TWI609233B - Manufacturing method of phase shift mask and phase shift mask - Google Patents

Manufacturing method of phase shift mask and phase shift mask Download PDF

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TWI609233B
TWI609233B TW103114106A TW103114106A TWI609233B TW I609233 B TWI609233 B TW I609233B TW 103114106 A TW103114106 A TW 103114106A TW 103114106 A TW103114106 A TW 103114106A TW I609233 B TWI609233 B TW I609233B
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phase shift
layer
phase
pattern
thickness
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TW201502693A (en
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望月聖
中村大介
小林良紀
影山景弘
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阿爾貝克成膜股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/28—Phase shift masks [PSM]; PSM blanks; Preparation thereof with three or more diverse phases on the same PSM; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/29—Rim PSM or outrigger PSM; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/80—Etching

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physical Vapour Deposition (AREA)

Description

相位移光罩之製造方法及相位移光罩 Phase shift mask manufacturing method and phase shift mask

本發明係關於一種可形成微細且高精度之曝光圖案的相位移光罩之製造方法及相位移光罩。尤其是關於一種平板顯示器之製造所使用之技術。 The present invention relates to a method of manufacturing a phase shift mask capable of forming a fine and highly precise exposure pattern, and a phase shift mask. In particular, it relates to the technology used in the manufacture of a flat panel display.

本案係基於2013年4月17日於日本提出申請之日本專利特願2013-086982號且主張優先權，並將其內容援用於本文中。 The present application is based on Japanese Patent Application No. 2013-086982, filed on Jan.

於半導體中，為了進行高密度安裝，而花費較長時間使圖案微細化。因此，使曝光波長短波長化，並且研究了改善曝光方法等各種各樣之手法。 In semiconductors, it takes a long time to make the pattern finer in order to perform high-density mounting. Therefore, the exposure wavelength is shortened, and various methods such as an improvement of the exposure method have been studied.

於光罩中亦為進行圖案微細化，而由使用複合波長且採用形成遮光膜圖案之光罩，以至於在圖案緣使用光干涉並使用單波長且採用可形成更微細之圖案的相位移光罩。於上述所示之半導體用相位移光罩中，如專利文獻1所示採用了使用有i射線單波長之邊緣加強型之相位移光罩，但為了進一步之微細化，而如專利文獻2所示使曝光波長縮短至ArF單波長且使用半透過型之相位移光罩。 In the reticle, pattern refinement is also performed, and a reticle using a composite wavelength and using a light-shielding film pattern is used, so that light interference is used at the edge of the pattern and a single wavelength is used, and phase-shifted light which can form a finer pattern is used. cover. In the phase shift mask for a semiconductor as described above, a phase shift mask using an edge-enhanced type having an i-ray single wavelength is used as shown in Patent Document 1, but for further miniaturization, as in Patent Document 2 The exposure wavelength is shortened to an ArF single wavelength and a semi-transmissive phase shift mask is used.

另一方面，於平板顯示器中，為了實現低價格化，必須以較高之產能進行生產，就曝光波長而言，亦利用g射線、h射線、i射線之複合波長下之曝光進行圖案形成。 On the other hand, in a flat panel display, in order to achieve a low price, it is necessary to produce at a high productivity, and in terms of an exposure wavelength, pattern formation is also performed by exposure at a complex wavelength of g-ray, h-ray, or i-ray.

最近，於上述平板顯示器中亦為了形成高精細之畫面而使圖案分佈更微細化，以至於如專利文獻3所示使用邊緣加強型之相位移光罩，而並非先前以來使用之將遮光膜圖案化而成之光罩。 Recently, in the above flat panel display, the pattern distribution is further refined in order to form a high-definition screen, so that the edge-enhanced phase shift mask is used as shown in Patent Document 3, instead of the light-shielding film pattern which has been used before. Made into a mask.

就平板用之邊緣加強型之相位移光罩而言，現狀為，於複合波長區域內曝光，於具有相位移效果以外之波長下存在相位移效果變得並不充分之問題，從而期待可獲得更高效率之相位移效果的相位移光罩。 In the case of the edge-enhanced phase-shifting reticle for a flat plate, the current situation is that exposure in a composite wavelength region has a problem that the phase shift effect is insufficient at a wavelength other than the phase shift effect, and thus it is expected to be available. A phase shift mask with a more efficient phase shift effect.

上述邊緣加強型相位移光罩中，除了於將遮光膜圖案化後形成相位移膜、進而將相位移膜圖案化之專利文獻3中記載之上置型相位移光罩以外，還存在自基板依序形成相位移膜、蝕刻終止膜、遮光膜並依序圖案化之下置型相位移光罩。然而，於上述下置型相位移光罩中亦具有同樣之問題，於含有包含相位移層之半透過膜的單層型相位移光罩中亦存在同樣之問題。 In the above-described edge-enhanced phase-shifting mask, in addition to the above-described phase-shifting mask described in Patent Document 3, which is formed by patterning a light-shielding film and then patterning the phase-shift film, there is also The phase shift film, the etch stop film, the light shielding film are sequentially formed, and the underlying phase shift mask is sequentially patterned. However, the same problem exists in the above-mentioned down-type phase shift mask, and the same problem exists in a single-layer phase shift mask including a semi-transmissive film including a phase shift layer.

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

[專利文獻1]日本專利特開平08-272071號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 08-272071

[專利文獻2]日本專利特開2006-78953號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-78953

[專利文獻3]日本專利特開2011-13283號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2011-13283

又，較佳為，於作為邊緣加強型之相位移光罩之圖案區域內，相位移圖案自遮光圖案露出寬幅之形狀，但於濕式蝕刻處理中，以特定厚度形成之相位移圖案塌陷、即厚度之減少程度與所設定之形狀不同，結果，依存於相位移層之厚度的光強度變為零之部位與所期望之狀態不同，由此，有如下問題：因存在圖案線寬(寬度尺寸)變粗等作為光罩之高精細性降低之可能性，故而欠佳。 Further, preferably, in the pattern region of the edge-retaining phase shift mask, the phase shift pattern exposes a wide shape from the light-shielding pattern, but in the wet etching process, the phase shift pattern formed with a specific thickness collapses. That is, the degree of reduction in thickness is different from the shape set, and as a result, the portion where the light intensity depending on the thickness of the phase shift layer becomes zero is different from the desired state, and thus, there is a problem in that the pattern line width is present ( The width dimension) becomes thicker or the like as a possibility that the high fineness of the mask is lowered, which is not preferable.

進而，現狀為，於形成平板之圖案時，使用複合波長區域內之曝光，但無法獲得活用所有複合波長之相位移效果，故而於形成進一步微細之圖案時存在限制，於複合波長區域內之曝光中亦期待充分發揮相位移效果而實現微細化之製程。 Further, in the current situation, when a pattern of a flat plate is formed, exposure in a composite wavelength region is used, but a phase shift effect of using all composite wavelengths is not obtained, so that there is a limitation in forming a fine pattern, and exposure in a composite wavelength region. It is also expected to achieve the process of miniaturization by fully exerting the phase shift effect.

近年來，伴隨平板顯示器之配線圖案之微細化，對平板顯示器之製造所使用之光罩而言，微細之線寬精度之要求亦提高。然而，僅依靠光罩之微細化之曝光條件、顯影條件等之研究係非常難以應對，從而尋求用以達成進一步之微細化之新技術。 In recent years, with the miniaturization of wiring patterns for flat panel displays, the requirements for fine line width accuracy have been increased for photomasks used in the manufacture of flat panel displays. However, research based on the exposure conditions and development conditions of the refining of the mask is extremely difficult to cope with, and a new technique for achieving further miniaturization is sought.

就於曝光中可應用上述波長範圍之複合波長、即曝光強度之觀點而言，要求可同時使用不同波長之光並且可同時維持高精細性。 From the viewpoint of the application of the composite wavelength of the above wavelength range, that is, the exposure intensity, it is required to simultaneously use light of different wavelengths while maintaining high definition.

本發明之態樣之目的在於提供一種適宜用於平板顯示器之製造，可形成微細且高精度之曝光圖案且可應用複合波長，並且可更有效率地獲得相位移效果的相位移光罩之製造方法及相位移光罩。 It is an object of the present invention to provide a phase-shift reticle suitable for use in the manufacture of flat panel displays, which can form a fine and highly accurate exposure pattern and which can apply a composite wavelength and can more effectively obtain a phase shift effect. Method and phase shift mask.

本發明之一態樣之相位移光罩之製造方法之特徵在於：其係製造相位移光罩之方法，該相位移光罩包括：透明基板；及相位移層，其具有於至少上述透明基板之表面以固定厚度形成之部分且以Cr為主成分，可對300nm以上且500nm以下之波長區域之任一種光具有180°之相位差；且該相位移光罩之製造方法包括如下步驟：於上述透明基板上多階地形成上述相位移層；及對上述相位移層進行濕式蝕刻，並以上述相位移層與上述透明基板於俯視時具有邊界部分之方式將上述相位移層圖案化，而形成相位移圖案；且於俯視時之上述相位移層與上述透明基板之邊界部分，形成將上述相位移層之厚度變化設定為多階之多階區域。 A method of manufacturing a phase shift mask according to an aspect of the present invention is characterized in that it is a method of manufacturing a phase shift mask, the phase shift mask comprises: a transparent substrate; and a phase shift layer having at least the transparent substrate The surface formed by the fixed thickness and containing Cr as a main component may have a phase difference of 180° for any one of wavelength regions of 300 nm or more and 500 nm or less; and the method for manufacturing the phase shift mask includes the following steps: The phase shift layer is formed on the transparent substrate in a plurality of stages; and the phase shift layer is wet-etched, and the phase shift layer is patterned such that the phase shift layer and the transparent substrate have a boundary portion in a plan view. And forming a phase shift pattern; and forming a multi-step region in which the thickness variation of the phase shift layer is set to a plurality of stages in a boundary portion between the phase shift layer and the transparent substrate in a plan view.

於上述態樣之製造方法中，於上述相位移層之形成步驟中，藉由設定成膜氛圍氣體中氧化性氣體之流量比，而可分別設定上述相位移層中之各階之蝕刻速率。 In the manufacturing method of the above aspect, in the step of forming the phase shift layer, the etching rate of each step in the phase shift layer can be set by setting a flow ratio of the oxidizing gas in the film forming atmosphere.

於上述態樣之製造方法中，於上述相位移層之多階區域內，上述各階之厚度可以於不同波長之光中具有180°之相位差之方式對應。 In the above manufacturing method, in the multi-step region of the phase shift layer, the thickness of each of the above steps may correspond to a phase difference of 180° among light of different wavelengths.

於上述態樣之製造方法中，作為上述相位移層中之各階之成膜氛圍的成膜氣體包含惰性氣體、氮化性氣體及氧化性氣體，或者包含氮化性氣體與氧化性氣體，且相對於總氣體流量，氧化性氣體之流量比選自3.68%~24.89%之範圍，進而，相對於每層之總氣體流量的氧化性氣體比率亦可不同。 In the manufacturing method of the above aspect, the film forming gas which is the film forming atmosphere of each step in the phase shifting layer contains an inert gas, a nitriding gas, and an oxidizing gas, or contains a nitriding gas and an oxidizing gas, and The flow ratio of the oxidizing gas is selected from the range of 3.68% to 24.89% with respect to the total gas flow rate, and further, the ratio of the oxidizing gas to the total gas flow rate of each layer may be different.

於上述態樣之製造方法中，包括於在上述透明基板上形成相位移膜後形成圖案之步驟，或者包括由遮光層形成遮光圖案，並於上述遮光圖案上由相位移層形成相位移圖案的步驟，或者進而亦可包括如下步驟：於上述透明基板上形成相位移層，於上述相位移層上介隔以選自Ni、Co、Fe、Ti、Si、Al、Nb、Mo、W及Hf中之至少1種金屬為主成分之蝕刻終止層形成，於上述蝕刻終止層上形成遮光層，並利用圖案形成而形成相位移圖案。 In the manufacturing method of the above aspect, the method includes forming a pattern after forming a phase shift film on the transparent substrate, or forming a light shielding pattern by the light shielding layer, and forming a phase shift pattern by the phase shift layer on the light shielding pattern. The step, or further comprising the steps of: forming a phase shifting layer on the transparent substrate, and interposing the phase shifting layer on the phase shifting layer to be selected from the group consisting of Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W, and Hf At least one metal is formed as an etch stop layer as a main component, a light shielding layer is formed on the etch stop layer, and a phase shift pattern is formed by patterning.

本發明之另一態樣之相位移光罩之特徵在於：其係藉由上述任一記載之製造方法而製造，且包括：透明基板；及相位移層，其具有於至少上述透明基板之表面以固定厚度形成之部分且以Cr為主成分，可對300nm以上且500nm以下之波長區域之任一種光具有180°之相位差；且 於上述相位移層，形成有俯視時具有相對於上述透明基板之邊界部分的相位移圖案，於俯視時之上述相位移層與上述透明基板之邊界部分，具有使上述相位移層之厚度多階地變化之多階區域。 A phase shift mask according to another aspect of the invention is characterized in that it is manufactured by the manufacturing method of any one of the above, and includes: a transparent substrate; and a phase shifting layer having at least a surface of the transparent substrate a portion formed by a fixed thickness and containing Cr as a main component, and having a phase difference of 180° for any one of wavelength regions of 300 nm or more and 500 nm or less; Forming, in the phase shifting layer, a phase shift pattern having a boundary portion with respect to the transparent substrate in a plan view, and having a thickness of the phase shift layer at a boundary portion between the phase shift layer and the transparent substrate in a plan view A multi-level region of ground change.

於上述態樣之相位移光罩中，於上述相位移層之多階區域內，上述各階之厚度可以不同波長之光具有相位差之方式對應。 In the phase shift mask of the above aspect, in the multi-step region of the phase shift layer, the thickness of each of the above steps may correspond to a phase difference of light of different wavelengths.

於上述態樣之相位移光罩中，上述相位移層之多階區域厚度可採用於g射線、h射線、i射線中具有180°之相位差的方法，或者上述相位移層之多階區域厚度可採用於h射線、i射線中具有180°之相位差的方法。 In the phase shift mask of the above aspect, the multi-step region thickness of the phase shift layer may be a method having a phase difference of 180° in g-ray, h-ray, or i-ray, or a multi-step region of the phase shift layer. The thickness can be a method having a phase difference of 180° in h-rays and i-rays.

作為以具有180°之相位差之方式設定之波長，如上所述可以包含g射線、h射線、i射線之方式設定，但亦可以包含h射線、i射線而不含g射線之方式設定。 The wavelength set so as to have a phase difference of 180° may be set so as to include g-rays, h-rays, and i-rays as described above, but may be set to include h-rays and i-rays without including g-rays.

本發明之另一態樣之相位移光罩之製造方法係包括透明基板、及相位移層之相位移光罩之製造方法，該相位移層具有於至少上述透明基板之表面以固定厚度形成之部分且以Cr為主成分，可對300nm以上且500nm以下之波長區域之任一種光具有180°之相位差，且該製造方法包括如下步驟：於上述透明基板上多階地形成上述相位移層；及對上述相位移層進行濕式蝕刻，並以上述相位移層與上述透明基板於俯視時具有邊界部分之方式將上述相位移層圖案化，而形成相位移圖案；且於俯視時之上述相位移層與上述透明基板之邊界部分，形成將上述相位移層之厚度變化設定為多階之多階區域，藉此，至少於透明基板上之相位移圖案之單層部分，形成以厚度朝向露出之透明基板表 面減少之方式將厚度變化設定為多階之多階區域，藉此，該多階區域於曝光所使用之各特定波長之光中與光強度變為零之厚度對應的部位沿相位移圖案之輪廓以特定之寬度尺寸形成。同時，與對應於成為上述波長區域之複合波長之光的厚度對應之部位係如對相位移圖案之輪廓呈相似形般以特定之寬度尺寸形成，藉此，針對與於曝光中上述波長範圍之複合波長中之各適合波長對應的厚度尺寸，於多階區域之各階中，各厚度尺寸於寬度方向上持續，藉此，該等各階可具有對應於各複合波長中之特定波長而將光強度設為零的特定之寬度。 A method for manufacturing a phase shift mask according to another aspect of the present invention includes a transparent substrate and a method of manufacturing a phase shift mask of a phase shifting layer, wherein the phase shift layer has a fixed thickness formed on at least a surface of the transparent substrate. And partially having Cr as a main component, and having a phase difference of 180° for any one of wavelength regions of 300 nm or more and 500 nm or less, and the manufacturing method includes the steps of: forming the phase shift layer in a plurality of stages on the transparent substrate. And performing wet etching on the phase shifting layer, and patterning the phase shifting layer by the phase shifting layer and the transparent substrate having a boundary portion in a plan view to form a phase shift pattern; a boundary portion of the phase shift layer and the transparent substrate is formed as a multi-step region in which a thickness variation of the phase shift layer is set to a plurality of steps, whereby a single layer portion of the phase shift pattern on at least the transparent substrate is formed in a thickness direction Exposed transparent substrate The method of reducing the thickness is to set the thickness variation to a multi-order multi-step region, whereby the multi-step region is along the phase shift pattern in the portion of the light of the specific wavelength used for the exposure corresponding to the thickness at which the light intensity becomes zero. The profile is formed in a specific width dimension. At the same time, the portion corresponding to the thickness of the light corresponding to the composite wavelength of the wavelength region is formed in a specific width dimension such that the contour of the phase shift pattern is similarly shaped, thereby, for the above-mentioned wavelength range in exposure a thickness dimension corresponding to each suitable wavelength of the composite wavelength, wherein each thickness dimension continues in the width direction in each of the plurality of stages, whereby the stages may have a light intensity corresponding to a specific wavelength of each composite wavelength Set to a specific width of zero.

藉此，將上述波長範圍之複合波長同時用於曝光，可確實地獲得相位移效果，因此，可製造一種能夠實現更進一步之高精細化、曝光時間之縮短、曝光效率之提高的相位移光罩。 Thereby, the composite wavelength of the above wavelength range is simultaneously used for exposure, and the phase shift effect can be surely obtained. Therefore, phase shift light which can achieve further high definition, shortened exposure time, and improved exposure efficiency can be manufactured. cover.

於上述態樣之製造方法中，於上述相位移層形成步驟中，藉由設定成膜氛圍氣體中氧化性氣體之流量比，而可分別設定上述相位移層中之各階之蝕刻速率，藉此，於俯視時之上述相位移層與上述透明基板之邊界部分，可形成將上述相位移層之厚度變化設定為多階之多階區域，且至少於透明基板上之相位移圖案之單層部分，可形成以厚度朝向露出之透明基板表面減少之方式將厚度變化設定為多階之多階區域。 In the manufacturing method of the aspect described above, in the phase shift layer forming step, by setting a flow ratio of the oxidizing gas in the film forming atmosphere, the etching rates of the respective stages in the phase shift layer can be set, thereby And forming a single-layer portion of the phase shift pattern on the transparent substrate by setting a thickness variation of the phase shift layer to a multi-step region at a boundary portion between the phase shift layer and the transparent substrate in a plan view. It is possible to form a multi-step region in which the thickness variation is set to be multi-step in such a manner that the thickness is reduced toward the surface of the exposed transparent substrate.

於上述態樣之製造方法中，於上述相位移層之多階區域內，上述各階之厚度以於不同波長之光中具有180°之相位差之方式對應，藉此，階可具有對應於各複合波長中之特定波長而將光強度設為零之特定之寬度。因此，可於各波長中將光強度設為零，容易應對高精細化。 In the manufacturing method of the above aspect, in the multi-step region of the phase shifting layer, the thickness of each of the steps is corresponding to a phase difference of 180° in light of different wavelengths, whereby the steps may have corresponding to each The specific wavelength of the composite wavelength sets the light intensity to a specific width of zero. Therefore, the light intensity can be set to zero at each wavelength, and it is easy to cope with high definition.

於上述態樣之製造方法中，作為上述相位移層中之各階之成膜氛圍的成膜氣體包含惰性氣體、氮化性及氧化性氣體、或者氮化性氣體與氧化性氣體，且相對於 總氣體流量，氧化性氣體之流量比選自3.68%~24.89%之範圍，藉此，可將上述多階區域中之膜厚狀態控制為所期望之狀態。藉此，以上述多階區域之各階之膜厚分別與於上述波長範圍之複合波長之光中光強度變為零之厚度對應的方式控制膜厚，可將上述波長範圍之複合波長同時用於曝光。 In the manufacturing method of the above aspect, the film forming gas which is the film forming atmosphere of each step in the phase shifting layer contains an inert gas, a nitrided or oxidizing gas, or a nitriding gas and an oxidizing gas, and The total gas flow rate and the flow rate ratio of the oxidizing gas are selected from the range of 3.68% to 24.89%, whereby the film thickness state in the above multi-stage region can be controlled to a desired state. Thereby, the film thickness is controlled in such a manner that the film thicknesses of the respective steps of the multi-step regions correspond to the thicknesses of the light beams of the composite wavelengths in the above-mentioned wavelength range, and the composite wavelengths of the above wavelength ranges can be simultaneously used. exposure.

於上述態樣之製造方法中，包括於在上述透明基板上形成相位移膜後形成圖案之步驟，或者包括由遮光層形成遮光圖案，並於上述遮光圖案上由相位移層形成相位移圖案的步驟，或者進而可包括於上述透明基板上形成相位移層，於上述相位移層上介隔以選自Ni、Co、Fe、Ti、Si、Al、Nb、Mo、W及Hf中之至少1種金屬為主成分之蝕刻終止層形成，於上述蝕刻終止層上形成遮光層，並利用圖案形成而形成相位移圖案的步驟，藉此，於曝光區域內，可對應於包含相位移層單層之相位移光罩、相位移層位於上側且遮光層位於其下側之所謂上置型相位移光罩、相位移層位於下側且介隔蝕刻終止層而使遮光層位於其上側之所謂下置型相位移光罩。再者，於任一情形時，包含多階區域之上述邊界部分被設為包含相位移層單層者。 In the manufacturing method of the above aspect, the method includes forming a pattern after forming a phase shift film on the transparent substrate, or forming a light shielding pattern by the light shielding layer, and forming a phase shift pattern by the phase shift layer on the light shielding pattern. a step, or further comprising forming a phase shift layer on the transparent substrate, and interposing at least one of Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W, and Hf on the phase shift layer Forming an etch stop layer as a main component, forming a light shielding layer on the etch stop layer, and forming a phase shift pattern by patterning, thereby corresponding to a single layer including a phase shift layer in the exposed region a so-called up-down type of a phase-shifting reticle, a phase-shifting layer on the upper side, and a so-called upper-type phase-shifting reticle having a light-shielding layer on the lower side thereof, a phase-shifting layer on the lower side, and an etch-stop layer interposing the light-shielding layer on the upper side thereof Phase shift mask. Furthermore, in either case, the above-described boundary portion including the multi-order region is set to include a single layer of the phase shift layer.

本發明之另一態樣之相位移光罩係藉由上述任一記載之製造方法而製造，且包括：透明基板；及相位移層，其具有於至少上述透明基板之表面以固定厚度形成之部分且以Cr為主成分，可對300nm以上且500nm以下之波長區域之任一種光具有180°之相位差；且於上述相位移層形成俯視時與上述透明基板具有邊界部分之相位移圖案， 於俯視時之上述相位移層與上述透明基板之邊界部分，具有使上述相位移層之厚度多階地變化之多階區域，藉此，至少於透明基板上之相位移圖案之單層部分，以厚度朝向露出之透明基板表面減少之方式將厚度變化設定為多階的多階區域於用於曝光之各特定波長之光中與光強度變為零之厚度對應的部位沿相位移圖案之輪廓具有特定之寬度尺寸，故而可確實地獲得相位移效果，可應對更進一步之高精細化。 A phase shift mask according to another aspect of the present invention, which is manufactured by the manufacturing method of any one of the above, comprising: a transparent substrate; and a phase shift layer having a fixed thickness formed on at least the surface of the transparent substrate a portion having a Cr component as a main component and having a phase difference of 180° with respect to any one of wavelength regions of 300 nm or more and 500 nm or less; and a phase shift pattern having a boundary portion with the transparent substrate in a plan view in the phase shift layer, a boundary portion of the phase shift layer and the transparent substrate in a plan view, having a multi-step region in which the thickness of the phase shift layer is changed in multiple steps, thereby at least a single layer portion of the phase shift pattern on the transparent substrate, The thickness variation is set to a multi-step multi-step region in such a manner that the thickness is reduced toward the surface of the exposed transparent substrate, and the contour of the phase shift pattern is along the portion of the light for each specific wavelength for exposure corresponding to the thickness at which the light intensity becomes zero. With a specific width dimension, the phase shift effect can be surely obtained, and further high definition can be coped with.

同時，與對應於成為上述波長區域之複合波長之光的厚度對應之部位係如對相位移圖案之輪廓呈相似形般以特定之寬度尺寸形成，藉此，針對與於曝光中上述波長範圍之複合波長中之各適合波長對應的厚度尺寸，於多階區域之各階中，各厚度尺寸於寬度方向上持續，該等各階可具有對應於各複合波長中之特定波長而將光強度設為零之特定之寬度，故而將上述波長範圍之複合波長同時用於曝光，可確實地獲得相位移效果，因此，可製造一種能夠實現更進一步之高精細化、曝光時間之縮短、曝光能量之效率化等曝光效率之提高的相位移光罩。 At the same time, the portion corresponding to the thickness of the light corresponding to the composite wavelength of the wavelength region is formed in a specific width dimension such that the contour of the phase shift pattern is similarly shaped, thereby, for the above-mentioned wavelength range in exposure a thickness dimension corresponding to each suitable wavelength in the composite wavelength, wherein each thickness dimension continues in the width direction in each of the plurality of stages, and the stages may have a light intensity set to zero corresponding to a specific wavelength of each composite wavelength Since the specific width of the above-mentioned wavelength range is simultaneously used for exposure, the phase shift effect can be surely obtained, and therefore, it is possible to manufacture a further high definition, shorten the exposure time, and improve the exposure energy. A phase shift mask that increases the exposure efficiency.

於上述態樣之相位移光罩中，於上述相位移層之多階區域內，上述各階之厚度係以不同波長之光具有相位差之方式對應，藉此，將上述波長範圍之複合波長同時用於曝光，可確實地獲得相位移效果，因此，可製造一種能夠實現更進一步之高精細化、曝光時間之縮短、曝光能量之效率化等曝光效率之提高的相位移光罩。 In the phase shift mask of the above aspect, in the multi-step region of the phase shift layer, the thickness of each of the steps is corresponding to a phase difference of light of different wavelengths, thereby simultaneously combining the composite wavelengths of the wavelength ranges For the exposure, the phase shift effect can be surely obtained. Therefore, it is possible to manufacture a phase shift mask which can achieve further improvement in the definition of high definition, shortened exposure time, and improved efficiency of exposure energy.

於上述態樣之相位移光罩中，上述相位移層之多階區域厚度可於g射線、h射線、i射線中具有180°之相位差，可將與於複合波長之光中光強度變為零之部位對應的相位移層之多階區域中的各階厚度設定為對應於g射線、h射線、i射 線之145.0nm、133.0nm、120.0nm。各階之膜厚並不僅限於上述值，亦可於140~150nm、128~138nm、115~125nm之範圍內獲得相位差180°。 In the phase shift mask of the above aspect, the multi-step region thickness of the phase shift layer may have a phase difference of 180° in the g-ray, the h-ray, and the i-ray, and the light intensity in the light at the composite wavelength may be changed. The thickness of each step in the multi-step region of the phase shift layer corresponding to the zero portion is set to correspond to g-ray, h-ray, and i-ray The lines are 145.0 nm, 133.0 nm, and 120.0 nm. The film thickness of each step is not limited to the above value, and a phase difference of 180° can be obtained in the range of 140 to 150 nm, 128 to 138 nm, and 115 to 125 nm.

根據本發明之態樣，可提供一種適宜用於平板顯示器之製造，可形成微細且高精度之曝光圖案的相位移光罩之製造方法及相位移光罩。 According to an aspect of the present invention, a method of manufacturing a phase shift mask and a phase shift mask which are suitable for use in the manufacture of a flat panel display and which can form a fine and highly precise exposure pattern can be provided.

11‧‧‧相位移層 11‧‧‧ phase shift layer

11a‧‧‧相位移圖案 11a‧‧‧ phase shift pattern

11b、11b1‧‧‧上層 11b, 11b1‧‧‧ upper level

11c、11c1‧‧‧中層 11c, 11c1‧‧‧ middle

11d、11d1‧‧‧下層 11d, 11d1‧‧‧ lower level

11e‧‧‧上層 11e‧‧‧Upper

11f‧‧‧中硬層 11f‧‧‧ medium hard layer

11g‧‧‧中層 11g‧‧‧ middle layer

11h‧‧‧下硬層 11h‧‧‧Under hard layer

11i‧‧‧下層 11i‧‧‧Under

11sh、11si、11t、11u‧‧‧端部 11sh, 11si, 11t, 11u‧‧‧ end

12‧‧‧蝕刻終止層 12‧‧‧etch stop layer

12a、12b‧‧‧蝕刻終止圖案 12a, 12b‧‧‧etch stop pattern

13‧‧‧遮光層 13‧‧‧Lighting layer

13a、13b‧‧‧遮光圖案 13a, 13b‧‧‧ shading pattern

13s‧‧‧傾斜面 13s‧‧‧ sloped surface

14‧‧‧光阻層 14‧‧‧ photoresist layer

14a‧‧‧光阻圖案 14a‧‧‧resist pattern

14p‧‧‧光阻層之曝光及顯影區域 Exposure and development area of the photoresist layer of 14p‧‧

B1‧‧‧邊界部分 B1‧‧‧ boundary section

B1a‧‧‧均勻厚度區域 B1a‧‧‧even thickness area

B1b‧‧‧多階區域 B1b‧‧‧ multi-level area

B1bh、B1bi‧‧‧階部 B1bh, B1bi‧‧‧

B2、B3‧‧‧遮光區域 B2, B3‧‧‧ shading area

C‧‧‧露出部分 C‧‧‧Exposed part

M1、M2、M3‧‧‧相位移光罩 M1, M2, M3‧‧‧ phase shift mask

MB‧‧‧相位移空白光罩 MB‧‧‧ phase shift blank mask

S‧‧‧玻璃基板(透明基板) S‧‧‧ glass substrate (transparent substrate)

T11、Tg、Th、Ti‧‧‧厚度 T11, Tg, Th, Ti‧‧‧ thickness

圖1(a)、(b)係表示本發明之第1實施形態之相位移光罩之模式剖面圖。 1(a) and 1(b) are schematic cross-sectional views showing a phase shift mask according to a first embodiment of the present invention.

圖2(a)~(j)係對本發明之第1實施形態之相位移光罩之製造步驟進行說明的步驟圖。 2(a) to 2(j) are process diagrams for explaining a manufacturing procedure of the phase shift mask according to the first embodiment of the present invention.

圖3(a)~(d)係對本發明之第1實施形態之相位移光罩之製造步驟中之相位移層製造步驟進行說明的步驟圖。 3(a) to 3(d) are process diagrams for explaining a phase shift layer manufacturing step in the manufacturing process of the phase shift mask according to the first embodiment of the present invention.

圖4(a)~(d)係對本發明之第1實施形態之相位移光罩之製造步驟中之相位移層製造步驟進行說明的步驟圖。 4(a) to 4(d) are process diagrams for explaining a phase shift layer manufacturing step in the manufacturing process of the phase shift mask according to the first embodiment of the present invention.

圖5係表示本發明之第2實施形態之相位移光罩之模式剖面圖。 Fig. 5 is a schematic cross-sectional view showing a phase shift mask according to a second embodiment of the present invention.

圖6(a)~(g)係對本發明之第2實施形態之相位移光罩之製造步驟進行說明的步驟圖。 6(a) to 6(g) are process diagrams for explaining a manufacturing procedure of a phase shift mask according to a second embodiment of the present invention.

圖7係表示本發明之第3實施形態之相位移光罩之模式剖面圖。 Fig. 7 is a schematic cross-sectional view showing a phase shift mask according to a third embodiment of the present invention.

圖8(a)~(l)係對本發明之第3實施形態之相位移光罩之製造步驟進行說明的步驟圖。 8(a) to (l) are process diagrams for explaining a manufacturing procedure of a phase shift mask according to a third embodiment of the present invention.

<第1實施形態> <First embodiment>

以下，基於圖式，對本發明之相位移光罩之製造方法之第1實施形態進行說明。 Hereinafter, a first embodiment of a method of manufacturing a phase shift mask according to the present invention will be described based on the drawings.

圖1係表示本實施形態之相位移光罩之模式剖面圖(a)及表示多階區域之放大圖(b)。於圖中，M1為相位移光罩。 Fig. 1 is a schematic cross-sectional view (a) showing a phase shift mask of the embodiment and an enlarged view (b) showing a multi-step region. In the figure, M1 is a phase shift mask.

如圖1所示，本實施形態之相位移光罩M1具有相位移圖案11a，其設置於玻璃基板(透明基板)S表面，且包含可具有180°之相位差之相位移層11單層。構成為針對例如FPD(Flat Panel Display，平板顯示器)用玻璃基板之圖案化用光罩。如下所述，於使用有該光罩之玻璃基板之圖案化中，曝光光可使用i射線、h射線及g射線之複合波長。 As shown in Fig. 1, the phase shift mask M1 of the present embodiment has a phase shift pattern 11a which is provided on the surface of a glass substrate (transparent substrate) S and which includes a single layer of the phase shift layer 11 which can have a phase difference of 180°. It is configured as a mask for patterning, for example, a glass substrate for an FPD (Flat Panel Display). As described below, in the patterning of the glass substrate using the photomask, the exposure light can use a composite wavelength of i-ray, h-ray, and g-ray.

相位移光罩M1係於形成有曝光圖案之曝光區域內，於當俯視時為露出玻璃基板S之部分C、與所形成之相位移圖案11a的邊界部分B1，具有相位移圖案11a之厚度被設為固定值T11之均勻厚度區域(均勻區域)B1a、及該厚度自固定值T11起多階地減少之多階區域B1b。 The phase shift mask M1 is in the exposed region in which the exposure pattern is formed, and has a thickness of the phase shift pattern 11a which is a portion C of the exposed glass substrate S and a boundary portion B1 of the phase shift pattern 11a formed when viewed from above. A uniform thickness region (uniform region) B1a of a fixed value T11 and a multi-step region B1b whose thickness is reduced in multiple steps from a fixed value T11.

相位移圖案11a係由蝕刻速率、折射率、透過率、反射率等不同之層積層而形成為多層，且均勻區域B1a及多階區域B1b之階部形狀對應於該層構成之厚度。 The phase shift pattern 11a is formed into a plurality of layers by a laminated layer having different etching rates, refractive indices, transmittances, reflectances, and the like, and the stepped shape of the uniform region B1a and the multi-step region B1b corresponds to the thickness of the layer configuration.

作為透明基板S，使用透明性及光學等向性優異之材料，例如可使用石英玻璃基板。透明基板S之大小並無特別限制，可根據使用該光罩進行曝光之基板(例如FPD用基板、半導體基板)而適當選定。於本實施形態中，可適用於直徑尺寸100mm左右之基板、或一邊為50~100mm左右至一邊為300mm以上之矩形基板，進而亦可使用縱450mm、橫550mm、厚度8mm之石英基板、或最大邊尺寸1000mm以上且厚度10mm以上之基板。 As the transparent substrate S, a material excellent in transparency and optical isotropic properties is used, and for example, a quartz glass substrate can be used. The size of the transparent substrate S is not particularly limited, and can be appropriately selected depending on the substrate (for example, the FPD substrate or the semiconductor substrate) that is exposed by using the mask. In the present embodiment, it can be applied to a substrate having a diameter of about 100 mm or a rectangular substrate having a side of about 50 to 100 mm to a side of 300 mm or more, and a quartz substrate having a length of 450 mm, a width of 550 mm, and a thickness of 8 mm, or a maximum of A substrate having a side dimension of 1000 mm or more and a thickness of 10 mm or more.

又，亦可藉由研磨透明基板S之表面而提高透明基板S之平坦度。透明基板S之平坦度例如可設為20μm以下。藉此，光罩之焦點深度變深，可大大有助於形成微細且高精度之圖案。進而若平坦度為10μm以下，則較小者更為良好。 Further, the flatness of the transparent substrate S can be improved by polishing the surface of the transparent substrate S. The flatness of the transparent substrate S can be, for example, 20 μm or less. Thereby, the depth of focus of the photomask becomes deep, which can greatly contribute to the formation of a fine and high-precision pattern. Further, when the flatness is 10 μm or less, the smaller one is more preferable.

相位移層11係以Cr為主成分者，具體而言，可由選自Cr單體、以 及Cr之氧化物、氮化物、碳化物、氮氧化物、氮碳化物及氮碳氧化物中之1者構成。又，亦可積層選自該等中之2種以上而構成。 The phase shift layer 11 is mainly composed of Cr, and specifically, may be selected from Cr monomers. And one of Cr oxide, nitride, carbide, nitrogen oxide, nitrogen carbide and nitrogen carbon oxide. Further, it is also possible to form a laminate of two or more selected from the above.

相位移層11係由蝕刻速率、折射率、透過率、反射率等不同之層積層而形成為多層。對應於該層構成之厚度而形成均勻區域B1a及多階區域B1b之階部形狀。 The phase shift layer 11 is formed in a plurality of layers by a laminated layer having different etching rates, refractive indices, transmittances, and reflectances. The step shape of the uniform region B1a and the multi-step region B1b is formed corresponding to the thickness of the layer structure.

相位移層11係以可對300nm以上且500nm以下之波長區域之任一種光(例如，波長436nm之g射線、波長405nm之h射線、波長365nm之i射線)具有大致180°之相位差的厚度(例如，90~170nm)形成。相位移層11例如可藉由濺鍍法、電子束蒸鍍法、雷射蒸鍍法、ALD(Atomic Layer Deposition，原子層沈積)法等成膜。 The phase shift layer 11 has a thickness of substantially 180° with respect to any one of wavelength regions of 300 nm or more and 500 nm or less (for example, g-ray having a wavelength of 436 nm, h-ray having a wavelength of 405 nm, and i-ray having a wavelength of 365 nm). (for example, 90 to 170 nm) is formed. The phase shift layer 11 can be formed, for example, by a sputtering method, an electron beam evaporation method, a laser vapor deposition method, an ALD (Atomic Layer Deposition) method, or the like.

相位移圖案11a中，均勻厚度區域B1a之厚度T11與該邊界部分B1以外之相位移圖案11a之厚度相等，並且該厚度T11被設為與對應於g射線之光強度變為零之厚度Tg(例如145.0nm)對應之值。或者相位移層11中之均勻區域B1a之厚度T11被設為大於Tg之值，從而可使對應於Th、Ti之厚度與多階區域B1b對應。 In the phase shift pattern 11a, the thickness T11 of the uniform thickness region B1a is equal to the thickness of the phase shift pattern 11a other than the boundary portion B1, and the thickness T11 is set to a thickness Tg corresponding to the light intensity corresponding to the g-ray becoming zero ( For example, 145.0 nm) corresponds to the value. Alternatively, the thickness T11 of the uniform region B1a in the phase shift layer 11 is set to be larger than the value of Tg, so that the thickness corresponding to Th and Ti can be made to correspond to the multi-step region B1b.

相位移圖案11a具有均勻區域B1a，於多階區域B1b內具有厚度朝向露出部分C減少之階部B1bh與階部B1bi。具體而言，多階區域B1b之寬度方向尺寸被設為均勻區域B1a之厚度T11之端部11t至露出部分C(相位移層之厚度為零且露出玻璃基板S之部分)之端部11u。於多階區域B1b內，於厚度減少之方向上設置其厚度尺寸不同之階部B1bh與階部B1bi。 The phase shift pattern 11a has a uniform region B1a having a step portion B1bh and a step portion B1bi whose thickness decreases toward the exposed portion C in the multi-step region B1b. Specifically, the width direction dimension of the multi-step region B1b is set to the end portion 11u of the thickness portion T11 of the uniform region B1a to the end portion 11u of the exposed portion C (the thickness of the phase shift layer is zero and the portion of the glass substrate S is exposed). In the multi-step region B1b, the step portion B1bh and the step portion B1bi having different thickness sizes are disposed in the direction in which the thickness is reduced.

多階區域B1b包括具有h射線具有180°之相位差且光強度變為零之厚度Th(例如133.0nm)的階部B1bh、及具有對應於i射線之光強度變為零之厚度Ti(例如120.0nm)的階部B1bi。於多階區域B1b內，至均勻厚度區域(均勻區域)B1a之端部11t被設為厚度Tg，該端部11t至端部11sh之階部B1bh被設為厚度Th，該端部11sh至端部11si之階部B1bi成 為厚度Ti的方式設定多階區域B1b之厚度狀態。 The multi-step region B1b includes a step portion B1bh having a thickness Th (for example, 133.0 nm) in which the h-ray has a phase difference of 180° and a light intensity becomes zero, and a thickness Ti having a light intensity corresponding to the i-ray becoming zero (for example, Step B1bi of 120.0 nm). In the multi-step region B1b, the end portion 11t to the uniform thickness region (uniform region) B1a is set to the thickness Tg, and the step portion B1bh of the end portion 11t to the end portion 11sh is set to the thickness Th, and the end portion 11sh to the end Part of the 11si step B1bi into The thickness state of the multi-step region B1b is set in the manner of the thickness Ti.

具體而言，於多階區域B1b內，以厚度減少之距離B1b相對於相位移圖案11a之厚度T11之比成為-3≦B1b/T11≦3的方式設定。此處，所謂於多階區域B1b內厚度減少之距離B1b係俯視時之多階區域B1b之寬度尺寸。 Specifically, in the multi-step region B1b, the ratio of the distance-reduced distance B1b to the thickness T11 of the phase shift pattern 11a is set to be -3≦B1b/T11≦3. Here, the distance B1b in which the thickness is reduced in the multi-step region B1b is the width dimension of the multi-step region B1b in a plan view.

於圖1(a)、(b)中，該距離B1b被設為相位移圖案11a之厚度T11之端部11t至厚度為零之端部11u，且將自均勻厚度區域B1a朝向玻璃基板S之露出部分C之方向設為正，將與自相位移圖案11a之厚度T11之端部11t朝向玻璃基板S之露出部分C之方向相反方向設為負。再者，於圖1(a)、(b)中，將自端部11t朝向右側之情形設為正，將朝向左側之情形設為負。 In FIGS. 1(a) and 1(b), the distance B1b is set to the end portion 11t of the thickness T11 of the phase shift pattern 11a to the end portion 11u having a thickness of zero, and the self-uniform thickness region B1a is directed toward the glass substrate S. The direction of the exposed portion C is set to be positive, and is opposite to the direction opposite to the direction from the end portion 11t of the thickness T11 of the phase shift pattern 11a toward the exposed portion C of the glass substrate S. In addition, in FIGS. 1(a) and 1(b), the case where the end portion 11t faces the right side is set to be positive, and the case where the direction is to the left side is set to be negative.

根據該相位移光罩M1，藉由將上述波長區域之光、尤其是包含g射線(436nm)、h射線(405nm)、i射線(365nm)之複合波長用作曝光光，根據相位之反轉作用而以光強度成為最小之方式形成圖案輪廓，從而可使曝光圖案更加鮮明。而且，針對該等寬之複合波長之光，任一波長均可獲得相位移效果。藉此，可大幅提高圖案精度，可形成微細且高精度之圖案。相位移層例如可由碳氮氧化鉻系材料形成，且上述相位移層之厚度可分別沿圖案輪廓形狀而形成對i射線、h射線或g射線同時具有大致180°之相位差之厚度。此處所謂「大致180°」意指180°或180°附近，例如為180°±10°以下、或180°±5°以下。根據該相位移光罩，藉由使用上述波長區域之光可基於相位移效果而實現圖案精度之提高，從而可形成微細且高精度之圖案。藉此，可製造高畫質之平板顯示器。 According to the phase shift mask M1, the phase of the light in the wavelength region, in particular, a composite wavelength including g-ray (436 nm), h-ray (405 nm), and i-ray (365 nm) is used as the exposure light. The pattern is formed in such a manner that the light intensity is minimized, so that the exposure pattern can be made more vivid. Moreover, a phase shift effect can be obtained for any wavelength of the composite wavelength of the same width. Thereby, the pattern precision can be greatly improved, and a fine and highly precise pattern can be formed. The phase shifting layer may be formed, for example, of a chromium oxycarbonitride-based material, and the thickness of the phase shifting layer may form a thickness of a phase difference of approximately 180° for the i-ray, the h-ray or the g-ray, respectively, along the contour of the pattern. Here, "substantially 180°" means 180 degrees or 180 degrees, for example, 180 degrees ± 10 degrees or less, or 180 degrees ± 5 degrees or less. According to the phase shift mask, by using the light of the above-mentioned wavelength region, the pattern precision can be improved based on the phase shift effect, and a fine and highly precise pattern can be formed. Thereby, a high-quality flat panel display can be manufactured.

本實施形態之相位移光罩可構成為針對例如FPD用玻璃基板之圖案化用光罩。如下所述，於使用有該光罩之玻璃基板之圖案化中，曝光光可使用i射線、h射線及g射線之複合波長。 The phase shift mask of this embodiment can be configured as a mask for patterning, for example, a glass substrate for FPD. As described below, in the patterning of the glass substrate using the photomask, the exposure light can use a composite wavelength of i-ray, h-ray, and g-ray.

以下，對製造本實施形態之相位移光罩M1之相位移光罩之製造方法進行說明。 Hereinafter, a method of manufacturing the phase shift mask for manufacturing the phase shift mask M1 of the present embodiment will be described.

圖2係模式性地表示本實施形態之相位移光罩之製造方法之概略的步驟圖，圖3係表示相位移層之製造方法之步驟圖。 Fig. 2 is a schematic view showing a schematic diagram of a method of manufacturing a phase shift mask of the embodiment, and Fig. 3 is a step diagram showing a method of manufacturing a phase shift layer.

如圖2(j)所示，本實施形態之相位移光罩M1係於曝光區域之與外側接觸之周邊部具有位置對準用之對準標記，該對準標記由遮光層13a形成。再者，此處係形成遮光層作為對準標記用，但可無遮光層，即便為包含相位移層之半透過膜亦具有作為對準標記之功能。 As shown in Fig. 2(j), the phase shift mask M1 of the present embodiment has an alignment mark for alignment in the peripheral portion of the exposed region in contact with the outer side, and the alignment mark is formed by the light shielding layer 13a. Further, although a light shielding layer is formed as an alignment mark here, the light shielding layer may be omitted, and even a semitransmissive film including a phase shift layer has a function as an alignment mark.

首先，如圖2(a)所示，於玻璃基板S上形成以Cr為主成分之遮光層13。其次，如圖2(b)所示，於遮光層13上形成光阻層14。光阻層14可為正型亦可為負型。接著，如圖2(c)所示，藉由對光阻層14進行曝光及顯影，而於遮光層13上形成光阻圖案14a。光阻圖案14a係作為遮光層13之蝕刻遮罩而發揮功能，並可根據遮光層13之蝕刻圖案而適當決定形狀。於圖2(c)中，揭示有為了使遮光層遍及玻璃基板S之周緣之特定範圍內殘留而形成有光阻圖案14a之例。作為光阻層14，使用有液狀光阻劑。 First, as shown in FIG. 2(a), a light shielding layer 13 mainly composed of Cr is formed on the glass substrate S. Next, as shown in FIG. 2(b), a photoresist layer 14 is formed on the light shielding layer 13. The photoresist layer 14 may be either positive or negative. Next, as shown in FIG. 2(c), the photoresist pattern 14 is formed on the light shielding layer 13 by exposing and developing the photoresist layer 14. The photoresist pattern 14a functions as an etching mask of the light shielding layer 13, and can appropriately determine the shape according to the etching pattern of the light shielding layer 13. In FIG. 2(c), an example in which the photoresist pattern 14a is formed in order to allow the light shielding layer to remain in a specific range around the periphery of the glass substrate S is disclosed. As the photoresist layer 14, a liquid photoresist is used.

接著，如圖2(d)所示，隔著該光阻圖案14a使用第1蝕刻液對遮光層13進行濕式蝕刻。作為第1蝕刻液，可使用包含硝酸鈰銨之蝕刻液，例如，較佳為使用含有硝酸或過氯酸等酸之硝酸鈰銨。 Next, as shown in FIG. 2(d), the light shielding layer 13 is wet-etched using the first etching liquid through the photoresist pattern 14a. As the first etching liquid, an etching solution containing cerium ammonium nitrate can be used. For example, ammonium cerium nitrate containing an acid such as nitric acid or perchloric acid is preferably used.

藉此，於玻璃基板S上形成圖案化為特定形狀之遮光層13a。於遮光層13a之圖案化後，如圖2(e)所示，光阻圖案14a被去除。於去除光阻圖案14a時，例如可使用氫氧化鈉水溶液。 Thereby, the light shielding layer 13a patterned into a specific shape is formed on the glass substrate S. After patterning of the light shielding layer 13a, as shown in FIG. 2(e), the photoresist pattern 14a is removed. When the photoresist pattern 14a is removed, for example, an aqueous sodium hydroxide solution can be used.

其次，形成相位移層11。如圖2(f)所示，相位移層11係以被覆遮光層13a之方式形成於玻璃基板S上。 Next, the phase shift layer 11 is formed. As shown in FIG. 2(f), the phase shift layer 11 is formed on the glass substrate S so as to cover the light shielding layer 13a.

作為相位移層11，可形成均勻區域B1a、多階區域B1b中厚度Th之階部B1bh、厚度Ti之階部B1bi，且積層有各層之蝕刻速率不同之複 數層。 As the phase shift layer 11, a uniform region B1a, a step portion B1bh of the thickness Th in the multi-step region B1b, and a step portion B1bi of the thickness Ti can be formed, and the etch rate of each layer is different. Several layers.

相位移層11例如包含碳氮氧化鉻系材料，且以DC(Direct Current，直流)濺鍍法成膜。該情形時，作為處理氣體，可使用惰性氣體、氮化性氣體、及氧化性氣體之混合氣體、或氮化性氣體與氧化性氣體之混合氣體。成膜壓力例如可設為0.1Pa~0.5Pa。作為惰性氣體，可應用鹵素、尤其是氬。 The phase shift layer 11 contains, for example, a chromium oxycarbonitride-based material and is formed by a DC (Direct Current) sputtering method. In this case, as the processing gas, a mixed gas of an inert gas, a nitriding gas, and an oxidizing gas, or a mixed gas of a nitriding gas and an oxidizing gas can be used. The film formation pressure can be, for example, 0.1 Pa to 0.5 Pa. As the inert gas, halogen, in particular argon, can be applied.

作為氧化性氣體，可使用CO、CO2、NO、N2O、NO2、O2等。作為氮化性氣體，可使用NO、N2O、NO2、N2等。作為惰性氣體，可使用Ar、He、或Xe等。典型而言，作為惰性氣體，使用有Ar。再者，於上述混合氣體中，亦可進而包含CH4等碳化性氣體。 As the oxidizing gas, CO, CO 2 , NO, N 2 O, NO 2 , O 2 or the like can be used. As the nitriding gas, NO, N 2 O, NO 2 , N 2 or the like can be used. As the inert gas, Ar, He, or Xe or the like can be used. Typically, as an inert gas, Ar is used. Further, the mixed gas may further contain a carbonizable gas such as CH 4 .

詳細而言，相位移層11係由蝕刻速率不同之層積層而形成為多層，且如下所述控制利用蝕刻之側面傾斜形成，以可形成多階區域B1b之方式成膜。因此，將混合氣體中之氮化性氣體及氧化性氣體之流量(濃度)設為重要之參數，決定相位移層11之蝕刻速率、及光學性質(透過率、折射率等)。藉由於成膜時調整氣體條件，而可使相位移層11中之各層蝕刻速率最佳化。此處，作為氧化性氣體，可列舉二氧化碳。 Specifically, the phase shift layer 11 is formed in a plurality of layers by a laminated layer having different etching rates, and is formed by tilting the side surface of the etching as described below, and forming a film so as to form the multi-step region B1b. Therefore, the flow rate (concentration) of the nitriding gas and the oxidizing gas in the mixed gas is an important parameter, and the etching rate and optical properties (transmittance, refractive index, and the like) of the phase shift layer 11 are determined. The etch rate of each layer in the phase shift layer 11 can be optimized by adjusting the gas conditions during film formation. Here, as the oxidizing gas, carbon dioxide is exemplified.

相位移層11如下所述對應於均勻區域B1a、階部B1bh及階部B1bi，可積層為至少3層、或5層、或其以上之多層。 The phase shift layer 11 corresponds to the uniform region B1a, the step portion B1bh, and the step portion B1bi as described below, and the stackable layer is a multilayer of at least 3 layers, or 5 layers, or more.

相位移層11之均勻區域B1a之厚度T11係於端部區域B1內，被設為可對位於300nm以上且500nm以下之波長區域之g射線、h射線及i射線具有180°之相位差的厚度。被賦予180°之相位差之光係藉由相位反轉，利用與未透過相位移層11之光之間之干涉作用消除該光之強度。根據此種相位移效果，形成光強度成為最小(例如零)之區域故而曝光圖案鮮明，從而可高精度地形成微細圖案。相位移層11如下所述可對應於厚度Tg之均勻區域B1a、厚度Th之階部B1bh、及厚度Ti之階 部B1bi，設定各層之膜厚。 The thickness T11 of the uniform region B1a of the phase shift layer 11 is in the end portion B1, and is set to have a thickness of 180° with respect to g-rays, h-rays, and i-rays in a wavelength region of 300 nm or more and 500 nm or less. . The light phase imparted with a phase difference of 180° is phase-reversed, and the intensity of the light is eliminated by interference with light that is not transmitted through the phase shift layer 11. According to such a phase shift effect, a region in which the light intensity is the smallest (for example, zero) is formed, so that the exposure pattern is sharp, and the fine pattern can be formed with high precision. The phase shift layer 11 can correspond to the uniform region B1a of the thickness Tg, the step portion B1bh of the thickness Th, and the step of the thickness Ti as described below. In the portion B1bi, the film thickness of each layer is set.

於本實施形態中，上述波長區域之光為i射線(波長365nm)、h射線(波長405nm)、及g射線(波長436nm)之複合光(多色光)，以可對設為目標之波長之光賦予180°之相位差的厚度形成相位移層11。上述設為目標之波長之光可為i射線、h射線、及g射線中之任一者，或者亦可為該等以外之波長區域之光。理應反轉相位之光越為短波長越可形成微細之圖案。 In the present embodiment, the light in the wavelength region is a composite light (polychromatic light) of an i-ray (wavelength: 365 nm), an h-ray (wavelength: 405 nm), and a g-ray (wavelength: 436 nm), which can be set to a target wavelength. The light imparts a phase difference of 180° to form the phase shift layer 11. The light having the wavelength of the target described above may be any one of an i-ray, an h-ray, and a g-ray, or may be light of a wavelength region other than the above. The thinner the wavelength of the light that should be reversed, the finer the pattern.

相位移層11之膜厚較佳為於透明基板S之面內於曝光區域內除邊界部分B1以外至少均勻。 The film thickness of the phase shift layer 11 is preferably at least uniform in the area of the transparent substrate S except for the boundary portion B1 in the exposed region.

相位移層11之反射率例如設為40%以下。藉此，於使用有該相位移光罩之被處理基板(平板基板或半導體基板)之圖案化時難以形成重影圖案，從而可確保良好之圖案精度。 The reflectance of the phase shift layer 11 is, for example, 40% or less. Thereby, it is difficult to form a ghost pattern when patterning the substrate to be processed (a flat substrate or a semiconductor substrate) using the phase shift mask, and it is possible to ensure good pattern accuracy.

相位移層11之透過率及反射率可根據成膜時之氣體條件而任意調整。根據上述混合氣體條件，關於i射線可獲得1%以上且20%以下之透過率、及40%以下之反射率。透過率亦可為0.5%以上。 The transmittance and reflectance of the phase shift layer 11 can be arbitrarily adjusted according to the gas conditions at the time of film formation. According to the mixed gas conditions, a transmittance of 1% or more and 20% or less and a reflectance of 40% or less can be obtained for the i-ray. The transmittance can also be 0.5% or more.

進而，作為成膜為多階之相位移層11之成膜條件，藉由於使各階成膜時設定各成膜氛圍氣體中氧化性氣體之流量比，而設定均勻區域B1a端部及多階區域B1b之形狀。 Further, as a film forming condition of the phase shifting layer 11 in which the film formation is multi-step, the end portion and the multi-step region of the uniform region B1a are set by setting the flow ratio of the oxidizing gas in each of the film forming atmospheres at the time of film formation in each step. The shape of B1b.

藉由分別調節相位移層11之各階成膜時之氧化性氣體之流量，而分別控制相位移層11之各階之蝕刻狀態，從而以具有均勻區域B1a、階部B1bh及階部B1bi之方式設定多階區域B1b之形狀。 By separately adjusting the flow rate of the oxidizing gas at the time of film formation of each phase of the phase shifting layer 11, the etching states of the respective stages of the phase shifting layer 11 are respectively controlled, thereby setting the uniform region B1a, the step B1bh, and the step B1bi. The shape of the multi-step region B1b.

於使成膜為多階之相位移層11之各階成膜時，作為各成膜氛圍之成膜氣體包含惰性氣體、氮化性氣體及氧化性氣體、或氮化性氣體與氧化性氣體，相對於總氣體流量而氧化性氣體之流量比選自3.68%~24.89%之範圍，並且藉由減少氧化性氣體之流量比，而使相位移圖案11a中均勻區域B1a、階部B1bh及階部B1bi之側面之傾斜增大，並且藉 由增加氧化性氣體之流量比，而使階部B1bh與階部B1bi之側面之傾斜減小。藉由如此針對每層使氧化性氣體變化而可決定傾斜區域。 When the film formation is performed at each order of the multi-step phase shift layer 11, the film forming gas for each film forming atmosphere includes an inert gas, a nitriding gas, an oxidizing gas, or a nitriding gas and an oxidizing gas. The flow ratio of the oxidizing gas is selected from the range of 3.68% to 24.89% with respect to the total gas flow rate, and the uniform region B1a, the step B1bh, and the step portion in the phase shift pattern 11a are made by reducing the flow ratio of the oxidizing gas. The slope of the side of B1bi increases, and borrows The inclination of the side faces of the step portion B1bh and the step portion B1bi is reduced by increasing the flow ratio of the oxidizing gas. The inclined region can be determined by changing the oxidizing gas for each layer in this manner.

根據氧化性氣體之流量比，如下所述，可於蝕刻時控制均勻區域B1a、階部B1bh及階部B1bi之側面之傾斜狀態，控制對應於均勻區域B1a、階部B1bh及階部B1bi之多層膜之積層膜厚，於將包含g射線(436nm)、h射線(405nm)、i射線(365nm)之複合波長用作曝光光時，根據相位之反轉作用而以光強度成為最小之方式形成圖案輪廓，從而可以成為使曝光圖案更鮮明之均勻區域B1a、階部B1bh及階部B1bi之寬度尺寸及厚度尺寸的方式設定邊界部分B1之均勻區域B1a與多階區域B1b之形狀。 According to the flow ratio of the oxidizing gas, as described below, the inclined state of the side faces of the uniform region B1a, the step B1bh, and the step B1bi can be controlled at the time of etching, and the multilayer corresponding to the uniform region B1a, the step B1bh, and the step B1bi can be controlled. The film thickness of the film is formed by using a composite wavelength including g-ray (436 nm), h-ray (405 nm), and i-ray (365 nm) as exposure light, and the light intensity is minimized according to the phase reversal action. The outline of the pattern can be set to the shape of the uniform region B1a and the multi-step region B1b of the boundary portion B1 in such a manner that the width and thickness of the uniform region B1a, the step portion B1bh, and the step portion B1bi of the exposure pattern are more vivid.

若舉例，則成膜壓力可設為0.4Pa，且可將濺鍍成膜時之混合氣體之流量比控制為Ar：N2：CO2=71：120：7.3~71：120：63.3。藉此，以上述傾斜區域之膜厚於上述波長範圍之複合波長之光中具有與光強度變為零之厚度對應之複數點的方式控制膜厚之減少程度，從而可將上述波長範圍之複合波長同時用於曝光。 For example, the film formation pressure can be set to 0.4 Pa, and the flow ratio of the mixed gas at the time of sputtering film formation can be controlled to Ar:N 2 :CO 2 =71:120:7.3 to 71:120:63.3. Thereby, the degree of reduction of the film thickness is controlled such that the film having the thickness of the composite region having the thickness of the inclined region in the wavelength range has a complex point corresponding to the thickness at which the light intensity becomes zero, so that the composite of the above wavelength ranges can be performed. The wavelength is used for exposure at the same time.

接著，如圖2(g)所示，於相位移層11上形成光阻層14。其次，如圖2(h)所示，藉由對光阻層14進行曝光及顯影，而於相位移層11上形成光阻圖案14a。光阻圖案14a係作為相位移層11之蝕刻遮罩而發揮功能，並可根據相位移層11之蝕刻圖案而適當決定形狀。 Next, as shown in FIG. 2(g), a photoresist layer 14 is formed on the phase shift layer 11. Next, as shown in FIG. 2(h), a photoresist pattern 14a is formed on the phase shift layer 11 by exposing and developing the photoresist layer 14. The photoresist pattern 14a functions as an etching mask of the phase shift layer 11, and can appropriately determine the shape according to the etching pattern of the phase shift layer 11.

接著，相位移層11被蝕刻為特定之圖案形狀。藉此，如圖2(i)所示，於玻璃基板S上形成圖案化為特定形狀之相位移圖案11a及玻璃基板S露出之部分C。 Next, the phase shift layer 11 is etched into a specific pattern shape. Thereby, as shown in FIG. 2(i), the phase shift pattern 11a patterned in a specific shape and the portion C in which the glass substrate S is exposed are formed on the glass substrate S.

對相位移層11之利用蝕刻而實現的具有多階區域B1b之相位移圖案11a的形成更詳細地進行說明。 The formation of the phase shift pattern 11a having the multi-step region B1b by the etching of the phase shift layer 11 will be described in more detail.

具體而言，如圖3(a)所示，於被設為多層膜之相位移層11上形成光阻層14。相位移層11自基板S側起積層有對應於階部B1bi之下層 11d、對應於階部B1bh之中層11c、對應於均勻區域B1a之上層11b。 Specifically, as shown in FIG. 3(a), the photoresist layer 14 is formed on the phase shift layer 11 which is a multilayer film. The phase shift layer 11 is laminated from the side of the substrate S to correspond to the layer below the step B1bi. 11d corresponds to the layer 11c in the step B1bh and corresponds to the layer 11b above the uniform region B1a.

下層11d係以對應於階部B1bi之方式具有厚度Ti，並且於該3層中具有最小之蝕刻速率。 The lower layer 11d has a thickness Ti in a manner corresponding to the step B1bi, and has a minimum etching rate in the three layers.

中層11c係以對應於階部B1bh之方式具有厚度(Th-Ti)，並且具有大於下層11d之蝕刻速率。又，上層1b具有厚度(Tg-Th)，並且具有大於中層11c之蝕刻速率。 The middle layer 11c has a thickness (Th-Ti) in a manner corresponding to the step B1bh, and has an etching rate greater than that of the lower layer 11d. Further, the upper layer 1b has a thickness (Tg-Th) and has an etching rate greater than that of the intermediate layer 11c.

下層11d、中層11c、上層11b之蝕刻速率係對應於側面之傾斜形狀、及階差之寬度尺寸B1bh及寬度尺寸B1bi之大小而設定。 The etching rate of the lower layer 11d, the intermediate layer 11c, and the upper layer 11b is set corresponding to the inclined shape of the side surface and the width dimension B1bh and the width dimension B1bi of the step.

如圖3(b)所示，藉由對光阻層14進行曝光及顯影而形成光阻圖案14a。 As shown in FIG. 3(b), the photoresist pattern 14a is formed by exposing and developing the photoresist layer 14.

其次，藉由將形成光阻圖案14a而去除光阻層14後之部分的相位移層11暴露於蝕刻液中，該部分之上層11b受到蝕刻，而如圖3(c)所示，俯視時成為沿光阻圖案14a之平面輪廓形狀，同時形成11b1、11c1、11d1。 Next, the phase shift layer 11 of the portion after the photoresist layer 14 is removed by exposing the photoresist pattern 14a is exposed to the etching liquid, and the portion of the upper layer 11b is etched, as shown in FIG. 3(c). The planar profile shape along the photoresist pattern 14a is formed while 11b1, 11c1, and 11d1 are formed.

此處，藉由以上層11b、中層11c、下層11d之蝕刻速率依序變小之方式設定，而於相位移層11受到蝕刻時，根據各自之蝕刻速率之差異而形成階差，從而可獲得如圖3(c)般包含上層11b1、中層11c1、下層11d1之形狀。 Here, the etching rate of the upper layer 11b, the middle layer 11c, and the lower layer 11d is set to be smaller in order, and when the phase shift layer 11 is etched, a step is formed according to the difference in the respective etching rates, thereby obtaining The shape of the upper layer 11b1, the middle layer 11c1, and the lower layer 11d1 is included as shown in Fig. 3(c).

於相位移層11a之圖案化後，如圖3(d)、圖2(j)所示，光阻圖案14a被去除。於去除光阻圖案14a時，例如可使用氫氧化鈉水溶液。 After patterning of the phase shift layer 11a, as shown in FIGS. 3(d) and 2(j), the photoresist pattern 14a is removed. When the photoresist pattern 14a is removed, for example, an aqueous sodium hydroxide solution can be used.

於本實施形態中，於形成相位移層11之步驟中，根據氧化性氣體之流量比而可控制邊界部分B1之多階區域B1b內之厚度自固定值T11多階地減少之距離B1bh與距離B1bi，藉此，相位移圖案11a之輪廓可以成為具有特定之寬度尺寸之多階形狀之方式形成，因此，可形成具有於i射線、h射線、g射線之複合波長之光中與光強度變為零之厚度對應的均勻區域B1a、階部B1bh及階部B1bi的邊界部分B1。即，可更 準確地設定相位移圖案11a之線寬、即光罩之線寬。藉此，可製造更高精細化且利用濕式處理形成之光罩。 In the present embodiment, in the step of forming the phase shift layer 11, the distance B1bh and the distance which are multi-steply reduced from the fixed value T11 by the thickness in the multi-step region B1b of the boundary portion B1 can be controlled according to the flow ratio of the oxidizing gas. B1bi, whereby the contour of the phase shift pattern 11a can be formed in a multi-step shape having a specific width dimension, and therefore, light having a composite wavelength of i-rays, h-rays, and g-rays can be formed and light intensity is changed. A uniform region B1a, a step B1bh, and a boundary portion B1 of the step B1bi corresponding to a thickness of zero. That is, it can be more The line width of the phase shift pattern 11a, that is, the line width of the mask, is accurately set. Thereby, it is possible to manufacture a photomask which is more refined and formed by wet processing.

以下，對使用有本實施形態之相位移光罩M1的平板顯示器之製造方法進行說明。 Hereinafter, a method of manufacturing a flat panel display using the phase shift mask M1 of the present embodiment will be described.

首先，於形成有絕緣層及配線層之玻璃基板之表面形成光阻層。於形成光阻層時，例如使用旋轉塗佈機。光阻層係於實施加熱(烘焙)處理後，實施使用有相位移光罩M1之曝光處理。於曝光步驟中，接近光阻層而配置相位移光罩M1。然後，經由相位移光罩M1對玻璃基板之表面照射包含300nm以上且500nm以下之g射線(436nm)、h射線(405nm)、i射線(365nm)之複合波長。於本實施形態中，對上述複合波長之光使用g射線、h射線、及i射線之複合光。 First, a photoresist layer is formed on the surface of a glass substrate on which an insulating layer and a wiring layer are formed. When a photoresist layer is formed, for example, a spin coater is used. The photoresist layer is subjected to an exposure treatment using a phase shift mask M1 after performing a heating (baking) process. In the exposure step, the phase shift mask M1 is disposed close to the photoresist layer. Then, the surface of the glass substrate is irradiated with a composite wavelength of g-rays (436 nm), h-rays (405 nm), and i-rays (365 nm) of 300 nm or more and 500 nm or less via the phase shift mask M1. In the present embodiment, composite light of g-rays, h-rays, and i-rays is used for the light of the composite wavelength.

藉此，將對應於相位移光罩M1之光罩圖案之曝光圖案轉印至光阻層。 Thereby, the exposure pattern corresponding to the mask pattern of the phase shift mask M1 is transferred to the photoresist layer.

根據本實施形態，相位移光罩M1具有可對300nm以上且500nm以下之波長區域之複合光具有180°之相位差的相位移層11a。因此，根據上述製造方法，藉由使用上述波長區域之光而可實現基於相位移效果之圖案精度之提高，進而可使焦點深度變深，可增強光之干涉而獲得使光強度為0、或接近於0之區域，故而可形成微細且高精度之圖案。藉此，可製造高畫質之平板顯示器。 According to the present embodiment, the phase shift mask M1 has the phase shift layer 11a which has a phase difference of 180° with respect to the composite light of a wavelength region of 300 nm or more and 500 nm or less. Therefore, according to the above manufacturing method, by using the light in the wavelength region, the pattern precision based on the phase shift effect can be improved, and the depth of focus can be deepened, and the light interference can be enhanced to obtain the light intensity of 0, or Close to the area of 0, a fine and highly precise pattern can be formed. Thereby, a high-quality flat panel display can be manufactured.

根據本發明者等人之實驗，可確認，於使用不具有該相位移圖案11a之光罩進行曝光之情形時，對設為目標之線寬(2±0.5μm)產生30%以上之圖案寬度之偏差，但於使用本實施形態之相位移光罩M1進行曝光之情形時，可抑制為7%左右之偏差。又，可使曝光能量效率提高15%。 According to experiments by the inventors of the present invention, it has been confirmed that when exposure is performed using a photomask having no phase shift pattern 11a, a pattern width of 30% or more is generated for a target line width (2±0.5 μm). However, when the exposure is performed using the phase shift mask M1 of the present embodiment, the deviation of about 7% can be suppressed. Moreover, the exposure energy efficiency can be improved by 15%.

其次，對形成本實施形態之相位移層11並利用蝕刻形成具有多階區域B1b之相位移圖案11a之其他例更詳細地進行說明。 Next, another example in which the phase shift layer 11 of the present embodiment is formed and the phase shift pattern 11a having the multi-step region B1b is formed by etching will be described in more detail.

該例與上述例不同之方面在於相位移層11被設為更多之5層。 The difference between this example and the above example is that the phase shift layer 11 is set to be more than five layers.

具體而言，如圖4(a)所示，作為相位移層11，自基板S側積層有下層11i、下硬層11h、中層11g、中硬層11f、上層11e。然後，於該被設為多層膜之相位移層11上形成光阻層14。 Specifically, as shown in FIG. 4(a), as the phase shift layer 11, a lower layer 11i, a lower hard layer 11h, a middle layer 11g, a middle hard layer 11f, and an upper layer 11e are laminated from the substrate S side. Then, a photoresist layer 14 is formed on the phase shift layer 11 which is a multilayer film.

於該例中，下層11i及下硬層11h對應於階部B1bi，中層11g及中硬層11f對應於階部B1bh，上層11e對應於均勻區域B1a。 In this example, the lower layer 11i and the lower hard layer 11h correspond to the step B1bi, the middle layer 11g and the middle hard layer 11f correspond to the step B1bh, and the upper layer 11e corresponds to the uniform region B1a.

即，下層11i及下硬層11h具有厚度Ti，中層11g及中硬層11f具有厚度(Th-Ti)，上層11e具有厚度(Tg-Th)。 That is, the lower layer 11i and the lower hard layer 11h have a thickness Ti, the middle layer 11g and the middle hard layer 11f have a thickness (Th-Ti), and the upper layer 11e has a thickness (Tg-Th).

又，下硬層11h及中硬層11f相對於其他3層具有最小之蝕刻速率。 Further, the lower hard layer 11h and the middle hard layer 11f have the smallest etching rate with respect to the other three layers.

下硬層11h及中硬層11f如下所述具有將蝕刻速率變更之厚度即可，較理想為儘可能較薄。 The lower hard layer 11h and the intermediate hard layer 11f may have a thickness that changes the etching rate as described below, and are preferably as thin as possible.

下層11i係於該下層11i、中層11g、上層11e中具有最小之蝕刻速率。 The lower layer 11i has a minimum etching rate in the lower layer 11i, the middle layer 11g, and the upper layer 11e.

中層11g具有大於下層11i之蝕刻速率。又，上層11e具有小於中層11g之蝕刻速率。 The middle layer 11g has an etching rate greater than that of the lower layer 11i. Further, the upper layer 11e has an etching rate smaller than that of the intermediate layer 11g.

下層11i、中層11g、上層11e之蝕刻速率係對應於側面之傾斜形狀、及階差之寬度尺寸B1bh及寬度尺寸B1bi之大小而設定其比。 The etching rate of the lower layer 11i, the intermediate layer 11g, and the upper layer 11e is set in accordance with the inclined shape of the side surface and the width dimension B1bh and the width dimension B1bi of the step.

如圖4(b)所示，藉由對光阻層14進行曝光及顯影而形成光阻圖案14a。 As shown in FIG. 4(b), the photoresist pattern 14a is formed by exposing and developing the photoresist layer 14.

其次，藉由將形成光阻圖案14a而去除光阻層14後之部分之相位移層11暴露於蝕刻液中，11e、11f、11g、11h、11i同時受到蝕刻，根據各層之蝕刻速率差異而可獲得如圖4(c)所示之形狀。 Next, the phase shifting layer 11 of the portion after the photoresist layer 14 is removed by exposing the photoresist pattern 14a is exposed to the etching liquid, and 11e, 11f, 11g, 11h, and 11i are simultaneously etched according to the etching rate difference of each layer. A shape as shown in Fig. 4(c) can be obtained.

此處，中硬層11f、下硬層11h之蝕刻速率小於上層11e、中層11g、下層11i之蝕刻速率，故而該等作為蝕刻速率變更層發揮作用。因此，於進行位於較上層11e更下側之層之蝕刻時，將位於中硬層11f 之上側之上層11e自側方蝕刻，與中硬層11f相比向均勻區域B1a裏側凹下而可形成階差B1bh。又，於進行位於較中層11g更下側之層之蝕刻時，將位於下硬層11h之上側之中層11g自側方蝕刻，與下硬層11h相比向均勻區域B1a裏側凹下而可形成階差B1bi。 Here, since the etching rates of the intermediate hard layer 11f and the lower hard layer 11h are smaller than the etching rates of the upper layer 11e, the middle layer 11g, and the lower layer 11i, these functions as an etching rate changing layer. Therefore, when etching the layer located on the lower side of the upper layer 11e, it will be located in the middle hard layer 11f. The upper side upper layer 11e is etched from the side, and is recessed toward the inner side of the uniform region B1a as compared with the middle hard layer 11f to form a step B1bh. Further, in the etching of the layer located on the lower side of the intermediate layer 11g, the layer 11g is etched from the side on the upper side of the lower hard layer 11h, and is recessed toward the inner side of the uniform region B1a as compared with the lower hard layer 11h. The step B1bi.

於相位移層11a之圖案化後，圖4(d)，光阻圖案14a被去除。於去除光阻圖案14a時，例如可使用氫氧化鈉水溶液。 After patterning of the phase shift layer 11a, the photoresist pattern 14a is removed in FIG. 4(d). When the photoresist pattern 14a is removed, for example, an aqueous sodium hydroxide solution can be used.

根據該例，藉由以上層11e、中層11g、下層11i之蝕刻速率依序變大之方式設定，而於中層11g受到蝕刻時，上層11e亦受到蝕刻，又，於下層11i受到蝕刻時，上層11f及中層11g亦受到蝕刻，從而如圖4(d)所示，形成階部B1bh與階部B1bi。 According to this example, the etching rate of the upper layer 11e, the middle layer 11g, and the lower layer 11i is set to be larger, and when the middle layer 11g is etched, the upper layer 11e is also etched, and when the lower layer 11i is etched, the upper layer is etched. 11f and the intermediate layer 11g are also etched to form the step B1bh and the step B1bi as shown in Fig. 4(d).

於本實施形態中，如圖1~圖4所示，根據形成相位移層11時之氧化性氣體之流量比之設定而控制蝕刻速率，藉此，可形成為多階區域B1b之側面大致垂直、即側面未傾斜。該情形時，可使成為對應於h射線、i射線之厚度的階部B1bh、階部B1bi位於更狹小之範圍，因此可更進一步地提高曝光圖案形狀之準確性。 In the present embodiment, as shown in FIGS. 1 to 4, the etching rate is controlled in accordance with the setting of the flow rate ratio of the oxidizing gas when the phase shift layer 11 is formed, whereby the side surface of the multi-step region B1b can be formed to be substantially vertical. That is, the side is not inclined. In this case, the step portion B1bh and the step portion B1bi corresponding to the thickness of the h-ray and the i-ray can be located in a narrower range, so that the accuracy of the shape of the exposure pattern can be further improved.

<第2實施形態> <Second embodiment>

以下，基於圖式對本發明之相位移光罩之製造方法之第2實施形態進行說明。 Hereinafter, a second embodiment of the method for manufacturing a phase shift mask of the present invention will be described based on the drawings.

圖5係表示本實施形態之相位移光罩之模式剖面圖，圖6係模式性地表示本實施形態之相位移光罩之製造方法之步驟圖，於圖中，M2為相位移光罩。再者，於圖5、圖6中，對與圖1~圖4對應之部分標註同一符號而省略其說明。 Fig. 5 is a schematic cross-sectional view showing a phase shift mask of the embodiment, and Fig. 6 is a view schematically showing a step of a method for manufacturing a phase shift mask according to the embodiment. In the figure, M2 is a phase shift mask. In addition, in FIGS. 5 and 6, the same reference numerals are given to the portions corresponding to those in FIGS. 1 to 4, and the description thereof is omitted.

如圖5所示，本實施形態之相位移光罩M2設置於玻璃基板(透明基板)S表面，且被設為可具有180°之相位差之相位移圖案11a位於下側、遮光圖案13b介隔蝕刻終止圖案12b位於其上側的所謂下置型之相位移光罩。 As shown in FIG. 5, the phase shift mask M2 of the present embodiment is disposed on the surface of the glass substrate (transparent substrate) S, and is provided with a phase shift pattern 11a having a phase difference of 180° on the lower side, and a light blocking pattern 13b. A so-called under-type phase shift mask having an etch stop pattern 12b on its upper side.

如圖5及圖6(g)所示，相位移光罩M2係於曝光圖案所形成之曝光區域內，具有俯視時為玻璃基板S之露出部分C與相位移圖案11a之邊界部分B1、及於相位移圖案11a之上側介隔蝕刻終止圖案12b而形成有遮光圖案13b之遮光區域B2。於遮光區域B2內，相位移圖案11a之厚度被設為固定值Tg，並且以俯視時包圍成為該曝光圖案之遮光區域B2之方式存在僅使相位移圖案11a成膜之邊界部分B1。於邊界部分B1，均勻厚度區域B1a位於遮光區域B2側，多階區域B1b位於玻璃基板S之露出部分C側。 As shown in FIG. 5 and FIG. 6(g), the phase shift mask M2 is in the exposure region formed by the exposure pattern, and has a boundary portion B1 between the exposed portion C of the glass substrate S and the phase shift pattern 11a in plan view. The light-shielding region B2 of the light-shielding pattern 13b is formed by interposing the etching termination pattern 12b on the upper side of the phase shift pattern 11a. In the light-shielding region B2, the thickness of the phase shift pattern 11a is set to a fixed value Tg, and a boundary portion B1 in which only the phase shift pattern 11a is formed is formed so as to surround the light-shielding region B2 which is the exposure pattern in plan view. In the boundary portion B1, the uniform thickness region B1a is located on the side of the light-shielding region B2, and the multi-step region B1b is located on the exposed portion C side of the glass substrate S.

如圖6(a)所示，本發明之相位移空白光罩MB係藉由於玻璃基板S上使用DC濺鍍法，使以Cr為主成分之相位移層11、以Ni為主成分之蝕刻終止層12及以Cr為主成分之遮光層13依序成膜而製造。該等各層係於玻璃基板S面內方向上，以均勻厚度成膜。 As shown in FIG. 6(a), the phase shift blank mask MB of the present invention is formed by etching a phase shift layer 11 mainly composed of Cr and using Ni as a main component by using a DC sputtering method on the glass substrate S. The termination layer 12 and the light shielding layer 13 mainly composed of Cr are sequentially formed into a film. These layers are formed in a plane having a uniform thickness in the in-plane direction of the glass substrate S.

於該相位移空白光罩MB之各相之成膜時，相位移層11之成膜時之成膜條件被設為上述實施形態中之成膜條件，藉由設定成膜時之膜厚及設定氛圍氣體中之氧化性氣體之流量比，而可於作為下一步驟之蝕刻時控制多階區域B1b之多階形狀。 When filming the phases of the phase shift blank mask MB, the film formation conditions at the time of film formation of the phase shift layer 11 are set as the film formation conditions in the above embodiment, and the film thickness at the time of film formation is set. The flow ratio of the oxidizing gas in the atmosphere gas is set, and the multi-step shape of the multi-step region B1b can be controlled at the time of etching as the next step.

以下，對由上述相位移空白光罩MB製造相位移光罩M2之相位移光罩之製造方法進行說明。 Hereinafter, a method of manufacturing a phase shift mask in which the phase shift mask M2 is manufactured by the phase shift blank mask MB will be described.

其次，如圖6(b)所示，於作為相位移空白光罩MB之最上層之遮光層13上形成光阻層14。光阻層14可為正型亦可為負型。作為光阻層14，使用有液狀光阻劑。 Next, as shown in FIG. 6(b), a photoresist layer 14 is formed on the light shielding layer 13 which is the uppermost layer of the phase shift blank mask MB. The photoresist layer 14 may be either positive or negative. As the photoresist layer 14, a liquid photoresist is used.

接著，如圖6(c)所示，藉由對光阻層14進行曝光及顯影而於遮光層13上形成光阻圖案14a。光阻圖案14a係作為遮光層13之蝕刻遮罩而發揮功能，並可根據遮光層13之蝕刻圖案而適當決定形狀。作為一例，於相位移區域PS內，設定為具有對應於形成之相位移圖案之開口寬度尺寸的開口寬度之形狀。 Next, as shown in FIG. 6(c), the photoresist pattern 14a is formed on the light shielding layer 13 by exposing and developing the photoresist layer 14. The photoresist pattern 14a functions as an etching mask of the light shielding layer 13, and can appropriately determine the shape according to the etching pattern of the light shielding layer 13. As an example, in the phase shift region PS, a shape having an opening width corresponding to the opening width dimension of the formed phase shift pattern is set.

其次，如圖6(d)所示，隔著該光阻圖案14a使用第1蝕刻液對遮光層13進行濕式蝕刻。作為第1蝕刻液，可使用包含硝酸鈰銨之蝕刻液，例如，較佳為使用含有硝酸或過氯酸等酸之硝酸鈰銨。此處，蝕刻終止層12對第1蝕刻液具有較高之耐受性，故而僅遮光層13經圖案化而形成遮光圖案13a。遮光圖案13a被設為具有對應於光阻圖案14a之開口寬度之形狀。 Next, as shown in FIG. 6(d), the light shielding layer 13 is wet-etched using the first etching liquid through the photoresist pattern 14a. As the first etching liquid, an etching solution containing cerium ammonium nitrate can be used. For example, ammonium cerium nitrate containing an acid such as nitric acid or perchloric acid is preferably used. Here, since the etching stopper layer 12 has high resistance to the first etching liquid, only the light shielding layer 13 is patterned to form the light shielding pattern 13a. The light shielding pattern 13a is set to have a shape corresponding to the opening width of the photoresist pattern 14a.

其次，如圖6(e)所示，隔著上述光阻圖案14a使用第2蝕刻液對蝕刻終止層12進行濕式蝕刻。作為第2蝕刻液，適宜使用硝酸中添加選自乙酸、過氯酸、過氧化氫水及鹽酸中之至少1種而成者。此處，遮光層13及相位移層11對第2蝕刻液具有較高之耐受性，故而僅蝕刻終止層12經圖案化而形成蝕刻終止圖案12a。蝕刻終止圖案12a被設為具有對應於遮光圖案13a及光阻圖案14a之開口寬度尺寸之開口寬度的形狀。 Next, as shown in FIG. 6(e), the etching stopper layer 12 is wet-etched using the second etching liquid through the photoresist pattern 14a. As the second etching liquid, at least one selected from the group consisting of acetic acid, perchloric acid, hydrogen peroxide water, and hydrochloric acid is preferably used. Here, the light shielding layer 13 and the phase shift layer 11 have high resistance to the second etching liquid, and therefore only the etching stopper layer 12 is patterned to form the etching termination pattern 12a. The etching termination pattern 12a is set to have a shape corresponding to the opening width of the opening width dimension of the light shielding pattern 13a and the photoresist pattern 14a.

其次，如圖6(f)所示，隔著光阻圖案14a、即於未去除光阻圖案14a之狀態下，使用第1蝕刻液對相位移層11進行濕式蝕刻。此處，遮光圖案13a係由與相位移層11相同之Cr系材料所構成，遮光圖案13a之側面露出，故而相位移層11經圖案化而形成相位移圖案11a。同時，形成玻璃基板S露出之部分C。 Next, as shown in FIG. 6(f), the phase shift layer 11 is wet-etched using the first etching liquid in a state where the photoresist pattern 14a is not removed, that is, the photoresist pattern 14a is not removed. Here, the light-shielding pattern 13a is made of the same Cr material as the phase shift layer 11, and the side surface of the light-shielding pattern 13a is exposed, so that the phase shift layer 11 is patterned to form the phase shift pattern 11a. At the same time, a portion C where the glass substrate S is exposed is formed.

此時，如圖3或圖4所示，形成為蝕刻速率不同之多層的相位移層11受到蝕刻，藉此，如圖5中揭示詳細情況般，成為形成有具有階部B1bh、階部B1bi之多階區域B1b之相位移圖案11a。同時，遮光圖案13a亦進而受到側面蝕刻，從而形成具有遮光區域B2之遮光圖案13b，該遮光區域B2具有大於相位移圖案11a之開口寬度尺寸之開口寬度。 At this time, as shown in FIG. 3 or FIG. 4, the phase shift layer 11 formed in a plurality of layers having different etching rates is etched, whereby, as shown in detail in FIG. 5, the step B1bh and the step B1bi are formed. The phase shift pattern 11a of the multi-step region B1b. At the same time, the light-shielding pattern 13a is further subjected to side etching to form a light-shielding pattern 13b having a light-shielding region B2 having an opening width larger than the opening width dimension of the phase-shift pattern 11a.

其次，使用第2蝕刻液對自遮光圖案13b之側面露出之蝕刻終止層12a進行濕式蝕刻，形成具有對應於遮光圖案13b之開口寬度尺寸之 開口寬度之蝕刻終止圖案12b，並去除光阻圖案14a。於去除光阻圖案14a時，可使用公知之光阻劑剝離液，故而此處省略詳細之說明。 Next, the etching stopper layer 12a exposed from the side surface of the light-shielding pattern 13b is wet-etched using the second etching liquid to form an opening width dimension corresponding to the light-shielding pattern 13b. The opening width etches the pattern 12b and removes the photoresist pattern 14a. When the photoresist pattern 14a is removed, a known photoresist stripping liquid can be used, and thus detailed description thereof is omitted here.

根據以上，如圖6(g)所示，以包圍遮光區域B2之方式形成僅由相位移圖案11a構成之邊界部分B1，且於邊界部分B1形成位於玻璃基板S之露出部分C側之多階區域B1b、及位於遮光區域B2側之均勻厚度區域B1a，從而可獲得遮光圖案13b(及蝕刻終止圖案12b)之開口寬度寬於相位移圖案11a之開口寬度的邊緣加強型之相位移光罩M2。 According to the above, as shown in FIG. 6(g), the boundary portion B1 composed only of the phase shift pattern 11a is formed so as to surround the light-shielding region B2, and the multi-step portion on the exposed portion C side of the glass substrate S is formed at the boundary portion B1. The region B1b and the uniform thickness region B1a on the side of the light-shielding region B2, so that the edge-enhancing phase shift mask M2 having the opening width of the light-shielding pattern 13b (and the etching termination pattern 12b) wider than the opening width of the phase shift pattern 11a can be obtained. .

於圖6中，以垂直地形成相位移圖案11a之側面之方式表示，但實際如圖5所示，形成有階部B1bh及階部B1bi。又，於圖6中，以垂直地形成遮光圖案13b之側面之方式表示，但實際如圖5所示，形成有傾斜面13s。 In FIG. 6, the side surface of the phase shift pattern 11a is vertically formed, but as shown in FIG. 5, the step B1bh and the step B1bi are formed. Further, in Fig. 6, the side surface of the light-shielding pattern 13b is formed vertically, but as shown in Fig. 5, an inclined surface 13s is actually formed.

根據本實施形態，於在透明基板S上依序積層相位移層11、蝕刻終止層12及遮光層13而構成相位移空白光罩MB時，藉由設定形成相位移層11時之氧化性氣體之流量比而控制蝕刻速率，藉此，可製造具有多階區域B1b之邊緣加強型之相位移光罩M2。因此，可製造高精細之視認性較高之相位移光罩M。 According to the present embodiment, when the phase shifting layer 11, the etching stopper layer 12, and the light shielding layer 13 are sequentially laminated on the transparent substrate S to form the phase shift blank mask MB, the oxidizing gas when the phase shift layer 11 is formed is set. The etch rate is controlled by the flow ratio, whereby the edge-shifted mask M2 having the edge-enhanced type of the multi-step region B1b can be manufactured. Therefore, it is possible to manufacture a phase shift mask M having a high definition and high visibility.

根據本實施形態，於在透明基板S上依序積層相位移圖案11a、蝕刻終止圖案12b及遮光圖案13b而成之相位移光罩M2中，形成僅積層有相位移圖案11a之邊界部分B1，且與上述單層之相位移光罩M1同樣地，藉由設定形成相位移層11時之氧化性氣體流量比，而將包含多階區域B1b之邊界部分B1之厚度設定以成為所期望之狀態之方式形成為多階，藉此，使於複合波長下對應於各波長之階部B1bh、階部B1bi位於沿遮光區域B2形狀(圖案輪廓)之特定之範圍而可製造高精細之邊緣加強型之相位移光罩M2。 According to the present embodiment, in the phase shift mask M2 in which the phase shift pattern 11a, the etching stop pattern 12b, and the light-shielding pattern 13b are sequentially laminated on the transparent substrate S, the boundary portion B1 in which only the phase shift pattern 11a is laminated is formed. Similarly to the above-described single-layer phase shift mask M1, the thickness of the boundary portion B1 including the multi-step region B1b is set to a desired state by setting the oxidizing gas flow ratio when the phase shift layer 11 is formed. The method is formed in a plurality of stages, whereby the step portion B1bh and the step portion B1bi corresponding to the respective wavelengths at the complex wavelength are located in a specific range along the shape (pattern profile) of the light-shielding region B2, and a high-definition edge-enhanced type can be manufactured. The phase shifts the mask M2.

又，相位移層11係由選自Cr之氧化物、氮化物、碳化物、氮氧化物、氮碳化物及氮碳氧化物中之任1種所構成，且具有以特定寬度具 有充分發揮相位移效果之膜厚的多階區域B1b。為了具有此種充分發揮相位移效果之膜厚，蝕刻時間以相對於遮光層13之蝕刻時間超過1倍之方式變長，但由於各層間之附著強度充分高，故而線粗糙度為大致直線狀，且就針對被設為複合波長之光之光學性而言，形成具有圖案剖面垂直地對應之階部B1bh、階部B1bi的多階區域B1b(邊界部分B1)。因此，作為光罩而可進行良好之圖案之形成。 Further, the phase shift layer 11 is composed of any one selected from the group consisting of oxides of Cr, nitrides, carbides, nitrogen oxides, nitrogen carbides, and nitrogen oxides, and has a specific width. The multi-step region B1b having a film thickness that sufficiently exerts the phase shift effect. In order to have such a film thickness that sufficiently exhibits the phase shift effect, the etching time is longer than the etching time of the light shielding layer 13 by more than one time. However, since the adhesion strength between the layers is sufficiently high, the line roughness is substantially linear. Further, for the optical property of the light set to the composite wavelength, the multi-step region B1b (boundary portion B1) having the step portion B1bh and the step portion B1bi corresponding to the pattern cross section vertically is formed. Therefore, a good pattern can be formed as a photomask.

又，藉由使用包含Ni之膜作為蝕刻終止層12，而可充分提高與包含Cr之遮光層13及包含Cr之相位移層11之附著強度。 Further, by using a film containing Ni as the etching stopper layer 12, the adhesion strength to the light-shielding layer 13 containing Cr and the phase shift layer 11 containing Cr can be sufficiently improved.

因此，於以濕式蝕刻液對遮光層13、蝕刻終止層12及相位移層11進行蝕刻時，蝕刻液未自遮光層13與蝕刻終止層12之界面、或蝕刻終止層12與相位移層11之界面滲入，因此，可提高所形成之遮光圖案13b、相位移圖案11a之CD精度，且可將膜之剖面形狀設為具有呈現對光罩而言良好之相位移效果之階部B1bh、階部B1bi的多階區域B1b(邊界部分B1)形狀。 Therefore, when the light shielding layer 13, the etch stop layer 12, and the phase shift layer 11 are etched by the wet etching solution, the etching liquid is not from the interface between the light shielding layer 13 and the etch stop layer 12, or the etch stop layer 12 and the phase shift layer. Since the interface of 11 is infiltrated, the CD precision of the formed light-shielding pattern 13b and the phase shift pattern 11a can be improved, and the cross-sectional shape of the film can be set to have a step B1bh which exhibits a good phase shift effect on the mask, The multi-order region B1b (boundary portion B1) shape of the step portion B1bi.

進而，遮光圖案13a之蝕刻速度受到遮光層13之組成或蝕刻終止層12與遮光層13之界面狀態之影響。例如於由以鉻為主成分之層及以氧化鉻為主成分之層之2層膜構成遮光層13的情形時，若提高以鉻為主成分之層之鉻成分之比率則可提高蝕刻速度，另一方面，若降低鉻成分之比率則可降低蝕刻速度。作為遮光圖案13a之蝕刻量，例如可於200nm~1000nm之範圍內設定。 Further, the etching speed of the light shielding pattern 13a is affected by the composition of the light shielding layer 13 or the interface state of the etching stopper layer 12 and the light shielding layer 13. For example, when the light shielding layer 13 is composed of a two-layer film of a layer mainly composed of chromium and a layer mainly composed of chromium oxide, the etching rate can be increased by increasing the ratio of the chromium component of the layer mainly composed of chromium. On the other hand, if the ratio of the chromium component is lowered, the etching rate can be lowered. The etching amount of the light-shielding pattern 13a can be set, for example, in the range of 200 nm to 1000 nm.

同時，藉由設定形成相位移層11時之氧化性氣體之流量比而可將蝕刻終止層12與遮光層13、蝕刻終止層12與相位移層11之各界面中的遮光層13與相位移層11之蝕刻速率設定為較佳之範圍。因此，控制遮光層13與蝕刻終止層12之界面、或蝕刻終止層12與相位移層11之界面附近之蝕刻量，可提高所形成之遮光圖案13b、相位移圖案11a之CD精度，且可將膜之剖面形狀設為具有對光罩而言良好之多階區域B1b 之形狀。 At the same time, the light-shielding layer 13 and the phase in each interface of the etch stop layer 12 and the light-shielding layer 13, the etch stop layer 12 and the phase shift layer 11 can be displaced by setting the flow ratio of the oxidizing gas when the phase shift layer 11 is formed. The etching rate of layer 11 is set to a preferred range. Therefore, by controlling the interface between the light shielding layer 13 and the etch stop layer 12 or the etching amount near the interface between the etch stop layer 12 and the phase shift layer 11, the CD precision of the formed light shielding pattern 13b and the phase shift pattern 11a can be improved, and The cross-sectional shape of the film is set to have a multi-step area B1b good for the mask The shape.

根據本實施形態，相位移光罩M1具有可對300nm以上且500nm以下之波長區域之任一種光具有180°之相位差之形成有具有階部B1bh、階部B1bi之多階區域B1b的相位移圖案11a。因此，根據上述製造方法，藉由使用上述波長區域之光而可實現基於相位移效果之圖案精度之提高，進而可使焦點深度變深，從而可形成微細且高精度之圖案。藉此，可製造高畫質之平板顯示器。 According to the present embodiment, the phase shift mask M1 has a phase shift in which a multi-step region B1b having a step portion B1bh and a step portion B1bi is formed with a phase difference of 180° for any one of wavelength regions of 300 nm or more and 500 nm or less. Pattern 11a. Therefore, according to the above-described manufacturing method, by using the light in the above-described wavelength region, the pattern accuracy based on the phase shift effect can be improved, and the depth of focus can be further deepened, whereby a fine and highly precise pattern can be formed. Thereby, a high-quality flat panel display can be manufactured.

又，於本實施形態中，於使遮光層13於玻璃基板S之整個表面成膜後，藉由對必要部位進行蝕刻而形成經圖案化而成之遮光層(遮光圖案)13，但代替此，亦可於形成遮光層13之形成區域開口之光阻圖案後，形成遮光層13。藉由在形成遮光層13後去除上述光阻圖案，而可於必要區域形成遮光層13(剝離法)。 Further, in the present embodiment, after the light shielding layer 13 is formed on the entire surface of the glass substrate S, the patterned portion of the light shielding layer (light shielding pattern) 13 is formed by etching the necessary portions. The light shielding layer 13 may be formed after forming a photoresist pattern in which the formation region of the light shielding layer 13 is opened. The light-shielding layer 13 can be formed in a necessary region by removing the photoresist pattern after the light-shielding layer 13 is formed (peeling method).

於本發明之相位移光罩中，該相位移光罩具備透明基板、形成於該透明基板之表面之以Cr為主成分之相位移層、形成於自上述透明基板離開之側之上述相位移層表面的以選自Ni、Co、Fe、Ti、Si、Al、Nb、Mo、W及Hf中之至少1種金屬為主成分之蝕刻終止層、及形成於遠離上述相位移層之側之上述蝕刻終止層上的以Cr為主成分之遮光層，且較俯視時形成於上述相位移層之相位移圖案之線寬而較窄地設定形成於上述遮光層之遮光圖案之線寬，且該相位移光罩之製造方法包括如下步驟：於上述透明基板形成上述相位移層、上述蝕刻終止層及上述遮光層；於上述遮光層上形成具有特定之開口圖案之光罩；隔著該形成之光罩依次對上述遮光層與上述蝕刻終止層進行蝕刻而形成遮光圖案與蝕刻終止圖案；隔著上述光罩對上述相位移層進行濕式蝕刻而形成具有多階區域B1b之相位移圖案；及進而對上述蝕刻終止層進行蝕刻；且藉由設定上述相位移層之蝕刻速率之上述透明基板側與上述蝕刻終止層側中之比，並控制蝕刻處理時間，而可將上述相位 移層之俯視時側面之寬度尺寸相對於厚度尺寸的比設定為特定之範圍。 In the phase shift mask of the present invention, the phase shift mask includes a transparent substrate, a phase shift layer mainly composed of Cr formed on a surface of the transparent substrate, and the phase shift formed on a side away from the transparent substrate. An etch stop layer having a surface selected from at least one of Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W, and Hf as a main component, and a side formed away from the phase shift layer a light-shielding layer containing Cr as a main component on the etch-stop layer, and a line width of a phase shift pattern formed in the phase shift layer in a plan view, and a line width of a light-shielding pattern formed on the light-shielding layer is set narrowly, and The method for manufacturing the phase shift mask includes the steps of: forming the phase shift layer, the etch stop layer, and the light shielding layer on the transparent substrate; forming a photomask having a specific opening pattern on the light shielding layer; The light mask sequentially etches the light shielding layer and the etching stopper layer to form a light shielding pattern and an etching termination pattern; and the phase shift layer is wet-etched via the photomask to form a multi-step region B1b a phase shift pattern; and further etching the etch stop layer; and by setting a ratio of an etch rate of the phase shift layer to a side of the transparent substrate side and the etch stop layer side, and controlling an etching process time, Phase The ratio of the width dimension of the side surface of the shift layer to the thickness dimension in the plan view is set to a specific range.

<第3實施形態> <Third embodiment>

以下，基於圖式對本發明之相位移光罩之製造方法之第3實施形態進行說明。 Hereinafter, a third embodiment of the method for producing a phase shift mask of the present invention will be described based on the drawings.

圖7係表示本實施形態之相位移光罩之模式剖面圖。圖8係模式性地表示本實施形態之相位移光罩之製造方法之步驟圖，於圖中，M3為相位移光罩。再者，於圖7、圖8中，對與圖1~圖6對應之部分標註同一符號而省略其說明。 Fig. 7 is a schematic cross-sectional view showing the phase shift mask of the embodiment. Fig. 8 is a view schematically showing a step of a method of manufacturing a phase shift mask according to the embodiment. In the figure, M3 is a phase shift mask. In addition, in FIGS. 7 and 8, the same reference numerals will be given to the portions corresponding to those in FIGS. 1 to 6 and the description thereof will be omitted.

如圖7所示，本實施形態之相位移光罩M3設置於玻璃基板(透明基板)S表面，且被設為可具有180°之相位差之相位移圖案11a位於上側、遮光圖案13a位於其下側之所謂上置型之相位移光罩。 As shown in Fig. 7, the phase shift mask M3 of the present embodiment is disposed on the surface of a glass substrate (transparent substrate) S, and is provided with a phase shift pattern 11a having a phase difference of 180° on the upper side, and a light blocking pattern 13a is located thereon. The so-called upper phase shift mask of the lower side.

如圖7及圖8(l)所示，相位移光罩M3係於曝光圖案所形成之曝光區域內，具有俯視時為玻璃基板S之露出部分C與相位移圖案11a之邊界部分B1、及於相位移圖案11a之下側形成有遮光圖案13a之遮光區域B3。於遮光區域B3內，相位移圖案11a之厚度被設為固定值T11，並且以俯視時包圍成為該曝光圖案之遮光區域B3之方式存在僅由相位移圖案11a構成之邊界部分B1。於邊界部分B1，被設為厚度Tg之均勻區域B1a位於遮光區域B3側，多階區域B1b位於玻璃基板S之露出部分C側。 As shown in FIG. 7 and FIG. 8(l), the phase shift mask M3 is in the exposure region formed by the exposure pattern, and has a boundary portion B1 between the exposed portion C of the glass substrate S and the phase shift pattern 11a in plan view. A light shielding region B3 of the light shielding pattern 13a is formed on the lower side of the phase shift pattern 11a. In the light-shielding region B3, the thickness of the phase shift pattern 11a is set to a fixed value T11, and the boundary portion B1 composed only of the phase shift pattern 11a is present so as to surround the light-shielding region B3 which is the exposure pattern in plan view. In the boundary portion B1, the uniform region B1a set to the thickness Tg is located on the side of the light-shielding region B3, and the multi-step region B1b is located on the exposed portion C side of the glass substrate S.

於本實施形態之相位移光罩之製造方法中，首先，如圖8(a)所示，於玻璃基板S上形成遮光層13。 In the method of manufacturing a phase shift mask of the present embodiment, first, as shown in FIG. 8(a), a light shielding layer 13 is formed on a glass substrate S.

其次，如圖8(b)所示，於遮光層13上形成光阻層14。接著，如圖8(c)、(d)所示，藉由對光阻層14進行曝光及顯影而去除光阻層14之區域14p並於遮光層13上形成光阻圖案14a。光阻圖案14a係作為遮光層13之蝕刻遮罩而發揮功能，並可根據遮光層13之蝕刻圖案而適當決定 形狀。 Next, as shown in FIG. 8(b), a photoresist layer 14 is formed on the light shielding layer 13. Next, as shown in FIGS. 8(c) and 8(d), the region 14p of the photoresist layer 14 is removed by exposure and development of the photoresist layer 14, and the photoresist pattern 14a is formed on the light shielding layer 13. The photoresist pattern 14a functions as an etching mask of the light shielding layer 13 and can be appropriately determined according to the etching pattern of the light shielding layer 13. shape.

接著，如圖8(e)所示，藉由蝕刻將遮光層13圖案化為特定之圖案形狀。藉此，於玻璃基板S上形成特定形狀之遮光圖案13a。於遮光層13之蝕刻步驟中，可應用濕式蝕刻法或乾式蝕刻法，尤其是於基板S為大型之情形時，由於基板較大故而就成本方面而言採用濕式蝕刻法。遮光層13之蝕刻液可適當選擇，於遮光層13為鉻系材料之情形時，例如可使用硝酸鈰銨與過氯酸之水溶液。該蝕刻液與玻璃基板之選擇比較高，故而於遮光層13之圖案化時可保護玻璃基板S。另一方面，於遮光層13由金屬矽化物系材料所構成之情形時，作為蝕刻液，例如可使用氟化氫銨。 Next, as shown in FIG. 8(e), the light shielding layer 13 is patterned into a specific pattern shape by etching. Thereby, the light-shielding pattern 13a of a specific shape is formed on the glass substrate S. In the etching step of the light shielding layer 13, a wet etching method or a dry etching method can be applied. Especially in the case where the substrate S is large, the wet etching method is used in terms of cost because the substrate is large. The etching liquid of the light shielding layer 13 can be suitably selected. When the light shielding layer 13 is a chromium-based material, for example, an aqueous solution of cerium ammonium nitrate and perchloric acid can be used. Since the etching liquid and the glass substrate are relatively high in selection, the glass substrate S can be protected when the light shielding layer 13 is patterned. On the other hand, when the light shielding layer 13 is composed of a metal halide material, for example, ammonium hydrogen fluoride can be used as the etching liquid.

於遮光層13之圖案化後，如圖8(f)所示，光阻圖案14a被去除。於去除光阻圖案14a時，例如可使用氫氧化鈉水溶液。 After the patterning of the light shielding layer 13, as shown in FIG. 8(f), the photoresist pattern 14a is removed. When the photoresist pattern 14a is removed, for example, an aqueous sodium hydroxide solution can be used.

其次，如圖8(g)所示，形成相位移層11。相位移層11係以被覆遮光圖案13a之方式形成於玻璃基板S之大致整個表面。 Next, as shown in Fig. 8(g), the phase shift layer 11 is formed. The phase shift layer 11 is formed on substantially the entire surface of the glass substrate S so as to cover the light shielding pattern 13a.

作為相位移層11之成膜方法，可應用電子束(EB)蒸鍍法、雷射蒸鍍法、原子層成膜(ALD)法、離子輔助濺鍍法等，尤其是於大型基板之情形時，藉由採用DC濺鍍法而實現膜厚均勻性優異之成膜。再者，不限於DC濺鍍法，亦可應用AC(Alternating Current，交流)濺鍍法或RF(Radio Frequency，射頻)濺鍍法。 As a film formation method of the phase shift layer 11, an electron beam (EB) vapor deposition method, a laser vapor deposition method, an atomic layer formation (ALD) method, an ion-assisted sputtering method, or the like can be applied, especially in the case of a large substrate. At this time, film formation excellent in film thickness uniformity is achieved by DC sputtering. Furthermore, it is not limited to the DC sputtering method, and an AC (Alternating Current) sputtering method or an RF (Radio Frequency) sputtering method can also be applied.

相位移層11係由鉻系材料所構成。尤其是於本實施形態中，相位移層11例如由碳氧氮化鉻所構成。根據鉻系材料，尤其是於大型之基板上可獲得良好之圖案化性。 The phase shift layer 11 is composed of a chromium-based material. In particular, in the present embodiment, the phase shift layer 11 is made of, for example, chromium oxycarbonitride. Good patterning can be obtained according to the chromium-based material, especially on a large substrate.

於相位移層11之成膜中，以與上述實施形態中之成膜條件同樣之方式，設定氧化性氣體(二氧化碳氣體)之氛圍氣體中之流量比，藉此，控制蝕刻步驟中之相位移層11之蝕刻速率，控制傾斜面11s之傾斜狀態。 In the film formation of the phase shift layer 11, the flow rate ratio in the atmosphere gas of the oxidizing gas (carbon dioxide gas) is set in the same manner as the film forming conditions in the above embodiment, thereby controlling the phase shift in the etching step. The etching rate of the layer 11 controls the tilt state of the inclined surface 11s.

接著，如圖8(h)所示，於相位移層11上形成光阻層14。其次，如圖8(i)、(j)所示，藉由對光阻層14進行曝光及顯影而於相位移層11上形成光阻圖案14a。光阻圖案14a係作為相位移層11之蝕刻遮罩而發揮功能，並可根據相位移層11之蝕刻圖案而適當決定形狀。 Next, as shown in FIG. 8(h), a photoresist layer 14 is formed on the phase shift layer 11. Next, as shown in FIGS. 8(i) and (j), the photoresist pattern 14a is formed on the phase shift layer 11 by exposing and developing the photoresist layer 14. The photoresist pattern 14a functions as an etching mask of the phase shift layer 11, and can appropriately determine the shape according to the etching pattern of the phase shift layer 11.

接著，如圖8(k)所示，將相位移層11蝕刻成特定之圖案形狀。藉此，於玻璃基板S上形成特定形狀之相位移圖案11a及玻璃基板S露出之部分C。相位移層11之蝕刻步驟尤其是於基板S為大型之情形時，就處理之面內均勻性及成本方面而言採用濕式蝕刻法。相位移層11之蝕刻液可適當選擇，於本實施形態中，可使用硝酸鈰銨與過氯酸之水溶液。該蝕刻液與玻璃基板之選擇比較高，故而於相位移層11之圖案化時可保護玻璃基板S。 Next, as shown in FIG. 8(k), the phase shift layer 11 is etched into a specific pattern shape. Thereby, the phase shift pattern 11a of a specific shape and the part C exposed by the glass substrate S are formed on the glass substrate S. The etching step of the phase shift layer 11 is particularly a wet etching method in terms of in-plane uniformity and cost of the treatment when the substrate S is large. The etching liquid of the phase shift layer 11 can be appropriately selected. In the present embodiment, an aqueous solution of cerium ammonium nitrate and perchloric acid can be used. Since the etching liquid and the glass substrate are selected to be relatively high, the glass substrate S can be protected during patterning of the phase shift layer 11.

此時，如圖2或圖3所示，形成為蝕刻速率不同之多層的相位移層11受到蝕刻，藉此，如圖5中揭示詳細情況般，成為形成有具有階部B1bh、階部B1bi之多階區域B1b之相位移圖案11a。 At this time, as shown in FIG. 2 or FIG. 3, the phase shift layer 11 formed in a plurality of layers having different etching rates is etched, whereby, as disclosed in detail in FIG. 5, the step B1bh and the step B1bi are formed. The phase shift pattern 11a of the multi-step region B1b.

於形成相位移圖案11a後去除光阻圖案14a，如圖8(l)所示，製造本實施形態之相位移光罩M3。於去除光阻圖案14a時，例如可使用氫氧化鈉水溶液。 After the phase shift pattern 11a is formed, the photoresist pattern 14a is removed, and as shown in Fig. 8(l), the phase shift mask M3 of the present embodiment is manufactured. When the photoresist pattern 14a is removed, for example, an aqueous sodium hydroxide solution can be used.

根據本實施形態，於透明基板S上之曝光區域內，依序積層作為遮光區域B3之遮光圖案13a、相位移圖案11a而成之相位移光罩M3形成僅使相位移圖案11a成膜之邊界部分B1，且與上述僅相位移圖案之相位移光罩M1或下置型之相位移光罩M2同樣地，藉由設定形成相位移層11時之氧化性氣體流量比，而可將包含多階區域B1b之邊界部分B1之厚度及多階形狀以成為所期望之狀態之方式控制。藉此，使於複合波長下對應於各波長之厚度部位位於沿遮光區域B3形狀(圖案輪廓)之特定之範圍而可製造高精細之邊緣加強型之相位移光罩M3。 According to the present embodiment, the phase shift mask M3 which is formed by sequentially arranging the light-shielding pattern 13a and the phase shift pattern 11a as the light-shielding region B3 in the exposure region on the transparent substrate S forms a boundary at which only the phase shift pattern 11a is formed. In the portion B1, similarly to the phase shift mask M1 of the phase shift only pattern or the phase shift mask M2 of the lower type, the oxidizing gas flow ratio when the phase shift layer 11 is formed can be set to include a plurality of stages. The thickness and multi-step shape of the boundary portion B1 of the region B1b are controlled in such a manner as to be in a desired state. Thereby, the phase shift mask M3 of the high-definition edge-enhancing type can be manufactured by the thickness part corresponding to each wavelength at the composite wavelength in the specific range of the shape (pattern outline) of the light-shielding area B3.

以上，對本發明之實施形態進行了說明，但當然本發明並不限 定於此，基於本發明之技術思想可進行各種變化。 Although the embodiments of the present invention have been described above, the present invention is not limited thereto. As such, various changes can be made based on the technical idea of the present invention.

尤其是關於邊界部分B1中之多階區域B1b，藉由設定形成相位移層11時之氧化性氣體流量比而如圖1、圖3~圖5、圖7般，設為具有階部B1bh及階部B1bi之2階作為膜厚自均勻區域B1a減少之多階區域B1b的側面形狀，但此始終為對應於包含g射線、h射線、i射線之3種波長之複合波長之光者，於用於曝光之波長與該3種波長不同之情形時，並不限於此。同時，對應於所應用之波長而該等階部之厚度設定亦變化。又，就光學性相位調整之必要性而言，亦可將該等階部之厚度控制為所期望之狀態。 In particular, the multi-step region B1b in the boundary portion B1 is set to have a step B1bh as shown in FIG. 1, FIG. 3 to FIG. 5, and FIG. 7 by setting the oxidizing gas flow rate ratio when the phase shift layer 11 is formed. The second order of the step B1bi is a side shape of the multi-step region B1b whose film thickness is reduced from the uniform region B1a, but this is always a light corresponding to a composite wavelength including three wavelengths of g-ray, h-ray, and i-ray. When the wavelength for exposure is different from the three kinds of wavelengths, it is not limited thereto. At the same time, the thickness settings of the equal-order portions also vary corresponding to the applied wavelength. Further, in terms of the necessity of optical phase adjustment, the thickness of the equal-order portions may be controlled to a desired state.

[實施例] [Examples]

作為對應於上述第1實施形態之實施例，進行以下實驗。即，於玻璃基板S上藉由濺鍍法，使相位移層11之鉻之碳氮氧化膜以145nm之厚度成膜。 The following experiment was carried out as an example corresponding to the first embodiment described above. That is, the chromium carbonitride oxide film of the phase shift layer 11 was formed on the glass substrate S by a sputtering method to a thickness of 145 nm.

於該相位移層11上形成光阻圖案14a，並隔著該光阻圖案14a使用硝酸鈰銨與過氯酸之混合蝕刻液對相位移層11進行蝕刻而形成相位移圖案11a，藉此，獲得如下之邊緣加強型之相位移光罩M1。 A photoresist pattern 14a is formed on the phase shift layer 11, and the phase shift layer 11 is etched by using a mixed etching solution of cerium ammonium nitrate and perchloric acid via the photoresist pattern 14a to form a phase shift pattern 11a. The edge-enhancing phase shift mask M1 is obtained as follows.

於上述製造步驟中，作為相位移層11之成膜條件而使氛圍氣體之氧化性氣體流量變化，測定蝕刻後之多階區域之寬度尺寸B1b之值。 In the above-described manufacturing step, the flow rate of the oxidizing gas of the atmosphere gas is changed as the film formation condition of the phase shift layer 11, and the value of the width dimension B1b of the multi-step region after the etching is measured.

將其結果以相對於相位移層11之厚度T11之比、與作為惰性氣體之Ar、作為氮化性氣體之N2及作為氧化性氣體之CO2之流量的關係進行表示。 The results are shown in relation to the ratio of the thickness T11 of the phase shift layer 11 to the flow rate of Ar as an inert gas, N 2 as a nitriding gas, and CO 2 as an oxidizing gas.

同時，以相對於相位移層11之厚度T11之比、與作為惰性氣體之Ar、作為氮化性氣體之N2及作為氧化性氣體之CO2之流量比的關係表示。 At the same time, it is expressed by the relationship of the ratio of the thickness T11 of the phase shift layer 11 to the ratio of the flow rate of Ar as an inert gas, N 2 as a nitriding gas, and CO 2 as an oxidizing gas.

此處，所謂流量比，係二氧化碳流量/(Ar氣體流量+N2氣體流量+CO2氣體流量)×100之 值， Here, the flow ratio is a value of carbon dioxide flow rate / (Ar gas flow rate + N 2 gas flow rate + CO 2 gas flow rate) × 100,

所謂距離/膜厚，係(俯視時之傾斜面11s之寬度B1b)/(相位移層11之厚度T11)之值。 The distance/film thickness is a value (the width B1b of the inclined surface 11s in plan view) / (the thickness T11 of the phase shift layer 11).

表1係作為對應於圖1所示之第1實施形態之具體例，為對i射線、h射線之2種波長之曝光具有效果的多階積層狀態之例。 Table 1 is an example of a multi-step laminated state which has an effect on exposure of two wavelengths of i-rays and h-rays as a specific example corresponding to the first embodiment shown in Fig. 1 .

表2、表3係作為對應於圖3所示之第1實施形態之具體例，表2、3中為對i射線、h射線、g射線之3種波長之曝光具有效果的多階積層狀態之例。 Tables 2 and 3 are specific examples corresponding to the first embodiment shown in Fig. 3, and Tables 2 and 3 are multi-step laminated states having effects on exposure of three wavelengths of i-ray, h-ray, and g-ray. An example.

根據表1~表3所示之結果可知，並不僅限於本實施例，蝕刻速率變更後之蝕刻速率變更層之厚度亦可設為1.0nm以外，又，蝕刻速率變更層成膜時之氧化性氣體之量係於以下條件下有效。且關於對應於曝光波長之膜厚之層、關於氣體條件均並不限定於表1~3之條件。 According to the results shown in Tables 1 to 3, it is not limited to the present embodiment, and the thickness of the etching rate changing layer after the etching rate is changed may be 1.0 nm or more, and the etching rate is changed to the oxidizing property at the time of film formation. The amount of gas is effective under the following conditions. Further, the layer corresponding to the film thickness of the exposure wavelength and the gas conditions are not limited to the conditions of Tables 1 to 3.

作為氣體流量之最佳範圍，可知於包含多階區域B1b之邊界部分B1之側面成為垂直、即成為剖面垂直之CO2低之條件下較佳為7.3-25sccm(即3.68%~11.60%)之範圍，於包含多階區域B1b之邊界部分B1之側面成為垂直、即成為剖面水平之CO2高之條件下較佳為25-63.3sccm(11.60%~24.89%)之範圍。 As the optimum range of the gas flow rate, it is understood that the side surface including the boundary portion B1 of the multi-step region B1b is vertical, that is, the CO 2 having a vertical cross-section is preferably 7.3 to 25 sccm (that is, 3.68% to 11.60%). The range is preferably 25-63.3 sccm (11.60% to 24.89%) under the condition that the side surface of the boundary portion B1 including the multi-step region B1b is vertical, that is, the CO 2 height at the cross-sectional level is high.

11a‧‧‧相位移圖案 11a‧‧‧ phase shift pattern

11sh、11si、11t、11u‧‧‧端部 11sh, 11si, 11t, 11u‧‧‧ end

B1‧‧‧邊界部分 B1‧‧‧ boundary section

B1a‧‧‧均勻厚度區域 B1a‧‧‧even thickness area

B1b‧‧‧多階區域 B1b‧‧‧ multi-level area

B1bh、B1bi‧‧‧階部 B1bh, B1bi‧‧‧

C‧‧‧露出部分 C‧‧‧Exposed part

M1‧‧‧相位移光罩 M1‧‧‧ phase shift mask

S‧‧‧玻璃基板(透明基板) S‧‧‧ glass substrate (transparent substrate)

T11、Tg、Th、Ti‧‧‧厚度 T11, Tg, Th, Ti‧‧‧ thickness

Claims (9)

一種相位移光罩之製造方法，其特徵在於：其係製造相位移光罩之方法，該相位移光罩包括：透明基板；及相位移層，其具有於至少上述透明基板之表面以固定厚度形成之部分且以Cr為主成分，可對300nm以上且500nm以下之波長區域之任一種光具有180°之相位差；且該相位移光罩之製造方法包括如下步驟：於上述透明基板上多階地形成上述相位移層；及對上述相位移層進行濕式蝕刻，並以上述相位移層與上述透明基板於俯視時具有邊界部分之方式將上述相位移層圖案化，而形成相位移圖案；且於上述相位移層之形成步驟中，藉由設定成膜氛圍氣體中氧化性氣體之流量比，而可分別設定上述相位移層中之各階之蝕刻速率，於俯視時之上述相位移層與上述透明基板之邊界部分，形成將上述相位移層之厚度變化設定為多階之多階區域。 A method for manufacturing a phase shift mask, characterized in that it is a method for manufacturing a phase shift mask, the phase shift mask comprises: a transparent substrate; and a phase shift layer having a fixed thickness on at least the surface of the transparent substrate The portion formed and containing Cr as a main component may have a phase difference of 180° for any one of wavelength regions of 300 nm or more and 500 nm or less; and the method for manufacturing the phase shift mask includes the following steps: Forming the phase shifting layer on the terrace; and wet etching the phase shifting layer, and patterning the phase shifting layer by the phase shifting layer and the transparent substrate having a boundary portion in a plan view to form a phase shifting pattern And in the forming step of the phase shifting layer, by setting a flow ratio of the oxidizing gas in the film forming atmosphere, the etching rate of each step in the phase shifting layer can be set separately, and the phase shifting layer in a plan view A multi-step region in which a thickness variation of the phase shift layer is set to a plurality of stages is formed at a boundary portion with the transparent substrate. 如請求項1之相位移光罩之製造方法，其中於上述相位移層之多階區域內，各階之厚度係以於不同波長之光中具有180°之相位差之方式對應。 The method of manufacturing a phase shift mask according to claim 1, wherein in the multi-step region of the phase shift layer, the thickness of each step corresponds to a phase difference of 180° in light of different wavelengths. 如請求項1之相位移光罩之製造方法，其中作為上述相位移層中之各階之成膜氛圍的成膜氣體包含惰性氣體、氮化性氣體及氧化性氣體，或者包含氮化性氣體與氧化性氣體，且相對於總氣體流量，上述氧化性氣體之流量比選自3.68%~24.89%之範圍。 The method of manufacturing a phase shift mask according to claim 1, wherein the film forming gas which is a film forming atmosphere of each of the phase shifting layers contains an inert gas, a nitriding gas, and an oxidizing gas, or contains a nitriding gas and The oxidizing gas, and the flow rate ratio of the oxidizing gas is selected from the range of 3.68% to 24.89% with respect to the total gas flow rate. 如請求項2之相位移光罩之製造方法，其中作為上述相位移層中 之各階之成膜氛圍的成膜氣體包含惰性氣體、氮化性氣體及氧化性氣體，或者包含氮化性氣體與氧化性氣體，且相對於總氣體流量，上述氧化性氣體之流量比選自3.68%~24.89%之範圍。 A method of manufacturing a phase shift mask according to claim 2, wherein the phase shift layer is used The film forming gas of each of the film forming atmospheres includes an inert gas, a nitriding gas, and an oxidizing gas, or a nitriding gas and an oxidizing gas, and the flow rate ratio of the oxidizing gas is selected from the total gas flow rate. The range is 3.68%~24.89%. 如請求項1至4中任一項之相位移光罩之製造方法，其包括於上述透明基板上由遮光層形成遮光圖案，並於上述遮光圖案上由上述相位移層形成上述相位移圖案的步驟，或者包括如下步驟：於上述透明基板上形成上述相位移層，於上述相位移層上介隔以選自Ni、Co、Fe、Ti、Si、Al、Nb、Mo、W及Hf中之至少1種金屬為主成分之蝕刻終止層形成，於上述蝕刻終止層上形成上述遮光層，並利用圖案形成而形成上述相位移圖案。 The method of manufacturing a phase shift mask according to any one of claims 1 to 4, comprising: forming a light shielding pattern on the transparent substrate by a light shielding layer, and forming the phase shift pattern on the light shielding pattern by the phase shift layer; And the step of: forming the phase shift layer on the transparent substrate, and interposing the phase shift layer on the phase shift layer selected from the group consisting of Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W, and Hf At least one metal is formed as an etch stop layer as a main component, and the light shielding layer is formed on the etching stopper layer, and the phase shift pattern is formed by patterning. 一種相位移光罩，其特徵在於：其係藉由如請求項1至5中任一項之相位移光罩之製造方法而製造，且包括：透明基板；及相位移層，其具有於至少上述透明基板之表面以固定厚度形成之部分且以Cr為主成分，可對300nm以上且500nm以下之波長區域之任一種光具有180°之相位差；且於上述相位移層，形成有俯視時具有相對於上述透明基板之邊界部分的相位移圖案，於俯視時之上述相位移層與上述透明基板之邊界部分，具有使上述相位移層之厚度多階地變化之多階區域。 A phase-shifting reticle, which is manufactured by the method of manufacturing a phase-shifting reticle according to any one of claims 1 to 5, and comprising: a transparent substrate; and a phase shifting layer having at least The surface of the transparent substrate is formed by a portion having a fixed thickness and containing Cr as a main component, and has a phase difference of 180° for any one of wavelength regions of 300 nm or more and 500 nm or less; and the phase shift layer is formed in a plan view. The phase shift pattern having a boundary portion with respect to the transparent substrate has a multi-step region in which the thickness of the phase shift layer is changed in multiple steps in a boundary portion between the phase shift layer and the transparent substrate in a plan view. 如請求項6之相位移光罩，其中於上述相位移層之上述多階區域內，各階之厚度以不同波長之光具有相位差之方式對應。 The phase shift mask of claim 6, wherein in the multi-step region of the phase shifting layer, the thickness of each step corresponds to a phase difference of light of different wavelengths. 如請求項7之相位移光罩，其中上述相位移層之多階區域厚度於g射線、h射線、i射線中具有180°之相位差。 The phase shift mask of claim 7, wherein the multi-step region thickness of the phase shifting layer has a phase difference of 180° in g rays, h rays, and i rays. 如請求項7之相位移光罩，其中上述相位移層之多階區域厚度於h射線、i射線中具有180°之相位差。 The phase shift mask of claim 7, wherein the multi-step region thickness of the phase shifting layer has a phase difference of 180° in the h-ray and the i-ray.
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6815731B2 (en) * 2016-01-27 2021-01-20 アルバック成膜株式会社 Phase shift mask blank and phase shift mask
JP6812236B2 (en) * 2016-12-27 2021-01-13 Hoya株式会社 A phase shift mask blank, a method for manufacturing a phase shift mask using the blank, and a method for manufacturing a display device.
WO2019003486A1 (en) * 2017-06-28 2019-01-03 アルバック成膜株式会社 Mask blank, phase shift mask, half-tone mask, mask blank manufacturing method, and phase shift mask manufacturing method
JP6998181B2 (en) * 2017-11-14 2022-02-04 アルバック成膜株式会社 Mask blank, phase shift mask and its manufacturing method
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JP6557381B1 (en) * 2018-05-08 2019-08-07 エスアンドエス テック カンパニー リミテッド Phase reversal blank mask and photomask
JP7402002B2 (en) * 2019-09-19 2023-12-20 アルバック成膜株式会社 Mask blanks, phase shift masks, manufacturing methods
KR102598440B1 (en) * 2019-12-20 2023-11-07 주식회사 에스앤에스텍 Phase-Shift Blankmask and Photomask for use in Flat Panel Display

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0234854A (en) * 1988-03-16 1990-02-05 Hitachi Ltd Mask, exposing device, and semiconductor element
JP2002116530A (en) * 1993-08-17 2002-04-19 Dainippon Printing Co Ltd Halftone phase shift photomask and blanks for the same
CN1530748A (en) * 2003-01-14 2004-09-22 Asml Embedded etching stopping layer for phase shift mask
JP2004333652A (en) * 2003-05-01 2004-11-25 Shin Etsu Chem Co Ltd Phase shift mask blank and phase shift photomask
TW201111905A (en) * 2009-06-30 2011-04-01 Ulvac Coating Corp Method for producing phase shift mask, method for producing flat panel display, and phase shift mask
TW201128295A (en) * 2009-09-29 2011-08-16 Ulvac Inc Photo-mask blanks, photo-mask and method for producing a photo-mask

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2967150B2 (en) * 1990-10-31 1999-10-25 ホーヤ株式会社 Phase shift mask, method of manufacturing the same, and exposure apparatus
JPH04254855A (en) * 1991-02-07 1992-09-10 Hitachi Ltd Photomask and its manufacture
JPH05134389A (en) * 1991-11-14 1993-05-28 Mitsubishi Electric Corp Mask for exposure
KR100311704B1 (en) * 1993-08-17 2001-12-15 기타오카 다카시 Halftone Phase Shift Photomask, Blanks for Halftone Phase Shift Photomask and Manufacturing Method of the Blanks
JPH11184063A (en) * 1997-12-25 1999-07-09 Ulvac Seimaku Kk Phase shift photomask blank and production of phase shift photomask as well as method for controlling side etching quantity

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0234854A (en) * 1988-03-16 1990-02-05 Hitachi Ltd Mask, exposing device, and semiconductor element
JP2002116530A (en) * 1993-08-17 2002-04-19 Dainippon Printing Co Ltd Halftone phase shift photomask and blanks for the same
CN1530748A (en) * 2003-01-14 2004-09-22 Asml Embedded etching stopping layer for phase shift mask
JP2004333652A (en) * 2003-05-01 2004-11-25 Shin Etsu Chem Co Ltd Phase shift mask blank and phase shift photomask
TW201111905A (en) * 2009-06-30 2011-04-01 Ulvac Coating Corp Method for producing phase shift mask, method for producing flat panel display, and phase shift mask
TW201128295A (en) * 2009-09-29 2011-08-16 Ulvac Inc Photo-mask blanks, photo-mask and method for producing a photo-mask

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