When the upper layer is different from the material of the lower layer, a metal silicide-based material that can be etched with the same wet etching solution as the MoZrSi-based material, for example, a MoSi-based material, a ZrSi-based material, a TaSi-based material, a WSi-based material, a TiSi-based material can be used

Moreover, as for the phase shift film 30, the said upper layer is smaller than the refractive index n in the representative wavelength (for example, 313 nm - 436 nm) of the exposure light in the said lower layer, and the material which consists of a material higher than the extinction coefficient k. By selecting, the back surface reflectance of the phase shift film 30 of the side into which exposure light injects can be reduced.

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

The etching mask film 40 is arrange|positioned above the phase shift film 30, and it is made of a material (different from the phase shift film 30 in etching selectivity) which has etching resistance with respect to the etchant which etches the phase shift film 30. is done In addition, the etching mask film 40 may have a function to block transmission of exposure light, and the film surface reflectance of the phase shift film 30 with respect to the light which injects from the phase shift film 30 side is 313 nm - 436 nm You may have a function of reducing a film surface reflectance so that it may become 15 % or less in a wavelength range. The etching mask film 40 is made of a chromium-based material containing chromium (Cr). More specifically, a material containing chromium (Cr) or chromium (Cr) and at least one of oxygen (O), nitrogen (N), and carbon (C) is mentioned as the chromium-based material. Alternatively, a material containing chromium (Cr), at least any one of oxygen (O), nitrogen (N), and carbon (C), and containing fluorine (F) is exemplified. Examples of the material constituting the etching mask film 40 include Cr, CrO, CrN, CrF, CrCO, CrCN, CrON, CrCON, and CrCONF.

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

When the etching mask film 40 has a function to block transmission of the exposure light, the portion where the phase shift film 30 and the etching mask film 40 are laminated WHEREIN: The optical density with respect to exposure light becomes like this. Preferably 3 It is more than, More preferably, it is 3.5 or more, More preferably, it is 4 or more.

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

The etching mask film 40 may be formed of a single film having a uniform composition depending on the function, or may be formed of a plurality of films having different compositions, and may be formed of a single film whose composition is continuously changed in the thickness direction. may be the case.

Moreover, although the phase shift mask blank 10 shown in FIG. 1 is equipped with the etching mask film 40 on the phase shift film 30, it is equipped with the etching mask film 40 on the phase shift film 30, The present invention is applicable also to a phase shift mask blank provided with a resist film on the etching mask film 40 .

Next, the manufacturing method of the phase shift mask blank 10 of this Embodiment 1 and 2 is demonstrated. The phase shift mask blank 10 shown in FIG. 1 is manufactured by performing the following phase shift film formation process and an etching mask film formation process. The phase shift mask blank 10 shown in FIG. 2 is manufactured by a phase shift film formation process.

Hereinafter, each process is demonstrated in detail.

1. Phase shift film formation process

First, the transparent substrate 20 is prepared. The transparent substrate 20 is made of any glass material such as synthetic quartz glass, quartz glass, aluminosilicate glass, soda lime glass, low thermal expansion glass (SiO ₂ -TiO _{2 glass, etc.) if it is transparent to exposure light.} it may be

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

Film-forming of the phase shift film 30 is a MoZrSi system target containing molybdenum (Mo) used as a main component of the material which comprises the phase shift film 30, zirconium (Zr), and silicon (Si), or molybdenum (Mo) Using a MoZrSiO-based target, MoZrSiN-based target, and MoZrSiON-based target containing zirconium (Zr), silicon (Si), oxygen (O) and/or nitrogen (N) as a sputter target, for example, helium gas, neon A sputtering gas atmosphere containing an inert gas containing at least one selected from the group consisting of gas, argon gas, krypton gas and xenon gas, or the inert gas and oxygen gas, nitrogen gas, carbon dioxide gas, nitrogen monoxide gas, It is performed in a sputtering gas atmosphere containing a mixed gas of an active gas selected from the group consisting of nitrogen dioxide gas and containing at least nitrogen. Mo, Zr, and Si in the MoZrSi-based target, MoZrSiO-based target, MoZrSiN-based target, and MoZrSiON-based target have an atomic ratio of Mo:Zr=1.5 in the MoZrSi-based material layer formed by sputtering. It is :1 to 1:4 (1:0.67 to 1:4), and it is adjusted so that the content ratio of silicon to the total of molybdenum, zirconium, and silicon is 70 to 88 atomic%. Moreover, you may make it form into a film using Mo target, Zr target, and Si target so that the phase shift film 30 may satisfy|fill the atomic ratio and content ratio of Mo, Zr, and Si mentioned above, and using MoSi target and ZrSi target, You can make it into a film.

The composition and thickness of the phase shift film 30 are adjusted so that the phase shift film 30 may become the said phase difference and transmittance|permeability. The composition of the phase shift film 30 is controllable by the content rate (for example, content rate of Mo, Zr, Si) of the element which comprises a sputtering target, the composition, flow volume, etc. of sputtering gas. The thickness of the phase shift film 30 is controllable by sputtering power, sputtering time, etc. Moreover, it is preferable to form the phase shift film 30 using an in-line sputtering apparatus. When a sputtering apparatus is an in-line sputtering apparatus, the thickness of the phase shift film 30 is controllable also with the conveyance speed of the transparent substrate 20.

When the phase shift film 30 consists of a single film|membrane, it performs the above-mentioned film-forming process only once, changing the composition and flow volume of sputtering gas with the elapsed time of a film-forming process. When the phase shift film 30 consists of several films|membrane from which a composition differs, the above-mentioned film-forming process changes the composition and flow volume of sputtering gas for every film-forming process, and performs it in multiple times. You may form the phase shift film 30 into a film using the target from which the content rate of the element which comprises a sputtering target differs. When performing a film-forming process multiple times, the sputtering power applied to a sputtering target can be made small.

In this way, the phase shift mask blank 10 of Embodiment 2 is obtained. The following etching mask film formation process is further performed for manufacture of the phase shift mask blank 10 of Embodiment 1.

3. Etching mask film forming process

After performing the surface treatment which adjusts the state of the surface oxidation of the surface of the phase shift film 30 as needed, the etching mask film 40 is formed on the phase shift film 30 by the sputtering method. The etching mask film 40 is preferably formed using an in-line sputtering apparatus. When the sputtering apparatus is an in-line sputtering apparatus, the thickness of the etching mask film 40 can be controlled also by the conveyance speed of the transparent substrate 20 .

The etching mask film 40 is formed using a sputter target containing chromium or a chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium oxynitride, carbide, etc.), for example, helium gas, neon A sputtering gas atmosphere containing an inert gas containing at least one selected from the group consisting of gas, argon gas, krypton gas, and xenon gas, or helium gas, neon gas, argon gas, krypton gas, and xenon gas from the group consisting of Mixing of an inert gas containing at least one selected It is performed in a sputtering gas atmosphere containing gas. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas.

When the etching mask film 40 is formed of a single film having a uniform composition, the above-described film forming process is performed only once without changing the composition and flow rate of the sputtering gas. When 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 by changing the composition and flow rate of the sputtering gas for each film formation process. When the etching mask film 40 is made of a single film whose composition continuously changes in the thickness direction, the above-described film formation process is performed only once while changing the composition and flow rate of the sputtering gas together with the elapsed time of the film formation process.

In this way, the phase shift mask blank 10 of Embodiment 1 is obtained.

In addition, since the phase shift mask blank 10 shown in FIG. 1 is equipped with the etching mask film 40 on the phase shift film 30, when manufacturing the phase shift mask blank 10, an etching mask film formation process do Moreover, when manufacturing the phase shift mask blank which equips the etching mask film 40 on the phase shift film 30 and the resist film on the etching mask film 40, after an etching mask film formation process, the etching mask film 40 ) to form a resist film. Moreover, in the phase shift mask blank 10 shown in FIG. 2, when manufacturing the phase shift mask blank provided with a resist film on the phase shift film 30, a resist film is formed after a phase shift film formation process.

The phase shift mask blank 10 of this Embodiment 1 and 2 can form the phase shift film pattern 30a with a favorable cross-sectional shape by wet etching and high transmittance in a short etching time. Therefore, there is no decrease in the transmittance of the transparent substrate 20 due to the damage to the transparent substrate 20 by the wet etching solution, and the phase shift mask 100 capable of transferring the high-precision phase shift film pattern 30a with high precision. The phase shift mask blank 10 which can manufacture is obtained.

Embodiment 3. 4.

In Embodiment 3, 4, the manufacturing method of the phase shift mask 100 is demonstrated.

3 : is a schematic diagram which shows the manufacturing method of the phase shift mask 100 which concerns on Embodiment 3. As shown in FIG. 4 : is a schematic diagram which shows the manufacturing method of the phase shift mask 100 which concerns on Embodiment 4. FIG.

The manufacturing method of 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 following phase shift mask blanks ( The step of forming a resist film on the etching mask film 40 of 10), and drawing and developing a desired pattern on the resist film to form a resist film pattern 50 (first resist film pattern formation step), The process of forming the etching mask film pattern 40a on the phase shift film 30 by wet-etching the etching mask film 40 using the resist film pattern 50 as a mask (1st etching mask film pattern formation process); , the process of forming the phase shift film pattern 30a on the transparent substrate 20 by wet-etching the phase shift film 30 using the said etching mask film pattern 40a as a mask (phase shift film pattern formation process) include and a second resist film pattern forming process and a second etching mask film pattern forming process.

The manufacturing method of 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 following phase shift mask blanks ( 10) A step of forming a resist film on the resist film, and drawing and developing a desired pattern on the resist film to form a resist film pattern 50 (first resist film pattern forming step), and the resist film pattern 50 is formed The process of forming the phase shift film pattern 30a on the transparent substrate 20 by wet-etching the phase shift film 30 as a mask (phase shift film pattern formation process) is included.

Hereinafter, each process of the manufacturing process of the phase shift mask 100 which concerns on Embodiment 3 and 4 is demonstrated in detail.

Manufacturing process of the phase shift mask 100 which concerns on Embodiment 3

1. First resist film pattern forming process

In a 1st resist film pattern formation process, a resist film is first formed on the etching mask film 40 of the phase shift mask blank 10 of Embodiment 1. As shown in FIG. The resist film material to be used is not particularly limited. For example, what is necessary is just to be photosensitive with respect to the laser beam which has any wavelength selected from the wavelength range of 350 nm - 436 nm mentioned later. In addition, the resist film may be either positive type or negative type.

Thereafter, a desired pattern is drawn on the resist film using laser light having a certain wavelength selected from a wavelength range of 350 nm to 436 nm. The pattern drawn on a resist film is a pattern formed in the phase shift film 30. A line-and-space pattern and a hole pattern are mentioned as a pattern drawn on a resist film.

Thereafter, the resist film is developed with a predetermined developer, and a first resist film pattern 50 is formed on the etching mask film 40 as shown in FIG. 3A.

2. First etching mask film pattern forming process

In the first etching mask film pattern forming process, first, the etching mask film 40 is etched using the first resist film pattern 50 as a mask to form the first etching mask film pattern 40a. 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, the etching solution containing cerium ammonium nitrate and perchloric acid is mentioned.

Thereafter, the first resist film pattern 50 is peeled off as shown in FIG. 3B by using a resist stripping solution or by ashing. You may perform the following phase shift film pattern formation process, without peeling the 1st resist film pattern 50 depending on a case.

3. Phase shift film pattern formation process

In a 1st phase shift film pattern formation process, the 1st etching mask film pattern 40a is used as a mask, the phase shift film 30 is wet-etched, and, as shown in FIG.3(c), the phase shift film pattern ( 30a) is formed. A line and space pattern and a hole pattern are mentioned as the phase shift film pattern 30a. The etching liquid which etches the phase shift film 30 will not be specifically limited if it can etch the phase shift film 30 selectively. For example, the etching liquid containing ammonium fluoride, phosphoric acid, and hydrogen peroxide, and the etching liquid containing ammonium hydrogen fluoride and hydrogen peroxide are mentioned.

In order for wet etching to make the cross-sectional shape of the phase shift film pattern 30a favorable, time (over) longer than time (just etching time) until the transparent substrate 20 is exposed in the phase shift film pattern 30a. etching time). As the over-etching time, in consideration of the influence on the transparent substrate 20 and the like, it is preferable to set the time of adding 10 to 20% of the just-etching time to the just-etching time.

4. Second resist film pattern forming process

In the second resist film pattern forming process, first, a resist film covering the first etching mask film pattern 40a is formed. The resist film material to be used is not particularly limited. For example, what is necessary is just to be photosensitive with respect to the laser beam which has any wavelength selected from the wavelength range of 350 nm - 436 nm mentioned later. In addition, any of a positive type and a negative type may be sufficient as a resist film.

Thereafter, a desired pattern is drawn on the resist film using laser light having a certain wavelength selected from a wavelength range of 350 nm to 436 nm. The pattern drawn on a resist film is the light-shielding band pattern which light-shields the outer periphery area|region of the area|region in which the phase shift film pattern 30a is formed, the light-shielding band pattern which light-shields the center part of the phase shift film pattern 30a, etc. Moreover, depending on the transmittance|permeability of the phase shift film 30 with respect to exposure light, the pattern drawn on a resist film may be a pattern without the light-shielding band pattern which shields the center part of the phase shift film pattern 30a from light.

Thereafter, the resist film is developed with a predetermined developer to form a second resist film pattern 60 on the first etching mask film pattern 40a as shown in FIG. 3D.

5. Second etching mask film pattern forming process

In the second etching mask film pattern forming step, the first etching mask film pattern 40a is etched using the second resist film pattern 60 as a mask, and as shown in FIG. 3E , the second etching mask A film pattern 40b is formed. The first etching mask film pattern 40a is formed of a chromium-based material containing chromium (Cr). The etching liquid for etching the first etching mask film pattern 40a is not particularly limited as long as it can selectively etch the first etching mask film pattern 40a. For example, an etching solution containing cerium ammonium nitrate and perchloric acid is mentioned.

Thereafter, the second resist film pattern 60 is removed using a resist stripping solution or by ashing.

In this way, the phase shift mask 100 is obtained. That is, the transfer pattern which the phase shift mask 100 which concerns on Embodiment 3 has may include the phase shift film pattern 30a and the 2nd etching mask film pattern 40b.

Moreover, although the said description demonstrated the case where the etching mask film 40 has the function which interrupts|blocks transmission of exposure light, the hard mask function when the etching mask film 40 simply etches the phase shift film 30 In the above description, in the case of having only The mask 100 is manufactured. That is, the transfer pattern which the phase shift mask 100 which concerns on Embodiment 3 has may be comprised only with the phase shift film pattern 30a. The transfer pattern may further include another film pattern. As another film, a film|membrane which suppresses reflection, an electroconductive film|membrane, etc. are mentioned, for example.

According to the manufacturing method of the phase shift mask 100 of this Embodiment 3, since the phase shift mask blank 10 of Embodiment 1 is used, the damage with respect to the transparent substrate 20 by a wet etching liquid was made into the origin. There is no fall of the transmittance|permeability of the board|substrate 20, and etching time can be shortened and the phase shift film pattern 30a with a cross-sectional shape, line edge roughness, and chemical resistance favorable can be formed. Therefore, the phase shift mask 100 which can transcribe|transfer the high-definition phase shift film pattern 30a with high precision can be manufactured. The phase shift mask 100 manufactured as described above can respond to line-and-space patterns or miniaturization of contact holes.

Manufacturing process of the phase shift mask 100 which concerns on Embodiment 4

1. Resist film pattern formation process

In a resist film pattern formation process, a resist film is first formed on the phase shift film 30 of the phase shift mask blank 10 of Embodiment 2. The resist film material to be used is the same as that described in the third embodiment. Moreover, before forming a resist film as needed, in order to make the phase shift film 30 and adhesiveness favorable, you may make it surface-modify processing to the phase shift film 30, even if it is made to perform a surface modification process. As described above, after the resist film is formed, a desired pattern is drawn on the resist film using laser light having a certain wavelength selected from a wavelength range of 350 nm to 436 nm. Then, a resist film is developed with a predetermined developing solution, and the resist film pattern 50 is formed on the phase shift film 30 as shown to Fig.4 (a).

2. Phase shift film pattern formation process

At a phase shift film pattern formation process, the phase shift film 30 is etched using a resist film pattern as a mask, and the phase shift film pattern 30a is formed as shown to FIG.4(b). Thereby, a transfer pattern is formed. The etching liquid and overetching time which etch the phase shift film pattern 30a and the phase shift film 30 are the same as what was demonstrated in Embodiment 3.

Thereafter, the resist film pattern 50 is peeled off using a resist stripping solution or by ashing (FIG. 4(c)).

In this way, the phase shift mask 100 is obtained. In addition, although the transfer pattern which the phase shift mask which concerns on this embodiment has is comprised only with the phase shift film pattern 30a, it can also contain another film pattern further. As another film, a film|membrane which suppresses reflection, an electroconductive film|membrane, etc. are mentioned, for example.

According to the manufacturing method of the phase shift mask 100 of this Embodiment 4, since the phase shift mask blank 10 of Embodiment 2 is used, the damage with respect to the transparent substrate 20 by a wet etching liquid was made into the origin. There is no fall of the transmittance|permeability of the board|substrate 20, and etching time can be shortened and the phase shift film pattern 30a with a cross-sectional shape, line edge roughness, and chemical resistance favorable can be formed. Therefore, the phase shift mask 100 which can transcribe|transfer the high-definition phase shift film pattern 30a with high precision can be manufactured. The phase shift mask 100 manufactured as described above can respond to line-and-space patterns or miniaturization of contact holes.

Embodiment 5.

In the fifth embodiment, a method for manufacturing a display device will be described. The display device uses the phase shift mask 100 manufactured using the phase shift mask blank 10 described above, or the phase shift mask 100 manufactured by the manufacturing method of the phase shift mask 100 described above. It is manufactured by performing the process (mask mounting process) of using and the process (exposure process) of exposing and transferring the transfer pattern containing the phase shift film pattern 30a to the resist film on the board|substrate for display devices.

Hereinafter, each process is demonstrated in detail.

1. Loading process

At a loading process, the phase shift mask 100 manufactured by Embodiment 3 or 4 is mounted on the mask stage of an exposure apparatus. Here, the phase shift mask 100 is arrange|positioned so that it may oppose the resist film formed on the display apparatus board|substrate through the projection optical system of an exposure apparatus.

2. Pattern transfer process

At a pattern transfer process, exposure light is irradiated to the phase shift mask 100, and the transfer pattern containing the phase shift film pattern 30a is transcribe|transferred to the resist film formed on the board|substrate for display devices. The exposure light is composite light including light of a plurality of wavelengths selected from a wavelength range of 365 nm to 436 nm, or monochromatic light selected by cutting a certain wavelength range from a wavelength range of 365 nm to 436 nm with a filter or the like. For example, exposure light is composite light containing at least one of i-line, h-line, and g-line, or monochromatic light of i-line. When the composite light is used as the exposure light, the exposure light intensity can be increased to increase the throughput, so that the manufacturing cost of the display device can be reduced.

According to the manufacturing method of the display device according to the fifth embodiment, it is possible to manufacture a high-definition display device having a high resolution and fine line-and-space pattern or contact hole.

[Example]

Example 1. A. Phase Shift Mask Blank

In order to manufacture the phase shift mask blank 10 of Example 1, first, as the transparent substrate 20, the synthetic|combination quartz glass substrate of 1214 size (1220 mm x 1400 mm) was prepared.

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

In order to form the phase shift film 30 on the other main surface of the transparent substrate 20, argon (Ar) gas and nitrogen (N2) in the 1st chamber of the state which made sputtering gas pressure into 0.5 Pa _first . A mixed gas composed of gas was introduced. And using a MoZrSi target in which the atomic ratio of Mo, Zr, and Si is Mo:Zr:Si=10:10:80, on the main surface of the transparent substrate 20 by reactive sputtering, molybdenum, zirconium, silicon and The phase shift film 30 of MoZrSiN system containing nitrogen was formed into a film with a film thickness of 143 nm. In addition, the atomic ratio in the said target for sputtering is an example, and can select suitably according to the composition of the desired phase shift film 30.

Next, import the transparent substrate 20 having a phase shift film 30 into the second chamber, and introducing a mixed gas of argon (Ar) gas and nitrogen (N ₂₎ gas in the second chamber, a reactive sputtering Thus, chromium nitride (CrN) containing chromium and nitrogen was formed on the phase shift film 30 (film thickness 15 nm). Next, a mixed gas of argon (Ar) gas and methane gas is introduced in a state in which the inside of the third chamber is set to a predetermined degree of vacuum, and chromium carbide (CrC) containing chromium and carbon is formed on CrN by reactive sputtering. was formed (film thickness 60 nm). Finally, a mixed gas of an argon (Ar) gas and a methane gas, a nitrogen (N ₂ ) gas, and an oxygen (O ₂ ) gas is introduced into the fourth chamber in a state of a predetermined vacuum degree, and by reactive sputtering On CrC, chromium carbonization oxynitride (CrCON) containing chromium, carbon, oxygen and nitrogen was formed (film thickness 30 nm). The etching mask film 40 of the lamination|stacking structure of a CrN layer, a CrC layer, and a CrCON layer was formed on the phase shift film 30 as mentioned above.

In this way, the 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.

With respect to the refractive index and extinction coefficient of the phase shift film 30 of the obtained phase shift mask blank 10, the phase shift film 30 was formed into a film on the main surface of the synthetic quartz glass substrate produced by setting it on the same tray, It measured using the board|substrate (dummy board|substrate) which has a phase shift film.

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

Moreover, with respect to the surface of the phase shift film 30 of the obtained phase shift mask blank 10, the transmittance|permeability and the phase difference were measured by MPM-100 by the Lasertec company. The transmittance|permeability of the phase shift film 30 and the measurement of the phase difference have the phase shift film by which the phase shift film 30 was formed into a film on the main surface of the synthetic quartz glass substrate which set on the same tray and produced similarly to what was mentioned above. A substrate (dummy substrate) was used. Before forming the etching mask film 40, the transmittance|permeability and phase difference of the phase shift film 30 took out and measured the board|substrate (dummy board|substrate) which has a phase shift film from a chamber. As a result, the transmittance was 50% (wavelength: 405 nm), the phase difference was 180° (wavelength: 405 nm), the back reflectance was 15.4% (wavelength: 405 nm), and the surface reflectance was 21.3% (wavelength: 405 nm).

Furthermore, the composition analysis of the depth direction by the X-ray photoelectron spectroscopy (XPS) was performed about the phase shift film 30 of the obtained phase shift mask blank 10.

The composition analysis result of the depth direction by XPS with respect to the phase shift mask blank 10 WHEREIN: The phase shift film 30 is the composition gradient area|region of the interface of the transparent substrate 20 and the phase shift film 30, and a phase Except for the composition gradient region of the interface between the shift film 30 and the etching mask film 40, the content rate of each constituent element is substantially constant toward the depth direction, Mo is 3 atomic %, Zr is 5 atomic %, Si is 42 atomic %, N 47 atomic %, O 3 atomic %. In addition, the atomic ratio of molybdenum and zirconium was 1:1, so it was in the range of Mo:Zr=1:0.67 to 1:4. Moreover, the content ratio of silicon with respect to the total of molybdenum, zirconium, and silicon was 84 atomic%, and thus [Si/(Mo+Zr+Si)]=70 to 88 atomic%. Moreover, it is thought that oxygen is contained in the phase shift film 30 by what a trace amount of oxygen existed in the chamber at the time of film-forming.

B. Phase shift mask and manufacturing method thereof

In order to manufacture the phase shift mask 100 using the phase shift mask blank 10 manufactured as described above, first, a resist coating apparatus is used on the etching mask film 40 of the phase shift mask blank 10 . Thus, a photoresist film was applied.

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

Then, the photoresist film was drawn using the laser drawing apparatus, and the resist film pattern of the hole pattern whose hole diameter is 1.5 micrometers was formed on the etching mask film through a developing and rinsing process.

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

Then, using the 1st etching mask film pattern 40a as a mask, the phase shift film 30 is wet-etched with the molybdenum silicide etching liquid which diluted the mixed solution of ammonium hydrogenfluoride and hydrogen peroxide with pure water, and phase shift film pattern ( 30a) was formed. This wet etching was performed at an overetching time of 10% in order to verticalize the cross-sectional shape and to form a required fine pattern.

Thereafter, the resist film pattern was peeled off.

Thereafter, using a resist coating device, a photoresist film was applied so as to cover the first etching mask film pattern 40a.

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

Thereafter, a photoresist film was drawn using a laser drawing apparatus, and a second resist film pattern 60 for forming a light-shielding band was formed on the first etching mask film pattern 40a through a development/rinsing process. .

Thereafter, using the second resist film pattern 60 as a mask, the first etching mask film pattern 40a formed in the transfer pattern formation region was wet-etched with a chromium etching solution containing cerium ammonium nitrate and perchloric acid.

Thereafter, the second resist film pattern 60 was peeled off.

Thus, in the transcription|transfer pattern formation area|region on the transparent substrate 20 in the lamination|stacking structure of the phase shift film pattern 30a whose hole diameter is 1.5 micrometers, the phase shift film pattern 30a, and the etching mask film pattern 40b The phase shift mask 100 in which the light-shielding band formed was obtained was obtained.

The cross section of the obtained phase shift mask was observed with the scanning electron microscope. The angle which the edge of the phase shift film pattern 30a of a phase shift mask saw from a cross section, and the main surface of the transparent substrate 20 made was 76 degrees, and the phase shift film pattern 30a had the cross-sectional shape near perpendicular|vertical. Moreover, when this phase shift film pattern 30a was observed from the top and LER of the said phase shift film pattern 30a was observed, the edge of the phase shift film pattern (hole pattern) 30a was smooth, it was substantially linear, and it was favorable. That is, in the edge of the phase shift film pattern 30a seen from the upper surface, the outstanding uneven|corrugated shape was not confirmed. The phase shift film pattern 30a formed in the phase shift mask of Example 1 had the cross-sectional shape which can fully exhibit a phase shift effect. Moreover, the surface of the exposed transparent substrate 20 after removing the phase shift film 30 was smooth, and the transmittance|permeability fall by the surface gap s of the transparent substrate 20 was negligible. Moreover, when the obtained phase shift mask 100 was observed by electron beam diffraction, it was able to confirm that it had become an amorphous structure. Moreover, penetration of etching liquid etc. was not seen in any of the interface with the etching mask film pattern 40b of the phase shift film pattern 30a, and the interface with the transparent substrate 20, and chemical resistance was also favorable. Therefore, in exposure light containing light in a wavelength range of 313 nm or more and 500 nm or less, more specifically, in exposure light of composite light containing at least one i-line, h-line, and g-line, excellent phase shift effect is obtained. The phase shift mask 100 which had was obtained.

For this reason, when the phase shift mask 100 of Example 1 is set on the mask stage of an exposure apparatus and exposure-transfer is carried out to the resist film on the board|substrate for display apparatuses, it can be said that a fine pattern of less than 2.0 micrometers can be transferred with high precision. have. Moreover, when the phase shift film 30 (phase shift film pattern 30a) becomes the minute film formed into a film in the state as low as a vacuum degree of 0.5 Pa or less, it is expectable that the light resistance in exposure light also becomes favorable.

Examples 2 to 4.

A. Phase Shift Mask Blank

In Examples 2-4, the phase shift mask blank 10 and the phase shift mask 100 were manufactured by the structure and method similar to Example 1 except the phase shift film 30. In Examples 2-4, the atomic ratio of sputtering target Mo at the time of forming the phase shift film 30 into a film in Example 1 mentioned above, Zr, and Si was adjusted suitably. Moreover, the phase shift film 30 adjusted film thickness suitably so that the transmittance|permeability in wavelength 405nm might become 20% or more and 80% or less, and phase difference might become the range of 160 degrees - 200 degrees.

As a result of analyzing the composition of the phase shift film 30 of the MoZrSiN system obtained similarly to Example 1, the atomic ratio of Mo and Zr became as follows.

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

Example 3 Mo:Zr=1:2,

Example 4 Mo:Zr=1:4,

Thus, also in any of Examples 2-4, it was in the range of Mo:Zr=1:0.67-1:4. Moreover, the content ratio of silicon with respect to the total of molybdenum, zirconium, and silicon was in the range of [Si/(Mo+Zr+Si)]=70-88 atomic% in any of Examples 2-4.

B. Phase shift mask and manufacturing method thereof

The surface state of the exposed transparent substrate 20 after carrying out similarly to Example 1 mentioned above, producing the phase shift mask 100, and removing the cross-sectional shape of the phase shift film pattern 30a, and the phase shift film 30 Confirmed. As a result, also in any one of Examples 2-4, the angle which the edge of the phase shift film pattern 30a of the phase shift mask 100 at the time of seeing from a cross section, and the main surface of the transparent substrate 20 makes 70 degrees It exceeded, and any phase shift film pattern 30a also had the cross-sectional shape near perpendicular|vertical. Moreover, similarly to Example 1, when LER of these phase shift film patterns 30a was observed, also in any of Examples 2-4, the edge of the phase shift film pattern (hole pattern) 30a is smooth and is substantially linear, and is favorable it was That is, in the edge of the phase shift film pattern 30a seen from the upper surface, the outstanding uneven|corrugated shape was not confirmed. The phase shift film pattern 30a formed in the phase shift mask of Examples 2-4 had the cross-sectional shape which can fully exhibit a phase shift effect. Moreover, also in any one of Examples 2-4, the surface of the exposed transparent substrate 20 after removing the phase shift film 30 is smooth, and the transmittance|permeability fall by surface s of the transparent substrate 20 is negligible. there was Moreover, when the obtained phase shift mask 100 was observed by electron beam diffraction, it was able to confirm that it had become an amorphous structure also in any of Examples 2-4. Moreover, in any one of Examples 2-4, permeation of etching liquid etc. is not seen in any of the interface with the etching mask film pattern 40b of the phase shift film pattern 30a, and the interface with the transparent substrate 20. Therefore, the tolerance was good. Therefore, in any one of Examples 2 to 4, exposure light containing light in a wavelength range of 313 nm or more and 500 nm or less, more specifically, composite light containing at least one of i-line, h-line, and g-line Exposure light WHEREIN: The phase shift mask 100 which has the outstanding phase shift effect was obtained.

For this reason, when the phase shift masks 100 of Examples 2 to 4 are set on the mask stage of the exposure apparatus and exposure-transferred to the resist film on the substrate for display apparatus, fine patterns smaller than 2.0 µm can be transferred with high precision. can do. Moreover, the phase shift film 30 (phase shift film pattern 30a) is expected that the light resistance in exposure light will become favorable by forming into a film in a state as low as a vacuum degree is 0.5 Pa or less, and setting it as a precise|minute film|membrane.

Example 5.

A. Phase Shift Mask Blank

The phase shift mask blank 10 of Example 5 is the phase shift mask blank 10 which reduced the back surface reflectance of the phase shift film 30 in exposure light. In the first chamber of the first In the sputtering gas pressure in the film forming 0.5㎩ state of the phase shift film 30 in accordance with the first embodiment described above, an argon (Ar) consisting of a gas and nitrogen (N ₂₎ gas A mixed gas was introduced. And using a MoZrSi target in which the atomic ratio of Mo, Zr, and Si is Mo:Zr:Si=10:10:80, on the main surface of the transparent substrate 20 by reactive sputtering, molybdenum, zirconium, silicon and A MoZrSiN-based underlayer film containing nitrogen was formed to a thickness of 105 nm. In addition, the atomic ratio in the said target for sputtering is an example, and can select suitably according to the composition of the desired phase shift film 30.

_{Thereafter, a mixed gas composed of argon (Ar) gas, nitrogen (N 2} ) gas, and nitrogen monoxide (NO) gas was introduced into the second chamber in a state where the sputtering gas pressure was 1.6 Pa. Then, using a MoSi target in which the atomic ratio of Mo and Si is Mo:Si=8:92, a MoSiON-based upper layer film containing molybdenum, silicon, oxygen and nitrogen is placed on the MoZrSiN-based lower layer film by reactive sputtering. It formed into a film at 44 nm, and the phase shift film 30 which consists of a laminated|stacked film which has the lower layer film of MoZrSiN system, and the upper layer film of MoSiON system was formed.

Next, it carries out similarly to Example 1, on the phase shift film 30, the etching mask film 40 of the lamination|stacking structure of a CrN layer, a CrC layer, and a CrCON layer is formed, and on the transparent substrate 20, the phase shift film ( 30) and the phase shift mask blank 10 in which the etching mask film 40 was formed were obtained.

The refractive index and extinction coefficient in the lower layer film and the upper layer film which comprise the phase shift film 30 of the obtained phase shift mask blank 10 were measured using the dummy board|substrate set in the same tray and produced.

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

Moreover, about the phase shift film 30 of the obtained phase shift mask blank 10, the transmittance|permeability and phase difference were measured similarly to Example 1. As a result, the transmittance was 51% (wavelength: 405 nm), the phase difference was 180° (wavelength: 405 nm), the back reflectance was 9.8% (wavelength: 405 nm), and the surface reflectance was 14.9% (wavelength: 405 nm).

Moreover, the composition analysis of the depth direction by X-ray photoelectron spectroscopy (XPS) was performed about the phase shift film 30 of the obtained phase shift mask blank 10 similarly to Example 1.

The composition analysis result of the depth direction by XPS with respect to the phase shift mask blank 10 WHEREIN: The phase shift film 30 is the composition gradient area|region of the interface of the transparent substrate 20 and the phase shift film 30, and a phase Except for the composition gradient region at the interface between the shift film 30 and the etching mask film 40, the content rate of each constituent element is almost constant toward the depth direction, and as for the underlayer film, Mo is 3 atomic % and Zr is 5 atomic %. , Si was 42 atomic %, N was 47 atomic %, and O was 3 atomic %. In addition, the atomic ratio of molybdenum and zirconium was Mo:Zr=1:1, so it was in the range of Mo:Zr=1:0.67 to 1:4. Moreover, the content ratio of silicon with respect to the total of molybdenum, zirconium, and silicon was 84 atomic%, and thus [Si/(Mo+Zr+Si)]=70 to 88 atomic%. In the upper layer film, Mo was 6 atomic %, Si was 41 atomic %, N was 47 atomic %, and O was 6 atomic %. In addition, it is thought that oxygen contained in the lower layer film is due to the presence of a trace amount of oxygen in the chamber at the time of film formation.

B. Phase shift mask and manufacturing method thereof

It carries out similarly to the Example mentioned above, produces the phase shift mask 100, and confirms the cross-sectional shape of the phase shift film pattern 30a, and the surface state of the exposed transparent substrate 20 after removing the phase shift film 30 did. The angle between the edge of the phase shift film pattern 30a of the phase shift mask 100 and the main surface of the transparent substrate 20 in a cross-sectional view exceeds 70 degrees at 72 degrees, and the phase shift film pattern 30a is It had a cross-sectional shape that was close to vertical. Moreover, similarly to Example 1, when LER of this phase shift film pattern 30a was observed, the edge of the phase shift film pattern (hole pattern) 30a was smooth, it was a substantially linear shape, and it was favorable. That is, in the edge of the phase shift film pattern 30a seen from the upper surface, the outstanding uneven|corrugated shape was not confirmed. The phase shift film pattern 30a formed in the phase shift mask 100 of Example 5 had the cross-sectional shape which can fully exhibit a phase shift effect. Moreover, the surface of the exposed transparent substrate 20 after removing the phase shift film 30 was smooth, and the transmittance|permeability fall by the surface gap s of the transparent substrate 20 was negligible. Moreover, when the obtained phase shift mask 100 was observed by electron beam diffraction, it was able to confirm that it had become an amorphous structure. Moreover, permeation of etching liquid etc. was not seen in any of the interface with the etching mask film pattern 40b of the phase shift film pattern 30a, and the interface with the transparent substrate 20, and chemical resistance was also favorable. Therefore, in exposure light containing light in a wavelength range of 313 nm or more and 500 nm or less, more specifically, in exposure light of composite light containing at least one of i-line, h-line, and g-line, excellent phase shift effect is obtained. The phase shift mask 100 which had was obtained.

For this reason, when the phase shift mask 100 of Example 5 is set on the mask stage of an exposure apparatus and exposure-transferred to the resist film on the board|substrate for display apparatuses, it can be said that a fine pattern of less than 2.0 micrometers can be transferred with high precision. have. Moreover, when the phase shift film 30 (phase shift film pattern 30a) becomes the minute film formed into a film in the state as low as a vacuum degree of 0.5 Pa or less, it is expectable that the light resistance in exposure light also becomes favorable.

Comparative Example 1.

A. Phase Shift Mask Blank

In the comparative example 1, the phase shift mask blank 10 and the phase shift mask 100 were manufactured by the structure and method similar to Example 1 except the phase shift film 30. In the comparative example 1, the atomic ratio of sputtering target Mo at the time of forming the phase shift film 30 into a film in Example 1 mentioned above, Zr, and Si was adjusted suitably. Moreover, the phase shift film adjusted film thickness suitably so that the transmittance|permeability in wavelength 405nm might become 20% or more and 80% or less, and phase difference might become the range of 160 degrees - 200 degrees.

As a result of analyzing the composition of the phase shift film 30 of the MoZrSiN system obtained similarly to Example 1, the atomic ratio of Mo and Zr became as follows.

Comparative Example 1

Mo:Zr=1:1, [Si/(Mo+Zr+Si)]=90 atomic%

Thus, in Comparative Example 1, Mo:Zr=1:0.67 to 1:4, but out of the range [Si/(Mo+Zr+Si)]=70 to 88 atomic%.

B. Phase shift mask and manufacturing method thereof

The surface state of the exposed transparent substrate 20 after carrying out similarly to Example 1 mentioned above, producing the phase shift mask 100, and removing the cross-sectional shape of the phase shift film pattern 30a, and the phase shift film 30 Confirmed.

As a result, in the comparative example 1, the cross-sectional shape of the phase shift film pattern 30a did not have a large difference compared with the other Example, and although it was favorable, the surface of the exposed transparent substrate 20 after removing the phase shift film 30 is It was rough, and even looking at it with the naked eye, it was in a cloudy state. Accordingly, the decrease in transmittance due to the surface thickness of the transparent substrate 20 was remarkable.

For this reason, when the phase shift mask 100 of Comparative Example 1 is set on the mask stage of the exposure apparatus and exposure-transferred to the resist film on the substrate for display apparatus, it is expected that a fine pattern of less than 2.0 µm cannot be transferred. .

Comparative Example 2.

A. Phase Shift Mask Blank

In the comparative example 2, the phase shift mask blank 10 and the phase shift mask 100 were manufactured by the structure and method similar to Example 1 except the phase shift film 30. In the comparative example 2, the atomic ratio of sputtering target Mo at the time of forming the phase shift film 30 into a film in Example 1 mentioned above, Zr, and Si was adjusted suitably. Moreover, the phase shift film 30 adjusted film thickness suitably so that the transmittance|permeability in wavelength 405nm might become 20% or more and 80% or less, and phase difference might become the range of 160 degrees - 200 degrees.

As a result of analyzing the composition of the phase shift film 30 of the MoZrSiN system obtained similarly to Example 1, the atomic ratio of Mo and Zr became as follows.

Comparative Example 2

Mo:Zr=1:1, [Si/(Mo+Zr+Si)]=65 atomic%

Thus, in Comparative Example 2, Mo:Zr=1:0.67 to 1:4, but out of the range [Si/(Mo+Zr+Si)]=70 to 88 atomic%.

B. Phase shift mask and manufacturing method thereof

The surface state of the exposed transparent substrate 20 after carrying out similarly to Example 1 mentioned above, producing the phase shift mask 100, and removing the cross-sectional shape of the phase shift film pattern 30a, and the phase shift film 30 Confirmed.

As a result, in the comparative example 2, the surface of the exposed transparent substrate 20 after removing the phase shift film 30 is smooth, and the transmittance|permeability fall by surface thickness s of the transparent substrate 20 is negligible. However, the cross-sectional shape of the phase shift film pattern 30a was bad and did not become the cross-sectional shape which can fully exhibit the phase shift effect.

For this reason, when the phase shift mask 100 of Comparative Example 2 is set on the mask stage of an exposure apparatus and exposure-transferred to a resist film on a substrate for a display device, it is expected that a fine pattern of less than 2.0 µm cannot be transferred. .

Comparative Example 3.

A. Phase Shift Mask Blank

In the comparative example 3, the phase shift mask blank 10 and the phase shift mask 100 were manufactured by the structure and method similar to Example 1 except the phase shift film 30. In the comparative example 3, the atomic ratio of sputtering target Mo at the time of forming the phase shift film 30 into a film in Example 1 mentioned above, Zr, and Si was adjusted suitably.

As a result of having analyzed the composition of the obtained MoZrSiN system phase shift film 30 similarly to Example 1, in the comparative example 3, an atomic ratio is Mo:Zr=2:1, and 1:0.67 - 1:4 outside the range it was On the other hand, the content ratio of silicon to the total of molybdenum, zirconium, and silicon was in the range of [Si/(Mo+Zr+Si)]=70 to 88 atomic%.

B. Phase shift mask and manufacturing method thereof

The surface state of the exposed transparent substrate 20 after carrying out similarly to Example 1 mentioned above, producing the phase shift mask 100, and removing the cross-sectional shape of the phase shift film pattern 30a, and the phase shift film 30 Confirmed.

As a result, in the comparative example 3, the surface of the exposed transparent substrate 20 after removing the phase shift film 30 is smooth, and the transmittance|permeability fall by surface gap s of the transparent substrate 20 is negligible. it was Moreover, the cross-sectional shape of the phase shift film pattern 30a did not have a big difference compared with another Example, and it was favorable. On the other hand, the transmittance|permeability in wavelength 405nm was less than 15 %, and sufficient transmittance|permeability was not obtained. Although the film thickness was adjusted similarly to the other Example and the comparative example, sufficient transmittance|permeability still could not be obtained.

For this reason, when the phase shift mask 100 of Comparative Example 3 is set on the mask stage of an exposure apparatus and exposure-transferred to a resist film on a substrate for a display device, it is expected that a fine pattern of less than 2.0 µm cannot be transferred. .

Comparative Example 4.

A. Phase Shift Mask Blank

In the comparative example 4, the phase shift mask blank 10 and the phase shift mask 100 were manufactured by the structure and method similar to Example 1 except the phase shift film 30. In the comparative example 4, the atomic ratio of sputtering target Mo at the time of forming a phase shift film into a film in Example 1 mentioned above, Zr, and Si was adjusted suitably. Moreover, the phase shift film 30 adjusted film thickness suitably so that the transmittance|permeability in wavelength 405nm might become 20% or more and 80% or less, and phase difference might become the range of 160 degrees - 200 degrees.

As a result of having analyzed the composition of the obtained MoZrSiN system phase shift film 30 similarly to Example 1, in the comparative example 4, the atomic ratio of molybdenum and zirconium is Mo:Zr=1:5, 1:0.67-1: 4 was out of range. On the other hand, the content ratio of silicon to the total of molybdenum, zirconium, and silicon was in the range of [Si/(Mo+Zr+Si)]=70 to 88 atomic%.

B. Phase shift mask and manufacturing method thereof

It carried out similarly to Example 1 mentioned above, produced the phase shift mask 100, and confirmed the cross-sectional shape of a phase shift film pattern, and the surface state of the exposed transparent substrate 20 after removing the phase shift film 30.

As a result, in the comparative example 4, the surface of the exposed transparent substrate 20 after removing the phase shift film 30 is smooth, and the transmittance|permeability fall by surface thickness s of the transparent substrate 20 is negligible. However, sufficient chemical resistance was not obtained, but the cross-sectional shape of the phase shift film pattern 30a had deteriorated compared with another Example. Moreover, both the surface reflectance and back surface reflectance in wavelength 405nm were high, and sufficient transcription|transfer precision was not acquired.

For this reason, when the phase shift mask 100 of Comparative Example 4 is set on the mask stage of the exposure apparatus and exposure-transferred to the resist film on the substrate for display apparatus, it is expected that a fine pattern of less than 2.0 µm cannot be transferred. .

10: phase shift mask blank
20: transparent substrate
30: phase shift film
30a: phase shift film pattern
40: etching mask film
40a: first etching mask film pattern
40b: second etching mask film pattern
50: first resist film pattern
60: second resist film pattern
100: phase shift mask

Claims (10)

It is a photomask blank which has a phase shift film on a transparent substrate,
The said photomask blank is an original plate for forming a photomask, this photomask is a photomask which has a phase shift film pattern obtained by wet-etching the said phase shift film on the said transparent substrate,
The phase shift film is composed of a single layer or multiple layers, and 50% or more and 100% or less of the total film thickness of the phase shift film is a material containing molybdenum (Mo), zirconium (Zr), silicon (Si), and nitrogen. Including a MoZrSi-based material layer made of,
The MoZrSi-based material layer is characterized in that the atomic ratio of molybdenum and zirconium is Mo:Zr=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% A photomask blank with According to claim 1,
The said phase shift film is equipped with the optical characteristic of 20 % or more and 80 % or less of transmittance with respect to the representative wavelength of exposure light, and phase difference is 160 degrees or more and 200 degrees or less A photomask blank characterized by the above-mentioned. 3. The method of claim 1 or 2,
The said phase shift film is a laminated|multilayer film containing the lower layer by the side of the said transparent substrate, and the upper layer laminated|stacked on the said lower layer, The said lower layer is the said MoZrSi system material layer, The photomask blank characterized by the above-mentioned. 4. The method of claim 3,
The upper layer is made of a material smaller than the refractive index of the lower layer and higher than the extinction coefficient at a representative wavelength of exposure light. 5. The method of claim 4,
As for the said phase shift film, the refractive index, extinction coefficient, and film thickness of each of the said upper layer and the said lower layer are set so that the back surface reflectance with respect to the representative wavelength of exposure light may be 15 % or less, The photomask blank characterized by the above-mentioned. 3. The method of claim 1 or 2,
On the said phase shift film, the etching mask film from which etching selectivity differs with respect to this phase shift film is provided, The photomask blank characterized by the above-mentioned. A step of preparing the photomask blank according to claim 1 or 2;
A resist film is formed on the said phase shift film, the said phase shift film is wet-etched using the resist film pattern formed from the said resist film as a mask, It has the process of forming a phase shift film pattern on the said transparent substrate, It is characterized by the above-mentioned A method of manufacturing a photomask. A step of preparing the photomask blank according to claim 6;
The process of forming a resist film on the said etching mask film, wet-etching the said etching mask film using the resist film pattern formed from the said resist film as a mask, and forming an etching mask film pattern on the said phase shift film;
The said etching mask film pattern is used as a mask, the said phase shift film is wet-etched, and it has the process of forming a phase shift film pattern on the said transparent substrate, The manufacturing method of the photomask characterized by the above-mentioned. The photomask obtained by the manufacturing method of the photomask of Claim 7 is mounted on the mask stage of exposure apparatus, The resist formed on the display apparatus board|substrate with the transcription|transfer pattern containing the said phase shift film pattern formed on the said photomask. A method of manufacturing a display device, comprising: an exposure step of performing exposure transfer to the . The photomask obtained by the manufacturing method of the photomask of Claim 8 is mounted on the mask stage of an exposure apparatus, The resist formed on the display apparatus board|substrate with the transcription|transfer pattern containing the said phase shift film pattern formed on the said photomask. A method of manufacturing a display device, comprising: an exposure step of performing exposure transfer to the .

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