TW201740183A - 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

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TW201740183A
TW201740183A TW106129835A TW106129835A TW201740183A TW 201740183 A TW201740183 A TW 201740183A TW 106129835 A TW106129835 A TW 106129835A TW 106129835 A TW106129835 A TW 106129835A TW 201740183 A TW201740183 A TW 201740183A
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Taiwan
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film
phase shift
light
transmissive film
light semi
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TW106129835A
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Chinese (zh)
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TWI631413B (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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  • Physics & Mathematics (AREA)
  • 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

A phase-shift mask blank is provided, which may be formed into a cross-sectional shape effectively exhibiting a phase effect by wet etching. The phase-shift mask blank comprises a transparent substrate, a light semi-transmissive film comprised of a metal silicide material formed on a main surface of the transparent substrate, and an etching mask film comprised of a chromium material formed on the light semi-transmissive film, and a compositionally gradient area P is formed at an interface between the light semi-transmissive film and etching mask film. In this compositionally gradient area P, the ratio of a component slowing down the wet etching speed of the light semi-transmissive film is gradually and/or sequentially increased toward a depth direction.

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 present invention relates to a phase shift mask substrate having a good cross-sectional shape of a phase shift film pattern formed by wet etching, a method of manufacturing the same, a phase shift mask using the phase shift mask substrate, and a method of manufacturing the same. Furthermore, the present invention relates to a phase shift mask substrate for manufacturing a display device, a method of manufacturing the same, a phase shift mask for manufacturing a display device using the phase shift mask substrate, a method of manufacturing the same, and a method of manufacturing the same A method of manufacturing a phase shift mask display device.

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At present, as a method employed in the liquid crystal display device, there are a VA (Vertical Alignment) method or an IPS (In Plane Switching) method. By these means, a liquid crystal display device with high definition, high-speed display performance, and wide viewing angle can be realized. In the liquid crystal display device of the above-described method, the pixel electrode is formed by the line and the gap pattern of the transparent conductive film, whereby the response speed and the viewing angle can be improved. Recently, in view of further improvement in response speed and viewing angle, or improvement in light use efficiency of a liquid crystal display device, that is, low power consumption or contrast improvement of a liquid crystal display device, it is required to have a fine width between a line and a gap pattern. Chemical. For example, it is preferable to narrow the width between the line and the gap pattern from 6 μm to 5 μm, and further narrow from 5 μm to 4 μm. Further, in the production of a liquid crystal display device or an organic EL (Electroluminescence) display device, an element such as a transistor is formed by laminating a plurality of layers of a conductive film or an insulating film which is patterned as necessary. At this time, in many cases, the patterning of each film of the deposited layer is performed by a photolithography process. For example, in the thin film transistor used in the display devices, there is a configuration in which a contact hole is formed in the insulating layer by a photolithography process, and the pattern of the upper layer is connected to the pattern of the lower layer. Recently, in such a display device, the demand for displaying a bright and fine image at a sufficient operation speed and reducing power consumption has increased. In order to satisfy such a request, it is required to make the constituent elements of the display device finer and more integrated. 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, it is preferable to use a reticle for manufacturing a display device which can cope with the miniaturization of the line and gap pattern or the contact hole. When the line and gap patterns or the contact holes are miniaturized, in the conventional mask, since the resolution limit of the exposure machine for manufacturing the display device is 3 μm, there is no need for sufficient process margin (Process Margin). In this case, an article with a minimum line width close to the resolution limit is produced. Therefore, there is a problem that the defective rate of the display device becomes high. For example, in consideration of a case where a photomask having a hole pattern for forming a contact hole is used and transferred to a transfer target, it can be rotated by a previous mask as long as it is a hole pattern having a diameter of more than 3 μm. Printed. However, it is very difficult to transfer a hole pattern having a diameter of 3 μm or less, particularly 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, it is also considered to be converted into, for example, an exposure machine having a high NA (Numerical Aperture), but a large investment is required. Therefore, in order to improve the resolution, the line and gap patterns or the contact holes are made fine, and as a mask for manufacturing a display device, a phase shift mask has been attracting attention. Recently, as a photomask for manufacturing a liquid crystal display device, a phase shift mask having a chromium phase shift film has been developed. Patent Document 1 describes a halftone phase shift mask comprising: a transparent substrate; a light shielding layer formed on the transparent substrate; and a phase shift layer formed around the light shielding layer to be 300 nm Any of the above light wavelength regions of 500 nm or less 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 coating the light shielding layer, and forming a photoresist layer on the phase shift layer. The photoresist pattern is formed by exposing and developing the photoresist layer, and the phase shift layer is patterned by using the photoresist pattern as an etch 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 inventors of the present invention have conducted intensive studies on a phase shift mask having a chromium-based phase shift film. As a result, it is understood that when the photoresist phase pattern is masked and the chromium phase shift film is patterned by wet etching, the wet etching solution penetrates into the interface between the photoresist film and the chromium phase shift film. The etching of the interface portion is performed faster. The cross-sectional shape of the edge portion of the formed chromium-based phase shift film pattern produces a gradient which becomes a wedge shape of the bottom extension. When the cross-sectional shape of the edge portion of the chromium phase shift film pattern is a wedge shape, the phase shift effect is weak as the film thickness of the edge portion of the chromium phase shift film pattern is reduced. Therefore, the phase shift effect cannot be fully exerted. Further, the penetration of the wet etching liquid into the interface between the photoresist film and the chromium phase shift film is caused by the poor adhesion between the chromium 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 thus it is extremely difficult to control the line width (CD). Further, the inventors of the present invention have conducted intensive studies on a method of perpendicularizing the cross-sectional shape of the edge portion of the phase shift film pattern in order to solve such problems. Heretofore, a method has been developed in which the film composition (for example, nitrogen content) of the phase shift film has a gradient to change the etching rate in the film thickness direction, or an additive (for example, Al, Ga) is added 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 phase-shifting reticle of a large area. Accordingly, the present invention has been 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 sufficiently exhibiting a phase shift effect by wet etching, and a method of manufacturing the same A phase shift mask having a phase shift film pattern capable of exhibiting a phase shift effect sufficiently, and a method for producing the same, in particular, a phase shift film can be patterned into a phase for manufacturing a display device capable of sufficiently exhibiting a cross-sectional shape of a phase shift effect A shift mask substrate, a method of manufacturing the same, a phase shift mask for manufacturing a display device having a phase shift film pattern capable of exhibiting a phase shift effect, a method of manufacturing the same, and a display device using the phase shift mask method. Further, an object of the present invention is to provide a phase shift mask substrate which can be patterned into a cross-sectional shape having a small CD unevenness by wet etching, a method for producing the same, and a phase having a small CD unevenness. Phase shift mask for moving film pattern and manufacturing method thereof, in particular, phase shift mask substrate for manufacturing display device, which can be patterned into a cross-sectional shape with less CD unevenness, and a method for manufacturing the same, having a CD A phase shift mask for manufacturing a display device having a relatively small phase shift film pattern, a method of manufacturing the same, and a method of manufacturing a display device using the phase shift mask. Further, an object of the present invention is to provide a phase shift mask substrate having uniform optical characteristics, a method of manufacturing the same, a phase shift mask having uniform optical characteristics, and a method of manufacturing the same, and particularly, a phase shift for manufacturing a display device with uniform optical characteristics A mask substrate, a method of manufacturing the same, a phase shift mask for manufacturing a display device having uniform optical characteristics, a method of manufacturing the same, and a method of manufacturing a display device using the phase shift mask. [Technical means for solving the problem] In order to solve the above problems, the present invention has the following configuration. (Configuration 1) A phase shift mask substrate comprising: a transparent substrate; a light semi-transmissive film formed on a main surface of the transparent substrate, having a property of changing a phase of exposed light and being composed of a metal telluride system And a etch mask film formed on the light semi-transmissive film and composed of a chromium-based material; and a composition gradient region is formed at an interface between the light semi-transmissive film and the etch mask film; In the composition gradient region, the ratio of the components which slow down the wet etching rate of the light semi-transmissive film increases in a stepwise and/or continuously manner in the depth direction. (Configuration 2) The phase shift mask substrate of the first aspect, wherein the light semi-transmissive film is apart from the interface between the light semi-transmissive film and the etching mask film, and the light semi-transmissive film and the transparent substrate The composition of the parts other than the interface is substantially uniform. (Configuration 3) The phase shift mask substrate of the first or second aspect, wherein the light semi-transmissive film is composed of a plurality of layers. (Configuration 4) The phase shift mask substrate of the first or second aspect, wherein the metal telluride-based material is a nitride of a metal telluride, a nitrogen oxide of a metal telluride, a carbon oxide of a metal telluride, Any of a nitrogen carbide of a metal telluride and a nitrogen oxide of a metal telluride. (Configuration 5) The phase shift mask substrate of the first or second embodiment, characterized in that the component for slowing down the wet etching rate is nitrogen or carbon. (Configuration 6) The phase shift mask substrate of the fifth aspect, characterized in that, when the component for slowing down the wet etching rate is nitrogen, the boundary with the etching mask film from the composition gradient region is In the above-mentioned etching mask film side, when the composition analysis is performed under the conditions of a measurement step of 0.5 minutes by X-ray photoelectron spectroscopy, nitrogen at a position of 原子 (Si) of 1 at% or more is detected for the first time (N). The maximum value of the ratio (N/Si) with respect to cerium (Si) is 3.0 or more and 30 or less. (Configuration 7) The phase shift mask substrate of the first or second aspect, characterized in that the etching mask film has a light blocking property. (Configuration 8) The phase shift mask substrate according to the first or second aspect, wherein the etching mask film includes a light shielding layer formed on the light semi-transmissive film side and an antireflection layer formed on the light shielding layer. (Configuration 9) The phase shift mask substrate according to the first or second aspect, wherein the etching mask film includes an insulating layer formed to be in contact with the light semi-transmissive film. (Structure 10) The phase shift mask substrate of the ninth aspect, wherein the insulating layer is made 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 shift mask substrate of the first or second aspect, wherein the phase shift mask base is a phase shift mask base for manufacturing a display device. (Configuration 12) A method of manufacturing a phase shift mask substrate, comprising: preparing a process for preparing a transparent substrate; and a semi-transmissive film forming process on the main surface of the transparent substrate by sputtering Forming a light semi-transmissive film having a property of changing the phase of the exposed light and consisting of a metal telluride-based material; and an etching mask forming process which is formed on the light semi-transmissive film by sputtering An etching mask formed of a chromium-based material; and the semi-transmissive film forming process includes a film forming process of forming a light semi-transmissive film composed of a metal telluride-based material by applying a sputtering power in a sputtering gas atmosphere, and Exposing the light semi-permeable membrane to an atmosphere containing a gas atmosphere that slows down a component of the wet etch rate of the light semi-permeable membrane, and the exposure process is performed without exposing the light semi-permeable membrane to the atmosphere The film forming process described above is continuously performed. (Configuration 13) The method for producing a phase shift mask base according to the configuration 12, wherein the film forming process is performed using a sputtering target containing a metal and a ruthenium in a sputtering gas atmosphere containing a mixed gas, The mixed gas includes an inert gas selected from at least one of the group consisting of helium, neon, argon, helium, and neon, and includes a gas selected from the group consisting of nitrogen, nitric oxide, nitrous oxide, and dioxide. An active gas containing a 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 nitrogen gas. (Configuration 14) A method of manufacturing a phase shift mask substrate comprising 12 or 13, characterized in that the exposure process is carried out in a gas atmosphere containing nitrogen or a nitrogen compound. (Configuration 15) A method of producing a phase shift mask substrate comprising 12 or 13, characterized in that the exposure process is carried out in a gas atmosphere containing carbon or a carbon compound. (Configuration 16) A method of manufacturing a phase shift mask substrate comprising 12 or 13, characterized in that the phase shift mask base is a phase shift mask base for manufacturing a display device. (Configuration 17) A phase shift mask comprising: a transparent substrate; and a light semi-transmissive film pattern formed on the main surface of the transparent substrate by wet etching, having a phase of changing the light of the exposure And consisting of a metal telluride-based material; and the light semi-transmissive film pattern has substantially uniform composition except for the upper surface and the interface between the light semi-permeable film pattern and the transparent substrate, and the light semi-transmissive film The cross-section of the pattern is formed by the upper surface, the lower side and the side of the upper surface, the lower surface and the side surface corresponding to the light semi-transmissive film pattern, and the contact between the upper side and the side edge and the film thickness falling from the upper surface a line connecting the positions of the side edges at a height of two, and an angle formed by the upper side with a range of 85 degrees to 120 degrees, and passing through the joint of the upper side and the side and opposite to a position of the first imaginary line perpendicular to the main surface of the transparent substrate and a position at a height of one tenth of a thickness of the film from the lower surface and opposite to the transparent base The width of the second imaginary line perpendicular to the main surface of the above-described film thickness of one-half or less. (Configuration 18) A phase shift mask 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 composed of a metal telluride-based material; and the composition of the light-transmissive film pattern except for the upper surface and the interface between the light-transmissive film pattern and the transparent substrate is substantially uniform, and the light half The cross section of the permeable film pattern is formed by the upper surface, the lower side and the side of the upper surface, the lower surface and the side surface corresponding to the light semi-transmissive film pattern, and the contact between the upper side and the side edge and the film thickness falling from the upper surface a straight line connecting the positions of the two sides at a height of two-thirds, and an angle formed by the upper side with the upper side being in the range of 85 degrees to 120 degrees, and passing through the joint of the upper side and the side a position of the first imaginary line perpendicular to the main surface of the transparent substrate and a position at a height of one tenth of a thickness of the film from the lower surface and opposite 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. (Configuration 19) The phase shift mask of the 17 or 18, wherein the light semi-transmissive film pattern is a metal halide nitride film, a metal halide nitride oxide film, a metal halide carbide oxide, or a metal Any of the oxynitrides of the telluride. (Structure 20) The phase shift mask of the 17 or 18, characterized in that the light semi-transmissive film pattern includes a line and a gap pattern. (Configuration 21) A phase shift mask comprising the 17 or 18, wherein the light semi-transmissive film pattern comprises a hole pattern. (Configuration 22) A method of manufacturing a phase shift mask, comprising: a photoresist pattern forming process on an etch mask film of the phase shift mask substrate of any one of 1 to 11; Or forming a photoresist pattern on the etch mask film of the phase shift mask substrate obtained by the method for fabricating the phase shift mask substrate of any one of 12 to 16; etching the mask film pattern forming process, The etching mask film is wet-etched by using the photoresist pattern as a mask to form an etch mask pattern; and the semi-transmissive film pattern forming process is performed by using the etch mask pattern as a mask pair The light semi-transmissive film is subjected to wet etching to form a light semi-transmissive film pattern. (Configuration 23) The method for producing a phase shift mask according to the configuration 22, wherein the semi-transmissive film pattern forming process is wet etching using an etching solution containing hydrofluoric acid or hydrofluoroantimonic acid. And at least one fluorine compound of ammonium hydrogen fluoride and at least one oxidizing agent selected from the group consisting of hydrogen peroxide, nitric acid, and sulfuric acid. (Configuration 24) The method of manufacturing a phase shift mask according to the configuration 22 or 23, wherein the phase shift mask is a phase shift mask for manufacturing a display device. (Configuration 25) A method of manufacturing a display device, comprising: a phase shift mask arrangement process for a substrate with a photoresist film on which a photoresist film is formed on a substrate, such as 17 to 21 A phase shifting reticle according to any one of the invention, or a phase shifting reticle obtained by the method for producing a phase shifting reticle according to any one of 22 to 24, which is disposed opposite to the photoresist film; The resist film exposure process is performed by irradiating the phase shift mask with the exposed light and exposing the photoresist film. (Configuration 26) The method of manufacturing a display device according to the aspect 25, characterized in that the exposed light includes light having a wavelength range of 300 nm or more and 500 nm or less. (Configuration 27) The method of manufacturing a display device according to 25 or 26, characterized in that the exposed light is a composite light including i-rays, h-rays, and g-rays. [Effects of the Invention] As described above, the phase shift mask substrate according to the present invention, particularly the phase shift mask substrate for manufacturing a display device used for manufacturing a display device, is provided on the main surface of the transparent substrate. A light semi-transmissive film composed of a metal telluride-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-transmissive film and the etching mask film, the ratio of the component which slows down the wet etching rate of the light semi-transmissive film increases stepwise and/or continuously toward the depth direction. Therefore, it is possible to obtain a phase shift mask substrate which can be patterned by wet etching to form a cross-sectional shape in which the phase shift effect can be sufficiently exhibited. Further, it is possible to obtain a phase shift mask substrate which can be patterned by wet etching to have a cross-sectional shape in which CD unevenness is small. Further, according to the method for manufacturing a phase shift mask substrate of the present invention, in particular, a method for manufacturing a phase shift mask substrate for manufacturing a display device used for manufacturing a display device, a metal germanium is formed on a main surface of the transparent substrate. The light semi-transmissive film composed of the material is formed on the light semi-transmissive film to form an etching mask made of a chromium-based material. The formation of the light semi-transmissive film is carried out by forming a light semi-transmissive film and continuously exposing the light semi-permeable film to the inclusion after the film formation without exposing the light semi-permeable film to the atmosphere. The gas atmosphere of the composition of the wet etch rate of the slow light semi-transmissive film. Therefore, it is possible to manufacture a phase shift mask substrate which can be patterned by wet etching to form a cross-sectional shape in which the phase shift effect can be sufficiently exhibited. Further, it is possible to manufacture a phase shift mask substrate which can be patterned by wet etching to have a cross-sectional shape in which CD unevenness is small. Further, the phase shift mask according to the present invention, in particular, a phase shift mask for manufacturing a display device used for manufacturing a display device, comprising a metal halide-based material formed on a main surface of a transparent substrate Light semi-transmissive film pattern. The composition of the light semi-permeable membrane 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 line connecting the position of the upper side and the side and the side of the height of the film which is two-thirds of the thickness of the film from the upper surface is connected to the upper side. The angle is in the range of 85 degrees to 120 degrees. Further, in the cross section of the light semi-transmissive film pattern, the first imaginary line perpendicular to the main surface of the transparent substrate by the contact between the upper side and the side and the height of one tenth of the film thickness rising from the lower surface The width of the second imaginary line perpendicular to the main surface of the transparent substrate at the position of the side of the position is one-half or less of the film thickness. Therefore, a phase shift mask having a light semi-transmissive film pattern capable of exerting a phase shift effect can be obtained. Further, a phase shift mask having a light semi-transmissive film pattern having a small CD unevenness can be obtained. The phase shift mask can cope with the miniaturization of line and gap patterns or contact holes. Further, according to the method for manufacturing a phase shift mask of the present invention, in particular, a method for manufacturing a phase shift mask for manufacturing a display device used for manufacturing a display device, the phase shift mask substrate or the phase shift described above is used. A phase shift mask substrate obtained by a method of manufacturing a mask substrate produces a phase shift mask. Therefore, it is possible to manufacture a phase shift mask having a light semi-transmissive film pattern capable of exerting a phase shift effect sufficiently. Further, it is possible to manufacture a phase shift mask having a light semi-transmissive film pattern having a small CD unevenness. The phase shift mask can cope with the miniaturization of line and gap patterns or contact holes. Further, according to the method of manufacturing a display device of the present invention, the phase shift mask or the phase shift mask obtained by the method for manufacturing the phase shift mask is used to manufacture a display device. Therefore, it is possible to manufacture a display device having a fine line and gap pattern or contact hole.

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 explaining the embodiment of the present invention, the difference in the phase shift effect due to the difference in the cross-sectional shape of the phase shift film pattern will be described using the simulation results. The simulation is based on the number of openings (NA) of 0.085, the homology factor (σ) of 0.9, and the exposure light is the combined light of g-ray, h-ray, and i-ray (intensity ratio is g-ray..h-ray..i-ray=0.95..0.8 ..1.0) Under exposure conditions. The simulation system was performed twice. In the first simulation, a phase shift mask having a cross-sectional shape in which the edge portion has a vertical phase shift film pattern (hereinafter, referred to as PSM (A)), and a cross-sectional shape having an edge portion as a wedge-shaped phase shift The phase shift mask of the film pattern (hereinafter, referred to as PSMTP (A)) and the binary mask (hereinafter referred to as Bin) are performed. In detail, the phase shift mask (PSM (A) and PSMTP (A)) is a line pattern having 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. The composition of the line and gap pattern. The binary photomask (Bin) has a line pattern having a light shielding film pattern and a line and gap pattern including a gap pattern of the light transmitting portion. The line pattern has a width of 2.0 μm and the gap pattern has a width of 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 disposed on the phase shift film pattern other than the edge portion. In the PSM (A), the edge portion of the phase shift film pattern has a transmittance of 6% for the i-ray, and the light transmitted through the edge portion of the phase shift film pattern and the light transmitted through the light transmitting portion have a phase difference of 180 degrees with respect to the i-ray. . 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 in a width of 0.05 μm. Among the edge portions of the ten stages, the portion closest to the light-shielding film pattern has a transmittance of 6% for the i-ray, and the phase difference between the light transmitted through the portion closest to the light-shielding film pattern and the light transmitted through the light-transmitting portion for the i-ray. It is 180 degrees. Among the edge portions of the 10 stages, the portion closest to the light transmitting portion has a transmittance of 57.5% for the i-ray, and the phase difference between the light passing through the portion closest to the light transmitting portion and the light passing through the transmitting portion for the i-ray is It is 20.19 degrees. Further, in the molybdenum oxynitride film (MoSiN) described in the following examples, the angle of the imaginary gradient surface of the edge portion of the ten stages was about 165 degrees. Figure 1 is a schematic diagram of the line and gap patterns used in the simulation. Figure 1 shows a portion of the line and gap pattern 1 in the PSM (A). In Fig. 1, a line pattern 2a located at the center, a line pattern 2b located on the left side of the line pattern 2a via the gap pattern 3a, and a line pattern 2c located on the right side of the line pattern 2a via the gap pattern 3b are shown. The left and right line patterns 2b, 2c display only the width of one half of the line pattern. In Fig. 1, the edge portion 4 of the phase shift film pattern constituting the line patterns 2a, 2b, and 2c, and the light shielding film pattern 5 are indicated by hatching. Table 1 and Figure 2 show the results of the first simulation. In Fig. 2, a curve a represents the result of PSM (A), curve b represents the result of PSMTP (A), and curve c represents the result of Bin. The horizontal axis of Fig. 2 indicates the position (μm) when the center of the line pattern is set to zero, and the vertical axis indicates 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. It can be seen from the simulation results shown in Table 1 and Fig. 2 that the cross-sectional shape of the edge portion of the phase shift film pattern is the case of the vertical phase shift mask (PSM (A)) and 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 a binary mask (Bin). Also, the case of PSMTP (A) is lower than that of Bin. In the case of PSMTP (A), since the edge portion of the phase shift film pattern has a wedge shape, the transmittance becomes high as the light transmitting portion approaches, and the phase difference becomes small. That is, as the light is transmitted close to the light transmitting portion, the amount of light leakage increases 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 has a vertical shape, so that a fixed transmittance (6%) and a phase difference (180 degrees) are maintained even if it is close to the light transmitting portion. That is, the transmittance is immediately changed from the boundary between the edge portion of the phase shift film pattern and the light transmitting portion. Therefore, in the case of PSM (A), although there is light leakage on the edge portion of the phase shift film pattern, the contrast becomes high as compared with the case of Bin. Therefore, it is understood that the phase shift effect can be sufficiently exhibited by making the cross-sectional shape of the edge portion of the phase shift film pattern vertical. In the second simulation, a phase shift mask having a cross-sectional shape in which the edge portion has a vertical phase shift film pattern (hereinafter, referred to as PSM (B)), and a cross-sectional shape having an edge portion as a wedge-shaped phase shift 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 mask (PSM (B) and PSMTP (B)) used for the second simulation was obtained by removing the light shielding film pattern from the PSM (A) and PSMTP (A) used for the first simulation. Specifically, the PSM (B) and the PSMTP (B) are configured to have a line pattern including a phase shift film pattern and a line and gap pattern including a gap pattern of the light transmitting portion. The binary mask (Bin) used for the second simulation is the same as the Bin used for the first simulation. Table 2 and Figure 3 show the results of the second simulation. In Fig. 3, the curve d represents the result of PSM (B), the curve e represents the result of PSMTP (B), and the curve f represents the result of Bin. The horizontal axis of Fig. 3 indicates the position (μm) when the center of the line pattern is set to zero, and the vertical axis indicates the light intensity. [Table 2] As shown in Table 2 and Figure 3, in 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. As can be seen from the simulation results shown in Table 2 and FIG. 3, the cross-sectional shape of the edge portion of the phase shift film pattern is the case of the 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 a binary mask (Bin). Therefore, it is understood that the phase shift effect can be sufficiently exerted 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 according to an embodiment of the present invention, 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 a method for using the same A method of manufacturing a display device having the phase shift mask will be described in detail. Embodiment 1. In Embodiment 1, a phase shift mask substrate for manufacturing a display device and a method of manufacturing the same will be described. In the method for fabricating a phase shift mask substrate for manufacturing a display device according to the first embodiment, a preparation process for preparing a transparent substrate and a semi-transmissive film forming process on the main surface of the transparent substrate are performed by a light semi-transmissive film formed of a metal halide material by sputtering; and an etching mask forming process which is formed on the light semi-transmissive film to form an etching mask made 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 shift mask substrate 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 transmits light to the light used for exposure. For example, synthetic quartz glass, soda lime glass, and alkali-free glass are mentioned. 2. Semi-transmissive film forming process Next, a light semi-transmissive film composed of a metal telluride-based material is formed on the main surface of the transparent substrate by sputtering. Specifically, in the semi-transmissive film forming process, first, a film forming process in which a sputtering power is applied in a sputtering gas atmosphere to form a light semi-transmissive film composed of a metal halide material is formed. Thereafter, in the case where the light semi-transmissive film is not exposed to the atmosphere, the exposure process is continuously performed after the film formation process: exposing the light semi-transmissive film to a wet etching rate including slowing down the semi-transmissive film. The gas atmosphere of the ingredients. The light semi-transmissive film has the property of changing the phase of the exposed light. By this property, a specific phase difference is produced between the light that is transmitted through the light-transmissive film and the light that is only transmitted through the transparent substrate. In the case where the light to be exposed is a composite light including light in a wavelength range of 300 nm or more and 500 nm or less, the light semi-transmissive film is formed to generate a specific phase difference with respect to light of a representative wavelength. For example, when the exposed light is a composite light including i-rays, h-rays, and g-rays, the light semi-transmissive film produces a phase difference of 180 degrees for any of i-rays, h-rays, and g-rays. The way is formed. Moreover, in order to exhibit the phase shift effect described above, the phase difference of the light semi-transmissive film is preferably set to a range of 180 degrees ± 20 degrees for each of the representative wavelengths of the i-ray, the h-ray, and the g-ray. Further, it is preferable that the phase difference of the light semi-transmissive film is set to a range of 180 degrees ± 10 degrees for each of the representative wavelengths of the i-ray, the h-ray, and the g-ray. Further, the transmittance of the light semi-transmissive film is preferably 1% or more and 20% or less at a representative wavelength of any one of the i-ray, the h-ray, and the g-ray. More preferably, the transmittance of the light semi-transmissive film is preferably 3% or more and 10% or less at a representative wavelength of any of i-rays, h-rays, and g-rays. The metal halide-based material constituting the light semi-transmissive film may contain a metal and a ruthenium as long as it has a specific transmittance and phase difference with respect to the light to be exposed, and may further contain other elements. As other elements, as long as it is an element capable of controlling the refractive index (n) and extinction coefficient (k) of the exposed light, it may be selected from the group consisting of oxygen (O), nitrogen (N), carbon (C), and fluorine (F). Choose among at least one of the elements. For example, an oxide of a metal telluride, a nitrogen oxide of a metal telluride, a nitride of a metal telluride, a nitrogen carbide of a metal telluride, a carbon oxide of a metal telluride, and a nitrogen oxide of a metal telluride may be mentioned. Wait. Further, from the viewpoint of pattern controllability of the wet etching, the metal halide material constituting the light semi-transmissive film is preferably a component containing a metal, a ruthenium, and a wet etching rate for slowing down the semi-transmissive film. s material. Examples of the component for slowing 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 halide-based material constituting the light semi-transmissive film include a nitride of a metal telluride, a nitrogen oxide of a metal telluride, a carbon oxide of a metal telluride, a nitrogen carbide of a metal telluride, and a metal telluride. Nitrogen oxides of matter. Specific examples thereof include a nitride of molybdenum molybdenum (MoSi), a nitride of tantalum telluride (TaSi), a nitride of tungsten germanium (WSi), a nitride of titanium telluride (TiSi), and a nitrogen of zirconium telluride (ZrSi). Nitrogen oxides of bismuth molybdenum oxide, oxynitrides of antimony telluride, oxynitrides of thorium telluride, oxynitrides of titanium telluride, nitrogen oxides of zirconium telluride, carbon oxides of antimony molybdenum, carbon oxides of antimony telluride Carbon oxides of titanium telluride, carbon oxides of thorium telluride, carbon oxides of zirconium telluride, nitrogen carbides of antimony molybdenum, nitrogen carbides of antimony telluride, nitrogen carbides of titanium telluride, nitrogen carbides of zirconium telluride, Nitrogen carbides of bismuth telluride, nitrogen oxycarbides of bismuth molybdenum, nitrogen oxycarbides of bismuth telluride, nitrogen oxycarbides of titanium telluride, nitrogen oxycarbides of thorium telluride, and oxynitrides of zirconium telluride. The composition of the metal, ruthenium, and nitrogen constituting the light semi-transmissive film is based on the required phase difference (180 degrees ± 20 degrees), transmittance (1% or more and 20% or less), and wet etching characteristics (for the exposure light). The light semi-transmissive film pattern has a cross-sectional shape or CD unevenness and chemical resistance. The ratio of metal to bismuth is preferably metal: 矽=1..1 or more and 1..9 or less. The content of nitrogen is preferably 25 atom% or more and 55 atom% or less, and more preferably 30 atom% or more and 50 atom% or less. The film forming process of the light semi-transmissive film is performed by using a sputtering target containing metal and germanium in a sputtering gas atmosphere containing a refractive index (n) under controllable light, and extinction A gas of the composition of the coefficient (k). As such a gas, oxygen (O 2 ), carbon monoxide gas (CO), carbon dioxide gas (CO 2 ), nitrogen (N 2 ), Nitric Oxide (NO), Nitrogen Oxide (NO) 2 ), nitrous oxide gas (N 2 O), hydrocarbon gas (CH 4 Etc.), carbonized fluorine-based gas (CF 4 Etc.), fluorine-based gas (NF) 3 Etc.) and other reactive gases. Moreover, from the viewpoint of pattern controllability of wet etching, the film forming process of the light semi-transmissive film preferably uses a sputtering target containing metal and germanium, and includes a wet etching speed having a slow light semi-transmissive film. The gas of the component is carried out under a sputtering gas atmosphere. As a component which slows down the wet etching rate of the light semi-transmissive film, as mentioned above, nitrogen (N) and carbon (C) are mentioned, for example. Examples of the gas having a component for slowing the wet etching rate of the light semi-permeable membrane include nitrogen gas, nitrogen monoxide gas, nitrogen dioxide gas, nitrous oxide gas, carbon monoxide gas, carbon dioxide gas, and hydrocarbon gas (CH). 4 Etc.), carbonized fluorine-based gas (CF 4 Etc.), fluorine-based gas (NF) 3 Etc.) and other reactive gases. In the atmosphere of the sputtering gas, helium, neon, argon, helium, and xenon may be contained as an inert gas. The sputtering gas atmosphere contains, for example, an inert gas containing at least one selected from the group consisting of helium, neon, argon, helium, and neon, and includes a gas selected from the group consisting of nitrogen, nitric oxide, and nitrogen dioxide. a mixed gas of at least one of the constituent gases of the group. The exposure process after the film formation of the light semi-transmissive film is performed by exposing the light semi-transmissive film to a gas atmosphere for exposure including a gas having a component for slowing the wet etching rate of the light semi-transmissive film. As a component which slows down the wet etching rate of the light semi-transmissive film, as mentioned above, nitrogen (N) is mentioned, for example. As the gas having a component for slowing down the wet etching rate of the light semi-transmissive film, an active gas such as nitrogen gas can be cited. Helium, helium, argon, helium, neon or the like as an inert gas may be contained in the atmosphere for exposure. When the atmosphere for exposure contains a mixed gas atmosphere of nitrogen and an inert gas, the ratio of nitrogen gas to inert gas (nitrogen/inert gas) is 20% or more, preferably 30% or more. The light semi-transmissive film may be in the case of one layer and the case of a plurality of layers. In the case where the semi-transmissive film is composed of a plurality of layers, the film forming process of the light semi-transmissive film and the exposure process after the film formation of the light semi-transmissive film are performed plural times. In the case of performing a plurality of film forming processes, the sputtering power applied to the sputtering target when the film is formed by the light semi-transmissive film can be reduced. 3. The etching mask forming process is followed by forming an etching mask made of a chromium-based material by sputtering on the light semi-transmissive film. The etching mask film may be either a light-shielding property or a light semi-transmissive property. 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 of chromium (Cr), chromium oxide, chromium nitride, chromium carbide, and chromium fluoride. The mask film forming process is performed using a sputtering target containing a chromium or chromium compound in a sputtering gas atmosphere containing a mixed gas, for example, selected from the group consisting of helium, neon, argon, xenon, and xenon. An inert gas of at least one of the group consisting of and an active gas containing at least one selected from the group consisting of oxygen, nitrogen, carbon dioxide gas, nitrogen oxide gas, hydrocarbon gas, and fluorine gas. The etching mask film may be either one of a layer and a plurality of layers. In the case where the etching mask is composed of a plurality of layers, for example, a laminated structure composed of a light shielding layer formed on the light semi-transmissive film side and an antireflection layer formed on the light shielding layer, or a light-emitting layer The case where the insulating layer formed by the semi-transmissive film contact, the light-shielding layer formed on the insulating layer, and the anti-reflection layer formed on the light-shielding layer have a laminated structure. The light shielding layer may be any of a case composed of one layer and a case 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 in the case of one layer and the case of a plurality of layers. As the antireflection layer, for example, a chromium oxynitride film (CrON) can be cited. The insulating layer is composed of, for example, CrCO or CrCON containing less than 50 atomic % of Cr, and has a thickness of 10 nm or more and 50 nm or less. When the etching mask film made of a chromium-based material is subjected to wet etching, the light-transmissive film composed of the metal ion free metal halide material is melted. At this time, electrons are generated. In the case where the insulating layer is formed in contact with the light semi-transmissive film, electrons generated when metal ions are ejected from the light semi-transmissive film can be prevented from being supplied to the etching mask film. Therefore, the etching speed in the plane when the etching mask film is wet-etched can be made uniform. The phase shift mask substrate for manufacturing a display device according to the first embodiment is manufactured by such a preparation process, a semi-transmissive film forming process, and an etching mask film forming process. 4 is a schematic view showing an example of a sputtering apparatus for forming a light semi-transmissive film and an etching mask film. The sputtering apparatus 11 shown in FIG. 4 is of an inline type and is carried into the chamber LL, the first sputtering chamber SP1, the buffer chamber BU, the second sputtering chamber SP2, and the unloading chamber ULL. It consists of 5 chambers. The five chambers are sequentially arranged in sequence. The transparent substrate 12 mounted on a tray (not shown) can be sequentially transported to the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second sputtering chamber at a specific conveying speed in the direction of the arrow S. Room SP2, and carry out the chamber ULL. Further, the transparent substrate 12 mounted on a tray (not shown) can be sequentially returned to the carry-out chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, and the first sputtering chamber in a 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 sputtering chamber SP2, and the carry-out chamber ULL are separated by a spacer. 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 constituted by a large container in which three chambers are connected. Further, the carry-in chamber LL and the carry-out chamber ULL can be spaced apart from the outside of the sputtering apparatus 11 by the spacer. 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 including a metal and a crucible for forming a light semi-transmissive film is disposed on the loading chamber LL side, and a first gas is disposed in the vicinity of the first sputtering target 13 Portal GA1 (not shown). Further, in the first sputtering chamber SP1, a second sputtering target 14 containing chromium to form an etching mask film is disposed on the buffer chamber BU side, and a second gas is disposed in the vicinity of the second sputtering target 14. Portal GA2 (not shown). In the second sputtering chamber SP2, a third sputtering target 15 containing chromium to form an etching mask film is disposed on the buffer chamber BU side, and a third gas introduction port is disposed in the vicinity of the third sputtering target 15. GA31 (not shown). Further, in the second sputtering chamber SP2, a fourth sputtering target 16 containing chromium to form an etching mask is disposed on the side of the carrying chamber ULL, and a fourth gas introduction is disposed in the vicinity of the fourth sputtering target. Port 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 indicated by hatching. When a semi-transmissive film and an etching mask are formed by using the continuous sputtering apparatus 11 shown in FIG. 4, first, in order to form a light semi-transmissive film, the substrate (not shown) is transparent. The substrate 12 is carried into the carry-in chamber LL. After the inside of the sputtering apparatus 11 has a specific degree of vacuum, the reactive gas having a specific flow rate is introduced from the first gas introduction port GA1, specifically, a component containing a wet etching rate for slowing down the 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, and includes a wet etching rate having a slow light semi-transmissive film. A specific gas is applied to the first sputtering target 13 by the gas for exposure of the component gas. The application of the sputtering power, the introduction of the sputtering gas, and the introduction of the gas for exposure continue until the transparent substrate 12 is transferred to the carry-out chamber ULL. Thereafter, the transparent substrate 12 mounted on a tray (not shown) is sequentially transported to the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second in a direction of the arrow S at a specific conveying speed. Sputter chamber SP2, and carry out chamber ULL. When the transparent substrate 12 passes through the vicinity of the first sputtering target 13 of the first sputtering chamber SP1, a metal telluride-based material having a specific film thickness is formed on the main surface of the transparent substrate 12 by reactive sputtering. The light that is formed is semi-permeable to the film. Further, 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 for slowing the wet etching rate of the light semi-transmissive film. When the film formation of the second layer light semi-transmissive film is performed, the transparent substrate 12 mounted on the tray (not shown) is sequentially returned to the carry-out chamber ULL and the second sputtering chamber in the direction opposite to the arrow S. The chamber SP2, the buffer chamber BU, the first sputtering chamber SP1, and the chamber LL are loaded, and the light semi-transmissive film is formed again. When returning the transparent substrate 12 to the carry-in chamber LL, it is preferable to introduce a gas containing a component having a wet etching rate for slowing down the semi-transmissive film into the first sputtering chamber SP1 and the second sputtering chamber SP2. The gas used for exposure. Thereby, during the return of the transparent substrate 12 to the carry-in chamber LL, the light semi-transmissive film can be exposed to a gas atmosphere for exposure including a gas having a component for slowing the wet etching rate of the light semi-transmissive film. The same applies to the case where the third layer and the fourth layer of the light semi-transmissive film are formed. When the light semi-transmissive film is formed on the main surface of the transparent substrate 12 in this manner, when the transparent substrate 12 is taken out to the outside of the sputtering apparatus 11 and the etching mask film is continuously formed, it is mounted on the tray. The transparent substrate 12 (not shown) is sequentially returned to the carry-out chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, the first sputtering chamber SP1, and the loading chamber in a direction opposite to the arrow S. LL. On the other hand, when the transparent substrate 12 is temporarily taken out to the outside of the sputtering apparatus 11 after the light semi-transmissive film is formed, when the etching mask film is formed, the transparent substrate 12 mounted on a tray (not shown) is used. After being carried into the loading chamber LL, as described above, the inside of the sputtering apparatus 11 is brought to a specific degree of vacuum. In the case where an etching mask film having a laminated structure composed of a light shielding layer and an antireflection layer is formed, the inside of the sputtering apparatus 11 is brought to a specific degree of vacuum, and the second gas introduction port GA2 is used. A specific flow of sputtering gas is introduced, and a specific sputtering power is applied to the second sputtering target 14. Further, 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. Further, 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 continue until the transparent substrate 12 is transferred to the carry-out chamber ULL. Thereafter, the transparent substrate 12 mounted on a tray (not shown) is sequentially transported to the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second in a direction of the arrow S at a specific conveying speed. Sputter chamber SP2, and carry out chamber ULL. When the transparent substrate 12 passes through the vicinity of 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. Further, when the transparent substrate 12 passes through the vicinity of the third sputtering target 15 and the fourth sputtering target 16 of the second sputtering chamber SP2, a specific film thickness is formed on the light shielding layer by reactive sputtering. The light shielding layer or the antireflection layer composed of the material is formed into a film. After the etching mask film having a laminated structure of a light shielding layer and an antireflection layer is formed on the light semi-transmissive film, the transparent substrate 12 is taken out to the outside of the sputtering apparatus 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 the light semi-transmissive film is formed on the transparent substrate 12, the sputtering apparatus 11 is When the inside reaches a specific degree of vacuum, a specific flow rate of the 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 transported to the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second in a direction of the arrow S at a specific conveying speed. Sputter chamber SP2, and carry out chamber ULL. When the transparent substrate 12 passes through the vicinity of the second sputtering target 14 of the first sputtering chamber SP1, an insulating 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. Thereafter, in order to form a light shielding layer and an antireflection layer, the transparent substrate 12 mounted on a tray (not shown) is sequentially returned to the carry-out 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 loading chamber LL form a light shielding layer and an antireflection layer as described above. After the etching mask film having a laminated structure composed of an insulating layer, a light shielding layer, and an antireflection layer is formed on the light semi-transmissive film, the transparent substrate 12 is taken out to the outside of the sputtering apparatus 11. The phase shift mask substrate 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 halide-based material formed on a main surface of the transparent substrate, And an etching mask film made of a chromium-based material formed on the light semi-transmissive film, and a composition gradient region is formed at an interface between the light semi-transmissive film and the etching mask film. Hereinafter, a description will be given of FIG. 5 showing the results of composition analysis in the depth direction obtained by X-ray photoelectron spectroscopy (XPS) for the phase shift mask substrate of Example 1. The composition gradient region P is based on the composition analysis result of the depth direction obtained by XPS for the phase shift mask base, and the 矽(矽:Si) peak and the molybdenum (Mo) peak caused by the light semi-transmissive film are present until A region where the chrome (Cr) peak caused by etching the mask film disappears. In the composition gradient region P, the ratio of the component (nitrogen (N) in FIG. 5) which slows down the wet etching rate of the light semi-transmissive film monotonically increases in phase and/or continuity toward the depth direction. Further, in the composition gradient region P, the ratio of the oxygen ratio to the oxygen in the composition uniform region Q hardly changes, and is substantially uniformly contained. The ratio (content) of oxygen in the composition gradient region P is 20 atom% or less, preferably 10 atom% or less, and more preferably 5 atom% or less. Further, the maximum value of the ratio (N/Si) of nitrogen (N) to 矽 (Si) at 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. 25 or less, further preferably 4.0 or more and 20 or less. In the above-described boundary system, when the phase shift mask substrate is subjected to composition analysis by X-ray photoelectron spectroscopy from the side of the etching mask film and the measurement step is 0.5 minute, 1 atom% is detected for the first time. The position of the above (Si). The composition of the light semi-permeable membrane 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 a region having a composition gradient is formed at the interface between the light semi-transmissive film and the transparent substrate, so that the composition of the portions is not uniform. The uniform region Q is formed in the composition analysis result of the depth direction by the XPS for the phase shift mask substrate, and the chromium (Cr) peak caused by the etching of the mask film disappears until the oxygen is caused by the transparent substrate (O The area where the peak appears. In the uniform region Q, the ratio of the components of the wet etching rate of the molybdenum (Mo), yttrium (Si), and the slow light permeable film (nitrogen (N) in FIG. 5) is 5 atom% or less. It is preferably 3 atom% or less. In the case where the semi-transmissive film is composed of a plurality of layers, the interface of each layer (in the case of sputtering time of 25 minutes in FIG. 5) slows down the composition of the wet etching rate of the light semi-transmissive film (nitrogen in FIG. 5). The composition of (N)) is reduced by 3 atom% or less with respect to the composition of the component (the nitrogen (N) in FIG. 5) which slows down the wet etching rate of the light semi-transmissive film in the vicinity of the center of the thickness direction of each layer. Preferably, it is 2 atom% or less. According to the manufacturing method of the phase shift mask substrate for manufacturing a display device according to the first embodiment, a light semi-transmissive film made of a metal telluride-based material is formed on the main surface of the transparent substrate, and is formed on the light semi-transmissive film. An etch mask made of a chrome-based material. The formation of the light semi-transmissive film is carried out by forming a light semi-transmissive film and continuously exposing the light semi-permeable film to the inclusion after the film formation without exposing the light semi-permeable film to the atmosphere. The gas atmosphere of the composition of the wet etch rate of the slow light semi-transmissive film. By continuously exposing the light semi-transmissive film to a gas atmosphere containing a component that slows down the wet etching rate of the semi-transmissive film after film formation, it is possible to prevent the component of the slow etch rate from being slowed down from the surface of the semi-transmissive film. Desorption. Therefore, by wet etching, it is possible to manufacture a phase shift mask substrate which can pattern a light semi-transmissive film into a nearly vertical cross-sectional shape capable of exerting a phase shift effect sufficiently. Further, by wet etching, it is possible to manufacture a phase shift mask substrate which can pattern a light semi-transmissive film into a cross-sectional shape having a small CD unevenness. Further, the phase shift mask substrate for manufacturing a display device according to the first embodiment includes a light semi-transmissive film made of a metal halide material formed on a main surface of the transparent substrate, and is formed in the light semi-transmissive film. An etch 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-transmissive film and the etching mask film, the ratio of the component which slows down the wet etching rate of the light semi-transmissive film increases stepwise and/or continuously toward the depth direction. Therefore, by wet etching, a phase shift mask substrate which can pattern a light semi-transmissive film into a nearly vertical cross-sectional shape capable of exerting a phase shift effect can be obtained. Further, by wet etching, a phase shift mask substrate which can pattern a light semi-transmissive film into a cross-sectional shape having a small CD unevenness can be obtained. Embodiment 2. In Embodiment 2, a phase shift mask for manufacturing a display device and a method of manufacturing the same will be described. In the method of manufacturing a phase shift mask for manufacturing a display device according to the second embodiment, first, a photoresist pattern forming process, that is, phase shifting light for manufacturing a display device described in the first embodiment is performed. Forming a photoresist pattern on the etch mask film of the phase shift mask substrate obtained by the method for manufacturing the cover substrate or the etch mask film for manufacturing the phase shift mask substrate of the display device described in Embodiment 1 . In detail, 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 to the photoresist film. Thereafter, the photoresist film is developed with a specific developer to form a photoresist pattern. As the pattern for drawing the photoresist film, a line and gap pattern or a hole pattern can be cited. Next, an etch mask patterning process is performed, that is, the etch mask film is wet etched with the photoresist pattern as a mask to form an etch mask pattern. The etching liquid for wet etching the etching mask film is not particularly limited as long as it can selectively etch the etching mask film. Specifically, an etching solution containing cerium (II) nitrate and perchloric acid can be mentioned. Next, a semi-transmissive film pattern forming process is performed in which the light semi-transmissive film pattern is formed by wet etching the light semi-transmissive film with the etching mask pattern as a mask. The etching liquid for wet etching the light semi-transmissive film is not particularly limited as long as it can selectively etch the light semi-permeable film. For example, an etching solution containing at least one fluorine compound selected from the group consisting of hydrofluoric acid, hydrofluoroantimonic acid, and ammonium hydrogen fluoride, and at least one oxidizing agent selected from the group consisting of hydrogen peroxide, nitric acid, and sulfuric acid may be mentioned. Specifically, an etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water can be mentioned. In the case of manufacturing a phase shift mask of the type having a light-shielding film pattern on a semi-transmissive film pattern, after the semi-transmissive film pattern is formed, the etching mask film pattern is patterned to be narrower than the specific pattern of the light semi-transmissive film pattern. pattern. In this case, the light semi-transmissive film pattern has a property of changing the phase of the exposed light, and the etching mask film pattern has light blocking properties. In the case of manufacturing a phase shift mask of a type having no light-shielding film pattern on the semi-transmissive film pattern, after the semi-transmissive film pattern is formed, the etching mask film pattern is peeled off. In this case, the light semi-transmissive film pattern has the property of changing the phase of the exposed light. A phase shift mask for manufacturing a display device is manufactured by such a photoresist pattern forming process, an etching mask film pattern forming process, and a semi-transmissive film pattern forming process. The phase shift mask for manufacturing a display device according to the second embodiment manufactured in this manner includes a transparent substrate and a light semi-transmissive film pattern composed of a metal telluride-based material formed on a main surface of the transparent substrate . When the semi-transmissive film pattern has a light-shielding film pattern, it further includes an etching mask film pattern made of a chromium-based material formed on the light-transmissive film pattern. The portion in which the light semi-transmissive film pattern is disposed constitutes a phase shift portion, and the portion where the transparent substrate is exposed constitutes a light transmitting portion. As the light semi-transmissive film pattern, a line and gap pattern or a hole pattern can be cited. The light semi-transmissive film pattern has the property of changing the phase of the exposed light. By this property, a specific phase difference is generated between the light that has passed through the phase shifting portion in which the light semi-transmissive film pattern is disposed and the light that has passed through the light transmitting portion that is transmitted through the transparent substrate. When the light to be exposed is a composite light containing light in a wavelength range of 300 nm or more and 500 nm or less, the light semi-transmissive film pattern generates a specific phase difference with respect to light of a representative wavelength. For example, when the light to be exposed is a composite light including i-rays, h-rays, and g-rays, the light semi-transmissive film pattern generates a phase difference of 180 degrees for any of i-rays, h-rays, and g-rays. Similarly to the above, the phase difference of the light semi-transmissive film pattern is preferably set to a range of 180 degrees ± 20 degrees for the representative wavelength of any of the i-ray, the h-ray, and the g-ray. Further, it is preferable that the phase difference of the light semi-transmissive film is set to a range of 180 degrees ± 10 degrees for the representative wavelength of any of the i-ray, the h-ray, and the g-ray. Further, the transmittance of the light semi-transmissive film is preferably 1% or more and 20% or less at a representative wavelength of any one of the i-ray, the h-ray, and the g-ray. More preferably, the transmittance of the light semi-transmissive film is preferably 3% or more and 10% or less at a representative wavelength of any of i-rays, h-rays, and g-rays. Further, the phase shift mask for manufacturing a display device of the present invention is used for projection exposure of a double exposure, and the phase shift effect is sufficiently exerted. In particular, as the exposure environment, the number of openings (NA) is preferably from 0.06 to 0.15, more preferably from 0.08 to 0.10, and the homology factor (σ) is preferably from 0.5 to 1.0. The light semi-transmissive film pattern may include a metal and a ruthenium as long as it has a specific transmittance and phase difference with respect to the light to be exposed, and may further contain other elements. As other elements, as long as it is an element capable of controlling the refractive index (n) and extinction coefficient (k) of the exposed light, it is selected from the group consisting of oxygen (O), nitrogen (N), carbon (C), and fluorine (F). Choose from at least one of the elements. For example, an oxide of a metal telluride, a nitrogen oxide of a metal telluride, a nitride of a metal telluride, a nitrogen carbide of a metal telluride, a nitrogen oxide of a metal telluride, or the like can be given. Further, from the viewpoint of pattern controllability of wet etching, the light semi-transmissive film pattern is preferably a metal telluride-based material containing a metal, a ruthenium, and a component which slows down the wet etching rate of the light semi-transmissive film. Composition. Examples of the component for slowing 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 halide-based material constituting the semi-permeable membrane pattern include a metal halide nitride, a metal halide nitrogen oxide, a metal halide metal oxide, a metal halide nitrogen carbide, and a metal halide. Nitrogen oxides. The composition of the metal, germanium, and nitrogen constituting the light semi-transmission pattern is based on the phase difference (180 degrees ± 20 degrees) required for the light to be exposed, the transmittance (1% or more and 20% or less), and the wet etching characteristics ( The light semi-transmissive film pattern has a cross-sectional shape or CD unevenness and chemical resistance. The ratio of metal to bismuth is preferably metal: 矽=1..1 or more and 1..9 or less. The content of nitrogen is preferably 25 atom% or more and 55 atom% or less, and more preferably 30 atom% or more and 50 atom% 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 a region having a composition gradient is formed at the interface between the light semi-transmissive film pattern and the transparent substrate, so that the composition of the portions is not uniform. The etched mask film pattern is composed of a chromium-based material containing chromium (Cr). Examples of the chromium-based material constituting the etching mask pattern include chromium nitride (CrN), chromium carbide (CrC), chromium carbonitride (CrCN), chromium oxynitride (CrON), and chromium oxycarbide (CrCO). Chromium oxynitride (CrCON). Hereinafter, a description will be given with reference to Fig. 7 showing a cross-sectional photograph of the phase shift mask of the first embodiment and Fig. 8 showing a cross-sectional photograph of the phase shift mask of the second embodiment. The cross section of the light semi-transmissive film pattern is composed of an upper surface, a lower surface, and a side edge 23 corresponding to the upper surface, the lower surface, and the side surface of the light semi-transmissive film pattern. In Figs. 7 and 8, the auxiliary line 21 indicates a position corresponding to the upper side of the upper surface of the light semi-transmissive film pattern, and the auxiliary line 22 indicates a position corresponding to the lower side of the lower surface of the light semi-transmissive film pattern. In this case, the straight line formed by the contact point 26 between the upper side and the side and the position 27 of the side at a height of two-thirds of the thickness of the falling film on the upper surface is formed at an angle θ of 85 degrees with the upper side. Up to 120 degrees. In Fig. 7, the auxiliary line 24 indicates the position at which the height of the film thickness from the upper surface is reduced by two-thirds. Further, the first imaginary line 29 which is perpendicular to the main surface of the transparent substrate by the contact 26 of the upper side and the side 23, and the side of the position which is raised by the height of one tenth of the thickness of the film from the lower surface The width of the second imaginary line 30 (hereinafter referred to as a bottom width) D at the position 28 and perpendicular to the main surface of the transparent substrate is one-half or less of the film thickness. In Fig. 8, the auxiliary line 25 indicates the position at which the height of one half of the film thickness rises from the lower surface. The phase shift mask may also have a light shielding film pattern that shields the exposed light from the light semi-transmissive film pattern. In the case where the light-shielding film pattern is provided on the light semi-transmissive film pattern, it is easy to recognize the mask pattern by the exposure machine. Further, it is possible to prevent filming of the photoresist film due to light that is transmitted through the light half-transmissive film pattern. According to the method for manufacturing a phase shift mask for manufacturing a display device according to the second embodiment, a phase shift mask obtained by the method for manufacturing a phase shift mask substrate for manufacturing a display device described in the first embodiment is used. A phase shift mask is manufactured on the substrate or the phase shift mask substrate for manufacturing a display device described in Embodiment 1. Therefore, it is possible to manufacture a phase shift mask having a light semi-transmissive film pattern of a nearly vertical cross-sectional shape capable of giving full play to the phase shift effect. Further, it is possible to manufacture a phase shift mask having a light semi-transmissive film pattern having a small bottom width D and a small CD unevenness. The phase shift mask can cope with the miniaturization of line and gap patterns or contact holes. According to the phase shifting mask for manufacturing a display device of the second embodiment, the light-transmissive film pattern made of a metal halide-based material formed on the main surface of the transparent substrate is provided. 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. Further, in the cross section of the light semi-transmissive film pattern, a straight line connecting the contact point 26 between the upper side and the side and the position 27 of the side at a position where the height of the upper surface is reduced by two-thirds of the thickness of the film is The angle θ formed by the upper side is in the range of 85 to 120 degrees. Further, in the cross section of the light semi-transmissive film pattern, the first imaginary line 29 which is perpendicular to the main surface of the transparent substrate by the contact point 26 between the upper side and the side, and one tenth of the thickness of the film which rises from the lower surface The width D of the position 28 of the side at the position of the height and the second imaginary line 30 perpendicular to the main surface of the transparent substrate is one-half or less of the film thickness. Therefore, a phase shift mask having a light semi-transmissive film pattern of a nearly vertical cross-sectional shape capable of exerting a phase shift effect can be obtained. Further, a phase shift mask having a light semi-transmissive film pattern having a small bottom width D and a 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, a method of manufacturing a display device will be described. In the method of manufacturing a display device according to the third embodiment, first, a phase shift mask arrangement process, that is, a substrate with a photoresist film on which a photoresist film is formed on a substrate, will be described in the second embodiment. The phase shift mask obtained by the method for manufacturing a phase shift mask for manufacturing a display device or the phase shift mask for manufacturing a display device described in the second embodiment is disposed opposite to the photoresist film. Next, the photoresist film exposure process is performed, that is, the phase shift mask is irradiated with the exposed light to expose the photoresist film. The light to be exposed is, for example, a composite light containing light in a wavelength range of 300 nm or more and 500 nm or less. Specifically, it is a composite light including an i-ray, an h-ray, and a g-ray. Further, as the exposure at the time of manufacture of the display device, projection exposure of an equal exposure is preferable. Regarding the exposure environment, the number of openings (NA) is preferably from 0.06 to 0.15, more preferably from 0.08 to 0.10, and the homology factor (σ) is preferably from 0.5 to 1.0. According to the method of manufacturing the display device of 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 phase shift mask for manufacturing a display device is used to manufacture a display device. Therefore, it is possible to manufacture a display device having a fine line and gap pattern or contact hole. [Examples] Hereinafter, the present invention will be more specifically described based on examples. Example 1. A. Phase shift mask substrate and method of manufacturing the same In order to manufacture the phase shift mask substrate of Example 1, first, a 3345 size (330 mm × 450 mm × 5 mm) synthetic quartz glass substrate 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 carried into the carrying chamber LL of the continuous sputtering apparatus 11 shown in FIG. In the first sputtering chamber SP1, a sputtering target containing molybdenum molybdenum (Mo..Si=1..4) is disposed as the first sputtering target 13 on the side of the loading chamber LL. Further, 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. Further, in the second sputtering chamber SP2, a sputtering target containing chromium is disposed as the third sputtering target 15 on the side of the buffer chamber BU, and a sputtering target containing chromium is disposed on the side of the carrying chamber ULL. 4 Sputter target 16. In order to form a light semi-transmissive film on the main surface of the synthetic quartz glass substrate, first, argon (Ar) gas is introduced from the first gas introduction port GA1 disposed in the vicinity of the first sputtering target 13 of the first sputtering chamber SP1. With nitrogen (N 2 Gas mixture (Ar: 50 sccm, N 2 : 90 sccm), a sputtering power of 8.0 kW was applied to the first sputtering target 13. Further, argon gas (Ar) is introduced from the third gas introduction port GA3 disposed in the vicinity of the third sputtering target 15 of the second sputtering chamber SP2 and the fourth gas introduction port GA4 disposed in the vicinity of the fourth sputtering target 16. Gas and nitrogen (N 2 Gas mixture (Ar: 50 sccm, N 2 : 90 sccm). Sputter power is applied to the first sputtering target 13 and Ar gas and N are introduced from the first gas introduction port GA1. 2 Mixed gas of gas, and introduction of Ar gas and N from third gas introduction port GA3 and fourth gas introduction port GA4 2 The gas mixture system continues until the synthetic quartz glass substrate is transferred to the carry-out chamber ULL. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is sequentially conveyed in the direction of the arrow S to the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second sputtering chamber. SP2, and move out of the chamber ULL. Further, the transport speed of the synthetic quartz glass substrate was set to 400 mm/min. When the synthetic quartz glass substrate passes through the vicinity of the first sputtering target 13 of the first sputtering chamber SP1, a nitrogen-containing molybdenum telluride film having a film thickness of 55.0 nm is formed on the main surface of the synthetic quartz glass substrate by reactive sputtering. The first layer of light semi-transmissive film of (MoSiN). During the passage of the synthetic quartz glass substrate through the second sputtering chamber SP2, the first layer of the semi-transmissive film is exposed to the Ar gas and the N 2 A mixed gas atmosphere of gas. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is sequentially transported to the carry-out chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, and the first sputtering in a direction opposite to the arrow S. The chamber SP1 and the carry-in chamber LL are returned to the carry-in chamber LL. During the return of the synthetic quartz glass substrate to the carry-in chamber LL, Ar gas and N are introduced from the first gas introduction port GA1. 2 Mixed gas of gas (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 Mixed gas of gas (Ar: 50 sccm, N 2 :90 sccm), exposing the first layer of light semi-permeable membrane to Ar gas and N 2 A mixed gas atmosphere of gas. Thereafter, 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 Mixed gas of gas, and introduction of Ar gas and N from third gas introduction port GA3 and fourth gas introduction port GA4 2 a gas mixed gas is formed on the first light semi-transmissive film by a method similar to the above method to form a second semi-transmissive film containing a molybdenum nitride molybdenum film (MoSiN) having a thickness of 55.0 nm, and is formed into a film. Thereafter, the second layer of light semi-permeable membrane is exposed to Ar gas and N 2 A mixed gas atmosphere of gas. In this manner, a light semi-transmissive film having a total thickness of 110 nm including two layers of molybdenum oxynitride film (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 conveyed in the opposite direction to the arrow S, and is returned to the loading chamber LL. During the return of the synthetic quartz glass substrate to the carrying chamber LL, the second layer of the semi-transmissive film is exposed to Ar gas and N by the same method as described above. 2 A mixed gas atmosphere of gas. Next, a light-shielding layer and an anti-reflection layer which are etching mask films are formed on the semi-transmissive film. The light-shielding layer and the anti-reflection layer are adjusted to be introduced into the second sputtering target 14 so that the film surface reflectance at a specific wavelength (for example, g-ray) is 15% or less and the optical density OD (Optical Density) is 3.0 or more. Types, flow rates, and synthetic quartz glass substrates of the third gas introduction port GA2, the third gas introduction port GA3, and the fourth gas introduction port 4 in the vicinity of the chromium target of the fourth sputtering target 16 The transfer speed is adjusted to appropriately adjust the sputtering power applied to each sputtering target. Introducing Ar gas and N from the second gas introduction port GA2 2 A mixed gas of gas is introduced into the Ar gas and methane from the third gas inlet GA3 (CH) 4 The mixed gas of the gas is introduced into the mixed gas of the Ar gas and the nitrogen monoxide (NO) gas from the fourth gas introduction port GA4. Further, sputtering power is applied to each sputtering target, and a mixed gas system is introduced from each gas introduction port until the synthetic quartz glass is transported to the carry-out chamber ULL. Further, the transport speed of the synthetic quartz glass substrate was set to 400 mm/min. As a result, a light-shielding layer including a chromium nitride film (CrN) having a film thickness of 25.0 nm and a chromium nitride film (CrCN) having a film thickness of 70.0 nm and a film thickness of 20.0 nm were formed on the light semi-transmissive film. A laminated film of an anti-reflective layer of a chromium oxynitride film (CrON). In this manner, an etching mask film having a laminated structure including a light shielding layer of a laminated film of CrN and CrCN and an antireflection layer containing CrON is sequentially formed on the light semi-transmissive film. Thereafter, after the second sputtering chamber and the carry-out chamber are completely separated by the spacer, the carry-out chamber is returned to the atmospheric pressure state, and the synthetic quartz having the light semi-permeable film and the etching mask film is taken out from the sputtering device 11. glass substrate. In this manner, a phase shift mask substrate in which a light semi-transmissive film and an etch mask film are formed on a synthetic quartz glass substrate is obtained. The transmittance and phase difference of the obtained light semi-transmissive film of the phase shift mask base were measured by MPM-100 manufactured by Lasertec Corporation of Japan. In the measurement of the transmittance and phase difference of the semi-transmissive film, two layers of molybdenum oxynitride film (MoSiN) were formed on the main surface of the synthetic quartz glass substrate prepared by mounting on the same tray (total film) A substrate (virtual substrate) with a light-transmissive semi-transmissive film of 110 nm thick. The transmittance and phase difference of the light semi-transmissive film were measured by taking out the substrate (dummy substrate) of the light-transmitting semi-transmissive film from the carry-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). Further, the film surface reflectance and the optical density of the obtained phase shift mask base were measured by a spectrophotometer SolidSpec-3700 manufactured by Shimadzu Corporation. The phase shift mask substrate (etch mask film) has a film surface reflectance of 10.0% (wavelength: 436 nm) and an optical density OD of 4.0 (wavelength: 436 nm). It is understood that the etch mask film functions as a light-shielding film having a low reflectance on the surface of the film. Further, the obtained phase shift mask substrate was subjected to composition analysis in the depth direction by X-ray photoelectron spectroscopy (XPS). Fig. 5 is a graph showing the result of composition analysis in the depth direction obtained by XPS for the phase shift mask substrate of Example 1. The horizontal axis of Fig. 5 represents the sputtering time (minutes), and the vertical axis represents the content (atomic %). In Fig. 5, a curve a indicates a change in the content of cerium (Si), a curve b indicates a change in the content of nitrogen (N), a curve c indicates a change in the content of oxygen (O), and a curve d indicates a change in the content of carbon (C), and a curve e It indicates a change in the content of chromium (Cr), and a curve f indicates a change in the content of molybdenum (Mo). As shown in FIG. 5, in the composition analysis result of the depth direction by the XPS for the phase shift mask substrate, after the occurrence of the 矽(Si) peak and the molybdenum (Mo) peak caused by the light semi-transmissive film, In the composition gradient region P of the region where the chromium (Cr) peak caused by the etching of the mask film disappears, the content of nitrogen (N) in the wet etching rate of the light semi-transmissive film is slowed toward the depth direction of the light semi-transmissive film. (The direction of the synthetic quartz glass substrate) is increased stepwise and/or continuously. Further, in the composition gradient region P, the content of oxygen is 5 atom% or less. Further, the maximum value of the ratio of nitrogen (N) to 矽 (Si) at the interface on the etching mask side in the gradient region P was 3.7. The content of molybdenum (Mo) is 15 atom% on average in the uniform composition region Q after the disappearance of the chromium (Cr) peak caused by the etching of the mask film until the occurrence of the oxygen (O) peak caused by the synthetic quartz glass substrate. The content of cerium (Si) is 38 atom% on average, the content of nitrogen (N) is 45 atom% on average, and the content of oxygen (O) is 2 atom% or less, and the variation in the content of each is 5 atom% or less. In the method of manufacturing a phase shift mask substrate described above, the light semi-transmissive film and the etching mask film are continuously formed while maintaining a specific degree of vacuum. In order to reliably obtain the effects of the present invention, it is preferred to continuously form the light semi-permeable film and the 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 of the composition from the outermost surface of the light semi-transmissive film to the synthetic quartz glass substrate. Further, even after the light semi-transmissive film is formed, it is stored in the air or the light semi-transmissive film is washed before the etching mask film is formed, and the composition can be obtained as long as the composition is changed within a fixed range. The same effect. B. Phase shifting reticle and method of manufacturing the same for manufacturing a phase shifting reticle using a phase shifting reticle substrate manufactured in the above manner, first, using a photoresist coating on an etch mask film of a phase shifting reticle substrate The device is coated with a photoresist film. Thereafter, a photoresist film having a film thickness of 1000 nm was formed by a heating and cooling process. Thereafter, the photoresist film is drawn using a laser drawing device, and a photoresist having a line pattern width of 2.0 μm and a gap pattern width of 2.0 μm is formed on the etching mask film by a developing and rinsing process. Agent pattern. Thereafter, the etching mask pattern is masked by a photoresist pattern, and the etching mask film is wet-etched by a chromium etching solution containing ammonium cerium (II) nitrate and perchloric acid to form an etching mask film pattern. Thereafter, the etched mask film pattern is used as a mask, and the light semi-permeable membrane is wet-etched by a molybdenum molybdenum etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water to form a light semi-permeable membrane. pattern. Thereafter, the photoresist pattern is peeled off. Thereafter, a photoresist film is applied in such a manner as to cover the etching mask pattern by using a photoresist coating device. Thereafter, a photoresist film having a film thickness of 1000 nm was formed by a heating and cooling process. Thereafter, the photoresist film was drawn using a laser drawing device, and a photoresist pattern having a line pattern having a width of 1.0 μm was formed on the etching mask film pattern by a developing and rinsing process. Thereafter, the photoresist pattern is used as a mask, and the etching mask pattern is wet-etched by a chromium etching solution containing ammonium cerium (II) nitrate and perchloric acid to form a width narrower than the pattern of the light semi-permeable film. Etching the mask film pattern. Thereafter, the photoresist pattern is peeled off. In this manner, a phase shift mask in which a light semi-transmissive film pattern and an etched mask film pattern narrower than the width of the light semi-transmissive film pattern are formed on the synthetic quartz glass substrate is obtained. The plane and cross section of the obtained phase shift mask were observed using a scanning electron microscope. In the following examples and comparative examples, a scanning electron microscope was used for the observation of the plane and the cross section of the phase shift mask. Figure 6 is a plan view of the phase shift mask of Embodiment 1. Figure 7 is a cross-sectional photograph of the phase shift mask of Example 1. In Figs. 6 and 7, QZ denotes a synthetic quartz glass substrate, PS denotes a light semi-transmissive film pattern, and Cr denotes an etching mask film pattern. As shown in FIG. 7, the cross section of the light semi-transmissive film pattern PS is such that the bottom portion of the portion in contact with the synthetic quartz glass substrate QZ is substantially perpendicular to the portion in contact with the etching mask film pattern Cr. Specifically, the light semi-transmissive film pattern PS has a cross section corresponding to the upper surface, the lower surface, and the upper side, the lower side, and the side 23 of the light semi-transmissive film pattern PS. The auxiliary line 21 indicates a position corresponding to the upper side of the upper surface of the light semi-transmissive film pattern PS, and the auxiliary line 22 indicates a position corresponding to the lower side 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 and the position 27 of the side at a height of two-thirds of the thickness of the falling film on the upper surface is formed at an angle θ of 105 degrees with the upper side. The auxiliary line 24 indicates a position at which the height of the film thickness from the upper surface is reduced by two-thirds. Further, the side of the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ by the contact 26 of the upper side and the side 23 and the side at the height of one tenth of the thickness of the film rising from the lower surface The width of the edge portion and the second imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ was 44 nm. As described above, the light semi-transmissive film pattern has a good cross-sectional shape, and the angle θ is 105 degrees, and the width is 44 nm (the thickness of the light semi-transmissive film is 110 nm, which is 1/2.5), thereby including 300 nm. The light having exposure of the light in the wavelength range of 500 nm or less, more specifically, the light including the combined light of the i-ray, the h-ray, and the g-ray, can be obtained with the PSM shown in Table 1 above ( A) A phase shift mask with the same phase shift effect. The CD unevenness of the light semi-transmissive film pattern of the phase shift mask was measured by SIR8000 manufactured by Seiko Instruments NanoTechnology Co., Ltd. The measurement of CD unevenness was performed at a portion of π mm × 390 mm excluding the peripheral region of the substrate at a portion of 5 × 5. The CD unevenness is the deviation width from the line and gap pattern (width of the line pattern: 2.0 μm, width of the gap pattern: 2.0 μm) as the target. In the following examples and comparative examples, the same apparatus was used for the measurement of CD unevenness. The CD unevenness was good and was 0.096 μm. As shown in FIG. 6, the edge E of the light semi-transmissive film pattern PS is linear, and it shows that CD unevenness is favorable. Example 2 In the second embodiment, a case where the light semi-permeable membrane is composed of four layers of molybdenum oxynitride film (MoSiN) will be described. A. Phase shift mask substrate and method of manufacturing the same In the manufacture of the phase shift mask substrate of Example 2, a synthetic quartz glass substrate having a size of 3345 was used as the transparent substrate 12. The synthetic quartz glass substrate was carried into the carrying chamber LL of the continuous sputtering apparatus 11 shown in Fig. 4 by the same method as in the first embodiment. 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 in the first embodiment was used. Thereafter, the inside of the sputtering apparatus 11 was brought to a specific degree of vacuum by the same method as in the first embodiment. The exhaust system continues until the stage of taking out the synthetic quartz glass substrate from the sputtering apparatus 11. Thereafter, Ar gas and N are introduced from the first gas introduction port GA1 disposed in the vicinity of the first sputtering target 13 of the first sputtering chamber SP1. 2 Gas mixture (Ar: 30 sccm, N 2 : 30 sccm), a sputtering power of 4.0 kW was applied to the first sputtering target 13. In addition, the third gas introduction port GA3 disposed in the vicinity of the third sputtering target 15 of the second sputtering chamber SP2 and the fourth gas introduction port GA4 disposed in the vicinity of the fourth sputtering target 16 are introduced with Ar gas and N. 2 Gas mixture (Ar: 30 sccm, N 2 :30 sccm). Sputter power is applied to the first sputtering target 13 and Ar gas and N are introduced from the first gas introduction port GA12. 2 Mixed gas of gas, and introduction of Ar gas and N from third gas introduction port GA3 and fourth gas introduction port GA4 2 The gas mixture system continues until the synthetic quartz glass substrate is transferred to the carry-out 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 carry-out chamber ULL. Further, the transport speed of the synthetic quartz glass substrate was set to 400 mm/min. When the synthetic quartz glass substrate passes through the vicinity of the first sputtering target 13 of the first sputtering chamber SP1, a molybdenum nitride film having a thickness of 27.5 nm is formed on the main surface of the synthetic quartz glass substrate by reactive sputtering. The first layer of light semi-transmissive film of (MoSiN). During the passage of the synthetic quartz glass substrate through the second sputtering chamber SP2, the first layer of the semi-transmissive film is exposed to the Ar gas and the N 2 A mixed gas atmosphere of gas. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is conveyed in the opposite direction to the arrow S, and is returned to the loading chamber LL. During the return of the synthetic quartz glass substrate to the carry-in chamber LL, Ar gas and N are introduced from the first gas introduction port GA1. 2 Gas mixture (Ar: 30 sccm, N 2 :30 sccm), introduction of Ar gas and N from the third gas introduction port GA3 2 Gas mixture (Ar: 30 sccm, N 2 : 30 sccm), exposing the first layer of light semi-permeable membrane to Ar gas and N 2 A mixed gas atmosphere of gas. Thereafter, the second layer, the third layer, and the fourth layer of the light semi-transmissive film are formed by the same method as the first layer of the light semi-transmissive film. After the second layer, the third layer, and the fourth layer of the light semi-transmissive film are formed, the synthetic quartz glass substrate mounted on a tray (not shown) is conveyed in a direction opposite to the arrow S, and is returned to the loading chamber LL. During the return of the synthetic quartz glass substrate to the carrying chamber LL, the second layer, the third layer, and the fourth layer of the light semi-transmissive film are exposed to Ar gas and N by the same method as described above. 2 A mixed gas atmosphere of gas. In this manner, a light semi-transmissive film having a total thickness of 110 nm including four layers of molybdenum oxynitride 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-transmissive film by the same method as in Example 1 to obtain a phase shift mask substrate having a light semi-transmissive film and an etching mask film formed on the synthetic quartz glass substrate. In the same manner as in the above-described first embodiment, composition analysis in the depth direction was performed by XPS on the obtained phase shift mask substrate. As a result, in the composition gradient region P, the content of nitrogen (N) in the wet etching of the light semi-transmissive film is continuously increased toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). Further, the maximum value of the ratio of nitrogen (N) to 矽 (Si) at the interface on the side of the etching mask film in the gradient region P was 3.6. B. Phase shift mask and manufacturing method Using the phase shift mask substrate manufactured in the above manner, an etching mask pattern and a light semi-transmissive film pattern were formed in the same manner as in Example 1. After forming the light semi-transmissive film pattern, the photoresist pattern is peeled off. Thereafter, the etching mask pattern is removed by a chromium etching solution containing cerium (II) nitrate and perchloric acid. In this manner, a phase shift mask in which a light semi-transmissive film pattern is formed on a synthetic quartz glass substrate is obtained. Figure 8 is a cross-sectional photograph of the phase shift mask of Embodiment 2. In Fig. 8, QZ denotes a synthetic quartz glass substrate, and PS denotes a light semi-transmissive film pattern. As shown in Fig. 8, the cross section of the light semi-transmissive film pattern PS is such that the bottom portion of the portion in contact with the synthetic quartz glass substrate QZ is substantially perpendicular to the portion in contact with the etching mask pattern. Specifically, the light semi-transmissive film pattern PS has a cross section corresponding to the upper surface, the lower surface, and the upper side, the lower side, and the side 23 of the light semi-transmissive film pattern PS. The auxiliary line 21 indicates a position corresponding to the upper side of the upper surface of the light semi-transmissive film pattern PS, and the auxiliary line 22 indicates a position corresponding to the lower side of the lower surface of the light semi-transmissive film pattern PS. The straight line formed by the contact between the upper side and the side contact point 26 and the side of the height of the two-thirds of the film thickness from the upper surface is formed at an angle of 105 degrees with respect to the upper side. Further, the first imaginary line 29 which is perpendicular to the main surface of the synthetic quartz glass substrate QZ by the contact 26 of the upper side and the side 23 and the height of one tenth of the thickness of the film raised from the lower surface The width D of the position 28 of the side and the second imaginary line 30 perpendicular to the main surface of the synthetic quartz glass substrate QZ is 48 nm. The auxiliary line 25 indicates a position at which the height of one half of the film thickness from the lower surface rises. As described above, the cross-sectional shape of the light semi-transmissive film pattern is good, and the angle θ is 105 degrees, and the width is 48 nm (about 1.3 cm with respect to the film thickness of the light semi-transmissive film of 110 nm), thereby including 300. The light having the exposure of light in the wavelength range of nm or more and 500 nm or less, more specifically, the light of the combined light including the i-ray, the h-ray, and the g-ray, can be obtained with the PSM shown in Table 2 above. (B) A phase shift mask with the same phase shift effect. Example 3. In Example 3, a case where the light semi-permeable membrane was composed of one layer of molybdenum oxynitride film (MoSiN) will be described. A. Phase shift mask base and method of manufacturing the same In the manufacture of the phase shift mask base of Example 3, a synthetic quartz glass substrate of the same size as the above-described Examples 1 and 2 was used as the transparent substrate 12. The synthetic quartz glass substrate was carried into the carrying chamber LL of the continuous sputtering apparatus 11 shown in Fig. 4 by the same method as in the first embodiment. 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 material as in the first embodiment was used. A sputtering power of 10.0 kW was applied to the first sputtering target 13 of the first sputtering chamber SP1. Further, Ar gas and N are introduced from the first gas introduction port GA1 disposed in the vicinity of the first sputtering target 13 2 Gas mixture (Ar: 50.0 sccm, N 2 :100.0 sccm). In addition, the third gas introduction port GA3 disposed in the vicinity of the third sputtering target 15 of the second sputtering chamber SP2 and the fourth gas introduction port GA4 disposed in the vicinity of the fourth sputtering target 16 are introduced with Ar gas and N. 2 Gas mixture (Ar: 50.0 sccm, N 2 :100.0 sccm). Sputter power is applied to the first sputtering target 13 and Ar gas and N are introduced from the first gas introduction port GA1. 2 Mixed gas of gas, and introduction of Ar gas and N from third gas introduction port GA3 and fourth gas introduction port GA4 2 The gas mixture system continues until the synthetic quartz glass substrate is transferred to the carry-out 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 carry-out chamber ULL. Further, the transport speed of the synthetic quartz glass substrate was set to 350 mm/min. When the synthetic quartz glass substrate passes through the vicinity of the first sputtering target 13 of the first sputtering chamber SP1, a silicon nitride molybdenum film having a thickness of 110 nm is formed on the main surface of the synthetic quartz glass substrate by reactive sputtering. The light of (MoSiN) is semi-permeable to the film. During the passage of the synthetic quartz glass substrate through the second sputtering chamber SP2, the light semi-transmissive film is exposed to Ar gas and N 2 A mixed gas atmosphere of gas. In this manner, a light semi-transmissive film having a film thickness of 110 nm including a layer of molybdenum oxynitride film (MoSiN) was formed on the main surface of the synthetic quartz glass substrate. Thereafter, the second sputtering chamber SP2 and the carry-out chamber ULL are completely separated by the spacer, and then the carry-out chamber ULL is returned to the atmospheric pressure state, and the synthetic quartz glass substrate on which the light semi-transmissive film is formed is taken out from the sputtering apparatus 11. . Thereafter, the synthetic quartz glass substrate on which the light semi-transmissive film was formed was stored in the air for about 2 days. Thereafter, the synthetic quartz glass substrate on which the light semi-transmissive film is formed is carried into the carrying chamber LL of the continuous sputtering apparatus 11 shown in FIG. Thereafter, an etching mask film was formed on the light semi-transmissive film by the same method as in Example 1 to obtain a phase shift mask substrate having a light semi-transmissive film and an etching mask film formed on the synthetic quartz glass substrate. In the same manner as in the above-described first embodiment, composition analysis in the depth direction was performed by XPS on the obtained phase shift mask substrate. As a result, in the composition gradient region P, the content of nitrogen (N) in the wet etching of the light semi-transmissive film is continuously increased toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). Further, the maximum value of the ratio of nitrogen (N) to 矽 (Si) at the interface on the etching mask side in the gradient region P was 8.2. B. Phase shift mask and method of manufacturing The phase shift mask was produced by the same method as in Example 1 using the phase shift mask substrate manufactured in the above manner. Figure 9 is a cross-sectional photograph of the phase shift mask of Embodiment 3. In Fig. 9, QZ denotes a synthetic quartz glass substrate, PS denotes a light semi-transmissive film pattern, and Cr denotes an etching mask film pattern. Fig. 9 is a cross-sectional photograph showing a state before forming an etching mask pattern which is narrower than the width of the light semi-transmissive film pattern. As shown in FIG. 9, the cross section of the light semi-transmissive film pattern PS is such that the bottom portion of the portion in contact with the synthetic quartz glass substrate QZ is substantially perpendicular to the portion in contact with the etching mask film pattern Cr. Specifically, the cross section of the light semi-transmissive film pattern PS is composed of the upper surface, the lower side, and the side of the upper surface, the lower surface, and the side surface corresponding to the light semi-transmissive film pattern PS. The line connecting the upper side and the side and the side of the height at the height of two-thirds of the film thickness from the upper surface is formed at a line which is 97 degrees from the upper side. Further, the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ by the contact of the upper side and the side, and the side of the position passing through the height of one tenth of the thickness of the film from the lower surface The width of the second imaginary line which is perpendicular to the main surface of the synthetic quartz glass substrate QZ is 20 nm. Further, 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), thereby including 300 nm. The light having exposure of the light in the wavelength range of 500 nm or less, more specifically, the light including the combined light of the i-ray, the h-ray, and the g-ray, can be obtained with the PSM shown in Table 1 above ( A) A phase shift mask with the same phase shift effect. Example 4. In Example 3, a synthetic quartz glass substrate on which a light semi-permeable membrane was formed was stored in the air for about 2 days. On the other hand, in Example 4, the synthetic quartz glass substrate in which the light semi-transmissive film was formed was stored in the air for one week. Except for this, a phase shift mask substrate and a phase shift mask were produced by the same method as in the third embodiment. In the same manner as in the above-described first embodiment, the composition of the obtained phase shift mask substrate was analyzed by XPS in the depth direction. 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-permeable membrane (the direction of the synthetic quartz glass substrate). Further, the maximum value of the ratio of nitrogen (N) to 矽 (Si) at the interface on the side of the etching mask film in the gradient region P was 3.2. Figure 10 is a cross-sectional photograph of the phase shifting reticle of Example 4. In Fig. 10, QZ denotes a synthetic quartz glass substrate, PS denotes a light semi-transmissive film pattern, and Cr denotes an etching mask film pattern. Fig. 10 is a cross-sectional photograph showing a state in which an etching mask pattern is formed narrower than the width of the light semi-transmissive film pattern. As shown in FIG. 10, the cross section of the light semi-transmissive film pattern PS is a linear wedge shape. Specifically, the cross section of the light semi-transmissive film pattern PS is composed of the upper surface, the lower side, and the side of the upper surface, the lower surface, and the side surface corresponding to the light semi-transmissive film pattern PS. The line connecting the upper side and the side and the side of the height at the height of two-thirds of the film thickness from the upper surface are connected to each other at an angle of 120 degrees with respect to the upper side. Further, the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ by the contact of the upper side and the side, and the side of the position passing through the height of one tenth of the thickness of the film from the lower surface The width of the second imaginary line which is perpendicular to the main surface of the synthetic quartz glass substrate QZ is 42 nm. Further, 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 2.6 parts with respect to the film thickness of the light semi-transmissive film of 110 nm), thereby including 300. An exposure light having a wavelength range of nm or more and a wavelength range of 500 nm or less, more specifically, an exposure light including a composite light of an i-ray, an h-ray, and a g-ray, can be obtained with the PSM shown in Table 1 above. (A) A phase shift mask with the same phase shift effect. According to the fourth embodiment, even if the light semi-permeable membrane is stored in the air for about one week, a good CD unevenness can be maintained as long as the composition of the fixed range is changed. Embodiment 5. In Embodiment 5, a case where an insulating layer is formed on a light semi-transmissive film will be described. A. Phase shift mask substrate and method of manufacturing the same In the manufacture of the phase shift 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-transmissive 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 conveyed in the opposite direction to the arrow S, and is returned to the loading chamber LL. During the return of the synthetic quartz glass substrate to the carrying chamber LL, the second layer of the semi-transmissive film is exposed to Ar gas and N by the same method as described above. 2 A mixed gas atmosphere of gas. Thereafter, Ar gas and N are introduced from the second gas introduction port GA2 disposed in the vicinity of 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. The 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 gas mixture system continues until the synthetic quartz glass substrate is transferred to the carry-out 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 carry-out chamber ULL. Further, the transport speed of the synthetic quartz glass substrate was set to 400 mm/min. When the synthetic quartz glass substrate passes through the vicinity of the second sputtering target 14 of the first sputtering chamber SP1, a chromium oxynitride film (CrCON) having a thickness of 200 nm is formed on the light semi-transmissive film by reactive sputtering. The insulating layer is formed into a film. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is conveyed in the opposite direction to the arrow S, and is returned to the loading chamber LL. Thereafter, a laminated film including a light shielding layer of a chromium carbonitride film (CrCN) and an antireflection layer containing a chromium oxynitride film (CrON) was formed on the insulating layer by the same method as in the first embodiment. In this manner, an etching mask film having a laminated structure in which an insulating layer containing CrCON, a light shielding layer containing CrCN, and an antireflection layer containing CrON are sequentially formed is formed on the light semi-transmissive film. Thereafter, after the second sputtering chamber and the carry-out chamber are completely separated by the spacer, the carry-out chamber is returned to the atmospheric pressure state, and the synthetic quartz having the light semi-permeable film and the etching mask film is taken out from the sputtering device 11. glass substrate. In this manner, a phase shift mask substrate in which a light semi-transmissive film and an etch mask film are formed on a synthetic quartz glass substrate is obtained. In the same manner as in the above-described first embodiment, composition analysis in the depth direction was performed by XPS on the obtained phase shift mask substrate. As a result, in the composition gradient region P, the content of nitrogen (N) in the wet etching of the light semi-transmissive film is continuously increased toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). Further, the maximum value of the ratio of nitrogen (N) to 矽 (Si) at the interface on the etching mask side in the gradient region P was 3.7. B. Phase shift mask and method of manufacturing The phase shift mask was produced by the same method as in Example 1 using the phase shift mask substrate manufactured in the above manner. The profile of the phase shift mask obtained was observed. Similarly to the first embodiment, the cross section of the light semi-transmissive film pattern is such that the bottom portion of the portion in contact with the synthetic quartz glass substrate is substantially perpendicular to the portion in contact with the etching mask pattern. Specifically, the cross section of the light semi-transmissive film pattern is composed of the upper surface, the lower side, and the side of the upper surface, the lower surface, and the side surface corresponding to the light semi-transmissive film pattern. The straight line formed by the contact between the upper side and the side and the side of the height at the height of two-thirds of the film thickness from the upper surface is formed at an angle of 105 degrees with the upper side. Further, the position of the side of the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate by the contact between the upper side and the side and the height of the film by the height of one tenth of the thickness from the lower surface The width of the second imaginary line perpendicular to the main surface of the synthetic quartz glass substrate was 44 nm. Further, the angle of the light semi-transmissive film pattern in contact with the synthetic quartz glass substrate was 60 degrees, and the angle of the light semi-transmissive film pattern in contact with the etching mask pattern was 75 degrees. Also, 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 (the thickness of the light semi-transmissive film is 110 nm, which is 1/2.5), so that 300 nm is included. The light having exposure of the light in the wavelength range of 500 nm or less, more specifically, the light including the combined light of the i-ray, the h-ray, and the g-ray, can be obtained with the PSM shown in Table 1 above ( A) A phase shift mask with the same phase shift effect. Reference Example 1. In Reference Example 1, the surface of the light semi-permeable membrane was not exposed to N after the film formation of the light semi-permeable membrane. 2 The case of the gas atmosphere will be described. A. Phase shift mask substrate and method of manufacturing the same 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. The synthetic quartz glass substrate was carried into the carrying chamber LL of the continuous sputtering apparatus 11 shown in Fig. 4 by the same method as in the first embodiment. 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 in the first embodiment was used. Ar gas and N are introduced from the first gas introduction port GA1 disposed in the vicinity of the first sputtering target 13 of the first sputtering chamber SP1. 2 Mixed gas of gas (Ar: 40 sccm, N 2 : 90 sccm), and a sputtering power of 8.5 kw was applied to the first sputtering target 13. In addition, Ar gas (130 sccm) is introduced from the third gas introduction port GA3 disposed in the vicinity of the third sputtering target 15 of the second sputtering chamber SP2 and the fourth gas introduction port GA4 disposed in the vicinity of the fourth sputtering target 16. ). Sputter 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 Ar gas system are introduced from the third gas introduction port GA3 and the fourth gas introduction port GA4 until the synthetic quartz glass substrate is transported to the carry-out chamber ULL. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is transported to the carry-out chamber ULL in the direction of the arrow S. Further, the transport speed of the synthetic quartz glass substrate was set to 400 mm/min. When the synthetic quartz glass substrate passes through the vicinity of the first sputtering target 13 of the first sputtering chamber SP1, a nitrogen-containing molybdenum telluride film having a film thickness of 55.0 nm is formed on the main surface of the synthetic quartz glass substrate by reactive sputtering. The first layer of light semi-transmissive film of (MoSiN). While the synthetic quartz glass substrate passes through the second sputtering chamber SP2, the first layer of the light semi-transmissive film is exposed to the Ar gas atmosphere. Thereafter, the synthetic quartz glass substrate mounted on a tray (not shown) is conveyed in the opposite direction to the arrow S, and is returned to the loading chamber LL. During the return of the synthetic quartz glass substrate to the carry-in chamber LL, the formed first light semi-transmissive film is in a vacuum state. Thereafter, a second layer light semi-transmissive film is formed by the same method as the first layer light semi-transmissive film. In this manner, a light semi-transmissive film having a total thickness of 110 nm including two layers of molybdenum oxynitride film (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 conveyed in the opposite direction to the arrow S, and is returned to the loading chamber LL. During the return of the synthetic quartz glass substrate to the carry-in chamber LL, the formed second light semi-transmissive film is in a vacuum state. Thereafter, an etching mask film was formed on the light semi-transmissive film by the same method as in Example 1 to obtain a phase shift mask substrate having a light semi-transmissive film and an etching mask film formed on the synthetic quartz glass substrate. For the phase shift mask substrate obtained, the composition analysis in the depth direction was performed using XPS. As a result, the content of nitrogen (N) is 46 to 47 atom% in the vicinity of the center in the thickness direction of each of the two layers constituting the light semi-permeable membrane. On the other hand, in the vicinity of the interface of the layer of 2, the content of nitrogen (N) was 44 atom%. A difference in the content of nitrogen (N) of 2-3 atom% can be seen in the vicinity of the center of each layer and in the vicinity of the interface between the two layers. Although the difference is a slight difference from the detection limit, it is presumed that the vacuum atmosphere is passed through the Ar gas atmosphere after the film formation of the light semi-permeable film, and then the tray is being returned to the LL chamber. This causes nitrogen to desorb from the surface of the first layer of light semi-permeable membrane. Further, by forming the second layer light semi-transmissive film, the content of nitrogen (N) is small in the vicinity of the interface between the first layer and the second layer. Further, in the composition gradient region P, the content of nitrogen (N) in the wet etching of the light semi-transmissive film is continuously increased toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). B. Phase shift mask and method of manufacturing The phase shift mask was produced by the same method as in Example 1 using the phase shift mask substrate manufactured in the above manner. Figure 11 is a plan view of the phase shift mask of Reference Example 1. Figure 12 is a cross-sectional photograph of the phase shift mask of Reference Example 1. In Figs. 11 and 12, QZ denotes a synthetic quartz glass substrate, PS denotes a light semi-transmissive film pattern, and Cr denotes an etching mask film pattern. Fig. 12 is a cross-sectional photograph showing a state in which an etching mask pattern is formed narrower than the width of the light semi-transmissive film pattern. As shown in FIG. 12, a large bite occurs at the interface between the first layer light semi-transmissive film pattern and the second layer light semi-transmissive film pattern. As described above, the vicinity of the interface between the first-layer light semi-permeable membrane and the second-layer light semi-permeable membrane is in a state in which the content of nitrogen (N) is small. It is considered that the vicinity of the interface in which the content of nitrogen is small is bitten by being etched more quickly. Specifically, the cross section of the light semi-transmissive film pattern PS is composed of the upper surface, the lower side, and the side of the upper surface, the lower surface, and the side surface corresponding to the light semi-transmissive film pattern PS. The line connecting the upper side and the side and the side of the height at the height of two-thirds of the film thickness from the upper surface are connected to each other at an angle of 80 degrees with respect to the upper side. Further, the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ by the contact of the upper side and the side, and the side of the position passing through the height of one tenth of the thickness of the film from the lower surface The width of the second imaginary line which is perpendicular to the main surface of the synthetic quartz glass substrate QZ is 45 nm. Also, the CDs are not all 0.252 μm. As shown in FIG. 11, the edge E1 of the light semi-transmissive film pattern PS has a zigzag shape, indicating that the CD unevenness is large. If the edge E1 of the light semi-transmissive film pattern PS is zigzag, the edge E2 of the etching mask film pattern Cr is also zigzag. The reason is considered to be that when the etching mask pattern Cr is formed, the etching liquid 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 pattern Cr, the shape of the light semi-transmissive film pattern PS is important. According to Reference Example 1, when a plurality of light semi-transmissive films are formed to form a light semi-transmissive film composed of a plurality of layers, the light semi-permeable film is not exposed during film formation and film formation. Slowing down the composition of the wet etch rate 2 In the gas atmosphere, biting occurs at the interface between the two adjacent layers of the light semi-transmissive film composed of the plurality of layers. It is speculated that N is not contained in the gas atmosphere exposed after film formation. 2 In the case of a gas, a small amount of nitrogen is desorbed from the surface of the semi-transmissive film to cause a slight change in the composition of the semi-transmissive film, thereby forming a portion which is easily etched at the interface. Reference Example 2 In the third embodiment, when the light semi-permeable membrane is formed, 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 a mixture of gases. On the other hand, in the reference example 2, when the light semi-transmissive film was formed, no gas 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 produced by the same method as in the third embodiment. In the same manner as in the above-described first embodiment, composition analysis in the depth direction was performed by XPS on the obtained phase shift mask substrate. As a result, in the composition gradient region P, the content of nitrogen (N) in the wet etching of the light semi-transmissive film is gradually increased 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 矽 (Si) at the interface on the side of the etching mask film in the gradient region P was 2.4. Figure 13 is a cross-sectional photograph of the phase shift mask of Reference Example 2. In Fig. 13, QZ denotes a synthetic quartz glass substrate, PS denotes a light semi-transmissive film pattern, and Cr denotes an etching mask film pattern. Fig. 13 is a cross-sectional photograph showing a state in which a light semi-transmissive film pattern is formed and before a photoresist pattern is peeled off. As shown in FIG. 13, the cross section of the light semi-transmissive film pattern PS is a linear wedge shape. Specifically, the cross section of the light semi-transmissive film pattern PS is composed of the upper surface, the lower side, and the side of the upper surface, the lower surface, and the side surface corresponding to the light semi-transmissive film pattern PS. The line connecting the upper side and the side and the side of the height at the height of two-thirds of the film thickness from the upper surface are connected to each other at an angle of 135 degrees with the upper side. Further, the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ by the contact of the upper side and the side, and the side of the position passing through the height of one tenth of the thickness of the film from the lower surface The width of the second imaginary line which is 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 has a wedge shape, the angle θ is 135 degrees, and the width is 85 nm (about 1.3 cm with respect to the film thickness of the light semi-transmissive film of 110 nm). Therefore, in the phase shift mask obtained, exposure of light including a wavelength range of 300 nm or more and 500 nm or less, more specifically, exposure of composite light including i-ray, h-ray, and g-ray Under the light, the degree of the phase shift effect equivalent to the PSM (A) shown in Table 1 above could not be obtained. Reference Example 3. In the third embodiment, when the light semi-transmissive film is formed, Ar gas and N are introduced from the gas introduction port GA3 and the gas introduction port GA4 of the second sputtering chamber SP2. 2 a mixture of gases. On the other hand, in the reference example 3, when the light semi-transmissive film is formed, only the Ar gas (150 sccm) is 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 produced by the same method as in the third embodiment. In the same manner as in the above-described first embodiment, composition analysis in the depth direction was performed by XPS on the obtained phase shift mask substrate. As a result, in the composition gradient region P, the content of nitrogen (N) in the wet etching of the light semi-transmissive film is gradually increased 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 cerium (Si) in the composition gradient region P is 2.6. Figure 14 is a cross-sectional photograph of the phase shift mask of Reference Example 3. In Fig. 14, QZ denotes a synthetic quartz glass substrate, PS denotes a light semi-transmissive film pattern, and Cr denotes an etching mask film pattern. Fig. 14 is a cross-sectional photograph showing a state in which the etching mask pattern is wet-etched to form an etching mask pattern which is narrower than the width of the light semi-transmissive film pattern. As shown in FIG. 14, the cross section of the light semi-transmissive film pattern PS is a linear wedge shape. Specifically, the cross section of the light semi-transmissive film pattern PS is composed of the upper surface, the lower side, and the side of the upper surface, the lower surface, and the side surface corresponding to the light semi-transmissive film pattern PS. The line connecting the upper side and the side and the side of the height at the height of two-thirds of the film thickness from the upper surface are connected to each other at an angle of 135 degrees with the upper side. Further, the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ by the contact of the upper side and the side, and the side of the position passing through the height of one tenth of the thickness of the film from the lower surface The width of the second imaginary line which is perpendicular to the main surface of the synthetic quartz glass substrate QZ is 89 nm. As described above, the cross-sectional shape of the light semi-transmissive film pattern has 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 of 110 nm). Therefore, in the phase shift mask obtained, exposure of light including a wavelength range of 300 nm or more and 500 nm or less, more specifically, exposure of composite light including i-ray, h-ray, and g-ray Under the light, the degree of the phase shift effect equivalent to the PSM (A) shown in Table 1 above could not be obtained. Comparative Example 1. In the third embodiment, when a light semi-transmissive film is formed, Ar gas and N are 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). Further, a sputtering power of 10.0 kW was applied to the first sputtering target 13 of the first sputtering chamber SP1. Further, the conveying speed of the synthetic quartz glass substrate was set to 350 mm/min. Further, the film thickness of the light semi-transmissive 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. Further, a sputtering power of 6.3 kW was applied to the first sputtering target 13 of the first sputtering chamber SP1. Further, the conveying speed of the synthetic quartz glass substrate was set to 200 mm/min. Further, the film thickness of the light semi-transmissive film was 115 nm. Further, after the light semi-transmissive film is formed, the surface of the light semi-permeable film is washed with ozone water. Except for this, a phase shift mask substrate and a phase shift mask were produced by the same method as in the third embodiment. In the same manner as in the above-described first embodiment, composition analysis in the depth direction was performed by XPS on the obtained phase shift mask substrate. As a result, in the composition gradient region P, there is a region in which the content of nitrogen (N) in the wet etching of the light semi-transmissive film is reduced toward the depth direction of the light semi-transmissive film (the direction of the synthetic quartz glass substrate). Further, the maximum value of the ratio of nitrogen (N) to 矽 (Si) at the interface on the side of the etching mask film in the gradient region P was 2.0. Figure 15 is a cross-sectional photograph of the phase shift mask of Comparative Example 1. In Fig. 15, QZ denotes a synthetic quartz glass substrate, PS denotes a light semi-transmissive film pattern, and Cr denotes an etching mask film pattern. Fig. 15 is a cross-sectional photograph showing a state in which an etching mask pattern is formed narrower than the width of the light semi-transmissive film pattern. As shown in Fig. 15, the cross section of the light semi-transmissive film pattern PS is a linear wedge shape. Specifically, the cross section of the light semi-transmissive film pattern PS is composed of the upper surface, the lower side, and the side of the upper surface, the lower surface, and the side surface corresponding to the light semi-transmissive film pattern PS. The line connecting the upper side and the side and the side of the height at the height of two-thirds of the film thickness from the upper surface are connected to each other at an angle of 160 degrees with respect to the upper side. Further, the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ by the contact of the upper side and the side, and the side of the position passing through the height of one tenth of the thickness of the film from the lower surface The width of the second imaginary line which is perpendicular to the main surface of the synthetic quartz glass substrate QZ is 295 nm. Further, the angle of the light semi-transmissive film pattern PS in contact with the synthetic quartz glass substrate QZ is 15 degrees, and the side of the upper side and the side side is at a position which is at a height of two-thirds of the thickness of the film from the upper surface. The line connecting the position and the angle formed by the upper side is 160 degrees. Further, the first imaginary line perpendicular to the main surface of the synthetic quartz glass substrate QZ through the contact of the upper side and the side T and the side edge at a position passing through the height of one tenth of the thickness of the film from the lower surface The width of the second imaginary line perpendicular to the main surface of the synthetic quartz glass QZ is 295 nm. Further, the angle of the light semi-transmissive film pattern PS in contact with the synthetic quartz glass substrate QZ was 15 degrees, and the angle of the light semi-transmissive film pattern PS in contact with the etching mask film pattern Cr was 165 degrees. The transfer speed of the synthetic quartz glass substrate is slow, and the exposure time of the semi-transmissive film is long after exposure to the Ar atmosphere. Therefore, it is considered that the nitrogen concentration at the interface between the light semi-permeable film and the etching mask film is further reduced, so that the bite is further Enter a larger one. As described above, the cross-sectional shape of the light semi-transmissive film pattern has 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 of 110 nm). Therefore, in the phase shift mask obtained, exposure of light including a wavelength range of 300 nm or more and 500 nm or less, more specifically, exposure of composite light including i-ray, h-ray, and g-ray Under the light, only the phase shift effect equivalent to PSMTP (A) shown in Table 1 above can be obtained. Also, the CDs are not all 0.230 μm. Furthermore, in the above embodiment, the Ar gas and the N are exposed after the formation of the molybdenum hydride molybdenum film. 2 An example of a mixed gas atmosphere is described, but even if exposed to N 2 The same effect can be obtained in the case of a gas atmosphere. Further, the same effect as the present invention can be obtained by replacing the nitrogen gas with a gas containing a nitrogen compound such as a nitrogen monoxide gas, a nitrous oxide gas or a nitrogen dioxide gas. Further, when the light semi-permeable membrane contains carbon which is a component for slowing the wet etching other than nitrogen, the same effect as the present invention is obtained even if a gas containing a carbon compound is used instead of nitrogen. Further, in the above embodiment, an example of the molybdenum oxynitride film is described as a material of the light semi-transmissive film, but the invention is not limited thereto. The material of the light semi-permeable membrane may also be a molybdenum oxynitride oxynitride film or a niobium oxynitride oxynitride film. Further, in the case of a metal telluride-based material other than molybdenum molybdenum, the same effects as described above can be obtained. Further, in the above embodiment, an example of a phase shift mask substrate for manufacturing a display device or a phase shift mask for manufacturing a display device has been described, but the invention is not limited thereto. The phase shift mask substrate or the phase shift mask of the present invention can also be applied to semiconductor device manufacturing, MEMS (Microelectromechanical Systems) manufacturing, printed circuit boards, and the like. Further, in the above embodiment, the example in which the size of the transparent substrate is 3345 size (330 mm × 450 mm) has been described, but the invention is not limited thereto. In the case of manufacturing a phase shift mask substrate for a display device, a large-sized transparent substrate having a length of one side of 10 inches or more is used. The size of the transparent substrate used for the phase shift mask substrate for manufacturing the display device is, for example, 330 mm × 450 mm or more and 2280 mm × 3130 mm or less. Further, 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, and the size of the transparent substrate is 9 inches on one side.吋The following. The size of the transparent substrate used in the phase shift mask substrate for the above use is, for example, 63.1 mm × 63.1 mm or more and 228.6 mm × 228.6 mm or less. Typically, for the manufacture of semiconductors, for the fabrication of MEMS, use 6025 size (152 mm × 152 mm) or 5009 size (126.6 mm × 126.6 mm); for the manufacture of printed substrates, use 7012 size (177.4 mm × 177.4 mm) ), or 9012 size (228.6 mm × 228.6 mm).

1‧‧‧線與間隙圖案
2a‧‧‧線圖案
2b‧‧‧線圖案
2c‧‧‧線圖案
3a‧‧‧間隙圖案
3b‧‧‧間隙圖案
4‧‧‧相移膜圖案之邊緣部分
5‧‧‧遮光膜圖案
11‧‧‧濺鍍裝置
12‧‧‧透明基板
13‧‧‧第1濺鍍靶
14‧‧‧第2濺鍍靶
15‧‧‧第3濺鍍靶
16‧‧‧第4濺鍍靶
21‧‧‧輔助線
22‧‧‧輔助線
23‧‧‧側邊
24‧‧‧輔助線
25‧‧‧輔助線
26‧‧‧接點
27‧‧‧側邊之位置
28‧‧‧側邊之位置
29‧‧‧第1假想線
30‧‧‧第2假想線
BU‧‧‧緩衝腔室
Cr‧‧‧蝕刻遮罩膜圖案
D‧‧‧寬度
E‧‧‧邊緣
E1‧‧‧邊緣
E2‧‧‧邊緣
LL‧‧‧搬入腔室
P‧‧‧組成梯度區域
PS‧‧‧光半透過膜圖案
Q‧‧‧組成均勻區域
QZ‧‧‧合成石英玻璃基板
S‧‧‧箭頭
SP1‧‧‧第1濺鍍腔室
SP2‧‧‧第2濺鍍腔室
ULL‧‧‧搬出腔室
θ‧‧‧角度1‧‧‧Line and gap pattern
2a‧‧‧ line pattern
2b‧‧‧ line pattern
2c‧‧‧ line pattern
3a‧‧‧ gap pattern
3b‧‧‧ gap pattern
4‧‧‧ Edge section of the phase shift film pattern
5‧‧‧Shade film pattern
11‧‧‧ Sputtering device
12‧‧‧Transparent substrate
13‧‧‧1st sputtering target
14‧‧‧2nd Sputtering Target
15‧‧‧3rd Sputtering Target
16‧‧‧4th sputtering target
21‧‧‧Auxiliary line
22‧‧‧Auxiliary line
23‧‧‧ Side
24‧‧‧Auxiliary line
25‧‧‧Auxiliary line
26‧‧‧Contacts
27‧‧‧The position of the side
28‧‧‧The position of the side
29‧‧‧1st imaginary line
30‧‧‧2nd imaginary line
BU‧‧‧ buffer chamber
Cr‧‧‧etched mask film pattern
D‧‧‧Width
E‧‧‧ edge
Edge of E1‧‧
E2‧‧‧ edge
LL‧‧‧ moving into the chamber
P‧‧‧forming gradient regions
PS‧‧‧Light semi-transmissive film pattern
Q‧‧‧Composed uniform area
QZ‧‧‧Synthetic quartz glass substrate
S‧‧‧ arrow
SP1‧‧‧1st sputtering chamber
SP2‧‧‧2nd sputtering chamber
ULL‧‧‧ moving out of the chamber 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 view showing the results of the first simulation. Fig. 3 is a view showing the results of the second simulation. 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 view showing the result of composition analysis in the depth direction of the phase shift mask substrate of the first embodiment. Figure 6 is a plan view of the phase shift mask of Embodiment 1. Figure 7 is a cross-sectional photograph of the phase shift mask of Example 1. Figure 8 is a cross-sectional photograph of the phase shift mask of Embodiment 2. Figure 9 is a cross-sectional photograph of the phase shift mask of Embodiment 3. Figure 10 is a cross-sectional photograph of the phase shifting reticle of Example 4. Figure 11 is a plan view of the phase shift mask of Reference Example 1. Figure 12 is a cross-sectional photograph of the phase shift mask of Reference Example 1. Figure 13 is a cross-sectional photograph of the phase shift mask of Reference Example 2. Figure 14 is a cross-sectional photograph of the phase shift mask of Reference Example 3. Figure 15 is a cross-sectional photograph of the phase shift mask of Comparative Example 1.

P‧‧‧組成梯度區域 P‧‧‧forming gradient regions

Q‧‧‧組成均勻區域 Q‧‧‧Composed uniform area

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 shift mask substrate, comprising: a transparent substrate; a light semi-transmissive film formed on a main surface of the transparent substrate, having a property of changing a phase of exposed light; and an etching mask film formed on the The light is semi-transmissive to the film and composed of a chromium-based material; and the light-transmissive film is a nitride of a metal telluride, a nitrogen oxide of a metal telluride, a carbon oxide of a metal telluride, and a nitrogen of a metal telluride. Any one of a carbide and a metal oxynitride oxynitride; and consisting of a plurality of layers; a composition gradient region is formed at an interface between the light semi-transmissive film and the etch mask film, and the composition gradient region is formed The ratio of nitrogen or carbon increases stepwise and/or continuously toward the depth direction. 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。The phase shift mask substrate of claim 1, wherein the light semi-transmissive film has a uniform region other than the interface between the light semi-transmissive film and the etch mask film and the interface between the light semi-transmissive film and the transparent substrate The composition of the parts 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。The phase shift mask substrate of claim 2, wherein the ratio of the nitrogen ratio of the uniform composition region is 5 atom% 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。The phase shift mask substrate of claim 1 or 2, wherein the step of determining the stepping is performed by X-ray photoelectron spectroscopy from the side of the etching mask film in the boundary between the composition gradient region and the etching mask film When the composition analysis was carried out under the conditions of 0.5 minute, the ratio of nitrogen (N) to cerium (Si) (N/Si) was 3.0 or more and 30 at the position where 原子 (Si) of 1 at% or more was detected 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。The phase shift mask substrate of claim 1 or 2, wherein the ratio of metal to germanium in the light semi-transmissive film is metal: 矽=1..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。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)。A phase shifting reticle substrate according to claim 6 wherein said 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。A phase shift mask substrate according to claim 1 or 2, wherein said etch mask film has a light blocking 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 reticle comprising: a light semi-transmissive film pattern formed by wet etching the light semi-transmissive film of the phase shift mask substrate according to any one of claims 1 to 8; and the light half The composition of the light transmissive film pattern is substantially uniform except that the upper surface of the film pattern and the portion of the light semi-permeable film pattern and the transparent substrate are substantially uniform, and the light semi-transmissive film pattern has a profile corresponding to the upper surface of the light semi-transmissive film pattern. The lower surface and the upper side, the lower side and the side of the side surface are formed, and the contact between the upper side and the side edge is connected to the position of the side edge at a position which is two-thirds of the height of the falling film from the upper surface. The straight line and the angle formed by the upper side are in the range of 85 to 120 degrees, and the first imaginary line perpendicular to the main surface of the transparent substrate is passed through the contact between the upper side and the side edge a width of the second imaginary line perpendicular to the main surface of the transparent substrate at a position at a height of one tenth of the thickness of the lower surface film and a thickness of the second imaginary line perpendicular to the main surface of the transparent substrate 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 of claim 9, wherein the light semi-transmissive film pattern comprises a line and 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 of claim 9, wherein the light semi-transmissive film pattern comprises 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 of manufacturing a phase shift mask, comprising: a photoresist pattern forming process, which is formed on an etch mask film of a phase shift mask substrate according to any one of claims 1 to 8, forming a photoresist An etch mask film pattern forming process for wet etching the etch mask film by using the photoresist pattern as a mask to form an etch mask pattern; and a semi-transmissive film pattern forming process The light semi-transmissive film pattern is formed by wet etching the light semi-transmissive film with the etching mask pattern as a mask. 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 manufacturing method of a display device, comprising: a phase shift mask arranging process for a substrate with a photoresist film formed with a photoresist film on a substrate, and a phase shift mask as claimed in claim 9 Or a phase shift mask obtained by the method of manufacturing a phase shift mask of claim 12 is disposed opposite to the photoresist film; and a photoresist film exposure process is performed on the phase shift mask The photoresist film is exposed to light by exposure to the above-mentioned exposure light. 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300 nm以上且500 nm以下之波長範圍之光。The method of manufacturing the display device of claim 13, wherein the exposed light comprises light in a wavelength range of 300 nm or more and 500 nm or less. 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 of manufacturing the display device of claim 14, wherein the exposed light is a composite light including i-rays, h-rays, and g-rays.
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