TWI711878B - Large-size photomask - Google Patents

Large-size photomask Download PDF

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TWI711878B
TWI711878B TW108108561A TW108108561A TWI711878B TW I711878 B TWI711878 B TW I711878B TW 108108561 A TW108108561 A TW 108108561A TW 108108561 A TW108108561 A TW 108108561A TW I711878 B TWI711878 B TW I711878B
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light
film
shielding
low
pattern
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TW108108561A
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TW201945832A (en
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今野冬木
三好建也
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日商大日本印刷股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
    • G03F1/46—Antireflective coatings

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Provided is a large-size photomask characterized by comprising a translucent substrate and a light-shielding pattern arranged on a surface of the translucent substrate, wherein the light-shielding pattern has a layered structure in which a first low reflection film, a light shielding film, and a second low reflection film are layered in this order from the translucent substrate side, and a reflection rate to light in a wavelength region of 313 nm to 436 nm of the translucent substrate side surface of the light-shielding pattern is 8% or less.

Description

大型光罩Large mask

本發明係關於一種用於製造顯示裝置所使用之顯示裝置用功能元件等之大型光罩。The present invention relates to a large-scale photomask used for manufacturing display device functional elements used in display devices.

於液晶顯示裝置、有機EL(Electro-Luminescence，電致發光)顯示裝置等平板顯示器領域中，近年來，人們期望更高清之顯示，並正在向高像素化發展。又，隨之，關於例如TFT(Thin Film Transistor，薄膜電晶體)基板、彩色濾光片等顯示裝置用功能元件，要求實施微細加工。In the field of flat-panel displays such as liquid crystal display devices and organic EL (Electro-Luminescence) display devices, in recent years, people have expected more high-definition displays, and they are developing toward higher pixelation. In addition, along with this, for example, functional elements for display devices such as TFT (Thin Film Transistor) substrates and color filters require microfabrication.

作為製造顯示裝置用功能元件時之微細加工方法，自先前起，較佳為採用使用光罩之光微影法。又，作為光罩，一般使用具有設於透光性基板之表面之遮光圖案且具備透光區域及遮光區域之光罩。As a microfabrication method when manufacturing a functional element for a display device, it is preferable to use a photolithography method using a photomask from the foregoing. In addition, as a photomask, a photomask having a light-shielding pattern provided on the surface of a light-transmitting substrate and having a light-transmitting area and a light-shielding area is generally used.

將此種光罩用於曝光裝置並向被轉印體轉印圖案時，於光罩對曝光之光之反射率較高之情形時，因曝光之光在光罩反射而產生之雜散光之影響，導致向被轉印體轉印圖案之精度下降。為了能夠抑制此種問題，採用了降低光罩對曝光之光之反射率之技術。作為此種技術，例如，於專利文獻1等中記載有一種於遮光圖案之表面側設有抗反射膜之光罩之構成。When this type of photomask is used in an exposure device and the pattern is transferred to the transferred body, when the reflectance of the photomask to the exposed light is high, the stray light generated by the reflection of the exposure light on the photomask is Influence, resulting in a decrease in the accuracy of pattern transfer to the body to be transferred. In order to suppress this problem, a technology to reduce the reflectivity of the photomask to the exposure light is adopted. As such a technique, for example, Patent Document 1 and the like describe a structure of a mask provided with an anti-reflection film on the surface side of a light shielding pattern.

另一方面，平板顯示器之製造技術隨著解像度之高清化逐年進步。隨之，面板製造商亦正在開發高精度地形成更微細之圖案之技術，但近年來，於向被轉印體轉印圖案之曝光技術領域中，為了高精度地形成更微細之圖案，存在使用高感度抗蝕劑之傾向。圖11係利用既有低感度抗蝕劑及近年來所使用之高感度抗蝕劑對轉印線寬偏移相對於曝光量之變動進行比較之圖表。如圖11所示，高感度之抗蝕劑相比低感度之抗蝕劑，硬化所需之曝光量較少，且曝光量較少之階段中之轉印線寬偏移之變動較大。On the other hand, the manufacturing technology of flat panel displays is progressing year by year as the resolution becomes higher. Along with this, panel manufacturers are also developing technologies to form finer patterns with high precision. However, in recent years, in the field of exposure technology for transferring patterns to transfer objects, there is a need to form finer patterns with high precision. The tendency to use high-sensitivity resists. FIG. 11 is a graph comparing the shift of the transfer line width with respect to the exposure amount using the existing low-sensitivity resist and the high-sensitivity resist used in recent years. As shown in FIG. 11, the high-sensitivity resist requires less exposure for curing than the low-sensitivity resist, and the shift in the transfer line width in the stage with less exposure is greater.

因此，隨著使用高感度抗蝕劑之傾向，產生了以下問題：由於先前可忽視影響之微弱雜散光於曝光時對抗蝕層產生影響，導致轉印至被轉印體上之圖案中出現不均或尺寸偏差。Therefore, with the tendency to use high-sensitivity resists, the following problem has arisen: because the weak stray light that can be ignored previously affects the resist layer during exposure, the pattern transferred to the transferred body appears to be non-existent. Average or size deviation.

進而，近年來，於高精度地形成大面積圖案之情形時，關於包含g線、h線、或i線之曝光之光，因照射至抗蝕層之曝光之光之能量不足，故要求使用包含g線、h線、i線等複數個波長之光之曝光之光，尤其要求使用包含該等光之中能量較大之j線之曝光之光。另一方面，於使用該等曝光之光之情形時，因感光時之抗蝕層之變化變大，故上述微弱雜散光對抗蝕層之影響進而變大，因此上述問題變得明顯。Furthermore, in recent years, when a large-area pattern is formed with high precision, the exposure light including g-line, h-line, or i-line is required to be used due to insufficient energy of the exposure light irradiated to the resist layer Exposure light including light of multiple wavelengths such as g-line, h-line, i-line, etc., especially requires the use of exposure light including j-line, which has the larger energy among these lights. On the other hand, when the exposure light is used, the change of the resist layer during exposure becomes larger, so the influence of the weak stray light on the resist layer becomes larger, and the above problem becomes obvious.

相對於此，關於上述專利文獻1等中所記載之構成，於曝光時，由於可充分降低因曝光之光在光罩反射而產生之雜散光之強度，故可抑制轉印至被轉印體上之圖案中出現不均或尺寸偏差。In contrast, with regard to the structure described in Patent Document 1 and the like, during exposure, the intensity of the stray light generated by the reflection of the exposure light on the photomask can be sufficiently reduced, so that transfer to the transfer target body can be suppressed Unevenness or size deviation appears in the above pattern.

[先前技術文獻] [專利文獻][Prior Technical Literature] [Patent Literature]

[專利文獻1]專利第4451391號公報[Patent Document 1] Patent No. 4451391

[發明所欲解決之問題][The problem to be solved by the invention]

本發明係鑒於上述問題點而成者，主要目的在於提供一種可抑制轉印至被轉印體上之圖案中出現不均或尺寸偏差之大型光罩。 [解決問題之技術手段]The present invention was made in view of the above-mentioned problems, and its main purpose is to provide a large-scale photomask that can suppress unevenness or dimensional deviation in the pattern transferred to the transferred body. [Technical means to solve the problem]

為解決上述問題，本發明提供一種大型光罩，其特徵在於：其係包含透光性基板、及設於上述透光性基板之表面之遮光圖案之大型光罩，上述遮光圖案具有第1低反射膜、遮光性膜及第2低反射膜自上述透光性基板側按照該順序積層而成之積層構造，且上述遮光圖案之上述透光性基板側之面對313 nm～436 nm之波長區域之光之反射率為8%以下。In order to solve the above-mentioned problems, the present invention provides a large-scale photomask characterized in that it is a large-scale photomask including a light-transmitting substrate and a light-shielding pattern provided on the surface of the light-transmitting substrate, and the light-shielding pattern has a first low The reflective film, the light-shielding film, and the second low-reflection film are laminated in this order from the light-transmitting substrate side, and the light-shielding pattern faces the wavelength of 313 nm to 436 nm on the light-transmitting substrate side The reflectivity of area light is below 8%.

根據本發明，可抑制轉印至被轉印體上之圖案中出現不均或尺寸偏差。According to the present invention, it is possible to suppress the occurrence of unevenness or dimensional deviation in the pattern transferred to the object to be transferred.

於上述發明中，較佳為上述遮光圖案之與上述透光性基板相反側之面對313 nm～436 nm之波長區域之光之反射率為10%以下。In the above-mentioned invention, it is preferable that the reflectance of light in the wavelength region of 313 nm to 436 nm on the opposite side of the light-shielding pattern to the translucent substrate is 10% or less.

又，於上述發明中，較佳為上述遮光性膜含有鉻，上述第1低反射膜及上述第2低反射膜含有氧化鉻。Furthermore, in the above-mentioned invention, it is preferable that the light-shielding film contains chromium, and the first low-reflection film and the second low-reflection film contain chromium oxide.

又，於上述發明中，較佳為上述遮光圖案相對於313 nm～436 nm之波長區域之光之光學密度(OD)為4.5以上。Furthermore, in the above-mentioned invention, it is preferable that the optical density (OD) of the light-shielding pattern with respect to light in the wavelength region of 313 nm to 436 nm is 4.5 or more.

又，於上述發明中，較佳為上述遮光性膜之側面相對於上述透光性基板之傾斜角度為80度以上90度以下。其原因在於可抑制照射至上述遮光性膜之側面之曝光之光之反射光的影響。Moreover, in the above-mentioned invention, it is preferable that the inclination angle of the side surface of the said light-shielding film with respect to the said light-transmitting substrate is 80 degrees or more and 90 degrees or less. The reason is that the influence of the reflected light of the exposure light irradiated to the side surface of the light-shielding film can be suppressed.

又，於上述發明中，較佳為上述第1低反射膜之側面或上述第2低反射膜之側面相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出。Furthermore, in the above invention, it is preferable that the side surface of the first low-reflection film or the side surface of the second low-reflection film protrude in a direction parallel to the surface of the translucent substrate with respect to the side surface of the light-shielding film.

尤佳為上述第1低反射膜之側面及上述第2低反射膜之側面之兩者相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出，進而，上述第1低反射膜之側面相較於上述第2低反射膜之側面在與上述透光性基板之表面平行之方向上更加突出。It is particularly preferable that both the side surface of the first low-reflection film and the side surface of the second low-reflection film protrude in a direction parallel to the surface of the translucent substrate with respect to the side surface of the light-shielding film, and further, the first 1 The side surface of the low-reflection film is more protruding in a direction parallel to the surface of the translucent substrate than the side surface of the second low-reflection film.

又，較佳為至少上述第1低反射膜之側面相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出，進而，上述第1低反射膜之側面相對於上述透光性基板之表面之角度為56°以下。其原因在於，易於利用清洗去除異物，可減少所存在之異物量。Furthermore, it is preferable that at least the side surface of the first low-reflection film protrudes in a direction parallel to the surface of the light-transmitting substrate with respect to the side surface of the light-shielding film, and further, the side surface of the first low-reflection film is opposite to the The angle of the surface of the translucent substrate is 56° or less. The reason is that it is easy to use cleaning to remove foreign matter, which can reduce the amount of foreign matter present.

又，於上述發明中，較佳為上述遮光性膜之側面為凹狀。Moreover, in the above-mentioned invention, it is preferable that the side surface of the said light-shielding film is concave shape.

進而，於上述發明中，較佳為具有用於分割曝光之分割圖案，且上述分割圖案係上述遮光圖案。 [發明之效果]Furthermore, in the above-mentioned invention, it is preferable to have a division pattern for division exposure, and the said division pattern is the said light-shielding pattern. [Effects of Invention]

於本發明中，發揮出可抑制轉印至被轉印體上之圖案中出現不均或尺寸偏差之效果。In the present invention, there is an effect of suppressing unevenness or dimensional deviation in the pattern transferred to the body to be transferred.

以下，對本發明之大型光罩進行詳細說明。Hereinafter, the large-scale photomask of the present invention will be described in detail.

本發明之大型光罩之特徵在於：其係包含透光性基板、及設於上述透光性基板之表面之遮光圖案之大型光罩，上述遮光圖案具有第1低反射膜、遮光性膜及第2低反射膜自上述透光性基板側按照該順序積層而成之積層構造，且上述遮光圖案之上述透光性基板側之面對313 nm～436 nm之波長區域之光之反射率為8%以下。The large-scale photomask of the present invention is characterized in that it is a large-scale photomask including a light-transmitting substrate and a light-shielding pattern provided on the surface of the light-transmitting substrate. The light-shielding pattern has a first low-reflection film, a light-shielding film, and The second low-reflection film has a multilayer structure in which the light-transmitting substrate side is laminated in this order, and the light-shielding pattern on the light-transmitting substrate side faces the reflectance of light in the wavelength region of 313 nm to 436 nm 8% or less.

對本發明之大型光罩之一例一面參照圖式一面進行說明。圖1係表示本發明之大型光罩之一例之概略剖視圖。又，圖2係表示使用圖1所示之大型光罩並藉由曝光將圖案轉印至被轉印體所具有之抗蝕層之步驟之概略剖視圖。An example of the large-scale photomask of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a large-sized mask of the present invention. In addition, FIG. 2 is a schematic cross-sectional view showing a step of transferring the pattern to the resist layer of the transfer body by exposure using the large-scale photomask shown in FIG. 1.

如圖1所示，大型光罩100具備透光性基板110、及設於透光性基板110之表面110a之遮光圖案120。遮光圖案120具有第1低反射膜122、遮光性膜124及第2低反射膜126自透光性基板110側按照該順序積層而成之積層構造。對於313 nm～436 nm之波長區域之任一光，遮光圖案120之透光性基板110側之面120a之反射率均為8%以下。As shown in FIG. 1, the large mask 100 includes a light-transmitting substrate 110 and a light-shielding pattern 120 provided on the surface 110 a of the light-transmitting substrate 110. The light-shielding pattern 120 has a laminated structure in which a first low-reflection film 122, a light-shielding film 124, and a second low-reflection film 126 are laminated in this order from the light-transmitting substrate 110 side. For any light in the wavelength region of 313 nm to 436 nm, the reflectance of the surface 120a on the transparent substrate 110 side of the light shielding pattern 120 is 8% or less.

因此，如圖2所示，於使用大型光罩100，藉由自光源(UV(Ultra Violet，紫外線)燈)放射包含上述波長區域之任一光之曝光之光之曝光，而將圖案轉印至基體210上形成有抗蝕層220之被轉印體200之情形時，藉由降低因上述曝光之光於遮光圖案120之透光性基板110側之面120a與曝光遮蔽板300之表面300a或透光性基板110及空氣(未圖示)之界面112等之間交替反射之多重反射等而產生之雜散光之強度，可將原本照射於利用曝光遮蔽板300遮擋曝光之光之照射之遮蔽區域之抗蝕層220上的雜散光La之強度降低至例如未達曝光照度之0.3%。藉此，可抑制轉印至遮蔽區域之抗蝕層220上之圖案中出現不均或尺寸偏差。Therefore, as shown in FIG. 2, when a large mask 100 is used, the pattern is transferred to the substrate by exposing light from a light source (UV (Ultra Violet, ultraviolet) lamp) that emits exposure light including any light in the above-mentioned wavelength range. In the case of the transfer object 200 with the resist layer 220 formed on the 210, the light on the transparent substrate 110 side surface 120a of the light shielding pattern 120 and the surface 300a of the exposure shielding plate 300 or the transmission The intensity of the stray light generated by alternate reflections between the interface 112 of the optical substrate 110 and the air (not shown), etc., can be originally irradiated to the shielded area where the exposure shield 300 is used to block the exposure of the light The intensity of the stray light La on the resist layer 220 is reduced to, for example, less than 0.3% of the exposure illuminance. Thereby, it is possible to suppress unevenness or size deviation in the pattern transferred to the resist layer 220 in the shielded area.

因此，根據本發明，於使用包含上述波長區域之任一光之曝光之光進行曝光時，藉由降低因曝光之光在上述遮光圖案之上述透光性基板側之面反射而產生之雜散光之強度，可抑制轉印至被轉印體上之圖案中出現不均或尺寸偏差。Therefore, according to the present invention, when using exposure light that includes any light in the above-mentioned wavelength range, the intensity of stray light generated by the reflection of the exposed light on the surface of the light-transmitting substrate of the light-shielding pattern is reduced. , Can suppress the unevenness or size deviation in the pattern transferred to the transferred body.

又，近年來，於平板顯示器之製造中，於高精度地形成大面積圖案之情形時，關於包含g線(波長436 nm)、h線(波長405 nm)、或i線(波長365 nm)之曝光之光，有時照射至抗蝕層之曝光之光之能量不足。因此，要求使用包含g線、h線、i線等複數個波長之光之曝光之光，尤其要求使用包含該等光之中能量較大之j線(波長313 nm)之曝光之光。In addition, in recent years, in the case of high-precision formation of large-area patterns in the manufacture of flat-panel displays, regarding the inclusion of g-line (wavelength 436 nm), h-line (wavelength 405 nm), or i-line (wavelength 365 nm) The exposure light sometimes has insufficient energy to irradiate the resist layer. Therefore, it is required to use exposure light containing light of multiple wavelengths such as g-line, h-line, i-line, etc., especially the exposure light containing j-line (wavelength 313 nm), which has the larger energy among these lights.

另一方面，利用包含複數個波長之光之曝光之光所進行之感光時之抗蝕層之變化較單一波長之曝光之光更大，尤其是利用包含j線之曝光之光所進行之感光時之抗蝕層之變化變大。因此，於使用包含複數個波長之光之曝光之光，尤其是包含j線之曝光之光之情形時，微弱雜散光對抗蝕劑之影響進而變大，因此轉印至被轉印體上之圖案中出現不均等之問題變得明顯。相對於此，於圖1所示之大型光罩100中，對於上述波長區域之任一光，上述反射率均為8%以下，因此對於g線、h線、i線及j線之任一者，均可將遮光圖案120之透光性基板110側之面120a之反射率降低至8%以下。On the other hand, the change in the resist layer when exposed to light containing multiple wavelengths of light is greater than that of light exposed to a single wavelength, especially when exposed to light containing j-line The change of the resist layer becomes larger over time. Therefore, when using exposure light containing multiple wavelengths of light, especially in the case of exposure light containing j-line, the influence of weak stray light on the resist becomes greater, so the transfer to the body The problem of unevenness in the pattern becomes obvious. On the other hand, in the large mask 100 shown in FIG. 1, the reflectance is 8% or less for any light in the above-mentioned wavelength range, so for any of the g-line, h-line, i-line, and j-line, The reflectivity of the surface 120a on the side of the light-transmitting substrate 110 of the light-shielding pattern 120 can be reduced to less than 8%.

因此，根據本發明，於使用其中包含g線、h線、i線等複數個波長之光之曝光之光，尤其是包含j線之曝光之光進行曝光時，可明顯抑制轉印至被轉印體上之圖案中出現不均等。Therefore, according to the present invention, when exposure light including light of multiple wavelengths such as g-line, h-line, i-line, etc., is used for exposure, especially the exposure light including j-line, the transfer to be transferred can be significantly suppressed. Unevenness appears in the patterns on the printed body.

1.遮光圖案 上述遮光圖案係設於上述透光性基板之表面者，其具有上述第1低反射膜、上述遮光性膜及上述第2低反射膜自上述透光性基板側按照該順序積層而成之積層構造，上述遮光圖案之上述透光性基板側之面對313 nm～436 nm之波長區域之光的反射率為8%以下。1. Shading pattern The light-shielding pattern is provided on the surface of the light-transmitting substrate, and has a laminated layer in which the first low-reflection film, the light-shielding film, and the second low-reflection film are laminated in this order from the side of the light-transmitting substrate The structure is such that the reflectance of light in the wavelength region of 313 nm to 436 nm facing the translucent substrate side of the light shielding pattern is 8% or less.

(1)對313 nm～436 nm之波長區域之光之反射率 上述遮光圖案之上述透光性基板側之面對313 nm～436 nm之波長區域之光的反射率為8%以下。即，對於上述波長區域之任一光，上述遮光圖案之上述透光性基板側之面之反射率均為8%以下。(1) Reflectance of light in the wavelength region of 313 nm～436 nm The reflectance of light in the wavelength region of 313 nm to 436 nm facing the translucent substrate side of the light shielding pattern is 8% or less. That is, for any light in the above-mentioned wavelength range, the reflectance of the surface of the light-shielding pattern on the transparent substrate side is 8% or less.

作為上述遮光圖案之上述透光性基板側之面，只要對上述波長區域之光之反射率為8%以下則無特別限定，但其中較佳為對365 nm～436 nm之波長區域之光之反射率為5%以下。於使用包含365 nm～436 nm之波長區域之任一光之曝光之光進行曝光時，可將圖2所示之雜散光La之強度降低至例如未達曝光照度之0.2%。其原因在於，藉此可將上述雜散光之強度自被轉印體之抗蝕層感光之分界線水準降低至完全不產生影響之水準。進而，尤佳為對313 nm～365 nm之波長區域之光之反射率為5%以下。其原因在於，於使用包含更廣範圍之波長區域之光的曝光之光進行曝光時，可獲得相同之效果。更具體而言，其原因在於不僅是使用365 nm～436 nm之波長區域之曝光之光之現行曝光裝置及抗蝕劑，而且使用313 nm～365 nm之波長區域之曝光之光之其他曝光裝置及抗蝕劑亦可獲得相同之效果。The surface of the light-shielding pattern on the translucent substrate side is not particularly limited as long as the reflectance of light in the wavelength region is 8% or less, but it is preferably the light in the wavelength region of 365 nm to 436 nm. The reflectivity is less than 5%. When using exposure light including any light in the wavelength region of 365 nm to 436 nm, the intensity of the stray light La shown in FIG. 2 can be reduced to, for example, less than 0.2% of the exposure illuminance. The reason is that, by this, the intensity of the above-mentioned stray light can be reduced from the boundary level of the photosensitive resist layer of the transferred body to a level that does not affect at all. Furthermore, it is particularly preferable that the reflectance of light in the wavelength region of 313 nm to 365 nm is 5% or less. The reason is that the same effect can be obtained when exposure light including light in a wider wavelength region is used for exposure. More specifically, the reason is not only the current exposure equipment and resists that use exposure light in the wavelength region of 365 nm to 436 nm, but also other exposure equipment that uses light exposure in the wavelength region of 313 nm to 365 nm And the resist can also obtain the same effect.

其中，於本發明中，作為上述遮光圖案之上述透光性基板側之面之上述反射率之測定方法，可使用以光電二極體陣列作為檢測器之裝置(大塚電子MCPD(Multi Channel Photo Detector，多通道分光光譜儀))。Among them, in the present invention, as the method for measuring the reflectance of the surface on the translucent substrate side of the light-shielding pattern, a device using a photodiode array as a detector (Otsuka Electronics MCPD (Multi Channel Photo Detector) , Multi-channel spectrophotometer)).

較佳為上述遮光圖案之與上述透光性基板相反側之面對313 nm～436 nm之波長區域之光的反射率為10%以下。即，較佳為對於上述波長區域之任一光，上述遮光圖案之與上述透光性基板相反側之面之反射率均為10%以下。It is preferable that the reflectance of light in the wavelength region of 313 nm to 436 nm on the side opposite to the translucent substrate of the light-shielding pattern is 10% or less. That is, it is preferable that the reflectance of the surface of the light-shielding pattern on the opposite side of the translucent substrate is 10% or less for any light in the aforementioned wavelength region.

再者，上述遮光圖案之與上述透光性基板相反側之面之上述反射率之測定方法係與上述遮光圖案之上述透光性基板側之面之上述反射率相同。Furthermore, the method for measuring the reflectance of the surface of the light shielding pattern opposite to the translucent substrate is the same as that of the surface of the light shielding pattern on the translucent substrate side.

於如圖1所示之大型光罩100中，對於313 nm～436 nm之波長區域之任一光，遮光圖案120之與透光性基板110相反側之面120b之反射率均為10%以下。因此，如圖2所示，於使用大型光罩100，並藉由使用包含上述波長區域之任一光之曝光之光進行曝光，而將圖案轉印至基體210上形成有抗蝕層220之被轉印體200之情形時，藉由降低因上述曝光之光於遮光圖案120之與透光性基板110相反側之面120b與空氣(未圖示)及抗蝕層220之界面212或抗蝕層220及基體210之界面214等之間交替反射之多重反射等而產生之雜散光的強度，可將原本照射於利用遮光圖案120之邊緣部分遮擋曝光之光之照射之抗蝕層220上的雜散光Lb之強度降低至例如未達曝光照度之2.0%。藉此，可抑制轉印至邊緣部分中之抗蝕層220上之圖案中出現尺寸偏差等。In the large mask 100 shown in FIG. 1, the reflectance of the surface 120b of the light shielding pattern 120 opposite to the translucent substrate 110 is 10% or less for any light in the wavelength region of 313 nm to 436 nm. Therefore, as shown in FIG. 2, when a large mask 100 is used, and the pattern is transferred to the substrate 210 where the resist layer 220 is formed on the substrate 210 by exposing by exposure light including any light in the above-mentioned wavelength range In the case of the printed body 200, the interface 212 or the resist layer between the surface 120b of the light-shielding pattern 120 opposite to the transparent substrate 110 and the air (not shown) and the resist layer 220 due to the above exposure is reduced The intensity of the stray light generated by the alternate reflections between the interface 214 of 220 and the substrate 210, etc., can be used to irradiate the stray light on the resist layer 220 that is irradiated by the edge of the light shielding pattern 120 to block the exposure light. The intensity of the astigmatism Lb is reduced to, for example, less than 2.0% of the exposure illumination. Thereby, it is possible to suppress dimensional deviations and the like in the pattern transferred to the resist layer 220 in the edge portion.

因此，較佳為對上述波長區域之光之反射率為10%以下。其原因在於，於使用包含上述波長區域之任一光之曝光之光進行曝光時，藉由降低因曝光之光在上述遮光圖案之與上述透光性基板相反側之面反射而產生之雜散光之強度，可有效抑制轉印至被轉印體上之圖案中出現尺寸偏差等。其原因在於，使用其中包含g線、h線、i線等複數個波長之光之曝光之光，尤其是包含j線之曝光之光進行曝光時，可更明顯地抑制轉印至被轉印體上之圖案中出現尺寸偏差等。Therefore, it is preferable that the reflectance of light in the above-mentioned wavelength range is 10% or less. The reason is that when using exposure light that includes any light in the above-mentioned wavelength region, the intensity of stray light generated by the reflection of the exposed light on the surface of the light-shielding pattern opposite to the translucent substrate is reduced. , It can effectively suppress the size deviation in the pattern transferred to the transferred body. The reason is that the use of exposure light containing light of multiple wavelengths such as g-line, h-line, i-line, etc., especially when exposure light containing j-line exposure, can more significantly inhibit transfer to the transferred There are dimensional deviations in the patterns on the body.

又，作為上述遮光圖案之與上述透光性基板相反側之面，較佳為對上述波長區域之光之反射率為10%以下，但其中較佳為對365 nm～436 nm之波長區域之光之反射率為5%以下。於使用包含365 nm～436 nm之波長區域之任一光之曝光之光進行曝光時，可將圖2所示之雜散光Lb之強度降低至例如未達曝光照度之1.0%。其原因在於，藉此可將上述雜散光之強度，在轉印至上述遮光圖案之邊緣部分中之被轉印體之抗蝕層上之圖案中出現尺寸偏差等之程度下自該抗蝕層感光之分界線水準降低至完全不出現上述尺寸偏差等之水準。進而，尤佳為對313 nm～365 nm之波長區域之光之反射率為5%以下。其原因在於，於使用包含更廣範圍之波長區域之光的曝光之光進行曝光時，可獲得相同之效果。更具體而言，其原因在於不僅是使用365 nm～436 nm之波長區域之曝光之光之現行曝光裝置及抗蝕劑，而且使用313 nm～365 nm之波長區域之曝光之光之其他曝光裝置及抗蝕劑亦可獲得相同之效果。In addition, as the light-shielding pattern, the surface opposite to the translucent substrate preferably has a reflectance of 10% or less to light in the wavelength region, but it is more preferred to have a reflectivity to the wavelength region of 365 nm to 436 nm. The reflectance of light is below 5%. When using exposure light including any light in the wavelength region of 365 nm to 436 nm, the intensity of the stray light Lb shown in FIG. 2 can be reduced to, for example, less than 1.0% of the exposure illuminance. The reason is that the intensity of the stray light can be transferred from the resist layer to the extent that the pattern on the resist layer of the transferred body in the edge portion of the light shielding pattern has a size deviation. The demarcation level of the photosensitive is reduced to a level where there is no such dimensional deviation. Furthermore, it is particularly preferable that the reflectance of light in the wavelength region of 313 nm to 365 nm is 5% or less. The reason is that the same effect can be obtained when exposure light including light in a wider wavelength region is used for exposure. More specifically, the reason is not only the current exposure equipment and resists that use exposure light in the wavelength region of 365 nm to 436 nm, but also other exposure equipment that uses light exposure in the wavelength region of 313 nm to 365 nm And the resist can also obtain the same effect.

(2)第1低反射膜 上述第1低反射膜於上述遮光圖案之積層構造中設於上述透光性基板側，其係實現將上述遮光圖案之上述透光性基板側之面對313 nm～436 nm之波長區域之光之反射率降低至8%以下之功能之膜。(2) The first low reflection film The first low-reflection film is provided on the translucent substrate side in the layered structure of the light-shielding pattern, which realizes that the light-shielding pattern on the translucent substrate side faces the light in the wavelength region of 313 nm to 436 nm A functional film whose reflectivity is reduced to below 8%.

上述遮光圖案藉由具有上述第1低反射膜，而於上述波長區域之光照射至上述遮光圖案之上述透光性基板側之面之情形時，在上述第1低反射膜之上述透光性基板側之面反射之光、在上述第1低反射膜之內部之界面反射之光、及由上述第1低反射膜與上述遮光性膜之交界反射之光因干涉相互削弱。藉此，可將上述遮光圖案之上述透光性基板側之面相對於上述波長區域之光之反射率降低至8%以下。The light-shielding pattern has the first low-reflection film, and when the light in the wavelength range is irradiated to the surface of the light-shielding pattern on the translucent substrate side, the light-transmitting property of the first low-reflection film The light reflected from the surface of the substrate, the light reflected at the interface inside the first low-reflection film, and the light reflected from the boundary between the first low-reflection film and the light-shielding film are attenuated by interference. Thereby, the reflectance of the light-transmitting substrate side surface of the light-shielding pattern with respect to the light in the wavelength region can be reduced to 8% or less.

如上所述，於使用其中包含g線、h線、i線等複數個波長之光之曝光之光，尤其是包含j線之曝光之光之情形時，微弱雜散光對抗蝕劑之影響進而變大，因此轉印至被轉印體上之圖案中出現不均等之問題變得明顯。另一方面，難以形成一種膜以解決此種問題，該膜係實現將上述遮光圖案之上述透光性基板側之面對上述波長區域之光之反射率降低至8%以下之功能。於本發明中，雖存在此種情況，但能夠形成一種實現將上述透光性基板側之面對上述波長區域之光之反射率降低至8%以下之功能之膜。As mentioned above, when using exposure light including light of multiple wavelengths such as g-line, h-line, i-line, etc., especially in the case of exposure light including j-line, the influence of weak stray light on the resist becomes Large, so the problem of unevenness in the pattern transferred to the transferred body becomes obvious. On the other hand, it is difficult to form a film to solve this problem. The film realizes the function of reducing the reflectance of the light in the wavelength region on the light-shielding pattern on the translucent substrate side to less than 8%. In the present invention, despite such a situation, it is possible to form a film that realizes the function of reducing the reflectance of light in the wavelength region on the side of the translucent substrate facing the wavelength region to 8% or less.

a.第1低反射膜 作為上述第1低反射膜之膜厚，只要能實現將上述遮光圖案之上述透光性基板側之面對上述波長區域之光之反射率降低至8%以下之功能則無特別限定，但較佳為膜厚處於10 nm～50 nm之範圍內。其原因在於，若過薄則降低上述反射率之功能會下降，若過厚則難以對上述遮光圖案進行高精度加工。a. The first low reflection film The film thickness of the first low-reflection film is not particularly limited as long as it can achieve the function of reducing the reflectance of light in the wavelength region on the translucent substrate side of the light-shielding pattern to 8% or less. It is preferable that the film thickness is in the range of 10 nm to 50 nm. The reason is that if it is too thin, the function of reducing the above-mentioned reflectance will be reduced, and if it is too thick, it will be difficult to process the above-mentioned light shielding pattern with high precision.

作為上述第1低反射膜之材料，只要為能將上述遮光圖案之上述透光性基板側之面對上述波長區域之光之反射率降低至8%以下之材料則無特別限定，例如，可列舉氧化鉻(CrOx)、氮氧化鉻(CrON)、氮化鉻(CrN)、氧化鈦(TiO)、氮氧化鈦(TiON)、氧化鉭(TaO)、鉭矽氧化物(TaSiO)、鎳氧化鋁(NiAlO)、鉬矽氧化物(MoSiO)及鉬矽氮氧化物(MoSiON)等。其中較佳為氧化鉻(CrOx)、氮氧化鉻(CrON)，尤佳為氧化鉻(CrOx)。The material of the first low-reflection film is not particularly limited as long as it can reduce the reflectance of light in the wavelength region on the light-shielding pattern on the translucent substrate side to less than 8%. For example, Examples include chromium oxide (CrOx), chromium oxynitride (CrON), chromium nitride (CrN), titanium oxide (TiO), titanium oxynitride (TiON), tantalum oxide (TaO), tantalum silicon oxide (TaSiO), nickel oxide Aluminum (NiAlO), molybdenum silicon oxide (MoSiO) and molybdenum silicon oxynitride (MoSiON), etc. Among them, chromium oxide (CrOx) and chromium oxynitride (CrON) are preferred, and chromium oxide (CrOx) is particularly preferred.

b.形成方法 作為上述第1低反射膜之形成方法，例如，可列舉濺鍍法、真空蒸鍍法及離子電鍍法等。更具體而言，例如，可列舉將Cr靶材安裝至真空室內，導入O2 、N2 、CO2 氣體，藉由真空環境下的反應性濺鍍成膜出膜之方法等。 再者，於該方法中，藉由相較於對普通二元光罩之遮光圖案中之低反射膜進行成膜時增加O2 氣體之比率，而將上述遮光圖案之上述透光性基板側之面對313 nm～436 nm之波長區域之光之反射率降低至8%以下。b. Formation method As the formation method of the above-mentioned first low-reflection film, for example, a sputtering method, a vacuum vapor deposition method, an ion plating method, etc. can be cited. More specifically, for example, a method of installing a Cr target in a vacuum chamber, introducing O 2 , N 2 , and CO 2 gas, and forming a film by reactive sputtering in a vacuum environment, etc. can be cited. Furthermore, in this method, the ratio of O 2 gas is increased compared to when the low-reflection film in the light-shielding pattern of the ordinary binary mask is formed, and the light-shielding pattern on the translucent substrate side The reflectance of light facing the wavelength region of 313 nm ~ 436 nm is reduced to below 8%.

(3)第2低反射膜 上述第2低反射膜於上述遮光圖案之積層構造中設於上述透光性基板相反側，其係實現降低上述遮光圖案之與上述透光性基板相反側之面對313 nm～436 nm之波長區域之光之反射率之功能的膜。(3) The second low reflection film The second low-reflection film is provided on the opposite side of the light-transmitting substrate in the laminated structure of the light-shielding pattern to reduce the wavelength of the light-shielding pattern on the opposite side of the light-transmitting substrate from 313 nm to 436 nm A film that functions as the reflectivity of regional light.

上述遮光圖案藉由具有上述第2低反射膜，而於上述波長區域之光入射至上述遮光圖案之與上述透光性基板相反側之面之情形時，由上述第2低反射膜之與上述透光性基板相反側之面反射之光、由上述第2低反射膜之內部之界面反射之光、及由上述第2低反射膜與上述遮光性膜之交界反射之光因干涉相互削弱。藉此，可降低上述遮光圖案之與上述透光性基板相反側之面對上述波長區域之光之反射率。The light-shielding pattern has the second low-reflection film, and when the light of the wavelength region is incident on the surface of the light-shielding pattern on the opposite side of the translucent substrate, the second low-reflection film and the The light reflected on the opposite side of the translucent substrate, the light reflected by the internal interface of the second low-reflection film, and the light reflected by the boundary between the second low-reflection film and the light-shielding film are attenuated by interference. Thereby, the reflectance of the light in the wavelength region on the opposite side of the light-transmitting substrate of the light-shielding pattern can be reduced.

a.第2低反射膜 作為上述第2低反射膜，只要為實現降低上述遮光圖案之與上述透光性基板相反側之面對313 nm～436 nm之波長區域之光之反射率之功能的膜則無特別限定，但較佳為實現將上述相反側之面對313 nm～436 nm之波長區域之光之反射率降低至10%以下之功能之膜。a. The second low reflection film The second low-reflection film is not particularly limited as long as it realizes the function of reducing the reflectance of light in the wavelength region of 313 nm to 436 nm on the side of the light shielding pattern opposite to the translucent substrate. Preferably, it is a film that realizes the function of reducing the reflectance of light in the wavelength region from 313 nm to 436 nm on the opposite side to less than 10%.

如上所述，於使用其中包含g線、h線、及i線等複數個波長之光之曝光之光，尤其是包含j線之曝光之光之情形時，微弱雜散光對抗蝕劑之影響進而變大，因此轉印至被轉印體上之圖案中出現尺寸偏差等之問題變得明顯。另一方面，難以形成一種抗反射膜以有效解決此種問題，該抗反射膜係實現將上述遮光圖案之與上述透光性基板相反側之面對上述波長區域之光之反射率降低至10%以下之功能。於本發明中，雖存在此種情況，但能夠形成一種實現將上述相反側之面對上述波長區域之光之反射率降低至10%以下之功能之膜。As described above, when using exposure light including light of multiple wavelengths such as g-line, h-line, and i-line, especially in the case of exposure light including j-line, the influence of weak stray light on the resist is further It becomes larger, so the problem of dimensional deviation in the pattern transferred to the transfer body becomes obvious. On the other hand, it is difficult to form an anti-reflection film to effectively solve this problem. The anti-reflection film can reduce the reflectance of the light in the above-mentioned wavelength region on the opposite side of the light-shielding pattern from the above-mentioned translucent substrate to 10 Functions below %. In the present invention, despite such a situation, it is possible to form a film that realizes the function of reducing the reflectance of light facing the wavelength region on the opposite side to 10% or less.

作為上述第2低反射膜之膜厚，只要能實現降低上述遮光圖案之與上述透光性基板相反側之面對上述波長區域之光之反射率之功能則無特別限定，但較佳為膜厚處於10 nm～50 nm之範圍內。其原因在於，若過薄則降低上述反射率之功能會下降，若過厚則難以對上述遮光圖案進行高精度加工。The thickness of the second low-reflection film is not particularly limited as long as it can reduce the reflectance of the light in the wavelength region on the side of the light-shielding pattern opposite to the translucent substrate, but it is preferably a film. The thickness is in the range of 10 nm to 50 nm. The reason is that if it is too thin, the function of reducing the above-mentioned reflectance will be reduced, and if it is too thick, it will be difficult to process the above-mentioned light shielding pattern with high precision.

關於上述第2低反射膜之材料係與上述第1低反射膜相同，因此此處省略說明。The material of the second low-reflection film is the same as that of the first low-reflection film, so the description is omitted here.

b.形成方法 作為將上述遮光圖案之與上述透光性基板相反側之面對313 nm～436 nm之波長區域之光之反射率降低至10%以下之上述第2低反射膜之形成方法係與上述第1低反射膜之形成方法相同，因此此處省略說明。b. Formation method The method of forming the second low-reflection film is the same as that of the first method for reducing the reflectance of light in the wavelength region of 313 nm to 436 nm on the side opposite to the translucent substrate of the light-shielding pattern to 10% or less. The method of forming the low-reflection film is the same, so the description is omitted here.

(4)遮光性膜 上述遮光性膜係於上述遮光圖案之積層構造中設於上述第1低反射膜與上述第2低反射膜之間之具有遮光性之膜。(4) Shading film The light-shielding film is a film having light-shielding properties provided between the first low-reflection film and the second low-reflection film in the laminated structure of the light-shielding pattern.

a.遮光性膜 作為上述遮光性膜之膜厚，雖無特別限定，但較佳為膜厚處於80 nm～180 nm之範圍內。其原因在於，若過薄則難以獲得所需之遮光性，若過厚則難以對上述遮光圖案進行高精度加工。a. Shading film Although the film thickness of the light-shielding film is not particularly limited, the film thickness is preferably in the range of 80 nm to 180 nm. The reason is that if it is too thin, it is difficult to obtain the required light-shielding property, and if it is too thick, it is difficult to process the above-mentioned light-shielding pattern with high precision.

作為上述遮光性膜之材料，只要為具有遮光性之材料則無特別限定，例如，可列舉鉻(Cr)、氮氧化鉻(CrON)、氮化鉻(CrN)、鉬矽氧化物(MoSiO)、鉬矽氮氧化物(MoSiON)、氧化鉭(TaO)及鉭矽氧化物(TaSiO)等。其中較佳為鉻(Cr)。The material of the light-shielding film is not particularly limited as long as it is a material with light-shielding properties. For example, chromium (Cr), chromium oxynitride (CrON), chromium nitride (CrN), molybdenum silicon oxide (MoSiO) , Molybdenum silicon oxynitride (MoSiON), tantalum oxide (TaO) and tantalum silicon oxide (TaSiO), etc. Among them, chromium (Cr) is preferred.

b.遮光性膜之形成方法 作為上述遮光性膜之形成方法，例如，可列舉濺鍍法、真空蒸鍍法及離子電鍍法等。b. Formation method of light-shielding film As a method of forming the above-mentioned light-shielding film, for example, a sputtering method, a vacuum vapor deposition method, an ion plating method, etc. can be cited.

又，作為將上述遮光圖案相對於上述波長區域之光之光學密度(OD)設為4.5以上之上述遮光性膜之形成方法，例如，可列舉較通常延長遮光性膜成膜時間之方法或增加成膜掃描次數之方法等。In addition, as a method of forming the light-shielding film in which the optical density (OD) of the light-shielding pattern with respect to the light in the wavelength region is 4.5 or more, for example, a method of extending the time for forming the light-shielding film or increasing The method of film formation scan times, etc.

(5)遮光圖案 a.光學密度(OD) 作為上述遮光圖案，較佳為對313 nm～436 nm之波長區域之光之光學密度(OD)為4.5以上。即，較佳為對於上述波長區域之任一光，光學密度(OD)均為4.5以上。(5) Shading pattern a. Optical density (OD) As the above-mentioned light-shielding pattern, it is preferable that the optical density (OD) of light in the wavelength region of 313 nm to 436 nm is 4.5 or more. That is, it is preferable that the optical density (OD) is 4.5 or more for any light in the above-mentioned wavelength range.

其中，本發明中，於針對上述波長區域之光之光學密度(OD)之測定方法中，可使用紫外/可見分光光度計(日立U-4000)。Among them, in the present invention, an ultraviolet/visible spectrophotometer (Hitachi U-4000) can be used in the method for measuring the optical density (OD) of light in the above-mentioned wavelength range.

於圖1所示之大型光罩100中，遮光圖案120相對於313 nm～436 nm之波長區域之光之光學密度(OD)為4.5以上。即，相對於該波長區域之任一光，遮光圖案120之光學密度(OD)均為4.5以上。因此，如圖2所示，於使用大型光罩100，並藉由使用包含上述波長區域之任一光之曝光之光進行曝光，而將圖案轉印至基體210上形成有抗蝕層220之被轉印體200之情形時，可將上述曝光之光透過遮光圖案120之透過光Lc之強度降低至例如曝光照度之0.001%以下。藉此，可抑制轉印至抗蝕層220上之圖案中出現不均等。In the large-scale photomask 100 shown in FIG. 1, the light-shielding pattern 120 has an optical density (OD) of 4.5 or more relative to light in the wavelength region of 313 nm to 436 nm. That is, the optical density (OD) of the light shielding pattern 120 is 4.5 or more with respect to any light in the wavelength range. Therefore, as shown in FIG. 2, when a large mask 100 is used, and the pattern is transferred to the substrate 210 where the resist layer 220 is formed on the substrate 210 by exposing by exposure light including any light in the above-mentioned wavelength range In the case of the printed body 200, the intensity of the above-mentioned exposure light passing through the light shielding pattern 120 can be reduced to less than 0.001% of the exposure illuminance, for example. Thereby, it is possible to suppress unevenness in the pattern transferred to the resist layer 220.

因此，較佳為上述光學密度(OD)為4.5以上。其原因在於，於使用包含上述波長區域之任一光之曝光之光進行曝光時，藉由降低上述曝光之光透過上述遮光圖案之透過光之強度，可有效抑制轉印至被轉印體上之圖案中出現不均等。其原因在於，使用其中包含g線、h線、i線等複數個波長之光的曝光之光，尤其是包含j線之曝光之光進行曝光時，可有效抑制轉印至被轉印體上之圖案中出現不均等。Therefore, it is preferable that the above-mentioned optical density (OD) is 4.5 or more. The reason is that when exposure is performed using exposure light that includes any light in the above-mentioned wavelength range, by reducing the intensity of the light that is exposed to light through the light-shielding pattern, it is possible to effectively prevent the pattern from being transferred to the body to be transferred Inequality occurs in. The reason is that the use of exposure light containing light of multiple wavelengths such as g-line, h-line, i-line, etc., especially when exposure light containing j-line exposure, can effectively inhibit transfer to the transferred body Unevenness appears in the pattern.

再者，一般而言，從遮光圖案變厚，難以進行高精度加工方面考慮，不宜提高光罩中之遮光圖案之光學密度(OD)。該傾向尤其在半導體積體電路之製造中所使用之光罩中較為明顯。Furthermore, generally speaking, it is not suitable to increase the optical density (OD) of the light-shielding pattern in the mask due to the thickening of the light-shielding pattern and difficulty in high-precision processing. This tendency is particularly evident in the photomask used in the manufacture of semiconductor integrated circuits.

b.尺寸 (a)寬度 作為上述遮光圖案之寬度，例如，可列舉0.1 μm以上且未達10.0 μm之寬度。作為上述遮光圖案之寬度，較佳為以次微米級對尺寸進行控制後之寬度。b. size (a) Width As the width of the light-shielding pattern, for example, a width of 0.1 μm or more and less than 10.0 μm can be cited. As the width of the light-shielding pattern, it is preferable to control the size in sub-micron order.

其中，上述遮光圖案之寬度係指由俯視形狀之短邊方向之尺寸規定者。又，上述以次微米級對尺寸進行控制後之寬度係指以0.1 μm為單位對尺寸進行控制後之寬度，例如，0.1 μm以上且未達1.0 μm之寬度。Wherein, the width of the above-mentioned light-shielding pattern refers to the one defined by the size of the short side direction of the top view shape. In addition, the above-mentioned width after the size is controlled in the sub-micron level refers to the width after the size is controlled in a unit of 0.1 μm, for example, a width of 0.1 μm or more and less than 1.0 μm.

(b)膜厚 作為上述遮光圖案之整體膜厚，雖無特別限定，但較佳為100 nm～250 nm之範圍內。其原因在於，若過薄則難以獲得所需之遮光性，若過厚則難以對上述遮光圖案進行高精度加工。(b) Film thickness Although the overall film thickness of the light-shielding pattern is not particularly limited, it is preferably in the range of 100 nm to 250 nm. The reason is that if it is too thin, it is difficult to obtain the required light-shielding property, and if it is too thick, it is difficult to process the above-mentioned light-shielding pattern with high precision.

c.剖面形狀 作為上述遮光圖案，較佳為相對於上述波長區域之光之光學密度(OD)為4.5以上，且具有所需之剖面形狀。以下，對遮光圖案之較佳之剖面形狀進行說明。c. Section shape As the above-mentioned light-shielding pattern, it is preferable that the optical density (OD) of light in the above-mentioned wavelength region is 4.5 or more and has a desired cross-sectional shape. Hereinafter, the preferred cross-sectional shape of the light-shielding pattern will be described.

圖3係將圖1所示之虛線框內之區域之圖式上下顛倒而表示的放大圖。如圖3所示，於圖1所示之大型光罩100中，遮光圖案120相對於313 nm～436 nm之波長區域之光之光學密度(OD)為4.5以上。於遮光圖案120之開口部120c中，遮光性膜124之側面124a相對於透光性基板110之傾斜角度α為80度以上90度以下。另一方面，圖4係表示先前技術之大型光罩中之與圖3對應之區域的概略剖視圖。如圖4所示，於先前技術之大型光罩100中，遮光性膜124之側面124a相對於透光性基板110之傾斜角度α未達80度。Fig. 3 is an enlarged view showing the area in the dashed frame shown in Fig. 1 upside down. As shown in FIG. 3, in the large-scale photomask 100 shown in FIG. 1, the optical density (OD) of the light shielding pattern 120 with respect to the light in the wavelength region of 313 nm to 436 nm is 4.5 or more. In the opening 120c of the light-shielding pattern 120, the inclination angle α of the side surface 124a of the light-shielding film 124 with respect to the translucent substrate 110 is 80 degrees or more and 90 degrees or less. On the other hand, FIG. 4 is a schematic cross-sectional view showing a region corresponding to FIG. 3 in a large-scale photomask of the prior art. As shown in FIG. 4, in the large-scale photomask 100 of the prior art, the inclination angle α of the side surface 124a of the light-shielding film 124 with respect to the light-transmitting substrate 110 is less than 80 degrees.

如圖3所示，於遮光性膜124之側面124a相對於透光性基板110之傾斜角度α為80度以上90度以下之情形時，與圖4所示上述傾斜角度α未達80度之情形不同，於將圖案轉印至被轉印體所具有之抗蝕層之曝光時，自光源側之斜方向照射至遮光性膜124之側面124a之曝光之光(雜散光)之反射光被誘導至遮光圖案120之開口部120c側之可能性增加。由此，可抑制該反射光照射於利用遮光圖案120之邊緣部分遮擋曝光之光之照射之抗蝕層上。藉此，可抑制轉印至邊緣部分中之抗蝕層上之圖案中出現尺寸偏差等。As shown in FIG. 3, when the inclination angle α of the side surface 124a of the light-shielding film 124 with respect to the translucent substrate 110 is 80 degrees or more and 90 degrees or less, the inclination angle α is less than 80 degrees as shown in FIG. The situation is different. When the pattern is transferred to the resist layer of the transferred body, the reflected light of the exposure light (stray light) irradiated from the oblique direction of the light source side to the side surface 124a of the light shielding film 124 is The possibility of being induced to the side of the opening 120c of the light shielding pattern 120 increases. As a result, the reflected light can be prevented from being irradiated on the resist layer that uses the edge portion of the light shielding pattern 120 to block the exposure of the light. Thereby, it is possible to suppress dimensional deviations and the like in the pattern transferred to the resist layer in the edge portion.

因此，作為相對於上述波長區域之光之光學密度(OD)為4.5以上之上述遮光圖案，如圖3所示，較佳為上述遮光性膜之側面相對於上述透光性基板之傾斜角度為80度以上90度以下。其原因在於，因使上述光學密度(OD)為4.5以上，上述遮光圖案成為厚膜，故而雖自光源側之斜方向照射至上述遮光性膜之側面之曝光之光之反射光之光量增多，但藉由該反射光之影響，可抑制轉印至被轉印體上之圖案中出現尺寸偏差等。Therefore, as the light-shielding pattern having an optical density (OD) of 4.5 or more with respect to the light in the wavelength region, as shown in FIG. 3, it is preferable that the inclination angle of the side surface of the light-shielding film with respect to the light-transmitting substrate is Above 80 degrees and below 90 degrees. The reason is that, since the optical density (OD) is 4.5 or more, the light shielding pattern becomes a thick film, so the amount of reflected light of the exposure light irradiated from the oblique direction of the light source side to the side surface of the light shielding film increases. However, due to the influence of the reflected light, it is possible to suppress dimensional deviations in the pattern transferred to the body to be transferred.

再者，上述遮光性膜之側面相對於上述透光性基板之傾斜角度係指圖3中以α所表示之上述遮光性膜之側面中之上述透光性基板側的邊緣之接線之傾斜角度。In addition, the inclination angle of the side surface of the light-shielding film with respect to the light-transmitting substrate refers to the inclination angle of the wiring of the edge on the side of the light-transmitting substrate in the side surface of the light-shielding film represented by α in FIG. 3 .

圖5～圖7係分別表示本發明之大型光罩之另一例中之與圖3對應之區域的概略剖視圖。FIGS. 5-7 are schematic cross-sectional views respectively showing areas corresponding to FIG. 3 in another example of the large-sized mask of the present invention.

於圖5所示之大型光罩100中，遮光圖案120相對於313 nm～436 nm之波長區域之光之光學密度(OD)為4.5以上。於遮光圖案120之開口部120c中，遮光性膜124之側面124a係與透光性基板110垂直之平面，第1低反射膜122之側面122a及第2低反射膜126之側面126a相對於遮光性膜124之側面124a在與透光性基板110平行之方向上僅突出長度L1。In the large-scale mask 100 shown in FIG. 5, the optical density (OD) of the light shielding pattern 120 relative to the light in the wavelength region of 313 nm to 436 nm is 4.5 or more. In the opening 120c of the light-shielding pattern 120, the side surface 124a of the light-shielding film 124 is a plane perpendicular to the translucent substrate 110, and the side surface 122a of the first low-reflection film 122 and the side surface 126a of the second low-reflection film 126 are opposite to the light-shielding film. The side surface 124a of the flexible film 124 protrudes only by the length L1 in the direction parallel to the translucent substrate 110.

又，於圖6所示之大型光罩100中，遮光圖案120相對於313 nm～436 nm之波長區域之光之光學密度(OD)為4.5以上。於遮光圖案120之開口部120c中，遮光性膜124之側面124a係包含複數個平面之凹狀面，第1低反射膜122之側面122a及第2低反射膜126之側面126a相對於遮光性膜124之側面124a在與透光性基板110平行之方向上突出，自距離開口部120c最遠之遮光性膜124之側面124a之位置突出長度L2。遮光性膜124之側面124a係自距開口部120c最接近之位置至距其最遠之位置在與透光性基板110平行之方向上凹入寬度W1。Moreover, in the large mask 100 shown in FIG. 6, the optical density (OD) of the light shielding pattern 120 with respect to the light in the wavelength region of 313 nm to 436 nm is 4.5 or more. In the opening 120c of the light-shielding pattern 120, the side surface 124a of the light-shielding film 124 includes a plurality of flat concave surfaces. The side surface 122a of the first low-reflection film 122 and the side surface 126a of the second low-reflection film 126 are relatively light-shielding. The side surface 124a of the film 124 protrudes in a direction parallel to the translucent substrate 110, and protrudes a length L2 from the position of the side surface 124a of the light-shielding film 124 furthest from the opening 120c. The side surface 124a of the light-shielding film 124 is recessed by a width W1 in a direction parallel to the light-transmitting substrate 110 from a position closest to the opening 120c to a position farthest from it.

進而，於圖7所示之大型光罩100中，遮光圖案120相對於313 nm～436 nm之波長區域之光之光學密度(OD)為4.5以上。於遮光圖案120之開口部120c中，遮光性膜124之側面124a為凹狀之曲面。遮光性膜124之側面124a係自距開口部120c最接近之位置至距其最遠位置在與透光性基板110平行之方向上凹入寬度W2。Furthermore, in the large-scale photomask 100 shown in FIG. 7, the optical density (OD) of the light shielding pattern 120 with respect to light in the wavelength region of 313 nm to 436 nm is 4.5 or more. In the opening 120c of the light-shielding pattern 120, the side surface 124a of the light-shielding film 124 is a concave curved surface. The side surface 124a of the light-shielding film 124 is recessed by a width W2 in a direction parallel to the light-transmitting substrate 110 from the position closest to the opening 120c to the farthest position thereof.

於圖5及圖6所示之大型光罩100中，第1低反射膜122之側面122a及第2低反射膜126之側面126a相對於遮光性膜124之側面124a在與透光性基板110之表面110a平行之方向上突出。因此，於將圖案轉印至被轉印體所具有之抗蝕層之曝光時，自光源側之斜方向照射至遮光性膜124之側面124a之曝光之光(雜散光)在由第1低反射膜122減弱強度後再照射至遮光性膜124之側面124a。又，照射至遮光性膜124之側面124a之曝光之光之反射光在由第2低反射膜126減弱強度後再照射至抗蝕層。由此，可藉由第1低反射膜122及第2低反射膜126抑制自光源側之斜方向照射至遮光性膜124之側面124a之曝光之光照射至抗蝕層時之強度。In the large mask 100 shown in FIGS. 5 and 6, the side surface 122a of the first low-reflection film 122 and the side surface 126a of the second low-reflection film 126 are in contact with the light-transmitting substrate 110 relative to the side surface 124a of the light-shielding film 124 The surface 110a protrudes in a parallel direction. Therefore, when the pattern is transferred to the resist layer of the object to be transferred, the exposure light (stray light) irradiated from the oblique direction of the light source side to the side surface 124a of the light-shielding film 124 changes from the first low The reflective film 122 weakens the intensity and then irradiates the side surface 124a of the light-shielding film 124. In addition, the reflected light of the exposure light irradiated to the side surface 124a of the light-shielding film 124 is irradiated to the resist layer after being weakened by the second low-reflection film 126. Thus, the first low-reflection film 122 and the second low-reflection film 126 can suppress the intensity of the exposure light irradiated to the side surface 124a of the light-shielding film 124 from the oblique direction of the light source side when irradiating the resist layer.

因此，作為相對於上述波長區域之光之光學密度(OD)為4.5以上之上述遮光圖案，如圖5及圖6所示，較佳為上述第1低反射膜之側面或上述第2低反射膜之側面相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出。其原因在於，為了使上述光學密度(OD)為4.5以上而使上述遮光圖案成為厚膜，藉此，雖自光源側之斜方向照射至上述遮光性膜之側面之曝光之光之反射光之光量增多，但藉由該反射光之影響，可抑制轉印至被轉印體上之圖案中出現不均等。Therefore, as the light-shielding pattern having an optical density (OD) of 4.5 or more with respect to the light in the wavelength region, as shown in FIGS. 5 and 6, it is preferable to be the side surface of the first low-reflection film or the second low-reflection film. The side surface of the film protrudes in a direction parallel to the surface of the translucent substrate with respect to the side surface of the light-shielding film. The reason for this is that the light shielding pattern is made into a thick film in order to make the optical density (OD) 4.5 or more, so that although the light from the light source side is irradiated in an oblique direction to the side surface of the light shielding film, the reflected light The amount of light increases, but due to the influence of the reflected light, unevenness in the pattern transferred to the body can be suppressed.

又，上述第1低反射膜之側面或上述第2低反射膜之側面作為相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出者，只要該等側面之任一者突出則無特別限定，但較佳為該等側面之兩者均突出。In addition, the side surface of the first low-reflection film or the side surface of the second low-reflection film protrudes in a direction parallel to the surface of the translucent substrate with respect to the side surface of the light-shielding film, and any of the side surfaces One protrusion is not particularly limited, but it is preferable that both of the sides protrude.

進而，上述第1低反射膜之側面或上述第2低反射膜之側面作為相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出者，於圖5及圖6中，較佳為L1及L2所表示之突出長度為上述遮光性膜之膜厚之1/2以上。其原因在於，藉由上述反射光之影響，可有效抑制轉印至被轉印體上之圖案中出現不均等。Furthermore, the side surface of the first low-reflection film or the side surface of the second low-reflection film as the side surface of the light-shielding film protruding in a direction parallel to the surface of the translucent substrate, as shown in FIGS. 5 and 6 Among them, it is preferable that the protrusion length represented by L1 and L2 is 1/2 or more of the film thickness of the light-shielding film. The reason is that, due to the influence of the above-mentioned reflected light, it is possible to effectively suppress unevenness in the pattern transferred to the transferred body.

再者，上述突出長度係指上述第1低反射膜之側面或上述第2低反射膜之側面自上述遮光性膜之凹狀側面中之距離上述遮光圖案之開口部最遠之位置在與上述透光性基板之表面平行之方向上突出之長度。Furthermore, the above-mentioned protrusion length refers to the position of the side surface of the first low-reflection film or the side surface of the second low-reflection film from the concave side surface of the light-shielding film that is farthest from the opening of the light-shielding pattern. The protruding length in the direction parallel to the surface of the transparent substrate.

又，於本發明中，根據以下理由，較佳為上述第1低反射膜之側面或上述第2低反射膜之側面相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出。Furthermore, in the present invention, it is preferable that the side surface of the first low-reflection film or the side surface of the second low-reflection film is parallel to the surface of the translucent substrate with respect to the side surface of the light-shielding film for the following reasons Prominent in the direction.

即，一般而言鉻等金屬膜之極性高於例如鉻氧化物等氧化金屬膜，因此存在異物易附著之傾向。因此，於上述遮光性膜為鉻之情形時，若上述遮光性膜之側面相對於上述第1低反射膜之側面或上述第2低反射膜之側面在與上述透光性基板之表面平行之方向上突出，則相對於上述遮光性膜異物附著之可能性增加，可能難以藉由之後之清洗去除異物。That is, metal films such as chromium are generally higher in polarity than metal oxide films such as chromium oxide, and therefore there is a tendency for foreign matter to adhere easily. Therefore, when the light-shielding film is chromium, if the side surface of the light-shielding film is parallel to the surface of the translucent substrate with respect to the side surface of the first low-reflection film or the side surface of the second low-reflection film Protruding in the direction, the possibility of foreign matter adhesion to the light-shielding film increases, and it may be difficult to remove the foreign matter by subsequent washing.

就此種異物附著之觀點而言，亦較佳為上述第1低反射膜之側面或上述第2低反射膜之側面相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出，尤佳為該等側面之兩者均突出。From the viewpoint of adhesion of such foreign matter, it is also preferable that the side surface of the first low-reflection film or the side surface of the second low-reflection film is in a direction parallel to the surface of the translucent substrate relative to the side surface of the light-shielding film The upper part is prominent, and it is particularly preferable that both of these sides are prominent.

於本發明中，作為在與上述透光性基板之表面平行之方向上突出之側面之順序，較佳為上述第1低反射膜之側面最突出，其次為第2低反射膜之側面、遮光性膜之側面之順序。其原因在於，於異物存在於該等積層體之側面附近之情形時，因上述第1低反射膜之側面最突出，故異物與氧化金屬膜接觸之面積較大，因此容易接觸，其結果，異物亦易於剝離。In the present invention, as the order of the side surfaces protruding in a direction parallel to the surface of the translucent substrate, it is preferable that the side surface of the first low-reflection film protrudes the most, followed by the side surface of the second low-reflection film and light-shielding The order of the sides of the sex film. The reason is that when foreign matter exists near the side surfaces of the laminates, since the side surface of the first low-reflection film is the most protruding, the area where the foreign matter comes into contact with the metal oxide film is relatively large and therefore easy to contact. As a result, Foreign matter is also easy to peel off.

另一方面，於本發明中，至少上述第1低反射膜之側面相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出，進而較佳為上述第1低反射膜之側面相對於上述透光性基板表面之角度為56°以下。On the other hand, in the present invention, at least the side surface of the first low-reflection film protrudes in a direction parallel to the surface of the light-transmitting substrate with respect to the side surface of the light-shielding film, and the first low-reflection film is more preferably The angle of the side surface of the film with respect to the surface of the translucent substrate is 56° or less.

圖12係表示此種態樣之大型光罩之一例之一部分者。於圖12所示之大型光罩100中，第1低反射膜122之側面122a及第2低反射膜126之側面126a相對於遮光性膜124之側面124a在與透光性基板110之表面110a平行之方向上突出。並且，上述第1低反射膜122之側面122a與上述透光性基板110之表面110a所成之角度α為56°以下之角度。Fig. 12 shows a part of an example of a large mask of this type. In the large mask 100 shown in FIG. 12, the side surface 122a of the first low-reflection film 122 and the side surface 126a of the second low-reflection film 126 are on the surface 110a of the translucent substrate 110 with respect to the side surface 124a of the light-shielding film 124 Protruding in a parallel direction. In addition, the angle α formed by the side surface 122a of the first low-reflection film 122 and the surface 110a of the translucent substrate 110 is an angle of 56° or less.

如上所述，因上述第1低反射膜之側面相對於上述透光性基板表面之角度為56°以下，故即使於異物附著之情形時，亦可增大清洗時之清洗用流體之接觸面積，因此可有效率地進行清洗，並可防止由清洗步驟後之異物之存在所引起之異常。As described above, since the angle of the side surface of the first low-reflection film with respect to the surface of the translucent substrate is 56° or less, even when foreign matter adheres, the contact area of the cleaning fluid during cleaning can be increased. Therefore, it can be cleaned efficiently and can prevent abnormalities caused by the presence of foreign objects after the cleaning step.

其中，上述第1低反射膜之側面相對於上述透光性基板表面之角度係指藉由將上述第1低反射膜122之側面122a與上述透光性基板110之表面110a相接之位置A與上述第1低反射膜122之膜厚開始減少之位置B用直線連接，並測定該直線與上述表面110a之角度而得之角度。Wherein, the angle of the side surface of the first low-reflection film relative to the surface of the translucent substrate refers to the position A where the side surface 122a of the first low-reflection film 122 is in contact with the surface 110a of the translucent substrate 110 The position B where the film thickness of the first low-reflection film 122 starts to decrease is connected with a straight line, and the angle between the straight line and the surface 110a is measured.

又，上述第1低反射膜122之側面122a相對於上述遮光性膜124之側面124a突出係指上述第1低反射膜122之膜厚開始減少之位置B相對於上述遮光性膜124之側面124a，在與透光性基板110之表面110a平行之方向上突出。In addition, the side surface 122a of the first low-reflection film 122 protruding from the side surface 124a of the light-shielding film 124 refers to the position B where the film thickness of the first low-reflection film 122 starts to decrease relative to the side surface 124a of the light-shielding film 124 , Protruding in a direction parallel to the surface 110a of the translucent substrate 110.

於本發明中，較佳為上述第1低反射膜之側面相對於上述透光性基板表面之角度為56°以下，其中較佳為40°以下。其原因在於可更有效率地進行清洗。再者，雖上述角度較小者較佳，但就實際製造困難這一製造方面之觀點而言，較佳為20°以上。In the present invention, the angle of the side surface of the first low-reflection film with respect to the surface of the translucent substrate is preferably 56° or less, and more preferably 40° or less. The reason is that cleaning can be performed more efficiently. Furthermore, although the above-mentioned angle is preferably smaller, it is preferably 20° or more from the viewpoint of manufacturing difficulty in actual manufacturing.

於本發明中，較佳為上述第2低反射膜之側面亦相較於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上更突出。其原因在於，可減少異物附著於遮光性膜之側面，該遮光性膜可能因與異物之接著性之影響而難以利用清洗去除異物。In the present invention, it is preferable that the side surface of the second low-reflection film also protrudes more than the side surface of the light-shielding film in a direction parallel to the surface of the light-transmitting substrate. The reason is that the adhesion of foreign matter to the side surface of the light-shielding film can be reduced, and the light-shielding film may be difficult to remove foreign matters by cleaning due to the influence of adhesion with the foreign matter.

於圖6及圖7所示之大型光罩100中，遮光性膜124之側面124a為凹狀。因此，於將圖案轉印至被轉印體所具有之抗蝕層之曝光時，自光源側之斜方向照射至遮光性膜124之側面124a之曝光之光(雜散光)之反射光被誘導至光源側或遮光圖案120之開口部120c側之可能性增加。由此，可抑制該反射光照射於利用遮光圖案120之邊緣部分遮擋曝光之光之照射之抗蝕層上。藉此，可抑制轉印至邊緣部分中之抗蝕層上之圖案中出現尺寸偏差等。In the large mask 100 shown in FIGS. 6 and 7, the side surface 124a of the light-shielding film 124 is concave. Therefore, when the pattern is transferred to the resist layer of the object to be transferred, the reflected light of the exposure light (stray light) irradiated from the oblique direction of the light source side to the side surface 124a of the light shielding film 124 is induced The possibility of reaching the light source side or the opening 120c side of the light shielding pattern 120 increases. As a result, the reflected light can be prevented from being irradiated on the resist layer that uses the edge portion of the light shielding pattern 120 to block the exposure of the light. Thereby, it is possible to suppress dimensional deviations and the like in the pattern transferred to the resist layer in the edge portion.

因此，作為相對於上述波長區域之光之光學密度(OD)為4.5以上之上述遮光圖案，如圖6及圖7所示，較佳為上述遮光性膜之側面為凹狀。其原因在於，為了使上述光學密度(OD)為4.5以上而使上述遮光圖案成為厚膜，藉此，雖自光源側之斜方向照射至上述遮光性膜之側面之曝光之光之反射光之光量增多，但藉由該反射光之影響，可抑制轉印至被轉印體上之圖案中出現尺寸偏差等。Therefore, as the light-shielding pattern having an optical density (OD) of 4.5 or more with respect to the light in the wavelength region, as shown in FIGS. 6 and 7, the side surface of the light-shielding film is preferably concave. The reason for this is that the light shielding pattern is made into a thick film in order to make the optical density (OD) 4.5 or more, so that although the light from the light source side is irradiated in an oblique direction to the side surface of the light shielding film, the reflected light The amount of light increases, but due to the influence of the reflected light, it is possible to suppress dimensional deviations and the like in the pattern transferred to the transferred body.

進而，作為上述遮光性膜之側面為凹狀之上述遮光圖案，於圖6及圖7中，較佳為W1及W2所表示之上述遮光性膜之側面之凹入寬度為上述遮光性膜之膜厚之1/2以上。此係因為藉由上述反射光之影響，可有效抑制轉印至被轉印體上之圖案中出現尺寸偏差等。Furthermore, as the light-shielding pattern in which the side surface of the light-shielding film is concave, in FIGS. 6 and 7, it is preferable that the recessed width of the side surface of the light-shielding film represented by W1 and W2 is that of the light-shielding film More than 1/2 of the film thickness. This is because due to the influence of the above-mentioned reflected light, it is possible to effectively suppress dimensional deviations in the pattern transferred to the transferred body.

再者，上述凹入寬度係指上述遮光性膜之側面中之自距上述遮光圖案之開口部最接近之位置至距其最遠之位置在與上述透光性基板之表面平行之方向上的寬度。Furthermore, the aforementioned recessed width refers to the side surface of the light-shielding film from the position closest to the opening of the light-shielding pattern to the farthest position in the direction parallel to the surface of the light-transmitting substrate width.

d.低反射膜及遮光性膜之交界構造 上述遮光性膜與上述第1低反射膜及上述第2低反射膜之交界可為明確交界，亦可為不明確交界。就易於個別地控制各膜之特性之觀點而言，較佳為具有上述明確交界之遮光圖案。又，就加工面平滑或可輕易製作之觀點而言，較佳為具有上述不明確交界之遮光圖案。d. Boundary structure of low reflection film and shading film The boundary between the light-shielding film, the first low-reflection film and the second low-reflection film may be a clear boundary or an unclear boundary. From the viewpoint of easily controlling the characteristics of each film individually, it is preferable to have the light-shielding pattern with the above-mentioned clear boundary. In addition, from the viewpoint of smooth processing surface or easy production, it is preferable to have the light-shielding pattern with the above-mentioned unclear boundary.

具有上述明確交界之遮光圖案可藉由以下方式製作：分別使用更換了氣體之濺鍍裝置個別地進行上述第1低反射膜、上述遮光性膜及上述第2低反射膜之成膜。又，具有上述不明確交界之遮光圖案可藉由以下方式製作：在不更換濺鍍裝置氣體之情況下連續地進行上述第1低反射膜、上述遮光性膜及上述第2低反射膜之成膜。The light-shielding pattern having the above-mentioned clear boundary can be produced by separately forming the first low-reflection film, the light-shielding film, and the second low-reflection film using a sputtering device with a gas exchanged. In addition, the light-shielding pattern having the above-mentioned unclear boundary can be produced by the following method: the formation of the first low-reflection film, the light-shielding film, and the second low-reflection film is continuously performed without replacing the sputtering device gas. membrane.

e.形成方法 作為上述遮光圖案之形成方法，例如，可列舉以下方法等：於合成石英玻璃之表面，形成具有第1低反射膜、遮光性膜及第2低反射膜按照該順序積層而成之積層構造之遮光層後，於遮光層之表面形成所需形狀之抗蝕圖案，並以抗蝕圖案為遮罩利用濕式蝕刻對遮光層進行加工。e. Formation method As a method of forming the above-mentioned light-shielding pattern, for example, the following method can be cited: on the surface of synthetic quartz glass, a layered structure having a first low-reflection film, a light-shielding film, and a second low-reflection film laminated in this order is formed After the light-shielding layer is formed, a resist pattern of a desired shape is formed on the surface of the light-shielding layer, and the light-shielding layer is processed by wet etching using the resist pattern as a mask.

2.透光性基板 作為上述透光性基板之大小，例如，只要可形成為至少一邊具有350 mm以上之大小之光罩即可，可根據本發明之大型光罩之用途等適當選擇，無特別限定，但較佳為330 mm×450 mm以上，其中較佳為處於330 mm×450 mm～1700 mm×1800 mm之範圍內。2. Translucent substrate As the size of the above-mentioned translucent substrate, for example, as long as it can be formed into a photomask having a size of 350 mm or more on at least one side, it can be appropriately selected according to the use of the large-scale photomask of the present invention, and is not particularly limited, but is preferably It is 330 mm×450 mm or more, and is preferably in the range of 330 mm×450 mm to 1700 mm×1800 mm.

作為上述透光性基板之膜厚，可根據大型光罩之材料或用途等適當選擇。作為上述透光性基板之膜厚，例如，係8 mm～17 mm左右。The film thickness of the above-mentioned translucent substrate can be appropriately selected according to the material or application of the large mask. The film thickness of the above-mentioned translucent substrate is, for example, about 8 mm to 17 mm.

作為上述透光性基板，其係具有光透過性，可使用普通大型光罩所使用之透光性基板。作為上述透光性基板，例如，可列舉光學研磨後之低膨脹玻璃(鋁硼矽酸玻璃、硼矽酸玻璃)、合成石英玻璃。於本發明中，其中較佳為使用合成石英玻璃。其原因在於，其熱膨脹率較小，易於製造大型光罩。又，於本發明中亦可使用樹脂製上述透光性基板。As the above-mentioned light-transmitting substrate, it has light-transmitting properties, and the light-transmitting substrate used in ordinary large-scale photomasks can be used. Examples of the above-mentioned translucent substrate include low-expansion glass (aluminoborosilicate glass, borosilicate glass) and synthetic quartz glass after optical polishing. In the present invention, among them, synthetic quartz glass is preferably used. The reason is that its thermal expansion rate is small, and it is easy to manufacture a large mask. In addition, the above-mentioned translucent substrate made of resin may also be used in the present invention.

作為上述透光性基板之光透過性，只要與普通大型光罩所使用之透光性基板為相同程度則無特別限定，但較佳為對313 nm～436 nm之波長區域之光之透過率為80%以上，其中較佳為85%以上，尤佳為90%以上。其原因在於，通過純度較高之透光性基板之光在材料內之散射較少，進而折射率亦較低，因此可抑制雜散光之產生。The light transmittance of the above-mentioned light-transmitting substrate is not particularly limited as long as it is the same level as the light-transmitting substrate used in a general large-scale photomask, but it is preferably the transmittance of light in the wavelength region of 313 nm to 436 nm It is 80% or more, of which 85% or more is preferable, and 90% or more is particularly preferable. The reason is that the light passing through the transparent substrate with higher purity is less scattered in the material, and the refractive index is also lower, so the generation of stray light can be suppressed.

3.其他 作為本發明之大型光罩，其係具備上述透光性基板及上述遮光圖案，只要上述遮光圖案之上述透光性基板側之面對上述波長區域之光之反射率為8%以下則無特別限定，但較佳為具有用於分割曝光之分割圖案，且上述分割圖案係上述遮光圖案。3. Other As the large-scale photomask of the present invention, it is provided with the above-mentioned translucent substrate and the above-mentioned light-shielding pattern, as long as the light-shielding pattern on the side of the light-transmitting substrate facing the above-mentioned wavelength region has a reflectivity of 8% or less It is limited, but it is preferable to have a split pattern for split exposure, and the split pattern is the light shielding pattern.

分割曝光係指以下方法：於被轉印體中將被轉印區域分割成複數個曝光區域，使用大型光罩對複數個曝光區域之各者個別地曝光，藉由將光罩之分割圖案轉印至複數個曝光區域之各者，而於被轉印體上形成大於光罩之分割圖案的連續圖案。Split exposure refers to the following method: the transferred area is divided into a plurality of exposure areas in the body to be transferred, and each of the plurality of exposure areas is individually exposed using a large mask, and the division pattern of the mask is transferred It is printed to each of a plurality of exposure areas, and a continuous pattern larger than the divided pattern of the mask is formed on the transferred body.

對此種優選大型光罩一面參照圖式一面進行說明。圖8係表示本發明之大型光罩之另一例之概略俯視圖。圖9係表示使用圖8所示之大型光罩根據被轉印體所製造之圖案轉印體之概略俯視圖。又，圖10(a)～圖10(b)係表示圖9所示之圖案轉印體之部分製造步驟之概略步驟剖視圖。The preferred large-sized mask will be described with reference to the drawings. Fig. 8 is a schematic plan view showing another example of the large mask of the present invention. FIG. 9 is a schematic plan view showing a pattern transfer body manufactured from a transfer body using the large mask shown in FIG. 8. 10(a) to 10(b) are schematic cross-sectional views showing a part of the manufacturing steps of the pattern transfer body shown in FIG. 9.

如圖8所示，大型光罩100具備透光性基板110、以及設於透光性基板110之表面110a之互異之第1分割圖案150a、第2分割圖案150b及第3分割圖案150c。第1分割圖案150a、第2分割圖案150b及第3分割圖案150c係分別與圖1所示之遮光圖案120相同，具有第1低反射膜122、遮光性膜124及第2低反射膜126自透光性基板110側按照該順序積層而成之積層構造之遮光圖案120。因此，第1分割圖案150a、第2分割圖案150b及第3分割圖案150c之透光性基板110側之面係與圖1所示之遮光圖案120相同，對313 nm～436 nm之波長區域之光之反射率為8%以下。As shown in FIG. 8, the large photomask 100 includes a translucent substrate 110 and a first division pattern 150a, a second division pattern 150b, and a third division pattern 150c that are provided on the surface 110a of the translucent substrate 110. The first division pattern 150a, the second division pattern 150b, and the third division pattern 150c are respectively the same as the light-shielding pattern 120 shown in FIG. 1, and have a first low-reflection film 122, a light-shielding film 124, and a second low-reflection film 126. The light-shielding pattern 120 of a laminated structure formed by laminating the transparent substrate 110 in this order. Therefore, the surface of the transparent substrate 110 side of the first divided pattern 150a, the second divided pattern 150b, and the third divided pattern 150c is the same as the light shielding pattern 120 shown in FIG. 1, and has a wavelength range from 313 nm to 436 nm. The reflectance of light is below 8%.

關於圖9所示之圖案轉印體200'，其係使用圖8所示之大型光罩100，藉由對被轉印體200所具有之抗蝕層220，針對第1分割圖案150a、第2分割圖案150b及第3分割圖案150c之各圖案，自光源(UV燈)放射包含上述波長區域之任一光之曝光之光的曝光製造而成者。Regarding the pattern transfer body 200' shown in FIG. 9, the large mask 100 shown in FIG. 8 is used, and the resist layer 220 of the transfer body 200 is applied to the first divided patterns 150a, Each pattern of the two-divided pattern 150b and the third-divided pattern 150c is manufactured by exposing exposure light including any light in the above-mentioned wavelength range from a light source (UV lamp).

於製造圖案轉印體200'之情形時，首先，於第1次曝光中，藉由利用曝光遮蔽板300(如圖10所圖示)遮蔽第2分割圖案150b及第3分割圖案150c，而僅經由第1～第3分割圖案中之第1分割圖案150a向抗蝕層220照射上述曝光之光。繼而，於第2次～第6次曝光中，藉由利用曝光遮蔽板300遮蔽第3分割圖案150c及第1分割圖案150a，而僅經由第1～第3分割圖案中之第2分割圖案150b向抗蝕層220照射上述曝光之光。繼而，於第7次曝光中，藉由利用曝光遮蔽板300遮蔽第1分割圖案150a及第2分割圖案150b，而僅經由第1～第3分割圖案中之第3分割圖案150c向抗蝕層220照射上述曝光之光。藉此，轉印有第1分割圖案150a之1個第1抗蝕圖案220a、分別轉印有第2分割圖案150b之5個第2抗蝕圖案220b及轉印有第3分割圖案150c之1個第3抗蝕圖案220c以於單一方向上相連之方式形成。其結果，形成連續之單一抗蝕圖案。In the case of manufacturing the pattern transfer body 200', first, in the first exposure, by using the exposure shielding plate 300 (as shown in FIG. 10) to shield the second divided pattern 150b and the third divided pattern 150c, The above-mentioned exposure light is irradiated to the resist layer 220 only through the first division pattern 150a among the first to third division patterns. Then, in the second to sixth exposures, the third division pattern 150c and the first division pattern 150a are shielded by the exposure shielding plate 300, and only the second division pattern 150b of the first to third division patterns is passed through The above-mentioned exposure light is irradiated to the resist layer 220. Then, in the seventh exposure, the exposure mask 300 shields the first division pattern 150a and the second division pattern 150b, and only passes through the third division pattern 150c of the first to third division patterns to the resist layer. 220 illuminate the above-mentioned exposure light. Thereby, one of the first resist pattern 220a to which the first division pattern 150a is transferred, the five second resist patterns 220b to which the second division pattern 150b is transferred, and one of the third division pattern 150c are transferred. The three third resist patterns 220c are formed to be connected in a single direction. As a result, a continuous single resist pattern is formed.

於上述第2次曝光中，如圖10(a)所示，與圖2所示步驟相同，藉由降低因上述曝光之光在第2分割圖案150b(遮光圖案120)之透光性基板110側之面120a反射而產生之雜散光之強度，可降低原本照射於利用曝光遮蔽板300遮擋曝光之光之照射之遮蔽區域(第3次曝光區域)之抗蝕層220上的雜散光La之強度。又，藉由降低因上述曝光之光在第2分割圖案150b之與透光性基板110相反側之面120b反射而產生之雜散光之強度，可降低原本照射於利用第2分割圖案150b之邊緣部分遮擋曝光之光之照射之第2次曝光區域之抗蝕層220上的雜散光Lb之強度。In the second exposure described above, as shown in FIG. 10(a), the steps are the same as those shown in FIG. 2, by reducing the light from the above exposure on the translucent substrate 110 of the second dividing pattern 150b (light-shielding pattern 120) The intensity of the stray light generated by reflection on the side surface 120a can reduce the stray light La originally irradiated on the resist layer 220 in the shielded area (third exposure area) that is shielded by the exposure shielding plate 300 strength. Furthermore, by reducing the intensity of the stray light generated by the above-mentioned exposure light reflected on the surface 120b of the second division pattern 150b opposite to the translucent substrate 110, it is possible to reduce the original irradiated edge of the second division pattern 150b The intensity of the stray light Lb on the resist layer 220 in the second exposure area where the exposure light is partially blocked.

於上述第3次曝光中，如圖10(b)所示，與第2次曝光相同，藉由降低雜散光之強度，可降低進而照射於第2次曝光中雜散光La照射過之區域之抗蝕層220上之雜散光Lb之強度，可降低進而照射於第2次曝光中雜散光Lb照射過之區域之抗蝕層220上之雜散光La之強度。In the third exposure described above, as shown in Figure 10(b), the same as the second exposure, by reducing the intensity of the stray light, the area irradiated by the stray light La in the second exposure can be reduced. The intensity of the stray light Lb on the resist layer 220 can reduce the intensity of the stray light La on the resist layer 220 that is then irradiated on the area irradiated by the stray light Lb in the second exposure.

因此，根據上述較佳之大型光罩，於分割曝光中，於使用大型光罩對被轉印體之複數個曝光區域之各者個別地曝光時，由於因上述遮光圖案之各面反射曝光之光而產生之雜散光照射至其他曝光區域，故即使於抗蝕層上產生上述雜散光之多重曝光之情形時，亦可降低上述雜散光之強度。因此，可明顯抑制轉印至被轉印體上之圖案中出現不均或尺寸偏差。Therefore, according to the above-mentioned preferred large-scale photomask, when the large-scale photomask is used to individually expose each of the plurality of exposure regions of the transferred body in the split exposure, the light from the exposure is reflected by each surface of the above-mentioned light-shielding pattern. The generated stray light irradiates other exposed areas, so even in the case of multiple exposures of the stray light generated on the resist layer, the intensity of the stray light can be reduced. Therefore, it is possible to significantly suppress unevenness or dimensional deviation in the pattern transferred to the transferred body.

再者，於分割曝光中，於相鄰曝光區域相連之部分中，有時會因曝光裝置之對準精度之影響而產生多重曝光。因此，於進而產生上述雜散光之多重曝光之情形時，轉印至被轉印體上之圖案中出現不均或尺寸偏差之問題容易變大。因此，可更明顯地獲得上述效果。Furthermore, in the split exposure, in the part where adjacent exposure areas are connected, sometimes multiple exposures may occur due to the influence of the alignment accuracy of the exposure device. Therefore, when the above-mentioned multiple exposure of the stray light is further generated, the problem of unevenness or dimensional deviation in the pattern transferred to the transferred body is likely to increase. Therefore, the above-mentioned effects can be obtained more clearly.

4.大型光罩之製造方法 作為本發明之大型光罩之製造方法，只要可製造具有上述構成之大型光罩則無特別限定，可與普通大型光罩之製造方法相同。4. Manufacturing method of large mask As the manufacturing method of the large-scale photomask of the present invention, there is no particular limitation as long as the large-scale photomask with the above-mentioned structure can be manufactured, and it can be the same as the manufacturing method of a general large-scale photomask.

例如，準備合成石英玻璃作為透光性基板，製作一種具備遮光層之光罩基板，該遮光層具有於合成石英玻璃之表面上由第1低反射膜、遮光性膜及第2低反射膜按照該順序積層而成之積層構造。繼而，藉由於遮光層之表面形成所需形狀之抗蝕圖案，並以抗蝕圖案為遮罩利用濕式蝕刻對遮光層進行加工，而根據遮光層形成遮光圖案。藉此，製作大型光罩。 又，作為上述濕式蝕刻所使用之蝕刻液，只要可對上述遮光層進行高精度加工，且不對上述透光性基板造成損傷則無特別限定，例如，可使用硝酸鈰銨溶液等。For example, synthetic quartz glass is prepared as a light-transmitting substrate, and a mask substrate with a light-shielding layer is produced. The light-shielding layer is formed on the surface of the synthetic quartz glass by a first low-reflection film, a light-shielding film, and a second low-reflection film. This layered structure is stacked in this order. Then, a resist pattern of a desired shape is formed on the surface of the light-shielding layer, and the light-shielding layer is processed by wet etching using the resist pattern as a mask, and a light-shielding pattern is formed according to the light-shielding layer. In this way, a large mask is produced. In addition, the etching solution used in the wet etching is not particularly limited as long as it can process the light shielding layer with high accuracy and does not damage the light-transmitting substrate. For example, a cerium ammonium nitrate solution can be used.

5.用途 本發明之大型光罩可較佳地用於例如製造顯示裝置所使用之顯示裝置用功能元件等之圖案轉印體時之光微影法。5. Purpose The large-scale photomask of the present invention can be preferably used in the photolithography method when manufacturing pattern transfer bodies such as functional elements for display devices used in display devices.

作為使用本發明之大型光罩所製造之顯示裝置用功能元件，例如，可列舉TFT基板、用於TFT基板等之帶金屬配線基板等、彩色濾光片及用於彩色濾光片之帶遮光部基板等。As a functional element for a display device manufactured using the large-scale photomask of the present invention, for example, a TFT substrate, a metal wiring substrate used for a TFT substrate, etc., a color filter and a light shielding for a color filter Department of substrates, etc.

作為使用本發明之大型光罩之顯示裝置用功能元件等之圖案轉印體之製造方法，並無特別限定，可與使用大型光罩之製造方法之普通製造方法相同。例如，可列舉以下製作方法：其具有曝光步驟及顯影步驟，該曝光步驟係準備具有抗蝕層之被轉印體，經由大型光罩照射曝光之光並對上述抗蝕層進行曝光，該顯影步驟係對曝光後之上述抗蝕層進行顯影。The manufacturing method of the pattern transfer body of the functional element for a display device using the large mask of the present invention is not particularly limited, and it can be the same as the general manufacturing method of the manufacturing method using the large mask. For example, the following manufacturing method can be cited: it has an exposure step and a development step. The exposure step is to prepare a transfer object with a resist layer, irradiate the exposed light through a large photomask, and expose the resist layer. The step is to develop the above-mentioned resist layer after exposure.

作為上述抗蝕層所使用之抗蝕劑，可與普通抗蝕劑相同，可為正型抗蝕劑，亦可為負型抗蝕劑。作為正型抗蝕劑，例如，可列舉酚醛樹脂、酚醛環氧樹脂、丙烯酸系樹脂、聚醯亞胺、環烯烴等。具體而言，可列舉IP3500(TOK(Tokyo Ohka Kogyo，東京應化工業株式會社)公司製)、PFI27(住友化學公司製)、ZEP7000(瑞翁公司製)、正型抗蝕劑(JSR公司製)等。其中較佳為正型抗蝕劑(JSR公司製)等。其原因在於，由於感度較高，故本發明之效果變得明顯。另一方面，作為負型抗蝕劑，例如，可列舉丙烯酸系樹脂等。具體而言，可列舉聚甲基丙烯酸縮水甘油酯(PGMA)、化學增幅型SAL601(CYPRES公司製)、負型抗蝕劑(JSR公司製)等。其中較佳為負型抗蝕劑(JSR公司製)等。其原因在於，由於感度較高，故本發明之效果變得明顯。又，於使用本發明之大型光罩所製造之顯示裝置用功能元件使用顯影後之抗蝕層作為構成構件之情形時，亦可使抗蝕層含有顏料及染料等著色劑、無機氧化物微粒子等功能性材料。The resist used for the above-mentioned resist layer may be the same as a normal resist, and may be a positive type resist or a negative type resist. Examples of positive resists include phenol resins, novolac epoxy resins, acrylic resins, polyimides, cycloolefins, and the like. Specifically, IP3500 (manufactured by TOK (Tokyo Ohka Kogyo, Tokyo Ohka Kogyo)), PFI27 (manufactured by Sumitomo Chemical Co., Ltd.), ZEP7000 (manufactured by Zeon Corporation), positive resist (manufactured by JSR) )Wait. Among them, positive resists (manufactured by JSR Corporation) and the like are preferred. The reason is that since the sensitivity is high, the effect of the present invention becomes obvious. On the other hand, as a negative resist, for example, acrylic resin etc. are mentioned. Specifically, polyglycidyl methacrylate (PGMA), chemically amplified SAL601 (manufactured by CYPRES), negative resist (manufactured by JSR), and the like can be mentioned. Among them, a negative resist (manufactured by JSR Corporation) and the like are preferable. The reason is that since the sensitivity is high, the effect of the present invention becomes obvious. In addition, when the functional element for a display device manufactured using the large-scale photomask of the present invention uses the developed resist layer as a constituent member, the resist layer may contain pigments, dyes, and other colorants, and inorganic oxide particles. And other functional materials.

作為抗蝕層之膜厚，並無特別限定，例如處於10 nm～10 μm之範圍內。關於抗蝕層之形成方法，由於可採用公知之方法，故省略此處之說明。The thickness of the resist layer is not particularly limited, and it is, for example, in the range of 10 nm to 10 μm. Regarding the formation method of the resist layer, since a known method can be used, the description here is omitted.

被轉印體通常具有用於形成抗蝕層之基體。又，亦可具有金屬層等。關於被轉印體，根據所製造之顯示裝置用功能元件之種類，適當選擇。The body to be transferred usually has a base for forming a resist layer. In addition, it may have a metal layer or the like. Regarding the to-be-transferred body, it is appropriately selected according to the type of the functional element for the display device to be manufactured.

作為上述曝光步驟中所使用之曝光之光，可使抗蝕層中之抗蝕劑產生反應，只要為包含313 nm～436 nm之波長區域之任一光者則無特別限定。作為曝光之光，較佳為包含g線、h線、i線等複數個波長之光之曝光之光，尤佳為包含j線之曝光之光。其原因在於，可提高照射至抗蝕層之曝光之光之能量，可以更短之曝光時間完成曝光，並且可明顯抑制轉印至被轉印體上之圖案中出現不均等。作為上述曝光之光之光源，例如，可使用超高壓水銀燈(超高壓UV燈)等。As the exposure light used in the above exposure step, the resist in the resist layer can react, and it is not particularly limited as long as it is any light in the wavelength region of 313 nm to 436 nm. The exposure light is preferably exposure light including light of multiple wavelengths such as g-line, h-line, and i-line, and particularly preferably exposure light including j-line. The reason is that the energy of the exposure light irradiated to the resist layer can be increased, the exposure can be completed in a shorter exposure time, and the unevenness in the pattern transferred to the transferred body can be significantly suppressed. As the light source of the above-mentioned exposure light, for example, an ultra-high pressure mercury lamp (ultra-high pressure UV lamp) or the like can be used.

作為上述顯影步驟中所使用之抗蝕層之顯影方法，可使用普通方法，並無特別限定。作為顯影方法，例如可較佳地採用使用顯影液之方法等。As a method for developing the resist layer used in the above-mentioned developing step, a common method can be used, and there is no particular limitation. As the developing method, for example, a method using a developing solution or the like can be preferably used.

再者，本發明並不受上述實施形態限定。上述實施形態係示例，其具有本發明之申請專利範圍中所記載之技術思想及實質上相同之構成，任何發揮相同之作用效果者均屬於本發明之技術範圍。 [實施例]In addition, the present invention is not limited by the above-mentioned embodiment. The above-mentioned embodiment is an example, which has the technical idea and substantially the same structure as described in the scope of the patent application of the present invention, and anything that exerts the same function and effect belongs to the technical scope of the present invention. [Example]

A.反射率及光學密度 首先，對反射率及光學密度使用實施例及比較例進行說明。A. Reflectivity and optical density First, the reflectance and optical density will be described using examples and comparative examples.

[實施例A1] 首先，製作一種光罩基板，其具備：合成石英玻璃(透光性基板)，其係縱×橫×膜厚為700 mm×800 mm×8 mm之精密研磨而成者；以及遮光層，其具有於合成石英玻璃之表面上膜厚30 nm之氧化鉻膜(CrOx)(第1低反射膜)、膜厚85 nm之鉻膜(Cr)(遮光性膜)及膜厚30 nm之氧化鉻膜(CrOx)(第2低反射膜)按照該順序積層而成之積層構造。[Example A1] First, a photomask substrate is produced, which is provided with: synthetic quartz glass (translucent substrate), which is precisely polished with a length × width × film thickness of 700 mm × 800 mm × 8 mm; and a light-shielding layer, which Chromium oxide film (CrOx) with a thickness of 30 nm (the first low-reflection film), a chromium film (Cr) with a film thickness of 85 nm (light-shielding film) and a chromium oxide film with a thickness of 30 nm on the surface of the synthetic quartz glass The film (CrOx) (second low-reflection film) is laminated in this order.

於光罩基板之製作中，遮光層係藉由使用濺鍍法，按照氧化鉻膜(第1低反射膜)、鉻膜(遮光性膜)及氧化鉻膜(第2低反射膜)之順序於合成石英玻璃之表面成膜而形成。此時，氧化鉻膜(第1低反射膜)、鉻膜(遮光性膜)及氧化鉻膜(第2低反射膜)之成膜分別使用更換了氣體之濺鍍裝置個別地進行。又，氧化鉻膜(第1低反射膜)及氧化鉻膜(第2低反射膜)係將Cr靶材安裝至真空室內，導入O2 、N2 、CO2 氣體，藉由真空環境下之反應性濺鍍而成膜。相較於普通二元光罩之遮光圖案中之低反射膜之成膜條件，氧化鉻膜(第1低反射膜)之成膜條件中增加O2 氣體之比率。又，氧化鉻膜(第2低反射膜)之成膜條件係與普通二元光罩之遮光圖案中之低反射膜之成膜條件相同。進而，鉻膜(遮光性膜)之成膜條件係與普通二元光罩之遮光圖案中之鉻膜之成膜條件相同。In the production of the mask substrate, the light-shielding layer is sputtered in the order of chromium oxide film (first low-reflection film), chromium film (light-shielding film), and chromium oxide film (second low-reflection film) It is formed by forming a film on the surface of synthetic quartz glass. At this time, the formation of the chromium oxide film (the first low-reflection film), the chromium film (the light-shielding film), and the chromium oxide film (the second low-reflection film) were performed individually using a sputtering device with a gas exchange. In addition, the chromium oxide film (the first low-reflection film) and the chromium oxide film (the second low-reflection film) are equipped with a Cr target in a vacuum chamber, and O 2 , N 2 , and CO 2 gases are introduced, and the Reactive sputtering to form a film. Compared with the formation conditions of the low-reflection film in the light-shielding pattern of the ordinary binary mask, the formation conditions of the chromium oxide film (the first low-reflection film) increase the ratio of O 2 gas. In addition, the film forming conditions of the chromium oxide film (the second low-reflection film) are the same as those of the low-reflection film in the light-shielding pattern of the ordinary binary mask. Furthermore, the film-forming conditions of the chromium film (light-shielding film) are the same as the film-forming conditions of the chromium film in the light-shielding pattern of the ordinary binary mask.

繼而，藉由於遮光層之表面形成所需形狀之抗蝕圖案，並以抗蝕圖案為遮罩利用濕式蝕刻對遮光層進行加工，而根據遮光層形成包含3.0 μm寬之遮光圖案之具有0.1 μm以上且未達10.0 μm之寬度的遮光圖案。藉此，製作出大型光罩。Then, by forming a resist pattern of a desired shape on the surface of the light-shielding layer, and using the resist pattern as a mask to process the light-shielding layer by wet etching, the light-shielding layer is formed with a light-shielding pattern with a width of 3.0 μm and has a thickness of 0.1 A light-shielding pattern above μm and less than 10.0 μm in width. In this way, a large mask is produced.

[實施例A2] 首先，製作一種光罩基板，其具備：合成石英玻璃(透光性基板)，其係縱×橫×膜厚為700 mm×800 mm×8 mm之精密研磨而成者；以及膜厚180 nm之遮光層，其具有氧化鉻膜(第1低反射膜)、鉻膜(遮光性膜)及氧化鉻膜(第2低反射膜)按照該順序積層於合成石英玻璃之表面而成之積層構造。[Example A2] First, a photomask substrate is produced, which is provided with: synthetic quartz glass (translucent substrate), which is precision ground with a thickness of 700 mm × 800 mm × 8 mm in length × width × thickness; and a thickness of 180 nm The light-shielding layer has a laminated structure in which a chromium oxide film (the first low-reflection film), a chromium film (a light-shielding film), and a chromium oxide film (the second low-reflection film) are laminated on the surface of the synthetic quartz glass in this order .

於光罩基板之製作中，遮光層係藉由使用濺鍍法，按照氧化鉻膜(第1低反射膜)、鉻膜(遮光性膜)及氧化鉻膜(第2低反射膜)之順序於合成石英玻璃之表面成膜而形成。此時，氧化鉻膜(第1低反射膜)、鉻膜及氧化鉻膜(第2低反射膜)之成膜係於不更換濺鍍裝置之氣體之情況下連續地進行。又，氧化鉻膜(第1低反射膜)及氧化鉻膜(第2低反射膜)係將Cr靶材安裝至真空室內，導入O2 、N2 、CO2 氣體，藉由真空環境下之反應性濺鍍而成膜。相較於普通二元光罩之遮光圖案中之低反射膜之成膜條件，氧化鉻膜(第1低反射膜)及氧化鉻膜(第2低反射膜)之成膜條件中增加O2 氣體之比率。進而，鉻膜(遮光性膜)之成膜條件係與普通二元光罩之遮光圖案中之鉻膜之成膜條件相同。In the production of the mask substrate, the light-shielding layer is sputtered in the order of chromium oxide film (first low-reflection film), chromium film (light-shielding film), and chromium oxide film (second low-reflection film) It is formed by forming a film on the surface of synthetic quartz glass. At this time, the formation of the chromium oxide film (the first low-reflection film), the chromium film, and the chromium oxide film (the second low-reflection film) is continuously performed without replacing the gas of the sputtering device. In addition, the chromium oxide film (the first low-reflection film) and the chromium oxide film (the second low-reflection film) are equipped with a Cr target in a vacuum chamber, and O 2 , N 2 , and CO 2 gases are introduced, and the Reactive sputtering to form a film. Compared with the formation conditions of the low-reflection film in the shading pattern of the ordinary binary mask, the formation conditions of the chromium oxide film (the first low-reflection film) and the chromium oxide film (the second low-reflection film) are increased by O 2 The ratio of gas. Furthermore, the film-forming conditions of the chromium film (light-shielding film) are the same as the film-forming conditions of the chromium film in the light-shielding pattern of the ordinary binary mask.

繼而，藉由於遮光層之表面形成所需形狀之抗蝕圖案，並以抗蝕圖案為遮罩利用濕式蝕刻對遮光層進行加工，而根據遮光層形成包含3.0 μm寬之遮光圖案之具有0.1 μm以上且未達10.0 μm之寬度的遮光圖案。藉此，製作出大型光罩。Then, by forming a resist pattern of a desired shape on the surface of the light-shielding layer, and using the resist pattern as a mask to process the light-shielding layer by wet etching, the light-shielding layer is formed with a light-shielding pattern with a width of 3.0 μm and has a thickness of 0.1 A light-shielding pattern above μm and less than 10.0 μm in width. In this way, a large mask is produced.

[實施例A3] 首先，製作一種光罩基板，其具備：合成石英玻璃(透光性基板)，其係縱×橫×膜厚為700 mm×800 mm×8 mm之精密研磨而成者；以及遮光層，其具有於合成石英玻璃之表面上膜厚30 nm之氧化鉻膜(第1低反射膜)、膜厚110 nm之鉻膜(遮光性膜)及膜厚30 nm之氧化鉻膜(第2低反射膜)按照該順序積層而成之積層構造。[Example A3] First, a photomask substrate is produced, which is provided with: synthetic quartz glass (translucent substrate), which is precisely polished with a length × width × film thickness of 700 mm × 800 mm × 8 mm; and a light-shielding layer, which It has a chromium oxide film with a thickness of 30 nm (the first low reflection film), a chromium film with a film thickness of 110 nm (light-shielding film), and a chromium oxide film with a film thickness of 30 nm (the second low reflection film) on the surface of the synthetic quartz glass Membrane) A layered structure formed by layering in this order.

於光罩基板之製作中，遮光層係藉由使用濺鍍法，按照氧化鉻膜(第1低反射膜)、鉻膜(遮光性膜)及氧化鉻膜(第2低反射膜)之順序於合成石英玻璃之表面成膜而形成。此時，氧化鉻膜(第1低反射膜)、鉻膜(遮光性膜)及氧化鉻膜(第2低反射膜)之成膜分別使用更換了氣體之濺鍍裝置個別地進行。又，氧化鉻膜(第1低反射膜)及氧化鉻膜(第2低反射膜)係將Cr靶材安裝至真空室內，導入O2 、N2 、CO2 氣體，藉由真空環境下之反應性濺鍍而成膜。相較於普通二元光罩之遮光圖案中之低反射膜之成膜條件，氧化鉻膜(第1低反射膜)及氧化鉻膜(第2低反射膜)之成膜條件中增加O2 氣體之比率。進而，相較於普通二元光罩之遮光圖案中之鉻膜之成膜條件，鉻膜(遮光性膜)之成膜條件中延長成膜時間。In the production of the mask substrate, the light-shielding layer is sputtered in the order of chromium oxide film (first low-reflection film), chromium film (light-shielding film), and chromium oxide film (second low-reflection film) It is formed by forming a film on the surface of synthetic quartz glass. At this time, the formation of the chromium oxide film (the first low-reflection film), the chromium film (the light-shielding film), and the chromium oxide film (the second low-reflection film) were performed individually using a sputtering device with a gas exchange. In addition, the chromium oxide film (the first low-reflection film) and the chromium oxide film (the second low-reflection film) are equipped with a Cr target in a vacuum chamber, and O 2 , N 2 , and CO 2 gases are introduced, and the Reactive sputtering to form a film. Compared with the formation conditions of the low-reflection film in the shading pattern of the ordinary binary mask, the formation conditions of the chromium oxide film (the first low-reflection film) and the chromium oxide film (the second low-reflection film) are increased by O 2 The ratio of gas. Furthermore, compared with the film forming conditions of the chromium film in the light-shielding pattern of the ordinary binary mask, the film-forming time of the chromium film (light-shielding film) is extended.

繼而，藉由於遮光層之表面形成所需形狀之抗蝕圖案，並以抗蝕圖案為遮罩利用濕式蝕刻對遮光層進行加工，而根據遮光層形成包含3.0 μm寬之遮光圖案之具有0.1 μm以上且未達10.0 μm之寬度的遮光圖案。藉此，製作出大型光罩。Then, by forming a resist pattern of a desired shape on the surface of the light-shielding layer, and using the resist pattern as a mask to process the light-shielding layer by wet etching, the light-shielding layer is formed with a light-shielding pattern with a width of 3.0 μm and has a thickness of 0.1 A light-shielding pattern above μm and less than 10.0 μm in width. In this way, a large mask is produced.

[比較例A] 首先，製作一種光罩基板，其具備：合成石英玻璃(透光性基板)，其係縱×橫×膜厚為700 mm×800 mm×8 mm之精密研磨而成者；以及遮光層，其具有於合成石英玻璃之表面上膜厚85 nm之鉻膜(遮光性膜)及膜厚30 nm之氧化鉻膜(低反射膜)按照該順序積層而成之積層構造。[Comparative Example A] First, a photomask substrate is produced, which is provided with: synthetic quartz glass (translucent substrate), which is precisely polished with a length × width × film thickness of 700 mm × 800 mm × 8 mm; and a light-shielding layer, which A chromium film (light-shielding film) with a thickness of 85 nm and a chromium oxide film (low reflection film) with a thickness of 30 nm are laminated in this order on the surface of the synthetic quartz glass.

於光罩基板之製作中，遮光層係藉由使用濺鍍法，按照鉻膜(遮光性膜)及氧化鉻膜(低反射膜)之順序於合成石英玻璃之表面成膜而形成。此時，鉻膜(遮光性膜)及氧化鉻膜(低反射膜)之成膜分別使用更換了氣體之濺鍍裝置個別地進行。又，氧化鉻膜(低反射膜)係將Cr靶材安裝至真空室內，導入O2 、N2 、CO2 氣體，藉由真空環境下之反應性濺鍍而成膜。氧化鉻膜(低反射膜)之成膜條件係與普通二元光罩之遮光圖案中之低反射膜之成膜條件相同。進而，鉻膜之成膜條件係與普通二元光罩之遮光圖案中之鉻膜之成膜條件相同。In the production of the mask substrate, the light-shielding layer is formed by forming a film on the surface of the synthetic quartz glass in the order of a chromium film (light-shielding film) and a chromium oxide film (low-reflection film) using a sputtering method. At this time, the film formation of the chromium film (light-shielding film) and the chromium oxide film (low-reflection film) was performed individually using a sputtering device in which the gas was changed. In addition, the chromium oxide film (low reflection film) is formed by installing a Cr target in a vacuum chamber, introducing O 2 , N 2 , and CO 2 gases, and forming a film by reactive sputtering in a vacuum environment. The filming conditions of the chromium oxide film (low-reflection film) are the same as the film-forming conditions of the low-reflection film in the shading pattern of the ordinary binary mask. Furthermore, the film forming conditions of the chromium film are the same as the film forming conditions of the chromium film in the light-shielding pattern of the ordinary binary mask.

繼而，藉由於遮光層之表面形成所需形狀之抗蝕圖案，並以抗蝕圖案為遮罩利用濕式蝕刻對遮光層進行加工，而根據遮光層形成包含3.0 μm寬之遮光圖案之具有0.1 μm以上且未達10.0 μm之寬度的遮光圖案。藉此，製作出大型光罩。Then, by forming a resist pattern of a desired shape on the surface of the light-shielding layer, and using the resist pattern as a mask to process the light-shielding layer by wet etching, the light-shielding layer is formed with a light-shielding pattern with a width of 3.0 μm and has a thickness of 0.1 A light-shielding pattern above μm and less than 10.0 μm in width. In this way, a large mask is produced.

[評價結果] a.低反射膜及遮光性膜之交界構造之觀察 藉由SEM(Scanning Electron Microscope，掃描式電子顯微鏡)觀察實施例A1～A3及比較例A中之遮光圖案之低反射膜及遮光性膜之交界構造。其結果，於實施例1及3中之遮光圖案之交界中，Cr之含有率非連續地變化，氧化鉻膜(第1低反射膜)與鉻膜(遮光性膜)之交界及鉻膜(遮光性膜)與氧化鉻膜(第2低反射膜)之交界變得明確。又，於實施例2中之遮光圖案之交界中，Cr之含有率連續地變化，氧化鉻膜(第1低反射膜)與鉻膜(遮光性膜)之交界及鉻膜(遮光性膜)與氧化鉻膜(第2低反射膜)之交界變得不明確。又，於比較例中之遮光圖案之交界中，Cr之含有率非連續地變化，鉻膜(遮光性膜)與氧化鉻膜(低反射膜)之交界變得明確。[Evaluation results] a. Observation of the junction structure of low reflection film and shading film The boundary structure of the low-reflection film and the light-shielding film of the light-shielding pattern in Examples A1 to A3 and Comparative Example A was observed by SEM (Scanning Electron Microscope). As a result, in the boundary between the light-shielding patterns in Examples 1 and 3, the content of Cr discontinuously changes, and the boundary between the chromium oxide film (first low-reflection film) and the chromium film (light-shielding film) and the chromium film ( The boundary between the light-shielding film) and the chromium oxide film (the second low-reflection film) becomes clear. In addition, in the boundary of the light-shielding pattern in Example 2, the content of Cr continuously changes, the boundary between the chromium oxide film (first low-reflection film) and the chromium film (light-shielding film) and the chromium film (light-shielding film) The boundary with the chromium oxide film (the second low-reflection film) becomes unclear. Moreover, in the boundary of the light-shielding pattern in the comparative example, the content of Cr discontinuously changes, and the boundary between the chromium film (light-shielding film) and the chromium oxide film (low-reflection film) becomes clear.

b.遮光圖案之背面反射率及表面反射率以及光學密度(OD) 關於實施例A1～A3及比較例A之大型光罩，測定遮光圖案對313 nm～436 nm之波長區域之光之背面反射率(合成石英玻璃側之面之反射率)、及遮光圖案對上述波長區域之光之表面反射率(與合成石英玻璃相反側之面之反射率)以及遮光圖案相對於上述波長區域之光之光學密度(OD)。b. The back reflectivity and surface reflectivity of the shading pattern and the optical density (OD) Regarding the large masks of Examples A1 to A3 and Comparative Example A, the back reflectivity of the light shielding pattern to light in the wavelength region of 313 nm to 436 nm (the reflectance of the surface on the synthetic quartz glass side) and the light shielding pattern to the above were measured The surface reflectance of light in the wavelength range (the reflectance of the surface opposite to the synthetic quartz glass) and the optical density (OD) of the shading pattern relative to the light in the above wavelength range.

上述背面反射率及上述表面反射率係使用分光光譜儀(大塚電子MCPD3000)，於上述波長區域之範圍內以1 nm為單位地進行測定。又，上述光學密度(OD)係使用紫外/可見分光光度計(日立U-4000)，於上述波長區域之範圍內對每1 nm進行測定。其等測定結果中之利用g線(波長436 nm)、h線(波長405 nm)、i線(波長365 nm)及j線(波長313 nm)之測定結果示於以下表3。The above-mentioned back surface reflectance and the above-mentioned surface reflectance were measured using a spectrophotometer (Otsuka Electronics MCPD3000) in the range of the above-mentioned wavelength region in units of 1 nm. In addition, the above-mentioned optical density (OD) was measured every 1 nm within the above-mentioned wavelength range using an ultraviolet/visible spectrophotometer (Hitachi U-4000). The measurement results using g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm) and j-line (wavelength 313 nm) among the measurement results are shown in Table 3 below.

上述分光分析機(大塚電子MCPD3000)之測定條件等彙總於表1，上述紫外/可見分光光度計(日立U-4000)之測定條件彙總於表2。The measurement conditions of the spectroscopic analyzer (Otsuka Electronics MCPD3000) are summarized in Table 1, and the measurement conditions of the ultraviolet/visible spectrophotometer (Hitachi U-4000) are summarized in Table 2.

[表1]

Figure 108108561-A0304-0001
[Table 1]
Figure 108108561-A0304-0001

[表2]

Figure 108108561-A0304-0002
[Table 2]
Figure 108108561-A0304-0002

c.抗蝕圖案之性狀 使用實施例A1～A3及比較例A之大型光罩，以形成所需形狀之抗蝕圖案為目的，針對形成於玻璃基板上之膜厚2.5 μm之抗蝕層(JSR公司製)，根據以下曝光條件，進行曝光步進式(縮小投影式)之近接式曝光。c. Properties of resist pattern The large-scale photomasks of Examples A1 to A3 and Comparative Example A were used to form a resist pattern of a desired shape. For a resist layer (manufactured by JSR) formed on a glass substrate with a thickness of 2.5 μm, the following Exposure conditions, exposure step-type (reduced projection type) close-up exposure.

(曝光條件) 曝光間隙：150 μm 光源：超高壓水銀燈 曝光之光：包含g線、h線、i線及j線之曝光之光 曝光量：200 mJ/cm2 (Exposure conditions) Exposure gap: 150 μm Light source: Ultra-high pressure mercury lamp exposure light: Light exposure including g-line, h-line, i-line and j-line exposure: 200 mJ/cm 2

作為使用實施例A1～A3及比較例A之大型光罩而形成之抗蝕圖案之性狀，對抗蝕圖案之不均部相對於正常部之膜厚變動(以下，有時為「不均部膜厚變動」)進行評價。具體而言，其係測定將比較例A之不均部膜厚變動設為100%時之實施例A1～A3之不均部膜厚變動之比率[%]。其結果示於以下表3。Regarding the properties of the resist pattern formed using the large-scale photomasks of Examples A1 to A3 and Comparative Example A, the film thickness of the uneven portion of the resist pattern relative to the normal portion varies (hereinafter, sometimes referred to as "uneven portion film Thickness change") to evaluate. Specifically, it measured the ratio [%] of the uneven portion film thickness variation of Examples A1 to A3 when the uneven portion film thickness variation of Comparative Example A was set to 100%. The results are shown in Table 3 below.

[表3]

Figure 108108561-A0304-0003
[table 3]
Figure 108108561-A0304-0003

於實施例A1～A3中，如上述表3所示，針對g線、h線、i線及j線之任一者，背面反射率均為8%以下，雖上述表3中未示出，但針對上述波長區域之其他波長之光亦為相同之結果。於實施例A2及A3中，進而，如上述表3所示，針對g線、h線、i線及j線之任一者，表面反射率均為10%以下，雖上述表3中未示出，但針對上述波長區域之其他波長之光亦為相同之結果。於實施例A3中，進而，如上述表3所示，針對g線、h線、i線及j線之任一者，光學密度(OD)均為4.5以上，雖上述表3中未示出，但針對上述波長區域之其他波長之光亦為相同之結果。相對於此，於比較例A中，如上述表3所示，針對g線、h線、i線及j線中之h線、i線及j線，背面反射率大於8%，針對g線、h線、i線及j線中之任一者，表面反射率均大於10%，光學密度(OD)未達4.5。In Examples A1 to A3, as shown in Table 3 above, for any of g-line, h-line, i-line, and j-line, the back surface reflectance is all 8% or less, although it is not shown in the above-mentioned Table 3. However, the same results are obtained for light of other wavelengths in the above-mentioned wavelength range. In Examples A2 and A3, further, as shown in Table 3 above, for any of g-line, h-line, i-line, and j-line, the surface reflectance is all 10% or less, although it is not shown in Table 3 above However, the results are the same for light of other wavelengths in the above-mentioned wavelength range. In Example A3, further, as shown in Table 3 above, the optical density (OD) for any of the g-line, h-line, i-line, and j-line is 4.5 or more, although it is not shown in Table 3 above , But it is the same result for light of other wavelengths in the above-mentioned wavelength range. In contrast, in Comparative Example A, as shown in Table 3 above, for the g-line, h-line, i-line, and j-line, the back surface reflectivity is greater than 8%, and for g-line , H line, i line and j line, the surface reflectance is greater than 10%, and the optical density (OD) is less than 4.5.

如上述表3所示，於實施例A1～A3中，相較於比較例，可抑制不均部膜厚變動。又，於實施例A2及A3中，相較於實施例A1，可有效抑制不均部膜厚變動。進而，於實施例A3中，相較於實施例A2，可明顯抑制不均部膜厚變動。As shown in Table 3 above, in Examples A1 to A3, the variation in the film thickness of the uneven portion can be suppressed compared to the comparative example. In addition, in Examples A2 and A3, compared with Example A1, variation in film thickness of the uneven portion can be effectively suppressed. Furthermore, in Example A3, compared with Example A2, the variation in film thickness of the uneven portion can be significantly suppressed.

B.利用清洗減少異物 繼而，關於利用清洗之異物之減少效果，使用實施例及比較例進行說明。B. Use cleaning to reduce foreign matter Next, the effect of reducing foreign matter by washing will be described using Examples and Comparative Examples.

[實施例B1] 以與上述實施例A3相同之方式製作大型光罩。 利用玻璃切刀將製成之大型光罩切割為20 mm(h)×30 mm(w)×8 mm(d)以內。用鉑金對切割面實施濺鍍處理(20 mA×12秒)，並用電子顯微鏡進行觀察。電子顯微鏡使用掃描型電子顯微鏡(日本電子株式會社製，JSM-6700F)，將加速電壓設為5.0 kV，將斜率設為0°，將模式設為SEI(Secondary Electron Image，二次電子像)(二次電子下方檢測)，將工作距離設為3.2 mm～3.3 mm(根據樣品高度進行微調整)，進而將累計次數設為1次(Fine View模式)，將觀察倍率設為×100 K。測定部位為3.0 μm寬之遮光圖案之部分。 測定結果可知，上述第1低反射膜之側面相對於上述透光性基板表面之角度為80°。再者，如上所述，該角度係藉由將上述第1低反射膜之側面與上述透光性基板之表面相接之位置與上述第1低反射膜之膜厚開始減少之位置用直線連接，並測定直線與上述表面之角度而得之角度。[Example B1] The large-scale photomask was produced in the same manner as in the above-mentioned embodiment A3. Use a glass cutter to cut the finished large mask into 20 mm(h)×30 mm(w)×8 mm(d). The cut surface was sputtered with platinum (20 mA×12 seconds) and observed with an electron microscope. The scanning electron microscope (JSM-6700F manufactured by JEOL Ltd.) was used as the electron microscope, the acceleration voltage was set to 5.0 kV, the slope was set to 0°, and the mode was set to SEI (Secondary Electron Image) ( Under the secondary electron detection), set the working distance to 3.2 mm～3.3 mm (fine adjustment according to the height of the sample), set the cumulative number of times to 1 (Fine View mode), and set the observation magnification to ×100 K. The measurement part is the part of the shading pattern with a width of 3.0 μm. The measurement result revealed that the angle of the side surface of the first low-reflection film with respect to the surface of the translucent substrate was 80°. Furthermore, as described above, the angle is connected by a straight line between the position where the side surface of the first low-reflection film meets the surface of the translucent substrate and the position where the film thickness of the first low-reflection film starts to decrease. , And measure the angle between the straight line and the above surface.

對於此種實施例B1之大型光罩，純水清洗300秒，於實施後進行乾燥，利用外觀檢查機之反射檢查並藉由可檢測1 μm以上之異物之感度測定清洗後之異物數。該測定值係對除去玻璃基板4邊之端部5 mm後之690 mm×790 mm之區域進行測定所得之值。 將上述測定值作為將後述比較例B之值設為100時之比率示於表4。For the large mask of this embodiment B1, cleaned with pure water for 300 seconds, dried after implementation, used the reflection inspection of the visual inspection machine, and measured the number of foreign objects after cleaning with the sensitivity of detecting foreign objects of 1 μm or more. The measured value is a value obtained by measuring an area of 690 mm × 790 mm after removing 5 mm from the 4 sides of the glass substrate. The above-mentioned measured value is shown in Table 4 as a ratio when the value of Comparative Example B described later is set to 100.

[實施例B2～B5] 將上述實施例B1之蝕刻條件向延長蝕刻時間之方向變更，並變更上述第1低反射膜之側面相對於上述透光性基板表面之角度，製作出下述表4所示之角度之大型光罩。角度之測定係以與上述實施例B1相同之方法進行。[Examples B2～B5] The etching conditions of the above example B1 were changed to the direction of extending the etching time, and the angle of the side surface of the first low-reflection film with respect to the surface of the translucent substrate was changed to produce a large light with the angle shown in Table 4 below. cover. The angle measurement was performed by the same method as in the above-mentioned Example B1.

藉由與實施例B1相同之方法清洗該等大型光罩，並以相同之方式測定異物數。將上述測定值作為將後述比較例B之值設為100時之比率示於表4。The large masks were cleaned by the same method as in Example B1, and the number of foreign objects was measured in the same manner. The above-mentioned measured value is shown in Table 4 as a ratio when the value of Comparative Example B described later is set to 100.

[比較例B] 以與上述比較例A相同之方式製作了大型光罩。 對所得之大型光罩，藉由與上述實施例B1相同之方法，測定上述第1低反射膜之側面相對於上述透光性基板表面之角度。 又，對所得之大型光罩，藉由與實施例B1相同之方法進行清洗，並以相同之方式測定異物數。結果為100%並示於表4。[Comparative Example B] A large mask was produced in the same manner as in Comparative Example A above. For the obtained large mask, the angle of the side surface of the first low-reflection film with respect to the surface of the translucent substrate was measured by the same method as in the above-mentioned Example B1. In addition, the obtained large mask was cleaned by the same method as in Example B1, and the number of foreign matter was measured in the same manner. The result is 100% and is shown in Table 4.

[表4]

Figure 108108561-A0304-0004
[Table 4]
Figure 108108561-A0304-0004

由表4之結果可明確，相對於比較例，實施例之異物數較少。可推定其原因在於比較例中之鉻膜及實施例中之氧化鉻膜與異物之親和性差異而不同。 又，已知於變更角度之情形時，結果為角度越小異物數越減少，尤其是在實施例B2與實施例B3之間，值大幅變化。From the results in Table 4, it is clear that the number of foreign objects in the example is smaller than that in the comparative example. It can be presumed that the reason is the difference in the affinity between the chromium film in the comparative example and the chromium oxide film in the example and foreign matter. In addition, it is known that when the angle is changed, the result is that the smaller the angle, the smaller the number of foreign objects. Especially, the value greatly changes between Example B2 and Example B3.

100‧‧‧大型光罩 110‧‧‧透光性基板 110a‧‧‧表面 112‧‧‧界面 120‧‧‧遮光圖案 120a‧‧‧面 120b‧‧‧面 120c‧‧‧開口部 122‧‧‧第1低反射膜 122a‧‧‧側面 124‧‧‧遮光性膜 124a‧‧‧側面 126‧‧‧第2低反射膜 126a‧‧‧側面 150a‧‧‧第1分割圖案 150b‧‧‧第2分割圖案 150c‧‧‧第3分割圖案 200‧‧‧被轉印體 200'‧‧‧圖案轉印體 210‧‧‧基體 212‧‧‧界面 214‧‧‧界面 220‧‧‧抗蝕層 220a‧‧‧第1抗蝕圖案 220b‧‧‧第2抗蝕圖案 220c‧‧‧第3抗蝕圖案 300‧‧‧曝光遮蔽板 300a‧‧‧表面 A‧‧‧位置 B‧‧‧位置 L1‧‧‧突出長度 L2‧‧‧突出長度 La‧‧‧雜散光 Lb‧‧‧雜散光 Lc‧‧‧透過光 W1‧‧‧凹入寬度 W2‧‧‧凹入寬度 α‧‧‧傾斜角度100‧‧‧Large mask 110‧‧‧Transparent substrate 110a‧‧‧surface 112‧‧‧Interface 120‧‧‧Shading pattern 120a‧‧‧noodles 120b‧‧‧noodles 120c‧‧‧Opening 122‧‧‧The first low reflection film 122a‧‧‧ side 124‧‧‧Light-shielding film 124a‧‧‧Side 126‧‧‧The second low reflection film 126a‧‧‧ side 150a‧‧‧First division pattern 150b‧‧‧Second division pattern 150c‧‧‧The third division pattern 200‧‧‧Subject 200'‧‧‧pattern transfer 210‧‧‧Matrix 212‧‧‧Interface 214‧‧‧Interface 220‧‧‧Resist layer 220a‧‧‧The first resist pattern 220b‧‧‧Second resist pattern 220c‧‧‧The third resist pattern 300‧‧‧Exposure mask 300a‧‧‧surface A‧‧‧Location B‧‧‧Location L1‧‧‧Projection length L2‧‧‧Projection length La‧‧‧Stray light Lb‧‧‧Stray light Lc‧‧‧Transmitted light W1‧‧‧Concave width W2‧‧‧Concave width α‧‧‧Tilt angle

圖1係表示本發明之大型光罩之一例之概略剖視圖。 圖2係表示使用圖1所示之大型光罩並藉由曝光將圖案轉印至被轉印體所具有之抗蝕層之步驟之概略剖視圖。 圖3係將圖1所示之虛線框內之區域之圖式上下顛倒而表示的放大圖。 圖4係表示先前技術之大型光罩中之與圖3對應之區域的概略剖視圖。 圖5係表示本發明之大型光罩之另一例中之與圖3對應之區域的概略剖視圖。 圖6係表示本發明之大型光罩之另一例中之與圖3對應之區域的概略剖視圖。 圖7係表示本發明之大型光罩之另一例中之與圖3對應之區域的概略剖視圖。 圖8係表示本發明之大型光罩之另一例之概略俯視圖。 圖9係表示使用圖8所示之大型光罩根據被轉印體所製造之圖案轉印體之概略俯視圖。 圖10(a)、(b)係表示圖9所示之圖案轉印體之部分製造步驟之概略步驟剖視圖。 圖11係利用既有低感度抗蝕劑及近年來所使用之高感度抗蝕劑對轉印線寬偏移相對於曝光量之變動進行比較之圖表。 圖12係表示本發明之大型光罩之另一例中之與圖3對應之區域的概略剖視圖。Fig. 1 is a schematic cross-sectional view showing an example of a large-sized mask of the present invention. Fig. 2 is a schematic cross-sectional view showing a step of transferring a pattern to a resist layer of a transfer target body by exposure using the large-scale photomask shown in Fig. 1. Fig. 3 is an enlarged view showing the area in the dashed frame shown in Fig. 1 upside down. FIG. 4 is a schematic cross-sectional view showing a region corresponding to FIG. 3 in a large-scale photomask of the prior art. Fig. 5 is a schematic cross-sectional view showing another example of the large-sized mask of the present invention corresponding to Fig. 3. Fig. 6 is a schematic cross-sectional view showing another example of the large-sized mask of the present invention corresponding to Fig. 3. FIG. 7 is a schematic cross-sectional view showing a region corresponding to FIG. 3 in another example of the large mask of the present invention. Fig. 8 is a schematic plan view showing another example of the large mask of the present invention. FIG. 9 is a schematic plan view showing a pattern transfer body manufactured from a transfer body using the large mask shown in FIG. 8. 10(a) and (b) are schematic cross-sectional views showing a part of the manufacturing steps of the pattern transfer body shown in FIG. 9. FIG. 11 is a graph comparing the shift of the transfer line width with respect to the exposure amount using the existing low-sensitivity resist and the high-sensitivity resist used in recent years. Fig. 12 is a schematic cross-sectional view showing a region corresponding to Fig. 3 in another example of the large mask of the present invention.

100‧‧‧大型光罩 100‧‧‧Large mask

110‧‧‧透光性基板 110‧‧‧Transparent substrate

110a‧‧‧表面 110a‧‧‧surface

120‧‧‧遮光圖案 120‧‧‧Shading pattern

120a‧‧‧面 120a‧‧‧noodles

120b‧‧‧面 120b‧‧‧noodles

120c‧‧‧開口部 120c‧‧‧Opening

122‧‧‧第1低反射膜 122‧‧‧The first low reflection film

124‧‧‧遮光性膜 124‧‧‧Light-shielding film

126‧‧‧第2低反射膜 126‧‧‧The second low reflection film

Claims (14)

一種大型光罩，其特徵在於：其係包含透光性基板、及設於上述透光性基板之表面之遮光圖案之大型光罩，上述遮光圖案具有第1低反射膜、遮光性膜及第2低反射膜自上述透光性基板側按照該順序積層而成之積層構造，且上述遮光圖案之上述透光性基板側之面對313nm至436nm之波長區域之光之反射率為8%以下。 A large-scale photomask, characterized in that it is a large-scale photomask comprising a translucent substrate and a light-shielding pattern provided on the surface of the translucent substrate, the light-shielding pattern having a first low-reflection film, a light-shielding film, and a 2 The low-reflection film is laminated in this order from the translucent substrate side, and the light-shielding pattern facing the translucent substrate side has a reflectance of 8% or less for light in the wavelength region of 313nm to 436nm . 如請求項1之大型光罩，其中上述遮光圖案之與上述透光性基板相反側之面對313nm至436nm之波長區域之光之反射率為10%以下。 The large-scale photomask of claim 1, wherein the light-shielding pattern on the opposite side of the translucent substrate has a reflectance of light in the wavelength region from 313 nm to 436 nm, which is less than 10%. 如請求項1之大型光罩，其中上述遮光性膜含有鉻，上述第1低反射膜及上述第2低反射膜含有氧化鉻。 The large-sized mask of claim 1, wherein the light-shielding film contains chromium, and the first low-reflection film and the second low-reflection film contain chromium oxide. 如請求項1之大型光罩，其中上述遮光圖案之與上述透光性基板相反側之面對313nm至436nm之波長區域之光之反射率為10%以下，且上述遮光性膜含有鉻，上述第1低反射膜及上述第2低反射膜含有氧化鉻。 The large-scale photomask of claim 1, wherein the light-shielding pattern on the opposite side of the translucent substrate has a reflectance of light in the wavelength region from 313nm to 436nm, and the light-shielding film contains chromium. The first low-reflection film and the second low-reflection film contain chromium oxide. 如請求項1之大型光罩，其中上述遮光圖案對313nm至436nm之波長區域之光之光學密度(OD)為4.5以上。 Such as the large-scale photomask of claim 1, wherein the above-mentioned shading pattern has an optical density (OD) of 4.5 or more for light in the wavelength region of 313 nm to 436 nm. 如請求項1之大型光罩，其中上述遮光圖案之與上述透光性基板相反側之面對313nm至436nm之波長區域之光之反射率為10%以下，且上述遮光圖案相對於313nm至436nm之波長區域之光之光學密度(OD)為4.5以上。 The large-scale mask of claim 1, wherein the light-shielding pattern on the opposite side of the translucent substrate has a reflectance of light in the wavelength region of 313nm to 436nm, and the reflectance of the light is 10% or less, and the light-shielding pattern is relative to 313nm to 436nm The optical density (OD) of light in the wavelength region is 4.5 or more. 如請求項1之大型光罩，其中上述遮光性膜含有鉻，上述第1低反射膜及上述第2低反射膜含有氧化鉻，且上述遮光圖案相對於313nm至436nm之波長區域之光之光學密度(OD)為4.5以上。 The large-scale photomask of claim 1, wherein the light-shielding film contains chromium, the first low-reflection film and the second low-reflection film contain chromium oxide, and the light-shielding pattern is relative to the optics of light in the wavelength region of 313nm to 436nm The density (OD) is 4.5 or more. 如請求項1之大型光罩，其中上述遮光圖案之與上述透光性基板相反側之面對313nm至436nm之波長區域之光之反射率為10%以下，上述遮光性膜含有鉻，上述第1低反射膜及上述第2低反射膜含有氧化鉻，且上述遮光圖案相對於313nm至436nm之波長區域之光之光學密度(OD)為4.5以上。 The large-scale mask of claim 1, wherein the light-shielding pattern on the opposite side of the light-transmitting substrate has a reflectance of light in the wavelength region from 313 nm to 436 nm, and the light-shielding film contains chromium. 1 The low-reflection film and the second low-reflection film contain chromium oxide, and the light-shielding pattern has an optical density (OD) of 4.5 or more with respect to light in the wavelength region of 313 nm to 436 nm. 如請求項5之大型光罩，其中上述遮光性膜之側面相對於上述透光性基板之傾斜角度為80度以上90度以下。 The large-scale photomask of claim 5, wherein the inclination angle of the side surface of the light-shielding film with respect to the light-transmitting substrate is 80 degrees or more and 90 degrees or less. 如請求項5之大型光罩，其中上述第1低反射膜之側面或上述第2低反射膜之側面相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出。 The large-scale mask of claim 5, wherein the side surface of the first low-reflection film or the side surface of the second low-reflection film protrudes in a direction parallel to the surface of the light-transmitting substrate relative to the side surface of the light-shielding film. 如請求項10之大型光罩，其中上述第1低反射膜之側面及上述第2低反射膜之側面之兩者相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出，且進而，上述第1低反射膜之側面相較於上述第2低反射膜之側面在與上述透光性基板之表面平行之方向上更加突出。 The large-scale mask of claim 10, wherein both the side surface of the first low-reflection film and the side surface of the second low-reflection film are in a direction parallel to the surface of the translucent substrate with respect to the side surface of the light-shielding film In addition, the side surface of the first low-reflection film protrudes more than the side surface of the second low-reflection film in a direction parallel to the surface of the translucent substrate. 如請求項10之大型光罩，其中至少上述第1低反射膜之側面相對於上述遮光性膜之側面在與上述透光性基板之表面平行之方向上突出，且進而，上述第1低反射膜之側面相對於上述透光性基板表面之角度為56°以下。 The large-scale photomask of claim 10, wherein at least the side surface of the first low-reflection film protrudes in a direction parallel to the surface of the light-transmitting substrate with respect to the side surface of the light-shielding film, and further, the first low-reflection film The angle of the side surface of the film with respect to the surface of the translucent substrate is 56° or less. 如請求項5之大型光罩，其中上述遮光性膜之側面為凹狀。 Such as the large-scale photomask of claim 5, wherein the side surface of the light-shielding film is concave. 一種大型光罩，其特徵在於：其係如請求項1至請求項13之任一項之大型光罩，且其具有用於分割曝光之分割圖案，上述分割圖案係上述遮光圖案。 A large-scale photomask is characterized in that it is a large-scale photomask as in any one of claim 1 to claim 13, and has a split pattern for split exposure, and the split pattern is the light shielding pattern.
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