TWI631413B - Phase-shift mask blank, phase-shift mask and its manufacturing method, and method for manufacturing display device - Google Patents

Phase-shift mask blank, phase-shift mask and its manufacturing method, and method for manufacturing display device Download PDF

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TWI631413B
TWI631413B TW106129835A TW106129835A TWI631413B TW I631413 B TWI631413 B TW I631413B TW 106129835 A TW106129835 A TW 106129835A TW 106129835 A TW106129835 A TW 106129835A TW I631413 B TWI631413 B TW I631413B
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film
light
light semi
phase shift
pattern
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TW201740183A (en
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坪井誠治
吉川裕
菅野美智雄
牛田正男
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Ｈｏｙａ股份有限公司
Ｈｏｙａ電子馬來西亞私人股份有限公司
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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
    • G03F1/20—Masks or mask blanks for imaging by charged particle beam [CPB] radiation, e.g. by electron beam; Preparation thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

本發明提供一種可藉由濕式蝕刻而形成為有效地表現相位效果之剖面形狀的相移光罩基底。 本發明之相移光罩基底具備透明基板、形成於透明基板之主表面上之由金屬矽化物系材料所構成之光半透過膜、及形成於該光半透過膜上之由鉻系材料所構成之蝕刻遮罩膜，且於光半透過膜與蝕刻遮罩膜之界面形成有組成梯度區域P，於該組成梯度區域P內，減慢光半透過膜之濕式蝕刻速度之成分之比率朝向深度方向階段性及/或連續性地增加。The present invention provides a phase shift mask substrate that can be formed into a cross-sectional shape that effectively expresses a phase effect by wet etching. The phase shift mask base of the present invention includes a transparent substrate, a light semi-transmissive film made of a metal silicide-based material formed on the main surface of the transparent substrate, and a chromium-based material formed on the light semi-transmissive film The etching mask film is formed, and a composition gradient region P is formed at the interface between the light semi-transmitting film and the etching mask film. Within the composition gradient region P, the ratio of the components that slow down the wet etching speed of the light semi-transmitting film Increasing gradually and / or continuously toward the depth.

Description

相移光罩基底、相移光罩及其製造方法、與顯示裝置之製造方法Phase shift mask base, phase shift mask, manufacturing method thereof, and display device manufacturing method

本發明係關於一種藉由濕式蝕刻而形成之相移膜圖案之剖面形狀良好的相移光罩基底及其製造方法、使用有該相移光罩基底之相移光罩及其製造方法。又，本發明係關於一種用於製造顯示裝置之相移光罩基底及其製造方法、使用有該相移光罩基底之用於製造顯示裝置之相移光罩及其製造方法、與使用有該相移光罩之顯示裝置之製造方法。The invention relates to a phase shift mask substrate with a good cross-sectional shape of a phase shift film pattern formed by wet etching and a method for manufacturing the same, a phase shift mask using the phase shift mask substrate, and a method for manufacturing the same. In addition, the present invention relates to a phase shift mask substrate for manufacturing a display device and a manufacturing method thereof, a phase shift mask for manufacturing a display device using the phase shift mask substrate, a manufacturing method thereof, and the use of the same. Method for manufacturing display device of phase shift mask.

現在，作為液晶顯示裝置中採用之方式，有VA(Vertical alignment，垂直配向)方式或IPS(In Plane Switching，共平面切換)方式。藉由該等方式可實現高精細、高速顯示性能、寬視角之液晶顯示裝置。應用有該等方式之液晶顯示裝置中，藉由以透明導電膜之線與間隙圖案來形成像素電極，而可改善回應速度、視角。最近，就回應速度及視角之進一步之提高、或液晶顯示裝置之光利用效率之提高、即液晶顯示裝置之低消耗電力化或對比度提高之觀點而言，要求有線與間隙圖案之間距寬度之微細化。例如，較理想為使線與間隙圖案之間距寬度自6 μm變窄為5 μm，進而自5 μm變窄為4 μm。 又，於製造液晶顯示裝置或有機EL(Electroluminescence，電致發光)顯示裝置時，藉由將實施必要之圖案化而成之複數層導電膜或絕緣膜積層而形成電晶體等元件。此時，大多情況下對所積層之各膜之圖案化利用光微影製程。例如，於該等顯示裝置中所使用之薄膜電晶體中，具有如下構成：藉由光微影製程，而於絕緣層形成接觸孔，從而將上層之圖案與下層之圖案連接。最近，於此種顯示裝置中，以充分之動作速度而顯示明亮、精細之像且降低消耗電力的需求增高。為了滿足此種要求，要求使顯示裝置之構成元件微細化、高積體化。例如，較理想為使接觸孔之直徑自2 μm縮小為1.5 μm。 根據此種背景，較理想為可應對線與間隙圖案或接觸孔之微細化的用於製造顯示裝置之光罩。 當實現線與間隙圖案或接觸孔之微細化時，先前之光罩中，由於用於製造顯示裝置之曝光機之解像極限為3 μm，故而須於無充分之製程裕度(Process Margin)之情況下生產接近解像極限之最小線寬的製品。因此，有顯示裝置之不良率變高之問題。 例如，於考慮到使用具有用以形成接觸孔之孔圖案之光罩、將其轉印至被轉印體的情形時，只要為直徑超過3 μm之孔圖案則能以先前之光罩進行轉印。然而，轉印直徑為3 μm以下之孔圖案、尤其是直徑為2.5 μm以下之孔圖案非常困難。為了轉印直徑為2.5 μm以下之孔圖案，亦考慮到轉換為例如具有高NA(Numerical Aperture，數值孔徑)之曝光機，但需要較大之投資。 因此，為了提高解像度而應對線與間隙圖案或接觸孔之微細化，作為用於製造顯示裝置之光罩，相移光罩受到關注。 最近，作為用於製造液晶顯示裝置之光罩，開發出具備鉻系相移膜之相移光罩。 於專利文獻1中，記載有一種半色調式相移光罩，其具備：透明基板；遮光層，其形成於透明基板上；及相移層，其形成於遮光層之周圍，可對300 nm以上且500 nm以下之波長區域之任一種光具有180度之相位差且包含氮氧化鉻系材料。該相移光罩係藉由如下方式製造：對透明基板上之遮光層進行圖案化，以被覆遮光層之方式於透明基板上形成相移層，於相移層上形成光阻劑層，藉由對光阻劑層進行曝光及顯影而形成光阻劑圖案，以光阻劑圖案為蝕刻遮罩對相移層進行圖案化。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2011-13283號公報Currently, as a method adopted in a liquid crystal display device, there is a VA (Vertical alignment) method or an IPS (In Plane Switching) method. By these methods, a high-definition, high-speed display performance, and wide viewing angle liquid crystal display device can be realized. In liquid crystal display devices to which these methods are applied, by forming pixel electrodes with lines and gap patterns of transparent conductive films, the response speed and viewing angle can be improved. Recently, from the viewpoints of further improvement of response speed and viewing angle, or improvement of light utilization efficiency of liquid crystal display devices, that is, lower power consumption of liquid crystal display devices or improvement of contrast ratio, a finer width of space between a wired pattern and a gap pattern is required. Into. For example, it is desirable to narrow the width of the gap between the line and the gap pattern from 6 μm to 5 μm, and then narrow from 5 μm to 4 μm. Furthermore, when manufacturing a liquid crystal display device or an organic EL (Electroluminescence) display device, elements such as transistors are formed by laminating a plurality of layers of a conductive film or an insulating film that are patterned as necessary. At this time, in most cases, the photolithography process is used for patterning the films of the layers to be laminated. For example, a thin film transistor used in such display devices has a structure in which a contact hole is formed in an insulating layer by a photolithography process, thereby connecting an upper layer pattern with a lower layer pattern. Recently, in such a display device, a demand for displaying bright and fine images at a sufficient operating speed and reducing power consumption has increased. In order to satisfy such a demand, it is required to make the constituent elements of the display device finer and more compact. For example, it is desirable to reduce the diameter of the contact hole from 2 μm to 1.5 μm. According to such a background, a photomask for manufacturing a display device that can cope with the miniaturization of a line and a gap pattern or a contact hole is ideal. When the miniaturization of the line and gap patterns or contact holes is realized, the conventional photomask has an insufficient process margin because the resolution limit of the exposure machine used to manufacture the display device is 3 μm. In this case, a minimum line width product close to the resolution limit is produced. Therefore, there is a problem that the defective rate of the display device becomes high. For example, when considering the use of a mask with a hole pattern for forming contact holes and transferring it to the transferee, if the hole pattern has a diameter of more than 3 μm, it can be transferred with the previous mask. Seal. However, it is very difficult to transfer a hole pattern having a diameter of 3 μm or less, especially a hole pattern having a diameter of 2.5 μm or less. In order to transfer a hole pattern having a diameter of 2.5 μm or less, conversion to, for example, an exposure machine having a high NA (Numerical Aperture) is also considered, but a large investment is required. Therefore, in order to improve the resolution, the miniaturization of the line and gap patterns or the contact holes is required. As a photomask used for manufacturing a display device, a phase shift photomask has attracted attention. Recently, as a photomask for manufacturing a liquid crystal display device, a phase shift photomask having a chromium-based phase shift film has been developed. Patent Document 1 describes a halftone type phase shift mask including a transparent substrate, a light-shielding layer formed on the transparent substrate, and a phase-shift layer formed around the light-shielding layer. Any one of the light in the wavelength range above and below 500 nm has a phase difference of 180 degrees and contains a chromium oxynitride-based material. The phase shift mask is manufactured by patterning a light shielding layer on a transparent substrate, forming a phase shift layer on the transparent substrate by covering the light shielding layer, and forming a photoresist layer on the phase shift layer. A photoresist pattern is formed by exposing and developing the photoresist layer, and patterning the phase shift layer with the photoresist pattern as an etching mask. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2011-13283

[發明所欲解決之問題] 本發明者等人對具備鉻系相移膜之相移光罩進行了銳意研究。其結果可知，於以光阻劑圖案為遮罩、藉由濕式蝕刻對鉻系相移膜進行圖案化之情形時，濕式蝕刻液滲入至光阻劑膜與鉻系相移膜之界面，界面部分之蝕刻進行地較快。所形成之鉻系相移膜圖案之邊緣部分之剖面形狀產生梯度，成為底部擴展之楔形狀。 於鉻系相移膜圖案之邊緣部分之剖面形狀為楔形狀之情形時，隨著鉻系相移膜圖案之邊緣部分之膜厚減少，相移效果較弱。因此，無法充分發揮相移效果。又，濕式蝕刻液向光阻劑膜與鉻系相移膜之界面之滲入係起因於鉻系相移膜與光阻劑膜之密接性欠佳。因此，難以嚴格地控制鉻系相移膜圖案之邊緣部分之剖面形狀，從而，非常難以控制線寬(CD)。 進而，本發明者等人為了解決該等問題而對將相移膜圖案之邊緣部分之剖面形狀垂直化之方法進行了銳意研究。目前為止開發出使相移膜之膜組成(例如，氮含量)具有梯度而使膜厚方向之蝕刻速度具有變化的方法、或對相移膜加入添加物(例如Al、Ga)而控制蝕刻時間的方法。然而，該等方法中，非常難以實現大面積之相移光罩整體中之透過率之均勻性。 因此，本發明係鑒於上述問題而完成者，其目的在於提供一種可藉由濕式蝕刻而將相移膜圖案化為能充分發揮相移效果之剖面形狀的相移光罩基底及其製造方法、具有能充分發揮相移效果之相移膜圖案的相移光罩及其製造方法、尤其是可將相移膜圖案化為能充分發揮相移效果之剖面形狀的用於製造顯示裝置之相移光罩基底及其製造方法、具有能充分發揮相移效果之相移膜圖案的用於製造顯示裝置之相移光罩及其製造方法、與使用有該相移光罩之顯示裝置之製造方法。 又，本發明之目的在於提供一種可藉由濕式蝕刻而將相移膜圖案化為CD不均較小之剖面形狀的相移光罩基底及其製造方法、具有CD不均較小之相移膜圖案的相移光罩及其製造方法、尤其是可將相移膜圖案化為CD不均較小之剖面形狀的用於製造顯示裝置之相移光罩基底及其製造方法、具有CD不均較小之相移膜圖案的用於製造顯示裝置之相移光罩及其製造方法、與使用有該相移光罩之顯示裝置之製造方法。 又，本發明之目的在於提供一種光學特性均勻之相移光罩基底及其製造方法、光學特性均勻之相移光罩及其製造方法、尤其是光學特性均勻之用於製造顯示裝置之相移光罩基底及其製造方法、光學特性均勻之用於製造顯示裝置之相移光罩及其製造方法、與使用有該相移光罩之顯示裝置之製造方法。 [解決問題之技術手段] 為了解決上述課題，本發明具有以下構成。 (構成1)一種相移光罩基底，其特徵在於具備： 透明基板； 光半透過膜，其形成於上述透明基板之主表面上，具有改變曝光之光之相位之性質且由金屬矽化物系材料所構成；及 蝕刻遮罩膜，其形成於該光半透過膜上，且由鉻系材料所構成；且 於上述光半透過膜與上述蝕刻遮罩膜之界面形成有組成梯度區域，於該組成梯度區域內，減慢上述光半透過膜之濕式蝕刻速度之成分之比率朝向深度方向階段性及/或連續性地增加。 (構成2)如構成1之相移光罩基底，其特徵在於：上述光半透過膜之、除該光半透過膜與上述蝕刻遮罩膜之界面及該光半透過膜與上述透明基板之界面以外之部分的組成實質上均勻。 (構成3)如構成1或2之相移光罩基底，其特徵在於：上述光半透過膜係由複數層所構成。 (構成4)如構成1或2之相移光罩基底，其特徵在於：上述金屬矽化物系材料為金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氧化物、金屬矽化物之氮碳化物、金屬矽化物之氮氧碳化物中之任一者。 (構成5)如構成1或2之相移光罩基底，其特徵在於：減慢上述濕式蝕刻速度之成分為氮或碳。 (構成6)如構成5之相移光罩基底，其特徵在於：於減慢上述濕式蝕刻速度之成分為氮之情形時，當自上述組成梯度區域內之與上述蝕刻遮罩膜之邊界中的上述蝕刻遮罩膜側，利用X射線光電子光譜法，於測定步進為0.5分鐘之條件下進行組成分析時，初次檢測到1原子%以上之矽(Si)之位置上的氮(N)相對於矽(Si)之比率(N/Si)之最大值為3.0以上且30以下。 (構成7)如構成1或2之相移光罩基底，其特徵在於：上述蝕刻遮罩膜具有遮光性。 (構成8)如構成1或2之相移光罩基底，其特徵在於：上述蝕刻遮罩膜包含形成於上述光半透過膜側之遮光層及形成於該遮光層上之抗反射層。 (構成9)如構成1或2之相移光罩基底，其特徵在於：上述蝕刻遮罩膜包含以與上述光半透過膜接觸之方式形成之絕緣層。 (構成10)如構成9之相移光罩基底，其特徵在於：上述絕緣層係由包含未達50原子%之Cr之CrCO或CrCON所構成，且具有10 nm以上且50 nm以下之厚度。 (構成11)如構成1或2之相移光罩基底，其特徵在於：上述相移光罩基底為顯示裝置製造用相移光罩基底。 (構成12)一種相移光罩基底之製造方法，其特徵在於包括： 準備製程，其係準備透明基板； 半透過膜形成製程，其係於上述透明基板之主表面上，藉由濺鍍而形成具有改變曝光之光之相位之性質且由金屬矽化物系材料所構成的光半透過膜；及 蝕刻遮罩膜形成製程，其係於上述光半透過膜上，藉由濺鍍而形成由鉻系材料所構成之蝕刻遮罩膜；且 上述半透過膜形成製程包含在濺鍍氣體氛圍下施加濺鍍功率而形成由金屬矽化物系材料所構成之光半透過膜的成膜製程、及使該光半透過膜曝露於包含減慢上述光半透過膜之濕式蝕刻速度之成分之氣體氛圍的曝露製程，且該曝露製程係在不使上述光半透過膜曝露於大氣的情況下於上述成膜製程後連續地進行。 (構成13)如構成12之相移光罩基底之製造方法，其特徵在於：上述成膜製程係使用包含金屬與矽之濺鍍靶、於含有混合氣體之濺鍍氣體氛圍下進行進行，該混合氣體包含選自由氦氣、氖氣、氬氣、氪氣及氙氣所組成之群中之至少一種之惰性氣體、及包含選自由氮氣、一氧化氮氣體、一氧化二氮氣體、及二氧化氮氣體所組成之群中之至少一種之包含氮或氮化合物之活性氣體、或者包含二氧化碳氣體或烴氣之包含碳化合物之活性氣體。 (構成14)如構成12或13之相移光罩基底之製造方法，其特徵在於：上述曝露製程係於包含氮或氮化合物之氣體氛圍下進行。 (構成15)如構成12或13之相移光罩基底之製造方法，其特徵在於：上述曝露製程係於包含碳或碳化合物之氣體氛圍下進行。 (構成16)如構成12或13之相移光罩基底之製造方法，其特徵在於：上述相移光罩基底為顯示裝置製造用相移光罩基底。 (構成17) 一種相移光罩，其特徵在於具備： 透明基板；及 光半透過膜圖案，其藉由濕式蝕刻而形成於該透明基板之主表面上，具有改變曝光之光之相位之性質且由金屬矽化物系材料所構成；且 上述光半透過膜圖案之、除上表面及該光半透過膜圖案與上述透明基板之界面以外之部分的組成實質上均勻， 上述光半透過膜圖案之剖面係由對應於該光半透過膜圖案之上表面、下表面及側面之上邊、下邊及側邊所構成，上述上邊與上述側邊之接點與自上述上表面下降膜厚之三分之二之高度之位置上的上述側邊之位置連成的直線、與上述上邊所成之角度為85度至120度之範圍內，且通過上述上邊與上述側邊之接點且相對於上述透明基板之上述主表面垂直之第1假想線、與通過自上述下表面上升膜厚之十分之一之高度之位置上的上述側邊之位置且相對於上述透明基板之上述主表面垂直之第2假想線的寬度為上述膜厚之二分之一以下。 (構成18)一種相移光罩，其係用於製造顯示裝置，其特徵在於具備： 透明基板；及 光半透過膜圖案，其形成於該透明基板之主表面上，具有改變曝光之光之相位之性質且由金屬矽化物系材料所構成；且 上述光半透過膜圖案之、除上表面及該光半透過膜圖案與上述透明基板之界面以外之部分的組成實質上均勻， 上述光半透過膜圖案之剖面係由對應於該光半透過膜圖案之上表面、下表面及側面之上邊、下邊及側邊所構成，上述上邊與上述側邊之接點與自上述上表面下降膜厚之三分之二之高度之位置上的上述側邊之位置連成的直線、與上述上邊所成之角度為85度至120度之範圍內，且通過上述上邊與上述側邊之接點且相對於上述透明基板之上述主表面垂直之第1假想線、與通過自上述下表面上升膜厚之十分之一之高度之位置上的上述側邊之位置且相對於上述透明基板之上述主表面垂直之第2假想線的寬度為上述膜厚之二分之一以下。 (構成19)如構成17或18之相移光罩，其特徵在於：上述光半透過膜圖案係由金屬矽化物氮化膜、金屬矽化物氮氧化膜、金屬矽化物之碳氧化物、金屬矽化物之氮氧碳化物中之任一者所構成。 (構成20)如構成17或18之相移光罩，其特徵在於：上述光半透過膜圖案包含線與間隙圖案。 (構成21)如構成17或18之相移光罩，其特徵在於：上述光半透過膜圖案包含孔圖案。 (構成22)一種相移光罩之製造方法，其特徵在於包括： 光阻劑圖案形成製程，其係於如構成1至11中任一項之相移光罩基底之蝕刻遮罩膜上、或藉由如構成12至16中任一項之相移光罩基底之製造方法所獲得的相移光罩基底之蝕刻遮罩膜上，形成光阻劑圖案； 蝕刻遮罩膜圖案形成製程，其係以上述光阻劑圖案為遮罩對上述蝕刻遮罩膜進行濕式蝕刻而形成蝕刻遮罩膜圖案；及 半透過膜圖案形成製程，其係以上述蝕刻遮罩膜圖案為遮罩對上述光半透過膜進行濕式蝕刻而形成光半透過膜圖案。 (構成23)如構成22之相移光罩之製造方法，其特徵在於：上述半透過膜圖案形成製程係使用蝕刻液進行濕式蝕刻，該蝕刻液包含選自氫氟酸、氫氟矽酸、及氟化氫銨中之至少一種氟化合物、及選自過氧化氫、硝酸、及硫酸中之至少一種氧化劑。 (構成24)如構成22或23之相移光罩之製造方法，其特徵在於：上述相移光罩為顯示裝置製造用相移光罩。 (構成25)一種顯示裝置之製造方法，其特徵在於包括： 相移光罩配置製程，其係對在基板上形成有光阻劑膜之附光阻劑膜之基板，將如構成17至21中任一項之相移光罩、或藉由如構成22至24中任一項之相移光罩之製造方法所獲得的相移光罩對向於上述光阻劑膜而配置；及 光阻劑膜曝光製程，其係對上述相移光罩照射上述曝光之光，對上述光阻劑膜進行曝光。 (構成26)如構成25之顯示裝置之製造方法，其特徵在於：上述曝光之光包含300 nm以上且500 nm以下之波長範圍之光。 (構成27)如構成25或26之顯示裝置之製造方法，其特徵在於：上述曝光之光為包含i射線、h射線及g射線之複合光。 [發明之效果] 如上所述，根據本發明之相移光罩基底、尤其是用於製造顯示裝置時所使用之顯示裝置製造用相移光罩基底，具備形成於透明基板之主表面上之由金屬矽化物系材料所構成之光半透過膜、及形成於光半透過膜上之由鉻系材料所構成之蝕刻遮罩膜。在形成於光半透過膜與蝕刻遮罩膜之界面之組成梯度區域內，減慢光半透過膜之濕式蝕刻速度之成分之比率朝向深度方向階段性及/或連續性地增加。因此，能獲得一種可藉由濕式蝕刻而將光半透過膜圖案化為能充分發揮相移效果之剖面形狀的相移光罩基底。又，能獲得一種可藉由濕式蝕刻而將光半透過膜圖案化為CD不均較小之剖面形狀的相移光罩基底。 又，根據本發明之相移光罩基底之製造方法、尤其是用於製造顯示裝置時所使用之顯示裝置製造用相移光罩基底之製造方法，於透明基板之主表面上形成由金屬矽化物系材料所構成之光半透過膜，於光半透過膜上形成由鉻系材料所構成之蝕刻遮罩膜。光半透過膜之形成係藉由如下方式進行：形成光半透過膜，並在不使光半透過膜曝露於大氣中的情況下，於成膜後連續地使光半透過膜曝露於包含減慢光半透過膜之濕式蝕刻速度之成分之氣體氛圍。因此，能製造一種可藉由濕式蝕刻而將光半透過膜圖案化為能充分發揮相移效果之剖面形狀的相移光罩基底。又，能製造一種可藉由濕式蝕刻而將光半透過膜圖案化為CD不均較小之剖面形狀的相移光罩基底。 又，根據本發明之相移光罩、尤其是用於製造顯示裝置時所使用之顯示裝置製造用相移光罩，具備形成於透明基板之主表面上之由金屬矽化物系材料所構成之光半透過膜圖案。 該光半透過膜圖案之組成實質上均勻。因此，能獲得一種光學特性均勻之相移光罩。 又，於該光半透過膜圖案之剖面中，上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度位於85度至120度之範圍內。進而，於光半透過膜圖案之剖面中，通過上邊與側邊之接點且相對於透明基板之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於透明基板之主表面垂直之第2假想線的寬度為膜厚之二分之一以下。因此，能獲得一種具有能充分發揮相移效果之光半透過膜圖案之相移光罩。又，能獲得一種具有CD不均較小之光半透過膜圖案之相移光罩。該相移光罩可應對線與間隙圖案或接觸孔之微細化。 又，根據本發明之相移光罩之製造方法、尤其是用於製造顯示裝置時所使用之顯示裝置製造用相移光罩之製造方法，使用上述相移光罩基底或藉由上述相移光罩基底之製造方法所獲得的相移光罩基底製造相移光罩。因此，能製造一種具有能充分發揮相移效果之光半透過膜圖案之相移光罩。又，能製造一種具有CD不均較小之光半透過膜圖案之相移光罩。該相移光罩可應對線與間隙圖案或接觸孔之微細化。 又，根據本發明之顯示裝置之製造方法，使用上述相移光罩或藉由上述相移光罩之製造方法所獲得的相移光罩而製造顯示裝置。因此，能製造一種具有微細之線與間隙圖案或接觸孔之顯示裝置。[Problems to be Solved by the Invention] The present inventors have intensively studied a phase shift mask provided with a chromium-based phase shift film. As a result, it was found that when the chromium-based phase shift film was patterned by wet etching using the photoresist pattern as a mask, the wet etching solution penetrated into the interface between the photoresist film and the chromium-based phase shift film. The etching of the interface part proceeds faster. The cross-sectional shape of the edge portion of the formed chromium-based phase-shifting film pattern has a gradient and becomes a wedge shape with a bottom expanding. When the cross-sectional shape of the edge portion of the chrome-based phase shift film pattern is a wedge shape, as the film thickness of the edge portion of the chrome-based phase shift film pattern decreases, the phase shift effect becomes weaker. Therefore, the phase shift effect cannot be fully exerted. In addition, the penetration of the wet etching solution into the interface between the photoresist film and the chromium-based phase shift film is due to poor adhesion between the chromium-based phase shift film and the photoresist film. Therefore, it is difficult to strictly control the cross-sectional shape of the edge portion of the chromium-based phase shift film pattern, and it is very difficult to control the line width (CD). Furthermore, in order to solve these problems, the present inventors have intensively studied a method of verticalizing a cross-sectional shape of an edge portion of a phase shift film pattern. So far, a method has been developed to make the film composition (for example, nitrogen content) of the phase shift film to have a gradient to change the etching rate in the thickness direction, or to add additives (such as Al, Ga) to the phase shift film to control the etching time Methods. However, in these methods, it is very difficult to achieve uniformity of transmittance in the entire area of the phase shift mask. Therefore, the present invention was made in view of the above problems, and an object thereof is to provide a phase shift mask substrate capable of patterning a phase shift film into a cross-sectional shape capable of fully exerting a phase shift effect by wet etching, and a method for manufacturing the same. A phase shift mask having a phase shift film pattern capable of fully exerting a phase shift effect and a manufacturing method thereof, particularly a phase for manufacturing a display device capable of patterning the phase shift film into a cross-sectional shape capable of fully exerting the phase shift effect. Light-shifting mask substrate and manufacturing method thereof, phase-shifting mask for manufacturing display device having phase-shifting film pattern capable of fully exerting phase-shifting effect and manufacturing method thereof, and manufacturing of display device using phase-shifting mask method. Another object of the present invention is to provide a phase shift mask substrate capable of patterning a phase shift film into a cross-sectional shape with small CD unevenness by wet etching, a method for manufacturing the same, and a phase having a small CD unevenness. Phase-shifting photomask with phase-shifting film pattern and manufacturing method thereof, particularly phase-shifting photomask substrate for manufacturing display device capable of patterning phase-shifting film into cross-sectional shape with small CD unevenness, manufacturing method thereof, and CD A phase shift film pattern with small unevenness in a phase shift film pattern and a method for manufacturing the same, and a method for manufacturing a display device using the phase shift mask. In addition, an object of the present invention is to provide a phase shift mask substrate with uniform optical characteristics and a manufacturing method thereof, a phase shift mask with uniform optical characteristics and a manufacturing method thereof, and in particular, a phase shift for manufacturing a display device with uniform optical characteristics. Photomask substrate and manufacturing method thereof, phase-shifting mask for manufacturing display device with uniform optical characteristics and manufacturing method thereof, and manufacturing method of display device using the same. [Means for Solving the Problems] In order to solve the problems described above, the present invention has the following configuration. (Composition 1) A phase-shifting photomask base, comprising: a transparent substrate; and a light semi-transmitting film formed on the main surface of the transparent substrate, which has a property of changing the phase of the light exposed and is made of a metal silicide system. Made of a material; and an etching mask film formed on the light semi-transmissive film and composed of a chrome-based material; and a composition gradient region is formed at an interface between the light semi-transmissive film and the etching mask film, and In this composition gradient region, the ratio of the components that slow down the wet etching rate of the light semi-transmissive film increases stepwise and / or continuously in the depth direction. (Structure 2) The phase-shifting mask base of Structure 1, wherein the light semi-transmitting film except the interface between the light semi-transmitting film and the etching mask film, and the light semi-transmitting film and the transparent substrate The composition of parts other than the interface is substantially uniform. (Composition 3) The phase shift mask base of constitution 1 or 2 is characterized in that the light semi-transmitting film is composed of a plurality of layers. (Composition 4) If the phase-shifting mask base of constitution 1 or 2 is characterized in that the metal silicide-based material is a nitride of metal silicide, a nitride of metal silicide, a carbon oxide of metal silicide, Either a nitrogen carbide of a metal silicide or an oxynitride of a metal silicide. (Composition 5) The phase shift mask base of constitution 1 or 2 is characterized in that the component that slows down the wet etching rate is nitrogen or carbon. (Structure 6) The phase-shifting mask substrate of Structure 5 is characterized in that when the component that slows down the wet etching speed is nitrogen, the boundary between the composition gradient region and the etching mask film is In the above-mentioned etching mask film side, when using X-ray photoelectron spectroscopy to perform a composition analysis under a measurement step of 0.5 minutes, nitrogen (N) at a position of silicon (Si) above 1 atomic% was detected for the first time. The maximum value of the ratio (N / Si) to silicon (Si) is 3.0 or more and 30 or less. (Composition 7) The phase-shifting mask base of constitution 1 or 2 is characterized in that the etching mask film has a light-shielding property. (Structure 8) The phase-shifting mask substrate according to Structure 1 or 2, wherein the etching mask film includes a light-shielding layer formed on the light semi-transmissive film side and an anti-reflection layer formed on the light-shielding layer. (Composition 9) The phase-shifting mask base of constitution 1 or 2, characterized in that the etching mask film includes an insulating layer formed in contact with the light semi-transmitting film. (Composition 10) The phase-shifting reticle substrate of constitution 9, wherein the above-mentioned insulating layer is composed of CrCO or CrCON containing less than 50 atomic% of Cr, and has a thickness of 10 nm or more and 50 nm or less. (Structure 11) The phase-shifting mask base of structure 1 or 2 is characterized in that the phase-shifting mask base is a phase-shifting mask base for manufacturing a display device. (Composition 12) A method for manufacturing a phase-shifting mask substrate, comprising: a preparation process, which prepares a transparent substrate; a semi-transmissive film formation process, which is formed on the main surface of the transparent substrate, and is formed by sputtering. Forming a light semi-transmitting film made of a metal silicide material having the property of changing the phase of the exposed light; and an etching mask film forming process, which is formed on the light semi-transmitting film, and is formed by sputtering An etching mask film made of a chromium-based material; and the above-mentioned semi-transmissive film forming process includes a film-forming process of forming a light semi-transmissive film composed of a metal silicide-based material by applying sputtering power under a sputtering gas atmosphere, and The light semi-transmissive film is exposed to a gas atmosphere exposure process including a component that slows down the wet etching rate of the light semi-transmissive film, and the exposure process is performed without exposing the light semi-transmissive film to the atmosphere. After the above-mentioned film formation process, it is continuously performed. (Structure 13) The manufacturing method of the phase shift mask base of Structure 12, wherein the film formation process is performed using a sputtering target containing metal and silicon in a sputtering gas atmosphere containing a mixed gas. The mixed gas includes at least one inert gas selected from the group consisting of helium, neon, argon, krypton, and xenon, and includes a gas selected from the group consisting of nitrogen, nitrogen monoxide, dinitrogen monoxide, and dioxide An active gas containing nitrogen or a nitrogen compound, or an active gas containing a carbon compound containing a carbon dioxide gas or a hydrocarbon gas, of at least one of the group consisting of a nitrogen gas. (Composition 14) The method for manufacturing a phase-shifting mask base according to constitution 12 or 13, characterized in that the above-mentioned exposure process is performed in a gas atmosphere containing nitrogen or a nitrogen compound. (Composition 15) The method for manufacturing a phase-shifting mask base according to constitution 12 or 13, characterized in that the above-mentioned exposure process is performed in a gas atmosphere containing carbon or a carbon compound. (Structure 16) The manufacturing method of the phase-shift mask base according to Structure 12 or 13, characterized in that the phase-shift mask base is a phase-shift mask base for manufacturing a display device. (Composition 17) A phase-shifting photomask, comprising: a transparent substrate; and a light transmissive film pattern formed on the main surface of the transparent substrate by wet etching, and having a phase for changing the phase of the exposed light. And is composed of a metal silicide-based material; and the composition of the light semi-transmissive film pattern except for the upper surface and the interface between the light semi-transmissive film pattern and the transparent substrate is substantially uniform; The cross section of the pattern is composed of upper, lower, and side edges corresponding to the light semi-transmissive film pattern. The contact point between the upper edge and the side edge and the thickness of the film falling from the upper surface is three. The straight line formed by the position of the side edge at the position of two-fifths of the height, and the angle formed by the upper side is in the range of 85 degrees to 120 degrees, and passes through the contact point between the upper side and the side edge and is relative to A position of the first imaginary line perpendicular to the main surface of the transparent substrate, and a position of the side at a position passing a height of one-tenth of the film thickness from the lower surface, with respect to the transparent substrate The width of the second imaginary line perpendicular to the main surface of the above-described film thickness of one-half or less. (Composition 18) A phase shift mask used for manufacturing a display device, comprising: a transparent substrate; and a light semi-transmissive film pattern formed on a main surface of the transparent substrate and having a light for changing exposure The nature of the phase is made of a metal silicide-based material; and the composition of the light semi-transmitting film pattern except for the upper surface and the interface between the light semi-transmitting film pattern and the transparent substrate is substantially uniform. The cross section of the transmissive film pattern is composed of upper, lower, and side edges corresponding to the light semi-transmissive film pattern. The contact points between the upper and lower sides and the film thickness from the upper surface are reduced. The straight line formed by the position of the above-mentioned side on the position of two-thirds of the height is within a range of 85 degrees to 120 degrees with the above-mentioned side, and passes through the contact point between the above-mentioned side and the above-mentioned side and A position of the first imaginary line perpendicular to the main surface of the transparent substrate and a height of one tenth of the thickness of the film rising from the lower surface, and the position of the side with respect to the upper side The width of the second imaginary line perpendicular to the main surface of the transparent substrate of the above one-half or less of the film thickness. (Composition 19) The phase shift mask of constitution 17 or 18, wherein the light semi-transmissive film pattern is composed of a metal silicide nitride film, a metal silicide oxynitride film, a metal silicide carbon oxide, a metal It is composed of silicide oxynitride. (Composition 20) The phase shift mask of constitution 17 or 18, wherein the light semi-transmissive film pattern includes a line and a gap pattern. (Composition 21) The phase shift mask of constitution 17 or 18, wherein the light semi-transmissive film pattern includes a hole pattern. (Composition 22) A method for manufacturing a phase-shifting photomask, comprising: a photoresist pattern forming process, which is formed on an etching mask film constituting the phase-shifting photomask substrate according to any one of 1 to 11, Or forming a photoresist pattern on an etch mask film of the phase shift mask substrate obtained by the method for manufacturing a phase shift mask substrate according to any one of 12 to 16; an etching mask film pattern forming process, It uses the photoresist pattern as a mask to wet-etch the etching mask film to form an etching mask film pattern; and a semi-transparent film pattern forming process, which uses the etching mask film pattern as a mask pair The light semi-transmitting film is subjected to wet etching to form a light semi-transmitting film pattern. (Structure 23) The manufacturing method of the phase shift mask according to Structure 22, wherein the semi-transmissive film pattern forming process is performed by wet etching using an etchant, and the etchant contains a material selected from hydrofluoric acid and hydrofluorosilicic acid. And at least one fluorine compound in ammonium hydrogen fluoride, and at least one oxidant selected from hydrogen peroxide, nitric acid, and sulfuric acid. (Structure 24) The manufacturing method of the phase shift mask according to Structure 22 or 23, wherein the phase shift mask is a phase shift mask for manufacturing a display device. (Composition 25) A method for manufacturing a display device, comprising: a phase-shifting mask configuration process for a substrate with a photoresist film on which a photoresist film is formed on a substrate. A phase shift mask according to any one of the above, or a phase shift mask obtained by the manufacturing method constituting the phase shift mask according to any one of 22 to 24, which is arranged to face the photoresist film; and The resist film exposure process involves irradiating the phase shift mask with the exposure light and exposing the photoresist film. (Structure 26) The manufacturing method of the display device according to Structure 25, wherein the exposure light includes light in a wavelength range of 300 nm to 500 nm. (Structure 27) The manufacturing method of the display device according to Structure 25 or 26, wherein the exposure light is a composite light including i rays, h rays, and g rays. [Effects of the Invention] As described above, the phase-shifting mask substrate according to the present invention, particularly the phase-shifting mask substrate for manufacturing a display device used when manufacturing a display device, has a A light semi-transmissive film made of a metal silicide-based material and an etching mask film made of a chromium-based material formed on the light semi-transmissive film. In the composition gradient region formed at the interface between the light semi-transmitting film and the etching mask film, the ratio of the components that slow down the wet etching rate of the light semi-transmitting film increases stepwise and / or continuously in the depth direction. Therefore, it is possible to obtain a phase-shifting mask substrate capable of patterning a light semi-transmitting film into a cross-sectional shape capable of fully exerting a phase-shifting effect by wet etching. In addition, a phase shift mask substrate capable of patterning a light semi-transmitting film into a cross-sectional shape with small CD unevenness by wet etching can be obtained. In addition, according to the method for manufacturing a phase-shifting mask substrate of the present invention, particularly the method for manufacturing a phase-shifting mask substrate for manufacturing a display device used in manufacturing a display device, a silicon silicide is formed on a main surface of a transparent substrate. A light semi-transmissive film made of a material based material, and an etching mask film made of a chrome-based material is formed on the light semi-transmissive film. The formation of the light semi-transmitting film is performed by forming the light semi-transmitting film and continuously exposing the light semi-transmitting film to the substrate after the film is formed without exposing the light semi-transmitting film to the atmosphere. A gaseous atmosphere of the components of the slow-light semi-transmitting film with a wet etching rate. Therefore, a phase shift mask substrate capable of patterning a light semi-transmitting film into a cross-sectional shape capable of fully exerting a phase shift effect by wet etching can be manufactured. In addition, a phase shift mask substrate capable of patterning a light semi-transmitting film into a cross-sectional shape with small CD unevenness by wet etching can be manufactured. Further, a phase shift mask according to the present invention, particularly a phase shift mask for manufacturing a display device used when manufacturing a display device, includes a metal silicide-based material formed on a main surface of a transparent substrate. Light semi-transmitting film pattern. The composition of the light semi-transmissive film pattern is substantially uniform. Therefore, a phase shift mask having uniform optical characteristics can be obtained. Further, in the cross section of the light semi-transmissive film pattern, a straight line formed by the contact between the contact point of the upper side and the side edge and the position of the side edge at a position two-thirds of the film thickness from the upper surface, and The angle formed is in the range of 85 degrees to 120 degrees. Furthermore, in the cross section of the light semi-transmissive film pattern, the height of the first imaginary line passing through the contact points of the upper side and the side and perpendicular to the main surface of the transparent substrate and one tenth of the film thickness rising from the lower surface The width of the second imaginary line at the position of the side and perpendicular to the main surface of the transparent substrate is equal to or less than one-half of the film thickness. Therefore, it is possible to obtain a phase shift mask having a light semi-transmissive film pattern capable of fully exerting a phase shift effect. In addition, a phase shift mask having a light semi-transmissive film pattern with small CD unevenness can be obtained. The phase shift mask can cope with the miniaturization of line and gap patterns or contact holes. In addition, according to the method for manufacturing a phase-shifting mask of the present invention, particularly the method for manufacturing a phase-shifting mask for manufacturing a display device used when manufacturing a display device, the above-mentioned phase-shifting mask substrate is used or the phase shift The phase shift mask base obtained by the manufacturing method of the mask base manufactures a phase shift mask. Therefore, a phase shift mask having a pattern of a light semi-transmissive film capable of fully exerting a phase shift effect can be manufactured. In addition, a phase shift mask having a light semi-transmissive film pattern with small CD unevenness can be manufactured. The phase shift mask can cope with the miniaturization of line and gap patterns or contact holes. In addition, according to the method for manufacturing a display device of the present invention, a display device is manufactured using the phase shift mask or a phase shift mask obtained by the method for manufacturing a phase shift mask. Therefore, a display device having a fine line and gap pattern or a contact hole can be manufactured.

於說明本發明之實施形態之前，使用模擬結果，對因相移膜圖案之剖面形狀之不同所的相移效果之差異進行說明。 模擬係於開口數(NA)為0.085、同調因子(σ)為0.9、曝光之光為g射線、h射線、i射線之複合光(強度比為g射線︰h射線︰i射線＝0.95︰0.8︰1.0)之曝光條件下進行。模擬係進行2次。 第1次模擬係對具備邊緣部分之剖面形狀為垂直之相移膜圖案的相移光罩(以下，有稱為PSM(A)之情形)、具備邊緣部分之剖面形狀為楔形狀之相移膜圖案的相移光罩(以下，有稱為PSMTP(A)之情形)、二元式光罩(binary mask)(以下，有稱為Bin之情形)進行。詳細而言，相移光罩(PSM(A)及PSMTP(A))成為具有包含相移膜圖案與形成於相移膜圖案上之遮光膜圖案之線圖案、及包含光透過部之間隙圖案的線與間隙圖案之構成。二元式光罩(Bin)成為具有包含遮光膜圖案之線圖案、及包含光透過部之間隙圖案的線與間隙圖案之構成。線圖案之寬度為2.0 μm，間隙圖案之寬度為2.0 μm。相移膜圖案之邊緣部分之寬度為0.5 μm。遮光膜圖案之寬度為1 μm。遮光膜圖案係配置於除邊緣部分以外之相移膜圖案上。 於PSM(A)中，相移膜圖案之邊緣部分對於i射線之透過率為6%，透過相移膜圖案之邊緣部分之光與透過光透過部之光對於i射線之相位差為180度。 於PSMTP(A)中，相移膜圖案之邊緣部分構成為透過率及相位差以0.05 μm之寬度分10個階段地發生變化。構成為10個階段之邊緣部分中、最接近遮光膜圖案之部分對於i射線之透過率為6%，透過最接近遮光膜圖案之部分之光與透過光透過部之光對於i射線的相位差為180度。構成為10個階段之邊緣部分中、最接近光透過部之部分對於i射線之透過率為57.5%，透過最接近光透過部之部分之光與透過光透過部之光對於i射線的相位差為20.19度。再者，就下述實施例中記載之氮矽化鉬膜(MoSiN)而言，構成為10個階段之邊緣部分之假想梯度面之角度為約165度。 圖1係模擬時使用之線與間隙圖案之模式圖。圖1表示PSM(A)中之線與間隙圖案1之一部分。圖1中，顯示位於中央之線圖案2a、隔著間隙圖案3a而位於線圖案2a之左側之線圖案2b、及隔著間隙圖案3b而位於線圖案2a之右側之線圖案2c。位於左右之線圖案2b、2c僅顯示線圖案之一半之寬度。圖1中，對構成線圖案2a、2b、2c之相移膜圖案之邊緣部分4、及遮光膜圖案5標註影線表示。 表1及圖2表示第1次之模擬結果。圖2中，曲線a表示PSM(A)之結果，曲線b表示PSMTP(A)之結果，曲線c表示Bin之結果。圖2之橫軸表示將線圖案之中心設為零時之位置(μm)，縱軸表示光強度。 [表1] 如表1及圖2所示，PSM(A)中，最大光強度為0.43198，最小光強度為0.08452，對比度(最大光強度與最小光強度之差/最大光強度與最小光強度之和)為0.67273。PSMTP(A)中，最大光強度為0.53064，最小光強度為0.13954，對比度為0.58359。Bin中，最大光強度為0.49192，最小光強度為0.12254，對比度為0.60114。 由表1及圖2所示之模擬結果可看出，相移膜圖案之邊緣部分之剖面形狀為垂直之相移光罩(PSM(A))的情形與相移膜圖案之邊緣部分之剖面形狀為楔形狀之相移光罩(PSMTP(A))之情形或二元式光罩(Bin)之情形相比，對比度較高。又，PSMTP(A)之情形較Bin之情形，對比度較低。於PSMTP(A)之情形時，相移膜圖案之邊緣部分為楔形狀，故而隨著接近光透過部而透過率變高且相位差變小。即，隨著接近光透過部而漏光量增加且失去相位效果。因此，PSMTP(A)之情形時，對比度變低。於PSM(A)之情形時，相移膜圖案之邊緣部分為垂直形狀，故而即便接近光透過部亦保持固定之透過率(6%)與相位差(180度)。即，透過率與相位於相移膜圖案之邊緣部分與光透過部之邊界立刻變化。因此，PSM(A)之情形與Bin之情形相比，雖然存在相移膜圖案之邊緣部分上之漏光，但對比度變高。因此，可知藉由使相移膜圖案之邊緣部分之剖面形狀垂直而能充分發揮相移效果。 第2次模擬係對具備邊緣部分之剖面形狀為垂直之相移膜圖案的相移光罩(以下，有稱為PSM(B)之情形)、具備邊緣部分之剖面形狀為楔形狀之相移膜圖案的相移光罩(以下，有稱為PSMTP(B)之情形)、二元式光罩(以下，有稱為Bin之情形)進行。用於第2次模擬之相移光罩(PSM(B)及PSMTP(B))係自用於第1次模擬之PSM(A)及PSMTP(A)中去除遮光膜圖案而成者。詳細而言，PSM(B)及PSMTP(B)成為具有包含相移膜圖案之線圖案、及包含光透過部之間隙圖案的線與間隙圖案之構成。用於第2次模擬之二元式光罩(Bin)係與用於第1次模擬之Bin相同。 表2及圖3表示第2次之模擬結果。圖3中，曲線d表示PSM(B)之結果，曲線e表示PSMTP(B)之結果，曲線f表示Bin之結果。圖3之橫軸表示將線圖案之中心設為零時之位置(μm)，縱軸表示光強度。 [表2] 如表2及圖3所示，PSM(B)中，最大光強度為0.40505，最小光強度為0.05855，對比度為0.74743。PSMTP(B)中，最大光強度為0.49925，最小光強度為0.09713，對比度為0.67426。Bin中，最大光強度為0.49192，最小光強度為0.12254，對比度為0.60114。 由表2及圖3所示之模擬結果可看出，相移膜圖案之邊緣部分之剖面形狀為垂直之相移光罩(PSM(B))的情形與相移膜圖案之邊緣部分之剖面形狀為楔形狀之相移光罩(PSMTP(B))之情形或二元式光罩(Bin)之情形相比，對比度較高。因此，可知藉由使相移膜圖案之邊緣部分之剖面形狀為垂直而能充分發揮相移效果。 以下，對本發明之實施形態之用於製造顯示裝置之相移光罩基底及其製造方法、使用有該相移光罩基底之用於製造顯示裝置之相移光罩及其製造方法、與使用有該相移光罩之顯示裝置之製造方法詳細地進行說明。 實施形態1. 於實施形態1中，對用於製造顯示裝置之相移光罩基底及其製造方法進行說明。 於實施形態1之用於製造顯示裝置之相移光罩基底之製造方法中，進行：準備製程，其係準備透明基板；半透過膜形成製程，其係於透明基板之主表面上，藉由濺鍍而形成由金屬矽化物系材料所構成之光半透過膜；及蝕刻遮罩膜形成製程，其係於光半透過膜上，藉由濺鍍而形成由鉻系材料所構成之蝕刻遮罩膜。 以下，對各製程詳細地進行說明。 1.準備製程 於製造用於製造顯示裝置之相移光罩基底之情形時，首先，準備透明基板。 透明基板之材料只要為對使用之曝光之光具有透光性之材料，則無特別限制。例如，可列舉合成石英玻璃、鈉鈣玻璃、無鹼玻璃。 2.半透過膜形成製程 其次，於透明基板之主表面上，藉由濺鍍而形成由金屬矽化物系材料所構成之光半透過膜。 詳細而言，於該半透過膜形成製程中，首先，進行如下成膜製程，即，於濺鍍氣體氛圍下施加濺鍍功率而形成由金屬矽化物系材料所構成之光半透過膜。其後，在不使光半透過膜曝露於大氣中的情況下，於成膜製程後連續地進行如下曝露製程：使光半透過膜曝露於包含減慢光半透過膜之濕式蝕刻速度之成分之氣體氛圍。 光半透過膜具有改變曝光之光之相位之性質。藉由該性質，使透過光半透過膜之曝光之光與僅透過透明基板之曝光之光之間產生特定之相位差。於曝光之光為包含300 nm以上且500 nm以下之波長範圍之光的複合光之情形時，光半透過膜係以對代表波長之光產生特定之相位差之方式形成。例如，於曝光之光為包含i射線、h射線及g射線之複合光之情形時，光半透過膜係以對於i射線、h射線及g射線之任一者均產生180度之相位差之方式形成。又，為了發揮上述中說明之相移效果，光半透過膜之相位差較佳為對於i射線、h射線及g射線之任一者之代表波長均設定為180度±20度之範圍。進而較佳為，光半透過膜之相位差較理想為對於i射線、h射線及g射線之任一者之代表波長均設定為180度±10度之範圍。又，光半透過膜之透過率於i射線、h射線及g射線之任一者之代表波長下，較佳為1%以上且20%以下。尤佳為，光半透過膜之透過率於i射線、h射線及g射線之任一者之代表波長下，較理想為3%以上且10%以下。 構成光半透過膜之金屬矽化物系材料只要為對曝光之光產生特定之透過率與相位差者，則包含金屬與矽即可，進而亦可包含其他元素。作為其他元素，只要為可控制曝光之光之折射率(n)、消光係數(k)之元素即可，可自選自氧(O)、氮(N)、碳(C)、氟(F)中之至少一種元素中選擇。例如，可列舉金屬矽化物之氧化物、金屬矽化物之氮氧化物、金屬矽化物之氮化物、金屬矽化物之氮碳化物、金屬矽化物之碳氧化物、金屬矽化物之氮氧碳化物等。又，就濕式蝕刻之圖案控制性之觀點而言，構成光半透過膜之金屬矽化物系材料較佳為設為包含金屬、矽、及減慢光半透過膜之濕式蝕刻速度之成分的材料。作為減慢光半透過膜之濕式蝕刻速度之成分，例如，可列舉氮(N)、碳(C)。作為金屬，可列舉鉬(Mo)、鉭(Ta)、鎢(W)、鈦(Ti)、鋯(Zr)等過渡金屬。作為構成光半透過膜之金屬矽化物系材料，例如，可列舉金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氧化物、金屬矽化物之氮碳化物、金屬矽化物之氮氧碳化物。具體而言，可列舉：矽化鉬(MoSi)之氮化物、矽化鉭(TaSi)之氮化物、矽化鎢(WSi)之氮化物、矽化鈦(TiSi)之氮化物、矽化鋯(ZrSi)之氮化物、矽化鉬之氮氧化物、矽化鉭之氮氧化物、矽化鎢之氮氧化物、矽化鈦之氮氧化物、矽化鋯之氮氧化物、矽化鉬之碳氧化物、矽化鉭之碳氧化物、矽化鈦之碳氧化物、矽化鎢之碳氧化物、矽化鋯之碳氧化物、矽化鉬之氮碳化物、矽化鉭之氮碳化物、矽化鈦之氮碳化物、矽化鋯之氮碳化物、矽化鎢之氮碳化物、矽化鉬之氮氧碳化物、矽化鉭之氮氧碳化物、矽化鈦之氮氧碳化物、矽化鎢之氮氧碳化物、矽化鋯之氮氧碳化物。 構成光半透過膜之金屬、矽、氮之組成係根據針對曝光之光的所需之相位差(180度±20度)、透過率(1%以上且20%以下)、濕式蝕刻特性(光半透過膜圖案之剖面形狀或CD不均)、耐化學品性之觀點進行調整。金屬與矽之比率較佳為金屬︰矽＝1︰1以上且1︰9以下。氮之含量較佳為25原子%以上且55原子%以下、進而較佳為30原子%以上且50原子%以下。 光半透過膜之成膜製程係使用包含金屬與矽之濺鍍靶，於如下濺鍍氣體氛圍下進行，該濺鍍氣體氛圍包含具有可控制曝光之光下的折射率(n)、與消光係數(k)之成分的氣體。作為此種氣體，可列舉氧氣(O2 )、一氧化碳氣體(CO)、二氧化碳氣體(CO2 )、氮氣(N2 )、一氧化氮氣體(NO)、二氧化氮氣體(NO2 )、一氧化二氮氣體(N2 O)、烴系氣體(CH4 等)、碳化氟系氣體(CF4 等)、氮化氟系氣體(NF3 等)等活性氣體。又，就濕式蝕刻之圖案控制性之觀點而言，光半透過膜之成膜製程較佳為使用包含金屬與矽之濺鍍靶，於包含具有減慢光半透過膜之濕式蝕刻速度之成分之氣體的濺鍍氣體氛圍下進行。作為減慢光半透過膜之濕式蝕刻速度之成分，如上所述，例如可列舉氮(N)、碳(C)。作為具有減慢光半透過膜之濕式蝕刻速度之成分之氣體，可列舉氮氣、一氧化氮氣體、二氧化氮氣體、一氧化二氮氣體、一氧化碳氣體、二氧化碳氣體、烴系氣體(CH4 等)、碳化氟系氣體(CF4 等)、氮化氟系氣體(NF3 等)等活性氣體。於濺鍍氣體氛圍中，亦可包含作為惰性氣體之氦氣、氖氣、氬氣、氪氣及氙氣等。濺鍍氣體氛圍含有例如包含選自由氦氣、氖氣、氬氣、氪氣及氙氣所組成之群中之至少一種之惰性氣體、及包含選自由氮氣、一氧化氮氣體及二氧化氮氣體所組成之群中之至少一種之活性氣體的混合氣體。 光半透過膜之成膜後之曝露製程係藉由使光半透過膜曝露於包含具有減慢光半透過膜之濕式蝕刻速度之成分之氣體的曝露用氣體氛圍而進行。作為減慢光半透過膜之濕式蝕刻速度之成分，如上所述，例如可列舉氮(N)。作為具有減慢光半透過膜之濕式蝕刻速度之成分之氣體，可列舉氮氣等活性氣體。於曝露用氣體氛圍中亦可包含作為惰性氣體之氦氣、氖氣、氬氣、氪氣、氙氣等。於曝露用氣體氛圍包含氮氣與惰性氣體之混合氣體氛圍之情形時，氮氣相對於惰性氣體之比率(氮氣/惰性氣體)為20%以上，較佳為30%以上。 光半透過膜可為由1層所構成之情形及由複數層所構成之情形之任一者。於光半透過膜由複數層所構成之情形時，光半透過膜之成膜製程及光半透過膜之成膜後之曝露製程係進行複數次。於進行複數次成膜製程之情形時，可縮小當光半透過膜之成膜時對濺鍍靶施加之濺鍍功率。 3.蝕刻遮罩膜形成製程 其次，於光半透過膜上，藉由濺鍍而形成由鉻系材料所構成之蝕刻遮罩膜。 蝕刻遮罩膜可為具有遮光性之情形及具有光半透過性之情形之任一者。構成蝕刻遮罩膜之鉻系材料只要為包含鉻(Cr)者則無特別限制。作為構成蝕刻遮罩膜之鉻系材料，例如，可列舉包含至少一種鉻(Cr)、鉻之氧化物、鉻之氮化物、鉻之碳化物、鉻之氟化物之材料。 該遮罩膜形成製程係使用包含鉻或鉻化合物之濺鍍靶、於含有混合氣體之濺鍍氣體氛圍下進行，該混合氣體例如包含選自由氦氣、氖氣、氬氣、氪氣及氙氣所組成之群中之至少一種之惰性氣體、及包含選自由氧氣、氮氣、二氧化碳氣體、氧化氮系氣體、烴系氣體及氟系氣體所組成之群中之至少一種之活性氣體。 蝕刻遮罩膜可為由1層所構成之情形及由複數層所構成之情形之任一者。於蝕刻遮罩膜由複數層所構成之情形時，例如存在由形成於光半透過膜側之遮光層及形成於遮光層上之抗反射層所構成之積層構造的情形、或由以與光半透過膜接觸之方式形成之絕緣層、形成於絕緣層上之遮光層及形成於遮光層上之抗反射層所構成之積層構造的情形。遮光層可為由1層所構成之情形及由複數層所構成之情形之任一者。作為遮光層，例如可列舉氮化鉻膜(CrN)、碳化鉻膜(CrC)、氮碳化鉻膜(CrCN)。抗反射層可為由1層所構成之情形及由複數層所構成之情形之任一者。作為抗反射層，例如可列舉氮氧化鉻膜(CrON)。絕緣層係由例如包含未達50原子%之Cr之CrCO或CrCON所構成，且具有10 nm以上且50 nm以下之厚度。當對由鉻系材料所構成之蝕刻遮罩膜進行濕式蝕刻時，金屬離子自由金屬矽化物系材料所構成之光半透過膜熔出。此時，產生電子。於以與光半透過膜接觸之方式形成絕緣層之情形時，可防止金屬離子自光半透過膜熔出時產生之電子被供給至蝕刻遮罩膜。因此，可使對蝕刻遮罩膜進行濕式蝕刻時之面內之蝕刻速度均勻。 實施形態1之用於製造顯示裝置之相移光罩基底係藉由此種準備製程、半透過膜形成製程、及蝕刻遮罩膜形成製程而製造。 圖4係表示用於光半透過膜及蝕刻遮罩膜之形成之濺鍍裝置之一例的模式圖。 圖4所示之濺鍍裝置11為連續(inline)式，且由搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL之5個腔室所構成。該等5個腔室依序連續地配置。 搭載於托盤(未圖示)之透明基板12能以特定之搬送速度向箭頭S之方向依序搬送至搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL。又，搭載於托盤(未圖示)之透明基板12可向與箭頭S相反之方向依序返回至搬出腔室ULL、第2濺鍍腔室SP2、緩衝腔室BU、第1濺鍍腔室SP1、及搬入腔室LL。 搬入腔室LL與第1濺鍍腔室SP1、第2濺鍍腔室SP2與搬出腔室ULL係藉由間隔板所間隔。第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2未由GV(閘閥)所間隔，而是由3個腔室連結而成之較大之容器所構成。 又，搬入腔室LL及搬出腔室ULL可藉由間隔板自濺鍍裝置11之外部間隔。 搬入腔室LL、緩衝腔室BU、及搬出腔室ULL係與進行排氣之排氣裝置(未圖示)連結。 於第1濺鍍腔室SP1中，於搬入腔室LL側配置有用以形成光半透過膜之包含金屬與矽之第1濺鍍靶13，於第1濺鍍靶13附近配置有第1氣體導入口GA1(未圖示)。又，於第1濺鍍腔室SP1中，於緩衝腔室BU側配置有用以形成蝕刻遮罩膜之包含鉻之第2濺鍍靶14，於第2濺鍍靶14附近配置有第2氣體導入口GA2(未圖示)。 於第2濺鍍腔室SP2中，於緩衝腔室BU側配置有用以形成蝕刻遮罩膜之包含鉻之第3濺鍍靶15，於第3濺鍍靶15附近配置有第3氣體導入口GA31(未圖示)。又，於第2濺鍍腔室SP2中，於搬出腔室ULL側配置有用以形成蝕刻遮罩膜之包含鉻之第4濺鍍靶16，於第4濺鍍靶附近配置有第4氣體導入口GA4(未圖示)。 圖4中，對第1濺鍍靶13、第2濺鍍靶14、第3濺鍍靶、及第4濺鍍靶15標註影線表示。 於使用圖4所示之連續式之濺鍍裝置11，形成光半透過膜及蝕刻遮罩膜之情形時，首先，為了形成光半透過膜，而將搭載於托盤(未圖示)之透明基板12搬入至搬入腔室LL。 於使濺鍍裝置11之內部成為特定之真空度後，自第1氣體導入口GA1導入特定之流量之上述活性氣體、具體而言為包含具有減慢光半透過膜之濕式蝕刻速度之成分之氣體的濺鍍氣體，又，自第3氣體導入口GA3及第4氣體導入口GA4之至少一者向第2濺鍍腔室SP2導入包含具有減慢光半透過膜之濕式蝕刻速度之成分之氣體的曝露用氣體，對第1濺鍍靶13施加特定之濺鍍功率。濺鍍功率之施加、濺鍍氣體之導入、曝露用氣體之導入係持續至透明基板12被搬送至搬出腔室ULL為止。 其後，將搭載於托盤(未圖示)之透明基板12以特定之搬送速度向箭頭S之方向依序搬送至搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL。當透明基板12通過第1濺鍍腔室SP1之第1濺鍍靶13附近時，藉由反應性濺鍍，於透明基板12之主表面上形成特定之膜厚之由金屬矽化物系材料所構成之光半透過膜。又，於透明基板12通過第2濺鍍腔室SP2期間，光半透過膜被曝露於包含具有減慢光半透過膜之濕式蝕刻速度之成分之氣體的曝露用氣體氛圍。 於進行第2層光半透過膜之成膜之情形時，將搭載於托盤(未圖示)之透明基板12向與箭頭S相反之方向依序返回至搬出腔室ULL、第2濺鍍腔室SP2、緩衝腔室BU、第1濺鍍腔室SP1、及搬入腔室LL，並再次進行上述光半透過膜之成膜。於將透明基板12返回至搬入腔室LL時，較佳為對第1濺鍍腔室SP1及第2濺鍍腔室SP2導入包含具有減慢光半透過膜之濕式蝕刻速度之成分之氣體的曝露用氣體。藉此，於將透明基板12返回至搬入腔室LL期間，可將光半透過膜曝露於包含具有減慢光半透過膜之濕式蝕刻速度之成分之氣體的曝露用氣體氛圍。 進行第3層及第4層光半透過膜之成膜之情形時亦同樣地進行。 當於以此種方式在透明基板12之主表面上形成光半透過膜後，不將透明基板12取出至濺鍍裝置11之外部而連續地形成蝕刻遮罩膜的情形時，將搭載於托盤(未圖示)之透明基板12向與箭頭S相反之方向依序返回至搬出腔室ULL、第2濺鍍腔室SP2、緩衝腔室BU、第1濺鍍腔室SP1、及搬入腔室LL。另一方面，當於形成光半透過膜後暫且將透明基板12取出至濺鍍裝置11之外部後，形成蝕刻遮罩膜的情形時，於將搭載於托盤(未圖示)之透明基板12搬入至搬入腔室LL後，如上所述，使濺鍍裝置11之內部達到特定之真空度。 於形成由遮光層與抗反射層所構成之積層構造之蝕刻遮罩膜之情形時，其後，於使濺鍍裝置11之內部達到特定之真空度之狀態下，自第2氣體導入口GA2導入特定之流量之濺鍍氣體，並對第2濺鍍靶14施加特定之濺鍍功率。又，自第3氣體導入口GA3導入特定之流量之濺鍍氣體，並對第3濺鍍靶15施加特定之濺鍍功率。又，自第4氣體導入口GA4導入特定之流量之濺鍍氣體，並對第4濺鍍靶16施加特定之濺鍍功率。濺鍍功率之施加、濺鍍氣體之導入係持續至透明基板12被搬送至搬出腔室ULL為止。 其後，將搭載於托盤(未圖示)之透明基板12以特定之搬送速度向箭頭S之方向依序搬送至搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL。當透明基板12通過第1濺鍍腔室SP1之第2濺鍍靶14附近時，藉由反應性濺鍍，於光半透過膜上使特定之膜厚之由鉻系材料所構成之遮光層成膜。又，當透明基板12通過第2濺鍍腔室SP2之第3濺鍍靶15及第4濺鍍靶16附近時，藉由反應性濺鍍，於遮光層上使特定之膜厚之由鉻系材料所構成之遮光層或抗反射層成膜。 於在光半透過膜上形成由遮光層與抗反射層所構成之積層構造之蝕刻遮罩膜後，將透明基板12取出至濺鍍裝置11之外部。 另一方面，於形成由絕緣層、遮光層及抗反射層所構成之積層構造之蝕刻遮罩膜之情形時，於在透明基板12上形成光半透過膜後，於使濺鍍裝置11之內部達到特定之真空度之狀態下，自第2氣體導入口GA2導入特定之流量之濺鍍氣體，並對第2濺鍍靶14施加特定之濺鍍功率。 其後，將搭載於托盤(未圖示)之透明基板12以特定之搬送速度向箭頭S之方向依序搬送至搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL。當透明基板12通過第1濺鍍腔室SP1之第2濺鍍靶14附近時，藉由反應性濺鍍，於光半透過膜上使特定之膜厚之由鉻系材料所構成之絕緣層成膜。 其後，為了進行遮光層及抗反射層之成膜，而將搭載於托盤(未圖示)之透明基板12向與箭頭S相反之方向依序返回至搬出腔室ULL、第2濺鍍腔室SP2、緩衝腔室BU、第1濺鍍腔室SP1、及搬入腔室LL，如上所述，使遮光層及抗反射層成膜。 於在光半透過膜上形成由絕緣層、遮光層及抗反射層所構成之積層構造之蝕刻遮罩膜後，將透明基板12取出至濺鍍裝置11之外部。 以此種方式製造而成之實施形態1之用於製造顯示裝置之相移光罩基底具備透明基板、形成於透明基板之主表面上之由金屬矽化物系材料所構成之光半透過膜、及形成於光半透過膜上之由鉻系材料所構成之蝕刻遮罩膜，且於光半透過膜與蝕刻遮罩膜之界面形成有組成梯度區域。 以下，參照表示針對實施例1之相移光罩基底之、利用X射線光電子光譜法(XPS)所得之深度方向之組成分析結果的圖5進行說明。 組成梯度區域P係於針對相移光罩基底之、利用XPS所得之深度方向之組成分析結果中，由光半透過膜所引起之矽(矽：Si)波峰及鉬(Mo)波峰出現後直至由蝕刻遮罩膜所引起之鉻(Cr)波峰消失為止的區域。 於組成梯度區域P內，減慢光半透過膜之濕式蝕刻速度之成分(圖5中為氮(N))之比率朝向深度方向階段性及/或連續性地單調遞增。 又，於組成梯度區域P內，氧之比率與組成均勻區域Q中之氧之比率幾乎未改變，實質上均勻地包含。組成梯度區域P中之氧之比率(含量)為20原子%以下，較佳為10原子%以下，進而較佳為5原子%以下。 又，組成梯度區域P中與上述蝕刻遮罩膜之邊界上之氮(N)相對於矽(Si)之比率(N/Si)之最大值為3.0以上且30以下，較佳為3.5以上且25以下，進而較佳為4.0以上且20以下。其中，上述邊界係設為當將上述相移光罩基底自上述蝕刻遮罩膜側利用X射線光電子光譜法，於測定步進為0.5分鐘之條件下進行組成分析時，初次檢測到1原子%以上之矽(Si)的位置。 光半透過膜之組成實質上均勻。然而，於光半透過膜與蝕刻遮罩膜之界面形成有上述組成梯度區域P，於光半透過膜與透明基板之界面亦形成有組成梯度之區域，故而該等部分之組成並不均勻。組成均勻區域Q係於針對相移光罩基底之利用XPS所得之深度方向之組成分析結果中，因蝕刻遮罩膜所引起之鉻(Cr)波峰消失後直至因透明基板所引起之氧(O)波峰出現為止的區域。 於組成均勻區域Q中，鉬(Mo)、矽(Si)及減慢光半透過膜之濕式蝕刻速度之成分(圖5中為氮(N))各自的比率之變動為5原子%以下，較佳為3原子%以下。 於光半透過膜由複數層所構成之情形時，各層之界面(圖5中於濺鍍時間為25分鐘時)中減慢光半透過膜之濕式蝕刻速度之成分(圖5中為氮(N))之組成相對於各層之厚度方向之中心附近中減慢光半透過膜之濕式蝕刻速度之成分(圖5中，氮(N))之組成的減少為3原子%以下，較佳為2原子%以下。 根據該實施形態1之用於製造顯示裝置之相移光罩基底之製造方法，於透明基板之主表面上形成由金屬矽化物系材料所構成之光半透過膜，於光半透過膜上形成由鉻系材料所構成之蝕刻遮罩膜。光半透過膜之形成係藉由如下方式進行：形成光半透過膜，並在不使光半透過膜曝露於大氣中的情況下，於成膜後連續地使光半透過膜曝露於包含減慢光半透過膜之濕式蝕刻速度之成分之氣體氛圍。藉由在成膜後連續地使光半透過膜曝露於包含減慢光半透過膜之濕式蝕刻速度之成分之氣體氛圍，可防止減慢濕式蝕刻速度之成分自光半透過膜之表面脫附。因此，藉由濕式蝕刻，能製造一種可將光半透過膜圖案化為能充分發揮相移效果之接近垂直之剖面形狀的相移光罩基底。又，藉由濕式蝕刻，能製造一種可將光半透過膜圖案化為CD不均較小之剖面形狀的相移光罩基底。 又，根據該實施形態1之用於製造顯示裝置之相移光罩基底，具備形成於透明基板之主表面上之由金屬矽化物系材料所構成之光半透過膜、及形成於光半透過膜上之由鉻系材料所構成之蝕刻遮罩膜。在形成於光半透過膜與蝕刻遮罩膜之界面之組成梯度區域P內，減慢光半透過膜之濕式蝕刻速度之成分之比率朝向深度方向階段性及/或連續性地增加。因此，藉由濕式蝕刻，能獲得一種可將光半透過膜圖案化為能充分發揮相移效果之接近垂直之剖面形狀的相移光罩基底。又，藉由濕式蝕刻，能獲得一種可將光半透過膜圖案化為CD不均較小之剖面形狀的相移光罩基底。 實施形態2. 於實施形態2中，對用於製造顯示裝置之相移光罩及其製造方法進行說明。 於實施形態2之用於製造顯示裝置之相移光罩之製造方法中，首先，進行光阻劑圖案形成製程，即，於藉由實施形態1中說明之用於製造顯示裝置之相移光罩基底之製造方法所獲得的相移光罩基底之蝕刻遮罩膜上、或實施形態1中說明之用於製造顯示裝置之相移光罩基底之蝕刻遮罩膜上，形成光阻劑圖案。 詳細而言，於該光阻劑圖案形成製程中，首先，於蝕刻遮罩膜上形成光阻劑膜。其後，對光阻劑膜描繪特定之尺寸之圖案。其後，以特定之顯影液對光阻劑膜進行顯影，形成光阻劑圖案。 作為對光阻劑膜進行描繪之圖案，可列舉線與間隙圖案或孔圖案。 其次，進行蝕刻遮罩膜圖案形成製程，即，以光阻劑圖案為遮罩對蝕刻遮罩膜進行濕式蝕刻而形成蝕刻遮罩膜圖案。 對蝕刻遮罩膜進行濕式蝕刻之蝕刻液只要為可對蝕刻遮罩膜選擇性地進行蝕刻者則無特別限制。具體而言，可列舉包含硝酸鈰(Ⅱ)銨與過氯酸之蝕刻液。 其次，進行半透過膜圖案形成製程，即，以蝕刻遮罩膜圖案為遮罩對光半透過膜進行濕式蝕刻而形成光半透過膜圖案。 對光半透過膜進行濕式蝕刻之蝕刻液只要為可對光半透過膜選擇性地進行蝕刻者則無特別限制。例如，可列舉包含選自氫氟酸、氫氟矽酸、及氟化氫銨中之至少一種氟化合物、及選自過氧化氫、硝酸、及硫酸中之至少一種氧化劑的蝕刻液。具體而言，可列舉將氟化氫銨與過氧化氫之混合溶液以純水稀釋所得之蝕刻液。 於製造在半透過膜圖案上具有遮光膜圖案之類型之相移光罩之情形時，於半透過膜圖案形成後，將蝕刻遮罩膜圖案圖案化為窄於光半透過膜圖案之特定之圖案。該情形時，光半透過膜圖案具有改變曝光之光之相位之性質，蝕刻遮罩膜圖案具有遮光性。 於製造在半透過膜圖案上不具有遮光膜圖案之類型之相移光罩之情形時，於半透過膜圖案形成後，剝離蝕刻遮罩膜圖案。該情形時，光半透過膜圖案具有改變曝光之光之相位之性質。 藉由此種光阻劑圖案形成製程、蝕刻遮罩膜圖案形成製程、及半透過膜圖案形成製程，製造用於製造顯示裝置之相移光罩。 以此種方式製造而成之實施形態2之用於製造顯示裝置之相移光罩具備透明基板、及形成於透明基板之主表面上之由金屬矽化物系材料所構成之光半透過膜圖案。於在半透過膜圖案上具有遮光膜圖案之類型之情形時，進而具備形成於光半透過膜圖案上之由鉻系材料所構成之蝕刻遮罩膜圖案。配置有光半透過膜圖案之部分構成相移部，透明基板露出之部分構成光透過部。 作為光半透過膜圖案，可列舉線與間隙圖案或孔圖案。 光半透過膜圖案具有改變曝光之光之相位之性質。藉由該性質，於透過配置有光半透過膜圖案之相移部的曝光之光與透過透明基板露出之光透過部的曝光之光之間產生特定之相位差。於曝光之光為包含300 nm以上且500 nm以下之波長範圍之光之複合光之情形時，光半透過膜圖案對代表波長之光產生特定之相位差。例如，於曝光之光為包含i射線、h射線及g射線之複合光之情形時，光半透過膜圖案對於i射線、h射線及g射線之任一者均產生180度之相位差。與上述同樣地，光半透過膜圖案之相位差較佳為對於i射線、h射線及g射線之任一者之代表波長設定為180度±20度之範圍。進而較佳為，光半透過膜之相位差較理想為對於i射線、h射線及g射線之任一者之代表波長設定為180度±10度之範圍。又，光半透過膜之透過率於i射線、h射線及g射線之任一者之代表波長下，較佳為1%以上且20%以下。尤佳為光半透過膜之透過率於i射線、h射線及g射線之任一者之代表波長下，較理想為3%以上且10%以下。 又，本發明之用於製造顯示裝置之相移光罩係用於等倍曝光之投影曝光而充分發揮相移效果。尤其是作為其曝光環境，開口數(NA)較佳為0.06～0.15、更佳為0.08～0.10，同調因子(σ)較佳為0.5～1.0。 光半透過膜圖案只要為對曝光之光產生特定之透過率與相位差者，則包含金屬與矽即可，進而亦可包含其他元素。作為其他元素，只要為可控制曝光之光之折射率(n)、消光係數(k)之元素即可，自選自氧(O)、氮(N)、碳(C)、氟(F)中之至少一種元素中選擇。例如，可列舉金屬矽化物之氧化物、金屬矽化物之氮氧化物、金屬矽化物之氮化物、金屬矽化物之氮碳化物、金屬矽化物之氮氧碳化物等。又，就濕式蝕刻之圖案控制性之觀點而言，光半透過膜圖案較佳為由包含金屬、矽、及減慢光半透過膜之濕式蝕刻速度之成分的金屬矽化物系材料所構成。作為減慢光半透過膜之濕式蝕刻速度之成分，例如，可列舉氮(N)、碳(C)。作為金屬，可列舉鉬(Mo)、鉭(Ta)、鎢(W)、鈦(Ti)等過渡金屬。作為構成半透過膜圖案之金屬矽化物系材料，例如，可列舉金屬矽化物氮化物、金屬矽化物氮氧化物、金屬矽化物之碳氧化物、金屬矽化物之氮碳化物、金屬矽化物之氮氧碳化物。構成光半透過圖案之金屬、矽、氮之組成係根據針對曝光之光之所需之相位差(180度±20度)、透過率(1%以上且20%以下)、濕式蝕刻特性(光半透過膜圖案之剖面形狀或CD不均)、耐化學品性之觀點進行調整。金屬與矽之比率較佳為金屬︰矽＝1︰1以上且1︰9以下。氮之含量較佳為25原子%以上且55原子%以下、進而較佳為30原子%以上且50原子%以下。 光半透過膜圖案之組成朝向膜之深度方向實質上均勻。然而，於光半透過膜圖案之上表面形成有上述組成梯度區域，於光半透過膜圖案與透明基板之界面亦形成有組成梯度之區域，故而該等部分之組成並不均勻。 蝕刻遮罩膜圖案係由包含鉻(Cr)之鉻系材料所構成。作為構成蝕刻遮罩膜圖案之鉻系材料，例如，可列舉氮化鉻(CrN)、碳化鉻(CrC)、氮碳化鉻(CrCN)、氮氧化鉻(CrON)、氧碳化鉻(CrCO)、氮氧碳化鉻(CrCON)。 以下，參照表示實施例1之相移光罩之剖面照片之圖7及表示實施例2之相移光罩之剖面照片之圖8進行說明。 光半透過膜圖案之剖面係由對應於光半透過膜圖案之上表面、下表面及側面之上邊、下邊及側邊23所構成。於圖7及圖8中，輔助線21表示對應於光半透過膜圖案之上表面之上邊之位置，輔助線22表示對應於光半透過膜圖案之下表面之下邊之位置。該情形時，上邊與側邊之接點26與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置27連成的直線、與上邊所成之角度θ為85度至120度之範圍內。於圖7中，輔助線24表示自上表面下降膜厚之三分之二之高度之位置。又，通過上邊與側邊23之接點26且相對於透明基板之主表面垂直之第1假想線29、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置28且相對於透明基板之主表面垂直之第2假想線30的寬度(以下，有稱為底寬之情形)D為膜厚之二分之一以下。於圖8中，輔助線25表示自下表面上升膜厚之十分之一之高度之位置。 相移光罩亦可於光半透過膜圖案上具有對曝光之光進行遮光之遮光膜圖案。於在光半透過膜圖案上具有遮光膜圖案之情形時，易於藉由曝光機識別光罩圖案。又，可防止因透過光半透過膜圖案之曝光之光所致的光阻劑膜之減膜。 根據該實施形態2之用於製造顯示裝置之相移光罩之製造方法，使用藉由實施形態1中說明之用於製造顯示裝置之相移光罩基底之製造方法所獲得的相移光罩基底、或實施形態1中說明之用於製造顯示裝置之相移光罩基底製造相移光罩。因此，能製造一種具有能充分發揮相移效果之接近垂直之剖面形狀之光半透過膜圖案的相移光罩。又，能製造一種具有底寬D較小、CD不均較小之光半透過膜圖案的相移光罩。該相移光罩可應對線與間隙圖案或接觸孔之微細化。 根據該實施形態2之用於製造顯示裝置之相移光罩，具備形成於透明基板之主表面上之由金屬矽化物系材料所構成之光半透過膜圖案。該光半透過膜圖案之組成遍及光半透過膜圖案之深度方向而實質上均勻。因此，能獲得光學特性均勻之相移光罩。又，於該光半透過膜圖案之剖面中，上邊與側邊之接點26與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置27連成的直線、與上邊所成之角度θ位於85度至120度之範圍內。進而，於光半透過膜圖案之剖面中，通過上邊與側邊之接點26且相對於透明基板之主表面垂直之第1假想線29、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置28且相對於透明基板之主表面垂直之第2假想線30的寬度D為膜厚之二分之一以下。因此，能獲得一種具有能充分發揮相移效果之接近垂直之剖面形狀之光半透過膜圖案的相移光罩。又，能獲得一種具有底寬D較小、CD不均較小之光半透過膜圖案的相移光罩。該相移光罩可應對線與間隙圖案或接觸孔之微細化。 實施形態3. 於實施形態3中，對顯示裝置之製造方法進行說明。 於實施形態3之顯示裝置之製造方法中，首先，進行相移光罩配置製程，即，對在基板上形成有光阻劑膜之附光阻劑膜之基板，將以實施形態2中說明之用於製造顯示裝置之相移光罩之製造方法所獲得的相移光罩或實施形態2中說明之用於製造顯示裝置之相移光罩對向於光阻劑膜而配置。 其次，進行光阻劑膜曝光製程，即，對相移光罩照射曝光之光，對光阻劑膜進行曝光。 曝光之光例如為包含300 nm以上且500 nm以下之波長範圍之光的複合光。具體而言，為包含i射線、h射線及g射線之複合光。又，作為顯示裝置之製造時之曝光，較佳為等倍曝光之投影曝光。關於曝光環境，開口數(NA)較佳為0.06～0.15、更佳為0.08～0.10，同調因子(σ)較佳為0.5～1.0。 根據該實施形態3之顯示裝置之製造方法，使用藉由實施形態2中說明之用於製造顯示裝置之相移光罩之製造方法所獲得的相移光罩、或實施形態2中說明之用於製造顯示裝置之相移光罩製造顯示裝置。因此，能製造一種具有微細之線與間隙圖案或接觸孔之顯示裝置。 [實施例] 以下，基於實施例對本發明更具體地進行說明。 實施例1. A.相移光罩基底及其製造方法 為了製造實施例1之相移光罩基底，首先，準備3345尺寸(330 mm×450 mm×5 mm)之合成石英玻璃基板作為透明基板12。 其後，將合成石英玻璃基板使主表面朝向下側搭載於托盤(未圖示)，搬入至圖4所示之連續式之濺鍍裝置11之搬入腔室LL。於第1濺鍍腔室SP1中，於搬入腔室LL側配置有包含矽化鉬(Mo︰Si＝1︰4)之濺鍍靶作為第1濺鍍靶13。又，於第1濺鍍腔室SP1中，於緩衝腔室BU側配置有包含鉻之濺鍍靶作為第2濺鍍靶14。又，於第2濺鍍腔室SP2中，於緩衝腔室BU側配置有包含鉻之濺鍍靶作為第3濺鍍靶15，於搬出腔室ULL側配置有包含鉻之濺鍍靶作為第4濺鍍靶16。 為了在合成石英玻璃基板之主表面上形成光半透過膜，首先，自配置於第1濺鍍腔室SP1之第1濺鍍靶13附近之第1氣體導入口GA1導入氬氣(Ar)氣體與氮氣(N2 )氣體之混合氣體(Ar：50 sccm，N2 ：90 sccm)，對第1濺鍍靶13施加8.0 kW之濺鍍功率。又，自配置於第2濺鍍腔室SP2之第3濺鍍靶15附近之第3氣體導入口GA3及配置於第4濺鍍靶16附近之第4氣體導入口GA4導入氬氣(Ar)氣體與氮氣(N2 )氣體之混合氣體(Ar：50 sccm，N2 ：90 sccm)。對第1濺鍍靶13施加濺鍍功率、自第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體、以及自第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體係持續至合成石英玻璃基板被搬送至搬出腔室ULL為止。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向箭頭S之方向依序搬送至搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL。再者，合成石英玻璃基板之搬送速度係設為400 mm/分鐘。當合成石英玻璃基板通過第1濺鍍腔室SP1之第1濺鍍靶13附近時，藉由反應性濺鍍，於合成石英玻璃基板之主表面上形成膜厚55.0 nm之包含氮矽化鉬膜(MoSiN)之第1層光半透過膜。於合成石英玻璃基板通過第2濺鍍腔室SP2期間，第1層光半透過膜被曝露於Ar氣體與N2 氣體之混合氣體氛圍。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向與箭頭S相反之方向依序搬送至搬出腔室ULL、第2濺鍍腔室SP2、緩衝腔室BU、第1濺鍍腔室SP1、及搬入腔室LL，返回至搬入腔室LL。於將合成石英玻璃基板返回至搬入腔室LL期間，自第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體(Ar：50 sccm，N2 ：90 sccm)，自第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體(Ar：50 sccm，N2 ：90 sccm)，將第1層光半透過膜曝露於Ar氣體與N2 氣體之混合氣體氛圍。 其後，對第1濺鍍靶13施加濺鍍功率、自第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體、以及自第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體，藉由與上述方法相同之方法，於第1層光半透過膜上形成膜厚55.0 nm之包含氮矽化鉬膜(MoSiN)之第2層光半透過膜，並於成膜後，將第2層光半透過膜曝露於Ar氣體與N2 氣體之混合氣體氛圍。 以此種方式，於合成石英玻璃基板之主表面上形成包含2層氮矽化鉬膜(MoSiN)之合計膜厚110 nm之光半透過膜。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向與箭頭S相反之方向搬送，返回至搬入腔室LL。於將合成石英玻璃基板返回至搬入腔室LL期間，藉由與上述方法相同之方法，將第2層光半透過膜曝露於Ar氣體與N2 氣體之混合氣體氛圍。 其次，於光半透過膜上形成成為蝕刻遮罩膜之遮光層、抗反射層。遮光層、抗反射層係以對特定波長(例如，g射線)之膜面反射率成為15%以下、光學濃度OD(Optical Density)成為3.0以上的方式，調整導入至第2濺鍍靶14、第3濺鍍靶15、第4濺鍍靶16之鉻靶附近之第2氣體導入口GA2、第3氣體導入口GA3、第4氣體導入口4之氣體之種類、流量、及合成石英玻璃基板之搬送速度，進而適當調整對各濺鍍靶施加之濺鍍功率。自第2氣體導入口GA2係導入Ar氣體與N2 氣體之混合氣體，自第3氣體導入口GA3係導入Ar氣體與甲烷(CH4 )氣體之混合氣體，自第4氣體導入口GA4係導入Ar氣體與一氧化氮(NO)氣體之混合氣體。再者，對各濺鍍靶施加濺鍍功率、自各氣體導入口導入混合氣體係持續至合成石英玻璃被搬送至搬出腔室ULL為止。再者，合成石英玻璃基板之搬送速度係設為400 mm/分鐘。 其結果為，於光半透過膜上形成包含膜厚25.0 nm之氮化鉻膜(CrN)與膜厚70.0 nm之氮碳化鉻膜(CrCN)之積層膜之遮光層、及包含膜厚20.0 nm之氮氧化鉻膜(CrON)之抗反射層的積層膜。 以此種方式，形成了於光半透過膜上依次形成有包含CrN與CrCN之積層膜之遮光層、包含CrON之抗反射層的積層構造之蝕刻遮罩膜。 其後，利用間隔板將第2濺鍍腔室與搬出腔室完全間隔後，使搬出腔室返回至大氣壓狀態，自濺鍍裝置11取出形成有光半透過膜與蝕刻遮罩膜之合成石英玻璃基板。 以此種方式，獲得在合成石英玻璃基板上形成有光半透過膜與蝕刻遮罩膜之相移光罩基底。 藉由日本Lasertec公司製造之MPM-100，對所獲得之相移光罩基底之光半透過膜測定透過率、相位差。於光半透過膜之透過率、相位差之測定中，使用有安裝於同一之托盤製作而成的於合成石英玻璃基板之主表面上成膜有2層氮矽化鉬膜(MoSiN)(合計膜厚110 nm)之附光半透過膜之基板(虛設基板)。光半透過膜之透過率、相位差係於形成蝕刻遮罩膜之前自搬出腔室ULL取出附光半透過膜之基板(虛設基板)而進行測定。其結果為，透過率為5.2%(波長：365 nm)，相位差為180度(波長：365 nm)。 又，藉由島津製作所公司製造之分光光度計SolidSpec-3700，對所獲得之相移光罩基底測定膜面反射率、光學濃度。相移光罩基底(蝕刻遮罩膜)之膜面反射率為10.0%(波長：436 nm)，光學濃度OD為4.0(波長：436 nm)。可知該蝕刻遮罩膜作為膜表面上之反射率較低之遮光膜發揮功能。 又，對所獲得之相移光罩基底，利用X射線光電子光譜法(XPS)進行深度方向之組成分析。圖5係表示針對實施例1之相移光罩基底的利用XPS所得之深度方向之組成分析結果。圖5之橫軸表示濺鍍時間(分鐘)，縱軸表示含量(原子%)。圖5中，曲線a表示矽(Si)之含量變化，曲線b表示氮(N)之含量變化，曲線c表示氧(O)之含量變化，曲線d表示碳(C)之含量變化，曲線e表示鉻(Cr)之含量變化，曲線f表示鉬(Mo)之含量變化。 如圖5所示，於針對相移光罩基底的利用XPS所得之深度方向之組成分析結果中，於作為由光半透過膜所引起之矽(Si)波峰及鉬(Mo)波峰出現後直至由蝕刻遮罩膜所引起之鉻(Cr)波峰消失為止之區域的組成梯度區域P內，減慢光半透過膜之濕式蝕刻速度之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)階段性及/或連續性地增加。 又，於組成梯度區域P內，氧之含量為5原子%以下。 又，組成梯度區域P中之蝕刻遮罩膜側之界面上之氮(N)相對於矽(Si)之比率之最大值為3.7。 於由蝕刻遮罩膜所引起之鉻(Cr)波峰消失後直至由合成石英玻璃基板所引起之氧(O)波峰出現為止之組成均勻區域Q中，鉬(Mo)之含量為平均15原子%、矽(Si)之含量為平均38原子%、氮(N)之含量為平均45原子%、氧(O)之含量為2原子%以下，各者之含量之變動為5原子%以下。 於上述相移光罩基底之製造方法中，於維持特定之真空度之狀態下連續地形成光半透過膜與蝕刻遮罩膜。為了確實地獲得本案發明之效果，較佳為於維持特定之真空度之狀態下連續地形成光半透過膜與蝕刻遮罩膜。藉由在維持特定之真空度之狀態下形成光半透過膜與蝕刻遮罩膜，可減小自光半透過膜之最表面起到達合成石英玻璃基板為止之組成之變動。 再者，即便於形成光半透過膜後將其於大氣中保管、或者於形成蝕刻遮罩膜前將光半透過膜洗淨，只要為固定之範圍之組成變化，便能獲得與實施例1同樣之效果。 B.相移光罩及其製造方法 為使用以上述方式製造而成之相移光罩基底製造相移光罩，首先，於相移光罩基底之蝕刻遮罩膜上使用光阻劑塗佈裝置塗佈光阻劑膜。 其後，經過加熱、冷卻製程，形成膜厚1000 nm之光阻劑膜。 其後，使用雷射描繪裝置描繪光阻劑膜，經過顯影、沖洗製程，於蝕刻遮罩膜上形成線圖案之寬度為2.0 μm及間隙圖案之寬度為2.0 μm之線與間隙圖案之光阻劑圖案。 其後，以光阻劑圖案為遮罩，藉由包含硝酸鈰(Ⅱ)銨與過氯酸之鉻蝕刻液對蝕刻遮罩膜進行濕式蝕刻，形成蝕刻遮罩膜圖案。 其後，以蝕刻遮罩膜圖案為遮罩，藉由將氟化氫銨與過氧化氫之混合溶液以純水稀釋所得之矽化鉬蝕刻液對光半透過膜進行濕式蝕刻，形成光半透過膜圖案。 其後，剝離光阻劑圖案。 其後，使用光阻劑塗佈裝置，以覆蓋蝕刻遮罩膜圖案之方式塗佈光阻劑膜。 其後，經過加熱、冷卻製程，形成膜厚1000 nm之光阻劑膜。 其後，使用雷射描繪裝置描繪光阻劑膜，經過顯影、沖洗製程，於蝕刻遮罩膜圖案上形成線圖案之寬度為1.0 μm之光阻劑圖案。 其後，以光阻劑圖案為遮罩，藉由包含硝酸鈰(Ⅱ)銨與過氯酸之鉻蝕刻液對蝕刻遮罩膜圖案進行濕式蝕刻，形成窄於光半透過膜圖案之寬度之蝕刻遮罩膜圖案。 其後，剝離光阻劑圖案。 以此種方式，獲得在合成石英玻璃基板上形成有光半透過膜圖案與窄於光半透過膜圖案之寬度之蝕刻遮罩膜圖案的相移光罩。 利用掃描式電子顯微鏡對所獲得之相移光罩之平面及剖面進行觀察。於以下實施例及比較例中，於相移光罩之平面及剖面之觀察中使用掃描式電子顯微鏡。圖6係實施例1之相移光罩之平面照片。圖7係實施例1之相移光罩之剖面照片。圖6、7中，QZ表示合成石英玻璃基板，PS表示光半透過膜圖案，Cr表示蝕刻遮罩膜圖案。 如圖7所示，光半透過膜圖案PS之剖面係如下形狀：與合成石英玻璃基板QZ接觸之部分的底部擴展、與蝕刻遮罩膜圖案Cr接觸之部分大致垂直。 詳細而言，光半透過膜圖案PS之剖面係由對應於光半透過膜圖案PS之上表面、下表面及側面之上邊、下邊及側邊23所構成。輔助線21表示對應於光半透過膜圖案PS之上表面之上邊之位置，輔助線22表示對應於光半透過膜圖案PS之下表面之下邊之位置。 上邊與側邊之接點26與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置27連成的直線、與上邊所成之角度θ為105度。輔助線24表示自上表面下降膜厚之三分之二之高度之位置。 又，通過上邊與側邊23之接點26且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃基板QZ之主表面垂直之第2假想線的寬度為44 nm。 如上所述，光半透過膜圖案之剖面形狀良好，上述角度θ為105度、上述寬度為44 nm(相對於光半透過膜之膜厚110 nm為2.5分之1)，從而於包含300 nm以上且500 nm以下之波長範圍之光的曝光之光、更具體而言為包含i射線、h射線及g射線之複合光之曝光之光下，能獲得具有與上述表1所示之PSM(A)同等之相移效果之相移光罩。 藉由Seiko Instruments NanoTechnology公司製造之SIR8000，對相移光罩之光半透過膜圖案之CD不均進行測定。CD不均之測定係針對將基板之周緣區域除外之270 mm×390 mm之區域，於5×5之部位進行測定。CD不均係自作為目標之線與間隙圖案(線圖案之寬度：2.0 μm，間隙圖案之寬度：2.0 μm)之偏離寬度。於以下實施例及比較例中，於CD不均之測定中使用有相同之裝置。 CD不均良好，為0.096 μm。如圖6所示，光半透過膜圖案PS之邊緣E為直線狀，表示CD不均良好。 實施例2. 於實施例2中，對光半透過膜由4層氮矽化鉬膜(MoSiN)所構成之情形進行說明。 A.相移光罩基底及其製造方法 於實施例2之相移光罩基底之製造中，使用有3345尺寸之合成石英玻璃基板作為透明基板12。 藉由與實施例1相同之方法，將合成石英玻璃基板搬入至圖4所示之連續式之濺鍍裝置11之搬入腔室LL。作為第1濺鍍靶13、第2濺鍍靶14、第3濺鍍靶15、第4濺鍍靶16，使用有與實施例1相同之濺鍍靶。 其後，藉由與實施例1相同之方法，使濺鍍裝置11之內部達到特定之真空度。排氣係持續至自濺鍍裝置11取出合成石英玻璃基板之階段為止。 其後，自配置於第1濺鍍腔室SP1之第1濺鍍靶13附近之第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體(Ar：30 sccm，N2 ：30 sccm)，對第1濺鍍靶13施加4.0 kW之濺鍍功率。又，自配置於第2濺鍍腔室SP2之第3濺鍍靶15附近之第3氣體導入口GA3及配置於第4濺鍍靶16附近之第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體(Ar：30 sccm，N2 ：30 sccm)。對第1濺鍍靶13施加濺鍍功率、自第1氣體導入口GA12導入Ar氣體與N2 氣體之混合氣體、以及自第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體係持續至合成石英玻璃基板被搬送至搬出腔室ULL為止。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向箭頭S之方向搬送至搬出腔室ULL為止。再者，合成石英玻璃基板之搬送速度係設為400 mm/分鐘。當合成石英玻璃基板通過第1濺鍍腔室SP1之第1濺鍍靶13附近時，藉由反應性濺鍍，於合成石英玻璃基板之主表面上使膜厚27.5 nm之包含氮矽化鉬膜(MoSiN)之第1層光半透過膜。於合成石英玻璃基板通過第2濺鍍腔室SP2期間，第1層光半透過膜被曝露於Ar氣體與N2 氣體之混合氣體氛圍。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向與箭頭S相反之方向搬送，返回至搬入腔室LL。於將合成石英玻璃基板返回至搬入腔室LL期間，自第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體(Ar：30 sccm，N2 ：30 sccm)，自第3氣體導入口GA3導入Ar氣體與N2 氣體之混合氣體(Ar：30 sccm，N2 ：30 sccm)，將第1層光半透過膜曝露於Ar氣體與N2 氣體之混合氣體氛圍。 其後，藉由與第1層光半透過膜相同之方法，形成第2層、第3層、第4層光半透過膜。於形成第2層、第3層、第4層光半透過膜後，將搭載於托盤(未圖示)之合成石英玻璃基板向與箭頭S相反之方向搬送，返回至搬入腔室LL。於將合成石英玻璃基板返回至搬入腔室LL期間，藉由與上述方法相同之方法，將第2層、第3層、第4層光半透過膜曝露於Ar氣體與N2 氣體之混合氣體氛圍。 以此種方式，於合成石英玻璃基板之主表面上形成包含4層氮矽化鉬膜(MoSiN)之合計膜厚110 nm之光半透過膜。 其後，藉由與實施例1相同之方法，於光半透過膜上形成蝕刻遮罩膜，獲得在合成石英玻璃基板上形成有光半透過膜與蝕刻遮罩膜的相移光罩基底。 與上述實施例1同樣地，針對所獲得之相移光罩基底，利用XPS進行深度方向之組成分析。其結果為，於上述組成梯度區域P內，減慢光半透過膜之濕式蝕刻之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)連續性地增加。 又，組成梯度區域P中之蝕刻遮罩膜側之界面上之氮(N)相對於矽(Si)之比率之最大值為3.6。 B.相移光罩及其製造方法 使用以上述方式製造而成之相移光罩基底，藉由與實施例1相同之方法，形成蝕刻遮罩膜圖案及光半透過膜圖案。 於形成光半透過膜圖案後，剝離光阻劑圖案。其後，藉由包含硝酸鈰(Ⅱ)銨與過氯酸之鉻蝕刻液去除蝕刻遮罩膜圖案。 以此種方式，獲得在合成石英玻璃基板上形成有光半透過膜圖案之相移光罩。 圖8係實施例2之相移光罩之剖面照片。圖8中，QZ表示合成石英玻璃基板，PS表示光半透過膜圖案。 如圖8所示，光半透過膜圖案PS之剖面係如下形狀：與合成石英玻璃基板QZ接觸之部分的底部擴展、與蝕刻遮罩膜圖案接觸之部分大致垂直。 詳細而言，光半透過膜圖案PS之剖面係由對應於光半透過膜圖案PS之上表面、下表面及側面之上邊、下邊及側邊23所構成。輔助線21表示對應於光半透過膜圖案PS之上表面之上邊之位置，輔助線22表示對應於光半透過膜圖案PS之下表面之下邊之位置。 上邊與側邊之接點26與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為105度。 又，通過上邊與側邊23之接點26且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線29、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置28且相對於合成石英玻璃基板QZ之主表面垂直之第2假想線30的寬度D為48 nm。輔助線25表示自下表面上升膜厚之十分之一之高度之位置。 如上所述，光半透過膜圖案之剖面形狀良好，上述角度θ為105度、上述寬度為48 nm(相對於光半透過膜之膜厚110 nm為約2.3分之1)，從而於包含300 nm以上且500 nm以下之波長範圍之光的曝光之光、更具體而言為包含i射線、h射線及g射線之複合光之曝光之光下，能獲得具有與上述表2所示之PSM(B)同等之相移效果之相移光罩。 實施例3. 於實施例3中，對光半透過膜由1層氮矽化鉬膜(MoSiN)所構成之情形進行說明。 A.相移光罩基底及其製造方法 於實施例3之相移光罩基底之製造中，使用有與上述實施例1、2相同之3345尺寸之合成石英玻璃基板作為透明基板12。 藉由與實施例1相同之方法，將合成石英玻璃基板搬入至圖4所示之連續式之濺鍍裝置11之搬入腔室LL。作為第1濺鍍靶13、第2濺鍍靶14、第3濺鍍靶15、第4濺鍍靶16，使用有與實施例1相同之濺鍍靶材料。 對第1濺鍍腔室SP1之第1濺鍍靶13施加10.0 kW之濺鍍功率。又，自配置於第1濺鍍靶13附近之第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體(Ar：50.0 sccm，N2 ：100.0 sccm)。又，自配置於第2濺鍍腔室SP2之第3濺鍍靶15附近之第3氣體導入口GA3及配置於第4濺鍍靶16附近之第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體(Ar：50.0 sccm，N2 ：100.0 sccm)。對第1濺鍍靶13施加濺鍍功率、自第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體、以及自第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體係持續至合成石英玻璃基板被搬送至搬出腔室ULL為止。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向箭頭S之方向搬送至搬出腔室ULL為止。再者，合成石英玻璃基板之搬送速度係設為350 mm/分鐘。當合成石英玻璃基板通過第1濺鍍腔室SP1之第1濺鍍靶13附近時，藉由反應性濺鍍，於合成石英玻璃基板之主表面上形成膜厚110 nm之包含氮矽化鉬膜(MoSiN)之光半透過膜。於合成石英玻璃基板通過第2濺鍍腔室SP2期間，光半透過膜被曝露於Ar氣體與N2 氣體之混合氣體氛圍。 以此種方式，於合成石英玻璃基板之主表面上形成包含1層氮矽化鉬膜(MoSiN)之膜厚110 nm之光半透過膜。 其後，利用間隔板將第2濺鍍腔室SP2與搬出腔室ULL完全間隔後，使搬出腔室ULL返回至大氣壓狀態，自濺鍍裝置11取出形成有光半透過膜之合成石英玻璃基板。 其後，將形成有光半透過膜之合成石英玻璃基板於大氣中保管2日左右。 其後，將形成有光半透過膜之合成石英玻璃基板搬入至圖4所示之連續式之濺鍍裝置11之搬入腔室LL。 其後，藉由與實施例1相同之方法，於光半透過膜上形成蝕刻遮罩膜，獲得在合成石英玻璃基板上形成有光半透過膜與蝕刻遮罩膜之相移光罩基底。 與上述實施例1同樣地，針對所獲得之相移光罩基底，利用XPS進行深度方向之組成分析。其結果為，於上述組成梯度區域P內，減慢光半透過膜之濕式蝕刻之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)連續性地增加。 又，組成梯度區域P中之蝕刻遮罩膜側之界面上之氮(N)相對於矽(Si)之比率之最大值為8.2。 B.相移光罩及其製造方法 使用以上述方式製造而成之相移光罩基底，藉由與實施例1相同之方法製造相移光罩。 圖9係實施例3之相移光罩之剖面照片。圖9中，QZ表示合成石英玻璃基板，PS表示光半透過膜圖案，Cr表示蝕刻遮罩膜圖案。圖9係表示形成窄於光半透過膜圖案之寬度之蝕刻遮罩膜圖案前之狀態下之剖面照片。 如圖9所示，光半透過膜圖案PS之剖面係如下形狀：與合成石英玻璃基板QZ接觸之部分的底部擴展、與蝕刻遮罩膜圖案Cr接觸之部分大致垂直。 詳細而言，光半透過膜圖案PS之剖面係由對應於光半透過膜圖案PS之上表面、下表面及側面之上邊、下邊及側邊所構成。 上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為97度。 又，通過上邊與側邊之接點且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃基板QZ之主表面垂直之第2假想線的寬度為20 nm。 又，CD不均良好，為0.098 μm。 如上所述，光半透過膜圖案之剖面形狀良好，上述角度θ為97度，上述寬度為20 nm(相對於光半透過膜之膜厚110 nm為5.5分之1)，從而於包含300 nm以上且500 nm以下之波長範圍之光的曝光之光、更具體而言為包含i射線、h射線及g射線之複合光之曝光之光下，能獲得具有與上述表1所示之PSM(A)同等之相移效果之相移光罩。 實施例4. 於實施例3中，將形成有光半透過膜之合成石英玻璃基板於大氣中保管約2日。 相對於此，於實施例4中，將形成有光半透過膜之合成石英玻璃基板於大氣中保管1週。除此以外，藉由與實施例3相同之方法製造相移光罩基底及相移光罩。 與上述實施例1同樣地，針對所獲得之相移光罩基底，利用XPS進行深度方向之組成分析，其結果為，於上述組成梯度區域P內，減慢光半透過膜之濕式蝕刻之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)連續性地增加。 又，組成梯度區域P中之蝕刻遮罩膜側之界面上之氮(N)相對於矽(Si)之比率之最大值為3.2。 圖10係實施例4之相移光罩之剖面照片。圖10中，QZ表示合成石英玻璃基板，PS表示光半透過膜圖案，Cr表示蝕刻遮罩膜圖案。圖10係表示形成窄於光半透過膜圖案之寬度之蝕刻遮罩膜圖案前之狀態下之剖面照片。 如圖10所示，光半透過膜圖案PS之剖面為直線性之楔形狀。 詳細而言，光半透過膜圖案PS之剖面係由對應於光半透過膜圖案PS之上表面、下表面及側面之上邊、下邊及側邊所構成。 上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為120度。 又，通過上邊與側邊之接點且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃基板QZ之主表面垂直之第2假想線的寬度為42 nm。 又，CD不均良好，為0.105 μm。 如上所述，光半透過膜圖案之剖面形狀良好，上述角度θ為120度，上述寬度為42 nm(相對於光半透過膜之膜厚110 nm為約2.6分之1)，從而於包含300 nm以上且500 nm以下之波長範圍之光的曝光之光、更具體而言為包含i射線、h射線及g射線之複合光之曝光之光下，能獲得具有與上述表1所示之PSM(A)同等之相移效果之相移光罩。 根據實施例4可知，即便將光半透過膜於大氣中保管1週左右，只要為固定之範圍之組成變化便可維持良好之CD不均。 實施例5. 於實施例5中，對在光半透過膜上形成有絕緣層之情形進行說明。 A.相移光罩基底及其製造方法 於實施例5之相移光罩基底之製造中，使用有3345尺寸之合成石英玻璃基板作為透明基板12。 藉由與實施例1相同之方法，於合成石英玻璃基板之主表面上形成光半透過膜。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向與箭頭S相反之方向搬送，返回至搬入腔室LL。於將合成石英玻璃基板返回至搬入腔室LL期間，藉由與上述方法相同之方法，將第2層光半透過膜曝露於Ar氣體與N2 氣體之混合氣體氛圍。 其後，自配置於第1濺鍍腔室SP1之第2濺鍍靶14附近之第2氣體導入口GA2導入Ar氣體、N2 氣體及CO2 氣體之混合氣體(Ar：55 sccm，N2 ：60 sccm，CO2 ：35 sccm)，並對第2濺鍍靶14施加5.0 kW之濺鍍功率。對第2濺鍍靶14施加濺鍍功率、自第2氣體導入口GA2導入Ar氣體、N2 氣體及CO2 氣體之混合氣體係持續至合成石英玻璃基板被搬送至搬出腔室ULL為止。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向箭頭S之方向搬送至搬出腔室ULL為止。再者，合成石英玻璃基板之搬送速度係設為400 mm/分鐘。當合成石英玻璃基板通過第1濺鍍腔室SP1之第2濺鍍靶14附近時，藉由反應性濺鍍，於光半透過膜上使膜厚200 nm之包含氮氧碳化鉻膜(CrCON)之絕緣層成膜。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向與箭頭S相反之方向搬送，返回至搬入腔室LL。 其後，藉由與實施例1相同之方法，於絕緣層上形成包含氮碳化鉻膜(CrCN)之遮光層及包含氮氧化鉻膜(CrON)之抗反射層的積層膜。 以此種方式，在光半透過膜上形成蝕刻遮罩膜，該蝕刻遮罩膜具有依序形成有包含CrCON之絕緣層、包含CrCN之遮光層、包含CrON之抗反射層的積層構造。 其後，利用間隔板將第2濺鍍腔室與搬出腔室完全間隔後，使搬出腔室返回至大氣壓狀態，自濺鍍裝置11取出形成有光半透過膜與蝕刻遮罩膜之合成石英玻璃基板。 以此種方式，獲得在合成石英玻璃基板上形成有光半透過膜與蝕刻遮罩膜之相移光罩基底。 與上述實施例1同樣地，針對所獲得之相移光罩基底，利用XPS進行深度方向之組成分析。其結果為，於上述組成梯度區域P內，減慢光半透過膜之濕式蝕刻之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)連續性地增加。 又，組成梯度區域P中之蝕刻遮罩膜側之界面上之氮(N)相對於矽(Si)之比率之最大值為3.7。 B.相移光罩及其製造方法 使用以上述方式製造而成之相移光罩基底，藉由與實施例1相同之方法製造相移光罩。 對所獲得之相移光罩之剖面進行觀察。 與實施例1同樣地，光半透過膜圖案之剖面係如下形狀：與合成石英玻璃基板接觸之部分的底部擴展、與蝕刻遮罩膜圖案接觸之部分大致垂直。 詳細而言，光半透過膜圖案之剖面係由對應於光半透過膜圖案之上表面、下表面及側面之上邊、下邊及側邊所構成。 上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為105度。 又，通過上邊與側邊之接點且相對於合成石英玻璃基板之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃基板之主表面垂直之第2假想線的寬度為44 nm。 又，與合成石英玻璃基板接觸之光半透過膜圖案之角度為60度，與蝕刻遮罩膜圖案接觸之光半透過膜圖案之角度為75度。 又，CD不均非常良好，為0.060 μm。 如上所述，光半透過膜圖案之剖面形狀良好，上述角度θ為105度，上述寬度為44 nm(相對於光半透過膜之膜厚110 nm為2.5分之1)，從而於包含300 nm以上且500 nm以下之波長範圍之光的曝光之光、更具體而言為包含i射線、h射線及g射線之複合光之曝光之光下，能獲得具有與上述表1所示之PSM(A)同等之相移效果之相移光罩。 參考例1. 於參考例1中，對在光半透過膜之成膜後未將光半透過膜表面曝露於包含N2 之氣體氛圍的情形進行說明。 A.相移光罩基底及其製造方法 於參考例1之相移光罩基底之製造中，使用有3345尺寸之合成石英玻璃基板作為透明基板12。 藉由與實施例1相同之方法，將合成石英玻璃基板搬入至圖4所示之連續式之濺鍍裝置11之搬入腔室LL。作為第1濺鍍靶13、第2濺鍍靶14、第3濺鍍靶15、第4濺鍍靶16，使用有與實施例1相同之濺鍍靶。 自配置於第1濺鍍腔室SP1之第1濺鍍靶13附近之第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體(Ar：40 sccm，N2 ：90 sccm)，並對第1濺鍍靶13施加8.5 kw之濺鍍功率。又，自配置於第2濺鍍腔室SP2之第3濺鍍靶15附近之第3氣體導入口GA3及配置於第4濺鍍靶16附近之第4氣體導入口GA4導入Ar氣體(130 sccm)。對第1濺鍍靶13施加濺鍍功率、自第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體、以及自第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體係持續至合成石英玻璃基板被搬送至搬出腔室ULL為止。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向箭頭S之方向搬送至搬出腔室ULL。再者，合成石英玻璃基板之搬送速度係設為400 mm/分鐘。當合成石英玻璃基板通過第1濺鍍腔室SP1之第1濺鍍靶13附近時，藉由反應性濺鍍，於合成石英玻璃基板之主表面上形成膜厚55.0 nm之包含氮矽化鉬膜(MoSiN)之第1層光半透過膜。於合成石英玻璃基板通過第2濺鍍腔室SP2期間，第1層光半透過膜被曝露於Ar氣體氛圍。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向與箭頭S相反之方向搬送，返回至搬入腔室LL。於將合成石英玻璃基板返回至搬入腔室LL期間，所形成之第1層光半透過膜處於真空狀態。 其後，藉由與第1層光半透過膜相同之方法，形成第2層光半透過膜。 以此種方式，於合成石英玻璃基板之主表面上形成包含2層氮矽化鉬膜(MoSiN)之合計膜厚110 nm之光半透過膜。 其後，將搭載於托盤(未圖示)之合成石英玻璃基板向與箭頭S相反之方向搬送，返回至搬入腔室LL。於將合成石英玻璃基板返回至搬入腔室LL期間，所形成之第2層光半透過膜處於真空狀態。 其後，藉由與實施例1相同之方法，於光半透過膜上形成蝕刻遮罩膜，獲得在合成石英玻璃基板上形成有光半透過膜與蝕刻遮罩膜之相移光罩基底。 針對所獲得之相移光罩基底，利用XPS進行深度方向之組成分析。其結果為，於構成光半透過膜之2層之各自之厚度方向之中心附近，氮(N)之含量為46-47原子%。相對於此，於2之層之界面附近，氮(N)之含量為44原子%。於各層之中心附近及2層之界面附近之間，可看到2-3原子%之氮(N)之含量差。該差雖為接近檢測極限之程度之微差，但可推測，係因在光半透過膜之成膜後通過Ar氣體氛圍、且其後正將托盤退回至LL腔室之過程中通過真空氛圍，導致氮自第1層光半透過膜之表面脫附。而且，藉由形成第2層光半透過膜，而於第1層與第2層之界面附近，成為氮(N)之含量較少之狀態。又，於上述組成梯度區域P內，減慢光半透過膜之濕式蝕刻之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)連續性地增加。 B.相移光罩及其製造方法 使用以上述方式製造而成之相移光罩基底，藉由與實施例1相同之方法製造相移光罩。 圖11係參考例1之相移光罩之平面照片。圖12係參考例1之相移光罩之剖面照片。圖11、12中，QZ表示合成石英玻璃基板，PS表示光半透過膜圖案，Cr表示蝕刻遮罩膜圖案。圖12係表示形成窄於光半透過膜圖案之寬度之蝕刻遮罩膜圖案前之狀態下之剖面照片。 如圖12所示，於第1層光半透過膜圖案與第2層光半透過膜圖案之界面產生較大之咬入。如上所述，第1層光半透過膜與第2層光半透過膜之界面附近為氮(N)之含量較少之狀態。認為該氮之含量較少之界面附近因更快地受到蝕刻故產生咬入。 詳細而言，光半透過膜圖案PS之剖面係由對應於光半透過膜圖案PS之上表面、下表面及側面之上邊、下邊及側邊所構成。 上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為80度。 又，通過上邊與側邊之接點且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃基板QZ之主表面垂直之第2假想線的寬度為45 nm。 又，CD不均為0.252 μm。如圖11所示，光半透過膜圖案PS之邊緣E1呈鋸齒狀，表示CD不均較大。若光半透過膜圖案PS之邊緣E1呈鋸齒狀，則蝕刻遮罩膜圖案Cr之邊緣E2亦呈鋸齒狀。認為其原因在於，當形成蝕刻遮罩膜圖案Cr時，蝕刻液沿光半透過膜圖案PS之邊緣E1之形狀滲入。為了控制蝕刻遮罩膜圖案Cr之形狀，光半透過膜圖案PS之形狀較為重要。 根據參考例1可知，於重複複數次光半透過膜之成膜而形成由複數層所構成之光半透過膜之情形時，當在成膜與成膜期間未將光半透過膜曝露於具有減慢濕式蝕刻速度之成分之N2 氣體氛圍時，於由複數層所構成之光半透過膜之鄰接之兩層之界面產生咬入。可推測，於在成膜後曝露之氣體氛圍中不含N2 氣體之情形時，會因微量之氮自光半透過膜之表面脫附而導致光半透過膜之組成有微小變化，從而於該界面形成易於受到蝕刻之部分。 參考例2. 於實施例3中，於形成光半透過膜時，自第2濺鍍腔室SP2之第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體。 相對於此，於參考例2中，於形成光半透過膜時，自第2濺鍍腔室SP2之第3氣體導入口GA3及第4氣體導入口GA4均未導入任何氣體。除此以外，藉由與實施例3相同之方法製造相移光罩基底及相移光罩。 與上述實施例1同樣地，針對所獲得之相移光罩基底，利用XPS進行深度方向之組成分析。其結果為，於上述組成梯度區域P內，減慢光半透過膜之濕式蝕刻之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)階段性地增加，但組成梯度區域P中之蝕刻遮罩膜側之界面上之氮(N)相對於矽(Si)之比率之最大值為2.4。 圖13係參考例2之相移光罩之剖面照片。圖13中，QZ表示合成石英玻璃基板，PS表示光半透過膜圖案，Cr表示蝕刻遮罩膜圖案。圖13係表示於形成光半透過膜圖案後且於剝離光阻劑圖案前之狀態下之剖面照片。 如圖13所示，光半透過膜圖案PS之剖面為直線性之楔形狀。 詳細而言，光半透過膜圖案PS之剖面係由對應於光半透過膜圖案PS之上表面、下表面及側面之上邊、下邊及側邊所構成。 上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為135度。 又，通過上邊與側邊之接點且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃基板QZ之主表面垂直之第2假想線的寬度為85 nm。 如上所述，光半透過膜圖案之剖面形狀成為楔形狀，上述角度θ為135度，上述寬度為85 nm(相對於光半透過膜之膜厚110 nm為約1.3分之1)。因此，於所獲得之相移光罩中，於包含300 nm以上且500 nm以下之波長範圍之光的曝光之光、更具體而言為包含i射線、h射線及g射線之複合光之曝光之光下，無法獲得與上述表1所示之PSM(A)同等之相移效果之程度。 參考例3. 於實施例3中，當形成光半透過膜時，自第2濺鍍腔室SP2之氣體導入口GA3及氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體。 相對於此，於參考例3中，當形成光半透過膜時，自第2濺鍍腔室SP2之第3氣體導入口GA3及第4氣體導入口GA4僅導入Ar氣體(150 sccm)。除此以外，藉由與實施例3相同之方法製造相移光罩基底及相移光罩。 與上述實施例1同樣地，針對所獲得之相移光罩基底，利用XPS進行深度方向之組成分析。其結果為，於上述組成梯度區域P內，減慢光半透過膜之濕式蝕刻之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)階段性地增加，但組成梯度區域P中之氮(N)相對於矽(Si)之比率之最大值為2.6。 圖14係參考例3之相移光罩之剖面照片。圖14中，QZ表示合成石英玻璃基板，PS表示光半透過膜圖案，Cr表示蝕刻遮罩膜圖案。圖14係表示對蝕刻遮罩膜圖案進行濕式蝕刻，形成窄於光半透過膜圖案之寬度之蝕刻遮罩膜圖案前之狀態下之剖面照片。 如圖14所示，光半透過膜圖案PS之剖面為直線性之楔形狀。 詳細而言，光半透過膜圖案PS之剖面係由對應於光半透過膜圖案PS之上表面、下表面及側面之上邊、下邊及側邊所構成。 上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為135度。 又，通過上邊與側邊之接點且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃基板QZ之主表面垂直之第2假想線的寬度為89 nm。 如上所述，光半透過膜圖案之剖面形狀成為楔形狀，上述角度θ為135度，上述寬度為89 nm(相對於光半透過膜之膜厚110 nm為約1.2分之1)。因此，於所獲得之相移光罩中，於包含300 nm以上且500 nm以下之波長範圍之光的曝光之光、更具體而言為包含i射線、h射線及g射線之複合光之曝光之光下，無法獲得與上述表1所示之PSM(A)同等之相移效果之程度。 比較例1. 於實施例3中，於形成光半透過膜時，自第1濺鍍腔室SP1之第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體(Ar：50.0 sccm，N2 ：100.0 sccm)，自第2濺鍍腔室SP2之第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體與N2 氣體之混合氣體(Ar：50.0 sccm，N2 ：100.0 sccm)。又，對第1濺鍍腔室SP1之第1濺鍍靶13施加濺鍍功率10.0 kW。又，合成石英玻璃基板之搬送速度係設為350 mm/分鐘。又，光半透過膜之膜厚為110 nm。 相對於此，於比較例1中，自第1濺鍍腔室SP1之第1氣體導入口GA1導入Ar氣體與N2 氣體之混合氣體(Ar：65 sccm，N2 ：50 sccm)，自第2濺鍍腔室SP2之第3氣體導入口GA3及第4氣體導入口GA4導入Ar氣體(120 sccm)。又，對第1濺鍍腔室SP1之第1濺鍍靶13施加濺鍍功率6.3 kW。又，合成石英玻璃基板之搬送速度係設為200 mm/分鐘。又，光半透過膜之膜厚為115 nm。又，於形成光半透過膜後，以臭氧水對光半透過膜之表面進行洗淨。除此以外，藉由與實施例3相同之方法製造相移光罩基底及相移光罩。 與上述實施例1同樣地，針對所獲得之相移光罩基底，利用XPS進行深度方向之組成分析。其結果為，於上述組成梯度區域P內，存在減慢光半透過膜之濕式蝕刻之氮(N)之含量朝向光半透過膜之深度方向(合成石英玻璃基板之方向)減少的區域。 又，組成梯度區域P中之蝕刻遮罩膜側之界面上之氮(N)相對於矽(Si)之比率之最大值為2.0。 圖15係比較例1之相移光罩之剖面照片。圖15中，QZ表示合成石英玻璃基板，PS表示光半透過膜圖案，Cr表示蝕刻遮罩膜圖案。圖15係表示形成窄於光半透過膜圖案之寬度之蝕刻遮罩膜圖案前之狀態下之剖面照片。 如圖15所示，光半透過膜圖案PS之剖面為直線性之楔形狀。 詳細而言，光半透過膜圖案PS之剖面係由對應於光半透過膜圖案PS之上表面、下表面及側面之上邊、下邊及側邊所構成。 上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為160度。 又，通過上邊與側邊之接點且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃基板QZ之主表面垂直之第2假想線的寬度為295 nm。 又，與合成石英玻璃基板QZ接觸之光半透過膜圖案PS之角度為15度，上邊與側邊之接點與自上表面下降膜厚之三分之二之高度之位置上的側邊之位置連成的直線、與上邊所成之角度為160度。 又，通過上邊與側邊T之接點且相對於合成石英玻璃基板QZ之主表面垂直之第1假想線、與通過自下表面上升膜厚之十分之一之高度之位置上的側邊之位置且相對於合成石英玻璃QZ之主表面垂直之第2假想線的寬度為295 nm。 又，與合成石英玻璃基板QZ接觸之光半透過膜圖案PS之角度為15度，與蝕刻遮罩膜圖案Cr接觸之光半透過膜圖案PS之角度為165度。合成石英玻璃基板之搬送速度較慢，於光半透過膜之成膜後曝露於Ar氛圍之時間較長，因此，認為光半透過膜與蝕刻遮罩膜之界面之氮濃度進一步減少，故而咬入較大。 如上所述，光半透過膜圖案之剖面形狀成為較大之楔形狀，上述角度θ為165度，上述寬度為295 nm(相對於光半透過膜之膜厚110 nm為約3倍)。因此，於所獲得之相移光罩中，於包含300 nm以上且500 nm以下之波長範圍之光的曝光之光、更具體而言為包含i射線、h射線及g射線之複合光之曝光之光下，僅能獲得與上述表1所示之PSMTP(A)同等之相移效果。 又，CD不均為0.230 μm。 再者，於上述實施例中，對在形成氮矽化鉬膜後曝露於Ar氣體與N2 氣體之混合氣體氛圍下之例進行了說明，但即便為曝露於N2 氣體氛圍下之情形亦能獲得同等之效果。又，即便為一氧化氮氣體、一氧化二氮氣體、二氧化氮氣體等包含氮化合物之氣體來代替氮氣亦取得與本發明同樣之效果。又，於在光半透過膜中包含除氮以外之作為減慢濕式蝕刻之成分之碳的情形時，即便為包含碳化合物之氣體來代替氮氣亦取得與本發明同樣之效果。 又，於上述實施例中，作為光半透過膜之材料對氮矽化鉬膜之例進行了說明，但並不限於此。作為光半透過膜之材料亦可為矽化鉬氮氧化膜或矽化鉬之氮氧碳化膜。又，矽化鉬以外之金屬矽化物系材料之情形時亦能獲得與上述同等之效果。 又，於上述實施例中，對用於製造顯示裝置之相移光罩基底、或用於製造顯示裝置之相移光罩之例進行了說明，但並不限於此。本發明之相移光罩基底或相移光罩亦可應用於半導體裝置製造用、MEMS(Microelectromechanical Systems，微機電系統)製造用、印刷基板用等。 又，於上述實施例中，對透明基板之尺寸為3345尺寸(330 mm×450 mm)之例進行了說明，但並不限於此。於用於製造顯示裝置之相移光罩基底之情形時，使用大型(Large Size)之透明基板，該透明基板之尺寸係一邊之長度為10英吋以上。用於用於製造顯示裝置之相移光罩基底之透明基板之尺寸例如為330 mm×450 mm以上且2280 mm×3130 mm以下。 又，就用於製造半導體裝置、用於製造MEMS、用於印刷基板之相移光罩基底之情形時，使用小型(Small Size)之透明基板，該透明基板之尺寸係一邊之長度為9英吋以下。上述用途之相移光罩基底中使用之透明基板之尺寸例如為63.1 mm×63.1 mm以上且228.6 mm×228.6 mm以下。通常，用於製造半導體、用於製造MEMS時，使用6025尺寸(152 mm×152 mm)或5009尺寸(126.6 mm×126.6 mm)；用於製造印刷基板時，使用7012尺寸(177.4 mm×177.4 mm)、或9012尺寸(228.6 mm×228.6 mm)。Before describing the embodiment of the present invention, the difference in the phase shift effect due to the cross-sectional shape of the phase shift film pattern will be described using simulation results. The simulation is based on the number of openings (NA) is 0.085, the coherence factor (σ) is 0.9, and the light exposure is g-ray, h-ray, and i-ray composite light (the intensity ratio is g-ray: h-ray: i-ray = 0.95: 0.8 : 1.0). The simulation was performed twice. The first simulation was a phase shift mask with a phase shift film pattern with a vertical cross-sectional shape at the edge portion (hereinafter, referred to as PSM (A)), and a phase shift with a wedge shape at the cross-section A phase shift mask of the film pattern (hereinafter, referred to as PSMTP (A)) and a binary mask (hereinafter, referred to as Bin) are performed. In detail, the phase shift masks (PSM (A) and PSMTP (A)) have a line pattern including a phase shift film pattern and a light shielding film pattern formed on the phase shift film pattern, and a gap pattern including a light transmitting portion Of lines and gaps. The binary mask (Bin) has a configuration including a line pattern including a light-shielding film pattern, and a line and a gap pattern including a gap pattern of a light transmitting portion. The width of the line pattern is 2.0 μm, and the width of the gap pattern is 2.0 μm. The width of the edge portion of the phase shift film pattern is 0.5 μm. The width of the light-shielding film pattern is 1 μm. The light-shielding film pattern is arranged on the phase-shifting film pattern except for the edge portion. In PSM (A), the transmittance of the edge portion of the phase shift film pattern to i-rays is 6%, and the phase difference between the light transmitted through the edge portion of the phase shift film pattern and the light transmitted through the light transmitting portion is 180 degrees for i rays. . In PSMTP (A), the edge portion of the phase shift film pattern is configured such that the transmittance and the phase difference are changed in 10 steps with a width of 0.05 μm. The 10-step edge portion, which is closest to the light-shielding film pattern, has a transmittance of 6% to i-rays, and the phase difference between the light passing through the portion closest to the light-shielding film pattern and the light transmitted through the light-transmitting portion is to i-rays. It's 180 degrees. The 10-stage edge portion, the portion closest to the light transmitting portion, has a transmittance of i-rays of 57.5%, and the phase difference between the light passing through the portion closest to the light transmitting portion and the light transmitting portion passes through the i-rays. It is 20.19 degrees. In addition, for the molybdenum nitride silicide film (MoSiN) described in the following examples, the angle of the imaginary gradient surface constituting the edge portion of the ten steps is about 165 degrees. Figure 1 is a schematic diagram of the line and gap patterns used in the simulation. FIG. 1 shows a part of the line and gap pattern 1 in the PSM (A). In FIG. 1, a line pattern 2a located in the center, a line pattern 2b located on the left side of the line pattern 2a across the gap pattern 3a, and a line pattern 2c located on the right side of the line pattern 2a across the gap pattern 3b are shown. The line patterns 2b and 2c located on the left and right show only a half of the width of the line pattern. In FIG. 1, the edge portion 4 and the light-shielding film pattern 5 of the phase shift film pattern constituting the line patterns 2a, 2b, and 2c are indicated by hatching. Tables 1 and 2 show the results of the first simulation. In FIG. 2, curve a indicates the result of PSM (A), curve b indicates the result of PSMTP (A), and curve c indicates the result of Bin. The horizontal axis in FIG. 2 represents the position (μm) when the center of the line pattern is set to zero, and the vertical axis represents the light intensity. [Table 1] As shown in Table 1 and Figure 2, in PSM (A), the maximum light intensity is 0.43198, the minimum light intensity is 0.08452, and the contrast (the difference between the maximum light intensity and the minimum light intensity / the sum of the maximum light intensity and the minimum light intensity) is 0.67273. In PSMTP (A), the maximum light intensity is 0.53064, the minimum light intensity is 0.13954, and the contrast is 0.58359. In Bin, the maximum light intensity is 0.49192, the minimum light intensity is 0.12254, and the contrast is 0.60114. From the simulation results shown in Table 1 and Figure 2, it can be seen that the cross-sectional shape of the edge portion of the phase shift film pattern is a vertical phase shift mask (PSM (A)) and the cross section of the edge portion of the phase shift film pattern The contrast is higher in the case of a wedge-shaped phase shift mask (PSMTP (A)) or the case of a binary mask (Bin). In the case of PSMTP (A), the contrast is lower than in the case of Bin. In the case of PSMTP (A), the edge portion of the phase shift film pattern has a wedge shape, so that the transmittance becomes higher and the phase difference becomes smaller as it approaches the light transmitting portion. That is, the amount of light leakage increases as the light transmission portion approaches, and the phase effect is lost. Therefore, in the case of PSMTP (A), the contrast becomes low. In the case of PSM (A), the edge portion of the phase shift film pattern is vertical, so even if it is close to the light transmitting portion, it maintains a fixed transmittance (6%) and a phase difference (180 degrees). That is, the transmittance and phase are immediately changed at the boundary between the edge portion of the phase shift film pattern and the light transmission portion. Therefore, in the case of PSM (A), compared with the case of Bin, although there is light leakage on the edge portion of the phase shift film pattern, the contrast becomes higher. Therefore, it can be seen that the phase shift effect can be fully exhibited by making the cross-sectional shape of the edge portion of the phase shift film pattern vertical. The second simulation is a phase shift mask with a phase shift film pattern having a vertical cross-sectional shape at the edge portion (hereinafter referred to as PSM (B)) and a phase shift with a wedge shape at the cross-section shape The phase shift mask of the film pattern (hereinafter, referred to as PSMTP (B)) and the binary mask (hereinafter, referred to as Bin) are performed. The phase shift masks (PSM (B) and PSMTP (B)) used in the second simulation are obtained by removing the light-shielding film pattern from the PSM (A) and PSMTP (A) used in the first simulation. Specifically, the PSM (B) and PSMTP (B) have a configuration including a line pattern including a phase shift film pattern and a line and a gap pattern including a gap pattern of a light transmitting portion. The binary mask (Bin) used for the second simulation is the same as that used for the first simulation. Table 2 and Figure 3 show the results of the second simulation. In FIG. 3, the curve d indicates the result of PSM (B), the curve e indicates the result of PSMTP (B), and the curve f indicates the result of Bin. The horizontal axis in FIG. 3 represents the position (μm) when the center of the line pattern is set to zero, and the vertical axis represents the light intensity. [Table 2] As shown in Table 2 and FIG. 3, in the PSM (B), the maximum light intensity is 0.40505, the minimum light intensity is 0.05855, and the contrast is 0.74743. In PSMTP (B), the maximum light intensity is 0.49925, the minimum light intensity is 0.09713, and the contrast is 0.67426. In Bin, the maximum light intensity is 0.49192, the minimum light intensity is 0.12254, and the contrast is 0.60114. From the simulation results shown in Table 2 and Figure 3, it can be seen that the cross-sectional shape of the edge portion of the phase shift film pattern is a vertical phase shift mask (PSM (B)) and the cross section of the edge portion of the phase shift film pattern. The contrast is higher in the case of a wedge-shaped phase shift mask (PSMTP (B)) or the binary mask (Bin). Therefore, it can be seen that the phase shift effect can be fully exhibited by making the cross-sectional shape of the edge portion of the phase shift film pattern vertical. Hereinafter, a phase shift mask substrate for manufacturing a display device and a method for manufacturing the same, a phase shift mask for manufacturing a display device using the phase shift mask substrate, a method for manufacturing the same, and use thereof A method for manufacturing a display device having the phase shift mask will be described in detail. Embodiment 1. In Embodiment 1, a phase shift mask base for manufacturing a display device and a manufacturing method thereof will be described. In the manufacturing method of the phase shift mask substrate for manufacturing a display device in Embodiment 1, the following steps are performed: a preparation process that prepares a transparent substrate; and a semi-permeable film formation process that is performed on the main surface of the transparent substrate. Sputtering to form a light semi-transmissive film composed of a metal silicide-based material; and an etching mask film forming process, which is formed on the light semi-transmitting film to form an etching mask composed of a chromium-based material by sputtering. Cover film. Hereinafter, each process will be described in detail. 1. Preparation Process In the case of manufacturing a phase-shifting mask base for manufacturing a display device, first, a transparent substrate is prepared. The material of the transparent substrate is not particularly limited as long as it is a material that is transparent to the light used for exposure. Examples include synthetic quartz glass, soda lime glass, and alkali-free glass. 2. Semi-transmissive film formation process Secondly, a light semi-transmissive film composed of a metal silicide-based material is formed on the main surface of the transparent substrate by sputtering. In detail, in this semi-transmissive film forming process, first, a film-forming process is performed in which a light semi-transmissive film made of a metal silicide-based material is formed by applying sputtering power in a sputtering gas atmosphere. Thereafter, without exposing the light semi-transmitting film to the atmosphere, the following exposure process is continuously performed after the film formation process: exposing the light semi-transmitting film to a method including slowing down the wet etching rate of the light semi-transmitting film. Gas atmosphere of ingredients. The light semi-transmitting film has a property of changing the phase of the exposed light. Due to this property, a specific phase difference occurs between the light that is transmitted through the light semi-transmitting film and the light that is transmitted only through the transparent substrate. In the case where the exposed light is a composite light including light in a wavelength range of 300 nm to 500 nm, the light semi-transmitting film is formed so as to generate a specific phase difference for light representing a wavelength. For example, when the exposed light is a composite light including i-rays, h-rays, and g-rays, the light semi-transmitting film is such that a phase difference of 180 degrees is generated for any of the i-rays, h-rays, and g-rays. Way to form. In order to exert the phase shift effect described above, the phase difference of the light semi-transmissive film is preferably set to a range of 180 ° ± 20 ° for a representative wavelength of any of i-ray, h-ray, and g-ray. It is further preferred that the phase difference of the light semi-transmitting film is preferably set to a range of 180 ° ± 10 ° for a representative wavelength of any of i-ray, h-ray, and g-ray. The transmittance of the light semi-transmissive film is preferably 1% or more and 20% or less at a representative wavelength of any of i-rays, h-rays, and g-rays. It is particularly preferred that the transmittance of the light semi-transmissive film is at least 3% and at most 10% at a representative wavelength of any of i-rays, h-rays, and g-rays. The metal silicide-based material constituting the light semi-transmitting film may include metal and silicon as long as it has a specific transmittance and phase difference with respect to the exposed light, and may further include other elements. The other elements may be elements that can control the refractive index (n) and extinction coefficient (k) of the light to be exposed, and may be selected from oxygen (O), nitrogen (N), carbon (C), and fluorine (F). Choose from at least one of the elements. Examples include metal silicide oxides, metal silicide oxynitrides, metal silicide nitrides, metal silicide nitrogen carbides, metal silicide carbon oxides, and metal silicide oxynitrides. Wait. From the viewpoint of pattern controllability of wet etching, the metal silicide-based material constituting the light semi-transmitting film is preferably a component containing metal, silicon, and a slow wet etching rate of the light semi-transmitting film. s material. Examples of the component that slows down the wet etching rate of the light semi-transmissive film include nitrogen (N) and carbon (C). Examples of the metal include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), and zirconium (Zr). Examples of the metal silicide-based material constituting the light semi-transmissive film include a metal silicide nitride, a metal silicide oxynitride, a metal silicide carbon oxide, a metal silicide nitrogen nitride, and a metal silicide. Nitrogen oxide carbides. Specific examples include: nitrides of molybdenum silicide (MoSi), nitrides of tantalum silicide (TaSi), nitrides of tungsten silicide (WSi), nitrides of titanium silicide (TiSi), nitrogen of zirconium silicide (ZrSi) Compounds, molybdenum silicide oxynitride, tantalum silicide oxynitride, tungsten silicide oxynitride, titanium silicide oxynitride, zirconium silicide oxynitride, molybdenum silicide oxycarbide, tantalum silicide oxycarbide 、 Carbon oxide of titanium silicide, Carbide of tungsten silicide, Carbide of zirconium silicide, Nitrogen carbide of molybdenum silicide, Nitrogen carbide of tantalum silicide, Nitrogen carbide of titanium silicide, Nitrogen carbide of zirconium silicide, Nitrogen carbide of tungsten silicide, molybdenum silicide of oxynitride, tantalum silicide of oxycarbide, titanium silicide of oxynitride, tungsten silicide of oxycarbide, zirconium oxycarbide. The composition of the metal, silicon, and nitrogen constituting the light semi-transmitting film is based on the required phase difference (180 degrees ± 20 degrees), the transmittance (1% to 20%), and the wet etching characteristics ( The cross-sectional shape of the light semi-transmissive film pattern or CD unevenness) and the viewpoint of chemical resistance are adjusted. The ratio of metal to silicon is preferably metal: silicon = 1: 1 or more and 1: 9 or less. The content of nitrogen is preferably 25 atomic% or more and 55 atomic% or less, and more preferably 30 atomic% or more and 50 atomic% or less. The film formation process of the light semi-transmissive film is performed using a sputtering target containing metal and silicon in a sputtering gas atmosphere including a refractive index (n) under a light with controlled exposure, and extinction. The gas of the component of the coefficient (k). Examples of such a gas include oxygen (O 2 ), Carbon monoxide gas (CO), carbon dioxide gas (CO 2 ), Nitrogen (N 2 ), Nitrogen monoxide (NO), nitrogen dioxide (NO) 2 ), Nitrous oxide gas (N 2 O), hydrocarbon gas (CH 4 Etc.), Fluorocarbon-based gas (CF 4 Etc.), fluorine nitride-based gas (NF 3 Etc.) and other reactive gases. From the viewpoint of pattern control of wet etching, it is preferable to use a sputtering target containing metal and silicon for the film formation process of the light semi-transmissive film, and to include a wet etching rate having a reduced light semi-transmissive film. The component gas is sputtered in an atmosphere of sputtering gas. As a component which slows down the wet etching rate of a light semi-transmitting film, as mentioned above, nitrogen (N) and carbon (C) are mentioned, for example. Examples of the gas having a component that slows down the wet etching rate of the light semi-transmissive film include nitrogen, nitrogen monoxide, nitrogen dioxide, nitrogen monoxide, carbon monoxide, carbon dioxide, and hydrocarbon-based gases (CH 4 Etc.), Fluorocarbon-based gas (CF 4 Etc.), fluorine nitride-based gas (NF 3 Etc.) and other reactive gases. The sputtering gas atmosphere may include helium, neon, argon, krypton, xenon and the like as inert gases. The sputtering gas atmosphere contains, for example, an inert gas including at least one selected from the group consisting of helium, neon, argon, krypton, and xenon, and includes a gas selected from nitrogen, nitrogen monoxide, and nitrogen dioxide. A mixed gas of at least one active gas in the group. The exposure process of the light semi-transmissive film after film formation is performed by exposing the light semi-transmissive film to a gas atmosphere for exposure including a gas having a component that slows down the wet etching rate of the light semi-transparent film. As a component which slows down the wet etching rate of a light semi-transmitting film, as mentioned above, nitrogen (N) is mentioned, for example. Examples of the gas having a component that slows down the wet etching rate of the light semi-transmissive film include an active gas such as nitrogen. The exposure gas atmosphere may include helium, neon, argon, krypton, xenon, and the like as inert gases. In the case where the exposure gas atmosphere includes a mixed gas atmosphere of nitrogen and an inert gas, the ratio of nitrogen to the inert gas (nitrogen / inert gas) is 20% or more, and preferably 30% or more. The light semi-transmissive film may be any one of a case composed of one layer and a case composed of a plurality of layers. In the case where the light semi-transmitting film is composed of a plurality of layers, the film forming process of the light semi-transmitting film and the exposure process after the film forming of the light semi-transmitting film are performed multiple times. In the case where a plurality of film forming processes are performed, the sputtering power applied to the sputtering target when the light semi-transmissive film is formed can be reduced. 3. The etching mask film forming process is followed by forming an etching mask film made of a chrome-based material on the light semi-transmissive film by sputtering. The etching mask film may be either a case having a light-shielding property or a case having a light semi-transmittance. The chromium-based material constituting the etching mask film is not particularly limited as long as it contains chromium (Cr). Examples of the chromium-based material constituting the etching mask film include materials containing at least one kind of chromium (Cr), chromium oxide, chromium nitride, chromium carbide, and chromium fluoride. The mask film forming process is performed using a sputtering target containing chromium or a chromium compound in a sputtering gas atmosphere containing a mixed gas, the mixed gas including, for example, selected from helium, neon, argon, krypton, and xenon. An inert gas of at least one of the group formed, and an active gas including at least one selected from the group consisting of oxygen, nitrogen, carbon dioxide gas, nitrogen oxide-based gas, hydrocarbon-based gas, and fluorine-based gas. The etching mask film may be any one of a case composed of one layer and a case composed of a plurality of layers. When the etching mask film is composed of a plurality of layers, for example, there is a case where a laminated structure is formed by a light-shielding layer formed on the light semi-transmissive film side and an anti-reflection layer formed on the light-shielding layer, or by using light In the case of a laminated structure composed of an insulating layer formed in a semi-transparent film contact manner, a light-shielding layer formed on the insulating layer, and an anti-reflection layer formed on the light-shielding layer. The light-shielding layer may be any one of a case composed of one layer and a case composed of a plurality of layers. Examples of the light-shielding layer include a chromium nitride film (CrN), a chromium carbide film (CrC), and a chromium nitride film (CrCN). The antireflection layer may be any one of a case composed of one layer and a case composed of a plurality of layers. Examples of the anti-reflection layer include a chromium oxynitride film (CrON). The insulating layer is made of, for example, CrCO or CrCON containing Cr of less than 50 atomic%, and has a thickness of 10 nm or more and 50 nm or less. When an etching mask film made of a chromium-based material is wet-etched, a light semi-transmissive film made of a metal ion free metal silicide-based material is melted out. At this time, electrons are generated. When the insulating layer is formed in contact with the light semi-transmissive film, electrons generated when metal ions are melted out of the light semi-transmissive film can be prevented from being supplied to the etching mask film. Therefore, the in-plane etching rate can be made uniform when the etching mask film is wet-etched. The phase shift mask substrate for manufacturing a display device according to Embodiment 1 is manufactured by such a preparation process, a semi-transmissive film formation process, and an etching mask film formation process. FIG. 4 is a schematic view showing an example of a sputtering apparatus for forming a light semi-transmitting film and an etching mask film. The sputtering apparatus 11 shown in FIG. 4 is a continuous (inline) type, and consists of the carrying-in chamber LL, the first sputtering chamber SP1, the buffer chamber BU, the second sputtering chamber SP2, and the carrying-out chamber ULL. Consists of 5 chambers. The five chambers are sequentially and sequentially arranged. The transparent substrate 12 mounted on a tray (not shown) can be sequentially transferred to the carry-in chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second sputtering chamber at a specific transfer speed in the direction of the arrow S. Chamber SP2, and the ULL chamber. The transparent substrate 12 mounted on a tray (not shown) can be sequentially returned to the unloading chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, and the first sputtering chamber in the direction opposite to the arrow S. SP1, and moved into the chamber LL. The carry-in chamber LL and the first sputtering chamber SP1, the second sputter chamber SP2, and the carry-out chamber ULL are separated by a partition plate. The first sputtering chamber SP1, the buffer chamber BU, and the second sputtering chamber SP2 are not separated by a GV (gate valve), but are formed by a large container connected by three chambers. The carry-in chamber LL and the carry-out chamber ULL can be spaced from the outside of the sputtering device 11 by a partition plate. The carry-in chamber LL, the buffer chamber BU, and the carry-out chamber ULL are connected to an exhaust device (not shown) that performs exhaust. In the first sputtering chamber SP1, a first sputtering target 13 containing metal and silicon, which is used to form a light semi-transmissive film, is disposed on the side of the carry-in chamber LL. A first gas is disposed near the first sputtering target 13. The inlet GA1 (not shown). In the first sputtering chamber SP1, a second sputtering target 14 containing chromium for forming an etching mask film is disposed on the buffer chamber BU side, and a second gas is disposed near the second sputtering target 14. The inlet GA2 (not shown). In the second sputtering chamber SP2, a third sputtering target 15 containing chromium for forming an etching mask film is disposed on the buffer chamber BU side, and a third gas introduction port is arranged near the third sputtering target 15. GA31 (not shown). In the second sputtering chamber SP2, a fourth sputtering target 16 containing chromium, which is used to form an etching mask film, is disposed on the ULL side of the carry-out chamber, and a fourth gas introduction is arranged near the fourth sputtering target.口 GA4 (not shown). In FIG. 4, the first sputtering target 13, the second sputtering target 14, the third sputtering target, and the fourth sputtering target 15 are hatched. When the continuous sputtering device 11 shown in FIG. 4 is used to form a light semi-transmissive film and an etching mask film, first, in order to form a light semi-transmissive film, a transparent plate mounted on a tray (not shown) is mounted. The substrate 12 is carried into the carry-in chamber LL. After the inside of the sputtering device 11 is brought to a specific degree of vacuum, the above-mentioned active gas having a specific flow rate is introduced from the first gas introduction port GA1, and specifically includes a component having a wet etching rate that slows down the light semi-transmissive film. The sputtering gas of the gas is introduced into the second sputtering chamber SP2 from at least one of the third gas introduction port GA3 and the fourth gas introduction port GA4. A gas for exposure of a component gas applies a specific sputtering power to the first sputtering target 13. The application of the sputtering power, the introduction of the sputtering gas, and the introduction of the exposure gas are continued until the transparent substrate 12 is transported to the carry-out chamber ULL. Thereafter, the transparent substrate 12 mounted on a tray (not shown) is sequentially transferred to the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second at a specific transfer speed in the direction of the arrow S. The sputtering chamber SP2 and the removal chamber ULL. When the transparent substrate 12 passes near the first sputtering target 13 of the first sputtering chamber SP1, a metal silicide-based material having a specific film thickness is formed on the main surface of the transparent substrate 12 by reactive sputtering. Light semi-transmitting film. During the passage of the transparent substrate 12 through the second sputtering chamber SP2, the light semi-transmissive film is exposed to a gas atmosphere for exposure including a gas having a component that slows down the wet etching rate of the light semi-transmissive film. In the case of forming the second-layer light transflective film, the transparent substrate 12 mounted on a tray (not shown) is sequentially returned to the unloading chamber ULL and the second sputtering chamber in a direction opposite to the arrow S. The chamber SP2, the buffer chamber BU, the first sputtering chamber SP1, and the carry-in chamber LL are again subjected to the film formation of the light semi-transmitting film. When returning the transparent substrate 12 to the carry-in chamber LL, it is preferable to introduce a gas containing a component having a slow wet etching rate of the light semi-transmissive film into the first sputtering chamber SP1 and the second sputtering chamber SP2. Gas for exposure. Thereby, during returning the transparent substrate 12 to the carry-in chamber LL, the light semi-transmitting film can be exposed to a gas atmosphere for exposure including a gas having a component that slows down the wet etching rate of the light semi-transmitting film. The same applies to the case where the third and fourth layers of light semi-transmitting films are formed. When a light semi-transmissive film is formed on the main surface of the transparent substrate 12 in this manner, the etching mask film is continuously formed without taking out the transparent substrate 12 to the outside of the sputtering device 11, and then it is mounted on a tray. The transparent substrate 12 (not shown) returns to the carrying-out chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, the first sputtering chamber SP1, and the carrying-in chamber in the direction opposite to the arrow S in this order. LL. On the other hand, when the transparent substrate 12 is temporarily taken out of the sputtering device 11 after the light semi-transmissive film is formed, an etching mask film is formed, and the transparent substrate 12 mounted on a tray (not shown) is formed. After being carried into the carrying-in chamber LL, as described above, the inside of the sputtering apparatus 11 is brought to a specific vacuum degree. In the case of forming an etching mask film having a laminated structure composed of a light-shielding layer and an anti-reflection layer, the second gas introduction port GA2 is then introduced from the second gas introduction port GA2 while the inside of the sputtering device 11 reaches a specific vacuum degree. A sputtering gas having a specific flow rate is introduced, and a specific sputtering power is applied to the second sputtering target 14. A sputtering gas having a specific flow rate is introduced from the third gas introduction port GA3, and a specific sputtering power is applied to the third sputtering target 15. A sputtering gas having a specific flow rate is introduced from the fourth gas introduction port GA4, and a specific sputtering power is applied to the fourth sputtering target 16. The application of the sputtering power and the introduction of the sputtering gas are continued until the transparent substrate 12 is transferred to the unloading chamber ULL. Thereafter, the transparent substrate 12 mounted on a tray (not shown) is sequentially transferred to the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second at a specific transfer speed in the direction of the arrow S. The sputtering chamber SP2 and the removal chamber ULL. When the transparent substrate 12 passes near the second sputtering target 14 of the first sputtering chamber SP1, a light-shielding layer made of a chromium-based material having a specific film thickness is formed on the light semi-transmissive film by reactive sputtering. Film formation. In addition, when the transparent substrate 12 passes near the third sputtering target 15 and the fourth sputtering target 16 of the second sputtering chamber SP2, a specific film thickness of chromium is formed on the light-shielding layer by reactive sputtering. The film is made of light-shielding layer or anti-reflection layer composed of materials. After forming an etching mask film having a laminated structure composed of a light shielding layer and an anti-reflection layer on the light semi-transmissive film, the transparent substrate 12 is taken out to the outside of the sputtering device 11. On the other hand, in the case of forming an etching mask film having a laminated structure composed of an insulating layer, a light-shielding layer, and an anti-reflection layer, after forming a light semi-transmissive film on the transparent substrate 12, the When the interior reaches a specific vacuum degree, a specific flow rate of sputtering gas is introduced from the second gas introduction port GA2, and a specific sputtering power is applied to the second sputtering target 14. Thereafter, the transparent substrate 12 mounted on a tray (not shown) is sequentially transferred to the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second at a specific transfer speed in the direction of the arrow S. The sputtering chamber SP2 and the removal chamber ULL. When the transparent substrate 12 passes near the second sputtering target 14 of the first sputtering chamber SP1, an insulating layer made of a chromium-based material is formed on the light semi-transmissive film with a specific film thickness by reactive sputtering. Film formation. Thereafter, in order to form a light-shielding layer and an anti-reflection layer, the transparent substrate 12 mounted on a tray (not shown) is sequentially returned to the unloading chamber ULL and the second sputtering chamber in a direction opposite to the arrow S. In the chamber SP2, the buffer chamber BU, the first sputtering chamber SP1, and the carry-in chamber LL, as described above, a light shielding layer and an antireflection layer are formed. After forming an etching mask film having a laminated structure composed of an insulating layer, a light-shielding layer, and an anti-reflection layer on the light semi-transmissive film, the transparent substrate 12 is taken out to the outside of the sputtering device 11. The phase shift mask base for manufacturing a display device according to the first embodiment manufactured in this manner includes a transparent substrate, a light semi-transmissive film made of a metal silicide material formed on the main surface of the transparent substrate, And an etching mask film made of a chrome-based material formed on the light semi-transmitting film, and a composition gradient region is formed at an interface between the light semi-transmitting film and the etching mask film. Hereinafter, FIG. 5 showing the composition analysis results of the phase shift mask substrate of Example 1 in the depth direction obtained by X-ray photoelectron spectroscopy (XPS) will be described. The composition gradient region P is from the composition analysis result of the depth direction obtained by using XPS for the phase shift mask substrate. The silicon (silicon: Si) peak and molybdenum (Mo) peak caused by the light semi-transmitting film appear until The area until the chromium (Cr) peak disappeared by the etching mask film. Within the composition gradient region P, the ratio of the component (nitrogen (N) in FIG. 5) that slows down the wet etching rate of the light semi-transmissive film monotonously increases stepwise and / or continuously toward the depth direction. In the composition gradient region P, the ratio of oxygen and the ratio of oxygen in the composition uniform region Q are hardly changed, and are contained substantially uniformly. The ratio (content) of oxygen in the composition gradient region P is 20 atomic% or less, preferably 10 atomic% or less, and further preferably 5 atomic% or less. The maximum value of the ratio (N / Si) of nitrogen (N) to silicon (Si) on the boundary between the composition gradient region P and the etching mask film is 3.0 or more and 30 or less, preferably 3.5 or more and 25 or less, more preferably 4.0 or more and 20 or less. Wherein, the boundary is such that when the phase shift mask substrate is analyzed from the etching mask film side by X-ray photoelectron spectroscopy and the composition is analyzed under the measurement step of 0.5 minutes, 1 atomic% is detected for the first time. The position of the above silicon (Si). The composition of the light semi-transmitting film is substantially uniform. However, the composition gradient region P is formed at the interface between the light semi-transmissive film and the etching mask film, and the composition gradient region is also formed at the interface between the light semi-transmissive film and the transparent substrate, so the composition of these parts is not uniform. The composition uniform area Q is the result of the composition analysis of the depth direction of the phase shift mask substrate by using XPS. The chromium (Cr) peak caused by etching the mask film disappears until the oxygen (O) caused by the transparent substrate. ) The area until the peak appears. In the uniform composition region Q, the variation of the respective ratios of molybdenum (Mo), silicon (Si), and a component (nitrogen (N) in FIG. 5) that slows down the wet etching rate of the light semi-transmissive film is 5 atomic% or less. Is preferably 3 atomic% or less. In the case where the light semi-transmitting film is composed of a plurality of layers, the component that slows down the wet etching rate of the light semi-transmitting film in the interface of each layer (when the sputtering time is 25 minutes in FIG. 5) (nitrogen in FIG. 5) The reduction in the composition of (N) with respect to the composition that slows down the wet etching rate of the light semi-transmitting film in the vicinity of the center of the thickness direction of each layer (in FIG. 5, the nitrogen (N)) composition is reduced by 3 atomic% or less, It is preferably at most 2 atomic%. According to the method for manufacturing a phase shift mask base for manufacturing a display device according to the first embodiment, a light semi-transmissive film made of a metal silicide-based material is formed on a main surface of a transparent substrate, and the light semi-transmissive film is formed on the main surface of the transparent substrate. An etch mask made of a chrome-based material. The formation of the light semi-transmitting film is performed by forming the light semi-transmitting film and continuously exposing the light semi-transmitting film to the substrate after the film is formed without exposing the light semi-transmitting film to the atmosphere. A gaseous atmosphere of the components of the slow-light semi-transmitting film with a wet etching rate. By continuously exposing the light semi-transmissive film to a gas atmosphere containing a component that slows down the wet etching rate of the light semi-transparent film after film formation, it is possible to prevent the component that slows down the wet etching rate from the surface of the light semi-transmissive film Desorption. Therefore, by wet etching, a phase shift mask substrate capable of patterning a light semi-transmissive film into a nearly vertical cross-sectional shape capable of fully exerting a phase shift effect can be manufactured. In addition, by wet etching, a phase shift mask substrate capable of patterning a light semi-transmitting film into a cross-sectional shape with small CD unevenness can be manufactured. In addition, the phase shift mask base for manufacturing a display device according to the first embodiment includes a light semi-transmissive film made of a metal silicide-based material formed on a main surface of a transparent substrate, and a light semi-transmitting film formed on the main surface of the transparent substrate. An etching mask film made of a chromium-based material on the film. In the composition gradient region P formed at the interface between the light semi-transmitting film and the etching mask film, the ratio of the components that slow down the wet etching rate of the light semi-transmitting film increases stepwise and / or continuously in the depth direction. Therefore, by wet etching, a phase shift mask substrate capable of patterning a light semi-transmissive film into a nearly vertical cross-sectional shape capable of fully exerting a phase shift effect can be obtained. In addition, by wet etching, a phase shift mask substrate capable of patterning a light semi-transmitting film into a cross-sectional shape with small CD unevenness can be obtained. Embodiment 2. In Embodiment 2, the phase shift mask used for manufacturing a display device, and its manufacturing method are demonstrated. In the method for manufacturing a phase shift mask for manufacturing a display device according to the second embodiment, first, a photoresist pattern forming process is performed, that is, the phase shift light for manufacturing a display device described in the first embodiment is performed. A photoresist pattern is formed on the etching mask film of the phase shift mask substrate obtained by the manufacturing method of the mask substrate or on the etching mask film of the phase shift mask substrate used for manufacturing the display device described in Embodiment 1. . Specifically, in the photoresist pattern forming process, first, a photoresist film is formed on the etching mask film. Thereafter, a pattern of a specific size is drawn on the photoresist film. Thereafter, the photoresist film is developed with a specific developer to form a photoresist pattern. Examples of the pattern for drawing the photoresist film include a line and gap pattern or a hole pattern. Next, an etching mask film pattern forming process is performed, that is, the etching mask film is wet-etched using the photoresist pattern as a mask to form an etching mask film pattern. There is no particular limitation on the etching solution for wet etching the etching mask film as long as it can selectively etch the etching mask film. Specifically, an etchant containing cerium (II) nitrate and perchloric acid is mentioned. Secondly, a semi-transmissive film pattern forming process is performed, that is, the light semi-transmissive film is wet-etched with the etching mask film pattern as a mask to form a light semi-transmissive film pattern. There is no particular limitation on the etchant for wet etching the light semi-transmitting film as long as it can selectively etch the light semi-transmitting film. For example, an etchant containing at least one fluorine compound selected from hydrofluoric acid, hydrofluorosilicic acid, and ammonium hydrogen fluoride, and at least one oxidant selected from hydrogen peroxide, nitric acid, and sulfuric acid can be cited. Specific examples thereof include an etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water. In the case of manufacturing a type of phase shift mask having a light-shielding film pattern on the semi-transmitting film pattern, after the semi-transmitting film pattern is formed, the etching mask film pattern is patterned to be narrower than a specific one of the light semi-transmitting film pattern. pattern. In this case, the light semi-transmitting film pattern has a property of changing the phase of the exposed light, and the etching mask film pattern has a light-shielding property. In the case of manufacturing a phase shift mask of a type that does not have a light-shielding film pattern on the semi-transmissive film pattern, the mask film pattern is peeled and etched after the semi-transmissive film pattern is formed. In this case, the light semi-transmitting film pattern has a property of changing the phase of the exposed light. Through such a photoresist pattern forming process, an etching mask film pattern forming process, and a semi-transmissive film pattern forming process, a phase shift photomask for manufacturing a display device is manufactured. The phase shift mask for manufacturing a display device according to the second embodiment manufactured in this way includes a transparent substrate and a light semi-transmissive film pattern made of a metal silicide material formed on the main surface of the transparent substrate. . In the case of a type having a light-shielding film pattern on the semi-transmissive film pattern, an etching mask film pattern made of a chrome-based material formed on the light semi-transmissive film pattern is further provided. The portion where the light semi-transmitting film pattern is arranged constitutes a phase shift portion, and the exposed portion of the transparent substrate constitutes a light transmitting portion. Examples of the light semi-transmissive film pattern include a line and gap pattern or a hole pattern. The light semi-transmissive film pattern has a property of changing the phase of the exposed light. Due to this property, a specific phase difference occurs between the light that is exposed through the phase shifting portion where the light semi-transmissive film pattern is arranged and the light that is exposed through the light transmitting portion exposed through the transparent substrate. In the case where the exposed light is a composite light including light in a wavelength range of 300 nm to 500 nm, the light semi-transmissive film pattern generates a specific phase difference to the light representing the wavelength. For example, when the exposed light is a composite light including i-rays, h-rays, and g-rays, the light semi-transmissive film pattern causes a phase difference of 180 degrees for any of the i-rays, h-rays, and g-rays. As in the above, the phase difference of the light semi-transmissive film pattern is preferably set to a range of 180 ° ± 20 ° for a representative wavelength of any of i-rays, h-rays, and g-rays. It is further preferred that the retardation of the light semi-transmitting film is more preferably set to a range of 180 ° ± 10 ° for a representative wavelength of any of i-rays, h-rays, and g-rays. The transmittance of the light semi-transmissive film is preferably 1% or more and 20% or less at a representative wavelength of any of i-rays, h-rays, and g-rays. It is particularly preferred that the transmittance of the light semi-transmissive film is at least 3% and at most 10% at a representative wavelength of any of i-rays, h-rays, and g-rays. In addition, the phase shift mask used for manufacturing the display device of the present invention is a projection exposure used for equal exposure to fully exert the phase shift effect. In particular, as the exposure environment, the number of openings (NA) is preferably 0.06 to 0.15, more preferably 0.08 to 0.10, and the coherence factor (σ) is preferably 0.5 to 1.0. The light semi-transmissive film pattern may include metal and silicon as long as it has a specific transmittance and phase difference with respect to the exposed light, and may further include other elements. As other elements, any element that can control the refractive index (n) and extinction coefficient (k) of the light to be exposed may be selected from the group consisting of oxygen (O), nitrogen (N), carbon (C), and fluorine (F). Choose from at least one element. Examples include metal silicide oxides, metal silicide oxynitrides, metal silicide nitrides, metal silicide nitride carbides, and metal silicide nitride oxide carbides. From the viewpoint of the pattern controllability of the wet etching, the light semi-transmissive film pattern is preferably made of a metal silicide-based material containing metal, silicon, and a component that slows down the wet etching rate of the light semi-transmissive film. Make up. Examples of the component that slows down the wet etching rate of the light semi-transmissive film include nitrogen (N) and carbon (C). Examples of the metal include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), and titanium (Ti). Examples of the metal silicide-based material constituting the semi-transmissive film pattern include metal silicide nitride, metal silicide oxynitride, metal silicide carbon oxide, metal silicide nitrogen carbide, and metal silicide. Nitrogen oxide carbide. The composition of the metal, silicon, and nitrogen constituting the light semi-transmission pattern is based on the required phase difference (180 degrees ± 20 degrees), the transmittance (1% to 20%), and the wet etching characteristics ( The cross-sectional shape of the light semi-transmissive film pattern or CD unevenness) and the viewpoint of chemical resistance are adjusted. The ratio of metal to silicon is preferably metal: silicon = 1: 1 or more and 1: 9 or less. The content of nitrogen is preferably 25 atomic% or more and 55 atomic% or less, and more preferably 30 atomic% or more and 50 atomic% or less. The composition of the light semi-transmissive film pattern is substantially uniform toward the depth direction of the film. However, the composition gradient region is formed on the upper surface of the light semi-transmissive film pattern, and the composition gradient region is also formed at the interface between the light semi-transmissive film pattern and the transparent substrate, so the composition of these parts is not uniform. The etching mask film pattern is made of a chromium-based material containing chromium (Cr). Examples of the chromium-based material constituting the etching mask film pattern include chromium nitride (CrN), chromium carbide (CrC), chromium nitrogen carbide (CrCN), chromium oxynitride (CrON), chromium oxycarbide (CrCO), Chromium Nitrogen Oxide Carbide (CrCON). Hereinafter, description will be made with reference to FIG. 7 showing a cross-sectional photograph of the phase shift mask of Example 1 and FIG. 8 showing a cross-sectional photograph of the phase shift mask of Example 2. The cross section of the light semi-transmissive film pattern is composed of upper, lower, and side edges 23 corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transparent film pattern. In FIGS. 7 and 8, the auxiliary line 21 indicates a position corresponding to the upper edge of the upper surface of the light semi-transparent film pattern, and the auxiliary line 22 indicates the position corresponding to the lower edge of the lower surface of the light semi-transparent film pattern. In this case, the straight line formed by the contact point 26 between the upper edge and the side edge and the position 27 of the side edge at a position two-thirds of the film thickness from the upper surface, and the angle θ formed with the upper edge is 85 degrees. To 120 degrees. In FIG. 7, the auxiliary line 24 indicates a position where a height of two thirds of the film thickness drops from the upper surface. In addition, the first imaginary line 29 passing through the contact point 26 of the upper side and the side 23 and perpendicular to the main surface of the transparent substrate, and the side of the side at a position where the height rises by one tenth of the film thickness from the lower surface. The width D of the second imaginary line 30 at the position 28 and perpendicular to the main surface of the transparent substrate (hereinafter, sometimes referred to as the bottom width) D is less than one-half of the film thickness. In FIG. 8, the auxiliary line 25 represents a position where the height of one tenth of the film thickness rises from the lower surface. The phase shift mask may also have a light-shielding film pattern on the light semi-transmitting film pattern that shields the exposed light. When a light-shielding film pattern is provided on the light semi-transmissive film pattern, it is easy to recognize the mask pattern by an exposure machine. In addition, the reduction of the photoresist film due to the exposed light of the semi-transmitting film pattern that transmits light can be prevented. According to the manufacturing method of the phase shift mask for manufacturing a display device according to the second embodiment, the phase shift mask obtained by the manufacturing method of the phase shift mask base for manufacturing a display device described in the first embodiment is used. The substrate, or the phase shift mask substrate for manufacturing a display device described in Embodiment 1, manufactures a phase shift mask. Therefore, it is possible to manufacture a phase-shifting photomask having a pattern of light semi-transmitting film having a nearly vertical cross-sectional shape capable of fully exerting a phase-shifting effect. In addition, a phase shift mask having a light semi-transmissive film pattern with a small base width D and small CD unevenness can be manufactured. The phase shift mask can cope with the miniaturization of line and gap patterns or contact holes. The phase shift mask for manufacturing a display device according to the second embodiment includes a light semi-transmissive film pattern made of a metal silicide-based material formed on a main surface of a transparent substrate. The composition of the light semi-transmissive film pattern is substantially uniform throughout the depth direction of the light semi-transmissive film pattern. Therefore, a phase shift mask having uniform optical characteristics can be obtained. In the cross section of the light semi-transmissive film pattern, a straight line formed by the contact point 26 between the upper and side edges and the position 27 of the side edge at a position that is two-thirds of the thickness of the film from the upper surface, and The angle θ formed by the upper side is in the range of 85 degrees to 120 degrees. Furthermore, in the cross section of the light semi-transmissive film pattern, the first imaginary line 29 passing through the upper and side contact points 26 and perpendicular to the main surface of the transparent substrate, and one tenth of the film thickness rising from the lower surface. The width D of the second imaginary line 30 perpendicular to the main surface of the transparent substrate at the position 28 of the side on the position of the height is equal to or less than one half of the film thickness. Therefore, it is possible to obtain a phase shift mask having a pattern of a light semi-transmitting film having a nearly vertical cross-sectional shape capable of fully exerting a phase shift effect. In addition, a phase shift mask having a light semi-transmissive film pattern with a small base width D and small CD unevenness can be obtained. The phase shift mask can cope with the miniaturization of line and gap patterns or contact holes. Embodiment 3. In Embodiment 3, the manufacturing method of a display device is demonstrated. In the method for manufacturing a display device according to the third embodiment, first, a phase shift mask arrangement process is performed, that is, a substrate with a photoresist film formed with a photoresist film on the substrate will be described in the second embodiment. The phase-shifting mask obtained by the method for manufacturing a phase-shifting mask for a display device or the phase-shifting mask for manufacturing a display device described in Embodiment 2 is arranged to face the photoresist film. Secondly, a photoresist film exposure process is performed, that is, the phase shift mask is irradiated with exposure light to expose the photoresist film. The exposed light is, for example, a composite light including light in a wavelength range of 300 nm to 500 nm. Specifically, it is a composite light including i rays, h rays, and g rays. Moreover, as the exposure at the time of manufacture of a display device, projection exposure with equal exposure is preferable. Regarding the exposure environment, the number of openings (NA) is preferably 0.06 to 0.15, more preferably 0.08 to 0.10, and the coherence factor (σ) is preferably 0.5 to 1.0. According to the method for manufacturing a display device according to the third embodiment, the phase shift mask obtained by the method for manufacturing a phase shift mask for manufacturing a display device described in the second embodiment is used, or the method described in the second embodiment is used. A display device is manufactured in a phase shift mask for manufacturing a display device. Therefore, a display device having a fine line and gap pattern or a contact hole can be manufactured. [Examples] Hereinafter, the present invention will be described more specifically based on examples. Example 1. A. Phase shift mask substrate and manufacturing method thereof In order to manufacture the phase shift mask substrate of Example 1, first, a synthetic quartz glass substrate having a size of 3345 (330 mm × 450 mm × 5 mm) was prepared as a transparent substrate. 12. Thereafter, the synthetic quartz glass substrate is mounted on a tray (not shown) with the main surface facing downward, and is carried into the carrying-in chamber LL of the continuous sputtering apparatus 11 shown in FIG. 4. In the first sputtering chamber SP1, a sputtering target containing molybdenum silicide (Mo: Si = 1: 4) is arranged as the first sputtering target 13 on the side of the carry-in chamber LL. In the first sputtering chamber SP1, a sputtering target containing chromium is disposed as the second sputtering target 14 on the buffer chamber BU side. In the second sputtering chamber SP2, a sputtering target containing chromium is disposed as the third sputtering target 15 on the buffer chamber BU side, and a sputtering target including chromium is disposed as the first sputtering target on the ULL side of the carry-out chamber. 4 sputtering target 16. In order to form a light semi-transmissive film on the main surface of a synthetic quartz glass substrate, first, an argon (Ar) gas is introduced from a first gas introduction port GA1 located near the first sputtering target 13 in the first sputtering chamber SP1. With nitrogen (N 2 ) Gas mixture (Ar: 50 sccm, N 2 : 90 sccm), and a sputtering power of 8.0 kW was applied to the first sputtering target 13. In addition, argon (Ar) is introduced from a third gas introduction port GA3 arranged near the third sputtering target 15 of the second sputtering chamber SP2 and a fourth gas introduction port GA4 arranged near the fourth sputtering target 16. Gas and nitrogen (N 2 ) Gas mixture (Ar: 50 sccm, N 2 : 90 sccm). Sputtering power is applied to the first sputtering target 13 and Ar gas and N are introduced from the first gas introduction port GA1. 2 A mixed gas of gases, and Ar gas and N are introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4. 2 The mixed gas system of the gas continues until the synthetic quartz glass substrate is transferred to the unloading chamber ULL. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is sequentially transferred in the direction of the arrow S to the carry-in chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second sputtering chamber. SP2, and ULL out of the chamber. The transfer speed of the synthetic quartz glass substrate was set to 400 mm / minute. When the synthetic quartz glass substrate passes near the first sputtering target 13 of the first sputtering chamber SP1, a 55.0 nm film containing molybdenum silicide is formed on the main surface of the synthetic quartz glass substrate by reactive sputtering. (MoSiN) first light semi-transmitting film. While the synthetic quartz glass substrate passed through the second sputtering chamber SP2, the first layer of light semi-transmitting film was exposed to Ar gas and N 2 Gas mixture atmosphere. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is sequentially transferred in the direction opposite to the arrow S to the unloading chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, and the first sputtering The chamber SP1 and the carry-in chamber LL are returned to the carry-in chamber LL. While returning the synthetic quartz glass substrate to the carry-in chamber LL, Ar gas and N were introduced from the first gas introduction port GA1. 2 Gas mixture (Ar: 50 sccm, N 2 : 90 sccm), Ar gas and N are introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4. 2 Gas mixture (Ar: 50 sccm, N 2 : 90 sccm), the first light semi-transmitting film is exposed to Ar gas and N 2 Gas mixture atmosphere. Thereafter, a sputtering power is applied to the first sputtering target 13 and Ar gas and N are introduced from the first gas introduction port GA1. 2 A mixed gas of gases, and Ar gas and N are introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4. 2 A mixed gas of gas was formed on the first light semi-transmitting film by the same method as the above method to form a second light semi-transmitting film including a molybdenum nitrogen silicide film (MoSiN) with a thickness of 55.0 nm on the first light semi-transmitting film and forming the film Then, the second light semi-transmitting film is exposed to Ar gas and N 2 Gas mixture atmosphere. In this way, a light transflective film having a total film thickness of 110 nm including two layers of molybdenum silicide films (MoSiN) was formed on the main surface of the synthetic quartz glass substrate. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transferred in a direction opposite to the arrow S, and returned to the loading chamber LL. While returning the synthetic quartz glass substrate to the carry-in chamber LL, the second layer of light semi-transmitting film was exposed to Ar gas and N by the same method as the above method. 2 Gas mixture atmosphere. Secondly, a light-shielding layer and an anti-reflection layer serving as an etching mask film are formed on the light semi-transmitting film. The light-shielding layer and the anti-reflection layer are adjusted to be introduced into the second sputtering target 14 so that the reflectance of the film surface for a specific wavelength (for example, g-ray) becomes 15% or less and the optical density OD (Optical Density) becomes 3.0 or more Type, flow rate, and synthetic quartz glass substrate of the second gas introduction port GA2, the third gas introduction port GA3, and the fourth gas introduction port 4 near the chromium target of the third sputtering target 15 and the fourth sputtering target 16 The transfer speed is adjusted, and the sputtering power applied to each sputtering target is appropriately adjusted. Ar gas and N are introduced from the second gas introduction port GA2 2 A mixed gas of gas is introduced from the third gas introduction port GA3 system to Ar gas and methane (CH 4 ) Gas, a mixed gas of Ar gas and nitric oxide (NO) gas is introduced from the fourth gas introduction port GA4. Furthermore, the sputtering power is applied to each sputtering target, and the mixed gas system is introduced from each gas introduction port until the synthetic quartz glass is transferred to the discharge chamber ULL. The transfer speed of the synthetic quartz glass substrate was set to 400 mm / minute. As a result, a light-shielding layer including a laminated film including a chromium nitride film (CrN) with a film thickness of 25.0 nm and a chromium nitride film (CrCN) with a film thickness of 70.0 nm was formed on the light semi-transmitting film, and a film thickness including 20.0 nm Laminated film of anti-reflection layer of chromium oxynitride film (CrON). In this way, an etching mask film is formed on the light semi-transmissive film in which a light-shielding layer including a laminated film of CrN and CrCN and a laminated structure including an anti-reflection layer of CrON are sequentially formed. After that, the second sputtering chamber is completely separated from the carry-out chamber by a partition plate, and the carry-out chamber is returned to the atmospheric pressure state. The synthetic quartz formed with the light semi-transmitting film and the etching mask film is taken out from the sputtering device 11 Glass base board. In this way, a phase-shifting mask substrate having a light semi-transmissive film and an etching mask film formed on a synthetic quartz glass substrate was obtained. With the MPM-100 manufactured by Japan Lasertec Corporation, the transmittance and phase difference of the light semi-transmitting film of the phase shift mask substrate obtained were measured. In the measurement of the transmittance and phase difference of the light semi-transmitting film, two layers of molybdenum silicon nitride film (MoSiN) (total film) were formed on the main surface of a synthetic quartz glass substrate manufactured by mounting on the same tray. 110 nm thick) substrate (dummy substrate) with light transmissive film. The transmittance and phase difference of the light semi-transmitting film were measured before taking out the substrate (dummy substrate) with the light semi-transmitting film from the carrying-out chamber ULL before forming the etching mask film. As a result, the transmittance was 5.2% (wavelength: 365 nm) and the phase difference was 180 degrees (wavelength: 365 nm). In addition, a film surface reflectance and an optical density were measured with respect to the obtained phase-shift mask substrate by using a spectrophotometer SolidSpec-3700 manufactured by Shimadzu Corporation. The film surface reflectance of the phase shift mask substrate (etching mask film) was 10.0% (wavelength: 436 nm), and the optical density OD was 4.0 (wavelength: 436 nm). It can be seen that the etching mask film functions as a light-shielding film having a low reflectance on the film surface. The obtained phase shift mask substrate was analyzed for composition in the depth direction by X-ray photoelectron spectroscopy (XPS). FIG. 5 shows the composition analysis results of the phase shift mask substrate of Example 1 in the depth direction obtained by using XPS. The horizontal axis in FIG. 5 indicates the sputtering time (minutes), and the vertical axis indicates the content (atomic%). In Figure 5, curve a shows the change in the content of silicon (Si), curve b shows the change in the content of nitrogen (N), curve c shows the change in content of oxygen (O), curve d shows the change in content of carbon (C), and curve e Represents the change in the content of chromium (Cr), and curve f indicates the change in the content of molybdenum (Mo). As shown in FIG. 5, in the composition analysis result of the depth direction obtained by using XPS for the phase shift mask substrate, the silicon (Si) peak and the molybdenum (Mo) peak caused by the light semi-transmissive film appear until In the composition gradient region P where the chromium (Cr) wave peak caused by the etching mask film disappears, the content of nitrogen (N), which slows down the wet etching rate of the light semi-transmissive film, faces the depth direction of the light semi-transmissive film. (Orientation of synthetic quartz glass substrate) Increasing stepwise and / or continuously. The content of oxygen in the composition gradient region P is 5 atomic% or less. The maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 3.7. The content of molybdenum (Mo) in the uniform region Q after the disappearance of the chromium (Cr) peak caused by the etching mask film until the appearance of the oxygen (O) peak caused by the synthetic quartz glass substrate is 15 atomic% The content of silicon (Si) is an average of 38 atomic%, the content of nitrogen (N) is an average of 45 atomic%, the content of oxygen (O) is 2 atomic% or less, and the variation of each content is 5 atomic% or less. In the above-mentioned method for manufacturing a phase shift mask substrate, a light semi-transmissive film and an etching mask film are continuously formed while maintaining a specific vacuum degree. In order to reliably obtain the effect of the present invention, it is preferable to continuously form a light semi-transmissive film and an etching mask film while maintaining a specific degree of vacuum. By forming the light semi-transmissive film and the etching mask film while maintaining a specific degree of vacuum, it is possible to reduce the variation in composition from the outermost surface of the light semi-transmissive film to the synthetic quartz glass substrate. Furthermore, even if the light semi-transmissive film is stored in the atmosphere after it is formed, or the light semi-transmissive film is washed before the etching mask film is formed, as long as the composition of the fixed range is changed, it can be obtained as in Example 1. The same effect. B. Phase-shifting photomask and manufacturing method thereof are to manufacture phase-shifting photomask using the phase-shifting photomask substrate manufactured in the above manner. First, a photoresist is applied to the etching mask film of the phase-shifting photomask substrate. The device is coated with a photoresist film. After that, a photoresist film having a film thickness of 1000 nm was formed through a heating and cooling process. Thereafter, a photoresist film was drawn using a laser drawing device. After development and processing, a photoresist with a line pattern width of 2.0 μm and a gap pattern width of 2.0 μm was formed on the etching mask film. Agent pattern. Thereafter, the photoresist pattern is used as a mask, and the etching mask film is wet-etched with a chromium etchant containing cerium (II) ammonium nitrate and perchloric acid to form an etching mask film pattern. Thereafter, the light semi-transmitting film is wet-etched with a molybdenum silicide etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water, using the etching mask film pattern as a mask to form a light semi-transmitting film. pattern. After that, the photoresist pattern was peeled. Thereafter, a photoresist film is applied using a photoresist coating device so as to cover the pattern of the etching mask film. After that, a photoresist film having a film thickness of 1000 nm was formed through a heating and cooling process. Thereafter, a photoresist film was drawn using a laser drawing device, and a photoresist pattern with a line pattern width of 1.0 μm was formed on the etching mask film pattern through a development and washing process. Thereafter, the photoresist pattern is used as a mask, and the etching mask film pattern is wet-etched with a chromium etchant containing cerium (II) ammonium nitrate and perchloric acid to form a width narrower than that of the light semi-transmissive film pattern. Etch mask film pattern. After that, the photoresist pattern was peeled. In this way, a phase-shifting mask is obtained in which a light semi-transmissive film pattern and an etching mask film pattern narrower than the width of the light semi-transmissive film pattern are formed on a synthetic quartz glass substrate. The scanning electron microscope was used to observe the plane and section of the obtained phase shift mask. In the following examples and comparative examples, a scanning electron microscope was used to observe the plane and cross section of the phase shift mask. FIG. 6 is a plan photograph of the phase shift mask of Embodiment 1. FIG. FIG. 7 is a cross-sectional photograph of the phase shift mask of Embodiment 1. FIG. In FIGS. 6 and 7, QZ represents a synthetic quartz glass substrate, PS represents a light semi-transmissive film pattern, and Cr represents an etching mask film pattern. As shown in FIG. 7, the cross-section of the light semi-transmissive film pattern PS has a shape in which the bottom portion of the portion in contact with the synthetic quartz glass substrate QZ expands and the portion in contact with the etching mask film pattern Cr is substantially perpendicular. In detail, the cross section of the light semi-transmissive film pattern PS is composed of upper, lower, and side edges 23 corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern PS. The auxiliary line 21 indicates a position corresponding to the upper edge of the upper surface of the light semi-transmissive film pattern PS, and the auxiliary line 22 indicates the position corresponding to the lower edge of the lower surface of the light semi-transmissive film pattern PS. The straight line formed by the contact point 26 between the upper side and the side edge and the side position 27 at the height of two thirds of the film thickness from the upper surface, and the angle θ formed with the upper side is 105 degrees. The auxiliary line 24 indicates a position where a height of two thirds of the film thickness drops from the upper surface. In addition, the first imaginary line passing through the contact point 26 of the upper side and the side 23 and perpendicular to the main surface of the synthetic quartz glass substrate QZ, and the side at a position that rises by a tenth of the film thickness from the lower surface The width of the second imaginary line at the side position and perpendicular to the main surface of the synthetic quartz glass substrate QZ is 44 nm. As described above, the cross-sectional shape of the light semi-transmissive film pattern is good, the angle θ is 105 degrees, and the width is 44 nm (1 / 2.5 of the film thickness of 110 nm with respect to the light semi-transmissive film), so that Under exposure light of light in a wavelength range above 500 nm and below, and more specifically exposure light including i-ray, h-ray, and g-ray composite light, a PSM ( A) Phase shift mask with equivalent phase shift effect. The CD unevenness of the light semi-transmitting film pattern of the phase shift mask was measured with SIR8000 manufactured by Seiko Instruments NanoTechnology. The measurement of the CD unevenness is performed on a 5 × 5 portion of a 270 mm × 390 mm area excluding a peripheral area of the substrate. The CD unevenness is the deviation width from the target line and gap pattern (width of line pattern: 2.0 μm, gap pattern width: 2.0 μm). In the following examples and comparative examples, the same device was used for the measurement of CD unevenness. The CD unevenness was good at 0.096 μm. As shown in FIG. 6, the edge E of the light semi-transmissive film pattern PS is linear, indicating that the CD unevenness is good. Example 2. In Example 2, a case where the light semi-transmissive film is composed of four layers of molybdenum silicide nitride films (MoSiN) will be described. A. Phase-shifting mask substrate and manufacturing method thereof In the manufacturing of the phase-shifting mask substrate of Example 2, a synthetic quartz glass substrate having a size of 3345 was used as the transparent substrate 12. By the same method as in Example 1, the synthetic quartz glass substrate was carried into the carrying-in chamber LL of the continuous sputtering apparatus 11 shown in FIG. 4. As the first sputtering target 13, the second sputtering target 14, the third sputtering target 15, and the fourth sputtering target 16, the same sputtering target as that of Example 1 was used. Thereafter, the inside of the sputtering device 11 was brought to a specific vacuum degree by the same method as in Example 1. The exhaust system is continued until the synthetic quartz glass substrate is taken out from the sputtering device 11. Thereafter, Ar gas and N are introduced from a first gas introduction port GA1 disposed near the first sputtering target 13 in the first sputtering chamber SP1. 2 Gas mixture (Ar: 30 sccm, N 2 : 30 sccm), and a sputtering power of 4.0 kW was applied to the first sputtering target 13. In addition, Ar gas and N are introduced from a third gas introduction port GA3 arranged near the third sputtering target 15 of the second sputtering chamber SP2 and a fourth gas introduction port GA4 arranged near the fourth sputtering target 16. 2 Gas mixture (Ar: 30 sccm, N 2 : 30 sccm). Sputtering power is applied to the first sputtering target 13 and Ar gas and N are introduced from the first gas introduction port GA12. 2 A mixed gas of gases, and Ar gas and N are introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4. 2 The mixed gas system of the gas continues until the synthetic quartz glass substrate is transferred to the unloading chamber ULL. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transported in the direction of the arrow S to the unloading chamber ULL. The transfer speed of the synthetic quartz glass substrate was set to 400 mm / minute. When the synthetic quartz glass substrate passed near the first sputtering target 13 of the first sputtering chamber SP1, a reactive silicon plating was used to form a 27.5 nm film containing molybdenum silicide on the main surface of the synthetic quartz glass substrate. (MoSiN) first light semi-transmitting film. While the synthetic quartz glass substrate passed through the second sputtering chamber SP2, the first layer of light semi-transmitting film was exposed to Ar gas and N 2 Gas mixture atmosphere. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transferred in a direction opposite to the arrow S, and returned to the loading chamber LL. While returning the synthetic quartz glass substrate to the carry-in chamber LL, Ar gas and N were introduced from the first gas introduction port GA1. 2 Gas mixture (Ar: 30 sccm, N 2 : 30 sccm), Ar gas and N are introduced from the third gas inlet GA3 2 Gas mixture (Ar: 30 sccm, N 2 : 30 sccm), the first light semi-transmitting film is exposed to Ar gas and N 2 Gas mixture atmosphere. Thereafter, the second layer, the third layer, and the fourth layer of the light semi-transmitting film were formed by the same method as the first layer of the light semi-transmitting film. After forming the second, third, and fourth light semi-transmitting films, the synthetic quartz glass substrate mounted on a tray (not shown) is transported in a direction opposite to the arrow S, and returned to the carrying chamber LL. During the return of the synthetic quartz glass substrate to the carry-in chamber LL, the second, third, and fourth light semi-transmitting films were exposed to Ar gas and N by the same method as above. 2 Gas mixture atmosphere. In this way, a light semi-transmissive film with a total film thickness of 110 nm including four layers of molybdenum silicide film (MoSiN) was formed on the main surface of the synthetic quartz glass substrate. Thereafter, an etching mask film was formed on the light semi-transmitting film by the same method as in Example 1, to obtain a phase-shifting mask substrate on which a light semi-transmitting film and an etching mask film were formed on a synthetic quartz glass substrate. As in the above-mentioned Embodiment 1, the composition of the obtained phase-shift mask base was analyzed in the depth direction by using XPS. As a result, in the composition gradient region P, the content of nitrogen (N) that slows the wet etching of the light semi-transmissive film continuously increases toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). The maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P is 3.6. B. Phase-shifting photomask and manufacturing method thereof The phase-shifting photomask substrate manufactured in the above manner is used, and an etching mask film pattern and a light transmissive film pattern are formed by the same method as in Example 1. After the light semi-transmissive film pattern is formed, the photoresist pattern is peeled off. Thereafter, the etching mask film pattern is removed by a chromium etchant containing cerium (II) ammonium nitrate and perchloric acid. In this way, a phase-shifting mask having a pattern of a light semi-transmissive film formed on a synthetic quartz glass substrate was obtained. FIG. 8 is a cross-sectional photograph of a phase shift mask of Embodiment 2. FIG. In FIG. 8, QZ indicates a synthetic quartz glass substrate, and PS indicates a light semi-transmissive film pattern. As shown in FIG. 8, the cross-section of the light semi-transmissive film pattern PS has a shape in which the bottom portion of the portion in contact with the synthetic quartz glass substrate QZ expands and the portion in contact with the etching mask film pattern is substantially perpendicular. In detail, the cross section of the light semi-transmissive film pattern PS is composed of upper, lower, and side edges 23 corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern PS. The auxiliary line 21 indicates a position corresponding to the upper edge of the upper surface of the light semi-transmissive film pattern PS, and the auxiliary line 22 indicates the position corresponding to the lower edge of the lower surface of the light semi-transmissive film pattern PS. The straight line formed by the contact point 26 between the upper side and the side edge and the position of the side edge at a position two-thirds of the thickness of the film falling from the upper surface, and the angle formed by the upper side is 105 degrees. In addition, the first imaginary line 29 passing through the contact 26 between the upper side and the side 23 and perpendicular to the main surface of the synthetic quartz glass substrate QZ and at a height of one tenth of the film thickness rising from the lower surface The width D of the second imaginary line 30 at the side position 28 and perpendicular to the main surface of the synthetic quartz glass substrate QZ is 48 nm. The auxiliary line 25 indicates a position where the height of one tenth of the film thickness rises from the lower surface. As described above, the cross-sectional shape of the light semi-transmissive film pattern is good, the angle θ is 105 degrees, and the width is 48 nm (about 1 / 2.3 of the film thickness of 110 nm with respect to the light semi-transmissive film). Under exposure light of a wavelength range of more than nm to 500 nm, and more specifically exposure light including a combination of i-rays, h-rays, and g-rays, a PSM having a PSM shown in Table 2 above can be obtained. (B) Phase shift mask with equivalent phase shift effect. Embodiment 3. In Embodiment 3, a case where the light semi-transmissive film is composed of a single layer of molybdenum silicide nitride film (MoSiN) will be described. A. Phase-shifting mask substrate and manufacturing method thereof In the manufacturing of the phase-shifting mask substrate of Embodiment 3, a synthetic quartz glass substrate having a size of 3345, which is the same as that of Embodiments 1 and 2, is used as the transparent substrate 12. By the same method as in Example 1, the synthetic quartz glass substrate was carried into the carrying-in chamber LL of the continuous sputtering apparatus 11 shown in FIG. 4. As the first sputtering target 13, the second sputtering target 14, the third sputtering target 15, and the fourth sputtering target 16, the same sputtering target materials as those of Example 1 were used. A sputtering power of 10.0 kW was applied to the first sputtering target 13 of the first sputtering chamber SP1. In addition, Ar gas and N are introduced from a first gas introduction port GA1 disposed near the first sputtering target 13. 2 Gas mixture (Ar: 50.0 sccm, N 2 : 100.0 sccm). In addition, Ar gas and N are introduced from a third gas introduction port GA3 arranged near the third sputtering target 15 of the second sputtering chamber SP2 and a fourth gas introduction port GA4 arranged near the fourth sputtering target 16. 2 Gas mixture (Ar: 50.0 sccm, N 2 : 100.0 sccm). Sputtering power is applied to the first sputtering target 13 and Ar gas and N are introduced from the first gas introduction port GA1. 2 A mixed gas of gases, and Ar gas and N are introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4. 2 The mixed gas system of the gas continues until the synthetic quartz glass substrate is transferred to the unloading chamber ULL. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transported in the direction of the arrow S to the unloading chamber ULL. The transfer speed of the synthetic quartz glass substrate was set to 350 mm / minute. When the synthetic quartz glass substrate passes near the first sputtering target 13 of the first sputtering chamber SP1, a reactive sputtering is used to form a film with a thickness of 110 nm on the main surface of the synthetic quartz glass substrate. (MoSiN) light transflective film. While the synthetic quartz glass substrate passed through the second sputtering chamber SP2, the light semi-transmitting film was exposed to Ar gas and N 2 Gas mixture atmosphere. In this way, a light semi-transmissive film with a thickness of 110 nm including a layer of a molybdenum nitride silicide film (MoSiN) was formed on the main surface of the synthetic quartz glass substrate. After that, the second sputtering chamber SP2 is completely separated from the carrying-out chamber ULL by a spacer plate, and then the carrying-out chamber ULL is returned to the atmospheric pressure state. The synthetic quartz glass substrate on which the light semi-transmitting film is formed is taken out from the sputtering apparatus 11 . Thereafter, the synthetic quartz glass substrate having the light semi-transmissive film formed thereon was stored in the atmosphere for about 2 days. Thereafter, the synthetic quartz glass substrate on which the light semi-transmitting film is formed is carried into the carrying-in chamber LL of the continuous sputtering apparatus 11 shown in FIG. 4. Thereafter, an etching mask film was formed on the light semi-transmitting film by the same method as in Example 1, to obtain a phase-shifting mask substrate having a light semi-transmitting film and an etching mask film formed on a synthetic quartz glass substrate. As in the above-mentioned Embodiment 1, the composition of the obtained phase-shift mask base was analyzed in the depth direction by using XPS. As a result, in the composition gradient region P, the content of nitrogen (N) that slows the wet etching of the light semi-transmissive film continuously increases toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). The maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 8.2. B. Phase-shifting photomask and manufacturing method thereof The phase-shifting photomask substrate manufactured in the above manner was used, and the phase-shifting photomask was manufactured by the same method as in Example 1. FIG. 9 is a sectional photograph of a phase shift mask of Embodiment 3. FIG. In FIG. 9, QZ indicates a synthetic quartz glass substrate, PS indicates a light semi-transmissive film pattern, and Cr indicates an etching mask film pattern. FIG. 9 is a cross-sectional photograph showing a state before an etch mask film pattern narrower than a width of the light semi-transmissive film pattern is formed. As shown in FIG. 9, the cross-section of the light semi-transmissive film pattern PS has a shape in which a bottom portion of a portion in contact with the synthetic quartz glass substrate QZ expands and a portion in contact with the etching mask film pattern Cr is substantially perpendicular. In detail, the cross section of the light semi-transmissive film pattern PS is composed of upper, lower, and side edges corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern PS. The angle formed by the straight line connecting the contact point between the upper side and the side with the position of the side at a position which is two-thirds of the film thickness from the upper surface and the upper side is 97 degrees. In addition, the first imaginary line passing through the contact point between the upper side and the side edge and perpendicular to the main surface of the synthetic quartz glass substrate QZ, and the side edge at a position that rises by a tenth of the film thickness from the lower surface The width of the second imaginary line at the position and perpendicular to the main surface of the synthetic quartz glass substrate QZ is 20 nm. The CD unevenness was good, and was 0.098 μm. As described above, the cross-sectional shape of the light semi-transmissive film pattern is good, the angle θ is 97 degrees, and the width is 20 nm (1 / 5.5 with respect to the film thickness of the light semi-transmissive film of 110 nm), so that it contains 300 nm Under exposure light of light in a wavelength range above 500 nm and below, and more specifically exposure light including i-ray, h-ray, and g-ray composite light, a PSM ( A) Phase shift mask with equivalent phase shift effect. Example 4. In Example 3, a synthetic quartz glass substrate on which a light semi-transmissive film was formed was stored in the atmosphere for about 2 days. On the other hand, in Example 4, the synthetic quartz glass substrate on which the light semi-transmissive film was formed was stored in the atmosphere for one week. Except for this, a phase shift mask substrate and a phase shift mask were manufactured by the same method as in Example 3. As in Example 1, the composition of the obtained phase-shift mask substrate was analyzed in the depth direction using XPS. As a result, in the composition gradient region P, the wet etching of the light semi-transmissive film was slowed down. The content of nitrogen (N) continuously increases toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). The maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 3.2. FIG. 10 is a sectional photograph of a phase shift mask of Embodiment 4. FIG. In FIG. 10, QZ indicates a synthetic quartz glass substrate, PS indicates a light semi-transmissive film pattern, and Cr indicates an etching mask film pattern. FIG. 10 is a cross-sectional photograph showing a state before an etch mask film pattern is formed which is narrower than the width of the light semi-transmissive film pattern. As shown in FIG. 10, the cross section of the light semi-transmitting film pattern PS is a linear wedge shape. In detail, the cross section of the light semi-transmissive film pattern PS is composed of upper, lower, and side edges corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern PS. The straight line connecting the contact point between the upper side and the side and the position of the side at the position where the height of the two-thirds of the film thickness drops from the upper surface is 120 degrees with the upper side. In addition, the first imaginary line passing through the contact point between the upper side and the side edge and perpendicular to the main surface of the synthetic quartz glass substrate QZ, and the side edge at a position that rises by a tenth of the film thickness from the lower surface The width of the second imaginary line at the position and perpendicular to the main surface of the synthetic quartz glass substrate QZ is 42 nm. The CD unevenness was good, and was 0.105 μm. As described above, the cross-sectional shape of the light semi-transmissive film pattern is good, the angle θ is 120 degrees, and the width is 42 nm (about 1 / 2.6 of the film thickness of 110 nm with respect to the light semi-transmissive film). Under exposure light in a wavelength range of more than 500 nm and less than 500 nm, and more specifically exposure light including a combination of i-rays, h-rays, and g-rays, a PSM having a PSM shown in Table 1 above can be obtained. (A) Phase shift mask with equivalent phase shift effect. According to Example 4, even if the light semi-transmitting film is stored in the air for about one week, as long as the composition within a fixed range is changed, good CD unevenness can be maintained. Example 5. In Example 5, a case where an insulating layer is formed on a light semi-transmissive film will be described. A. Phase-shifting mask substrate and manufacturing method thereof In the manufacturing of the phase-shifting mask substrate of Example 5, a synthetic quartz glass substrate having a size of 3345 was used as the transparent substrate 12. A light semi-transmitting film was formed on the main surface of the synthetic quartz glass substrate by the same method as in Example 1. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transferred in a direction opposite to the arrow S, and returned to the loading chamber LL. While returning the synthetic quartz glass substrate to the carry-in chamber LL, the second layer of light semi-transmitting film was exposed to Ar gas and N by the same method as the above method. 2 Gas mixture atmosphere. Thereafter, Ar gas and N are introduced from a second gas introduction port GA2 located near the second sputtering target 14 of the first sputtering chamber SP1. 2 Gas and CO 2 Gas mixture (Ar: 55 sccm, N 2 : 60 sccm, CO 2 : 35 sccm), and a sputtering power of 5.0 kW was applied to the second sputtering target 14. Sputtering power is applied to the second sputtering target 14, and Ar gas and N are introduced from the second gas introduction port GA2. 2 Gas and CO 2 The mixed gas system of the gas continues until the synthetic quartz glass substrate is transferred to the unloading chamber ULL. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transported in the direction of the arrow S to the unloading chamber ULL. The transfer speed of the synthetic quartz glass substrate was set to 400 mm / minute. When the synthetic quartz glass substrate passed near the second sputtering target 14 of the first sputtering chamber SP1, a reactive nitrogen sputtering was performed on the light semi-transmissive film to make a 200 nm-thick chromium nitride oxide film (CrCON) ). Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transferred in a direction opposite to the arrow S, and returned to the loading chamber LL. Thereafter, by the same method as in Example 1, a laminated film including a light-shielding layer including a chromium nitride film (CrCN) and an anti-reflection layer including a chromium nitride oxide film (CrON) was formed on the insulating layer. In this way, an etching mask film is formed on the light semi-transmitting film, and the etching mask film has a laminated structure in which an insulating layer including CrCON, a light shielding layer including CrCN, and an anti-reflection layer including CrON are sequentially formed. After that, the second sputtering chamber is completely separated from the carry-out chamber by a partition plate, and the carry-out chamber is returned to the atmospheric pressure state. The synthetic quartz formed with the light semi-transmitting film and the etching mask film is taken out from the sputtering device 11 Glass base board. In this way, a phase-shifting mask substrate having a light semi-transmissive film and an etching mask film formed on a synthetic quartz glass substrate was obtained. As in the above-mentioned Embodiment 1, the composition of the obtained phase-shift mask base was analyzed in the depth direction by using XPS. As a result, in the composition gradient region P, the content of nitrogen (N) that slows the wet etching of the light semi-transmissive film continuously increases toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). The maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P was 3.7. B. Phase-shifting photomask and manufacturing method thereof The phase-shifting photomask substrate manufactured in the above manner was used, and the phase-shifting photomask was manufactured by the same method as in Example 1. Observe the cross section of the obtained phase shift mask. As in Example 1, the cross-section of the light semi-transmissive film pattern has a shape in which the bottom portion of the portion in contact with the synthetic quartz glass substrate is expanded and the portion in contact with the etching mask film pattern is substantially perpendicular. In detail, the cross section of the light semi-transmissive film pattern is composed of upper, lower, and side edges corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern. The angle formed by the straight line connecting the contact point between the upper side and the side with the position of the side at a position which is two-thirds of the film thickness from the upper surface and the upper side is 105 degrees. In addition, the position of the side edge at a position that passes through the contact point between the upper side and the side edge and is perpendicular to the main surface of the synthetic quartz glass substrate and at a height of one tenth of the film thickness from the lower surface. The width of the second imaginary line perpendicular to the main surface of the synthetic quartz glass substrate is 44 nm. The angle of the light semi-transmitting film pattern in contact with the synthetic quartz glass substrate is 60 degrees, and the angle of the light semi-transmitting film pattern in contact with the etching mask film pattern is 75 degrees. The CD unevenness was very good, and was 0.060 μm. As described above, the cross-sectional shape of the light semi-transmissive film pattern is good, the angle θ is 105 degrees, and the width is 44 nm (1 / 2.5 of the thickness of the light transmissive film 110 nm), so Under exposure light of light in a wavelength range above 500 nm and below, and more specifically exposure light including i-ray, h-ray, and g-ray composite light, a PSM ( A) Phase shift mask with equivalent phase shift effect. Reference Example 1. In Reference Example 1, the surface of the light semi-transmissive film was not exposed to N-containing film after the film was formed. 2 The gas atmosphere will be described. A. Phase shift mask substrate and manufacturing method thereof In the manufacture of the phase shift mask substrate of Reference Example 1, a synthetic quartz glass substrate having a size of 3345 was used as the transparent substrate 12. By the same method as in Example 1, the synthetic quartz glass substrate was carried into the carrying-in chamber LL of the continuous sputtering apparatus 11 shown in FIG. 4. As the first sputtering target 13, the second sputtering target 14, the third sputtering target 15, and the fourth sputtering target 16, the same sputtering target as that of Example 1 was used. Ar gas and N are introduced from a first gas introduction port GA1 located near the first sputtering target 13 in the first sputtering chamber SP1. 2 Gas mixture (Ar: 40 sccm, N 2 : 90 sccm), and a sputtering power of 8.5 kw was applied to the first sputtering target 13. Further, an Ar gas (130 sccm) is introduced from a third gas introduction port GA3 arranged near the third sputtering target 15 of the second sputtering chamber SP2 and a fourth gas introduction port GA4 arranged near the fourth sputtering target 16. ). Sputtering power is applied to the first sputtering target 13 and Ar gas and N are introduced from the first gas introduction port GA1. 2 The mixed gas of the gas and the introduction of the Ar gas system from the third gas introduction port GA3 and the fourth gas introduction port GA4 are continued until the synthetic quartz glass substrate is transferred to the unloading chamber ULL. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transferred to the unloading chamber ULL in the direction of the arrow S. The transfer speed of the synthetic quartz glass substrate was set to 400 mm / minute. When the synthetic quartz glass substrate passes near the first sputtering target 13 of the first sputtering chamber SP1, a 55.0 nm film containing molybdenum silicide is formed on the main surface of the synthetic quartz glass substrate by reactive sputtering. (MoSiN) first light semi-transmitting film. While the synthetic quartz glass substrate passed through the second sputtering chamber SP2, the first light semi-transmitting film was exposed to the Ar gas atmosphere. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transferred in a direction opposite to the arrow S, and returned to the loading chamber LL. During the period when the synthetic quartz glass substrate is returned to the carry-in chamber LL, the first-layer light semi-transmitting film formed is in a vacuum state. Thereafter, a second-layer light semi-transmitting film was formed in the same manner as the first-layer light semi-transmitting film. In this way, a light transflective film having a total film thickness of 110 nm including two layers of molybdenum silicide films (MoSiN) was formed on the main surface of the synthetic quartz glass substrate. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transferred in a direction opposite to the arrow S, and returned to the loading chamber LL. During the period when the synthetic quartz glass substrate is returned to the carry-in chamber LL, the second-layer light semi-transmitting film formed is in a vacuum state. Thereafter, an etching mask film was formed on the light semi-transmitting film by the same method as in Example 1, to obtain a phase-shifting mask substrate having a light semi-transmitting film and an etching mask film formed on a synthetic quartz glass substrate. With respect to the obtained phase shift mask substrate, XPS was used to analyze the composition in the depth direction. As a result, the content of nitrogen (N) in the vicinity of the center in the thickness direction of each of the two layers constituting the light semi-transmitting film was 46 to 47 atomic%. On the other hand, the content of nitrogen (N) near the interface of the layer 2 is 44 atomic%. In the vicinity of the center of each layer and the interface of the two layers, a difference in nitrogen (N) content of 2-3 atomic% can be seen. Although this difference is slightly close to the detection limit, it can be presumed that it was caused by passing through the Ar gas atmosphere after the formation of the light semi-transmitting film, and then passing the vacuum atmosphere while the tray was being returned to the LL chamber. , Causing nitrogen to desorb from the surface of the first light semi-transmitting film. In addition, by forming the second light semi-transmitting film, the content of nitrogen (N) is reduced near the interface between the first layer and the second layer. In the composition gradient region P, the content of nitrogen (N) that slows the wet etching of the light semi-transmissive film continuously increases toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). B. Phase-shifting photomask and manufacturing method thereof The phase-shifting photomask substrate manufactured in the above manner was used, and the phase-shifting photomask was manufactured by the same method as in Example 1. FIG. 11 is a plan view of a phase shift mask of Reference Example 1. FIG. FIG. 12 is a sectional photograph of the phase shift mask of Reference Example 1. FIG. In FIGS. 11 and 12, QZ indicates a synthetic quartz glass substrate, PS indicates a light semi-transmissive film pattern, and Cr indicates an etching mask film pattern. 12 is a cross-sectional photograph showing a state before an etch mask film pattern having a width narrower than a width of the light semi-transmitting film pattern is formed. As shown in FIG. 12, a large bite is generated at the interface between the first light semi-transmitting film pattern and the second light semi-transmitting film pattern. As described above, the vicinity of the interface between the first light semi-transmitting film and the second light semi-transmitting film is in a state where the content of nitrogen (N) is small. It is considered that the vicinity of the interface where the nitrogen content is small is bite due to being etched more quickly. In detail, the cross section of the light semi-transmissive film pattern PS is composed of upper, lower, and side edges corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern PS. The straight line formed by the contact point between the upper side and the side edge and the position of the side edge at the height of two thirds of the film thickness falling from the upper surface, and the angle formed by the upper side is 80 degrees. In addition, the first imaginary line passing through the contact point between the upper side and the side edge and perpendicular to the main surface of the synthetic quartz glass substrate QZ, and the side edge at a position that rises by one tenth of the film thickness from the lower surface. The width of the second imaginary line at the position and perpendicular to the main surface of the synthetic quartz glass substrate QZ is 45 nm. In addition, all of the CDs are 0.252 μm. As shown in FIG. 11, the edge E1 of the light semi-transmissive film pattern PS is jagged, which indicates that the CD unevenness is large. If the edge E1 of the light semi-transmissive film pattern PS is jagged, the edge E2 of the etching mask film pattern Cr is also jagged. The reason is considered to be that when the etching mask film pattern Cr is formed, the etchant penetrates along the shape of the edge E1 of the light semi-transmissive film pattern PS. In order to control the shape of the etching mask film pattern Cr, the shape of the light semi-transmissive film pattern PS is more important. According to Reference Example 1, in a case where a light semi-transmitting film composed of a plurality of layers is formed by repeating the film formation of the light semi-transmitting film multiple times, the light semi-transmitting film is not exposed to N that slows down the wet etching rate 2 In a gas atmosphere, biting occurs at the interface between two adjacent layers of a light semi-transmissive film composed of a plurality of layers. Presumably, N is not contained in the gas atmosphere exposed after film formation 2 In the case of a gas, a slight change in the composition of the light semi-transmissive film is caused by the desorption of a small amount of nitrogen from the surface of the light semi-transmissive film, thereby forming a portion easily etched at the interface. Reference Example 2. In Example 3, when a light semi-transmissive film was formed, Ar gas and N were introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4 of the second sputtering chamber SP2. 2 A mixture of gases. On the other hand, in Reference Example 2, no gas was introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4 of the second sputtering chamber SP2 when the light semi-transmissive film was formed. Except for this, a phase shift mask substrate and a phase shift mask were manufactured by the same method as in Example 3. As in the above-mentioned Embodiment 1, the composition of the obtained phase-shift mask base was analyzed in the depth direction by using XPS. As a result, in the composition gradient region P, the content of nitrogen (N) that slows the wet etching of the light semi-transmissive film gradually increases toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). However, the maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface of the etching mask film side in the composition gradient region P is 2.4. FIG. 13 is a cross-sectional photograph of a phase shift mask of Reference Example 2. FIG. In FIG. 13, QZ indicates a synthetic quartz glass substrate, PS indicates a light semi-transmitting film pattern, and Cr indicates an etching mask film pattern. FIG. 13 is a cross-sectional photograph showing a state after the light semi-transmissive film pattern is formed and before the photoresist pattern is peeled. As shown in FIG. 13, the cross section of the light semi-transmitting film pattern PS is a linear wedge shape. In detail, the cross section of the light semi-transmissive film pattern PS is composed of upper, lower, and side edges corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern PS. The angle formed by the straight line connecting the contact point between the upper side and the side with the position of the side at a position which is two-thirds of the thickness of the film which is lowered from the upper surface, is 135 degrees with the upper side. In addition, the first imaginary line passing through the contact point between the upper side and the side edge and perpendicular to the main surface of the synthetic quartz glass substrate QZ, and the side edge at a position that rises by one tenth of the film thickness from the lower surface. The width of the second imaginary line at the position and perpendicular to the main surface of the synthetic quartz glass substrate QZ is 85 nm. As described above, the cross-sectional shape of the light semi-transmissive film pattern is a wedge shape, the angle θ is 135 degrees, and the width is 85 nm (about 1 / 1.3 with respect to the film thickness of the light semi-transmissive film 110 nm). Therefore, in the obtained phase-shifting reticle, exposure to light including light in a wavelength range of 300 nm to 500 nm, and more specifically, exposure to composite light including i-rays, h-rays, and g-rays Under the light, the degree of phase shift effect equivalent to that of PSM (A) shown in Table 1 above cannot be obtained. Reference Example 3. In Example 3, when a light semi-transmissive film was formed, Ar gas and N were introduced from the gas introduction port GA3 and the gas introduction port GA4 of the second sputtering chamber SP2. 2 A mixture of gases. In contrast, in Reference Example 3, when a light semi-transmissive film was formed, only Ar gas (150 sccm) was introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4 of the second sputtering chamber SP2. Except for this, a phase shift mask substrate and a phase shift mask were manufactured by the same method as in Example 3. As in the above-mentioned Embodiment 1, the composition of the obtained phase-shift mask base was analyzed in the depth direction by using XPS. As a result, in the composition gradient region P, the content of nitrogen (N) that slows the wet etching of the light semi-transmissive film gradually increases toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). However, the maximum value of the ratio of nitrogen (N) to silicon (Si) in the composition gradient region P is 2.6. 14 is a cross-sectional photograph of a phase shift mask of Reference Example 3. FIG. In FIG. 14, QZ indicates a synthetic quartz glass substrate, PS indicates a light semi-transmissive film pattern, and Cr indicates an etching mask film pattern. FIG. 14 is a cross-sectional photograph showing a state in which the etching mask film pattern is wet-etched to form an etching mask film pattern narrower than the width of the light semi-transmissive film pattern. As shown in FIG. 14, the cross section of the light semi-transmitting film pattern PS is a linear wedge shape. In detail, the cross section of the light semi-transmissive film pattern PS is composed of upper, lower, and side edges corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern PS. The angle formed by the straight line connecting the contact point between the upper side and the side with the position of the side at a position which is two-thirds of the thickness of the film which is lowered from the upper surface, is 135 degrees with the upper side. In addition, the first imaginary line passing through the contact point between the upper side and the side edge and perpendicular to the main surface of the synthetic quartz glass substrate QZ, and the side edge at a position that rises by one tenth of the film thickness from the lower surface. The width of the second imaginary line at the position and perpendicular to the main surface of the synthetic quartz glass substrate QZ was 89 nm. As described above, the cross-sectional shape of the light semi-transmissive film pattern is a wedge shape, the angle θ is 135 degrees, and the width is 89 nm (about 1 / 1.2 with respect to the film thickness of the light semi-transmissive film 110 nm). Therefore, in the obtained phase-shifting reticle, exposure to light including light in a wavelength range of 300 nm to 500 nm, and more specifically, exposure to composite light including i-rays, h-rays, and g-rays Under the light, the degree of phase shift effect equivalent to that of PSM (A) shown in Table 1 above cannot be obtained. Comparative Example 1. In Example 3, when a light semi-transmissive film was formed, Ar gas and N were introduced from the first gas introduction port GA1 of the first sputtering chamber SP1. 2 Gas mixture (Ar: 50.0 sccm, N 2 : 100.0 sccm), Ar gas and N are introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4 of the second sputtering chamber SP2 2 Gas mixture (Ar: 50.0 sccm, N 2 : 100.0 sccm). In addition, a sputtering power of 10.0 kW was applied to the first sputtering target 13 of the first sputtering chamber SP1. The transfer speed of the synthetic quartz glass substrate was set to 350 mm / minute. The film thickness of the light semi-transmitting film was 110 nm. On the other hand, in Comparative Example 1, Ar gas and N were introduced from the first gas introduction port GA1 of the first sputtering chamber SP1. 2 Gas mixture (Ar: 65 sccm, N 2 : 50 sccm), Ar gas (120 sccm) is introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4 of the second sputtering chamber SP2. In addition, a sputtering power of 6.3 kW was applied to the first sputtering target 13 of the first sputtering chamber SP1. The transfer speed of the synthetic quartz glass substrate was 200 mm / min. The film thickness of the light semi-transmitting film was 115 nm. After the light semi-transmissive film is formed, the surface of the light semi-transmissive film is washed with ozone water. Except for this, a phase shift mask substrate and a phase shift mask were manufactured by the same method as in Example 3. As in the above-mentioned Embodiment 1, the composition of the obtained phase-shift mask base was analyzed in the depth direction by using XPS. As a result, in the composition gradient region P, there is a region in which the content of nitrogen (N) that slows the wet etching of the light semi-transmitting film decreases toward the depth direction of the light semi-transmitting film (the direction of the synthetic quartz glass substrate). The maximum value of the ratio of nitrogen (N) to silicon (Si) at the interface on the etching mask film side in the composition gradient region P is 2.0. FIG. 15 is a sectional photograph of a phase shift mask of Comparative Example 1. FIG. In FIG. 15, QZ indicates a synthetic quartz glass substrate, PS indicates a light semi-transmitting film pattern, and Cr indicates an etching mask film pattern. 15 is a cross-sectional photograph showing a state before an etch mask film pattern having a width smaller than a width of the light semi-transmitting film pattern is formed. As shown in FIG. 15, the cross-section of the light semi-transmissive film pattern PS has a linear wedge shape. In detail, the cross section of the light semi-transmissive film pattern PS is composed of upper, lower, and side edges corresponding to the upper surface, the lower surface, and the side surfaces of the light semi-transmissive film pattern PS. The angle formed by the straight line connecting the contact point between the upper side and the side with the position of the side at a position which is two-thirds of the film thickness from the upper surface and the upper side is 160 degrees. In addition, the first imaginary line passing through the contact point between the upper side and the side edge and perpendicular to the main surface of the synthetic quartz glass substrate QZ, and the side edge at a position that rises by one tenth of the film thickness from the lower surface. The width of the second imaginary line at the position and perpendicular to the main surface of the synthetic quartz glass substrate QZ is 295 nm. In addition, the angle of the light semi-transmissive film pattern PS in contact with the synthetic quartz glass substrate QZ is 15 degrees, and the angle between the contact point of the upper edge and the side edge and the height of two thirds of the film thickness from the upper surface is lower. The straight line formed by the positions and the angle formed by the top line are 160 degrees. In addition, the side that passes through the contact point of the upper side and the side T and is perpendicular to the main surface of the synthetic quartz glass substrate QZ and the side that is at a height of one tenth of the film thickness from the lower surface The width of the second imaginary line at the position perpendicular to the main surface of the synthetic quartz glass QZ is 295 nm. The angle of the light semi-transmitting film pattern PS in contact with the synthetic quartz glass substrate QZ is 15 degrees, and the angle of the light semi-transmitting film pattern PS in contact with the etching mask film pattern Cr is 165 degrees. The transport speed of synthetic quartz glass substrates is slow, and the exposure time to the Ar atmosphere is longer after the formation of the light semi-transmissive film. Therefore, it is considered that the nitrogen concentration at the interface between the light semi-transmissive film and the etching mask film is further reduced.入 large. As described above, the cross-sectional shape of the light semi-transmissive film pattern is a large wedge shape, the angle θ is 165 degrees, and the width is 295 nm (about 3 times the film thickness of the light semi-transmissive film at 110 nm). Therefore, in the obtained phase-shifting reticle, exposure to light including light in a wavelength range of 300 nm to 500 nm, and more specifically, exposure to composite light including i-rays, h-rays, and g-rays Under the light, only the phase shift effect equivalent to that of PSMTP (A) shown in Table 1 above can be obtained. In addition, all of the CDs were 0.230 μm. Furthermore, in the above-mentioned embodiment, after the formation of the molybdenum nitride silicide film, exposure to Ar gas and N 2 An example of a mixed gas atmosphere has been described, but even for exposure to N 2 The same effect can be obtained in a gas atmosphere. Further, even if a gas containing a nitrogen compound such as a nitrogen monoxide gas, a nitrogen monoxide gas, or a nitrogen dioxide gas is used instead of the nitrogen gas, the same effect as that of the present invention can be obtained. When the light semi-transmitting film contains carbon other than nitrogen as a component for slowing wet etching, the same effect as that of the present invention can be obtained even if a gas containing a carbon compound is used instead of nitrogen. Moreover, in the above-mentioned embodiment, although the example of the molybdenum silicide film was demonstrated as a material of a light semi-transmitting film, it is not limited to this. The material used as the light semi-transmissive film may also be a molybdenum silicide oxynitride film or a molybdenum silicide oxynitride film. In addition, in the case of a metal silicide-based material other than molybdenum silicide, the same effect as the above can be obtained. Moreover, in the above-mentioned embodiment, although the example of the phase shift mask base used for manufacturing a display device, or the phase shift mask used for manufacturing a display device was demonstrated, it is not limited to this. The phase shift reticle substrate or phase shift reticle of the present invention can also be applied to semiconductor device manufacturing, MEMS (Microelectromechanical Systems) manufacturing, printed substrates, and the like. In the above-mentioned embodiment, the example in which the size of the transparent substrate is 3345 (330 mm × 450 mm) has been described, but it is not limited to this. In the case of manufacturing a phase shift mask substrate for a display device, a large-size transparent substrate is used. The size of the transparent substrate is 10 inches or more on one side. The size of a transparent substrate used for manufacturing a phase shift mask base for a display device is, for example, 330 mm × 450 mm or more and 2280 mm × 3130 mm or less. In the case of manufacturing a semiconductor device, a MEMS, and a phase shift mask substrate for a printed substrate, a small-size transparent substrate is used. The size of the transparent substrate is 9 inches on one side. Inches or less. The size of the transparent substrate used in the phase shift mask base of the above-mentioned application is, for example, 63.1 mm × 63.1 mm or more and 228.6 mm × 228.6 mm or less. Generally, when manufacturing semiconductors and MEMS, 6025 size (152 mm × 152 mm) or 5009 size (126.6 mm × 126.6 mm) is used; when manufacturing printed substrates, 7012 size (177.4 mm × 177.4 mm) is used. ), Or 9012 size (228.6 mm × 228.6 mm).

1‧‧‧線與間隙圖案1‧‧‧ line and gap pattern

2a‧‧‧線圖案2a‧‧‧ line pattern

2b‧‧‧線圖案2b‧‧‧line pattern

2c‧‧‧線圖案2c‧‧‧ line pattern

3a‧‧‧間隙圖案3a‧‧‧Gap pattern

3b‧‧‧間隙圖案3b‧‧‧Gap pattern

4‧‧‧相移膜圖案之邊緣部分4‧‧‧ Edge portion of phase shift film pattern

5‧‧‧遮光膜圖案5‧‧‧ light-shielding film pattern

11‧‧‧濺鍍裝置11‧‧‧Sputtering device

12‧‧‧透明基板12‧‧‧ transparent substrate

13‧‧‧第1濺鍍靶13‧‧‧The first sputtering target

14‧‧‧第2濺鍍靶14‧‧‧Second sputtering target

15‧‧‧第3濺鍍靶15‧‧‧The third sputtering target

16‧‧‧第4濺鍍靶16‧‧‧The fourth sputtering target

21‧‧‧輔助線21‧‧‧ auxiliary line

22‧‧‧輔助線22‧‧‧ auxiliary line

23‧‧‧側邊23‧‧‧ side

24‧‧‧輔助線24‧‧‧ auxiliary line

25‧‧‧輔助線25‧‧‧ auxiliary line

26‧‧‧接點26‧‧‧Contact

27‧‧‧側邊之位置27‧‧‧ side position

28‧‧‧側邊之位置28‧‧‧ side position

29‧‧‧第1假想線29‧‧‧The first imaginary line

30‧‧‧第2假想線30‧‧‧ 2nd imaginary line

BU‧‧‧緩衝腔室BU‧‧‧ buffer chamber

Cr‧‧‧蝕刻遮罩膜圖案Cr‧‧‧Etching mask film pattern

D‧‧‧寬度D‧‧‧Width

E‧‧‧邊緣E‧‧‧Edge

E1‧‧‧邊緣E1‧‧‧Edge

E2‧‧‧邊緣E2‧‧‧Edge

LL‧‧‧搬入腔室LL‧‧‧ moved into the chamber

P‧‧‧組成梯度區域P‧‧‧ composes gradient area

PS‧‧‧光半透過膜圖案PS‧‧‧light semi-transmitting film pattern

Q‧‧‧組成均勻區域Q‧‧‧ composes uniform area

QZ‧‧‧合成石英玻璃基板QZ‧‧‧ synthetic quartz glass substrate

S‧‧‧箭頭S‧‧‧ Arrow

SP1‧‧‧第1濺鍍腔室SP1‧‧‧The first sputtering chamber

SP2‧‧‧第2濺鍍腔室SP2‧‧‧Second Sputtering Chamber

ULL‧‧‧搬出腔室ULL‧‧‧ moved out of the chamber

θ‧‧‧角度θ‧‧‧ angle

圖1係模擬時使用之線與間隙圖案之模式圖。 圖2係表示第1次之模擬結果之圖。 圖3係表示第2次之模擬結果之圖。 圖4係表示用於光半透過膜及蝕刻遮罩膜之形成之濺鍍裝置的模式圖。 圖5係表示針對實施例1之相移光罩基底的深度方向之組成分析結果之圖。 圖6係實施例1之相移光罩之平面照片。 圖7係實施例1之相移光罩之剖面照片。 圖8係實施例2之相移光罩之剖面照片。 圖9係實施例3之相移光罩之剖面照片。 圖10係實施例4之相移光罩之剖面照片。 圖11係參考例1之相移光罩之平面照片。 圖12係參考例1之相移光罩之剖面照片。 圖13係參考例2之相移光罩之剖面照片。 圖14係參考例3之相移光罩之剖面照片。 圖15係比較例1之相移光罩之剖面照片。Figure 1 is a schematic diagram of the line and gap patterns used in the simulation. FIG. 2 is a graph showing the results of the first simulation. FIG. 3 is a graph showing the results of the second simulation. FIG. 4 is a schematic view showing a sputtering apparatus for forming a light semi-transmissive film and an etching mask film. FIG. 5 is a graph showing a composition analysis result in the depth direction of the phase shift mask substrate of Example 1. FIG. FIG. 6 is a plan photograph of the phase shift mask of Embodiment 1. FIG. FIG. 7 is a cross-sectional photograph of the phase shift mask of Embodiment 1. FIG. FIG. 8 is a cross-sectional photograph of a phase shift mask of Embodiment 2. FIG. FIG. 9 is a sectional photograph of a phase shift mask of Embodiment 3. FIG. FIG. 10 is a sectional photograph of a phase shift mask of Embodiment 4. FIG. FIG. 11 is a plan view of a phase shift mask of Reference Example 1. FIG. FIG. 12 is a sectional photograph of the phase shift mask of Reference Example 1. FIG. FIG. 13 is a cross-sectional photograph of a phase shift mask of Reference Example 2. FIG. 14 is a cross-sectional photograph of a phase shift mask of Reference Example 3. FIG. FIG. 15 is a sectional photograph of a phase shift mask of Comparative Example 1. FIG.

Claims (15)

一種相移光罩基底，其特徵在於具備：透明基板；光半透過膜，其形成於上述透明基板之主表面上，具有改變曝光之光之相位之性質；及蝕刻遮罩膜，其形成於該光半透過膜上，且由鉻系材料所構成；且上述光半透過膜為金屬矽化物之氮化物，金屬矽化物之氮氧化物，金屬矽化物之碳氧化物，金屬矽化物之氮碳化物，金屬矽化物之氮氧碳化物中之任一者，且由複數層所構成；於上述光半透過膜與上述蝕刻遮罩膜之界面形成有組成梯度區域，於該組成梯度區域內，氮或碳之比率朝向深度方向階段性及/或連續性地增加。A phase-shifting mask substrate, comprising: a transparent substrate; a light semi-transmitting film formed on the main surface of the transparent substrate and having a property of changing the phase of light exposed; and an etching mask film formed on The light semi-transmitting film is composed of a chromium-based material; and the light semi-transmitting film is a nitride of a metal silicide, a nitrogen oxide of the metal silicide, a carbon oxide of the metal silicide, and a nitrogen of the metal silicide. Any one of carbide, oxynitride of metal silicide, and composed of a plurality of layers; a composition gradient region is formed at an interface between the light semi-transmitting film and the etching mask film, and within the composition gradient region The ratio of nitrogen or carbon increases stepwise and / or continuously toward the depth. 如請求項1之相移光罩基底，其中上述光半透過膜之除該光半透過膜與上述蝕刻遮罩膜之界面及該光半透過膜與上述透明基板之界面以外之組成均勻區域之部分的組成實質上均勻。For example, the phase shift mask substrate of claim 1, wherein the light semi-transmitting film has a uniform area except the interface between the light semi-transmitting film and the etching mask film and the interface between the light semi-transmitting film and the transparent substrate. The composition of the portions is substantially uniform. 如請求項2之相移光罩基底，其中上述組成均勻區域之氮的比率之變動為5原子%以下。For example, the phase shift mask substrate of claim 2, wherein the variation of the ratio of nitrogen in the uniform composition region is 5 atomic% or less. 如請求項1或2之相移光罩基底，其中當自上述組成梯度區域內之與上述蝕刻遮罩膜之邊界中的上述蝕刻遮罩膜側，利用X射線光電子光譜法，於測定步進為0.5分鐘之條件下進行組成分析時，在初次檢測到1原子%以上之矽(Si)之位置上，氮(N)相對於矽(Si)之比率(N/Si)為3.0以上且30以下。For example, the phase shift mask substrate of claim 1 or 2, wherein when the etching mask film side in the boundary between the composition gradient region and the etching mask film is used, the step is measured by X-ray photoelectron spectroscopy. When the composition analysis was performed under the condition of 0.5 minutes, the ratio of nitrogen (N) to silicon (Si) (N / Si) was 3.0 or more and 30 at the position where silicon (Si) was detected for 1 atomic% or more for the first time. the following. 如請求項1或2之相移光罩基底，其中上述光半透過膜中金屬與矽之比率為金屬：矽=1：1以上且1：9以下。For example, the phase shift mask substrate of claim 1 or 2, wherein the ratio of metal to silicon in the light semi-transmitting film is metal: silicon = 1 or more and 1: 9 or less. 如請求項1或2之相移光罩基底，其中上述金屬為鉬(Mo)、鉭(Ta)、鎢(W)、鈦(Ti)、鋯(Zr)中之任一者。For example, the phase shift mask substrate of claim 1 or 2, wherein the metal is any one of molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), and zirconium (Zr). 如請求項6之相移光罩基底，其中上述金屬為鋯(Zr)。The phase shift mask substrate of claim 6, wherein the metal is zirconium (Zr). 如請求項1或2之相移光罩基底，其中上述蝕刻遮罩膜具有遮光性。The phase shift mask substrate according to claim 1 or 2, wherein the etching mask film has light-shielding property. 一種相移光罩，其特徵在於具備對如請求項1至8中任一項之相移光罩基底之上述光半透過膜進行濕式蝕刻而形成之光半透過膜圖案；且上述光半透過膜圖案之除上表面及該光半透過膜圖案與上述透明基板之界面以外之部分的組成實質上均勻，上述光半透過膜圖案之剖面係由對應於該光半透過膜圖案之上述上表面、下表面及側面之上邊、下邊及側邊所構成，上述上邊與上述側邊之接點與自上述上表面下降膜厚之三分之二之高度之位置上的上述側邊之位置連成的直線、與上述上邊所成之角度為85度至120度之範圍內，且通過上述上邊與上述側邊之接點且相對於上述透明基板之上述主表面垂直之第1假想線、與通過自上述下表面上升膜厚之十分之一之高度之位置上的上述側邊之位置且相對於上述透明基板之上述主表面垂直之第2假想線的寬度為上述膜厚之二分之一以下。A phase-shifting photomask comprising a light-transmitting film pattern formed by wet-etching the light-transmitting film of the phase-shifting photomask substrate according to any one of claims 1 to 8; The composition of the transmissive film pattern except for the upper surface and the interface between the light semi-transmissive film pattern and the transparent substrate is substantially uniform. The upper side, lower side, and side edges of the surface, the lower surface, and the sides are formed, and the contact points of the upper side and the side edge are connected to the position of the side edge at a position that is two-thirds of the film thickness from the upper surface. A first imaginary line formed by a straight line, an angle between the upper side and the upper side within a range of 85 to 120 degrees, and passing through the contact point between the upper side and the side and perpendicular to the main surface of the transparent substrate, and The width of the second imaginary line passing through the position of the side at a position which is a height of one tenth of the film thickness from the lower surface and perpendicular to the main surface of the transparent substrate is half of the film thickness. One of the following. 如請求項9之相移光罩，其中上述光半透過膜圖案包含線與間隙圖案。The phase shift mask according to claim 9, wherein the light semi-transmissive film pattern includes a line and a gap pattern. 如請求項9之相移光罩，其中上述光半透過膜圖案包含孔圖案。The phase shift mask according to claim 9, wherein the light semi-transmissive film pattern includes a hole pattern. 一種相移光罩之製造方法，其特徵在於包括：光阻劑圖案形成製程，其係於如請求項1至8中任一項之相移光罩基底之蝕刻遮罩膜上，形成光阻劑圖案；蝕刻遮罩膜圖案形成製程，其係以上述光阻劑圖案為遮罩對上述蝕刻遮罩膜進行濕式蝕刻而形成蝕刻遮罩膜圖案；及半透過膜圖案形成製程，其係以上述蝕刻遮罩膜圖案為遮罩對上述光半透過膜進行濕式蝕刻而形成光半透過膜圖案。A method for manufacturing a phase-shifting photomask, comprising: a photoresist pattern forming process, which is formed on an etching mask film of the phase-shifting photomask substrate according to any one of claims 1 to 8 to form a photoresist Agent pattern; etching mask film pattern forming process, which uses the photoresist pattern as a mask to wet-etch the etching mask film to form an etching mask film pattern; and a semi-permeable film pattern forming process, which is The light semi-transmitting film is wet-etched by using the etching mask film pattern as a mask to form a light semi-transmitting film pattern. 一種顯示裝置之製造方法，其特徵在於包括：相移光罩配置製程，其係對在基板上形成有光阻劑膜之附上述光阻劑膜之上述基板，將如請求項9之相移光罩、或藉由如請求項12之相移光罩之製造方法所獲得的相移光罩對向於上述光阻劑膜而配置；及光阻劑膜曝光製程，其係對上述相移光罩照射上述曝光之光，對上述光阻劑膜進行曝光。A method for manufacturing a display device, comprising: a phase-shifting photomask disposition process, wherein the substrate with a photoresist film and a photoresist film formed on the substrate is subjected to a phase shift as requested in item 9 A photomask, or a phase-shift photomask obtained by the method of manufacturing a phase-shift photomask according to claim 12, arranged opposite to the above-mentioned photoresist film; and a photoresist film exposure process for the above-mentioned phase shift The photomask irradiates the exposure light to expose the photoresist film. 如請求項13之顯示裝置之製造方法，其中上述曝光之光包含300nm以上且500nm以下之波長範圍之光。The method for manufacturing a display device according to claim 13, wherein the exposed light includes light in a wavelength range of 300 nm to 500 nm. 如請求項14之顯示裝置之製造方法，其中上述曝光之光為包含i射線、h射線及g射線之複合光。The method for manufacturing a display device according to claim 14, wherein the exposed light is a composite light including i-rays, h-rays, and g-rays.
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