TW201525608A - Phase shift mask substrate and manufacturing method thereof, and phase shift mask manufacturing method - Google Patents

Phase shift mask substrate and manufacturing method thereof, and phase shift mask manufacturing method Download PDF

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TW201525608A
TW201525608A TW103141083A TW103141083A TW201525608A TW 201525608 A TW201525608 A TW 201525608A TW 103141083 A TW103141083 A TW 103141083A TW 103141083 A TW103141083 A TW 103141083A TW 201525608 A TW201525608 A TW 201525608A
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phase shift
film
shift mask
chromium
transparent substrate
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TW103141083A
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TWI631414B (en
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Seiji Tsuboi
Masayuki Miyoshi
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Hoya Corp
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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
    • G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof

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

Abstract

An objective of the present invention is to provide a phase shift mask substrate, as well as a manufacturing method thereof, which has a cross-sectional shape enabling a phase shift film pattern to provide a sufficient phase shift effect by applying wet etching and is also to provide a manufacturing method of a phase shift mask comprising a phase shift film pattern providing a sufficient phase shift effect. A phase shift mask substrate 1 is formed by forming a phase shift film 3 containing chromium, oxygen, and nitrogen on a transparent substrate 2. A gradient area R1 is formed from the outermost surface 3a of the phase shift film 3 in a film depth direction. In the gradient area R1, the maximum of the reduction of a ratio (O/Cr) of oxygen to chromium in the film depth direction from the outermost surface 3a is greater than two, and the maximum of the reduction of a ratio (N/Cr) of nitrogen to chromium in the film depth direction from the outermost surface 3a is less than 0.45.

Description

相位偏移光罩基底及其製造方法、與相位偏移光罩之製造方法 Phase shift mask substrate, method of manufacturing the same, and method of manufacturing phase shift mask

本發明係關於一種顯示裝置製造用之相位偏移光罩基底及其製造方法、與使用該相位偏移光罩基底之顯示裝置製造用之相位偏移光罩之製造方法。 The present invention relates to a phase shift mask substrate for manufacturing a display device, a method of manufacturing the same, and a method of manufacturing a phase shift mask for manufacturing a display device using the phase shift mask substrate.

目前，作為液晶顯示裝置中採用之方式，存在VA(Vertical alignment，垂直配向)方式或IPS(In Plane Switching，共平面切換)方式。藉由該等方式，謀求高精細、高速顯示性能、廣視角之液晶顯示裝置之實現。應用有該等方式之液晶顯示裝置中，由透明導電膜之線與間隙圖案(line and space pattern)形成像素電極，藉此可改善應答速度、視角。最近，自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耗電化或對比度提高的觀點而言，要求線與間隙圖案之間距寬度之微細化。例如，期望使線與間隙圖案之間距寬度(線寬度L與間隙寬度S之合計)自6μm變窄至5μm，進而自5μm變窄至4μm。於該情形時，線寬度L、間隙寬度S至少任一者未達3μm之情形較多。例如，L<3μm，或L≦2μm，或S<3μm，或S≦2μm之情形不少。 At present, as a method employed in a liquid crystal display device, there is a VA (Vertical Alignment) method or an IPS (In Plane Switching) method. By such methods, realization of a liquid crystal display device with high definition, high-speed display performance, and wide viewing angle is sought. In a liquid crystal display device using such a method, a pixel electrode is formed by a line and a space pattern of a transparent conductive film, whereby a response speed and a viewing angle can be improved. Recently, from the viewpoint of further improvement in response speed and viewing angle, or improvement in light use efficiency of a liquid crystal display device, that is, reduction in power consumption or contrast of a liquid crystal display device, it is required to miniaturize the width between lines and gap patterns. . For example, it is desirable to narrow the width between the line and the gap pattern (the total of the line width L and the gap width S) from 6 μm to 5 μm, and further narrow from 5 μm to 4 μm. In this case, at least one of the line width L and the gap width S is less than 3 μm. For example, L<3 μm, or L≦2 μm, or S<3 μm, or S≦2 μm is quite a few.

又，於液晶顯示裝置或有機EL(Electroluminescence，電致發光)顯示裝置之製造時，藉由將經過需要之圖案化處理之複數個導電膜或絕緣膜積層而形成電晶體等元件。此時，所積層之各個膜之圖案化中多利用光微影步驟。例如，就使用於該等顯示裝置中之薄膜電晶體 (Thin Film Transistor，「TFT」)而言，係採用如下構成：構成TFT之複數個圖案中、形成於鈍化膜(絕緣層)之接觸孔貫通絕緣層，且與位於其下層側之連接部導通。此時，若上層側與下層側之圖案未準確定位，且接觸孔之形狀未確實形成，則無法保證顯示裝置之準確之動作。而且，此處，亦必須提高顯示性能，並且實現元件圖案之高積體化，尋求圖案之微細化。即，需要有孔圖案之直徑亦低於3μm者。例如，需要直徑為2.5μm以下、進而是直徑為2.0μm以下之孔圖案，不久之將來，考慮到期望亦形成具有低於其之1.5μm以下之直徑的圖案。 Further, in the production of a liquid crystal display device or an organic EL (Electroluminescence) display device, an element such as a transistor is formed by laminating a plurality of conductive films or insulating films which have undergone necessary patterning treatment. At this time, the photolithography step is often used in the patterning of the respective films of the laminate. For example, a thin film transistor used in such display devices (Thin Film Transistor, "TFT") is a configuration in which a contact hole formed in a passivation film (insulating layer) penetrates the insulating layer and is electrically connected to a connection portion located on the lower layer side thereof in a plurality of patterns constituting the TFT. . At this time, if the pattern on the upper layer side and the lower layer side is not accurately positioned, and the shape of the contact hole is not formed, the accurate operation of the display device cannot be ensured. Further, here, it is also necessary to improve the display performance, and to realize a high integration of the element patterns, and to seek to refine the pattern. That is, it is necessary that the diameter of the hole pattern is also less than 3 μm. For example, a hole pattern having a diameter of 2.5 μm or less and further a diameter of 2.0 μm or less is required, and in the near future, a pattern having a diameter of less than 1.5 μm or less is formed in consideration of the expectation.

根據此種背景，期望有可應對線與間隙圖案或接觸孔之微細化的顯示裝置製造用之光罩。 In view of such a background, it is desirable to have a photomask for manufacturing a display device that can cope with the minimization of line and gap patterns or contact holes.

於實現線與間隙圖案或接觸孔之微細化時，先前之光罩中，由於顯示裝置製造用之曝光機之解像界限為3μm，故而，於無充分之製程範圍(Process Margin)的情況下，不得不生產出接近解像界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。 In the case of realizing the miniaturization of the line and gap patterns or the contact holes, in the conventional mask, since the resolution limit of the exposure machine for manufacturing the display device is 3 μm, in the case of not having a sufficient process range (Process Margin) Had to produce a product with a minimum line width close to the resolution limit. Therefore, there is a problem that the defective rate of the display device becomes high.

例如，於考慮到使用具有用以形成接觸孔之孔圖案之光罩、將其轉印至被轉印體之情形時，若為直徑超過3μm之孔圖案則可利用先前之光罩進行轉印。然而，轉印直徑為3μm以下之孔圖案，尤其直徑為2.5μm以下之孔圖案則非常困難。為了轉印直徑為2.5μm以下之孔圖案，例如亦考慮轉換為具有高NA(numerical aperture，數值孔徑)之曝光機，但需要較大之投資。 For example, in consideration of a case where a photomask having a hole pattern for forming a contact hole is used and transferred to a transfer target, if it is a hole pattern having a diameter of more than 3 μm, the transfer can be performed using the previous photomask. . However, it is very difficult to transfer a hole pattern having a diameter of 3 μm or less, especially a hole pattern having a diameter of 2.5 μm or less. In order to transfer a hole pattern having a diameter of 2.5 μm or less, for example, an exposure machine having a high NA (numerical aperture) is also considered, but a large investment is required.

因此，為了提高解像度，應對線與間隙圖案或接觸孔之微細化，作為顯示裝置製造用之光罩，相位偏移光罩備受矚目。 Therefore, in order to improve the resolution, the line and gap patterns or the contact holes are made fine, and as a mask for manufacturing a display device, a phase shift mask has been attracting attention.

最近，作為液晶顯示裝置製造用之光罩，已開發出具備鉻系相位偏移膜之相位偏移光罩。 Recently, as a photomask for manufacturing a liquid crystal display device, a phase shift mask having a chromium-based phase shift film has been developed.

於專利文獻1中記載有如下半色調式相位偏移光罩，其具備：透 明基板；遮光層，其形成於透明基板上；及相位偏移層，其形成於遮光層之周圍，相對於300nm以上500nm以下之波長區域之任一種光可具有180度之相位差，且包含氧化氮化鉻系材料。該相位偏移光罩係藉由如下方式而製造：使透明基板上之遮光層圖案化，以覆蓋遮光層之方式將相位偏移層形成於透明基板上，於相位偏移層上形成光阻劑層，藉由將光阻劑層曝光及顯影而形成光阻劑膜圖案，將光阻劑膜圖案作為蝕刻光罩而使相位偏移層圖案化。 Patent Document 1 describes a halftone phase shift mask having a transparent a light-shielding layer formed on the transparent substrate; and a phase-shift layer formed around the light-shielding layer, and having a phase difference of 180 degrees with respect to any one of wavelength regions of 300 nm or more and 500 nm or less, and including Chromium oxide nitride based material. The phase shift mask is manufactured by patterning a light shielding layer on a transparent substrate, forming a phase shift layer on the transparent substrate to cover the light shielding layer, and forming a photoresist on the phase shift layer. In the agent layer, a photoresist film pattern is formed by exposing and developing the photoresist layer, and the phase shift layer is patterned by using the photoresist film pattern as an etching mask.

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

[專利文獻1]日本專利特開2011-13283號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2011-13283

本發明者等人對具備鉻系相位偏移膜之相位偏移光罩進行了銳意研究。其結果得知，於將光阻劑膜圖案作為光罩，藉由濕式蝕刻而使鉻系相位偏移膜圖案化之情形時，濕式蝕刻液滲入至光阻劑膜與鉻系相位偏移膜之界面，界面部分之蝕刻較快地進行。因此，所形成之鉻系相位偏移膜圖案之邊緣部分之剖面形狀成為遍及邊緣部分整體而傾斜、向透明基板拖尾之錐形形狀。 The inventors of the present invention have conducted intensive studies on a phase shift mask having a chromium-based phase shift film. As a result, when the photoresist film pattern is used as a mask and the chromium-based phase shift film is patterned by wet etching, the wet etching solution penetrates into the photoresist film and the chromium phase is phase-shifted. At the interface of the film transfer, the etching of the interface portion is performed faster. Therefore, the cross-sectional shape of the edge portion of the formed chromium-based phase shift film pattern is a tapered shape which is inclined over the entire edge portion and is trailing toward the transparent substrate.

於鉻系相位偏移膜圖案之邊緣部分之剖面形狀為錐形形狀之情形時，隨著鉻系相位偏移膜圖案之邊緣部分之膜厚減少，相位偏移效果減弱。因此，鉻系相位偏移膜圖案無法充分發揮相位偏移效果。又，濕式蝕刻液向光阻劑膜與鉻系相位偏移膜之界面之滲入係起因於鉻系相位偏移膜與光阻劑膜之密接性不佳。因此，難以嚴格控制鉻系相位偏移膜圖案之邊緣部分之剖面形狀，無法充分獲得解像性，控制線寬(CD)非常困難。 When the cross-sectional shape of the edge portion of the chrome-based phase shift film pattern is a tapered shape, the phase shift effect is weakened as the film thickness of the edge portion of the chrome-based phase shift film pattern is reduced. Therefore, the chrome-based phase shift film pattern cannot sufficiently exhibit the phase shift effect. Further, the penetration of the wet etching liquid into the interface between the photoresist film and the chromium-based phase shift film is caused by poor adhesion between the chromium-based phase shift film and the photoresist film. Therefore, it is difficult to strictly control the cross-sectional shape of the edge portion of the chromium-based phase shift film pattern, and the resolution cannot be sufficiently obtained, and it is extremely difficult to control the line width (CD).

進而，本發明者等人為了解決該等問題點而對使鉻系相位偏移 膜圖案之邊緣部分之剖面形狀垂直化的方法進行了銳意研究。至今為止，例如，已開發出如下方法：藉由調整使蝕刻速度變快之氮之含量或使蝕刻速度變慢之碳之含量，而使鉻系相位偏移膜之膜組成具有梯度、使膜厚方向之蝕刻速度具有變化。然而，該方法中，實現大面積之相位偏移光罩整體中之透過率之均一性非常困難。 Further, the inventors of the present invention have shifted the chrome phase in order to solve the problems. The method of perpendicularizing the cross-sectional shape of the edge portion of the film pattern was studied intensively. Heretofore, for example, a method has been developed in which the film composition of the chromium-based phase shift film has a gradient and a film by adjusting the content of nitrogen which makes the etching rate faster or the content of carbon which slows the etching rate. The etching speed in the thick direction has a change. However, in this method, it is very difficult to achieve uniformity of transmittance in the entire phase shift mask of a large area.

因此，本發明係鑒於上述問題點而開發者，其目的在於提供可藉由濕式蝕刻而使相位偏移膜圖案化為可充分發揮相位偏移效果之剖面形狀的相位偏移光罩基底及其製造方法、與具有可充分發揮相位偏移效果之相位偏移膜圖案的相位偏移光罩之製造方法。 Accordingly, the present invention has been made in view of the above problems, and an object thereof is to provide a phase shift mask substrate capable of patterning a phase shift film into a cross-sectional shape capable of sufficiently exhibiting a phase shift effect by wet etching, and A method of manufacturing the same, and a method of manufacturing a phase shift mask having a phase shift film pattern capable of exhibiting a phase shift effect.

為了解決上述問題，本發明具有以下之構成。 In order to solve the above problems, the present invention has the following constitution.

(構成1)一種相位偏移光罩基底，其特徵在於，其係於透明基板上形成有含有鉻、氧及氮之相位偏移膜者，且於上述相位偏移膜，自其最表面朝向膜深度方向形成有組成梯度區域，該組成梯度區域中，自上述最表面朝向膜深度方向減少之氧相對於鉻之比例(O/Cr)之最大值為2以上，且，自上述最表面朝向膜深度方向減少之氮相對於鉻之比例(N/Cr)之最大值為0.45以下。 (Configuration 1) A phase shift mask substrate characterized in that a phase shift film containing chromium, oxygen, and nitrogen is formed on a transparent substrate, and the phase shift film is oriented from the outermost surface thereof. a composition gradient region is formed in the film depth direction, and the maximum value of the ratio of oxygen to chromium (O/Cr) which decreases from the outermost surface toward the film depth direction is 2 or more, and is oriented from the outermost surface. The maximum value of the ratio of nitrogen to chromium (N/Cr) which is reduced in the depth direction of the film is 0.45 or less.

(構成2)如構成1之相位偏移光罩基底，其特徵在於，上述相位偏移膜之上述組成梯度區域係藉由對上述最表面之真空紫外線照射處理而形成。 (Configuration 2) The phase shift mask substrate of the first aspect, wherein the composition gradient region of the phase shift film is formed by vacuum ultraviolet irradiation treatment on the outermost surface.

(構成3)如構成1或2之相位偏移光罩基底，其特徵在於，上述相位偏移膜之上述最表面之膜密度為2.0g/cm3以上。 (Configuration 3) The phase shift mask substrate of the first or second aspect, wherein the film density of the outermost surface of the phase shift film is 2.0 g/cm 3 or more.

(構成4)如構成1至3中任一項之相位偏移光罩基底，其特徵在於，上述組成梯度區域之膜厚為0.1nm以上10nm以下。 (Aspect 4) The phase shift mask substrate according to any one of 1 to 3, wherein the composition gradient region has a film thickness of 0.1 nm or more and 10 nm or less.

(構成5)如構成1至4中任一項之相位偏移光罩基底，其特徵在於，除上述組成梯度區域及上述透明基板之附近區域以外的上述相位 偏移膜中之膜深度方向之各元素之組成比大致均一。 (Claim 5) The phase shift mask substrate according to any one of 1 to 4, characterized in that the phase other than the composition gradient region and the vicinity of the transparent substrate The composition ratio of each element in the depth direction of the film in the offset film is substantially uniform.

(構成6)如構成1至5中任一項之相位偏移光罩基底，其特徵在於，上述相位偏移膜進而含有碳。 (Aspect 6) The phase shift mask substrate according to any one of 1 to 5, wherein the phase shift film further contains carbon.

(構成7)一種相位偏移光罩基底之製造方法，其特徵在於，其係藉由濺鍍法而於透明基板上形成含有鉻、氧及氮之相位偏移膜者，且包含：成膜步驟，其係於上述透明基板上成膜上述相位偏移膜；及真空紫外線照射處理步驟，其係對所成膜之上述相位偏移膜之最表面進行真空紫外線照射處理；該真空紫外線照射處理步驟中，於自上述相位偏移膜之上述最表面朝向膜深度方向形成之組成梯度區域中，將自上述最表面朝向膜深度方向減少之氧相對於鉻之比例(O/Cr)之最大值改為2以上，且，將自上述最表面朝向膜深度方向減少之氮相對於鉻之比例(N/Cr)之最大值改為0.45以下。 (Configuration 7) A method of manufacturing a phase shift mask substrate, characterized in that a phase shift film containing chromium, oxygen, and nitrogen is formed on a transparent substrate by sputtering, and includes: film formation a step of forming the phase shift film on the transparent substrate; and a vacuum ultraviolet irradiation treatment step of performing vacuum ultraviolet irradiation on the outermost surface of the phase shift film formed; the vacuum ultraviolet irradiation treatment In the step, in the composition gradient region formed from the outermost surface of the phase shift film toward the film depth direction, the maximum ratio of oxygen to chromium (O/Cr) decreased from the outermost surface toward the film depth direction The value is changed to 2 or more, and the maximum value of the ratio of nitrogen to chromium (N/Cr) which decreases from the outermost surface toward the film depth direction is changed to 0.45 or less.

(構成8)如構成7之相位偏移光罩基底之製造方法，其特徵在於，上述真空紫外線照射處理步驟係將上述相位偏移膜之上述最表面之膜密度改為2.0g/cm3以上。 (Configuration 8) The method for producing a phase shift mask base according to the seventh aspect, wherein the vacuum ultraviolet irradiation processing step changes the film density of the outermost surface of the phase shift film to 2.0 g/cm 3 or more. .

(構成9)如構成7或8之相位偏移光罩基底之製造方法，其特徵在於，除上述組成梯度區域及上述透明基板之附近區域以外的上述相位偏移膜中之膜深度方向之各元素之組成比大致均一。 (Configuration 9) The method of manufacturing a phase shift mask substrate of the seventh or eighth aspect, wherein each of the phase shifting films other than the composition gradient region and the vicinity of the transparent substrate has a film depth direction The composition ratio of the elements is roughly uniform.

(構成10)如構成7至9中任一項之相位偏移光罩基底之製造方法，其特徵在於，上述成膜步驟係積層相同材料而成膜上述相位偏移膜。 (Aspect 10) The method for producing a phase shift mask substrate according to any one of the items 7 to 9, characterized in that, in the film forming step, the phase shift film is formed by laminating the same material.

(構成11)如構成7至10中任一項之相位偏移光罩基底之製造方法，其特徵在於，上述成膜步驟係藉由使用包含鉻之濺鍍靶，且利用包含惰性氣體與使該相位偏移膜氧化及氮化之活性氣體之混合氣體實施反應性濺鍍而進行。 (Claim 11) The method for producing a phase shift mask substrate according to any one of Items 7 to 10, wherein the film forming step is performed by using a sputtering target containing chromium and using an inert gas The mixed gas of the phase shifting film oxidation and nitriding active gas is subjected to reactive sputtering.

(構成12)如構成11之相位偏移光罩基底之製造方法，其特徵在於，上述混合氣體進而包含使上述相位偏移膜碳化之活性氣體。 (Configuration 12) The method for producing a phase shift mask base according to the configuration 11, characterized in that the mixed gas further includes an active gas that carbonizes the phase shift film.

(構成13)如構成11或12之相位偏移光罩基底之製造方法，其特徵在於，上述成膜步驟係利用連續(inline)式濺鍍裝置而進行。 (Structure 13) A method of manufacturing a phase shift mask substrate according to Embodiment 11 or 12, wherein the film forming step is performed by an in-line sputtering apparatus.

(構成14)如構成13之相位偏移光罩基底之製造方法，其特徵在於，自上述濺鍍靶附近之上述透明基板之搬送方向上的、該濺鍍靶之下游側，供給上述混合氣體。 (Configuration 14) The method of manufacturing a phase shift mask base according to the configuration 13, wherein the mixed gas is supplied from a downstream side of the sputtering target in a transport direction of the transparent substrate in the vicinity of the sputtering target .

(構成15)如構成7至14中任一項之相位偏移光罩基底之製造方法，其特徵在於，上述真空紫外線照射處理步驟中，對於上述組成梯度區域中之氧相對於鉻之比例(O/Cr)之減少率，使上述真空紫外線照射處理後的減少率大於上述真空紫外線照射處理前的減少率，且，對於氮相對於鉻之比例(N/Cr)之減少率，使上述真空紫外線照射處理後的減少率小於上述真空紫外線照射處理前的減少率。 (Claim 15) The method for producing a phase shift mask substrate according to any one of the items 7 to 14, wherein in the vacuum ultraviolet irradiation treatment step, the ratio of oxygen to chromium in the composition gradient region is The reduction rate of O/Cr) is such that the reduction rate after the vacuum ultraviolet irradiation treatment is larger than the reduction rate before the vacuum ultraviolet irradiation treatment, and the vacuum is made to decrease the ratio of nitrogen to chromium (N/Cr). The reduction rate after the ultraviolet irradiation treatment is smaller than the reduction rate before the vacuum ultraviolet irradiation treatment.

(構成16)一種相位偏移光罩之製造方法，其特徵在於，於如構成1至6中任一項之相位偏移光罩基底、或藉由如構成7至15中任一項之相位偏移光罩基底之製造方法而製作的相位偏移光罩基底之上述相位偏移膜上形成光阻劑膜圖案，將該光阻劑膜圖案作為光罩而對上述相位偏移膜進行濕式蝕刻，於上述透明基板上形成相位偏移膜圖案。 (Configuration 16) A method of manufacturing a phase shift mask, characterized in that the phase shift mask substrate according to any one of Compositions 1 to 6 or the phase as constituted by any one of Items 7 to 15 Forming a photoresist film pattern on the phase shift film of the phase shift mask substrate produced by the method for manufacturing the offset mask substrate, and using the photoresist film pattern as a mask to wet the phase shift film Etching, forming a phase shift film pattern on the transparent substrate.

如上所述，根據本發明之相位偏移光罩基底，於透明基板上形成有含有鉻、氧及氮之相位偏移膜。於該相位偏移膜，自其最表面朝向膜深度方向形成組成梯度區域，該組成梯度區域中，自上述最表面朝向膜深度方向減少之氧相對於鉻之比例(O/Cr)之最大值為2以上，且，自上述最表面朝向膜深度方向減少之氮相對於鉻之比例(N/Cr)之最大值為0.45以下。因此，該相位偏移光罩基底中，可藉由濕式蝕刻而使其相位偏移膜圖案化為可充分發揮相位偏移效果之剖面形狀。該 相位偏移光罩基底係可使藉由使其相位偏移膜圖案化而獲得之相位偏移膜圖案之邊緣部分之剖面形狀成為可充分發揮相位偏移效果之剖面形狀者，故而可形成使解像度提高、具有具備良好之CD特性之相位偏移膜圖案的相位偏移光罩之製造用原版。 As described above, according to the phase shift mask substrate of the present invention, a phase shift film containing chromium, oxygen and nitrogen is formed on the transparent substrate. In the phase shifting film, a composition gradient region is formed from the outermost surface thereof toward the film depth direction, and the ratio of the ratio of oxygen to chromium (O/Cr) which decreases from the outermost surface toward the film depth direction in the composition gradient region The maximum value of the ratio of nitrogen to chromium (N/Cr) which is reduced from the outermost surface toward the film depth direction is 0.45 or less. Therefore, in the phase shift mask substrate, the phase shift film can be patterned by wet etching into a cross-sectional shape in which the phase shift effect can be sufficiently exhibited. The In the phase shift mask base, the cross-sectional shape of the edge portion of the phase shift film pattern obtained by patterning the phase shift film can be formed into a cross-sectional shape in which the phase shift effect can be sufficiently exhibited, so that it can be formed A master for manufacturing a phase shift mask having improved resolution and a phase shift film pattern having good CD characteristics.

又，根據本發明之相位偏移光罩基底之製造方法，包含：成膜步驟，其係藉由濺鍍法而於透明基板上成膜含有鉻、氧及氮之相位偏移膜；及真空紫外線照射處理步驟，其係對所成膜之上述相位偏移膜之最表面進行真空紫外線照射處理。該真空紫外線照射處理步驟係如下步驟：於自上述相位偏移膜之上述最表面朝向膜深度方向形成之組成梯度區域中，將自上述最表面朝向膜深度方向減少之氧相對於鉻之比例(O/Cr)之最大值改為2以上，且，將自上述最表面朝向膜深度方向減少之氮相對於鉻之比例(N/Cr)之最大值改為0.45以下。因此，可製造如下相位偏移光罩基底：可藉由濕式蝕刻而使相位偏移膜圖案化為可充分發揮相位偏移效果之剖面形狀。由於可使相位偏移膜圖案之邊緣部分之剖面形狀成為可充分發揮相位偏移效果之剖面形狀，故而可製造使解像度提高、可圖案化為具備良好之CD特性之相位偏移膜圖案的相位偏移光罩基底。 Further, a method of manufacturing a phase shift mask substrate according to the present invention includes: a film forming step of forming a phase shift film containing chromium, oxygen, and nitrogen on a transparent substrate by sputtering; and vacuum The ultraviolet irradiation treatment step is a vacuum ultraviolet irradiation treatment on the outermost surface of the phase shift film formed on the film. The vacuum ultraviolet irradiation treatment step is a step of reducing a ratio of oxygen to chromium from the outermost surface toward the film depth direction in a composition gradient region formed from the outermost surface of the phase shift film toward the film depth direction ( The maximum value of O/Cr) is changed to 2 or more, and the maximum value of the ratio of nitrogen to chromium (N/Cr) which decreases from the outermost surface toward the film depth direction is changed to 0.45 or less. Therefore, it is possible to manufacture a phase shift mask substrate in which the phase shift film can be patterned by wet etching into a cross-sectional shape in which the phase shift effect can be sufficiently exerted. Since the cross-sectional shape of the edge portion of the phase shift film pattern can be made into a cross-sectional shape that can sufficiently exhibit the phase shift effect, it is possible to manufacture a phase shifting film pattern having improved CD characteristics and having a good CD characteristic. Offset the reticle base.

又，根據本發明之相位偏移光罩之製造方法，使用上述相位偏移光罩基底來製造相位偏移光罩。因此，可製造具有可充分發揮相位偏移效果之相位偏移膜圖案的相位偏移光罩。由於相位偏移膜圖案可充分發揮相位偏移效果，故而可製造使解像度提高、具有具備良好之CD特性之相位偏移膜圖案的相位偏移光罩。該相位偏移光罩可應對線與間隙圖案或接觸孔之微細化。 Further, according to the method of manufacturing a phase shift mask of the present invention, the phase shift mask is manufactured using the phase shift mask substrate. Therefore, a phase shift mask having a phase shift film pattern capable of exerting a phase shift effect can be manufactured. Since the phase shift film pattern can sufficiently exhibit the phase shift effect, it is possible to manufacture a phase shift mask having a phase shift film pattern having improved CD characteristics and having improved resolution. The phase shift mask can cope with the miniaturization of the line and gap patterns or contact holes.

1‧‧‧相位偏移光罩基底 1‧‧‧ phase shift mask base

2‧‧‧透明基板 2‧‧‧Transparent substrate

3‧‧‧相位偏移膜 3‧‧‧ phase offset film

3'‧‧‧相位偏移膜圖案 3 ' ‧‧‧ phase offset film pattern

3a‧‧‧最表面 3a‧‧‧Most surface

4‧‧‧遮光膜 4‧‧‧Shade film

4'‧‧‧遮光膜圖案 4 ' ‧‧‧ shading film pattern

5‧‧‧光阻劑膜 5‧‧‧ photoresist film

5'‧‧‧光阻劑膜圖案 5 ' ‧‧‧ photoresist film pattern

10‧‧‧相位偏移光罩基底 10‧‧‧ phase shift mask base

11‧‧‧濺鍍裝置 11‧‧‧ Sputtering device

13‧‧‧第1濺鍍靶 13‧‧‧1st sputtering target

14‧‧‧第2濺鍍靶 14‧‧‧2nd Sputtering Target

15‧‧‧第3濺鍍靶 15‧‧‧3rd Sputtering Target

30‧‧‧相位偏移光罩 30‧‧‧ phase offset mask

31‧‧‧相位偏移光罩 31‧‧‧ phase offset mask

B‧‧‧主體部 B‧‧‧ Main Body

BU‧‧‧緩衝腔室 BU‧‧‧ buffer chamber

C1‧‧‧交點 C1‧‧‧ intersection

C2‧‧‧交點 C2‧‧‧ intersection

F‧‧‧被蝕刻剖面 F‧‧‧etched profile

GA11‧‧‧第1氣體導入口 GA11‧‧‧1st gas inlet

GA12‧‧‧第2氣體導入口 GA12‧‧‧2nd gas inlet

GA21‧‧‧第3氣體導入口 GA21‧‧‧3rd gas inlet

GA22‧‧‧第4氣體導入口 GA22‧‧‧4th gas inlet

GA31‧‧‧第5氣體導入口 GA31‧‧‧5th gas inlet

GA32‧‧‧第6氣體導入口 GA32‧‧‧6th gas inlet

LL‧‧‧搬入腔室 LL‧‧‧ moving into the chamber

R1‧‧‧組成梯度區域 R1‧‧‧ composition gradient region

R2‧‧‧透明基板附近區域 R2‧‧‧near the transparent substrate

SP1‧‧‧第1濺鍍腔室 SP1‧‧‧1st sputtering chamber

SP2‧‧‧第2濺鍍腔室 SP2‧‧‧2nd sputtering chamber

T‧‧‧膜厚 T‧‧‧ film thickness

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

θ‧‧‧剖面角度 Θ‧‧‧section angle

圖1係表示本發明之實施形態1之相位偏移光罩基底之構成的剖視圖。 Fig. 1 is a cross-sectional view showing the configuration of a phase shift mask base according to a first embodiment of the present invention.

圖2(a)及(b)係表示圖1所示之相位偏移光罩基底之製造方法之各步驟的剖視圖。 2(a) and 2(b) are cross-sectional views showing respective steps of a method of manufacturing the phase shift mask substrate shown in Fig. 1.

圖3係表示可使用於相位偏移光罩基底之成膜的連續式濺鍍裝置之模式圖。 Figure 3 is a schematic view showing a continuous sputtering apparatus which can be used for film formation of a phase shift mask substrate.

圖4(a)~(e)係表示本發明之實施形態2之相位偏移光罩之製造方法之各步驟之剖視圖。 4(a) to 4(e) are cross-sectional views showing respective steps of a method of manufacturing a phase shift mask according to a second embodiment of the present invention.

圖5係表示本發明之實施形態3之相位偏移光罩基底之構成之剖視圖。 Fig. 5 is a cross-sectional view showing the configuration of a phase shift mask base according to a third embodiment of the present invention.

圖6(a)~(g)係表示圖5所示之相位偏移光罩基底之製造方法之各步驟之剖視圖。 6(a) to 6(g) are cross-sectional views showing respective steps of a method of manufacturing the phase shift mask substrate shown in Fig. 5.

圖7(a)~(e)係表示本發明之實施形態4之相位偏移光罩之製造方法之各步驟之剖視圖。 7(a) to 7(e) are cross-sectional views showing respective steps of a method of manufacturing a phase shift mask according to a fourth embodiment of the present invention.

圖8係表示相對於比較例1之相位偏移光罩基底之相位偏移膜的深度方向之組成分析結果之圖。 Fig. 8 is a view showing the results of composition analysis in the depth direction of the phase shift film of the phase shift mask substrate of Comparative Example 1.

圖9係表示相對於實施例1之相位偏移光罩基底之相位偏移膜的深度方向之組成分析結果之圖。 Fig. 9 is a view showing the result of composition analysis in the depth direction of the phase shift film of the phase shift mask substrate of Example 1.

圖10係表示關於實施例1之相位偏移光罩基底與比較例1之相位偏移光罩基底，氧相對於鉻之比例(O/Cr)與膜深度之關係之圖。 Fig. 10 is a graph showing the relationship between the ratio of oxygen to chromium (O/Cr) and the film depth in the phase shift mask substrate of Example 1 and the phase shift mask substrate of Comparative Example 1.

圖11係表示關於實施例1之相位偏移光罩基底與比較例1之相位偏移光罩基底，氮相對於鉻之比例(N/Cr)與膜深度之關係之圖。 Fig. 11 is a graph showing the relationship between the ratio of nitrogen to chromium (N/Cr) and the film depth in the phase shift mask substrate of Example 1 and the phase shift mask substrate of Comparative Example 1.

圖12係表示實施例1之相位偏移膜圖案之邊緣部分之剖面形狀之剖面照片。 Fig. 12 is a cross-sectional view showing the cross-sectional shape of the edge portion of the phase shift film pattern of the first embodiment.

圖13係表示比較例1之相位偏移光罩之相位偏移膜圖案之邊緣部分之剖面形狀之剖面照片。 Fig. 13 is a cross-sectional view showing the cross-sectional shape of the edge portion of the phase shift film pattern of the phase shift mask of Comparative Example 1.

圖14係用以說明相位偏移光罩之相位偏移膜圖案之邊緣部分之剖面中之剖面角度的剖視圖。 Figure 14 is a cross-sectional view for explaining a cross-sectional angle in a cross section of an edge portion of a phase shift film pattern of a phase shift mask.

圖15係表示實施例2之相位偏移光罩之相位偏移膜圖案之邊緣部分之剖面形狀的剖面照片。 Fig. 15 is a cross-sectional view showing the cross-sectional shape of the edge portion of the phase shift film pattern of the phase shift mask of the second embodiment.

圖16係表示比較例2之相位偏移光罩之相位偏移膜圖案之邊緣部分之剖面形狀的剖面照片。 Fig. 16 is a cross-sectional view showing the cross-sectional shape of the edge portion of the phase shift film pattern of the phase shift mask of Comparative Example 2.

以下，對本發明之實施形態之相位偏移光罩基底及其製造方法、與使用該相位偏移光罩基底之相位偏移光罩之製造方法進行詳細說明。 Hereinafter, a phase shift mask base according to an embodiment of the present invention, a method of manufacturing the same, and a method of manufacturing a phase shift mask using the phase shift mask base will be described in detail.

實施形態1. Embodiment 1.

實施形態1中，對顯示裝置製造用之相位偏移光罩基底(透明基板/相位偏移膜)及其製造方法進行說明。 In the first embodiment, a phase shift mask base (transparent substrate/phase shift film) for manufacturing a display device and a method of manufacturing the same will be described.

圖1係表示本發明之實施形態1之相位偏移光罩基底之構成的剖視圖，圖2(a)及圖2(b)係表示圖1所示之相位偏移光罩基底之製造方法之各步驟的剖視圖，圖3係表示可使用於相位偏移光罩基底之成膜的連續式濺鍍裝置之模式圖。 1 is a cross-sectional view showing a configuration of a phase shift mask substrate according to Embodiment 1 of the present invention, and FIGS. 2(a) and 2(b) are views showing a method of manufacturing the phase shift mask substrate shown in FIG. 1. A cross-sectional view of each step, and Fig. 3 is a schematic view showing a continuous sputtering apparatus which can be used for film formation of a phase shift mask base.

如圖1所示，實施形態1之相位偏移光罩基底1係具有於透明基板2上形成有含有鉻、氧及氮之相位偏移膜3之構成。 As shown in FIG. 1, the phase shift mask base 1 of the first embodiment has a configuration in which a phase shift film 3 containing chromium, oxygen, and nitrogen is formed on a transparent substrate 2.

以此方式構成之實施形態1之相位偏移光罩基底1的製造方法包含：準備步驟，其係準備透明基板2；成膜步驟(以下，存在稱為相位偏移膜形成步驟之情形)，其係藉由濺鍍而於透明基板2之主表面上成膜含有鉻、氧及氮之相位偏移膜3；及真空紫外線照射處理步驟，其係對所成膜之相位偏移膜3之最表面3a進行真空紫外線(以下，存在稱為VUV之情形)照射處理。 The method for manufacturing the phase shift mask substrate 1 of the first embodiment configured in this manner includes a preparation step of preparing a transparent substrate 2, and a film forming step (hereinafter, there is a case where a phase shift film forming step is performed). Forming a phase shift film 3 containing chromium, oxygen and nitrogen on the main surface of the transparent substrate 2 by sputtering; and a vacuum ultraviolet irradiation treatment step for the phase shift film 3 of the formed film The outermost surface 3a is subjected to irradiation treatment of vacuum ultraviolet rays (hereinafter, there is a case called VUV).

以下，對各步驟進行詳細說明。 Hereinafter, each step will be described in detail.

1.準備步驟 1. Preparation steps

首先，準備透明基板2。 First, the transparent substrate 2 is prepared.

透明基板2之材料只要為相對於所使用之曝光之光具有透光性之材料，則並無特別限制。例如，可列舉合成石英玻璃、鈉鈣玻璃、無鹼玻璃。 The material of the transparent substrate 2 is not particularly limited as long as it is a material having light transmissivity with respect to the light to be used for exposure. For example, synthetic quartz glass, soda lime glass, and alkali-free glass are mentioned.

2.相位偏移膜形成步驟 2. Phase shift film formation step

其次，如圖2(a)所示，藉由濺鍍而於透明基板2之主表面上形成含有鉻、氧及氮之相位偏移膜3。 Next, as shown in FIG. 2(a), a phase shift film 3 containing chromium, oxygen, and nitrogen is formed on the main surface of the transparent substrate 2 by sputtering.

詳細而言，該相位偏移膜形成步驟中進行如下成膜步驟：使用包含鉻之濺鍍靶，施加濺鍍功率，藉由利用包含惰性氣體與使相位偏移膜氧化及氮化之活性氣體之混合氣體進行反應性濺鍍，而成膜含有鉻、氧及氮之相位偏移膜3。 In detail, in the phase shift film forming step, a film forming step is performed in which sputtering power is applied using a sputtering target containing chromium, and an active gas containing an inert gas and oxidizing and nitriding the phase shift film is used. The mixed gas is subjected to reactive sputtering to form a phase shift film 3 containing chromium, oxygen and nitrogen.

相位偏移膜3具有改變曝光之光之相位之性質(相位偏移效果)。藉由該性質，而於透過相位偏移膜3曝光之光與僅透過透明基板2之曝光之光之間產生特定之相位差。於曝光之光為包含300nm以上500nm以下之波長範圍之光的複合光之情形時，相位偏移膜3以相對於代表波長之光產生特定之相位差之方式而形成。例如，於曝光之光為包含i射線、h射線及g射線之複合光之情形時，相位偏移膜3以相對於i射線、h射線及g射線中之任一者產生180度之相位差之方式而形成。又，為了發揮相位偏移效果，例如，將i射線下之相位偏移膜3之相位差設定為180度±10度之範圍，較佳為設定為大致180度。又，例如，較佳為將i射線下之相位偏移膜3之透過率設定為1%以上20%以下之範圍。尤其是，如下所述之真空紫外線照射處理會對相位偏移膜3之最表面之膜質帶來影響，結果，於設為利用濕式蝕刻之相位偏移膜之圖案化中可充分發揮相位效果的剖面形狀的方面，較佳為形成為使i射線下之相位偏移膜3之透過率為3%以上15%以下之範圍的膜組成。 The phase shift film 3 has a property of changing the phase of the exposed light (phase shift effect). By this property, a specific phase difference is generated between the light that is exposed through the phase shift film 3 and the light that is only transmitted through the transparent substrate 2. When the light to be exposed is a composite light including light having a wavelength range of 300 nm or more and 500 nm or less, the phase shift film 3 is formed to generate a specific phase difference with respect to light of a representative wavelength. For example, when the exposed light is a composite light including i-rays, h-rays, and g-rays, the phase shift film 3 generates a phase difference of 180 degrees with respect to any of the i-rays, h-rays, and g-rays. Formed by the way. Further, in order to exhibit the phase shift effect, for example, the phase difference of the phase shift film 3 under the i-ray is set to a range of 180 degrees ± 10 degrees, preferably set to approximately 180 degrees. Further, for example, it is preferable to set the transmittance of the phase shift film 3 under the i-ray to a range of 1% or more and 20% or less. In particular, the vacuum ultraviolet irradiation treatment as described below affects the film quality of the outermost surface of the phase shift film 3, and as a result, the phase effect can be sufficiently exhibited in the patterning of the phase shift film by wet etching. In terms of the cross-sectional shape, it is preferable to form a film composition in which the transmittance of the phase shift film 3 under the i-ray is in the range of 3% or more and 15% or less.

相位偏移膜3由至少含有鉻(Cr)、氧(O)及氮(N)之鉻系材料而構成。於該鉻系材料中，除了上述三個元素以外，亦可根據需要，進而 含有碳(C)。於為包含碳之鉻系材料之情形時，可提高相位偏移膜3之耐藥性、耐洗淨性。 The phase shift film 3 is composed of a chromium-based material containing at least chromium (Cr), oxygen (O), and nitrogen (N). In addition to the above three elements, the chromium-based material may be further as needed. Contains carbon (C). In the case of a chromium-containing material containing carbon, the chemical resistance and the washing resistance of the phase shift film 3 can be improved.

具體而言，作為構成相位偏移膜3之鉻系材料，例如，可列舉鉻氧化氮化物(CrON)、鉻碳化氧化氮化物(CrCON)。進而，於不脫離本發明之效果之範圍內，該等鉻系材料亦可包含氫(H)、氟(F)。 Specifically, examples of the chromium-based material constituting the phase shift film 3 include chromium oxide nitride (CrON) and chromium carbonized oxide nitride (CrCON). Further, the chromium-based material may contain hydrogen (H) or fluorine (F) without departing from the effects of the present invention.

相位偏移膜3例如可藉由如以下之濺鍍靶、濺鍍氣體環境而成膜。 The phase shift film 3 can be formed, for example, by a sputtering target or a sputtering gas atmosphere as follows.

作為使用於相位偏移膜3之成膜的濺鍍靶，可選擇包含鉻(Cr)者。具體而言，可列舉鉻(Cr)、鉻之氮化物、鉻之氧化物、鉻之碳化物、鉻之氧化氮化物、鉻之碳化氮化物、鉻之氧化碳化物、及鉻之氧化碳化氮化物。 As the sputtering target used for film formation of the phase shift film 3, those containing chromium (Cr) may be selected. Specific examples thereof include chromium (Cr), chromium nitride, chromium oxide, chromium carbide, chromium oxide nitride, chromium carbonitride, chromium oxidized carbide, and chromium oxynitride nitrogen. Compound.

相位偏移膜3之成膜時之濺鍍氣體環境包括包含惰性氣體與使相位偏移膜氧化及氮化之活性氣體的混合氣體。作為惰性氣體，可列舉氦(He)氣體、氖(Ne)氣體、氬(Ar)氣體、氪(Kr)氣體、及氙(Xe)氣體，且可選擇該等氣體中之至少一種氣體。作為活性氣體，可列舉氧(O2)氣體、氮(N2)氣體、一氧化氮(NO)氣體、二氧化氮(NO2)氣體、及一氧化二氮(N2O)氣體，且可選擇該等氣體中之至少一種氣體。又，於上述混合氣體中，可包含使相位偏移膜碳化之活性氣體。作為使之碳化之活性氣體，可列舉一氧化碳(CO)氣體、二氧化碳(CO2)氣體、及碳化氫系氣體，可選擇該等氣體中之至少一種氣體。作為碳化氫系氣體，例如，可列舉甲烷氣體、丁烷氣體、丙烷氣體、苯乙烯氣體。進而，於上述混合氣體中，亦可以不脫離本發明之效果之範圍之供給量而包含作為活性氣體的氟系氣體。作為氟系氣體，例如，可列舉CF4氣體、CHF3氣體、SF6氣體或於該等氣體中混合O2氣體的氣體。 The sputtering gas atmosphere at the time of film formation of the phase shift film 3 includes a mixed gas containing an inert gas and an active gas which oxidizes and nitrides the phase shift film. Examples of the inert gas include helium (He) gas, neon (Ne) gas, argon (Ar) gas, krypton (Kr) gas, and xenon (Xe) gas, and at least one of these gases may be selected. Examples of the active gas include oxygen (O 2 ) gas, nitrogen (N 2 ) gas, nitrogen monoxide (NO) gas, nitrogen dioxide (NO 2 ) gas, and nitrous oxide (N 2 O) gas, and At least one of the gases may be selected. Further, the mixed gas may include an active gas that carbonizes the phase shift film. Examples of the active gas which carbonizes include carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, and hydrocarbon gas, and at least one of these gases can be selected. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas. Further, in the mixed gas, a fluorine-based gas as an active gas may be contained without departing from the supply amount in the range of the effect of the present invention. Examples of the fluorine-based gas include CF 4 gas, CHF 3 gas, SF 6 gas, or a gas in which O 2 gas is mixed with the gas.

上述濺鍍靶之形成材料與濺鍍氣體環境之氣體之種類之組合、或濺鍍氣體環境中之活性氣體與惰性氣體之混合比例可根據構成相位 偏移膜3之材料之種類或組成而適當決定。 The combination of the material of the sputtering target and the type of gas in the sputtering gas environment, or the mixing ratio of the active gas and the inert gas in the sputtering gas environment may be based on the composition phase The type or composition of the material of the offset film 3 is appropriately determined.

相位偏移膜3之膜厚可於80nm以上180nm以下之範圍適當調整，以獲得所期望之光學特性(相位差)。 The film thickness of the phase shift film 3 can be appropriately adjusted in the range of 80 nm or more and 180 nm or less to obtain desired optical characteristics (phase difference).

相位偏移膜3亦可為單層膜及積層膜中之任一者。於相位偏移膜3為積層膜之情形時，自於各層之界面間使組成一致、例如使濕式蝕刻時之蝕刻速度固定、且防止被蝕刻剖面中之所謂侵蝕現象之產生之觀點而言，較佳為將相同材料積層而成膜相位偏移膜3。又，於積層膜之情形時，較佳為相位偏移膜3之成膜步驟以相同之成膜條件進行複數次。較佳為複數次之成膜步驟係於相同之濺鍍裝置中連續地進行。於連續地進行複數次之成膜步驟之情形時，較佳為使用如下所述之連續式濺鍍裝置。再者，於成膜步驟進行複數次之情形時，於相位偏移膜3之成膜時可使施加至濺鍍靶之濺鍍功率變小。 The phase shift film 3 may be either a single layer film or a laminate film. In the case where the phase shift film 3 is a laminated film, the composition is uniform from each other, for example, the etching rate at the time of wet etching is fixed, and the so-called erosion phenomenon in the etched cross section is prevented. Preferably, the same material is laminated to form the film phase shift film 3. Further, in the case of a laminated film, it is preferred that the film forming step of the phase shift film 3 be performed plural times under the same film forming conditions. Preferably, the plurality of film forming steps are carried out continuously in the same sputtering apparatus. In the case where the film formation step is carried out plural times in succession, it is preferred to use a continuous sputtering apparatus as described below. Further, in the case where the film formation step is performed plural times, the sputtering power applied to the sputtering target can be made small at the time of film formation of the phase shift film 3.

此種相位偏移膜形成步驟例如可使用圖3所示之連續式濺鍍裝置11進行。 Such a phase shift film forming step can be performed, for example, using the continuous sputtering apparatus 11 shown in FIG.

濺鍍裝置11係連續式，且包括搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL該等5個腔室。該等5個腔室係依序地連續配置。 The sputtering apparatus 11 is of a continuous type and includes five chambers such as a loading chamber LL, a first sputtering chamber SP1, a buffer chamber BU, a second sputtering chamber SP2, and a carry-out chamber ULL. The five chambers are sequentially arranged in series.

搭載於托盤(未圖示)之透明基板2可以特定之搬送速度向箭頭S之方向且以搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL之順序被搬送。又，搭載於托盤(未圖示)之透明基板2可向與箭頭S相反之方向且以搬出腔室ULL、第2濺鍍腔室SP2、緩衝腔室BU、第1濺鍍腔室SP1、及搬入腔室LL之順序返回。 The transparent substrate 2 mounted on a tray (not shown) can be loaded into the chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second sputtering chamber SP2 at a specific conveying speed in the direction of the arrow S. And the order of moving out of the chamber ULL is carried. Further, the transparent substrate 2 mounted on a tray (not shown) can be moved out of the chamber ULL, the second sputtering chamber SP2, the buffer chamber BU, and the first sputtering chamber SP1 in the direction opposite to the arrow S. And the order of moving into the chamber LL is returned.

搬入腔室LL與第1濺鍍腔室SP1、第2濺鍍腔室SP2與搬出腔室ULL藉由分隔板而分隔。又，搬入腔室LL及搬出腔室ULL係藉由分隔板而與濺鍍裝置11之外部分隔。 The carry-in chamber LL and the first sputtering chamber SP1, the second sputtering chamber SP2, and the carry-out chamber ULL are partitioned by a partition plate. Further, the carry-in chamber LL and the carry-out chamber ULL are partially separated from the outside of the sputtering apparatus 11 by the partition plate.

搬入腔室LL、緩衝腔室BU、及搬出腔室ULL連接於進行排氣之 排氣裝置(未圖示)。 The moving chamber LL, the buffer chamber BU, and the carry-out chamber are connected to the exhaust gas. Exhaust device (not shown).

於第1濺鍍腔室SP1，於搬入腔室LL側，配置有包含用以形成相位偏移膜3之鉻的第1濺鍍靶13，於第1濺鍍靶13附近之透明基板2之箭頭S所示之搬送方向上之、相對於第1濺鍍靶13為上游側的位置配置有第1氣體導入口GA11，於相對於第1濺鍍靶13為下游側的位置配置有第2氣體導入口GA12。又，於第1濺鍍腔室SP1，於緩衝腔室BU側，配置有包含用以形成相位偏移膜3之鉻的第2濺鍍靶14，於第2濺鍍靶14附近之透明基板2之箭頭S所示之搬送方向上之、相對於第2濺鍍靶14為上游側的位置配置有第3氣體導入口GA21，於相對於第2濺鍍靶14為下游側的位置配置有第4氣體導入口GA22。 In the first sputtering chamber SP1, a first sputtering target 13 including chromium for forming the phase shift film 3 is disposed on the side of the loading chamber LL, and the transparent substrate 2 in the vicinity of the first sputtering target 13 is disposed. In the transport direction indicated by the arrow S, the first gas introduction port GA11 is disposed at a position on the upstream side of the first sputtering target 13, and the second gas placement port GA11 is disposed on the downstream side of the first sputtering target 13 Gas introduction port GA12. Further, in the first sputtering chamber SP1, a second sputtering target 14 including chromium for forming the phase shift film 3 and a transparent substrate in the vicinity of the second sputtering target 14 are disposed on the buffer chamber BU side. In the transport direction indicated by the arrow S, the third gas introduction port GA21 is disposed at a position on the upstream side of the second sputtering target 14, and the downstream side of the second sputtering target 14 is disposed. The fourth gas introduction port GA22.

此處，第1濺鍍靶13與下游側之第2氣體導入口GA12之間隔設定得較第1濺鍍靶13與上游側之第1氣體導入口GA11之間隔更寬。與其相同，第2濺鍍靶14與下游側之第4氣體導入口GA22之間隔設定得較第2濺鍍靶14與上游側之第3氣體導入口GA21之間隔更寬。 Here, the distance between the first sputtering target 13 and the downstream second gas introduction port GA12 is set to be wider than the interval between the first sputtering target 13 and the upstream first gas introduction port GA11. Similarly to this, the distance between the second sputtering target 14 and the fourth gas inlet port GA22 on the downstream side is set to be wider than the interval between the second sputtering target 14 and the third gas inlet port GA21 on the upstream side.

再者，於第1濺鍍腔室SP1中，較佳為，濺鍍靶與下游側之氣體導入口之間隔例如設定為15cm以上50cm以下，濺鍍靶與上游側之氣體導入口之間隔例如設定為1cm以上5cm以下。 In the first sputtering chamber SP1, the distance between the sputtering target and the gas inlet port on the downstream side is preferably set to, for example, 15 cm or more and 50 cm or less, and the distance between the sputtering target and the gas inlet port on the upstream side is, for example. It is set to 1 cm or more and 5 cm or less.

於第2濺鍍腔室SP2，於緩衝腔室BU側，配置有包含用以形成相位偏移膜3之鉻的第3濺鍍靶15，於第3濺鍍靶15附近之透明基板2之箭頭S所示之搬送方向上之、相對於第3濺鍍靶15為上游側的位置配置有第5氣體導入口GA31，於相對於第3濺鍍靶15為下游側的位置配置有第6氣體導入口GA32。 In the second sputtering chamber SP2, a third sputtering target 15 including chromium for forming the phase shift film 3 is disposed on the buffer chamber BU side, and the transparent substrate 2 in the vicinity of the third sputtering target 15 is disposed. In the transport direction indicated by the arrow S, the fifth gas introduction port GA31 is disposed at a position upstream of the third sputtering target 15, and the sixth gas placement port GA31 is disposed at a position downstream of the third sputtering target 15 Gas introduction port GA32.

此處，與第1濺鍍腔室SP1相同，第3濺鍍靶15與下游側之第5氣體導入口GA31之間隔設定得較第3濺鍍靶15與上游側之第6氣體導入口GA32之間隔更寬。 Here, the distance between the third sputtering target 15 and the fifth gas inlet port GA31 on the downstream side is set to be smaller than the third sputtering target 15 and the sixth gas introduction port GA32 on the upstream side, similarly to the first sputtering chamber SP1. The interval is wider.

再者，於第2濺鍍腔室SP2中，亦與第1濺鍍腔室SP1相同，較佳 為濺鍍靶與下游側之氣體導入口之間隔例如設定為15cm以上50cm以下，濺鍍靶與上游側之氣體導入口之間隔例如設定為1cm以上5cm以下。 Further, in the second sputtering chamber SP2, it is also the same as the first sputtering chamber SP1, preferably. The distance between the sputtering target and the gas inlet port on the downstream side is, for example, 15 cm or more and 50 cm or less, and the distance between the sputtering target and the gas inlet port on the upstream side is set to, for example, 1 cm or more and 5 cm or less.

圖3中，對第1濺鍍靶13、第2濺鍍靶14、及第3濺鍍靶15標註影線而表示。 In FIG. 3, the first sputtering target 13, the second sputtering target 14, and the third sputtering target 15 are indicated by hatching.

此處，對成膜包括單層膜之相位偏移膜3之情形(1次成膜)進行說明。 Here, the case where the phase shift film 3 including the single layer film is formed (first film formation) will be described.

首先，將搭載於托盤(未圖示)之透明基板2搬入至濺鍍裝置11之搬入腔室LL。 First, the transparent substrate 2 mounted on a tray (not shown) is carried into the carrying chamber LL of the sputtering apparatus 11.

其次，使濺鍍裝置11之內部成為特定之真空度之後，例如，自第1濺鍍靶13之下游側之第2氣體導入口GA12將特定之流量之濺鍍氣體導入至第1濺鍍腔室SP1，對第1濺鍍靶13施加特定之濺鍍功率。繼續進行濺鍍功率之施加、濺鍍氣體之導入，直至透明基板2被搬送至搬出腔室ULL為止。 Next, after the inside of the sputtering apparatus 11 is made to have a specific degree of vacuum, for example, the second gas introduction port GA12 on the downstream side of the first sputtering target 13 introduces a specific flow rate of the sputtering gas into the first sputtering chamber. The chamber SP1 applies a specific sputtering power to the first sputtering target 13. The application of the sputtering power and the introduction of the sputtering gas are continued until the transparent substrate 2 is transferred to the carry-out chamber ULL.

其後，對於搭載於托盤(未圖示)之透明基板2，以特定之搬送速度向箭頭S之方向、以搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL之順序進行搬送。於透明基板2通過第1濺鍍腔室SP1之第1濺鍍靶13附近時，藉由反應性濺鍍，如圖2(a)所示，於透明基板2之主表面上，成膜特定膜厚之由鉻系材料而構成之包括單層膜之相位偏移膜3。 Thereafter, the transparent substrate 2 mounted on a tray (not shown) is loaded into the chamber LL, the first sputtering chamber SP1, the buffer chamber BU, and the second sputtering at a specific conveying speed in the direction of the arrow S. The plating chamber SP2 and the carry-out chamber ULL are sequentially transported. When the transparent substrate 2 passes through the vicinity of the first sputtering target 13 of the first sputtering chamber SP1, it is formed by sputtering on the main surface of the transparent substrate 2 by reactive sputtering as shown in Fig. 2(a). The phase shift film 3 including a single layer film composed of a chromium-based material has a film thickness.

再者，亦可取代上述第1濺鍍靶13而使用第2濺鍍靶14以進行包括單層膜之相位偏移膜3之成膜。於該情形時，自第2濺鍍靶14之下游側之第4氣體導入口GA22將特定之流量之濺鍍氣體導入至第1濺鍍腔室SP1，對第2濺鍍靶14施加特定之濺鍍功率。又，亦可取代第1濺鍍腔室SP1之第1濺鍍靶13或第2濺鍍靶14而使用第2濺鍍腔室SP2之第3濺鍍靶15以進行包括單層膜之相位偏移膜3之成膜。於該情形時，自 第3濺鍍靶15之下游側之第6氣體導入口GA32將特定之流量之濺鍍氣體導入至第2濺鍍腔室SP2，對第3濺鍍靶15施加特定之濺鍍功率。 Further, instead of the first sputtering target 13, the second sputtering target 14 may be used to form a film of the phase shift film 3 including a single layer film. In this case, the fourth gas introduction port GA22 on the downstream side of the second sputtering target 14 introduces a specific flow rate of the sputtering gas into the first sputtering chamber SP1, and applies a specific coating to the second sputtering target 14. Sputter power. Further, instead of the first sputtering target 13 or the second sputtering target 14 of the first sputtering chamber SP1, the third sputtering target 15 of the second sputtering chamber SP2 may be used to perform the phase including the single layer film. The film of the offset film 3 is formed. In this case, from The sixth gas introduction port GA32 on the downstream side of the third sputtering target 15 introduces a specific flow rate of the sputtering gas into the second sputtering chamber SP2, and applies a specific sputtering power to the third sputtering target 15.

對成膜包括積層膜之相位偏移膜3之情形(複數次成膜)進行說明。 The case where the phase shift film 3 including the laminated film is formed (the plurality of film formations) will be described.

於該情形時，存在如下方法：第1成膜方法，其係重複進行透明基板2之箭頭S之方向之搬送、與跟箭頭S相反之方向之搬送，每次於箭頭S之方向之搬送中，將構成相位偏移膜3之一部分之鉻系材料層依序積層，藉此成膜相位偏移膜3；第2成膜方法，其係於透明基板2向箭頭S之方向之1次搬送中，使用第1濺鍍靶13、第2濺鍍靶14、及第3濺鍍靶15之中至少2個，將構成相位偏移膜3之一部分之鉻系材料層依序積層而成膜相位偏移膜3；及將第1成膜方法與第2成膜方法組合之第3成膜方法。該等成膜方法可根據相位偏移膜3之層數而適當選擇。 In this case, there is a method in which the first film formation method repeats the conveyance in the direction of the arrow S of the transparent substrate 2 and the conveyance in the direction opposite to the arrow S, and is carried in the direction of the arrow S. The layer of the chromium-based material constituting one of the phase shifting films 3 is sequentially laminated to form the phase-shifting film 3, and the second film-forming method is carried out by the transparent substrate 2 in the direction of the arrow S. In the case where at least two of the first sputtering target 13, the second sputtering target 14, and the third sputtering target 15 are used, the chromium-based material layer constituting one of the phase shifting films 3 is sequentially laminated. The phase shift film 3; and a third film forming method in which the first film forming method and the second film forming method are combined. These film formation methods can be appropriately selected depending on the number of layers of the phase shift film 3.

第1成膜方法中，例如，按照以下之順序。 In the first film formation method, for example, the following order is used.

將以上述方式成膜之單層膜作為構成相位偏移膜3之一部分之鉻系材料層之第1層，其後，使透明基板2向與箭頭S相反之方向自搬出腔室ULL按順序返回至搬入腔室LL為止，再次，與上述第1層之鉻系材料層之成膜相同地，進行構成相位偏移膜3之一部分之鉻系材料層之第2層的成膜。 The single layer film formed as described above is used as the first layer of the chromium-based material layer constituting one of the phase shifting films 3, and thereafter, the transparent substrate 2 is moved out of the chamber ULL in the opposite direction to the arrow S. The film is returned to the loading chamber LL, and the second layer of the chromium-based material layer constituting one of the phase shifting films 3 is formed in the same manner as the film formation of the chromium-based material layer of the first layer.

於進行構成相位偏移膜3之一部分的鉻系材料層之第3層以後之成膜之情形時，亦同樣地進行。 The same applies to the case where the film formation of the third layer of the chromium-based material layer constituting one of the phase shifting films 3 is performed.

藉由使用此種第1成膜方法之成膜步驟，如圖2(a)所示，於透明基板2之主表面上，成膜特定膜厚之由鉻系材料而構成且包括2層或3層以上之積層構造之積層膜的相位偏移膜3。 By using the film formation step of the first film formation method, as shown in FIG. 2(a), a chromium-based material having a specific film thickness is formed on the main surface of the transparent substrate 2 and includes two layers or The phase shift film 3 of the laminated film having a laminated structure of three or more layers.

第2成膜方法中，例如，按照以下之順序。 In the second film formation method, for example, the following order is used.

首先，將透明基板2搬入至濺鍍裝置11之搬入腔室LL。 First, the transparent substrate 2 is carried into the carry-in chamber LL of the sputtering apparatus 11.

其次，使濺鍍裝置11之內部成為特定之真空度之後，自第1濺鍍 靶13之下游側之第2氣體導入口GA12將特定之流量之濺鍍氣體導入至第1濺鍍腔室SP1，自第3濺鍍靶15之下游側之第6氣體導入口GA32，將與導入至第1濺鍍腔室SP1之濺鍍氣體相同成分之濺鍍氣體以特定之流量導入至第2濺鍍腔室SP2，對第1濺鍍靶13及第3濺鍍靶15分別施加特定之濺鍍功率。繼續進行濺鍍功率之施加、濺鍍氣體之導入，直至透明基板2被搬送至搬出腔室ULL為止。 Next, after the inside of the sputtering apparatus 11 is made to have a specific degree of vacuum, the first sputtering is performed. The second gas introduction port GA12 on the downstream side of the target 13 introduces a specific flow rate of the sputtering gas into the first sputtering chamber SP1, and the sixth gas introduction port GA32 on the downstream side of the third sputtering target 15 The sputtering gas of the same composition as the sputtering gas introduced into the first sputtering chamber SP1 is introduced into the second sputtering chamber SP2 at a specific flow rate, and the first sputtering target 13 and the third sputtering target 15 are respectively colored. Sputter power. The application of the sputtering power and the introduction of the sputtering gas are continued until the transparent substrate 2 is transferred to the carry-out chamber ULL.

其後，將透明基板2以特定之搬送速度向箭頭S之方向、自搬入腔室LL按順序搬送至搬出腔室ULL為止。於透明基板2通過第1濺鍍腔室SP1之第1濺鍍靶13附近時，藉由反應性濺鍍，於透明基板2之主表面上成膜特定之膜厚之鉻系材料層的第1層。 Thereafter, the transparent substrate 2 is transported to the carry-out chamber ULL in order from the carry-in chamber LL in the direction of the arrow S at a specific conveyance speed. When the transparent substrate 2 passes through the vicinity of the first sputtering target 13 of the first sputtering chamber SP1, a chromium-based material layer having a specific film thickness is formed on the main surface of the transparent substrate 2 by reactive sputtering. 1 story.

其後，於透明基板2通過第2濺鍍腔室SP2之第3濺鍍靶15附近時，藉由反應性濺鍍，於第1層之鉻系材料層上成膜特定之膜厚之鉻系材料層的第2層。 Thereafter, when the transparent substrate 2 passes through the vicinity of the third sputtering target 15 of the second sputtering chamber SP2, a chromium having a specific film thickness is formed on the chromium-based material layer of the first layer by reactive sputtering. The second layer of the material layer.

於進行包括3層構造之積層膜之相位偏移膜3之成膜之情形時，除了上述濺鍍靶以外，進而使用第1濺鍍腔室SP1之第2濺鍍靶14，自該第2濺鍍靶14之下游側之第4氣體導入口GA22以特定之流量供給濺鍍氣體，對第2濺鍍靶14施加特定之濺鍍功率。於該情形時，通過第2濺鍍靶14附近時成膜之鉻系材料層成為相位偏移膜3之第2層，通過第3濺鍍靶15附近時成膜之鉻系材料層成為相位偏移膜3之第3層。 In the case of performing film formation of the phase shift film 3 including the laminated film having a three-layer structure, in addition to the sputtering target, the second sputtering target 14 of the first sputtering chamber SP1 is used, from the second The fourth gas introduction port GA22 on the downstream side of the sputtering target 14 supplies a sputtering gas at a specific flow rate, and applies a specific sputtering power to the second sputtering target 14. In this case, the chromium-based material layer formed by the vicinity of the second sputtering target 14 becomes the second layer of the phase shift film 3, and the chromium-based material layer formed by the vicinity of the third sputtering target 15 becomes the phase. The third layer of the offset film 3.

藉由使用此種第2成膜方法之成膜步驟，如圖2(a)所示，於透明基板2之主表面上，成膜特定膜厚之由鉻系材料而構成、且包括2層或3層以上之積層構造之積層膜的相位偏移膜3。 By using the film formation step of the second film formation method, as shown in FIG. 2(a), a chromium-based material having a specific film thickness is formed on the main surface of the transparent substrate 2, and includes two layers. Or a phase shift film 3 of a laminated film having a laminated structure of three or more layers.

第3成膜方法中，亦可先進行上述第1成膜方法及第2成膜方法中之任一者。 In the third film formation method, any of the first film formation method and the second film formation method may be performed first.

例如，先進行第2成膜方法，於1次之透明基板2之搬送中積層多層之鉻系材料層，其後，進行第1成膜方法，進而積層需要層數之鉻 系材料層，藉此可進行包括具有積層預定數之層數之積層膜的相位偏移膜3之成膜。 For example, the second film forming method is performed, and a plurality of layers of the chromium-based material layer are laminated in the transfer of the transparent substrate 2 once, and then the first film forming method is performed, and then the number of layers of chromium is required to be laminated. The material layer is formed, whereby the film formation of the phase shift film 3 including the laminated film having the number of layers of the predetermined number of layers can be performed.

藉由使用此種第3成膜方法之成膜步驟，如圖2(a)所示，於透明基板2之主表面上，成膜特定膜厚之由鉻系材料而構成、且包括具有3層以上之多數層之積層膜之相位偏移膜3。 By using the film formation step of the third film formation method, as shown in FIG. 2(a), a chromium-based material having a specific film thickness is formed on the main surface of the transparent substrate 2, and includes 3 The phase shift film 3 of the laminated film of the plurality of layers above the layer.

如此一來於透明基板2之主表面上形成相位偏移膜3之後，將透明基板2取出至濺鍍裝置11之外部。 After the phase shift film 3 is formed on the main surface of the transparent substrate 2, the transparent substrate 2 is taken out to the outside of the sputtering apparatus 11.

3.VUV照射步驟 3.VUV irradiation step

其次，如圖2(b)所示，對相位偏移膜3之最表面3a進行VUV照射處理。 Next, as shown in FIG. 2(b), the VUV irradiation treatment is performed on the outermost surface 3a of the phase shift film 3.

此處，所謂VUV照射處理，係指一面於作為被照射體之相位偏移膜3之最表面3a上，沿著其面方向且隔開特定之間隔，將VUV照射裝置(未圖示)之照射部(未圖示)進行掃描，一面自其照射部(未圖示)對最表面3a照射VUV而進行之改質處理。 Here, the VUV irradiation treatment refers to a VUV irradiation device (not shown) on the outermost surface 3a of the phase shift film 3 as the object to be irradiated, and at a predetermined interval along the surface direction thereof. The irradiation unit (not shown) scans and irradiates the outermost surface 3a with VUV from the irradiation unit (not shown) to perform a modification process.

所謂使用於VUV照射處理中之VUV，係指紫外線之中波長亦較短者。眾所周知，VUV主要因於大氣中被吸收而衰減，但於真空中可防止衰減。本發明中，所謂VUV係指波長為10nm~200nm之紫外線，較佳為使用波長為100nm~200nm者。具體而言，作為VUV，例如，可使用波長126nm(氬)、波長146nm(氪)、波長172nm(氙)之準分子光，本發明中，較佳為使用波長172nm之氙準分子光。再者，亦可伴隨上述VUV照射而進行加熱處理，或於VUV照射後進行加熱處理。但，特別是，即便不進行高溫(例如，200℃以上)之加熱，亦可獲得改質效果。 The VUV used in the VUV irradiation treatment refers to a shorter wavelength among ultraviolet rays. It is well known that VUV is mainly attenuated by absorption in the atmosphere, but it prevents attenuation in a vacuum. In the present invention, VUV means ultraviolet light having a wavelength of 10 nm to 200 nm, and preferably used at a wavelength of 100 nm to 200 nm. Specifically, as the VUV, for example, excimer light having a wavelength of 126 nm (argon), a wavelength of 146 nm (氪), and a wavelength of 172 nm (氙) can be used. In the present invention, it is preferable to use xenon excimer light having a wavelength of 172 nm. Further, the heat treatment may be performed in conjunction with the VUV irradiation or the heat treatment may be performed after the VUV irradiation. However, in particular, the modification effect can be obtained even if heating at a high temperature (for example, 200 ° C or higher) is not performed.

關於VUV照射處理中之VUV照射條件，較佳為如以下般。 The VUV irradiation conditions in the VUV irradiation treatment are preferably as follows.

照射環境並無特別限制，可設為氮等惰性氣體或真空，即便於大氣中亦可獲得改質效果。但，於在大氣中進行VUV照射處理之情形 時，較佳為考慮VUV之衰減率，減小VUV照射裝置之照射部(未圖示)與相位偏移膜之最表面之距離。 The irradiation environment is not particularly limited, and an inert gas such as nitrogen or a vacuum can be used, and the modification effect can be obtained even in the atmosphere. However, in the case of VUV irradiation treatment in the atmosphere In the case of the VUV attenuation rate, it is preferable to reduce the distance between the irradiation portion (not shown) of the VUV irradiation device and the outermost surface of the phase shift film.

作為VUV照射能量，重要的是設為足以對相位偏移膜3進行改質處理的能量。例如，對相位偏移膜3之最表面3a，設為20J/cm2以上，較佳為30J/cm2以上，更佳為40J/cm2以上。又，自照射效率之觀點而言，較佳為60J/cm2以下。 As the VUV irradiation energy, it is important to set the energy sufficient for the phase shifting film 3 to be reformed. For example, the outermost surface 3a of the phase shift film 3 is set to 20 J/cm 2 or more, preferably 30 J/cm 2 or more, and more preferably 40 J/cm 2 or more. Further, from the viewpoint of irradiation efficiency, it is preferably 60 J/cm 2 or less.

VUV照射例如可使用具備照度30W/cm2~50W/cm2之光源(未圖示)的照射部(未圖示)，對相位偏移膜3之最表面3a，進行20分鐘以上之照射(於藉由掃描對最表面3a之相同部位進行複數次之照射之情形時，為其合計時間之照射)。具體而言，於將光源(未圖示)設為照度40W/cm2、將照射區域之長度設為200mm、將掃描速度設為10mm/秒、將衰減率設為70%之情形時，可藉由20分鐘左右之VUV照射，而對最表面3a賦予45J/cm2之照射能量。此處，設為衰減率，係指衰減後之殘存量相對於來自照射部(未圖示)之照射量之比例。 For the VUV irradiation, for example, an irradiation unit (not shown) having a light source (not shown) having an illuminance of 30 W/cm 2 to 50 W/cm 2 can be used to irradiate the outermost surface 3 a of the phase shift film 3 for 20 minutes or longer ( When the same portion of the outermost surface 3a is irradiated for a plurality of times by scanning, the total time is irradiated). Specifically, when the light source (not shown) has an illuminance of 40 W/cm 2 , the length of the irradiation region is 200 mm, the scanning speed is 10 mm/sec, and the attenuation rate is 70%, The irradiation energy of 45 J/cm 2 was applied to the outermost surface 3a by VUV irradiation for about 20 minutes. Here, the attenuation rate means the ratio of the amount of residual after the attenuation to the amount of irradiation from the irradiation unit (not shown).

再者，自透明基板2之衰減率或照射效率之觀點而言，VUV照射較佳為並非自透明基板2側而是自相位偏移膜3之最表面3a側進行。 Further, from the viewpoint of the attenuation rate or the irradiation efficiency of the transparent substrate 2, the VUV irradiation is preferably performed not from the side of the transparent substrate 2 but from the side of the outermost surface 3a of the phase shift film 3.

以此方式製造之實施形態1之相位偏移光罩基底1中，其相位偏移膜3藉由VUV照射步驟而改質。於相位偏移膜3，自其最表面3a朝向膜深度方向形成有組成梯度區域R1，於與透明基板2之界面之附近形成有透明基板附近區域R2，於除組成梯度區域R1及透明基板附近區域R2以外之中間區域形成有主體部B。 In the phase shift mask substrate 1 of the first embodiment manufactured in this manner, the phase shift film 3 is modified by the VUV irradiation step. In the phase shift film 3, a composition gradient region R1 is formed from the outermost surface 3a toward the film depth direction, and a transparent substrate vicinity region R2 is formed in the vicinity of the interface with the transparent substrate 2, in addition to the composition gradient region R1 and the transparent substrate. A main body portion B is formed in an intermediate portion other than the region R2.

組成梯度區域R1顯現出如下特性：自相位偏移膜3之最表面3a朝向膜深度方向減少之氧相對於鉻之比例(以下，有時稱為O/Cr)之最大值為2以上，且，自最表面3a朝向膜深度方向減少之氮相對於鉻之比例(以下，有時稱為N/Cr)之最大值為0.45以下。再者，O/Cr係氧原子數相對於鉻原子數之比，N/Cr係氮原子數相對於鉻原子數之比。 The composition gradient region R1 exhibits a characteristic that the maximum value of the ratio of oxygen to chromium (hereinafter, sometimes referred to as O/Cr) which decreases from the outermost surface 3a of the phase shift film 3 toward the film depth direction is 2 or more, and The maximum value of the ratio of nitrogen to chromium (hereinafter sometimes referred to as N/Cr) which decreases from the outermost surface 3a toward the film depth direction is 0.45 or less. Further, the ratio of the number of O/Cr oxygen atoms to the number of chromium atoms, and the ratio of the number of N/Cr nitrogen atoms to the number of chromium atoms.

顯現出此種特性之組成梯度區域R1由於包含相位偏移膜3之最表面3a，故而係相位偏移膜3之上側表層區域，其膜厚例如較佳為0.1nm以上10nm以下，但並不限定於該範圍。 Since the composition gradient region R1 exhibiting such characteristics includes the outermost surface 3a of the phase shift film 3, it is the surface layer region on the upper side of the phase shift film 3, and the film thickness thereof is preferably 0.1 nm or more and 10 nm or less, but is not Limited to this range.

組成梯度區域R1之最表面3a之膜密度為2.0g/cm3以上。關於最表面3a之膜密度，自耐藥性及耐洗淨性之提高之觀點而言較佳為2.0g/cm3以上，更佳為2.2g/cm3以上。 The film density of the outermost surface 3a constituting the gradient region R1 is 2.0 g/cm 3 or more. The film density of the outermost surface 3a is preferably 2.0 g/cm 3 or more, and more preferably 2.2 g/cm 3 or more from the viewpoint of improvement in self-resistance and washing resistance.

透明基板附近區域R2係如組成梯度區域R1般，顯現出O/Cr或N/Cr向膜深度方向梯度之特性的相位偏移膜3之下側表層區域。 The region R2 in the vicinity of the transparent substrate, like the composition gradient region R1, exhibits a phase shifting film on the lower side of the film 3 in which the O/Cr or N/Cr is in the direction of the film depth direction gradient.

主體部B與上述組成梯度區域R1及透明基板附近區域R2不同，係顯現出膜深度方向之各元素之組成比大致均一之特性的相位偏移膜3之內部區域。 Unlike the composition gradient region R1 and the transparent substrate vicinity region R2, the main body portion B exhibits an inner region of the phase shift film 3 in which the composition ratio of each element in the film depth direction is substantially uniform.

構成相位偏移膜3之各元素之含量可以成為所期望之光學特性(相對於曝光之光之透過率，相位差)之方式而適當調整。 The content of each element constituting the phase shift film 3 can be appropriately adjusted so as to have a desired optical characteristic (transparency with respect to light of exposure, phase difference).

又，於使構成相位偏移膜3之材料為CrON之情形時，主體部B之各元素之含量若以藉由X射線光電子分光分析法(X-ray Photoelectron Spectroscopy：以下，有時稱為XPS)而分析之結果表示，則鉻可於35原子%以上65原子%以下之範圍調整，氧可於16原子%以上50原子%以下之範圍調整，氮可於6原子%以上30原子%以下之範圍調整。較佳為，鉻為41原子%以上58原子%以下，氧為21原子%以上43原子%以下，氮為11原子%以上24原子%以下。 Further, when the material constituting the phase shift film 3 is CrON, the content of each element of the main body portion B is X-ray photoelectron spectroscopy (hereinafter, sometimes referred to as XPS). And the analysis results show that the chromium can be adjusted in the range of 35 atom% or more and 65 atom% or less, and the oxygen can be adjusted in the range of 16 atom% or more and 50 atom% or less, and the nitrogen can be 6 atom% or more and 30 atom% or less. Range adjustment. Preferably, the chromium is 41 atom% or more and 58 atom% or less, the oxygen is 21 atom% or more and 43 atom% or less, and the nitrogen is 11 atom% or more and 24 atom% or less.

於使構成相位偏移膜3之材料為CrCON之情形時，主體部B之各元素之含量若以藉由XPS而分析之結果表示，則鉻可於35原子%以上60原子%以下之範圍調整，氧可於15原子%以上45原子%以下之範圍調整，氮可於5原子%以上25原子%以下之範圍調整，碳於2原子%以上15原子%以下之範圍調整。較佳為，鉻為40原子%以上55原子%以下，氧為20原子%以上40原子%以下，氮為10原子%以上20原子%以 下，碳為3原子%以上10原子%以下。 When the material constituting the phase shift film 3 is CrCON, the content of each element of the main body portion B is expressed by the result of XPS, and the chromium can be adjusted in the range of 35 atom% or more and 60 atom% or less. The oxygen can be adjusted in the range of 15 atom% or more and 45 atom% or less, and the nitrogen can be adjusted in the range of 5 atom% or more and 25 atom% or less, and the carbon can be adjusted in the range of 2 atom% or more and 15 atom% or less. Preferably, the chromium is 40 atom% or more and 55 atom% or less, the oxygen is 20 atom% or more and 40 atom% or less, and the nitrogen is 10 atom% or more and 20 atom% or more. Next, the carbon is 3 atom% or more and 10 atom% or less.

又，主體部B中，如上所述，膜深度方向之各元素之組成比大致均一。此處，所謂膜深度方向之各元素之組成比大致均一，係指以於上述成膜步驟中之成膜條件下而獲得之相位偏移膜3之膜深度方向之各元素之含量之中心值為基準，將主體部B之各元素之含量控制於相對於該中心之含量之特定之變動幅度之範圍內。例如，於使構成相位偏移膜3之材料為CrON之情形時，鉻之變動幅度相對於鉻之中心之含量為±5.0原子%，氧之變動幅度相對於氧之中心之含量為±6.5原子%，氮之變動幅度相對於氮之中心之含量為±4.5原子%。較佳為，鉻之變動幅度為±3.5原子%，氧之變動幅度為±5.5原子%，氮之變動幅度為±3.5原子%。又，於使構成相位偏移膜3之材料為CrCON之情形時，鉻之變動幅度相對於鉻之中心之含量為±5.0原子%，氧之變動幅度相對於氧之中心之含量為±6.5原子%，氮之變動幅度相對於氮之中心之含量為±4.5原子%，碳之變動幅度相對於碳之中心之含量為±4.0原子%。較佳為，鉻之變動幅度為±3.5原子%，氧之變動幅度為±5.5原子%，氮之變動幅度為±3.5原子%，碳之變動幅度為±3.0原子%。 Further, in the main body portion B, as described above, the composition ratio of each element in the film depth direction is substantially uniform. Here, the composition ratio of each element in the film depth direction is substantially uniform, and refers to the central value of the content of each element in the film depth direction of the phase shift film 3 obtained under the film formation conditions in the film forming step. For the purpose of the reference, the content of each element of the main body portion B is controlled within a range of a specific fluctuation range with respect to the content of the center. For example, when the material constituting the phase shift film 3 is CrON, the fluctuation range of the chromium is ±5.0 atom% with respect to the center of the chromium, and the fluctuation range of the oxygen is ±6.5 atom with respect to the center of the oxygen. %, the fluctuation range of nitrogen is ±4.5 atom% with respect to the center of nitrogen. Preferably, the fluctuation range of chromium is ±3.5 atom%, the fluctuation range of oxygen is ±5.5 atom%, and the fluctuation range of nitrogen is ±3.5 atom%. Further, when the material constituting the phase shift film 3 is CrCON, the fluctuation range of chromium is ±5.0 atom% with respect to the center of the chromium, and the fluctuation range of oxygen is ±6.5 atom with respect to the center of the oxygen. %, the fluctuation range of nitrogen is ±4.5 atom% with respect to the center of nitrogen, and the variation range of carbon is ±4.0 atom% with respect to the center of carbon. Preferably, the fluctuation range of chromium is ±3.5 atom%, the fluctuation range of oxygen is ±5.5 atom%, the fluctuation range of nitrogen is ±3.5 atom%, and the fluctuation range of carbon is ±3.0 atom%.

再者，主體部B中之膜深度方向之各元素之組成比之大致均一係以賦予膜厚方向之階段性或連續性之組成變化為目的，藉由如下而達成，即，於成膜步驟中，不進行使濺鍍原料或濺鍍氣體之供給方法或供給量變化之操作，成膜相位偏移膜3。 Further, the composition ratio of each element in the film depth direction in the main body portion B is substantially uniform in order to impart a stepwise or continuous composition change in the film thickness direction, and is achieved by the film forming step. In the middle, the operation of changing the supply method or the supply amount of the sputtering material or the sputtering gas is not performed, and the phase shift film 3 is formed.

相位偏移膜3係藉由VUV照射步驟而具有如以下之特性。 The phase shift film 3 has the following characteristics by the VUV irradiation step.

(1)VUV照射步驟可進行如下之改質，即，於組成梯度區域R1中，將O/Cr之最大值改為2以上，且，將N/Cr之最大值改為0.45以下。藉由此種改質處理，而使相位偏移膜3經圖案化而獲得之相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之剖面形狀成為可充分發揮相位偏移效果之剖面形狀。 (1) The VUV irradiation step can be modified in such a manner that the maximum value of O/Cr is changed to 2 or more in the composition gradient region R1, and the maximum value of N/Cr is changed to 0.45 or less. By such a modification process, the cross-sectional shape of the etched cross section of the edge portion of the phase shift film pattern 3 ' obtained by patterning the phase shift film 3 is a cross-sectional shape in which the phase shift effect can be sufficiently exhibited.

相對於此，於先前之相位偏移光罩基底中，亦自其相位偏移膜之最表面朝向膜深度方向形成有組成梯度區域，該組成梯度區域亦自最表面朝向膜深度方向顯現出O/Cr或N/Cr之減少傾向。然而，先前之相位偏移膜由於未進行VUV照射步驟，故而未經過由VUV照射處理而進行之改質。因此，先前之相位偏移膜之組成梯度區域由於不滿足上述O/Cr之最大值或N/Cr之最大值之條件，故而使其相位偏移膜經圖案化而獲得之相位偏移膜圖案之邊緣部分之被蝕刻剖面之剖面形狀成為遍及其邊緣部分整體而傾斜、朝向透明基板拖尾之錐形形狀，無法充分發揮相位偏移效果。 In contrast, in the previous phase shift mask substrate, a composition gradient region is also formed from the outermost surface of the phase shift film toward the film depth direction, and the composition gradient region also appears from the outermost surface toward the film depth direction. The tendency of /Cr or N/Cr to decrease. However, since the previous phase shift film was not subjected to the VUV irradiation step, it was not subjected to the modification by the VUV irradiation treatment. Therefore, since the composition gradient region of the previous phase shift film does not satisfy the above-mentioned maximum value of O/Cr or the maximum value of N/Cr, the phase shift film pattern obtained by patterning the phase shift film is obtained. The cross-sectional shape of the etched cross section of the edge portion is a tapered shape which is inclined over the entire edge portion and is slanted toward the transparent substrate, and the phase shift effect cannot be sufficiently exerted.

(2)VUV照射步驟可進行使最表面3a之膜密度大幅變化之改質。作為相位偏移膜3之最表面3a之膜密度上升之理由，認為係因為藉由VUV照射處理，對存在於最表面3a之鉻原子之周邊之孔隙供給其他原子而填埋孔隙。作為其他原子，例如可列舉氧原子。認為，於該情形時，孔隙由氧原子填埋，藉此，最表面3a中之「CrO」之密度上升，結果，最表面3a之膜密度上升。 (2) The VUV irradiation step can be modified to greatly change the film density of the outermost surface 3a. The reason why the film density of the outermost surface 3a of the phase shift film 3 rises is considered to be that the pores are supplied to the pores existing around the chromium atoms of the outermost surface 3a by the VUV irradiation treatment to fill the pores. As another atom, an oxygen atom is mentioned, for example. In this case, it is considered that the pores are filled with oxygen atoms, whereby the density of "CrO" in the outermost surface 3a rises, and as a result, the film density of the outermost surface 3a rises.

具體而言，可藉由VUV照射步驟，而使最表面3a之膜密度改為2.0g/cm3以上。再者，認為最表面3a之膜密度之上升可能成為使對相位偏移膜3之圖案化時使用之光阻劑膜5之密接性提高的一個原因。 Specifically, the film density of the outermost surface 3a can be changed to 2.0 g/cm 3 or more by the VUV irradiation step. In addition, it is considered that the increase in the film density of the outermost surface 3a may be one of the reasons for improving the adhesion of the photoresist film 5 used for patterning the phase shift film 3.

進而，若假設最表面3a之膜密度之上升如上所述來自「CrO」之密度之上升，則認為該假設藉由如下效果而證實，可使相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之剖面形狀成為可充分發揮相位偏移效果之剖面形狀。即，若對最表面3a供給氧(O)，則使蝕刻速度加快之氮(N)之含量相對地減少，故而於對相位偏移膜3之圖案化時之等向蝕刻(濕式蝕刻)中，該邊緣部分之被蝕刻剖面之中的、光阻劑膜5附近之被蝕刻剖面(最表面3a附近)部分之蝕刻速度變慢。因此，其原因在於，認為其光阻劑膜5附近之被蝕刻剖面部分藉由蝕刻而使透明基板2 之主表面露出之後，可維持至邊緣部分之下側部分為止，於光阻劑膜5附近之被蝕刻剖面部分，由蝕刻液而產生之所謂侵蝕現象之產生變少。 Further, if the increase in the film density of the outermost surface 3a is as described above from the increase in the density of "CrO", it is considered that the assumption is confirmed by the effect that the edge portion of the phase shift film pattern 3 ' can be etched. The cross-sectional shape of the cross section is a cross-sectional shape that can sufficiently exhibit the phase shift effect. In other words, when oxygen (O) is supplied to the outermost surface 3a, the content of nitrogen (N) which accelerates the etching rate is relatively reduced, so that the etching (wet etching) is performed when patterning the phase shift film 3 is performed. Among them, the etching speed of the portion to be etched (near the outermost surface 3a) in the vicinity of the photoresist film 5 among the etched cross sections of the edge portion becomes slow. Therefore, it is considered that the portion to be etched in the vicinity of the photoresist film 5 is exposed to the main surface of the transparent substrate 2 by etching, and then maintained to the lower portion of the edge portion, in the photoresist film 5 In the vicinity of the portion to be etched, the occurrence of the so-called erosion phenomenon caused by the etching liquid is reduced.

再者，最表面3a之膜密度例如可藉由X射線反射率分析法(XRR)而測定。實施例、比較例中之最表面3a之膜密度之值係藉由如下模擬條件而獲得：顯現出藉由於相位偏移膜3之膜厚方向分割為複數個進行模擬而擬合(fitting)時之擬合之妥當性之數值指標Fit R成為0.025以下。 Further, the film density of the outermost surface 3a can be measured, for example, by X-ray reflectance analysis (XRR). The values of the film densities of the outermost surfaces 3a in the examples and the comparative examples were obtained by the following simulation conditions: when the fitting was performed by the division of the film thickness direction of the phase shifting film 3 into a plurality of simulations. The numerical value of Fit R, Fit R, is 0.025 or less.

(3)VUV照射步驟中，不使主體部B之膜深度方向之各元素之組成比變化。因此，主體部B之膜深度方向之各元素之組成比與不進行VUV照射步驟之情形時相同，保持大致均一。即，即便進行VUV照射步驟，亦可不會對VUV照射步驟前之相位偏移膜3之主體部B之膜深度方向的各元素之組成比賦予較大之變化，故而相位偏移膜3可維持所期望之光學特性(透過率、相位差)。 (3) In the VUV irradiation step, the composition ratio of each element in the film depth direction of the main body portion B is not changed. Therefore, the composition ratio of each element in the film depth direction of the main body portion B is the same as that in the case where the VUV irradiation step is not performed, and remains substantially uniform. In other words, even if the VUV irradiation step is performed, the composition ratio of each element in the film depth direction of the main body portion B of the phase shift film 3 before the VUV irradiation step is not largely changed, so that the phase shift film 3 can be maintained. The desired optical properties (transmittance, phase difference).

(4)VUV照射步驟可進行如下改質，即，對於組成梯度區域R1中之O/Cr之減少率，使VUV照射處理後之減少率大於VUV照射處理前之減少率，且，對於N/Cr之減少率，使VUV照射處理後之減少率小於VUV照射處理前之減少率。即，於對由鉻系材料而構成之相位偏移膜3之圖案化時之等向蝕刻(濕式蝕刻)中，組成梯度區域R1中，使蝕刻速度不怎麼變化之氧之含量與VUV照射處理前相比，以較大之減少率變化。另一方面，使蝕刻速度加快之氮之含量與VUV照射處理前相比，以較小之減少率變化。因此，於蝕刻向膜深度方向進行時，VUV照射處理後之組成梯度區域R1中，與VUV照射處理前相比，蝕刻速度平緩地變快。藉由此種組成梯度區域R1中之蝕刻速度之增加傾向之緩和特性，而於蝕刻自組成梯度區域R1向主體部B移行而進行時，可將主體部B中之與蝕刻速度之較大之差距消除，蝕刻速度連續性地 變化，邊緣部分之被蝕刻剖面形成為連續面。 (4) The VUV irradiation step may be modified such that the reduction rate of the O/Cr in the composition gradient region R1 is such that the reduction rate after the VUV irradiation treatment is larger than the reduction rate before the VUV irradiation treatment, and, for N/ The reduction rate of Cr is such that the reduction rate after the VUV irradiation treatment is smaller than the reduction rate before the VUV irradiation treatment. In other words, in the etching (wet etching) in the patterning of the phase shift film 3 made of a chromium-based material, the content of oxygen and the VUV irradiation in the composition gradient region R1 are not changed so much. Compared with before the treatment, it changes with a large reduction rate. On the other hand, the content of nitrogen which accelerates the etching rate is changed at a smaller reduction rate than before the VUV irradiation treatment. Therefore, when the etching is performed in the film depth direction, the etching rate is gradually increased in the composition gradient region R1 after the VUV irradiation treatment as compared with that before the VUV irradiation treatment. When the etch is progressed from the composition gradient region R1 to the main body portion B by the relaxation characteristic of the increase in the etching rate in the composition gradient region R1, the etching speed can be made larger in the main body portion B. Gap elimination, etch rate continuously The etched section of the edge portion is changed to form a continuous surface.

(5)透明基板附近區域R2中，如上所述，與上述主體部B不同，O/Cr或N/Cr向膜深度方向梯度，但認為，於自最表面3a側進行之VUV照射步驟中，透明基板附近區域R2中之O/Cr或N/Cr之梯度組成不受VUV照射處理之影響。 (5) In the region R2 in the vicinity of the transparent substrate, as described above, unlike the main body portion B, O/Cr or N/Cr is gradient in the depth direction of the film, but it is considered that in the VUV irradiation step performed from the side of the outermost surface 3a, The gradient composition of O/Cr or N/Cr in the region R2 near the transparent substrate is not affected by the VUV irradiation treatment.

(6)VUV照射步驟中，如上所述，幾乎不改變成膜時之相位偏移膜3之透過率，可使相位偏移膜3經圖案化而獲得之相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之剖面形狀與不進行VUV照射步驟之情形時完全不同，形成為可充分發揮相位偏移效果之剖面形狀。又，VUV照射步驟幾乎不改變成膜時之相位偏移膜3之反射率。認為該情況係顯現出可將相位偏移膜圖案3'之CD不均控制於非常窄之範圍之可能性者，於該方面，VUV照射步驟亦有效。 (6) In the VUV irradiation step, as described above, the transmittance of the phase shift film 3 at the time of film formation is hardly changed, and the edge of the phase shift film pattern 3 ' obtained by patterning the phase shift film 3 can be obtained. The cross-sectional shape of the partially etched cross section is completely different from that in the case where the VUV irradiation step is not performed, and is formed into a cross-sectional shape in which the phase shift effect can be sufficiently exerted. Further, the VUV irradiation step hardly changes the reflectance of the phase shift film 3 at the time of film formation. It is considered that this case shows a possibility that the CD unevenness of the phase shift film pattern 3 ' can be controlled to a very narrow range, and in this respect, the VUV irradiation step is also effective.

實施形態1之相位偏移光罩基底1係藉由此種準備步驟、相位偏移膜形成步驟、及VUV照射步驟而製造。 The phase shift mask substrate 1 of the first embodiment is manufactured by such a preparation step, a phase shift film forming step, and a VUV irradiation step.

根據以此方式製造之實施形態1之相位偏移光罩基底1，於透明基板2上形成有含有鉻、氧及氮之相位偏移膜3。於該相位偏移膜3，自其最表面3a朝向膜深度方向形成有組成梯度區域R1，組成梯度區域R1中，自最表面3a朝向膜深度方向減少之O/Cr之最大值為2以上，且，自最表面3a朝向膜深度方向減少之N/Cr之最大值為0.45以下。因此，該相位偏移光罩基底1中，其相位偏移膜3可藉由濕式蝕刻，而使相位偏移膜圖案化為可充分發揮相位偏移效果之剖面形狀。該相位偏移光罩基底1由於可使藉由使其相位偏移膜3圖案化而獲得之相位偏移膜圖案之邊緣部分之被蝕刻剖面之剖面形狀成為可充分發揮相位偏移效果之剖面形狀，故而可形成使解像度提高、具有具備良好之CD特性之相位偏移膜圖案的相位偏移光罩之製造用原版。 According to the phase shift mask substrate 1 of the first embodiment manufactured in this manner, the phase shift film 3 containing chromium, oxygen, and nitrogen is formed on the transparent substrate 2. In the phase shift film 3, a composition gradient region R1 is formed from the outermost surface 3a toward the film depth direction, and in the composition gradient region R1, the maximum value of O/Cr which decreases from the outermost surface 3a toward the film depth direction is 2 or more. Further, the maximum value of N/Cr which decreases from the outermost surface 3a toward the film depth direction is 0.45 or less. Therefore, in the phase shift mask substrate 1, the phase shift film 3 can be patterned by wet etching to form a cross-sectional shape in which the phase shift effect can be sufficiently exhibited. The phase shift mask substrate 1 has a cross-sectional shape of an etched cross section of an edge portion of the phase shift film pattern obtained by patterning the phase shift film 3 so as to have a phase shift effect effect. Since the shape is formed, it is possible to form a precursor for manufacturing a phase shift mask having improved phase resolution and a phase shift film pattern having excellent CD characteristics.

又，根據實施形態1之相位偏移光罩基底1之製造方法，包含： 成膜步驟，其係藉由濺鍍法而於透明基板2上成膜含有鉻、氧及氮之相位偏移膜3；及VUV照射處理步驟，其係對所成膜之相位偏移膜3之最表面3a進行VUV照射處理。該VUV照射處理步驟係如下步驟：於自相位偏移膜3之最表面3a朝向膜深度方向形成之組成梯度區域R1中，將自最表面3a朝向膜深度方向減少之O/Cr之最大值改為2以上，且，將自最表面3a朝向膜深度方向減少之N/Cr之最大值改為0.45以下。因此，可製造如下相位偏移光罩基底1：可藉由濕式蝕刻而使相位偏移膜3圖案化為可充分發揮相位偏移效果之剖面形狀。由於可使相位偏移膜圖案之邊緣部分之被蝕刻剖面之剖面形狀成為可充分發揮相位偏移效果之剖面形狀，故而可製造使解像度提高、可圖案化為具備良好之CD特性之相位偏移膜圖案的相位偏移光罩基底1。 Further, according to the method of manufacturing the phase shift mask substrate 1 of the first embodiment, the method includes: a film forming step of forming a phase shift film 3 containing chromium, oxygen, and nitrogen on the transparent substrate 2 by sputtering; and a VUV irradiation treatment step of the phase shift film 3 formed by the film formation The outermost surface 3a is subjected to VUV irradiation treatment. The VUV irradiation processing step is a step of changing the maximum value of the O/Cr from the outermost surface 3a toward the film depth direction in the composition gradient region R1 formed from the outermost surface 3a of the phase shift film 3 toward the film depth direction. It is 2 or more, and the maximum value of N/Cr which is reduced from the outermost surface 3a toward the film depth direction is changed to 0.45 or less. Therefore, the phase shift mask substrate 1 can be manufactured by patterning the phase shift film 3 into a cross-sectional shape in which the phase shift effect can be sufficiently exhibited by wet etching. Since the cross-sectional shape of the etched cross section of the edge portion of the phase shift film pattern can be made into a cross-sectional shape that can sufficiently exhibit the phase shift effect, the resolution can be improved and the phase shift can be patterned to have a good CD characteristic. The phase of the film pattern is shifted by the mask substrate 1.

再者，實施形態1中，組成梯度區域R1例如係作為藉由對成膜後之狀態之相位偏移膜3之最表面3a之VUV照射處理而形成者進行了說明，但並不限定於此。組成梯度區域R1只要為可以具有如上所述之特性之方式進行改質的處理，則亦可為藉由VUV照射處理以外之任何處理所形成者。 In the first embodiment, the composition gradient region R1 is formed by, for example, VUV irradiation treatment on the outermost surface 3a of the phase shift film 3 in the state after film formation. However, the present invention is not limited thereto. . The composition gradient region R1 may be formed by any treatment other than the VUV irradiation treatment as long as it can be modified so as to have the characteristics described above.

又，對藉由實施形態1中之相位偏移膜形成步驟而成膜之透明基板2之相位偏移膜3，既可於其成膜之後進行作為後步驟之VUV照射步驟，或者，亦可於成膜後之特定之期間、且於保管於特定之盒內後進行VUV照射步驟。保管亦可為例如1個月左右之期間，但並不限定於此。若於保管前進行VUV處理步驟，則例如即便於1個月左右之保管後，無關於有無洗淨(除硫酸洗淨以外)，將光阻劑圖案作為光罩藉由濕式蝕刻而形成之相位偏移膜圖案之剖面形狀與未進行VUV處理之剖面形狀相比均良好。於保管後進行VUV照射步驟時，必須進行特定之膜洗淨。於保管中，相位偏移膜3之最表面3a等之露出部分可能會被稍微污染，但即便於被污染之狀態下，亦不會對VUV照射步驟之改質 效果帶來影響。較佳為，較理想的是於光阻劑膜形成之前進行VUV照射步驟。又，於光罩基底之製造過程中，若將相位偏移膜3之表面硫酸洗淨，其後於相位偏移膜3上形成光阻劑圖案，則相位偏移膜圖案之剖面形狀成為錐形形狀，藉由於相位偏移膜3之硫酸洗淨後，光阻劑膜形成前進行VUV照射，而存在相位偏移膜圖案之剖面形狀不易成為錐形形狀而是垂直化之可能性。即，若將相位偏移膜3之表面硫酸洗淨，則光阻劑膜與相位偏移膜3之膜表面之密接性明顯降低，故而使光阻劑圖案作為光罩之濕式蝕刻製程後之剖面形狀成為非常大之錐形形狀，故而無法有效地活用相位偏移膜之解像度。即便於相位偏移膜3之硫酸洗淨後進行VUV照射步驟，藉此可大幅改善相位偏移膜圖案之剖面形狀。進而，藉由於使向相位偏移膜3之硫酸洗淨後之沖洗強化且使硫磺成分極力減少後進行VUV照射步驟，存在使相位偏移膜圖案之剖面形狀垂直化之可能性。 Further, the phase shift film 3 of the transparent substrate 2 formed by the phase shift film forming step in the first embodiment may be subjected to a VUV irradiation step as a subsequent step after the film formation, or The VUV irradiation step is performed after a specific period after the film formation and after being stored in a specific box. The storage may be, for example, a period of about one month, but is not limited thereto. If the VUV treatment step is carried out before storage, for example, even after storage for about one month, there is no need to clean (except for sulfuric acid washing), and the photoresist pattern is formed as a mask by wet etching. The cross-sectional shape of the phase shift film pattern was good as compared with the cross-sectional shape not subjected to VUV treatment. When the VUV irradiation step is carried out after storage, it is necessary to perform a specific film cleaning. During storage, the exposed portion of the outermost surface 3a of the phase shifting film 3 may be slightly contaminated, but even in the contaminated state, the VUV irradiation step is not modified. The effect has an impact. Preferably, it is preferred to carry out the VUV irradiation step prior to formation of the photoresist film. Further, in the manufacturing process of the photomask substrate, if the surface of the phase shift film 3 is sulfurized, and then a photoresist pattern is formed on the phase shift film 3, the cross-sectional shape of the phase shift film pattern becomes a cone. The shape is formed by VUV irradiation before the formation of the photoresist film by the sulfuric acid of the phase shift film 3, and there is a possibility that the cross-sectional shape of the phase shift film pattern is less likely to be a tapered shape but is perpendicularized. That is, when the surface of the phase shift film 3 is sulfuric acid washed, the adhesion between the photoresist film and the film surface of the phase shift film 3 is remarkably lowered, so that the photoresist pattern is used as a mask after the wet etching process. Since the cross-sectional shape is a very large tapered shape, the resolution of the phase shift film cannot be effectively utilized. That is, the VUV irradiation step is facilitated after the sulfuric acid of the phase shift film 3 is washed, whereby the cross-sectional shape of the phase shift film pattern can be greatly improved. Further, the VUV irradiation step is performed by rinsing the sulfuric acid after washing the sulfuric acid to the phase shifting film 3 and reducing the sulfur component as much as possible, and the cross-sectional shape of the phase shift film pattern may be made vertical.

已進行VUV照射步驟之實施形態1之相位偏移光罩基底1亦可於其VUV照射步驟之後，用作相位偏移光罩之製造方法中之製造用原版。又，即便將相位偏移光罩基底1於特定之盒內保管特定之期間，亦可維持VUV照射處理對相位偏移膜3的改質效果。因此，於保管後，可用作相位偏移光罩之製造方法中之製造用原版。如此，由於可保管相位偏移光罩基底1，故而可存儲固定量之相位偏移光罩基底1，可利用於出廠時或相位偏移光罩之製造時等，可提高其操作性。再者，保管亦可為例如2個星期左右之期間，但並不限定於此。 The phase shift mask substrate 1 of the first embodiment in which the VUV irradiation step has been performed may be used as a manufacturing original plate in the manufacturing method of the phase shift mask after the VUV irradiation step. Further, even if the phase shift mask base 1 is stored in a specific cassette for a predetermined period of time, the effect of modifying the phase shift film 3 by the VUV irradiation treatment can be maintained. Therefore, after storage, it can be used as a manufacturing original in the manufacturing method of a phase shift mask. In this manner, since the phase shift mask base 1 can be stored, a fixed amount of the phase shift mask base 1 can be stored, and it can be used at the time of shipment or during the manufacture of the phase shift mask, and the operability can be improved. Further, the storage may be, for example, a period of about two weeks, but is not limited thereto.

實施形態1中，對成膜步驟中使用上述構成之連續式濺鍍裝置11之情形進行了說明，但亦可使用其他構成之連續式濺鍍裝置。作為其他構成之連續式濺鍍裝置，例如，可列舉如下構成：於第2濺鍍腔室SP2，於搬出腔室ULL側，配置有包含用以形成相位偏移膜3之鉻的第4濺鍍靶(未圖示)，於第4濺鍍靶附近之透明基板2之箭頭S所示之搬送 方向上之相對於第4濺鍍靶為上游側之位置配置有第7氣體導入口(未圖示)，於相對於第4濺鍍靶為下游側之位置配置有第8氣體導入口(未圖示)。如此，於配置第4濺鍍靶(未圖示)之情形時，亦跟其他濺鍍靶與配置其搬送方向上之兩側之氣體導入口之配置關係相同，較佳為將第4濺鍍靶(未圖示)與下游側之第8氣體導入口(未圖示)之間隔設定得較第4濺鍍靶(未圖示)與上游側之第7氣體導入口(未圖示)之間隔更寬。 In the first embodiment, the case where the continuous sputtering device 11 having the above configuration is used in the film formation step has been described, but a continuous sputtering device having another configuration may be used. As a continuous sputtering device having another configuration, for example, in the second sputtering chamber SP2, a fourth splash including the chrome for forming the phase shift film 3 is disposed on the side of the carry-out chamber ULL. A plating target (not shown) is conveyed by the arrow S of the transparent substrate 2 in the vicinity of the fourth sputtering target A seventh gas introduction port (not shown) is disposed at a position on the upstream side of the fourth sputtering target in the direction, and a sixth gas introduction port is disposed at a position downstream of the fourth sputtering target (not shown). Graphic). As described above, when the fourth sputtering target (not shown) is disposed, the arrangement relationship between the other sputtering targets and the gas introduction ports on both sides in the conveying direction is the same, and the fourth sputtering is preferably performed. The distance between the target (not shown) and the eighth gas introduction port (not shown) on the downstream side is set to be larger than the fourth sputtering target (not shown) and the seventh gas introduction port (not shown) on the upstream side. The interval is wider.

已對上述相位偏移膜形成步驟中自濺鍍靶之下游側之氣體導入口供給濺鍍氣體進行成膜之情形進行了說明，但作為其他濺鍍氣體之供給方法，亦可自濺鍍靶之上游側之氣體導入口供給濺鍍氣體進行成膜。於任一之情形時，就所成膜之相位偏移膜3而言，於進行下文詳細敍述之VUV照射步驟之後，藉由濕式蝕刻而獲得之相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之剖面形狀(參照下述實施例1、2)與未進行VUV照射步驟之先前之相位偏移膜圖案之邊緣部分之被蝕刻剖面之剖面形狀(參照下述比較例1、2)相比，均不易成為錐形形狀。尤其是，如上述成膜步驟般，於自下游側之氣體導入口供給濺鍍氣體之情形時，亦可使相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之剖面形狀成為最可發揮相位偏移效果之垂直剖面形狀。 In the above-described phase shift film forming step, a case where a sputtering gas is supplied from a gas introduction port on the downstream side of the sputtering target has been described. However, as a method of supplying another sputtering gas, a sputtering target may be used. The gas introduction port on the upstream side is supplied with a sputtering gas to form a film. In either case, with respect to the phase-shift film 3 formed, the edge portion of the phase-shift film pattern 3 ' obtained by wet etching after the VUV irradiation step described in detail below is performed. The cross-sectional shape of the cross-sectional shape of the etched cross section (refer to the following Examples 1 and 2) and the edge portion of the previous phase shift film pattern in which the VUV irradiation step was not performed (see Comparative Examples 1 and 2 below) In comparison, it is not easy to become a tapered shape. In particular, when the sputtering gas is supplied from the gas inlet port on the downstream side as in the film forming step, the cross-sectional shape of the etched cross section of the edge portion of the phase shift film pattern 3 ' can be maximized. The vertical profile shape of the phase shift effect.

實施形態2. Embodiment 2.

實施形態2中，對顯示裝置製造用之相位偏移光罩(透明基板/相位偏移膜圖案)之製造方法進行說明。 In the second embodiment, a method of manufacturing a phase shift mask (transparent substrate/phase shift film pattern) for manufacturing a display device will be described.

圖4(a)~圖4(e)係表示本發明之實施形態2之相位偏移光罩之製造方法之各步驟之剖視圖，對與圖1~圖3相同構成要素標註相同符號並省略重複說明。 4(a) to 4(e) are cross-sectional views showing respective steps of a method of manufacturing a phase shift mask according to a second embodiment of the present invention, and the same components as those in Figs. 1 to 3 are denoted by the same reference numerals, and the description thereof is omitted. Description.

實施形態2之相位偏移光罩30具有於透明基板2上形成有相位偏移膜圖案3'之構成。 The phase shift mask 30 of the second embodiment has a configuration in which a phase shift film pattern 3 ' is formed on the transparent substrate 2.

以此方式構成之實施形態2之相位偏移光罩之製造方法中，首先，進行光阻劑膜圖案形成步驟，該光阻劑膜圖案形成步驟係於實施形態1中所說明之相位偏移光罩基底1(參照圖1)、或藉由實施形態1所說明之相位偏移光罩基底之製造方法而獲得之相位偏移光罩基底1(參照圖2(b))之相位偏移膜3上，形成光阻劑膜圖案5'。 In the method of manufacturing a phase shift mask according to the second embodiment configured as described above, first, a photoresist film pattern forming step is performed, and the photoresist film pattern forming step is the phase shift described in the first embodiment. Phase shift of the phase shift mask substrate 1 (see FIG. 2(b)) obtained by the mask substrate 1 (see FIG. 1) or the phase shift mask substrate manufacturing method described in the first embodiment On the film 3, a photoresist film pattern 5 ' is formed .

詳細而言，該光阻劑膜圖案形成步驟中，首先，如圖4(a)所示，準備於透明基板2上形成有由鉻系材料而構成之相位偏移膜3之相位偏移光罩基底1。其後，如圖4(b)所示，於相位偏移膜3上形成光阻劑膜5。其後，如圖4(c)所示，對光阻劑膜5描畫特定之尺寸之圖案之後，利用特定之顯影液將光阻劑膜5顯影，形成光阻劑膜圖案5'。 Specifically, in the photoresist film pattern forming step, first, as shown in FIG. 4(a), phase shift light of the phase shift film 3 made of a chromium-based material is formed on the transparent substrate 2. Cover substrate 1. Thereafter, as shown in FIG. 4(b), a photoresist film 5 is formed on the phase shift film 3. Thereafter, as shown in FIG. 4(c), after the photoresist film 5 is drawn with a pattern of a specific size, the photoresist film 5 is developed with a specific developer to form a photoresist film pattern 5 ' .

作為描畫於光阻劑膜5之圖案，可列舉線與間隙圖案或孔圖案。 As the pattern drawn on the photoresist film 5, a line and gap pattern or a hole pattern can be cited.

其次，如圖4(d)所示，進行相位偏移膜圖案形成步驟，即，將光阻劑膜圖案5'作為光罩而對相位偏移膜3進行濕式蝕刻，形成相位偏移膜圖案3'。 Next, as shown in FIG. 4(d), a phase shift film pattern forming step is performed in which the phase shift film 3 is wet-etched using the photoresist film pattern 5 ' as a mask to form a phase shift film. Pattern 3 ' .

對相位偏移膜3進行濕式蝕刻之蝕刻液只要可選擇性地蝕刻由鉻系材料而構成之相位偏移膜3，則並無特別限制。具體而言，可列舉包含硝酸鈰銨與過氯酸之蝕刻液。 The etching liquid for wet etching the phase shift film 3 is not particularly limited as long as it can selectively etch the phase shift film 3 made of a chromium-based material. Specifically, an etching solution containing cerium ammonium nitrate and perchloric acid can be mentioned.

於相位偏移膜圖案3'之形成後，如圖4(e)所示，將光阻劑膜圖案5'剝離。 After the formation of the phase shift film pattern 3 ' , as shown in Fig. 4(e), the photoresist film pattern 5 ' is peeled off.

實施形態2之相位偏移光罩30係藉由此種光阻劑膜圖案形成步驟與相位偏移膜圖案形成步驟而製造。 The phase shift mask 30 of the second embodiment is manufactured by the photoresist film pattern forming step and the phase shift film pattern forming step.

相位偏移膜圖案3'與相位偏移光罩基底1之相位偏移膜3相同，具有改變曝光之光之相位之性質。藉由該性質，而使透過相位偏移膜圖案3'之曝光之光與僅透過透明基板2之曝光之光之間產生特定的相位差。於曝光之光為包含300nm以上500nm以下之波長範圍之光的複合光之情形時，相位偏移膜圖案3'以相對於代表波長之光產生特定之相 位差之方式而形成。例如，於曝光之光為包含i射線、h射線及g射線的複合光之情形時，相位偏移膜圖案3'以相對於i射線、h射線及g射線中之任一者產生180度之相位差之方式而形成。又，為了發揮相位偏移效果，例如，將i射線下之相位偏移膜圖案3'之相位差設定為180度±10度之範圍，較佳為設定為大致180度。又，例如，i射線下之相位偏移膜圖案3'之透過率較佳為設定為1%以上20%以下，尤佳為3%以上15%以下之範圍。 The phase shift film pattern 3 ' is the same as the phase shift film 3 of the phase shift mask substrate 1, and has a property of changing the phase of the exposed light. By this property, a specific phase difference is generated between the light that has passed through the phase shift film pattern 3 ' and the light that has passed through only the transparent substrate 2. In the case where the light to be exposed is a composite light including light in a wavelength range of 300 nm or more and 500 nm or less, the phase shift film pattern 3 ' is formed so as to generate a specific phase difference with respect to light of a representative wavelength. For example, when the exposed light is a composite light including i-rays, h-rays, and g-rays, the phase-shifted film pattern 3 ' is 180 degrees with respect to any of the i-rays, h-rays, and g-rays. Formed by the way of phase difference. Further, in order to exhibit the phase shift effect, for example, the phase difference of the phase shift film pattern 3 ' under the i-ray is set to a range of 180 degrees ± 10 degrees, preferably set to substantially 180 degrees. Further, for example, the transmittance of the phase shift film pattern 3 ' under the i-ray is preferably set to be 1% or more and 20% or less, and more preferably in the range of 3% or more and 15% or less.

關於相位偏移膜圖案3'之各元素之組成比，於除自相位偏移膜圖案3'之最表面朝向膜深度方向形成之組成梯度區域及相位偏移膜圖案3'與透明基板2之界面附近之透明基板附近區域以外的主體部中大致均一。但，於自相位偏移膜圖案3'之最表面朝向膜深度方向形成之組成梯度區域及透明基板附近區域中，由於形成有組成梯度之區域，故而該等之部分之組成並不均一。 On the outermost surface of the phase shift film pattern 3 'of the composition ratio of each element, since in addition to the phase shift film pattern 3' is formed in the depth direction of the film toward the area and phase composition gradient film pattern 3 'of the transparent substrate 2 The body portion other than the vicinity of the transparent substrate near the interface is substantially uniform. However, in the composition gradient region formed from the outermost surface of the phase shift film pattern 3 ' toward the film depth direction and the vicinity of the transparent substrate, since the composition gradient region is formed, the composition of the portions is not uniform.

就此種相位偏移膜圖案3'之邊緣部分之被蝕刻剖面的剖面形狀而言，由於相位偏移膜3之最表面3a受上述VUV照射處理，組成梯度區域R1被改質，故而不易成為錐形形狀。 With respect to the cross-sectional shape of the etched cross section of the edge portion of the phase shift film pattern 3 ' , since the outermost surface 3a of the phase shift film 3 is subjected to the above-described VUV irradiation treatment, the composition gradient region R1 is modified, so that it is not easy to be a cone. Shape.

此處，關於相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之剖面角度(θ)(參照下述圖14)，自充分發揮相位偏移效果之觀點而言，較理想的是儘可能為90度或接近該90度之角度。 Here, regarding the cross-sectional angle (θ) of the etched cross section of the edge portion of the phase shift film pattern 3 ′ (see FIG. 14 below), it is preferable to use the phase shift effect as much as possible. It is 90 degrees or close to the angle of 90 degrees.

但，剖面角度(θ)即便不為90度或接近該90度之角度，亦可充分發揮相位偏移效果。例如，於相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之中的、接近透明基板2之邊緣部分之被蝕刻剖面部分即便存在若干裙擺部分，接近光阻劑膜圖案5'之相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之較多部分只要為90度或接近該90度之角度，則可充分發揮相位偏移效果。 However, the cross-sectional angle (θ) can sufficiently exert the phase shift effect even if it is not 90 degrees or close to the angle of 90 degrees. For example, among the etched sections of the edge portion of the phase shift film pattern 3 ', the portion of the etched portion near the edge portion of the transparent substrate 2 is close to the phase of the photoresist film pattern 5 ' even if there are a plurality of skirt portions. When a large portion of the etched cross section of the edge portion of the offset film pattern 3 ' is 90 degrees or close to the angle of 90 degrees, the phase shift effect can be sufficiently exerted.

以此方式製造之顯示裝置製造用之相位偏移光罩30使用於等倍 曝光之投影曝光且充分發揮相位偏移效果。尤其是，作為其曝光環境，數值孔徑(NA)較佳為0.06~0.15，更佳為0.08~0.10，同調因子(σ)較佳為0.5~1.0。 The phase shift mask 30 for manufacturing a display device manufactured in this manner is used for equal magnification The projection of the exposure is exposed and the phase shift effect is fully exerted. In particular, as the exposure environment, the numerical aperture (NA) is preferably from 0.06 to 0.15, more preferably from 0.08 to 0.10, and the homology factor (σ) is preferably from 0.5 to 1.0.

根據實施形態2之相位偏移光罩之製造方法，使用實施形態1中所說明之相位偏移光罩基底1、或藉由實施形態1中所說明之相位偏移光罩基底之製造方法而獲得之相位偏移光罩基底1來製造相位偏移光罩30。因此，可製造具有可充分發揮相位偏移效果之相位偏移膜圖案3'之相位偏移光罩30。由於相位偏移膜圖案3'可充分發揮相位偏移效果，故而可製造使解像度提高、具有具備良好之CD特性之相位偏移膜圖案3'的相位偏移光罩30。該相位偏移光罩30可應對線與間隙圖案或接觸孔之微細化。 According to the method of manufacturing a phase shift mask according to the second embodiment, the phase shift mask base 1 described in the first embodiment or the method of manufacturing the phase shift mask base described in the first embodiment is used. The phase shift mask substrate 1 is obtained to produce a phase shift mask 30. Therefore, the phase shift mask 30 having the phase shift film pattern 3 ' which can sufficiently exert the phase shift effect can be manufactured. Since the phase shift film pattern 3 ' can sufficiently exhibit the phase shift effect, the phase shift mask 30 having the phase shift film pattern 3 ' having excellent CD characteristics can be manufactured with improved resolution. The phase shift mask 30 can cope with the miniaturization of the line and gap patterns or contact holes.

再者，實施形態2中，作為相位偏移光罩30之製造用原版，已使用具有透明基板/相位偏移膜之構成之相位偏移光罩基底1進行了說明，但並不限定於此。例如，亦可將具有透明基板/相位偏移膜/光阻劑膜之構成(參照圖4(b))之相位偏移光罩基底作為相位偏移光罩30之製造用原版。 In the second embodiment, the original substrate for manufacturing the phase shift mask 30 has been described using the phase shift mask substrate 1 having a transparent substrate/phase shift film. However, the present invention is not limited thereto. . For example, a phase shift mask base having a configuration of a transparent substrate/phase shift film/resist film (see FIG. 4(b)) may be used as a master for manufacturing the phase shift mask 30.

又，實施形態2中，亦可於光阻劑膜圖案形成步驟前，對相位偏移光罩基底1之相位偏移膜3，根據需要進行膜洗淨。膜洗淨可使用公知之洗淨方法。但，較佳為使用利用包含硫磺(S)成分之洗淨液(例如，硫酸過氧化氫混合物)之洗淨方法以外的洗淨方法。於使用包含硫磺(S)成分之洗淨液之膜洗淨中，其硫磺(S)成分會殘留於相位偏移膜3上。因此，其原因在於，因該殘留之硫磺(S)成分，而使得於使相位偏移膜3圖案化獲得相位偏移膜圖案3'時，其邊緣部分之被蝕刻剖面之剖面形狀容易成為錐形形狀。 Further, in the second embodiment, the phase shift film 3 of the phase shift mask base 1 may be subjected to film cleaning as needed before the photoresist film pattern forming step. A well-known washing method can be used for film washing. However, it is preferable to use a washing method other than the washing method using a washing liquid containing a sulfur (S) component (for example, a sulfuric acid hydrogen peroxide mixture). In the membrane cleaning using the cleaning solution containing the sulfur (S) component, the sulfur (S) component remains on the phase shifting film 3. Therefore, the reason is that, when the phase shift film 3 is patterned to obtain the phase shift film pattern 3 ' due to the residual sulfur (S) component, the cross-sectional shape of the etched section of the edge portion is easily tapered. Shape.

實施形態3. Embodiment 3.

實施形態3中，對顯示裝置製造用之相位偏移光罩基底(透明基板 /遮光膜圖案/相位偏移膜)及其製造方法進行說明。 In the third embodiment, a phase shift mask substrate (transparent substrate) for manufacturing a display device / light-shielding film pattern / phase shift film) and its manufacturing method will be described.

圖5係表示本發明之實施形態3之相位偏移光罩基底之構成之剖視圖，圖6(a)~圖6(g)係表示圖5所示之相位偏移光罩基底之製造方法之各步驟之剖視圖，對與圖1~圖4相同構成要素標註相同符號並省略重複說明。 5 is a cross-sectional view showing a configuration of a phase shift mask base according to a third embodiment of the present invention, and FIGS. 6(a) to 6(g) are views showing a method of manufacturing the phase shift mask base shown in FIG. 5. The same components as those in FIGS. 1 to 4 are denoted by the same reference numerals, and the description thereof will not be repeated.

如圖5所示，實施形態3之相位偏移光罩基底10包括：透明基板2；遮光膜圖案4'，其形成於該透明基板2之主表面上；以及相位偏移膜3，其形成於該遮光膜圖案4'及透明基板2之主表面上。 As shown in FIG. 5, the phase shift mask substrate 10 of Embodiment 3 includes: a transparent substrate 2; a light shielding film pattern 4 ' formed on a main surface of the transparent substrate 2; and a phase shift film 3 formed On the main surface of the light shielding film pattern 4 ' and the transparent substrate 2.

以此方式構成之實施形態3之相位偏移光罩基底10之製造方法包含：準備步驟，其係準備透明基板2；成膜步驟(以下，有時稱為遮光膜形成步驟)，其藉由濺鍍而於透明基板2之主表面上成膜遮光膜4；遮光膜圖案形成步驟，其係使遮光膜4圖案化而形成遮光膜圖案4'；相位偏移膜形成步驟，其係於遮光膜圖案4'上，成膜含有鉻、氧及氮之相位偏移膜3；及VUV照射步驟，其係對所成膜之相位偏移膜3之最表面3a進行VUV照射處理。 The method for manufacturing the phase shift mask substrate 10 of the third embodiment configured in this manner includes a preparation step of preparing a transparent substrate 2, and a film formation step (hereinafter sometimes referred to as a light shielding film forming step) by a light-shielding film 4 is formed on the main surface of the transparent substrate 2 by sputtering; a light-shielding film pattern forming step of patterning the light-shielding film 4 to form a light-shielding film pattern 4 ' ; and a phase-shifting film forming step for shading On the film pattern 4 ' , a phase shift film 3 containing chromium, oxygen, and nitrogen is formed, and a VUV irradiation step is performed for VUV irradiation treatment on the outermost surface 3a of the phase shift film 3 to be formed.

以下，對各步驟進行詳細說明。 Hereinafter, each step will be described in detail.

1.準備步驟 1. Preparation steps

首先，準備透明基板2。 First, the transparent substrate 2 is prepared.

該準備步驟與實施形態1中之準備步驟同樣地進行。 This preparation step is carried out in the same manner as the preparation step in the first embodiment.

2.遮光膜形成步驟 2. Light shielding film forming step

其次，如圖6(a)所示，藉由濺鍍而於透明基板2之主表面上形成遮光膜4。 Next, as shown in FIG. 6(a), the light shielding film 4 is formed on the main surface of the transparent substrate 2 by sputtering.

詳細而言，該遮光膜形成步驟中，進行成膜步驟，即，於濺鍍氣體環境中施加濺鍍功率而成膜由特定之材料而構成之遮光膜4。 Specifically, in the light shielding film forming step, a film forming step of applying a sputtering power to a sputtering gas atmosphere to form a light shielding film 4 made of a specific material is formed.

遮光膜4係以與相位偏移膜3之合計，相對於曝光之光之光學濃度為2.8以上，較佳為3.0以上之方式，調整構成遮光膜4之材料或膜 厚。 The light-shielding film 4 is adjusted so that the optical density of the light to be exposed is 2.8 or more, preferably 3.0 or more, in combination with the phase shift film 3, and the material or film constituting the light-shielding film 4 is adjusted. thick.

構成遮光膜4之材料並不特別限定，但較佳為使用於光罩基底之材料。作為使用於光罩基底之材料，例如，可列舉包含鉻之材料、包含鉭之材料、及包含金屬與矽(Si)之材料(金屬矽化物材料)。作為包含鉻之材料，只要為包含鉻(Cr)者，則並無特別限制，例如，可列舉鉻(Cr)、鉻之氧化物、鉻之氮化物、鉻之碳化物、及鉻之氟化物。作為包含鉭之材料，只要為包含鉭(Ta)者，則並無特別限制，例如，可列舉鉭(Ta)、鉭之氧化物、及鉭之氮化物。作為金屬矽化物材料，例如，可列舉金屬矽化物之氮化物、金屬矽化物之氧化物、金屬矽化物之氧化氮化物、金屬矽化物之碳化氮化物、金屬矽化物之氧化碳化物、及金屬矽化物之氧化碳化氮化物。作為金屬，可列舉鉬(Mo)、鉭(Ta)、鎢(W)、鈦(Ti)等過渡金屬。金屬與矽之組成係自遮光膜4之光學特性之觀點而調整。金屬與矽之比率可根據金屬之種類或遮光膜所要求之光學特性而適當選擇，較佳為金屬：矽=1：1以上1：9以下。 The material constituting the light shielding film 4 is not particularly limited, but is preferably a material used for the reticle base. Examples of the material used for the base of the photomask include a material containing chromium, a material containing niobium, and a material containing metal and niobium (Si) (metal chelate material). The material containing chromium is not particularly limited as long as it contains chromium (Cr), and examples thereof include chromium (Cr), chromium oxide, chromium nitride, chromium carbide, and chromium fluoride. . The material containing ruthenium is not particularly limited as long as it contains ruthenium (Ta), and examples thereof include ruthenium (Ta), an oxide of ruthenium, and a nitride of ruthenium. Examples of the metal telluride material include a nitride of a metal telluride, an oxide of a metal telluride, an oxide nitride of a metal telluride, a carbonitride of a metal telluride, an oxidized carbide of a metal telluride, and a metal. An oxidized carbonitride of a telluride. Examples of the metal include transition metals such as molybdenum (Mo), tantalum (Ta), tungsten (W), and titanium (Ti). The composition of the metal and tantalum is adjusted from the viewpoint of the optical characteristics of the light-shielding film 4. The ratio of the metal to the ruthenium can be appropriately selected depending on the kind of the metal or the optical characteristics required for the light-shielding film, and is preferably metal: 矽 = 1:1 or more and 1:9 or less.

再者，構成遮光膜4之材料亦可根據需要，包含氧(O)、氮(N)、碳(C)等其他元素。 Further, the material constituting the light shielding film 4 may contain other elements such as oxygen (O), nitrogen (N), and carbon (C) as needed.

遮光膜4亦可為由1層而構成之情形及由複數層而構成之情形中之任一者。於遮光膜4由複數層而構成之情形時，例如，存在由形成於相位偏移膜3側之遮光層與形成於遮光層上之抗反射層而構成之積層構造之情形。遮光層亦可為由1層而構成之情形及由複數層而構成之情形中之任一者。作為遮光層，例如，可列舉鉻氮化膜(CrN)、鉻碳化膜(CrC)、鉻碳化氮化膜(CrCN)。抗反射層係以降低曝光之光之反射率之目的而設置於遮光膜之表面，抗反射層亦可為由1層而構成之情形及由複數層而構成之情形。作為抗反射層，例如，可列舉鉻氧化氮化膜(CrON)。 The light shielding film 4 may be formed of one layer and one of a plurality of layers. In the case where the light-shielding film 4 is composed of a plurality of layers, for example, there is a case where a light-shielding layer formed on the phase shift film 3 side and an anti-reflection layer formed on the light-shielding layer are laminated. The light shielding layer may be either one of a single layer and one of a plurality of layers. Examples of the light shielding layer include a chromium nitride film (CrN), a chromium carbonization film (CrC), and a chromium carbide nitride film (CrCN). The antireflection layer is provided on the surface of the light shielding film for the purpose of reducing the reflectance of the exposed light, and the antireflection layer may be composed of one layer and a plurality of layers. As the antireflection layer, for example, a chromium oxide nitride film (CrON) can be cited.

遮光膜4之成膜使用簇型濺鍍裝置、連續式濺鍍裝置等濺鍍裝 置。 The film formation of the light shielding film 4 is performed by using a cluster type sputtering device, a continuous sputtering device, or the like. Set.

遮光膜4例如可藉由如以下之濺鍍靶、濺鍍氣體環境而成膜。 The light shielding film 4 can be formed, for example, by a sputtering target or a sputtering gas atmosphere as follows.

作為使用於由包含鉻之材料而構成之遮光膜4之成膜的濺鍍靶，可選擇包含鉻(Cr)或鉻化合物者。具體而言，可列舉鉻(Cr)、鉻之氮化物、鉻之氧化物、鉻之碳化物、鉻之氧化氮化物、鉻之碳化氮化物、鉻之氧化碳化物、及鉻之氧化碳化氮化物。 As a sputtering target used for film formation of the light-shielding film 4 which consists of a material containing chromium, a chromium (Cr) or chromium compound can be selected. Specific examples thereof include chromium (Cr), chromium nitride, chromium oxide, chromium carbide, chromium oxide nitride, chromium carbonitride, chromium oxidized carbide, and chromium oxynitride nitrogen. Compound.

由包含鉻之材料構成之遮光膜4之成膜時的濺鍍氣體環境包含活性氣體與惰性氣體之混合氣體，上述活性氣體包含選自由氮(N2)氣體、一氧化氮(NO)氣體、二氧化氮(NO2)氣體、一氧化二氮(N2O)氣體、一氧化碳(CO)氣體、二氧化碳(CO2)氣體、氧(O2)氣體、碳化氫系氣體及氟系氣體組成之群中之至少一種，上述惰性氣體包含選自由氦(He)氣體、氖(Ne)氣體、氬(Ar)氣體、氪(Kr)氣體及氙(Xe)氣體組成之群中之至少一種。作為碳化氫系氣體，例如，可列舉甲烷氣體、丁烷氣體、丙烷氣體、苯乙烯氣體。 The sputtering gas atmosphere at the time of film formation of the light shielding film 4 made of a material containing chromium includes a mixed gas of an active gas and an inert gas, and the active gas includes a gas selected from nitrogen (N 2 ) gas and nitrogen monoxide (NO). Nitrogen dioxide (NO 2 ) gas, nitrous oxide (N 2 O) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, oxygen (O 2 ) gas, hydrocarbon gas and fluorine gas At least one of the group, the inert gas comprising at least one selected from the group consisting of helium (He) gas, neon (Ne) gas, argon (Ar) gas, krypton (Kr) gas, and xenon (Xe) gas. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, and styrene gas.

上述濺鍍靶之形成材料與濺鍍氣體環境之氣體之種類之組合、或濺鍍氣體環境中之活性氣體與惰性氣體之混合比例可根據構成遮光膜4之鉻系材料之種類或組成而適當決定。 The combination of the material of the sputtering target and the type of the gas in the sputtering gas atmosphere, or the mixing ratio of the active gas and the inert gas in the sputtering gas atmosphere may be appropriately selected depending on the kind or composition of the chromium-based material constituting the light shielding film 4. Decide.

作為使用於由包含鉭之材料而構成之遮光膜4之成膜的濺鍍靶，可選擇包含鉭(Ta)或鉭化合物者。具體而言，可列舉鉭(Ta)、鉭之氧化物、及鉭之氮化物。 As a sputtering target used for film formation of the light-shielding film 4 which consists of a material containing a ruthenium, you may select a cerium (Ta) or a bismuth compound. Specifically, tantalum (Ta), an oxide of cerium, and a nitride of cerium are exemplified.

由包含鉭之材料而構成之遮光膜4之成膜時之濺鍍氣體環境包含活性氣體與惰性氣體之混合氣體，上述活性氣體包含選自由氮(N2)氣體、一氧化氮(NO)氣體、二氧化氮(NO2)氣體、一氧化二氮(N2O)氣體、一氧化碳(CO)氣體、二氧化碳(CO2)氣體及氧(O2)氣體組成之群中之至少一種，上述惰性氣體包含選自由氦(He)氣體、氖(Ne)氣體、氬(Ar)氣體、氪(Kr)氣體及氙(Xe)氣體組成之群中之至少一種。 The sputtering gas atmosphere at the time of film formation of the light shielding film 4 composed of the material containing germanium includes a mixed gas of an active gas and an inert gas, and the active gas contains a gas selected from nitrogen (N 2 ) gas and nitrogen monoxide (NO) gas. At least one of a group consisting of nitrogen dioxide (NO 2 ) gas, nitrous oxide (N 2 O) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, and oxygen (O 2 ) gas, the above inert The gas contains at least one selected from the group consisting of helium (He) gas, neon (Ne) gas, argon (Ar) gas, krypton (Kr) gas, and xenon (Xe) gas.

上述濺鍍靶之形成材料與濺鍍氣體環境之氣體之種類之組合、或濺鍍氣體環境中之活性氣體與惰性氣體之混合比例可根據包含構成遮光膜4之鉭之材料之種類或組成而適當決定。 The combination of the material of the sputtering target and the type of the gas in the sputtering gas environment, or the mixing ratio of the active gas and the inert gas in the sputtering gas atmosphere may be based on the type or composition of the material including the material constituting the light shielding film 4. Make the appropriate decision.

作為使用於由金屬矽化物材料而構成之遮光膜4之成膜的濺鍍靶，可選擇包含金屬與矽(Si)者。具體而言，可列舉金屬矽化物、金屬矽化物之氮化物、金屬矽化物之氧化物、金屬矽化物之碳化物、金屬矽化物之氧化氮化物、金屬矽化物之碳化氮化物、金屬矽化物之氧化碳化物、及金屬矽化物之氧化碳化氮化物。 As a sputtering target used for film formation of the light-shielding film 4 which consists of a metal telluride material, the metal and 矽(Si) can be selected. Specific examples thereof include metal tellurides, nitrides of metal tellurides, oxides of metal tellurides, carbides of metal tellurides, oxynitrides of metal tellurides, carbonitrides of metal tellurides, and metal tellurides An oxidized carbide, and an oxidized carbonitride of a metal halide.

由金屬矽化物材料而構成之遮光膜4之成膜時的濺鍍氣體環境包含活性氣體與惰性氣體之混合氣體，上述活性氣體包含選自由氮(N2)氣體、一氧化氮(NO)氣體、二氧化氮(NO2)氣體、一氧化二氮(N2O)氣體、一氧化碳(CO)氣體、二氧化碳(CO2)氣體及氧(O2)氣體組成之群中之至少一種，上述惰性氣體包含選自由氦(He)氣體、氖(Ne)氣體、氬(Ar)氣體、氪(Kr)氣體及氙(Xe)氣體組成之群中之至少一種。 The sputtering gas atmosphere at the time of film formation of the light shielding film 4 composed of the metal telluride material includes a mixed gas of an active gas and an inert gas, and the active gas contains a gas selected from nitrogen (N 2 ) gas and nitrogen monoxide (NO) gas. At least one of a group consisting of nitrogen dioxide (NO 2 ) gas, nitrous oxide (N 2 O) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, and oxygen (O 2 ) gas, the above inert The gas contains at least one selected from the group consisting of helium (He) gas, neon (Ne) gas, argon (Ar) gas, krypton (Kr) gas, and xenon (Xe) gas.

上述濺鍍靶之形成材料與濺鍍氣體環境之氣體之種類之組合、或濺鍍氣體環境中之活性氣體與惰性氣體之混合比例可根據構成遮光膜4之金屬矽化物材料之種類或組成而適當決定。 The combination of the material of the sputtering target and the type of gas in the sputtering gas environment, or the mixing ratio of the active gas and the inert gas in the sputtering gas atmosphere may be based on the kind or composition of the metal halide material constituting the light shielding film 4. Make the appropriate decision.

遮光膜形成步驟例如可使用圖3所示之濺鍍裝置11來進行。 The light shielding film forming step can be performed, for example, using the sputtering apparatus 11 shown in FIG.

此處，以形成由包含鉻之材料而構成之遮光膜4之情形為例進行說明。 Here, a case where the light shielding film 4 composed of a material containing chromium is formed will be described as an example.

首先，例如，於形成由遮光層與抗反射層而構成之積層構造之遮光膜4之情形時，於第1濺鍍腔室SP1，配置包含用以形成遮光膜4之遮光層之鉻的第1濺鍍靶13，於第2濺鍍腔室SP2，配置包含用以形成遮光膜4之抗反射層之鉻的第3濺鍍靶15。 First, for example, in the case where the light shielding film 4 having a laminated structure composed of a light shielding layer and an antireflection layer is formed, the first sputtering chamber SP1 is provided with a chromium containing a light shielding layer for forming the light shielding film 4. The sputtering target 13 is provided in the second sputtering chamber SP2, and the third sputtering target 15 including the chromium for forming the antireflection layer of the light shielding film 4 is disposed.

其後，為了形成遮光膜4，而將搭載於托盤(未圖示)之透明基板2搬入至搬入腔室LL。 Thereafter, in order to form the light shielding film 4, the transparent substrate 2 mounted on a tray (not shown) is carried into the carrying chamber LL.

其後，在使濺鍍裝置11之內部成為特定之真空度之狀態下，自第2氣體導入口GA12導入特定之流量之濺鍍氣體，對第1濺鍍靶13施加特定之濺鍍功率。又，自第6氣體導入口GA32導入特定之流量之濺鍍氣體，對第3濺鍍靶15施加特定之濺鍍功率。繼續進行濺鍍功率之施加、濺鍍氣體之導入，直至將透明基板2搬送至搬出腔室ULL。 Then, in a state where the inside of the sputtering apparatus 11 is made to have a specific degree of vacuum, a sputtering gas having a specific flow rate is introduced from the second gas introduction port GA12, and a specific sputtering power is applied to the first sputtering target 13. Further, a sputtering gas having a specific flow rate is introduced from the sixth gas introduction port GA32, and a specific sputtering power is applied to the third sputtering target 15. The application of the sputtering power and the introduction of the sputtering gas are continued until the transparent substrate 2 is transferred to the carry-out chamber ULL.

其後，以特定之搬送速度向箭頭S之方向、按照搬入腔室LL、第1濺鍍腔室SP1、緩衝腔室BU、第2濺鍍腔室SP2、及搬出腔室ULL之順序搬送搭載於托盤(未圖示)之透明基板2。於透明基板2通過第1濺鍍腔室SP1之第1濺鍍靶13附近時，藉由反應性濺鍍，而於透明基板2之主表面上，成膜特定膜厚之由鉻系材料而構成之遮光層。又，於透明基板2通過第2濺鍍腔室SP2之第3濺鍍靶15附近時，藉由反應性濺鍍，而於遮光層上，成膜特定膜厚之由鉻系材料而構成之抗反射層。 Thereafter, the transport is carried out in the order of the arrow S in the direction of the arrow S, in the order of the loading chamber LL, the first sputtering chamber SP1, the buffer chamber BU, the second sputtering chamber SP2, and the carry-out chamber ULL. A transparent substrate 2 on a tray (not shown). When the transparent substrate 2 passes through the vicinity of the first sputtering target 13 of the first sputtering chamber SP1, a chromium-based material having a specific film thickness is formed on the main surface of the transparent substrate 2 by reactive sputtering. A light-shielding layer. Further, when the transparent substrate 2 passes through the vicinity of the third sputtering target 15 of the second sputtering chamber SP2, a chromium-based material having a specific film thickness is formed on the light shielding layer by reactive sputtering. Anti-reflective layer.

於透明基板2之主表面上，形成由遮光層與抗反射層而構成之積層構造之遮光膜4之後，將透明基板2取出至濺鍍裝置11之外部。 After the light shielding film 4 having a laminated structure composed of a light shielding layer and an antireflection layer is formed on the main surface of the transparent substrate 2, the transparent substrate 2 is taken out to the outside of the sputtering apparatus 11.

3.遮光膜圖案形成步驟 3. Light-shielding film pattern forming step

其次，進行遮光膜圖案形成步驟，即，於透明基板2之主表面上形成遮光膜圖案4'。 Next, a light shielding film pattern forming step of forming a light shielding film pattern 4 ' on the main surface of the transparent substrate 2 is performed.

詳細而言，該遮光膜圖案形成步驟中，首先，如圖6(b)所示，於遮光膜4上形成光阻劑膜5。其後，如圖6(c)所示，對光阻劑膜5描畫特定之尺寸之圖案之後，利用特定之顯影液將光阻劑膜5顯影，形成光阻劑膜圖案5'。 Specifically, in the light shielding film pattern forming step, first, as shown in FIG. 6(b), the photoresist film 5 is formed on the light shielding film 4. Thereafter, as shown in FIG. 6(c), after the photoresist film 5 is drawn with a pattern of a specific size, the photoresist film 5 is developed with a specific developer to form a photoresist film pattern 5 ' .

作為描畫於光阻劑膜5之圖案，可列舉線與間隙圖案或孔圖案。 As the pattern drawn on the photoresist film 5, a line and gap pattern or a hole pattern can be cited.

其次，如圖6(d)所示，進行遮光膜圖案形成步驟，即，將光阻劑膜圖案5'作為光罩對遮光膜4進行濕式蝕刻形成遮光膜圖案4'。 Next, FIG. 6 (d), the light-shielding film for patterning step, i.e., the photoresist film pattern 5 'as a mask on the light-shielding film 4 is formed by wet etching the light shielding film pattern 4'.

於遮光膜4由鉻系材料而構成之情形時，對該遮光膜4進行濕式蝕刻之蝕刻液只要為可選擇性地蝕刻遮光膜4者，則並無特別限制。 具體而言，可列舉包含硝酸鈰銨與過氯酸之蝕刻液。 When the light shielding film 4 is made of a chromium-based material, the etching liquid for wet etching the light shielding film 4 is not particularly limited as long as it can selectively etch the light shielding film 4. Specifically, an etching solution containing cerium ammonium nitrate and perchloric acid can be mentioned.

於遮光膜4由金屬矽化物材料而構成之情形時，對該遮光膜4進行濕式蝕刻之蝕刻液只要為可選擇性地蝕刻遮光膜4者，則並無特別限制。例如，可列舉包含選自氫氟酸、氫氟矽酸、及氟化氫銨之至少一種氟化合物與選自過氧化氫、硝酸、及硫酸之至少一種氧化劑的蝕刻液。具體而言，可列舉將氟化氫銨與過氧化氫之混合溶液利用純水稀釋而成之蝕刻液。 When the light shielding film 4 is made of a metal halide material, the etching liquid for wet etching the light shielding film 4 is not particularly limited as long as it can selectively etch the light shielding film 4. For example, an etching solution containing at least one fluorine compound selected from the group consisting of hydrofluoric acid, hydrofluoroantimonic acid, and ammonium hydrogen fluoride, and at least one oxidizing agent selected from the group consisting of hydrogen peroxide, nitric acid, and sulfuric acid may be mentioned. Specifically, an etching solution obtained by diluting a mixed solution of ammonium hydrogen fluoride and hydrogen peroxide with pure water can be mentioned.

於遮光膜4由鉭系材料而構成之情形時，對該遮光膜4進行濕式蝕刻之蝕刻液只要為可選擇性地蝕刻遮光膜4者，則並無特別限制。具體而言，可列舉包含氫氧化鈉與過氧化氫之蝕刻液。 When the light shielding film 4 is made of a lanthanoid material, the etching liquid for wet etching the light shielding film 4 is not particularly limited as long as it can selectively etch the light shielding film 4. Specifically, an etching solution containing sodium hydroxide and hydrogen peroxide can be mentioned.

於遮光膜圖案4'之形成後，如圖6(e)所示，將光阻劑膜圖案5'剝離。 After the formation of the light-shielding film pattern 4 ' , as shown in Fig. 6(e), the photoresist film pattern 5 ' is peeled off.

4.相位偏移膜形成步驟 4. Phase shift film formation step

其次，如圖6(f)所示，進行相位偏移膜形成步驟，即，於透明基板2上之遮光膜圖案4'上成膜相位偏移膜3。 Next, as shown in FIG. 6(f), a phase shift film forming step of forming the phase shift film 3 on the light shielding film pattern 4 ' on the transparent substrate 2 is performed.

該相位偏移膜形成步驟係與實施形態1中之相位偏移膜形成步驟同樣地進行。 This phase shift film forming step is performed in the same manner as the phase shift film forming step in the first embodiment.

5.VUV照射步驟 5.VUV irradiation step

其次，如圖6(g)所示，對相位偏移膜3之最表面3a進行VUV照射處理。 Next, as shown in Fig. 6(g), the VUV irradiation treatment is performed on the outermost surface 3a of the phase shift film 3.

該VUV照射步驟係與實施形態1中之VUV照射步驟同樣地進行。 This VUV irradiation step was carried out in the same manner as the VUV irradiation step in the first embodiment.

經過此種VUV照射步驟之相位偏移膜3藉由該VUV照射步驟，而以具有與實施形態1之相位偏移光罩基底1中之相位偏移膜3相同之特性之方式被改質。 The phase shift film 3 subjected to the VUV irradiation step is modified in the same manner as the phase shift film 3 in the phase shift mask substrate 1 of the first embodiment by the VUV irradiation step.

實施形態3之相位偏移光罩基底10係藉由此種準備步驟、遮光膜形成步驟、遮光膜圖案形成步驟、相位偏移膜形成步驟、及VUV照射 步驟而製造。 The phase shift mask substrate 10 of the third embodiment is subjected to such a preparation step, a light shielding film forming step, a light shielding film pattern forming step, a phase shift film forming step, and VUV irradiation. The steps are made.

根據以此方式製造之實施形態3之相位偏移光罩基底10，於透明基板2之主表面上經由遮光膜圖案4'而形成含有鉻、氧及氮之相位偏移膜3，且於透明基板2之主表面上直接形成含有鉻、氧及氮之相位偏移膜3。相位偏移膜3之組成梯度區域R1中，自最表面3a朝向膜深度方向減少之O/Cr之最大值為2以上，且，自最表面3a朝向膜深度方向減少之N/Cr之最大值為0.45以下。因此，該相位偏移光罩基底10中，其相位偏移膜3藉由濕式蝕刻，可圖案化為可充分發揮相位偏移效果之剖面形狀。該相位偏移光罩基底10中，由於可使藉由使其相位偏移膜3圖案化而獲得之相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之剖面形狀成為可充分發揮相位偏移效果之剖面形狀，故而可形成使解像度提高、具有具備良好之CD特性之相位偏移膜圖案的相位偏移光罩之製造用原版。 According to the phase shift mask substrate 10 of the third embodiment manufactured in this manner, the phase shift film 3 containing chromium, oxygen and nitrogen is formed on the main surface of the transparent substrate 2 via the light shielding film pattern 4 ' , and is transparent. A phase shift film 3 containing chromium, oxygen, and nitrogen is directly formed on the main surface of the substrate 2. In the composition gradient region R1 of the phase shift film 3, the maximum value of O/Cr which decreases from the outermost surface 3a toward the film depth direction is 2 or more, and the maximum value of N/Cr decreases from the outermost surface 3a toward the film depth direction. It is 0.45 or less. Therefore, in the phase shift mask substrate 10, the phase shift film 3 can be patterned into a cross-sectional shape in which the phase shift effect can be sufficiently exhibited by wet etching. In the phase shift mask substrate 10, the cross-sectional shape of the etched cross section of the edge portion of the phase shift film pattern 3 ' obtained by patterning the phase shift film 3 can be sufficiently utilized. By shifting the cross-sectional shape of the effect, it is possible to form a precursor for manufacturing a phase shift mask having an improved resolution and a phase shift film pattern having excellent CD characteristics.

又，根據實施形態3之相位偏移光罩基底之製造方法，包含：成膜步驟，其係藉由濺鍍法而於透明基板2之主表面上經由遮光膜圖案4'而成膜含有鉻、氧及氮之相位偏移膜3，且於透明基板2之主表面上直接成膜含有鉻、氧及氮之相位偏移膜3；及VUV照射處理步驟，其係對所成膜之相位偏移膜3之最表面3a進行VUV照射處理。該VUV照射處理步驟係如下步驟：於組成梯度區域R1中，將自最表面3a朝向膜深度方向減少之O/Cr之最大值改為2以上，且，將自最表面3a朝向膜深度方向減少之N/Cr之最大值改為0.45以下。因此，可製造可藉由濕式蝕刻而使相位偏移膜圖案化可充分發揮相位偏移效果之剖面形狀之相位偏移光罩基底10。又，由於可使相位偏移膜圖案3'之邊緣部分之被蝕刻剖面之剖面形狀成為可充分發揮相位偏移效果之剖面形狀，故而可製造使解像度提高、可圖案化為具備良好之CD特性之相位偏移膜圖案的相位偏移光罩基底10。 Further, the method of manufacturing a phase shift mask base according to the third embodiment includes a film forming step of forming a film on the main surface of the transparent substrate 2 via a light shielding film pattern 4 ' by sputtering. a phase shifting film 3 of oxygen and nitrogen, and directly forming a phase shift film 3 containing chromium, oxygen and nitrogen on the main surface of the transparent substrate 2; and a VUV irradiation treatment step for phase-forming the film The outermost surface 3a of the offset film 3 is subjected to a VUV irradiation treatment. The VUV irradiation treatment step is a step of changing the maximum value of O/Cr reduced from the outermost surface 3a toward the film depth direction to 2 or more in the composition gradient region R1, and decreasing from the outermost surface 3a toward the film depth direction. The maximum value of N/Cr is changed to 0.45 or less. Therefore, it is possible to manufacture the phase shift mask substrate 10 in which the phase shift film can be patterned by wet etching to sufficiently exhibit the phase shift effect. Further, since the cross-sectional shape of the etched cross section of the edge portion of the phase shift film pattern 3 ' can be made into a cross-sectional shape in which the phase shift effect can be sufficiently exhibited, the resolution can be improved and the pattern can be patterned to have good CD characteristics. The phase of the phase shift film pattern is shifted from the mask substrate 10.

實施形態4. Embodiment 4.

實施形態4中，對顯示裝置製造用之相位偏移光罩(透明基板/遮光膜圖案/相位偏移膜圖案)之製造方法進行說明。 In the fourth embodiment, a method of manufacturing a phase shift mask (transparent substrate/light shielding film pattern/phase shift film pattern) for manufacturing a display device will be described.

圖7(a)~圖7(e)係表示使用圖5所示之相位偏移光罩基底之本發明之實施形態4之相位偏移光罩之製造方法之各步驟的剖視圖，對與圖1~圖6相同構成要素標註相同符號並省略重複說明。 7(a) to 7(e) are cross-sectional views showing respective steps of a method of manufacturing a phase shift mask according to a fourth embodiment of the present invention using the phase shift mask substrate shown in Fig. 5, and The same components as those in FIG. 6 are denoted by the same reference numerals and the description thereof will not be repeated.

利用實施形態4之相位偏移光罩基底之製造方法而製造的相位偏移光罩31具有如下構成：於透明基板2之主表面上經由遮光膜圖案4'而形成含有鉻、氧及氮之相位偏移膜圖案3'，且於透明基板2之主表面上直接形成含有鉻、氧及氮之相位偏移膜圖案3'。 The phase shift mask 31 manufactured by the method for manufacturing a phase shift mask base according to the fourth embodiment has a configuration in which chromium, oxygen, and nitrogen are formed on the main surface of the transparent substrate 2 via the light shielding film pattern 4 ' . The phase shift film pattern 3 ' is formed, and a phase shift film pattern 3 ' containing chromium, oxygen, and nitrogen is directly formed on the main surface of the transparent substrate 2.

如此構成之實施形態4之相位偏移光罩之製造方法中，首先，進行光阻劑膜圖案形成步驟，該光阻劑膜圖案形成步驟係於實施形態3中所說明之相位偏移光罩基底10(參照圖5)、或藉由實施形態3中所說明之相位偏移光罩基底之製造方法而獲得之相位偏移光罩基底10(參照圖6(g))之相位偏移膜3上，形成光阻劑膜圖案5'。 In the method of manufacturing a phase shift mask according to the fourth embodiment configured as described above, first, a photoresist film pattern forming step is performed, and the photoresist film pattern forming step is the phase shift mask described in the third embodiment. A phase shifting film of the phase shift mask substrate 10 (see FIG. 6(g)) obtained by the substrate 10 (see FIG. 5) or the phase shift mask substrate manufacturing method described in the third embodiment On the 3, a photoresist film pattern 5 ' is formed .

詳細而言，該光阻劑膜圖案形成步驟中，首先，如圖7(a)所示，準備於透明基板2之主表面上經由遮光膜圖案4'而形成有含有鉻、氧及氮之相位偏移膜3、且於透明基板2之主表面上直接形成有含有鉻、氧及氮之相位偏移膜3的相位偏移光罩基底10。其後，如圖7(b)所示，於相位偏移膜3上形成光阻劑膜5。其後，如圖7(c)所示，對光阻劑膜5描畫特定之尺寸之圖案之後，利用特定之顯影液將光阻劑膜5顯影，形成光阻劑膜圖案5'。 Specifically, in the photoresist film pattern forming step, first, as shown in FIG. 7( a ), a surface containing the chromium, oxygen, and nitrogen is formed on the main surface of the transparent substrate 2 via the light shielding film pattern 4 ′ . The phase shift film 3 and the phase shift mask substrate 10 including the phase shift film 3 of chromium, oxygen, and nitrogen are directly formed on the main surface of the transparent substrate 2. Thereafter, as shown in FIG. 7(b), a photoresist film 5 is formed on the phase shift film 3. Thereafter, as shown in FIG. 7(c), after the photoresist film 5 is drawn with a pattern of a specific size, the photoresist film 5 is developed with a specific developer to form a photoresist film pattern 5 ' .

作為描畫於光阻劑膜5之圖案，可列舉線與間隙圖案或孔圖案。 As the pattern drawn on the photoresist film 5, a line and gap pattern or a hole pattern can be cited.

其次，如圖7(d)所示，進行相位偏移膜圖案形成步驟，即，將光阻劑膜圖案5'作為光罩對相位偏移膜3進行濕式蝕刻而形成相位偏移膜圖案3'。 Next, as shown in FIG. 7(d), a phase shift film pattern forming step is performed in which the phase shift film 3 is wet-etched by using the photoresist film pattern 5 ' as a mask to form a phase shift film pattern. 3 ' .

對相位偏移膜3進行濕式蝕刻之蝕刻液只要為可選擇性地蝕刻由鉻系材料而構成之相位偏移膜3者，則並無特別限制。具體而言，可列舉包含硝酸鈰銨與過氯酸之蝕刻液。 The etching liquid for wet etching the phase shift film 3 is not particularly limited as long as it can selectively etch the phase shift film 3 composed of a chromium-based material. Specifically, an etching solution containing cerium ammonium nitrate and perchloric acid can be mentioned.

所獲得之相位偏移膜圖案3'與實施形態2中之相位偏移膜圖案3'相同，具有改變曝光之光之相位之性質，其邊緣部分之被蝕刻剖面之剖面形狀由於相位偏移膜3之最表面3a受上述VUV照射處理，組成梯度區域R1被改質，故而不易成為錐形形狀。 The obtained phase shift film pattern 'of the phase shift film pattern 2 and Embodiment 3' 3 are the same, has a property of changing a phase of exposure light, the cross-sectional shape of the edge portions of the phase shift due to the cross-sectional view of the etched film The outermost surface 3a of 3 is subjected to the above-described VUV irradiation treatment, and the composition gradient region R1 is modified, so that it is not easy to become a tapered shape.

於相位偏移膜圖案3'之形成後，如圖7(e)所示，將光阻劑膜圖案5'剝離。 After the formation of the phase shift film pattern 3 ' , as shown in Fig. 7(e), the photoresist film pattern 5 ' is peeled off.

實施形態4之相位偏移光罩31係藉由此種光阻劑膜圖案形成步驟與相位偏移膜圖案形成步驟而製造。 The phase shift mask 31 of the fourth embodiment is manufactured by the photoresist film pattern forming step and the phase shift film pattern forming step.

如此製造之顯示裝置製造用之相位偏移光罩31使用於等倍曝光之投影曝光而充分發揮相位偏移效果。尤其是，作為其曝光環境，數值孔徑(NA)較佳為0.06~0.15，更佳為0.08~0.10，同調因子(σ)較佳為0.5~1.0。 The phase shift mask 31 for manufacturing a display device manufactured in this manner is used for projection exposure of a double exposure to sufficiently exhibit a phase shift effect. In particular, as the exposure environment, the numerical aperture (NA) is preferably from 0.06 to 0.15, more preferably from 0.08 to 0.10, and the homology factor (σ) is preferably from 0.5 to 1.0.

根據實施形態4之相位偏移光罩之製造方法，使用實施形態3中所說明之相位偏移光罩基底10、或藉由實施形態3中所說明之相位偏移光罩基底之製造方法而獲得之相位偏移光罩基底10來製造相位偏移光罩31。因此，可製造具有可充分發揮相位偏移效果之相位偏移膜圖案3'之相位偏移光罩31。由於相位偏移膜圖案3'可充分發揮相位偏移效果，故而可製造使解像度提高、具有具備良好之CD特性之相位偏移膜圖案3'的相位偏移光罩31。該相位偏移光罩31可應對線與間隙圖案或接觸孔之微細化。 According to the method of manufacturing a phase shift mask according to the fourth embodiment, the phase shift mask substrate 10 described in the third embodiment or the method of manufacturing the phase shift mask substrate described in the third embodiment is used. The phase shift mask substrate 10 is obtained to produce a phase shift mask 31. Therefore, the phase shift mask 31 having the phase shift film pattern 3 ' which can sufficiently exert the phase shift effect can be manufactured. Since the phase shift film pattern 3 ' can sufficiently exhibit the phase shift effect, the phase shift mask 31 having the phase shift film pattern 3 ' having excellent CD characteristics can be manufactured with improved resolution. The phase shift mask 31 can cope with the miniaturization of the line and gap patterns or contact holes.

再者，實施形態4中，作為相位偏移光罩31之製造用原版，已使用具有透明基板/遮光膜圖案/相位偏移膜之構成之相位偏移光罩基底10進行了說明，但並不限定於此。例如，亦可將具有透明基板/遮光 膜圖案/相位偏移膜/光阻劑膜之構成(參照圖7(b))之相位偏移光罩基底作為相位偏移光罩31之製造用原版。 Further, in the fourth embodiment, the original substrate for manufacturing the phase shift mask 31 has been described using the phase shift mask substrate 10 having a transparent substrate/light shielding film pattern/phase shift film structure, but It is not limited to this. For example, it is also possible to have a transparent substrate/shading The phase shift mask substrate of the film pattern/phase shift film/resist film structure (see FIG. 7(b)) is used as a master for manufacturing the phase shift mask 31.

又，實施形態4中，與實施形態2相同，亦可於上述光阻劑膜圖案形成步驟前，對相位偏移光罩基底10之相位偏移膜3，根據需要進行膜洗淨。膜洗淨可使用公知之洗淨方法。但，較佳為使用利用包含硫磺(S)成分之洗淨液(例如，硫酸過氧化氫混合物)之洗淨方法以外之洗淨方法。 Further, in the fourth embodiment, as in the second embodiment, the phase shift film 3 of the phase shift mask substrate 10 may be subjected to film cleaning as needed before the photoresist film pattern forming step. A well-known washing method can be used for film washing. However, it is preferred to use a washing method other than the washing method using a cleaning liquid containing a sulfur (S) component (for example, a sulfuric acid hydrogen peroxide mixture).

【實施例】 [Examples]

以下，基於實施例對本發明更具體地進行說明。 Hereinafter, the present invention will be more specifically described based on examples.

實施例1及比較例1. Example 1 and Comparative Example 1.

實施例1及比較例1中，對具有相位偏移膜(材料：CrCON)之相位偏移光罩基底及使用該相位偏移光罩基底製造之相位偏移光罩進行說明。 In the first embodiment and the comparative example 1, a phase shift mask substrate having a phase shift film (material: CrCON) and a phase shift mask manufactured using the phase shift mask substrate will be described.

再者，實施例1之相位偏移光罩基底1係對其相位偏移膜3之最表面3a進行VUV照射步驟而製造，相對於此，比較例1之相位偏移光罩基底係不對其相位偏移膜之最表面進行VUV照射步驟而製造，於該方面兩者不同。 Further, the phase shift mask substrate 1 of the first embodiment is manufactured by subjecting the outermost surface 3a of the phase shift film 3 to a VUV irradiation step. On the other hand, the phase shift mask base of the comparative example 1 is not The outermost surface of the phase shifting film is produced by a VUV irradiation step, which is different in this respect.

A.相位偏移光罩基底及其製造方法 A. Phase shift mask substrate and method of manufacturing the same

為了製造上述構成之實施例1及比較例1之相位偏移光罩基底1，首先，準備3345尺寸(330mm×450mm×5mm)之合成石英玻璃基板，作為透明基板2。 In order to manufacture the phase shift mask base 1 of the first embodiment and the comparative example 1 described above, first, a synthetic quartz glass substrate of 3345 size (330 mm × 450 mm × 5 mm) was prepared as the transparent substrate 2.

其後，將透明基板2搬入至圖3所示之配置有由鉻而構成之濺鍍靶之連續式濺鍍裝置11，如圖1及圖2(a)所示，於透明基板2之主表面上成膜由鉻氧化碳化氮化物(CrOCN)而構成之相位偏移膜3(膜厚125nm)。 Thereafter, the transparent substrate 2 is carried into the continuous sputtering apparatus 11 having the sputtering target formed of chromium as shown in FIG. 3, as shown in FIG. 1 and FIG. 2(a), and is mainly the main body of the transparent substrate 2. A phase shift film 3 (film thickness: 125 nm) composed of chromium oxide carbide nitride (CrOCN) was formed on the surface.

再者，相位偏移膜3係自配置於由鉻而構成之第1濺鍍靶13之下 游側之第2氣體導入口GA12，導入包含氬(Ar)氣體、二氧化碳(CO2)氣體及氮(N2)氣體之混合氣體(Ar：46sccm，N2：46sccm，CO2：35sccm)，濺鍍功率為3.55kw，將透明基板2之搬送速度設為200mm/分鐘，藉由反應性濺鍍而於透明基板2上成膜。利用1次成膜，形成相位偏移膜3(膜厚125nm)。 In addition, the phase shift film 3 is introduced from the second gas introduction port GA12 on the downstream side of the first sputtering target 13 made of chromium, and is introduced with argon (Ar) gas, carbon dioxide (CO 2 ) gas, and nitrogen. a mixed gas of (N 2 ) gas (Ar: 46 sccm, N 2 : 46 sccm, CO 2 : 35 sccm), a sputtering power of 3.55 kw, and a transport speed of the transparent substrate 2 of 200 mm/min, by reactive sputtering On the transparent substrate 2, a film is formed. The phase shift film 3 (film thickness: 125 nm) was formed by one film formation.

其後，對相位偏移膜3之最表面3a進行VUV照射處理。 Thereafter, the VUV irradiation treatment is performed on the outermost surface 3a of the phase shift film 3.

VUV照射處理係使用以40mW/cm2之能量照射VUV(氙準分子光，波長172nm)之照射裝置(未圖示)，對相位偏移膜3之最表面3a進行相當於照射能量45J/cm2之照射。 In the VUV irradiation treatment, an irradiation device (not shown) that irradiates VUV (氙 分子 excimer light, wavelength 172 nm) with an energy of 40 mW/cm 2 is used, and the surface of the phase shift film 3 is irradiated with an energy equivalent of 45 J/cm. 2 irradiation.

如此一來，如圖2(b)所示，獲得於透明基板2上形成有經過VUV照射步驟之相位偏移膜3的實施例1之相位偏移光罩基底1。 As a result, as shown in FIG. 2(b), the phase shift mask substrate 1 of the first embodiment in which the phase shift film 3 subjected to the VUV irradiation step is formed on the transparent substrate 2 is obtained.

另一方面，獲得於透明基板2上形成有未經過VUV照射步驟之相位偏移膜3的比較例1之相位偏移光罩基底。 On the other hand, a phase shift mask substrate of Comparative Example 1 in which the phase shift film 3 which has not undergone the VUV irradiation step is formed on the transparent substrate 2 is obtained.

對實施例1及比較例1之相位偏移光罩基底1之相位偏移膜3，藉由X射線反射率分析法(XRR)而測定最表面3a之膜密度。 With respect to the phase shift film 3 of the phase shift mask substrate 1 of Example 1 and Comparative Example 1, the film density of the outermost surface 3a was measured by X-ray reflectance analysis (XRR).

再者，最表面3a之膜密度係測定自表層深度方向2.2nm中之相位偏移膜3之膜密度。其結果，實施例1之相位偏移膜3之最表面3a之膜密度為2.33g/cm3，比較例1之相位偏移膜3之最表面3a之膜密度為1.92g/cm3。再者，表示計算膜密度時之擬合之妥當性之數值指標Fit R於實施例1中為0.013，於比較例1中為0.012。 Further, the film density of the outermost surface 3a was measured from the film density of the phase shift film 3 in the depth direction of 2.2 nm from the surface layer. As a result, the film density of the outermost surface 3a of the phase shift film 3 of Example 1 was 2.33 g/cm 3 , and the film density of the outermost surface 3a of the phase shift film 3 of Comparative Example 1 was 1.92 g/cm 3 . Further, the numerical index Fit R indicating the appropriateness of fitting when calculating the film density was 0.013 in Example 1, and 0.012 in Comparative Example 1.

對實施例1之相位偏移光罩基底1之相位偏移膜3及比較例1之相位偏移光罩基底之相位偏移膜，藉由X射線光電子分光法(XPS)進行深度方向之組成分析。 The phase shift film 3 of the phase shift mask substrate 1 of Example 1 and the phase shift film of the phase shift mask base of Comparative Example 1 were subjected to depth direction composition by X-ray photoelectron spectroscopy (XPS). analysis.

圖8表示對比較例1之相位偏移光罩基底之藉由XPS而進行之深度方向之組成分析結果，圖9表示對實施例1之相位偏移光罩基底1之藉由XPS而進行之深度方向之組成分析結果。圖8及圖9之橫軸表示距相 位偏移膜3之最表面3a之深度(nm)，縱軸表示原子組成百分比(原子%)。 8 shows the results of composition analysis of the phase shift mask substrate of Comparative Example 1 by XPS, and FIG. 9 shows the phase shift mask substrate 1 of Example 1 by XPS. Analysis of the composition of the depth direction. The horizontal axis of Figures 8 and 9 represents the phase The depth (nm) of the outermost surface 3a of the offset film 3, and the vertical axis represents the atomic composition percentage (atomic %).

若參照圖8，則比較例1中之相位偏移膜之主體部為各元素之含量幾乎不變化之深度約10.0nm~約115nm的區域。組成梯度區域係各元素之含量大幅變化、自最表面(約0.1nm)至主體部之最淺端(約10.0nm)為止的區域。矽(Si)出現之深部為合成石英玻璃基板(透明基板2)，故而矽(Si)開始出現之深度約127nm附近為相位偏移膜3與透明基板2之界面。透明基板附近區域係自該界面向最表面側之約10nm之區域。 Referring to Fig. 8, the main portion of the phase shift film in Comparative Example 1 is a region having a depth of about 10.0 nm to about 115 nm in which the content of each element hardly changes. The composition of the gradient region is a region in which the content of each element largely changes from the outermost surface (about 0.1 nm) to the shallowest end (about 10.0 nm) of the main body portion. The deep portion of the bismuth (Si) is a synthetic quartz glass substrate (transparent substrate 2). Therefore, the depth at which 矽(Si) starts to appear is about 127 nm, which is the interface between the phase shift film 3 and the transparent substrate 2. The region in the vicinity of the transparent substrate is a region of about 10 nm from the interface toward the outermost surface.

若參照圖9，則實施例1中之相位偏移膜3之主體部B係各元素之含量幾乎不變化之深度約10.0nm~約115nm的區域。組成梯度區域R1係各元素之含量大幅變化、自最表面3a(約0.1nm)至主體部B之最淺端(約10.0nm)為止的區域。矽(Si)出現之深部為合成石英玻璃基板(透明基板2)，故而矽(Si)開始出現之深度約125nm附近為相位偏移膜3與透明基板2之界面。透明基板附近區域R2係自該界面向最表面側之約10nm之區域。 Referring to Fig. 9, the main body portion B of the phase shift film 3 in the first embodiment has a region where the content of each element hardly changes from about 10.0 nm to about 115 nm. The content of each element constituting the gradient region R1 largely changes from the most surface 3a (about 0.1 nm) to the shallowest end (about 10.0 nm) of the main body portion B. The deep portion of bismuth (Si) appears as a synthetic quartz glass substrate (transparent substrate 2). Therefore, the depth at which 矽(Si) begins to appear is about 125 nm, which is the interface between the phase shift film 3 and the transparent substrate 2. The region R2 in the vicinity of the transparent substrate is a region of about 10 nm from the interface toward the outermost surface side.

於比較例1及實施例1之任一者中，主體部中，鉻(Cr)、氧(O)、氮(N)及碳(C)之各元素之含量之變動幅度均較小，大致均一。於比較例1及實施例1之任一者中，組成梯度區域及透明基板附近區域中，鉻(Cr)、氧(O)、氮(N)及碳(C)之各元素之含量均大幅變化。 In any of Comparative Example 1 and Example 1, the content of each element of chromium (Cr), oxygen (O), nitrogen (N), and carbon (C) in the main body portion is small, and is substantially small. Uniform. In any of Comparative Example 1 and Example 1, the content of each element of chromium (Cr), oxygen (O), nitrogen (N), and carbon (C) was significantly increased in the composition gradient region and the vicinity of the transparent substrate. Variety.

關於根據圖8及圖9之數值資料計算出之、自最表面3a朝向膜深度方向減少之氧相對於鉻之比例(O/Cr)與自最表面3a朝向膜深度方向減少之氮相對於鉻之比例(N/Cr)，將實施例1與比較例1進行比較。 The ratio of oxygen to chromium (O/Cr) which decreases from the outermost surface 3a toward the film depth direction and the decrease of nitrogen from the outermost surface 3a toward the film depth with respect to chromium calculated from the numerical data of Figs. 8 and 9 In the ratio (N/Cr), Example 1 was compared with Comparative Example 1.

圖10表示藉由XPS而進行之深度方向之O/Cr之分析結果，圖11表示藉由XPS而進行之深度方向之N/Cr之分析結果。圖10及圖11之橫軸表示距相位偏移膜3之最表面3a之深度(nm)，圖10之縱軸表示O/Cr， 圖11之縱軸表示N/Cr。 Fig. 10 shows the results of analysis of O/Cr in the depth direction by XPS, and Fig. 11 shows the results of analysis of N/Cr in the depth direction by XPS. 10 and 11, the horizontal axis represents the depth (nm) from the outermost surface 3a of the phase shift film 3, and the vertical axis of Fig. 10 represents O/Cr. The vertical axis of Fig. 11 indicates N/Cr.

首先，根據圖10明白，關於組成梯度區域中之膜深度方向之O/Cr之變化，將實施例1與比較例1進行比較。實施例1之O/Cr於最表面3a表示最大值(2.20)，自最表面3a朝向膜深度方向減少，直至約3nm之膜深度為止急遽地減少。相對於此，比較例1之O/Cr於最表面表示最大值(1.96)，自最表面朝向膜深度方向減少，直至約3nm之膜深度為止減少。即，自比較例1之O/Cr之最大值(1.96)向實施例1之O/Cr之最大值(2.20)變大。又，實施例1之O/Cr之減少率較比較例1之O/Cr之減少率更大。根據該結果可知，實施例1與比較例1之差異係因為VUV照射處理之有無，藉由VUV照射處理，而使O/Cr之最大值變大，O/Cr之減少率亦變大。而且，根據圖10，可謂之實施例1之O/Cr之最大值為2以上。 First, it is understood from Fig. 10 that Example 1 is compared with Comparative Example 1 with respect to the change in O/Cr in the film depth direction in the composition gradient region. The O/Cr of Example 1 indicates the maximum value (2.20) on the outermost surface 3a, and decreases from the outermost surface 3a toward the film depth direction, and is drastically reduced until the film depth of about 3 nm. On the other hand, O/Cr of Comparative Example 1 showed a maximum value (1.96) on the outermost surface, and decreased from the outermost surface toward the film depth direction, and decreased to a film depth of about 3 nm. That is, the maximum value (1.96) of O/Cr from Comparative Example 1 was increased to the maximum value (2.20) of O/Cr of Example 1. Further, the reduction ratio of O/Cr of Example 1 was larger than that of Comparative Example 1. According to the results, it is understood that the difference between the first embodiment and the comparative example 1 is due to the presence or absence of the VUV irradiation treatment, and the maximum value of O/Cr is increased by the VUV irradiation treatment, and the rate of decrease in O/Cr is also increased. Further, according to Fig. 10, it can be said that the maximum value of O/Cr in the first embodiment is 2 or more.

其次，根據圖11明白，關於組成梯度區域中之膜深度方向之N/Cr之變化，將實施例1與比較例1進行比較。比較例1之N/Cr於最表面表示最大值(0.49)，自最表面朝向膜深度方向減少，直至約3nm之膜深度為止急遽地減少。相對於此，實施例1之N/Cr於最表面3a表示最大值(0.34)，自最表面3a朝向膜深度方向減少，直至約3nm之膜深度為止減少。即，自實施例1之N/Cr之最大值(0.34)向比較例1之N/Cr之最大值(0.49)變小。又，實施例1之N/Cr之減少率較比較例1之N/Cr之減少率更小。根據該結果可知，實施例1與比較例1之差異係因為VUV照射處理之有無，藉由VUV照射處理，而使N/Cr之最大值變小，N/Cr之減少率亦變小。而且，根據圖11，可謂之實施例1之N/Cr之最大值為0.45以下。 Next, it is understood from Fig. 11 that Example 1 is compared with Comparative Example 1 with respect to the change in N/Cr in the film depth direction in the composition gradient region. The N/Cr of Comparative Example 1 showed a maximum value (0.49) on the outermost surface, and decreased from the outermost surface toward the film depth direction, and drastically decreased until a film depth of about 3 nm. On the other hand, N/Cr of Example 1 showed the maximum value (0.34) on the outermost surface 3a, and decreased from the outermost surface 3a toward the film depth direction, and decreased to a film depth of about 3 nm. That is, the maximum value (0.34) of N/Cr from Example 1 was decreased to the maximum value (0.49) of N/Cr of Comparative Example 1. Further, the reduction ratio of N/Cr of Example 1 was smaller than that of Comparative Example 1. From the results, it is understood that the difference between the first embodiment and the comparative example 1 is due to the presence or absence of the VUV irradiation treatment, and the maximum value of N/Cr is reduced by the VUV irradiation treatment, and the reduction ratio of N/Cr is also small. Further, according to Fig. 11, it can be said that the maximum value of N/Cr of the first embodiment is 0.45 or less.

再者，關於實施例1及比較例1之各相位偏移光罩基底1之相位偏移膜3，藉由日立高新技術公司製造之分光光度計U-4100而測定透過率，藉由Lasertec公司製造之MPM-100而測定相位差。再者，實施例1 及比較例1中之透過率之值均為Air基準之值。 Further, with respect to the phase shift film 3 of each phase shift mask substrate 1 of Example 1 and Comparative Example 1, the transmittance was measured by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Co., Ltd., by Lasertec Co., Ltd. The phase difference was measured by manufacturing MPM-100. Furthermore, embodiment 1 The values of the transmittances in Comparative Example 1 are all values based on the Air standard.

相位偏移膜3之透過率及相位差之測定係使用帶相位偏移膜之基板(虛設基板)，該帶相位偏移膜之基板(虛設基板)係於設置於相同之基板固持器(未圖示)之6025尺寸(152mm×152mm)之透明基板2之主表面上、成膜有相位偏移膜3(膜厚125nm)。 The transmittance and phase difference of the phase shift film 3 are measured by using a substrate with a phase shift film (dummy substrate), and the substrate with a phase shift film (dummy substrate) is provided on the same substrate holder (not On the main surface of the 6025-size (152 mm × 152 mm) transparent substrate 2, a phase shift film 3 (film thickness: 125 nm) was formed.

其結果，波長200nm~800nm之實施例1之透過率光譜係與未進行VUV照射處理之比較例1之透過率光譜大致相同。根據該結果可知，即便進行VUV照射處理，亦不會對進行VUV照射處理之前之透過率光譜賦予變化，可維持所期望之透過率光譜。 As a result, the transmittance spectrum of Example 1 having a wavelength of 200 nm to 800 nm was substantially the same as the transmittance spectrum of Comparative Example 1 which was not subjected to VUV irradiation treatment. From this result, it is understood that even if the VUV irradiation treatment is performed, the transmittance spectrum before the VUV irradiation treatment is not changed, and the desired transmittance spectrum can be maintained.

波長365nm下之實施例1及比較例1之相位差為184.6度。根據該結果可知，即便進行VUV照射處理，亦不會對進行VUV照射處理之前之相位差賦予變化，可維持所期望之相位差。 The phase difference between Example 1 and Comparative Example 1 at a wavelength of 365 nm was 184.6 degrees. From this result, it is understood that even if the VUV irradiation treatment is performed, the phase difference before the VUV irradiation treatment is not changed, and the desired phase difference can be maintained.

又，關於實施例1及比較例1之相位偏移光罩基底1之相位偏移膜3，藉由日立高新技術公司製造之分光光度計U-4100而測定反射率。 Further, with respect to the phase shift film 3 of the phase shift mask base 1 of Example 1 and Comparative Example 1, the reflectance was measured by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation.

其結果，波長200nm~800nm下之實施例1之反射率光譜係與未進行VUV照射處理之比較例1之反射率光譜大致相同。根據該結果可知，即便進行VUV照射處理，亦不會對進行VUV照射處理之前之反射率光譜賦予變化，可維持所期望之反射率光譜。 As a result, the reflectance spectrum of Example 1 at a wavelength of 200 nm to 800 nm was substantially the same as the reflectance spectrum of Comparative Example 1 which was not subjected to VUV irradiation treatment. From this result, it is understood that even if the VUV irradiation treatment is performed, the reflectance spectrum before the VUV irradiation treatment is not changed, and the desired reflectance spectrum can be maintained.

B.相位偏移光罩及其製造方法 B. Phase shift mask and manufacturing method thereof

為了使用以上述方式製造之實施例1及比較例1之相位偏移光罩基底而製造實施例1及比較例1之相位偏移光罩，首先，於實施例1及比較例1之相位偏移光罩基底之相位偏移膜3上，使用光阻劑塗佈裝置塗佈光阻劑膜5。 In order to manufacture the phase shift masks of the first embodiment and the comparative example 1 using the phase shift mask substrates of the first embodiment and the comparative example 1 manufactured as described above, first, the phase shifts of the first embodiment and the comparative example 1 were made. On the phase shift film 3 of the transfer cover substrate, the photoresist film 5 is coated using a photoresist coating device.

其後，經過加熱、冷卻步驟，形成膜厚1000nm之光阻劑膜5。 Thereafter, a photoresist film 5 having a film thickness of 1000 nm is formed by a heating and cooling step.

其後，使用雷射描畫裝置描畫光阻劑膜5，經過顯影、沖洗步驟，於相位偏移膜3上，形成線圖案之寬度為2.0μm及間隙圖案之寬 度為2.0μm之線與間隙圖案之光阻劑膜圖案5'。 Thereafter, the photoresist film 5 is drawn using a laser drawing device, and a line and gap pattern having a line pattern width of 2.0 μm and a gap pattern width of 2.0 μm is formed on the phase shift film 3 through development and rinsing steps. Photoresist film pattern 5 ' .

其後，將光阻劑膜圖案5'作為光罩，藉由包含硝酸鈰銨與過氯酸之鉻蝕刻液而對相位偏移膜3進行濕式蝕刻，形成相位偏移膜圖案3'。 Thereafter, the photoresist film pattern 5 ' is used as a photomask, and the phase shift film 3 is wet-etched by a chromium etching solution containing cerium ammonium nitrate and perchloric acid to form a phase shift film pattern 3 ' .

其後，將光阻劑膜圖案5'剝離。 Thereafter, the photoresist film pattern 5 ' is peeled off.

如此一來，獲得於透明基板2上形成有使經過VUV照射步驟之相位偏移膜3圖案化之相位偏移膜圖案3'的實施例1之相位偏移光罩30(透明基板/相位偏移膜圖案)。 In this manner, the phase shift mask 30 of the first embodiment in which the phase shift film pattern 3 ' patterned by the phase shift film 3 of the VUV irradiation step is formed on the transparent substrate 2 is obtained (transparent substrate/phase shift) Transfer film pattern).

另一方面，獲得於透明基板2上形成有使未經過VUV照射步驟之相位偏移膜3圖案化之相位偏移膜圖案3'的比較例1之相位偏移光罩(透明基板/相位偏移膜圖案)。 On the other hand, a phase shift mask (transparent substrate/phase shift ) of Comparative Example 1 in which a phase shift film pattern 3 ' which is patterned without the phase shift film 3 of the VUV irradiation step is formed on the transparent substrate 2 is obtained. Transfer film pattern).

於光阻劑膜圖案5'之剝離前，利用掃描式電子顯微鏡觀察實施例1之相位偏移光罩30及比較例1之相位偏移光罩之各相位偏移膜圖案3'之邊緣部分之被蝕刻剖面。 Before the peeling of the photoresist film pattern 5 ' , the phase shift mask of Example 1 and the edge portion of each phase shift film pattern 3 ' of the phase shift mask of Comparative Example 1 were observed by a scanning electron microscope. The section being etched.

圖12係實施例1之相位偏移光罩之相位偏移膜圖案3'之邊緣部分之剖面照片，圖13係比較例1之相位偏移光罩之相位偏移膜圖案3'之邊緣部分之剖面照片，圖14係用以說明成為邊緣部分之剖面形狀之判斷指標之剖面角度(θ)之剖視圖。 12 FIG. 3 based phase shift film pattern phase shift mask of Example 1 of the embodiment 'of the edge portion of cross-sectional photograph, Comparative Example 13-based phase shift of a phase shift photomask film pattern 3' of the edge portion FIG. 14 is a cross-sectional view for explaining a cross-sectional angle (θ) of a judgment index of a cross-sectional shape of an edge portion.

於圖14中，將相位偏移膜3之膜厚設為T，將自最表面3a畫至T/10之深度之輔助線設為L1，將自透明基板2之主表面側畫至T/10之高度之輔助線設為L2，將相位偏移膜3之被蝕刻剖面F與輔助線L1之交點設為C1，將被蝕刻剖面F與輔助線L2之交點設為C2。此處，剖面角度(θ)為將交點C1與交點C2連接之連接線與透明基板2之主表面所成之角度。 In FIG. 14, the film thickness of the phase shift film 3 is set to T, the auxiliary line drawn from the outermost surface 3a to the depth of T/10 is set to L1, and the main surface side of the transparent substrate 2 is drawn to T/. The auxiliary line of the height of 10 is set to L2, the intersection of the etched section F of the phase shift film 3 and the auxiliary line L1 is C1, and the intersection of the etched section F and the auxiliary line L2 is C2. Here, the cross-sectional angle (θ) is an angle formed by the connection line connecting the intersection point C1 and the intersection point C2 with the main surface of the transparent substrate 2.

又，光阻劑界面角度為光阻劑附近之被蝕刻剖面F與最表面3a所成之角度，透明基板界面角度為透明基板附近之被蝕刻剖面F與透明 基板之主表面所成之角度。 Moreover, the interface angle of the photoresist is an angle formed by the etched profile F near the photoresist and the outermost surface 3a, and the interface angle of the transparent substrate is the etched profile F and transparent near the transparent substrate. The angle formed by the major surface of the substrate.

進而，錐形下表面長度為將光阻劑附近之被蝕刻剖面F與最表面3a之交叉部之一點直接於垂直方向投影至透明基板之主表面上的地點、與透明基板附近之被蝕刻剖面F之裙擺部分之前端部之一點的長度。 Further, the tapered lower surface length is a point at which a point of intersection between the etched section F and the outermost surface 3a in the vicinity of the photoresist is directly projected in a vertical direction onto the main surface of the transparent substrate, and an etched section near the transparent substrate The length of a point at the front end of the skirt portion of F.

圖12所示之實施例1之邊緣部分之被蝕刻剖面之光阻劑界面角度為90度，透明基板界面角度為90度，錐形下表面長度為0nm，剖面角度(θ)為90度。 The edge portion of the etched section of the embodiment 1 shown in Fig. 12 has a photoresist interface angle of 90 degrees, a transparent substrate interface angle of 90 degrees, a tapered lower surface length of 0 nm, and a section angle (θ) of 90 degrees.

另一方面，圖13所示之比較例1之邊緣部分之被蝕刻剖面之光阻劑界面角度為140度，透明基板界面角度為38度，錐形下表面長度為150nm，剖面角度(θ)為38度。又，未進行VUV照射步驟之比較例1之被蝕刻剖面成為拖尾之錐形形狀。 On the other hand, the photoresist portion of the edge portion of Comparative Example 1 shown in Fig. 13 has an interface angle of 140 degrees, a transparent substrate interface angle of 38 degrees, a tapered lower surface length of 150 nm, and a section angle (θ). It is 38 degrees. Further, the etched cross section of Comparative Example 1 in which the VUV irradiation step was not performed was a tapered shape.

根據該等結果可知，實施例1中之被蝕刻剖面具有較比較例1中之被蝕刻剖面特別大之剖面角度(θ)，更接近垂直剖面形狀。即，藉由VUV照射處理，而使邊緣部分之被蝕刻剖面之剖面角度(θ)變大。 From these results, it is understood that the etched cross section in Example 1 has a cross-sectional angle (θ) which is particularly larger than the etched cross section in Comparative Example 1, and is closer to the vertical cross-sectional shape. That is, the cross-sectional angle (θ) of the etched section of the edge portion is increased by the VUV irradiation treatment.

其次，藉由精工電子奈米科技公司製造之SIR8000而測定實施例1之相位偏移光罩之相位偏移膜圖案之CD不均。CD不均之測定係對基板之周緣區域除外之270mm×390mm之區域，測定5×5個地點。CD不均為自作為目標之線與間隙圖案(線圖案之寬度：2.0μm，間隙圖案之寬度：2.0μm)偏移之寬度。於以下之實施例及比較例中，CD不均之測定使用相同裝置。 Next, the CD unevenness of the phase shift film pattern of the phase shift mask of Example 1 was measured by SIR8000 manufactured by Seiko Instruments Inc. The measurement of CD unevenness was performed on 5 × 5 sites in a region of 270 mm × 390 mm excluding the peripheral region of the substrate. The CD is not the width of the offset from the target line and the gap pattern (the width of the line pattern: 2.0 μm, the width of the gap pattern: 2.0 μm). In the following examples and comparative examples, the same apparatus was used for the measurement of CD unevenness.

CD不均為0.05μm，非常良好。 The CDs were not all 0.05 μm and were very good.

可知，比較例1之相位偏移光罩之相位偏移膜圖案之CD不均為0.20μm，較實施例1更大。 It can be seen that the CD of the phase shift film pattern of the phase shift mask of Comparative Example 1 is not 0.20 μm, which is larger than that of the first embodiment.

實施例2及比較例2. Example 2 and Comparative Example 2.

實施例2及比較例2中，對具有以與實施例1及比較例1不同之成 膜條件成膜之相位偏移膜(材料：CrCON)之相位偏移光罩基底、及使用該相位偏移光罩基底製造之相位偏移光罩進行說明。 In Example 2 and Comparative Example 2, the composition was different from Example 1 and Comparative Example 1. A phase shift mask substrate of a phase shift film (material: CrCON) formed by film conditions, and a phase shift mask manufactured using the phase shift mask substrate will be described.

再者，實施例2之相位偏移光罩基底1係對其相位偏移膜3之最表面3a進行VUV照射步驟而製造，相對於此，比較例2之相位偏移光罩基底係不對其相位偏移膜之最表面進行VUV照射步驟而製造，於該方面兩者不同。 Further, the phase shift mask substrate 1 of the second embodiment is manufactured by performing a VUV irradiation step on the outermost surface 3a of the phase shift film 3, whereas the phase shift mask base of the comparative example 2 is not The outermost surface of the phase shifting film is produced by a VUV irradiation step, which is different in this respect.

A.相位偏移光罩基底及其製造方法 A. Phase shift mask substrate and method of manufacturing the same

作為透明基板2準備與實施例1及比較例1相同尺寸之合成石英玻璃基板，。 A synthetic quartz glass substrate having the same dimensions as those of Example 1 and Comparative Example 1 was prepared as the transparent substrate 2.

實施例2及比較例2中，於相位偏移膜形成步驟中，自圖3所示之濺鍍裝置11之、配置於由鉻而構成之第1濺鍍靶13之上游側之第1氣體導入口GA11，導入與實施例1及比較例1相同成分之混合氣體，且將濺鍍功率設為3.40kw。除此以外之成膜條件與實施例1及比較例1相同，利用1次成膜，形成相位偏移膜3(膜厚125nm)。 In the second embodiment and the second comparative example, in the phase shift film forming step, the first gas disposed on the upstream side of the first sputtering target 13 made of chromium is applied from the sputtering apparatus 11 shown in FIG. At the inlet GA11, a mixed gas of the same composition as in Example 1 and Comparative Example 1 was introduced, and the sputtering power was set to 3.40 kW. The film formation conditions other than the above were the same as those of Example 1 and Comparative Example 1, and the phase shift film 3 (film thickness: 125 nm) was formed by one film formation.

其後，與實施例1相同，對相位偏移膜3之最表面3a進行VUV照射步驟而獲得實施例2之相位偏移光罩基底1。 Thereafter, in the same manner as in the first embodiment, the VUV irradiation step was performed on the outermost surface 3a of the phase shift film 3 to obtain the phase shift mask substrate 1 of the second embodiment.

另一方面，獲得於透明基板2上形成有未經過VUV照射步驟之相位偏移膜3之比較例2之相位偏移光罩基底。 On the other hand, a phase shift mask substrate of Comparative Example 2 in which the phase shift film 3 which has not undergone the VUV irradiation step is formed on the transparent substrate 2 is obtained.

關於實施例2之相位偏移光罩基底1之相位偏移膜3及比較例2之相位偏移光罩基底之相位偏移膜，藉由XPS而進行深度方向之組成分析。 The phase shift film 3 of the phase shift mask substrate 1 of Example 2 and the phase shift film of the phase shift mask base of Comparative Example 2 were subjected to composition analysis in the depth direction by XPS.

其結果，實施例2之組成梯度區域R1中之O/Cr中，於最表面3a表示2以上之最大值(2.19)，自最表面3a朝向膜深度方向減少。相對於此，比較例2之組成梯度區域中之O/Cr中，於最表面表示未達2之最大值(1.95)，自最表面朝向膜深度方向減少。又，比較例2之組成梯度區域中之N/Cr中，於最表面表示超過0.45之最大值(0.49)，自最表面朝 向膜深度方向減少。相對於此，實施例2之組成梯度區域R1中之N/Cr中，於最表面3a表示0.45以下之最大值(0.32)，自最表面3a朝向膜深度方向減少。 As a result, in the O/Cr in the composition gradient region R1 of the second embodiment, the maximum value (2.19) of 2 or more is indicated on the outermost surface 3a, and decreases from the outermost surface 3a toward the film depth direction. On the other hand, in the composition gradient region of Comparative Example 2, the maximum value of the O/Cr in the composition gradient region was less than 2 (1.95), and decreased from the outermost surface toward the film depth direction. Further, in the composition gradient region of Comparative Example 2, in the N/Cr, the maximum surface indicates a maximum value (0.49) exceeding 0.45, from the most surface toward Reduced in the direction of film depth. On the other hand, in the N/Cr in the composition gradient region R1 of the second embodiment, the maximum value (0.32) of 0.45 or less is represented on the outermost surface 3a, and decreases from the outermost surface 3a toward the film depth direction.

關於實施例2及比較例2之相位偏移光罩基底之相位偏移膜，與實施例1及比較例1相同，藉由X射線反射率分析法(XRR)而測定最表面3a之膜密度。 The phase shift film of the phase shift mask base of Example 2 and Comparative Example 2 was measured for the film density of the outermost surface 3a by X-ray reflectance analysis (XRR) as in Example 1 and Comparative Example 1. .

其結果，實施例2之相位偏移光罩基底1之相位偏移膜3之最表面3a之膜密度為2.28g/cm3，比較例2之相位偏移光罩基底1之相位偏移膜3之最表面3a之膜密度為1.89g/cm3。 As a result, the film density of the outermost surface 3a of the phase shift film 3 of the phase shift mask substrate 1 of Example 2 was 2.28 g/cm 3 , and the phase shift film of the phase shift mask substrate 1 of Comparative Example 2 was obtained. The film density of the outermost surface 3a of 3 was 1.89 g/cm 3 .

再者，與實施例1與比較例1之關係相同，實施例2之相位偏移光罩基底1之相位偏移膜3與未進行VUV照射處理之比較例2之相位偏移光罩基底之相位偏移膜相比，透過率、反射率及相位差幾乎不變化。 Further, in the same manner as in the first embodiment and the comparative example 1, the phase shift film 3 of the phase shift mask substrate 1 of the second embodiment and the phase shift mask base of the comparative example 2 which was not subjected to the VUV irradiation treatment were used. The transmittance, reflectance, and phase difference hardly change as compared with the phase shift film.

B.相位偏移光罩及其製造方法 B. Phase shift mask and manufacturing method thereof

使用以上述方式製造之實施例2及比較例2之相位偏移光罩基底，與實施例1相同地製造實施例2及比較例2之相位偏移光罩。 The phase shift masks of Example 2 and Comparative Example 2 were produced in the same manner as in Example 1 using the phase shift mask substrates of Example 2 and Comparative Example 2 produced as described above.

如此一來，獲得於透明基板2上形成有使經過VUV照射步驟之相位偏移膜3圖案化之相位偏移膜圖案3'的實施例2之相位偏移光罩30(透明基板/相位偏移膜圖案)。 In this manner, the phase shift mask 30 of the second embodiment in which the phase shift film pattern 3 ' patterned by the phase shift film 3 of the VUV irradiation step is formed on the transparent substrate 2 is obtained (transparent substrate/phase shift) Transfer film pattern).

另一方面，獲得於透明基板2上形成有使未經過VUV照射步驟之相位偏移膜3圖案化之相位偏移膜圖案3'的比較例2之相位偏移光罩(透明基板/相位偏移膜圖案)。 On the other hand, a phase shift mask (transparent substrate/phase shift ) of Comparative Example 2 in which the phase shift film pattern 3 ' which is patterned without the phase shift film 3 of the VUV irradiation step is formed on the transparent substrate 2 is obtained. Transfer film pattern).

於光阻劑膜圖案5'之剝離前，利用掃描式電子顯微鏡觀察實施例2之相位偏移光罩30及比較例2之相位偏移光罩之各相位偏移膜圖案3'之邊緣部分之被蝕刻剖面。 Before the peeling of the photoresist film pattern 5 ' , the phase shift mask of Example 2 and the edge portion of each phase shift film pattern 3 ' of the phase shift mask of Comparative Example 2 were observed by a scanning electron microscope. The section being etched.

如圖15所示，實施例2之邊緣部分之被蝕刻剖面之光阻劑界面角度為130度，透明基板界面角度為50度，錐形下表面長度為80nm，剖 面角度(θ)為50度。 As shown in FIG. 15, the edge of the etched section of the embodiment 2 has a photoresist interface angle of 130 degrees, the transparent substrate interface angle of 50 degrees, and the tapered lower surface length of 80 nm. The face angle (θ) is 50 degrees.

另一方面，如圖16所示，比較例2之邊緣部分之被蝕刻剖面之光阻劑界面角度為150度，透明基板界面角度為28度，錐形下表面長度為230nm，剖面角度(θ)為30度。即，未進行VUV照射步驟之比較例2之被蝕刻剖面成為較實施例2或上述比較例1更長地拖尾之錐形形狀。 On the other hand, as shown in FIG. 16, the photoresist interface of the edge portion of Comparative Example 2 has an interface angle of 150 degrees, a transparent substrate interface angle of 28 degrees, and a tapered lower surface length of 230 nm, and a profile angle (θ). ) is 30 degrees. That is, the etched cross section of Comparative Example 2 in which the VUV irradiation step was not performed was a tapered shape which was longer than that of Example 2 or Comparative Example 1.

根據該等結果可知，實施例2中之被蝕刻剖面具有較比較例2中之被蝕刻剖面特別大之剖面角度(θ)，更接近垂直剖面形狀。即，藉由VUV照射處理，而使邊緣部分之被蝕刻剖面之剖面角度(θ)變大。又，可知於成膜使CrCON為構成材料之相位偏移膜3之情形時，將其相位偏移膜形成步驟中之混合氣體(濺鍍氣體)自與相位偏移膜之成膜相關之濺鍍靶之下游側供給之情形時(實施例1)的剖面角度(θ)較自其濺鍍靶之上游側供給之情形時(實施例2)的剖面角度(θ)更大。 From these results, it is understood that the etched cross section in the second embodiment has a cross-sectional angle (θ) which is particularly larger than the etched cross-section in Comparative Example 2, and is closer to the vertical cross-sectional shape. That is, the cross-sectional angle (θ) of the etched section of the edge portion is increased by the VUV irradiation treatment. Further, it is understood that when CrCON is used as the phase shift film 3 constituting the material, the phase shifting film (sputtering gas) in the film forming step is splashed from the film formation of the phase shift film. When the downstream side of the plating target is supplied (the first embodiment), the cross-sectional angle (θ) is larger than the cross-sectional angle (θ) of the case where the sputtering target is supplied from the upstream side of the sputtering target (Example 2).

其次，與實施例1相同地測定實施例2之相位偏移光罩30之相位偏移膜圖案之CD不均。 Next, CD unevenness of the phase shift film pattern of the phase shift mask 30 of Example 2 was measured in the same manner as in the first embodiment.

CD不均為0.12μm，良好。 The CD is not all 0.12 μm, which is good.

可知，比較例2之相位偏移光罩之相位偏移膜圖案之CD不均為0.22μm，較實施例2更大。 It can be seen that the CD of the phase shift film pattern of the phase shift mask of Comparative Example 2 is not 0.22 μm, which is larger than that of the second embodiment.

實施例3. Example 3.

實施例3中，對相位偏移膜3之材料為CrON之相位偏移光罩基底及使用該相位偏移光罩基底製造之相位偏移光罩進行說明。 In the third embodiment, a phase shift mask substrate in which the material of the phase shift film 3 is CrON and a phase shift mask manufactured using the phase shift mask substrate will be described.

A.相位偏移光罩基底及其製造方法 A. Phase shift mask substrate and method of manufacturing the same

準備與實施例1相同尺寸之合成石英玻璃基板，作為透明基板2。 A synthetic quartz glass substrate having the same dimensions as in Example 1 was prepared as the transparent substrate 2.

其後，將透明基板2導入至圖3之連續式濺鍍裝置11，於透明基板2之主表面上利用1次成膜形成由鉻氧化氮化物(CrON)而構成之相位偏移膜3(膜厚157nm)，從而獲得相位偏移光罩基底1。 Thereafter, the transparent substrate 2 is introduced into the continuous sputtering apparatus 11 of FIG. 3, and a phase shift film 3 composed of chromium oxide nitride (CrON) is formed on the main surface of the transparent substrate 2 by one film formation ( The film thickness was 157 nm), thereby obtaining the phase shift mask substrate 1.

相位偏移膜3係自由鉻而構成之第1濺鍍靶13之下游側之第2氣體導入口GA12，導入包含氬(Ar)氣體與一氧化氮(NO)氣體之混合氣體(Ar：46sccm，NO：70sccm)，濺鍍功率為8.0kw，將透明基板2之搬送速度設為約400mm/分鐘，藉由反應性濺鍍，而於透明基板2上成膜。 The phase shift film 3 is a second gas introduction port GA12 on the downstream side of the first sputtering target 13 which is formed of chromium, and is introduced with a mixed gas containing argon (Ar) gas and nitrogen monoxide (NO) gas (Ar: 46 sccm). NO: 70 sccm), the sputtering power was 8.0 kw, and the transport speed of the transparent substrate 2 was set to about 400 mm/min, and the film was formed on the transparent substrate 2 by reactive sputtering.

其後，以與實施例1相同之照射條件，對相位偏移膜3之最表面3a進行VUV照射處理。 Thereafter, the VUV irradiation treatment was performed on the outermost surface 3a of the phase shift film 3 under the same irradiation conditions as in the first embodiment.

如此一來，獲得於透明基板2上形成有經過VUV照射步驟之相位偏移膜3之相位偏移光罩基底1。 In this manner, the phase shift mask substrate 1 on which the phase shift film 3 subjected to the VUV irradiation step is formed on the transparent substrate 2 is obtained.

對實施例3之相位偏移光罩基底1之相位偏移膜3，藉由XPS而進行深度方向之組成分析。 The phase shift film 3 of the phase shift mask substrate 1 of Example 3 was subjected to composition analysis in the depth direction by XPS.

其結果，組成梯度區域R1中之O/Cr中，於最表面3a表示2以上之最大值(2.11)，自最表面3a朝向膜深度方向減少。又，組成梯度區域R1中之N/Cr中，於最表面3a表示0.45以下之最大值(0.32)，自最表面3a朝向膜深度方向減少。 As a result, in the O/Cr in the composition gradient region R1, the maximum value (2.11) of 2 or more is represented on the outermost surface 3a, and decreases from the outermost surface 3a toward the film depth direction. Further, among the N/Crs in the composition gradient region R1, the maximum value (0.32) of 0.45 or less is represented on the outermost surface 3a, and decreases from the outermost surface 3a toward the film depth direction.

對實施例3之相位偏移光罩基底1之相位偏移膜3a，與實施例1相同地藉由X射線反射率分析法(XRR)而測定膜密度。 The film density of the phase shift film 3a of the phase shift mask substrate 1 of Example 3 was measured by X-ray reflectance analysis (XRR) in the same manner as in Example 1.

其結果，實施例3之相位偏移光罩基底1之相位偏移膜3之最表面3a之膜密度自VUV照射處理前之1.85g/cm3上升至2.21g/cm3為止。 As a result, the film density of the outermost surface 3a of the phase shift film 3 of the phase shift mask substrate 1 of Example 3 was raised from 1.85 g/cm 3 before the VUV irradiation treatment to 2.21 g/cm 3 .

再者，實施例3之相位偏移光罩基底1之相位偏移膜3與VUV照射處理前相比，透過率、反射率及相位差幾乎不變化。 Further, in the phase shift film 3 of the phase shift mask substrate 1 of the third embodiment, the transmittance, the reflectance, and the phase difference hardly change as compared with before the VUV irradiation treatment.

B.相位偏移光罩及其製造方法 B. Phase shift mask and manufacturing method thereof

藉由與實施例1相同之方法，而獲得於透明基板2上形成有使經過VUV照射處理之相位偏移膜3圖案化之相位偏移膜圖案3'的相位偏移光罩30。 By the same method as in the first embodiment, the phase shift mask 30 in which the phase shift film pattern 3 ' patterned by the VUV irradiation treatment of the phase shift film 3 is formed on the transparent substrate 2 is obtained.

於光阻劑膜圖案5'之剝離前，利用掃描式電子顯微鏡觀察實施例 3之相位偏移光罩30之相位偏移膜圖案3'之邊緣部分之被蝕刻剖面。 Before the peeling of the photoresist film pattern 5 ', the etched cross section of the edge portion of the phase shift film pattern 3 ' of the phase shift mask 30 of Example 3 was observed by a scanning electron microscope.

其結果，實施例3之邊緣部分之被蝕刻剖面之光阻劑界面角度為90度，透明基板界面角度為90度，錐形下表面長度為0nm，剖面角度(θ)為90度。即，將CrON作為構成材料之實施例3之相位偏移膜圖案3'之被蝕刻剖面與將CrCON作為構成材料之實施例1之相位偏移膜圖案3'之被蝕刻剖面相同，完全無裙擺、完全成為垂直剖面形狀。 As a result, the photoresist interface cross-section of the edge portion of Example 3 had an interface angle of 90 degrees, the transparent substrate interface angle was 90 degrees, the tapered lower surface length was 0 nm, and the cross-sectional angle (θ) was 90 degrees. That same cross-section is etched, the CrON material constituting a phase of Example 3 of the shift film pattern 3 'is etched cross section of the embodiment of the CrCON as the phase of the material constituting the pattern of a shift film 3', the skirt completely The pendulum is completely vertical.

其次，與實施例1相同地測定實施例3之相位偏移光罩30之相位偏移膜圖案之CD不均。 Next, CD unevenness of the phase shift film pattern of the phase shift mask 30 of Example 3 was measured in the same manner as in Example 1.

CD不均為0.055μm，良好。 CD is not 0.055 μm, which is good.

實施例4. Example 4.

實施例4中，對具有以與實施例3不同之成膜條件成膜之相位偏移膜(材料：CrON)之相位偏移光罩基底、及使用該相位偏移光罩基底製造之相位偏移光罩進行說明。 In the fourth embodiment, a phase shift mask substrate having a phase shift film (material: CrON) formed by film formation conditions different from that of the third embodiment, and a phase shift manufactured using the phase shift mask substrate The hood is described.

A.相位偏移光罩基底及其製造方法 A. Phase shift mask substrate and method of manufacturing the same

準備與實施例1相同尺寸之合成石英玻璃基板，作為透明基板2。 A synthetic quartz glass substrate having the same dimensions as in Example 1 was prepared as the transparent substrate 2.

實施例4中，於相位偏移膜形成步驟中，自圖3所示之濺鍍裝置11之、配置於由鉻而構成之第1濺鍍靶13之上游側之第1氣體導入口GA11，導入與實施例3相同成分之混合氣體。除此以外之成膜條件與實施例3相同地、利用1次成膜形成相位偏移膜3(膜厚157nm)。 In the fourth embodiment, in the phase shift film forming step, the first gas introduction port GA11 disposed on the upstream side of the first sputtering target 13 made of chromium is placed from the sputtering apparatus 11 shown in FIG. A mixed gas of the same composition as in Example 3 was introduced. The film formation conditions other than the above were the same as in Example 3, and the phase shift film 3 (film thickness: 157 nm) was formed by one film formation.

其後，以與實施例1相同之照射條件對相位偏移膜3之最表面3a進行VUV照射處理。 Thereafter, the VSG irradiation treatment was performed on the outermost surface 3a of the phase shift film 3 under the same irradiation conditions as in the first embodiment.

如此一來，獲得於透明基板2上形成有使經過VUV照射步驟之相位偏移膜3圖案化之相位偏移膜3的相位偏移光罩基底1。 In this manner, the phase shift mask substrate 1 having the phase shift film 3 patterned by the phase shift film 3 subjected to the VUV irradiation step is formed on the transparent substrate 2.

對實施例4之相位偏移光罩基底1之相位偏移膜3，藉由XPS而進行深度方向之組成分析。 The phase shift film 3 of the phase shift mask substrate 1 of Example 4 was subjected to composition analysis in the depth direction by XPS.

其結果，組成梯度區域R1中之O/Cr中，於最表面3a表示2以上之最大值(2.10)，自最表面3a朝向膜深度方向減少。又，組成梯度區域R1中之N/Cr中，於最表面3a表示0.45以下之最大值(0.31)，自最表面3a朝向膜深度方向減少。 As a result, among the O/Crs in the composition gradient region R1, the maximum value (2.10) of 2 or more is represented on the outermost surface 3a, and decreases from the outermost surface 3a toward the film depth direction. Further, among the N/Crs in the composition gradient region R1, the maximum value (0.31) of 0.45 or less is represented on the outermost surface 3a, and decreases from the outermost surface 3a toward the film depth direction.

對實施例4之相位偏移光罩基底1之相位偏移膜3a，與實施例1相同地藉由X射線反射率分析法(XRR)而測定膜密度。 The film density of the phase shift film 3a of the phase shift mask substrate 1 of Example 4 was measured by X-ray reflectance analysis (XRR) in the same manner as in Example 1.

其結果，實施例4之相位偏移光罩基底1之相位偏移膜3之最表面3a之膜密度自VUV照射處理前之1.84g/cm3上升至2.19g/cm3為止。 As a result, the film density of the outermost surface 3a of the phase shift film 3 of the phase shift mask substrate 1 of Example 4 increased from 1.84 g/cm 3 before the VUV irradiation treatment to 2.19 g/cm 3 .

再者，實施例4之相位偏移光罩基底1之相位偏移膜3與VUV照射處理前相比，透過率、反射率及相位差幾乎不變化。 Further, in the phase shifting film 3 of the phase shift mask substrate 1 of the fourth embodiment, the transmittance, the reflectance, and the phase difference hardly change as compared with that before the VUV irradiation treatment.

B.相位偏移光罩及其製造方法 B. Phase shift mask and manufacturing method thereof

藉由與實施例1相同之方法，獲得於透明基板2上形成有相位偏移膜圖案3'的相位偏移光罩30。 A phase shift mask 30 having a phase shift film pattern 3 ' formed on the transparent substrate 2 was obtained by the same method as in the first embodiment.

於光阻劑膜圖案5'之剝離前，利用掃描式電子顯微鏡觀察實施例4之相位偏移光罩30之相位偏移膜圖案3'之邊緣部分之被蝕刻剖面。 Before the peeling of the photoresist film pattern 5 ', the etched cross section of the edge portion of the phase shift film pattern 3 ' of the phase shift mask 30 of Example 4 was observed by a scanning electron microscope.

其結果，實施例4之邊緣部分之被蝕刻剖面之光阻劑界面角度為122度，透明基板界面角度為58度，錐形下表面長度為70nm，剖面角度(θ)為58度。 As a result, the photoresist interface of the edge portion of Example 4 had an interface angle of 122 degrees, the transparent substrate interface angle was 58 degrees, the tapered lower surface length was 70 nm, and the sectional angle (θ) was 58 degrees.

根據該結果可知，實施例4中之被蝕刻剖面具有較比較例1及2中之被蝕刻剖面特別大之剖面角度(θ)，且更接近垂直剖面形狀。又，即便於成膜使CrON為構成材料之相位偏移膜3之情形時(實施例3、4)，亦與成膜使CrCON為構成材料之相位偏移膜3之情形時(實施例1、2)相同地，使將相位偏移膜形成步驟中之混合氣體(濺鍍氣體)自與相位偏移膜之成膜相關之濺鍍靶之下游側供給之情形時(實施例3)的剖面角度(θ)較自該濺鍍靶之上游側供給之情形時(實施例4)的剖面角度(θ)變大。 From this result, it is understood that the etched cross section in Example 4 has a cross-sectional angle (θ) which is particularly larger than the etched cross-sections in Comparative Examples 1 and 2, and is closer to the vertical cross-sectional shape. In addition, even when CrON is used as the phase shift film 3 constituting the material (Examples 3 and 4), and when CrCON is used as the phase shift film 3 constituting the material (Example 1) 2) Similarly, when the mixed gas (sputter gas) in the phase shift film forming step is supplied from the downstream side of the sputtering target related to the film formation of the phase shift film (Example 3) When the cross-sectional angle (θ) is supplied from the upstream side of the sputtering target (the fourth embodiment), the cross-sectional angle (θ) becomes large.

其次，與實施例1相同地測定實施例4之相位偏移光罩之相位偏移膜圖案之CD不均。 Next, CD unevenness of the phase shift film pattern of the phase shift mask of Example 4 was measured in the same manner as in Example 1.

CD不均為0.115μm，良好。 CD is not 0.115 μm, which is good.

再者，上述實施例中，已列舉使形成於透明基板2上之相位偏移膜3為單層膜之相位偏移光罩基底1之例進行了說明，但並不限定於此。即便使相位偏移膜3為由相同材料而構成之2層構造、3層構造、4層構造等之積層膜，亦能發揮與上述實施例相同之效果。 In the above embodiment, the phase shift film 3 formed on the transparent substrate 2 is an example of a phase shift mask base 1 which is a single layer film. However, the present invention is not limited thereto. Even if the phase shift film 3 is a laminated film of a two-layer structure, a three-layer structure, a four-layer structure or the like which is formed of the same material, the same effects as those of the above-described embodiment can be exhibited.

又，上述實施例中，對於透明基板2上僅形成有相位偏移膜3之相位偏移光罩基底1、及於透明基板2上僅形成有相位偏移膜圖案3'之相位偏移光罩30之例進行了說明，但並不限定於此。即便於在透明基板2上具有遮光膜圖案4'及相位偏移膜3之相位偏移光罩基底10(參照圖5)之情形時、於透明基板2上具有相位偏移膜3及光阻劑膜5之相位偏移光罩基底(參照圖6(b))之情形時、於透明基板2上具有遮光膜圖案4'及相位偏移膜圖案3'之相位偏移光罩31(參照圖7(e))，亦能發揮與上述實施例相同之效果。 Further, in the above 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 shift light in which only the phase shift film pattern 3 ' is formed on the transparent substrate 2 The cover 30 has been described as an example, but is not limited thereto. That is, when the light-shielding film pattern 4 ' and the phase shift film 3 are phase-shifted to the mask substrate 10 (see FIG. 5) on the transparent substrate 2, the phase shift film 3 and the photoresist are provided on the transparent substrate 2. When the phase of the film 5 is shifted from the mask substrate (see FIG. 6(b)), the phase shift mask 31 having the light shielding film pattern 4 ' and the phase shift film pattern 3 ' on the transparent substrate 2 is referred to (refer to Fig. 7(e)) can also exert the same effects as the above embodiment.

又，於在透明基板2上具有相位偏移膜3與遮光膜4之相位偏移光罩基底(未圖示)中，亦可使形成於相位偏移膜3上之遮光膜4為遮光層、遮光層及抗反射層之積層構造。 Further, in the phase shift film substrate (not shown) having the phase shift film 3 and the light shielding film 4 on the transparent substrate 2, the light shielding film 4 formed on the phase shift film 3 may be a light shielding layer. The laminated structure of the light shielding layer and the antireflection layer.

1‧‧‧相位偏移光罩基底 1‧‧‧ phase shift mask base

2‧‧‧透明基板 2‧‧‧Transparent substrate

3‧‧‧相位偏移膜 3‧‧‧ phase offset film

3a‧‧‧最表面 3a‧‧‧Most surface

B‧‧‧主體部 B‧‧‧ Main Body

R1‧‧‧組成梯度區域 R1‧‧‧ composition gradient region

R2‧‧‧透明基板附近區域 R2‧‧‧near the transparent substrate

Claims (16)

一種相位偏移光罩基底，其特徵在於，其係於透明基板上形成有含有鉻、氧及氮之相位偏移膜者，且於上述相位偏移膜，自其最表面朝向膜深度方向形成有組成梯度區域，該組成梯度區域中，自上述最表面朝向膜深度方向減少之氧相對於鉻之比例(O/Cr)之最大值為2以上，且，自上述最表面朝向膜深度方向減少之氮相對於鉻之比例(N/Cr)之最大值為0.45以下。 A phase shift mask substrate characterized in that a phase shift film containing chromium, oxygen and nitrogen is formed on a transparent substrate, and the phase shift film is formed from a front surface thereof toward a film depth direction. There is a composition gradient region in which the maximum value of the ratio of oxygen to chromium (O/Cr) which decreases from the outermost surface toward the film depth direction is 2 or more, and decreases from the outermost surface toward the film depth direction. The maximum value of the ratio of nitrogen to chromium (N/Cr) is 0.45 or less. 如請求項1之相位偏移光罩基底，其中上述相位偏移膜之上述組成梯度區域係藉由對上述最表面之真空紫外線照射處理而形成。 The phase shift mask substrate of claim 1, wherein the composition gradient region of the phase shift film is formed by vacuum ultraviolet irradiation treatment on the outermost surface. 如請求項1或2之相位偏移光罩基底，其中上述相位偏移膜之上述最表面之膜密度為2.0g/cm3以上。 The phase shift mask substrate according to claim 1 or 2, wherein a film density of said outermost surface of said phase shifting film is 2.0 g/cm 3 or more. 如請求項1或2之相位偏移光罩基底，其中上述組成梯度區域之膜厚為0.1nm以上10nm以下。 The phase shift mask substrate of claim 1 or 2, wherein the composition gradient region has a film thickness of 0.1 nm or more and 10 nm or less. 如請求項1或2之相位偏移光罩基底，其中除上述組成梯度區域及上述透明基板之附近區域以外的上述相位偏移膜中之膜深度方向之各元素之組成比大致均一。 The phase shift mask substrate of claim 1 or 2, wherein a composition ratio of each element in a film depth direction of the phase shift film other than the composition gradient region and the vicinity of the transparent substrate is substantially uniform. 如請求項1或2之相位偏移光罩基底，其中上述相位偏移膜進而含有碳。 The phase shift mask substrate of claim 1 or 2 wherein the phase shifting film further contains carbon. 一種相位偏移光罩基底之製造方法，其特徵在於，其係藉由濺鍍法而於透明基板上形成含有鉻、氧及氮之相位偏移膜者，且包含：成膜步驟，其係於上述透明基板上成膜上述相位偏移膜；及真空紫外線照射處理步驟，其係對所成膜之上述相位偏移膜 之最表面進行真空紫外線照射處理；該真空紫外線照射處理步驟中，於自上述相位偏移膜之上述最表面朝向膜深度方向形成之組成梯度區域中，將自上述最表面朝向膜深度方向減少之氧相對於鉻之比例(O/Cr)之最大值改為2以上，且，將自上述最表面朝向膜深度方向減少之氮相對於鉻之比例(N/Cr)之最大值改為0.45以下。 A method for manufacturing a phase shift mask substrate, characterized in that a phase shift film containing chromium, oxygen and nitrogen is formed on a transparent substrate by sputtering, and a film forming step is included Forming the phase shifting film on the transparent substrate; and vacuum ultraviolet irradiation processing step of the phase shifting film formed on the film The outermost surface is subjected to vacuum ultraviolet irradiation treatment; in the vacuum ultraviolet irradiation treatment step, the composition gradient region formed from the outermost surface of the phase shift film toward the film depth direction is reduced from the outermost surface toward the film depth direction The maximum value of the ratio of oxygen to chromium (O/Cr) is changed to 2 or more, and the maximum value of the ratio of nitrogen to chromium (N/Cr) which decreases from the outermost surface toward the film depth is changed to 0.45 or less. . 如請求項7之相位偏移光罩基底之製造方法，其中上述真空紫外線照射處理步驟係將上述相位偏移膜之上述最表面之膜密度改為2.0g/cm3以上。 The method of manufacturing a phase shift mask substrate according to claim 7, wherein the vacuum ultraviolet irradiation processing step changes the film density of the outermost surface of the phase shift film to 2.0 g/cm 3 or more. 如請求項7或8之相位偏移光罩基底之製造方法，其中除上述組成梯度區域及上述透明基板之附近區域以外的上述相位偏移膜中之膜深度方向之各元素之組成比大致均一。 The method of manufacturing a phase shift mask substrate according to claim 7 or 8, wherein a composition ratio of each element in a film depth direction of the phase shift film other than the composition gradient region and the vicinity of the transparent substrate is substantially uniform . 如請求項7或8之相位偏移光罩基底之製造方法，其中上述成膜步驟係積層相同材料而成膜上述相位偏移膜。 A method of manufacturing a phase shift mask substrate according to claim 7 or 8, wherein said film forming step is formed by laminating the same material to form said phase shift film. 如請求項7或8之相位偏移光罩基底之製造方法，其中上述成膜步驟係藉由使用包含鉻之濺鍍靶、且利用包含惰性氣體與使該相位偏移膜氧化及氮化之活性氣體之混合氣體實施反應性濺鍍而進行。 A method of fabricating a phase shift mask substrate according to claim 7 or 8, wherein the film forming step is performed by using a sputtering target containing chromium and oxidizing and nitriding the phase shifting film by using an inert gas. The mixed gas of the reactive gas is subjected to reactive sputtering. 如請求項11之相位偏移光罩基底之製造方法，其中上述混合氣體進而包含使上述相位偏移膜碳化之活性氣體。 A method of manufacturing a phase shift mask substrate according to claim 11, wherein said mixed gas further comprises an active gas which carbonizes said phase shift film. 如請求項11之相位偏移光罩基底之製造方法，其中上述成膜步驟係利用連續式濺鍍裝置而進行。 A method of fabricating a phase shift mask substrate according to claim 11, wherein said film forming step is performed using a continuous sputtering apparatus. 如請求項13之相位偏移光罩基底之製造方法，其中自上述濺鍍靶附近之上述透明基板之搬送方向上之該濺鍍靶之下游側，供給上述混合氣體。 A method of manufacturing a phase shift mask substrate according to claim 13, wherein the mixed gas is supplied from a downstream side of the sputtering target in a transport direction of the transparent substrate in the vicinity of the sputtering target. 如請求項7或8之相位偏移光罩基底之製造方法，其中上述真空 紫外線照射處理步驟中，係使上述組成梯度區域中之氧相對於鉻之比例(O/Cr)之減少率，於上述真空紫外線照射處理後的減少率大於上述真空紫外線照射處理前的減少率，且，使氮相對於鉻之比例(N/Cr)之減少率，於上述真空紫外線照射處理後的減少率小於上述真空紫外線照射處理前的減少率。 A method of fabricating a phase shift mask substrate according to claim 7 or 8, wherein said vacuum In the ultraviolet irradiation treatment step, the rate of decrease in the ratio of oxygen to chromium (O/Cr) in the composition gradient region is greater than the reduction rate before the vacuum ultraviolet irradiation treatment after the vacuum ultraviolet irradiation treatment. Further, the rate of decrease in the ratio of nitrogen to chromium (N/Cr) is smaller than the rate of decrease after the vacuum ultraviolet irradiation treatment. 一種相位偏移光罩之製造方法，其特徵在於，於如請求項1至6中任一項之相位偏移光罩基底、或藉由如請求項7至15中任一項之相位偏移光罩基底之製造方法而製作的相位偏移光罩基底之上述相位偏移膜上形成光阻劑膜圖案，將該光阻劑膜圖案作為光罩而對上述相位偏移膜進行濕式蝕刻，於上述透明基板上形成相位偏移膜圖案。 A method of manufacturing a phase shift mask, characterized by a phase shift mask substrate according to any one of claims 1 to 6, or a phase shift by any one of claims 7 to 15 Forming a photoresist film pattern on the phase shift film of the phase shift mask substrate produced by the method of manufacturing the mask base, and wet etching the phase shift film by using the photoresist film pattern as a mask Forming a phase shift film pattern on the transparent substrate.
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