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TW201801148A - Phase-shift mask blank for display device manufacture, phase-shift mask for display device manufacture and its manufacturing method, and method for manufacturing display device - Google Patents

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

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Publication number
TW201801148A
TW201801148A TW106134106A TW106134106A TW201801148A TW 201801148 A TW201801148 A TW 201801148A TW 106134106 A TW106134106 A TW 106134106A TW 106134106 A TW106134106 A TW 106134106A TW 201801148 A TW201801148 A TW 201801148A
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TW
Taiwan
Prior art keywords
phase shift
film
phase
shift mask
pattern
Prior art date
Application number
TW106134106A
Other languages
Chinese (zh)
Other versions
TWI655670B (en
Inventor
坪井誠治
吉川裕
牛田正男
Original Assignee
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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Publication of TW201801148A publication Critical patent/TW201801148A/en
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Publication of TWI655670B publication Critical patent/TWI655670B/en

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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
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • 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
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

A phase-shift mask blank for display device manufacture is provided, which comprises a phase-shift film exhibiting an optical property with restrained wavelength dependence with respect to exposure light. A phase-shift mask blank 1 comprises a transparent substrate 2, and a phase-shift film 3 formed on the transparent substrate 2. The phase-shift film 3 comprises a monolayer film or laminated film comprising at least one metal silicide material layer including metal, silicon, and either one element of nitrogen and/or oxygen. In the phase-shift film 3, transmittance at a wavelength of 365nm is between 3.5% and 8% inclusive, phase difference at a wavelength of 365nm is between 160 degrees and 200 degrees inclusive, and wavelength-dependent variation of transmittance within a wavelength range between 365nm and 436nm inclusive is within 5.5%.

Description

顯示裝置製造用相偏移光罩基底、顯示裝置製造用相偏移光罩及其製造方法、以及顯示裝置之製造方法Phase shift mask substrate for manufacturing display device, phase shift mask for manufacturing display device, method for manufacturing same, and method for manufacturing display device

本發明係關於顯示裝置製造用之相偏移光罩基底，使用該相偏移光罩基底之顯示裝置製造用之相偏移光罩及其製造方法、以及使用該相偏移光罩之顯示裝置之製造方法。The present invention relates to a phase shift mask substrate for manufacturing a display device, a phase shift mask for manufacturing a display device using the phase shift mask substrate, a method of manufacturing the same, and a display using the phase shift mask The manufacturing method of the device.

現在，作為液晶顯示裝置所採用之方式，有VA(Vertical alignment：垂直對準)方式或IPS(In Plane Switching：面板內切換)方式。藉由該等方式，可謀求實現高精細、高速顯示性能、廣視角之液晶顯示裝置。於應用該等方式之液晶顯示裝置中，可藉由利用例如光微影步驟使透明導電膜圖案化，形成線隙圖案之像素電極，從而改善應答速度、視角。最近，根據應答速度及視角之進一步提高、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，追求線隙圖案之間距寬度之微細化。例如，期望將線隙圖案之間距寬度自6 μm縮窄至5 μm，進而自5 μm縮窄至 4 μm。 又，在液晶顯示裝置或有機EL顯示裝置之製造時，藉由積層已實施必要之圖案化之複數個導電膜或絕緣膜，而形成電晶體等之半導體元件。此時，對所積層之各個膜之圖案化，亦多利用光微影步驟。例如，於該等顯示裝置所使用之薄膜電晶體或LSI，有具有藉由光微影步驟於絕緣層形成接觸孔，並連接上層圖案與下層圖案之構成者。最近，於此種顯示裝置中，以足夠快之動作速度顯示明亮精細之圖像且降低電力消耗之需求高漲。為滿足此種需求，追求使顯示裝置之構成元件微細化、高積體化。例如，期望將接觸孔之徑自3 μm縮小至2.5 μm、2 μm、1.5 μm。 根據此種背景，期望可與線隙圖案或接觸孔之微細化對應之顯示裝置製造用之光罩。 實現線隙圖案或接觸孔之微細化時，因於先前之光罩中，顯示裝置製造用之曝光機之解析極限為3 μm，故沒有足夠的製程裕度(Process Margin)，必須生產接近解析極限之最小線寬之製品。因此，存在顯示裝置之不良率變高之問題。 例如，考慮使用具有用以形成接觸孔之孔圖案之光罩，且將其轉印至被轉印體之情形時，若為直徑超過3 μm之孔圖案，則可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，雖亦可考慮轉換為例如具有高NA之曝光機，但需要較大之投資。 因此，為提高解析度，且與線隙圖案或接觸孔之微細化對應，而著眼於相偏移光罩作為顯示裝置製造用之光罩。 最近，作為液晶顯示裝置製造用之光罩，已開發具備鉻系相偏移膜之相偏移光罩。 於專利文獻1中，記述有一種半色調型相偏移光罩，其具備透明基板、形成於透明基板上之遮光層、及形成於遮光層周圍且包含對300 nm以上500 nm以下之波長區域之任意光可具有180度之相差之氮氧化鉻系材料之單層之相偏移層。該相偏移光罩係藉由如下步驟而製造：使透明基板上之遮光層圖案化；以被覆遮光層之方式於透明基板上形成相偏移層；於相偏移層上形成光阻層；藉由於光微影步驟中使光阻層曝光及顯影，而形成抗蝕劑圖案；將抗蝕劑圖案作為蝕刻遮罩使相偏移層圖案化。 另，該單層之鉻系相偏移層係於包含含有氮(N2 )氣體與二氧化碳(CO2 )氣體之混合氣體之濺鍍氣體氛圍中成膜(參照專利文獻1之圖2之樣本No.1~5)。因此，推斷該相偏移層係除了鉻之氮氧化物(CrON)外，亦有由鉻之碳氮氧化物(CrOCN)形成之情形。 此種相偏移光罩接收自各種曝光機輸出之多種波長之曝光光。 例如，於液晶顯示裝置製造用之相偏移光罩之情形時，作為光微影步驟所使用之曝光機，已知有例如具備輸出於i線(365 nm)、h線(405 nm)、及g線(436 nm)分別具有峰值強度之複合光之光源(超高壓UV燈)者。例如，作為於隨著近年來之液晶顯示裝置之大型化而尺寸放大之母玻璃基板之主表面上轉印相偏移光罩之光罩圖案之情形之曝光光，若使用該複合光，則可獲得光量，且可謀求縮短作業時間。 又，已知一般於某波長之光中顯示某程度之透射率之膜其包含該透射率之光學特性依存於波長而變化，即具有波長依存性。 相偏移膜係具有改變曝光光之相之性質之膜，因而其性質上，於該曝光光中顯示某程度之透射率。因此，根據上述見解，相偏移膜係於曝光光之透射率、反射率及相差存在波長依存性。 且於專利文獻2中，記述有具有抑制相差偏差或透射率偏差之相偏移膜之光罩。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2011-13283號公報 [專利文獻2]日本特開2012-230379號公報At present, as a liquid crystal display device, there are a VA (Vertical Alignment) method or an IPS (In Plane Switching) method. According to these methods, a liquid crystal display device having high definition, high-speed display performance, and wide viewing angle can be realized. In the liquid crystal display device to which the above-described methods are applied, the transparent conductive film can be patterned by, for example, a photolithography step to form a pixel electrode of the line gap pattern, thereby improving the response speed and the viewing angle. Recently, the miniaturization of the width between the line gap patterns has been pursued from the viewpoint of further improvement in response speed and viewing angle, or improvement in light use efficiency of the liquid crystal display device, that is, improvement in power consumption and contrast of the liquid crystal display device. For example, it is desirable to narrow the width of the line 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 display device, a plurality of conductive films or insulating films which have been subjected to necessary patterning are laminated to form a semiconductor element such as a transistor. At this time, the photolithography step is also often used for patterning the respective films of the deposited layers. For example, a thin film transistor or LSI used in such display devices has a structure in which a contact hole is formed in an insulating layer by a photolithography step, and an upper layer pattern and a lower layer pattern are connected. Recently, in such a display device, the demand for displaying a bright and fine image at a sufficiently fast moving speed and reducing power consumption has been increasing. In order to satisfy such a demand, it is desired 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 3 μm to 2.5 μm, 2 μm, and 1.5 μm. According to such a background, a photomask for manufacturing a display device which can correspond to the miniaturization of a line gap pattern or a contact hole is desired. When the line gap pattern or the contact hole is miniaturized, since the resolution limit of the exposure machine for manufacturing the display device is 3 μm in the previous mask, there is not enough process margin (Process Margin), and it is necessary to produce close analysis. The product of the minimum line width of the limit. Therefore, there is a problem that the defective rate of the display device becomes high. For example, when a reticle having a hole pattern for forming a contact hole is used and transferred to a transfer target, if it is a hole pattern having a diameter of more than 3 μm, the transfer can be performed by the previous reticle. . 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 conceivable to convert to, for example, an exposure machine having a high NA, but a large investment is required. Therefore, in order to improve the resolution and to correspond to the miniaturization of the line gap pattern or the contact hole, attention is paid to the phase shift mask as a photomask for manufacturing a display device. 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 including a transparent substrate, a light shielding layer formed on the transparent substrate, and a wavelength region of 300 nm or less and 500 nm or less formed around the light shielding layer. Any of the light may have a phase offset layer of a single layer of a chromium oxynitride-based material having a phase difference of 180 degrees. 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. Forming a resist pattern by exposing and developing the photoresist layer in the photolithography step; patterning the phase shift layer by using the resist pattern as an etch mask. Further, the single-layered chromium-based phase shifting layer is formed in a sputtering gas atmosphere containing a mixed gas containing a nitrogen (N 2 ) gas and a carbon dioxide (CO 2 ) gas (refer to the sample of FIG. 2 of Patent Document 1). No.1~5). Therefore, it is inferred that the phase offset layer is formed of chromium oxynitride (CrOCN) in addition to chromium oxynitride (CrON). Such phase shifting reticles receive exposure light of a plurality of wavelengths output from various exposure machines. For example, in the case of a phase shift mask for manufacturing a liquid crystal display device, as an exposure machine used in the photolithography step, for example, an output is provided on the i line (365 nm) and the h line (405 nm). And the g-line (436 nm) has a peak intensity composite light source (ultra-high pressure UV lamp). For example, as the exposure light in the case where the mask pattern of the phase shifting mask is transferred on the main surface of the mother glass substrate which is enlarged in size as the size of the liquid crystal display device has increased in recent years, if the composite light is used, The amount of light can be obtained, and the working time can be shortened. Further, it is known that a film which exhibits a certain degree of transmittance in light of a certain wavelength generally has an optical property depending on the wavelength, that is, has a wavelength dependency. The phase shifting film has a film that changes the properties of the phase of the exposure light, and thus exhibits a certain degree of transmittance in the exposure light. Therefore, according to the above findings, the phase shift film has wavelength dependence on the transmittance, reflectance, and phase difference of the exposure light. Further, in Patent Document 2, a photomask having a phase shift film that suppresses a phase difference variation or a transmittance deviation is described. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2011-13283 [Patent Document 2] JP-A-2012-230379

[發明所欲解決之問題] 然而，上述專利文獻1、2中具體記述之相偏移膜係任一者皆為單層之鉻系相偏移膜之情形。因此，使用藉由此種相偏移膜材料獲得之相偏移光罩，轉印例如接觸孔徑為2.5 μm或2 μm之類微細圖案之情形時，曝光光之透射率等之波長依存性不充分，或相偏移膜圖案之剖面形狀無法垂直化，而存在無法獲得足夠之解析度之問題。 又，於光罩製作用之描繪機、或顯示裝置製造時所使用之曝光機中，為了辨識設置於光罩之對準標記而設置有對準用光源。作為對準光，使用例如波長365~700 nm之光，利用該對準光中的透明基板與對準標記之透射率之差，檢測對準標記。對準光(波長365~700 nm)之透射率之差越大，對準之辨識越簡單，而對準精度提高，因而可提高相偏移光罩之處理性。然而，上述專利文獻1、2之相偏移光罩不能說於處理性上一定具有足夠之特性。 又，作為光罩檢查裝置，已知具備例如輸出波長365 nm或546 nm之光之光源者。已知有利用該光罩檢查裝置之檢查光中的透明基板與光罩圖案之反射率之差或透射率之差，識別光罩圖案者。若使用此種光罩檢查裝置，可掌握例如光罩圖案之形狀不良缺陷、或光罩圖案上有無附著異物。然而，上述之專利文獻1、2之相偏移光罩不能說一定具有足夠之特性作為光罩檢查中的相偏移膜之光學特性。 因此，本發明係鑑於上述問題點而完成者，目的在於提供一種具備顯示針對曝光光之各光學特性之波長依存性受抑制之光學特性之相偏移膜的顯示裝置製造用之相偏移光罩基底、使用該相偏移光罩基底之相偏移光罩及其製造方法、以及使用該相偏移光罩之顯示裝置之製造方法。 [解決問題之技術手段] 為解決上述課題，本發明具有以下構成。 (構成1)一種相偏移光罩基底，其係顯示裝置製造用之相偏移光罩基底，其特徵在於包含： 透明基板；及 形成於該透明基板上之相偏移膜；且 上述相偏移膜包含至少具有一層含金屬與矽、氮及/或氧之任一元素之金屬矽化物系材料層之單層膜或積層膜； 上述相偏移膜係如下者： 波長365 nm之光之透射率為3.5%以上8%以下之範圍； 波長365 nm之光之相差為160度以上200度以下之範圍； 波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量為5.5%以內。 (構成2)如構成1之相偏移光罩基底，其中上述相偏移膜係如下者： 波長365 nm以上700 nm以下之範圍內透射率之依存於波長之變化量為20%以內。 (構成3)如構成1或2之相偏移光罩基底，其中上述相偏移膜係如下者： 波長365 nm中被賦予之相差、與波長436 nm中被賦予之相差之差為30度以下。 (構成4)如構成1至3中任一項之相偏移光罩基底，其中上述相偏移膜係如下者： 波長365 nm以上700 nm以下之範圍內反射率為5%以上45%以下。 (構成5)如構成4之相偏移光罩基底，其中上述相偏移膜係波長365 nm以上700 nm以下之範圍內反射率之依存於波長之變化量為5%以內。 (構成6)如構成1至5中任一項之相偏移光罩基底，其中上述相偏移膜係由至少一層之金屬矽化物系材料層、與至少一層之鉻系材料層構成。 (構成7)如構成1至6中任一項之相偏移光罩基底，其中上述金屬矽化物系材料層係由金屬矽化物之氮化物、金屬矽化物之氧化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物、金屬矽化物之碳氧化物、及金屬矽化物之碳氮氧化物中至少一種材料構成。 (構成8)如構成6之相偏移光罩基底，其中上述鉻系材料層係由鉻之氮化物、鉻之氧化物、鉻之碳化物、鉻之氮氧化物、鉻之碳氮化物、鉻之碳氧化物、及鉻之碳氮氧化物中至少一種材料構成。 (構成9)如構成6之相偏移光罩基底，其中上述金屬矽化物系材料層之膜厚大於上述鉻系材料層之膜厚。 (構成10)如構成1至9中任一項之相偏移光罩基底，其中包含形成於上述相偏移膜上之遮光膜。 (構成11)一種相偏移光罩，其係顯示裝置製造用之相偏移光罩，其特徵在於包含： 透明基板；及 形成於該透明基板上之相偏移膜圖案； 上述相偏移膜圖案係包含具有至少一層含金屬與矽、氮及/或氧之任一元素之金屬矽化物系材料層之單層膜或積層膜； 上述相偏移膜圖案係如下者： 波長365 nm之光之透射率為3.5%以上8%以下之範圍； 波長365 nm之波長光之相差為160度以上200度以下之範圍； 波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量為5.5%以內。 (構成12)如構成11之相偏移光罩，其中上述相偏移膜圖案係如下者： 波長365 nm以上700 nm以下之範圍內透射率之依存於波長之變化量為20%以內。 (構成13)如構成11或12之相偏移光罩，其中上述相偏移膜圖案係如下者： 波長365 nm中被賦予之相差、與波長436 nm中被賦予之相差之差為30度以下。 (構成14)如構成11至13中任一項之相偏移光罩，其中上述相偏移膜圖案係如下者： 波長365 nm以上700 nm以下之範圍內反射率為15%以上30%以下。 (構成15)如構成14之相偏移光罩，其中上述相偏移膜圖案係如下者： 波長365 nm以上700 nm以下之範圍內反射率之依存於波長之變化量為5%以內。 (構成16)如構成11至15中任一項之相偏移光罩，其中包含形成於上述相偏移膜圖案上之遮光膜圖案。 (構成17)如構成11至16中任一項之相偏移光罩，其中包含形成於上述相偏移膜圖案之下之遮光膜圖案。 (構成18)一種相偏移光罩之製造方法，其係顯示裝置製造用之相偏移光罩之製造方法，其特徵在於包含： 抗蝕劑圖案形成步驟，其係於如構成1至9中任一項之相偏移光罩基底之相偏移膜上形成抗蝕劑圖案；及 相偏移膜圖案形成步驟，其將上述抗蝕劑圖案設為遮罩，濕蝕刻上述相偏移膜，形成相偏移膜圖案。 (構成19)一種相偏移光罩之製造方法，其係顯示裝置製造用之相偏移光罩之製造方法，其特徵在於包含： 抗蝕劑圖案形成步驟，其係於如構成10之相偏移光罩基底之遮光膜上，形成抗蝕劑圖案； 遮光膜圖案形成步驟，其將上述抗蝕劑圖案設為遮罩，濕蝕刻上述遮光膜，形成遮光膜圖案；及 相偏移膜圖案形成步驟，其將上述遮光膜圖案設為遮罩，濕蝕刻相偏移膜，形成相偏移膜圖案。 (構成20)一種顯示裝置之製造方法，其係顯示裝置之製造方法，其特徵在於包含： 相偏移光罩配置步驟，其係對於基板上形成有抗蝕劑膜之附抗蝕劑膜基板，使如構成11至17中任一項之相偏移光罩、或藉由如構成18或19之相偏移光罩之製造方法獲得之相偏移光罩與上述抗蝕劑膜對向而配置；及 抗蝕劑膜曝光步驟，其係對上述相偏移光罩照射包含i線、h線及g線之複合曝光光，而使上述抗蝕劑膜曝光。 [發明之效果] 如上所述，根據本發明之顯示裝置製造用之相偏移光罩基底，具備有透明基板、及形成於該透明基板上之相偏移膜。相偏移膜係包含具有至少一層含金屬與矽、氮及/或氧之任一元素之金屬矽化物系材料層之單層膜或積層膜。相偏移膜其波長365 nm之光之透射率為3.5%以上8%以下之範圍，波長365 nm之光之相差為160度以上200度以下之範圍，波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量為5.5%以內。此種相偏移膜係顯示波長365 nm以上436 nm以下之範圍之光的透射率之波長依存性受抑制之光學特性。 因此，在接收該波長範圍之曝光光時，可充分發揮相偏移效果，且可獲得具備可謀求提高解析度之相偏移膜之相偏移光罩基底。又，可獲得具備相偏移膜之相偏移光罩基底，該相偏移膜可對能獲得使圖案邊界部分之光強度傾斜增強，使解析度提高，具有良好CD特性之期望之轉印圖案形狀的相偏移膜圖案進行圖案化。 又，根據本發明之顯示裝置製造用之相偏移光罩，具備有透明基板、及形成於該透明基板上之相偏移膜圖案。相偏移膜圖案係包含具有至少一層含金屬與矽、氮及/或氧之任一元素之金屬矽化物系材料層之單層膜或積層膜。相偏移膜圖案其波長365 nm之光之透射率為3.5%以上8%以下之範圍，波長365 nm之光之相差為160度以上200度以下之範圍，波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量為5.5%以內。此種相偏移膜圖案係顯示波長365 nm以上436 nm以下之範圍之光的透射率之波長依存性受抑制之光學特性。 因此，可獲得具備能獲得在接收該波長範圍之曝光光時，能充分發揮相偏移效果，且能提高圖案邊界部分之光強度傾斜，具有良好CD特性之期望之轉印圖案形狀的相偏移膜圖案之相偏移光罩。該相偏移光罩係可與線隙圖案或接觸孔之微細化對應。 又，根據本發明之顯示裝置製造用之相偏移光罩之製造方法，使用上述之相偏移光罩基底製造相偏移光罩。因此，可製造具備顯示針對曝光光之波長依存性受抑制之光學特性的相偏移膜圖案之相偏移光罩。根據該相偏移光罩，可獲得可充分發揮相偏移效果，且可使圖案邊界部分之光強度傾斜增強，具有良好CD特性之期望之轉印圖案形狀。 又，根據本發明之顯示裝置製造用之相偏移光罩之製造方法，使用具備形成於上述之相偏移光罩基底之相偏移膜上之遮光膜的相偏移光罩基底，製造具備形成於相偏移膜圖案上之遮光膜圖案之相偏移光罩。因此，可製造具備顯示針對曝光光之波長依存性受抑制之光學特性的相偏移膜圖案之相偏移光罩。根據該相偏移光罩，可獲得可充分發揮相偏移效果，且可增強未積層遮光膜圖案之相偏移膜圖案之圖案邊界部分之光強度傾斜，並具有良好CD特性之期望之轉印圖案形狀。 又，根據本發明之顯示裝置之製造方法，藉由使用上述之相偏移光罩或利用上述之相偏移光罩之製造方法獲得之相偏移光罩製造顯示裝置，可製造具有微細之線隙圖案或接觸孔之顯示裝置。進而，可使顯示裝置之線隙圖案或接觸孔正確對準，而亦可提高顯示裝置之製造成品率。[Problems to be Solved by the Invention] However, any of the phase shifting films specifically described in Patent Documents 1 and 2 is a single-layered chromium-based phase shifting film. Therefore, when a phase shift mask obtained by such a phase shift film material is used to transfer a fine pattern such as a contact hole diameter of 2.5 μm or 2 μm, the wavelength dependence of the transmittance of the exposure light or the like is not The cross-sectional shape of the sufficient or phase-shifted film pattern cannot be perpendicularized, and there is a problem that sufficient resolution cannot be obtained. Further, in the image forming apparatus for mask production or the exposure machine used in the manufacture of the display device, an alignment light source is provided in order to recognize the alignment mark provided on the mask. As the alignment light, for example, light having a wavelength of 365 to 700 nm is used, and the alignment mark is detected by the difference in transmittance between the transparent substrate and the alignment mark in the alignment light. The greater the difference in transmittance between the alignment light (wavelength 365-700 nm), the simpler the alignment identification, and the higher the alignment accuracy, thus improving the rationality of the phase-shifting mask. However, the phase shift masks of the above Patent Documents 1 and 2 cannot be said to have sufficient characteristics in terms of handleability. Further, as a mask inspection device, it is known to provide, for example, a light source that outputs light having a wavelength of 365 nm or 546 nm. It is known that the difference between the reflectance of the transparent substrate and the reticle pattern in the inspection light by the reticle inspection device or the difference in transmittance is recognized, and the reticle pattern is recognized. When such a mask inspection apparatus is used, it is possible to grasp, for example, a defective shape of the mask pattern or the presence or absence of foreign matter adhering to the mask pattern. However, the phase shift masks of the above-mentioned Patent Documents 1 and 2 cannot be said to have sufficient characteristics as the optical characteristics of the phase shift film in the mask inspection. Therefore, the present invention has been made in view of the above problems, and an object of the invention is to provide phase-shifted light for manufacturing a display device including a phase shift film that exhibits optical characteristics in which wavelength dependence of optical characteristics of exposure light is suppressed. A cover substrate, a phase shift mask using the phase shift mask base, 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, which is a phase shift mask substrate for manufacturing a display device, comprising: a transparent substrate; and a phase shift film formed on the transparent substrate; and the phase The offset film comprises a single layer film or a laminated film having at least one layer of a metal halide material layer containing a metal and any element of cerium, nitrogen and/or oxygen; the phase shifting film is as follows: light having a wavelength of 365 nm The transmittance is in the range of 3.5% or more and 8% or less; the phase difference of the light having a wavelength of 365 nm is in the range of 160 degrees or more and 200 degrees or less; and the transmittance in the range of 365 nm or more and 436 nm or less is dependent on the wavelength. Within 5.5%. (Configuration 2) The phase shift mask substrate of the first aspect, wherein the phase shift film is as follows: The transmittance in the range of 365 nm or more and 700 nm or less depends on the amount of change in wavelength of 20% or less. (Configuration 3) The phase shift mask substrate constituting 1 or 2, wherein the phase shift film is as follows: a difference between the phase difference given at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm is 30 degrees. the following. (Aspect 4) The phase shift mask substrate according to any one of the above 1 to 3, wherein the phase shift film is as follows: a reflectance of 5% or more and 45% or less in a wavelength range of 365 nm or more and 700 nm or less . (Configuration 5) The phase shift mask substrate of the fourth aspect, wherein the phase shift film has a reflectance in a range of 365 nm or more and 700 nm or less in a range of 5% or less depending on the wavelength. (Claim 6) The phase shift mask substrate according to any one of 1 to 5, wherein the phase shifting film is composed of at least one layer of a metal telluride-based material layer and at least one layer of a chromium-based material layer. (Structure 7) The phase shift mask substrate according to any one of 1 to 6, wherein the metal halide material layer is a nitride of a metal telluride, an oxide of a metal telluride, or a nitrogen of a metal telluride. The oxide, the metal halide, the carbon oxide of the metal halide, and the carbon oxynitride of the metal halide are at least one material. (Configuration 8) The phase shift mask substrate of the sixth aspect, wherein the chromium-based material layer is made of a nitride of chromium, an oxide of chromium, a carbide of chromium, a nitrogen oxide of chromium, a carbonitride of chromium, It is composed of at least one of chromium carbon oxide and chromium carbonitride. (Configuration 9) The phase shift mask substrate of the sixth aspect, wherein the metal telluride-based material layer has a film thickness larger than a film thickness of the chromium-based material layer. (Claim 10) The phase shift mask substrate according to any one of 1 to 9, which comprises a light-shielding film formed on the phase shift film. (Configuration 11) A phase shift mask which is a phase shift mask for manufacturing a display device, comprising: a transparent substrate; and a phase shift film pattern formed on the transparent substrate; The film pattern comprises a single layer film or a laminated film having at least one layer of a metal halide material layer containing a metal and any element of cerium, nitrogen and/or oxygen; the phase shifting film pattern is as follows: wavelength 365 nm The transmittance of light is in the range of 3.5% or more and 8% or less; the phase difference of light having a wavelength of 365 nm is in the range of 160 degrees or more and 200 degrees or less; and the transmittance in the range of 365 nm or more and 436 nm or less depends on the wavelength change. The amount is within 5.5%. (Structure 12) The phase shift mask of the configuration 11, wherein the phase shift film pattern is as follows: The transmittance in the range of 365 nm or more and 700 nm or less depends on the amount of change in wavelength within 20%. (Structure 13) The phase shift mask of the configuration 11 or 12, wherein the phase shift film pattern is as follows: a difference between the phase difference given at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm is 30 degrees. the following. (Aspect 14) The phase shift mask according to any one of the items 11 to 13, wherein the phase shift film pattern is as follows: a reflectance of 15% or more and 30% or less in a wavelength range of 365 nm or more and 700 nm or less . (Configuration 15) The phase shift mask of the configuration 14 is characterized in that the phase shift film pattern is as follows: The reflectance in the range of 365 nm or more and 700 nm or less depends on the amount of change in wavelength within 5%. (Structure 16) The phase shift mask of any one of Embodiments 11 to 15, comprising a light shielding film pattern formed on the phase shift film pattern. (Structure 17) The phase shift mask of any one of Embodiments 11 to 16, comprising a light shielding film pattern formed under the phase shift film pattern. (Configuration 18) A method of manufacturing a phase shift mask, which is a method of manufacturing a phase shift mask for manufacturing a display device, comprising: a resist pattern forming step, such as forming 1 to 9 Forming a resist pattern on the phase shift film of the phase shift mask substrate; and a phase shift film pattern forming step of masking the resist pattern and wet etching the phase shift The film forms a phase offset film pattern. (Configuration 19) A method of manufacturing a phase shift mask, which is a method of manufacturing a phase shift mask for manufacturing a display device, comprising: a resist pattern forming step of a phase such as composition 10. a resist pattern is formed on the light shielding film of the offset mask base; a light shielding film pattern forming step of masking the resist pattern, wet etching the light shielding film to form a light shielding film pattern; and a phase shift film A pattern forming step of forming the light shielding film pattern as a mask and wet etching the phase shift film to form a phase shift film pattern. (Configuration 20) A method of manufacturing a display device, which is characterized by comprising: a phase shift mask arrangement step for attaching a resist film substrate on which a resist film is formed on a substrate a phase shift mask obtained by any one of the structures 11 to 17 or a phase shift mask obtained by a method of manufacturing a phase shift mask of 18 or 19, which is opposed to the resist film And a resist film exposure step of irradiating the phase shift mask with composite exposure light including an i-line, an h-line, and a g-line to expose the resist film. [Effects of the Invention] As described above, the phase shift mask substrate for manufacturing a display device according to the present invention includes a transparent substrate and a phase shift film formed on the transparent substrate. The phase shifting film comprises a single layer film or a laminated film having at least one layer of a metal telluride-based material containing a metal and any element of cerium, nitrogen and/or oxygen. The phase shift film has a transmittance of light of 365 nm at a wavelength of 3.5% or more and 8% or less, and a phase difference of light of 365 nm is in a range of 160 degrees or more and 200 degrees or less, and a wavelength of 365 nm or more and 436 nm or less. The transmittance depends on the amount of change in wavelength within 5.5%. Such a phase shift film exhibits an optical property in which the wavelength dependence of the transmittance of light having a wavelength in the range of 365 nm or more and 436 nm or less is suppressed. Therefore, when the exposure light of the wavelength range is received, the phase shift effect can be sufficiently exhibited, and a phase shift mask substrate having a phase shift film capable of improving the resolution can be obtained. Further, a phase shift mask substrate having a phase shift film capable of obtaining a desired transfer of the light intensity of the boundary portion of the pattern, enhancing the resolution, and having good CD characteristics can be obtained. The phase-shifted film pattern of the pattern shape is patterned. Moreover, the phase shift mask for manufacturing a display device according to the present invention includes a transparent substrate and a phase shift film pattern formed on the transparent substrate. The phase shift film pattern comprises a single layer film or a laminate film having at least one layer of a metal halide material layer containing a metal and any element of cerium, nitrogen and/or oxygen. The phase shift film pattern has a transmittance of light of 365 nm at a wavelength of 3.5% or more and 8% or less, a phase difference of light of 365 nm and a range of 160 degrees or more and 200 degrees or less, and a wavelength of 365 nm or more and 436 nm or less. The internal transmittance depends on the amount of change in wavelength within 5.5%. Such a phase shift film pattern exhibits optical characteristics in which the wavelength dependence of the transmittance of light having a wavelength in the range of 365 nm or more and 436 nm or less is suppressed. Therefore, it is possible to obtain a phase shift which is capable of obtaining a desired transfer pattern shape in which the phase shift effect can be sufficiently exhibited when the exposure light of the wavelength range is received, and the light intensity of the pattern boundary portion is increased and the desired CD characteristic is obtained. The phase shifting mask of the film shifting pattern. The phase shift mask can correspond to the miniaturization of the line gap pattern or the contact hole. Further, according to the method of manufacturing a phase shift mask for manufacturing a display device of the present invention, a phase shift mask is manufactured using the phase shift mask substrate described above. Therefore, it is possible to manufacture a phase shift mask having a phase shift film pattern that exhibits optical characteristics in which the wavelength dependence of exposure light is suppressed. According to this phase shift mask, it is possible to obtain a desired transfer pattern shape which can sufficiently exhibit the phase shift effect and which can increase the light intensity of the boundary portion of the pattern and have a good CD characteristic. Further, according to the method for manufacturing a phase shift mask for manufacturing a display device of the present invention, a phase shift mask substrate having a light shielding film formed on the phase shift film of the phase shift mask substrate is used, and is manufactured. A phase shift mask having a light shielding film pattern formed on the phase shift film pattern. Therefore, it is possible to manufacture a phase shift mask having a phase shift film pattern that exhibits optical characteristics in which the wavelength dependence of exposure light is suppressed. According to the phase shift mask, it is possible to obtain a desired shift in the light intensity of the pattern boundary portion of the phase shift film pattern of the unstacked light-shielding film pattern, and to enhance the phase shift effect. Print pattern shape. Further, according to the method of manufacturing a display device of the present invention, the phase shift mask manufacturing display device obtained by using the phase shift mask described above or the method for manufacturing the phase shift mask described above can be manufactured to have fineness. A display device for a line gap pattern or contact hole. Further, the line gap pattern or the contact hole of the display device can be correctly aligned, and the manufacturing yield of the display device can be improved.

以下，詳細說明本發明之實施形態之顯示裝置製造用之相偏移光罩基底、使用該相偏移光罩基底之顯示裝置製造用之相偏移光罩及其製造方法、以及使用該相偏移光罩之顯示裝置之製造方法。 實施形態1. 於實施形態1中，說明顯示裝置製造用之相偏移光罩基底及其製造方法。 首先，說明實施形態1之顯示裝置製造用之相偏移光罩基底。 圖1係顯示本發明之實施形態1之顯示裝置製造用之相偏移光罩基底之構成之剖面圖。 實施形態1之相偏移光罩基底1具備透明基板2、及形成於該透明基板2上之相偏移膜3。另，亦可採用於相偏移膜3上形成有遮光膜4之構成。又，可採用於相偏移膜3或遮光膜4上形成有抗蝕劑膜5之構成。 透明基板2係對所使用之曝光光具有透光性者。透明基板2之材料係若為對所使用之曝光光具有透光性之材料，則無特別限制。作為具有透光性之材料，例舉合成石英玻璃、鈉鈣玻璃、無鹼玻璃。 相偏移膜3係包含至少具有一層含有金屬與矽、氮及/或氧之任一者之元素之金屬矽化物系材料層之單層膜或積層膜者。相偏移膜3整體之光學特性係於相偏移膜3包含單層膜之情形時，由根據構成形成該相偏移膜3之材料層的材料之種類或膜厚等所決定之材料層之例如折射率、透射率及反射率等之光學特性而定，於相偏移膜3包含積層膜之情形時，由根據構成形成該相偏移膜3之複數個材料層的材料之種類或膜厚等所決定之該光學特性之組合、以及各材料層之積層順序及積層數等之構成而定。此處，於相偏移膜3包含單層膜之情形時，該單層膜係由單一材料形成之膜。因此，包含單一材料之積層構造之膜亦為單層膜。又，於相偏移膜3包含積層膜之情形時，該積層膜係藉由自單一材料或同種材料所形成之膜、及由與該膜不同之材料形成之膜之組合而構成之膜。 此種相偏移膜3係藉由選擇構成相偏移膜3之材料層，而將特定波長之光之透射率控制於如下述般之範圍內，又，將特定波長之光之透射率及相差控制於如下述般之範圍內，再者，將特定之波長範圍之光之透射率、相差、及反射率之依存於波長之變化量抑制於如下述般之範圍內。 具體而言，相偏移膜3其波長365 nm之透射率(以下，有時稱為T%(365))為3.5%以上8%以下之範圍。因此，圖案邊界部分之光強度傾斜變強，可實現解析度之提高。T%(365)不足3.5%時，難以獲得能充分發揮期望之相偏移效果所必要之透射光之光量。又，若T%(365)超過8%，則圖案邊界部分之光強度傾斜變弱，難以實現解析度之提高。 又，相偏移膜3其波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量(以下有時稱為ΔT%(436-365))為5.5%以內。因該波長範圍之透射率之波長依存性受抑制，故圖案邊界部分之光強度傾斜變強，而可實現解析度之提高。若ΔT%(436-365)超過5.5%，則受到i線(365 nm)以外之具有峰值強度之h線(405 nm)及g線(436 nm)之透射光之影響，圖案邊界部分之光強度傾斜變弱，難以實現解析度之提高。另，相偏移膜3係因在g線(436 nm)之透射率不足10%之情形時解析性特別提高，故而較為理想。 又，相偏移膜3其波長365 nm之相差(以下，有時稱為P(365))為160度以上200度以下之範圍。因此，可獲得大致180度附近之相差，可充分發揮相偏移效果。在P(365)不足160度之情形或超過200度之情形時，無法獲得大致180度附近之相差，而難以發揮相偏移效果。 又，相偏移膜3較佳為波長365 nm以上700 nm以下之範圍內透射率之依存於波長之變化量(以下，有時稱為ΔT%(700-365))為20%以內。該情形時，相偏移膜3係因即使於該波長範圍內，亦可抑制透射率之波長依存性，故在顯示裝置製造時之曝光機中，容易辨識設置於光罩之對準標記，從而對準精度提高。又，在光罩檢查裝置中，利用透明基板與光罩圖案之透射率之差，識別光罩圖案之檢查裝置之情形時，因容易辨識光罩圖案之形狀不良缺陷等之缺陷，故而較佳。 又，相偏移膜3其波長365 nm中被賦予之相差與波長436 nm中被賦予之相差之差(ΔP(365-436))為30度以下。因該波長範圍之相差之波長依存性受抑制，故可進而充分發揮相偏移效果，使圖案邊界部分之光強度傾斜變強，可實現解析度之提高。 又，相偏移膜3較佳為波長365 nm以上700 nm以下之範圍之反射率(以下，有時稱為R%(700-365))為5%以上45%以下。再者，相偏移膜3較佳為波長365 nm以上700 nm以下之範圍之反射率(R%(700-365))為5%以上45%以下，且波長365 nm以上700 nm以下之範圍內反射率之依存於波長之變化量(以下，有時稱為ΔR%(700-365))為5%以內。該情形時，相偏移膜3係在於相偏移膜3上形成抗蝕劑膜，且藉由雷射描繪機等進行圖案描繪時，較少受到因描繪時使用之光與其反射光重合而產生之駐波之影響。因此，於圖案描繪時，可抑制相偏移膜3上之抗蝕劑圖案剖面之邊緣部分之粗糙度，從而可提高圖案精度。又，因容易取得圖案描繪時之對準，而容易利用長尺寸(MMS)測定進行光罩圖案計測，故可高精度地辨識光罩圖案。此外，在使用相偏移光罩進行圖案轉印且製造顯示裝置之情形，利用透明基板與對準標記之反射率之差檢測對準標記之情形時，容易辨識光罩對準，從而對準精度提高。又，在使用相偏移光罩進行圖案轉印而製造顯示裝置之情形時，因可抑制眩光現象之影響，故可獲得良好之CD特性，且可實現解析度之提高，而可獲得期望之轉印圖案形狀。 顯示此種光學特性之相偏移膜3係如上所述，由具有至少一層包含金屬與矽、氮及/或氧之任一者之元素之金屬矽化物系材料層之單層膜或積層膜構成。 於特定之波長範圍中，為抑制相偏移膜3之透射率、相差、反射率之波長依存性，進而較佳為採用由光學特性不同之複數個材料層構成之積層膜。作為光學特性不同之複數個材料層，較佳為由至少一層之金屬矽化物系材料層、與至少一層之鉻系材料層構成。且於該情形時，相偏移膜3整體之光學特性係由根據構成金屬矽化物系材料層或鉻系材料層的材料之種類或膜厚等決定之該各材料層之例如折射率、透射率及反射率等之光學特性之組合、以及該各材料層之積層順序及積層數等之構成而定。 具體而言，相偏移膜3係可採用具有由形成於透明基板2上之金屬矽化物系材料層、與形成於該金屬矽化物系材料層上之鉻系材料層構成之二層構造之積層膜。又，可採用具有由與形成於該鉻系材料層上之第二層之金屬矽化物系材料層構成之三層構造之積層膜。另，於該情形時，亦可進而積層鉻系材料層或金屬矽化物系材料層，將相偏移膜3設為四層以上。 又，相偏移膜3係可採用具有由形成於透明基板2上之鉻系材料層、與形成於該鉻系材料層上之金屬矽化物系材料層構成之二層構造之積層膜。又，可採用具有由與形成於該金屬矽化物系材料層上之第二層之鉻系材料層構成之三層構造之積層膜。另，於該情形時，亦可進而積層金屬矽化物系材料層或鉻系材料層，將相偏移膜3設為四層以上。 此種構成之相偏移膜3係顯示特定波長範圍之透射率、相差、反射率之波長依存性受抑制之光學特性。因此，於受到該波長範圍之曝光光時，可充分發揮相偏移效果，且可實現解析度之提高。 又，構成相偏移膜3之金屬矽化物系材料層及鉻系材料層係任一者皆可分別由一層形成，又可由複數層形成。在將金屬矽化物系材料層及鉻系材料層分別由複數層形成之情形時，構成各材料層之各層之材料可各層不同，又可各層相同。 相偏移膜3由至少一層之金屬矽化物系材料層、與至少一層之鉻系材料層構成之情形時，作為形成於透明基板2側之相偏移膜3之最下層，採用鉻系材料層，此點在透射率、相差、反射率之波長依存性之抑制效果、以及將相偏移膜3圖案化時對透明基板2之損傷抑制方面較佳。又，於相偏移膜3上形成抗蝕劑膜5之情形時，作為相偏移膜3之最上層，採用鉻系材料層，此點在抗蝕劑膜之密著性提高，且可使相偏移膜3之圖案形狀垂直化方面較佳。 此種相偏移膜3之膜厚係為了獲得發揮該相偏移效果所必要之於曝光光中被賦予之期望之相差、及曝光光之期望之透射率或反射率，而根據構成相偏移膜3之金屬矽化物系材料層或鉻系材料層之各形成材料、積層順序、膜厚等適當決定。 又，構成相偏移膜3之金屬矽化物系材料層之厚度係考慮於該金屬矽化物系材料層、或金屬矽化物系材料層、及形成於其下或上之鉻系材料層之組合中，使相偏移膜3顯示期望之相差或透射率而適當決定。相偏移膜3之金屬矽化物系材料層之厚度較佳為例如90 nm以上140 nm以下之範圍，但並未限定於此。 又，相偏移膜3為至少具有金屬矽化物系材料層與鉻系材料層之構成之情形時，鉻系材料層之厚度係考慮於與形成於該鉻系材料層之下或上之金屬矽化物系材料層之組合中，使相偏移膜3顯示期望之相差或透射率而適當決定，例如，較佳為2.5 nm以上15 nm以下之範圍，但並未限定於此。實質上很難以不足2.5 nm之厚度使鉻系材料層成膜。又，若以超過15 nm之厚度使鉻系材料層成膜，則透射率降低，例如，波長365 nm之相偏移膜3之透射率有可能低於3.5%。 構成金屬矽化物系材料層之金屬矽化物系材料若為包含金屬、矽(Si)者，則無特別限制。構成金屬矽化物系材料層之金屬與矽(Si)之組成係根據相偏移膜3整體之光學特性之觀點進行調整。金屬與矽之比例係根據金屬種類或金屬矽化物系材料層所要求之光學特性適當選擇，較佳為金屬：矽=1：1以上1：9以下。 作為金屬，例舉鉬(Mo)、鉭(Ta)、鎢(W)、鈦(Ti)等過渡金屬。作為構成金屬矽化物系材料層之金屬矽化物系材料，例舉金屬矽化物之氮化物、金屬矽化物之氧化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物、金屬矽化物之碳氧化物、及金屬矽化物之碳氮氧化物中至少一種之材料。 如本發明之顯示裝置製造用時使用之相偏移光罩基底係一般一邊為350 mm以上之大型相偏移光罩基底，因而於相偏移光罩製作中採用濕蝕刻。又，根據大型之相偏移光罩之缺陷修正之觀點，於相偏移光罩基底之相偏移膜之缺陷品質，亦要求某品質以上者。根據相偏移膜之缺陷品質、利用濕蝕刻進行之相偏移膜圖案之剖面形狀之控制性、相偏移膜之透射率、相差之控制性之觀點，金屬矽化物系材料較佳為採用含氮之材料。作為金屬矽化物系材料，較佳為金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮氧化物，尤其較佳為金屬矽化物之氮化物。 若相偏移膜圖案之剖面形狀被控制成垂直，則因針對相偏移膜圖案與透明基板之圖案邊界部分可取得足夠之對比度，故容易增強圖案邊界部分之光強度傾斜。 以下，具體例舉金屬矽化物系材料。 於矽化鉬(MoSi)之情形時，例舉矽化鉬(MoSi)之氮化物、矽化鉬(MoSi)之氧化物、矽化鉬(MoSi)之氮氧化物、矽化鉬(MoSi)之碳氮化物、矽化鉬(MoSi)之碳氧化物、矽化鉬(MoSi)之碳氮氧化物。 於矽化鉭(TaSi)之情形時，例舉矽化鉭(TaSi)之氮化物、矽化鉭(TaSi)之氧化物、矽化鉭(TaSi)之氮氧化物、矽化鉭(TaSi)之碳氮化物、矽化鉭(TaSi)之碳氧化物、矽化鉭(TaSi)之碳氮氧化物。 於矽化鎢(WSi)之情形時，例舉矽化鎢(WSi)之氮化物、矽化鎢(WSi)之氧化物、矽化鎢(WSi)之氮氧化物、矽化鎢(WSi)之碳氮化物、矽化鎢(WSi)之碳氧化物、矽化鎢(WSi)之碳氮氧化物。 於矽化鈦(TiSi)之情形時，例舉矽化鈦(TiSi)之氮化物、矽化鈦(TiSi)之氧化物、矽化鈦(TiSi)之氮氧化物、矽化鈦(TiSi)之碳氮化物、矽化鈦(TiSi)之碳氧化物、矽化鈦(TiSi)之碳氮氧化物。 另，於此種金屬矽化物系材料，如上所述，根據利用濕蝕刻進行之相偏移膜圖案之剖面形狀之控制性之觀點，較佳為包含有減緩金屬矽化物系材料層之濕蝕刻速度之成分。作為減緩金屬矽化物系材料層之濕蝕刻速度之成分，例舉上述之氮(N)。於該情形時，構成金屬矽化物系材料層之金屬與矽(Si)與氮之組成係根據相偏移膜3整體之光學特性之觀點進行調整。含氮之情形之氮含量較佳為25原子%以上55原子%以下，進而更佳為30原子%以上50原子%以下。又，於金屬矽化物系材料中，在未脫離本發明之效果之範圍內，亦可包含上述所舉之例以外之元素。 作為構成鉻系材料層之鉻系材料，使用包含鉻(Cr)、及選自氧(O)、氮(N)、碳(C)之至少一種之鉻化合物。作為鉻化合物，例舉鉻(Cr)之氮化物、鉻之氧化物、鉻之碳化物、鉻之氮氧化物、鉻之碳氮化物、鉻之碳氧化物、及鉻之碳氮氧化物中至少一種材料。 此種鉻系材料中，鉻之氮化物、或鉻之氮氧化物係在容易控制透射率之波長依存性方面較佳。 又，於鉻系材料中，在未脫離本發明之效果之範圍內，亦可包含有上述所舉之例以外之元素。 又，如上述說明，實施形態1之相偏移光罩基底1亦可採用具有透明基板2、形成於該透明基板2上之相偏移膜3、及形成於該相偏移膜3上之遮光膜4之構成。 遮光膜4可為由一層構成之情形及由複數層構成之情形之任一者。 由複數層構成遮光膜4之情形時，例如包含具有由形成於相偏移膜3側之遮光層與形成於遮光層上之防反射層構成之二層構造之情形、或具有由以與相偏移膜3連接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防反射層構成之三層構造之情形。 遮光層亦可為由一層構成之情形及由複數層構成之情形之任一者。作為遮光層，例舉氮化鉻膜(CrN)、碳化鉻膜(CrC)、碳氮化鉻膜(CrCN)、矽化鉬膜(MoSi)、矽化鉬氮化膜(MoSiN)等。 防反射層亦可為由一層構成之情形及由複數層構成之情形之任一者。作為防反射層，例舉氮氧化鉻膜(CrON)、矽化鉬氧化膜(MoSiO)、矽化鉬氮氧化膜(MoSiON)等。 絕緣層係例如由含不足50原子%之Cr之CrCO或CrOCN構成，且具有10 nm以上50 nm以下之厚度。最表層具有金屬矽化物系材料層之相偏移膜3上，在形成由鉻系材料構成之遮光膜4之相偏移光罩基底之情形中，對由鉻系材料構成之遮光膜4進行濕蝕刻時，自於最表層具有金屬矽化物系材料層之相偏移膜3熔出金屬離子。此時，產生電子。在以與相偏移膜3連接之方式形成絕緣層之情形時，可防止自相偏移膜3熔出金屬離子時產生之電子被供給至遮光膜。因此，可使濕蝕刻遮光膜4時面內之蝕刻速度均一。又，作為遮光膜4，較佳為碳化鉻膜(CrC)之遮光層與氮氧化鉻膜(CrON)之防反射層之組合、或矽化鉬膜(MoSi)之遮光層與矽化鉬氮氧化膜(MoSiON)之防反射層之組合，但並非限定於此等。 具有上述構成之相偏移光罩基底1之相偏移膜3、遮光膜4係可藉由周知之成膜方法形成。作為成膜方法，一般例舉濺鍍法。作為濺鍍裝置，可為叢集型濺鍍裝置、串聯型濺鍍裝置之任一者。 構成相偏移膜3或遮光膜4之金屬矽化物系材料層或鉻系材料層係例如可藉由如以下之濺鍍靶材、濺鍍氣體氛圍而成膜。 在使用具備此種相偏移膜3或遮光膜4之相偏移光罩基底1製造相偏移光罩之情形時，藉由於相偏移膜圖案上設置較相偏移膜圖案狹窄之遮光膜圖案，可獲得例如使將曝光光之相改變大致180度之相偏移部由未積層遮光膜圖案之相偏移膜圖案之部分構成，使遮光部由積層有相偏移膜圖案與遮光膜圖案之部分構成，且使光透射部由露出透明基板2之部分構成之相偏移光罩。 作為金屬矽化物系材料層之成膜所使用之濺鍍靶材，選擇包含金屬、矽(Si)者。具體而言，例舉金屬矽化物、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、及金屬矽化物之碳氮氧化物。 金屬矽化物系材料層之成膜時之濺鍍氣體氛圍係包含具有選自包括氮氣(N2 )、一氧化氮(NO)氣體、二氧化氮(NO2 )氣體、一氧化二氮(N2 O)氣體、一氧化碳(CO)氣體、二氧化碳(CO2 )氣體及氧氣(O2 )之群之至少一種之活性氣體、與具有選自包括氦氣(He)、氖氣(Ne)、氬氣(Ar)、氪氣(Kr)、及氙氣(Xe)之群之至少一種之惰性氣體之混合氣體。 上述之濺鍍靶材之形成材料與濺鍍氣體氛圍之氣體種類之組合、或濺鍍氣體氛圍中活性氣體與惰性氣體之混合比例係根據構成金屬矽化物系材料層之金屬矽化物系材料之種類或組成適當決定。 作為鉻系材料層之成膜所使用之濺鍍靶材，選擇包含鉻(Cr)或鉻化合物者。具體而言，例舉鉻(Cr)、鉻之氮化物、鉻之氧化物、鉻之碳化物、鉻之氮氧化物、鉻之碳氮化物、鉻之碳氧化物、及鉻之碳氮氧化物。 鉻系材料層之成膜時之濺鍍氣體氛圍係包含具有選自包括氮氣(N2 )、一氧化氮(NO)氣體、二氧化氮(NO2 )氣體、一氧化二氮(N2 O)氣體、一氧化碳(CO)氣體、二氧化碳(CO2 )氣體、氧氣(O2 )、烴系氣體及氟系氣體之群之至少一種之活性氣體、與具有選自包括氦氣(He)、氖氣(Ne)、氬氣(Ar)、氪氣(Kr)、及氙氣(Xe)之群之至少一種之惰性氣體之混合氣體。作為烴系氣體，例舉甲烷氣體、丁烷氣體、丙烷氣體、苯乙烯氣體。 上述之濺鍍靶材之形成材料與濺鍍氣體氛圍之氣體種類之組合、或濺鍍氣體氛圍中活性氣體與惰性氣體之混合比例係根據構成鉻系材料層之鉻系材料之種類或組成適當決定。 上述說明之實施形態1之顯示裝置製造用之相偏移光罩基底1係具備：透明基板2；及相偏移膜3，其形成於透明基板2之主表面上，且係由具有至少一層包含金屬與矽、氮及/或氧之任一者之元素之金屬矽化物系材料層之單層膜或積層膜構成。相偏移膜3係如上所述，波長365 nm之光之透射率為3.5%以上8%以下之範圍，波長365 nm之光之相差為160度以上200度以下之範圍，波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量為5.5%以內。該相偏移膜3係顯示波長365 nm以上436 nm以下之範圍之光的透射率之波長依存性受抑制之光學特性。 因此，可獲得具備於接收該波長範圍之曝光光時，能充分發揮相偏移效果，且能謀求提高解析度之相偏移膜之相偏移光罩基底。又，可獲得具備相偏移膜3之相偏移光罩基底，該相偏移膜3可對能獲得使圖案邊界部分之光強度傾斜增強，且提高解析度，具有良好CD特性之期望之轉印圖案形狀之相偏移膜圖案進行圖案化。 又，實施形態1之顯示裝置製造用之相偏移光罩基底1係在波長365 nm以上700 nm以下之範圍內相偏移膜3之透射率之依存於波長之變化量為20%以內之情形時，於該波長範圍中，亦可抑制相偏移膜3之透射率之波長依存性，因而於顯示裝置製造時之曝光機中，容易辨識設置於光罩之對準標記，對準精度提高。又，於光罩檢查裝置中，在利用透明基板與光罩圖案之透射率之差，識別光罩圖案之檢查裝置之情形時，容易辨識光罩圖案之形狀不良缺陷等之缺陷。 又，實施形態1之顯示裝置製造用之相偏移光罩基底1係在波長365 nm中被賦予之相差與波長436 nm中被賦予之相差之差為30度以下之情形時，抑制該波長範圍之相差之波長依存性，因而可進而充分發揮相偏移效果，使圖案邊界部分之光強度傾斜變強，可謀求提高解析度。 又，實施形態1之顯示裝置製造用之相偏移光罩基底1係波長365 nm以上700 nm以下之範圍內相偏移膜3之反射率為5%以上45%以下，進而較佳之實施形態1之顯示裝置製造用之相偏移光罩基底1係波長365 nm以上700 nm以下之範圍內相偏移膜3之反射率為5%以上45%以下，且波長365 nm以上700 nm以下之範圍內反射率之依存於波長之變化量為5%以內之情形時，於相偏移膜3上形成抗蝕劑膜，在利用雷射描繪機等進行圖案描繪時，較少受到因描繪時使用之光與其反射光重合而產生之駐波之影響。因此，於圖案描繪時，可抑制相偏移膜3上之抗蝕劑圖案剖面之邊緣部分之粗糙度，從而可提高圖案精度。又，因容易取得圖案描繪時之對準，且容易利用長尺寸(MMS)測定進行光罩圖案計測，故可高精度地辨識光罩圖案。此外，在使用相偏移光罩進行圖案轉印且製造顯示裝置之情形、及利用透明基板與對準標記之反射率之差檢測對準標記之情形時，容易辨識光罩對準，對準精度提高。又，在使用相偏移光罩進行圖案轉印且製造顯示裝置之情形時，因可抑制眩光現象之影響，故可獲得良好之CD特性，且可謀求解析度之提高，並可獲得期望之轉印圖案形狀。 又，實施形態1之顯示裝置製造用之相偏移光罩基底1、及後述之實施形態2之顯示裝置製造用之相偏移光罩30係於等倍曝光之投影曝光所使用之相偏移光罩基底、相偏移光罩尤其發揮效果。尤其，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，相干係數(σ)較佳為0.5~1.0。 實施形態2. 於實施形態2中，使用圖2、圖3說明顯示裝置製造用之相偏移光罩及其製造方法。圖2係顯示本發明之實施形態2之顯示裝置製造用之相偏移光罩之構成之剖面圖。圖3係用以說明使用於相偏移膜3上形成有遮光膜4之相偏移光罩基底之相偏移光罩之製造方法之步驟圖。於圖2及圖3中，於與圖1相同之構成要件標註相同符號且省略重複說明。 實施形態2之相偏移光罩30係具備透明基板2、及形成於該透明基板2上之相偏移膜圖案3'(圖2(a)，以下有時稱為第1類型之相偏移光罩)。另，亦可採用於相偏移膜圖案3'上形成有遮光膜圖案4'之構成(圖2(b)，以下有時稱為第2類型之相偏移光罩)。又，亦可採用於相偏移膜圖案3'之下形成有遮光膜圖案4'之構成(圖2(c)，以下有時稱為第3類型之相偏移光罩)。 第1類型之相偏移光罩30係藉由由相偏移膜圖案3'構成之相偏移部、與由露出透明基板2之部分構成之光透射部構成。 第2、第3類型之相偏移光罩30係藉由於相偏移膜圖案3'上或下未形成遮光膜圖案4'之相偏移膜圖案3'之部分之相偏移部、於相偏移膜圖案3'上或下形成有遮光膜圖案4'之積層部分之遮光部、及露出透明基板2之部分之光透射部構成。第2、第3類型之相偏移光罩30係可防止因透射相偏移部之曝光光而引起形成於被轉印體之抗蝕劑膜之減膜。 於上述之第1類型、第2類型或第3類型之相偏移光罩30中，相偏移膜圖案3'係包含至少具有一層具備金屬與矽、氮及/或氧之任一元素之金屬矽化物系材料層之單層膜或積層膜者。相偏移膜圖案3'整體之光學特性係於相偏移膜圖案3'包含單層膜之情形時，根據構成形成該相偏移膜圖案3'之材料層的材料之種類或膜厚等所決定之各材料層之例如折射率、透射率及反射率等之光學特性而定，於相偏移膜圖案3'包含積層膜之情形時，根據構成形成該相偏移膜圖案3'之複數個材料層的材料之種類或膜厚等所決定之該光學特性之組合、以及各材料層之積層順序及積層數等之構成而定。 此種相偏移膜圖案3'係藉由構成相偏移膜圖案3'之材料層之組合，而將特定波長之光之透射率控制於如下述之範圍內，又，將特定波長之光之透射率及相差控制於如下述之範圍內，再者，將特定之波長範圍之光之透射率、相差及反射率之依存於波長之變化量抑制於如下述之範圍內。 具體而言，相偏移膜圖案3'係波長365 nm之透射率為3.5%以上8%以下之範圍，波長365 nm之相差為160度以上200度以下之範圍，波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量為5.5%以內。此種相偏移膜圖案3'係顯示波長365 nm以上436 nm以下之範圍之光的透射率之波長依存性受抑制之光學特性。 因此，相偏移膜圖案3'接收該波長及該波長範圍之光時，可充分發揮相偏移效果，且可增強圖案邊界部分之光強度傾斜，因而可獲得具備能獲得具有良好CD特性之期望之轉印圖案形狀之相偏移膜圖案3'之相偏移光罩30。該相偏移光罩30係可與線隙圖案或接觸孔之微細化對應。 又，於上述之第1類型、第2類型或第3類型之相偏移光罩30中，相偏移膜圖案3'係於波長365 nm以上700 nm以下之範圍內透射率之依存於波長之變化量為20%以內之情形時，於該波長範圍內，亦可抑制透射率之波長依存性，故在顯示裝置製造時之曝光機中，容易辨識設置於光罩之對準標記，對準精度提高。又，在光罩檢查裝置中，利用透明基板與光罩圖案之透射率之差，識別光罩圖案之檢查裝置之情形時，容易辨識光罩圖案之形狀不良缺陷等之缺陷。 又，於上述之第1類型、第2類型或第3類型之相偏移光罩30中，相偏移膜圖案3'係於波長365nm中被賦予之相差與波長436 nm中被賦予之相差之差(ΔP(365-436))為30度以下之情形時，該波長範圍之相差之波長依存性受抑制，故可進而充分發揮相偏移效果，使圖案邊界部分之光強度傾斜變強，可謀求解析度之提高。 又，於上述之第1類型、第2類型或第3類型之相偏移光罩30中，相偏移膜圖案3'於波長365 nm以上700 nm以下之範圍之反射率為5%以上45%以下，再者，相偏移膜圖案3'於波長365 nm以上700 nm以下之範圍之反射率為5%以上45%以下，且波長365 nm以上700 nm以下之範圍內反射率之依存於波長之變化量(ΔR%(700-365))為5%以內之情形時，容易利用長尺寸(MMS)測定進行光罩圖案計測，故可高精度地辨識光罩圖案。此外，在使用相偏移光罩進行圖案轉印且製造顯示裝置之情形、及利用透明基板與對準標記之反射率之差檢測對準標記之情形時，容易辨識光罩對準，對準精度提高。又，在使用相偏移光罩進行圖案轉印且製造顯示裝置之情形時，因可抑制眩光現象之影響，故可獲得良好之CD特性，且可謀求解析度之提高，並可獲得期望之轉印圖案形狀。 其次，使用圖3說明實施之顯示裝置製造用之相偏移光罩之製造方法。如圖3所示之相偏移光罩之製造方法係上述之第1類型、第2類型之相偏移光罩30之製造方法。 於第1類型、第2類型之顯示裝置製造用之相偏移光罩之製造方法中，首先，進行於實施形態1之顯示裝置製造用之相偏移光罩基底1之遮光膜4上形成抗蝕劑圖案之抗蝕劑圖案形成步驟。 詳細而言，於該抗蝕劑圖案形成步驟中，首先如圖3(a)所示，於遮光膜4上形成抗蝕劑膜5。其後，對抗蝕劑膜5描繪特定尺寸之圖案。其後，以特定顯影液將抗蝕劑膜5進行顯影，如圖3(b)所示，形成抗蝕劑圖案5'。 作為描繪至抗蝕劑膜5之圖案，例舉線隙圖案或孔圖案。 其次，如圖3(c)所示，進行將抗蝕劑圖案5'設為遮罩對遮光膜4進行濕蝕刻且形成遮光膜圖案4'之遮光膜圖案形成步驟。 對遮光膜4進行濕蝕刻之蝕刻液若為可選擇性蝕刻形成遮光膜4之鉻系材料或金屬矽化物系材料者，則未特別限制。遮光膜4之形成材料為鉻系材料之情形時，例舉包含硝酸鈰銨與過氧二硫酸銨之蝕刻液。又，遮光膜4之形成材料為金屬矽化物系材料之情形時，例舉包含選自氫氟酸、氟矽酸氫氟酸、及氟化氫銨之至少一種氟化物、與選自過氧化氫、硝酸、及硫酸之至少一種氧化劑之蝕刻液。具體而言，例舉以去離子水稀釋氟化氫銨與過氧化氫之混合溶液之蝕刻液。 其次，如圖3(d)所示，在剝離抗蝕劑圖案5'後，如圖3(e)所示，進行將遮光膜圖案4'設為遮罩且對相偏移膜3進行濕蝕刻而形成相偏移膜圖案3'之相偏移膜圖案形成步驟。 對相偏移膜3進行濕蝕刻之蝕刻液若為可分別選擇性蝕刻構成相偏移膜3之鉻系材料層及金屬矽化物系材料層者，則未特別限制。例如，作為濕蝕刻鉻系材料層之蝕刻液，例舉包含硝酸鈰銨與過氧二硫酸銨之蝕刻液。又，作為對金屬矽化物系材料層進行濕蝕刻之蝕刻液，例舉包含選自氫氟酸、氟矽酸氫氟酸、及氟化氫銨之至少一種氟化物、與選自過氧化氫、硝酸、及硫酸之至少一種氧化劑之蝕刻液。 另，於金屬矽化物系材料層上形成有鉻系材料層之相偏移膜3之情形，對鉻系材料層進行濕蝕刻時，自其下層之金屬矽化物系材料層熔出金屬離子，且電子被供給至鉻系材料層，產生鉻系材料層之濕蝕刻變慢之現象。然而，於鉻系材料層上形成有金屬矽化物系材料層之相偏移膜3之情形時，不會產生此種現象。因此，可使濕蝕刻相偏移膜3時之面內之蝕刻速度均一。 其次，在製造具有由相偏移膜圖案3'構成之相偏移部、及由露出透明基板2之部分構成之光透射部之類型之相偏移光罩30(第1類型之相偏移光罩)之情形時，於相偏移膜圖案形成步驟後，如圖3(f)所示，剝離遮光膜圖案4'。 又，製造於相偏移膜圖案3'上設置較相偏移膜圖案3'更狹窄之遮光膜圖案4'，且具有由未積層遮光膜圖案4'之相偏移膜圖案3'之部分構成之相偏移部、由積層有相偏移膜圖案3'與遮光膜圖案4'之部分構成之遮光部、及由露出透明基板2之部分構成之光透射部之類型之相偏移光罩30(第2類型之相偏移光罩)之情形時，在相偏移膜圖案形成步驟後，如圖3(g)所示，使遮光膜圖案4'圖案化成較相偏移膜圖案3'更狹窄之特定圖案。 藉由此種抗蝕劑圖案形成步驟、遮光膜圖案形成步驟、及相偏移膜圖案形成步驟，製造顯示裝置製造用之相偏移光罩30。 另，上述之第1類型、第2類型之相偏移光罩30之製造方法並未限定於上述方法。於第1類型之相偏移光罩30中，作為實施形態1之顯示裝置製造用之相偏移光罩基底1，使用未形成遮光膜4之構成者，且進行於相偏移膜3上形成抗蝕劑圖案5'之抗蝕劑圖案形成步驟，其後，進行以抗蝕劑圖案5'為遮罩，濕蝕刻相偏移膜3且形成相偏移膜圖案3'之相偏移膜圖案形成步驟，最後剝離抗蝕劑圖案5'，可獲得第1類型之相偏移光罩30。 又，根據實施形態2之顯示裝置製造用之相偏移光罩之製造方法，使用實施形態1之相偏移光罩基底1製造相偏移光罩。因此，可製造具備可獲得能充分發揮相偏移效果，且能增強圖案邊界部分之光強度傾斜，並具有良好CD特性之期望之轉印圖案形狀之相偏移膜圖案3'之相偏移光罩30。 另，上文中對第1類型、第2類型之相偏移光罩30之製造方法進行說明，關於在主表面上之一部分中已形成遮光膜圖案之透明基板2之主表面上形成有相偏移膜圖案3'之相偏移光罩30(第3類型之相偏移光罩)，亦可應用本發明。該情形時，藉由使相偏移膜圖案3'覆蓋已形成於主表面上之一部分之遮光膜圖案4'，或形成於未形成遮光膜圖案4'之主表面上，可將未積層該遮光膜圖案與相偏移膜圖案3'之部分設為相偏移部，且可於該相偏移部中，發揮相偏移效果。 此種於主表面上之一部分中已形成遮光膜圖案4'之透明基板2之主表面上形成有相偏移膜圖案3'之第3類型之相偏移光罩30係例如藉由如下步驟而製造：遮光膜形成步驟，其係於透明基板2之主表面上，利用濺鍍形成遮光膜；遮光膜圖案形成步驟，其係於該遮光膜形成步驟後，利用濕蝕刻使該遮光膜圖案化而形成遮光膜圖案；相偏移膜形成步驟，其係於該遮光膜圖案形成步驟後，於透明基板2之主表面上以覆蓋該遮光膜圖案之方式形成相偏移膜3；及相偏移膜圖案形成步驟，其係於該相偏移膜形成步驟後，利用濕蝕刻使該相偏移膜3圖案化而形成相偏移膜圖案3'。 實施形態3. 於實施形態3中，說明使用實施形態2之相偏移光罩之顯示裝置之製造方法。 於實施形態3之顯示裝置之製造方法中，首先對於基板上形成有抗蝕劑膜之附抗蝕劑膜基板，進行將藉由實施形態2中說明之顯示裝置製造用之相偏移光罩之製造方法所獲得之相偏移光罩30或實施形態2中說明之顯示裝置製造用之相偏移光罩30與抗蝕劑膜對向配置之相偏移光罩配置步驟。 其次，進行對相偏移光罩30照射曝光光，而曝光抗蝕劑膜之抗蝕劑膜曝光步驟。 曝光光係例如包含300 nm以上700 nm以下之波長範圍之光之複合光。具體而言，為包含i線、h線及g線之複合光。使用於曝光光之複合光中i線、h線及g線之強度比係可根據顯示裝置之製造，將i線：h線：g線之強度比例適當變更為1：1：1或2：1：1等。 根據本實施形態3之顯示裝置之製造方法，藉由實施形態2中說明之顯示裝置製造用之相偏移光罩之製造方法所獲得之相偏移光罩30、或實施形態2中說明之顯示裝置製造用之相偏移光罩30製造顯示裝置。因此，可製造具有細微之線隙圖案或接觸孔之顯示裝置。 [實施例] 以下，基於實施例更具體地說明本發明。 另，下文中將合成石英玻璃基板簡稱為QZ。又，在表述為QZ/A/B/C時，表示於QZ上使A層、B層、C層以該順序成膜之構成。 實施例1. 於實施例1中，說明QZ/CrON/MoSiN構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 為製造上述構成之相偏移光罩基底1，首先，作為透明基板2，準備3345尺寸(330 mm×450 mm×5 mm)之合成石英玻璃基板。 其後，將透明基板2導入於配置有包含鉻之濺鍍靶材、與包含矽化鉬(Mo：Si=1：4)之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含鉻之氮氧化物(CrON)之鉻系材料層(膜厚：10 nm)，並於鉻系材料層上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：120 nm)，獲得形成有相偏移膜3(合計膜厚：130 nm)之相偏移光罩基底1。 另，鉻系材料層係於鉻靶材附近，導入包含氬氣(Ar)與一氧化氮(NO)氣體之混合氣體(Ar：30 sccm，NO：30 sccm)，以濺鍍功率4.0 kW、透明基板2之搬送速度400 mm/分，藉由反應性濺鍍而成膜於透明基板2之主表面上。 又，金屬矽化物系材料層係於矽化鉬靶材附近，導入氬氣(Ar)與氮氣(N2 )之混合氣體(Ar：30 sccm，N2 ：70 sccm)，以濺鍍功率8.0 kW、透明基板2之搬送速度400 mm/分，藉由反應性濺鍍而成膜於鉻系材料層上。另，金屬矽化物系材料層係為了獲得期望之膜厚120 nm而以同條件複數次積層。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由日本日立高新技術公司製造之分光光度計U-4100測定透射率，且藉由日本lasertec公司製造之MPM-100測定相差。於以下之實施例、比較例中，透射率或相差之測定時，分別使用相同裝置。另，以下之實施例、比較例之透射率值係任一者皆為Air基準之值。 相偏移膜3之透射率、相差之測定時，於固著於同一基板支架(未圖示)之6025尺寸(152 mm×152 mm)之透明基板2之主表面上，使用成膜有由包含鉻之氮氧化物(CrON)之鉻系材料層與包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層構成之積層構造之相偏移膜3(合計膜厚130 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖4所示，波長200 nm~800 nm之實施例1之透射率光譜係與下述比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例1之具體透射率之測定結果。波長365 nm之透射率(以下有時稱為T%(365))為4.41%，ΔT%(436-365)為3.91%。因此，可知實施例1之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為13.35%。因此，可知實施例1之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。波長365 nm中被賦予之相差(以下有時稱為P(365))為181.7度，ΔP(365-436)為28.7度。因此，可知實施例1之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由日本日立高新技術公司製造之分光光度計U-4100測定反射率。於以下之實施例、比較例及參考例中，反射率之測定時使用相同裝置。 其結果，如圖6所示，波長200 nm~800 nm之實施例1之反射率光譜係與下述之比較例1及2相比，具有反射率變化較小之特性。圖8中顯示實施例1之具體反射率之測定結果。波長365 nm以上700 nm以下之範圍之反射率(以下有時稱為R%(700-365))為17.9%以上22.4%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為4.5%。因此，可知實施例1之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之反射率之波長依存性受抑制之光學特性。 B.相偏移光罩及其製造方法 為了使用以上述方式製造之相偏移光罩基底1製造相偏移光罩30，首先於相偏移光罩基底1之相偏移膜3上，使用抗蝕劑塗佈裝置塗佈抗蝕劑材料。 其後，經過加熱、冷卻步驟，形成膜厚1000 nm之抗蝕劑膜5。 其後，使用雷射描繪裝置描繪抗蝕劑膜5，且經過顯影、洗淨步驟，於相偏移膜3上，形成具有2.5 μm見方之接觸孔圖案(未圖示)之抗蝕劑圖案5'。 其後，將抗蝕劑圖案5'設為遮罩，藉由以去離子水稀釋氟化氫銨與過氧化氫之混合溶液之矽化鉬蝕刻液，對相偏移膜3之包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層進行濕蝕刻。 其後，將抗蝕劑圖案5'設為遮罩，藉由包含硝酸鈰銨與過氧二硫酸銨之鉻蝕刻液，對相偏移膜3之包含鉻之氮氧化物(CrON)之鉻系材料層進行濕蝕刻，形成相偏移膜圖案3'。 其後，剝離抗蝕劑圖案5'。 如此，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 對具有上述相偏移膜圖案之相偏移光罩之相偏移效果，進行模擬。模擬係開口數(NA)=0.1，相干係數(σ)=0.5，作為曝光光，採用包含i線(365 nm)、h線(405 nm)及g線(436 nm)，且具有i線：h線：g線=2：1：1之光強度比之複合光。 圖9中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之結果(光強度分佈)。 圖9之橫軸係轉印至被轉印體上之抗蝕劑膜之接觸孔圖案距離接觸孔中心之位置(μm)，縱軸係強度比(將自相偏移光罩透射之最大光量設為1時之強度比)。圖9之光強度分佈曲線係於接觸孔中心時透射光之光強度達到峰值，隨著自其中心遠離，透射光之光強度逐漸降低。於圖9之光強度分佈曲線中，距離顯示峰值強度之接觸孔中心±1 μm之位置，係相當於形成於被轉印體上之抗蝕劑膜之2.0 μm見方之接觸孔圖案之邊界部分(接觸孔圖案之直線部分)。該圖案邊界部分之光強度傾斜可根據圖案邊界部分附近之光強度之差獲得。 如圖9所示，實施例1之光強度分佈曲線顯示與下述比較例相比，於接觸孔中心具有較尖之峰值強度，於圖案邊界部分，光強度變化較大，於圖案邊界部分之外側周邊區域，光強度變化較小。 圖案邊界部分之光強度傾斜(解析度)為0.446。因此，可知於實施例1之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 實施例2. 於實施例2中，說明QZ/CrN/MoSiN構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含鉻之濺鍍靶材、與包含矽化鉬(Mo：Si=1：4)之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含鉻之氮化物(CrN)之鉻系材料層(膜厚：10 nm)，並於鉻系材料層上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：120 nm)，獲得形成有相偏移膜3(合計膜厚：130 nm)之相偏移光罩基底1。 另，鉻系材料層係於鉻靶材附近，導入包含氬氣(Ar)與氮氣(N2 )之混合氣體(Ar：30 sccm，N2 ：70 sccm)，以濺鍍功率4.0 kW、透明基板2之搬送速度400 mm/分，藉由反應性濺鍍而成膜於透明基板2之主表面上。 又，金屬矽化物系材料層係以與實施例1相同之條件(為了獲得期望之膜厚120 nm而以同條件複數次積層)成膜。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/CrN/MoSiN構成之相偏移膜3(合計膜厚130 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖4所示，波長200 nm~800 nm之實施例2之透射率光譜係與下述之比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例2之具體透射率之測定結果。T%(365)為3.34%，ΔT%(436-365)為3.28%。因此，可知實施例2之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為12.68%。因此，可知實施例2之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。P(365)為182.7度，ΔP(365-436)為27.7度。因此，可知實施例2之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，如圖6所示，波長200 nm~800 nm之實施例2之反射率光譜係與下述之比較例1及2相比，具有反射率變化較小之特性。圖8中顯示實施例2之具體反射率之測定結果。R%(700-365)為16.6%以上24.8%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為8.2%。因此，可知實施例2之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之反射率之波長依存性受抑制之光學特性。 B.相偏移光罩及其製造方法 藉由與實施例1相同之方法，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 圖10中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖10所示，實施例2之光強度分佈曲線顯示與下述比較例相比，於接觸孔中心具有較尖之峰值強度，於圖案邊界部分，光強度變化較大，於圖案邊界部分之外側周邊區域，光強度變化較小。 圖案邊界部分之光強度傾斜為0.447。因此，可知於實施例2之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 實施例3. 於實施例3中，說明QZ/CrON/MoSiN/CrON構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含鉻之濺鍍靶材、與包含矽化鉬(Mo：Si=1：4)之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含鉻之氮氧化物(CrON)之鉻系材料層(膜厚：5 nm)，於鉻系材料層上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：120 nm)，於金屬矽化物系材料層上成膜包含鉻之氮氧化物(CrON)之鉻系材料層(膜厚：5 nm)，獲得形成有相偏移膜3(合計膜厚：130 nm)之相偏移光罩基底1。 另，鉻系材料層係除了將透明基板2之搬送速度設為800 mm/分以外，以與實施例1相同之條件成膜。又，金屬矽化物系材料層亦以與實施例1相同之條件(為獲得期望之膜厚120 nm而以相同條件複數次積層)成膜。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/CrON/MoSiN/CrON構成之相偏移膜3(合計膜厚130 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖5所示，波長200 nm~800 nm之實施例3之透射率光譜係與下述之比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例3之具體透射率之測定結果。T%(365)為4.03%，ΔT%(436-365)為3.32%。因此，可知實施例3之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖7所示，ΔT%(700-365)為12.49%。因此，可知實施例3之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖7中顯示相差之測定結果。P(365)為181.0度，ΔP(365-436)為28.3度。因此，可知實施例3之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，如圖7所示，波長200 nm~800 nm之實施例3之反射率光譜係與下述比較例1及2相比，具有反射率變化較小之特性。圖8中顯示實施例3之具體反射率之測定結果。R%(700-365)為26.4%以上30.0%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為3.5%。因此，可知實施例3之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之反射率之波長依存性受抑制之光學特性。 B.相偏移光罩及其製造方法 為了藉由與實施例1相同之方法，使用以上述方式製造之相偏移光罩基底1製造相偏移光罩30，首先，於相偏移光罩基底1之相偏移膜3上，形成具有2.5 μm見方之接觸孔圖案之抗蝕劑圖案5'。 其後，將抗蝕劑圖案5'設為遮罩，藉由包含硝酸鈰銨與過氧二硫酸銨之鉻蝕刻液，對相偏移膜3之第二層之包含鉻之氮氧化物(CrON)之鉻系材料層進行濕蝕刻。 其後，將抗蝕劑圖案5'設為遮罩，藉由以去離子水稀釋氟化氫銨與過氧化氫之混合溶液之矽化鉬蝕刻液，對相偏移膜3之包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層進行濕蝕刻。 其後，將抗蝕劑圖案5'設為遮罩，藉由包含硝酸鈰銨與過氧二硫酸銨之鉻蝕刻液，對相偏移膜3之第一層之包含鉻之氮氧化物(CrON)之鉻系材料層進行濕蝕刻，形成相偏移膜圖案3'。 其後，剝離抗蝕劑圖案5'。 如此，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 圖9中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖9所示，實施例3之光強度分佈曲線顯示與下述比較例相比，於接觸孔中心具有較尖之峰值強度，於圖案邊界部分，光強度變化較大，於圖案邊界部分之外側周邊區域，光強度變化較小。 圖案邊界部分之光強度傾斜為0.447。因此，可知於實施例3之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 實施例4. 於實施例4中，說明QZ/CrN/MoSiN/CrN構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含鉻之濺鍍靶材、與包含矽化鉬(Mo：Si=1：4)之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含鉻之氮化物(CrN)之鉻系材料層(膜厚：5 nm)，於鉻系材料層上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：120 nm)，於金屬矽化物系材料層上成膜包含鉻之氮化物(CrN)之鉻系材料層(膜厚：5 nm)，獲得形成有相偏移膜3(合計膜厚：130 nm)之相偏移光罩基底1。 另，鉻系材料層係除了將透明基板2之搬送速度設為800 mm/分以外，以與實施例1相同之條件成膜。又，金屬矽化物系材料層亦以與實施例1相同之條件(為獲得期望之膜厚120 nm而以相同條件複數次積層)成膜。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/CrN/MoSiN/CrN構成之相偏移膜3(合計膜厚130 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖5所示，波長200 nm~800 nm之實施例4之透射率光譜係與下述比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例4之具體透射率之測定結果。T%(365)為3.82%，ΔT%(436-365)為3.33%。因此，可知實施例4之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為14.64%。因此，可知實施例4之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖7中顯示相差之測定結果。P(365)為180.2度，ΔP(365-436)為26.8度。因此，可知實施例4之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，如圖7所示，波長200 nm~800 nm之實施例4之反射率光譜係與下述比較例1及2相比，具有反射率變化較小之特性。圖8中顯示實施例4之具體反射率之測定結果。R%(700-365)為22.4%以上27.5%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為5.0%。因此，可知實施例4之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之反射率之波長依存性受抑制之光學特性。 B.相偏移光罩及其製造方法 藉由與實施例3相同之方法，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。圖10中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖10所示，實施例4之光強度分佈曲線顯示與下述比較例相比，於接觸孔中心具有較尖之峰值強度，於圖案邊界部分，光強度變化較大，於圖案邊界部分之外側周邊區域，光強度變化較小。 圖案邊界部分之光強度傾斜為0.447。因此，可知於實施例4之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 實施例5. 於實施例5中，說明QZ/MoSiN/CrN構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含矽化鉬(Mo：Si=1：4)之濺鍍靶材、與包含鉻之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：120 nm)，於金屬矽化物系材料層上成膜包含鉻之氮化物(CrN)之鉻系材料層(膜厚：10 nm)，獲得形成有相偏移膜3(合計膜厚：130 nm)之相偏移光罩基底1。 另，金屬矽化物系材料層係於矽化鉬靶材附近，導入氬氣(Ar)與氮氣(N2 )之混合氣體(Ar：30 sccm，N2 ：70 sccm)，以濺鍍功率8.0 kW、透明基板2之搬送速度400 mm/分，藉由反應性濺鍍而成膜於透明基板2之主表面上。為獲得期望之膜厚120 nm而以相同條件複數次積層。 又，鉻系材料層係於鉻靶材附近，導入包含氬氣(Ar)與氮氣(N2 )之混合氣體(Ar：30 sccm，N2 ：70 sccm)，以濺鍍功率4.0 kW、透明基板2之搬送速度800 mm/分，藉由反應性濺鍍而成膜於金屬矽化物系材料層上。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/MoSiN/CrN構成之相偏移膜3(合計膜厚130 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖4所示，波長200 nm~800 nm之實施例5之透射率光譜係與下述比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例5之具體透射率之測定結果。T%(365)為3.16%，ΔT%(436-365)為2.88%。因此，可知實施例5之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為12.21%。因此，可知實施例5之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。P(365)為178.4度，ΔP(365-436)為26.6度。因此，可知實施例5之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，如圖6所示，波長200 nm~800 nm之實施例5之反射率光譜係與下述比較例1及2相比，具有反射率變化較小之特性。圖8中顯示實施例5之具體反射率之測定結果。R%(700-365)為33.6%以上44.6%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為11.0%。因此，可知實施例5之相偏移膜3與下述之比較例1及2相比，顯示波長365 nm以上700 nm以下之範圍之反射率之波長依存性受抑制之光學特性。 B.相偏移光罩及其製造方法 藉由與實施例5相同之方法，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 圖10中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖10所示，實施例5之光強度分佈曲線顯示與下述比較例相比，於接觸孔中心具有較尖之峰值強度，於圖案邊界部分，光強度變化較大，於圖案邊界部分之外側周邊區域，光強度變化較小。 圖案邊界部分之光強度傾斜為0.448。因此，可知於實施例5之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 實施例6. 於實施例6中，說明QZ/MoSiN/CrON構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含矽化鉬(Mo：Si=1：4)之濺鍍靶材、與包含鉻之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：120 nm)，於金屬矽化物系材料層上成膜包含鉻之氮氧化物(CrON)之鉻系材料層(膜厚：10 nm)，獲得形成有相偏移膜3(合計膜厚：130 nm)之相偏移光罩基底1。 另，金屬矽化物系材料層係以與實施例5相同之條件成膜。 又，鉻系材料層係於鉻靶材附近，導入包含氬氣(Ar)與一氧化氮(NO)之混合氣體(Ar：30 sccm，NO：30 sccm)，以濺鍍功率4.0 kW、透明基板2之搬送速度800 mm/分，藉由反應性濺鍍而成膜於金屬矽化物系材料層上。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/MoSiN/CrON構成之相偏移膜3(合計膜厚130 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖4所示，波長200 nm~800 nm之實施例6之透射率光譜係與下述比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例6之具體透射率之測定結果。T%(365)為4.21%，ΔT%(436-365)為3.5%。因此，可知實施例6之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為12.88%。因此，可知實施例6之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。P(365)為178.8度，ΔP(365-436)為28度。因此，可知實施例6之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，如圖6所示，波長200 nm~800 nm之實施例6之反射率光譜係與下述比較例1及2相比，具有反射率變化較小之特性。圖8中顯示實施例6之具體反射率之測定結果。R%(700-365)為30.7%以上39.4%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為8.7%。因此，可知實施例6之相偏移膜3與下述之比較例1及2相比，顯示波長365 nm以上700 nm以下之範圍之反射率之波長依存性受抑制之光學特性。 B.相偏移光罩及其製造方法 為了使用以上述方式製造之相偏移光罩基底1製造相偏移光罩30，首先，於相偏移光罩基底1之相偏移膜3上，使用抗蝕劑塗佈裝置塗佈抗蝕劑材料。 其後，經過加熱、冷卻步驟，形成膜厚1000 nm之抗蝕劑膜5。 其後，使用雷射描繪裝置描繪抗蝕劑膜5，且經過顯影、洗淨步驟，於相偏移膜3上形成具有2.5 μm見方之接觸孔圖案(未圖示)之抗蝕劑圖案5'。 其後，將抗蝕劑圖案5'設為遮罩，藉由包含硝酸鈰銨與過氧二硫酸銨之鉻蝕刻液，對相偏移膜3之包含鉻之氮氧化物(CrON)之鉻系材料層進行濕蝕刻。 其後，將抗蝕劑圖案5'設為遮罩，藉由以去離子水稀釋氟化氫銨與過氧化氫之混合溶液之矽化鉬蝕刻液，對相偏移膜3之包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層進行濕蝕刻，而形成相偏移膜圖案3'。 其後，剝離抗蝕劑圖案5'。 如此，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 其結果，圖案邊界部分之光強度傾斜係與實施例5同等。因此，可知於實施例6之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 實施例7. 於實施例7中，說明QZ/MoSiN/CrON/MoSiN構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含矽化鉬(Mo：Si=1：4)之濺鍍靶材、與包含鉻之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：60 nm)，於金屬矽化物系材料層上成膜包含鉻之氮氧化物(CrON)之鉻系材料層(膜厚：10 nm)，於鉻系材料層上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：60 nm)，獲得形成有相偏移膜3(合計膜厚：130 nm)之相偏移光罩基底1。 另，金屬矽化物系材料層係除了將透明基板2之搬送速度設為约800 mm/分以外，以與實施例6相同之條件成膜。又，铬系材料層亦以與實施例6相同之條件成膜。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/MoSiN/CrON/MoSiN構成之相偏移膜3(合計膜厚130 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖5所示，波長200 nm~800 nm之實施例7之透射率光譜係與下述比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例7之具體透射率之測定結果。T%(365)為4.49%，ΔT%(436-365)為3.92%。因此，可知實施例7之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為23.78%。因此，可知實施例7之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。P(365)為178.8度，ΔP(365-436)為24度。因此，可知實施例7之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 圖7中顯示其結果。又，圖8中顯示實施例7之具體反射率之測定結果。R%(700-365)為5.4%以上24.4%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為19.0%。 B.相偏移光罩及其製造方法 為了藉由與實施例1相同之方法，使用以上述方式製造之相偏移光罩基底1製造相偏移光罩30，首先，於相偏移光罩基底1之相偏移膜3上，形成具有2.5 μm見方之接觸孔圖案之抗蝕劑圖案5'。 其後，將抗蝕劑圖案5'設為遮罩，藉由以去離子水稀釋氟化氫銨與過氧化氫之混合溶液之矽化鉬蝕刻液，對相偏移膜3之包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層進行濕蝕刻。 其後，將抗蝕劑圖案5'設為遮罩，藉由包含硝酸鈰銨與過氧二硫酸銨之鉻蝕刻液，對相偏移膜3之第一層之包含鉻之氮氧化物(CrON)之鉻系材料層進行濕蝕刻。 其後，將抗蝕劑圖案5'設為遮罩，藉由以去離子水稀釋氟化氫銨與過氧化氫之混合溶液之矽化鉬蝕刻液，對相偏移膜3之包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層進行濕蝕刻，而形成相偏移膜圖案3'。 其後，剝離抗蝕劑圖案5'。 如此，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 圖9中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖9所示，實施例7之光強度分佈曲線顯示與下述比較例相比，於接觸孔中心具有較尖之峰值強度，於圖案邊界部分，光強度變化較大，於圖案邊界部分之外側周邊區域，光強度變化較小。 圖案邊界部分之光強度傾斜為0.446。因此，可知於實施例7之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 實施例8. 於實施例8中，說明QZ/MoSiN/CrN/MoSiN構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含矽化鉬(Mo：Si=1：4)之濺鍍靶材、與包含鉻之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：59 nm)，於金屬矽化物系材料層上成膜包含鉻之氮化物(CrN)之鉻系材料層(膜厚：10 nm)，於鉻系材料層上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：59 nm)，獲得形成有相偏移膜3(合計膜厚：128 nm)之相偏移光罩基底1。 另，金屬矽化物層係除了將透明基板2之搬送速度設為約800 mm/分以外，以與實施例5相同之條件成膜。又，鉻系材料層亦以與實施例5相同之條件成膜。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/MoSiN/CrN/MoSiN構成之相偏移膜3(合計膜厚128 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖5所示，波長200 nm~800 nm之實施例8之透射率光譜係與下述比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例8之具體透射率之測定結果。T%(365)為3.55%，ΔT%(436-365)為3.65%。因此，可知實施例8之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為23.62%。因此，可知實施例8之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。P(365)為178.3度，ΔP(365-436)為22度。因此，可知實施例8之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，顯示於圖7。又，圖8中顯示實施例8之具體反射率之測定結果。R%(700-365)為5.1%以上24.8%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為19.7%。 B.相偏移光罩及其製造方法 藉由與實施例7相同之方法，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 圖10中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖10所示，實施例8之光強度分佈曲線顯示與下述比較例相比，於接觸孔中心具有較尖之峰值強度，於圖案邊界部分，光強度變化較大，於圖案邊界部分之外側周邊區域，光強度變化較小。 圖案邊界部分之光強度傾斜為0.447。因此，可知於實施例8之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 實施例9. 於實施例9中，說明QZ/MoSiN構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含矽化鉬(Mo：Si=1：4)之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含矽化鉬氮化物(MoSiN)之金屬矽化物系材料層(膜厚：120 nm)，獲得相偏移光罩基底1。 另，金屬矽化物系材料層係於矽化鉬靶材附近，導入氬氣(Ar)與氮氣(N2 )之混合氣體(Ar：30 sccm，N2 ：70 sccm)，以濺鍍功率8.0 kW、透明基板2之搬送速度400 mm/分，藉由反應性濺鍍而成膜於透明基板2上。為獲得期望之膜厚120 nm而以相同條件複數次積層。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/MoSiN構成之相偏移膜3(膜厚110 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖4所示，波長200 nm~800 nm之實施例9之透射率光譜係與下述比較例1及2相比，具有透射率變化較小之特性。圖8中顯示實施例9之具體透射率之測定結果。T%(365)為4.36%，ΔT%(436-365)為3.97%。因此，可知實施例9之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為21.60%。因此，可知實施例9之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。P(365)為180.00度，ΔP(365-436)為24.00度。因此，可知實施例9之相偏移膜3顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，如圖6所示，波長200 nm~800 nm之實施例9之反射率光譜係與下述比較例1及2相比，具有反射率變化較小之特性。圖8中顯示實施例9之具體反射率之測定結果。R%(700-365)為18.0%以上28.3%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為10.4%。因此，可知實施例9之相偏移膜3顯示波長365 nm以上700 nm以下之範圍之反射率之波長依存性受抑制之光學特性。 B.相偏移光罩及其製造方法 藉由與實施例1相同之方法，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 圖9中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖9所示，實施例9之光強度分佈曲線顯示與下述比較例相比，於接觸孔中心具有較尖之峰值強度，於圖案邊界部分，光強度變化較大，於圖案邊界部分之外側周邊區域，光強度變化較小。 圖案邊界部分之光強度傾斜為0.444。因此，可知於實施例9之相偏移光罩中，與下述之比較例相比，顯示較強之光強度傾斜，使解析度提高。 比較例1. 於比較例1中，說明CrON構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含鉻之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含鉻之氮氧化物(CrON)之鉻系材料層(膜厚：157 nm)，獲得相偏移光罩基底1。 另，鉻系材料層係於鉻靶材附近，導入包含氬氣(Ar)與一氧化氮(NO)之混合氣體(Ar：46 sccm，NO：70 sccm)，以濺鍍功率8.0 kW、透明基板2之搬送速度約400 mm/分，藉由反應性濺鍍而成膜於透明基板2上。為獲得期望之膜厚157 nm而以相同條件複數次積層。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/CrON構成之相偏移膜3(膜厚157 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖4及圖5所示，波長200 nm~800 nm之比較例1之透射率光譜係顯示透射率變化自超過波長300 nm之附近急劇變大，且自超過波長700 nm之附近透射率變化變小之大致S型曲線。圖8中顯示比較例1之具體透射率之測定結果。T%(365)為7.73%，ΔT%(436-365)為9.82%。因此，可知比較例1之相偏移膜3與上述實施例相比，不能說顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為48.00%。因此，可知比較例1之相偏移膜3與上述實施例相比，不能說顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。P(365)為181.3度，ΔP(365-436)為32.5度。因此，可知比較例1之相偏移膜3與上述實施例相比，不能說顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，如圖6及圖7、以及圖8之具體反射率之測定結果所示，R%(700-365)為7.60%以上18.45%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為10.8%，與上述之實施例6無大差別，故良好。 B.相偏移光罩及其製造方法 藉由與實施例1相同之方法，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 圖10中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖10所示，比較例1之光強度分佈曲線顯示與上述實施例相比，接觸孔中心之光強度之峰值不那麼尖，於圖案邊界部分中，光強度變化不那麼大，而於圖案邊界部分之外側之周邊區域中，光強度變化較大。 圖案邊界部分之光強度傾斜為0.432。因此，可知於比較例1之相偏移光罩中，與上述之實施例相比，顯示較弱之光強度傾斜。 比較例2. 於比較例2中，說明CrOCN構成之相偏移光罩基底。 A.相偏移光罩基底及其製造方法 作為透明基板2，準備與實施例1相同尺寸之透明基板2。 其後，將透明基板2導入於配置有包含鉻之濺鍍靶材之串聯型濺鍍裝置(未圖示)，且於透明基板2之主表面上成膜包含鉻之碳氮氧化物(CrOCN)之鉻系材料層(膜厚117 nm)，獲得相偏移光罩基底1。 另，鉻系材料層係於鉻靶材附近，導入包含氬氣(Ar)、二氧化碳(CO2 )、與氮氣(N2 )之混合氣體(Ar：46 sccm，CO2 ：35 sccm，N2 ：46 sccm)，以濺鍍功率8.0 kW、透明基板2之搬送速度約400 mm/分，藉由反應性濺鍍而成膜於透明基板2上。為獲得期望之膜厚117 nm而以相同條件複數次積層。 如此，獲得於透明基板2上形成有相偏移膜3之相偏移光罩基底1。 對於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定透射率及相差。 於透射率、相差之測定時使用成膜有QZ/CrOCN構成之相偏移膜3(膜厚117 nm)之附相偏移膜基板(虛設基板)。 其結果，如圖4及圖5所示，波長200 nm~800 nm之比較例2之透射率光譜係顯示透射率變化自超過波長300 nm之附近急劇變大，且自超過波長600 nm之附近透射率變化變小之大致S型曲線。圖8中顯示比較例2之具體透射率之測定結果。T%(365)為5.10%，ΔT%(436-365)為7.58%。因此，可知比較例2之相偏移膜3與上述實施例相比，不能說顯示波長365 nm以上436 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 又，如圖8所示，ΔT%(700-365)為50.63%。因此，可知比較例2之相偏移膜3與上述實施例相比，不能說顯示波長365 nm以上700 nm以下之範圍之透射率之波長依存性受抑制之光學特性。 圖8中顯示相差之測定結果。P(365)為182.1度，ΔP(365-436)為31.0度。因此，可知比較例2之相偏移膜3與上述實施例相比，不能說顯示波長365 nm以上436 nm以下之範圍之相差之波長依存性受抑制之光學特性。 又，關於所獲得之相偏移光罩基底1之相偏移膜3，藉由與實施例1相同之方法測定反射率。 其結果，如圖6及圖7、以及圖8之具體反射率之測定結果所示，R%(700-365)為11.4%以上28.7%以下，700 nm至365 nm之範圍之值域(最大值與最小值之差)為17.3%，與上述之實施例5無大差別，故良好。 B.相偏移光罩及其製造方法 藉由與實施例1相同之方法，獲得於透明基板2上形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案3'之相偏移光罩30。 藉由與實施例1相同之方法，對相偏移光罩30之相偏移效果進行模擬。 圖9中顯示對通過形成有具有2.5 μm見方之接觸孔圖案之相偏移膜圖案之相偏移光罩的光之空間圖像進行模擬之光強度分佈曲線。 如圖9所示，比較例2之光強度分佈曲線顯示與上述實施例相比，接觸孔中心之光強度之峰值不那麼尖，於圖案邊界部分中，光強度變化不那麼大，而於圖案邊界部分之外側之周邊區域中，光強度變化較大。 圖案邊界部分之光強度傾斜為0.440。因此，可知於比較例2之相偏移光罩中，與上述之實施例相比，顯示較弱之光強度傾斜。 另，於上述實施例中，作為構成相偏移膜3之金屬矽化物系材料層之材料，說明了矽化鉬氮化物(MoSiN)之例，但並未限定於此等。作為金屬矽化物系材料層之材料，亦可為矽化鉬氧化物(MoSiO)、矽化鉬碳氮化物(MoSiCN)、矽化鉬碳氧化物(MoSiOC)。又，於矽化鉬以外之金屬矽化物系材料之情形時，亦可獲得與上述同等之效果。 又，於上述之實施例中，作為構成相偏移膜3之鉻系材料層之材料，已說明鉻之氮化物(CrN)、鉻之氮氧化物(CrON)之例，但並未限定於此等。作為鉻系材料層之材料，亦可為鉻之氧化物(CrO)、鉻之碳化物(CrC)、鉻之碳氮化物(CrCN)、鉻之碳氧化物(CrCO)、鉻之碳氮氧化物(CrOCN)。 又，上述之實施例中，已說明於透明基板2上僅形成有相偏移膜3之相偏移光罩基底1、及於透明基板2上僅形成有相偏移膜圖案3'之相偏移光罩30之例，但並未限定於此等。亦可為於透明基板2上具有相偏移膜3與遮光膜4之相偏移光罩基底，又，為於透明基板2上具有相偏移膜圖案3'與遮光膜圖案4'之相偏移光罩，亦可發揮與上述實施例相同之效果。 又，在上述說明之透明基板2上具有相偏移膜3、遮光膜4之相偏移光罩基底中，作為形成於相偏移膜3上之遮光膜，亦可採用遮光層、遮光層及防反射層之積層構造、以及絕緣層、遮光層及防反射層之積層構造。 又，於上述之實施例中，說明了藉由濕蝕刻製作相偏移光罩30之製造方法，但並未限定於此。作為構成相偏移光罩基底1之材料，於金屬矽化物系材料層之情形時，亦可藉由使用氟系氣體(例如，CF4 氣體、CHF3 氣體、SF6 氣體、或於該等氣體中混合有O2 氣體者)之乾蝕刻進行圖案化，又，於鉻系材料層之情形時，可藉由利用氯系氣體(例如，Cl2 氣體與O2 氣體之混合氣體)之乾蝕刻進行圖案化。Hereinafter, a phase shift mask base for manufacturing a display device according to an embodiment of the present invention, a phase shift mask for manufacturing a display device using the phase shift mask base, a method for manufacturing the same, and a method for manufacturing the same, and a method for using the same A method of manufacturing a display device for an offset mask. Embodiment 1. In Embodiment 1, a phase shift mask base for manufacturing a display device and a method of manufacturing the same will be described. First, a phase shift mask substrate for manufacturing a display device according to the first embodiment will be described. Fig. 1 is a cross-sectional view showing the structure of a phase shift mask base for manufacturing a display device according to a first embodiment of the present invention. The phase shift mask substrate 1 of the first embodiment includes a transparent substrate 2 and a phase shift film 3 formed on the transparent substrate 2. Alternatively, a configuration in which the light shielding film 4 is formed on the phase shift film 3 may be employed. Further, a configuration in which the resist film 5 is formed on the phase shift film 3 or the light shielding film 4 can be employed. The transparent substrate 2 is translucent to the exposure light used. The material of the transparent substrate 2 is not particularly limited as long as it is a material that transmits light to the exposure light used. As a material having light transmissivity, synthetic quartz glass, soda lime glass, and alkali-free glass are exemplified. The phase shift film 3 is a single layer film or laminated film having at least one layer of a metal halide material layer containing a metal and an element of either of cerium, nitrogen and/or oxygen. The optical property of the phase shift film 3 as a whole is a material layer determined by the kind or film thickness of the material constituting the material layer of the phase shift film 3 when the phase shift film 3 includes a single layer film. The optical characteristics of the refractive index, the transmittance, the reflectance, and the like, for example, when the phase shift film 3 includes a laminated film, the type of material depending on the plurality of material layers constituting the phase shift film 3 or The combination of the optical characteristics determined by the film thickness and the like, and the order of the layers of the respective material layers and the number of layers are determined. Here, in the case where the phase shift film 3 includes a single layer film, the single layer film is a film formed of a single material. Therefore, a film comprising a laminate structure of a single material is also a single layer film. Further, when the phase shift film 3 includes a laminated film, the laminated film is a film formed by a combination of a film formed of a single material or the same material and a film formed of a material different from the film. The phase shifting film 3 controls the transmittance of light of a specific wavelength within a range as described below by selecting a material layer constituting the phase shift film 3, and the transmittance of light of a specific wavelength and The phase difference is controlled within the range as described below, and the amount of change in the transmittance, the phase difference, and the reflectance of the light in the specific wavelength range is suppressed within the range as described below. Specifically, the phase shift film 3 has a transmittance of 365 nm (hereinafter, sometimes referred to as T% (365)) in a range of 3.5% or more and 8% or less. Therefore, the light intensity of the boundary portion of the pattern becomes strong, and the resolution can be improved. When T% (365) is less than 3.5%, it is difficult to obtain the amount of transmitted light necessary to sufficiently exhibit the desired phase shift effect. Further, when T% (365) exceeds 8%, the light intensity at the boundary portion of the pattern is weakened, and it is difficult to achieve an improvement in resolution. Further, the phase shift film 3 has a transmittance (in some cases, ΔT% (436-365)) depending on the wavelength in the range of 365 nm or more and 436 nm or less, which is within 5.5%. Since the wavelength dependence of the transmittance in the wavelength range is suppressed, the light intensity at the boundary portion of the pattern becomes strong, and the resolution can be improved. If ΔT% (436-365) exceeds 5.5%, it is affected by the transmitted light of the h-line (405 nm) and the g-line (436 nm) having peak intensity other than the i-line (365 nm). The intensity tilt becomes weak, and it is difficult to achieve an improvement in resolution. Further, the phase shift film 3 is preferable because the reflectance is particularly improved when the transmittance of the g line (436 nm) is less than 10%. Further, the phase shift film 3 has a phase difference of 365 nm (hereinafter, sometimes referred to as P(365)) in a range of 160 degrees or more and 200 degrees or less. Therefore, a phase difference of approximately 180 degrees can be obtained, and the phase shift effect can be sufficiently exerted. When P (365) is less than 160 degrees or exceeds 200 degrees, a phase difference of approximately 180 degrees is not obtained, and it is difficult to exert a phase shift effect. Further, the phase shift film 3 preferably has a transmittance (in some cases, ΔT% (700-365)) depending on the wavelength in the range of 365 nm or more and 700 nm or less, which is within 20%. In this case, since the phase shift film 3 can suppress the wavelength dependency of the transmittance even in the wavelength range, it is easy to recognize the alignment mark provided in the mask in the exposure machine at the time of manufacture of the display device. Thereby the alignment accuracy is improved. Further, in the mask inspection apparatus, when the inspection apparatus of the mask pattern is recognized by the difference in transmittance between the transparent substrate and the mask pattern, it is preferable to easily recognize defects such as shape defects of the mask pattern. . Further, the difference (ΔP (365-436)) between the phase difference imparted by the phase shift film 3 at a wavelength of 365 nm and the wavelength given at 436 nm is 30 degrees or less. Since the wavelength dependence of the phase difference in the wavelength range is suppressed, the phase shift effect can be sufficiently exerted, and the light intensity at the boundary portion of the pattern can be made steeper, and the resolution can be improved. Further, the phase shift film 3 preferably has a reflectance (hereinafter, referred to as R% (700-365)) in a range of 365 nm or more and 700 nm or less of 5% or more and 45% or less. Further, the phase shift film 3 preferably has a reflectance (R% (700-365)) in a range of 365 nm or more and 700 nm or less of 5% or more and 45% or less, and a wavelength range of 365 nm or more and 700 nm or less. The internal reflectance depends on the amount of change in wavelength (hereinafter, sometimes referred to as ΔR% (700-365)) within 5%. In this case, the phase shift film 3 is formed by forming a resist film on the phase shift film 3, and when patterning is performed by a laser scanner or the like, it is less likely to be caused by the light used for drawing and the reflected light. The effect of the standing wave generated. Therefore, at the time of pattern drawing, the roughness of the edge portion of the resist pattern cross section on the phase shift film 3 can be suppressed, and the pattern accuracy can be improved. Moreover, since it is easy to obtain the alignment at the time of pattern drawing, it is easy to measure the mask pattern by the long-size (MMS) measurement, and the mask pattern can be recognized with high precision. Further, in the case of pattern transfer using a phase shift mask and manufacturing of a display device, when the alignment mark is detected by the difference in reflectance between the transparent substrate and the alignment mark, it is easy to recognize the mask alignment, thereby aligning Increased accuracy. Further, when a display device is manufactured by pattern transfer using a phase shift mask, since the influence of the glare phenomenon can be suppressed, good CD characteristics can be obtained, and the resolution can be improved, and desired. Transfer pattern shape. The phase shift film 3 exhibiting such optical characteristics is a single layer film or a laminated film having at least one metal halide material layer containing an element of either metal, neon, and/or oxygen as described above. Composition. In order to suppress the wavelength dependence of the transmittance, phase difference, and reflectance of the phase shift film 3 in a specific wavelength range, it is preferable to use a laminated film composed of a plurality of material layers having different optical characteristics. The plurality of material layers having different optical characteristics are preferably composed of at least one layer of a metal halide material layer and at least one layer of a chromium-based material layer. In this case, the optical characteristics of the entire phase-shifted film 3 are determined by, for example, refractive index and transmission depending on the kind or film thickness of the material constituting the metal halide-based material layer or the chromium-based material layer. The combination of the optical characteristics such as the ratio and the reflectance, and the order of the layers of the respective material layers and the number of layers are determined. Specifically, the phase shift film 3 may have a two-layer structure including a metal halide-based material layer formed on the transparent substrate 2 and a chromium-based material layer formed on the metal halide-based material layer. Laminated film. Further, a laminated film having a three-layer structure composed of a metal halide-based material layer formed on the second layer formed on the chromium-based material layer may be used. Further, in this case, a chromium-based material layer or a metal halide-based material layer may be further laminated, and the phase-shift film 3 may be formed in four or more layers. Further, the phase shift film 3 may be a laminated film having a two-layer structure composed of a chromium-based material layer formed on the transparent substrate 2 and a metal halide-based material layer formed on the chromium-based material layer. Further, a laminated film having a three-layer structure composed of a chromium-based material layer formed on the second layer of the metal halide-based material layer may be used. Further, in this case, a metal halide-based material layer or a chromium-based material layer may be laminated, and the phase-shift film 3 may be four or more layers. The phase shift film 3 having such a configuration exhibits optical characteristics in which the transmittance, phase difference, and reflectance of the specific wavelength range are suppressed in wavelength dependence. Therefore, when the exposure light of the wavelength range is received, the phase shift effect can be sufficiently exerted, and the resolution can be improved. Further, any of the metal halide material layer and the chromium material layer constituting the phase shift film 3 may be formed of one layer or a plurality of layers. When the metal telluride-based material layer and the chromium-based material layer are each formed of a plurality of layers, the materials constituting each layer of each material layer may be different from each other, or the layers may be the same. When the phase shift film 3 is composed of at least one layer of a metal halide-based material layer and at least one layer of a chromium-based material layer, as the lowermost layer of the phase-shift film 3 formed on the side of the transparent substrate 2, a chromium-based material is used. This layer is preferable in terms of the effect of suppressing the wavelength dependence of the transmittance, the phase difference, and the reflectance, and the suppression of damage to the transparent substrate 2 when the phase shift film 3 is patterned. Further, when the resist film 5 is formed on the phase shift film 3, a chromium-based material layer is used as the uppermost layer of the phase shift film 3, and the adhesion to the resist film is improved, and It is preferable to make the pattern shape of the phase shift film 3 vertical. The film thickness of the phase shift film 3 is required to obtain a desired phase difference in the exposure light and a desired transmittance or reflectance of the exposure light necessary for exhibiting the phase shift effect, and to form a phase shift according to the composition. The respective forming materials, the lamination order, and the film thickness of the metal telluride-based material layer or the chromium-based material layer of the transfer film 3 are appropriately determined. Further, the thickness of the metal halide-based material layer constituting the phase shift film 3 is considered in consideration of the metal telluride-based material layer, or the metal-telluride-based material layer, and a combination of the chromium-based material layer formed thereon or above. In the middle, the phase shift film 3 is appropriately determined by displaying a desired phase difference or transmittance. The thickness of the metal halide-based material layer of the phase shift film 3 is preferably in the range of, for example, 90 nm or more and 140 nm or less, but is not limited thereto. Further, when the phase shift film 3 is composed of at least a metal halide-based material layer and a chromium-based material layer, the thickness of the chromium-based material layer is considered in consideration of a metal formed under or on the chromium-based material layer. In the combination of the telluride-based material layers, the phase shift film 3 is appropriately determined by exhibiting a desired phase difference or transmittance. For example, it is preferably in the range of 2.5 nm or more and 15 nm or less, but is not limited thereto. It is substantially difficult to form a chromium-based material layer with a thickness of less than 2.5 nm. Further, when the chromium-based material layer is formed into a film with a thickness exceeding 15 nm, the transmittance is lowered. For example, the transmittance of the phase shift film 3 having a wavelength of 365 nm may be less than 3.5%. The metal halide-based material constituting the metal halide-based material layer is not particularly limited as long as it contains a metal or bismuth (Si). The composition of the metal and bismuth (Si) constituting the metal halide material layer is adjusted in accordance with the optical characteristics of the entire phase shift film 3. The ratio of the metal to the ruthenium is appropriately selected depending on the metal type or the optical characteristics required for the metal halide material layer, and is preferably metal: 矽 = 1:1 or more and 1:9 or less. As the metal, a transition metal such as molybdenum (Mo), tantalum (Ta), tungsten (W), or titanium (Ti) is exemplified. Examples of the metal telluride-based material constituting the metal halide-based material layer include a nitride of a metal telluride, an oxide of a metal telluride, a nitrogen oxide of a metal telluride, a carbonitride of a metal telluride, and a metal telluride. a material of at least one of a carbon oxide and a metal oxycarbide. The phase shift mask substrate used in the manufacture of the display device of the present invention is generally a large phase shift mask substrate having a side of 350 mm or more, and thus wet etching is employed in the fabrication of the phase shift mask. Further, according to the defect correction of the large phase shift mask, the defect quality of the phase shift film of the phase shift mask base is also required to be higher than or equal to a certain quality. The metal telluride-based material is preferably used in view of the defect quality of the phase-shift film, the controllability of the cross-sectional shape of the phase-shifted film pattern by wet etching, the transmittance of the phase-shift film, and the controllability of the phase difference. Nitrogen-containing material. The metal telluride-based material is preferably a nitride of a metal telluride, a nitrogen oxide of a metal telluride, or a carbonitride of a metal telluride, and particularly preferably a nitride of a metal telluride. If the cross-sectional shape of the phase shift film pattern is controlled to be vertical, since sufficient contrast can be obtained for the pattern boundary portion of the phase shift film pattern and the transparent substrate, it is easy to enhance the light intensity tilt of the pattern boundary portion. Hereinafter, a metal telluride-based material is specifically exemplified. In the case of molybdenum molybdenum (MoSi), a nitride of molybdenum molybdenum (MoSi), an oxide of molybdenum molybdenum (MoSi), a nitrogen oxide of molybdenum molybdenum (MoSi), a carbonitride of molybdenum molybdenum (MoSi), Carbon oxides of molybdenum molybdenum (MoSi) and carbon oxynitrides of molybdenum molybdenum (MoSi). In the case of TaSi, a nitride of tantalum (TaSi), an oxide of tantalum (TaSi), a nitrogen oxide of tantalum (TaSi), a carbonitride of tantalum (TaSi), Carbon oxides of tantalum (TaSi) and carbonitrides of tantalum telluride (TaSi). In the case of tungsten germanium (WSi), a nitride of tungsten telluride (WSi), an oxide of tungsten germanium (WSi), a nitrogen oxide of tungsten germanium (WSi), a carbonitride of tungsten germanium (WSi), Carbon oxides of tungsten (WSi) and carbonitrides of tungsten (WSi). In the case of titanium telluride (TiSi), a nitride of titanium telluride (TiSi), an oxide of titanium telluride (TiSi), a nitrogen oxide of titanium telluride (TiSi), a carbonitride of titanium telluride (TiSi), A carbon oxide of titanium telluride (TiSi) or a carbon oxynitride of titanium telluride (TiSi). Further, as described above, in view of the controllability of the cross-sectional shape of the phase-shifted film pattern by wet etching, it is preferable to include wet etching of the metal halide-based material layer. The component of speed. As a component which slows down the wet etching rate of the metal telluride-based material layer, the above-mentioned nitrogen (N) is exemplified. In this case, the metal constituting the metal halide-based material layer and the composition of cerium (Si) and nitrogen are adjusted in accordance with the optical characteristics of the entire phase shift film 3 as a whole. The nitrogen content in the case of containing nitrogen is preferably 25 atom% or more and 55 atom% or less, and more preferably 30 atom% or more and 50 atom% or less. Further, the metal halide-based material may contain elements other than the above-described examples without departing from the effects of the present invention. As the chromium-based material constituting the chromium-based material layer, a chromium compound containing at least one of chromium (Cr) and at least one selected from the group consisting of oxygen (O), nitrogen (N), and carbon (C) is used. As the chromium compound, a chromium (Cr) nitride, a chromium oxide, a chromium carbide, a chromium oxynitride, a chromium carbonitride, a chromium carbon oxide, and a chromium carbon oxynitride are exemplified. At least one material. Among such chromium-based materials, chromium nitride or chromium nitrogen oxide is preferred in terms of easily controlling the wavelength dependence of transmittance. Further, in the chromium-based material, elements other than the above-described examples may be included without departing from the effects of the present invention. Further, as described above, the phase shift mask substrate 1 of the first embodiment may have a transparent substrate 2, a phase shift film 3 formed on the transparent substrate 2, and a phase shift film 3 formed on the phase shift film 3. The structure of the light shielding film 4. The light shielding film 4 may be any one of a layered one and a plurality of layers. When the light shielding film 4 is composed of a plurality of layers, for example, a case having a two-layer structure composed of a light shielding layer formed on the phase shift film 3 side and an antireflection layer formed on the light shielding layer, or having a phase and a phase The case where the offset film 3 is connected to form an insulating layer, a light shielding layer formed on the insulating layer, and a three-layer structure formed of an antireflection layer formed on the light shielding layer. 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), a chromium carbonitride film (CrCN), a molybdenum telluride film (MoSi), and a molybdenum nitride nitride film (MoSiN). The antireflection layer may be either a case composed of one layer or a case composed of a plurality of layers. Examples of the antireflection layer include a chromium oxynitride film (CrON), a molybdenum oxide oxide film (MoSiO), and a molybdenum oxynitride oxynitride film (MoSiON). The insulating layer is made of, for example, CrCO or CrOCN containing less than 50 at% of Cr, and has a thickness of 10 nm or more and 50 nm or less. The phase shift film 3 having the metal telluride-based material layer on the outermost layer is formed on the light-shielding film 4 made of a chromium-based material in the case where the phase of the light-shielding film 4 made of the chromium-based material is offset from the mask base. At the time of wet etching, metal ions are melted from the phase shift film 3 having the metal telluride-based material layer on the outermost layer. At this time, electrons are generated. When the insulating layer is formed in such a manner as to be connected to the phase shift film 3, electrons generated when the metal ions are melted from the phase shift film 3 can be prevented from being supplied to the light shielding film. Therefore, the etching speed in the plane when the light-shielding film 4 is wet-etched can be made uniform. Further, as the light shielding film 4, a combination of a light shielding layer of a chromium carbide film (CrC) and an antireflection layer of a chromium oxynitride film (CrON), or a light shielding layer of a molybdenum oxide film (MoSi) and a molybdenum oxynitride oxynitride film are preferable. The combination of the antireflection layer of (MoSiON) is not limited thereto. The phase shift film 3 and the light shielding film 4 having the phase shift mask base 1 having the above configuration can be formed by a known film forming method. As a film formation method, a sputtering method is generally exemplified. The sputtering apparatus may be any of a cluster type sputtering apparatus and a series type sputtering apparatus. The metal halide material layer or the chromium material layer constituting the phase shift film 3 or the light shielding film 4 can be formed, for example, by a sputtering target or a sputtering gas atmosphere. When a phase shift mask is manufactured using the phase shift mask substrate 1 having such a phase shift film 3 or a light shielding film 4, the light is blocked by a phase shift film pattern on the phase shift film pattern. In the film pattern, for example, a phase shifting portion that changes the phase of the exposure light by substantially 180 degrees is formed by a portion of the phase shift film pattern of the unlaminated light-shielding film pattern, and the light-shielding portion is laminated with a phase-shifted film pattern and shading A portion of the film pattern is formed, and the light transmitting portion is made of a phase shift mask formed by a portion exposing the transparent substrate 2. As a sputtering target used for film formation of a metal telluride-based material layer, a metal or bismuth (Si) is selected. Specifically, a metal telluride, a nitride of a metal telluride, an oxide of a metal telluride, a carbide of a metal telluride, a nitrogen oxide of a metal telluride, a carbonitride of a metal telluride, a metal telluride Carbon oxides, and carbon oxynitrides of metal halides. The sputtering gas atmosphere at the time of film formation of the metal telluride-based material layer includes having a selected from the group consisting of nitrogen (N) 2 ), nitric oxide (NO) gas, nitrogen dioxide (NO 2 Gas, nitrous oxide (N 2 O) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas and oxygen (O 2 At least one of the active gas of the group and at least one selected from the group consisting of helium (He), neon (Ne), argon (Ar), helium (Kr), and xenon (Xe) a mixture of inert gases. The combination of the material for forming the sputtering target and the gas species of the sputtering gas atmosphere, or the mixing ratio of the reactive gas and the inert gas in the sputtering gas atmosphere is based on the metal halide material constituting the metal halide material layer. The type or composition is appropriately determined. As the sputtering target used for film formation of the chromium-based material layer, those containing chromium (Cr) or chromium compounds are selected. Specifically, chromium (Cr), chromium nitride, chromium oxide, chromium carbide, chromium nitrogen oxide, chromium carbonitride, chromium carbon oxide, and chromium carbonitride are exemplified. Things. The sputtering gas atmosphere at the time of film formation of the chromium-based material layer includes having a selected from the group consisting of nitrogen (N) 2 ), nitric oxide (NO) gas, nitrogen dioxide (NO 2 Gas, nitrous oxide (N 2 O) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, oxygen (O 2 An active gas of at least one of a hydrocarbon gas and a fluorine-based gas, and having an atmosphere selected from the group consisting of helium (He), neon (Ne), argon (Ar), helium (Kr), and helium ( a mixed gas of at least one inert gas of the group of Xe). Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas. The combination of the material for forming the sputtering target and the gas type of the sputtering gas atmosphere, or the mixing ratio of the reactive gas and the inert gas in the sputtering gas atmosphere is appropriately determined according to the type or composition of the chromium-based material constituting the chromium-based material layer. Decide. The phase shift mask substrate 1 for manufacturing a display device according to the first embodiment described above includes a transparent substrate 2 and a phase shift film 3 formed on the main surface of the transparent substrate 2 and having at least one layer A monolayer film or a laminate film comprising a layer of a metal halide material layer of a metal and an element of any of niobium, nitrogen, and/or oxygen. As described above, the phase shift film 3 has a transmittance of light of 365 nm at a wavelength of 3.5% or more and 8% or less, and a phase difference of light of 365 nm is in a range of 160 degrees or more and 200 degrees or less, and a wavelength of 365 nm or more 436. The transmittance in the range below nm is dependent on the change in wavelength within 5.5%. The phase shift film 3 exhibits optical characteristics in which the wavelength dependence of the transmittance of light having a wavelength of 365 nm or more and 436 nm or less is suppressed. Therefore, it is possible to obtain a phase shift mask substrate having a phase shift film which can sufficiently exhibit a phase shift effect when receiving exposure light in the wavelength range and which can improve the resolution. Further, a phase shift mask substrate having the phase shift film 3 can be obtained, and the phase shift film 3 can obtain a desired improvement in the light intensity of the boundary portion of the pattern, and the resolution is improved, and the CD characteristics are good. The phase shift film pattern of the transfer pattern shape is patterned. Further, in the phase shift mask substrate 1 for manufacturing a display device according to the first embodiment, the transmittance of the phase shift film 3 in the range of 365 nm or more and 700 nm or less depends on the amount of change in wavelength within 20%. In this case, in the wavelength range, the wavelength dependence of the transmittance of the phase shift film 3 can also be suppressed, so that the alignment mark provided in the mask can be easily recognized in the exposure machine at the time of manufacture of the display device, and the alignment precision is obtained. improve. Further, in the mask inspection apparatus, when the inspection apparatus of the mask pattern is recognized by the difference in transmittance between the transparent substrate and the mask pattern, it is easy to recognize defects such as defective shape defects of the mask pattern. Further, in the phase shift mask substrate 1 for manufacturing a display device according to the first embodiment, when the difference between the phase difference provided at a wavelength of 365 nm and the phase difference given at a wavelength of 436 nm is 30 degrees or less, the wavelength is suppressed. Since the wavelength dependence of the range is different, the phase shift effect can be sufficiently exerted, and the light intensity at the boundary portion of the pattern can be made steeper, and the resolution can be improved. Further, in the phase shift mask base 1 for manufacturing a display device according to the first embodiment, the reflectance of the phase shift film 3 in the range of 365 nm or more and 700 nm or less is 5% or more and 45% or less, and further preferred embodiment The phase shift mask base 1 for manufacturing a display device of the first embodiment has a reflectance of 5% or more and 45% or less in a range of 365 nm or more and 700 nm or less, and a wavelength of 365 nm or more and 700 nm or less. When the reflectance in the range depends on the amount of change in the wavelength within 5%, a resist film is formed on the phase shift film 3, and when the pattern is drawn by a laser scanner or the like, it is less likely to be drawn. The effect of standing waves generated by the light used to coincide with its reflected light. Therefore, at the time of pattern drawing, the roughness of the edge portion of the resist pattern cross section on the phase shift film 3 can be suppressed, and the pattern accuracy can be improved. Moreover, since the alignment at the time of pattern drawing can be easily acquired, and the mask pattern measurement can be easily performed by the long-size (MMS) measurement, the mask pattern can be recognized with high precision. Further, in the case where the phase shift mask is used for pattern transfer and the display device is manufactured, and the alignment mark is detected by the difference in reflectance between the transparent substrate and the alignment mark, the mask alignment is easily recognized, and the alignment is easy. Increased accuracy. Further, when pattern transfer is performed using a phase shift mask and a display device is manufactured, since the influence of the glare phenomenon can be suppressed, good CD characteristics can be obtained, and the resolution can be improved, and desired. Transfer pattern shape. Further, the phase shift mask base 1 for manufacturing a display device according to the first embodiment and the phase shift mask 30 for manufacturing a display device according to the second embodiment to be described later are used for the projection exposure of the double exposure. The shift mask substrate and the phase shift mask are particularly effective. 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 coherence coefficient (σ) is preferably from 0.5 to 1.0. Embodiment 2. In Embodiment 2, a phase shift mask for manufacturing a display device and a method of manufacturing the same will be described with reference to FIGS. 2 and 3. Fig. 2 is a cross-sectional view showing the configuration of a phase shift mask for manufacturing a display device according to a second embodiment of the present invention. 3 is a flow chart for explaining a method of manufacturing a phase shift mask for use in a phase shift mask substrate in which the light shielding film 4 is formed on the phase shift film 3. In FIG. 2 and FIG. 3, the same components as those in FIG. 1 are denoted by the same reference numerals and the description thereof will not be repeated. The phase shift mask 30 of the second embodiment includes a transparent substrate 2 and a phase shift film pattern 3' formed on the transparent substrate 2 (Fig. 2(a), hereinafter sometimes referred to as a first type of phase shift Shift cover). Further, a configuration in which the light shielding film pattern 4' is formed on the phase shift film pattern 3' may be employed (Fig. 2(b), hereinafter sometimes referred to as a second type of phase shift mask). Further, a configuration in which the light shielding film pattern 4' is formed under the phase shift film pattern 3' may be employed (Fig. 2(c), hereinafter sometimes referred to as a third type phase shift mask). The first type of phase shift mask 30 is composed of a phase shifting portion composed of a phase shift film pattern 3' and a light transmitting portion composed of a portion exposing the transparent substrate 2. The phase shifting masks 30 of the second and third types are caused by the phase shifting portion of the portion of the phase shifting film pattern 3' in which the light-shielding film pattern 4' is not formed on or under the phase-shifting film pattern 3'. The phase shift film pattern 3' is formed by a light-shielding portion in which a laminated portion of the light-shielding film pattern 4' is formed, or a light-transmitting portion in which a portion of the transparent substrate 2 is exposed. The phase shift mask 30 of the second and third types can prevent the film of the resist film formed on the transfer target from being reduced by the exposure light of the shifted portion of the transmission phase. In the phase shift mask 30 of the first type, the second type, or the third type described above, the phase shift film pattern 3' includes at least one layer having a metal and any element of germanium, nitrogen, and/or oxygen. A single layer film or laminated film of a metal halide material layer. The optical characteristics of the phase-shifted film pattern 3' as a whole are in the case where the phase-shifted film pattern 3' includes a single-layer film, depending on the kind or film thickness of the material constituting the material layer forming the phase-shifted film pattern 3'. The optical properties of the respective material layers determined, for example, such as the refractive index, the transmittance, and the reflectance, are such that when the phase-shifted film pattern 3' includes a laminated film, the phase-shifted film pattern 3' is formed according to the configuration. The combination of the material characteristics of the plurality of material layers, the combination of the optical characteristics determined by the film thickness, and the order of the layers of the respective material layers and the number of layers are determined. The phase shift film pattern 3' is controlled by a combination of material layers constituting the phase shift film pattern 3' to control the transmittance of light of a specific wavelength within a range as described below, and further, light of a specific wavelength The transmittance and the phase difference are controlled within the range described below, and the amount of change in the transmittance, the phase difference, and the reflectance of the light in the specific wavelength range is suppressed within the range as described below. Specifically, the phase shift film pattern 3' has a transmittance of 365 nm at a wavelength of 3.5% or more and 8% or less, a phase difference of 365 nm, a range of 160 degrees or more and 200 degrees or less, and a wavelength of 365 nm or more and 436 nm or less. The transmittance in the range depends on the amount of change in wavelength within 5.5%. The phase shift film pattern 3' is an optical characteristic in which the wavelength dependence of the transmittance of light having a wavelength of 365 nm or more and 436 nm or less is suppressed. Therefore, when the phase shift film pattern 3' receives light of the wavelength and the wavelength range, the phase shift effect can be sufficiently exerted, and the light intensity tilt of the boundary portion of the pattern can be enhanced, so that it is possible to obtain a film having good CD characteristics. The phase shifting film pattern 3' of the desired transfer pattern shape is offset from the mask 30. The phase shift mask 30 can correspond to the miniaturization of the line gap pattern or the contact hole. Further, in the phase shift mask 30 of the first type, the second type or the third type described above, the phase shift film pattern 3' is dependent on the wavelength in the range of 365 nm or more and 700 nm or less. When the amount of change is within 20%, the wavelength dependence of the transmittance can be suppressed in the wavelength range. Therefore, in the exposure machine at the time of manufacture of the display device, the alignment mark provided on the mask is easily recognized. The quasi-precision is improved. Further, in the mask inspection apparatus, when the inspection apparatus of the mask pattern is recognized by the difference in transmittance between the transparent substrate and the mask pattern, it is easy to recognize defects such as defective shape defects of the mask pattern. Further, in the phase shift mask 30 of the first type, the second type or the third type described above, the phase shift film pattern 3' is distinguished by a phase difference given at a wavelength of 365 nm and a wavelength difference of 436 nm. When the difference (ΔP (365-436)) is 30 degrees or less, the wavelength dependence of the phase difference in the wavelength range is suppressed, so that the phase shift effect can be sufficiently exerted, and the light intensity at the boundary portion of the pattern is made stronger. , can improve the resolution. Further, in the phase shift mask 30 of the first type, the second type, or the third type described above, the phase shift film pattern 3' has a reflectance of 5% or more in a range of 365 nm or more and 700 nm or less. % or less, and the reflectance of the phase shift film pattern 3' in the range of 365 nm or more and 700 nm or less is 5% or more and 45% or less, and the reflectance in the range of 365 nm or more and 700 nm or less depends on the reflectance. When the amount of change in wavelength (ΔR% (700-365)) is within 5%, the mask pattern measurement can be easily performed by the long-length (MMS) measurement, so that the mask pattern can be recognized with high precision. Further, in the case where the phase shift mask is used for pattern transfer and the display device is manufactured, and the alignment mark is detected by the difference in reflectance between the transparent substrate and the alignment mark, the mask alignment is easily recognized, and the alignment is easy. Increased accuracy. Further, when pattern transfer is performed using a phase shift mask and a display device is manufactured, since the influence of the glare phenomenon can be suppressed, good CD characteristics can be obtained, and the resolution can be improved, and desired. Transfer pattern shape. Next, a method of manufacturing a phase shift mask for manufacturing a display device to be implemented will be described with reference to FIG. The method of manufacturing the phase shift mask shown in FIG. 3 is a method of manufacturing the phase shift mask 30 of the first type and the second type described above. In the method of manufacturing a phase shift mask for manufacturing a display device of the first type and the second type, first, it is formed on the light shielding film 4 of the phase shift mask substrate 1 for manufacturing the display device according to the first embodiment. A resist pattern forming step of the resist pattern. Specifically, in the resist pattern forming step, first, as shown in FIG. 3(a), a resist film 5 is formed on the light shielding film 4. Thereafter, a pattern of a specific size is drawn to the resist film 5. Thereafter, the resist film 5 is developed with a specific developer, and as shown in FIG. 3(b), a resist pattern 5' is formed. As a pattern drawn to the resist film 5, a line gap pattern or a hole pattern is exemplified. Next, as shown in FIG. 3(c), a light-shielding film pattern forming step of wet etching the light-shielding film 4 with the resist pattern 5' as a mask and forming the light-shielding film pattern 4' is performed. The etching liquid for wet etching the light-shielding film 4 is not particularly limited as long as it is a chromium-based material or a metal halide-based material which can selectively etch the light-shielding film 4. When the material for forming the light-shielding film 4 is a chromium-based material, an etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate is exemplified. When the material for forming the light-shielding film 4 is a metal halide-based material, it is exemplified to include at least one fluoride selected from the group consisting of hydrofluoric acid, hydrofluoric acid hydrofluoric acid, and ammonium hydrogen fluoride, and hydrogen peroxide, and An etchant of at least one oxidizing agent of nitric acid and sulfuric acid. Specifically, an etching solution in which a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water is exemplified. Next, as shown in FIG. 3(d), after the resist pattern 5' is peeled off, as shown in FIG. 3(e), the light-shielding film pattern 4' is masked and the phase-shift film 3 is wet. The phase offset film pattern forming step of etching the phase shift film pattern 3' is formed. The etching liquid for wet etching the phase shift film 3 is not particularly limited as long as it can selectively etch the chromium-based material layer and the metal halide-based material layer constituting the phase shift film 3, respectively. For example, as an etching liquid for wet etching a chromium-based material layer, an etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate is exemplified. Further, the etching liquid for wet etching the metal telluride-based material layer includes at least one fluoride selected from the group consisting of hydrofluoric acid, hydrofluoric acid hydrofluoric acid, and ammonium hydrogen fluoride, and is selected from the group consisting of hydrogen peroxide and nitric acid. And an etchant of at least one oxidizing agent of sulfuric acid. Further, when the phase shift film 3 of the chromium-based material layer is formed on the metal halide-based material layer, when the chromium-based material layer is wet-etched, metal ions are melted from the metal halide-based material layer of the lower layer. Further, electrons are supplied to the chromium-based material layer, and the wet etching of the chromium-based material layer becomes slow. However, in the case where the phase shift film 3 of the metal halide-based material layer is formed on the chromium-based material layer, such a phenomenon does not occur. Therefore, the etching speed in the plane when the wet etching phase is shifted by the film 3 can be made uniform. Next, a phase shift mask 30 of the type having a phase shifting portion composed of the phase shift film pattern 3' and a light transmitting portion composed of a portion exposing the transparent substrate 2 is produced (phase shift of the first type) In the case of the photomask, after the phase shift film pattern forming step, as shown in FIG. 3(f), the light shielding film pattern 4' is peeled off. Further, a light-shielding film pattern 4' having a narrower phase-shifted film pattern 3' is provided on the phase-shifted film pattern 3', and has a portion of the phase-shifted film pattern 3' which is formed by the un-layered light-shielding film pattern 4'. The phase shifting portion of the type, the light-shielding portion formed by the portion in which the phase-shifted film pattern 3' and the light-shielding film pattern 4' are laminated, and the phase-shifted light of the type of the light-transmitting portion formed by the portion exposing the transparent substrate 2 In the case of the cover 30 (the phase shift mask of the second type), after the phase shift film pattern forming step, as shown in FIG. 3(g), the light shielding film pattern 4' is patterned into a phase shift film pattern. 3' narrower specific pattern. The phase shift mask 30 for manufacturing a display device is manufactured by the resist pattern forming step, the light shielding film pattern forming step, and the phase shift film pattern forming step. Further, the method of manufacturing the phase shift mask 30 of the first type and the second type described above is not limited to the above method. In the phase shift mask 30 of the first type, the phase shift mask substrate 1 for manufacturing the display device of the first embodiment is formed on the phase shift film 3 by using a structure in which the light shielding film 4 is not formed. A resist pattern forming step of forming the resist pattern 5', after which the phase shift of the phase shift film 3 is performed with the resist pattern 5' as a mask, and the phase shift film pattern 3' is formed. In the film pattern forming step, the resist pattern 5' is finally peeled off, and the phase shift mask 30 of the first type can be obtained. Further, according to the method of manufacturing a phase shift mask for manufacturing a display device according to the second embodiment, the phase shift mask is manufactured using the phase shift mask base 1 of the first embodiment. Therefore, it is possible to manufacture a phase shift of the phase shift film pattern 3' which is capable of obtaining a desired transfer pattern shape which can sufficiently exhibit the phase shift effect and which enhances the light intensity tilt of the pattern boundary portion and has good CD characteristics. Photomask 30. Further, a method of manufacturing the phase shift mask 30 of the first type and the second type will be described above, and a phase shift is formed on the main surface of the transparent substrate 2 on which a light shielding film pattern has been formed in one portion of the main surface. The present invention can also be applied to the phase shift mask 30 of the film shift pattern 3' (the phase shift mask of the third type). In this case, by covering the phase-shifting film pattern 3' with the light-shielding film pattern 4' which has been formed on one portion of the main surface, or on the main surface where the light-shielding film pattern 4' is not formed, the layer may be unlayered. The portion of the light-shielding film pattern and the phase-shift film pattern 3' is set as a phase shifting portion, and a phase shifting effect can be exerted in the phase shifting portion. The phase shift mask 30 of the third type in which the phase shift film pattern 3' is formed on the main surface of the transparent substrate 2 on which the light shielding film pattern 4' has been formed in one of the main surfaces is, for example, the following steps And manufacturing: a light-shielding film forming step on the main surface of the transparent substrate 2, forming a light-shielding film by sputtering; a light-shielding film pattern forming step, after the light-shielding film forming step, using the wet etching to make the light-shielding film pattern Forming a light-shielding film pattern; a phase-shifting film forming step of forming a phase-shift film 3 on the main surface of the transparent substrate 2 so as to cover the light-shielding film pattern after the light-shielding film pattern forming step; The offset film pattern forming step is performed by patterning the phase shift film 3 by wet etching after the phase shift film forming step to form the phase shift film pattern 3'. (Embodiment 3) In the third embodiment, a method of manufacturing a display device using the phase shift mask of the second embodiment will be described. In the method of manufacturing a display device according to the third embodiment, first, a resist film substrate on which a resist film is formed on a substrate, and a phase shift mask for manufacturing the display device described in the second embodiment are used. The phase shift mask 30 obtained by the manufacturing method or the phase shift mask 30 for manufacturing the display device described in the second embodiment is disposed in a phase shifting mask arrangement step opposite to the resist film. Next, a step of exposing the exposure film to the phase shift mask 30 and exposing the resist film to the resist film is performed. The exposure light system is, for example, a composite light containing light in a wavelength range of 300 nm or more and 700 nm or less. Specifically, it is a composite light including an i line, an h line, and a g line. The intensity ratio of the i-line, the h-line, and the g-line in the composite light used for the exposure light can be appropriately changed to 1:1:1 or 2 according to the manufacturing ratio of the i-line:h-line:g-line according to the manufacture of the display device: 1:1 and so on. According to the method of manufacturing the display device of the third embodiment, the phase shift mask 30 obtained by the method for manufacturing a phase shift mask for manufacturing a display device according to the second embodiment, or the second embodiment A phase shift mask 30 for manufacturing a display device manufactures a display device. Therefore, a display device having a fine line gap pattern or contact hole can be manufactured. [Examples] Hereinafter, the present invention will be more specifically described based on examples. In addition, the synthetic quartz glass substrate will be simply referred to as QZ hereinafter. Further, when expressed as QZ/A/B/C, it is shown that the A layer, the B layer, and the C layer are formed in this order on the QZ. Embodiment 1. In Embodiment 1, a phase shift mask substrate composed of QZ/CrON/MoSiN will be described. A. Phase-shifting reticle substrate and manufacturing method thereof for manufacturing the phase-shifting reticle substrate 1 of the above configuration, first, as a transparent substrate 2, preparing a synthetic quartz glass substrate of 3345 size (330 mm × 450 mm × 5 mm) . Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium and a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) are disposed, and A chromium-based material layer (film thickness: 10 nm) containing chromium oxynitride (CrON) is formed on the main surface of the transparent substrate 2, and a film containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer. A metal halide material layer (film thickness: 120 nm) was obtained, and a phase shift mask substrate 1 on which a phase shift film 3 (total film thickness: 130 nm) was formed was obtained. Further, the chromium-based material layer is placed in the vicinity of the chromium target, and a mixed gas containing Ar (30) and nitrogen monoxide (NO) gas (Ar: 30 sccm, NO: 30 sccm) is introduced to have a sputtering power of 4.0 kW. The transport speed of the transparent substrate 2 was 400 mm/min, and the film was formed on the main surface of the transparent substrate 2 by reactive sputtering. Further, the metal telluride-based material layer is in the vicinity of the molybdenum molybdenum target, and argon (Ar) and nitrogen (N) are introduced. 2 Mixed gas (Ar: 30 sccm, N 2 : 70 sccm) was formed on the chromium-based material layer by reactive sputtering at a sputtering power of 8.0 kW and a transport speed of the transparent substrate 2 of 400 mm/min. Further, the metal telluride-based material layer is laminated in plural times under the same conditions in order to obtain a desired film thickness of 120 nm. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. The phase shift film 3 of the obtained phase shift mask substrate 1 was measured for transmittance by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies, Japan, and the phase difference was measured by MPM-100 manufactured by Lasertec Corporation of Japan. . In the following examples and comparative examples, the same apparatus was used for the measurement of the transmittance or the phase difference. In addition, any of the transmittance values of the following examples and comparative examples are values based on the Air standard. When the transmittance and phase difference of the phase shift film 3 are measured, the film is formed on the main surface of the transparent substrate 2 of 6025 size (152 mm × 152 mm) fixed on the same substrate holder (not shown). A phase shifting film 3 (total film thickness: 130 nm) of a laminated structure comprising a chromium-based material layer of chromium oxide (CrON) and a metal halide-based material layer containing molybdenum nitride nitride (MoSiN) Offset film substrate (dummy substrate). As a result, as shown in FIG. 4, the transmittance spectrum of Example 1 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement result of the specific transmittance of Example 1 is shown in FIG. The transmittance at a wavelength of 365 nm (hereinafter sometimes referred to as T% (365)) was 4.41%, and ΔT% (436-365) was 3.91%. Therefore, it is understood that the phase shift film 3 of the first embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 13.35%. Therefore, it is understood that the phase shift film 3 of the first embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. The phase difference (hereinafter sometimes referred to as P(365)) at a wavelength of 365 nm is 181.7 degrees, and ΔP (365-436) is 28.7 degrees. Therefore, it is understood that the phase shift film 3 of the first embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, regarding the phase shift film 3 of the obtained phase shift mask substrate 1, the reflectance was measured by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. In the following examples, comparative examples, and reference examples, the same apparatus was used for the measurement of the reflectance. As a result, as shown in FIG. 6, the reflectance spectrum of Example 1 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 described below. The measurement results of the specific reflectance of Example 1 are shown in FIG. The reflectance in the range of 365 nm or more and 700 nm or less (hereinafter sometimes referred to as R% (700-365)) is 17.9% or more and 22.4% or less, and the range of values from 700 nm to 365 nm (maximum and minimum values) The difference) is 4.5%. Therefore, it is understood that the phase shift film 3 of the first embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and method of manufacturing the same for manufacturing phase-shifting reticle 30 using phase-shifting reticle substrate 1 manufactured in the above manner, first on phase-shifting film 3 of phase-shifting reticle substrate 1, The resist material is applied using a resist coating device. Thereafter, a resist film 5 having a film thickness of 1000 nm is formed by a heating and cooling step. Thereafter, the resist film 5 is drawn using a laser drawing device, and a resist pattern having a contact hole pattern (not shown) of 2.5 μm square is formed on the phase shift film 3 through development and cleaning steps. 5'. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched. Thereafter, the resist pattern 5' is used as a mask, and the chromium-containing oxynitride (CrON) chromium of the phase shift film 3 is obtained by a chromium etching solution containing cerium ammonium nitrate and ammonium peroxodisulfate. The material layer is wet etched to form a phase offset film pattern 3'. Thereafter, the resist pattern 5' is peeled off. Thus, a phase shift mask 30 having a phase shift film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained. The phase shift effect of the phase shift mask having the phase shift film pattern described above was simulated. The number of openings of the simulation system (NA) = 0.1, the coherence coefficient (σ) = 0.5, and as the exposure light, the i-line (365 nm), the h-line (405 nm), and the g-line (436 nm) are included, and the i-line is included: h line: g line = 2: 1:1 light intensity ratio composite light. The result of simulating the spatial image of the light by the phase shift mask formed with the phase shift film pattern having the contact hole pattern of 2.5 μm square is shown in Fig. 9 (light intensity distribution). The horizontal axis of Fig. 9 is the position (μm) of the contact hole pattern of the resist film transferred onto the transfer target from the center of the contact hole, and the vertical axis intensity ratio (the maximum amount of light transmitted from the phase shift mask) Set to 1 intensity ratio). The light intensity distribution curve of Fig. 9 is the peak intensity of the transmitted light when it is at the center of the contact hole, and the intensity of the transmitted light gradually decreases as it moves away from its center. In the light intensity distribution curve of FIG. 9, the distance from the center of the contact hole showing the peak intensity is ±1 μm, which corresponds to the boundary portion of the 2.0 μm square contact hole pattern of the resist film formed on the transfer target. (The straight line portion of the contact hole pattern). The light intensity tilt of the boundary portion of the pattern can be obtained from the difference in light intensity near the boundary portion of the pattern. As shown in FIG. 9, the light intensity distribution curve of Example 1 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity tilt (resolution) of the boundary portion of the pattern was 0.446. Therefore, it is understood that the phase shift mask of the first embodiment exhibits a stronger light intensity inclination and improves the resolution as compared with the comparative example described below. Embodiment 2. In Embodiment 2, a phase shift mask substrate composed of QZ/CrN/MoSiN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium and a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) are disposed, and A chromium-based material layer (film thickness: 10 nm) containing chromium nitride (CrN) is formed on the main surface of the transparent substrate 2, and a metal containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer. A vapor-based material layer (film thickness: 120 nm) was obtained, and a phase shift mask substrate 1 on which a phase shift film 3 (total film thickness: 130 nm) was formed was obtained. In addition, the chromium-based material layer is in the vicinity of the chromium target, and the introduction includes argon (Ar) and nitrogen (N). 2 Mixed gas (Ar: 30 sccm, N 2 : 70 sccm) was formed on the main surface of the transparent substrate 2 by reactive sputtering at a sputtering power of 4.0 kW and a transport speed of the transparent substrate 2 of 400 mm/min. Further, the metal telluride-based material layer was formed under the same conditions as in Example 1 (in order to obtain a desired film thickness of 120 nm and laminated under the same conditions). Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/CrN/MoSiN was formed was used for measurement of transmittance and phase difference. As a result, as shown in FIG. 4, the transmittance spectrum of Example 2 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 described below. The measurement results of the specific transmittance of Example 2 are shown in FIG. T% (365) was 3.34%, and ΔT% (436-365) was 3.28%. Therefore, it is understood that the phase shift film 3 of the second embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 12.68%. Therefore, it is understood that the phase shift film 3 of the second embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P(365) was 182.7 degrees and ΔP (365-436) was 27.7 degrees. Therefore, it is understood that the phase shift film 3 of the second embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 6, the reflectance spectrum of Example 2 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 described below. The measurement results of the specific reflectance of Example 2 are shown in FIG. R% (700-365) is 16.6% or more and 24.8% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 8.2%. Therefore, it is understood that the phase shift film 3 of the second embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the first embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Example 2 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.447. Therefore, in the phase shift mask of the second embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 3. In Embodiment 3, a phase shift mask substrate composed of QZ/CrON/MoSiN/CrON will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium and a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) are disposed, and A chromium-based material layer (film thickness: 5 nm) containing chromium oxynitride (CrON) is formed on the main surface of the transparent substrate 2, and a metal containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer. a germanide-based material layer (film thickness: 120 nm), and a chromium-based material layer (film thickness: 5 nm) containing chromium oxynitride (CrON) is formed on the metal telluride-based material layer to obtain a phase shift The phase shifting mask substrate 1 of the film 3 (total film thickness: 130 nm) was transferred. In addition, the chromium-based material layer was formed under the same conditions as in Example 1 except that the transport speed of the transparent substrate 2 was set to 800 mm/min. Further, the metal telluride-based material layer was also formed under the same conditions as in Example 1 (to obtain a desired film thickness of 120 nm and laminated in the same condition several times). Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/CrON/MoSiN/CrON was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 5, the transmittance spectrum of Example 3 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 described below. The measurement results of the specific transmittance of Example 3 are shown in FIG. T% (365) was 4.03%, and ΔT% (436-365) was 3.32%. Therefore, it is understood that the phase shift film 3 of the third embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 7, ΔT% (700-365) was 12.49%. Therefore, it is understood that the phase shift film 3 of the third embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) was 181.0 degrees and ΔP (365-436) was 28.3 degrees. Therefore, it is understood that the phase shift film 3 of the third embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 7, the reflectance spectrum of Example 3 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 3 are shown in FIG. R% (700-365) is 26.4% or more and 30.0% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 3.5%. Therefore, it is understood that the phase shift film 3 of the third embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and method of manufacturing the same, in order to manufacture the phase-shifting reticle 30 using the phase-shifting reticle substrate 1 manufactured in the above manner by the same method as in Embodiment 1, first, phase-shifted light On the phase shift film 3 of the cover substrate 1, a resist pattern 5' having a contact hole pattern of 2.5 μm square was formed. Thereafter, the resist pattern 5' is used as a mask, and the chromium oxide oxynitride of the second layer of the phase shift film 3 is replaced by a chromium etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate ( The chromium-based material layer of CrON) is subjected to wet etching. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched. Thereafter, the resist pattern 5' is used as a mask, and the first layer of the phase shift film 3 containing chromium oxynitride is contained by a chromium etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate ( The chromium-based material layer of CrON) is wet-etched to form a phase-shifted film pattern 3'. Thereafter, the resist pattern 5' is peeled off. Thus, a phase shift mask 30 having a phase shift film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 9, the light intensity distribution curve of Example 3 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity changes greatly at the boundary portion of the pattern, and is at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.447. Therefore, it is understood that the phase shift mask of the third embodiment exhibits a stronger light intensity inclination and improves the resolution as compared with the comparative example described below. Embodiment 4. In Embodiment 4, a phase shift mask substrate composed of QZ/CrN/MoSiN/CrN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium and a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) are disposed, and A chromium-based material layer (film thickness: 5 nm) containing chromium nitride (CrN) is formed on the main surface of the transparent substrate 2, and a metal telluride containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer. a material layer (film thickness: 120 nm), a chromium-based material layer (film thickness: 5 nm) containing chromium nitride (CrN) was formed on the metal telluride-based material layer to obtain a phase-shifted film. 3 (total film thickness: 130 nm) phase shift mask substrate 1. In addition, the chromium-based material layer was formed under the same conditions as in Example 1 except that the transport speed of the transparent substrate 2 was set to 800 mm/min. Further, the metal telluride-based material layer was also formed under the same conditions as in Example 1 (to obtain a desired film thickness of 120 nm and laminated in the same condition several times). Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. For the measurement of the transmittance and the phase difference, a phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/CrN/MoSiN/CrN was formed was used. As a result, as shown in FIG. 5, the transmittance spectrum of Example 4 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 4 are shown in FIG. T% (365) was 3.82%, and ΔT% (436-365) was 3.33%. Therefore, it is understood that the phase shift film 3 of the fourth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 14.64%. Therefore, it is understood that the phase shift film 3 of the fourth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P(365) was 180.2 degrees and ΔP (365-436) was 26.8 degrees. Therefore, it is understood that the phase shift film 3 of the fourth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 7, the reflectance spectrum of Example 4 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 4 are shown in FIG. R% (700-365) is 22.4% or more and 27.5% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 5.0%. Therefore, it is understood that the phase shift film 3 of the fourth embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the third embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Example 4 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, and is at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.447. Therefore, in the phase shift mask of the fourth embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 5. In Embodiment 5, a phase shift mask substrate composed of QZ/MoSiN/CrN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a sputtering device (not shown) in which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) and a sputtering target containing chromium are disposed, and A metal telluride-based material layer (film thickness: 120 nm) containing molybdenum nitride nitride (MoSiN) is formed on the main surface of the transparent substrate 2, and a chromium-containing nitride (CrN) is formed on the metal telluride-based material layer. A chromium-based material layer (film thickness: 10 nm) was obtained, and a phase shift mask substrate 1 on which a phase shift film 3 (total film thickness: 130 nm) was formed was obtained. In addition, the metal telluride material layer is in the vicinity of the molybdenum molybdenum target, and argon (Ar) and nitrogen (N) are introduced. 2 Mixed gas (Ar: 30 sccm, N 2 : 70 sccm) was formed on the main surface of the transparent substrate 2 by reactive sputtering at a sputtering power of 8.0 kW and a transport speed of the transparent substrate 2 of 400 mm/min. In order to obtain a desired film thickness of 120 nm, the layers were laminated in the same conditions. Further, the chromium-based material layer is in the vicinity of the chromium target, and is introduced to contain argon (Ar) and nitrogen (N). 2 Mixed gas (Ar: 30 sccm, N 2 : 70 sccm) was deposited on the metal halide-based material layer by reactive sputtering at a sputtering power of 4.0 kW and a transport speed of the transparent substrate 2 of 800 mm/min. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. For the measurement of the transmittance and the phase difference, a phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/MoSiN/CrN was formed was used. As a result, as shown in FIG. 4, the transmittance spectrum of Example 5 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 5 are shown in FIG. T% (365) was 3.16% and ΔT% (436-365) was 2.88%. Therefore, it is understood that the phase shift film 3 of the fifth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 12.21%. Therefore, it is understood that the phase shift film 3 of the fifth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) was 178.4 degrees and ΔP (365-436) was 26.6 degrees. Therefore, it is understood that the phase shift film 3 of the fifth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 6, the reflectance spectrum of Example 5 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 5 are shown in FIG. R% (700-365) is 33.6% or more and 44.6% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 11.0%. Therefore, it is understood that the phase shift film 3 of the fifth embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed as compared with the comparative examples 1 and 2 described below. B. Phase-shifting reticle and manufacturing method thereof A phase-shifted light in which a phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square is formed on a transparent substrate 2 is obtained by the same method as in Embodiment 5. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Example 5 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, and is at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.448. Therefore, in the phase shift mask of the fifth embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 6. In Embodiment 6, a phase shift mask substrate composed of QZ/MoSiN/CrON will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a sputtering device (not shown) in which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) and a sputtering target containing chromium are disposed, and A metal telluride-based material layer (film thickness: 120 nm) containing molybdenum nitride nitride (MoSiN) is formed on the main surface of the transparent substrate 2, and oxynitride containing chromium is formed on the metal telluride-based material layer ( A Cr-based material layer (film thickness: 10 nm) of CrON) was obtained as a phase shift mask substrate 1 on which a phase shift film 3 (total film thickness: 130 nm) was formed. Further, a metal telluride-based material layer was formed into a film under the same conditions as in Example 5. Further, the chromium-based material layer is placed in the vicinity of the chromium target, and a mixed gas containing argon (Ar) and nitrogen monoxide (NO) (Ar: 30 sccm, NO: 30 sccm) is introduced, and the sputtering power is 4.0 kW and transparent. The substrate 2 was transported at a rate of 800 mm/min, and was deposited on the metal halide-based material layer by reactive sputtering. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. For the measurement of the transmittance and the phase difference, a phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/MoSiN/CrON was formed was used. As a result, as shown in FIG. 4, the transmittance spectrum of Example 6 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 6 are shown in FIG. T% (365) was 4.21%, and ΔT% (436-365) was 3.5%. Therefore, it is understood that the phase shift film 3 of the sixth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 12.88%. Therefore, it is understood that the phase shift film 3 of the sixth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) is 178.8 degrees and ΔP (365-436) is 28 degrees. Therefore, it is understood that the phase shift film 3 of the sixth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 6, the reflectance spectrum of Example 6 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 6 are shown in FIG. R% (700-365) is 30.7% or more and 39.4% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 8.7%. Therefore, it is understood that the phase shift film 3 of the sixth embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed as compared with the comparative examples 1 and 2 described below. B. Phase-shifting reticle and method of manufacturing the same for manufacturing phase-shifting reticle 30 using phase-shifting reticle substrate 1 manufactured in the above manner, first, on phase-shifting film 3 of phase-shifting reticle substrate 1 The resist material is applied using a resist coating device. Thereafter, a resist film 5 having a film thickness of 1000 nm is formed by a heating and cooling step. Thereafter, the resist film 5 is drawn using a laser drawing device, and a resist pattern 5 having a contact hole pattern (not shown) of 2.5 μm square is formed on the phase shift film 3 through development and cleaning steps. '. Thereafter, the resist pattern 5' is used as a mask, and the chromium-containing oxynitride (CrON) chromium of the phase shift film 3 is obtained by a chromium etching solution containing cerium ammonium nitrate and ammonium peroxodisulfate. The material layer is wet etched. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched to form a phase offset film pattern 3'. Thereafter, the resist pattern 5' is peeled off. Thus, a phase shift mask 30 having a phase shift film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. As a result, the light intensity inclination of the pattern boundary portion was the same as that of the fifth embodiment. Therefore, in the phase shift mask of the sixth embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 7. In Embodiment 7, a phase shift mask substrate composed of QZ/MoSiN/CrON/MoSiN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a sputtering device (not shown) in which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) and a sputtering target containing chromium are disposed, and A metal telluride-based material layer (film thickness: 60 nm) containing molybdenum nitride nitride (MoSiN) is formed on the main surface of the transparent substrate 2, and oxynitride containing chromium is formed on the metal telluride-based material layer ( CrON) chromium-based material layer (film thickness: 10 nm), and a metal telluride-based material layer (film thickness: 60 nm) containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer to obtain a phase The phase shifting mask substrate 1 of the offset film 3 (total film thickness: 130 nm). Further, the metal halide-based material layer was formed under the same conditions as in Example 6 except that the transport speed of the transparent substrate 2 was set to about 800 mm/min. Further, a chromium-based material layer was also formed under the same conditions as in Example 6. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 130 nm) composed of QZ/MoSiN/CrON/MoSiN was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 5, the transmittance spectrum of Example 7 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 7 are shown in FIG. T% (365) was 4.49% and ΔT% (436-365) was 3.92%. Therefore, it is understood that the phase shift film 3 of the seventh embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 23.78%. Therefore, it is understood that the phase shift film 3 of the seventh embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) is 178.8 degrees and ΔP (365-436) is 24 degrees. Therefore, it is understood that the phase shift film 3 of the seventh embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. The results are shown in Figure 7. Further, the measurement results of the specific reflectance of Example 7 are shown in Fig. 8. R% (700-365) is 5.4% or more and 24.4% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 19.0%. B. Phase-shifting reticle and method of manufacturing the same, in order to manufacture the phase-shifting reticle 30 using the phase-shifting reticle substrate 1 manufactured in the above manner by the same method as in Embodiment 1, first, phase-shifted light On the phase shift film 3 of the cover substrate 1, a resist pattern 5' having a contact hole pattern of 2.5 μm square was formed. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched. Thereafter, the resist pattern 5' is used as a mask, and the first layer of the phase shift film 3 containing chromium oxynitride is contained by a chromium etching solution containing ammonium cerium nitrate and ammonium peroxodisulfate ( The chromium-based material layer of CrON) is subjected to wet etching. Thereafter, the resist pattern 5' is used as a mask, and the molybdenum nitride nitride containing the phase shift film 3 is diluted by the molybdenum molybdenum etching solution in which the mixed solution of ammonium hydrogen fluoride and hydrogen peroxide is diluted with deionized water. The metal halide material layer of MoSiN) is wet etched to form a phase offset film pattern 3'. Thereafter, the resist pattern 5' is peeled off. Thus, a phase shift mask 30 having a phase shift film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 9, the light intensity distribution curve of Example 7 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.446. Therefore, it is understood that the phase shift mask of the seventh embodiment exhibits a stronger light intensity inclination and improves the resolution as compared with the comparative example described below. Embodiment 8. In Embodiment 8, a phase shift mask substrate composed of QZ/MoSiN/CrN/MoSiN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a sputtering device (not shown) in which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) and a sputtering target containing chromium are disposed, and A metal telluride-based material layer (film thickness: 59 nm) containing molybdenum nitride nitride (MoSiN) is formed on the main surface of the transparent substrate 2, and a chromium-containing nitride (CrN) is formed on the metal telluride-based material layer. a chromium-based material layer (film thickness: 10 nm), and a metal telluride-based material layer (film thickness: 59 nm) containing molybdenum nitride nitride (MoSiN) is formed on the chromium-based material layer to obtain a phase shift The phase shifting mask substrate 1 of the film 3 (total film thickness: 128 nm) was transferred. Further, the metal telluride layer was formed under the same conditions as in Example 5 except that the transport speed of the transparent substrate 2 was set to about 800 mm/min. Further, a chromium-based material layer was also formed under the same conditions as in Example 5. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (total film thickness: 128 nm) composed of QZ/MoSiN/CrN/MoSiN was formed was used for measurement of transmittance and phase difference. As a result, as shown in FIG. 5, the transmittance spectrum of Example 8 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 8 are shown in FIG. T% (365) was 3.55% and ΔT% (436-365) was 3.65%. Therefore, it is understood that the phase shift film 3 of the eighth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 23.62%. Therefore, it is understood that the phase shift film 3 of the eighth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) is 178.3 degrees and ΔP (365-436) is 22 degrees. Therefore, it is understood that the phase shift film 3 of the eighth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. The result is shown in FIG. Further, the measurement results of the specific reflectance of Example 8 are shown in Fig. 8. R% (700-365) is 5.1% or more and 24.8% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 19.7%. B. Phase-shifting reticle and manufacturing method thereof A phase-shifted light in which a phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square is formed on a transparent substrate 2 is obtained by the same method as in Embodiment 7. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Example 8 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity varies greatly at the boundary portion of the pattern, at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.447. Therefore, in the phase shift mask of the eighth embodiment, it is understood that the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Embodiment 9. In Embodiment 9, a phase shift mask substrate composed of QZ/MoSiN will be described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) on which a sputtering target containing molybdenum molybdenum (Mo:Si=1:4) is disposed, and is formed on the main surface of the transparent substrate 2. The film contains a metal telluride-based material layer (film thickness: 120 nm) of molybdenum nitride nitride (MoSiN), and a phase shift mask substrate 1 was obtained. In addition, the metal telluride material layer is in the vicinity of the molybdenum molybdenum target, and argon (Ar) and nitrogen (N) are introduced. 2 Mixed gas (Ar: 30 sccm, N 2 : 70 sccm) was formed on the transparent substrate 2 by reactive sputtering at a sputtering power of 8.0 kW and a transport speed of the transparent substrate 2 of 400 mm/min. In order to obtain a desired film thickness of 120 nm, the layers were laminated in the same conditions. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (film thickness: 110 nm) composed of QZ/MoSiN was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 4, the transmittance spectrum of Example 9 having a wavelength of 200 nm to 800 nm has a characteristic that the transmittance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific transmittance of Example 9 are shown in FIG. T% (365) was 4.36% and ΔT% (436-365) was 3.97%. Therefore, it is understood that the phase shift film 3 of the ninth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed. Further, as shown in Fig. 8, ΔT% (700-365) was 21.60%. Therefore, it is understood that the phase shift film 3 of the ninth embodiment exhibits optical characteristics in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed. The measurement result of the phase difference is shown in FIG. P (365) was 180.00 degrees and ΔP (365-436) was 24.00 degrees. Therefore, it is understood that the phase shift film 3 of the ninth embodiment exhibits optical characteristics in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in FIG. 6, the reflectance spectrum of Example 9 having a wavelength of 200 nm to 800 nm has a characteristic that the reflectance change is small as compared with Comparative Examples 1 and 2 below. The measurement results of the specific reflectance of Example 9 are shown in FIG. R% (700-365) is 18.0% or more and 28.3% or less, and the range of the range of 700 nm to 365 nm (the difference between the maximum value and the minimum value) is 10.4%. Therefore, it is understood that the phase shift film 3 of the ninth embodiment exhibits optical characteristics in which the wavelength dependence of the reflectance in the range of 365 nm or more and 700 nm or less is suppressed. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the first embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 9, the light intensity distribution curve of Example 9 shows a sharp peak intensity at the center of the contact hole compared with the comparative example described below, and the light intensity changes greatly at the boundary portion of the pattern, and is at the boundary portion of the pattern. In the outer peripheral area, the light intensity changes little. The light intensity of the boundary portion of the pattern is inclined to 0.444. Therefore, it can be seen that in the phase shift mask of the ninth embodiment, the light intensity is inclined and the resolution is improved as compared with the comparative example described below. Comparative Example 1. In Comparative Example 1, a phase shift mask substrate composed of CrON was described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium is disposed, and a chromium oxide (CrON) containing chromium is formed on the main surface of the transparent substrate 2. A chromium-based material layer (film thickness: 157 nm) was obtained to obtain a phase-shifted reticle substrate 1. In addition, the chromium-based material layer is in the vicinity of the chromium target, and a mixed gas containing argon (Ar) and nitrogen monoxide (NO) (Ar: 46 sccm, NO: 70 sccm) is introduced, and the sputtering power is 8.0 kW and transparent. The substrate 2 was transported at a speed of about 400 mm/min, and was formed on the transparent substrate 2 by reactive sputtering. In order to obtain a desired film thickness of 157 nm, the layers were laminated in the same conditions. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (film thickness: 157 nm) composed of QZ/CrON was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 4 and FIG. 5, the transmittance spectrum of Comparative Example 1 having a wavelength of 200 nm to 800 nm shows that the transmittance change sharply increases from the vicinity of the wavelength exceeding 300 nm, and is close to the wavelength exceeding 700 nm. A roughly S-shaped curve in which the change in transmittance becomes small. The measurement result of the specific transmittance of Comparative Example 1 is shown in FIG. T% (365) was 7.73%, and ΔT% (436-365) was 9.82%. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 cannot exhibit an optical characteristic in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment. Further, as shown in Fig. 8, ΔT% (700-365) was 48.00%. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 cannot exhibit an optical characteristic in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed as compared with the above-described embodiment. The measurement result of the phase difference is shown in FIG. P (365) is 181.3 degrees and ΔP (365-436) is 32.5 degrees. Therefore, it is understood that the phase shift film 3 of Comparative Example 1 cannot exhibit an optical characteristic in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in the measurement results of the specific reflectances of FIG. 6 and FIG. 7 and FIG. 8, R% (700-365) is 7.60% or more and 18.45% or less, and the range of the range of 700 nm to 365 nm (maximum The difference between the value and the minimum value was 10.8%, which was not significantly different from the above-described Example 6, and was therefore good. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the first embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 10, the light intensity distribution curve of Comparative Example 1 shows that the peak of the light intensity at the center of the contact hole is not so sharp as compared with the above embodiment, and the light intensity does not change so much in the pattern boundary portion. In the peripheral region on the outer side of the boundary portion, the light intensity changes greatly. The light intensity of the boundary portion of the pattern is inclined to 0.432. Therefore, it is understood that the phase shift mask of Comparative Example 1 exhibits a weaker light intensity than the above-described embodiment. Comparative Example 2. In Comparative Example 2, a phase shift mask substrate composed of CrOCN was described. A. Phase-shifting reticle substrate and method of manufacturing the same As the transparent substrate 2, a transparent substrate 2 having the same size as that of Example 1 was prepared. Thereafter, the transparent substrate 2 is introduced into a tandem sputtering apparatus (not shown) in which a sputtering target containing chromium is disposed, and a carbon oxynitride containing chromium (CrOCN) is formed on the main surface of the transparent substrate 2. A chromium-based material layer (film thickness: 117 nm) was obtained to obtain a phase-shifted mask substrate 1. In addition, the chromium-based material layer is in the vicinity of the chromium target and is introduced to contain argon (Ar) and carbon dioxide (CO). 2 ), with nitrogen (N 2 Mixed gas (Ar: 46 sccm, CO 2 :35 sccm,N 2 : 46 sccm), a sputtering power of 8.0 kW, a transfer speed of the transparent substrate 2 of about 400 mm/min, and a film formed on the transparent substrate 2 by reactive sputtering. In order to obtain a desired film thickness of 117 nm, the layers were laminated in the same conditions. Thus, the phase shift mask substrate 1 on which the phase shift film 3 is formed on the transparent substrate 2 is obtained. With respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the transmittance and the phase difference were measured by the same method as in Example 1. A phase-shifted film substrate (virtual substrate) on which a phase shift film 3 (thickness: 117 nm) composed of QZ/CrOCN was formed was used for the measurement of the transmittance and the phase difference. As a result, as shown in FIG. 4 and FIG. 5, the transmittance spectrum of Comparative Example 2 having a wavelength of 200 nm to 800 nm shows that the transmittance change sharply increases from the vicinity of the wavelength exceeding 300 nm, and is close to the wavelength exceeding 600 nm. A roughly S-shaped curve in which the change in transmittance becomes small. The measurement results of the specific transmittance of Comparative Example 2 are shown in FIG. T% (365) was 5.10%, and ΔT% (436-365) was 7.58%. Therefore, it is understood that the phase shift film 3 of Comparative Example 2 cannot exhibit an optical characteristic in which the wavelength dependence of the transmittance in the range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment. Further, as shown in Fig. 8, ΔT% (700-365) was 50.63%. Therefore, it is understood that the phase shift film 3 of Comparative Example 2 cannot exhibit an optical characteristic in which the wavelength dependence of the transmittance in the range of 365 nm or more and 700 nm or less is suppressed as compared with the above-described embodiment. The measurement result of the phase difference is shown in FIG. P (365) is 182.1 degrees and ΔP (365-436) is 31.0 degrees. Therefore, it is understood that the phase shift film 3 of Comparative Example 2 cannot exhibit an optical characteristic in which the wavelength dependence of the phase difference of the wavelength range of 365 nm or more and 436 nm or less is suppressed as compared with the above-described embodiment. Further, with respect to the obtained phase shift film 3 of the phase shift mask substrate 1, the reflectance was measured in the same manner as in Example 1. As a result, as shown in the measurement results of the specific reflectances of FIG. 6 and FIG. 7 and FIG. 8, R% (700-365) is a range of 11.4% or more and 28.7% or less, and a range of 700 nm to 365 nm (maximum The difference between the value and the minimum value was 17.3%, which was not significantly different from the above-described Example 5, and was therefore good. B. Phase-shifting reticle and manufacturing method thereof The phase-shifted light having the phase-shifted film pattern 3' having a contact hole pattern of 2.5 μm square formed on the transparent substrate 2 was obtained by the same method as in the first embodiment. Cover 30. The phase shift effect of the phase shift mask 30 was simulated by the same method as in the first embodiment. A light intensity distribution curve simulating a spatial image of light through a phase shift mask formed with a phase offset film pattern having a contact pattern of 2.5 μm square is shown in FIG. As shown in FIG. 9, the light intensity distribution curve of Comparative Example 2 shows that the peak of the light intensity at the center of the contact hole is not so sharp as compared with the above embodiment, and the light intensity does not change so much in the pattern boundary portion. In the peripheral region on the outer side of the boundary portion, the light intensity changes greatly. The light intensity of the boundary portion of the pattern is inclined to 0.440. Therefore, it is understood that the phase shift mask of Comparative Example 2 exhibits a weaker light intensity than the above-described embodiment. Further, in the above-described embodiment, an example of the molybdenum nitride nitride (MoSiN) is described as the material of the metal halide material layer constituting the phase shift film 3, but the invention is not limited thereto. The material of the metal halide material layer may be molybdenum oxide (MoSiO), molybdenum carbide (MoSiCN), or molybdenum carbide (MoSiOC). Further, in the case of a metal halide-based material other than molybdenum molybdenum, the same effects as described above can be obtained. Further, in the above-described embodiment, examples of the chromium-based material layer constituting the phase shift film 3 include chromium nitride (CrN) and chromium nitrogen oxide (CrON), but are not limited thereto. This is the case. As a material of the chromium-based material layer, it may also be chromium oxide (CrO), chromium carbide (CrC), chromium carbonitride (CrCN), chromium carbon oxide (CrCO), chromium carbonitride. (CrOCN). Further, in the above-described embodiment, the phase shift mask substrate 1 in which only the phase shift film 3 is formed on the transparent substrate 2, and the phase in which only the phase shift film pattern 3' is formed on the transparent substrate 2 have been described. The example of the offset mask 30 is not limited to this. The phase of the phase shift film 3 and the light shielding film 4 on the transparent substrate 2 may be offset from the mask substrate, and the phase of the phase shift film pattern 3 ′ and the light shielding film pattern 4 ′ may be formed on the transparent substrate 2 . The offset mask can also exert the same effects as the above embodiment. Further, in the phase shift mask substrate having the phase shift film 3 and the light shielding film 4 on the transparent substrate 2 described above, a light shielding layer or a light shielding layer may be used as the light shielding film formed on the phase shift film 3. And a laminated structure of the antireflection layer and a laminated structure of the insulating layer, the light shielding layer, and the antireflection layer. Further, in the above-described embodiment, a method of manufacturing the phase shift mask 30 by wet etching has been described, but the invention is not limited thereto. As a material constituting the phase shift mask substrate 1, in the case of a metal halide material layer, a fluorine-based gas (for example, CF) can also be used. 4 Gas, CHF 3 Gas, SF 6 Gas, or mixed with O in these gases 2 Gas etching) is patterned by dry etching, and in the case of a chromium-based material layer, by using a chlorine-based gas (for example, Cl) 2 Gas and O 2 The dry gas of the gas mixture is patterned by dry etching.

1‧‧‧相偏移光罩基底
2‧‧‧透明基板
3‧‧‧相偏移膜
3'‧‧‧相偏移膜圖案
4‧‧‧遮光膜
4'‧‧‧遮光膜圖案
5‧‧‧抗蝕劑膜
5'‧‧‧抗蝕劑膜圖案
30‧‧‧相偏移光罩1‧‧‧phase offset mask base
2‧‧‧Transparent substrate
3‧‧‧ phase offset film
3'‧‧‧ phase offset film pattern
4‧‧‧Shade film
4'‧‧‧Shade film pattern
5‧‧‧resist film
5'‧‧‧resist film pattern
30‧‧‧phase offset mask

圖1係顯示本發明之實施形態1之顯示裝置製造用之相偏移光罩基底之構成之剖面圖。 圖2(a)-(c)係用以說明本發明之實施形態2之顯示裝置製造用之相偏移光罩之構成之剖面圖。 圖3(a)-(g)係用以說明使用相偏移光罩基底之相偏移光罩之製造方法之步驟圖。 圖4係相偏移光罩基底(實施例1、2、5、6及9、比較例1及2)之各相偏移膜之透射率光譜。 圖5係相偏移光罩基底(實施例3、4、7、8及9、比較例1及2)之各相偏移膜之透射率光譜。 圖6係顯示相偏移光罩基底(實施例1、2、5、6及9、比較例1及2)之各相偏移膜之反射率之反射率光譜。 圖7係顯示相偏移光罩基底(實施例3、4、7、8及9、比較例1及2)之各相偏移膜反射率之反射率光譜。 圖8係顯示相偏移光罩基底之相偏移膜之光學特性之表。 圖9係通過相偏移光罩(實施例1、3、7及9、比較例2)之光之空間圖像之模擬結果(光強度分佈)。 圖10係通過相偏移光罩(實施例2、4、6及8、比較例1)之光之空間圖像之模擬結果(光強度分佈)。Fig. 1 is a cross-sectional view showing the structure of a phase shift mask base for manufacturing a display device according to a first embodiment of the present invention. 2(a) through 2(c) are cross-sectional views showing the configuration of a phase shift mask for manufacturing a display device according to a second embodiment of the present invention. 3(a)-(g) are process diagrams for explaining a method of manufacturing a phase shift mask using a phase shift mask base. Figure 4 is a transmission spectrum of each phase offset film of the phase shift mask substrate (Examples 1, 2, 5, 6 and 9, Comparative Examples 1 and 2). Figure 5 is a transmission spectrum of each phase offset film of the phase shift mask substrate (Examples 3, 4, 7, 8, and 9, and Comparative Examples 1 and 2). Fig. 6 is a graph showing the reflectance spectra of the reflectances of the phase shifting films of the phase shift mask substrates (Examples 1, 2, 5, 6 and 9, and Comparative Examples 1 and 2). Fig. 7 is a graph showing the reflectance spectra of the phase shift film reflectances of the phase-shifted mask substrates (Examples 3, 4, 7, 8, and 9, and Comparative Examples 1 and 2). Figure 8 is a table showing the optical characteristics of a phase shifting film of a phase shift mask substrate. Fig. 9 is a simulation result (light intensity distribution) of a spatial image of light passing through a phase shift mask (Examples 1, 3, 7 and 9, and Comparative Example 2). Fig. 10 is a simulation result (light intensity distribution) of a spatial image of light passing through a phase shift mask (Examples 2, 4, 6 and 8, and Comparative Example 1).

1‧‧‧相偏移光罩基底 1‧‧‧phase offset mask base

2‧‧‧透明基板 2‧‧‧Transparent substrate

3‧‧‧相偏移膜 3‧‧‧ phase offset film

Claims (23)

一種相偏移光罩基底，其係用以製作適用於曝光裝置而進行曝光之相偏移光罩者，該曝光裝置具備：具有開口數(NA)為0.06~0.15之光學系、且以包含300 nm以上700 nm以下之波長範圍之光之複合光作為光源之曝光環境；該相偏移光罩基底之特徵在於包含： 透明基板；及 形成於該透明基板上之相偏移膜；且 上述相偏移膜包含至少具有一層含金屬、矽與氮之金屬矽化物系材料層之單層膜或積層膜； 上述相偏移膜係如下： 波長365 nm之透射率為3.5%以上8%以下之範圍； 波長365 nm之相差為160度以上200度以下之範圍； 波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量為5.5%以內。A phase shift mask substrate for fabricating a phase shift mask suitable for exposure by an exposure apparatus, the exposure apparatus comprising: an optical system having a number of openings (NA) of 0.06 to 0.15, and including a composite light having a wavelength range of 300 nm or more and a wavelength range of 700 nm or less as a light source; the phase shift mask substrate is characterized by: a transparent substrate; and a phase shift film formed on the transparent substrate; The phase shift film comprises a single layer film or a laminate film having at least one metal halide layer containing metal, bismuth and nitrogen; the phase shift film is as follows: transmittance at a wavelength of 365 nm is 3.5% or more and 8% or less The range of wavelengths of 365 nm is in the range of 160 degrees or more and 200 degrees or less; the transmittance in the range of 365 nm or more and 436 nm or less depends on the wavelength change amount within 5.5%. 如請求項1之相偏移光罩基底，其中上述金屬矽化物系材料層係由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、及金屬矽化物之碳氮氧化物中至少一種材料構成。The phase shift mask substrate of claim 1, wherein the metal halide material layer is a nitride of a metal telluride, a nitrogen oxide of a metal telluride, a carbonitride of a metal telluride, and a metal telluride. It is composed of at least one material of carbon oxynitride. 如請求項1之相偏移光罩基底，其中上述相偏移膜係如下： 波長365 nm以上700 nm以下之範圍內透射率之依存於波長之變化量為20%以內。The phase shift mask substrate of claim 1 wherein the phase shifting film is as follows: The transmittance in the range of 365 nm or more and 700 nm or less depends on the wavelength change amount within 20%. 如請求項1之相偏移光罩基底，其中上述相偏移膜係如下： 波長365 nm中被賦予之相差、與波長436 nm中被賦予之相差之差為30度以下。The phase shift mask substrate of claim 1 wherein the phase shifting film is as follows: a difference between the phase difference imparted at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm is 30 degrees or less. 如請求項1之相偏移光罩基底，其中上述相偏移膜係如下： 波長365 nm以上700 nm以下之範圍內反射率為5%以上45%以下。The phase shift mask substrate of claim 1 wherein the phase shifting film is as follows: The reflectance in the range of 365 nm or more and 700 nm or less is 5% or more and 45% or less. 如請求項2之相偏移光罩基底，其中上述金屬矽化物系材料層係由包含金屬、矽與氮之金屬矽化物之氮化物構成。The phase shift mask substrate of claim 2, wherein said metal halide material layer is comprised of a nitride comprising a metal, germanium and nitrogen metal halide. 如請求項1之相偏移光罩基底，其中上述金屬矽化物系材料層中金屬與矽之比例為金屬：矽=1：1以上1：9以下。The phase shift mask substrate of claim 1, wherein the ratio of metal to germanium in the metal germanide material layer is metal: 矽=1:1 or more and 1:9 or less. 如請求項1之相偏移光罩基底，其中上述金屬矽化物系材料層中氮含量為25原子%以上55原子%以下。The phase shift mask substrate according to claim 1, wherein the metal halide-based material layer has a nitrogen content of 25 atom% or more and 55 atom% or less. 如請求項1之相偏移光罩基底，其中上述相偏移膜係由至少一層之金屬矽化物系材料層、與至少一層之鉻系材料層構成， 上述鉻系材料層係由鉻之氮化物、或鉻之氮氧化物構成。The phase shift mask substrate of claim 1, wherein the phase shifting film is composed of at least one layer of a metal telluride-based material layer and at least one layer of a chromium-based material layer, the chromium-based material layer being composed of chromium nitrogen It is composed of a compound or a nitrogen oxide of chromium. 如請求項1之相偏移光罩基底，其中包含形成於上述相偏移膜上之遮光膜。The phase shift mask substrate of claim 1 comprising a light shielding film formed on said phase shifting film. 一種相偏移光罩，其特徵在於：其係適用於曝光裝置而進行曝光者，該曝光裝置具備：具有開口數(NA)為0.06~0.15之光學系、且以包含300 nm以上700 nm以下之波長範圍之光之複合光作為光源之曝光環境，且包含： 透明基板；及 形成於該透明基板上之相偏移膜圖案； 上述相偏移膜圖案係包含具有至少一層含金屬、矽與氮之金屬矽化物系材料層之單層膜或積層膜； 上述相偏移膜圖案係如下： 波長365 nm之透射率為3.5%以上8%以下之範圍； 波長365 nm之相差為160度以上200度以下之範圍； 波長365 nm以上436 nm以下之範圍內透射率之依存於波長之變化量為5.5%以內。A phase shift mask characterized in that it is suitable for exposure to an exposure apparatus, and the exposure apparatus includes an optical system having a number of openings (NA) of 0.06 to 0.15 and including 300 nm or more and 700 nm or less. a composite light of a wavelength range of light as an exposure environment of the light source, and comprising: a transparent substrate; and a phase shift film pattern formed on the transparent substrate; the phase shift film pattern comprises at least one layer containing metal, germanium and a single-layer film or a laminate film of a metal halide material layer of nitrogen; the phase shift film pattern is as follows: a transmittance of 365 nm at a wavelength of 3.5% or more and 8% or less; a phase difference of 365 nm is 160 degrees or more The range of 200 degrees or less; the transmittance in the range of 365 nm or more and 436 nm or less depends on the wavelength change amount within 5.5%. 如請求項11之相偏移光罩，其中上述金屬矽化物系材料層係由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、及金屬矽化物之碳氮氧化物中至少一種材料構成。The phase shift mask of claim 11, wherein the metal halide material layer is a nitride of a metal telluride, a nitrogen oxide of a metal telluride, a carbonitride of a metal telluride, and a carbon of a metal telluride. It is composed of at least one material of nitrogen oxides. 如請求項11之相偏移光罩，其中上述相偏移膜圖案係如下： 波長365 nm以上700 nm以下之範圍內透射率之依存於波長之變化量為20%以內。The phase shift mask of claim 11, wherein the phase shift film pattern is as follows: The transmittance in the range of 365 nm or more and 700 nm or less depends on the wavelength change amount within 20%. 如請求項11之相偏移光罩，其中上述相偏移膜圖案係如下： 波長365 nm中被賦予之相差、與波長436 nm中被賦予之相差之差為30度以下。The phase shift mask of claim 11, wherein the phase shift film pattern is as follows: a difference between a phase difference given at a wavelength of 365 nm and a phase difference given at a wavelength of 436 nm is 30 degrees or less. 如請求項11之相偏移光罩，其中上述相偏移膜係如下： 波長365 nm以上700 nm以下之範圍內反射率為5%以上45%以下。The phase shifting mask of claim 11, wherein the phase shifting film is as follows: The reflectance in the range of 365 nm or more and 700 nm or less is 5% or more and 45% or less. 如請求項11之相偏移光罩，其中上述金屬矽化物系材料層係由包含金屬、矽與氮之金屬矽化物之氮化物構成。The phase shift mask of claim 11 wherein said metal halide material layer is comprised of a nitride comprising a metal, germanium and nitrogen metal halide. 如請求項11之相偏移光罩，其中上述金屬矽化物系材料層中金屬與矽之比例為金屬：矽=1：1以上1：9以下。The phase shift mask of claim 11, wherein the ratio of the metal to the germanium in the metal halide material layer is metal: 矽=1:1 or more and 1:9 or less. 如請求項11之相偏移光罩，其中上述金屬矽化物系材料層中氮含量為25原子%以上55原子%以下。The phase shift mask of claim 11, wherein the metal halide material layer has a nitrogen content of 25 atom% or more and 55 atom% or less. 如請求項11之相偏移光罩，其中上述相偏移膜係由至少一層之金屬矽化物系材料層、與至少一層之鉻系材料層構成， 上述鉻系材料層係由鉻之氮化物、或鉻之氮氧化物構成。The phase shifting mask of claim 11, wherein the phase shifting film is composed of at least one layer of a metal telluride-based material layer and at least one layer of a chromium-based material layer, the chromium-based material layer being a nitride of chromium Or a chromium oxide of chromium. 如請求項11之相偏移光罩，其中包含形成於上述相偏移膜圖案上之遮光膜圖案。A phase shift mask as claimed in claim 11, comprising a light shielding film pattern formed on said phase shift film pattern. 一種顯示裝置之製造方法，其係顯示裝置之製造方法，其特徵在於包含： 相偏移光罩配置步驟，其係對於基板上形成有抗蝕劑膜之附抗蝕劑膜基板，將如請求項11至20中任一項之相偏移光罩與上述抗蝕劑膜對向而配置；及 抗蝕劑膜曝光步驟，其係使用具有開口數(NA)為0.06~0.15之光學系、且以包含300 nm以上700 nm以下之波長範圍之光之複合光作為光源之曝光裝置，對上述相偏移光罩照射上述複合光，使上述抗蝕劑膜曝光。A manufacturing method of a display device, which is characterized by comprising: a phase shift mask arrangement step for attaching a resist film substrate on which a resist film is formed on a substrate, as requested a phase shift mask according to any one of items 11 to 20, which is disposed opposite to the resist film; and a resist film exposure step of using an optical system having a number of openings (NA) of 0.06 to 0.15, Further, the composite light having the composite light of light having a wavelength range of 300 nm or more and 700 nm or less is used as a light source, and the composite light is irradiated onto the phase shift mask to expose the resist film. 如請求項21之顯示裝置之製造方法，其中上述複合光為包含i線、h線及g線之複合光。The method of manufacturing the display device of claim 21, wherein the composite light is a composite light including an i-line, an h-line, and a g-line. 如請求項21之顯示裝置之製造方法，其中上述曝光環境之相干係數(σ)為0.5~1.0。The method of manufacturing the display device of claim 21, wherein the exposure environment has a coherence coefficient (σ) of 0.5 to 1.0.
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