以下，一面參照圖式一面具體地說明本發明之實施形態。再者，以下之實施形態係將本發明具體化時之一形態，而並非將本發明限定於其範圍內者。圖中，存在對相同或等效之部分標註相同符號並簡化甚至省略其說明之情形。 (本發明之實施形態) 首先，對本發明之實施形態之相位偏移光罩基底進行說明。 ＜相位偏移光罩基底＞ 本發明之實施形態之相位偏移光罩基底之特徵在於： 其係相位偏移光罩之母版，該相位偏移光罩係於透明基板上藉由濕式蝕刻將相位偏移膜、蝕刻阻止膜、遮光膜分別圖案化，藉此形成包含遮光部、相位偏移部、透光部之轉印圖案而成，且該相位偏移光罩係藉由使透過上述相位偏移部之光之相位與透過上述透光部之光之相位不同，而使通過上述相位偏移部與上述透光部之邊界部附近之光相互抵消從而提高邊界部之對比度；且 上述相位偏移光罩基底於上述透明基板上依序形成有相位偏移膜、蝕刻阻止膜、遮光膜， 上述相位偏移膜包括含有鉻與選自氧、氮、碳、氟中之至少一者之鉻化合物， 上述蝕刻阻止膜包括含有金屬與矽之金屬矽化物， 上述相位偏移膜與上述遮光膜係能夠藉由同一種蝕刻液A進行蝕刻之材料，且以上述遮光膜面對上述蝕刻液A之濕式蝕刻速度快於上述相位偏移膜面對上述蝕刻液A之濕式蝕刻速度之方式進行調整， 上述蝕刻阻止膜係對上述遮光膜之蝕刻液A具有抗蝕性之材料，且以直至上述蝕刻阻止膜藉由能夠對其進行蝕刻之蝕刻液B而剝離所需之時間為15分鐘以下之方式調整上述蝕刻阻擋膜之膜厚、材料、組成比。 參照圖1，對本發明之實施形態之相位偏移光罩基底之具體構成進行說明。 如圖1所示，本發明之實施形態之相位偏移光罩基底10係於透明基板11上依序形成相位偏移膜12、蝕刻阻止膜13、遮光膜14而成。 而且，可藉由準備以上述方式形成之相位偏移光罩基底10，並將相位偏移膜12、蝕刻阻止膜13、遮光膜14圖案化而製造相位偏移光罩。 其次，對本發明之實施形態之相位偏移光罩進行說明。 ＜相位偏移光罩＞ 藉由使透過相位偏移部之光之相位與透過透光部之光之相位不同，而使通過上述相位偏移部與上述透光部之邊界部附近之光相互抵消從而提高邊界部之對比度的相位偏移光罩主要多用於半導體製造領域。已知該等相位偏移光罩係使用對曝光之光(例如，KrF或ArF之準分子雷射)之透過率為5～10%左右且使該曝光之光之相位大致偏移180度之相位偏移膜。 其中，該領域中所使用之相位偏移光罩通常係應用乾式蝕刻而製造，故而不存在因為採用上述濕式蝕刻而產生之問題點凸顯化之情形。然而，於顯示裝置製造用之相位偏移光罩中，如上所述，透明基板之尺寸相對大型(使用一邊為300 mm以上之矩形形狀之基板)，且其尺寸之種類多種多樣，故而相較於使用乾式蝕刻，應用濕式蝕刻更為有利。顯示裝置製造用之相位偏移光罩中所使用之矩形形狀之透明基板之尺寸例如可使用330 mm×450 mm至1620 mm×1780 mm。 本發明之相位偏移光罩(光罩，photomask)係於透明基板上藉由濕式蝕刻將相位偏移膜、蝕刻阻止膜、遮光膜分別圖案化，藉此形成包含遮光部、相位偏移部、透光部之轉印圖案而成的相位偏移光罩，且係藉由使透過上述相位偏移部之光之相位與透過上述透光部之光之相位不同，而使通過上述相位偏移部與上述透光部之邊界部附近之光相互抵消從而提高邊界部之對比度的相位偏移光罩。 此處，參照圖2對本發明之一實施態樣之相位偏移光罩進行說明。其中，圖2係形成有線與間隙圖案之第1實施態樣之相位偏移光罩之剖視圖(下側)及對應之俯視圖(上側)。 相位偏移光罩10a可藉由準備於圖1所示之透明基板11上依序形成相位偏移膜12、蝕刻阻止膜13、遮光膜14而成之相位偏移光罩基底10，並將相位偏移膜12、蝕刻阻止膜13、遮光膜14圖案化而製造。 但亦可於不妨礙本發明之效果之範圍內，於該等膜之間、或任一膜與透明基板11之間介置其他膜。 圖2之上側之圖係相位偏移光罩10a之俯視圖，於自上方觀察相位偏移光罩10a之情形時，可看到圖案化後之遮光膜14(即遮光膜圖案14a)之部分構成遮光部18，可看到圖案化後之相位偏移膜12(即相位偏移膜圖案12a)之部分構成相位偏移部16，未被相位偏移膜12、蝕刻阻止膜13及遮光膜14中任一者覆蓋而露出透明基板11之部分構成透光部17。該透光部17與上述相位偏移部16具有邊界部(鄰接部分)。 於使用本發明之相位偏移光罩進行顯示裝置之圖案形成之情形時，作為轉印特性良好之線與間隙圖案，例如較佳為4(μm)≦間距P＜6(μm)且線寬L≧1.5(μm)，間隙寬S≦3.5(μm)。於重視圖案轉印時之對比度之高度之情形時，於間距P＜6(μm)之微細之線與間隙圖案中，較佳為線寬L≧間隙寬S，包含與遮光部之邊緣鄰接之固定寬度之相位偏移部之邊緣寬度(rim width)R較佳為R≧0.8(μm)。再者，於線與間隙圖案中，通常設置有包含與遮光部之兩側鄰接之固定寬度之相位偏移部之邊緣寬度。該情形時之上述邊緣寬度R較理想亦為上述範圍R≧0.8(μm)。 此處，遮光部18係透明基板11上之至少形成有遮光膜圖案14a之部分，其對曝光之光之透過率實質上為零。相位偏移部16係於透明基板11上形成具有特定透過率(例如6%(i線：波長365 nm))之相位偏移膜圖案12a而成之部分，與透光部17之相位差為特定相位差(例如180度(i線：波長365 nm))。 如此，本發明之相位偏移光罩10a具有轉印用圖案，該轉印用圖案係於透明基板11上基於特定之圖案設計藉由濕式蝕刻將相位偏移膜12、蝕刻阻止膜13、遮光膜14分別圖案化而形成。 於此種構成之下，透過相位偏移部16之曝光之光使其相位相對於透過透光部17之曝光之光大致偏移180度，從而與透過透光部17後之曝光之光於鄰接部分相互干涉。藉此該部分之光之對比度提高，曝光之光之強度曲線之邊緣形狀變得更加銳利。因此，本發明之相位偏移光罩10a亦可應對近年來所要求之顯示裝置製造中之微細圖案。 此處，相位偏移光罩基底10、及相位偏移光罩10a之構成可設定為如下。 (透明基板11) 透明基板11之材料只要係對所使用之曝光之光具有透光性之材料便不加以特別限制。例如可列舉合成石英玻璃、鈉鈣玻璃、無鹼玻璃。 (相位偏移膜12) 本發明中之相位偏移膜12因透過曝光之光之一部分，而可說成是半透光性之膜。又，具有使曝光之光之相位偏移特定量之作用。 該相位偏移膜12包括含有鉻與選自氧、氮、碳、氟中之至少一者之鉻化合物。 本發明中之相位偏移膜12包括含有鉻之材料。例如，較佳為含有鉻氧化物(CrOx)、鉻氮化物(CrNx)、鉻碳化物(CrCx)、鉻氮氧化物(CrOxNy)、鉻碳氮化物(CrCxNy)、鉻碳氧化物(CrOxCy)、鉻碳氮氧化物(CrOxNyCz)、鉻氟化物(CrFx)中任一者。相位偏移膜12之膜厚較佳為80～180 nm。 於上述相位偏移膜12之濕式蝕刻中可使用公知之蝕刻液。例如，可使用硝酸鈰銨與過氯酸之混合水溶液。 於相位偏移光罩10a中，相位偏移膜12對曝光之光之透過率可為1～50%、1.5～30%、2～15%，更佳可為3～8%。此處，曝光之光可使用為LCD曝光裝置通常所採用之光源且包含i線、h線、g線中任一者之光，更佳為使用包含該等全部之光。作為曝光之光之透過率，將上述中任一者作為代表波長，而定義透過率及相位差(或相位偏移量)。 又，於相位偏移光罩10a中，將相位偏移膜12所具有之曝光之光(例如將i線作為代表波長)之相位偏移量設為大致180度。此處，所謂大致180度係指可為160度～200度，較佳可為170～190度。 又，就上述相位偏移膜12而言，波長365 nm(i線)至436 nm(g線)範圍內之光之相位偏移量之變動幅度(波長365 nm至436 nm之、於相位偏移膜12之最大相位偏移量與最小相位偏移量之差)較佳為40度以內，更佳為30度以內。藉由使上述變動幅度處於此種範圍內，可充分獲得使代表波長之相位偏移量為大致180度之效果。 (蝕刻阻止膜13) 蝕刻阻止膜13係包括含有金屬與矽之金屬矽化物，且對下述遮光膜之蝕刻液A(於遮光膜為包含Cr之鉻化合物之情形時，該蝕刻液A例如為硝酸鈰銨與過氯酸之混合水溶液)具有抗蝕性之材料，且以直至蝕刻阻止膜藉由能夠對其進行蝕刻之蝕刻液B(例如，氟化氫銨與過氧化氫之混合水溶液、或過氧化氫、氟化銨及磷酸之混合水溶液)而剝離所需之時間為15分鐘以下、較佳為10分鐘以下之方式選定膜厚、材料、組成比。以下對蝕刻阻止膜13之膜厚、材料、組成比進行說明。 蝕刻阻止膜13之膜厚較佳為5 nm以上且75 nm以下。 為了發揮作為蝕刻阻止膜13之功能，其膜厚較佳為5 nm以上。若蝕刻阻止膜13之膜厚過厚，則藉由蝕刻液B剝離蝕刻阻止膜13時，蝕刻液B與透明基板(玻璃基板)11之接觸時間較長，會發生因玻璃基板遭到腐蝕而導致之透過率降低、或因龜裂而導致之凹缺陷。又，於自缺陷品質之方面考慮而以中途停用蝕刻液之方式進行蝕刻製程之情形時，一旦膜厚較厚則蝕刻液B之消耗量便會非常多。就該等方面而言蝕刻阻止膜13之膜厚較佳為75 nm以下。 此處，蝕刻阻止膜13係含有金屬與矽之金屬矽化物(金屬矽化物系材料)，其中尤為金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物、或金屬矽化物之碳氮氧化物，且氮之含量較佳為20原子%以上且50原子%以下。蝕刻阻止膜13中之氮之含量更佳為25原子%以上且45原子%以下。 構成蝕刻阻止膜13之金屬矽化物系材料只要係包含金屬與矽者便不加以特別限制。為了使藉由濕式蝕刻而形成之蝕刻阻止膜圖案之剖面形狀良好，進而使將蝕刻阻止膜圖案作為遮罩藉由濕式蝕刻而形成之相位偏移膜圖案之剖面形狀良好，金屬與矽之比率較佳為金屬：矽＝1：2以上且1：9以下。 若金屬與矽之比率係比起1：2金屬之含量更多(金屬：矽之比率未達1：2)，則於形成具有粗圖案與密圖案之圖案時，難以精度較佳地形成圖案。又，若金屬與矽之比率係比起1：9矽之含量更多(金屬：矽之比率超過1：9)，則蝕刻速度變慢，故而會發生與上述相同之不良狀況。 尤佳地，構成蝕刻阻止膜13之金屬矽化物系材料中之金屬與矽之比率較理想為金屬：矽＝1：2以上且1：8以下。作為金屬，可列舉鉬(Mo)、鉭(Ta)、鎢(W)、鈦(Ti)、鋯(Zr)等過渡金屬。 作為構成蝕刻阻止膜13之金屬矽化物系材料，例如可列舉金屬矽化物、金屬矽化物之氮化物、金屬矽化物之氧化物、金屬矽化物之碳化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物、金屬矽化物之碳氧化物、或金屬矽化物之碳氮氧化物。具體而言，可列舉：鉬矽化物(MoSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物；鉭矽化物(TaSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物；鎢矽化物(WSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物；鈦矽化物(TiSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物；鋯矽化物(ZrSi)及其氮化物、氧化物、碳化物、氮氧化物、碳氮化物、碳氧化物、碳氮氧化物。 就與相位偏移膜12之密接性之提高以及相位偏移膜12及蝕刻阻止膜13之剖面控制性之方面而言，其中尤以金屬矽化物系材料係金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物為佳。於該情形時，氮之含量較理想為25原子%以上且45原子%以下。又，為了使蝕刻阻止膜13具有反射率降低功能，較佳為進而含有氧。 對於上述蝕刻阻止膜13，以直至該蝕刻阻止膜13藉由能夠對其進行蝕刻之蝕刻液B(例如，氟化氫銨與過氧化氫之混合水溶液、或過氧化氫、氟化銨及磷酸之混合水溶液)而剝離所需之時間為10分鐘以下之方式調整、選定蝕刻阻止膜13之膜厚、材料、組成比。本發明中所使用之顯示裝置製造用之相位偏移光罩基底一般是一邊之長度為300 mm以上之較大尺寸，故而於向基板面內供給蝕刻液時容易產生蝕刻不均。若考慮到蝕刻不均，則直至上述蝕刻阻止膜13藉由能夠對其進行蝕刻之蝕刻液B而剝離所需之時間較佳為10秒以上。進而較佳地，上述時間較理想為10秒以上且15分鐘以下，更理想為10秒以上且10分鐘以下。 考慮到蝕刻液B對玻璃基板所造成之損傷，於形成上述蝕刻阻止膜圖案時所使用之蝕刻液B為包含過氧化氫、氟化銨、以及選自磷酸、硫酸及硝酸中至少一者之氧化劑的蝕刻液之情形時，較佳為以直至藉由蝕刻液B而剝離所需之時間為10秒以上且20分鐘以下之方式調整上述蝕刻阻止膜13之膜厚、材料、組成比。又，就相同之觀點而言，於形成上述蝕刻阻止膜圖案時所使用之蝕刻液B為包含選自氫氟酸、氟矽酸、及氟化氫銨中至少一者之氟化合物與選自過氧化氫、硝酸、及硫酸中至少一者之氧化劑的蝕刻液之情形時，較佳為以直至藉由蝕刻液B而剝離所需之時間為10秒以上且10分鐘以下之方式調整上述蝕刻阻止膜13之膜厚、材料、組成比。 (遮光膜14) 遮光膜14較佳為於與相位偏移膜12、蝕刻阻止膜13積層之狀態下具有充分之遮光性(光學濃度(OD)為3以上)。更佳為僅以遮光膜14便具有充分之遮光性(光學濃度(OD)為3以上)。又，遮光膜14較佳為具有與蝕刻阻止膜13之蝕刻選擇性。即，較理想為蝕刻阻止膜13對能夠蝕刻遮光膜14之蝕刻液具有抗蝕性。 作為遮光膜14之材料，可較佳地使用包含Cr者。例如，除含有鉻以外，較佳為含有鉻氧化物(CrOx)、鉻氮化物(CrNx)、鉻碳化物(CrCx)、鉻氮氧化物(CrOxNy)、鉻碳氮化物(CrCxNy)、鉻碳氧化物(CrOxCy)、鉻碳氮氧化物(CrOxNyCz)中任一者。 遮光膜14亦可於其表面設置抗反射層。於該情形時，抗反射層可為鉻氧化物、鉻氮化物及鉻酸氮化物中任一者。 又，上述相位偏移膜12與上述遮光膜14為能夠藉由同一種蝕刻液(A)(例如，硝酸鈰銨與過氯酸之混合水溶液)進行蝕刻之材料，且以上述遮光膜面對上述蝕刻液(A)之濕式蝕刻速度快於上述相位偏移膜面對蝕刻液(A)之濕式蝕刻速度之方式，藉由添加於上述相位偏移膜12或上述遮光膜14中之氧、氮、碳、氟之含量而進行調整。 遮光膜14之膜厚可為50～200 nm，更佳為80～150 nm，進而更佳為90～130 nm。 作為遮光膜14之蝕刻液並不加以特別限制，可使用先前公知者，於遮光膜14係利用包含鉻之材料而形成之情形時，對遮光膜14所使用之蝕刻液與上述相位偏移膜12中所述者相同。 相位偏移光罩10a可使露出於表面之面全部為鉻系之膜，故而耐化學品性較高，較為有利。作為成膜方法，相位偏移光罩10a之各構成膜均可採用濺鍍法、離子鍍覆法、或蒸鍍法等，就提高2個膜之界面密接性之方面而言較佳為濺鍍法。 如此，本發明之相位偏移光罩10a可較佳地應用於例如包含形成顯示裝置之像素電極等之線與間隙圖案作為轉印圖案之光罩。 又，如圖3所示，轉印圖案亦可應用於包含形成接觸孔之孔圖案者。作為孔圖案，包含具有固定之規則性(間距)且複數個接觸孔排列者。 此處，圖3係本發明之孔圖案用之相位偏移光罩10b之剖視圖(下側)及對應之俯視圖(上側)。 如圖3所示，孔圖案具有特定孔徑之透光部17、包圍透光部17之固定寬度之相位偏移部16、及包圍上述相位偏移部16之遮光部18。 此處，透光部17之孔徑(於正方形之情形時為1邊之長度，於長方形之情形時為短邊之長度，於圓形之情形時為直徑)可為1.5～5(μm)，相位偏移部16之寬度(邊緣寬度R)可為0.3(μm)≦R≦1.5(μm)。 ＜相位偏移光罩之製造方法＞ 本發明之相位偏移光罩之製造方法具有以下步驟： 於上文所說明之本發明之實施形態之上述相位偏移光罩基底上形成抗蝕膜； 對上述抗蝕膜進行特定圖案之繪圖、顯影處理，而形成抗蝕圖案； 將上述抗蝕圖案作為遮罩，藉由上述蝕刻液A對上述遮光膜進行濕式蝕刻，而形成臨時遮光膜圖案； 將上述臨時遮光膜圖案作為遮罩，藉由上述蝕刻液B對上述蝕刻阻止膜進行濕式蝕刻，而形成臨時蝕刻阻止膜圖案； 將上述臨時蝕刻阻止膜圖案作為遮罩，藉由上述蝕刻液A對上述相位偏移膜進行濕式蝕刻，而形成基於相位偏移膜圖案之相位偏移部，並藉由對上述臨時遮光膜圖案進行側面蝕刻而形成遮光膜圖案； 將上述遮光膜圖案作為遮罩，藉由上述蝕刻液B對上述蝕刻阻止膜進行濕式蝕刻，而形成蝕刻阻止膜圖案，於上述相位偏移膜圖案上形成基於上述蝕刻阻止膜圖案與上述遮光膜圖案之遮光部；及 去除上述抗蝕圖案。 以此方式操作，製造於透明基板上具備具有相位偏移部、遮光部、透光部之轉印圖案之相位偏移光罩。 而且，於相位偏移膜12、蝕刻阻止膜13、及遮光膜14之圖案化中可包括以下步驟。 此處，首先參照圖4對作為參考例之相位偏移光罩10c之製造方法進行說明，以使本發明之相位偏移光罩10a、10b之製造方法之特徵更加明確。 ＜參考例之相位偏移光罩10c之製造方法＞ 參考例之相位偏移光罩10c之製造方法係於製作該相位偏移光罩10c時兩次形成抗蝕膜之相位偏移光罩之製造方法。 圖4係表示參考例之態樣之相位偏移光罩10c的製造方法之例之圖。 首先，準備圖1所示之相位偏移光罩基底10，於相位偏移光罩基底10之遮光膜14上形成第1光阻膜15(圖4(a))。 其後，藉由對第1光阻膜15進行繪圖及顯影而形成第1抗蝕圖案15a，並藉由將第1抗蝕圖案15a作為遮罩，利用蝕刻液A對遮光膜14進行濕式蝕刻，而形成遮光膜圖案14a(圖4(b))。 其次，剝離第1抗蝕圖案15a(圖4(c))。 其次，於形成有遮光膜圖案14a之透明基板11整面形成第2光阻膜19(圖4(d))， 並藉由對第2光阻膜19進行繪圖及顯影而形成第2抗蝕圖案19a(圖4(e))。 其次，將第2抗蝕圖案19a作為遮罩，利用蝕刻液B對蝕刻阻止膜13進行濕式蝕刻，而形成蝕刻阻止膜圖案13a(圖4(f))。 其次，將所獲得之蝕刻阻止膜圖案13a作為遮罩，利用蝕刻液A對相位偏移膜12進行濕式蝕刻，而形成相位偏移膜圖案12a，其後，剝離第2抗蝕圖案19a(圖4(g))。 最後，將遮光膜圖案14a作為遮罩，利用蝕刻液B對蝕刻阻止膜圖案13a進行濕式蝕刻，則相位偏移光罩10c完成((圖4(h))。 然而，於上述相位偏移光罩10c之參考製法中，如圖4所示，兩次形成光阻膜(第1光阻膜15、第2光阻膜19)，並對第1光阻膜15及第2光阻膜19分別進行繪圖及顯影，藉此兩次形成抗蝕圖案(第1抗蝕圖案15a、第2抗蝕圖案19a)，而進行濕式蝕刻。 於此種作為參考例之相位偏移光罩之製造方法中，由於係兩次形成光阻膜(第1抗蝕膜15、第2抗蝕膜19)，並對該等光阻膜兩次進行繪圖及顯影，而形成光阻圖案(第1抗蝕圖案15a、第2抗蝕圖案19a)，故而於最終所獲得之相位偏移光罩10c中難以使遮光膜圖案14a與相位偏移膜圖案12a之中心吻合。 本發明之相位偏移光罩10a之製造方法係解決於上述作為參考例之相位偏移光罩之製造方法中難以使遮光膜圖案14a與相位偏移膜圖案12a之中心吻合者。即，於本發明之相位偏移光罩10a之製造方法中，使用一次抗蝕膜僅進行一次繪圖及顯影，故而能以遮光膜圖案14a與相位偏移膜圖案12a之中心吻合之方式製造相位偏移光罩10a。 以下，參照圖5詳細地對本發明之相位偏移光罩10a之製造方法進行說明(本發明之相位偏移光罩10b之製造方法亦與此相同)。 ＜本發明之相位偏移光罩之製造方法＞ 如圖5所示，首先準備如圖1所示之相位偏移光罩基底10，於相位偏移光罩基底10之遮光膜14上形成第1光阻膜15(圖5(a))。 其次，對第1光阻膜15進行特定圖案之繪圖、顯影處理，而形成抗蝕圖案15a，並將抗蝕圖案15a作為遮罩，藉由蝕刻液A對遮光膜14進行濕式蝕刻，而形成臨時遮光膜圖案14a(圖5(b))。 其次，將臨時遮光膜圖案14a作為遮罩，藉由蝕刻液B對蝕刻阻止膜13進行濕式蝕刻，而形成臨時蝕刻阻止膜圖案13a(圖5(c))。 其次，將臨時蝕刻阻止膜圖案13a作為遮罩，藉由蝕刻液A對相位偏移膜12進行濕式蝕刻，而形成基於相位偏移膜圖案12a之相位偏移部，並藉由對臨時遮光膜圖案14a進行側面蝕刻而形成遮光膜圖案14b(圖5(d))。 最後，去除抗蝕圖案15a，將遮光膜圖案14b作為遮罩，藉由蝕刻液B對臨時蝕刻阻止膜圖案13a進行濕式蝕刻，而形成蝕刻阻止膜圖案13b，於相位偏移膜圖案12a上形成基於蝕刻阻止膜圖案13b與遮光膜圖案14b之遮光部(圖5(e))。 以此方式操作，如圖5(e)所示於透明基板11上具備具有相位偏移部、遮光部、透光部之轉印圖案之相位偏移光罩10a完成。 此處，對蝕刻阻止膜13之膜厚、材料、組成比加以調整、選定，而使蝕刻阻止膜圖案之形成時間為10秒以上且15分鐘以下或10秒以上且10分鐘以下。因此，能抑制製作相位偏移光罩時、尤其是形成蝕刻阻止膜圖案時之蝕刻液B之消耗量，又，因蝕刻液B對透明基板11之接觸時間較短，故而能減少透明基板之損傷，從而可抑制凹缺陷之發生。 再者，說明對蝕刻阻止膜13進行濕式蝕刻時所使用之蝕刻液B。 (蝕刻液B) 對蝕刻阻止膜13進行濕式蝕刻之蝕刻液B只要係可實質上不蝕刻遮光膜14及相位偏移膜12而選擇性地對蝕刻阻止膜13進行蝕刻者，便不加以特別限制。蝕刻液B例如可列舉包含選自氫氟酸、氟矽酸、及氟化氫銨中之至少一者之氟化合物與選自過氧化氫、硝酸、及硫酸中之至少一者之氧化劑的蝕刻液。具體而言可列舉利用純水稀釋氟化氫銨與過氧化氫之混合溶液而獲得之蝕刻液。又，可列舉包含過氧化氫、氟化銨、以及選自磷酸、硫酸及硝酸中至少一者之氧化劑的蝕刻液。具體而言可列舉利用純水稀釋過氧化氫、氟化銨及磷酸之混合溶液而獲得之蝕刻液。 又，根據本發明之相位偏移光罩之製造方法，優點在於以下幾點：僅進行一次繪圖與顯影即可，從而可消除由複數次繪圖步驟所引起之相互對準偏移之影響。尤其優異在可準確地形成微細寬度之相位偏移部16。 又，根據本發明之相位偏移光罩之製造方法，使用一個抗蝕圖案僅進行一次繪圖及顯影，故而能以如圖5(e)之中心線X所示遮光膜圖案14b與相位偏移膜圖案12a之中心吻合之方式製造相位偏移光罩10a。 其次，對本發明之顯示裝置之製造方法進行說明。 ＜顯示裝置之製造方法＞ 本發明之顯示裝置之製造方法包括以下步驟： 準備上文所說明之本發明之實施形態之上述相位偏移光罩；及 使用照射曝光之光之顯示裝置製造用曝光裝置，曝光相位偏移光罩之轉印圖案，而將轉印圖案轉印於被轉印體上。 所使用之曝光裝置可為LCD用之標準等倍曝光之曝光裝置。即，藉由使用包含i線、h線、g線之波長區域之光源(亦稱為寬波長光源)作為光源，可獲得充分之照射光量。其中，亦可使用光學濾光片，而僅使用特定波長之光(例如i線)。 曝光裝置之光學系統可將數值孔徑NA設於0.06～0.10，將同調因子σ設於0.5～1.0之範圍。此種曝光裝置一般將3 μm左右設為解像極限。 當然，本發明亦可於使用更大範圍之曝光裝置進行轉印時應用。例如，NA可設於0.06～0.14、或0.06～0.15之範圍。對於NA超過0.08之高解像度之曝光裝置亦產生有需求，本發明亦可應用於該等。 (蝕刻阻止膜(蝕刻終止膜)中之氮之添加與蝕刻速度之關係) 首先，調查包含金屬矽化物之蝕刻阻止膜中之氮之添加與蝕刻速度之關係。 於合成石英玻璃基板(QZ基板)上形成組成比不同之蝕刻阻止膜13(蝕刻終止膜)，調查氮之添加與蝕刻速度之關係。將調查結果示於表1。 使用氟化氫銨與過氧化氫之水溶液(22℃)作為蝕刻液，，使用MoSi靶(Mo：Si＝1：4)，使用氬氣與氮氣作為濺鍍氣體，而於合成石英玻璃基板上形成蝕刻阻止膜(蝕刻終止膜)。 [表1]
根據上述表1之結果可知：隨著成膜中所含之氮(N2
)含量變多，蝕刻阻止膜中所含之氮(N)含量亦變多。 又，可知：隨著蝕刻阻止膜中所含之氮(N)含量變多，在藉由對蝕刻阻止膜進行蝕刻時所使用之蝕刻液B(氟化氫銨與過氧化氫之水溶液)而產生之合成石英玻璃基板(QZ基板)之刻蝕量相當於5度相位偏移量之蝕刻時間內所能蝕刻之蝕刻阻止膜之膜厚變薄。 根據以上內容可知：隨著蝕刻阻止膜中所含之氮(N)含量變多，蝕刻阻止膜之蝕刻速度變慢。 雖未詳細說明，但於蝕刻液B為過氧化氫、氟化銨及磷酸之水溶液之情形時亦為與上述相同之傾向。 (蝕刻阻止膜13之膜厚、材料、組成比之特定) (1)製作本發明之相位偏移光罩時，如圖5(d)所示，使用蝕刻液A同時對遮光膜14與相位偏移膜12進行蝕刻，故而蝕刻阻止膜13殘留於相位偏移膜圖案12a上。為了成為圖5(e)所示之最終之相位偏移光罩之形態，需要去除蝕刻阻止膜13，但用以去除蝕刻阻止膜13之蝕刻液B(例如，氟化氫銨與過氧化氫之水溶液)通常會使合成石英玻璃基板產生損傷，故而較理想為儘量縮短蝕刻阻止膜13之蝕刻時間。再者，蝕刻阻止膜13之蝕刻時間係由蝕刻阻止膜13之蝕刻速度×蝕刻阻止膜之膜厚所決定。 (2)LCD之曝光裝置中所使用之曝光之光(例如，i線(波長：365 nm))之QZ基板之相位差係相對於QZ基板之2.1 nm刻蝕量產生1度相位差(相對於空氣而言(Air基準))。一般而言，於顯示裝置製造用之相位偏移光罩中，要求將所需之相位偏移量(相位差)抑制於±5度以內(例如，180度±5度)。 (3)為了將QZ基板之刻蝕量抑制於相位偏移量5度以內，必須將蝕刻量抑制於2.1 nm×5＝10.5 nm，於面對蝕刻液B之QZ基板之蝕刻速度為1.2 nm/分鐘之情形時，需要將蝕刻時間抑制於10.5 nm÷1.2 nm/分鐘＝9分鐘左右。 (4)包含金屬矽化物之蝕刻阻止膜13需要極力於較短時間內加以蝕刻以避免對合成石英玻璃基板造成損傷。又，作為蝕刻相位偏移膜12時之蝕刻阻止膜13，需為可對相位偏移膜12進行保護之膜厚。蝕刻阻止膜13之膜厚之下限值就保護相位偏移膜12之觀點而言，較佳為7.5 nm以上，而關於蝕刻阻止膜13之膜厚之上限值，蝕刻時間會因蝕刻阻止膜13中所含之氮含量而異，需根據蝕刻時間而特定蝕刻阻止膜13之膜厚與氮含量。 (5)以蝕刻阻止膜13之膜厚為10 nm，且成膜中之氣體組成(混合氣體中所含之氮氣體組成)為39.0%之成膜條件進行成膜後，確認：於使用蝕刻液B之情形時，可於2分鐘內去除蝕刻阻止膜13。即便蝕刻液B與QZ基板接觸2分鐘，亦僅產生2.4 nm左右之損傷，故而該損傷所致之相位偏移量較少，為1度左右。 以下，作為實施例之蝕刻阻止膜13，選定了以膜厚為10 nm且成膜中之氣體組成(混合氣體中所含之氮氣體組成)為39.0%之成膜條件成膜所得之MoSiN膜(Mo：16.7原子%，Si：41.1原子%，N：42.2原子%)。 以下，基於實施例更加具體地說明本發明之相位偏移光罩基底及相位偏移光罩。 [實施例] (實施例1) 參照圖6，首先，於相位偏移光罩基底之製作中，使用大型玻璃基板(合成石英玻璃，厚度為10 mm，尺寸為850 mm×1200 mm)作為透明基板11。使用大型線內(inline)型濺鍍裝置，於該透明基板11成膜相位偏移膜12、蝕刻阻止膜13、遮光膜14。 各相位偏移膜12、蝕刻阻止膜13、遮光膜14之成膜係以如下方式進行。 (相位偏移膜12) 相位偏移膜12之成膜係使用大型線內濺鍍裝置而進行。向配置有Cr靶之濺鍍室內導入包含氬氣、氮氣及二氧化碳氣體之濺鍍氣體，藉由反應性濺鍍而成膜122 nm之CrCON層。 對於所成膜之相位偏移膜12，藉由Lasertec公司製造之MPM-100測定透過率、相位差。相位偏移膜12之透過率、相位差之測定係使用帶相位偏移膜之基板(虛設基板)而進行，該帶相位偏移膜之基板係設置於同一托盤而製作之、於合成石英玻璃基板之主表面上成膜CrCON膜(膜厚為122 nm)而成。 相位偏移膜12之透過率、相位差係於形成蝕刻阻止膜之前將帶相位偏移膜之基板(虛設基板)自搬出室取出而測定。其結果，透過率為5.0%(波長：365 nm)，相位差為180度(波長：365 nm)。又，波長365 nm～436 nm之相位差(相位偏移量)之變動幅度為25度。 (蝕刻阻止膜13) 其次，向配置有MoSi靶(Mo：Si=1：4)之濺鍍室內導入包含氬氣與氮氣之濺鍍氣體，藉由反應性濺鍍而成膜10 nm之MoSiN層。成膜中之氣體組成(N2
/Ar＋N2
)為39%。 (遮光膜14) 於實施例1中，如圖6所示遮光膜14為遮光層140與反射降低層143之積層構造。而且，遮光層140包括下層部141與上層部142。 關於遮光膜14之成膜，於配置在大型線內濺鍍裝置內之各空間(濺鍍室)分別配置Cr靶，以連續成膜方式，首先將氬氣、甲烷氣體及氮氣作為濺鍍氣體，藉由反應性濺鍍而成膜50 nm之CrCN層(遮光層140之下層部141)，其次同樣將氬氣、甲烷氣體及氮氣作為濺鍍氣體，藉由反應性濺鍍而成膜55 nm之CrCN層(遮光層140之上層部142)，繼而將氬氣與一氧化碳氣體作為濺鍍氣體，藉由反應性濺鍍而成膜25 nm之CrON層(反射降低層143)。實施例1之反射降低層143為單層膜。成膜後，利用純水進行刷洗，從而製作出相位偏移光罩基底10。 再者，上述遮光層140係適當調整甲烷氣體與氮氣之流量以加快膜深方向之蝕刻速度而進行成膜。 具體而言，使成膜遮光層140之下層部141時之濺鍍氣體中所含之氮氣之含量多於成膜遮光層140之上層部142時之濺鍍氣體中所含之氮氣之含量，進而，使成膜遮光層140之下層部141時之濺鍍氣體中所含之甲烷氣體之含量少於成膜遮光層140之上層部142時之濺鍍氣體中所含之甲烷氣體之含量而進行成膜。又，為了獲得遮光層140(上層部141、下層部142)及遮光膜14所需之光學濃度(OD)，亦適當調整施加於各Cr靶之功率而進行成膜。 將遮光膜14之各層之特性示於下文。分別地光學濃度係利用透過濃度計而測定，反射率係利用反射率計而測定。此處，遮光層140之下層部141及上層部142之光學濃度係對在合成石英玻璃基板上以與上述相同之成膜條件成膜各層(單層)而成之試樣進行測定所得之值。 遮光層140： 下層部141：CrCN(膜厚：50 nm)，光學濃度：2.3(波長：436 nm)、2.5(波長：365 nm) 上層部142：CrCN(膜厚：55 nm)，光學濃度：2.1(波長：436 nm)、2.3(波長：365 nm) 反射降低層143：CrON(膜厚：25 nm) 遮光膜14之合計膜厚：130 nm 遮光膜14整體之光學濃度：4.6(波長：436 nm)、5.0(波長：365 nm)，正面反射率：10%(波長：436 nm)，背面反射率：55%(波長：436 nm) 再者，於上述相位偏移光罩基底10之製造方法中，未於中途將構成遮光膜14之各層膜重置於大氣中，而是於減壓真空狀態之下連續地形成。藉由如此於減壓真空狀態之下連續地形成，可減小自遮光膜14之最表面(包含CrON之反射降低層143之表面)到達透明基板11之間之組成之變動。 使用以如上方式製作出之相位偏移光罩基底10製造實施例1之相位偏移光罩。 參照圖5，首先使用狹縫式塗佈機於遮光膜14上塗佈酚醛系雷射繪圖用光阻劑，並進行加熱、冷卻而形成膜厚為1000 nm之抗蝕膜15(圖5(a))。 其次，藉由雷射繪圖於抗蝕膜15繪製線與間隙(L/S)圖案，並實施顯影，而形成抗蝕圖案15a。該L/S圖案為如下線寬之抗蝕圖案：假定相位偏移膜圖案形成時所產生之底切(與以蝕刻阻止膜圖案之線寬為基準時之相位偏移膜圖案之線寬之差)，以基於最終所獲得之相位偏移光罩之相位偏移膜圖案的L/S圖案之寬度成為3 μm之方式，使單側加粗0.12 μm(兩側共加粗0.24 μm)。 其次，藉由將抗蝕圖案15a作為遮罩，利用濕式蝕刻液A(硝酸鈰銨與過氧化氫之水溶液)對遮光膜14進行蝕刻，而形成臨時遮光膜圖案14a(圖5(b))。 其次，藉由將抗蝕圖案15a、及臨時遮光膜圖案14a作為遮罩，利用濕式蝕刻液B(氟化氫銨與過氯酸之水溶液)進行蝕刻，而形成臨時蝕刻阻止膜圖案13a(圖5(c))。 其次，藉由將臨時蝕刻阻止膜圖案13a作為遮罩，利用濕式蝕刻液A(硝酸鈰銨與過氧化氫之水溶液)對相位偏移膜12進行蝕刻，而形成相位偏移膜圖案12a，進而藉由對上述臨時遮光膜圖案14a進行側面蝕刻，而形成遮光膜圖案14b(圖5(d))。 其次，藉由將遮光膜圖案14b作為遮罩，利用濕式蝕刻液B(包含氟化氫銨與過氧化氫之混合水溶液)對臨時蝕刻阻止膜圖案13a進行蝕刻，而於相位偏移膜圖案12a上形成基於蝕刻阻止膜圖案13b與遮光膜圖案14b之遮光部。 最後，利用抗蝕層剝離液剝離抗蝕圖案15a，而獲得本發明之相位偏移光罩(圖5(e))。 上述實施例1之遮光膜14之適當蝕刻時間為45秒，且遮光膜14之膜厚為130 nm，故而面對蝕刻液A(硝酸鈰銨與過氯酸之水溶液)之遮光膜14之濕式蝕刻速度為2.9 nm/秒。 又，為了於形成相位偏移膜圖案12a之同時，對藉由臨時遮光膜圖案14a之側面蝕刻而形成之遮光膜圖案14b所構成之邊緣寬度(相位偏移部之寬度為0.5 μm)進行調整，而相對於相位偏移膜12之適當蝕刻時間94秒追加71秒蝕刻，使之為合計165秒，而製作相位偏移光罩。再者，面對蝕刻液A(硝酸鈰銨與過氯酸之水溶液)之相位偏移膜12之濕式蝕刻速度為1.3 nm/秒(面對蝕刻液A之遮光膜之濕式蝕刻速度為相位偏移膜之濕式蝕刻速度之約2.2倍)。 其結果，獲得於3 μm之L/S(線與間隙)之相位偏移膜圖案上形成有遮光膜圖案(邊緣寬度(單側：0.503 μm))之相位偏移光罩。又，因可將作為所獲得之相位偏移光罩之透光部的透明基板之露出部之刻蝕抑制於2 nm左右，故而滿足相位偏移光罩之要求規格180度±5度，並且未發現凹缺陷。 (實施例2) 除減少實施例1中之遮光膜14成膜時之甲烷氣體之含量而調整遮光膜14之蝕刻速率以外，與實施例1同樣地製作相位偏移光罩基底及相位偏移光罩。 上述實施例2之遮光膜14之適當蝕刻時間為30秒，且遮光膜14之膜厚為130 nm，故而面對蝕刻液A(硝酸鈰銨與過氯酸之水溶液)之遮光膜14之濕式蝕刻速度為4.3 nm/秒。 又，為了於形成相位偏移膜圖案12a之同時，對藉由臨時遮光膜圖案14a之側面蝕刻而形成之遮光膜圖案14b所構成之邊緣寬度(相位偏移部之寬度為0.8 μm)進行調整，而相對於相位偏移膜12之適當蝕刻時間94秒追加69秒蝕刻，使之為合計163秒，而製作相位偏移光罩。再者，面對蝕刻液A(硝酸鈰銨與過氯酸之水溶液)之相位偏移膜12之濕式蝕刻速度為1.3 nm/秒(面對蝕刻液A之遮光膜之濕式蝕刻速度為相位偏移膜之濕式蝕刻速度之約3.3倍)。 其結果，獲得於3 μm之L/S(線與間隙)之相位偏移膜圖案上形成有遮光膜圖案(邊緣寬度(單側：0.801 μm))之相位偏移光罩。又，因可將作為所獲得之相位偏移光罩之透光部的透明基板之露出部之刻蝕抑制於2 nm左右，故而滿足相位偏移光罩之要求規格180度±5度，並且未發現凹缺陷。 (實施例3) 除添加實施例2中之相位偏移膜12成膜時之甲烷氣體而調整相位偏移膜12之蝕刻速率以外，與實施例2同樣地製作相位偏移光罩基底及相位偏移光罩。再者，將相位偏移膜12之膜厚設為125 nm。又，基於抗蝕膜之L/S圖案設為如下線寬之抗蝕圖案：假定相位偏移膜圖案形成時所產生之底切，以基於最終所獲得之相位偏移光罩之相位偏移膜圖案的L/S圖案成為3 μm之方式，使單側加粗0.16 μm(兩側共加粗0.32 μm)。 上述實施例3之遮光膜14之適當蝕刻時間為30秒，遮光膜14之膜厚為130 nm，故而面對蝕刻液A(硝酸鈰銨與過氯酸之水溶液)之遮光膜14之濕式蝕刻速度為4.3 nm/秒。 又，為了於形成相位偏移膜圖案12a之同時，對藉由臨時遮光膜圖案14a之側面蝕刻而形成之遮光膜圖案14b所構成之邊緣寬度(相位偏移部之寬度為1.0 μm)進行調整，而相對於相位偏移膜12之適當蝕刻時間120秒追加76秒，使之為合計196秒，而製作相位偏移光罩。再者，面對蝕刻液A(硝酸鈰銨與過氯酸之水溶液)之相位偏移膜12之濕式蝕刻速度為1.0 nm/秒(面對蝕刻液A之遮光膜之濕式蝕刻速度為相位偏移膜之濕式蝕刻速度之4.3倍)。 其結果，獲得於3 μm之L/S(線與間隙)之相位偏移膜圖案上形成有遮光膜圖案(邊緣寬度(單側：1.0 μm))之相位偏移光罩。又，因可將作為所獲得之相位偏移光罩之透光部的透明基板之露出部之刻蝕抑制於2 nm左右，故而滿足相位偏移光罩之要求規格180度±5度，並且未發現凹缺陷。 (實施例4) 除將實施例1中所使用之蝕刻液B改為包含過氧化氫、氟化銨及磷酸之混合水溶液以外，與實施例1同樣地製作相位偏移光罩基底及相位偏移光罩。 其結果，獲得於3 μm之L/S(線與間隙)之相位偏移膜圖案上形成有遮光膜圖案(邊緣寬度(單側：0.801 μm))之相位偏移光罩，又，因可將作為所獲得之相位偏移光罩之透光部的透明基板之露出部之刻蝕抑制於1 nm左右，故而滿足相位偏移光罩之要求規格180度±5度，並且未發現凹缺陷。 (比較例1) 除增加實施例1中之遮光膜14成膜時之甲烷氣體之含量而調整遮光膜14之蝕刻速率以外，與實施例1同樣地製作相位偏移光罩基底及相位偏移光罩。比較例1係以面對蝕刻液A(硝酸鈰銨與過氯酸之水溶液)之遮光膜14之濕式蝕刻速度慢於相位偏移膜12之濕式蝕刻速度之方式進行調整。 上述比較例1之遮光膜14之膜厚為120 nm，適當蝕刻時間為94秒，且相位偏移膜12之膜厚為122 nm，適當蝕刻時間為94秒。面對蝕刻液A(硝酸鈰銨與過氯酸之水溶液)之遮光膜14之濕式蝕刻速度為1.3 nm/秒，相位偏移膜12之濕式蝕刻速度為1.3 nm/秒。 將適當蝕刻時間設為94秒以形成相位偏移膜圖案12a而製作相位偏移光罩。 其結果，獲得於3 μm之L/S(線與間隙)之相位偏移膜圖案上形成有遮光膜圖案(邊緣寬度(單側：0.153 μm))之相位偏移光罩。如此，僅產生0.15 μm之邊緣寬度。所獲得之相位偏移光罩之包含相位偏移部之邊緣寬度較小，為0.15 μm，故而無法充分發揮基於相位偏移效果之圖案轉印之對比度提高效果。 (比較例2) 除將實施例1中之蝕刻阻止膜成膜中之氣體組成改為(N2
/Ar＋N2
)46.1%，膜厚改為30 nm以外，與實施例1同樣地製作相位偏移光罩基底及相位偏移光罩。 其結果，獲得於3 μm之L/S(線與間隙圖案)之相位偏移膜圖案上形成有遮光膜圖案(邊緣寬度(單側：0.5 μm))之相位偏移光罩。然而，藉由蝕刻液B去除膜厚為30 nm之蝕刻阻止膜所需之時間為18分鐘，與實施例1相比蝕刻液之消耗量增加至1.8倍，並且就形成於玻璃基板上之相位偏移膜圖案周圍所形成之透光部(露出透明基板之區域)而言，藉由視位置而去除蝕刻阻止膜時所使用之蝕刻液B，於透明基板上產生21.6 nm之刻蝕，結果相對於假定之相位差產生10.3度偏移。又，於所獲得之相位偏移光罩之作為透光部之透明基板之露出部的多處發現凹缺陷。 以上，對本發明之實施形態及實施例進行了說明，但該等僅為例示，並不限定申請專利範圍。申請專利範圍所記載之技術中包含對以上所例示之具體例進行各種變化、變更而成者。Hereinafter, the embodiments of the present invention will be specifically described with reference to the drawings. In addition, the following embodiment is an aspect when the present invention is embodied, and is not intended to limit the present invention within its scope. In the figure, there are situations in which the same or equivalent parts are labeled with the same symbols and their descriptions are simplified or even omitted. (Embodiment of the present invention) First, the phase shift mask substrate of the embodiment of the present invention will be described. <Phase shift mask substrate> The phase shift mask substrate of the embodiment of the present invention is characterized in that it is the master of the phase shift mask, and the phase shift mask is wetted on a transparent substrate. The phase shift film, the etching stop film, and the light-shielding film are respectively patterned by etching to form a transfer pattern including the light-shielding part, the phase shift part, and the light-transmitting part, and the phase shift mask is formed by using The phase of the light passing through the phase shift portion is different from the phase of the light passing through the light transmitting portion, so that the light passing through the vicinity of the boundary portion between the phase shift portion and the light transmitting portion cancels each other out, thereby improving the contrast of the boundary portion; And the phase shift mask base is sequentially formed with a phase shift film, an etching stop film, and a light-shielding film on the transparent substrate. The phase shift film includes chromium and at least one selected from oxygen, nitrogen, carbon, and fluorine. One of the chromium compounds, the etching stop film includes a metal silicide containing metal and silicon, the phase shift film and the light shielding film are materials that can be etched by the same etching solution A, and the light shielding film faces The wet etching speed of the etching solution A is adjusted to be faster than that of the phase shift film facing the wet etching speed of the etching solution A, and the etching stop film is resistant to the etching solution A of the light-shielding film Material, and the film thickness, material, and composition ratio of the etching stopper film are adjusted so that the time required for the etching stopper film to be peeled off by the etching solution B that can be etched is 15 minutes or less. 1, the specific structure of the phase shift mask substrate according to the embodiment of the present invention will be described. As shown in FIG. 1, the phase shift mask base 10 of the embodiment of the present invention is formed by sequentially forming a phase shift film 12, an etching stop film 13, and a light shielding film 14 on a transparent substrate 11. Furthermore, the phase shift mask substrate 10 formed in the above-described manner can be prepared, and the phase shift film 12, the etching stop film 13, and the light shielding film 14 are patterned to produce a phase shift mask. Next, the phase shift mask of the embodiment of the present invention will be described. <Phase shift mask> By making the phase of the light passing through the phase shifting part different from the phase of the light passing through the light-transmitting part, the light passing through the vicinity of the boundary between the phase shifting part and the light-transmitting part mutually The phase shift mask that cancels and improves the contrast of the boundary is mainly used in the field of semiconductor manufacturing. It is known that these phase shift masks have a transmittance of about 5 to 10% for exposure light (for example, KrF or ArF excimer laser), and the phase of the exposure light is approximately 180 degrees shifted. Phase shift film. Among them, the phase shift mask used in this field is usually manufactured by dry etching, so there is no situation where the problems caused by the above-mentioned wet etching are not highlighted. However, in the phase shift mask used in the manufacture of display devices, as described above, the size of the transparent substrate is relatively large (a rectangular substrate with a side of 300 mm or more is used), and there are many types of sizes. To use dry etching, it is more advantageous to use wet etching. The size of the rectangular transparent substrate used in the phase shift mask for manufacturing the display device can be, for example, 330 mm×450 mm to 1620 mm×1780 mm. The phase shift photomask (photomask) of the present invention is formed by wet etching the phase shift film, the etching stop film, and the light shielding film on a transparent substrate, thereby forming a light shielding part and a phase shifting film. The phase shift mask formed by the transfer pattern of the light-transmitting portion and the light-transmitting portion, and the phase of the light passing through the phase shifting portion is different from the phase of the light passing the light-transmitting portion, so that the phase A phase shift mask that cancels out the light in the vicinity of the boundary between the shift portion and the above-mentioned light-transmitting section to increase the contrast of the boundary portion. Here, a phase shift mask of one embodiment of the present invention will be described with reference to FIG. 2. Among them, FIG. 2 is a cross-sectional view (lower side) and corresponding plan view (upper side) of the phase shift mask of the first embodiment in which line and gap patterns are formed. The phase shift mask 10a can be prepared by sequentially forming a phase shift film 12, an etching stop film 13, and a light shielding film 14 on the transparent substrate 11 shown in FIG. The phase shift film 12, the etching stop film 13, and the light-shielding film 14 are patterned and manufactured. However, other films may be interposed between the films or between any film and the transparent substrate 11 within a range that does not hinder the effects of the present invention. The upper side of Figure 2 is a top view of the phase shift mask 10a. When the phase shift mask 10a is viewed from above, the patterned light shielding film 14 (ie, the light shielding film pattern 14a) can be seen In the light-shielding part 18, it can be seen that the patterned phase shift film 12 (that is, the phase shift film pattern 12a) constitutes the phase shift part 16, and the phase shift film 12, the etching stop film 13 and the light-shielding film 14 are not included. A portion where any one of them covers and exposes the transparent substrate 11 constitutes the light-transmitting portion 17. The light-transmitting portion 17 and the above-mentioned phase shift portion 16 have a boundary portion (adjacent portion). When the phase shift mask of the present invention is used for pattern formation of a display device, as a line and gap pattern with good transfer characteristics, for example, 4 (μm)≦pitch P<6 (μm) and line width are preferred L≧1.5(μm), the gap width S≦3.5(μm). When attaching importance to the height of the contrast during pattern transfer, in fine line and gap patterns with a pitch P<6 (μm), the line width L≧gap width S is preferred, including those adjacent to the edge of the light-shielding part The rim width R of the phase shift part of the fixed width is preferably R≧0.8 (μm). Furthermore, in the line and gap pattern, an edge width including a phase shift portion of a fixed width adjacent to both sides of the light-shielding portion is usually provided. In this case, the above-mentioned edge width R is preferably also the above-mentioned range R≧0.8 (μm). Here, the light-shielding portion 18 is a part of the transparent substrate 11 where at least the light-shielding film pattern 14a is formed, and the transmittance of the light to the exposure light is substantially zero. The phase shift portion 16 is formed by forming a phase shift film pattern 12a having a specific transmittance (for example, 6% (i-line: wavelength 365 nm)) on the transparent substrate 11, and the phase difference with the light-transmitting portion 17 is Specific phase difference (for example, 180 degrees (i-line: wavelength 365 nm)). In this way, the phase shift mask 10a of the present invention has a transfer pattern, and the transfer pattern is formed on the transparent substrate 11 based on a specific pattern design by wet etching the phase shift film 12, the etching stop film 13, and The light-shielding films 14 are respectively patterned and formed. With this configuration, the exposure light passing through the phase shifting portion 16 has its phase shifted by approximately 180 degrees with respect to the exposing light passing through the light-transmitting portion 17, so as to differ from the light exposed after passing the light-transmitting portion 17. Adjacent parts interfere with each other. As a result, the contrast of the light in this part is improved, and the edge shape of the intensity curve of the exposure light becomes sharper. Therefore, the phase shift mask 10a of the present invention can also cope with the fine patterns in the display device manufacturing required in recent years. Here, the configuration of the phase shift mask substrate 10 and the phase shift mask 10a can be set as follows. (Transparent substrate 11) The material of the transparent substrate 11 is not particularly limited as long as it is a material that is transparent to the light used for exposure. For example, synthetic quartz glass, soda lime glass, and alkali-free glass can be cited. (Phase shift film 12) The phase shift film 12 in the present invention can be said to be a translucent film because it transmits a part of the exposed light. In addition, it has the effect of shifting the phase of the exposure light by a specific amount. The phase shift film 12 includes a chromium compound containing chromium and at least one selected from oxygen, nitrogen, carbon, and fluorine. The phase shift film 12 in the present invention includes a material containing chromium. For example, it preferably contains chromium oxide (CrOx), chromium nitride (CrNx), chromium carbide (CrCx), chromium oxynitride (CrOxNy), chromium carbonitride (CrCxNy), chromium oxycarbide (CrOxCy) , Chromium carbon oxynitride (CrOxNyCz), chromium fluoride (CrFx) any one. The film thickness of the phase shift film 12 is preferably 80 to 180 nm. For the wet etching of the above-mentioned phase shift film 12, a known etching solution can be used. For example, a mixed aqueous solution of cerium ammonium nitrate and perchloric acid can be used. In the phase shift mask 10a, the transmittance of the phase shift film 12 to the exposure light may be 1-50%, 1.5-30%, 2-15%, and more preferably 3-8%. Here, the light for exposure can be used as a light source commonly used in LCD exposure devices and includes any one of i-line, h-line, and g-line, and it is more preferable to use light that includes all of them. As the transmittance of exposure light, any one of the above is used as a representative wavelength, and the transmittance and phase difference (or phase shift amount) are defined. In addition, in the phase shift mask 10a, the phase shift amount of the exposure light (for example, the i-line is used as the representative wavelength) of the phase shift film 12 is set to approximately 180 degrees. Here, the so-called approximately 180 degrees means that it can be 160 degrees to 200 degrees, preferably 170 to 190 degrees. In addition, regarding the above-mentioned phase shift film 12, the variation range of the phase shift amount of light in the wavelength range of 365 nm (i-line) to 436 nm (g-line) (with a wavelength of 365 nm to 436 nm, the phase shift The difference between the maximum phase shift amount and the minimum phase shift amount of the film 12 is preferably within 40 degrees, more preferably within 30 degrees. By making the above-mentioned variation range within such a range, the effect of making the phase shift amount of the representative wavelength approximately 180 degrees can be sufficiently obtained. (Etching stop film 13) The etching stop film 13 includes a metal silicide containing metal and silicon, and is an etching solution A for the following light-shielding film (when the light-shielding film is a chromium compound containing Cr, the etching liquid A is, for example, A mixed aqueous solution of cerium ammonium nitrate and perchloric acid) is a material with corrosion resistance, and the etching stopper film can be etched by etching solution B (for example, a mixed aqueous solution of ammonium bifluoride and hydrogen peroxide, or The time required for peeling is 15 minutes or less, preferably 10 minutes or less, to select the film thickness, material, and composition ratio. The film thickness, material, and composition ratio of the etching stopper film 13 will be described below. The film thickness of the etching stopper film 13 is preferably 5 nm or more and 75 nm or less. In order to function as the etching stopper film 13, its film thickness is preferably 5 nm or more. If the film thickness of the etching stopper film 13 is too thick, when the etching stopper film 13 is peeled off by the etching solution B, the contact time between the etching solution B and the transparent substrate (glass substrate) 11 is long, and corrosion of the glass substrate may occur. The resulting transmittance is reduced, or concave defects caused by cracks. In addition, when the etching process is performed by stopping the etching solution from the viewpoint of defect quality, once the film thickness is thick, the consumption of the etching solution B will be very large. In these respects, the film thickness of the etching stopper film 13 is preferably 75 nm or less. Here, the etching stop film 13 contains metal and silicon metal silicides (metal silicide-based materials), especially metal silicide nitride, metal silicide oxynitride, metal silicide carbonitride, or The carbon oxynitride of the metal silicide, and the content of nitrogen is preferably 20 atomic% or more and 50 atomic% or less. The content of nitrogen in the etching stopper film 13 is more preferably 25 atomic% or more and 45 atomic% or less. The metal silicide-based material constituting the etching stopper film 13 is not particularly limited as long as it contains metal and silicon. In order to make the cross-sectional shape of the etching stop film pattern formed by wet etching good, and to make the phase shift film pattern formed by wet etching using the etching stop film pattern as a mask, the cross-sectional shape of the phase shift film pattern is good, metal and silicon The ratio is preferably metal: silicon = 1:2 or more and 1:9 or less. If the ratio of metal to silicon is more than that of 1:2 (the ratio of metal to silicon is less than 1:2), it will be difficult to form patterns with better precision when forming patterns with coarse and dense patterns . In addition, if the ratio of metal to silicon is more than the content of 1:9 silicon (the ratio of metal:silicon exceeds 1:9), the etching speed will be slower, and the same defects as described above will occur. More preferably, the ratio of metal to silicon in the metal silicide-based material constituting the etching stopper film 13 is preferably metal: silicon=1:2 or more and 1:8 or less. Examples of metals include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), and zirconium (Zr). As the metal silicide material constituting the etching stopper film 13, for example, metal silicide, metal silicide nitride, metal silicide oxide, metal silicide carbide, metal silicide oxynitride, metal Carbonitride of silicide, oxycarbide of metal silicide, or oxycarbonitride of metal silicide. Specifically, it can include: molybdenum silicide (MoSi) and its nitrides, oxides, carbides, oxynitrides, carbonitrides, oxycarbides, oxycarbonitrides; tantalum silicide (TaSi) and its nitrogen Compounds, oxides, carbides, oxynitrides, carbonitrides, oxycarbons, oxycarbonitrides; tungsten silicides (WSi) and its nitrides, oxides, carbides, oxynitrides, carbonitrides, Carbon oxide, carbon oxynitride; titanium silicide (TiSi) and its nitrides, oxides, carbides, oxynitrides, carbonitrides, carbon oxides, carbon oxynitrides; zirconium silicide (ZrSi) and Its nitrides, oxides, carbides, oxynitrides, carbonitrides, oxycarbides, and oxycarbonitrides. In terms of the improvement of the adhesion with the phase shift film 12 and the cross-sectional controllability of the phase shift film 12 and the etching stop film 13, among them, the nitride of the metal silicide and the metal silicide are particularly used. Nitride oxides and carbonitrides of metal silicides are preferred. In this case, the content of nitrogen is more preferably 25 atomic% or more and 45 atomic% or less. Moreover, in order for the etching stopper film 13 to have a reflectance reduction function, it is preferable to further contain oxygen. For the above-mentioned etching stopper film 13, until the etching stopper film 13 is etched by etching solution B (for example, a mixed aqueous solution of ammonium hydrogen fluoride and hydrogen peroxide, or a mixture of hydrogen peroxide, ammonium fluoride and phosphoric acid) Aqueous solution) and the time required for peeling is adjusted to 10 minutes or less, and the film thickness, material, and composition ratio of the etching stopper film 13 are selected. The phase shift mask substrate used in the present invention for manufacturing the display device generally has a large size with a length of one side of 300 mm or more. Therefore, uneven etching is likely to occur when the etching solution is supplied into the substrate surface. In consideration of uneven etching, the time required for the etching stopper film 13 to be peeled off by the etching solution B capable of etching it is preferably 10 seconds or more. More preferably, the above-mentioned time is more preferably 10 seconds or more and 15 minutes or less, and more preferably 10 seconds or more and 10 minutes or less. Considering the damage caused by the etching solution B to the glass substrate, the etching solution B used in the formation of the above-mentioned etching stop film pattern contains hydrogen peroxide, ammonium fluoride, and at least one selected from phosphoric acid, sulfuric acid, and nitric acid. In the case of an etching solution of an oxidizing agent, it is preferable to adjust the film thickness, material, and composition ratio of the etching stopper film 13 so that the time required for peeling by the etching solution B is 10 seconds or more and 20 minutes or less. In addition, from the same point of view, the etching solution B used in the formation of the above-mentioned etching stop film pattern is composed of a fluorine compound selected from at least one of hydrofluoric acid, fluorosilicic acid, and ammonium bifluoride, and a fluorine compound selected from peroxides. In the case of an etching solution of an oxidizing agent of at least one of hydrogen, nitric acid, and sulfuric acid, it is preferable to adjust the etching stopper film so that the time required for peeling by the etching solution B is 10 seconds or more and 10 minutes or less 13 film thickness, material, composition ratio. (Light-shielding film 14) It is preferable that the light-shielding film 14 has sufficient light-shielding properties (optical density (OD) is 3 or more) in the state of being laminated with the phase shift film 12 and the etching stop film 13. It is more preferable that only the light-shielding film 14 has sufficient light-shielding properties (optical density (OD) is 3 or more). In addition, the light-shielding film 14 preferably has an etching selectivity to that of the etching stopper film 13. That is, it is preferable that the etching stopper film 13 has resistance to an etching solution capable of etching the light-shielding film 14. As the material of the light-shielding film 14, one containing Cr can be preferably used. For example, in addition to containing chromium, it is preferable to contain chromium oxide (CrOx), chromium nitride (CrNx), chromium carbide (CrCx), chromium oxynitride (CrOxNy), chromium carbonitride (CrCxNy), chromium carbon Any one of oxide (CrOxCy) and chromium oxynitride (CrOxNyCz). The light-shielding film 14 may also be provided with an anti-reflection layer on its surface. In this case, the anti-reflection layer may be any one of chromium oxide, chromium nitride, and chromate nitride. In addition, the phase shift film 12 and the light-shielding film 14 are materials that can be etched by the same etching solution (A) (for example, a mixed aqueous solution of cerium ammonium nitrate and perchloric acid), and face the light-shielding film The wet etching speed of the etching solution (A) is faster than the wet etching speed of the phase shift film facing the etching solution (A) by adding to the phase shift film 12 or the light shielding film 14 Adjust the content of oxygen, nitrogen, carbon and fluorine. The thickness of the light-shielding film 14 may be 50-200 nm, more preferably 80-150 nm, and still more preferably 90-130 nm. The etching solution for the light-shielding film 14 is not particularly limited. A known one can be used. When the light-shielding film 14 is formed of a material containing chromium, the etching liquid used for the light-shielding film 14 and the above-mentioned phase shift film The same as described in 12. The phase shift mask 10a can make all the surfaces exposed on the surface a chromium-based film, so it has higher chemical resistance, which is more advantageous. As the film formation method, each constituent film of the phase shift mask 10a can be sputtered, ion-plated, or vapor-deposited. In terms of improving the interface adhesion between the two films, sputtering is preferred. Plating method. In this way, the phase shift mask 10a of the present invention can be preferably applied to, for example, a mask including a line and gap pattern forming a pixel electrode of a display device as a transfer pattern. In addition, as shown in FIG. 3, the transfer pattern can also be applied to a hole pattern including a contact hole. As the hole pattern, there is a fixed regularity (pitch) and a plurality of contact holes are arranged. Here, FIG. 3 is a cross-sectional view (lower side) and corresponding plan view (upper side) of the phase shift mask 10b for the hole pattern of the present invention. As shown in FIG. 3, the hole pattern has a light-transmitting portion 17 of a specific aperture, a phase shift portion 16 of a fixed width surrounding the light-transmitting portion 17, and a light shielding portion 18 surrounding the phase shift portion 16. Here, the aperture of the light-transmitting portion 17 (the length of one side in the case of a square, the length of the short side in the case of a rectangle, and the diameter in the case of a circle) can be 1.5-5 (μm), The width (edge width R) of the phase shift portion 16 may be 0.3 (μm)≦R≦1.5 (μm). <The manufacturing method of the phase shift photomask> The manufacturing method of the phase shift photomask of the present invention has the following steps: forming a resist film on the above-mentioned phase shift photomask substrate of the embodiment of the present invention described above; Drawing and developing a specific pattern on the above-mentioned resist film to form a resist pattern; Using the above-mentioned resist pattern as a mask, the above-mentioned light-shielding film is wet-etched with the above-mentioned etching solution A to form a temporary light-shielding film pattern ; Using the temporary light-shielding film pattern as a mask, the etching stop film is wet-etched by the etching solution B to form a temporary etching stop film pattern; Using the temporary etching stop film pattern as a mask, the etching Liquid A wet-etches the above-mentioned phase shift film to form a phase shift part based on the phase shift film pattern, and forms a light-shielding film pattern by side-etching the temporary light-shielding film pattern; As a mask, the etching stopper film is wet-etched by the etching solution B to form an etching stopper film pattern, and a light-shielding portion based on the etching stopper film pattern and the light-shielding film pattern is formed on the phase shift film pattern ; And remove the above-mentioned resist pattern. In this way, a phase shift mask with a transfer pattern of a phase shift part, a light-shielding part, and a light-transmitting part is manufactured on a transparent substrate. Furthermore, the following steps may be included in the patterning of the phase shift film 12, the etching stop film 13, and the light shielding film 14. Here, first, a method of manufacturing the phase shift mask 10c as a reference example will be described with reference to FIG. 4, so that the characteristics of the method of manufacturing the phase shift masks 10a and 10b of the present invention will be more clarified. <The manufacturing method of the phase shift photomask 10c of the reference example> The manufacturing method of the phase shift photomask 10c of the reference example is a phase shift photomask in which a resist film is formed twice when the phase shift photomask 10c is manufactured Production method. FIG. 4 is a diagram showing an example of a method of manufacturing the phase shift mask 10c in the aspect of the reference example. First, the phase shift mask substrate 10 shown in FIG. 1 is prepared, and the first photoresist film 15 is formed on the light shielding film 14 of the phase shift mask substrate 10 (FIG. 4(a)). Thereafter, the first resist pattern 15a is formed by drawing and developing the first photoresist film 15, and by using the first resist pattern 15a as a mask, the light-shielding film 14 is wet-processed with etchant A. By etching, the light-shielding film pattern 14a is formed (FIG. 4(b)). Next, the first resist pattern 15a is peeled off (FIG. 4(c)). Next, a second photoresist film 19 is formed on the entire surface of the transparent substrate 11 on which the light-shielding film pattern 14a is formed (FIG. 4(d)), and the second photoresist film 19 is drawn and developed to form a second resist Pattern 19a (Figure 4(e)). Next, using the second resist pattern 19a as a mask, the etching stopper film 13 is wet-etched with the etchant B to form an etching stopper film pattern 13a (FIG. 4(f)). Next, using the obtained etching stopper film pattern 13a as a mask, the phase shift film 12 is wet-etched with the etchant A to form the phase shift film pattern 12a, and thereafter, the second resist pattern 19a is peeled off ( Figure 4(g)). Finally, the light-shielding film pattern 14a is used as a mask, and the etching stopper film pattern 13a is wet-etched with the etching solution B, and the phase shift mask 10c is completed ((FIG. 4(h)). However, in the above-mentioned phase shift) In the reference manufacturing method of the photomask 10c, as shown in FIG. 4, the photoresist film (the first photoresist film 15, the second photoresist film 19) is formed twice, and the first photoresist film 15 and the second photoresist film 19 is drawn and developed separately to form resist patterns (the first resist pattern 15a, the second resist pattern 19a) twice, and wet etching is performed. In this phase shift mask as a reference example In the manufacturing method, the photoresist film (the first resist film 15, the second resist film 19) is formed twice, and the photoresist film is drawn and developed twice to form a photoresist pattern (first resist film). The resist pattern 15a and the second resist pattern 19a), it is difficult to match the center of the light-shielding film pattern 14a and the phase shift film pattern 12a in the phase shift mask 10c finally obtained. The phase shift light of the present invention The manufacturing method of the mask 10a solves the problem that it is difficult to match the center of the light-shielding film pattern 14a with the center of the phase shift film pattern 12a in the above-mentioned method of manufacturing the phase shift mask as a reference example. That is, in the phase shift light of the present invention In the manufacturing method of the mask 10a, only one drawing and development are performed using a resist film once, so the phase shift mask 10a can be manufactured in such a way that the center of the light-shielding film pattern 14a and the phase shift film pattern 12a coincide. 5 The manufacturing method of the phase shift mask 10a of the present invention will be described in detail (the manufacturing method of the phase shift mask 10b of the present invention is also the same as this). <The manufacturing method of the phase shift mask of the present invention> As As shown in FIG. 5, the phase shift mask substrate 10 shown in FIG. 1 is first prepared, and the first photoresist film 15 is formed on the light shielding film 14 of the phase shift mask substrate 10 (FIG. 5(a)). , The first photoresist film 15 is subjected to specific pattern drawing and development processing to form a resist pattern 15a, and the resist pattern 15a is used as a mask, and the light shielding film 14 is wet-etched by the etching solution A to form Temporary light-shielding film pattern 14a (FIG. 5(b)). Next, using the temporary light-shielding film pattern 14a as a mask, the etching stopper film 13 is wet-etched by etching solution B to form a temporary etching stopper film pattern 13a (FIG. 5(c)) Next, using the temporary etching stopper film pattern 13a as a mask, the phase shift film 12 is wet-etched by the etching solution A to form a phase shift portion based on the phase shift film pattern 12a. The temporary light-shielding film pattern 14a is side-etched to form a light-shielding film pattern 14b (FIG. 5(d)). Finally, the resist pattern 15a is removed, and the light-shielding film pattern 14b is used as a mask. The etching stopper film pattern 13a is wet-etched to form an etching stopper film pattern 13b, and a light shielding portion based on the etching stopper film pattern 13b and the light shielding film pattern 14b is formed on the phase shift film pattern 12a (FIG. 5(e)). In this way, as shown in FIG. 5(e), a phase shift mask 10a with a transfer pattern having a phase shift portion, a light shielding portion, and a light transmitting portion is completed on the transparent substrate 11 as shown in FIG. 5(e). Here, the film thickness, material, and composition ratio of the etching stop film 13 are adjusted and selected so that the formation time of the etching stop film pattern is 10 seconds or more and 15 minutes or less or 10 seconds or more and 10 minutes or less. Therefore, it is possible to suppress the consumption of the etching solution B when making the phase shift mask, especially when forming the etching stop film pattern, and since the contact time of the etching solution B to the transparent substrate 11 is short, the amount of the transparent substrate can be reduced. Damage to prevent the occurrence of concave defects. Furthermore, the etching liquid B used when performing wet etching on the etching stopper film 13 is demonstrated. (Etching solution B) The etching solution B for wet etching the etching stopper film 13 is not used as long as it can selectively etch the etching stopper film 13 without substantially etching the light shielding film 14 and the phase shift film 12 Special restrictions. The etching solution B includes, for example, an etching solution containing a fluorine compound selected from at least one of hydrofluoric acid, fluorosilicic acid, and ammonium hydrogen fluoride, and an oxidizing agent selected from at least one of hydrogen peroxide, nitric acid, and sulfuric acid. Specifically, an etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water can be cited. In addition, an etching solution containing hydrogen peroxide, ammonium fluoride, and an oxidizing agent selected from at least one of phosphoric acid, sulfuric acid, and nitric acid can be cited. Specifically, an etching solution obtained by diluting a mixed solution of hydrogen peroxide, ammonium fluoride, and phosphoric acid with pure water can be cited. In addition, the method for manufacturing a phase shift mask according to the present invention has the following advantages: only one drawing and development are required, so that the influence of mutual alignment shift caused by multiple drawing steps can be eliminated. In particular, it is excellent in that the phase shift portion 16 with a fine width can be formed accurately. Furthermore, according to the manufacturing method of the phase shift mask of the present invention, only one resist pattern is used for drawing and development, so the light-shielding film pattern 14b and the phase shift as shown by the center line X of FIG. 5(e) The phase shift mask 10a is manufactured in such a way that the centers of the film patterns 12a coincide. Next, the manufacturing method of the display device of the present invention will be described. <Manufacturing method of display device> The manufacturing method of the display device of the present invention includes the following steps: preparing the above-mentioned phase shift mask of the embodiment of the present invention described above; and exposure for manufacturing the display device using light for exposure The device exposes the transfer pattern of the phase shift mask, and transfers the transfer pattern to the transferred body. The exposure device used can be a standard equal magnification exposure device for LCD. That is, by using a light source (also referred to as a wide-wavelength light source) in the wavelength region including i-line, h-line, and g-line as the light source, a sufficient amount of irradiation light can be obtained. Among them, optical filters can also be used, and only light of a specific wavelength (for example, i-line) is used. The optical system of the exposure device can set the numerical aperture NA in the range of 0.06 to 0.10, and the coherence factor σ in the range of 0.5 to 1.0. This type of exposure device generally sets about 3 μm as the resolution limit. Of course, the present invention can also be applied when a wider range of exposure devices are used for transfer. For example, NA can be set in the range of 0.06 to 0.14, or 0.06 to 0.15. There is also a demand for high-resolution exposure devices with NA exceeding 0.08, and the present invention can also be applied to them. (The relationship between the addition of nitrogen in the etching stop film (etch stop film) and the etching rate) First, the relationship between the addition of nitrogen in the etching stop film containing metal silicide and the etching rate was investigated. An etching stopper film 13 (etch stop film) with different composition ratios was formed on a synthetic quartz glass substrate (QZ substrate), and the relationship between the addition of nitrogen and the etching rate was investigated. The survey results are shown in Table 1. Use an aqueous solution of ammonium bifluoride and hydrogen peroxide (22°C) as an etching solution, use a MoSi target (Mo:Si=1:4), and use argon and nitrogen as sputtering gases to form an etching on a synthetic quartz glass substrate Stop film (etch stop film). [Table 1] According to the results of Table 1 above, it can be seen that as the content of nitrogen (N 2 ) contained in the film formation increases, the content of nitrogen (N) contained in the etching stop film also increases. In addition, it can be seen that as the content of nitrogen (N) contained in the etching stop film increases, it is generated by the etching solution B (aqueous solution of ammonium hydrogen fluoride and hydrogen peroxide) used when the etching stop film is etched The etching amount of the synthetic quartz glass substrate (QZ substrate) is equivalent to the thinning of the film thickness of the etching stop film that can be etched within the etching time of the phase shift of 5 degrees. According to the above content, as the content of nitrogen (N) contained in the etching stop film increases, the etching speed of the etching stop film becomes slower. Although not described in detail, it has the same tendency as the above when the etching solution B is an aqueous solution of hydrogen peroxide, ammonium fluoride, and phosphoric acid. (Specification of the film thickness, material, and composition ratio of the etching stop film 13) (1) When the phase shift mask of the present invention is produced, as shown in FIG. 5(d), the etching solution A is used to simultaneously treat the light shielding film 14 and the phase The shift film 12 is etched, so the etching stopper film 13 remains on the phase shift film pattern 12a. In order to achieve the final phase shift mask form shown in FIG. 5(e), the etching stopper film 13 needs to be removed, but the etching solution B used to remove the etching stopper film 13 (for example, an aqueous solution of ammonium bifluoride and hydrogen peroxide) ) Usually, the synthetic quartz glass substrate is damaged, so it is desirable to shorten the etching time of the etching stop film 13 as much as possible. Furthermore, the etching time of the etching stopper film 13 is determined by the etching speed of the etching stopper film 13×the film thickness of the etching stopper film. (2) The phase difference of the QZ substrate of the exposure light used in the exposure device of the LCD (for example, i-line (wavelength: 365 nm)) is 1 degree phase difference (relative to the 2.1 nm etching amount of the QZ substrate). For air (Air benchmark)). Generally speaking, in the phase shift mask used in the manufacture of display devices, it is required to suppress the required phase shift amount (phase difference) within ±5 degrees (for example, 180 degrees ±5 degrees). (3) In order to suppress the etching amount of the QZ substrate within 5 degrees of the phase shift, the etching amount must be suppressed to 2.1 nm×5=10.5 nm, and the etching speed of the QZ substrate facing the etching solution B is 1.2 nm In the case of /min, it is necessary to suppress the etching time to 10.5 nm÷1.2 nm/min=9 minutes. (4) The etching stopper film 13 containing metal silicide needs to be etched in a relatively short time to avoid damage to the synthetic quartz glass substrate. In addition, as the etching stopper film 13 when the phase shift film 12 is etched, it is necessary to have a film thickness that can protect the phase shift film 12. From the viewpoint of protecting the phase shift film 12, the lower limit of the film thickness of the etching stopper film 13 is preferably 7.5 nm or more. Regarding the upper limit of the film thickness of the etching stopper film 13, the etching time will be affected by the etching stop. The content of nitrogen contained in the film 13 varies, and the film thickness and the nitrogen content of the etching stopper film 13 need to be specified according to the etching time. (5) After forming the film under the film forming conditions that the film thickness of the etching stop film 13 is 10 nm, and the gas composition in the film formation (the nitrogen gas composition contained in the mixed gas) is 39.0%, it is confirmed that: In the case of solution B, the etching stopper film 13 can be removed within 2 minutes. Even if the etching solution B is in contact with the QZ substrate for 2 minutes, only damage of about 2.4 nm is generated, so the phase shift caused by the damage is less, about 1 degree. Hereinafter, as the etching stopper film 13 of the embodiment, a MoSiN film formed under film forming conditions with a film thickness of 10 nm and a gas composition (composition of nitrogen gas contained in the mixed gas) of 39.0% is selected (Mo: 16.7 at%, Si: 41.1 at%, N: 42.2 at%). Hereinafter, the phase shift mask substrate and the phase shift mask of the present invention will be described in more detail based on the embodiments. [Example] (Example 1) Referring to Figure 6, first, in the production of the phase shift mask base, a large glass substrate (synthetic quartz glass, thickness of 10 mm, size of 850 mm × 1200 mm) is used as transparent The substrate 11. Using a large-scale inline sputtering device, a phase shift film 12, an etching stopper film 13, and a light-shielding film 14 are formed on the transparent substrate 11. The film formation of each phase shift film 12, etching stopper film 13, and light shielding film 14 is performed as follows. (Phase shift film 12) The film formation of the phase shift film 12 is performed using a large-scale in-line sputtering apparatus. A sputtering gas containing argon, nitrogen, and carbon dioxide is introduced into the sputtering chamber where the Cr target is disposed, and a 122 nm CrCON layer is formed by reactive sputtering. For the formed phase shift film 12, the transmittance and phase difference were measured by MPM-100 manufactured by Lasertec. The transmittance and phase difference of the phase shift film 12 are measured using a substrate (dummy substrate) with a phase shift film. The substrate with a phase shift film is set on the same tray and manufactured. It is made of synthetic quartz glass. A CrCON film (with a thickness of 122 nm) is formed on the main surface of the substrate. The transmittance and phase difference of the phase shift film 12 are measured by taking out the substrate with the phase shift film (dummy substrate) from the carry-out chamber before forming the etching stop film. As a result, the transmittance was 5.0% (wavelength: 365 nm), and the phase difference was 180 degrees (wavelength: 365 nm). In addition, the variation range of the phase difference (phase shift amount) with a wavelength of 365 nm to 436 nm is 25 degrees. (Etching stop film 13) Next, a sputtering gas containing argon and nitrogen is introduced into the sputtering chamber where the MoSi target (Mo:Si=1:4) is placed, and a 10 nm MoSiN film is formed by reactive sputtering Floor. The gas composition (N 2 /Ar+N 2 ) in the film formation is 39%. (Light-shielding film 14) In Example 1, the light-shielding film 14 as shown in FIG. 6 has a laminated structure of a light-shielding layer 140 and a reflection reduction layer 143. Moreover, the light shielding layer 140 includes a lower layer portion 141 and an upper layer portion 142. Regarding the film formation of the light-shielding film 14, a Cr target is arranged in each space (sputtering chamber) arranged in a large-scale in-line sputtering device. In a continuous film formation method, first, argon, methane and nitrogen are used as sputtering gases , A 50 nm CrCN layer (lower part 141 of the light-shielding layer 140) is formed by reactive sputtering, followed by the same sputtering gas with argon, methane, and nitrogen, and a film is formed by reactive sputtering 55 The CrCN layer (the upper layer portion 142 of the light shielding layer 140) of nm is then used as sputtering gas with argon gas and carbon monoxide gas, and a 25 nm CrON layer (reflection reduction layer 143) is formed by reactive sputtering. The reflection reduction layer 143 of Embodiment 1 is a single-layer film. After the film is formed, it is brushed with pure water, so that the phase shift mask substrate 10 is manufactured. Furthermore, the above-mentioned light shielding layer 140 is formed by appropriately adjusting the flow rate of methane gas and nitrogen gas to increase the etching rate in the depth direction of the film. Specifically, the content of nitrogen contained in the sputtering gas when the lower portion 141 of the light-shielding layer 140 is formed is greater than the content of nitrogen contained in the sputtering gas when the upper portion 142 of the light-shielding layer 140 is formed. Furthermore, the content of methane gas contained in the sputtering gas when the lower portion 141 of the light-shielding layer 140 is formed is less than the content of methane gas contained in the sputtering gas when the upper portion 142 of the light-shielding layer 140 is formed. Perform film formation. In addition, in order to obtain the optical density (OD) required for the light-shielding layer 140 (upper layer portion 141 and lower layer portion 142) and the light-shielding film 14, the power applied to each Cr target is appropriately adjusted to form a film. The characteristics of each layer of the light-shielding film 14 are shown below. The optical density is measured with a transmission densitometer, and the reflectance is measured with a reflectance meter. Here, the optical density of the lower layer portion 141 and the upper layer portion 142 of the light shielding layer 140 is a value obtained by measuring a sample obtained by forming each layer (single layer) on a synthetic quartz glass substrate under the same film forming conditions as above. . Light shielding layer 140: Lower layer part 141: CrCN (film thickness: 50 nm), optical density: 2.3 (wavelength: 436 nm), 2.5 (wavelength: 365 nm) Upper layer part 142: CrCN (film thickness: 55 nm), optical density : 2.1 (wavelength: 436 nm), 2.3 (wavelength: 365 nm) Reflection reduction layer 143: CrON (film thickness: 25 nm) Total film thickness of light-shielding film 14: 130 nm Optical density of light-shielding film 14 as a whole: 4.6 (wavelength : 436 nm), 5.0 (wavelength: 365 nm), front reflectance: 10% (wavelength: 436 nm), back reflectance: 55% (wavelength: 436 nm) In addition, the phase shift mask substrate 10 In the manufacturing method, the layers of the light-shielding film 14 are not reset to the atmosphere in the middle, but are continuously formed under a reduced pressure vacuum state. By continuously forming in a reduced-pressure vacuum state in this way, the variation of the composition from the outermost surface of the light-shielding film 14 (the surface of the reflection reducing layer 143 including CrON) to the transparent substrate 11 can be reduced. The phase shift mask substrate 10 manufactured in the above manner was used to manufacture the phase shift mask of Example 1. 5, first use a slit coater to coat a phenolic-based laser drawing photoresist on the light shielding film 14, and heat and cool to form a resist film 15 with a film thickness of 1000 nm (FIG. 5( a)). Next, a line and gap (L/S) pattern is drawn on the resist film 15 by laser drawing, and development is performed to form a resist pattern 15a. The L/S pattern is a resist pattern with the following line width: assuming that the undercut generated when the phase shift film pattern is formed (and the line width of the phase shift film pattern based on the line width of the etching stop film pattern) Difference), so that the width of the L/S pattern based on the phase shift film pattern of the phase shift mask finally obtained becomes 3 μm, and one side is thickened by 0.12 μm (both sides are thickened by 0.24 μm in total). Next, by using the resist pattern 15a as a mask, the light-shielding film 14 is etched with a wet etching solution A (aqueous solution of cerium ammonium nitrate and hydrogen peroxide) to form a temporary light-shielding film pattern 14a (FIG. 5(b)) ). Next, by using the resist pattern 15a and the temporary light-shielding film pattern 14a as a mask, etching is performed with a wet etching solution B (aqueous solution of ammonium hydrogen fluoride and perchloric acid) to form a temporary etching stop film pattern 13a (FIG. 5 (c)). Next, by using the temporary etching stop film pattern 13a as a mask, the phase shift film 12 is etched with a wet etching solution A (aqueous solution of cerium ammonium nitrate and hydrogen peroxide) to form the phase shift film pattern 12a, Furthermore, by side-etching the said temporary light-shielding film pattern 14a, the light-shielding film pattern 14b is formed (FIG. 5(d)). Next, by using the light-shielding film pattern 14b as a mask, the temporary etching stop film pattern 13a is etched with a wet etching solution B (a mixed aqueous solution containing ammonium hydrogen fluoride and hydrogen peroxide), and the phase shift film pattern 12a A light shielding portion based on the etching stop film pattern 13b and the light shielding film pattern 14b is formed. Finally, the resist pattern 15a is peeled off with a resist stripping solution to obtain the phase shift mask of the present invention (FIG. 5(e)). The proper etching time of the light-shielding film 14 of the above embodiment 1 is 45 seconds, and the film thickness of the light-shielding film 14 is 130 nm, so it faces the wetness of the light-shielding film 14 of the etching solution A (aqueous solution of cerium ammonium nitrate and perchloric acid). The etching rate is 2.9 nm/sec. In addition, in order to form the phase shift film pattern 12a at the same time, adjust the edge width of the light shielding film pattern 14b formed by side etching of the temporary light shielding film pattern 14a (the width of the phase shifting portion is 0.5 μm) , And 71 seconds of etching was added to the appropriate etching time of 94 seconds for the phase shift film 12 to make a total of 165 seconds, and a phase shift mask was produced. Furthermore, the wet etching rate of the phase shift film 12 facing etching solution A (aqueous solution of cerium ammonium nitrate and perchloric acid) is 1.3 nm/sec (the wet etching rate of the light-shielding film facing etching solution A is The wet etching speed of the phase shift film is about 2.2 times). As a result, a phase shift mask with a light-shielding film pattern (edge width (single side: 0.503 μm)) formed on a phase shift film pattern of 3 μm L/S (line and gap) was obtained. In addition, since the etching of the exposed part of the transparent substrate as the transparent part of the obtained phase shift mask can be suppressed to about 2 nm, the required specification of the phase shift mask is 180 degrees ± 5 degrees, and No concave defects were found. (Example 2) Except for reducing the methane gas content during the film formation of the light-shielding film 14 in Example 1 and adjusting the etching rate of the light-shielding film 14, a phase shift mask base and phase shift were produced in the same manner as in Example 1. Photomask. The proper etching time of the light-shielding film 14 of the above-mentioned embodiment 2 is 30 seconds, and the film thickness of the light-shielding film 14 is 130 nm, so it faces the wetness of the light-shielding film 14 of the etching solution A (aqueous solution of cerium ammonium nitrate and perchloric acid). The etching rate is 4.3 nm/sec. In addition, in order to form the phase shift film pattern 12a at the same time, adjust the edge width of the light shielding film pattern 14b formed by side etching of the temporary light shielding film pattern 14a (the width of the phase shift portion is 0.8 μm) Then, an etching of 69 seconds was added to the appropriate etching time of 94 seconds of the phase shift film 12 to make a total of 163 seconds, and a phase shift mask was produced. Furthermore, the wet etching rate of the phase shift film 12 facing etching solution A (aqueous solution of cerium ammonium nitrate and perchloric acid) is 1.3 nm/sec (the wet etching rate of the light-shielding film facing etching solution A is The wet etching speed of the phase shift film is about 3.3 times). As a result, a phase shift mask with a light-shielding film pattern (edge width (single side: 0.801 μm)) formed on a phase shift film pattern of 3 μm L/S (line and gap) was obtained. In addition, since the etching of the exposed part of the transparent substrate as the transparent part of the obtained phase shift mask can be suppressed to about 2 nm, the required specification of the phase shift mask is 180 degrees ± 5 degrees, and No concave defects were found. (Example 3) Except for adding methane gas during film formation of the phase shift film 12 in Example 2 to adjust the etching rate of the phase shift film 12, a phase shift mask base and phase were produced in the same manner as in Example 2. Offset the mask. Furthermore, the film thickness of the phase shift film 12 is 125 nm. In addition, the L/S pattern based on the resist film is set as a resist pattern with the following line width: the undercut generated when the phase shift film pattern is formed is assumed to be based on the phase shift of the phase shift mask finally obtained The L/S pattern of the film pattern is 3 μm, and one side is thickened by 0.16 μm (both sides are thickened by 0.32 μm in total). The appropriate etching time of the light-shielding film 14 of the above-mentioned embodiment 3 is 30 seconds, and the film thickness of the light-shielding film 14 is 130 nm, so it faces the wet type of the light-shielding film 14 of etching solution A (aqueous solution of cerium ammonium nitrate and perchloric acid) The etching rate is 4.3 nm/sec. In addition, in order to form the phase shift film pattern 12a at the same time, the edge width (the width of the phase shift portion is 1.0 μm) formed by the light shielding film pattern 14b formed by side etching of the temporary light shielding film pattern 14a is adjusted In addition, 76 seconds were added to the appropriate etching time of 120 seconds for the phase shift film 12 to make a total of 196 seconds, and a phase shift mask was produced. Furthermore, the wet etching rate of the phase shift film 12 facing etching solution A (aqueous solution of cerium ammonium nitrate and perchloric acid) is 1.0 nm/sec (the wet etching rate of the light-shielding film facing etching solution A is 4.3 times the wet etching speed of the phase shift film). As a result, a phase shift mask with a light-shielding film pattern (edge width (single side: 1.0 μm)) formed on a phase shift film pattern of 3 μm L/S (line and gap) was obtained. In addition, since the etching of the exposed part of the transparent substrate as the transparent part of the obtained phase shift mask can be suppressed to about 2 nm, the required specification of the phase shift mask is 180 degrees ± 5 degrees, and No concave defects were found. (Example 4) Except that the etching solution B used in Example 1 was changed to a mixed aqueous solution containing hydrogen peroxide, ammonium fluoride, and phosphoric acid, a phase shift mask substrate and phase shift were produced in the same manner as in Example 1. Shift the mask. As a result, a phase shift mask with a light-shielding film pattern (edge width (one side: 0.801 μm)) formed on a phase shift film pattern of L/S (line and gap) of 3 μm is obtained. The etching of the exposed part of the transparent substrate, which is the light-transmitting part of the obtained phase shift mask, is suppressed to about 1 nm, so the required specification of the phase shift mask is 180°±5°, and no concave defects are found. . (Comparative Example 1) Except for increasing the methane gas content during the film formation of the light-shielding film 14 in Example 1 and adjusting the etching rate of the light-shielding film 14, a phase shift mask base and phase shift were produced in the same manner as in Example 1. Photomask. In Comparative Example 1, the wet etching speed of the light-shielding film 14 facing the etching solution A (aqueous solution of cerium ammonium nitrate and perchloric acid) was adjusted to be slower than the wet etching speed of the phase shift film 12. The film thickness of the light-shielding film 14 of Comparative Example 1 is 120 nm, the appropriate etching time is 94 seconds, and the film thickness of the phase shift film 12 is 122 nm, and the appropriate etching time is 94 seconds. The wet etching rate of the light-shielding film 14 facing the etching solution A (aqueous solution of cerium ammonium nitrate and perchloric acid) is 1.3 nm/sec, and the wet etching rate of the phase shift film 12 is 1.3 nm/sec. The appropriate etching time was set to 94 seconds to form the phase shift film pattern 12a to produce a phase shift mask. As a result, a phase shift mask with a light-shielding film pattern (edge width (single side: 0.153 μm)) formed on a phase shift film pattern of 3 μm L/S (line and gap) was obtained. In this way, only an edge width of 0.15 μm is produced. The obtained phase shift mask has a relatively small edge width of 0.15 μm including the phase shift portion, so the contrast improvement effect of pattern transfer based on the phase shift effect cannot be fully exerted. (Comparative Example 2) The phase shift was produced in the same manner as in Example 1, except that the gas composition in the formation of the etching stop film in Example 1 was changed to (N 2 /Ar + N 2) 46.1% and the film thickness was changed to 30 nm. Shift mask base and phase shift mask. As a result, a phase shift mask with a light-shielding film pattern (edge width (single side: 0.5 μm)) formed on a 3 μm L/S (line and gap pattern) phase shift film pattern was obtained. However, the time required to remove the etching stopper film with a film thickness of 30 nm by etching solution B is 18 minutes. Compared with Example 1, the consumption of etching solution is increased to 1.8 times, and the phase is formed on the glass substrate. For the light-transmitting part (the area where the transparent substrate is exposed) formed around the offset film pattern, the etching solution B used when the etching stop film is removed depending on the position results in 21.6 nm etching on the transparent substrate. Relative to the assumed phase difference, there is a 10.3 degree shift. In addition, concave defects were found in many places in the exposed part of the transparent substrate as the light-transmitting part of the obtained phase shift mask. The embodiments and examples of the present invention have been described above, but these are only examples and do not limit the scope of patent applications. The technology described in the scope of the patent application includes various changes and modifications to the specific examples illustrated above.
