KR101935171B1 - Phase-shift mask blank for display device manufacture, phase-shift mask for display device manufacture and its manufacturing method, and method for manufacturing display device - Google Patents

Abstract

There is provided a phase shift mask blank for device fabrication having a phase shift film exhibiting optical characteristics in which wavelength dependency of exposure light is suppressed.
The phase shift mask blank 1 includes a transparent substrate 2 and a phase shift film 3 formed on the transparent substrate 2. [ The phase shift film 3 includes a single-layer film or a laminate film having at least one metal silicide-based material layer containing a metal, silicon and any one element of nitrogen and / or oxygen. The phase shift film 3 has a transmittance at a wavelength of 365 nm in a range of 3.5% to 8%, a phase difference at a wavelength of 365 nm in a range of 160 to 200 degrees, a wavelength in a range of 365 nm to 436 nm The change amount of the transmittance depending on the wavelength is within 5.5%.

Description

TECHNICAL FIELD [0001] The present invention relates to a phase shift mask blank for use in manufacturing a display device, a phase shift mask for manufacturing a display device, a method of manufacturing the same, and a manufacturing method of a display device. AND METHOD FOR MANUFACTURING DISPLAY DEVICE}

The present invention relates to a phase shift mask blank for manufacturing a display device, a phase shift mask for manufacturing a display device using the phase shift mask blank, a method of manufacturing the same, and a method of manufacturing a display device using the phase shift mask.

At present, there are a VA (vertical alignment) method and an IPS (In Plane Switching) method as a method adopted in a liquid crystal display device. With this method, realization of a liquid crystal display device with high precision, high-speed display performance, and wide viewing angle is being realized. In the liquid crystal display device to which this method is applied, the response speed and the viewing angle can be improved by patterning the transparent conductive film by, for example, a photolithography process and forming a pixel electrode of a line-and-space pattern. In recent years, from the viewpoints of further improving the response speed and the viewing angle, and improving the light utilization efficiency of the liquid crystal display device, that is, lowering the power consumption and improving the contrast of the liquid crystal display device, . For example, it is desired to narrow the pitch width of the line-and-space pattern from 6 탆 to 5 탆 and from 5 탆 to 4 탆.

In manufacturing a liquid crystal display device or an organic EL display device, a semiconductor device such as a transistor is formed by stacking a plurality of conductive films and insulating films which are subjected to necessary patterning. At this time, a photolithography process is often used for patterning individual films to be laminated. For example, a thin film transistor or LSI used in this display device has a structure in which a contact hole is formed in an insulating layer by a photolithography process, and a pattern in an upper layer and a pattern in a lower layer are connected. In recent years, there has been a growing demand for displaying a bright, detailed image with a sufficient operation speed and reducing power consumption in such a display device. In order to meet such a demand, it is required that the constitutional elements of the display device are made finer and highly integrated. For example, it is desired to reduce the diameter of the contact hole from 3 탆 to 2.5 탆, 2 탆 and 1.5 탆.

From such a background, there is a demand for a photomask for manufacturing a display device capable of coping with the miniaturization of line-and-space patterns and contact holes.

In realizing a line-and-space pattern or a contact hole, in the conventional photomask, since the resolution limit of the exposure apparatus for manufacturing a display device is 3 m, the minimum line width close to the marginal limit The product must be produced. As a result, there has been a problem that the defective rate of the display device is increased.

For example, in the case of using a photomask having a hole pattern for forming a contact hole and considering transferring the photomask to a transfer target, if the hole pattern has a diameter exceeding 3 mu m, the transfer can be performed using a conventional photomask. However, it is very difficult to transfer a hole pattern having a diameter of 3 mu m or less, particularly, a hole pattern having a diameter of 2.5 mu m or less. In order to transfer a hole pattern having a diameter of 2.5 mu m or less, it is conceivable to switch to, for example, an exposure machine having a high NA, but a large investment is required.

Therefore, a phase shift mask has attracted attention as a photomask for manufacturing a display device in order to cope with miniaturization of a line-and-space pattern and a contact hole by improving the resolution.

In recent years, a phase shift mask having a chrome phase shift film has been developed as a photomask for manufacturing a liquid crystal display device.

Patent Document 1 discloses a transparent substrate, a light-shielding layer formed on the transparent substrate, chromium oxynitride (CrO), which is capable of imparting a retardation of 180 degrees to light of any one of wavelengths from 300 nm to 500 nm Type phase shift mask including a phase shift layer including a single-phase phase shift layer including a single-phase phase shift material. The phase shift mask is formed by patterning a light shielding layer on a transparent substrate, forming a phase shift layer on the transparent substrate so as to cover the light shielding layer, forming a photoresist layer on the phase shift layer, Forming a resist pattern by exposure and development, and patterning the phase shift layer using the resist pattern as an etching mask.

The chromium phase shift layer of this single layer is formed in a sputter gas atmosphere containing a mixed gas of nitrogen (N ₂ ) gas and carbon dioxide (CO ₂ ) gas (see the sample No. 2 in FIG. 2 of Patent Document 1). 1 to 5). Therefore, it is presumed that the phase-shifting layer is formed of chromium oxynitride (CrOCN) as well as chromium oxide (CrON).

Such phase shift masks receive exposure light of various wavelengths outputted from various exposure apparatuses.

For example, in the case of a phase shift mask for manufacturing a liquid crystal display device, as an exposure device used in a photolithography process, for example, an i-line (365 nm), h line (405 nm), and g line (436 nm) And a light source (ultrahigh-pressure UV lamp) for outputting composite light. For example, when the complex light is used as the exposure light for transferring the mask pattern of the phase shift mask onto the main surface of the mother glass substrate whose size has been enlarged in accordance with recent enlargement of the liquid crystal display device, And it is possible to shorten the tact time.

In general, it is known that, in a light having a certain wavelength, a film showing a certain degree of transmittance has a wavelength dependency, that is, a wavelength dependency, in optical characteristics including its transmittance.

Since the phase shift film is a film having a property of changing the phase of exposure light, it exhibits a certain degree of transmittance in the exposure light in its nature. Therefore, according to the above knowledge, the phase shift film has wavelength dependency on transmittance, reflectance and phase difference in exposure light.

Patent Document 2 discloses a photomask having a phase shift film in which a retardation deviation and a transmittance deviation are suppressed.

Japanese Patent Application Laid-Open No. 11-13283 Japanese Patent Application Laid-Open No. 230309/1989

However, the phase shift films specifically described in the above-mentioned Patent Documents 1 and 2 are all chromium phase shift films in a single layer. Therefore, when a fine pattern such as a contact hole diameter of 2.5 占 퐉 or 2 占 퐉 is transferred using a phase shift mask obtained by using such a phase shift film material, wavelength dependency such as transmittance in exposure light is sufficient Or the sectional shape of the phase shift film pattern can not be verticalized, there is a problem that the resolution can not be sufficiently obtained.

In order to recognize an alignment mark provided on a mask, a light source for alignment is provided in a drawing device for mask production or an exposure device used in manufacturing a display device. As the alignment light, for example, light having a wavelength of 365 to 700 nm is used, and the alignment mark is detected by using the difference in transmittance between the transparent substrate and the alignment mark in the alignment light. The greater the difference in the transmittance in the alignment light (wavelength 365 to 700 nm), the easier the alignment is recognized and the alignment accuracy is improved, so that it is possible to improve the handleability of the phase shift mask. However, the phase shift masks of Patent Documents 1 and 2 described above can not necessarily have sufficient characteristics in handling properties.

It is known that a mask inspection apparatus is provided with a light source for outputting light having a wavelength of 365 nm or 546 nm, for example. It is known to identify the mask pattern by using the difference between the reflectance of the transparent substrate and the mask pattern in the inspection light of the mask inspection apparatus and the difference in transmittance. By using such a mask inspection apparatus, it becomes possible to grasp, for example, defective shape defects of the mask pattern and presence or absence of foreign matter adhering to the mask pattern. However, the phase shift masks described in Patent Documents 1 and 2 can not necessarily have sufficient characteristics as the optical characteristics of the phase shift film in the mask inspection.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a phase shift mask blank for manufacturing a display device having a phase shift film exhibiting optical characteristics in which the wavelength dependency of each optical characteristic to exposure light is suppressed, It is an object of the present invention to provide a phase shift mask using a mask blank, a manufacturing method thereof, and a manufacturing method of a display device using the phase shift mask.

In order to solve the above-described problems, the present invention has the following configuration.

(Composition 1) In a phase shift mask blank for producing a display device,

A transparent substrate,

The phase shift film formed on the transparent substrate

And,

Wherein the phase shift film includes a single layer film or a lamination film having at least one layer of a metal silicide-based material layer containing a metal, silicon and any one element of nitrogen and / or oxygen,

The phase-

The transmittance in the light having a wavelength of 365 nm is in the range of 3.5% or more and 8% or less,

The retardation in the light having a wavelength of 365 nm is in the range of 160 to 200 degrees,

The amount of change in the transmittance in the wavelength range of 365 nm or more and 436 nm or less depending on the wavelength is within 5.5%

Wherein the phase shift mask blank is a phase shift mask blank.

(Constitution 2)

The phase shift mask blank according to Structure 1, wherein the amount of change in the transmittance in the wavelength range of 365 nm to 700 nm is within 20%.

(Constitution 3) The phase-

Wherein a difference between a retardation imparted at a wavelength of 365 nm and a retardation imparted at a wavelength of 436 nm is 30 degrees or less,

Wherein the phase shift mask blank is a phase shift mask blank.

(Constitution 4) The phase-

The phase shift mask blank according to any one of Structures 1 to 3, wherein the reflectance in the wavelength range of 365 nm to 700 nm is 5% or more and 45% or less.

(Constitution 5) The phase shift mask blank according to Structure 4, wherein the phase shift film has a variation of wavelength dependence of the reflectance in a wavelength range of 365 nm to 700 nm within 5%.

(Constitution 6) The phase shift mask blank according to any one of Structures 1 to 5, wherein the phase shift film is composed of at least one metal silicide-based material layer and at least one chromium-based material layer.

(Composition 7) The metal silicide-based material layer may be formed of at least one of a nitride of a metal suicide, an oxide of a metal suicide, an oxynitride of a metal suicide, a carbonitride of a metal suicide, an oxycarbide of a metal suicide, Of the phase shift mask blank according to any one of Structures 1 to 6.

(Constitution 8) The chromium-based material layer is made of at least one material selected from among nitride of chromium, oxide of chromium, carbide of chromium, nitride of oxynitride of chromium, carbonitride of chromium, oxide of carbide of chromium and oxide carbonitride of chromium Wherein the phase shift mask blank is configured such that the phase shift mask blank is configured such that the phase shift mask blank is formed.

(Constitution 9) The phase shift mask blank according to Structure 6, wherein the film thickness of the metal silicide-based material layer is larger than the film thickness of the chromium-based material layer.

(Constitution 10) The phase shift mask blank according to any one of Structures 1 to 9, characterized by comprising a light shielding film formed on the phase shift film.

(Configuration 11) In a phase shift mask for manufacturing a display device,

A transparent substrate,

The phase shift film pattern formed on the transparent substrate

And,

Wherein the phase shift film pattern includes a single layer film or a laminated film having at least one layer of a metal silicide-based material layer containing a metal, silicon and any one element of nitrogen and / or oxygen,

The phase shift film pattern may be formed,

The transmittance in the light having a wavelength of 365 nm is in the range of 3.5% or more and 8% or less,

The phase difference at a wavelength of 365 nm is in the range of 160 to 200 degrees,

Wherein the amount of change in the transmittance in the wavelength range from 365 nm to 436 nm is within 5.5%

Wherein the phase shift mask is a phase shift mask.

(Constitution 12) In the phase shift film pattern,

The phase shift mask according to Structure 11, characterized in that the amount of change in the transmittance in the wavelength range of 365 nm to 700 nm is 20% or less.

(Constitution 13) The phase shift film pattern according to <

Wherein the difference between the retardation imparted at a wavelength of 365 nm and the retardation imparted at a wavelength of 436 nm is 30 degrees or less.

(Constitution 14) The phase shift film pattern is characterized in that,

The phase shift mask according to any one of Structures 11 to 13, wherein the reflectance in the wavelength range of 365 nm to 700 nm is 15% or more and 30% or less.

(Constitution 15) In the phase shift film pattern,

The phase shift mask according to Structure 14, characterized in that the amount of change in wavelength dependence of the reflectance in the wavelength range of 365 nm to 700 nm is within 5%.

(Constitution 16) The phase shift mask according to any one of structures 11 to 15, characterized by comprising a light-shielding film pattern formed on the phase shift film pattern.

(Constitution 17) The phase shift mask according to any one of structures 11 to 16, further comprising a light-shielding film pattern formed under the phase shift film pattern.

(Constitution 18) A method of manufacturing a phase shift mask for manufacturing a display device,

A resist pattern forming step of forming a resist pattern on the phase shift film of the phase shift mask blank according to any one of Structures 1 to 9,

A phase shift film pattern forming step of wet-etching the phase shift film using the resist pattern as a mask to form a phase shift film pattern

Wherein the phase shift mask is formed on the substrate.

(Constitution 19) A method of manufacturing a phase shift mask for manufacturing a display device,

A resist pattern forming step of forming a resist pattern on the light-shielding film of the phase shift mask blank described in Structure 10,

Forming a light-shielding film pattern by wet-etching the light-shielding film using the resist pattern as a mask;

A phase shift film pattern forming step of wet-etching the phase shift film using the light-shielding film pattern as a mask to form a phase shift film pattern

Wherein the phase shift mask is formed on the substrate.

(Composition 20) A method of manufacturing a display device,

A phase shift mask according to any one of Structures 11 to 17 or a phase shift mask obtained by a method for manufacturing a phase shift mask according to Structure 18 or 19 is applied to a substrate having a resist film on which a resist film is formed on the substrate, A phase shift mask disposing step of disposing the phase shift mask,

a resist film exposing step for exposing the resist film by irradiating the phase shift mask with composite exposure light including i line, h line and g line,

The method comprising the steps of:

As described above, according to the phase shift mask blank for manufacturing a display device according to the present invention, a transparent substrate and a phase shift film formed on the transparent substrate are provided. The phase shift film includes a single layer film or a laminated film having at least one layer of metal, silicon, and a metal silicide-based material layer containing any one element of nitrogen and / or oxygen. The phase shift film has a transmittance in a wavelength of 365 nm in a range of 3.5% to 8%, a retardation in a wavelength of 365 nm in a range of 160 to 200 degrees, a transmittance in a wavelength range of 365 nm to 436 nm Of the wavelength-dependent variation is within 5.5%. Such a phase shift film exhibits optical characteristics in which the wavelength dependence of the transmittance in the light in the wavelength range of 365 nm or more and 436 nm or less is suppressed.

This makes it possible to obtain a phase shift mask blank provided with a phase shift film which can sufficiently exhibit the phase shift effect and improve the resolution when exposure light of the wavelength range is received. Further, a phase shift mask blank having a phase shift film capable of patterning into a phase shift film pattern capable of enhancing the resolution and enhancing the light intensity tilt at the pattern boundary portion and obtaining a desired transfer pattern shape having good CD characteristics Can be obtained.

Further, according to the phase shift mask for manufacturing a display device according to the present invention, a transparent substrate and a phase shift film pattern formed on the transparent substrate are provided. The phase shift film pattern includes a single layer film or a laminated film having at least one layer of a metal silicide-based material layer containing a metal, silicon, and any one element of nitrogen and / or oxygen. The phase shift film pattern has a transmittance in a wavelength of 365 nm in a range of 3.5% to 8%, a phase difference in a wavelength of 365 nm in a range of 160 to 200 degrees, a wavelength in a range of 365 nm to 436 nm Of the transmittance depending on the wavelength is within 5.5%. Such a phase shift film pattern exhibits optical characteristics in which the wavelength dependence of the transmittance in the light in the wavelength range of 365 nm or more and 436 nm or less is suppressed.

This makes it possible to sufficiently exhibit the phase shift effect when exposure light of the wavelength range is received, to strengthen the inclination of the optical intensity at the pattern boundary portion, to provide a phase shift capable of obtaining a desired transferred pattern shape having good CD characteristics A phase shift mask having a film pattern can be obtained. This phase shift mask can cope with the miniaturization of a line-and-space pattern or a contact hole.

Further, according to the method for manufacturing a phase shift mask for manufacturing a display device according to the present invention, the phase shift mask is manufactured using the phase shift mask blank described above. This makes it possible to produce a phase shift mask having a phase shift film pattern exhibiting optical characteristics in which the wavelength dependence of the exposure light is suppressed. According to this phase shift mask, the phase shift effect can be sufficiently exhibited, the optical intensity gradient at the pattern boundary portion can be strengthened, and a desired transfer pattern shape having good CD characteristics can be obtained.

According to the method of manufacturing a phase shift mask for manufacturing a display device according to the present invention, a phase shift mask blank having a light shielding film formed on the phase shift film of the above-mentioned phase shift mask blank is used, Thereby producing a phase shift mask having a pattern. This makes it possible to produce a phase shift mask having a phase shift film pattern exhibiting optical characteristics in which the wavelength dependence of the exposure light is suppressed. According to this phase shift mask, the phase shift effect can be sufficiently exhibited, the optical intensity gradient at the pattern boundary portion of the phase shift film pattern in which the light-shielding film pattern is not laminated can be strengthened, and the desired transfer pattern shape Can be obtained.

Further, according to the method for manufacturing a display device according to the present invention, by manufacturing the display device using the phase shift mask or the phase shift mask obtained by the above-mentioned method for manufacturing a phase shift mask, A display device having a hole can be manufactured. In addition, it is possible to precisely align the line-and-space pattern of the display device and the contact hole, thereby improving the manufacturing yield of the display device.

1 is a cross-sectional view showing the structure of a phase shift mask blank for manufacturing a display device according to Embodiment 1 of the present invention.
2 is a cross-sectional view for explaining a configuration of a phase shift mask for manufacturing a display device according to Embodiment 2 of the present invention.
3 is a view for explaining a method of manufacturing a phase shift mask using a phase shift mask blank.
4 is a transmittance spectrum of each phase shift film of the phase shift mask blank (Examples 1, 2, 5, 6 and 9, Comparative Examples 1 and 2).
5 is a transmittance spectrum of each phase shift film of the phase shift mask blank (Examples 3, 4, 7, 8 and 9, Comparative Examples 1 and 2).
6 is a reflectance spectrum showing the reflectance of each phase shift film of the phase shift mask blank (Examples 1, 2, 5, 6 and 9, and Comparative Examples 1 and 2).
7 is a reflectance spectrum showing the phase shift film reflectance of the phase shift mask blank (Examples 3, 4, 7, 8 and 9, Comparative Examples 1 and 2).
8 is a table showing the optical characteristics of the phase shift film of the phase shift mask blank.
9 is a simulation result (light intensity distribution) on the space of light that has passed through the phase shift mask (Embodiments 1, 3, 7 and 9 and Comparative Example 2).
10 is a simulation result (light intensity distribution) on the space of light that has passed through the phase shift mask (Examples 2, 4, 6 and 8 and Comparative Example 1).

Hereinafter, a phase shift mask blank for manufacturing a display device according to an embodiment of the present invention, a phase shift mask for manufacturing a display device using the phase shift mask blank, a method for manufacturing the same, and a method for manufacturing a display device using the phase shift mask Will be described in detail.

Embodiment 1

In Embodiment 1, a phase shift mask blank for manufacturing a display device and a manufacturing method thereof will be described.

First, the phase shift mask blank for manufacturing the display device of Embodiment 1 will be described.

1 is a cross-sectional view showing a structure of a phase shift mask blank for manufacturing a display device according to Embodiment 1 of the present invention.

The phase shift mask blank 1 according to the first embodiment includes a transparent substrate 2 and a phase shift film 3 formed on the transparent substrate 2. Alternatively, the light shielding film 4 may be formed on the phase shift film 3. Alternatively, the resist film 5 may be formed on the phase shift film 3 or the light-shielding film 4.

The transparent substrate 2 has transparency to the exposure light to be used. The material of the transparent substrate 2 is not particularly limited as long as it is a material having translucency to the exposure light to be used. Examples of the material having translucency include synthetic quartz glass, soda lime glass, and alkali-free glass.

The phase shift film 3 includes a single layer film or a lamination film having at least one layer of a metal silicide-based material layer containing a metal, silicon, and any one element of nitrogen and / or oxygen. The optical characteristics of the entire phase shift film 3 are determined depending on the kind of the material constituting the material layer constituting the phase shift film 3 and the film thickness or the like when the phase shift film 3 includes a single layer film In the case where the phase shift film 3 is determined by optical properties such as refractive index, transmittance and reflectance of the material layer and includes a laminated film, a plurality of material layers constituting the phase shift film 3 are constituted The combination of the optical characteristics determined in accordance with the kind of the material and the thickness of the material to be formed, the order of lamination of the respective material layers, and the number of laminated layers. Here, the single-layer film in the case where the phase shift film 3 includes a single-layer film is a film formed of a single material. Therefore, the film of the laminated structure including a single material is also a single layer film. The laminated film in the case where the phase shift film 3 includes a laminated film refers to a laminated film formed by combining a film formed of a single material or a similar material and a film formed of a material different from the film to be.

The phase shift film 3 is formed by selecting the material layer constituting the phase shift film 3 so that the transmittance in the light of the specific wavelength is controlled in the following range and the transmittance in the light of the specific wavelength And the phase difference are controlled in the following ranges, and the amount of change in the transmittance, the phase difference, and the reflectance depending on the wavelength in the light in the specific wavelength range is suppressed to the following range.

Specifically, the phase shift film 3 has a transmittance at a wavelength of 365 nm (hereinafter sometimes referred to as T% (365)) in the range of 3.5% or more and 8% or less. As a result, the light intensity gradient at the pattern boundary becomes strong, and the resolution can be improved. If T% (365) is less than 3.5%, it is difficult to collect the light amount of the transmitted light necessary to sufficiently exhibit the desired phase shift effect. If T% (365) exceeds 8%, the light intensity gradient at the pattern boundary becomes weak, and it becomes difficult to improve the resolution.

The phase shift film 3 is within 5.5% of the change amount depending on the wavelength (hereinafter sometimes referred to as? T% (436-365)) of the transmittance in the wavelength range of 365 nm or more and 436 nm or less. Since the wavelength dependence of the transmittance in the wavelength range is suppressed, the optical intensity inclination at the pattern boundary portion becomes strong, and it becomes possible to improve the resolution. (405 nm) and g-line (436 nm) having peak intensities other than the i-line (365 nm) when ΔT% 436-365 exceeds 5.5% And it is difficult to improve the resolution. Further, the phase shift film 3 is preferable because the transmittance of the g line (436 nm) is less than 10%, particularly the resolution is improved.

The phase shift film 3 has a retardation at a wavelength of 365 nm (hereinafter sometimes referred to as P (365)) in the range of 160 to 200 degrees. Therefore, a phase difference of about 180 degrees can be obtained, and the phase shift effect can be sufficiently exhibited. When the P 365 is less than 160 degrees or more than 200 degrees, a phase difference of about 180 degrees can not be obtained, and it becomes difficult to exhibit the phase shift effect.

The phase shift film 3 preferably has a variation amount (hereinafter sometimes referred to as? T% (700-365)) of the transmittance in a wavelength range of 365 nm to 700 nm, within 20% Do. In this case, since the wavelength shift of the transmittance is suppressed in the wavelength range of the phase shift film 3, it is easy to recognize the alignment mark provided in the mask in the exposure apparatus in the display device manufacturing, do. Further, in the case of the inspection apparatus for identifying the mask pattern by using the difference in the transmittance between the transparent substrate and the mask pattern in the mask inspection apparatus, defects such as defective shape of the mask pattern can be easily recognized.

In the phase shift film 3, the difference (? P (365-436)) between the retardation imparted at a wavelength of 365 nm and the retardation imparted at a wavelength of 436 nm is 30 degrees or less. Since the wavelength dependency of the retardation in the wavelength range is suppressed, the phase shift effect can be sufficiently exerted, and the optical intensity gradient at the pattern boundary portion becomes strong, thereby making it possible to improve the resolution.

The phase shift film 3 preferably has a reflectance (hereinafter, referred to as R% (700-365)) in a range of 365 nm or more and 700 nm or less in a range of 5% or more and 45% or less. The phase shift film 3 preferably has a reflectivity (R% (700-365)) of 5% or more and 45% or less in a wavelength range of 365 nm or more and 700 nm or less and a reflectance in a wavelength range of 365 nm or more and 700 nm or less, It is preferable that the change amount depending on the wavelength (hereinafter sometimes referred to as? R% (700-365)) is within 5%. In this case, the phase shift film 3 is formed by forming a resist film on the phase shift film 3 and, when the pattern drawing is performed by a laser beam machine or the like, the influence of the standing wave generated by superimposing the light used for drawing and the reflected light . This makes it possible to suppress the roughness of the edge portion of the cross section of the resist pattern on the phase shift film 3 at the time of patterning, thereby improving the pattern accuracy. In addition, the alignment can be easily obtained at the time of patterning, and the measurement of the mask pattern by the measurement of the length dimension (MMS) becomes easy, so that it becomes possible to recognize the mask pattern with high accuracy. In the case of manufacturing a display device by performing pattern transfer using a phase shift mask, mask alignment is easily recognized when the alignment marks are detected using the difference in reflectance between the transparent substrate and the alignment marks, . In addition, when the display device is manufactured by performing pattern transfer using the phase shift mask, the influence of the flare phenomenon can be suppressed, so that good CD characteristics can be obtained and resolution can be improved, Can be obtained.

As described above, the phase shift film 3 exhibiting such optical characteristics is formed by a single-layer film having at least one metal silicide-based material layer containing a metal, silicon, and any one element of nitrogen and / Film.

In order to suppress the wavelength dependency of the transmittance, the phase difference, and the reflectance of the phase shift film 3 within a predetermined wavelength range, it is more preferable to use a laminated film composed of a plurality of material layers having different optical characteristics. The plurality of material layers having different optical characteristics are preferably composed of at least one layer of a metal silicide-based material layer and at least one layer of a chromium-based material layer. In this case, the optical characteristics of the entire phase shift film 3 are the same as those of the respective material layers, which are determined depending on the type and thickness of the material constituting the metal silicide-based material layer and the chromium-based material layer A combination of optical characteristics such as refractive index, transmittance and reflectance, and the number of layers and the number of layers of the respective material layers.

Specifically, the phase shift film 3 is a laminated film having a two-layer structure composed of a metal silicide-based material layer formed on the transparent substrate 2 and a chromium-based material layer formed on the metal silicide-based material layer . Further, a laminated film having a three-layered structure composed of the second-layer metal silicide-based material layer formed on the chromium-based material layer can be obtained. In this case, the chromium-based material layer or the metal silicide-based material layer may also be laminated so that the phase shift film 3 has four or more layers.

The phase shift film 3 may be a laminated film having a two-layer structure composed of a chromium-based material layer formed on the transparent substrate 2 and a metal silicide-based material layer formed on the chromium-based material layer. Further, a laminated film having a three-layer structure composed of the chromium-based material layer of the second layer formed on the metal silicide-based material layer can be obtained. In this case, the metal silicide-based material layer or the chromium-based material layer may also be laminated to form four or more phase shift films 3.

The phase shift film 3 having such a structure exhibits optical characteristics in which the wavelength dependence of transmittance, phase difference, and reflectance in a predetermined wavelength range is suppressed. As a result, when the exposure light in the wavelength range is received, the phase shift effect can be sufficiently exhibited, and the resolution can be improved.

In addition, the metal silicide-based material layer and the chromium-based material layer constituting the phase shift film 3 may be all formed of one layer or may be formed of a plurality of layers. When each of the metal silicide-based material layer and the chromium-based material layer is formed of a plurality of layers, the material constituting each layer of each material layer may be different for each layer or may be the same for each layer.

In the case where the phase shift film 3 is composed of at least one metal silicide-based material layer and at least one chromium-based material layer, the phase shift film 3 formed on the transparent substrate 2 side As the lowermost layer, it is preferable to use a chromium-based material layer from the viewpoint of suppressing the wavelength dependence of the transmittance, the phase difference, the reflectance, and the damage suppression to the transparent substrate 2 when patterning the phase shift film 3. In the case where the resist film 5 is formed on the phase shift film 3, the uppermost layer of the phase shift film 3 is preferably made of a chromium-based material layer to improve the adhesion of the resist film, 3) can be verticalized.

The film thickness of the phase shift film 3 is adjusted by changing the thickness of the phase shift film 3 so as to obtain a desired phase difference imparted in the exposure light and a desired transmittance and reflectance in the exposure light, The material of the metal silicide-based material layer or the chromium-based material layer, the order of lamination, the thickness of the film, and the like.

Further, the thickness of the metal silicide-based material layer constituting the phase shift film 3 is preferably in the range of, in combination with the metal silicide-based material layer or the metal silicide-based material layer and the chromium-based material layer formed below or above , And the phase shift film 3 indicates a desired phase difference or transmittance. The thickness of the metal silicide-based material layer in the phase shift film 3 is preferably in a range of, for example, 90 nm or more and 140 nm or less, but is not limited thereto.

In the case where the phase shift film 3 has at least a metal silicide-based material layer and a chromium-based material layer, the thickness of the chromium- In the combination with the material layer, it is appropriately determined in consideration of the fact that the phase shift film 3 exhibits the desired phase difference and transmittance. For example, it is preferably within the range of 2.5 nm or more and 15 nm or less, but the present invention is not limited thereto. It is practically difficult to form the chromium-based material layer to a thickness of less than 2.5 nm. When the chromium-based material layer is formed to a thickness exceeding 15 nm, the transmittance is lowered, and the transmittance of the phase shift film 3 at a wavelength of 365 nm may be lower than 3.5%, for example.

The metal silicide-based material constituting the metal silicide-based material layer is not particularly limited as long as it contains a metal and silicon (Si). The composition of the metal and silicon (Si) constituting the metal silicide-based material layer is adjusted in view of the optical characteristics of the entire phase shift film 3. The ratio of metal to silicon is appropriately selected according to the kind of metal and optical characteristics required for the metal silicide-based material layer, and is preferably 1: 1 or more and 1: 9 or less of metal: silicon.

Examples of metals include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), and titanium (Ti). As the metal suicide-based material constituting the metal silicide-based material layer, for example, a nitride of a metal suicide, an oxide of a metal suicide, an oxynitride of a metal suicide, a carbonitride of a metal suicide, an oxide carbide of a metal suicide, And at least one material of carbonitride.

Since the phase shift mask blank used for manufacturing the display device according to the present invention is generally a large phase shift mask blank having one side of 350 mm or more, wet etching is employed in the production of the phase shift mask. Further, from the viewpoint of defect correction in a large phase shift mask, a defect quality of the phase shift film in the phase shift mask blank is required to be higher than a certain quality. From the viewpoint of the defect quality of the phase shift film, the controllability of the cross-sectional shape of the phase shift film pattern by wet etching, the transmittance of the phase shift film, and the controllability of the phase difference, the metal silicide material is preferably made of a material containing nitrogen . As the metal silicide-based material, a nitride of a metal suicide, an oxynitride of a metal suicide, and an oxidized carbonitride of a metal suicide are preferable, and a nitride of a metal suicide is particularly preferable.

If the cross-sectional shape of the phase shift film pattern is vertically controlled, a sufficient contrast can be obtained with respect to the pattern boundary portion of the phase shift film pattern and the transparent substrate, so that the inclination of the light intensity at the pattern boundary portion becomes easy.

Hereinafter, a metal silicide-based material is specifically mentioned.

In the case of molybdenum silicide (MoSi), a nitride of molybdenum silicide (MoSi), an oxide of molybdenum silicide (MoSi), an oxide nitride of molybdenum silicide (MoSi), a carbonitride of molybdenum silicide (MoSi) Carbide, and oxycarbonitride of molybdenum silicide (MoSi).

In the case of tantalum silicide (TaSi), a nitride of tantalum silicide (TaSi), an oxide of tantalum silicide (TaSi), an oxynitride of tantalum silicide (TaSi), a carbonitride of tantalum silicide (TaSi), an oxide of tantalum silicide Carbide, and oxycarbonitride of tantalum silicide (TaSi).

In the case of tungsten suicide (WSi), a nitride of tungsten suicide (WSi), an oxide of tungsten suicide (WSi), an oxynitride of tungsten suicide (WSi), a carbonitride of tungsten suicide (WSi), an oxide of tungsten suicide Carbide, and oxycarbonitride of tungsten suicide (WSi).

In the case of titanium silicide (TiSi), a nitride of titanium silicide (TiSi), an oxide of titanium silicide (TiSi), an oxynitride of titanium silicide (TiSi), a carbonitride of titanium silicide (TiSi), an oxide of titanium silicide Carbide, and oxycarbonitride of titanium silicide (TiSi).

It is preferable that such a metal silicide-based material contains a component that slows the wet etching rate of the metal silicide-based material layer from the viewpoint of controllability of the cross-sectional shape of the phase shift film pattern by wet etching as described above Do. As a component for slowing the wet etching rate of the metal silicide-based material layer, for example, the above-mentioned nitrogen (N) can be mentioned. In this case, the composition of the metal constituting the metal silicide-based material layer and silicon (Si) and nitrogen is adjusted in view of the optical characteristics of the entire phase shift film 3. The nitrogen content in the case of containing nitrogen is preferably 25 atomic% or more and 55 atomic% or less, more preferably 30 atomic% or more and 50 atomic% or less. The metal silicide-based material may contain an element other than the above-mentioned elements within a range not deviating from the effect of the present invention.

As the chromium-based material constituting the chromium-based material layer, chromium (Cr) and a chromium compound containing at least one selected from oxygen (O), nitrogen (N) and carbon (C) are used. Examples of the chromium compound include at least one of a nitride of chromium (Cr), an oxide of chromium, a carbide of chromium, an oxynitride of chromium, a nitride of chromium, an oxide carbide of chromium and an oxide carbonitride of chromium .

Of these chromium-based materials, a nitride of chromium or an oxynitride of chromium is preferable from the viewpoint of easily controlling the wavelength dependence of the transmittance.

The chromium-based material may contain elements other than the above-mentioned elements within a range not deviating from the effect of the present invention.

As described above, the phase shift mask blank 1 according to the first embodiment includes the transparent substrate 2, the phase shift film 3 formed on the transparent substrate 2, Shielding film 4 may be formed on the light-shielding film 3.

The light-shielding film 4 may be either a single layer or a plurality of layers.

In the case where the light-shielding film 4 is composed of a plurality of layers, for example, the case where the light-shielding film 4 has a two-layer structure composed of the light-shielding layer formed on the side of the phase shift film 3 and the antireflection layer formed on the light- Layer structure composed of an insulating layer formed to be in contact with the film 3, a light-shielding layer formed on the insulating layer, and an antireflection layer formed on the light-shielding layer.

The light-shielding layer may be either a single layer or a plurality of layers. Examples of the light-shielding layer include a chromium nitride film (CrN), a chromium carbide film (CrC), a chromium carbide nitride film (CrCN), a molybdenum silicide film (MoSi), and a molybdenum silicide nitride film (MoSiN).

The antireflection layer may be composed of a single layer or a plurality of layers. As the antireflection layer, for example, a chromium oxynitride film (CrON), a molybdenum silicide oxide film (MoSiO), a molybdenum silicide oxynitride film (MoSiON) and the like can be given.

The insulating layer is made of, for example, CrCO 3 or CrOCN containing less than 50 atom% Cr, and has a thickness of 10 nm or more and 50 nm or less. In the case of the phase shift mask blank in which the light-shielding film 4 made of a chromium-based material is formed on the phase shift film 3 having the metal silicide-based material layer as the outermost layer, the light- When performing wet etching, metal ions are eluted from the phase shift film 3 having the metal silicide-based material layer as the outermost layer. At that time, electrons are generated. When the insulating layer is formed so as to be in contact with the phase shift film 3, electrons generated when metal ions are eluted from the phase shift film 3 can be prevented from being supplied to the light shield film. This makes it possible to make the etching rate in the plane when wet etching the light-shielding film 4 uniform. As the light-shielding film 4, a combination of a light-shielding layer of a chromium carbide film (CrC) and an antireflection layer of a chromium oxynitride film (CrON) or a combination of a shielding layer of a molybdenum silicide film (MoSi) and a shielding film of a molybdenum silicide A combination of antireflection layers is preferable, but the present invention is not limited thereto.

The phase shift film 3 and the light shielding film 4 in the phase shift mask blank 1 having the above-described structure can be formed by a known film formation method. As a film forming method, a sputtering method is generally used. The sputtering apparatus may be a cluster-type sputtering apparatus or an in-line sputtering apparatus.

The metal silicide-based material layer or the chromium-based material layer constituting the phase shift film 3 or the light-shielding film 4 can be formed by, for example, a sputtering target and a sputter gas atmosphere as described below.

When the phase shift mask blank 1 including the phase shift film 3 and the light shielding film 4 is used to manufacture a phase shift mask, a light shielding film pattern narrower than the phase shift film pattern is provided on the phase shift film pattern, For example, the phase shifting portion for changing the phase of the exposure light by approximately 180 degrees is constituted by a portion of the phase shift film pattern where the light shielding film pattern is not laminated, and the light shielding portion is formed by the portion where the phase shift film pattern and the light shielding film pattern are stacked And a phase shift mask in which the light transmitting portion is constituted by the portion where the transparent substrate 2 is exposed can be obtained.

As the sputtering target used for forming the metal silicide-based material layer, a material containing a metal and silicon (Si) is selected. Specifically, there can be mentioned metal silicide, nitride of metal suicide, oxide of metal suicide, carbide of metal suicide, oxynitride of metal suicide, carbonitride of metal suicide, oxycarbide of metal suicide and oxycarbonitride of metal suicide .

The atmosphere of the sputter gas at the time of forming the metal silicide-based material layer may be at least one of nitrogen (N ₂ ) gas, nitrogen monoxide (NO) gas, nitrogen dioxide (NO ₂ ) gas, nitrous oxide (N ₂ O) gas, gas, carbon dioxide (CO ₂₎ gas and oxygen (O ₂₎ an active gas, and a helium (He) gas, neon (Ne) gas, argon (Ar) gas including at least one kind selected from the group consisting of gas, A mixed gas of an inert gas containing at least one species selected from the group consisting of krypton (Kr) gas and xenon (Xe) gas.

The combination of the above-described material for forming the sputtering target and the kind of gas in the sputtering gas atmosphere or the mixing ratio of the active gas and the inert gas in the sputtering gas atmosphere is not particularly limited as long as the kind of the metal silicide- It is appropriately determined according to the composition.

As the sputtering target used for film formation of the chromium-based material layer, one containing chromium (Cr) or a chromium compound is selected. Specifically, examples thereof include chromium (Cr), a nitride of chromium, an oxide of chromium, a carbide of chromium, an oxide nitride of chromium, a carbon nitride of chromium, an oxide carbide of chromium and an oxide carbonitride of chromium.

The atmosphere of the sputter gas at the time of forming the chromium-based material layer is a gas atmosphere of nitrogen (N ₂ ) gas, nitrogen monoxide (NO) gas, nitrogen dioxide (NO ₂ ) gas, nitrous oxide (N ₂ O) gas, carbon monoxide A helium (He) gas, a neon (Ne) gas, an oxygen (O ₂ ) gas, an oxygen (O ₂ ) gas, a hydrocarbon gas and a fluorine gas, And a mixed gas of an inert gas containing at least one species selected from the group consisting of argon (Ar) gas, krypton (Kr) gas and xenon (Xe) gas. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas and styrene gas.

The combination of the above-described material for forming the sputtering target and the kind of the gas in the sputter gas atmosphere or the mixing ratio of the inert gas and the active gas in the sputter gas atmosphere is not limited to the kind and composition of the chromium-based material constituting the chromium- Is determined accordingly.

The phase shift mask blank 1 for use in manufacturing the display device according to the first embodiment described above has a transparent substrate 2 and a transparent substrate 2 on which a metal and silicon and either nitrogen or oxygen And a phase shift film 3 composed of a single-layer film or a laminate film having at least one layer of a metal silicide-based material including one element. As described above, the phase shift film 3 has a transmittance in a range of from 3.5% to 8% in a light having a wavelength of 365 nm, a retardation in a range of from 160 to 200 degrees in a light having a wavelength of 365 nm, The amount of change in the transmittance in the range of 365 nm or more and 436 nm or less depending on the wavelength is within 5.5%. The phase shift film 3 exhibits optical characteristics in which the wavelength dependence of the transmittance in the light having a wavelength of 365 nm or more and 436 nm or less is suppressed.

This makes it possible to obtain a phase shift mask blank having a phase shift film which can sufficiently exhibit the phase shift effect when exposure light of the wavelength range is received and can improve the resolution. Further, a phase shift film 3 having a phase shift film 3 capable of patterning into a phase shift film pattern capable of enhancing the light intensity gradient at the pattern boundary portion and improving the resolution and obtaining a desired transfer pattern shape having good CD characteristics A shift mask blank can be obtained.

The phase shift mask blank 1 for use in manufacturing the display device according to the first embodiment is characterized in that when the amount of change in the transmittance of the phase shift film 3 in the wavelength range from 365 nm to 700 nm, Since the wavelength dependency of the transmittance of the phase shift film 3 is suppressed even in the wavelength range, it is easy to recognize the alignment mark provided in the mask in the exposure apparatus for manufacturing a display device, and the alignment accuracy is improved. Further, in the mask inspection apparatus, in the case of the inspection apparatus for identifying the mask pattern by using the difference in transmittance between the transparent substrate and the mask pattern, defects such as defective shape of the mask pattern can be easily recognized.

The phase shift mask blank 1 for use in manufacturing the display device according to Embodiment 1 has a wavelength dependence of the phase difference in the wavelength range in the wavelength band of 365 nm and a retardation imparted at the wavelength of 436 nm of 30 degrees or less, Therefore, the phase shift effect can be sufficiently exerted, and the light intensity gradient at the pattern boundary portion becomes strong, thereby making it possible to improve the resolution.

The phase shift mask blank 1 for manufacturing the display device according to Embodiment 1 has a reflectance of 5% or more and 45% or less in the phase shift film 3 in a wavelength range of 365 nm to 700 nm, The phase shift mask blank 1 for producing a display device of the present invention is characterized in that the reflectance of the phase shift film 3 in the wavelength range of 365 nm to 700 nm is 5% or more and 45% or less and the wavelength is in a range of 365 nm or more and 700 nm or less A resist film is formed on the phase shift film 3, and when patterning is performed by a laser beam machine or the like, the light used for drawing and the reflected light are superimposed on each other It is less affected by the standing waves generated. This makes it possible to suppress the roughness of the edge portion of the cross section of the resist pattern on the phase shift film 3 at the time of patterning, thereby improving the pattern accuracy. In addition, the alignment at the time of patterning can be easily obtained, and the measurement of the mask pattern by the measurement of the length dimension (MMS) becomes easy, so that it becomes possible to recognize the mask pattern with high accuracy. In the case of manufacturing a display device by performing pattern transfer using a phase shift mask, mask alignment is easily recognized when the alignment marks are detected using the difference in reflectance between the transparent substrate and the alignment marks, . In addition, when a display device is manufactured by performing pattern transfer using a phase shift mask, the influence of the flare phenomenon can be suppressed, so that good CD characteristics can be obtained and resolution can be improved. Can be obtained.

The phase shift mask blank 1 for manufacturing the display device according to Embodiment 1 and the phase shift mask 30 for manufacturing a display device according to Embodiment 2 described later are the phase shift mask blank used for the projection exposure of equal exposure, The phase shift mask is particularly effective. In particular, as the exposure environment, the numerical aperture (NA) is preferably 0.06 to 0.15, more preferably 0.08 to 0.10, and the coherence factor (sigma) is preferably 0.5 to 1.0.

Embodiment 2 Fig.

In Embodiment 2, a phase shift mask for manufacturing a display device and a manufacturing method thereof will be described with reference to Figs. 2 and 3. Fig. 2 is a cross-sectional view showing the structure of a phase shift mask for manufacturing a display device according to Embodiment 2 of the present invention. 3 is a diagram for explaining a method of manufacturing a phase shift mask using a phase shift mask blank in which a light shielding film 4 is formed on a phase shift film 3. In Figs. 2 and 3, the same components as those in Fig. 1 are denoted by the same reference numerals, and redundant description is omitted.

The phase shift mask 30 according to the second embodiment includes a transparent substrate 2 and a phase shift film pattern 3 'formed on the transparent substrate 2 (FIG. 2A, Referred to as a phase shift mask of the first type). Alternatively, the light-shielding film pattern 4 'may be formed on the phase shift film pattern 3' (FIG. 2 (b), hereinafter also referred to as a second type phase shift mask). Alternatively, the light shielding film pattern 4 'may be formed under the phase shift film pattern 3' (FIG. 2 (c)).

The first type of phase shift mask 30 is constituted by a phase shifting portion composed of a phase shift film pattern 3 'and a light transmitting portion composed of a portion where the transparent substrate 2 is exposed.

The second and third types of phase shift masks 30 are formed on the portion of the phase shift film pattern 3 'on which the light shield film pattern 4' is not formed on or below the phase shift film pattern 3 ' The light shielding portion of the laminated portion where the light shielding film pattern 4 'is formed on or below the phase shift film pattern 3' and the portion where the transparent substrate 2 is exposed are constituted by the light transmitting portion . The second and third types of phase shift masks 30 can prevent the film thickness of the resist film formed on the transferred body by the exposure light transmitted through the phase shift portion.

In the phase shift mask 30 of the first type, the second type or the third type described above, the phase shift film pattern 3 'includes any one of metal, silicon, nitrogen and / or oxygen A single-layer film or a laminated film having at least one metal silicide-based material layer. The overall optical characteristics of the phase shift film pattern 3 'are such that when the phase shift film pattern 3' includes a single layer film, the kind of the material constituting the material layer constituting the phase shift film pattern 3 ' The phase shift film pattern 3 'is determined by the optical characteristics such as refractive index, transmittance and reflectance of each material layer determined by the film thickness or the like, and the phase shift film pattern 3' The combination of the optical characteristics determined by the kind and the thickness of the material constituting the plurality of material layers constituting the material layer, and the number of layers and the number of layers of each material layer.

The phase shift film pattern 3 'is controlled such that the transmittance of light of a specific wavelength is controlled in the following range by the combination of the material layers constituting the phase shift film pattern 3' The transmittance and phase difference in the light are controlled in the following ranges, and the amount of change in the transmittance, the phase difference, and the reflectance depending on the wavelength in the light in the specific wavelength range is suppressed to the following range.

Specifically, the phase shift film pattern 3 'has a transmittance at a wavelength of 365 nm in a range of 3.5% to 8%, a phase difference at a wavelength of 365 nm in a range of 160 to 200 degrees, a wavelength of 365 nm or more The amount of change in the transmittance in the range of 436 nm or less depending on the wavelength is within 5.5%. This phase shift film pattern 3 'exhibits optical characteristics in which the wavelength dependence of the transmittance in the light in the wavelength range of 365 nm to 436 nm is suppressed.

Therefore, when the phase shift film pattern 3 'receives light of the wavelength and the wavelength range of interest, the phase shift effect can be sufficiently exhibited and the optical intensity gradient at the pattern boundary portion can be strengthened, A phase shift mask pattern 30 'having a phase shift film pattern 3' capable of obtaining a desired transfer pattern shape having a desired pattern shape can be obtained. This phase shift mask 30 can cope with miniaturization of the line-and-space pattern and the contact hole.

In the phase shift mask 30 of the first type, the second type or the third type described above, it is preferable that the phase shift film pattern 3 'has a wavelength dependence of the transmittance in the wavelength range of 365 nm to 700 nm The wavelength dependence of the transmittance is suppressed even in the wavelength range, and therefore, the alignment mark provided on the mask can be easily recognized in the exposure machine for manufacturing the display device, and the alignment accuracy can be improved. Further, in the mask inspection apparatus, in the case of the inspection apparatus for identifying the mask pattern by using the difference in transmittance between the transparent substrate and the mask pattern, defects such as defective shape of the mask pattern can be easily recognized.

In the phase shift mask 30 of the first type, the second type or the third type described above, the phase shift film pattern 3 'has a difference in phase difference imparted at a wavelength of 365 nm and a phase difference imparted at a wavelength of 436 nm (? P (365-436)) is 30 degrees or less, the wavelength dependency of the retardation in the wavelength range is suppressed, so that the phase shift effect can be sufficiently exerted, the optical intensity gradient at the pattern boundary becomes strong, It is possible to improve the performance.

In the phase shift mask 30 of the first type, the second type or the third type described above, it is preferable that the phase shift film pattern 3 'has a reflectance in the range of 365 nm to 700 nm, And the reflectance of the phase shift film pattern 3 'is in the range of 365 nm to 700 nm inclusive and 5% to 45% inclusive, and the reflectance in the wavelength range of 365 nm to 700 nm inclusive The mask pattern can be easily measured by measuring the length dimension (MMS) when the change amount (? R% (700-365)) is less than 5%. When a display device is manufactured by transferring a pattern using a phase shift mask, mask alignment is easily recognized when the alignment marks are detected using the difference in reflectance between the transparent substrate and the alignment marks, and alignment accuracy . In addition, when the display device is manufactured by performing pattern transfer using the phase shift mask, the influence of the flare phenomenon can be suppressed, so that good CD characteristics can be obtained and resolution can be improved, Can be obtained.

Next, a method of manufacturing a phase shift mask for manufacturing a display device according to the embodiment will be described with reference to Fig. The manufacturing method of the phase shift mask shown in Fig. 3 is a manufacturing method of the phase shift mask 30 of the first type and the second type described above.

In the method of manufacturing the phase shift mask for manufacturing the first and second types of display devices, first, a resist film is formed on the light-shielding film 4 of the phase shift mask blank 1 for manufacturing a display device according to the first embodiment, A pattern forming process is performed.

Specifically, in this resist pattern forming step, a resist film 5 is first formed on the light-shielding film 4, as shown in Fig. 3 (a). Thereafter, a pattern of a predetermined size is drawn on the resist film 5. Thereafter, the resist film 5 is developed with a predetermined developer, and a resist pattern 5 'is formed as shown in Fig. 3 (b).

As a pattern to be drawn on the resist film 5, a line-and-space pattern or a hole pattern can be given.

Then, as shown in FIG. 3C, the light-shielding film pattern forming step for forming the light-shielding film pattern 4 'by wet-etching the light-shielding film 4 using the resist pattern 5' as a mask is performed.

The etching solution for wet etching the light-shielding film 4 is not particularly limited as long as it can selectively etch a chromium-based material or a metal silicide-based material forming the light-shielding film 4. When the material for forming the light-shielding film 4 is a chromium-based material, for example, an etching solution containing ceric ammonium nitrate and perchloric acid may be used. When the material for forming the light-shielding film 4 is a metal silicide-based material, for example, at least one fluorine compound selected from hydrofluoric acid, hydrofluoric acid and hydrogen fluoride and at least one fluorine compound selected from hydrogen peroxide, And an etching solution containing an oxidizing agent. Specifically, an etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water can be mentioned.

3 (d), after the resist pattern 5 'is peeled off, using the light-shielding film pattern 4' as a mask, as shown in FIG. 3 (e) The phase shift film pattern 3 'is wet-etched to form the phase shift film pattern 3'.

The etching solution for wet etching the phase shift film 3 is not particularly limited as long as it can selectively etch the chromium-based material layer and the metal silicide-based material layer constituting the phase shift film 3, respectively. For example, as the etching solution for wet etching the chromium-based material layer, an etching solution containing ceric ammonium nitrate and perchloric acid may be mentioned. Further, an etching solution containing at least one fluorine compound selected from hydrofluoric acid, hydrofluoric acid and ammonium hydrogen fluoride and at least one oxidizing agent selected from hydrogen peroxide, nitric acid and sulfuric acid as an etching solution for wet-etching the metal silicide- .

In the case of the phase shift film 3 in which the chromium-based material layer is formed on the metal silicide-based material layer, when the chromium-based material layer is wet-etched, metal ions are eluted from the underlying metal silicide- A phenomenon occurs that the wet etching of the chromium-based material layer is slowed down. However, in the case of the phase shift film 3 in which the metal silicide-based material layer is formed on the chromium-based material layer, such phenomenon does not occur. This makes it possible to make the etching rate in the plane when the phase shift film 3 is wet-etched uniform.

Subsequently, a phase shift mask 30 of the type having a phase shifting portion composed of the phase shift film pattern 3 'and a light transmitting portion composed of a portion where the transparent substrate 2 is exposed (a phase shift mask of a first type Shielding film pattern 4 'is peeled off, as shown in FIG. 3 (f), after the phase shift film pattern forming step.

A light shielding film pattern 4 'narrower than the phase shift film pattern 3' is provided on the phase shift film pattern 3 'and a phase shift film pattern 3' on which the light shielding film pattern 4 ' And a portion where the phase shift film pattern 3 'and the light-shielding film pattern 4' are laminated and a portion where the transparent substrate 2 is exposed When a phase shift mask 30 (second phase shift mask) of a type having a light transmitting portion is manufactured, after the phase shift film pattern forming process, as shown in FIG. 3 (g) 4 ') in a predetermined pattern narrower than the phase shift film pattern 3'.

The phase shift mask 30 for manufacturing a display device is manufactured by the resist pattern forming step, the light-shielding film pattern forming step, and the phase shift film pattern forming step.

The method of manufacturing the phase shift mask 30 of the first type and the second type described above is not limited to the above-described method. In the phase shift mask 30 of the first type, a phase shift mask blank 1 for manufacturing a display device according to Embodiment 1 is formed by using a structure in which the light shielding film 4 is not formed, The phase shift film 3 is subjected to wet etching to form the phase shift film pattern 3 'using the resist pattern 5' as a mask, And the resist pattern 5 'is finally peeled off to obtain the phase shift mask 30 of the first type.

Further, according to the method of manufacturing a phase shift mask for manufacturing a display device of Embodiment 2, a phase shift mask is manufactured using the phase shift mask blank 1 of Embodiment 1. This makes it possible to sufficiently exhibit the phase shift effect, to strengthen the inclination of the optical intensity at the pattern boundary portion, to obtain a phase with the phase shift film pattern 3 'capable of obtaining a desired transferred pattern shape having good CD characteristics The shift mask 30 can be manufactured.

Although the method of manufacturing the phase shift mask 30 of the first type and the second type has been described above, the phase shift film 30 may be formed on the main surface of the transparent substrate 2 on which the light- The present invention can also be applied to the phase shift mask 30 (phase shift mask of the third type) in which the pattern 3 'is formed. In this case, the phase shift film pattern 3 'is formed so as to cover the light-shielding film pattern 4' already formed on a part of the main surface or on the main surface on which the light-shielding film pattern 4 'is not formed, The portion where the light-shielding film pattern and the phase shift film pattern 3 'are not laminated can be used as the phase shift portion, and the phase shift effect can be exerted in the phase shift portion.

The phase shift mask 30 of the third type in which the phase shift film pattern 3 'is formed on the main surface of the transparent substrate 2 on which the light shielding film pattern 4' is already formed on a part of the main surface, A light shielding film pattern forming step of forming a light shielding film pattern by patterning the light shielding film by wet etching after the light shielding film forming step and forming a light shielding film pattern by sputtering on the main surface of the transparent substrate 2, A phase shift film forming step of forming a phase shift film 3 so as to cover the light-shielding film pattern on the main surface of the transparent substrate 2 after the light-shielding film pattern forming step; And a phase shift film pattern forming step of forming the phase shift film pattern 3 'by patterning the phase shift film 3.

Embodiment 3:

In Embodiment 3, a manufacturing method of a display device using a phase shift mask according to Embodiment 2 will be described.

In the method of manufacturing the display device according to Embodiment 3, first, the phase shift mask 30 or the phase shift mask 30 obtained by the method for manufacturing a phase shift mask for manufacturing a display device described in Embodiment Mode 2 is applied to a substrate with a resist film, A phase shift mask arranging step for arranging the phase shift mask 30 for manufacturing a display device described in Embodiment 2 to face the resist film is performed.

Then, exposure light is applied to the phase shift mask 30, and a resist film exposure process for exposing the resist film is performed.

The exposure light is, for example, a composite light containing light in a wavelength range of 300 nm or more and 700 nm or less. Specifically, it is composite light including i-line, h-line and g-line. The intensity ratio of the i-line, the h-line and the g-line in the composite light used for the exposure light is set to be 1: 1: 1 or 2: 1: 1 And so on.

According to the manufacturing method of the display device of the third embodiment, the phase shift mask 30 obtained by the method of manufacturing the phase shift mask for manufacturing a display device described in the second embodiment, or the phase for manufacturing the display device described in the second embodiment A shift mask 30 is used to manufacture a display device. Thus, a display device having a fine line-and-space pattern and a contact hole can be manufactured.

[Example]

Hereinafter, the present invention will be described more specifically based on examples.

In the following, the abbreviation of the synthetic quartz glass substrate is QZ. When QZ / A / B / C is used, QZ / A / B / C indicates that the layers A, B, and C are formed in this order on QZ.

Example 1.

In Embodiment 1, a phase shift mask blank having a QZ / CrON / MoSiN structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

In order to manufacture the phase shift mask blank 1 having the above-described configuration, a synthetic quartz glass substrate of 3345 size (330 mm x 450 mm x 5 mm) was first prepared as the transparent substrate 2.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) having a sputtering target containing chromium and a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) A chromium-based material layer (film thickness: 10 nm) including chromium oxide nitride (CrON) and a metal silicide-based material layer (molybdenum silicide nitride) (MoSiN) Thickness: 120 nm) was formed to obtain a phase shift mask blank 1 in which the phase shift film 3 (total film thickness: 130 nm) was formed.

The chromium-based material layer was formed by introducing a mixed gas (Ar: 30 sccm, NO: 30 sccm) containing argon (Ar) gas and nitrogen monoxide (NO) gas near the chromium target, The film was formed on the main surface of the transparent substrate 2 by reactive sputtering at a conveyance speed of 400 mm / minute.

The metal silicide material layer was formed by introducing a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) of argon (Ar) gas and nitrogen (N ₂ ) gas near the molybdenum silicide target, The film was formed on the chromium-based material layer by reactive sputtering at a transporting speed of the substrate 2 of 400 mm / min. Further, the metal silicide-based material layer was laminated a plurality of times under the same conditions to obtain a desired film thickness of 120 nm.

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The phase shift film 3 of the resulting phase shift mask blank 1 was measured for transmittance by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation and the phase difference was measured by MPM-100 manufactured by Laser Tex. In the following Examples and Comparative Examples, the same apparatus was used for measurement of transmittance and phase difference, respectively. The values of the transmittance in the following examples and comparative examples are values based on Air.

The transmittance and the phase difference of the phase shift film 3 were measured by using chromium oxynitride (CrON) on the main surface of a 6025 size (152 mm × 152 mm) transparent substrate 2 set on the same substrate holder (not shown) (Dummy substrate) on which a phase shift film 3 (total thickness of 130 nm) having a laminated structure composed of a chromium-based material layer and a metal silicide-based material layer containing molybdenum silicide nitride (MoSiN) Respectively.

As a result, as shown in Fig. 4, the transmittance spectrum of Example 1 at a wavelength of 200 nm to 800 nm has characteristics that transmittance variation is small compared to Comparative Examples 1 and 2 described later. The measurement results of the specific transmittance of Example 1 are shown in Fig. The transmittance at a wavelength of 365 nm (hereinafter, also referred to as T% (365)) was 4.41%, and ΔT% (436-365) was 3.91%. As a result, it was found that the phase shift film 3 of Example 1 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm or more and 436 nm or less was suppressed.

Further, as shown in Fig. 8,? T% (700-365) was 13.35%. As a result, it was found that the phase shift film 3 of Example 1 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm was suppressed.

The measurement result of the phase difference is shown in Fig. (Hereinafter also referred to as P (365)) given at a wavelength of 365 nm was 181.7 degrees, and? P (365-436) was 28.7 degrees. Thus, it was found that the phase shift film 3 of Example 1 exhibited optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm or more and 436 nm or less was suppressed.

Further, the phase shift film 3 of the obtained phase-shift mask blank 1 was measured for its reflectance by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. In the following Examples, Comparative Examples and Reference Examples, the same apparatus was used for measuring the reflectance.

As a result, as shown in Fig. 6, the reflectance spectrum of Example 1 at a wavelength of 200 nm to 800 nm has characteristics that reflectance changes are smaller than those of Comparative Examples 1 and 2 described later. The results of measurement of the specific reflectance of Example 1 are shown in Fig. The reflectance (hereinafter also referred to as R% (700-365)) in the wavelength range of 365 nm to 700 nm is 17.9% or more and 22.4% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm is 4.5 %. Thus, it was found that the phase shift film 3 of Example 1 exhibited optical characteristics in which the wavelength dependency of the reflectance was suppressed in the wavelength range of 365 nm to 700 nm.

B. Phase shift masks and methods for making them

In order to manufacture the phase shift mask 30 using the phase shift mask blank 1 manufactured as described above, a resist coating apparatus is first used on the phase shift film 3 of the phase shift mask blank 1 And the resist material was applied.

Thereafter, a resist film 5 having a film thickness of 1000 nm was formed through a heating and cooling process.

Thereafter, the resist film 5 is drawn using a laser beam drawing apparatus, and a resist pattern 5 (not shown) having a contact hole pattern (not shown) of 2.5 mu m square on the phase shift film 3 is developed and rinsed, ').

Thereafter, using the resist pattern 5 'as a mask, a molybdenum silicide etchant in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water is used to etch the metal silicide (MoSiN) containing the molybdenum silicide nitride (MoSiN) Based material layer was wet-etched.

Thereafter, using the resist pattern 5 'as a mask, a chromium-based material layer containing chromium nitride (CrON) of the phase shift film 3 is wet-etched by a chromium etchant containing ceric ammonium nitrate and perchloric acid, To form a phase shift film pattern 3 '.

Thereafter, the resist pattern 5 'was peeled off.

Thus, a phase shift mask 30 having a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square formed on the transparent substrate 2 was obtained.

The phase shift effect of the phase shift mask having the phase shift film pattern described above was simulated. The simulation includes the numerical aperture (NA) = 0.1, the coherence factor (sigma) = 0.5, exposure light including i line (365 nm), h line (405 nm), and g line (436 nm) And a line: g line = 2: 1: 1.

(Light intensity distribution) obtained by simulating the spatial image of light passing through the phase shift mask having the phase shift film pattern having the contact hole pattern of 2.5 mu m square is shown in Fig.

9, the abscissa axis indicates the position (μm) of the contact hole pattern transferred to the resist film on the transfer body from the center of the contact hole, and the ordinate axis indicates the intensity ratio (the maximum intensity of light transmitted from the phase shift mask is 1 Intensity ratio). In the light intensity distribution curve in Fig. 9, the light intensity of the transmitted light at the center of the contact hole becomes a peak, and the light intensity of the transmitted light gradually decreases as the distance from the center becomes large. In the light intensity distribution curve of Fig. 9, the position of +/- 1 mu m from the center of the contact hole showing the peak intensity is the boundary portion of the contact hole pattern of 2.0 mu m square formed in the resist film on the transfer body Portion). The light intensity gradient in this pattern boundary portion can be obtained from the difference in light intensity near the pattern boundary portion.

As shown in Fig. 9, the light intensity distribution curve of Example 1 has sharp peak intensity at the center of the contact hole, a change in light intensity is large at the pattern boundary portion, And the change in light intensity is small in the outer peripheral region.

The light intensity gradient (resolution) at the pattern boundary was 0.446. As a result, it was found that the phase shift mask of Example 1 showed a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Example 2.

In Embodiment 2, a phase shift mask blank having a QZ / CrN / MoSiN structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) having a sputtering target containing chromium and a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) On the main surface of the substrate 2, a chromium-based material layer (film thickness: 10 nm) containing chromium nitride (CrN) and a metal silicide-based material layer containing molybdenum silicide nitride (MoSiN) : 120 nm) was formed to obtain a phase shift mask blank 1 in which a phase shift film 3 (total film thickness: 130 nm) was formed.

In the chrome-based material layer, a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) containing argon (Ar) gas and nitrogen (N ₂ ) gas was introduced near the chromium target, The film was formed on the main surface of the transparent substrate 2 by reactive sputtering at a conveying speed of the substrate 2 of 400 mm / min.

In addition, the metal silicide-based material layer was formed under the same conditions as in Example 1 (laminated a plurality of times under the same conditions to obtain a desired film thickness of 120 nm).

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation were measured for the obtained phase shift film 3 of the phase shift mask blank 1 by the same method as in Example 1. [

(Dummy substrate) on which a phase shift film 3 of QZ / CrN / MoSiN structure (total film thickness 130 nm) was formed was used for measurement of transmittance and phase difference.

As a result, as shown in Fig. 4, the transmittance spectrum of Example 2 at a wavelength of 200 nm to 800 nm has characteristics that transmittance variation is small compared to Comparative Examples 1 and 2 described later. The measurement results of the specific transmittance of Example 2 are shown in Fig. T% (365) was 3.34% and ΔT% (436-365) was 3.28%. Thus, it was found that the phase shift film 3 of Example 2 exhibits optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm or more and 436 nm or less is suppressed.

Further, as shown in Fig. 8,? T% (700-365) was 12.68%. Thus, it was found that the phase shift film 3 of Example 2 exhibits optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.

The measurement result of the phase difference is shown in Fig. P (365) was 182.7 degrees, and? P (365-436) was 27.7 degrees. As a result, it was found that the phase shift film 3 of Example 2 exhibited optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm to 436 nm was suppressed.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

As a result, as shown in Fig. 6, the reflectance spectrum of Example 2 at a wavelength of 200 nm to 800 nm has characteristics that reflectance change is small compared to Comparative Examples 1 and 2 described later. The results of measurement of the specific reflectance of Example 2 are shown in Fig. The R% (700-365) was 16.6% or more and 24.8% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 8.2%. Thus, it was found that the phase shift film 3 of Example 2 exhibited optical characteristics in which the wavelength dependency of the reflectance was suppressed in the wavelength range of 365 nm to 700 nm.

B. Phase shift masks and methods for making them

A phase shift mask 30 in which a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square was formed on the transparent substrate 2 was obtained in the same manner as in Example 1. [

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

10 shows a light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square.

As shown in Fig. 10, the light intensity distribution curve of Example 2 has a sharp peak intensity at the center of the contact hole, a larger light intensity change at the pattern boundary, And the change in light intensity is small in the outer peripheral region.

The light intensity gradient at the pattern boundary was 0.447. As a result, it was found that the phase shift mask of Example 2 exhibited a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Example 3.

In Embodiment 3, a phase shift mask blank having a QZ / CrON / MoSiN / CrON structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 was introduced into an in-line sputtering apparatus (not shown) having a sputtering target containing chromium and a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) A chromium-based material layer (film thickness: 5 nm) including chromium oxide nitride (CrON) and a metal silicide-based material layer (molybdenum silicide nitride) (MoSiN) And a chromium-based material layer (film thickness: 5 nm) containing chromium oxide (CrON) was formed on the metal silicide-based material layer to form the phase shift film 3 (total film thickness: 130 nm) A phase shift mask blank 1 was obtained.

The chromium-based material layer was formed under the same conditions as in Example 1, except that the transporting speed of the transparent substrate 2 was 800 mm / min. Further, the metal silicide-based material layer was also formed under the same conditions as in Example 1 (laminated a plurality of times under the same conditions to obtain a desired film thickness of 120 nm).

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation were measured for the obtained phase shift film 3 of the phase shift mask blank 1 by the same method as in Example 1. [

(Dummy substrate) on which a phase shift film 3 (total film thickness: 130 nm) having a QZ / CrON / MoSiN / CrON structure was formed was used for measurement of transmittance and phase difference.

As a result, as shown in Fig. 5, the transmittance spectrum of Example 3 at a wavelength of 200 nm to 800 nm has characteristics of a small change in transmittance as compared with Comparative Examples 1 and 2 described later. The measurement results of the specific transmittance of Example 3 are shown in Fig. T% (365) was 4.03%, and ΔT% (436-365) was 3.32%. As a result, it was found that the phase shift film 3 of Example 3 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm or more and 436 nm or less was suppressed.

Further, as shown in Fig. 7,? T% (700-365) was 12.49%. Thus, it was found that the phase shift film 3 of Example 3 exhibits optical characteristics in which the wavelength dependence of transmittance is suppressed in the wavelength range of 365 nm to 700 nm.

The measurement result of the phase difference is shown in Fig. P (365) was 181.0 degrees, and? P (365-436) was 28.3 degrees. Thus, it was found that the phase shift film 3 of Example 3 exhibited optical characteristics in which the wavelength dependency of retardation in a wavelength range of 365 nm or more and 436 nm or less was suppressed.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

As a result, as shown in Fig. 7, the reflectance spectrum of Example 3 at a wavelength of 200 nm to 800 nm has characteristics of a small change in reflectance as compared with Comparative Examples 1 and 2 described later. The results of measurement of the specific reflectance of Example 3 are shown in Fig. The R% (700-365) was 26.4% or more and 30.0% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 3.5%. As a result, it was found that the phase shift film 3 of Example 3 exhibited optical characteristics in which the wavelength dependence of the reflectance was suppressed in the wavelength range of 365 nm to 700 nm.

B. Phase shift masks and methods for making them

In order to manufacture the phase shift mask 30 using the phase shift mask blank 1 manufactured as described above by the same method as in Embodiment 1, first, the phase shift mask blank 1 On the film 3, a resist pattern 5 'having a contact hole pattern of 2.5 mu m square was formed.

Thereafter, using the resist pattern 5 'as a mask, a chromium-based material (CrON) containing the second layer chromium oxide (CrON) is deposited on the phase shift film 3 by a chromium etchant containing ceric ammonium nitrate and perchloric acid The layer was wet etched.

Thereafter, using the resist pattern 5 'as a mask, a molybdenum silicide etchant in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water is used to etch the metal silicide (MoSiN) containing the molybdenum silicide nitride (MoSiN) Based material layer was wet-etched.

Thereafter, using the resist pattern 5 'as a mask, a chromium-based material (CrON) containing the first layer chromium oxide nitride (CrON) of the phase shift film 3 is etched by a chromium etchant containing ceric ammonium nitrate and perchloric acid Layer was wet-etched to form a phase shift film pattern 3 '.

Thereafter, the resist pattern 5 'was peeled off.

Thus, a phase shift mask 30 having a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square formed on the transparent substrate 2 was obtained.

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

A light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square is shown in Fig.

As shown in Fig. 9, the light intensity distribution curve of Example 3 has a sharp peak intensity at the center of a contact hole, a change in light intensity is large at the pattern boundary, And the change in light intensity is small in the outer peripheral region.

The light intensity gradient at the pattern boundary was 0.447. As a result, it was found that the phase shift mask of Example 3 showed a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Example 4.

In Embodiment 4, a phase shift mask blank having a QZ / CrN / MoSiN / CrN structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 was introduced into an in-line sputtering apparatus (not shown) having a sputtering target containing chromium and a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) On the main surface of the substrate 2, a chromium-based material layer (film thickness: 5 nm) containing chromium nitride (CrN) and a metal silicide-based material layer containing molybdenum silicide nitride (MoSiN) And a chromium-based material layer (film thickness: 5 nm) including chromium nitride (CrN) was formed on the metal silicide-based material layer to form a phase shift film 3 (total film thickness: 130 nm) Thereby obtaining a mask blank (1).

The chromium-based material layer was formed under the same conditions as in Example 1, except that the transporting speed of the transparent substrate 2 was 800 mm / min. Further, the metal silicide-based material layer was also formed under the same conditions as in Example 1 (laminated a plurality of times under the same conditions to obtain a desired film thickness of 120 nm).

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.

(Dummy substrate) on which a phase shift film 3 of QZ / CrN / MoSiN / CrN composition (total film thickness 130 nm) was formed was used for measurement of transmittance and phase difference.

As a result, as shown in Fig. 5, the transmittance spectrum of Example 4 at a wavelength of 200 nm to 800 nm has characteristics that transmittance change is small compared with Comparative Examples 1 and 2 described later. The measurement results of the specific transmittance of Example 4 are shown in Fig. T% (365) was 3.82%, and ΔT% (436-365) was 3.33%. As a result, it was found that the phase shift film 3 of Example 4 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm to 436 nm was suppressed.

Further, as shown in Fig. 8,? T% (700-365) was 14.64%. Thus, it was found that the phase shift film 3 of Example 4 exhibits optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.

The measurement result of the phase difference is shown in Fig. P (365) was 180.2 degrees and? P (365-436) was 26.8 degrees. Thus, it was found that the phase shift film 3 of Example 4 exhibits optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm to 436 nm is suppressed.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

As a result, as shown in Fig. 7, the reflectance spectrum of Example 4 at a wavelength of 200 nm to 800 nm has characteristics that reflectance change is small compared to Comparative Examples 1 and 2 described later. The results of measurement of the specific reflectance of Example 4 are shown in Fig. The R% (700-365) was 22.4% or more and 27.5% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 5.0%. Thus, it was found that the phase shift film 3 of Example 4 exhibited optical characteristics in which the wavelength dependency of the reflectance was suppressed in the wavelength range of 365 nm to 700 nm.

B. Phase shift masks and methods for making them

A phase shift mask 30 in which a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square was formed on the transparent substrate 2 was obtained by the same method as in the third embodiment.

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment. 10 shows a light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square.

As shown in Fig. 10, the light intensity distribution curve of Example 4 has a sharp peak intensity at the center of the contact hole, a larger light intensity change at the pattern boundary, And the change in light intensity is small in the outer peripheral region.

The light intensity gradient at the pattern boundary was 0.447. As a result, it was found that the phase shift mask of Example 4 exhibited a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Example 5.

In Embodiment 5, a phase shift mask blank having a QZ / MoSiN / CrN structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 is introduced into a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) and an in-line sputtering apparatus (not shown) in which a sputtering target containing chromium is disposed, On the main surface of the substrate 2, a metal silicide-based material layer (film thickness: 120 nm) including molybdenum silicide nitride (MoSiN) and a chromium-based material layer Thickness: 10 nm) was deposited to obtain a phase shift mask blank 1 in which the phase shift film 3 (total film thickness: 130 nm) was formed.

The metal silicide material layer was formed by introducing a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) of argon (Ar) gas and nitrogen (N ₂ ) gas near the molybdenum silicide target, The film was formed on the main surface of the transparent substrate 2 by reactive sputtering at a conveying speed of the substrate 2 of 400 mm / min. And laminated a plurality of times under the same conditions to obtain a desired film thickness of 120 nm.

In the chrome-based material layer, a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) containing argon (Ar) gas and nitrogen (N ₂ ) gas was introduced near the chromium target, The substrate 2 was formed on the metal silicide-based material layer by reactive sputtering at a transporting speed of 800 mm / min.

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.

(Dummy substrate) on which a phase shift film 3 of QZ / MoSiN / CrN composition (total film thickness 130 nm) was formed was used for measurement of transmittance and phase difference.

As a result, as shown in FIG. 4, the transmittance spectrum of Example 5 at a wavelength of 200 nm to 800 nm has characteristics that transmittance change is small compared to Comparative Examples 1 and 2 described later. The measurement results of the specific transmittance of Example 5 are shown in Fig. T% (365) was 3.16% and ΔT% (436-365) was 2.88%. As a result, it was found that the phase shift film 3 of Example 5 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm or more and 436 nm or less was suppressed.

Further, as shown in Fig. 8,? T% (700-365) was 12.21%. As a result, it was found that the phase shift film 3 of Example 5 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm to 700 nm was suppressed.

The measurement result of the phase difference is shown in Fig. P (365) was 178.4 degrees, and? P (365-436) was 26.6 degrees. As a result, it was found that the phase shift film 3 of Example 5 exhibited optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm or more and 436 nm or less was suppressed.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

As a result, as shown in Fig. 6, the reflectance spectrum of Example 5 at a wavelength of 200 nm to 800 nm has characteristics that reflectance change is small compared to Comparative Examples 1 and 2 described later. The results of measurement of the specific reflectance of Example 5 are shown in Fig. R% (700-365) was 33.6% or more and 44.6% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 11.0%. As a result, it was found that the phase shift film 3 of Example 5 exhibited optical characteristics in which the wavelength dependence of the reflectance was suppressed in the wavelength range of 365 nm to 700 nm, as compared with Comparative Examples 1 and 2 to be described later.

B. Phase shift masks and methods for making them

A phase shift mask 30 in which a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square was formed on a transparent substrate 2 was obtained in the same manner as in Example 5. [

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

10 shows a light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square.

As shown in Fig. 10, the light intensity distribution curve of Example 5 has a sharp peak intensity at the center of the contact hole, a larger light intensity change at the pattern boundary, And the change in light intensity is small in the outer peripheral region.

The slope of the light intensity at the pattern boundary was 0.448. As a result, it was found that the phase shift mask of Example 5 showed a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Example 6.

In Embodiment 6, a phase shift mask blank having a QZ / MoSiN / CrON structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 is introduced into a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) and an in-line sputtering apparatus (not shown) in which a sputtering target containing chromium is disposed, A metal silicide-based material layer (film thickness: 120 nm) including molybdenum silicide nitride (MoSiN) and a chromium-based material layer (chromium oxide) containing chromium oxynitride (CrON) on the metal silicide- Film thickness: 10 nm) was formed to obtain a phase shift mask blank 1 in which the phase shift film 3 (total film thickness: 130 nm) was formed.

The metal silicide-based material layer was formed under the same conditions as in Example 5.

The chromium-based material layer was formed by introducing a mixed gas (Ar: 30 sccm, NO: 30 sccm) containing argon (Ar) gas and nitrogen monoxide (NO) gas near the chromium target, The film was formed on the metal silicide-based material layer by reactive sputtering at a transporting speed of 800 mm / min.

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation were measured for the obtained phase shift film 3 of the phase shift mask blank 1 by the same method as in Example 1. [

(Dummy substrate) on which a phase shift film 3 of QZ / MoSiN / CrON structure (total thickness of 130 nm) was formed was used for measurement of transmittance and phase difference.

As a result, as shown in Fig. 4, the transmittance spectrum of Example 6 at a wavelength of 200 nm to 800 nm has characteristics that transmittance change is small compared to Comparative Examples 1 and 2 described later. The measurement results of the specific transmittance of Example 6 are shown in Fig. T% (365) was 4.21% and ΔT% (436-365) was 3.5%. As a result, it was found that the phase shift film 3 of Example 6 exhibited optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 436 nm was suppressed.

In addition, as shown in Fig. 8,? T% (700-365) was 12.88%. Thus, it was found that the phase shift film 3 of Example 6 exhibits optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.

The measurement result of the phase difference is shown in Fig. P (365) was 178.8 degrees, and? P (365-436) was 28 degrees. As a result, it was found that the phase shift film 3 of Example 6 exhibits optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm to 436 nm is suppressed.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

As a result, as shown in Fig. 6, the reflectance spectrum of Example 6 at a wavelength of 200 nm to 800 nm has characteristics that reflectance change is small compared with Comparative Examples 1 and 2 described later. The results of measurement of the reflectance in Example 6 are shown in Fig. R% (700-365) was 30.7% or more and 39.4% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 8.7%. As a result, it was found that the phase shift film 3 of Example 6 exhibited optical characteristics in which the wavelength dependency of the reflectance was suppressed in the wavelength range of 365 nm to 700 nm, as compared with Comparative Examples 1 and 2 to be described later.

B. Phase shift masks and methods for making them

In order to manufacture the phase shift mask 30 using the phase shift mask blank 1 manufactured as described above, a resist coating apparatus is first used on the phase shift film 3 of the phase shift mask blank 1 And the resist material was applied.

Thereafter, a resist film 5 having a film thickness of 1000 nm was formed through a heating and cooling process.

Thereafter, the resist film 5 is drawn using a laser beam drawing apparatus, and a resist pattern 5 (not shown) having a contact hole pattern (not shown) of 2.5 mu m square on the phase shift film 3 is developed and rinsed, ').

Thereafter, using the resist pattern 5 'as a mask, a chromium-based material layer containing chromium nitride (CrON) of the phase shift film 3 is wet-etched by a chromium etchant containing ceric ammonium nitrate and perchloric acid, Etched.

Thereafter, using the resist pattern 5 'as a mask, a molybdenum silicide etchant in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water is used to etch the metal silicide (MoSiN) containing the molybdenum silicide nitride (MoSiN) The base material layer was wet-etched to form the phase shift film pattern 3 '.

Thereafter, the resist pattern 5 'was peeled off.

Thus, a phase shift mask 30 having a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square formed on the transparent substrate 2 was obtained.

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

As a result, the light intensity gradient at the pattern boundary was the same as in Example 5. [ As a result, it was found that the phase shift mask of Example 6 exhibited a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Example 7.

In Embodiment 7, a phase shift mask blank having a QZ / MoSiN / CrON / MoSiN structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) having a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) and a sputtering target containing chromium, (Film thickness: 60 nm) including molybdenum silicide nitride (MoSiN) and a chromium-based material layer (chromium-based material layer) including chromium oxide nitride (CrON) on the metal silicide- (Thickness: 10 nm) and a metal silicide-based material layer (film thickness: 60 nm) including molybdenum silicide nitride (MoSiN) were formed on the chromium-based material layer to form a phase shift film 3 A phase shift mask blank 1 was obtained.

The metal silicide-based material layer was formed under the same conditions as in Example 6 except that the transporting speed of the transparent substrate 2 was set to about 800 mm / min. The chromium-based material layer was also formed under the same conditions as in Example 6.

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.

(Dummy substrate) on which a phase shift film 3 of QZ / MoSiN / CrON / MoSiN structure (total thickness of 130 nm) was formed was used for measurement of transmittance and phase difference.

As a result, as shown in Fig. 5, the transmittance spectrum of Example 7 at a wavelength of 200 nm to 800 nm has characteristics that transmittance variation is small compared to Comparative Examples 1 and 2 described later. The results of measurement of the specific transmittance of Example 7 are shown in Fig. T% (365) was 4.49% and ΔT% (436-365) was 3.92%. Thus, it was found that the phase shift film 3 of Example 7 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm or more and 436 nm or less was suppressed.

Further, as shown in Fig. 8,? T% (700-365) was 23.78%. As a result, it was found that the phase shift film 3 of Example 7 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm to 700 nm was suppressed.

The measurement result of the phase difference is shown in Fig. P (365) was 178.8 degrees, and? P (365-436) was 24 degrees. As a result, it was found that the phase shift film 3 of Example 7 exhibited optical characteristics in which the wavelength dependence of retardation in a wavelength range of 365 nm or more and 436 nm or less was suppressed.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

The results are shown in Fig. The results of measurement of the reflectance of Example 7 are shown in Fig. The R% (700-365) was 5.4% or more and 24.4% or less, and the range (difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 19.0%.

B. Phase shift masks and methods for making them

In order to manufacture the phase shift mask 30 using the phase shift mask blank 1 manufactured as described above by the same method as in Embodiment 1, first, the phase shift mask blank 1 On the film 3, a resist pattern 5 'having a contact hole pattern of 2.5 mu m square was formed.

Thereafter, using the resist pattern 5 'as a mask, a molybdenum silicide etchant in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water is used to etch the metal silicide (MoSiN) containing the molybdenum silicide nitride (MoSiN) Based material layer was wet-etched.

Thereafter, using the resist pattern 5 'as a mask, a chromium-based material (CrON) containing the first layer chromium oxide nitride (CrON) of the phase shift film 3 is etched by a chromium etchant containing ceric ammonium nitrate and perchloric acid The layer was wet etched.

Thereafter, using the resist pattern 5 'as a mask, a molybdenum silicide etchant in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with pure water is used to etch the metal silicide (MoSiN) containing the molybdenum silicide nitride (MoSiN) The base material layer was wet-etched to form the phase shift film pattern 3 '.

Thereafter, the resist pattern 5 'was peeled off.

Thus, a phase shift mask 30 having a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square formed on the transparent substrate 2 was obtained.

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

A light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square is shown in Fig.

As shown in Fig. 9, the light intensity distribution curve of Example 7 has a sharp peak intensity at the center of the contact hole, a larger light intensity change at the pattern boundary, And the change in light intensity is small in the outer peripheral region.

The light intensity gradient at the pattern boundary was 0.446. As a result, it was found that the phase shift mask of Example 7 exhibited a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Example 8.

In Embodiment 8, a phase shift mask blank having a QZ / MoSiN / CrN / MoSiN structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) having a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) and a sputtering target containing chromium, (Film thickness: 59 nm) including molybdenum silicide nitride (MoSiN) and a chromium-based material layer (chromium nitride (CrN)) containing chromium nitride (CrN) on the metal silicide- And a metal silicide material layer (film thickness: 59 nm) including molybdenum silicide nitride (MoSiN) were formed on the chromium-based material layer to form a phase shift film 3 (total film thickness: 128 nm) To obtain a shift mask blank (1).

The metal silicide layer was formed under the same conditions as in Example 5 except that the transporting speed of the transparent substrate 2 was set at about 800 mm / min. The chromium-based material layer was also formed under the same conditions as in Example 5.

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.

(Dummy substrate) on which a phase shift film 3 of QZ / MoSiN / CrN / MoSiN structure (total thickness of 128 nm) was formed was used for measurement of transmittance and phase difference.

As a result, as shown in Fig. 5, the transmittance spectrum of Example 8 at a wavelength of 200 nm to 800 nm has characteristics that transmittance change is small compared to Comparative Examples 1 and 2 described later. The measurement results of the specific transmittance of Example 8 are shown in Fig. T% (365) was 3.55% and ΔT% (436-365) was 3.65%. As a result, it was found that the phase shift film 3 of Example 8 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm or more and 436 nm or less was suppressed.

In addition, as shown in Fig. 8,? T% (700-365) was 23.62%. As a result, it was found that the phase shift film 3 of Example 8 exhibits optical characteristics in which the wavelength dependency of the transmittance in the wavelength range of 365 nm to 700 nm is suppressed.

The measurement result of the phase difference is shown in Fig. P (365) was 178.3 degrees and DELTA P (365-436) was 22 degrees. Thus, it was found that the phase shift film 3 of Example 8 exhibited optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm to 436 nm was suppressed.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

The results are shown in Fig. The specific reflectance measurement results of Example 8 are shown in Fig. The R% (700-365) was 5.1% or more and 24.8% or less, and the range (the difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 19.7%.

B. Phase shift masks and methods for making them

A phase shift mask 30 in which a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square was formed on the transparent substrate 2 was obtained in the same manner as in Example 7. [

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

10 shows a light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square.

As shown in Fig. 10, the light intensity distribution curve of Example 8 has a sharp peak intensity at the center of the contact hole, a larger light intensity change at the pattern boundary, And the change in light intensity is small in the outer peripheral region.

The light intensity gradient at the pattern boundary was 0.447. As a result, it was found that the phase shift mask of Example 8 exhibited a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Example 9.

In Embodiment 9, a phase shift mask blank having a QZ / MoSiN structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 was introduced into an in-line sputtering apparatus (not shown) having a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) A metal silicide-based material layer (film thickness: 120 nm) including molybdenum silicide nitride (MoSiN) was deposited to obtain a phase shift mask blank 1.

The metal silicide material layer was formed by introducing a mixed gas (Ar: 30 sccm, N ₂ : 70 sccm) of argon (Ar) gas and nitrogen (N ₂ ) gas near the molybdenum silicide target, The film was formed on the transparent substrate 2 by reactive sputtering at a transporting speed of the substrate 2 of 400 mm / min. And laminated a plurality of times under the same conditions to obtain a desired film thickness of 120 nm.

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation were measured for the obtained phase shift film 3 of the phase shift mask blank 1 by the same method as in Example 1. [

A substrate with a phase shift film (dummy substrate) having a QZ / MoSiN phase shift film 3 (110 nm film thickness) formed thereon was used for measurement of transmittance and phase difference.

As a result, as shown in Fig. 4, the transmittance spectrum of Example 9 at a wavelength of 200 nm to 800 nm has characteristics of a small change in transmittance as compared with Comparative Examples 1 and 2 described later. The measurement results of the specific transmittance of Example 9 are shown in Fig. T% (365) was 4.36% and ΔT% (436-365) was 3.97%. As a result, it was found that the phase shift film 3 of Example 9 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm or more and 436 nm or less was suppressed.

Further, as shown in Fig. 8,? T% (700-365) was 21.60%. As a result, it was found that the phase shift film 3 of Example 9 exhibited optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm to 700 nm was suppressed.

The measurement result of the phase difference is shown in Fig. P (365) was 180.00 degrees, and? P (365-436) was 24.00 degrees. As a result, it was found that the phase shift film 3 of Example 9 exhibited optical characteristics in which the wavelength dependency of the retardation in the wavelength range of 365 nm to 436 nm was suppressed.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

As a result, as shown in Fig. 6, the reflectance spectrum of Example 9 at a wavelength of 200 nm to 800 nm has characteristics that reflectance change is small compared to Comparative Examples 1 and 2 described later. The results of measurement of the specific reflectance of Example 9 are shown in Fig. The R% (700-365) was 18.0% or more and 28.3% or less, and the range (the difference between the maximum value and the minimum value) in the range of 700 nm to 365 nm was 10.4%. Thus, it was found that the phase shift film 3 of Example 9 exhibited optical characteristics in which the wavelength dependency of the reflectance was suppressed in the wavelength range of 365 nm to 700 nm.

B. Phase shift masks and methods for making them

A phase shift mask 30 in which a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square was formed on the transparent substrate 2 was obtained in the same manner as in Example 1. [

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

A light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square is shown in Fig.

As shown in Fig. 9, the light intensity distribution curve of Example 9 has a sharp peak intensity at the center of the contact hole, a larger light intensity change at the pattern boundary, And the change in light intensity is small in the outer peripheral region.

The light intensity gradient at the pattern boundary was 0.444. As a result, it was found that the phase shift mask of Example 9 exhibited a strong light intensity gradient and improved resolution as compared with the comparative example described later.

Comparative Example 1

In Comparative Example 1, a phase shift mask blank having a CrON structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputtering target containing chromium is disposed, and chromium (Cr) containing chromium oxide nitride (CrON) (Film thickness: 157 nm) was deposited to obtain a phase shift mask blank (1).

In the chromium-based material layer, a mixed gas (Ar: 46 sccm, NO: 70 sccm) containing argon (Ar) gas and nitrogen monoxide (NO) gas was introduced near the chromium target and a sputtering power of 8.0 kw, The film was formed on the transparent substrate 2 by reactive sputtering at a conveyance speed of about 400 mm / minute. And laminated a plurality of times under the same conditions to obtain a desired film thickness of 157 nm.

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.

(Dummy substrate) on which a phase shift film 3 (film thickness: 157 nm) having a QZ / CrON structure was formed was used for measurement of transmittance and phase difference.

As a result, as shown in FIG. 4 and FIG. 5, the transmittance spectrum of Comparative Example 1 at a wavelength of 200 nm to 800 nm showed a sharp change from the vicinity of a wavelength exceeding 300 nm to a wavelength exceeding 700 nm Shows a substantially S-shaped curve in which the transmittance change decreases. The measurement results of the specific transmittance of Comparative Example 1 are shown in Fig. T% (365) is 7.73%, and? T% (436-365) is 9.82%. As a result, it was found that the phase shift film 3 of Comparative Example 1 can not necessarily exhibit the optical characteristics in which the wavelength dependence of the transmittance in the wavelength range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment.

Further, as shown in Fig. 8,? T% (700-365) was 48.00%. As a result, it was found that the phase shift film 3 of the comparative example 1 can not necessarily exhibit the optical characteristics in which the wavelength dependence of the transmittance is suppressed in the wavelength range of 365 nm to 700 nm as compared with the above-mentioned embodiment.

The measurement result of the phase difference is shown in Fig. P (365) was 181.3 degrees, and? P (365-436) was 32.5 degrees. As a result, it was found that the phase shift film 3 of the comparative example 1 can not necessarily exhibit the optical characteristics in which the wavelength dependence of the retardation in the wavelength range of 365 nm or more and 436 nm or less is suppressed as compared with the above embodiment.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

As a result, as shown in the specific reflectance measurement results of Figs. 6 and 7 and Fig. 8, the R% (700-365) was 7.60% or more and 18.45% or less, and the range in the range of 700 nm to 365 nm And the minimum value) was 10.8%, which was satisfactory without significant difference from the above-described sixth embodiment.

B. Phase shift masks and methods for making them

A phase shift mask 30 in which a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square was formed on the transparent substrate 2 was obtained in the same manner as in Example 1. [

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

10 shows a light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square.

As shown in Fig. 10, the light intensity distribution curve of Comparative Example 1 shows that the peak of the light intensity at the center of the contact hole is not so sharp as compared with the above embodiment, the light intensity change is not so large at the pattern boundary portion , And the light intensity change is large in the outer peripheral region of the pattern boundary portion.

The light intensity gradient at the pattern boundary was 0.432. As a result, it was found that the phase shift mask of Comparative Example 1 exhibited a weak light intensity gradient compared to the above-described embodiment.

Comparative Example 2

In Comparative Example 2, a phase shift mask blank having a CrOCN structure will be described.

A. Phase Shift Mask Blank and Manufacturing Method Thereof

As the transparent substrate 2, a transparent substrate 2 having the same size as that in Example 1 was prepared.

Thereafter, the transparent substrate 2 is introduced into an in-line sputtering apparatus (not shown) in which a sputtering target containing chromium is disposed, and chromium oxide carbonitride (CrOCN) is deposited on the main surface of the transparent substrate 2 A chrome-based material layer (film thickness: 117 nm) was deposited to obtain a phase shift mask blank (1).

In addition, chromium-based material layer is in the vicinity of chromium target, argon (Ar) gas and carbon dioxide (CO ₂₎ gas mixture comprising a gas and a nitrogen (N ₂₎ gas (Ar: 46sccm, CO _2: 35 sccm, N ₂ : 46 sccm) was introduced, and the sputtering power was 8.0 kw, and the transporting speed of the transparent substrate 2 was about 400 mm / min. The film was formed on the transparent substrate 2 by reactive sputtering. And laminated a plurality of times under the same conditions to obtain a desired film thickness of 117 nm.

Thus, the phase shift mask blank 1 having the phase shift film 3 formed on the transparent substrate 2 was obtained.

The transmittance and the retardation of the phase shift film 3 of the obtained phase shift mask blank 1 were measured in the same manner as in Example 1.

A phase shift film-provided substrate (dummy substrate) having a QZ / CrOCN phase shift film 3 (film thickness: 117 nm) formed thereon was used for measurement of transmittance and phase difference.

As a result, as shown in Fig. 4 and Fig. 5, the transmittance spectrum of Comparative Example 2 at a wavelength of 200 nm to 800 nm showed a sharp change from the vicinity of a wavelength exceeding 300 nm to a wavelength exceeding 600 nm Shows a substantially S-shaped curve in which the transmittance change decreases. The measurement results of the specific transmittance of Comparative Example 2 are shown in Fig. T% (365) was 5.10% and ΔT% (436-365) was 7.58%. As a result, it was found that the phase shift film 3 of Comparative Example 2 did not exhibit the optical characteristics in which the wavelength dependence of the transmittance was suppressed in the wavelength range of 365 nm or more and 436 nm or less as compared with the above-mentioned Examples.

In addition, as shown in Fig. 8,? T% (700-365) was 50.63%. As a result, the phase shift film 3 of the comparative example 2 can not necessarily exhibit the optical characteristics in which the wavelength dependence of the transmittance is suppressed in the wavelength range of 365 nm to 700 nm, as compared with the above embodiment.

The measurement result of the phase difference is shown in Fig. P (365) was 182.1 degrees, and? P (365-436) was 31.0 degrees. As a result, it was found that the phase shift film 3 of Comparative Example 2 does not exhibit the optical characteristics in which the wavelength dependence of the retardation in the wavelength range of 365 nm or more and 436 nm or less is suppressed as compared with the above embodiment.

The reflectance was measured for the phase shift film 3 of the obtained phase shift mask blank 1 by the same method as in Example 1. [

As a result, as shown in the specific reflectance measurement results of Figs. 6 and 7 and Fig. 8, the R% (700-365) is 11.4% or more and 28.7% or less and the range in the range of 700 nm to 365 nm And the minimum value) was 17.3%, which was satisfactory without any significant difference from the above-described fifth embodiment.

B. Phase shift masks and methods for making them

A phase shift mask 30 in which a phase shift film pattern 3 'having a contact hole pattern of 2.5 mu m square was formed on the transparent substrate 2 was obtained in the same manner as in Example 1. [

Simulation was performed on the phase shift effect of the phase shift mask 30 by the same method as in the first embodiment.

A light intensity distribution curve simulating a spatial image of light passing through a phase shift mask having a phase shift film pattern having a contact hole pattern of 2.5 mu m square is shown in Fig.

As shown in Fig. 9, the light intensity distribution curve of Comparative Example 2 shows that the light intensity peak at the center of the contact hole is not so sharp as compared with the above embodiment, the light intensity variation is not so large at the pattern boundary portion, And the change in the light intensity is large in the outer peripheral region of the pattern boundary portion.

The light intensity gradient at the pattern boundary was 0.440. As a result, it was found that the phase shift mask of Comparative Example 2 exhibited a weak light intensity gradient compared to the above-described embodiment.

In the above-described embodiments, examples of the molybdenum silicide nitride (MoSiN) as the material of the metal silicide-based material layer constituting the phase shift film 3 are described, but the present invention is not limited thereto. The material of the metal silicide-based material layer may be molybdenum silicide oxide (MoSiO), molybdenum silicide carbonitride (MoSiCN), or molybdenum silicide oxide carbide (MoSiOC). Also, in the case of a metal silicide-based material other than molybdenum silicide, the same effect as described above can be obtained.

In the above-described embodiments, examples of chromium nitride (CrN) and chromium oxide nitride (CrON) as the material of the chromium-based material layer constituting the phase shift film 3 have been described, but the present invention is not limited thereto. The material of the chromium-based material layer may be chromium oxide (CrO), chromium carbide (CrC), chromium carbide nitride (CrCN), chromium oxide carbide (CrCO), and chromium oxide carbonitride (CrOCN).

In the embodiment described above, the phase shift mask blank 1 in which only the phase shift film 3 is formed on the transparent substrate 2, and the phase shift mask 3 in which only the phase shift film pattern 3 'is formed on the transparent substrate 2 Although an example of the mask 30 has been described, it is not limited thereto. The phase shift mask pattern 3 'and the light shielding film pattern 4' may be formed on the transparent substrate 2. The phase shift mask pattern 3 'and the light shielding film pattern 4' The same effect as in the above-described embodiment can be obtained.

The light shielding film formed on the phase shift film 3 in the phase shift mask blank having the phase shift film 3 and the light shielding film 4 on the transparent substrate 2 described above is not limited to the light shielding film, A laminated structure of an anti-reflection layer, an insulating layer, a light-shielding layer, and an anti-reflection layer.

In the above-described embodiment, the manufacturing method of manufacturing the phase shift mask 30 by wet etching has been described, but the present invention is not limited to this. Has a material of the phase shift mask blank (1) of the material layer of metal silicide-based, fluorine-based gas (e.g., CF ₄ gas, CHF ₃ gas, SF ₆ gas or a mixture of O ₂ gas in the gas In addition, in the case of the chromium-based material layer, patterning can be performed by dry etching using a chlorine-based gas (for example, a mixed gas of Cl ₂ gas and O ₂ gas) .

1: phase shift mask blank 2: transparent substrate
3: phase shift film 4: light shield film
5: resist film 3 ': phase shift film pattern
4 ': light-shielding film pattern 5': resist film pattern
30: Phase shift mask

Claims (23)

A phase shift for manufacturing a display device for exposure by applying an exposure apparatus having an optical system having a numerical aperture (NA) of 0.06 to 0.15 and an exposure environment using a composite light containing light in a wavelength range of 300 nm to 700 nm as a light source, A phase shift mask blank for fabricating a mask,
A transparent substrate,
The phase shift film formed on the transparent substrate
And,
Wherein the phase shift film includes a single layer film or a laminated film having at least one layer of a metal silicide-based material layer composed of a metal and a nitride of a metal silicide including silicon and nitrogen,
The phase-
The transmittance at a wavelength of 365 nm is in the range of 3.5% or more and 8% or less,
The retardation at a wavelength of 365 nm is in the range of 160 to 200 degrees,
Wherein the amount of change in the transmittance in the wavelength range from 365 nm to 436 nm is within 5.5%
Wherein the phase shift mask blank is a phase shift mask blank. The method according to claim 1,
The phase-
Wherein the amount of change in the transmittance in the wavelength range from 365 nm to 700 nm is 20% or less. 3. The method according to claim 1 or 2,
The phase-
Wherein a difference between a retardation imparted at a wavelength of 365 nm and a retardation imparted at a wavelength of 436 nm is 30 degrees or less. 3. The method according to claim 1 or 2,
The phase-
Wherein a reflectance in a wavelength range of 365 nm to 700 nm is 5% or more and 45% or less. delete 3. The method according to claim 1 or 2,
Wherein the ratio of metal to silicon in the metal silicide-based material layer is metal: silicon = 1: 1 or more and 1: 9 or less. 3. The method according to claim 1 or 2,
Wherein the metal silicide-based material layer has a nitrogen content of 25 atomic% or more and 55 atomic% or less. 3. The method according to claim 1 or 2,
Wherein the phase shift film is composed of at least one layer of a metal silicide-based material layer and at least one layer of a chromium-based material layer,
Wherein the chromium-based material layer is composed of a nitride of chromium or an oxide of chromium. 3. The method according to claim 1 or 2,
And a light shielding film formed on the phase shift film. A phase shift for manufacturing a display device for exposure by applying an exposure apparatus having an optical system having a numerical aperture (NA) of 0.06 to 0.15 and an exposure environment using a composite light containing light in a wavelength range of 300 nm to 700 nm as a light source, As a mask,
A transparent substrate,
The phase shift film pattern formed on the transparent substrate
And,
Wherein the phase shift film pattern includes a single layer film or a lamination film having at least one layer of a metal silicide-based material layer composed of a metal and a nitride of a metal silicide including silicon and nitrogen,
The phase shift film pattern may be formed,
The transmittance at a wavelength of 365 nm is in the range of 3.5% or more and 8% or less,
The retardation at a wavelength of 365 nm is in the range of 160 to 200 degrees,
Wherein the amount of change in the transmittance in the wavelength range from 365 nm to 436 nm is within 5.5%
Wherein the phase shift mask is a phase shift mask. 11. The method of claim 10,
The phase shift film pattern may be formed,
Wherein the amount of change in the transmittance in the wavelength range from 365 nm to 700 nm is 20% or less. The method according to claim 10 or 11,
The phase shift film pattern may be formed,
Wherein the difference between the retardation imparted at a wavelength of 365 nm and the retardation imparted at a wavelength of 436 nm is 30 degrees or less. The method according to claim 10 or 11,
The phase shift film pattern may be formed,
Wherein a reflectance in a wavelength range of 365 nm to 700 nm is 5% or more and 45% or less. delete The method according to claim 10 or 11,
Wherein a ratio of metal to silicon in the metal silicide-based material layer is metal: silicon = 1: 1 or more and 1: 9 or less. The method according to claim 10 or 11,
Wherein the metal silicide-based material layer has a nitrogen content of 25 atomic% or more and 55 atomic% or less. The method according to claim 10 or 11,
Wherein the phase shift film pattern is composed of at least one metal silicide-based material layer and at least one chromium-based material layer,
Wherein the chromium-based material layer is composed of a nitride of chromium or an oxide of chromium. The method according to claim 10 or 11,
And a light shielding film pattern formed on the phase shift film pattern. A manufacturing method of a display device,
A phase shift mask disposing step of disposing the phase shift mask according to claim 10 or 11 on a resist film provided substrate on which a resist film is formed so as to face the resist film;
The composite light is irradiated to the phase shift mask using an exposure apparatus having an optical system having a numerical aperture (NA) of 0.06 to 0.15 and a composite light containing light in a wavelength range of 300 nm to 700 nm as a light source, A resist film exposing process for exposing the resist film
And a step of forming a plurality of pixel electrodes. 20. The method of claim 19,
Wherein the composite light is composite light including i-line, h-line, and g-line. 20. The method of claim 19,
Wherein the exposure environment has a coherence factor (sigma) of 0.5 to 1.0. A method of manufacturing a phase shift mask for manufacturing a display device,
A resist pattern forming step of forming a resist pattern on the phase shift film of the phase shift mask blank according to claim 1;
A phase shift film pattern forming step of forming a phase shift film pattern by wet-etching the phase shift film using the resist pattern as a mask
≪ / RTI > characterized in that the step of forming the phase shift mask comprises: A method of manufacturing a phase shift mask for manufacturing a display device,
A resist pattern forming step of forming a resist pattern on the light-shielding film of the phase shift mask blank according to claim 9;
Forming a light-shielding film pattern by wet-etching the light-shielding film using the resist pattern as a mask;
A phase shift film pattern forming step of wet-etching the phase shift film using the light-shielding film pattern as a mask to form a phase shift film pattern
≪ / RTI > characterized in that the step of forming the phase shift mask comprises:

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